Calo, Joseph

Overview

Professor Calo contributed to the founding and development of the Chemical Engineering Program at Brown. Previously, he held positions at the Air Force Geophysics Laboratory, Exxon Research & Engineering Co., and Princeton University.

Professor Calo served as the Conference Chair of carbon2004, the international conference on carbon materials, held at Brown University in July, 2004. He also served on the Executive Committee of the American Carbon Society, and of the Division of Fuel Chemistry of the American Chemical Society, for which he served as Treasurer Councilor, and Technical Program Secretary. He is also a Fellow of the American Chemical Society.

Brown Affiliations

Engineering

Research Areas

carbon materials | electrochemical remediation of heavy metal compounds | fluid-particulate environmental technology

Research

Research Overview

A central theme in Professor Calo's work is the application of principles of chemical kinetics and transport phenomena to problems in science and engineering. Chemical rate processes, combined with transport limitations and surface-specific characteristics, are of central importance in a diverse range of applications such as the optimization of chemical reactors for chemicals and fuels production, the composition of the earth's atmosphere, or the solution of environmental problems.

Research Statement

Recent work includes the determination of the kinetic mechanisms of heterogeneous gas-solid reactions relevant to gasification and oxidation of coal and carbon materials. The oxidizing gases (e.g., O2, CO2, H2O, NO, etc.) form oxygen complexes on carbon surfaces. At low temperatures, these complexes are permanently chemisorbed, while at higher temperatures they desorb as the oxides of carbon, thereby "gasifying" the material. The key to unraveling the kinetics of these reactions lies in understanding the role and energetics of the oxygen surface complex intermediates. This is a complex problem in view of the variable and evolving physical and chemical nature of the solid reactant which manifests itself in such phenomena as a continually evolving pore structure and a distribution of desorption activation energies of the complexes, among other problems. Related problems include the structural transformation/ordering of carbonaceous materials, as well as the development of characterization techniques for these materials. Examples of the latter incxlude small-angle X-ray scattering (SAXS), contrast matching, and small angle neutron scattering (SANS) to monitor porosity development.

Another major research direction in Professor Calo's laboratory involves addressing technological problems of environmental import. A new research project is directed at the development of novel spouted-bed particulate electrodes for the removal of metals from aqueous waste streams. Both electrowinning and elecrosorption/desorption of heavy metal species are amenable to this novel approach.

Another project involves a liquid-fluidization technique for the micro-sorting of waste plastic particles for recycling. The process involves separation of plastic particles by density via liquid-fluidized bed classification (LFBC) and particle size/density modification technique (e.g., selective swelling or shrinking of particles as a result of thermal waves imposed on the liquid-fluidized bed or selective swelling solvents). Yet another more recent project involves the application of related segregation in liquid-fluidized beds to coal beneficiation.

