Research Papers: Evaporation, Boiling, and Condensation

High Temperature Thermal Decomposition of Diethyl Carbonate by Pool Film Boiling

[+] Author and Article Information
C. Thomas Avedisian

Sibley School of Mechanical
and Aerospace Engineering,
Cornell University,
Ithaca, NY 14853-7501
e-mail: cta2@cornell.edu

Wei-Chih Kuo

Sibley School of Mechanical
and Aerospace Engineering,
Cornell University,
Ithaca, NY 14853-7501
e-mail: wk253@cornell.edu

Wing Tsang

Physical and Chemical Properties Division,
National Institute of Standards and Technology,
Gaithersburg, MD 20899
e-mail: wingtsang2000@yahoo.com

Adam Lowery

Sibley School of Mechanical
and Aerospace Engineering,
Cornell University,
Ithaca, NY 14853-7501
e-mail: al659@cornell.edu

1Corresponding author.

2Present address: CGG, 10300 Town Park Drive, Houston, TX 77072.

3Present address: Department of Mechanical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061.

Contributed by the Heat Transfer Division of ASME for publication in the JOURNAL OF HEAT TRANSFER. Manuscript received March 15, 2017; final manuscript received September 19, 2017; published online February 27, 2018. Editor: Portonovo S. Ayyaswamy.This work is in part a work of the U.S. Government. ASME disclaims all interest in the U.S. Government's contributions.

J. Heat Transfer 140(6), 061501 (Feb 27, 2018) (10 pages) Paper No: HT-17-1145; doi: 10.1115/1.4038572 History: Received March 15, 2017; Revised September 19, 2017

We use the configuration of film boiling on a horizontal tube positioned in a stagnant pool of saturated diethyl carbonate (DEC, (C2H5O)2CO) to study DEC decomposition at temperatures up to 1500 K. The composition of bubbles that percolate through the liquid pool is measured and the results are used to infer the decomposition reactions. The results show that below tube temperatures of about 1100 K, the decomposition products are ethylene (C2H4), carbon dioxide (CO2), and ethanol (EtOH, C2H5OH) with a molar ratio nC2H4/nCO2∼1, which is consistent with a first-order decomposition process. At higher temperatures, nC2H4/nCO2 > 1 which is explained by an additional route to forming C2H4 from radicals in the system (created by EtOH decomposition) attacking DEC. The presence of H2, CO, CH4, and C2H6 in the product stream was noted at all temperatures examined with concentrations that increased from trace values at low temperatures to values comparable to the DEC unimolecular process at the highest temperatures. Formation of a carbon layer on the tube was observed but did not appear to influence the decomposition process. A scale analysis shows that the rate constant controls decomposition compared to the residence time, which has a weaker dependence on temperature.

