(707a) Advancing the Production of Olefins and Aromatics from Natural Gas Via Methanol: Chemical Looping for Syngas Generation

Due to technological advances in the shale gas industry, the supply of natural gas in the United States has greatly increased (37% since 2008¹) and its price has significantly dropped ($2.52/MMBtu in 2016²). The shale gas boom has not only revitalized the U.S. economy, but also rejuvenated interests in C1 catalysis toward the production of chemicals typically derived from petroleum refining³. Olefins (ethylene, propylene, butane isomers, butadiene) and aromatics (benzene, toluene, xylenes) are examples of valuable chemicals in high demand.

As diesel continues to command a larger portion of the crude oil usage, less naphtha will be available for petrochemical production. Given its availability, low cost, and hydrogen-rich composition, natural gas is an attractive feedstock for the on-purpose production of chemicals⁴. Conversion of natural gas to a methanol intermediate for further upgrading to chemicals is a potential avenue for chemicals production and is a promising commercial candidate for natural gas based refineries. Currently, methanol is almost entirely produced from syngas.

However, a judicious utilization of natural gas resources necessitates a systematic analysis of all available processing routes. To this aim, a gas to olefins and aromatics (GTOA) superstructure has been developed^5,6 and includes several olefins and aromatics production technologies. Previous works investigated reforming as the primary method to convert natural gas to syngas and demonstrated the profitability of GTOA processes. Recently, the benefits of chemical looping^7,8 for syngas generation have been observed in lowering the breakeven oil prices for a gas to liquids (GTL) process⁹. In this work, we incorporate chemical looping into the GTOA superstructure as an alternative to reforming and study its impact on chemicals production.

Process synthesis of the GTOA superstructure forms a large-scale nonconvex mixed-integer nonlinear model (MINLP). A tailored deterministic global optimization branch-and-bound algorithm¹⁰ is used to solve the MINLP and determine optimal natural gas refineries with the highest profit. Several case studies are investigated to compare chemical looping against reforming for natural gas conversion. The effect of different plant capacities and product ratios are explored as well. Key topological selection of process technologies will be discussed.

1. U.S. Energy Information Administration. “Monthly Energy Review – March 2017”. Available at: http://www.eia.gov/totalenergy/data/monthly/pdf/mer.pdf. Accessed April 2017.

2. U.S. Energy Information Administration. “Henry Hub Natural Gas Spot Price”. Available at: http://www.eia.gov/dnav/ng/hist/rngwhhdm.htm. Accessed April 2017.

3. Mokrani T., Scurrel M. Gas conversion to liquid fuels and chemicals: the methanol route-catalysis and processes development. Catalysis Reviews 2009, 51, 1-145

4. Floudas, C. A.; Niziolek, A. M.; Onel, O.; Matthews, L. R. Multi-scale systems engineering for energy and the environment: Challenges and opportunities. AIChE Journal 2016, 62 (3), 602-623.

5. Onel, O.; Niziolek, A. M; Floudas, C. A Optimal Production of Light Olefins from Natural Gas via the Methanol Intermediate. Industrial & Engineering Chemistry Research 2016, 55 (11), 3043-3063.

6. Niziolek, A.M.; Onel, O.; Floudas, C.A. Production of Benzene, Toulene, and Xylenes from Natural Gas via Methanol: Process Synthesis and Global Optimization. AIChE Journal 2016, 62 (5), 1531-1556.

7. Luo, S.; Zeng, L.; Xu, D.; Kathe, M.; Chung, E.; Deshpande, N.; Qin, L.; Majumder, A.; Hsieh, T.-L.; Tong, A.; Sun, Z.; Fan, L.-S. Shale gas-to-syngas chemical looping process for stable shale gas conversion to high purity syngas with a H2:CO ratio of 2:1. Energy & Environmental Science 2014, 7 (12), 4104–4117.

8. de Diego, L. F.; Ortiz, M.; García-Labiano, F.; Adánez, J.; Abad, A.; Gayán, P. Hydrogen production by chemical-looping reforming in a circulating fluidized bed reactor using Ni-based oxygen carriers. Journal of Power Sources 2009, 192 (1), 27–34.

9. Tso, W.W.; Niziolek, A.M.; Onel, O.; Demirhan, C.D.; Floudas, C.A.; Pistikopoulos, E.N.; Enhancing Natural Gas-to-Liquids (GTL) Processes Through Chemical Looping for Syngas Production: Process Synthesis and Global Optimization. In preparation.

10. Baliban, R. C; Elia, J. A; Misener, R.; Floudas, C. A Global optimization of a MINLP process synthesis model for thermochemical based conversion of hybrid coal, biomass, and natural gas to liquid fuels. Computers & Chemical Engineering 2012, 42, 64-86.