• Vol 10, No 7 (2019)
  • Mechanical Engineering

Synthesis, Characterizations, and Adsorption Isotherms of CO2 on Chromium Terephthalate (MIL-101) Metal-organic Frameworks (Mofs)

Fayza Yulia, Vania Juliani Utami, Nasruddin , Agustino Zulys

Corresponding email: nasruddin@eng.ui.ac.id


Cite this article as:
Yulia, F., Utami, V.J., Nasruddin, Zulys, A., 2019. Synthesis, Characterizations, and Adsorption Isotherms of CO2 on Chromium Terephthalate (MIL-101) Metal-organic Frameworks (Mofs). International Journal of Technology. Volume 10(7), pp. 1427-1436
50
Downloads
Fayza Yulia Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia
Vania Juliani Utami Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia
Nasruddin Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia
Agustino Zulys Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok, 16424, Indonesia
Email to Corresponding Author

Abstract
image

The concentration of CO2 in the atmosphere caused by fossil fuels, power plants, and transportation is the most significant environmental issue in the world today. Intensive efforts have been made to minimize CO2 levels to reduce global warming. Metal-organic frameworks (MOFs), crystalline porous materials, exhibit great potential to adsorb carbon dioxide. In the present study, research was conducted on the synthesis, characterization, and adsorption isotherms of MIL-101. MIL-101, one type of mesoporous MOF, can adsorb enormous amounts of CO2. The synthesis was carried out using a fluorine-free hydrothermal reaction method. The porous properties, structure, morphology, thermal stability, and chemical functionalities of MIL-101 Cr were measured by N2 adsorption/desorption isotherms, X-ray diffraction (XRD), scanning electron microscope (SEM), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR) analysis, respectively. The volumetric uptakes of CO2 were experimentally measured at temperatures of 298-308 K and pressure of up to 600 kPa. The experimental result was correlated with the Toth isotherm model, showing the heterogeneity of the adsorbent. The heat of adsorption of MIL-101 was determined from the measured isotherm data, indicating the strength between the adsorbent and adsorbate molecule.

Adsorbent characteristics; Adsorption isotherms; CO2 uptakes; MIL-101; Metal-organic frameworks

Introduction

The combination of a strong El Niño has given an impact of global temperature anomaly (GTA) temperature increases up to 0.9oC and carbon dioxide emissions as high as 400 ppm (Szulejko et al., 2017). It is crucial to undertake serious efforts to reduce carbon dioxide emissions to control the rate of global warming. The 21st annual Conference of the Parties, which was held in Paris in 2015 resulted in a negotiated agreement among 195 countries to keep the global temperature below 2°C above pre-industrial levels (Szulejko et al., 2017). Various efforts have been made to reduce the levels of carbon and gas emissions in processing and chemical industries. One such effort is the use of carbon capture technology. Many types of industries have applied this method, such as cement production (Cormos et al., 2017), iron and steel (Cormos, 2016), and power plants (Kanniche et al., 2010).  However,  many  challenges  remain  in  maximizing  efficiency  and economy in implementing this technology.

The adsorption method, which is part of the carbon capture and storage (CCS) technology, is considered an efficient and economical method for replacing conventional technology in the CO2 scrubbing process, since the technology of amine solvents is deficient in corrosion and toxicity (Kartohardjono et al., 2017; Kusrini et al., 2018).  Moreover, large amounts of energy are required to recycle amines, which diminishes the efficiency of energy usage, creates high costs in power plants, and produces corrosion in the pipeline (Ye et al., 2013; Mutyala et al., 2019). Another type of CCS technology is the membrane separation method, but this method is expensive in design and synthesis (Brunetti et al., 2010). Therefore, the most effective method in CCS technology is the adsorption method, which does not require large energy inputs in regeneration, does not cause corrosion, is inexpensive, and has a high capacity and high selectivity of CO2 gas uptakes (Gargiulo et al., 2014). Recently, the most-studied types of adsorbents have been activated carbon, zeolite, and molecular carbon sieves, as conducted by Sarker et al. (2017), who carried out a comparative study of these three adsorbents in terms of their CO2 adsorption capacity in equilibrium conditions. The results showed that GCA-1240 activated carbon had a large volumetric uptake of 10 mmol/g at 293 K, followed by Zeolite 13 X, Zeolite 5 A, and a molecular carbon sieve (MSC-3R) with the adsorption capacity reaching to 7, 4.7, and 4.2 mmol/g in sequence (Sarker et al., 2017).

