Production of Norbornadiene

PROJECTED CMMC LEVEL REQUIREMENT
Level 2 (Self)
TECHNOLOGY AREAS
None
MODERNIZATION PRIORITIES
Advanced Materials
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Hypersonics
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Sustainment & Logistics
KEYWORDS
Chemical Synthesis; Chemical Engineering; Manufacturing; Norbornadiene; Technoeconomic Analysis; Bio-feedstocks
OBJECTIVE
Develop efficient and scalable methods for the production of norbornadiene from abundant domestic feedstocks.
DESCRIPTION
Norbornadiene is a critical chemical used in the manufacture of fuels and cross-linked polymers. The conventional process for production of norbornadiene relies on a Diels-Alder coupling reaction between cyclopentadiene and acetylene. Acetylene air mixtures can be explosive, which has increased the cost of norbornadiene and reliance on foreign supply chains. The intent of this STTR topic is to establish a manufacturing process that will enable the safe and efficient domestic production of norbornadiene, which will in turn reduce acquisition costs.
Ultimately, this topic seeks to establish a process for the domestic production of norbornadiene at > 500 metric tons/year with target acquisition costs below $20/kg. The norbornadiene synthesized in this effort should have a purity > 97%. The utilization of advanced manufacturing techniques that generate acetylene on demand or incorporate novel methods for the safe storage of acetylene on-site are encouraged. Other approaches that generate norbornadiene via unique intermediates are also of interest. A preferred approach is to utilize domestic bio-feedstocks, including hemicellulose and furfural, as substrates for the production of norbornadiene.
PHASE I
Identify a chemical process for the synthesis of norbornadiene. Particular attention will be paid to the safe handling of acetylene and other reactants/reagents and solvents used in the manufacturing process. The use of domestic biomass feedstocks as the carbon source for norbornadiene production is preferred. A preliminary technoeconomic analysis will be conducted with a target selling price < $20/kg. Awardee(s) will conduct laboratory scale reactions and demonstrate the ability to generate small quantities of norbornadiene (10-100 mL) at purities comparable to commercial norbornadiene (> 97%). The purity of the product will be confirmed through standard analytical techniques including NMR spectroscopy and gas chromatography.
PHASE II
Demonstrate a prototype scalable approach for the synthesis of norbornadiene and provide 1 kg of material for evaluation by Navy researchers. Demonstrate production of norbornadiene at the 100 kg scale and develop plans for a facility capable of producing > 500 metric tons/year. An updated technoeconomic analysis will be performed utilizing information obtained during the pilot-scale production runs. The assessment will include a comparison of processes utilizing inputs from both conventional petrochemicals and biofeedstocks. At the completion of Phase II, 100 kg of norbornadiene with a purity > 97% will be delivered to the Government.
PHASE III DUAL USE APPLICATIONS
Assist the government in the establishment a CONUS facility capable of producing norbornadiene at the estimated scale of 10-20 metric tons/year, likely doing this in collaboration with a larger chemical supplier. Informed by the standup of this facility, update the plans and technoeconomic analysis for a facility capable of producing > 500 metric tons/year.
REFERENCES
Julius, H.; Ernest, F.; Lidov, R. E. and Co, S. D. "US2875256A - Dienic hydrocarbons and derivatives thereof."United States Patent Office, Patented Feb. 24, 1959. https://patents.google.com/patent/US2875256A/en and https://patentimages.storage.googleapis.com/5e/34/56/120b4f96d69fde/US2875256.pdf
"CN1580014A - Method for preparing 2,5-norbornadiene from dicyclopentadiene." Sinopec Shanghai Petrochemical Co Ltd, 14 August 2003. https://patents.google.com/patent/CN1580014A/en
"RU2228324C1 - Norbornadiene preparation method." https://patents.google.com/patent/RU2228324C1/en?oq=RU2228324C1
Zhang, X. et al. "Integration of Bio-JP-10 Synthetic Route from Furfuryl Alcohol." Catalysis Today, 443, 1 January 2025, 114987. https://www.sciencedirect.com/science/article/pii/S0920586124004814
Xie, J. et al. "Synthesis of JP-10 Analogues High-Density Fuels via One-Pot Diels-Alder/Hydrodeoxygenation Reaction." Fuel 2024, 361, 1 April 2024, 130738. https://www.sciencedirect.com/science/article/abs/pii/S0016236123033525
Li, G. et al. "Making JP-10 Superfuel Affordable with a Lignocellulosic Platform Compound" Chem. Int. Ed. 2019, 58, 12154