Article pubs.acs.org/cm
Magnetic Induction Swing Adsorption: An Energy Efficient Route to Porous Adsorbent Regeneration M. Munir Sadiq,† Haiqing Li,‡ Anita J. Hill,‡ Paolo Falcaro,‡,§ Matthew R. Hill,*,‡,∥ and Kiyonori Suzuki*,† †
Department of Materials Science and Engineering, Monash University, Clayton, VIC 3168, Australia CSIRO, Private Bag 33, Clayton South MDC, VIC 3169, Australia § Graz University of Technology, Stremayrgasse 9/Z2, 8010 Graz, Austria ∥ Department of Chemical Engineering, Monash University, Clayton, VIC 3168, Australia ‡
S Supporting Information *
ABSTRACT: Metal−organic frameworks (MOFs) are promising nanomaterials with unprecedented capacity to store small molecules. Despite this huge capacity, proposed methods for releasing these molecules are not yet feasible at a meaningful scale, largely because of the strong binding of the molecules and the thermally insulating nature of the adsorbent. It is likely that large amounts of energy would be required for operation at scale. Furthermore, the high adsorption capacity of MOFs is not typically matched by a high working capacity; adsorbed molecules are not readily retrieved. Here we show a series of magnetic framework composites (MFCs) synthesized from ferri-magnetic MgFe2O4 nanoparticles and the Zr-based MOF UiO-66 can be deployed in a magnetic induction swing adsorption process for CO2 capture and release. Exposure of the MFCs to an alternating current magnetic field resulted in the generation of heat by the embedded magnetic nanoparticle and fast release of CO2 from the MOF, with an unprecedented 100% of adsorbed CO2 released under a 42 mT field. This was achieved at a regeneration time of 240 s. The efficiency of the MISA process was shown to be dependent on the amount of MFC used, with efficiencies reaching 60% at just a gram scale. These local “nanoheaters” overcome the thermally insulating nature of the adsorbent, which has promising implications for use at scale. Additionally, the ability to access 100% of the adsorption capacity permits the use of strongly adsorbing, high-capacity MOFs that were previously discarded.
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INTRODUCTION Over the past century, an increase in the level of anthropogenic carbon dioxide (CO2) concentrations in the atmosphere has been observed by scientists.1 In 2012, the global energy consumption exceeded 520 quadrillion Btu, which resulted in the release of more than 32 billion t of CO2 into the atmosphere,2 with fossil-based fuels responsible for a significant percentage.3 Postcombustion carbon capture and storage (CCS) has been identified as a potential process that could significantly contribute to global greenhouse gas emission reduction targets.4 The use of porous adsorbent materials or the chemical absorption process for CCS from large point sources is yet to gain widespread applicability as a result of the energy penalty associated with implementing these processes. Regeneration of adsorbents via temperature swing adsorption (TSA) and regeneration of adsorbents via pressure swing adsorption (PSA) are two commonly used energy intensive processes5−7 with an estimated 25−40%6,8 increase in the energy requirement of a power plant. Chemical absorption of CO2 by aminebased solvents is another process that has proven to be very effective for CCS processes, but the regeneration process involves the use of large amounts of energy9 to liberate the © 2016 American Chemical Society
