Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1456—Removing acid components
  • B01D53/1475—Removing carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
  • B01D53/1493—Selection of liquid materials for use as absorbents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/62—Carbon oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/77—Liquid phase processes
  • B01D53/78—Liquid phase processes with gas-liquid contact
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/0206—Polyalkylene(poly)amines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/2041—Diamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20436—Cyclic amines
  • B01D2252/20468—Cyclic amines containing a pyrrolidone-ring
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/20—Organic absorbents
  • B01D2252/204—Amines
  • B01D2252/20478—Alkanolamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
  • B01D2252/50—Combinations of absorbents
  • B01D2252/504—Mixtures of two or more absorbents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • 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

Definitions

• This present disclosure is directed to methods and compositions for carbon capture, more specifically, there is disclosed various solvent compositions used in carbon capture and methods of using such.
• a solvent composition for extracting carbon dioxide from a gaseous mixture comprising:
• a solvent composition for extracting carbon dioxide from a gaseous mixture comprising l-(2- hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMD A), and water.
• PR l-(2- hydroxyethyl)pyrrolidine
• HMD A hexamethylenediamine
• PR is present in molar concentration ranging from 2.0M to 4.0M.
• HMDA is present in molar concentration ranging from O.lM to 1.5M.
• PEI is present in molar concentration ranging from 0.00 IM to 0.5M.
• the total molar concentration of the solvent composition is in the range of 2.10M to 6.9M.
• the solvent consists essentially of l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMD A), polyethylenimine (PEI), and water.
• PR is present in molar concentration of 3 ,6M
• HMDA is present in molar concentration of 1.0M
• PEI is present in molar concentration of 0.01M.
• the solvent has a heat duty below 160 kJ/mol CO 2 .
• the solvent composition has a heat duty below 120.0 kJ/mol CO2.
• the solvent composition has an initial absorption rate g 0 reater than 0.40
• the solvent composition has an initial desorption rate g 0 reater than 35.0
• the solvent composition has a cyclic capacity greater than 0.95 •
• the solvent composition has a cyclic capacity is greater than 1.05 m L o . l s C ol°tn 2 .
• the solvent composition has a lean loading of 0 at 110° C.
• the solvent composition has a viscosity below 10mPa-s at 30°C.
• the solvent composition has an alkalinity in the range of 9.5 to 11.0 pKa at room temperature.
• a solvent composition for extracting carbon dioxide from a gaseous mixture comprising PR, HMDA, and a PEI, wherein PR is present in molar concentration ranging from 3.0M to 5.0M and HMDA is present in molar concentration ranging from 0. IM to 1 ,5M.
• PR is present in molar concentration ranging from 3.3M to 3.9M
• HMDA is present in molar concentration ranging from 0.5M to 1.2M
• PEI is present in molar concentration ranging from 0.005M to 0.015M.
• PEI is present in molar concentration of 0.0 IM.
• a method of performing carbon capture comprising collecting a flue gas comprising carbon dioxide from a flue gas emitting source and exposing the collected flue gas to a solvent composition according to a preferred embodiment of the present invention for a period of time sufficient to remove at least a portion of said carbon dioxide gas present in said flue gas.
• an apparatus for performing carbon capture comprising components configured to perform a method of performing carbon capture comprising: collecting a flue gas, comprising carbon dioxide from a flue gas emitting source; and exposing the collected flue gas to a solvent composition according to a preferred embodiment of the present invention for a period of time sufficient to remove at least a portion of said carbon dioxide gas present in said flue gas.
• a system for performing carbon capture comprising components configured to perform a method of performing carbon capture comprising: collecting a flue gas, comprising carbon dioxide from a flue gas emitting source; and exposing the collected flue gas to a solvent composition according to a preferred embodiment of the present invention for a period of time sufficient to remove at least a portion of said carbon dioxide gas present in said flue gas.
• a solvent composition according to a preferred embodiment of the present invention to perform carbon capture.
• a solvent composition for extracting carbon dioxide from a gaseous mixture the solvent composition comprising:
• compound II comprises two primary amino groups, having a chemical formula of NH 2 - (C m H 2m )-NH 2 , where m is an integer between 4 to 8.
• the solvent composition comprises one or more of l-(2- hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA), polyethylenimine (PEI), and water.
• PR l-(2- hydroxyethyl)pyrrolidine
• HMDA hexamethylenediamine
• PEI polyethylenimine
• the molar concentration of the PR is in the range of 2.0M to 5 ,0M.
• the molar concentration of the PR is 3.6M
• the molar concentration of the HMD A is 1.0M
• the molar concentration of the PEI is 0.0 IM.
• the PR has the CAS Registry Number #2955-88-6.
