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2000 Progress Report: Multiphase Reactive Equilibria In CO2-Based Systems
EPA Grant Number: R826734Title: Multiphase Reactive Equilibria In CO2-Based Systems
Investigators: Brennecke, Joan F. , Stadtherr, Mark A.
Institution: University of Notre Dame
EPA Project Officer: Karn, Barbara
Project Period: October 1, 1998 through September 30, 2001
Project Period Covered by this Report: October 1, 1999 through September 30, 2000
Project Amount: $295,000
RFA: Technology for a Sustainable Environment (1998)
Research Category: Pollution Prevention/Sustainable Development
Description:
Objective:The objective of this work is to develop experimental, modeling, and computational methodologies that will facilitate the design and evaluation of equilibrium limited chemical reaction processes using supercritical carbon dioxide as an environmentally benign replacement solvent. Supercritical carbon dioxide, which is non-toxic, non-flammable, readily available and inexpensive, has been shown to be a viable reaction medium for a wide variety of reactions. However, the phase behavior, which determines the conditions needed to ensure single phase operation, is frequently the limiting factor. For equilibrium limited reactions it is a combination of phase and reaction equilibrium limitations that will determine operating pressures and temperatures and, thus the viability of CO2 as a replacement solvent. Reliable measurement, modeling and computation of high pressure multiphase reaction equilibrium is needed for the design and evaluation of these systems. Progress Summary:
Our most important accomplish on this project in the last year has been the study of the effect of CO2 pressure on the esterification of acetic acid with ethanol. We show that the application of just 58.6 bar pressure at 333 K shifts the equilibrium conversion from 63 percent in neat solution to 72 percent in CO2. Thus, we demonstrate that CO2 is an excellent substitute solvent to replace VOC solvents, and that it can be used to alter (improve) the extent of reaction of equilibrium-limited reactions. In addition, we have made significant progress in the development of a completely reliable computation method to model the high pressure phase behavior of equilibrium-limited reactions. It allows us to reliably calculate complex phase and reaction equilibria of high pressure CO2-based systems using equation of state models. Finally, we have used some funds from this grant to explore an exciting new potential application of supercritical CO2; the extraction of solutes from ionic liquids. Ionic liquids are organic salts with negligible vapor pressure that are being explored as non-volatile replacements for organic solvents. Thus, the use of CO2 to remove products from ionic liquids represents the combination of two different environmentally benign solvent technologies. This newly-developed project has already resulted in several important publications, as listed below. Future Activities:
The primary goal of the final year of this grant is to complete the development of the completely reliable computational method for the calculation of combined phase and reaction equilibria at high pressure. The secondary goal is to conduct an in-depth analysis of data collected by Dr. Tapan Das, a post-doctoral research associate who conducted experiments at DuPont during the first year of this grant.
Journal Articles on this Report: 8 Displayed | Download in RIS Format
| Other project views: | All 13 publications | 9 publications in selected types | All 8 journal articles |
| Type | Citation | ||
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Blanchard LA, Brennecke JF. Esterification of acetic acid with ethanol in carbon dioxide. Green Chemistry 2001;3(1):17-19. |
R826734 (2000) |
not available |
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Blanchard LA, Gu ZY, Brennecke JF. High-pressure phase behavior of ionic liquid/CO2 systems. Journal of Physical Chemistry B 2001;105(12):2437-2444 |
R826734 (2000) |
not available |
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Blanchard LA, Brennecke JF. Recovery of organic products from ionic liquids using supercritical carbon dioxide. Industrial Engineering and Chemical Research 2001;40(1):287-292. |
R826734 (2000) |
not available |
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Gau CY, Stadtherr MA. Reliable nonlinear parameter estimation using interval analysis: error-in-variable approach. Computers & Chemical Engineering 2000;24(2-7):631-637 |
R826734 (2000) |
not available |
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Maier RW, Brennecke JF, Stadtherr MA. Reliable computation of reactive azeotropes. Computers and Chemical Engineering 2000;24:1851-1858. |
R826734 (2000) |
not available |
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Scurto AM, Lubbers CM, Xu G, Brennecke JF. Experimental measurement and modeling of the vapor-liquid equilibrium of carbon dioxide + chloroform. Fluid Phase Equilibria 2001, Volume: 190, Number: 1-2 (NOV 1), Page: 135-147. |
R826734 (2000) |
not available |
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Stradi BA, Brennecke JF, Kohn JP, Stadtherr MA. Reliable computation of mixture critical points. American Institute of Chemical Engineers Journal 2001;47:212-221. |
R826734 (2000) |
not available |
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Xu G, Scurto AM, Castier M, Brennecke JF, Stadtherr MA. Reliable computation of high-pressure solid-fluid equilibrium. Industrial & Engineering Chemistry Research 2000;39(6):1624-1636 |
R826734 (2000) |
not available |
pollution prevention, green chemistry, solvent substitution. , Industry Sectors, Sustainable Industry/Business, Scientific Discipline, RFA, Technology for Sustainable Environment, Sustainable Environment, Chemical Engineering, Manufacturing - NAIC 31-33, cleaner production/pollution prevention, Environmental Chemistry, Economics and Business, chemical reaction systems, cleaner production, environmentally-friendly chemical synthesis, waste reduction, carbon dioxide reaction systems, green chemistry, alternative chemical synthesis, waste minimization, green process systems, environmentally benign solvents, source reduction, reaction solvent, modeling, chemical manufacturing, high pressure system, solvent substitute, multiphase reactive equilibria
Relevant Websites:
http://www.nd.edu/~jfb 
http://www.nd.edu/~markst
Progress and Final Reports:
Original Abstract