Article pubs.acs.org/IECR
Speeding Up Chemisorption Analysis by Direct IR-Heat-Release Measurements (Infrasorp Technology): A Screening Alternative to Breakthrough Measurements Fabien Sandra,† Nicole Klein,‡ Matthias Leistner,‡ Martin R. Lohe,† Matthias Benusch,‡ Michelle Woellner,‡ Julia Grothe,*,† and Stefan Kaskel†,‡ †
Inorganic Chemistry, Dresden University of Technology, Bergstrasse 66, D-01062 Dresden, Germany Fraunhofer Institut für Werkstoff und Strahltechnik (IWS), Winterbergstrasse 28, D-01277 Dresden, Germany
‡
S Supporting Information *
ABSTRACT: In this study, a new innovative adsorption screening method, Infrasorp technology, is presented as a quick and efficient measurement tool for the determination of H2S adsorption capacity and compared to breakthrough measurements. Using zinc oxide nanoparticles and metal−organic framework materials, a clear correlation between those two techniques was found, showing the broad applicability of the method for different classes of materials and the potential of Infrasorp to be used as an alternative or preliminary analysis to breakthrough measurements. This tool saves time and costs and speeds up characterization of new materials thanks to the feasibility of a quick and easy wide screening using a small amount of adsorbent.
1. INTRODUCTION
different characteristics for various types of adsorbents in a very short time. In this manuscript, we will present a new tool that can help to answer this demand: Infrasorp technology (Figure 1,
Research on hydrogen sulfide (H2S) adsorption materials has been active for decades because of its highly corrosive and poisonous impact toward nature, human health, and technology.1,2 This gas is a toxic pollutant resulting from different origins: natural gas and syngas, agricultural sewage,3,4 and chemical and petrochemical industries. It has a strong and unpleasant odor perceived by humans at a very low concentration ( ZnOs > ZnOc), and by comparing the breakthrough measurement values with Infrasorp signal, a satisfying correlation is observed. Thus, the Infrasorp can be used as a routine technique for an initial screening tool in order to submit only most effective materials to breakthrough measurements, allowing one to save time and money, or this method can be used as an alternative to breakthrough measurements if the purpose is only to make a quick screening without a precise determination of the H2S uptake by mass units of adsorbent. The Infrasorp shows some advantages: saving time (minutes instead of hours) with a very high speed, accurate detection of H2S adsorption capacity, and requiring a low quantity of sample, which permits screening of a large batch of materials in a short time. This is especially valuable for new adsorbents such as MOFs and COFs that are often initially synthesized in milligram quantities. Moreover, in addition to the possibility to use inert and corrosive gases in the machine, the Infrasorp allows for increasing the accuracy of the measurement by repeating the analysis several times thanks to the rapidity of one measurement. Finally, it was shown that this tool can be applied to oxides and MOFs and that it could be extended to a large variety of materials.
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diffraction, and N2 adsorption/desorption isotherms. The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecr.5b01404.
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AUTHOR INFORMATION
Corresponding Author
*Tel.: +4935146333632. Fax: +4935146337287. E-mail: julia.
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We thank the German Federal Ministry of Education and Research (BMBF) for financial support (03X0126C).
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REFERENCES
(1) Swisher, J. H.; Jhunjhunwala, M.; Gasper-Galvin, L. D.; Gardner, T. H.; Hammerbeck, K. Properties of Sulfur Sorbents Containing Dispersed Nickel in an Al2O3 Matrix. J. Mater. Eng. Perform. 1996, 5, 247. (2) Samokhvalov, A.; Tatarchuk, B. J. Characterization of Active Sites, Determination of Mechanisms of H2S, COS and CS2 Sorption and Regeneration of ZnO Low-Temperature Sorbents: Past, Current and Perspectives. Phys. Chem. Chem. Phys. 2011, 13, 3197. (3) Orr, W. L. Geologic and Geochemical Controls on the Distribution of Hydrogen Sulfide in Natural Gas. In Advances in Organic Geochemistry 1975; Campos, R., Goni, J., Eds.; Empresa Nacional Adaro de Investigaciones Mineras, Inc.: Madrid, 1977; p 571. (4) Song, H. S.; Park, M. G.; Ahn, W.; Lim, S. N.; Yi, K. B.; Croiset, E.; Chen, Z.; Nam, S. C. Enhanced Adsorption of Hydrogen Sulfide
ASSOCIATED CONTENT
* Supporting Information S
General information about materials characterization, data of Infrasorp and breakthrough measurements, powder X-ray E
DOI: 10.1021/acs.iecr.5b01404 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Article