Funded Research

"Gas-Surface Interactions in Cryogenic Whole Air Sampling," Air Force Geophysics Laboratory, Hanscom AFB, MA; $80,000, l976-l979.
"Photoionization of Molecular Clusters," Air Force Office of Scientific Research, Bolling AFB, Washington, DC; $l52,2l2, l977-l980.
"Chemical Reactions and Molecular Aggregation in Cryogenic Whole Air Sample Matrices," Air Force Geophysics Laboratory, Hanscom AFB, MA; $59,888, l979-l98l.
"The Heterogeneous Kinetics of Coal Gasification," Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA; $112,760, l98l-l983.
"Experimental Studies of the Infrared Spectroscopy of Atmospheric and Other Molecular Complexes," National Science Foundation, Washington, DC, $438,435, l98l-l984.
"Active Sites in Char Gasification," Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA; $200,000, l983-l986.
Exxon Education Foundation Unrestricted Research Grant, $5,000, 1985-86.
"A Study of Micropore Diffusion in Coal Chars Under Reactive Conditions," Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA; $175,000, 1986-1989.
"A Mechanistic Study of the Energetic Heterogeneity of Coal Chars," Department of Energy, Morgantown Energy Technology Center, Morgantown, WV; $221,644; 1987-1989.
"The Application of Percolation Theory to Modeling the Hydrodynamics of an Acid Hydrolysis Percolation Reactor," Solar Energy Research Institute, Golden, CO; $98,310, 1987-1990.
"NO-Char Reactions--Kinetics and Transport Aspects," Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA; $200,000, 1988-1991.
"The Development of Laboratory Ion Sources for Mass Spectrometer Calibration," Air Force Geophysics Laboratory, Hanscom AFB, MA; $10,000, 1991-93.
"Continuous Micro-sorting of Plastic Particles Via Liquid-Fluidized Classification (LFBC)," Plastics Recycling Foundation, Washington, D.C.; $69,000, 1993-1994.
"Reactivity of 'Young Chars' Via Energetic Distribution Measurements," Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA; $217,550, 1990-1993.
"Characterization of Coal Char Porosity Via Secondary Reactions, " Department of Energy, Pittsburgh Energy Technology Center, Pittsburgh, PA; $217,550, 1991-1994.
"A Novel Course in Industrial Ecology," DoD via the Pollution Prevention Consortium of New England Universities, $21,000, 1995-96.
"High Temperature/High Pressure TGA," DOE University Research Instrumentation Grant, DOE, Washington, DC; $212,040, 1995-97.
"The Removal of Technetium From Radiocontaminated Nickel," Covofinish Co., Inc., $35,000, 1995-97.
1996 AT&T and Lucent Technologies Industrial Ecology Faculty Fellowship Award, $50,000, 1996-97.
"Structure-Based Predictive Models for Coal Char Combustion," Department of Energy, Federal Energy Technology Center, Pittsburgh, PA; $656,000, 1996-1999.
"Transient Studies of the Effects of Fire Suppressants in a Well-Stirred Combustor," AFOSR via RDL, $25,000, 1997.
1997 AT&T and Lucent Technologies Industrial Ecology Faculty Fellowship Award, $50,000, 1997-98.
"Development of High Activity, Coal-Derived, Promoted Catalytic Systems for NOx Reduction at Low Temperatures," Department of Energy, Federal Energy Technology Center, Pittsburgh, PA; $220,000, 1997-2001.
"Spouted Bed Electrolytic Recovery of Metals for Source Reduction and Waste Minimization," U.S.E.P.A., ORD, 1997-2002; $316,619.
"Coal Cleaning Via Liquid-Fluidized Bed Classification (LFBC) With Selective Solvent Swelling," Department of Energy, Federal Energy Technology Center, Pittsburgh, PA; $55,000, 1998-2000.
"Continuous Micro-sorting of Complex Waste Plastic Particle Mixtures Via Liquid-Fluidized Bed Classification (LFBC) for Waste Minimization and Recycling," jointly funded by the NSF and EPA, $260,000, 1999-2002.
"Fundamental Investigation of Fuel Transformations in Advanced Coal Combustion and Gasification Technologies," Department of Energy, National Energy Technology Laboratory, Pittsburgh, PA; $534,190, 2000-2004.
"Characterization of Carbon Monolith Materials for Fuel Gas Storage Via Small Angle Neutron Scattering," UT-Battelle, LLC, Oak Ridge National Laboratory, Oak Ridge, Tennessee; $20,000, 2001-2004.
"Spouted Bed Electrodes (SBE) for Direct Utilization of Carbon in Fuel Cells," Department of Energy, National Energy Technology Laboratory, Pittsburgh, PA; $55,000 2003-2004.
"Metals Removal Via Spouted Bed Electrolytic Reactors (SBER)," Project 5, Superfund Basic Research Program, National Institute of Environmental Health Sciences, Washington, DC; ~$600,000 (direct cost), 2005-2009.

Scholarly Work

Hu, X, and Calo, JM. Plastic particle separation via liquid-fluidized bed classification. AIChE J. 2006; 52(4): 1333-1342.

Shirvanian, PA, Calo, JM, and Hradil, G. Numerical simulation of fluid-particle hydrodynamics in a rectangular spouted vessel. Int. J. Multiphase Flow, 2006. accepted, in press.

Shirvanian, PA, and Calo, JM. Copper recovery in a particulate spouted bed electrode. J. Appl. Electrochem. 2005; 35(1): 101-111.

Hu, X, and Calo, JM. Enhancement of liquid fluidized bed classification (LFBC) of plastic particle mixtures via selective thermal particle modification. Powder Tech. 2005; 151(1-3): 44-53.

