Kinetic characterization for pretreatment of timber varieties and switchgrass using diluted acid hydrolysis

In recent years, growing attention has been devoted to the use of lignocellulosic biomass as a feedstock to produce renewable carbohydrates as a source of energy products, including liquid alternatives to fossil fuels. The benefits of developing woody biomass to ethanol technology are to increase the long-term national energy security, reduce fossil energy consumption, lower greenhouse gas emissions, use renewable rather than depletable resources, and create local jobs. Currently, research is driven by the need to reduce the cost of biomass-ethanol production. One of the preferred methods is to thermochemically pretreat the biomass material and subsequently, enzymatically hydrolyze the pretreated material to fermentable sugars that can then be converted to ethanol using specialized microorganisms. The goals of pretreatment are to remove the hemicellulose fraction from other biomass components, reduce bioconversion time, enhance enzymatic conversion of the cellulose fraction, and, hopefully, obtain a higher ethanol yield. The primary goal of this research is to obtain kinetic detailed data for dilute acid hydrolysis for several timber species from the Upper Peninsula of Michigan and switchgrass. These results will be used to identify optimum reaction conditions to maximize production of fermentable sugars and minimize production of non-fermentable byproducts. The structural carbohydrate analysis of the biomass species used in this project was performed using the procedure proposed by National Renewable Energy Laboratory (NREL). Subsequently, dilute acid-catalyzed hydrolysis of biomass, including aspen, basswood, balsam, red maple, and switchgrass, was studied at various temperatures, acid concentrations, and particle sizes in a 1-L well-mixed batch reactor (Parr Instruments, ii Model 4571). 25 g of biomass and 500 mL of diluted acid solution were added into a 1-L glass liner, and then put into the reactor. During the experiment, 5 mL samples were taken starting at 100°C at 3 min intervals until reaching the targeted temperature (160, 175, or 190°C), followed by 4 samples after achieving the desired temperature. The collected samples were then cooled in an ice bath immediately to stop the reaction. The cooled samples were filtered using 0.2 μm MILLIPORE membrane filter to remove suspended solids. The filtered samples were then analyzed using High Performance Liquid Chromatography (HPLC) with a Bio-Rad Aminex HPX-87P column, and refractive index detection to measure monomeric and polymeric sugars plus degradation byproducts. A first order reaction model was assumed and the kinetic parameters such as activation energy and pre-exponential factor from Arrhenius equation were obtained from a match between the model and experimental data. The reaction temperature increases linearly after 40 minutes during experiments. Xylose and other sugars were formed from hemicellulose hydrolysis over this heat up period until a maximum concentration was reached at the time near when the targeted temperature was reached. However, negligible amount of xylose byproducts and small concentrations of other soluble sugars, such as mannose, arabinose, and galactose were detected during this initial heat up period. Very little cellulose hydrolysis yielding glucose was observed during the initial heat up period. On the other hand, later in the reaction during the constant temperature period xylose was degraded to furfural. Glucose production from cellulose was increased during this constant temperature period at later time points in the reaction. The kinetic coefficient governing the generation of xylose from hemicellulose and the generation of furfural from xylose presented a coherent dependence on both temperature and acid concentration. However, no effect was observed in the particle size. There were three types of biomass used in this project; hardwood (aspen, basswood, and red maple), softwood (balsam), and a herbaceous crop (switchgrass). The activation energies and the pre-exponential factors of the timber species and switchgrass were in a range of 49 - 180 kJ/mol and from 7.5x104 - 2.6x1020 min-1, respectively, for the xylose formation model. In addition, for xylose degradation, the activation energies and the preexponential factors ranged from 130 - 170 kJ/mol and from 6.8x1013 - 3.7x1017 min-1, respectively. The results compare favorably with the literature values given by Ranganathan et al, 1985. Overall, up to 92 % of the xylose was able to generate from the dilute acid hydrolysis in this project.

Evaluating the relationship between moisture induced expansion and horizontal stress orientation in samples from the nonesuch formation

High horizontal stresses can cause numerous ground control problems in mines and other underground structures ultimately impacting worker safety, productivity and the economics of an underground operation. Mine layout and design can be optimized when the presence and orientation of these stresses are recognized and their impact minimized. A simple technique for correlating the principal horizontal stress direction in a sedimentary rock mass with the preferential orientation of moisture induced expansion in a sample of the same rock was introduced in the 1970s and has since gone un-reported and unused. This procedure was reexamined at a locality near the original test site at White Pine, Michigan in order to validate the original research and to consider its usefulness in mining and civil engineering applications in high horizontal stress conditions. This procedure may also be useful as an economical means for characterizing regional stress fields.

The Copper Strike of 1968-1969

In May of 1968, workers at the Kingston mine, a branch of the Calumet Division of Universal Oil Products walked off the site in protest of a safety issue involving a man-car. Knowing their contracts were due for negotiation in just a few months, the workers quickly returned, only to find themselves striking yet again just three months later, when negotiations failed. Requesting pay equal to that of the workers at the nearby White Pine mine was unacceptable to the heads of Universal Oil, the corporation which bought the long running Calumet & Hecla just a year earlier in 1968. The strike would last for nine months, ending in a total shutdown of all mining operations on the Keweenaw Peninsula, and bring an economic hardship to the area that would take decades to recover from. The Copper Strike of 1968-1969 is often forgotten, though extremely important to the story of the copper industry in Michigan, as well as to the United States. This paper has not yet been submitted.

Spatial and Temporal Evolution of the Volcanics and Sediments of the Kenya Rift

New volumetric and mass flux estimates have been calculated for the Kenya Rift. Spatial and temporal histories for volcanic eruptions, lacustrine deposition, and hominin fossil sites are presented, aided by the compilation of a new digital geologic map. Distribution of volcanism over time indicates several periods of southward expansion followed by relative positional stasis. Volcanism occurs throughout the activated rift length, with no obvious abandonment as the rift system migrated. The main exception is a period of volcanic concentration around 10 Ma, when activity was constrained within 2° of the equator. Volumes derived from seismic data indicate a total volume of c. 310,000 km3 (2.47 x 1010 kg/yr ), which is significantly more than the map-derived volumes found here or published previously. Map-based estimates are likely affected by a bias against recognizing small volume events in the older record. Such events are, however, the main driver of erupted volume over the last 5 Ma. A technique developed here to counter this bias results in convergence of the two volume estimation techniques. Relative erupted composition over time is variable. Overall, the erupted material has a mafic to silicic ratio of 0.9:1. Basalts are distinctly more common in the Turkana region, which previously experienced Mesozoic rifting. Despite the near equal ratio of mafic to silicic products, the Kenya Rift otherwise fits the definition of a SLIP. It is proposed that the compositions would better fit the published definition if the Turkana region was not twice-rifted. Lacustrine sedimentation post-dates initial volcanism by about 5 million years, and follows the same volcanic trends, showing south and eastward migration over time. This sedimentation delay is likely related to timing of fault displacements. Evidence of hominin habitation is distinctly abundant in the northern and southern sections of the Kenya Rift, but there is an observed gap in the equatorial rift between 4 and 0.5 million years ago. After 0.5 Ma, sites appear to progress towards the equator. The pattern and timing of hominid site distributions suggests that the equatorial gap in habitation may be the result of active volcanic avoidance.