• the PEI is a branched PEI.
• the molar mass of the PEI ranges from 400g/mol to 1200g/mol.
• the molar mass of the PEI ranges from 600g/mol to lOOOg/mol.
• the molar mass for the PEI is approximately 800g/mol.
• the PEI has the CAS Registry Number CAS #25987- 06-8.
• the solvent composition has a viscosity below 10mPa-s at 30°C.
• the solvent composition has an alkalinity in the range of 9.5 to 11.0 pKa at room temperature.
• some preferred embodiments of the solvent composition may have a heat duty that is about 3.85 times lower than that of MEA.
• some preferred embodiments of the solvent composition may have a heat duty below about 120 kJ/mol CO2. This can provide a major reduction in energy input costs and operating costs for carbon capture methods, systems and/or apparatuses that use the solvent composition.
• some preferred embodiments of the solvent composition may have an initial absorp 1 tion rate that is g 0 reater than about 0.25 — — L.s U olt m n°*m 1 C in° 2 . This can reduce the size and/or cost of carbon capture systems and/or apparatuses that use the solvent composition.
• some preferred embodiments of the solvent composition may have an initial desorption rate that is about 3.85 times higher than that of MEA.
• some preferred embodiments of the solvent composition may have an initial desorption rate that is greater than about 25.0 — — L.s U olt m n°*m 1 C in° 2 .
• some preferred embodiments of the solvent composition may have a cyclic capacity that is 85% higher than that of MEA.
• some preferred embodiments of the solvent composition may have a cyclic capacity greater than 1.15 (e.g., greater than about 1.20) solta 2 ' ' q ' s can re prise the volume of the solvent composition required in carbon capture processes and reduce the size and/or cost of carbon capture systems and/or apparatuses that use the solvent composition.
• some preferred embodiments of the solvent composition may have a lean loading of approximately 0 at 110°C.
• the solvent composition may have at least one of the following properties: a heat duty below 120 kJ/mol CO2, an initial absorption
• the solvent composition may have at least one of the following properties: a heat duty below 120 kJ/mol CO2, an initial absorption rate greater than 0.25 — — kJmo1 c ° 2 an initial desorption rate greater than 25 — — a cyclic capacity greater than 1.20 m ° 1 C ° 2 , a lean loading of 0 at 110° C, a viscosity below 10mPa-s at 30°C, and an alkalinity in the range of 9.5 to 11.0 pKa at room temperature.
• Another aspect of the present invention relates to a method of performing carbon capture.
• the method comprises collecting flue gas from a flue gas emitting source and reacting the collected flue gas with the solvent composition described herein.
• systems for performing carbon capture Preferably, such systems comprise components configured to perform methods of performing carbon capture using the solvent compositions described herein.
• Other aspects of the present invention relate to an apparatus for performing carbon capture. Preferably, such apparatus comprises components configured to perform methods of performing carbon capture using the solvent compositions described herein. 50.
• Another aspect of the present invention relates to the use of a solvent composition according to a preferred embodiment of the present invention, to perform carbon capture by collecting a flue gas comprising carbon dioxide from a flue gas emitting source and exposing the collected flue gas to said solvent composition for a period of time sufficient to remove at least a portion of said carbon dioxide gas present in said flue gas.
• FIG. 1 is a flowchart depicting a method of carbon capture according to a preferred embodiment of the present invention.
• FIG. 2 illustrates an experimental set-up used to measure the absorption and desorption characteristics of various exemplary solvent compositions of the present invention.
• FIG. 3A illustrates the absorption profile of a 5M MEA solvent composition produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 3B illustrates the desorption profile of a 5M MEA solvent composition produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 4 shows the experimentally measured absorption performance of a baseline MEA solvent composition and various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 5 is a plot of the CO2 loading profiles, by mol, of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 6 shows the experimentally measured CO2 loading, by mol, of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 7 is a plot of the CO2 desorption profiles, by mol, of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 8 shows the experimentally measured desorption performance of a baseline MEA solvent composition and various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 9 shows the experimentally measured heat duty of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 10 shows the experimentally measured CO2 loading of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 11 shows the experimentally measured cyclic capacity of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 12 shows the experimentally measured absorption/desorption parameter of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 2 experimental set-up.
• FIG. 13 illustrates an experimental set-up used to measure the degradation and NH3 emission characteristics of various exemplary solvent compositions of the present invention.
• FIG. 14 a), b), c), d), e) and f) shows the degradation profde of 5M MEA, 3.6M D, 3.6M PR, Component D in EN23, and Component PR in EN23A1 produced by an experiment performed using the FIG. 13 experimental set-up;
• FIG. 15 shows the NH3 emission profdes of various exemplary solvent compositions of the present invention produced by an experiment performed using the FIG. 13 experimental set-up.