Calo, JM, and Hall, PJ. The application of small angle scattering (SAS) techniques to porosity characterization in carbons. Carbon 2004; 42:1299-1304.

Shirvanian, PA, and Calo, JM. Hydrodynamic scaling of a rectangular spouted vessel with a draft duct. Chem. Eng. J. 2004; 103/1-3:29-34.

Hall, PJ, Brown, SD, Hitchman, MJ, and Calo, JM. Effect of temperature and pressure treatment on the porosity of expanded polytetrafluoroethylene films. J. Appl. Polymer Sci. 2003; 89:1579-1582.

Calo, JM, Hu, X, Logan, T, Choi, D, Apicello, J. Coal cleaning via liquid-fluidized bed classification (LFBC) with selective particle modification. J. Separation Sci. 2003; 26:1429-1435.

Calo, JM, Hall, PJ, Houtmann, S, Winans, RE, and Seifert, S. "Real time" determination of porosity development in carbons: a combined SAXS/TGA approach," in Studies in Surface Science and Catalysis, Characterization of Porous Solids VI, F. Rodríguez-Reinoso, B. McEnaney, J. Rouquerol, and K. Unger, eds., 2002. Elsevier, Amsterdam.

Zhang, L-H, and Calo, JM. Thermal desorption methods for porosity characterization of carbons and chars. Colloids and Surfaces A: Physicochemical and Engineering Aspects; 2001; 187-188: 207-218.

Hurt, RH, and Calo, JM. Semi-global intrinsic kinetics for char combustion modeling. Combustion and Flame. 2001; 125: 1138-1149.

Calo, JM, Hall, PJ, and Antxustegi, M. Carbon porosity characterization via small angle neutron scattering," Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2001; 187-188: 219-232.

Hall, PJ, Brown, S, Fernandez, J, and Calo, JM. The effects of the electronic structure of micropores on the small angle scattering of X-rays and neutrons. Carbon. 2000; 38: 1257-1259.

Hall, PJ, Brown, SD, and Calo, JM. The pore structure of the Argonne Coals as Interpreted from contrast matching small angle neutron scattering. Fuel. 2000; 79: 1327-1332.

Hu, Y, Hurt, R, Calo, JM, and Kerstein, A. Kinetics of orientation order/disorder transitions and their application to carbon material synthesis. Modelling Simul. Mater. Sci. Eng. 1999; 7: 275-288.

Calo, JM, Suuberg, EM, Aarna, I, Linares-Solano, A, Salinas-Martínez de Lecea, C, and Illán-Goméz, MJ. The role of surface area in the NO-carbon reaction. Energy & Fuels. 1999; 13: 761-762.

Antxustegi, MM, Hall, PJ, and Calo, JM. The use of contrast matching small angle neutron scattering techniques to monitor closed porosity in carbons. J. Coll. Intf. Sci. 1998; 202: 490-498.

Hall, PJ, Antxustegi, MM, and Calo, JM. Development of porosity in Pittsburgh no. 8 coal char as investigated by contrast-matching small angle neutron scattering and gas adsorption techniques. Energy & Fuels. 1998; 12: 542-546.

Mondragon, F, Quintero, G, Jaramillo, A, Fernandez, J, Ruiz, W, Hall, PJ, and Calo, JM. The production of high surface carbons from coal using pre-swelling in solvents to disperse coking catalysts. J. Material Sci. 1997; 32: 1455-1459.

Hall, PJ, Berlouis, LEAB, Mackinnon, AJ, Wilson, J, Browning, D, Morris, S, Jones, P, and Calo, JM. Analysis of FeTi hydride alloys by thermal analysis, small angle neutron scattering and positron annihilation. J. Alloys and Compounds, 1997; 253: 195-200.

Hall, PJ, Gascon Galan, D, Ruiz Machado, W, Mondragon, F, Barrientos Barria, E, Sherrington, DC, and Calo, JM. Use of contrast-enhanced small-angle neutron scattering to monitor the effects of solvent swelling on the pore structure of styrene-divinylbenzene resins. J. Chem. Soc. Far. Trans. 1997; 93(3): 463-466.

