Patent Application
20230294071
Embodiments described herein generally relate to compositions for carbon dioxide (CO2) absorption and CO2 desorption, and to processes for making such compositions. Embodiments described herein also generally relate to processes for CO2 absorption and for CO2 desorption.
Carbon dioxide (CO2) is a primary greenhouse gas that makes a great contribution to global warming, owing to the excessive emissions from the combustion of fossil fuels. Carbon capture, utilization, and storage (CCUS) is the mature technology that can be carried out to alleviate the CO2 discharge, which is urgently needed for achieving the goals set in the Paris Climate Accord. Amine-based CO2 absorption is a potentially cost-effective options for capturing CO2 from both gas streams (for example, flue gas) and the atmosphere. CO2 capture is critical because of its increasing importance as a resource for material and fuel synthesis.
A fundamental challenge of chemisorption-based technologies is the slow absorption and desorption reaction kinetics when CO2 desorption is at temperatures greater than 100° C. Here, excessive energies may be needed to vaporize a large amount of liquid water during the CO2 desorption operation and condense the same amount of water vapor prior to CO2 desorption during cyclic CO2 sorption and desorption. Monoethanolamine (MEA) solution has low price and high reactivity with CO2, which apply to the benchmark solvent for evaluating amine-based CO2 capture processes at small scale. However, this technology is still not acceptable for versatile and large-scale uses mainly, attributed to (1) the critical limitations for >100° C. CO2 desorption or very energy intensive MEA regeneration process, and (2) the resultant aggregated MEA degradation, as well as (3) severe corrosion at such high temperatures. In other words, to render fast CO2 desorption from aqueous solvent, high temperature (120-140° C.) conditions are utilized with state-of-the-art methods, resulting in excessive energy demands for the water vaporization.
There is a need for new and improved compositions for the absorption, desorption, and/or capture of CO2 that overcomes one or more deficiencies in the art. There is also a need for new and improved processes for the absorption, desorption, and/or capture of CO2 that overcomes one or more deficiencies in the art.
Embodiments described herein generally relate to compositions for CO2 absorption, desorption, and/or capture and processes for making such compositions. Embodiments described herein also generally relate to processes for CO2 absorption, CO2 desorption, and/or CO2 capture.
In an embodiment, a composition for absorbing or desorbing carbon dioxide is provided. The composition includes an organic amine. The composition further includes a carbon organic framework, an ion thereof, or combinations thereof, the carbon organic framework comprising a plurality of carboxylic acids.
Implementations may include one or more of the following. The organic amine of the composition can exist in an ionic state or non-ionic state in the composition. The composition can further include water. The composition can include greater than 0 wt % and about 1 wt % (about 10,000 ppm) or less of the carbon organic framework based on a total wt % of the composition, the total wt % of the composition not to exceed 100 wt %. The composition can include greater than 0 wt % about 0.05 wt % (about 500 ppm) or less of the carbon organic framework based on a total wt % of the composition, the total wt % of the composition not to exceed 100 wt %. The composition can include about 0.005 wt % (about 50 ppm) to about 0.015 wt % (about 150 ppm) of the carbon organic framework based on a total wt % of the composition, the total wt % of the composition not to exceed 100 wt %. The organic amine of the composition can include a primary organic amine compound, a secondary organic amine compound, a tertiary organic amine compound, or combinations thereof. The organic amine of the composition can include monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, monomethyl-ethanolamine, methyldiethanolamine, diethyl-monoethanolamine, or combinations thereof. The organic amine of the composition can include a polyethylene amine, the polyethylene amine comprising diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetraacetylethylenediamine, pentaethylenehexamine, polyethyleneimine, or combinations thereof.
In another embodiment, a process for capturing carbon dioxide (CO2) from a gas stream is provided. The process includes introducing the gas stream with a composition described herein under absorption conditions, the gas stream comprising CO2. The process further includes forming a CO2-enriched composition.
Implementations may include one or more of the following. The organic amine of the composition utilized in the process can be selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, monomethyl-ethanolamine, methyldiethanolamine, diethyl-monoethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tetraacetylethylenediamine, pentaethylenehexamine, polyethyleneimine, or combinations thereof. The composition utilized in the process can include greater than 0 wt % and about 1 wt % (about 10,000 ppm) or less of the carbon organic framework based on a total wt % of the composition, the total wt % of the composition not to exceed 100 wt %. The composition used in the process can include about 10 wt % to about 30 wt % of the organic amine based on a total wt % of the composition, the total wt % of the composition not to exceed 100 wt %. The composition used in the process can further include water, an ion thereof, or combinations thereof. At least a portion of the composition used in the process can be ultrasonically pretreated.
In another embodiment, a process for capturing CO2 from a gas stream is provided. The process includes contacting the gas stream, under absorption conditions, with a composition described herein in an absorption unit to form a CO2-enriched composition, the gas stream comprising CO2. The process further includes passing the CO2-enriched composition to a desorption unit, heating at least a portion of the CO2-enriched composition in the desorption unit, and separating CO2 from the CO2-enriched composition to form a CO2-depleted composition. The process further includes regenerating the composition from at least a portion of the CO2-depleted composition, recycling at least a portion of the CO2-depleted composition to the absorption unit, or both. Implementations may include heating the at least a portion of the CO2-enriched composition at a temperature of about 100° C. or less.