• solvent compositions that substantially outperform conventional solvent compositions (e.g. 5M MEA) used in carbon capture applications. Unless context dictates otherwise, such solvent composition compositions may be referred to herein as solvent compositions.
• solvent as used herein, can be interchangeably referred to as a composition and may be a compound or a blend or mixture of a plurality of compounds (i.e., a "solvent blend” or a “solvent mixture”).
• Carbon capture solvent compositions as described herein typically comprise a first compound, which may be referred to herein as "Compound I”, and/or a second compound, which may be referred to herein as "Compound II".
• solvent composition is meant to refer to a liquid, more preferably a homogeneous liquid.
• compound I is a tertiary amine, having a chemical formula of (Ri)(R2)N(C n H2n-OH), where R1 and R2 together form a ring with a carbon number between 3 to 6, preferably between 3 to 5, more preferably where there are 4 carbons, and n is an integer between 1 to 6, preferably between 2 to 4, more preferably n is 2.
• compound I is l-(2- hydroxyethyl)pyrrolidine .
• PR refers to a tertiary amine.
• the richness of electrons on the amino group reaction center can enhance the CO2 and amine reactivity.
• additional electrons supplied to the PR's amino nitrogen increases its reaction absorption rate with CO2.
• PR also has a fast CO2 desorption rate. Since PR is a tertiary amine, bicarbonate (HCO3 ) and carbonate (CO3 2 ) are only formed from the absorption reaction. Due to the negative charges on the two anionic products, they are also attracted to the protonated amine generated also in the solution.
• compound II contains two primary amino groups, having a chemical formula of NH 2 - (CmH 2 m)-NH 2 , where m is an integer between 2 to 10, preferably between 4 to 8.
• compound II can be, for example, hexamethylenediamine.
• hexamethylenediamine or "HMDA” refers to a diamine whose molecule comprises two (2) primary amino groups connected to each other by six (6) carbons.
• HMDA The primary amino groups in HMDA structure are able to provide a maximum of two (2) active sites for the CO 2 absorption reaction to take place. This also implies that one (1) molecule of HMDA can take a maximum of two (2) molecules of CO 2 . In comparison to conventional primary amines such as MEA, the CO 2 access to a reaction reactive site on the MEA molecule is limited to one (1), thus the absorption reaction occurs only on the basis of one (1) molecule of MEA per one (1) molecule of CO 2 . Hence, HMDA helps to increase the CO 2 amount absorbed per cycle as compared to that obtained from MEA. According to a preferred embodiment of the present invention, carbon capture solvent compositions described herein may also comprise one or more additional compounds in addition to Compound I and/or Compound II described above.
• carbon capture solvent compositions described herein may comprise polyethylenimine.
• polyethylenimine or “PEI” refers to a polymeric amine whose structure contains: (a) multiple groups of primary, secondary, and tertiary amine encased in a branched polymeric structure; (b) multiple groups of primary and tertiary amine encased in a branched polymeric structure; or (c) multiple groups of secondary amine in a linear polymeric structure.
• Branched polyethylenimines with all of primary, secondary, tertiary amino groups are preferred in some embodiments of the present invention.
• the absorption capacity of PEI benefits from its primary and secondary amino groups while secondary and tertiary amino groups facilitate its desorption of CO 2 .
• the PEI has up to fifteen (15) active amino groups that have affinity toward CO2 in the absorption reaction. This implies that the CO2 amount captured per amine molecule of PEI can far exceed those of conventional amines like MEA and MDEA, whose CO2 capacities are known to be limited to 0.5 and 1 respectively. Thus, the CO2 capture capacity of PEI can be several -fold more than those of the single amines.
• the carbon capture solvent composition comprises one or more of: l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMD A), and polyethylenimine (PEI).
• the carbon capture solvent blend may be an aqueous solution comprising one or more of: l-(2- hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA), and polyethylenimine (PEI).
• the solvent composition comprises PR with a molar concentration in the range of 2.0M to 5.0M (e.g., 2.0M, 2.05M, 2.10M, 2.15M, 2.20M, 2.25M, 2.30M, 2.35M, 2.40M, 2.45M, 2.50M, 2.55M, 2.60M, 2.65M, 2.70M, 2.75M, 2.80M, 2.85M, 2.90M, 2.95M, 3.00M,
• the solvent composition comprises HMDA with a molar concentration in the range of O.lOM to 1.50M (e.g., 0.10M, 0.15M, 0.20M, 0.25M, 0.30M, 0.35M, 0.40M, 0.45M, 0.50M, 0.55M, 0.60M, 0.65M, 0.70M, 0.75M, 0.80M, 0.85M, 0.90M, 0.95M, 1.00M, 1.05M, 1.10M, 1.15M, 1.20M, 1.25M, 1.30M, 1.35M, 1.40M, 1.45M, 1.50M, or any value therebetween).
