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Researchers at Argonne National Laboratory have developed a low-cost process that accelerates biological methane production rates at least fivefold — the Enhanced Renewable Methane Production System. The system could enhance biological methane production at wastewater treatment plants, farms, and landfills. This system addresses one of the largest barriers to the expansion of renewable methane — the naturally slow rate of production. To overcome this challenge, Argonne researchers examined the natural biology of methane production, the natural processes for carbon dioxide sequestration, and the environmental quality of the water found in coal bed methane wells. Their research led to the novel, low-cost treatment to accelerate biological methane production while sequestering CO2. The treatment enhances the heating value of biogas, delivering a gas that is close to pipeline quality. In addition, the renewable methane process leaves coal's environmental pollutants, such as sulfur and mercury, in the ground, avoiding their emissions.
The Enhanced Renewable Methane Production System provides a method for biological methane production from a carbonaceous feedstock to generate methane, while simultaneously sequestering the CO2 produced during the process by reacting with magnesium and calcium silicate rocks. This process links the biological conversion (renewable carbon source being converted to methane and carbon dioxide) to a geochemical mechanism (producing solid carbonate-enriched minerals), thus sequestering the CO2.
NREL has developed the following laboratory analytical procedures (LAPs) for standard biomass analysis. The American Society for Testing and Materials (ASTM) and the Technical Association of the Pulp and Paper Industry (TAPPI) may have adopted similar procedures. ASTM and TAPPI versions may be ordered from those organizations.
Near-infrared (NIR) calibration models are created by applying multivariate calibration methods to the combination of wet chemistry data and NIR spectra of a given set of biomass samples. Wet chemical compositional data and NIR spectra exist for the following types of biomass samples: corn stover, switchgrass, mixed hardwoods, mixed softwoods, sorghum, and miscanthus. These samples may be feedstock samples, washed and dried solids from one or more pretreatment processes, liquors derived from one or more pretreatment processes, or whole pretreated slurries.
Recent investigations by a number of groups have shown that a beta zeolite catalyst (and other solid Brønsted acids) will convert methanol and/or dimethyl ether (DME) to iso-alkanes such as triptane (2,2,3-trimethylbutane), with uniquely high selectivity to C4 and C7 (termed the DME to high octane gasoline process or DTHOG). In comparison, the Exxon-Mobil methanol to gasoline (MTG) process produces a broader mixture of hydrocarbons, which is heavy in benzene, toluene, and xylene (BTX). DTHOG is milder than MTG (350-450 °F vs. 650-950 °F and 130 psia vs. 315 psia), thus offering the benefit of reduced capital and operating costs for the reactor. However, similar to MTG, this new low-temperature, selective production of alkanes is still a hydrogen-deficient process. That is, to produce alkanes, a quantitative production of aromatics is required to maintain stoichiometry—a result of oxygen from methanol or DME being rejected as water.
Scientists at the National Renewable Energy Laboratory (NREL) have developed a catalyst formulation and structure that is capable of incorporating hydrogen from gaseous co-fed H2 into methylation and alkylation products without altering aliphatic hydrocarbon selectivity or lowering reaction rates. Volumetric and gravimetric activities are increased and the rate of formation of heavy aromatic residues is decreased. The catalysts are comprised of a beta zeolite modified with Cu, Ga, other non-noble metals, and combinations thereof. The metals provide sites for H2 dissociation, hydrogen addition, and hydrogen abstraction, all of which modulate critical reaction steps—providing H for alkane formation and H removal for alkene formation, bringing products back into the carbon chain growth pathway and minimizing side-reactions that produce unwanted byproducts. The metals work with the Brønsted acids of the zeolite, which act as the catalyst for alkene methylation and carbon chain growth. Physical mixtures of the metal catalyst and zeolite do not yield the same benefits. Metal loadings are low (< 5 wt%) and include metals in metallic clusters, oxide clusters, and cationic forms.