In another embodiment, a process for making a composition for absorbing or desorbing carbon dioxide (CO2) is provided. The process includes ultrasonically treating a mixture of a carbon organic framework and water. The process further includes adding an organic amine to the ultrasonically-treated mixture of the carbon organic framework and the water to form the composition.
In another embodiment, a process for desorption of carbon dioxide (CO2) from a CO2-enriched composition is provided. The process includes heating a CO2-enriched composition under desorption conditions, the CO2-enriched composition derived from a composition comprising an organic amine, an ion thereof, or a combination thereof, and a carbon organic framework, an ion thereof, or combinations thereof, the carbon organic framework comprising a plurality of carboxylic acids. The process further includes separating CO2 from the CO2-enriched composition to form a CO2-depleted composition. Implementations may include one or more of the following. The composition can further include water.
So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, and may admit to other equally effective embodiments.
To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
Embodiments described herein generally relate to compositions for CO2 absorption and CO2 desorption, and to processes for making such compositions. Embodiments described herein also generally relate to processes for CO2 absorption and for CO2 desorption.
Briefly, and in some embodiments, the compositions can include an organic amine and a carbon organic framework. The carbon organic framework (COF) accelerates and/or catalyzes both sorption and desorption from the organic amine (for example, monoethanolamine (MEA)). In some examples, the COF can be utilized at very low concentrations (for example, less than about 100 ppm, such as about 80 ppm). In some examples, even with the use of such low concentrations of catalysts, when the absorption achieves 90% CO2 capture (the target from the U.S. Department of Energy (DOE) for CO2 capture efficiency), the amount of CO2 desorption can be increased by 305.1% at 85° C., which makes use of low-temperature waste heat and avoids secondary pollution during CO2 capture feasible.
For purposes of the present disclosure, the term “carbon organic framework” is used interchangeably with the term “catalyst” such that reference to one includes reference to the other. For example, reference to carbon organic framework includes reference to both carbon organic framework and catalyst, and vice-versa. The carbon organic framework (and/or ion thereof) can serve to, for example, catalyze the absorption of CO2 to the organic amine and/or catalyze the desorption of CO2 from the organic amine. During sorption and/or desorption, one or more components of the composition can exist as ion(s).
For purposes of the present disclosure, the term “catalyst” refers to both [COOH]x—COF and COF. Compositions can include varying amounts of an organic amine and varying amounts of a catalyst. Compositions described herein can include one or more additional components such as solvent, for example, water.
The use of headings is for purposes of convenience only and does not limit the scope of the present disclosure. Embodiments described herein can be combined with other embodiments.
As used herein, a “composition” can include component(s) of the composition, reaction product(s) of two or more components of the composition, a remainder balance of remaining starting component(s), or combinations thereof. Compositions of the present disclosure can be prepared by any suitable mixing process.
In solution or suspension, the carbon organic framework and/or the organic amine may exist as one or more ions in the composition. For example, the carbon organic framework (having ionizable groups, for example, —COOH, may exist in its ionic state). In some examples, at least a portion of the solvent can exist as an ion in the composition.
Embodiments of the present disclosure generally relate to compositions for absorbing, desorbing, and/or capturing of carbon dioxide (CO2). Compositions described herein generally include a solution or suspension that includes an organic amine and a carbon organic framework. Compositions described herein can further include one or more additional components such as a solvent. Any suitable solvent such as water can be. The solvent may be used for solubilizing and/or suspending at least a portion of the carbon organic framework, the organic amine, or combinations thereof.
The carbon organic framework can serve to, for example, catalyze and/or accelerate absorption of CO2, desorption of CO2, and/or capture of CO2 by the organic amine of the composition. The carbon organic framework useful for compositions described herein can comprise, consist essentially of, or consist of comprises one or more compounds represented by formula (I), an ion thereof, or combinations thereof:
In some embodiments, x of formula (I) is any suitable number such as from 1 to 200, such as from 5 to 80, such as from 10 to 50, such as from 15 to 35. In at least one embodiment, x of formula (I) can be from 17 to 100, such as 17, 33, 50, 67, or 100. The carbon organic framework (also referred to as [COOH]x-COF) of formula (I) has a plurality of carboxylic acid groups that can be ionizable. Such ionizable carboxylic acid groups can be beneficial in generating organic amine-COO− species (for example, MEACOO−), carbonate (CO32−) species, bicarbonate (HCO3−) species, or combinations thereof, among others, during absorption and/or desorption of CO2. More than one carbon organic framework can be utilized in compositions described herein if desired.
The organic amine can serve to, for example, capture and/or absorb CO2. The organic amine(s) used in compositions described herein can include primary organic amine compounds, secondary organic amine compounds, tertiary organic amine compounds, or combinations thereof. More than one organic amine compound can be utilized in compositions described herein.
