Ted R. Aulich

Higher-alcohols biorefinery: improvement of catalyst for ethanol conversion.

The concept of a biorefinery for higher-alcohol production is to integrate ethanol and methanol formation via fermentation and biomass gasification, respectively, with, conversion of these simple alcohol intermediates into higher alcohols via the Guerbet reaction. 1-Butanol results from the selfcondensation of ethanol in this multistep reaction occurring on a single catalytic bed. Combining methanol with ethanol gives a mixture of propanol, isobutanol, and 2-methyl-1-butanol. All of these higher alcohols are usefulas solvents, chemical intermediates, and fuel additives and, consequently, have higher market values than the simple alcohol intermediates. Several new catalysts for the condensation of ethanol and alcohol mixtures to higher alcohols were designed and tested under a variety of conditions. Reactions of methanol ethanol mixtures gave as high as 100% conversion of the ethanol to form high yields of isobutanol with smaller amounts of 1-propanol, the amounts in the mixture depending on the starting mixture. The most successful catalysts are multifunctional with basic and hydrogen transfer components.

Impacts of Biodiesel on Pollutant Emissions of a JP-8–Fueled Turbine Engine

Abstract The impacts of biodiesel on gaseous and particulate matter (PM) emissions of a JP-8–fueled T63 engine were investigated. Jet fuel was blended with the soybean oil-derived methyl ester biofuel at various concentrations and combusted in the turbine engine. The engine was operated at three power settings, namely ground idle, cruise, and takeoff power, to study the impact of the biodiesel at significantly different pressure and temperature conditions. Particulate emissions were characterized by measuring the particle number density (PND; particulate concentration), the particle size distribution, and the total particulate mass. PM samples were collected for off-line analysis to obtain information about the effect of the biodiesel on the polycyclic aromatic hydrocarbon (PAH) content. In addition, temperature-programmed oxidation was performed on the collected soot samples to obtain information about the carbonaceous content (elemental or organic). Major and minor gaseous emissions were quantified using a total hydrocarbon analyzer, an oxygen analyzer, and a Fourier Transform IR analyzer. Test results showed the potential of biodiesel to reduce soot emissions in the jet-fueled turbine engine without negatively impacting the engine performance. These reductions, however, were observed only at the higher power settings with relatively high concentrations of biodiesel. Specifically, reductions of ∼15% in the PND were observed at cruise and takeoff conditions with 20% biodiesel in the jet fuel. At the idle condition, slight increases in PND were observed; however, evidence shows this increase to be the result of condensed uncombusted biodiesel. Most of the gaseous emissions were unaffected under all of the conditions. The biodiesel was observed to have minimal effect on the formation of polycyclic aromatic hydrocarbons during this study. In addition to the combustion results, discussion of the physical and chemical characteristics of the blended fuels obtained using standard American Society for Testing and Materials (ASTM) fuel specifications methods are presented.

Gasoline Evaporation–Ethanol and Nonethanol Blends

Tests were performed to compare the evaporation rate of 10 volume percent (vol%) ethanol-blended gasoline (E10) with the evaporation rate of its base gasoline. Weight loss, temperature, pressure, and humidity were monitored as lab-blended E10 and base gasolines were evaporated concurrently from glass cylinders placed on balances located side by side under an exhaust hood. The averaged results of four tests at about 70°F showed that the E10 lost more total weight to evaporation than the base fuel, but less gasoline. The increased weight was due to ethanol, which was present in the E10 evaporative emissions at concentrations of about 13 weight percent (wt%). In two-hour tests at temperatures near 70°F, during which 4.5 to 5.3 wt% of initial fuel samples were evaporated, E10 fuels lost an average of about 5% less gasoline than their base fuels. A similar result was obtained for a one-hour test, during which about 2.4 to 2.5 wt% of the initial fuel samples were evaporated. Gas chromatography (GC) component an...