The search for the most effective adsorbent has continued for the past five years. Metal-organic frameworks (MOFs) have attracted attention because of their higher thermal stability, good crystallinity, large surface area, and high pore volume (Yulia et al., 2019). MIL-101 is the most attractive MOF for study due to its high thermal and chemical stability, moisture resistance, rapid kinetics, good cyclability, and high adsorption capacity (Liu et al., 2013; Montazerolghaem et al., 2016). MIL-101 is an expected candidate in the future as it is eco-friendly and has better physicochemical properties. MIL-101 has been tested with various types of gas adsorption and coupled by molecular simulation. Llewellyn et al. (2008) conducted experiments on the adsorption of CH4 and CO2 gas in MIL-101. Lin et al. (2014). carried out a CO2 adsorption analysis with polyethyleneimine incorporated MIL-101, and it was found from their report that the CO2 adsorption capacity reached 4.2 mmol/g at 25°C. Many adsorption experiments are still being conducted on the MIL-101 adsorbent, but different methods and experiments produce various results.

The present research explores the synthesis evaluation of the MIL-101 adsorbent, which is then examined using various experimental techniques to observe porous, structural, morphological, and chemical functionalities and thermal stability by N2 adsorption/desorption isotherms, X-ray diffraction (XRD) techniques, scanning electron microscope (SEM), thermogravimetric (TGA) analysis, and Fourier transform infrared spectroscopy (FTIR), sequentially. Next, using the volumetric method, measurements of CO2 adsorption were carried out for MIL-101 Cr adsorbent at temperatures of 298-308 K and pressures of up to 600 kPa. The data obtained from the volumetric test was then regressed with the Toth isotherm model, which represents the heterogeneity of the adsorbent capacity of MIL-101. Analysis of the heat of adsorption was also undertaken for the carbondioxide-MIL-101 system, which depends on the temperature and concentration obtained from the results of the data measurements.


Conclusion

The synthesis of the MOF chromium terephthalate with a hydrothermal reaction without using HF solvents was performed. We evaluated the characterization of the adsorbent MOF with various experimental methods, such as XRD, SEM, TGA, FTIR, and N2 adsorption/desorption isotherms. The experiment using the volumetric apparatus was carried out with a CO2 gas adsorbate. Temperature and pressure variations were observed in isothermal adsorption tests at temperatures of 298 K to 308 K and pressures of up to 600 kPa. The maximum capacity in the isothermal adsorption test occurred at a temperature of 298 K, reaching 2.28 mmol/g at a pressure of 600 kPa. The experimental data was also regressed with the Toth isotherm adsorption model representing the heterogeneity of the adsorbent. In addition, a decreasing trend was found in the calculation of the isosteric heat of adsorption due to a strong heterogeneity in the surface structure.



Figure 7 Adsorption isotherms of CO2 on MIL-101 (?, 298 K; ?, 300 K; ?, 308 K). Solid lines represent the Toth model for CO2 adsorption



Figure 8 Isosteric heat of adsorption for CO2 on MIL-101

Acknowledgement

The authors are grateful for financial support from the Indonesian Ministry of Research, Technology and Higher Education (PMDSU grant nos. 1/E1/KP.PTNBH/2019 and 234234/PKS/R/UI/2019) and the Osaka Gas Foundation.

 

References

Alhamid, M.I., Perdana, M.B., 2015. Effect of Methane Gas Flow Rate on Adsorption Capacity and Temperature Distribution of Activated Carbon. International Journal of Technology, Volume 6(4), pp. 584–593

Brunetti, A., Scura, F., Barbieri, G., Drioli, E., 2010. Membrane Technologies for CO2 Separation. Journal of Membrane Science, Volume 359(1-2), pp. 115–125

Cormos, A.-M., Cormos, C.C., 2017. Reducing the Carbon Footprint of Cement Industry by Post-Combustion CO2 Capture: Techno-economic and Environmental Assessment of A CCS Project in Romania. Chemical Engineering Research and Design, Volume 123, pp. 230–239

Cormos, C.C., 2016. Evaluation of Reactive Absorption and Adsorption Systems for Post-combustion CO2 Capture Applied to Iron and Steel Industry. Applied Thermal Engineering, Volume 105, pp. 56–64

Férey, G., Mellot-Draznieks, C., Serre, C., Millange, F., Dutour, J., Surblé, S., Margiolaki, I., 2005. A Chromium Terephthalate-based Solid with Unusually Large Pore Volumes and Surface Area. Science, Volume 309(5743), pp. 2040–2042

Gargiulo, N., Pepe, F. ,Caputo, D., 2014. CO2 Adsorption by Functionalized Nanoporous Materials: A Review. Journal of Nanoscience and Nanotechnology, Volume 14(2), pp. 1811–1822

Hong, D.Y., Hwang, Y.K., Serre, C., Ferey., G., Chang, J.S., 2009. Porous Chromium Terephthalate MIL?101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and Catalysis. Advanced Functional Materials, Volume 19(10), pp. 1537–1552

