Rational design of polymer-based absorbents: application to the fermentation inhibitor furfural

BACKGROUND: Reducing the amount of water-soluble fermentation inhibitors like furfural is critical for downstream bio-processing steps to biofuels. A theoretical approach for tailoring absorption polymers to reduce these pretreatment contaminants would be useful for optimal bioprocess design. RESULTS: Experiments were performed to measure aqueous furfural partitioning into polymer resins of 5 bisphenol A diglycidyl ether (epoxy) and polydimethylsiloxane (PDMS). Experimentally measured partitioning of furfural between water and PDMS, the more hydrophobic polymer, showed poor performance, with the logarithm of PDMS-to-water partition coefficient falling between −0.62 and −0.24 (95% confidence). In contrast, the fast setting epoxy was found to effectively partition furfural with the logarithm of the epoxy-to-water partition coefficient falling between 0.41 and 0.81 (95% confidence). Flory-Huggins theory is used to predict the partitioning of furfural into diverse polymer absorbents and is useful for predicting these results. CONCLUSION: We show that Flory-Huggins theory can be adapted to guide the selection of polymer adsorbents for the separation of low molecular weight organic species from aqueous solutions. This work lays the groundwork for the general design of polymers for the separation of a wide range of inhibitory compounds in biomass pretreatment streams

On-line analysis and in situ pH monitoring of mixed acid fermentation by Escherichia coli using combined FTIR and Raman techniques

We introduce an experimental setup allowing continuous monitoring of bacterial fermentation processes by simultaneous optical density (OD) measurements, long-path FTIR headspace monitoring of CO2, acetaldehyde and ethanol, and liquid Raman spectroscopy of acetate, formate, and phosphate anions, without sampling. We discuss which spectral features are best suited for detection, and how to obtain partial pressures and concentrations by integrations and least squares fitting of spectral features. Noise equivalent detection limits are about 2.6 mM for acetate and 3.6 mM for formate at 5 min integration time, improving to 0.75 mM for acetate and 1.0 mM for formate at 1 h integration. The analytical range extends to at least 1 M with a standard deviation of percentage error of about 8%. The measurement of the anions of the phosphate buffer allows the spectroscopic, in situ determination of the pH of the bacterial suspension via a modified Henderson-Hasselbalch equation in the 6–8 pH range with an accuracy better than 0.1. The 4 m White cell FTIR measurements provide noise equivalent detection limits of 0.21 μbar for acetaldehyde and 0.26 μbar for ethanol in the gas phase, corresponding to 3.2 μM acetaldehyde and 22 μM ethanol in solution, using Henry’s law. The analytical dynamic range exceeds 1 mbar ethanol corresponding to 85 mM in solution. As an application example, the mixed acid fermentation of Escherichia coli is studied. The production of CO2, ethanol, acetaldehyde, acids such as formate and acetate, and the changes in pH are discussed in the context of the mixed acid fermentation pathways. Formate decomposition into CO2 and H2 is found to be governed by a zeroth-order kinetic rate law, showing that adding exogenous formate to a bioreactor with E. coli is expected to have no beneficial effect on the rate of formate decomposition and biohydrogen production

Current pretreatment technologies for the development of cellulosic ethanol and biorefineries

Lignocellulosic materials, such as forest, agriculture, and agroindustrial residues, are among the most important resources for biorefineries to provide fuels, chemicals, and materials in such a way to substitute for, at least in part, the role of petrochemistry in modern society. Most of these sustainable biorefinery products can be produced from plant polysaccharides (glucans, hemicelluloses, starch, and pectic materials) and lignin. In this scenario, cellulosic ethanol has been considered for decades as one of the most promising alternatives to mitigate fossil fuel dependence and carbon dioxide accumulation in the atmosphere. However, a pretreatment method is required to overcome the physical and chemical barriers that exist in the lignin–carbohydrate composite and to render most, if not all, of the plant cell wall components easily available for conversion into valuable products, including the fuel ethanol. Hence, pretreatment is a key step for an economically viable biorefinery. Successful pretreatment method must lead to partial or total separation of the lignocellulosic components, increasing the accessibility of holocellulose to enzymatic hydrolysis with the least inhibitory compounds being released for subsequent steps of enzymatic hydrolysis and fermentation. Each pretreatment technology has a different specificity against both carbohydrates and lignin and may or may not be efficient for different types of biomasses. Furthermore, it is also desirable to develop pretreatment methods with chemicals that are greener and effluent streams that have a lower impact on the environment. This paper provides an overview of the most important pretreatment methods available, including those that are based on the use of green solvents (supercritical fluids and ionic liquids)

Emerging technologies for the production of renewable liquid transport fuels from biomass sources enriched in plant cell walls

