Tag Archives: Low-pressure Ammonia Synthesis

A Low Pressure Membrane Based Renewable Ammonia Synthesis

Posted on December 14, 2018 by | Leave a comment

Sarbjit Giddey, CSIRO, Australia

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

Ammonia is currently mostly produced by the highly energy and carbon-intensive Haber–Bosch process, which requires temperatures of 450–500 °C and pressures of up to 200 bar. The feedstock for this process is hydrogen from natural gas (NG), coal or oil, and nitrogen produced from air by cryogenic route or pressure swing adsorption (PSA). The share of NG, coal and fuel oil feedstock for the global production of ammonia is 72%, 22% and 4% respectively, contributing to approximately 420 million tons of CO2 emissions per annum, representing over 1% of global energy related emissions. The energy consumed for ammonia synthesis by Haber-Bosch process is in the 10 to 15 MWh/tonne range, depending on the type of fossil fuel feedstock used.

In an alternative route renewable hydrogen produced by an electrolyser can be fed to the Haber-Bosch reactor along with nitrogen for ammonia synthesis, and this route has been suggested to consume energy around 12 MWh/tonne of ammonia.

CSIRO has developed a metal membrane based ammonia synthesis process that uses hydrogen and nitrogen as feedstock. The materials and catalyst developed for the process allow the synthesis process at much lower pressures (~ 10 bar) at 450 °C. The synthesis rates achieved are two orders of magnitude higher than with any electrochemical route. The catalyst and the metal / catalyst interfacial structure have been specifically tailored for low pressure ammonia synthesis. The low pressure membrane reactor allows direct coupling to an electrolyser and air separation unit (ASU) operated by a renewable source, thus promising over 25% reduction in the energy input, substantial capital savings on reactors compared to conventional Haber-Bosch process, and allows distributed or centralised ammonia production. Continue reading →

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Advanced Catalysts Development for Small, Distributed, Clean Haber-Bosch Reactors

Posted on December 13, 2018 by | 1 comment

Adam Welch*, Jonathan Kintner, Joseph Beach, Starfire Energy, USA; Jason Ganley, Christopher Cadigan, Ryan O’Hayre, Colorado School of Mines, USA

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

The traditional Haber-Bosch (HB) synthesis of anhydrous ammonia will adapt to clean power by sourcing the hydrogen from renewable electrolysis. However, the very large scale of current HB plant designs are not well-matched to smaller and more distributed clean power resources. Plant/reactor designs need to be made at a smaller scale in order to best utilize clean hydrogen. Small, megawatt scale HB reactors have an additional advantage of being better able ramp up and down with variable renewable power. This talk will detail ARPA-e funded work into the design and optimization of these smaller, clean NH3 reactors, which utilize much higher and variable space velocities, lower pressures, and gas adsorption rather than condensation for NH3 extraction.

The different synthesis conditions at smaller scale also require a rethinking of the existing HB iron catalysts, which have been optimized for large, low space velocity reactors. New, advanced heterogeneous catalysts, capable of 5X faster nitrogen fixation, will be discussed. This talk will detail the development of the catalyst, including the ternary oxide support and metal nanoclusters, both of which play a key role in the catalyst performance. Many phases of the ternary system were synthesized, characterized for surface area and metal dispersion, and tested in a differential reactor to map catalytic performance to support composition and structure. Additionally, different active metals were attached to the best performing oxide support, to study the activity dependence on metal species.

Read the abstract at the AIChE website.

