Source: PROTON ENERGY SYSTEMS, INC. submitted to NRP
HIGH EFFICIENCY LOW COST ELECTROCHEMICAL AMMONIA PRODUCTION
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
Reporting Frequency
Annual
Accession No.
1006869
Grant No.
2015-33610-23793
Cumulative Award Amt.
$500,000.00
Proposal No.
2015-03281
Multistate No.
(N/A)
Project Start Date
Sep 1, 2015
Project End Date
Aug 31, 2017
Grant Year
2015
Program Code
[8.4]- Air, Water and Soils
Recipient Organization
PROTON ENERGY SYSTEMS, INC.
10 TECHNOLOGY DR
WALLINGFORD,CT 064921955
Performing Department
(N/A)
Non Technical Summary
The Haber-Bosch process, one of the most impactful developments in human history, has provided enough fertilizer to the world that it is estimated nearly half of the nitrogen found in our bodies originated in a Haber-Bosch chemical plant. However, this technological marvel comes at a price. On U.S. farms, 29% of energy consumed (directly and indirectly) is in the form of fertilizers, and these same fertilizers are the second largest contributor to green house gas emissions. This is because the Haber-Bosch process must operate at high pressures and high temperatures to convert highly inert nitrogen gas to fertilizer. In addition, to obtain hydrogen for the reaction, fossil fuel reforming is used, resulting in a high carbon foot print. The extreme conditions and pre- and post-processing steps combined with the low equilibrium conversion makes these facilities highly capital intensive, inefficient and polluting. More sustainable and economical ammonia production methods will be required to support growing world demand for fertilizer.One alternative approach is to use electricity to drive the ammonia production reaction, decreasing the need for high pressure and heat thereby decreasing the energy demand and making the process more efficient. This electrochemically driven process is compatible with the use of renewable electricity, eliminating CO2 emissions from the production step. A natural synergy exists in using wind power for fertilizer production. In the Plains and Upper Midwest, excess wind production capacity, transmission limitations, and high regional demand for N-fertilizers combine to create excellent economic drivers for this technology. In addition, because electrolysis technology is highly scalable, further reduction of emissions will be realized through the reduced need for ammonia transport. Products could be envisioned that support a range of small to mid-sized farms, or could be designed on a larger scale to distribute ammonia locally for multiple farms.Our team proposes development of an efficient solid state electrochemical process utilizing anion exchange membrane (AEM) technology, which can be optimized for use with distributed renewable energy sources. This AEM-based technology is ideal for ammonia synthesis because the membranes are not expected to readily react with ammonia, enable low-cost materials of construction, and they allow the utilization of a wider array of low-cost catalysts. Results from our Phase I work showed that our AEM-based electrochemical technology is uniquely capable of low temperature and low pressure ammonia generation at an efficiency which will match the energy requirements of the Haber-Bosch process. The team has extensive competencies in cell design, tailoring of membrane and catalyst properties, and balance of plant design and integration, providing a strong foundation for the proposed work.
Animal Health Component
17%
Research Effort Categories
Basic
17%
Applied
17%
Developmental
66%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
1330199200050%
1330199202050%
Goals / Objectives
The major goal will be to design and construct a breadboard system capable of operating at a relavent performance level for small-scale applications. To achieve this goal, and answer the above questions, specific objectives for the Phase 2 approach include:1) Plan and execute modifications to existing Proton hardware for ammonia production.2) Develop a nanostructured catalyst that has increased stability and efficiency over Phase 1 formulations.3) Develop a membrane system that maximizes membrane lifetime and conductivity while minimizing ammonia crossover and is fully integrated with the catalyst in the electrode.4) Evaluate performance of down-selected membrane and catalyst materials in breadboard device capable of 10 mA/cm2 and 10% efficiency.5) Compare performance and cost metrics to competing technologies.
Project Methods
1) Plan and execute modifications to existing Proton hardware for ammonia production.The Phase 1 test program was conducted using lab-scale 25 cm2 cell hardware. In Phase 2, Proton will transition to commercial-level cell hardware (28-86 cm2). This configuration leverages existing endplates, MEA tooling, and other equipment in order to focus research funding on demonstration experiments and materials development.Proton will leverage the Phase 1 proof-of-concept system for the scale-up effort, reducing the overall cost burden. It is expected that major modifications will include safety sensors and circuits for unattended operation and greater control over important system parameters including temperature and pressure. This effort will rely heavily on Proton's past experience in translating its expertise to workable prototypes for multiple types of electrochemical devices. While the main hazard in this case will be ammonia exposure, the experience gained from the successful safety review held in Phase 1 will be flexed in the scale up design for Phase 2.2) Develop a nanostructured catalyst that has increased stability and efficiency over Phase 1 formulations.Nanoparticle catalysts will be synthesized in collaboration with Lauren Greenlee who has substantial experience with the characterization of these materials. Dr. Greenlee also developed a modified electrochemical setup during Phase 1 of this project to capture ammonia produced, and many pH experiments were performed to establish the relationship between pH and ammonia measurement and identify the best assay. These developments in experimental procedure will be continued in Phase 2 of the project.3) Develop a membrane system that maximizes membrane lifetime and conductivity while minimizing ammonia crossover and is fully integrated with the catalyst in the electrode.AEM membrane selection will be tailored to optimize conductivity, durability and crossover in the ammonia system. Dr. Herring leads a Multidisciplinary University Research Initiative (MURI) sponsored by the Army Research Office to optimize the properties of these polymers and has already developed many simple hydrocarbon materials based on co-polymers an isoprene or ethylene with benzyltrimethyl ammonium cations. For this project we will start with materials for which a solubilized form is available, that can easily be modified and that have already been shown to have high ionic conductivity, suitable mechanical properties, and stability.The Herring group will expose the AEMs to ammonia/hydroxide to determine their stability in the system, as an accelerated aging test. IEC and conductivity will be determined before and after testing. The team will also demonstrate that a solubilized version of the membrane can be applied to the base AEM and that the layer does not delaminate under the conditions of the test. Adhesion quality will be observed and documented before and after testing.4) Evaluate performance of down-selected membrane and catalyst materials in breadboard device capable of 10 mA/cm2 and 10% efficiency.A general approach for the scaled-up demonstration will be to establish operability with baseline catalyst and membrane materials before implementing down-selected materials from Andrew Herring and Lauren Greenlee. Tests exploring operational parameters such as residence time, recirculation, cell configuration, temperature and pressure will be added to the test matrix in Phase 2.5) Compare performance and cost metrics to competing technologies.Results from down-selected performance tests will be used to estimate cost and compared to literature and the current industry standard. The final products include cost and performance estimates of down-selected materials (e.g. estimated kWh/ton NH3 produced, or projected production rates) compared to current technology and baseline.