Plant cell walls are composed predominantly of cellulose, a range of non-cellulosic polysaccharides and lignin. The walls account for a large proportion not only of crop residues such as wheat straw and sugarcane bagasse, but also of residues of the timber industry and specialist grasses and other plants being grown specifically for biofuel production. The polysaccharide components of plant cell walls have long been recognized as an extraordinarily large source of fermentable sugars that might be used for the production of bioethanol and other renewable liquid transport fuels. Estimates place annual plant cellulose production from captured light energy in the order of hundreds of billions of tons. Lignin is synthesized in the same order of magnitude and, as a very large polymer of phenylpropanoid residues, lignin is also an abundant, high energy macromolecule. However, one of the major functions of these cell wall constituents in plants is to provide the extreme tensile and compressive strengths that enable plants to resist the forces of gravity and a broad range of other mechanical forces. Over millions of years these wall constituents have evolved under natural selection to generate extremely tough and resilient biomaterials. The rapid degradation of these tough cell wall composites to fermentable sugars is therefore a difficult task and has significantly slowed the development of a viable lignocellulose-based biofuels industry. However, good progress has been made in overcoming this so-called recalcitrance of lignocellulosic feedstocks for the biofuels industry, through modifications to the lignocellulose itself, innovative pre-treatments of the biomass, improved enzymes and the development of superior yeasts and other microorganisms for the fermentation process. Nevertheless, it has been argued that bioethanol might not be the best or only biofuel that can be generated from lignocellulosic biomass sources and that hydrocarbons with intrinsically higher energy densities might be produced using emerging and continuous flow systems that are capable of converting a broad range of plant and other biomasses to bio-oils through so-called 'agnostic' technologies such as hydrothermal liquefaction. Continued attention to regulatory frameworks and ongoing government support will be required for the next phase of development of internationally viable biofuels industries.Hwei-Ting Tan, Kendall R. Corbin and Geoffrey B. Finche

Improving the bioconversion yield of carbohydrates and ethanol from lignocellulosic biomass

Thesis (Ph.D.)--University of Washington, 2012Improving the efficiency of lignocellulosic ethanol production is of the utmost importance if cellulosic bioethanol is to be competitive with fossil fuels and first generation bioethanol from starch and sucrose. Improvements in individual processes (pretreatment, saccharification, fermentation) have been ongoing, but few researchers have considered the effect that the incoming raw biomass can have on the process. It is important to understand how biomass can be altered to provide the maximum yield of hydrolysable and fermentable sugars from whatever is available. Since the moisture content is highly variable and easily altered, the effect of drying and rewetting on bioconversion was studied on switchgrass, sugarcane bagasse and hybrid poplar. For switchgrass and sugarcane bagasse, the ethanol yield after simultaneous saccharification and fermentation was improved 18-24% by increasing the moisture content by soaking prior to pretreatment. It was also found that soaking had no effect when the samples were not catalyzed with SO2 confirming that the effect of moisture content is directly related to SO2 uptake and diffusion into the biomass. In hybrid poplar, the results were similar to herbaceous biomass for chips with less than 2% absorbed SO2. However, when the SO2 uptake was increased to 3% even the air dried chips exhibited high digestibility, indicating that increased SO2 uptake can overcome the poor diffusion in dried biomass. Alongside controlling the biomass moisture content, improving knowledge and control of the processes can also increase efficiency and product yields. By monitoring reactions continuously with accurate, robust, on-line sensors, operators can detect when reactions deviate from the norm, and when they are complete. Avoiding process upsets and contamination could be the difference between an economically viable biorefinery and one that struggles to compete. Real time, continuous Raman spectroscopy was used to continuously monitor both a synthetic glucose and a lignocellulosic hydrolysate fermentation and measure glucose and ethanol. Models developed using offline HPLC validation samples had extremely high correlation between predicted and observed values for ethanol in both fermentations (R2 = 0.98 and 0.94 for synthetic and hydrolysate, respectively) while glucose proved more difficult to detect in the hydrolysate fermentation (R2 = 0.92 and 0.51). This work showed that it is possible to monitor the ethanol and glucose in a hydrolysate with a high fluorescent background

Bioconversion of mountain pine beetle-killed lodgepole pine to ethanol

Global warming is widely acknowledged as being caused by an increase in the production of greenhouse gases, largely CO₂, generated from the burning of fossil fuels such as gasoline. By offsetting a portion of gasoline usage with alternative fuels, such as ethanol, CO₂ emissions could be reduced. Bioethanol can be produced from many types of biomass, including softwoods. For maximal ethanol yield from softwoods, the most effective bioconversion process is considered by many to be SO₂-catalysed steam explosion followed by separate or simultaneous hydrolysis and fermentation. This method has been shown to be effective on both spruce and Radiata pine, although past research at UBC on Douglas-fir showed that additional delignification was necessary in order to obtain satisfactory sugar recovery and hydrolytic conversion. Another promising softwood species for bioconversion in British Columbia is lodgepole pine, which has been severely affected by the mountain pine beetle and its associated fungus and is consequently widely available and relatively inexpensive. Prior to investigating the bioconversion of lodgepole pine, the UBC steam explosion process was evaluated and was found to be comparable to that used at Lund University in Sweden. Following this, optimization of pretreatment conditions of beetle-killed lodgepole pine for maximal ethanol yield revealed that the highest ethanol yield after SSF, 77% of theoretical, was derived from substrates pretreated at 200°C, 5 min, 4% SO₂. When these and other conditions were applied to healthy, and mixed (50/50 healthy/beetle-killed) wood, the beetle-killed substrate provided higher sugar recovery after pretreatment, higher hydrolytic conversion, and higher overall ethanol yield after SSF. This was likely a result of two factors. The first, reduced uptake of SO₂ during the impregnation step effectively reduced the pretreatment severity and increased sugar recovery and fermentability. Secondly, increased fines may have improved the enzymatic digestibility of the substrate. The work in this thesis established the technical feasibility of producing ethanol from lodgepole pine in a two-step process consisting of SO₂-catalyzed steam explosion followed by SSF of the combined liquid and solid fractions. In addition, the short residence time required for SSF as well as the reduced cost of the raw material suggest that the process could be economically attractive as well.Forestry, Faculty ofGraduat