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Eckhoff, R. K. , 2016, “ Water Vapour Explosions—A Brief Review,” J. Loss Prev. Process Ind., 40, pp. 188–198. [CrossRef]
Anderson, M. H. , Meekunnasombat, P. , and Corradini, M. L. , 2001, “ Experimental Behavior of Molten SnxLiy Impacted by a Vertical Column of Water,” Fusion Sci. Technol., 39, pp. 966–969.
Vanderhaegen, M. , and Le Belguett, A. , 2014, “ Review on Sodium Boiling Phenomena in Reactor Systems,” Nucl. Sci. Eng., 176(2), pp. 115–137. [CrossRef]
Witte, L. C. , Cox, J. E. , and Bouvier, J. E. , 1970, “ The Vapour Explosion,” J. Met., 22(2), pp. 39–44.
Okyuama, K. , and Iida, Y. , 1994, “ Film-Boiling Heat Transfer With a Catalytic Decomposition Reaction,” Jpn. Soc. Mech. Eng. Int. J., Ser. B, 37(1), pp. 123–131.
Zhukov, S. A. , Rafeev, V. A. , Afansev, S. Y. , Echmaev, S. B. , and Korsunksii, B. L. , 2004, “ Characteristic Features of the Implementation of Film Boiling of Organic Liquids,” Heat Transfer Res., 35(1–2), pp. 171–179.
Epstein, M. , Leung, J. C. , Hauser, G. M. , and Henry, R. E. , 1984, “ Film Boiling on a Reactive Surface,” Int. J. Heat Mass Transfer, 27(8), pp. 1365–1378. [CrossRef]
Choi, S. R. , Evangelista, J. W. , Avedisian, C. T. , and Tsang, W. , 2011, “ Experimental Study of Chemical Conversion of Methanol and Ethylene Glycol in a Film Boiling Reactor,” Int. J. Heat Mass Transfer, 54(1–3), pp. 500–511. [CrossRef]
Kuo, W. C. , Avedisian, C. T. , Choi, K. W. , and Tsang, W. , 2014, “ On Using Film Boiling to Thermally Decompose Liquid Organic Chemicals: Application to Ethyl Acetate as a Model Compound,” Int. J. Heat Mass Transfer, 68, pp. 456–465. [CrossRef]
Evangelista, J. W. , Avedisian, C. T. , and Tsang, W. , 2012, “ Thermal and Catalytic Decomposition of Aqueous Ethylene Glycol Mixtures by Film Boiling,” Int. J. Heat Mass Transfer, 55(23–24), pp. 6425–6434. [CrossRef]
Wang, J. P. , Qian, J. M. , Qiao, G. J. , and Jin, Z. H. , 2006, “ Improvement of Film Boiling Chemical Vapor Infiltration Process for Fabrication of Large Size C/C Composite,” Mater. Lett., 60(9–10), pp. 1269–1272. [CrossRef]
Wang, J. P. , Qian, J. M. , Qiao, G. J. , and Jin, Z. H. , 2006, “ Microstructure of C/C Composites Prepared by Chemical Vapor Infiltration Method With Vaporized Kerosene as a Precursor,” Mater. Sci. Eng. A, 419(1–2), pp. 162–167. [CrossRef]
Zhang, Y. , Gamo, M. N. , and Nakagawa, K. , 2002, “ Synthesis of Aligned Carbon Nanotubes in Organic Liquids,” J. Mater. Res., 17(9), pp. 2457–2464. [CrossRef]
Zhang, Y. , Gamo, M. N. , Xiao, M. N. , and Ando, C. Y. T. , 2002, “ Liquid Phase Synthesis of Carbon Nanotubes,” Physica B, 323(1–4), pp. 293–295. [CrossRef]
Shukal, K. , and Srivastava, V. C. , 2016, “ Diethyl Carbonate: Critical Review of Synthesis, Routes, Catalysts Used and Engineering Aspects,” RSC Adv., 6(39), pp. 32624–32645. [CrossRef]
Lewandowski, A. , and Swiderska-Mocek, A. , 2009, “ Ionic Liquids and Electrolytes for Li-Ion Batteries—An Overview of Electrochemical Studies,” J. Power Sources, 194(2), pp. 601–609. [CrossRef]
Roh, N. S. , Dunn, B. C. , Eyring, E. M. , Pugmire, R. J. , and Meuzelaar, H. L. C. , 2003, “ Production of Diethyl Carbonate From Ethanol and Carbon Monoxide Over a Heterogeneous Catalytic Flow Reactor,” Fuel Process. Technol., 83(1–3), pp. 27–38. [CrossRef]
Pacheco, M. A. , and Marshall, C. L. , 1997, “ Review of Dimethyl Carbonate (DMC) Manufacture and Its Characteristics as a Fuel Additive,” Energy Fuels, 11(1), pp. 2–29. [CrossRef]
Malecki, H. , Deng, G. , Anani, A. , and Howard, J. , 1999, “ Thermal Stability Studies of Li-Ion Cells and Components,” J. Electrochem. Soc., 146(9), pp. 3224–3229. [CrossRef]
Domi, Y. , Ochida, M. , Tsubouchi, S. , Nakagawa, H. , Yamanaka, T. , Doi, T. , Abe, T. , and Ogumi, Z. , 2011, “ In Situ AFM Study of Surface Film Formation on the Edge Plane of HOPG for Lithium-Ion Batteries,” J. Phys. Chem. C, 115(51), pp. 25484–25489. [CrossRef]
Matsushita, T. , Dokko, K. , and Kanamura, K. , 2005, “ In Situ FT-IR Measurement for Electrochemical Oxidation of Electrolyte With Ethylene Carbonate and Diethyl Carbonate on Cathode Active Material Used in Rechargeable Lithium Batteries,” J. Power Sources, 146(1–2), pp. 360–364. [CrossRef]
