@article{ruan_akutsu_yang_zayan_dou_liu_bose_brody_lamb_li_2023, title={Hydrogenation of bio-oil-derived oxygenates at ambient conditions via a two-step redox cycle}, volume={4}, ISSN={["2666-3864"]}, url={https://doi.org/10.1016/j.xcrp.2023.101506}, DOI={10.1016/j.xcrp.2023.101506}, abstractNote={A key challenge in upgrading bio-oils to renewable fuels and chemicals resides in developing effective and versatile hydrogenation systems. Herein, a two-step solar thermochemical hydrogenation process that sources hydrogen directly from water and concentrated solar radiation for furfural upgrading is reported. High catalytic performance is achieved at room temperature and atmospheric pressure, with up to two-orders-of-magnitude-higher hydrogen utilization efficiency compared with state-of-the-art catalytic hydrogenation. A metal or reduced metal oxide provides the active sites for furfural adsorption and water dissociation. The in situ-generated reactive hydrogen atoms hydrogenate furfural and biomass-derived oxygenates, eliminating the barriers to hydrogen dissolution and the subsequent dissociation at the catalyst surface. Hydrogenation selectivity can be conveniently mediated by solvents with different polarity and metal/reduced metal oxide catalysts with varying oxophilicity. This work provides an efficient and versatile strategy for bio-oil upgrading and a promising pathway for renewable energy storage.}, number={7}, journal={CELL REPORTS PHYSICAL SCIENCE}, author={Ruan, Chongyan and Akutsu, Ryota and Yang, Kunran and Zayan, Noha M. and Dou, Jian and Liu, Junchen and Bose, Arnab and Brody, Leo and Lamb, H. Henry and Li, Fanxing}, year={2023}, month={Jul} }
 @article{cai_brody_tian_neal_bose_li_2023, title={Numerical modeling of chemical looping oxidative dehydrogenation of ethane in parallel packed beds}, volume={469}, ISSN={["1873-3212"]}, url={https://doi.org/10.1016/j.cej.2023.143930}, DOI={10.1016/j.cej.2023.143930}, abstractNote={Chemical looping oxidative dehydrogenation (CL-ODH) of ethane has the potential to be a highly efficient alternative to steam cracking for ethylene production. Accurate reactor modeling is of critical importance to efficiently scale up and optimize this new technology. This study reports a one-dimensional, heterogeneous packed bed model to simulate the CL-ODH of ethane to ethylene with a Na2MoO4-promoted CaTi0.1Mn0.9O3 redox catalyst. The overall reaction kinetics was well-described by coupling the gas-phase steam cracking of ethane with the reduction kinetics of the redox catalyst by H2 and C2H4. The impact of H2 on the formation rate of CO2 byproduct from C2H4 conversion was also thoroughly investigated to validate the applicability of the kinetic model under operational environments. The temperature variation within the different CL-ODH steps and the temperature distribution along the bed were also carefully considered. The accuracy of the model was validated by experiments conducted in a large lab-scale packed bed reactor (200 g catalyst loading), with an average deviation of 2.8% in terms of ethane conversion and ethylene yield. The model was subsequently used to optimize the operating parameters of the CL-ODH reactor, indicating that up to 63.7% single-pass C2 + olefin yield can be achieved with the current redox catalyst bed whereas further optimization of the redox catalyst to inhibit C2H4 activation can result in 69.4% single-pass C2 + yield while maintaining low CO2 selectivity.}, journal={CHEMICAL ENGINEERING JOURNAL}, author={Cai, Runxia and Brody, Leo and Tian, Yuan and Neal, Luke and Bose, Arnab and Li, Fanxing}, year={2023}, month={Aug} }