In some embodiments, the organic amine compound can include any suitable organic amine compound such as, for example, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), diisopropanolamine (DIPA), monomethyl-ethanolamine (MMEA), methyldiethanolamine (MDEA), diethyl-monoethanolamine (DEMEA), or combinations thereof. In at least one embodiment, the organic amine can include an amine-functionalized polymer such as a polyethylene amine. Illustrative, but non-limiting, examples of polyethylene amines can include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), tetraacetylethylenediamine (TAED), polyethylenehexamine such as pentaethylenehexamine (PEHA), polyethyleneimine (PEI), or combinations thereof.
A total weight percent (wt %) of the composition is based on a total amount (in wt %) of carbon organic framework, a total amount (in wt %) of organic amine, and a total amount (in wt %) of optional components. The total wt % of the composition does not exceed 100 wt %.
In some examples, a total amount of carbon organic framework in compositions described herein can be greater than 0 wt % and about 1 wt % (10,000 ppm) or less, such as about 0.5 wt % (5,000 ppm) or less, such as about 0.1 wt % (1,000 ppm) or less, such as about 0.075 wt % (750 ppm) or less based on a total weight of the composition. In at least one embodiment, the total amount of carbon organic framework in the composition can be 0.001 wt % (10 ppm), 0.002 wt % (20 ppm), 0.003 wt % (30 ppm), 0.004 wt % (40 ppm), 0.005 wt % (50 ppm), 0.006 wt % (60 ppm), 0.007 wt % (70 ppm), 0.008 wt % (80 ppm), 0.009 wt % (90 ppm), 0.01 wt % (100 ppm), 0.011 wt % (110 ppm), 0.012 wt % (120 ppm), 0.013 wt % (130 ppm), 0.014 wt % (140 ppm), 0.015 wt % (150 ppm), 0.016 wt % (160 ppm), 0.017 wt % (170 ppm), 0.018 wt % (180 ppm), 0.019 wt % (190 ppm), 0.02 wt % (200 ppm), 0.021 wt % (210 ppm), 0.022 wt % (220 ppm), 0.023 wt % (230 ppm), 0.024 wt % (240 ppm), 0.025 wt % (250 ppm), 0.026 wt % (260 ppm), 0.027 wt % (270 ppm), 0.028 wt % (280 ppm), 0.029 wt % (290 ppm), 0.03 wt % (300 ppm), 0.031 wt % (310 ppm), 0.032 wt % (320 ppm), 0.033 wt % (330 ppm), 0.034 wt % (340 ppm), 0.035 wt % (350 ppm), 0.036 wt % (360 ppm), 0.037 wt % (370 ppm), 0.038 wt % (380 ppm), 0.039 wt % (390 ppm), 0.04 wt % (400 ppm), 0.041 wt % (410 ppm), 0.042 wt % (420 ppm), 0.043 wt % (430 ppm), 0.044 wt % (440 ppm), 0.045 wt % (450 ppm), 0.046 wt % (460 ppm), 0.047 wt % (470 ppm), 0.048 wt % (480 ppm), 0.049 wt % (490 ppm), 0.05 wt % (500 ppm), 0.051 wt % (510 ppm), 0.052 wt % (520 ppm), 0.053 wt % (530 ppm), 0.054 wt % (540 ppm), 0.055 wt % (550 ppm), 0.056 wt % (560 ppm), 0.057 wt % (570 ppm), 0.058 wt % (580 ppm), 0.059 wt % (590 ppm), 0.06 wt % (600 ppm), 0.061 wt % (610 ppm), 0.062 wt % (620 ppm), 0.063 wt % (630 ppm), 0.064 wt % (640 ppm), 0.065 wt % (650 ppm), 0.066 wt % (660 ppm), 0.067 wt % (670 ppm), 0.068 wt % (680 ppm), 0.069 wt % (690 ppm), 0.07 wt % (700 ppm), 0.071 wt % (710 ppm), 0.072 wt % (720 ppm), 0.073 wt % (730 ppm), 0.074 wt % (740 ppm), 0.075 wt % (750 ppm), 0.076 wt % (760 ppm), 0.077 wt % (770 ppm), 0.078 wt % (780 ppm), 0.079 wt % (790 ppm), 0.08 wt % (800 ppm), 0.081 wt % (810 ppm), 0.082 wt % (820 ppm), 0.083 wt % (830 ppm), 0.084 wt % (840 ppm), 0.085 wt % (850 ppm), 0.086 wt % (860 ppm), 0.087 wt % (870 ppm), 0.088 wt % (880 ppm), 0.089 wt % (890 ppm), 0.09 wt % (900 ppm), 0.091 wt % (910 ppm), 0.092 wt % (920 ppm), 0.093 wt % (930 ppm), 0.094 wt % (940 ppm), 0.095 wt % (950 ppm), 0.096 wt % (960 ppm), 0.097 wt % (970 ppm), 0.098 wt % (980 ppm), 0.099 wt % (990 ppm), or 0.10 (1,000 ppm), or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. For example, the total amount of carbon organic framework in the composition can be about 0.005 wt % (50 ppm) or more, about 0.005 wt % (50 ppm) to about 0.015 wt % (150 ppm), about 0.03 wt % (300 ppm) or less, or at least about 0.008 wt % (80 ppm). Other amounts are contemplated.