Calo, JM, Cazorla-Amorós, D, Linares-Solano, A, Román-Martínez, MC, and Salinas-Martínez de Lecea, C. The effects of hydrogen on thermal desorption of oxygen surface complexes. Carbon. 1997; 35: 543.

Calo, JM, Lilly, WD, Hradil, G, and and Mohsen, P. Separation of waste plastic particles via liquid-fluidized bed classification (LFBC). Adv. Filtration Separation Tech. 1996; 10: 399.

Calo, JM, Hradil G, and Wunderlich, TK, Jr. Characterization of aspen wood chip beds via stimulus-response tracer techniques. Biotech. & Bioeng. 1993; 41: 354.

Illán-Gómez, MJ, Linares-Solano, A, Salinas-Martínez de Lecea, C, and Calo, JM. NO reduction by activated carbons - I. the role of carbon porosity and surface area. Energy & Fuels, 1993; 7:146.

Teng, H, Suuberg, EM, and Calo, JM. Studies on the reduction of nitric oxide by carbon: the NO-carbon gasification reaction. Energy & Fuels. 1992; 6: 398.

"Applications of Energetic Distributions of Oxygen Surface Complexes to Carbon and Char Reactivity and Characterization," with P.J. Hall, in Fundamental Issues in the Control of Carbon Gasification Reactivity, J. Lahaye and P. Ehrburger, eds, NATO ASI Series, Series E: Applied Sciences, Vol. 192, p. 329, Kluwer Academic Publishers, Dordrecht, 1991.

The Nature of Isothermal Desorption Of Carbon-Oxygen Surface Complexes Following Gasification," in Fundamental Issues in the Control of Carbon Gasification Reactivity, J. Lahaye and P. Ehrburger, eds, NATO ASI Series, Series E: Applied Sciences, Vol. 192, p. 369, Kluwer Academic Publishers, Dordrecht, 1991.

Suuberg, EM, Teng, H, and Calo, JM. Studies on the kinetics and mechanism of the reaction of NO with carbon. Proc. 23rd Symp. (Int.) Combustion. 1990; pp. 1199-1205.

Lawandy, NM, and Calo, JM. Laser-induced separations (LIS). Recent Developments in Separation Science, Vol. IX, N. N. Li and J. M. Calo, Eds., CRC Press, Inc., Boca Raton, FL, 1986.

Gallagher, CC, Pieri, RV, Faucher, G, Forsberg, C, and Calo, JM. Oxides of nitrogen content of whole air samples obtained at altitudes from l2 to 30 km. J. Geophys. Res. 1985; 90:7899.

Hunton, DE, and Calo, JM. Low energy ions in the shuttle environment: evidence for strong ambient-contaminant interactions. Planet. Space Sci. 1985; 33:945.

Kramer MA, Rabitz, HA, and Calo, JM. Sensitivity analysis of oscillatory systems. Appl. Math Modelling. 1984; 8:328.

Kramer MA, Rabitz, HA, Kee, RJ, and Calo, JM. Sensitivity analysis in chemical kinetics: recent developments and computational comparisons. Int. J. Chem. Kin. 1984; 16:559.

Kramer MA, Rabitz, HA, and Calo, JM. Parametric scaling of mathematical models. Appl. Math Modelling. 1984; 8:341.

Chang, H-C, Saucier, M, and Calo, JM. Design criterion for radial flow fixed-bed reactors. AIChE J. 1983; 29:1039.

Fezza, RJ, and Calo, JM. Atmospheric gases on cold surfaces—condensation thermal desorption, and chemical reactions. Heterogeneous Atmospheric Chemistry, D. Schryer, Ed., Geophysical Monograph Series, Vol. 26, American Geophysical Union, 1982, p. 157.

Leighton, DT, and Calo, JM. Distribution coefficients of chlorinated hydrocarbons in dilute air-water systems for groundwater contamination applications. J. Chem. Eng. Data. 1981; 26:381.

Bowles, RS, Kolstad, JJ, Andres, RP, and Calo, JM. Generation of molecular clusters of controlled size. Surf. Sci. 1981; 106:117.

Calo, JM. The modeling of multiphase chemical reactors, in Multiphase Chemical Reactors, Vol. II—Design Methods, Rodrigues, Calo, and Sweed, eds., NATO Advanced Study Institute Series, Sijthoff and Noordhoff, The Netherlands, 1981.