 @article{brody_rukh_cai_bosari_schomaecker_li_2023, title={Sorption-enhanced steam reforming of toluene using multifunctional perovskite phase transition sorbents in a chemical looping scheme}, volume={5}, ISSN={["2515-7655"]}, url={https://doi.org/10.1088/2515-7655/acdbe9}, DOI={10.1088/2515-7655/acdbe9}, abstractNote={Sorption-enhanced steam reforming (SESR) of toluene (SESRT) using catalytic CO2 sorbents is a promising route to convert the aromatic tar byproducts formed in lignocellulosic biomass gasification into hydrogen (H2) or H2-rich syngas. Commonly used sorbents such as CaO are effective in capturing CO2 initially but are prone to lose their sorption capacity over repeated cycles due to sintering at high temperatures. Herein, we present a demonstration of SESRT using A- and B-site doped Sr1−x A’ x Fe1−y B’ y O3−δ (A’ = Ba, Ca; B’ = Co) perovskites in a chemical looping scheme. We found that surface impregnation of 5–10 mol% Ni on the perovskite was effective in improving toluene conversion. However, upon cycling, the impregnated Ni tends to migrate into the bulk and lose activity. This prompted the adoption of a dual bed configuration using a pre-bed of NiO/γ–Al2O3 catalyst upstream of the sorbent. A comparison is made between isothermal operation and a more traditional temperature-swing mode, where for the latter, an average sorption capacity of ∼38% was witnessed over five SESR cycles with H2-rich product syngas evidenced by a ratio of H2: CO x > 4.0. XRD analysis of fresh and cycled samples of Sr0.25Ba0.75Fe0.375Co0.625O3-δ reveal that this material is an effective phase transition sorbent—capable of cyclically capturing and releasing CO2 without irreversible phase changes occurring.}, number={3}, journal={JOURNAL OF PHYSICS-ENERGY}, author={Brody, Leo and Rukh, Mahe and Cai, Runxia and Bosari, Azin Saberi and Schomaecker, Reinhard and Li, Fanxing}, year={2023}, month={Jul} }
 @article{brody_neal_liu_li_2022, title={Autothermal Chemical Looping Oxidative Dehydrogenation of Ethane: Redox Catalyst Performance, Longevity, and Process Analysis}, volume={7}, ISSN={["1520-5029"]}, DOI={10.1021/acs.energyfuels.2c01293}, abstractNote={Energy-efficient upgrading of stranded ethane from shale gas to olefins holds the promise of increasing the supply of useful chemical feedstocks while reducing flaring-based CO2 emissions. Previously, we reported a modular ethane-to-liquids (M-ETL) system based on a chemical looping oxidative dehydrogenation (CL-ODH) scheme. In this article, we present long-term (>1200 h) results of Li2CO3-promoted La0.8Sr0.2FeO3 corresponding to ∼4125 CL-ODH cycles in a large laboratory-scale packed bed reactor. Temperature monitoring along the bed length confirmed the exothermicity of both the oxidative dehydrogenation and regeneration steps, enabling an autothermal operation. Product gas analysis indicated that the redox catalyst maintains a high C2+ selectivity (∼90%) and ethane conversion (∼67%) at 735 °C after continuous cycling of >1000 h. Product distributions and heats of reactions were used to update our M-ETL process model for revised techno-economic analysis, demonstrating that the current system is economically viable with relatively low required selling prices across a wide range of operating scenarios.}, journal={ENERGY & FUELS}, author={Brody, Leo and Neal, Luke and Liu, Junchen and Li, Fanxing}, year={2022}, month={Jul} }