• the solvent composition comprises PEI with a molar concentration in the range of 0.005Mto 0.50M (e.g., 0.005M, 0.01M, 0.015M, 0.02M, 0.025M, 0.03M, 0.035M, 0.04M, 0.045M, 0.05M, 0.10M, 0.15M, 0.20M, 0.25M, 0.30M, 0.35M, 0.40M, 0.45M, 0.50M, or any value therebetween).
• the solvent composition comprises PEI having a molecular weight of between about 750 Da to about 850 Da (e.g., 800 Da). In some embodiments, the number of repeating units of the PEI in the solvent composition is about 1.5.
• the solvent composition has a total molar concentration of 6.9M or less (i.e., beyond which precipitation issues and phase separation issues may occur).
• the solvent composition has a total molar concentration of about 6.0M (e.g., within ⁇ 0.0 IM), preferably of about 5.5M (e.g., within ⁇ 0.01M), more preferably of about 5.0M (e.g., within ⁇ 0.0 IM), even more preferably of about 4.5M (e.g., within ⁇ 0.0 IM) and yet even more preferably, 4.0M (e.g., within ⁇ 0.0 IM).
• the solvent composition comprises 3.6M PR, 1.0M HMDA, and 0.01M PEI (e.g., within ⁇ 0.001M for each of PR, HMDA, and PEI).
• the solvent composition has a lean loading of ⁇ 0 at 110°C (i.e., implying that the solvent composition can be used at relatively lower temperatures while achieving lean loadings close to 0).
• the solvent composition has a viscosity below 10mPa- s at 30°C (e.g., 9.5mPa-s, 9.0mPa-s, 8.5mPa-s, 8.0mPa-s, 7.5mPa-s, 7.0mPa-s, 6.5mPa-s, 6.0mPa-s, 5.5mPa-s, 5.0mPa-s, 4.5mPa-s, 4.0mPa-s, 3.5mPa-s, 3.0mPa- s, 2.5mPa-s, 2.0mPa-s, 1.5mPa-s, 1.0mPa-s, or any value therebetween at 30°C).
• the solvent composition has an alkalinity in the range of 9.5 to 11.0 pKa at room temperature (e.g., 9.55pKa, 9.60pKa, 9.65pKa, 9.70pKa, 9.75pKa, 9.80pKa, 9.85pKa, 9.90pKa, 9.95pKa, lO.OOpKa, 10.05pKa, lO.
• PEI a multi amine polymer
• a branched PEI with about fifteen (15) amine groups increased the CO2 absorption kinetics and the CO2 carrying capacity of the solvent blend.
• PEI is a very viscous amine and can be preferably used at concentrations at and below about 0.3M.
• a component with a high performing desorption ability was incorporated into the solvent composition. It was recognized that tertiary amines, which are typically known to have high desorption performance, have low absorption performance due to the absence of a hydrogen atom on the central nitrogen atom. In view of this, a tertiary amine whose structure can allow it to absorb CO2 faster than a traditional tertiary amine would was incorporated into the solvent composition. According to a preferred embodiment of the present invention, a solvent composition described herein provides improved performance over conventional solvent compositions used in carbon capture processes.
• some solvent blends described herein provide an initial CO2 absorption rate that is up to about 14% higher than that of convention MEA solvents (e.g., Solvent EN 23 A- 1 described below had a higher initial CO2 absorption rate than 5M MEA).
• some solvent blends described herein provide an initial CO2 desorption rate that is up to about 3.85 times higher than that of conventional MEA solvents.
• some solvent blends described herein provide cyclic capacity that is up to about 85% higher than that of conventional MEA solvents.
• some solvent blends described herein have much lower NH3 emission rates than those of conventional MEA solvents.
• solvent compositions described herein use HMDA as an accelerant, thereby increasing the absorption rate; • In comparison with other solvent composition formulas that require the absorbing process to be provided at 1 bar or higher and/or the desorbing process to be provided at O.Olbar and higher (i.e., other solvent composition formulas can require a pressurized CO2 capture system), solvent compositions described herein can be used in both atmospheric and pressurized CO2 absorption systems; While HMDA has been proposed for use in applications related to carbon capture, existing technologies are limited to using HMDA in association with solid sorbents, using HMDA in a biphasic scrubbing solution, and using HMDA as a cluster stabilizer.