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RELATED NH3 FUEL CONFERENCE PAPERS

2018: Rapid Ramp NH3 Prototype Reactor Update
2017: Fast-Ramping Reactor for CO2-Free NH3 Synthesis

LINKS

Starfire Energy
Ammonia Synthesis for Fuel, Energy Storage, and Agriculture Applications, ARPA-E OPEN program, 2015
Learn more about the 2018 NH3 Fuel Conference

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Vanadium As a Potential Catalytic Membrane Reactor Material for NH3 Production

Posted on December 11, 2018 by | Leave a comment

Simona Liguori*, Jennifer Wilcox, Worcester Polytechnic Institute, USA

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

In solid or liquid states, ammonia salts and solutions are the active components of most synthetic fertilizers used in agriculture, which consume 83% of the world’s ammonia. Today, ammonia for fertilizers is industrially produced via the Haber-Bosch process at 400-500 °C and at pressures up to 30 MPa (300 bar). These harsh operating conditions are necessary due to the high affinity of dissociated nitrogen atoms towards the catalyst surface in addition to the high barrier associated with N2 dissociation. For these reasons, the need for advanced catalytic methods for the reduction of N2 to ammonia remains a requirement for sustainability in the food and energy cycle.

The aim of this work is to explore the potential of metallic membranes for N2 separation with the final intent to produce NH3. Based on a preliminary theoretical investigation using density functional theory, the Group V transition metals (e.g., vanadium (V), niobium (Nb) and tantalum (Ta)) show strong affinity toward N2. Continue reading →

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Ammonia Absorption and Desorption in Ammines

Posted on December 10, 2018 by | 1 comment

Collin Smith, Mahdi Malmali, Chen-Yu Liu, Alon McCormick, E L Cussler*, University of Minnesota, USA

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

While adsorption onto solids is a common separation process, absorption into solids is much less often used. The reason is that absorption is usually assumed ineffective because it includes very slow solute diffusion into the solid. An exception may be the separation of ammonia from nitrogen and hydrogen using ammines, especially at temperatures close to those used in ammonia synthesis. There, ammonia can be selectively absorbed by calcium chloride; nitrogen and hydrogen are not absorbed. The kinetics of ammonia release seem to be diffusion controlled. The kinetics of absorption are consistent with a first order reaction and diffusion in series, so the rate controlling step changes with the amount of absorption. The potential of this separation in the distributed production of ammonia is discussed both as a source of fertilizer and as a means of wind energy storage.

Read the abstract at the AIChE website.

DOWNLOAD

Download this presentation [PDF].

RELATED NH3 FUEL CONFERENCE PAPERS

2018: Design Optimization of an Ammonia-Based Distributed Sustainable Agricultural Energy System
2017: Design Optimization of a Distributed Ammonia Generation System
2017: Lower Pressure Ammonia Synthesis
2016: Small Scale Low-Pressure Ammonia Synthesis
2015: Potential Strategies for Distributed, Small-Scale Sustainable Ammonia Production [PDF]
2014: Life-cycle greenhouse gas and energy balance of community-scale wind powered ammonia production
2013: Ammonia Production Using Wind Energy
2012: Lessons Learned in Developing a Wind-to-Ammonia Pilot Plant [PDF]
2011: Production of Anhydrous Ammonia from Wind Energy — Anatomy of a Pilot Plant, The Sequel [PDF]
2010: Production of Anhydrous Ammonia from Wind Energy — Anatomy of a Pilot Plant [PDF]
2009: Ammonia from Wind, Progress Update [PDF]
2008: Ammonia from Wind, an Update [PDF]
2007: Ammonia from Wind, an Update [PDF]
2006: Wind to Ammonia [PDF]

LINKS

Department of Chemical Engineering and Materials Science, University of Minnesota
West Central Research & Outreach Center, University of Minnesota
Learn more about the 2018 NH3 Fuel Conference

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Functionalized Ordered Mesoporous Silica Composites As Potential Ammonia Storage Materials