Progress 09/01/15 to 08/31/17

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?This project involved collaboration with Colorado School of Mines and University of Arkansas. The primary graduate student from UArk visited Proton and had the opportunity to give a talk as well as to tour the facility and see the breadth of applied research from early lab experiments to commercial product. She also interacted closely with Proton engineers to understand impact of cell design and operational conditions on the chemistry she was working on. How have the results been disseminated to communities of interest?Multiple presentations have been given by the involved institutions over the course of the project, primarily to the NH3 Fuel Association. This year the conference was held in conjunction with the National AIChE meeting in Minneapolis, which provided significantly more exposure. An Interface article was also written for the Electrochemical Society as an overview of ammonia production and the approach taken in this project. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Successful low temperature electrochemical ammonia generation required significant materials understanding, and development of a commercial device will rely on additional refinement in operating conditions, cell design, and extension of the materials knowledge developed in this program. Anion exchange membranes are still relatively immature in general, and properties had to be optimized for mechanical strength under hydrated conditions. At the same time, it was discovered in this program that polymers containing nitrogen in the backbones could contribute to ammonia signals due to degradation of the membrane. Through significant work in polymer development, stable configurations were obtained. In parallel, different approaches in catalyst design were explored to suppress hydrogen evolution while enhancing nitrogen absorption and splitting of the N-N triple bond. A combination of composition, chemical structure (alloy vs. core-shell), and electrode structure (engineered porosity and particle size) resulted in improvements in Faradaic efficiency, with very promising short term efficiency meeting the project goals. Higher pressure operation also enhanced the ammonia reaction. Overall learnings from this program included the importance of test conditions and controls for electrochemical ammonia generation at low temperature. Ammonia contamination can be present from many sources, including absorption on catalyst and porous surfaces, degradation of membrane, and residuals from previous tests. Robust testing protocols have been developed which should enhance the whole field, and a test system with pressurized testing capability has been developed which will provide higher ammonia generation rates. Tracking production with direct measurement of the outlet gases would also provide real time evaluation of the ammonia production rate. The advancements in catalyst and membrane functionality also set strategic pathways for additional improvements in ammonia output and efficiency. As the cell performance is improved, design for water management will also need to be optimized for stable performance.

Publications

  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: "Design of Iron-Nickel Nanocatalysts for Low-Temperature Electrochemical Ammonia Generation" Lauren Greenlee*, Shelby Foster, Prashant Acharya, David Suttmiller, Charles Loney, Julie Renner, Wayne Gellett, Katherine Ayers NH3 Fuel Conference at 2017 Fall AIChE meeting
  • Type: Conference Papers and Presentations Status: Other Year Published: 2017 Citation: "Exploring Peptide-Bound Catalysts for Electrochemical Ammonia Generation" Charles Loney, Ashley Graybill, Cheyan Xu, Julie Renner*, Prashant Acharya, David Suttmiller, Lauren Greenlee, Luke Wiles, Katherine Ayers, Wayne Gellett NH3 Fuel Conference at 2017 Fall AIChE meeting