Researchers at the Joint BioEnergy Institute (JBEI) have developed a hyperthermophilic cellobiohydrolase protein (CBH) to break down cellulose into cellobiose at high temperatures. The JBEI CBH can be used in concert with JBEI endoglucanases (or any other endoglucanase with a similar temperature and ph profile) in high concentrations of ionic liquid. There is no loss of activity in ionic liquid concentrations up to 20%, and the enzyme cocktail is tolerant of ionic liquid concentrations of up to 50%. Therefore, the JBEI technology opens the possibility of one pot saccharification of lignocellulosic biomass. In addition, the JBEI technology is compatible, theoretically, with other pretreatment methods such as dilute acid and ammonia fiber explosion.
The JBEI CBH, isolated from Caldicellulosiruptor saccarolyticus, shows high CBH activity against insoluble substrates and has a higher tolerance to ionic liquid than a commercial enzyme cocktail developed for enzymatic hydrolysis of biomass. The enzyme retained more than 75% of the original activity over four days of incubation at 70ºC. Further, the technology functions at high temperatures (up to 80ºC), thus reducing the risk of contamination by other microorganisms
Current techniques treat biomass with a combination of high temperatures and an acid or base, or chemicals such as lime. One disadvantage of this method is that the industrial enzymes used to break down cellulose are not compatible with such harsh treatments. Therefore, single pot pretreatment/saccharification is impossible. In addition, current approaches create unwanted byproducts that interfere with the downstream hydrolysis and fermentation and do not lead to complete hydrolysis of the cellulose to sugars.
Ionic liquids have been shown to be effective in fully solubilizing lignocellulosic biomass. However, the addition of anti-solvents to separate the solubilized components of biomass (cellulose, hemicellulose and lignin) is an expensive and time consuming step. This new JBEI technology eliminates this step and maximizes hydrolysis.
EIO-2745 is compatible with JBEI invention EJIB-2666, Thermophilic Cellulases Compatible with Ionic Liquid Pretreatment.
FOLIUM is a research project aimed at producing high-density liquid fuels in the green biomass of tobacco. By introducing genetic material from microorganisms and other plants, tobacco can synthesize hydrocarbon fuels in its leaves and stems. Also, tobacco can be engineered to increase efficiency of CO2 uptake and solar energy capture. Coupled with improvements in agricultural practices, these approaches will increase the yield of fuel production in tobacco.
FOLIUM is an innovative technology created by LBNL scientists in conjunction with the University of California, Berkeley, the Kentucky Tobacco Research and Development Center at the University of Kentucky, and the Department of Energy’s Advanced Research Projects Agency – Energy, that genetically engineers tobacco plants to act as biological factories to produce hydrocarbons, chemicals that can be used as substitutes for crude oil. LBNL scientists’ patented gene modifications that allow tobacco plants to generate alkanes and terpenes (the foundations of petroleum) in the tobacco leaves provide the ability to create advanced biofuels with lower carbon intensity than gasoline and first-generation biofuels.
This technology has the potential to overcome the three key challenges of second-generation biofuels due to a mix of advantages provided by the plant itself, the gene modifications, and the co-products extracted.
Ethanol is the clean, renewable, domestic form of gasoline the U.S. needs to decrease its dependence on foreign oil and mitigate pollution from vehicles. However, the current high cost of ethanol production is preventing this renewable fuel from becoming widespread.
NREL has addressed this cost issue in the fermentation step of ethanol production by developing genetically engineered bacteria known as Zymomonas mobilis 8b. Traditional yeasts have the ability to ferment six-carbon sugars, but are unable to ferment five-carbon sugars. This makes for a low yield of ethanol, or if fermented by two separate organisms in two separate fermentation tanks, a high capital cost for ethanol. In response, NREL scientists have taken the bacterium Zymomonas mobilis, which naturally only ferments six-carbon sugars, and genetically engineered it to express foreign genes encoding enzymes needed to ferment five-carbon sugars.