absorbed CO2 coupled with the corrosive and volatile amine vapor produced, which poses serious environmental concerns.10 Metal−organic frameworks (MOFs) are promising crystalline nanoadsorbents with exceptional porosity;11−13 they have been explored for use in storage of energy-related gases (H2 and CH4),3,14−17 separation,18−21 and catalysis,22−24 because of their tunable pore surfaces,16 low density, thermal, and mechanical stability25 MOFs can thus be engineered to replace zeolites and activated carbons in gas storage and separation applications.13 Several MOFs have been reported with very good properties suitable for CO2 separation,18,26−29 methane storage,14−16,30 and hydrogen storage.31,32 The ability to regenerate MOFs through the use of mild trigger conditions12 makes them a more viable and attractive option for gas separation and storage applications. A new approach that incorporates MOFs with a range of functional materials33,34 with the aim of extending and/or improving the properties35−37 of MOFs is currently being Received: June 15, 2016 Revised: August 5, 2016 Published: August 7, 2016 6219
DOI: 10.1021/acs.chemmater.6b02409 Chem. Mater. 2016, 28, 6219−6226
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Chemistry of Materials explored by several groups.38,39 A class of such materials that combines magnetic nano- or microparticles with MOF crystals are known as magnetic framework composites (MFCs).38 Table S2 highlights the development and application of such composites in a number of areas. Incorporation of MOFs with magnetic nanoparticles capable of generating heat on exposure to an alternating current (ac) magnetic field could significantly reduce the energy penalty associated with adsorbent regeneration in CCS processes. The concept of using the power losses of ferro/ferrimagnetic materials for remote heating40 was introduced as early as in the 1950s for hyperthermia treatment of cancerous cells.41,42 This approach utilizes heat generated as a result of static hysteresis and dynamic core losses of ferro/ferrimagnetic particles induced by an external ac magnetic field. The generation of heat via induction heating occurs remotely, and resultant heat is targeted, making the heating process isolated and thus energy efficient. A recent work by Li et al.43 demonstrated the use of Fe3O4 nanoparticles embedded in Mg-MOF-74 to trigger the release of CO2 via magnetic field irradiation. The composite showed an enhancement of CO2 uptake of ≤9.8% compared to that of the bare MOF with ≤49% CO2 removal efficiency at a field strength of 81 mT. The work, however, did not estimate the energy required to effect the adsorbent regeneration as a result of the applied magnetic field. Lyndon et al.8 investigated the use of light responsive organic groups within the pore structure of a zinc-based MOF, with results showing a remarkable release of up 64% CO2 adsorbed on exposure to UV light with up to 42% desorption capacity under static conditions. A limitation to the application of such MOFs is the challenge in scaling up due to the opaque nature of MOFs that will limit the penetration depth of light when the process is used on a larger scale. Herein, we report the first detailed study of the use of an MFC to estimate the energy required to trigger the release of a guest molecule in a magnetic induction swing adsorption (MISA) process. Ferrimagnetic MgFe2O4 nanospheres with strong heating ability44 were embedded in a thermal and water vapor stable45 zirconium-based MOF, UiO-66, to form a MFC. The MFC was then used to demonstrate the energy efficient MISA process. Dynamic triggered release experiments performed on a series of MFCs achieved a 61% CO2 release efficiency at a magnetic field μoH (where μo is the permeability of vacuum) of 21 mT and 100% release efficiency at 32 and 42 mT. The ability of the MISA process to access 100% of the adsorbed molecules is shown in Figure 1.
Figure 1. Demonstration of the maximal regeneration capability of MFCs through MISA as compared to conventional TSA.
Figure S3b, the micrographs show that the nanospheres are 200−700 nm in size and are composed of smaller primary particles tightly packed together as a result of the attractive magnetic force pulling them toward each other.46 The hysteresis loop (Figure 2) for the nanospheres was recorded using a vibrating sample magnetometer. The
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Figure 2. Hysteresis loops of bare MgFe2O4, UiO-66 (control), and MFC-mg series (arrows indicate the y axis corresponding to each material).
