Robert A. Dagle

Steam reforming of methanol over highly active Pd/ZnO catalyst

Abstract Pd/ZnO catalysts were investigated for steam reforming of methanol. Unlike precious metal-based catalysts, Pd/ZnO catalysts not only exhibited high activity, but more importantly very low selectivity to CO for methanol steam reforming. Under the conditions examined, the decomposition activity is minimal. The novel function is attributed to the formation of highly structured Pd–Zn alloy at moderate temperatures under mild reducing environments. The current catalytic system was characterized by TPR, transmission electron microscopy (TEM), H 2 chemisorption, and X-ray diffraction (XRD).

Methanol steam reforming over Pd/ZnO: Catalyst preparation and pretreatment studies

Abstract The preparation and the pretreatment of Pd/ZnO catalysts were studied for methanol steam reforming. The presence of nitric acid in Pd nitrate precursor significantly altered the porosities and crystalline structures of the ZnO support. The dissolution of ZnO and extent of mixing between the Zn 2+ and Pd 2+ cations during catalyst preparation may have an impact on the PdZn alloy formation and its catalytic properties. The pretreatment of Pd/ZnO, which is critical to the PdZn alloy formation, depends not only on the reduction temperature but also on the reaction conditions under which hydrogen is formed.

Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts

A Pd/ZnO/Al2O3 catalyst was developed for the synthesis of methanol and dimethyl ether (DME) from syngas with temperatures of operation ranging from 250 °C to 380 °C. High temperatures (e.g. 380 °C) are of interest when combining methanol and DME synthesis with a methanol to gasoline (MTG) process in a single reactor bed. A commercial Cu/ZnO/Al2O3 catalyst, utilized industrially for the synthesis of methanol at 220–280 °C, suffers from a rapid deactivation when the reaction is conducted at high temperature (> 320 °C). On the contrary, a Pd/ZnO/Al2O3 catalyst was found to be highly stable for methanol and DME synthesis at 375 °C. The Pd/ZnO/Al2O3 catalyst was thus further investigated for methanol and DME synthesis at P = 34–69 bar, T = 250–380 °C, GHSV = 5000–18 000 h−1, and molar feeds H2/CO = 1, 2, and 3. Selectivity to DME increased with decreasing operating temperature, and increasing operating pressure. Higher space velocity and H2/CO syngas feed ratios also enhanced DME selectivity. Undesirable CH4 formation was observed, however, it could be lessen through choice of process conditions and by catalyst design. By studying the effect of the Pd loading and the Pd : Zn molar ratio the formulation of the Pd/ZnO/Al2O3 catalyst was optimized. A catalyst with 5% Pd and a Pd : Zn molar ratio of 0.25 : 1 has been identified as the preferred catalyst. Results indicate that PdZn particles are more active than Pdo particles for the synthesis of methanol and less active for CH4 formation. A correlation between DME selectivity and concentration of acid sites has been established. Hence, two types of sites are required for the direct conversion of syngas to DME: (1) PdZn particles are active for the synthesis of methanol from syngas, and (2) acid sites which are active for the conversion of methanol to DME. Additionally, CO2 formation was problematic as PdZn was found to be active for the water-gas-shift (WGS) reaction, under all the conditions evaluated.

Single-step syngas-to-distillates (S2D) process based on biomass-derived syngas – A techno-economic analysis

This study compared biomass gasification based syngas-to-distillate (S2D) systems using techno-economic analysis (TEA). Three cases, state of technology (SOT), goal, and conventional, were compared in terms of performance and cost. The SOT case represented the best available experimental results for a process starting with syngas using a single-step dual-catalyst reactor for distillate generation. The conventional case mirrored a conventional two-step S2D process consisting of separate syngas-to-methanol and methanol-to-gasoline (MTG) processes. The goal case assumed the same performance as the conventional, but with a single-step S2D technology. TEA results revealed that the SOT was more expensive than the conventional and goal cases. The SOT case suffers from low one-pass yield and high selectivity to light hydrocarbons, both of which drive up production cost. Sensitivity analysis indicated that light hydrocarbon yield and single pass conversion efficiency were the key factors driving the high cost for the SOT case.

Miniature Fuel Processors for Portable Fuel Cell Power Supplies

Miniature and micro-scale fuel processors are discussed. The enabling technologies for these devices are the novel catalysts and the micro-technology-based designs. The novel catalyst allows for methanol reforming at high gas hourly space velocities of 50,000 hr-1 or higher, while maintaining a carbon monoxide levels at 1% or less. The micro-technology-based designs enable the devices to be extremely compact and lightweight. The miniature fuel processors can nominally provide between 25-50 watts equivalent of hydrogen which is ample for soldier or personal portable power supplies. The integrated processors have a volume less than 50 cm3, a mass less than 150 grams, and thermal efficiencies of up to 83%. With reasonable assumptions on fuel cell efficiencies, anode gas and water management, parasitic power loss, etc., the energy density was estimated at 1700 Whr/kg. The miniature processors have been demonstrated with a carbon monoxide clean-up method and a fuel cell stack. The micro-scale fuel processors have been designed to provide up to 0.3 watt equivalent of power with efficiencies over 20%. They have a volume of less than 0.25 cm3 and a mass of less than 1 gram.