The amount of carbon organic framework used for the compositions can be based on the dry weight of the carbon organic framework (for example, the carbon organic framework without moisture).
In contrast to conventional CO2 capture using carbon organic frameworks at high concentrations (for example, greater than 2,000 ppm or greater than 3,000 ppm), the carbon organic frameworks described herein can be utilized at much lower concentrations if desired.
In some examples, a total amount of organic amine in compositions described herein can be about 1 wt % or more and/or about 99 wt % or less, such as from about 5 wt % to about 95 wt %, such as from about 10 wt % to about 90 wt %, such as from about 15 wt % to about 85 wt %, such as from about 20 wt % to about 80 wt %, such as from about 25 wt % to about 75 wt %, such as from about 30 wt % to about 70 wt %, such as from about 35 wt % to about 65 wt %, such as from about 40 wt % to about 60 wt %, such as from about 45 wt % to about 55 wt %, based on a total weight of the composition. In at least one embodiment, the total amount (in wt %) of organic amine in compositions described herein can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 91, 92, 93, 94, 95, 96, 97, 98, or 99, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. For example, the amount (wt %) of organic amine in the composition is about 10 wt % or more, about 15 wt % to about 25 wt %, about 50 wt % or less, or at least about 20 wt %, based on a total weight of the composition. Other amounts are contemplated.
As described above, compositions described herein can include one or more additional components. The one or more additional components can include a solvent such as water. In some embodiments, the solvent (such as water) can be used in an amount to achieve 100 wt %. For example, and in some embodiments, a total mass of a composition can be about 100 g. This 100 g composition can include an organic amine (about 20 wt %), carbon organic framework (about 0.008 wt % (about 80 ppm), and the remainder solvent.
Embodiments of the present disclosure also generally relate to processes for making a composition for absorbing or desorbing CO2. In general, compositions described herein can be made or formed by introducing the materials (the carbon organic framework, the organic amine, and optionally an additional component) of the composition to one another and mixing the materials. The carbon organic framework, the organic amine, and optionally an additional component, can be charged to a vessel and stirred, mixed, or otherwise agitated under mixing (or pretreatment) conditions effective to form a composition. “Pretreatment” refers to operations performed during and/or after formation of the composition, but before use of the composition for CO2 absorption and/or CO2 desorption
Pretreatment conditions can include mixing the components at a pressure of about 0.7 atm (about 70 kPa) to about 1.3 atm (about 130 kPa), such as from about 0.8 atm (about 80 kPa) to about 1.2 atm (about 120 kPa), such as from about 0.9 atm (about 90 kPa) to about 1.1 atm (about 110 kPa), though other pressures are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Pretreatment conditions can include elevated temperatures if desired, such as from about 30° C. to about 50° C., such as from about 35° C. to about 45° C., though other temperatures are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
Pretreatment conditions can include stirring, mixing, agitating, or combinations thereof components of the composition by using suitable devices such as a mechanical stirrer.
The pretreatment conditions can include use of suitable devices such as a mechanical stirrer (for example, an overhead stirrer), a magnetic stirrer (for example, placing a magnetic stir bar in the vessel above a magnetic stirrer), a sonicator, or other suitable devices. Sonication can be performed using an ultrasonic bath or an ultrasonic probe. Ultrasonic frequencies (for example, about 20 kHz or more) can be used for ultrasonication, though other ultrasonic frequencies are contemplated. In some examples, one or more components of the composition can be subjected to ultrasound. The ultrasound, in some embodiments, can have one or more of the following:
(a) A power for the ultrasonic pretreatment of 5 W to 15 W, such as from 7 W to 12 W, such as 7 W, 8 W, 9 W, 10 W, 11 W, or 12 W. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other power values are contemplated.
(b) A time of ultrasonic pretreatment of 1 min to 300 min, such as from 10 min to 180 min, such as from 20 min to 120 min, such as 30 min, 45 min, 60 min, 75 min, 90 min, or 120 min. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other periods are contemplated.
(c) A temperature during ultrasonic pretreatment of 10° C. to 70° C., such as from 20° C. to 60° C., such as from 30° C. to 50° C., such as 30° C., 35° C., 40° C., 45° C., or 50° C. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other temperatures are contemplated.
Pretreatment conditions can include elevated temperatures if desired, such as from about 30° C. to about 50° C., such as from about 35° C. to about 45° C., though other temperatures are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
In some examples, two or more components of the composition can be subjected to mixing (for example, ultrasonication) prior to introducing the third component to the composition. For example, a mixture of the carbon organic framework and water can be subjected to ultrasonic treatment. The ultrasonically-treated mixture can be introduced with the organic amine to form a composition described herein. The ultrasonically-treated mixture and the one or more organic amines can be mixed by suitable methods such as those described above.