• Fig. 1 is a flowchart depicting a method 100 of performing carbon capture according to a preferred embodiment.
• Method 100 begins at step 1000, where flue gas is collected from one or more CO2 sources (e.g., an industrial facility, a plant, a machine, an engine, etc.). The flue gas may be collected using any suitable method in step 1000.
• CO2 sources e.g., an industrial facility, a plant, a machine, an engine, etc.
• step 1100 a solvent composition is reacted with the collected flue gas to separate CO2 from the rest of the flue gas.
• the solvent composition is understood to be any one of the preferred solvent compositions according to the present invention.
• step 1100 comprises reacting the collected flue gas with a solvent blend comprising one or more of: l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA), and polyethylenimine (PEI).
• PR l-(2-hydroxyethyl)pyrrolidine
• HMDA hexamethylenediamine
• PEI polyethylenimine
• step 1100 comprises reacting the collected flue gas with a solvent blend comprising l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA), and polyethylenimine (PEI). In some embodiments, step 1100 comprises reacting the collected flue gas with an aqueous solution comprising l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA), and polyethylenimine (PEI).
• PR l-(2-hydroxyethyl)pyrrolidine
• HMDA hexamethylenediamine
• PEI polyethylenimine
• Step 1100 may comprise reacting the collected flue gas with a solvent composition comprising l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA) and/or polyethylenimine (PEI), where each compound may have any suitable concentration (e.g., any concentration described herein). 80.
• a solvent composition comprising l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA) and/or polyethylenimine (PEI), where each compound may have any suitable concentration (e.g., any concentration described herein). 80.
• PR l-(2-hydroxyethyl)pyrrolidine
• HMDA hexamethylenediamine
• PEI polyethylenimine
• amine/amines comprised one or more of the following compounds: 2-l-(2-hydroxyethyl)pyrrolidine (PR), hexamethylenediamine (HMDA), polyethylenimine (PEI, branch), 2-diethylaminoethanol (DEAE), 4-Amino-l -butanol (E), 3 -diethylamino- 1,2-propanediol (F), 3 -diethylamino- 1 -propanol (3D), and monoethanolamine (MEA).
• PR 2-l-(2-hydroxyethyl)pyrrolidine
• HMDA hexamethylenediamine
• PEI polyethylenimine
• DEAE 2-diethylaminoethanol
• E 4-Amino-l -butanol
• E 3 -diethylamino- 1,2-propanediol
• F 3 -diethylamino- 1 -propanol
• MEA monoethanolamine
• Table 1 Shows the composition of the solvents used by the inventors to perform experiments
• the CO2 absorption rate of the solvent compositions was evaluated and listed in Table 1.
• the CO2 absorption rate was evaluated by performing experiments using the apparatus 200 shown in FIG. 2.
• the apparatus 200 has a three-necked round bottomed flask 210 with a condenser 211 installed at the middle neck, a thermometer 212 at one neck for amine solution temperature measurement, and a gas dispersion tube 213 on the other neck for feeding the gas 214.
• the three-necked round bottomed flask 210 is immersed in an oil bath 215 and placed on top of, and heated by, a hot plate 216.
• a magnetic stirring bar 217 is placed inside the flask 210. 87.
• aprepared amine solution 220 of 150 ml contained in the flask 210 was fully immersed in the oil bath 215 in order for the amine solution 220 to reach the temperature of 40 ⁇ °C.
• the gas 214 (4% CO2 and 96% N2) was then bubbled into the amine solution 220 through the gas dispersion tube 213 at a constant flow rate of 300ml/min ( ⁇ 2 accuracy). Samples were then taken at regular intervals of 10 min for the first 1 hour, and then 30 min interval until at the end of 9 hours. The final loading recorded at the 9 th hour was taken as the rich loading. Samples were analyzed using a Chittick apparatus to obtain the CO2 loading at each time period, and a plot of CO2 loading versus time was generated based on the data.
• Equation (1) The Absorption Profile of 5M MEA is shown in FIG. 3A and the initial absorption rate of such a solution is calculated as shown in Equation (1) below:
• E 23 recorded the highest rate of 4.1 x 10-3 mol CCE/L.min while an equivalent rate of 4.0 x 10-3 mol C02/L.min was measured for E 23A-1. These values for E 23 and E 23A-1 are seen to be about 17% and 15% higher than the initial absorption rate obtained for benchmark MEA solvent, respectively. Similar to the trend observed in rich loading, E 23B recorded the minimum initial rate of CO2 absorption. Other than that, significant rate values ranging from 3.5 to 3.9 (x 10-3mol C02/L.min) were obtained forthe remaining solvent compositions.
• FIG. 4 details a summary of the initial absorption rates measured for all the solvent compositions.