Kanniche, M., Gros-Bonnivard, R., Jaud, P., Valle-Marcos, J., Amann, J.M., Bouallou, C., 2010. Pre-combustion, Post-combustion and Oxy-combustion in Thermal Power Plant for CO2 Capture. Applied Thermal Engineering, Volume 30(1), pp. 53–62

Kartohardjono, S., Paramitha, A., Putri, A.A., Andriant, R., 2017. Effects of Absorbent Flow Rate on CO2 Absorption Through a Super Hydrophobic Hollow Fiber Membrane Contactor. International Journal of Technology, Volume 8(8), pp. 1429–1435

Kayal, S., Chakraborty, A., 2018. Activated Carbon (Type Maxsorb-III) and MIL-101 (Cr) Metal Organic Framework Based Composite Adsorbent for Higher CH4 Storage and CO2 Capture. Chemical Engineering Journal, Volume 334, pp. 780–788

Kayal, S., Sun, B.,Chakraborty, A., 2015. Study of Metal-organic Framework MIL-101 (Cr) for Natural Gas (Methane) Storage and Compare with other MOFs (Metal-Organic Frameworks). Energy, Volume 91, pp. 772–781

Kusrini, E., Utami, C.S., Usman, A.,Tito, K.A., 2018. CO2 Capture using Graphite Waste Composites and Ceria. International Journal of Technology, Volume 9(2), pp. 287–296

Lebedev, O., Millange, F., Serre, C., Van, T.G., Férey, G., 2005. First Direct Imaging of Giant Pores of the Metal? Organic Framework MIL-101. Chemistry of Materials, Volume 17(26), pp. 6525–6527

Lin, Y., Lin, H., Wang, H., Suo, Y., Li, B., Kong, C., Chen, L., 2014. Enhanced Selective CO2 Adsorption on Polyamine/MIL-101 (Cr) Composites. Journal of Materials Chemistry A, Volume 2(35), pp. 14658–14665

Liu, Q., Ning, L., Zheng, S., Tao, M., Shi, Y., He, Y., 2013. Adsorption of Carbon Dioxide by MIL-101 (Cr): Regeneration Conditions and Influence of Flue Gas Contaminants. Scientific Reports, Volume 3(2916), pp. 1–6

Llewellyn, P.L., Bourrelly, S., Serre, C., Vimont, A., Daturi, M., Hamon, L., De Weireld, G., Chang, J.S., Hong, D.Y., Kyu Hwang, Y., 2008. High Uptakes of CO2 and CH4 in Mesoporous Metal Organic Frameworks Mil-100 and Mil-101. Langmuir, Volume 24(14), pp. 7245–7250

Martin, A., Loh, W.S., Rahman, K.A., Thu, K., Surayawan, B., Alhamid, M.I., Ng, K.C., 2011., Adsorption Isotherms of CH4 on Activated Carbon from Indonesian Low Grade Coal. Journal of Chemical & Engineering Data, Volume 56(3), pp. 361–367

Montazerolghaem, M., Aghamiri, S.F., Tangestaninejad, S., Talaie, M.R., 2016., A Metal–Organic Framework MIL-101 Doped with Metal Nanoparticles (Ni & Cu) and its Effect on CO2 Adsorption Properties. RSC Advances, Volume 6(1), pp. 632–640

Mutyala, S., Jonnalagadda, M., Mitta, H., Gundeboyina, R., 2019., CO2 Capture and Adsorption Kinetic Study of Amine-Modified MIL-101 (Cr). Chemical Engineering Research and Design, Volume 143, pp. 241–248

Sarker, A.I., Aroonwilas, A.,Veawab, A., 2017. Equilibrium and Kinetic Behaviour of CO2 Adsorption onto Zeolites, Carbon Molecular Sieve and Activated Carbons. Energy Procedia, Volume 114, pp. 2450–2459

Szulejko, J.E., Kumar, P., Deep, A., Kim, K.H., 2017. Global Warming Projections to 2100 using Simple CO2 Greenhouse Gas Modeling and Comments on CO2 Climate Sensitivity Factor. Atmospheric Pollution Research, Volume 8(1), pp. 136–140

Ye, S., Jiang, X., Ruan, L.W., Liu, B., Wang, Y.M., Zhu, J.F. ,Qiu, L.G., 2013. Post-combustion CO2 Capture with the HKUST-1 and MIL-101 (Cr) Metal–Organic Frameworks: Adsorption, Separation and Regeneration Investigations. Microporous and Mesoporous Materials, Volume 179, pp. 191–197

Yulia, F., Zulys, A., Ruliandini, R., 2019. Metal-Organic Framework Based Chromium Terephthalate (MIL-101 Cr) Growth for Carbon Dioxide Capture: A Review. Journal of Advanced Research in Fluid Mechanics and Thermal Sciences, Volume 57(2), pp. 158–174