Embodiments of the present disclosure also generally relate to uses of compositions described herein. In some embodiments, compositions described herein can be utilized in processes for absorbing CO2, desorbing CO2, and/or capturing CO2, or combinations thereof. Other uses are contemplated.
Briefly, and in some embodiments, CO2 is present in a gas or a gas stream at any suitable concentration. The gas or gas stream is introduced and/or contacted with a composition described herein, and a CO2-enriched composition is formed. The gas or gas stream can have any suitable amount of one or more additional gases. For example, the gas or gas stream can include CO2 with one or more additional gases such as N2 and/or O2 in any suitable concentrations.
In some embodiments, a process for absorbing CO2 and/or capturing CO2 includes contacting or introducing, under absorption conditions, a gas or gas stream with a composition described herein to form a CO2-enriched composition. The contacting, introducing, or combinations thereof can occur in an absorption unit. An example absorption unit is shown in
The absorption conditions can include various temperatures, pressures, times, flow rates of the gas (or gas stream), combinations thereof, or other parameters suitable for absorption.
Absorption conditions can include stirring, mixing, or otherwise agitating the composition while contacting or introducing the gas stream with the composition. Stirring, mixing, agitating, or combinations thereof can be performed using any suitable device such as a mechanical stirrer (for example, an overhead stirrer), a magnetic stirrer (for example, placing a magnetic stir bar in the vessel above a magnetic stirrer), a sonicator, or other suitable devices.
Absorption conditions can include a pressure of about 0.7 atm (about 70 kPa) to about 1.3 atm (about 130 kPa), such as from about 0.8 atm (about 80 kPa) to about 1.2 atm (about 120 kPa), such as from about 0.9 atm (about 90 kPa) to about 1.1 atm (about 110 kPa). In some embodiments, the pressure (kPa) during absorption can be 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, or 130, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other pressures are contemplated.
Absorption conditions can include heating the composition to a temperature of about 5° C. to about 100° C., such as from about 10° C. to about 90° C., such as from about 15° C. to about 85° C., such as from about 20° C. to about 80° C., such as from about 25° C. to about 75° C., such as from about 30° C. to about 70° C., such as from about 35° C. to about 65° C., such as from about 40° C. to about 60° C., such as from about 45° C. to about 55° C. In at least one embodiment, the composition can be heated at a temperature (° C.) of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other temperatures are contemplated. The temperature of the composition can be monitored by a thermocouple as shown in the Examples.
Absorption conditions can include an absorption time. The absorption time is the period that begins with introducing the gas or the gas stream to the composition (for example, turning on the flow of the gas or gas stream) and ends with ceasing introduction of the gas or the gas stream (for example, stopping the flow of the gas or gas stream). The absorption time can be any suitable amount of time, such as about 1 minute (min) or more, about 72 hours (h) or less, or combinations thereof. In some embodiments, the absorption time can be from about 1 min to about 48 h, such as from about 5 min to about 24 h, such as from about 10 min to about 10 h, such as from about 30 min to about 5 h, such as from about 1 h to about 3 h, though other periods are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. In at least one embodiment, the absorption time can be from about 1 min to about 60 min, such as from about 5 min to about 45 min, such as from about 10 min to about 30 min, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 min, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other periods are contemplated.
Absorption conditions can include a flow rate of the gas or gas stream that contacts or is introduced with the composition can be any suitable flow rate. In some embodiments, a flow rate of the gas or gas stream can be from about 50 mL/min to about 5,000 mL/min, such as from about 100 mL/min to about 4,500 mL/min, such as from about 250 mL/min to about 3,000 mL/min, such as from about 500 mL/min to about 2,000 mL/min, though other flow rates are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. In at least one embodiment, a flow rate of the gas or gas stream can be from about 10 mL/min to about 1,000 mL/min, such as from about 50 mL/min to about 950 mL/min, such as from about 100 mL/min to about 900 mL/min, such as from about 150 mL/min to about 850 mL/min, such as from about 200 mL/min to about 800 mL/min, such as from about 250 mL/min to about 750 mL/min, such as from about 300 mL/min to about 700 mL/min, such as from about 350 mL/min to about 650 mL/min, such as from about 400 mL/min to about 600 mL/min, such as from about 450 mL/min to about 550 mL/min, such as about 500 mL/min, though other flow rates are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
The gas or gas stream that contacts the composition during absorption can comprise, consist essentially of, or consist of CO2. When the gas or gas stream includes another gas besides CO2, the amount of CO2 in the gas or gas stream can be any suitable amount, such as about 0.01 volume percent (vol %) CO2 or more, about 99.9 vol % CO2 or less, or combinations thereof, based on a total vol % of the gas or gas stream, the total vol % of the gas or gas stream not to exceed 100 vol %. In some embodiments, the amount of CO2 in the gas or gas stream can be about 1 vol % to about 100 vol %, such as from about 5 vol % to about 90 wt %, such as from about 10 vol % to about 80 vol %, such as from about 20 vol % to about 50 vol %, based on a total vol % of the gas or gas stream. In at least one embodiment, the amount (in vol %) of CO2 in the gas or gas stream, based on the total vol % of the gas or gas stream, can be 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or 100, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other amounts are contemplated.