• Rich loading indicates the amount of CO2 that the amine solvent composition is able to hold at a given temperature. It is, therefore, used as a criterion to determine the maximum CO2 absorption capacity of a solvent composition. From the absorption profdes in FIG. 5, the rich loadings for all the different solvent compositions after the 9 hours were determined and are summarized in FIG. 6 (on a mol basis). From the result illustrated in FIG. 6, in contrast to E 23, the measured rich loading for E 23A-1 (0.39 mol CCE/mol solvent composition) was comparable and marginally higher than that of MEA (0.37 mol CCE/mol solvent composition). It should be noted that solvent compositions including E 23C-1 and E 23B-1 precipitated either after or during the absorption process.
• the rich loading of E 23 A- 1 corresponds to a percentage enhancement of about 26% relative to the measured value obtained for E 23 solvent composition.
• the increase in concentration of H component from 0 ,4M to 1.0M accounted for this enhancement.
• H concentrations above IM a decrease in loading resulting from a reduction in mass transfer owing to an increase in solvent composition viscosity was observed for E-23A-4.
• each desorption profile was fitted with non-linear (logarithmic) regression model. Consequently, each model was differentiated at time zero (0) to evaluate the initial rate of desorption. Based on the obtained results as shown in FIG. 8, the solvent compositions ranked in increasing order of MEA ⁇ E 23C-3 ⁇ E 23A-4 ⁇ E 23A-3 ⁇ E 23B ⁇ E 23B-2 ⁇ E 23B-3 ⁇ E 23A-2 ⁇ E 23A ⁇ E 23C-2 ⁇ E 23 A- 1 ⁇ E 23.
• the initial desorption rate was calculated by determining the slope of the linear section of the desorption as most of the removable CO2 had been removed within that section. For example, the Desorption Profile of 5M MEA is shown in FIG. 3B and the initial desorption rate was calculated by multiplying the slope by the amine concentration shown in Equation (2) below: T . mo] CO2 > mol amine mol CO2
• E 23 recorded the highest desorption rate of 48 x 10-2 mol CCE/L.min. This was followed by E 23A-1 and E 23C-2 with values of 46 and 45 (x 10-2 mol CCE/L.min) respectively.
• MEA recorded the least initial rate of desorption of 13 x 10-2 mol CCE/Lmin. This is because, the main constituent in each formulated blend (being PR, F or 3D) is tertiary amine which results in the formation of extremely low energy bicarbonates from the absorption process. Considering this, minimum amount of energy is required for their stripping process which will occur at faster rates, hence, their relatively high desorption rate when compared with that of MEA.
• the heat duty of the solvent composition based on the heat rate and the CO 2 desorption rate was determined.
• the heat duty was calculated by determining the ratio of the steady state heat transfer to the amount of CO2 removed during desorption over a 5 min period (i.e., the linear portion of the desorption kinetics profile).
• Equation (3) Fourier's equation of molecular heat transport to calculate the heat supplied from the oil bath as shown in Equation (3):
• Equation (3) where q is the rate of heat transfer at steady state in J/s, k is the thermal conductivity of the Pyrex glass used for the flask material in W/m K, A is the cross-sectional area normal to the direction of heat flow in m 2 , and dT/dx is the temperature gradient (K 1 m 1 ).
• the temperature difference, dT was taken as the difference between the oil temperature and the inner wall temperature of the flask, while dx was the glass wall thickness.
• the heat duty was then calculated using Equation (4):
• Heat DutyMEA 534 91 kJ mol CO 2 103 The heat duty of the various different solvent compositions is shown in in FIG. 9 and listed in Table 3 below. From FIG. 9, the heat duty is contrary to the trend observed in the initial CO2 desorption rate data. It is believed that this is because, for a constant heat supply, as in the case for this work, the higher the initial rate of CO2 desorption, the lower the solvent composition regeneration heat duty.
• Lean loading is an indication of the efficiencies of the proposed solvent compositions’ regeneration capacity and their ability to give off the CO2 that was absorbed. It is the amount of CO2 that is undesorbed from the solvent composition after the desorption process. Typically, a lower CO2 lean loading is desired for an ideal CO2 capture solvent composition since a relative higher CO2 lean loading limits its ability to capture more CO2 per cycle.
• solvent composition EN 23 A-4 recorded the highest lean loading of 0.47 mol CC /Lsitch while the minimum was measured for EN 23B. From the data in FIG. 10, the lean loading ranks in increasing order of EN 23B ⁇ EN 23A-2 ⁇ EN 23 ⁇ EN 23A ⁇ EN 23A-3 ⁇ EN 23A-KEN 23A-4 ⁇ MEA.