Integrated process for the catalytic conversion of biomass-derived syngas into transportation fuels

Efficient synthesis of renewable fuels that will enable cost competitiveness with petroleum-derived fuels remains a grand challenge. In this paper, we report on an integrated catalytic approach for producing transportation fuels from biomass-derived syngas. This novel process represents an alternative to conventional fuel synthesis routes (e.g., Fischer–Tropsch, Methanol-to-Gasoline) that have drawbacks, particularly at the scale of biomass. Composition of the resulting hydrocarbon fuel can be modulated to produce predominantly middle distillates, which is constantly increasing in demand compared to gasoline fraction. In this process biomass-derived syngas is first converted over an Rh-based catalyst into a complex aqueous mixture of condensable C2+ oxygenated compounds (predominantly ethanol, acetic acid, acetaldehyde, ethyl acetate). This multi-component aqueous mixture then is fed to a second reactor loaded with a ZnxZryOz mixed oxide catalyst, which has tailored acid–base sites, to produce an olefin mixture rich in isobutene. The olefins then are oligomerized using a solid acid catalyst (e.g., Amberlyst-36) to form condensable olefins with molecular weights that can be targeted for gasoline, jet, and/or diesel fuel applications. The product rich in long-chain olefins (C7+) is finally sent to a fourth reactor required for hydrogenation of the olefins into paraffin fuels. Simulated distillation of the hydrotreated oligomerized liquid product indicates that ∼75% of the hydrocarbons (iso-paraffins and cyclic compounds) are in the jet-fuel range. Process optimization for the oligomerization step could further improve yield to the jet-fuel range. All of these catalytic steps have been demonstrated in sequence, thus providing proof-of-concept for a new integrated process for the production of drop-in biofuels. Overall, we demonstrate approximately 41% carbon efficiency for converting syngas into jet-range hydrocarbons. This unique and flexible process does not require external hydrogen and also could be applied to non-syngas derived feedstock, such as fermentation products (e.g., ethanol, acetic acid, etc.), other oxygenates, and mixtures thereof containing alcohols, acids, aldehydes and/or esters.

Molecular Active Sites in Heterogeneous Ir-La/C-Catalyzed Carbonylation of Methanol to Acetates.

We report that when Ir and La halides are deposited on carbon, exposure to CO spontaneously generates a discrete molecular heterobimetallic structure, containing an Ir-La covalent bond that acts as a highly active, selective, and stable heterogeneous catalyst for the carbonylation of methanol to produce acetic acid. This catalyst exhibits a very high productivity of ∼1.5 mol acetyl/mol Ir·s with >99% selectivity to acetyl (acetic acid and methyl acetate) without detectable loss in activity or selectivity for more than 1 month of continuous operation. The enhanced activity can be mechanistically rationalized by the presence of La within the ligand sphere of the discrete molecular Ir-La heterobimetallic structure, which acts as a Lewis acid to accelerate the normally rate-limiting CO insertion in Ir-catalyzed carbonylation. Similar approaches may provide opportunities for attaining molecular (single site) behavior similar to homogeneous catalysis on heterogeneous surfaces for other industrial applications.

Carbon dioxide conversion to valuable chemical products over composite catalytic systems

Abstract This paper reports an experimental study on catalytic conversion of carbon dioxide to methanol, ethanol and acetic acid. Catalysts having different catalytic functions were synthesized and combined in different ways to enhance the selectivity to desired products. The combined catalyst system possessed the following functions: methanol synthesis, Fischer-Tropsch synthesis, water-gas-shift and hydrogenation. Results showed that the methods of integrating these catalytic functions played an important role in achieving the desired product selectivity. We speculate that if methanol synthesis sites were located adjacent to the C–C chain growth sites, the formation rate of C2 oxygenates would be enhanced. The advantage of using a high temperature methanol catalyst PdZnAl in the combined catalyst system was demonstrated. In the presence of PdZnAl catalyst, the combined catalyst system was stable at 380 °C. It was observed that, at high temperature, kinetics favored oxygenate formation. The results implied that the process can be intensified by operating at high temperature using Pd-based methanol synthesis catalyst. Steam reforming of the byproduct organics was demonstrated as a means to provide supplemental hydrogen. Preliminary process design, simulation, and economic analysis of the proposed CO2 conversion process were carried out. Economic analysis indicates how ethanol production cost was affected by the price of CO2 and hydrogen.

Development and Demonstration of a Prototype Solar Methane Reforming System for Thermochemical Energy Storage - Including Preliminary Shakedown Testing Results

12 Infinia Corporation This paper reports on the design, fabrication and preliminary testing of a solar steam- methane reforming system including a parabolic dish solar concentrator, the endothermic chemical reactor and associated heat exchangers. During shakedown testing, methane conversions exceeded 90% and solar-to-chemical energy conversions of about 63 ± 4% were obtained, based on the change in the higher heating value of the stream. Potential applications include thermochemical energy storage for concentrating solar power generation facilities and solar augments of fossil and biomass fuels for power generation and/or synthetic fuel production.

Fuel processor development for a soldierportable fuel cell system

The remarkable recent advances in wireless and portable communications devices (e.g., laptop computers, cellular phones, portable digital assistants) have fueled a need for high-energy-density portable power sources for consumer use. Similarly, interest in portable power sources has increased in the military and intelligence communities. Currently, portable military electronics are dependent on batteries to supply electrical power for long-duration missions. This poses two major problems which result from the low energy density of current battery systems: excessive weight/bulk, and reduced mission duration.