Posted on December 9, 2018 by | Leave a comment

Zhu Ming*, Pan Xingxiang, Mei Hua, NJtech, Nanjing, China

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

Ammonia may provide an alternative energy supplier for its strong capability as hydrogen carrier. However, it is a problem that how to storage this kind of chemical at relatively high temperature, for example 300°C in fuel cell. In this work, a composite material based on metal halides and ordered mesoporous silica framework is developed and used to target ammonia at relatively high temperature. The silica framework is fabricated via evaporation induced self-assembly method and has tunable mesoporous structure with addition of hexadecyl trimethyl ammonium bromide (CTAB). Several metal salts at various concentrations are added to the mesoporous framework via wetness impregnation method. It is reported that ammonia storage capability is further enhanced by functionalization with relative metal sites. Along with capacity measurements, the incorporation of metal salts on mesoporous silica is studied using microscopy, X-ray diffraction and porosity characterization techniques. Results show that well-dispersed metal crystal trapped in submicron-sized porous structure can improve diffusion rate and increase pore accessibility while maintaining structural integrity at relatively high temperature. Capacity measurements show that functionalized metal/silica composite can work as potential materials for ammonia storage. It is also a thermal stable material for only 3% weight loss over 300°C. Continue reading →

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Design Optimization of an Ammonia-Based Distributed Sustainable Agricultural Energy System

Posted on December 8, 2018 by | 1 comment

Matthew J. Palys*, Anatoliy Kuznetsov, Joel Tallaksen, Michael Reese, Prodromos Daoutidis, University of Minnesota, USA

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

Small-scale, distributed production of ammonia better enables the use of renewable energy for its synthesis than the current paradigm of large-scale, centralized production. Pursuant to this idea, a small-scale Haber-Bosch process has been installed at the West Central Research and Outreach Center (WCROC) in Morris, MN [1] and there is ongoing work on an absorbent-enhanced process at the University of Minnesota [2], [3]. Using renewables to make ammonia would greatly improve the sustainability of fertilizer production, which currently accounts for 1% of total global energy consumption [4]. The promise of renewable-powered, distributed ammonia production for sustainability is in fact not limited to fertilizer, because ammonia also has potential as an energy-dense, carbon-neutral fuel. For example, using ammonia produced from renewable energy for nitrogen fertilizer, grain drying fuel and tractor fuel at the WCROC farm would reduce more than 90% of the fossil energy footprint associated with corn production [5].

In this light, we envision a distributed sustainable agricultural (farm) energy system (DSAE) fundamentally based on the idea of ammonia as not only a fertilizer, but also a fuel and a method of energy storage. Specifically, this system will use only renewable energy to produce ammonia for use as fertilizer and agricultural fuel (for cropping equipment and grain drying) at the scale of a single farm or an agricultural cooperative. It will also use renewables to meet local power and heat demands in a manner synergistic to distributed ammonia production; the difference in power and heat (hourly) and ammonia (monthly or biannually) demand time scales gives rise to opportunities for temporally flexible ammonia production and locally controllable power generation using ammonia. Heat integration will also be possible due to the exothermic nature of ammonia synthesis. Continue reading →

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Demonstration of CO2-Free Ammonia Synthesis Using Renewable Energy-Generated Hydrogen

Posted on December 8, 2018 by | 2 comments

Mototaka Kai*, Yasushi Fujimura, Takayoshi Fujimoto, JGC Corporation, Japan; Hideyuki Takagi, Yuichi Manaka, National Institute of Advanced Industrial Science and Technology (AIST), Japan; Tetsuya Nanba, Fukushima Renewable Energy Institute, AIST (FREA), Japan

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

In Japan, the government funding project SIP, Strategic Innovation Promotion Program, supports the research, development and demonstration of “Energy Carriers”. The concept of the “Energy Carriers” value chain is to produce hydrogen energy carriers overseas from fossil resources using CCS or renewable energy, and transport it to Japan for utilization as clean energy. The purpose of the program is to help realize a low-carbon society in Japan by using hydrogen. Among energy carriers, ammonia is the one of the most promising carriers, because of the ease of transportation as a liquid, higher hydrogen density, and proven technologies for commercial and industrial scale, not only for production, storage, and transportation, but also its utilization in chemical plants and DeNOx units for electric power plants.