RESULTS AND DISCUSSION Ferrimagnetic MgFe2O4 nanospheres were synthesized using a solvothermal reduction reaction of MgCl2, FeCl3, and ethylene glycol with polyethylene glycol (MN = 4000) serving as a surfactant.46,47 X-ray diffraction (XRD) was used to characterize the crystal structure of the nanospheres. As shown in Figure S3a, the patterns can be easily indexed to the single-phase cubic spinel structure of the MgFe2O4 phase. The observed reflection peaks matched the standard powder diffraction data (ICSD 00036-0398) of the MgFe2O4 phase. No diffraction peaks of impurity phases were observed from the XRD pattern. The average crystallite size of the nanoparticles was determined by Scherrer’s formula and was found to be ∼13.6 nm, which is also evident from the broadened nature of the peaks. Scanning electron microscopy (SEM) was used to study the morphology and size of the spherelike MgFe2O4 particles. As shown in
saturation magnetization (Ms) and coercivity (μoHc) recorded for the nanospheres are 67 Am2 kg−1 and 10.5 mT, respectively. The high Ms of the particles, which is comparable to values reported in the literature,46,48 can be related to the strong heating ability of the dry powder upon exposure to an ac magnetic field. Using an Opsens Pico M optic fiber temperature sensor, the heating ability of the powder was estimated by recording the temperature rise profile of 10 mg of dry powder dispersed in 1 mL of water and then calculating its specific absorption rate (SAR). The SARs for the nanospheres were calculated to be 32.4, 46.7, and 55.4 W g−1 at μoH values of 21, 32, and 42 mT, respectively (see the Supporting Information for details). The high SAR of MgFe2O4 nanospheres is comparable to reported values49 and makes it suitable for the 6220
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Chemistry of Materials synthesis of MFCs that could be regenerated by magnetic field irradiation. The synthesized MgFe2O4 nanospheres were then used to synthesize a series of MFCs with varying concentrations. The MFCs were synthesized using the embedding approach described in the work of Ricco et al.38 Figure 3 demonstrates
Figure 3. Scheme demonstrating the process of embedding MgFe2O4 nanospheres in a UiO-66 MOF.
the approach used in embedding the magnetic nanospheres in the MOF. The process involves dispersion of the magnetic nanospheres in a solution containing the MOF precursors. The mixture is then subjected to solvothermal conditions during which the MOF gradually nucleates on the surface of the magnetic nanosphere with the final composite comprised of polycrystalline MOF domains with the magnetic nanospheres enclosed within the porous crystals.50 Four UiO-66 precursor solutions were prepared with low, medium, and high concentrations of the nanospheres and also a control (pure UiO-66). The MgFe2O4 content of the MFCs was analyzed using inductive coupled plasma (ICP) analysis and was found to be 2.03% for MFC-mg1, 3.74% for MFC-mg2, and 4.06% for MFC-mg3. The Ms for each of the MFCs as seen in Figure 2 increases with an increase in MgFe2O4 nanosphere content in the composites. MFC-mg1 had an Ms of 1.65 Am2 kg−1, MFCmg2 a value of 3.86 Am2 kg−1, and MFC-mg3 a value of 3.98 Am2 kg−1. Powder XRD analysis of the composites revealed diffraction patterns (Figure 4a) identical to that of the control sample with no magnetic material and also diffraction patterns reported in the literature.45 The coverage of the growth of the MOF nanoparticles on the surface of the nanospheres as shown by SEM analysis (Figure 4b) also resulted in no diffraction peaks of the MgFe2O4 nanospheres being observed. Energy-dispersive X-ray (EDX) mapping microanalysis of one of the composites (Figure 4c) shows the distribution of the nanospheres with MOF nucleation on their surface and also magnetic nanoparticles embedded within the MOF. Low-pressure N2 (0−100 kPa) isotherms were collected for the control and MFC series to determine the porosity of the samples. The synthesized samples were dried and evacuated at 120 °C for 24 h. All samples exhibited type I adsorption behaviors with Brunauer−Emmett−Teller (BET) and Langmuir surface areas decreasing with an increase in MgFe2O4 content; such behavior has also been reported by Lu et al.51 and Falcaro et al.,39 who showed that the introduction of Co
Figure 4. (a) XRD pattern of bare MOF, bare MgFe2O4, and MFCs. (b) SEM micrograph of MFCs. (c) Elemental mapping of MFC-mg3.
