Progress 07/01/08 to 06/30/10

Outputs
OUTPUTS: Activities comprised 1) conducting laboratory-scale experiments to optimize an electrochemical process for production of ammonia using inputs of electricity, nitrogen, and synthesis gas (carbon monoxide and hydrogen) generated via gasification of biomass or reforming of landfill or anaerobic digester gas, 2) disseminating experimental results and their implications in regard to the economic viability of small-scale commercial production of ammonia and ammonia-based fertilizers via reports and presentations given to the North Dakota and Minnesota Corn Growers' Associations, and 3) preparing and filing a "continuation-in-part" (CIP) patent application entitled "Electrochemical Process for the Preparation of Nitrogen Fertilizers." Identifying information for the CIP application includes the following: Filing date: October 15, 2010; Serial Number 12/905, 6000. PARTICIPANTS: Dr. Junhua Jiang, Principal Investigator, with assistance from Dr. Alexey Ignatchenko, developed 1) an electrolytic method for extracting ammonia synthesis-quality high-purity hydrogen from a synthesis gas and 2) a high-activity ammonia synthesis catalyst, with input from collaborators North Dakota Corn Utilization Council and Minnesota Corn Research and Promotion Council. Ted Aulich, Project Manager, assisted in project technical activities and assumed responsibility for project reporting and administrative requirements. TARGET AUDIENCES: Upper Midwest regional farmers and agricultural and forest product processors, ethanol producers, electric and agricultural product cooperatives, regional and state economic development agencies, and all other agricultural-related audiences. PROJECT MODIFICATIONS: None.

Impacts
Outcomes include the development and demonstration of 1) an electrolytic method for extracting high-purity hydrogen from a synthesis gas and 2) a high-activity ammonia synthesis catalyst. The electrolytic hydrogen extraction technology enables one-step, low-cost generation of hydrogen at a purity level of at least 99.95%, which is sufficient to enable use of the hydrogen for ammonia synthesis and avoid catalyst poisoning. Because the extraction/purification occurs in one step, it offers the potential of reduced ammonia production capital and operating costs versus traditional hydrogen purification processes that include multiple carbon dioxide removal, carbon monoxide conversion to methane, and methane removal steps. Because of its high activity, the project-developed ammonia synthesis catalyst enables high single-pass ammonia generation at ambient pressure versus the high (1100 to 2500 pounds per square inch) pressures traditionally used for commercial ammonia production. Because it negates the need for high-cost compressors and high-pressure-compatible reactor vessels, valves, and piping, the catalyst offers the potential for significantly reduced ammonia production capital and operating costs.

Publications

• Jiang, J.; Aulich, T.; Collings, M.; Sohn, C. High-Pressure Electrochemical Hydrogen Purification Process Using a High-Temperature Polybenzimidazole (PBI) Membrane. ECS Transactions 2010, 28 (26), 91-100.

Progress 07/01/08 to 06/30/09

Outputs
OUTPUTS: National Alternative Fuels Laboratory (NAFL) activities during the reporting period include 1) conducting laboratory-scale experiments to optimize an electrochemical process for production of renewable ammonia using inputs of electricity (ideally generated from wind energy), nitrogen, and renewable synthesis gas (carbon monoxide and hydrogen generated via gasification of lignocellulosic biomass) and 2) conducting laboratory-scale experiments to optimize the second step of a two-step renewable isobutanol production process comprising conversion of renewable synthesis gas to a mixture of normal alcohols containing primarily methanol with lesser amounts of ethanol, propanol, and butanol, followed by conversion of the normal alcohol mixture to a mixture of primarily isobutanol with lesser amounts of branched pentanols and hexanols. The ammonia process optimization experiments were conducted using simulated synthesis gas mixtures, a project-designed and -fabricated electrochemical cell, and project-developed electrocatalysts and membrane electrode assemblies. The isobutanol process optimization experiments were conducted using normal C1 to C4 alcohol mixtures, a project-designed and -fabricated reactor system, and project-developed alcohol condensation catalysts. Information regarding a patent application filed during the project reporting period is as follows: Title: Electrochemical Process for the Preparation of Nitrogen Fertilizers Authors: Junhua Jiang, Edwin Olson, and Ted Aulich Filing date: 8/21/2008 Application No.: 12/206,621 PARTICIPANTS: Dr. Junhua Jiang, Principal Investigator, developed electrochemical methods for producing ammonia and other nitrogen-based fertilizers, with input from collaborators North Dakota Corn Utilization Council and Minnesota Corn Research and Promotion Council. Dr. Ramesh Sharma optimized thermocatalytic methods for converting mixed normal alcohols to isobutanol and other isoalcohols, in collaboration with Syntec Biofuel, Inc., of Vancouver, British Columbia, Canada. Ted Aulich, Project Manager, assisted in project technical activities and assumed responsibility for project reporting and administrative requirements. TARGET AUDIENCES: Upper Midwest regional farmers and agricultural and forest product processors, ethanol producers, electric and agricultural product cooperatives, regional and state economic development agencies, and all other agricultural-related audiences. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Ammonia process optimization activities resulted in development of a cathode catalyst with an activity of 60 millimoles of ammonia produced per hour per gram of catalyst. Based on a recently conducted literature search and conversations with commercial ammonia production catalyst producers, this activity level appears to be a new record in catalyst performance. After the catalyst underwent endurance testing for over 1 month, no reduction in catalyst activity was observed. Because it operates at significantly lower temperature and pressure than the traditional natural gas-based ammonia production process, the NAFL-developed electrochemical ammonia process offers the possibility of lower-cost, distributed-scale domestic ammonia production. In pursuing development of the process, NAFL is collaborating with the North Dakota Corn Utilization Council and the Minnesota Corn Research and Promotion Council. Renewable isobutanol process optimization activities resulted in development of a catalyst that enabled conversion of a methanol-rich normal alcohol mixture to a branched alcohol mixture comprising 65% isobutanol and lesser quantities of isopentanols, isohexanols, and isooctanols. According to Argonne National Laboratory, use of cellulosic ethanol to displace gasoline reduces greenhouse gases by 85%. By extension, the use of cellulosic isobutanol and higher isoalcohols to replace gasoline should reduce greenhouse gases by a similar amount. Because isobutanol and higher isoalcohols are relatively nonpolar, they offer the possibility of sufficient gasoline compatibility to enable their transport (as blends with gasoline) in pipelines, which would further reduce greenhouse gas emissions and significantly improve product distribution economics.

Publications

• No publications reported this period