• Each of the proposed solvent compositions has a zero or almost zero lean loading characteristic. This observation is owed to the presence of tertiary amine as opposed to the primary constituent of each formulation.
• E 23 A- 1 and E 23 A-4 recorded relatively high lean loading of about 0.1 mol CCE/mol solvent composition. This can be explained in terms of the higher rich loadings obtained for the two. Regardless of a high lean loading value for E 23A-1, it is about 150% lower than the lean loading of MEA.
• Cyclic capacity is a measure of the effective quantity of CO2 that is removed from the flue gas stream per volume of amine solvent composition used per a solvent composition circulation cycle. The difference between the solvent composition's rich and lean loading is used in the estimation of its cyclic capacity.
• the cyclic capacity of the solvent composition based on the rich loading, the lean loading, and the molar concentration of the amine was determined.
• the cyclic capacity refers to how much CO2 has been removed in a cycle.
• the cyclic capacity is calculated using Equation (5):
• Cyclic Capacity for 5M MEA is calculated as follows:
• E 23A-1 effectively removed the maximum amount of CO2. It recorded a cyclic capacity of 1.38 mol CO2/L of solvent composition which corresponds to about 30% enhancement relative to that of E 23. This was followed by E 23A-3 and E 23C-2 with cyclic capacities of 1.30 and 1.25 mol CO2/L of solvent composition respectively. Of all the formulated solvent compositions, E 23B recorded the minimum cyclic capacity of about 1.0 mol CO2/L of solvent composition.
• a method of measuring the performance of the various solvent compositions was developed. The method involved combining the various performance criteria into an absorption parameter and a desorption parameter that can account for the absorption performance as well as the desorption performance.
• the absorption parameter was defined as the initial CO2 absorption rate (IO -2 mol CCE/L.soltn).
• the desorption parameter was defined as a combination of the desorption rate, the cyclic capacity and the regeneration heat duty as set out in Equation (6):
• FIG. 12 shows absorption performance plotted against desorption performance (i.e., based on the Absorption Parameter and the Desorption Parameter) for the solvent compositions listed in Table 1.
• Solvent compositions at the top right comer are solvent compositions with both high absorption performance as well as high desorption performance.
• a summary of all the absorption and desorption screening results is tabulated in Table 3.
• the vapor pressure for some formulated solvent compositions were determined using an autoclave reactor by varying autoclave temperature from 40 to 120°C. Also, pursuant to lack of available vapor pressure data for pure amine compounds, each of the components constituting the different blends excluding PEI and HMDA were tested for their vapor pressures. For the pure components, high temperature range could not be considered due to the relatively low flash point values recorded for some components. For 100% MEA, the temperature range considered was from 25 to 85°C, while that of 100% PR and 100% D were analyzed from 25 to 45°C.
• the density of a number of solvent compositions were measured using Anton Paar’s DMA 4500 M density meter with an accuracy of 0.00001 g/cm3 for density and 0.01°C for temperature.
• a liquid sample with a volume of approximately 3 ml was used to take the density reading and a new sample was fed into the U-tube for density measurements at each temperature, ensuring that there were no bubbles in the U-tube.
• the equipment was cleaned with distilled water and acetone and well dried. The density of each sample was measured three times and the average of the readings recorded as the result.
• Heat capacity is the quantity of heat absorbed per unit mass of the material when its temperature increases 1 K (or 1 °C).
• the heat capacities for each one of solvent compositions E 23A-1, E 23, MEA and E 23B-1 were evaluated. From the results obtained, it was determined that, when compared to MEA and E 23, lower heat capacity values were recorded as a function of temperature for E 23A-1.
• This trend analysis of the solvent composition heat capacity studies indicates that, when compared, less thermal energy would be required for the regeneration of the optimum E 23 A- 1 solvent composition. With this observation, enormous savings on the capital cost of the lean-rich (L-R) heat exchanger could be realized given its reduced size.
• Table 6 Relative enhancements/reduction in performance indicators measured for E 23A-1.
• Negative value indicates a reduction in activity.
• Solvent composition improvement is one of the primary ways that can be used to effectively improve the efficiency of the amine-based post-combustion capture process. Experiments were conducted to test the degradation of amines and NH3 emissions of the improved E23A-1. For comparison with the previous solvent compositions, the experiment also included the following solvent compositions: E23 solvent composition; 5M MEA; 3.6M D; 3.6M PR; and EN23 (with 100%N 2 ).
• the oxidative degradation reaction of 250 ml CCL-loadcd amine solution was carried out at 60 °C for 28 days.
• the oxidative reaction was performed using 10% O2 under nitrogen balance which was regulated at the flow rate of 200 mL/min.