nanoparticles in MOF-5 resulted in a 4% loss of surface area. The control sample and MFCs all displayed a microporous nature with a steep increase in the rate of N2 uptake at very low pressures (see Figure S4). The BET surface area and total pore volume of the synthesized UiO-66 (control) and MFC samples are higher than those reported in the literature. Table S3 summarizes the BET and Langmuir surface areas for all samples The aim of this work is to investigate the suitability of MFCs in significantly reducing the energy penalty associated with using solid adsorbents for postcombustion CO2 capture. The isotherms (see Figures S5 and S6) for CO2 uptake at 300 and 273 K were estimated at P/Po = 100 kPa for the control and MFCs. The CO2 uptake at 300 K for the control was higher than the reported literature value of 1.8 mmol g−1,52,53 but slightly lower for the MFCs. The CO2 adsorption at 273 K showed an increase in uptake for the MFC with the lowest concentration of magnetic particles as compared to the control sample but a decrease in uptake as the concentration of the particles increased. Magnetic Induction Swing Adsorption (MISA). Dynamic triggered release of adsorbed CO2 from the MFCs was performed using a combination of an induction heating machine and Tristar Micrometrics adsorption equipment (see Figure S1). The process involves magnetic field irradiation of the MFCs, which resulted in an increase in the surface energy of the composite, where intermolecular interactions between 6221
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to the fraction of CO2 desorbed during the dynamic uptake and release experiments. An important parameter that determines the viability of postcombustion carbon capture through the use of adsorbents is the regeneration energy that estimates the energy required to heat the adsorbent and also the energy required to undo the adsorption process.55,56 To estimate these energies, the heat of adsorption and heat capacity (Cp) of the MFC were determined experimentally (see the Supporting Information). Thermal conductivities of MOFs have been reported to be extremely low (MOF-5, 0.31 W mK−1;57 ZIF-8, 0.165 W mK−158) and similar to those of insulating materials like asbestos, thus increasing the energy requirement for the desorption process. Another parameter that has a significant impact on the regeneration energy of adsorbents is the working capacity. This is the amount of CO2 remaining in the adsorbent after regeneration at high temperatures and is a better parameter used in estimating the performance of different adsorbent materials as compared to their absolute CO2 uptake.5,59 The energy penalty, size of the regeneration system, and purity of the CO2 to be captured can also be directly estimated from the working capacity of the adsorbent material.59 The working capacity of MFC-mg2 was estimated by measuring the CO2 adsorption isotherm at 21, 32, and 42 mT, which correspond to temperatures of 80, 95, and 130 °C, respectively (Figure 6a). The working capacity for MFC-mg2 achieved a maximal value of 1.80 wt % at a desorption temperature of 130 °C, 1.56 wt % at 95 °C, and 0.82 wt % at 80 °C, outperforming MOF-177, which was reported not to exhibit a positive working capacity at desorption temperatures of up to 200 °C. The working capacity is estimated as the difference between the uptake at 15 kPa and 27 °C (point a on Figure 6a) and the uptake at 100 kPa at the magnetic fieldinduced desorption temperatures (points b, b′, and b″ in Figure 6a). Figure 7 presents the regeneration energy of MFC-mg2 as a function of desorption temperature. Upon exposure of the composite to a μoH of 32 mT, a regeneration energy of 5.16 MJ (kg of CO2)−1 was achieved, corresponding to a temperature of 95 °C in the adsorbent. High regeneration energies of 7.21 and 6.92 MJ (kg of CO2)−1 were obtained at μoH values of 21 and 42 mT, respectively. Despite the high temperatures generated by the embedded magnetic particles, calculated regeneration energies are still higher than those of monoethanolamine (MEA) systems (3.5− 4.8 MJ/kg of CO2 captured)60,61 and Mg-MOF 74 (2.2−2.3 MJ/kg of CO2 captured)62 reported by McDonald et al. This is not unexpected as the maximal working capacity of our composite is 1.8 wt % at a desorption temperature of 130 °C (0.416 mmol g−1) as compared to the value of Mg-MOF 74 at 200 °C reported as 17.6 wt % (4.85 mmol g−1).5 The advantage of our proposed MISA process over conventional TSA processes for CCS lies in the regeneration efficiency that could be achieved because of the remote and localized form of heating possible through magnetic induction. With the MISA process, it is possible to access 100% of the captured CO2 gas while utilizing just a fraction (∼22%) of the heat generated by the MFC (Table S5), which satisfies the regeneration energy requirement of the MFC. The heat generated by the MFC is estimated by determining the power (PSAR) generated by the MFC, which is then multiplied by time it took to regenerate the adsorbent (see the Supporting Information for details).