The gas or gas stream that contacts the composition during absorption can optionally include one or more additional gases such as nitrogen (N2), oxygen (O2), hydrogen (H2), argon (Ar), helium (He), water (H2O), or combinations thereof, among others. A total amount of the one or more optional gases in the gas or gas stream can be about 0.01 vol % or more, about 99.9 vol % or less, or combinations thereof, based on a total vol % of the gas or gas stream. In some embodiments, the total amount of the one or more optional gases in the gas or gas stream can be about 1 vol % to about 99 vol %, such as from about 50 vol % to about 95 wt %, such as from about 75 vol % to about 90 vol %, such as from about 80 vol % to about 85 vol %, based on a total vol % of the gas or gas stream. In at least one embodiment, the total amount (in vol %) of the one or more optional gases in the gas or gas stream, based on the total vol % of the gas or gas stream, can be 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, 42, 43, 44, 45, 46, 47, 48, 49, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 81, 82, 83, 84, 85, 86, 87, 88, 89, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other amounts are contemplated. Each of the foregoing numbers can be used to describe the amount of one optional gas or the amount of multiple optional gases.
In at least one embodiment, a gas or gas stream for absorption comprises, consists essentially of, or consists of CO2, N2, and O2. An amount of CO2 in the gas or gas stream can be from about 1 vol % to about 40 vol %, such as from about 5 vol % to about 15 vol %, such as those amounts described above; an amount of N2 in the gas or gas stream can be from about 59 vol % to about 99 vol %, such as from about 75 vol % to about 85 vol %, such as those amounts described above; and the remainder can be O2, such as from about 5 vol % to about 15 vol %, such as those amounts described above.
Absorption of CO2 by compositions described herein can be performed according to the following non-limiting procedure. A composition described herein can be placed in a vessel equipped with a mechanical stirrer. CO2 or a gas stream comprising CO2 can be fed to the vessel at a selected flow rate (for example, about 500 mL/min) while the composition is stirring. The CO2 or a gas stream comprising CO2 can be fed to the headspace above the composition, fed into the composition (for example, via a bubbler or other appropriate apparatus), or combinations thereof. Absorption can be performed for about 30 minutes.
After absorption of CO2 by the composition from the gas or gas stream, a CO2-enriched composition is formed. In some embodiments, at least a portion of the CO2 in the CO2-enriched composition can be desorbed (for example, removed or otherwise separated) from the CO2-enriched composition under desorption conditions. Such desorption can be performed in a desorption unit. The desorption unit can be the same unit as the absorption unit or a different unit. Additionally, or alternatively, the CO2-enriched composition can be passed to a separate desorption unit for the desorption operation. An example desorption unit is shown in
Desorption conditions can include stirring, mixing, or otherwise agitating the CO2-enriched composition. Stirring, mixing, agitating, or combinations thereof can be performed using any suitable device such as a mechanical stirrer (for example, an overhead stirrer), a magnetic stirrer (for example, placing a magnetic stir bar in the vessel above a magnetic stirrer), a sonicator, or other suitable devices.
Desorption conditions can include a pressure of about 0.7 atm (about 70 kPa) to about 1.3 atm (about 130 kPa), such as from about 0.8 atm (about 80 kPa) to about 1.2 atm (about 120 kPa), such as from about 0.9 atm (about 90 kPa) to about 1.1 atm (about 110 kPa). In some embodiments, the pressure (kPa) during desorption can be 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, or 130, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other pressures are contemplated.
Desorption conditions can include heating the CO2-enriched composition to a temperature that is at or below a boiling point of a component of the composition (for example, at or below a boiling point of the organic amine or at or below a boiling point of the solvent). In some embodiments, desorption can be performed at a temperature of about 5° C. to about 100° C., such as from about 10° C. to about 90° C., such as from about 15° C. to about 85° C., such as from about 20° C. to about 80° C., such as from about 25° C. to about 75° C., such as from about 30° C. to about 70° C., such as from about 35° C. to about 65° C., such as from about 40° C. to about 60° C., such as from about 45° C. to about 55° C. In at least one embodiment, the CO2-enriched composition can be heated at a temperature (° C.) of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other temperatures are contemplated. The temperature can be monitored by a thermocouple as shown in the Examples.
During desorption, the CO2-enriched composition can be contacted or introduced with a carrier gas. The carrier gas can be used to facilitate removal of CO2 from the CO2-enriched composition. This carrier gas, can include nitrogen (N2), oxygen (O2), hydrogen (H2), argon (Ar), helium (He), water (H2O), or combinations thereof, among others. The carrier gas can be a single gas or a mixture of gases in any suitable proportions.