• the off-gas ammonia (NH3) produced by the degradation reaction was collected in the impinger set by means of acid-base reaction with 0.05M H2SO4.
• the amine solution and NH3 emission samples were collected every single day until 28 days where the experiment was terminated.
• the samples were analyzed for concentrations of amine and NH 3 which were further used to determine amine degradation and NH 3 emission rates.
• the experimental set-up for oxidative degradation of amine solutions is shown in FIG. 13.
• the experimental conditions for the degradation study are shown in Table 7.
• the experimental set-up shown in FIG. 13 involved a 500 mL four-necked round-bottom reaction flask 1300.
• the central neck of this flask 1300 was connected to a condenser 1301 equipped with a cooling circulating bath 1310.
• the outlet temperature of the condenser 1301 was maintained at the same temperature as the inlet feed gas 1303 (room temperature) to maintain moisture balance within the reaction flask 1300.
• the second neck 1319 was fitted with a thermometer 1320 using a thermometer adapter for measuring the temperature of the amine solution 1321.
• a diffuser tube 1330 was inserted through the third neck 1328 to bubble the feed gas 1303 into the amine solution 1321.
• the last neck 1329 was closed with a glass stopper.
• Off-gas NH3 produced from the reaction was collected by the connecting outlet 1350 of the condenser 1301 to the inlet 1351 of an impinger bottle 1355 filled with 50 mL of 0.05M H2SO4 1356 to trap the NH 3 molecules.
• the impinger bottle 1355 was in an ice bath 1360 at a temperature below 5 °C for the whole time during sampling to assist the NH3 being collected in the impinger solution 1356.
• the impinger bottle's outlet 1370 was connected to a rotameter 1375 and then a vacuum pump 1380.
• the rotameter 1375 was maintained at a regulated flow of 200 ⁇ 2 mL/min, matching the feed gas flow rate setting.
• GC-MS method 1 was used for MEA solvent and method 2 was for EN23, EN23A, 3.6M PR, and 3.6M D solvents.
• Equation (8) For amine vaporization, the amine vapor in the off-gas stream was collected for the period of 6 hr by condensing it into an empty impinger which was soaked in the iced bath at 5 °C throughout the test.
• the condensed liquid was transferred to a 10 mb volumetric flask and adjusted the volume with DI water.
• the amount of amine in the collected samples was quantified by using GC-MS.
• the vaporization rates of amine (mmol/day) and water (mL/day) were used to correct the amine degradation rate results.
• the examples and corresponding diagrams used herein are for illustrative purposes only.
• the principles discussed herein with reference to determination of equilibrium dissociation constants can be implemented in other systems and apparatuses. Different configurations and terminology can be used without departing from the principles expressed herein. For instance, steps, equipment, components, and modules can be added, deleted, modified, or re-arranged without departing from these principles.
• the amine vaporization rates of 5M MEA, 3.6M D, 3.6M PR, EN23 (with 100%N2), EN23, and EN23A1 solvent compositions also reported in Table 9 were found to be 0.798, 7.059, 0.725, 4.918, 5.490, and 0.705 mmol/day, respectively. It must be pointed out that the amine vaporization rate of EN23A1 measured based on PR component was much lower than that E23 measured based on the D component. This is a substantial improvement in reducing the rate of amine vaporization of E23 to that of E23A1 by replacing the D component to the PR. The rate of amine loss of E23A1 was also very similar to that of MEA in the benchmark MEA solvent.
• Table 9 Degradation rate, NH3 emission rate, water vaporization rate, and amine vaporization rate comparison of amine solvent compositions 38.
• Solvent composition E 23 A- 1 with a molar concentration of 4.6 IM was identified amidst rigorous testing and analysis as a highly desirable solvent composition for carbon capture. Beyond the batch-scale glassware solvents screening, data obtained from a full -cycle performance analysis of E 23A-1 in a bench-scale mini -pilot plant (50m3/day) confirmed its excellent capture performance. 39. Moreover, on average, the maximum CO2 capture efficiency (95%), highest cyclic capacity (indicating a lower solvent circulation rate) and the least regeneration consumption energy (15 GJ/tonne CO2) were recorded for solvent composition E 23A-1. 40.
• This invention includes variations on described compositions that would be apparent to the skilled addressee, including variations obtained by: replacing features, elements and/or chemical compounds with equivalent features, elements and/or chemical compounds; mixing and matching of features, elements and/or chemical compounds from different examples; combining features, elements and/or chemical compounds from examples as described herein with features, elements and/or chemical compounds of other technology; omitting and/or combining features, elements and/or chemical compounds from described examples. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions, omissions and subcombinations as may reasonably be inferred. The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.

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