Wilke, S. , Schweitzer, B. , Khateeb, S. , and Al-Hallaj, S. , 2017, “ Preventing Thermal Runaway Propagation in Lithium Ion Battery Packs Using a Phase Change Composite Material: An Experimental Study,” J. Power Sources, 340, pp. 51–59. [CrossRef]
Harrisa, S. J. , Timmonsa, A. , and Pitz, W. J. , 2009, “ A Combustion Chemistry Analysis of Carbonate Solvents Used in Li-Ion Batteries,” J. Power Sources, 193(2), pp. 855–858. [CrossRef]
Spotnitz, R. M. , Weaver, J. , Yeduvaka, G. , Doughty, D. H. , and Roth, E. P. , 2007, “ Simulation of Abuse Tolerance of Lithium-Ion Battery Packs,” J. Power Sources, 163(2), pp. 1080–1086. [CrossRef]
Kim, G. H. , Pesaran, A. , and Spotnitz, R. , 2007, “ A Three-Dimensional Thermal Abuse Model for Lithium-Ion Cells,” J. Power Sources, 170(2), pp. 476–489. [CrossRef]
Mandal, B. K. , Padhi, A. K. , Shi, Z. , Chakraborty, S. , and Filler, R. , 2006, “ Thermal Runaway Inhibitors for Lithium Battery Electrolytes,” J. Power Sources, 161(2), pp. 1341–1345. [CrossRef]
Bigley, D. B. , and Wren, C. M. , 1972, “ Pyrolysis of Carbonates—Part 1: The Gas-Phase Pyrolysis of Some Symmetrical Primary Alkyl Carbonates,” J. Chem. Soc. Perkin Trans., 2(2), pp. 926–928. [CrossRef]
Mogi, R. , Inaba, M. , Iriyama, Y. , Abe, T. , and Ogumi, Z. , 2003, “Study on the Decomposition Mechanism of Alkyl Carbonate on Lithium Metal by Pyrolysis-Gas Chromatography-Mass Spectroscopy,” J. Power Sources, 119–121, pp. 597–603.
Cross, J. T. D. , Hunter, R. , and Stimson, R. , 1976, “ The Thermal Decomposition of Simple Carbonate Esters,” Aust. J. Chem., 29(7), pp. 1477–1481. [CrossRef]
Notario, R. , Quijano, J. , Sanchez, C. , and Velez, E. , 2005, “ Theoretical Study of the Mechanism of Thermal Decomposition of Carbonate Esters in the Gas Phase,” J. Phys. Org. Chem., 18(2), pp. 134–141. [CrossRef]
Gordon, A. S. , and Norris, W. P. , 1965, “ A Study of the Pyrolysis of Methyl Ethyl and Diethyl Carbonates in the Gas Phase,” J. Phys. Chem., 69(9), pp. 3013–3017. [CrossRef]
Ritchie, P. D. , 1935, “ Studies in Pyrolysis—Part III: The Pyrolysis of Carbonic and Sulphurous Esters,” J. Chem. Soc., 400(Pt. 1), pp. 1054–1061. [CrossRef]
Herzler, J. , Manion, J. A. , and Tsang, W. , 1997, “ Single-Pulse Shock Tube Studies of the Decomposition of Ethoxy Compounds,” J. Phys. Chem. A., 101(30), pp. 5494–5499. [CrossRef]
Lienhard, J. H., IV , and Lienhard, J. H., V , 2003, A Heat Transfer Textbook, 3rd ed., Phlogiston, Cambridge, MA, pp. 429–431, 468, 483–486.
Special Metals, 2008, “ Inconel Alloy 600,” Special Metals Corp., Huntington, WV, accessed Dec. 7, 2017, http://www.specialmetals.com/assets/smc/documents/alloys/inconel/inconel-alloy-600.pdf
Bradfield, W. S. , 1966, “ Liquid-Solid Contact in Stable Film Boiling,” Ind. Eng. Chem. Fundam., 5(2), pp. 200–204. [CrossRef]
Dhuga, D. S. , and Winterton, R. H. S. , 1986, “ Measurement of Liquid-Solid Contact in Boiling,” J. Phys. E: Sci. Instrum., 19(1), pp. 69–75. [CrossRef]
Kikuchi, Y. , Ebisus, T. , and Michiyoshi, I. , 1992, “ Measurement of Liquid-Solid Contact in Film Boiling,” Int. J. Heat Mass Transfer, 35(6), pp. 1589–1594. [CrossRef]
Chang, K. H. , and Witte, L. C. , 1990, “ Liquid-Solid Contact During Flow Film Boiling of Subcooled Freon-11,” ASME J. Heat Transfer, 112(2), pp. 465–471. [CrossRef]
Avedisian, C. T. , 1985, “ The Homogeneous Nucleation Limits of Liquids,” J. Phys. Chem. Ref. Data, 14(3), pp. 695–720. [CrossRef]
Park, J. , Zhu, R. S. , and Lin, M. C. , 2002, “ Thermal Decomposition of Ethanol—I: Ab Initio Molecular Orbital/Rice–Ramsperger–Kassel–Marcus Prediction of Rate Constant and Product Branching Ratios,” J. Chem. Phys., 117(7), pp. 3224–3231. [CrossRef]
Amran, T. , Abdullay, T. , and Croiset, E. , 2014, “ Evaluation of an Inconel-625 Reactor and its Wall Effects on Ethanol Reforming in Supercritical Water,” Ind. Eng. Chem. Res., 53(6), pp. 2121–2129.
Bromley, L. A. , 1950, “ Heat Transfer in Stable Film Boiling,” Chem. Eng. Prog., 46(5), pp. 221–227.
Urban, B. J. , Avedisian, C. T. , and Tsang, W. , 2006, “ The Film Boiling Reactor: A New Environment for Chemical Processing,” AIChE J., 52(7), pp. 2582–2595. [CrossRef]
Benson, S. W. , 1960, The Foundation of Chemical Kinetics, McGraw-Hill, New York, Chap. 11.