the CO2 molecules and the surface weakened and thus triggered an instantaneous CO2 release.8 A series of MFCs with low, medium, and high levels of MgFe2O4 nanospheres were prepared. The magnetic properties, porosity, CO2 uptake, heat capacity, and heat of adsorption of the MFCs were determined as described in the experimental section of the Supporting Information. The localized heating capability of the MFCs was investigated by irradiating known quantities of each sample at μoH values of 21, 32, and 42 mT. Figure 5 shows the dynamic uptake and release of CO2 from MFC-mg2 at different μoH values. The maximal temperature
Figure 5. Dynamic uptake and release of CO2 from MFC-mg2. Note that UiO-66 (control) showed no desorption effect upon exposure to a magnetic field.
rise recorded for each sample corresponds to the desorption temperature for the MFCs during the MISA process. MFC-mg3 yielded the highest desorption temperature of 140 °C at a μoH value of 42 mT, with MFC-mg1 yielding the lowest desorption temperature of 60 °C at 21 mT. The performance of the MFCs in the proposed MISA process was then investigated by periodically irradiating the MFCs with an ac magnetic field during uptake, which then induces remote heating, resulting in the instantaneous release of adsorbed CO2. Points 1−3 in Figure 5 correspond to magnetic induction trigger points. The pressure of point 1 was carefully selected to fall within the CO2 partial pressure range in flue gas streams of large industrial sites (estimated to be 3−15 kPa54). The CO2 adsorbed when the magnetic field is switched on is then forced out of the MFC as a result of the increase in temperature, which weakens the intermolecular interactions between the CO2 molecules and the adsorbent surface. This is represented by the red colored region in Figure 5, which corresponds to maximal temperature rises of 80, 95, and 130 °C at 21, 32, and 42 mT, respectively, for MFC-mg2. All of the MFCs displayed a high CO2 removal capability at the highest μoH of 42 mT with 93% removal for MFC-mg1 and 100% removal for MFC-mg2 and MFC-mg3 (Table S4 and Figure S7). The fraction of adsorbed gas released via the magnetic trigger represents a significant improvement in the lighttriggered release approach reported by Lyndon et al.8 Thermal Energy Requirement. MFC-mg2 was used to demonstrate the thermal energy requirement for the MISA process because of its slightly better performance with respect 6222
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Figure 6b shows the heat generated by MFC-mg2 as a function of temperature. With a regeneration time of ∼240 s, a maximal heat generation of 110 J was achieved at a μoH value of 42 mT with a 100% desorption efficiency. Lower heat generation values were recorded at 21 and 32 mT with desorption efficiencies of 86 and 98%, respectively. The relatively low working capacity of our MFCs implies that the energy utilization per kilogram of desorbed CO2 reaches ∼32 MJ (Table S5) at investigated μoH values. However, this number is expected to be reduced by >90% when high-working capacity MOFs like Mg-MOF 74 (4.85 mmol g−1)5 are deployed in the MISA process. The implementation of TSA processes for CCS has been shown to result in a loss in electricity production output due to steam diversion from the turbines to drive the desorption process for both adsorbent and MEA-based processes. For coalfired plants, this loss is estimated to be approximately 30−40% of the plant output,7,63,64 though a more recent estimate was even higher.65 In the proposed MISA process, such an energy penalty will not exist as the heat generation in the composites is as a result of static hysteresis and dynamic core losses induced by an external ac magnetic field. However, it is important to evaluate the efficiency of the magnetic coupling between the composites and the applied field. To ascertain the energy conversion efficiency of the induction heating system used in this work, the SAR of pure MgFe2O4 nanospheres was compared to the energy input to the induction system at different loadings of the magnetic particles. This resulted in a value of ∼5.4% at a loading of 100 mg and ∼59% at a loading of 1 g (Figure 8). For practical applications,
Figure 6. (a) CO2 adsorption isotherms at different μoH values for MFC-mg2. a corresponds to the uptake at 15 kPa and 27 °C, while b, b′, and b‴ correspond to the uptake at 100 kPa at each magnetic fieldinduced desorption temperature. (b) Working capacity and heat generation as a function of desorption temperature for MFC-mg2.
