skip to main content

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 11:00 PM ET on Friday, December 13 until 2:00 AM ET on Saturday, December 14 due to maintenance. We apologize for the inconvenience.


Title: Superlocal chemical reaction equilibrium in low temperature plasma
Abstract

Low temperature plasmas (LTP) are a unique class of open‐driven systems in which chemical reactions are unpredictable using established concepts. The terminal state of chemical reactions in LTP, termed thesuperlocalequilibrium state, is hypothesized to be defined by a proposed set of state variables. Using a LTP reactor wherein the state variables have been measured, it is shown that CO2spontaneously splits and the effluent speciation is independent of the influent speciation if the state variables are held constant and the residence time is long. CO2conversion at long residence times, which is expected to be nominally zero from equilibrium thermodynamics, can be as high as 70% in the LTP. The employed low pressure plasma reactor (P= 10 mbar) had a similar volume, productivity, and energy efficiency compared to an atmospheric pressure dielectric barrier discharge reactor, thanks to reaction rates that were three orders of magnitude faster.

 
more » « less
Award ID(s):
1847469 1702334
PAR ID:
10457005
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
AIChE Journal
Volume:
66
Issue:
6
ISSN:
0001-1541
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Process intensification options are explored for near‐carbon‐neutral, natural‐gas‐fueled combined cycle (CC) power plants, wherein the conventional combustor is replaced by a series of chemical‐looping combustion (CLC) reactors. Dynamic modeling and optimization are deployed to design CLC‐CC power plants with optimal configuration and performance. The overall plant efficiency is improved by optimizing the CLC reactor design and operation, and modifying the CC plant configuration and design. The optimal CLC‐CC power plant has a time‐averaged efficiency of 52.52% and CO2capture efficiency of 96%. The main factor that limits CLC‐CC power plant efficiency is the reactor temperature, which is constrained by the oxygen carrier material. CLC exhaust gas temperature during heat removal and gas compressor to gas turbine pressure ratio are the most important operating variables and if properly tuned, CLC‐CC power plants can reach high thermodynamic efficiencies. © 2018 American Institute of Chemical EngineersAIChE J, 65: e16516 2019

     
    more » « less
  2. Abstract

    A comprehensive computational fluid dynamic (CFD) model of CEES‐developed polyethylenimine impregnated protonated titanate nanotubes (PEI‐PTNTs) was developed using the Multiphase Flow with Interphase eXchanges (MFiX) package to evaluate the performance of the PEI‐PTNTs in a 1‐MW pilot‐scale carbon capture reactor developed by the National Energy Technology Laboratory (NETL). In this CFD model, the momentum, continuity, and energy transport equations were integrated with the first‐order chemistry model for chemical kinetics of heterogeneous reactions to predict the adsorption of CO2onto amine‐based sorbent particles and the reactor temperature. Based on the amount of the CO2adsorption obtained in the small‐scale experiment, the coefficients for the chemical reaction equations of PEI‐PTNTs are adjusted. The adjusted PEI‐PTNTs model is applied to the simplified numerical model of 1‐MW pilot‐scale carbon capture system, which is calibrated through the comparison between our simulation results and the results provided by NETL. This calibrated CFD model is used for selecting the optimized flow rate of the gas phase. Our study shows that the optimized gas flow rate to absorb 100% CO2without loss is 1.5 kg/s, but if higher absorption rate is preferable despite some loss of CO2absorption in the reactor, a higher flow rate than 1.5 kg/s can be selected.

     
    more » « less
  3. Nanoparticle surface structure and geometry generally dictate where chemical transformations occur, with higher chemical activity at sites with lower activation energies. Here, we show how optical excitation of plasmons enables spatially modified phase transformations, activating otherwise energetically unfavorable sites. We have designed a crossed-bar Au-PdHxantenna-reactor system that localizes electromagnetic enhancement away from the innately reactive PdHxnanorod tips. Using optically coupled in situ environmental transmission electron microscopy, we track the dehydrogenation of individual antenna-reactor pairs with varying optical illumination intensity, wavelength, and hydrogen pressure. Our in situ experiments show that plasmons enable new catalytic sites, including dehydrogenation at the nanorod faces. Molecular dynamics simulations confirm that these new nucleation sites are energetically unfavorable in equilibrium and only accessible through tailored plasmonic excitation.

     
    more » « less
  4. Abstract

    Chemical‐looping combustion (CLC) is a promising and efficient method for power generation with in situ CO2capture. In this work, we focus on high‐pressure fixed‐bed CLC reactors integrated with combined cycle (CC) power plants. Specifically, the dynamic nature of fixed‐bed chemical‐looping reactors and the many kinetically controlled reactions necessitate the use of dynamic modeling to evaluate power plant performance, efficiency, stability, and feasibility under transient operation. We present a dynamic model for an integrated CLC–CC power plant and transient analyses of the integrated plant performance. A network of dynamically operated fixed‐bed reactors fed with natural gas comprises the CLC plant component. A dynamic model is developed and tuned to match the performance of a commercial combined cycle power plant. The transient variations of the integrated plant in terms of power, temperature, and pressure profiles are presented. The simulation results show that despite the inherent batch‐type operation of the CLC reactor, the operation of the combined cycle is relatively unaffected, and there are small oscillations of approximately 2 % around the desired steady‐state conditions.

     
    more » « less
  5. Abstract

    The degassing of CO2and S from arc volcanoes is fundamentally important to global climate, eruption forecasting, ore deposits, and the cycling of volatiles through subduction zones. However, all existing thermodynamic/empirical models have difficulties reproducing CO2‐H2O‐S trends observed in melt inclusions and provide widely conflicting results regarding the relationships between pressure and CO2/SO2in the vapor. In this study, we develop an open‐source degassing model, Sulfur_X, to track the evolution of S, CO2, H2O, and redox states in melt and vapor in ascending mafic‐intermediate magma. Sulfur_X describes sulfur degassing by parameterizing experimentally derived sulfur partition coefficients for two equilibria: RxnI. FeS (m) + H2O (v H2S (v) + FeO (m), and RxnII. CaSO4(m)  SO2(v) + O2(v) + CaO (m), based on the sulfur speciation in the melt (m) and co‐existing vapor (v). Sulfur_X is also the first to track the evolution offO2and sulfur and iron redox states accurately in the system using electron balance and equilibrium calculations. Our results show that a typical H2O‐rich (4.5 wt.%) arc magma with high initial S6+/ΣS ratio (>0.5) will degas much more (∼2/3) of its initial sulfur at high pressures (>200 MPa) than H2O‐poor ocean island basalts with low initial S6+/ΣS ratio (<0.1), which will degas very little sulfur until shallow pressures (<50 MPa). The pressure‐S relationship in the melt predicted by Sulfur_X provides new insights into interpreting the CO2/STratio measured in high‐T volcanic gases in the run‐up to the eruption.

     
    more » « less