Grahic Jump Location
Fig. 2

Schematic of the apparatus

Grahic Jump Location
Fig. 1

Schematic of film boiling on a horizontal tube of outside diameter Do. The gas flow in the vapor film (the “reactor”) is driven by buoyancy and the gases decompose during their transport. Departing bubbles contain decomposition products along with unreacted DEC. This schematic view corresponds to section a–a of the inset photograph in Fig. 4.

Grahic Jump Location
Fig. 3

Calibration of Inconel 600 electrical resistivity with temperature. Data are from Ref. [35] up to 1200 K. Curve-fit is linear, ρ(μΩ − m) = 0.99027 + 1.4266 × 10−4T (K). Dotted line is extrapolation of linear fit above 1200 K.

Grahic Jump Location
Fig. 4

Variation of heat flux with average tube temperature for DEC. Symbols in the film boiling regime come from a quadratic fit to the heat flux data while the bars indicate standard deviations of the fluxes around the data. The upper temperature is determined by the thermal integrity of the tube material and the lower temperature (as measured in the experiments) corresponds to the onset of destabilization of the film initiated by liquid/solid contacts. The inset is a photograph showing the film boiling configuration at a tube temperature of 868 K. A schematic of section a–a is shown in Fig. 1.

Grahic Jump Location
Fig. 6

Volumetric fluxes of noncondensable products in exhaust gas. CO2 and C2H4 are products of DEC decomposition (Eq. (1)). The other species are speculated to form from EtOH decomposition due to radical reactions.

Grahic Jump Location
Fig. 5

Variation of total volumetric flux of exhaust gases with temperature. Reaction rate is low below about 700 K, which also coincides with destabilization of the vapor film.

Grahic Jump Location
Fig. 7

Variation of [C2H4]/[CO2] (data from Fig. 7) with tube temperature (K)

Grahic Jump Location
Fig. 8

(a) EDX analysis of a carbon flake with insert SEM image and (b) EDX analysis of a bare tube with SEM image shown in inset

Grahic Jump Location
Fig. 9

Schematic of temperature variation across δ. Tt is a threshold temperature defined by ε (Eq. (A2)) and δt is the corresponding reaction boundary layer that supplies product gases from decomposition. The product species are formed mainly over y < δt/δ at an average temperature within this layer while the remaining supply of product gases comes from δt/δ < y < 1.

Grahic Jump Location
Fig. 10

(a) Variation of ε across the vapor film for Eq. (1) corresponding to the indicated Tw and (b) variation of ΔT = Tw − Tmr with ε. Inset expands the scale around ε = 1.

Grahic Jump Location
Fig. 11

Schematic of vapor film showing the coordinates for scale analysis to determine the buoyant gas velocity (VB), residence time (tr), and vapor film thickness (δ). δ is shown as nearly constant though in reality it varies with θ.




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