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High-performance biomass molecule for better Diesel fuel

In our previous blog posts we have discussed resource recovery from waste related to the wastewater treatment and showed improved and enforced regulations have a positive impact on water quality and public health. Now we show that clever catalytic processes can be used to extract valuable commodities from waste agricultural products.

Low-cost waste biomass can serves as renewable source to produce a sustainable alternative to fossil carbon resources in order to meet the need for the environmentally friendly energy. For example, the C2 and C4 ethers derived from carboxylic acids obtained from biomass are promising fuel candidates. It has been reported, that when using ethers biofuel parameters such as ignition quality and sooting have significantly improved compared to commercial petrodiesel (>86% yield sooting index reduction). Ignition quality (cetane number) was improved by more than 56%.

The scientists from National Renewable Energy Laboratory, together with their colleagues from Yale University, Argonne National Laboratory, and Oak Ridge National Laboratory are working on a joint project with the goal of co-optimization of fuels and engines. The research focuses on improving fuel economy and vehicle performance while at the same time reducing emissions through identification of blendstock derived from biomass.

In their recent article, published in the renown journal PNAS, a novel molecule, 4-butoxyheptane, has been isolated in a high-yielding catalytic process from lignocellulosic biomass. Due to its high oxygen content, this advantageous blendstock can improve the performance of diesel fuel by reducing the intrinsic sooting tendency of the fuel upon burning.

The research team has reported a “fuel-property-first” approach in order to accelerate the development process of producing suitable oxygenate diesel blendstocks.

This rational approach is based on following steps:

  1. Fuel Property Characterization – includes mapping and identification of accessible oxygenates products; predicting fuel properties of those products a priori by computationally screening
  2. Production process – development of the conversion pathway starting from biomass. Includes continuous, solvent-free synthesis process based on a metal/acid catalyst on a liter-scale production of the chosen compound
  3. Testing and analysis – with the goal to validate and compare fuel property measurements against predictions

Fuel properties of target oxygenates that have been investigated are related to the health- and safety- aspects such as flash point, biodegradation potential, and toxicity/water solubility, as well as market and environmental aspects such as ignition quality (cetane number), viscosity, lower heating value and sooting potential reduction with oxygenated blendstocks. As a result, 4-butoxyheptane, looked as the most promising molecule to blend with and improve traditional diesel. It has been shown, that the fuel property measurements largely agreed with predictive estimations, validating accuracy of the a priori approach for blendstock selection.

The mixture at 20-30% blend of 4-butoxyheptane molecule into diesel fuel has been suggested as favorable. The improvement in autoignition quality as well as significant reduction of yield sooting index from 215 to 173 (20% reduction) demonstrates that the incorporation of this molecule could improve diesel emission properties without sacrificing performance. In terms of flammability, toxicity, and storage stability, the oxygenate fuel has been evaluated to be at low-risk.

Life-cycle analysis show that this mixture could be cost-competitive and have the potential in significant greenhouse gas reductions (by 50 to 271%) in comparison to petrodiesel.

As research is a perpetual process, more of it is necessary and should include testing of the bioblendstock in an actual engine and production of the biofuel in an integrated process directly from biomass.

(Mima Varničić, 2020, photo: Pixabay)

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Bioelectrically engineered fuel produced by yeasts

Yeasts such as Saccharomyces cerevisiae are, as the name suggests, used for large scale production of beer and other alcoholic beverages. Their high salt and ethanol tolerance not only makes them useful for the production of beverages, but also suitable for the production of combustion fuels at high alcohol concentrations. Besides ethanol, long-chain fusel alcohols are of high interest for biofuel production as well. Bioethanol is already mixed with gasoline and thus improves the CO2 balance of internal combustion engines. This liquid biofuel is made from either starch or lignocellulose. The production and use of bioethanol supports local economies, reduces CO2 emissions and promotes self-sufficiency. The latter is especially important for resource-depleted landlocked countries.