 @article{brody_cai_thornton_liu_yu_li_2022, title={Perovskite-Based Phase Transition Sorbents for Sorption-Enhanced Oxidative Steam Reforming of Glycerol}, volume={10}, ISSN={["2168-0485"]}, DOI={10.1021/acssuschemeng.2c01323}, abstractNote={Sorption-enhanced steam reforming represents an efficient strategy to produce concentrated hydrogen from superfluous carbonaceous feedstocks. However, commonly used CaO-based sorbents are prone to sintering, leading to a rapid loss in CO2 sorption capacity and activity under repeated reaction cycles. Herein, we report perovskite-based phase transition sorbents (PTSs) capable of avoiding sintering and retaining both catalytic activity and sorption capacity. Specifically, A- and B-site doped SrFeO3−δ, that is, Sr1–xCaxFe1–yNiyO3−δ (SCFN), were evaluated as PTSs for the sorption-enhanced steam reforming of glycerol. Packed bed reactor experiments were performed in conjunction with redox, bulk, surface, and morphology characterizations to evaluate SCFN’s performance and the underlying phase transition scheme. These characterizations revealed that reduced oxides from the A-site of the PTS (SrO, CaO) are carbonated during the reforming step before reversibly undergoing decarbonation at a higher temperature under an oxidizing environment. This study demonstrates that SCFN is a trifunctional material capable of (i) catalyzing the reforming of glycerol, (ii) absorbing CO2 in situ, and (iii) reversibly releasing oxygen from lattice sites to enhance glycerol conversion. While all of the screened compositions achieved >87 vol % pre-breakthrough H2 purities, SCFN-4691 (Sr0.4Ca0.6Fe0.9Ni0.1O3−δ) and SCFN-5591 (Sr0.5Ca0.5Fe0.9Ni0.1O3−δ) showed particularly high (95.6–97.3%) H2 purities with stable CO2 sorption capacities.}, number={19}, journal={ACS SUSTAINABLE CHEMISTRY & ENGINEERING}, author={Brody, Leo and Cai, Runxia and Thornton, Alajia and Liu, Junchen and Yu, Hao and Li, Fanxing}, year={2022}, month={May}, pages={6434–6445} }
 @article{brody_neal_haribal_li_2021, title={Ethane to liquids via a chemical looping approach - Redox catalyst demonstration and process analysis}, volume={417}, ISSN={["1873-3212"]}, url={http://www.scopus.com/inward/record.url?eid=2-s2.0-85102136078&partnerID=MN8TOARS}, DOI={10.1016/j.cej.2021.128886}, abstractNote={The inability to economically transport ethane from distributed shale gas production sites results in the “rejection”, i.e. flaring or reinjection, of this important petrochemical feedstock. Therefore, a technology capable of efficiently converting geographically isolated ethane into transportable liquid fuels would effectively exploit this abundant yet wasted resource. We proposed a modular ethane-to-liquids (M−ETL) system that employs a chemical looping-oxidative dehydrogenation (CL-ODH) scheme to convert ethane into olefins via cyclic redox reactions. The olefins would subsequently undergo oligomerization to form mid-distillate liquid fuels. In this study, a sodium molybdate promoted CaTi0.1Mn0.9O3 core-shell redox catalyst (CaTi0.1Mn0.9O3@Na2MoO4) is presented as a potentially viable, redox-active catalyst for the CL-ODH of ethane to ethylene. Performance data were collected from 1,600 + hours (>4,000CL-ODH cycles) of packed bed operations at varying temperatures and space velocities. 52 – 58% single-pass olefin yields at 725 and 730 °C were obtained with relatively low (2.5 – 8%) COx selectivity. The experimental data were used as inputs to an ASPEN Plus® based M−ETL system model to evaluate its performance. Sensitivity analyses were performed on the CL-ODH and oligomerization sections of the M−ETL system, and the results were used to inform economic analysis of the process. The techno-economic analysis (TEA) indicates that the introduction of recycle to the system provides flexibility for profit generation for both high (Xethane = 0.75) and low (Xethane = 0.58) conversion cases. Additionally, TEA results demonstrate that electrical cogeneration can be economically attractive under certain scenarios.}, journal={CHEMICAL ENGINEERING JOURNAL}, author={Brody, Leo and Neal, Luke and Haribal, Vasudev and Li, Fanxing}, year={2021}, month={Aug} }