Zymomonas mobilis is known for its ability to rapidly and efficiently convert cellulosic glucose (six-carbon) substrates into ethanol at a low pH in an anaerobic culture, and in a medium which contains the inhibitory compounds typically associated with lignocellulosic hydrolysis. However, six-carbon sugars only make up 30-40% of a typical biomass feedstock and Z. mobilis cannot ferment the remaining five-carbon sugars, such as the xylose from hemicellulose and arabinose from switchgrass and corn fiber. Thus, achieving a high rate of conversion efficiency in the fermentation of five-carbon sugars is vital to the commercial production of fuels and chemicals from renewable substrates.
In response to this challenge, researchers at NREL have utilized a transposon and a plasmid shuttle vector for stable insertion of four exogenous genes from the yeast Saccharomyces cervisiae into the bacterial genome of Zymomonas mobilis. The transposon is useful for stable insertion of foreign genes into a bacterial genome and comprises of at least one operon having structural genes encoding enzymes from the group xylAsylB, araBAD, and tal/tkt, and at least one promoter for expression of the structural genes in the bacterium, a pair of inverted insertion sequences, the operons contained inside the insertion sequences, and a transposase gene located outside of the insertion sequences. The plasmid shuttle vector is useful for the transformation of foreign genes into a bacterial genome.
Previous variants of Z. mobilis are capable of fermenting glucose, xylose, and arabinose at very low conversion efficiency. Additionally, these strains frequently become unstable when grown in the absence of selection pressure or when they have to compete with other organisms such as those in the simultaneous-saccharification-fermentation processes. Z. mobilis 8b exhibits substantially improved stability and can retain native activity for producing pentose and hexose-fermenting enzymes for 80-160 generations, up to 4x more stable than other strains of Zymomonas.
The market for unsaturated polyesters, or UPEs, is projected to reach an excess of 10 Billion USD in 2020. UPE resins are versatile materials used in various industries due to their role in forming durable, light weight structures when cross-linked with monomers. Cross-linking monomers with unsaturated polyesters creates structures called fiber reinforced plastics, or FRPs. The current composite materials used in the production of FRPs possess limited recyclability and negatively impact the environment.
The current reports of producing UPE with renewable resources focus on utilizing itaconic acid to form unsaturated double bonds or using partially hydrogenated muconic acid to form unsaturated single bonds and are used to create polyamides.
NREL researchers have developed molecularly tunable UPEs through the use of bio-derived muconic acid. Bio-derived muconic acid is a value-added renewable monomer that is useful in the production of cross-linkable resins. This bio-derived muconic acid is also useful in the synthesis of linear biopolymers to use as UPEs. Using bio-based materials allows for the UPE to be molecularly tunable and alter its' thermal properties of glass transition, degradation, and melting temperatures. Molecularly tunable UPEs are desirable and advantageous because of their durability and rigidness, their ability to generate economic savings, and their ability to lessen the impact on the environment.
The global demand for ammonia (NH3) is projected to reach 160 million tons in 2020, according to the Research and Markets report, Ammonia Global Market to 2020. In addition, the production of NH3, which makes up the single largest input of fixed nitrogen (N) into the global biogeochemical cycle, accounts for approximately 1% to 2% of the world’s energy consumption. The process of producing NH3 is a kinetically complex and energetically challenging multistep reaction, where, in the Haber Bosch process, NH3 is produced via a dissociative reaction involving co-activation of H2 and N2 over a Fe-based catalyst. However, this process ultimately yields significant amounts of CO2 and uses fossil fuels to produce the H2 used in the reaction through steam reforming and to achieve the high temperatures and pressures necessary to drive the reaction. Therefore, there is a need for a more energy-efficient and sustainable method of producing NH3.
Scientists at NREL have developed an energy-efficient and sustainable method of producing NH3 that involves the use of novel biohybrid naoparticle comprised of cadmium sulfide (CdS) nanocrystals and a nitrogenase molybedenum-iron (MoFe) enzyme. These biohybride complexes photocatalytically drive the enzymatic reduction of N2 to NH3. The resulting NH3 and H can then be separated to isolate NH3. Furthermore, this novel process does not emit CO2, and can utilize excess energy generated from the light-harvesting process for modular production.