A flow rate of the carrier gas that contacts or is introduced with the CO2-enriched composition can be any suitable flow rate. In some embodiments, a flow rate of the carrier gas can be from about 50 mL/min to about 5,000 mL/min, such as from about 100 mL/min to about 4,500 mL/min, such as from about 250 mL/min to about 3,000 mL/min, such as from about 500 mL/min to about 2,000 mL/min, though other flow rates are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. In at least one embodiment, a flow rate of the carrier gas can be from about 10 mL/min to about 1,000 mL/min, such as from about 50 mL/min to about 950 mL/min, such as from about 100 mL/min to about 900 mL/min, such as from about 150 mL/min to about 850 mL/min, such as from about 200 mL/min to about 800 mL/min, such as from about 250 mL/min to about 750 mL/min, such as from about 300 mL/min to about 700 mL/min, such as from about 350 mL/min to about 650 mL/min, such as from about 400 mL/min to about 600 mL/min, such as from about 450 mL/min to about 550 mL/min, such as about 500 mL/min, though other flow rates are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range.
Desorption conditions can include a desorption time. The desorption time can be any suitable amount of time, such as about 1 minute (min) or more, about 72 hours (h) or less, or combinations thereof. In some embodiments, the desorption time can be from about 1 min to about 48 h, such as from about 5 min to about 24 h, such as from about 10 min to about 10 h, such as from about 30 min to about 5 h, such as from about 1 h to about 3 h, though other periods are contemplated. Any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. In at least one embodiment, the desorption time can be from about 1 min to about 120 min, such as from about 10 min to about 90 min, such as from about 20 min to about 60 min, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, or 120 min, or ranges thereof. Each of the foregoing numbers can be preceded by the word “about,” “at least about,” “less than about,” or “more than about” and any of the foregoing numbers can be used singly to describe an open-ended range or in combination to describe a close-ended range. Other periods are contemplated.
Desorption of CO2 from the CO2-enriched composition can be performed according to the following non-limiting procedure. The CO2-enriched composition can be placed in a vessel equipped with a mechanical stirrer and can be heated at a temperature of about 85° C. A carrier gas (for example, N2) can be fed to the vessel at a selected flow rate (for example, about 500 mL/min) while the CO2-enriched composition is stirring. Desorption can be performed for about 30 minutes to about 60 minutes.
After desorption, removal, or separation of CO2 from the CO2-enriched composition, a CO2-depleted composition is formed. The CO2-depleted composition can still contain an amount of CO2.
In some embodiments, after desorbing, removing, or otherwise separating CO2 from the CO2-enriched composition to form the CO2-depleted composition, a composition described herein can be regenerated from at least a portion of the CO2-depleted composition and then be used to absorb or capture CO2. Additionally, or alternatively, at least a portion of the CO2-depleted composition can be recycled to the absorption unit where it can be used to absorb or capture CO2.
The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use aspects of the present disclosure, and are not intended to limit the scope of aspects of the present disclosure. Efforts have been made to ensure accuracy with respect to numbers used (for example, amounts, dimensions, etc.) but some experimental errors and deviations should be accounted for.
As used in the examples, the term “catalyst” refers to both [COOH]x-COF or COF. Compositions in the non-limiting examples can include varying amounts of monoethanolamine (MEA) (for example, about 20 wt % MEA), varying amounts of the catalyst (the COF), and a solvent (for example, water). The MEA serves to, for example, capture CO2.
FT-IR spectra were collected with a Thermo Nicolet Magna IR 760 spectrometer. Thermal gravimetric analysis (TGA) was obtained using a thermal gravimetric analyzer. The TGA process settings were as follows: (1) a heating ramp of about 5° C./min within the temperature range of about 20-100° C. with a nitrogen flow rate of about 60 mL/min; (2) held isothermally at about 100° C. for about 180 min with a nitrogen flow rate of about 60 mL/min; (3) a heating ramp of about 5° C./min within the temperature range of about 100-600° C. with a nitrogen flow rate of about 60 mL/min.
The non-limiting examples described herein utilize a [COOH]17-COF catalyst as a catalyst for CO2 absorption and desorption.
TGA was utilized to determine the water content of the [COOH]17—COF catalyst. As shown in
CO2 absorption and desorption investigations were performed utilizing the example apparatus 400 shown in
A gas inlet 406 is positioned in the reactor 401 such that a gas (or mixture of gases) can be introduced into the composition 403 (below the top surface of the composition 403). Alternatively, or additionally, the gas inlet 406 can be positioned above the composition 403 (above the top surface of the composition 403) such that the gas (or mixture of gases) can be fed into the headspace above the composition 403. The gas (or mixture of gases) can be fed to the composition 403 through the gas inlet 406 from N2 cylinder 411, 02 cylinder 412, a CO2 cylinder 413 via a mass flow controller 410. The mass flow controller 410 is utilized to control the flow rate of the individual gases from the gas cylinders 411-413 to the reactor 401.