Under the theme of “Development of ammonia synthesis from CO2-free hydrogen” of SIP ”Energy Carriers”, JGC is developing the advanced ammonia synthesis process using renewable energy, such as Photovoltaic and Wind Turbine Power Generation, to be able to produce “Green” ammonia, aiming to contribute to a low-carbon society. Also, utilizing the catalysts developed by the National Institute of Advanced Industrial Science and Technology (hereinafter “AIST”), National Institute of Technology Numazu College, and JGC C&C, AIST and JGC designed and constructed an ammonia synthesis demonstration plant in FREA, the Fukushima Renewable Energy Institute, AIST by the end of fiscal year 2017. From April 2018, the plant started operation to evaluate the performance of the developed catalysts and acquire the engineering data for scaling up in the future.

In this paper, we would like to explain the details of the ammonia synthesis demonstration plant in FREA, such as process flow, plant operation conditions, its capacity, and the status of plant operation. Continue reading →

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Rapid Ramp NH3 Prototype Reactor Update

Posted on December 8, 2018 by | Leave a comment

Joseph Beach*, Jonathan Kintner, Adam Welch, Starfire Energy, USA

15th Annual NH3 Fuel Conference, Pittsburgh, PA, October 31, 2018
NH3 Energy+ Topical Conference at the AIChE Annual Meeting

ABSTRACT

Starfire Energy has built and operated a low pressure, fast-ramping prototype reactor using its Rapid Ramp NH3 process. It has synthesized, captured, and liquefied NH3 with all system pressures staying below 12.5 bar. The prototype reactor’s performance will be discussed. Continue reading →

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Nitride-Based Step Catalysis for Ammonia Synthesis at Atmospheric Pressure

Posted on October 1, 2017 by | 1 comment

Peter Pfromm, Michael Heidlage*, Bin Liu, Nannan Shan, Viktor Chikan, Hongfu Luo, Nate Flesher
Kansas State University, United States

NH3 Fuel Conference, Minneapolis, November 2, 2017
AIChE Annual Meeting, Topical Conference: NH3 Energy+

ABSTRACT

Formation of metal nitrides to activate dinitrogen is one avenue to ammonia and other nitrogen compounds. Attractive aspects are operation at atmospheric pressure and moderate temperatures, formation of stable chemical intermediates rather than reliance on somewhat sensitive heterogeneous catalysis, and inexpensive materials. If a single metal is used, however, one encounters tradeoffs somewhat akin to the well-known tradeoffs for Haber-Bosch catalysts. Results will be presented for metal nitride-based ammonia synthesis, and new metal alloys that can address some of the tradeoffs between affinity for nitrogen, and formation of ammonia when hydrogen is added. Options using water instead of hydrogen will also be included. Continue reading →

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Influence of H2 / N2 Ratio on Dynamic Behavior of Ammonia Production on Ru Catalyst Under Low Pressure Condition

Posted on October 1, 2017 by | Leave a comment

Hideyuki Matsumoto*, Javaid Rahat, Tetsuya Nanba
National Institute of Advanced Industrial Science and Technology (AIST), Japan

NH3 Fuel Conference, Minneapolis, November 2, 2017
AIChE Annual Meeting, Topical Conference: NH3 Energy+

ABSTRACT

Recently deployment of renewable energy such as sunlight and wind power or deployment of process technologies for carbon dioxide capture and storage (CCS) is indispensable to reduce the CO2-emission. However, there are some issues to be solved in order to accelerate the mass deployment of renewable energy. Since amount of renewable energy quite changes unstably with time, which depends on weather and place, development of process systems technology is an issue for stable and effective utilization of electric power that is generated by fluctuating renewable energy.

Those in national institute of National Institute of Advanced Industrial Science and Technology (AIST) agree that process technologies on energy conversion of renewable electricity into hydrogen energy carrier are very useful to deploy long-term storage and long-distance transport of much more renewable inside and outside Japan. Ammonia is a potential hydrogen carrier that contains 17.6 wt% of hydrogen. Moreover, as an energy carrier, ammonia is thought to be a clean fuel as only water and nitrogen are produced on direct combustion. Continue reading →

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