This Small Business Innovation Research Phase II project will expand on the successful work from Phase I project on synthesis and characterization of metal oxide nanocomposite materials that can capture HBr and be regenerated to produce bromine. The capture and regeneration capabilities of these materials are integral to the economic viability of the GRT Gas-to-Fuels/Chemicals rocess and the GRT Propane-to-Propylene Process. In the GRT Processes, natural gas alkanes are (1) reacted with bromine to form reactive lkyl bromides that are (2) reacted over catalysts to produce alkanes, aromatic compounds and olefins. The metal oxide nanocomposite was ound very efficient at sequestering HBr produced in the process as a metal bromide. The use of metal oxides allows for a very inexpensive eparation of HBr from the hydrocarbon products. Subsequent oxidation of the metal bromide produces bromine. Thus the bromine needed in 1) is generated in situ as necessary and is fully contained within the process. During Phase I, we identified metal oxide nanocomposite materials with favorable capacity and capture-regeneration cycle stability that makes industrial use economic. The proposed work is targeted at conducting further testing of these composite nanomaterials on a larger scale and in combination with other Process steps.

The broader impact/commercial potential of this project is that it can contribute to the urgent need for methods to economically produce renewable hydrocarbon fuels and high value chemicals that are more efficient than existing technologies. GRT is developing novel processes for the conversion of methane, ethane and propane into higher value hydrocarbons suitable for gasoline and jet fuel blend stocks, aromatic compounds or high value chemicals which can cost-effectively utilize stranded and/or small reserves of natural gas and shale gas. This upgrade of inexpensive natural gas to high value transportation fuels and chemicals at the source is very valuable because it eliminates the need for gas processing and pipeline transportation. The commercial viability of these technologies depends on energy efficiency and the capital cost of plant equipment. Improvement in the performance and stability of solid reactant/metal oxide nanocomposite materials will make substantial improvements in both of these metrics and hence in the commercial viability of the GRT Processes.

Project Report

"Development of the Reaction35, LLC On-Purpose Propane-to-Propylene Process Technology" NSF Proposal Number 1152638 Grant Period: April 15, 2012 – March 31, 2014 Reaction35, LLC’s SBIR Phase II efforts focused on performing research and development to commercialize its on-purpose Propane to Propylene (P2P) Technology that cost-effectively converts domestically sourced propane into polymer-grade propylene in an on-purpose manner. The Reaction35 effort has resulted in 1) better understanding of the chemistry of the key process reactions, 2) characterization of two catalyst materials and 3) development of a Front End Engineering Design (FEED) Package for a pilot-scale plant based on the P2P Technology. Propylene represents the second largest organic chemical market in the world (after ethylene), yet largely due to the reduction in naphtha cracking, it is projected that by 2015 there will be a 20% gap between propylene supply and demand.[i] To fill the propylene gap, technologies that can produce propylene as the sole, or at least the primary product (referred to in the industry as "on-purpose"), must be utilized. As propane is found in shale gas and thus in large supply, technologies that can produce propylene from propane, such as Propane Dehydration (PDH) are of particular interest. Concerns over the high capital cost, operating expense, carbon footprint and energy demand of PDH technology has limited its adoption as several facilities proposed recently have already been cancelled. There is therefore an opportunity for a more energy and cost efficient on-purpose propylene technology to meet current and future propylene demand. Reaction 35, LLC, headquartered in Houston, TX, has developed a three-step process for converting alkanes to high-value petrochemicals and fuels and has applied this process to the conversion of propane to polymer grade (³ 99.5% purity) propylene, shown in Figure 1. In step 1, propane is reacted with bromine under relatively mild conditions to form bromopropanes and hydrogen bromide. In step 2, bromopropane is converted to propylene and hydrogen bromide over a non-precious metal based proprietary catalyst developed by Reaction 35. This low cost catalyst provides for high selectivity (> 99.5%) and conversion. Hydrogen bromide produced in both steps 1 and 2 is reacted with oxygen (air) over another proprietary catalyst in step 3 to regenerate bromine, which is completely recovered for reuse in the process. Consequently, all the bromine required for the process is fully recycled, and the process does not consume any bromine. The Reaction35 P2P Process has a number of competitive advantages over conventional PDH, resulting in a significantly lower cost of production. The relatively mild bromination and dehydrobromination reaction temperatures, coupled with the efficacy of the dehydrobromination catalyst, results in negligible byproduct formation and an increase in feedstock efficiency over PDH. In addition, the thermodynamics of the P2P Process chemistry are such that the entire process may be run without the need for compression or refrigeration between the reaction and separation steps. When combined, the advantages of the P2P Process result in lower capital and operating costs compared to PDH, as evaluated by a Tier-1 engineering company. [i] "Propylene: Chemical Economics Handbook", Information Handling Services (IHS) Chemical, 2011.

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Grt, Inc.
Santa Barbara
United States
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