A condenser 407a is positioned above, and is coupled to, the reactor 401. The condenser 407a has a cooling liquid inlet and a cooling liquid outlet coupled to a cooling liquid unit 407b. Gas exits the reactor 401 through outlet 408 via a tube 409. The tube is coupled to a moisture remover 414 to remove moisture from the gas exiting the reactor 401. The moisture remover 414 is coupled to an in-line gas analyzer 415. The gas analyzer 415 is utilized to measure concentrations of gases in the gas exiting the reactor 401. The gas analyzer is coupled to a data recording unit 416 (for example, a computer)
The [COOH]17—COF catalyst was synthesized as described above.
The example compositions used for the data shown in
The data shown in
For the CO2 absorption data shown in
Overall, the data indicated that both the [COOH]17—COF catalyst, with or without ultrasonic pretreatment, can promote CO2 absorption and desorption. As shown in
The data shown in
The peak desorption rate improvement was determined to be about 68.8% (without ultrasonic pretreatment) and about 106.3% (with ultrasonic pretreatment). Meanwhile, the quantities of CO2 desorbed from the uncatalyzed solution, the catalytic solution without ultrasonic pretreatment, and the catalytic solution with ultrasonic pretreatment were determined to be about 17.13 mmol, about 23.16 mmol, and about 26.3 mmol, respectively.
The catalyzed solution and uncatalyzed solution for the data of
As shown in
Overall, the data shown in
Notably, the catalyst dosage was only about 80 ppm under the conditions tested. This is the lowest catalyst dosage to be reported for achieving such a significant effect on the catalytic capture of CO2. Therefore, the experimental results demonstrate that, for example, catalysts described herein are very effective for catalyzing CO2 absorption and CO2 desorption.
For the data shown in
As shown in
Overall, the results shown in
Overall, the data shown in
As described above, the catalytic effect of the [COOH]17—COF catalyst in the MEA aqueous solutions (with and without ultrasonic pretreatment) was clearly observed with the significant enhancement of CO2 absorption and CO2 desorption. The associated mechanism was also investigated. To this end, FI—IR spectroscopy was utilized to investigate the catalytic effect of the [COOH]17—COF catalyst on CO2 absorption and desorption.
As shown in
With the use of the [COOH]17—COF catalyst, the changes in the peak intensities attributed to the HCO3− species in the CO2 absorption process (
Under the conditions tested, Differences are more obvious for the desorption tests as shown in
As shown in
The FT-IR spectra of the [COOH]17—COF catalyst with CO2 absorption (used COF) and without CO2 absorption (fresh COF) are shown in
The main characteristic peak positions of used COF remained unchanged from the fresh COF, which indicated that the structure of [COOH]17—COF was unchanged. However, the bands from about 400 to about 445 cm−1 in the used COF (
As shown by the FT-IR spectra of
Embodiments described herein generally relate to compositions for CO2 absorption and CO2 desorption, and to processes for making such compositions. Embodiments described herein also generally relate to processes for CO2 absorption and for CO2 desorption using the compositions. The compositions for CO2 absorption and CO2 desorption generally include a carbon organic framework (COF) and an organic amine. The COF can accelerate and/or catalyze both absorption and desorption of from the organic amine. Additionally, the COF can be utilized at very low concentrations. Even with the use of low concentrations of catalysts, when the absorption achieves 90% CO2 capture (the target from the U.S. Department of Energy (DOE) for CO2 capture efficiency), the amount of CO2 desorption can be significantly increased relative to conventional technologies.
All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text.
As is apparent from the foregoing general description and the specific aspects, while forms of the aspects have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including.” Likewise whenever a composition, an element, a group of elements, or a method is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition, method, or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “Is” preceding the recitation of the composition, element, elements, or method, and vice versa, such as the terms “comprising,” “consisting essentially of,” “consisting of” also include the product of the combinations of elements listed after the term.
For purposes of this present disclosure, and unless otherwise specified, all numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and consider experimental error and variations that would be expected by a person having ordinary skill in the art. For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. For example, the recitation of the numerical range 1 to 5 includes the subranges 1 to 4, 1.5 to 4.5, 1 to 2, among other subranges. As another example, the recitation of the numerical ranges 1 to 5, such as 2 to 4, includes the subranges 1 to 4 and 2 to 5, among other subranges. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. For example, the recitation of the numerical range 1 to 5 includes the numbers 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, among other numbers. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
As used herein, the indefinite article “a” or “an” shall mean “at least one” unless specified to the contrary or the context clearly indicates otherwise. For example, aspects comprising “an organic amine” includes aspects comprising one, two, or more organic amines, unless specified to the contrary or the context clearly indicates only one organic amine is included.
Certain molecules disclosed herein may contain one or more ionizable groups [groups from which a proton can be removed (for example, —COOH) or added (for example, amines) or which can be quaternized (for example, amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein.
While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
This application claims priority to U.S. Provisional Application No. 63/321,568, filed Mar. 18, 2022, which is incorporated herein by reference in its entirety.
The invention was made with government support under Grant No. 1632899 awarded by the National Science Foundation. The government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 63321568 | Mar 2022 | US |