Preparation of deuterated aromatic hydrocarbons, heteroatom-containing aromatics, and polychlorinated biphenyls as internal standards for GC/MS analysis

SummaryDeuterated alkyl benzenes, polycyclic aromatic hydrocarbons (PAHs), and N-, S-, O-, and Cl-containing aromatics were prepared using a single reagent containing D2O, DCl, and chromium. The method requires little specialized equipment or synthesis expertise, and results in the exchange of all aromatic protons for deuterium. The isotopic purities of the deuterated products were controlled by the amount of reagent added, and in most cases, isotopic purities of 95% were achieved. Under appropriate conditions of temperature and time, no significant chemical degradation of the aromatic compounds occurred. The method also works well with complex mixtures and large (30 g) quantities of aromatic compounds as demonstrated by the deuteration of a mixture of polychlorinated biphenyls (Aroclor 1254) and a coal-derived anthracene oil.

Ester fuels and chemicals from biomass

Bench-scale research demonstrated that using an efficient esterification step to integrate an ethanol with a carboxylic acid fermentation stream offers potential for producing valuable ester feedstocks and fuels. Polar organic acids from bacterial fermentations are difficult to extract and purify, but formation of the ammonium salts and their conversion to esters facilitates the purifications. An improved esterification procedure gave high yields of esters, and this method will lower the cost of ester production. Fuel characteristics have been determined for a number of ester-gasoline blends with promising results for lowering Reid vapor pressure and raising octane numbers.

Gasoline evaporative emissions -- Ethanol effects on vapor control canister sorbent performance

Tests were performed at the University of North Dakota Energy and Environmental Research Center (EERC) to compare the evaporation rate of 10 volume percent ethanol-blended gasoline (E10) with the evaporation rate of its base gasoline. Averaged results of the tests demonstrated that at 70 F the E10 fuel lost more total weight to evaporation than its base fuel, but less gasoline. The increased weight was due to ethanol, which was present in the E10 evaporative emissions at concentrations of about 13 weight percent.Subsequently, a test system was designed to investigate how the presence of ethanol in the evaporative emission affects the fuel evaporation canister sorbent performance. The system is equipped with a Fourier transform infrared spectrometer (FT-IR) to monitor sorbent breakthrough emission concentrations and compound types. Preliminary data obtained using sorbent from commercial canisters have shown that ethanol vapor breakthrough occurs significantly later than gasoline hydrocarbon vapor breakthrough.

Literature Survey of Crude Oil Properties Relevant to Handling and Fire Safety in Transport.

Several fiery rail accidents in 2013-2015 in the U.S. and Canada carrying crude oil produced from the Bakken region of North Dakota have raised questions at many levels on the safety of transporting this, and other types of crude oil, by rail. Sandia National Laboratories was commissioned by the U.S. Department of Energy to investigate the material properties of crude oils, and in particular the so-called “tight oils” like Bakken that comprise the majority of crude oil rail shipments in the U.S. at the current time. The current report is a literature survey of public sources of information on crude oil properties that have some bearing on the likelihood or severity of combustion events that may occur around spills associated with rail transport. The report also contains background information including a review of the notional “tight oil” field operating environment, as well a basic description of crude oils and potential combustion events in rail transport.