Industrial & Engineering Chemistry Research and Regeneration Ability on the Composites of Zinc Oxide with Reduced Graphite Oxide. Chem. Eng. J. 2014, 253, 264. (5) Kidnay, A. J.; Parrish, W. R. Overview of the Natural Gas Industry. In Fundamentals of Natural Gas Processing; CRC/Taylor & Francis: Boca Raton, FL, 2006; pp 121−148. (6) Pahalagedara, L. R.; Poyraz, A. S.; Song, W.; Kuo, C. H.; Pahalagedara, M. N.; Meng, Y. T.; Suib, S. L. Low Temperature Desulfurization of H2S: High Sorption Capacities by Mesoporous Cobalt Oxide via Increased H2S Diffusion. Chem. Mater. 2014, 26, 6613. (7) Gabriel, D.; Deshusses, M. A. Retrofitting Existing Chemical Scrubbers to Biotrickling Filters for H2S Emission Control. Proc. Natl. Acad. Sci. U.S.A. 2003, 100, 6308. (8) Seredych, M.; Mabayoje, O.; Bandosz, T. J. Visible-LightEnhanced Interactions of Hydrogen Sulfide with Composites of Zinc (Oxy)hydroxide with Graphite Oxide and Graphene. Langmuir 2012, 28, 1337. (9) Garces, H. F.; Galindo, H. M.; Garces, L. J.; Hunt, J.; Morey, A.; Suib, S. L. Low Temperature H2S Dry-Desulfurization with Zinc Oxide. Microporous Mesoporous Mater. 2010, 127, 190. (10) Garces, H. F.; Espinal, A. E.; Suib, S. L. Tunable Shape Microwave Synthesis of Zinc Oxide Nanospheres and Their Desulfurization Performance Compared with Nanorods and Plateletlike Morphologies for the Removal of Hydrogen Sulfide. J. Phys. Chem. C 2012, 116, 8465. (11) Westmoreland, P. R.; Harrison, D. P. Evaluation of Candidate Solids for High-Temperature Desulfurization of Low-Btu Gases. Environ. Sci. Technol. 1976, 10, 659. (12) Westmoreland, P. R.; Gibson, J. B.; Harrison, D. P. Comparative Kinetics of High-Temperature Reaction Between Hydrogen Sulfide and Selected Metal Oxides. Environ. Sci. Technol. 1977, 11, 488. (13) Hamon, L.; Serre, C.; Devic, T.; Loiseau, T.; Millange, F.; Ferey, G.; Weireld, G. Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-47(V), MIL-100(Cr), and MIL-101(Cr) Metal-Organic Frameworks at Room Temperature. J. Am. Chem. Soc. 2009, 131, 8775. (14) Nickerl, G.; Leistner, M.; Helten, S.; Bon, V.; Senkovska, I.; Kaskel, S. Integration of Accessible Secondary Metal Sites into MOFs for H2S Removal. Inorg. Chem. Front. 2014, 1, 325. (15) Kaskel, S.; Wollmann, P.; Leistner, M. Verfahren und Vorrichtung zur Bestimmung der Adsorption Eines Gases an Werkstoffen. German patent no. DE102009031764A1, January 5, 2011, and international patent no. WO2010149152A1, December 29, 2010. (16) Wollmann, P.; Leistner, M.; Stoeck, U.; Grünker, R.; Gedrich, K.; Klein, N.; Throl, O.; Grählert, W.; Senkovska, I.; Dreisbach, F.; Kaskel, S. High-Throughput Screening: Speeding Up Porous Materials Discovery. Chem. Commun. 2011, 47, 5151. (17) Wollmann, P.; Leistner, M.; Grählert, W.; Throl, O.; Dreisbach, F.; Kaskel, S. Infrasorb: Optical Detection of the Heat of Adsorption for High Throughput Adsorption Screening of Porous Solids. Microporous Mesoporous Mater. 2012, 149, 86. (18) Leistner, M.; Grählert, W.; Kaskel, S. Screening of Porous Materials by Thermal Response Measurements. Chem. Ing. Tech. 2013, 85, 747. (19) Beercroft, T.; Miller, A. W.; Ross, J. R. H. The Use of Differential Scanning Calorimetry in Catalyst Studies. The Methanation of Carbon Monoxide over Nickel/Alumina Catalysts. J. Catal. 1975, 40, 281. (20) Lantz, J. B.; Gonzalez, R. D. Development of a New Isothermal Calorimeter; Heats of Hydrogen Adsorption on Supported Platinum vs Crystallite Size. J. Catal. 1976, 41, 293. (21) Chou, P.; Vannice, M. A. Calorimetric Heat of Adsorption Measurements on Palladium: I. Influence of Crystallite Size and Support on Hydrogen Adsorption. J. Catal. 1987, 104, 1. (22) Chou, P.; Vannice, M. A. Calorimetric Heat of Adsorption Measurements on Palladium: II. Influence of Crystallite Size and Support on CO Adsorption. J. Catal. 1987, 104, 17.
(23) Sen, B.; Chou, P.; Vannice, M. A. Direct Measurements of Heats of Adsorption on Platinum Catalysts: III. Potential Error with Differential Scanning Calorimeters. J. Catal. 1986, 101, 517. (24) Childers, D.; Saha, A.; Schweitzer, N.; Rioux, R. M.; Miller, J. T.; Meyer, R. J. Correlating Heat of Adsorption of CO to Reaction Selectivity: Geometric Effects vs Electronic Effects in Neopentane Isomerization over Pt and Pd Catalysts. ACS Catal. 2013, 3, 2487. (25) Liu, Z.-S.; Peng, Y.-H.; Huang, C.-Y.; Hung, M.-J. Application of Thermogravimetry and Differential Scanning Calorimetry for the Evaluation of CO2 Adsorption on Chemically Modified Adsorbents. Thermochim. Acta 2015, 602, 8. (26) Alkhabbaz, M. A.; Bollini, P.; Foo, G. S.; Sievers, C.; Jones, C. W. Important Roles of Enthalpic and Entropic Contributions to CO2 Capture from Simulated Flue Gas and Ambient Air Using Mesoporous Silica Grafted Amines. J. Am. Chem. Soc. 2014, 136, 13170. (27) Vargas, D. P.; Giraldo, L.; Moreno-Pirajàn, J. C. Calorimetric Study of the CO2 Adsorption on Carbon Materials. J. Therm. Anal. Calorim. 2014, 117, 1299. (28) Korrir, A.; El Kasmi, A.; Assebban, M.; Souikny, A.; Haffane, S.; Achak, O.; Chafik, T. Non-Calorimetric Determination of the Adsorption Heat of Volatile Organic Compounds under Dynamic Conditions. Catalysts 2015, 5, 653−670.
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DOI: 10.1021/acs.iecr.5b01404 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
