Technoeconomic and life-cycle analysis of single-step catalytic conversion of wet ethanol into fungible fuel blendstocks

Technoeconomic and life-cycle analyses are presented for catalytic conversion of ethanol to fungible hydrocarbon fuel blendstocks, informed by advances in catalyst and process development. Whereas prior work toward this end focused on 3-step processes featuring dehydration, oligomerization, and hydrogenation, the consolidated alcohol dehydration and oligomerization (CADO) approach described here results in 1-step conversion of wet ethanol vapor (40 wt% in water) to hydrocarbons and water over a metal-modified zeolite catalyst. A development project increased liquid hydrocarbon yields from 36% of theoretical to >80%, reduced catalyst cost by an order of magnitude, scaled up the process by 300-fold, and reduced projected costs of ethanol conversion 12-fold. Current CADO products conform most closely to gasoline blendstocks, but can be blended with jet fuel at low levels today, and could potentially be blended at higher levels in the future. Operating plus annualized capital costs for conversion of wet ethanol to fungible blendstocks are estimated at $2.00/GJ for CADO today and$1.44/GJ in the future, similar to the unit energy cost of producing anhydrous ethanol from wet ethanol ($1.46/GJ). Including the cost of ethanol from either corn or future cellulosic biomass but not production incentives, projected minimum selling prices for fungible blendstocks produced via CADO are competitive with conventional jet fuel when oil is$100 per barrel but not at $60 per barrel. However, with existing production incentives, the projected minimum blendstock selling price is competitive with oil at$60 per barrel. Life-cycle greenhouse gas emission reductions for CADO-derived hydrocarbon blendstocks closely follow those for the ethanol feedstock

Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbons: Dilute-Acid and Enzymatic Deconstruction of Biomass to Sugars and Biological Conversion of Sugars to Hydrocarbons

This report describes one potential conversion process to hydrocarbon products by way of biological conversion of lingnocellulosic-dervied sugars. The process design converts biomass to a hydrocarbon intermediate, a free fatty acid, using dilute-acid pretreatement, enzymatic saccharification, and bioconversion. Ancillary areas--feed handling, hydrolysate conditioning, product recovery and upgrading (hydrotreating) to a final blendstock material, wastewater treatment, lignin combusion, and utilities--are also included in the design

Single-Step Syngas-to-Distillates (S2D) Synthesis via Methanol and Dimethyl Ether Intermediates: Final Report

The objective of the work was to enhance price-competitive, synthesis gas (syngas)-based production of transportation fuels that are directly compatible with the existing vehicle fleet (i.e., vehicles fueled by gasoline, diesel, jet fuel, etc.). To accomplish this, modifications to the traditional methanol-to-gasoline (MTG) process were investigated. In this study, we investigated direct conversion of syngas to distillates using methanol and dimethyl ether intermediates. For this application, a Pd/ZnO/Al2O3 (PdZnAl) catalyst previously developed for methanol steam reforming was evaluated. The PdZnAl catalyst was shown to be far superior to a conventional copper-based methanol catalyst when operated at relatively high temperatures (i.e., >300°C), which is necessary for MTG-type applications. Catalytic performance was evaluated through parametric studies. Process conditions such as temperature, pressure, gas-hour-space velocity, and syngas feed ratio (i.e., hydrogen:carbon monoxide) were investigated. PdZnAl catalyst formulation also was optimized to maximize conversion and selectivity to methanol and dimethyl ether while suppressing methane formation. Thus, a PdZn/Al2O3 catalyst optimized for methanol and dimethyl ether formation was developed through combined catalytic material and process parameter exploration. However, even after compositional optimization, a significant amount of undesirable carbon dioxide was produced (formed via the water-gas-shift reaction), and some degree of methane formation could not be completely avoided. Pd/ZnO/Al2O3 used in combination with ZSM-5 was investigated for direct syngas-to-distillates conversion. High conversion was achieved as thermodynamic constraints are alleviated when methanol and dimethyl are intermediates for hydrocarbon formation. When methanol and/or dimethyl ether are products formed separately, equilibrium restrictions occur. Thermodynamic relaxation also enables the use of lower operating pressures than what would be allowed for methanol synthesis alone. Aromatic-rich hydrocarbon liquid (C5+), containing a significant amount of methylated benzenes, was produced under these conditions. However, selectivity control to liquid hydrocarbons was difficult to achieve. Carbon dioxide and methane formation was problematic. Furthermore, saturation of the olefinic intermediates formed in the zeolite, and necessary for gasoline production, occurred over PdZnAl. Thus, yield to desirable hydrocarbon liquid product was limited. Evaluation of other oxygenate-producing catalysts could possibly lead to future advances. Potential exists with discovery of other types of catalysts that suppress carbon dioxide and light hydrocarbon formation. Comparative techno-economics for a single-step syngas-to-distillates process and a more conventional MTG-type process were investigated. Results suggest operating and capital cost savings could only modestly be achieved, given future improvements to catalyst performance. Sensitivity analysis indicated that increased single-pass yield to hydrocarbon liquid is a primary need for this process to achieve cost competiveness

Application of a Pyroprobe–Deuterium NMR System: Deuterium Tracing and Mechanistic Study of Upgrading Process for Lignin Model Compounds

In this study, a pyroprobe–deuterium (²H) NMR system has been used to identify isotopomer products formed during the deuteration and ring opening of lignin model compounds. Several common model compounds for lignin and its upgraded products, including guaiacol, syringol, toluene, <i>p</i>-xylene, phenol, catechol, cyclohexane, methylcyclohexane, and methylcyclopentane, have been examined for selective ring opening. Similar pathways for upgrading of toluene and <i>p</i>-xylene has been found, which will undergo hydrogenation, methyl group elimination, and ring opening process, and benzene, cyclohexane, and methylcyclohexane have been found as major intermediates before ring opening. Very interestingly, the ²H NMR analysis for the deuterium-traced ring opening of catechol on Ir/γ-Al₂O₃ is almost identical to the ring opening process for phenol. The ring opening processes for guaiacol and syringol appeared to be very complicated, as expected. Benzene, phenol, toluene, cyclohexane, and methylcyclohexane have been determined to be the major products