GAS INDUSTRY GROUNDWATER RESEARCH PROGRAM

The objective of the research described in this report was to provide data and insights that will enable the natural gas industry to (1) significantly improve the assessment of subsurface glycol-related contamination at sites where it is known or suspected to have occurred and (2) make scientifically valid decisions concerning the management and/or remediation of that contamination. The described research was focused on subsurface transport and fate issues related to triethylene glycol (TEG), diethylene glycol (DEG), and ethylene glycol (EG). TEG and DEG were selected for examination because they are used in a vast majority of gas dehydration units, and EG was chosen because it is currently under regulatory scrutiny as a drinking water pollutant. Because benzene, toluene, ethylbenzene, and xylenes (collectively referred to as BTEX) compounds are often very closely associated with glycols used in dehydration processes, the research necessarily included assessing cocontaminant effects on waste mobility and biodegradation. BTEX hydrocarbons are relatively water-soluble and, because of their toxicity, are of regulatory concern. Although numerous studies have investigated the fate of BTEX, and significant evidence exists to indicate the potential biodegradability of BTEX in both aerobic and anaerobic environments (Kazumi and others, 1997; Krumholz and others, 1996; Lovely and others, 1995; Gibson and Subramanian, 1984), relatively few investigations have convincingly demonstrated in situ biodegradation of these hydrocarbons (Gieg and others, 1999), and less work has been done on investigating the fate of BTEX species in combination with miscible glycols. To achieve the research objectives, laboratory studies were conducted to (1) characterize glycol related dehydration wastes, with emphasis on identification and quantitation of coconstituent organics associated with TEG and EG wastes obtained from dehydration units located in the United States and Canada, (2) evaluate the biodegradability of TEG and DEG under conditions relevant to subsurface environments and representative of natural attenuation processes, and (3) examine the possibility that high concentrations of glycol may act as a cosolvent for BTEX compounds, thereby enhancing their subsurface mobility. To encompass a wide variety of potential wastes representative of different natural gas streams and dehydration processes, raw, rich, and lean glycol solutions were collected from 12 dehydration units at eight different gas-processing facilities located at sites in Texas, Louisiana, New Mexico, Oklahoma, and Alberta. To generate widely applicable environmental fate data, biodegradation and mobility experiments were performed using four distinctly different soils: three obtained from three gas-producing areas of North America (New Mexico, Louisiana, and Alberta), and one obtained from a North Dakota wetland to represent a soil with high organic matter content.

On-Demand Hydrogen via High-Pressure Water Reforming for Military Fuel Cell Applications

Researchers have developed a high-pressure water-reforming (HPWR) process that produces high-pressure hydrogen from a jet fuel feedstock. Converting petroleum-based fuels to hydrogen for fuel cell use is a unique approach to reducing military petroleum consumption by improving petroleum utilization efficiency. HPWR is an attractive option because, unlike traditional steam methane reforming, it does not require postreformer hydrogen compression and storage. A HPWR apparatus was designed and manufactured. Several catalysts were tested for their ability to produce high-pressure hydrogen from jet fuel. S-8, which is a jet fuel derived from natural gas, was used as a model feedstock for initial experiments because the fuel is sulfur and aromatics free. After optimizing with S-8, JP-8 will be utilized for future experiments. The most promising catalyst produced a 4000 psi (gauge) product gas stream that contained 54 trial % hydrogen. These experimental results show that HPWR is a promising solution for high-pressure hydrogen production as a key step toward reducing military petroleum use.

Subtask 3.9 - Direct Coal Liquefaction Process Development

The Energy and Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) and Accelergy Corporation, an advanced fuels developer with technologies exclusively licensed from ExxonMobil, undertook Subtask 3.9 to design, build, and preliminarily operate a bench-scale direct coal liquefaction (DCL) system capable of converting 45 pounds/hour of pulverized, dried coal to a liquid suitable for upgrading to fuels and/or chemicals. Fabrication and installation of the DCL system and an accompanying distillation system for off-line fractionation of raw coal liquids into 1) a naphtha middle distillate stream for upgrading and 2) a recycle stream was completed in May 2012. Shakedown of the system was initiated in July 2012. In addition to completing fabrication of the DCL system, the project also produced a 500-milliliter sample of jet fuel derived in part from direct liquefaction of Illinois No. 6 coal, and submitted the sample to the Air Force Research Laboratory (AFRL) at Wright Patterson Air Force Base, Dayton, Ohio, for evaluation. The sample was confirmed by AFRL to be in compliance with all U.S. Air Force-prescribed alternative aviation fuel initial screening criteria.