In order to efficiently produce ethanol and other alcohols from lignocellulose hydrolysates, yeasts must use both glucose and pentoses such as xylose and arabinose. This is because biomass is rich in both lignocellulose and thus glucose and xylose. However, this is also the main disadvantage of using Saccharomyces cerevisiae because it does not ferment xylose. Consequently, the identification of another yeast strains capable of fermenting both these sugars could solve the problem. Highly efficient yeasts can be grown in co-cultures with other yeasts capable of lignocellulose fermentation for ethanol production. Such a yeast is, for example, Wickerhamomyces anomalous.

To further improve ethanol production, bioelectric fermentation technology supporting traditional fermentation can be used. The microbial metabolism can thus be controlled electrochemically. There are many benefits of this technology. The fermentation process becomes more selective due to the application of an electrochemical potential. This, in turn, increases the efficiency of sugar utilization. In addition, the use of additives to control the redox equilibrium and the pH is minimized. Ultimately cell growth can be stimulated, further increasing alcohol production.

Such bioelectric reactors are galvanic cells. The electrodes used in such a bioelectric reactor may act as electron acceptors (anodes) or source (cathodes). Such electrochemical changes affect the metabolism and cell regulation as well as the interactions between the yeasts used. Now, a research group from Nepal (a resource-depleted landlocked country) has used new yeast strains of Saccharomyces cerevisiae and Wickerhamomyces anomalous in a bioelectric fermenter to improve ethanol production from biomass. The results were published in the journal Frontiers in Energy Research.

For their study, the researchers chose Saccharomyces cerevisiae and Wickerhamomyces anomalus as both are good ethanol producers. The latter is to be able to convert xylose to ethanol. After the researchers applied a voltage to the bioelectrical system, ethanol production doubled. Both yeasts formed a biofilm on the electrodes, making the system ideal for use as a flow-through system because the microorganisms are not washed out.

Saccharomyces cerevisiae cells in a brightfield microscopic image of 600-fold magnification (Foto: Amanda Luraschi)

The researchers speculated that the increased ethanol production was due to the better conversion of pyruvate to ethanol − the yeast’s central metabolic mechanism. The researchers attributed this to accelerated redox reactions at the anode and cathode. The applied external voltage polarized the ions present in the cytosol, thus facilitating the electron transfer from the cathode. This and the accelerated glucose oxidation probably led to increased ethanol production.

Normally, pyruvate is converted into ethanol in fermentation yeast. External voltage input can control the kinetics of glucose metabolism in Saccharomyces cerevisiae under both aerobic and anaerobic conditions. Intracellular and transplasmembrane electron transfer systems play an important role in electron transport across the cell membrane. The electron transfer system consists of cytochromes and various redox enzymes, which confer redox activity to the membrane at certain sites.

The authors also found that an increased salt concentration improved conductivity and therefore ethanol production. The increased ethanol production from lignocellulosic biomass may have been also be due to the presence of various natural compounds that promoted yeast growth. When the cellulose acetate membrane was replaced by a Nafion™ membrane, ethanol production also increased. This was perhaps due to improved transport of xylose through the Nafion™ membrane as well as the decrease of the internal resistance. A further increase of ethanol production was observed when the bioelectrical reactor was operated with fine platinum particles coated on the platinum anode and neutral red deposited on the graphite cathode.

Several yeast cultures from left to right: Saccharomyces cerevisiae, Candida utilis, Aureobasidium pullulans, Trichosporum cutaneum, Saccharomycopsis capsularis, Saccharomycopsis lipolytica, Hanseniaspora guilliermondii, Hansenula capsulata, Saccharomyces carlsbergensis, Saccharomyces rouxii, Rhodotorula rubra, Phaffia rhodozyba, Cryptococcus laurentii, Metschnikowia pulcherrima, Rhodotorula pallida

At Frontis Energy, we think that the present study is promising. However, long-chain fusel alcohols should be considered in the future as they are less volatile and better compatible with current internal combustion engines. These can also be easily converted into the corresponding long-chain hydrocarbons.