An ORNL invention uses a unique molecular surface imprinting technique to make sorbent materials that can be tailored to target specific molecules. The mesoporous, ordered sorbents can sense, quantify, and remove toxic ions from effluents. The method offers a new class of chemical tools for industrial cleanup processes.
A major challenge facing mining and energy industries is the removal of toxic metal ions from process water or gas. The ORNL invention improves on existing technology by offering mesoporous sorbents that feature fast kinetics, high capacity, high selectivity, and molecule-specific capability. The invention can separate toxic metals from process effluents and detect and target amino acids, drugs, herbicides, and TNT in composites. Existing bulk molecular imprinting techniques have unfavorable process kinetics because the mass molecular transfer takes place through microporous channels. In addition, the cavities of conventional methods are extremely diverse, which reduces their ability to select target molecules.
The invention entails mixing a template molecule with an ordered mesoporous substrate. In solution, the template molecule binds to a bifunctional ligand in the substrate. When treated with an acid solution, evaporated, and titrated to a neutral pH, a highly tooled mesoporous sorbent results. The invention is a generic technique and can be applied to make solid-state sorbents for any toxic ion.
Researchers at ORNL developed a method to engineer and fabricate nanoscale reaction vessels that mimic biological cells. The picoliter-size reaction vessls have nanoscale pores that allow molecules to enter and exit based on their size, much as molecules do in living cells. This method can eventually be used to contain and create more complex networks. The invention holds great promise for industry and research, where synthetic biologists can match the scale of biological systems and create biologically inspired devices.
In this invention, a reaction vessel is made in a microchannel by etching a
substrate. The microchannel has a width of 1000 micrometers (millionths of a
meter) or less and the device has side walls on the order of 2 micrometers. Pores
in the sidewall of the device have a width of 1 to 500 nanometers (billionths of
a meter) and are etched to create an opening between the interior of the vessel
and the microfluidically controlled environment. Nucleic acids and enzymes can
then be located inside the vessel and the pores can be modified to have physical
or chemical properties that selectively restrict passage of these materials into or
out of the vessel. Further, a coating on the pore can be used to control the pore
opening when a signal is applied.
A faster, less expensive, more accurate and more reliable method for DNA sequencing has been developed at ORNL. The method takes a high-frequency measurement on a single strand of DNA or RNA deposited on a substrate using an alternating current (AC). The data is used as a criterion to identify the genetic sequence.
Sequencing DNA is crucial for future breakthroughs in biological and biomedical research. Until now, DNA sequencing for medical applications has been restricted by the high cost of the work. The technology includes one electrode located on the dielectric surface of a substrate and a second that is separated from the first by a gap enabling a nucleic acid strand to pass through. An AC capacitance measurement assembly is connected to the first and second electrodes and configured to generate measurement data. The nucleic acid strand transport mechanism located on the dielectric surface of the substrate is also configured to generate measurement data.
Biorenewable fuels and chemicals are becoming increasingly important as we continue to deplete our petroleum resources. A great deal of effort is being expended in industry and academia to develop chemistries and processes to produce infrastructure-compatible fuels and chemical intermediates from biobased sources that can replace petrochemicals in existing products as well as create new products with useful properties.
Hydroxymethylfurfural (HMF) derivatives are newly developed biorenewable chemicals that could potentially be used in a broad array of industrial products and chemical manufacturing applications. This potential has long been recognized. Now, several HMF derivatives can be successfully produced via catalytic oxidation.
HMF oxidation occurs sequentially though several intermediate products. The challenge is to selectively produce a single one—which one depends on the desired application—in preference to all of the others. Methods now have been developed to form the various oxidation products with good selectivities and in high yields using continuous catalytic processes with air as oxidant.