Kramer MA, Rabitz, HA, and Calo, JM. An improved computational method for sensitivity analysis - the Green's function method with AIM. Appl. Math. Modelling. 1981; 5:432.

Chang, H-C, and Calo, JM. Exact universal uniqueness criteria for the adiabatic tubular packed bed reactor. Chem. Eng. Sci. 1980; 35:1611.

Calo, JM, and Narcisi, RS. van der waals molecules—possible roles in the atmosphere. Geophys. Res. Lett. 1980; 7:289.

Chang, H-C, and Calo, JM. Catastrophe theory and chemical reactors—exact uniqueness criteria for the CSTR, catalyst particle, and packed bed reactor. Chem. Eng. Sci. 1980; 35:264.

Chang, H-C, and Calo, JM. A priori estimation of chemical relaxation oscillations via a singular perturbation technique. Chem. Eng. Comm. 1979; 3:431.

Chang, H-C, and Calo, JM. Exact criteria for uniqueness and multiplicity of an nth order chemical reaction via a catastrophe theory approach. Chem. Eng. Sci. 1979; 34:285.

Calo, JM. Cell model studies of radial flow, fixed bed reactors. Chemical Reaction Engineering - Houston, V. W. Weekman, Jr., and Dan Luss, Editors, ACS Symposium Series 65, Washington, DC. 1978, p. 550.

Calo, JM. Dimer formation in supersonic water-vapor molecular beams. J. Chem. Phys. 1975; 62:4904.

Calo, JM, and Brown, JH. The calculation of equilibrium mole fractions of polar-polar, nonpolar-polar, and ion dimmers. J. Chem. Phys. 1974; 61:3931.

Calo, JM, and Bailey, AD. Phase sensitive pulse counting in modulated beam mass spectrometry. Rev. Sci. Instrum. 1974; 45:1325.

Calo, JM. Heteromolecular clusters of H2O , SO2, CO2, CO and NO. Nature, 1974; 248:665.

Background

Education and Training

Year	Degree	Institution
1970	PhD	Princeton University
1966	BS	Newark College of Engineering

Honors and Awards

Union Carbide Corporation Scholarship at Newark College of Engineering, 1962-1966.
United States Atomic Energy Commission Special Fellowship in Nuclear Science and Engineering at Princeton University, 1966-1969.
United States Air Force Commendation Medal (for research contributions at the Air Force Cambridge Research Laboratories), 1974.
NATO Travel Grant for scientific exchange with Centre de Recherches sur la Physico-Chimie des Surfaces Solides, CNRS, Mulhouse, France, 1990.
Visiting Scholar, Department of Pure & Applied Chemistry, University of Strathclyde, Scotland, UK, 1992.
Visiting Scholar, Departmento de Química Inorgánica of the Universidad de Alicante, 1992.
Air Force Office of Scientific Research Summer Faculty Research Associate, 1995, 1996.
Lucent Technologies Industrial Ecology Faculty Fellow, 1996-97, 1997-98.
Outstanding Service Award (Treasurer), American Chemical Society Division of Fuel Chemistry, 2004.
Invited Plenary Lecturer, "Catalysis on Carbon Surfaces: Some Energy and Environmental Applications," VIII Reunión del Grupo Español del Carbon, Universidad Internacional de Andalucia, Baeza (Jaen), Spain, 9 November 2005.
Outstanding Leadership Award (Conference Chair), American Carbon Society, 2004.
Visiting Scholar, BESSRC/Advanced Photon Source, Argonne National L:aboratory, Argonne, IL, 2006.
Visiting Senior IUnvestigator, Departmento de Química Inorgánica de la Universidad de Alicante, Alicante, Spain, 2006.
Fellow of the American Chemical Society, 2012.

Affiliations

American Chemical Society
American Carbon Society
American Institute of Chemical Engineers

Teaching

ENGN 1120 - Reaction Kinetics and Reactor Design

Researchers@Brown

Researchers@Brown

Joseph M Calo

Professor Emeritus of Engineering

Overview

Brown Affiliations

Research Areas

Research

Research Overview

Research Statement

Funded Research

Scholarly Work

Background

Education and Training

Honors and Awards

Affiliations

Affiliations

Teaching

Teaching