skip to main content

Attention:

The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Thursday, October 10 until 2:00 AM ET on Friday, October 11 due to maintenance. We apologize for the inconvenience.


Title: Chemical Looping of Manganese to Synthesize Ammonia at Atmospheric Pressure: Sodium as Promoter
Abstract

Affordable synthetic ammonia (NH3) enables the production of nearly half of the food we eat and is emerging as a renewable energy carrier. Sodium‐promoted chemical looping NH3synthesis at atmospheric pressure using manganese (Mn) is here demonstrated. The looping process may be advantageous when inexpensive renewable hydrogen from electrolysis is available. Avoiding the high pressure of the Haber‐Bosch process by chemical looping using earth‐abundant materials may reduce capital cost, facilitate intermittent operation, and allow operation in geographic areas where infrastructure is less sophisticated. At this early stage, the data suggest that 0.28 m3of a 50 % porosity solid Mn bed may suffice to produce 100 kg NH3per day by chemical looping, with abundant opportunities for improvement.

 
more » « less
Award ID(s):
1856084
NSF-PAR ID:
10255134
Author(s) / Creator(s):
 ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Chemical Engineering & Technology
Volume:
43
Issue:
10
ISSN:
0930-7516
Page Range / eLocation ID:
p. 2126-2133
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The purpose of this work is to quantitatively compare the energy cost of design alternatives for a process to produce ammonia (NH 3 ) from air, water, and renewable electricity. It is assumed that a Haber–Bosch (H–B) synthesis loop is available to produce 1000 metric tons (tonnes) of renewable NH 3 per day. The overall energy costs per tonne of NH 3 will then be estimated at U.S.$195, 197, 158, and 179 per tonne of NH 3 when H 2 is supplied by (i) natural gas reforming (reference), (ii) liquid phase electrolysis, (iii) solid oxide electrolysis (SOE) of water only, and (iv) simultaneous SOE of water and air. A renewable electricity price of U.S.$0.02 per kWh electric , and U.S.$6 per 10 6 BTU for natural gas is assumed. SOE provides some energy cost advantage but incurs the inherent risk of an emerging process. The last consideration is replacement of the H–B loop with atmospheric pressure chemical looping for ammonia synthesis (CLAS) combined with SOE for water electrolysis, and separately oxygen removal from air to provide N 2 , with energy costs of U.S.$153 per tonne of NH 3 . Overall, the most significant findings are (i) the energy costs are not substantially different for the alternatives investigated here and (ii) the direct SOE of a mixture of steam and air, followed by a H.–B. synthesis loop, or SOE to provide H 2 and N 2 separately, followed by CLAS may be attractive for small scale production, modular systems, remote locations, or stranded electricity resources with the primary motivation being process simplification rather than significantly lower energy cost. 
    more » « less
  2. Abstract

    NH3has long been predicted to be an important component of outer solar system bodies, yet detection of this compound suggests a low abundance or absence on many objects where it would be expected. Here, we demonstrate that a thermally driven oxidation reaction between ammonia (NH3) and ozone (O3) in a H2O + NH3+ O3mixture may contribute to the low abundance of NH3on some of these objects, as this reaction efficiently occurs at temperatures as low as 70 K. We determined the overall activation energy for this reaction to be 17 ± 2 kJ mol−1, which is consistent with other chemical systems that react at cryogenic temperatures. The loss of these two compounds coincides with the formation ofNH4+andNO3at low temperatures, both of which are observable with infrared spectroscopy. Warming our H2O + NH3+ O3mixtures through sublimation, we find a number of higher-temperature phases, such as ammonia hemihydrate, nitric acid, and ammonium nitrate (NH4NO3). The most stable of these is NH4NO3, which remains on the substrate until temperatures near 270 K. The salt product within this sample contains near-infrared spectral features between 2.0 and 2.22μm, which is a spectral region of interest for several outer solar system objects, including the Uranian satellites Miranda, Ariel and Umbriel, and Pluto's satellite Charon.

     
    more » « less
  3. Abstract

    Chemical looping combustion is a clean combustion technology for fossil or renewable fuels. We have previously shown that the process can also be used to enable CO2activation through reduction to CO with Fe oxygen carriers in so‐called “chemical looping dry reforming” (CLDR). Although Fe shows good reactivity with CO2, its reactivity with methane as a fuel is low. In contrast, Ni is highly reactive for methane conversion but cannot be oxidized with CO2. Here, we demonstrate that Fe–Ni alloys combine the reactivities of each metal synergistically. By combining materials synthesis and characterization with reactive evaluation in multicycle CLDR operation, we demonstrate that relatively low amounts of Ni suffice to activate the carrier for methane conversion and that the presence of Fe enables the reoxidation of Ni with CO2. Moreover, the weak oxidant CO2allows the controlled oxidation of the Fe–Ni alloy, which enables CH4upgrading through syngas (CO+H2) production.

     
    more » « less
  4. Abstract

    We present spatially resolved (0.″1–1.″0) radio maps of Neptune taken from the Very Large Array and Atacama Large Millimeter/submillimeter Array between 2015 and 2017. Combined, these observations probe from just below the main methane cloud deck at ∼1 bar down to the NH4SH cloud at ∼50 bar. Prominent latitudinal variations in the brightness temperature are seen across the disk. Depending on wavelength, the south polar region is 5–40 K brighter than the mid-latitudes and northern equatorial region. We use radiative transfer modeling coupled to Markov Chain Monte Carlo methods to retrieve H2S, NH3, and CH4abundance profiles across the disk, though only strong constraints can be made for H2S. Below all cloud formation, the data are well fit by53.813.4+18.9×and3.93.1+2.1×protosolar enrichment in the H2S and NH3abundances, respectively, assuming a dry adiabat. Models in which the radio-cold mid-latitudes and northern equatorial region are supersaturated in H2S are statistically favored over models following strict thermochemical equilibrium. H2S is more abundant at the equatorial region than at the poles, indicative of strong, persistent global circulation. Our results imply that Neptune's sulfur-to-nitrogen ratio exceeds unity, as H2S is more abundant than NH3in every retrieval. The absence of NH3above 50 bar can be explained either by partial dissolution of NH3in an ionic ocean at GPa pressures or by a planet formation scenario in which hydrated clathrates preferentially delivered sulfur rather than nitrogen onto planetesimals, or a combination of these hypotheses.

     
    more » « less
  5. Abstract

    The chemical stabilities of hybrid perovskite materials demand further improvement toward long‐term and large‐scale photovoltaic applications. Herein, the enhanced chemical stability of CH3NH3PbI3is reported by doping the divalent anion Se2−in the form of PbSe in precursor solutions to enhance the hydrogen‐bonding‐like interactions between the organic cations and the inorganic framework. As a result, in 100% humidity at 40 °C, the 10% w/w PbSe‐doped CH3NH3PbI3films exhibited >140‐fold stability improvement over pristine CH3NH3PbI3films. As the PbSe‐doped CH3NH3PbI3films maintained the perovskite structure, a top efficiency of 10.4% with 70% retention after 700 h aging in ambient air is achieved with an unencapsulated 10% w/w PbSe:MAPbI3‐based cell. As a bonus, the incorporated Se2−also effectively suppresses iodine diffusion, leading to enhanced chemical stability of the silver electrodes.

     
    more » « less