Figure 8. Induction heating efficiency of MgFe2O4 nanospheres with an increase in loading.
where it is expected to apply these composites at a much larger scale (kilograms), the energy conversion efficiency is expected to be higher (>60%), as a result of better coupling of the magnetic component of the MFC when the magnetic field is applied. The implication of having better efficiency would result in a reduction in the potential penalty because of the electricity use for the MISA process to be significantly slowed. The efficiency of the MISA process could be further improved by utilizing induction heating systems with no cooling water
Figure 7. Regeneration energy of MFC-mg2 as a function of temperature.
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requirements as against the system used for this work where the induction coil is continuously cooled with water. Such systems have been reported to achieve up to 90% efficiency with very low electrical power consumption.66,67 Consequently, such high-efficiency induction heating systems when used in the MISA process at industrial scale will significantly minimize the overall electricity requirement for magnetic field generation. It is also expected that this method can be extended and improved by exploring the huge MOF database in which composites with higher CO2 working capacity and lower regeneration energies62 can be synthesized and utilized in an optimized MISA process to achieve an effective and energy efficient CCS process for industrial sites and power plants
AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected]. *E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The authors acknowledge use of facilities within the Monash Centre for Electron Microscopy. M.R.H. acknowledges the ARC for support (FT130100345).
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CONCLUSION The main objective of this work was to address the “elephant in the room” when it comes to utilizing the promising properties of nanoporous materials such as MOFs in a viable and wider scale. Despite their huge capacity for the storage of small molecules, the proposed methods for releasing these molecules are not yet feasible at a meaningful scale, largely because of the strong binding energy of the stored molecules and the thermally insulating nature of the adsorbent. While desorption from similar adsorbents such as zeolites has been overcome by the passing of hot gas through the bed, this is at an efficiency cost and lowers the versatility of use. This problem is even more acute given the potential platform applications of MOFs where large flows of hot gas are often not at all possible. The performance of a Zr-MOF-based composite was evaluated in the proposed MISA process. The heat generation capability of the magnetic content of the composite ensured a swift and rapid temperature swing that showed CO2 removal efficiencies of 82, 96, and 100% at 21, 32, and 42 mT, respectively. Despite the insulating nature of the carrier MOF, the high percentage of CO2 removal can be attributed to the remote and localized form of heating associated with the induction heating system. The induction heating efficiency of the MISA process was found to be strongly dependent on the composition by mass of the magnetic material in the composite, with gram scale compositions achieving 59% energy conversion efficiency. The energy penalty associated with steam diversion for TSA processes and the consequent electricity output loss for the best performing MOFs stands at 727−850 kJ (kg of CO2)−1 for coal flue gases56 and between 0.471 and 0.145 MWh/t of CO2 for a state-of-the-art amine carbon capture process.4,55 The MISA process can be extended to these same MOFs, thereby significantly minimizing this huge penalty with no loss of electricity output but rather the cost associated with using electricity to drive the magnetic induction process. Analysis and comparison of these costs for the MISA process relative to the energy penalty and output loss of the TSA process will be the focus of future research.
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REFERENCES
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.6b02409. Detailed experimental procedures, regeneration energy calculations, and estimation of heat generation by MFCs (PDF) 6224
DOI: 10.1021/acs.chemmater.6b02409 Chem. Mater. 2016, 28, 6219−6226
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DOI: 10.1021/acs.chemmater.6b02409 Chem. Mater. 2016, 28, 6219−6226
