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256 records · Page 15

Tar Formation and Mitigation in Pressurized Biomass and Cofired Gasification

Biomass gasification with CO2 capture has the potential to provide carbon-negative heat, power, and feedstock for sustainable hydrocarbon fuels. In a pressurized gasifier, precombustion solvent systems can capture CO2 with less energy than needed for amine-based postcombustion CO2 capture, and pressurized syngas is generally more suitable for fuel synthesis. Although precombustion capture has been used for many decades in large-scale fossil-based plants, it has not been well-demonstrated in smaller-scale biomass gasification. Precombustion solvents and product streams could be particularly impacted by tar and other organic compounds that tend to form in high concentrations during low-temperature biomass gasification. A pressurized pilot-scale gasifier was used to examine tar formation and fate when using CO2 capture with various blends of biomass and coal. The syngas was fully conditioned to remove particulate matter; capture sulfur; adjust syngas chemistry using water-gas shift; quench out moisture and condensable organics; and capture CO2. Tar concentrations were measured in the raw syngas, the product gas, and in the liquid streams over the course of several weeks. The gasifier was operated both as a high-pressure oxygen-blown system to mimic large-scale centralized gasification and at lower pressures under air-blown conditions to mimic a more likely small-scale system. A second high-temperature stage with oxidant injection was used to crack tars. The overall results showed how gasifier and CO2 capture performance change as fuel is blended between coal to biomass and what the fate of tar is through a precombustion CO2 capture system.

Strege, Josh [University of North Dakota EERC] (OR↗

NIR Dataset and Models (Near-Infrared Spectroscopy Calibration Dataset for Butanediol Fermentation and Multivariate Calibration Models) [SWR-22-60]

2,3-butanediol (2,3-BDO) is an economically important platform chemical that can be used in a variety of chemical feedstocks, liquid fuels, and biosynthetic building blocks. While 2,3-BDO can be efficiently produced by fermentation, the fermentation requires continuous monitoring and control to maximize 2,3-BDO yields and minimize inhibitory coproducts. Because of the time required for sampling and at-line measurement of fermentation samples with high pressure liquid chromatography (HPLC), the ability for operators to perform real-time modification to fermentation conditions is limited. To overcome this challenge, researchers from the National Renewable Energy Laboratory (NREL) have developed a calibration model which can predict the concentration of several analytes in real-time using near-infrared (NIR) spectra of the filtered fermentation broth. While significantly reducing the need for off-line sampling, NREL expects this technology to play a critical role in maximizing 2,3-BDO production. 2,3-butanediol (2,3-BDO) is a useful chemical platform that can be used to create a variety of products. For instance, 2,3-BDO can be (1) dehydrated and converted into methyl ethyl ketone, a liquid fuel additive or (2) deoxydehydrated into 1,3-butadiene for synthetic rubber, which can also be oligomerized in high yields to gasoline, diesel, and jet fuel. In order to maximize 2,3-BDO production, frequent measurement of fermentation samples is needed, as small changes in oxygen concentration can drive the fermentation to undesired products. For example, oxygen-deficient conditions result in glycerol production, while excess oxygen concentrations result in acetoin production. This results in the need for measuring dissolved oxygen, glucose, and xylose concentrations in order to optimize the aeration rate of the fermentation. Traditional monitoring methods occurs off-line and can take up to 30 minutes per sample. With multiple fermenters and high-pressure liquid chromatography (HPLC) injectors, resulting in the need for multiple samples, the sampling process can take hours to complete. NREL’s calibration model can predict the glucose, xylose, 2,3-BDO, acetoin, and glycerol concentrations from NIR spectra of filtered fermentation liquor samples. Using a partial least-squares (PLS) calibration model, NREL’s model can monitor the concentration of these analytes during subsequent fermentations at bench- and pilot-scale, demonstrating the utility of NIR spectroscopy combined with chemometrics for real-time, at-line monitoring of 2,3-BDO fermentations.

Wolfrum, Edward↗

Pilot plant reliability metrics for grinding and fast pyrolysis of woody residues

Here we report on the effects of loblolly pine residue variability on material throughput, pilot plant uptime, operator intervention, product yield, and product quality for grinding, fast pyrolysis, and hydrotreating operations. Preprocessing throughput using a hammer mill varied between 31-48% of nameplate capacity (5 tons/hr). Grinder overloads in the size reduction step were more prevalent for lower ash and higher moisture materials. Fast pyrolysis throughput varied between 57-72% of nameplate capacity (20 kg/hr) and bio-oil yields varied between 46-53% (feedstock carbon to oil, dry basis). During fast pyrolysis operations, downtime was caused by bridging in the feed and char removal systems and plugging in the condensation system. Cohesion of feedstock and char leading to system plugging was less frequent for higher ash feedstocks, and differences in condenser plugging behavior between high and low ash feedstocks were observed. The catalyst stability of the bio-oil stabilization step was strongly dependent on the sulfur content in the bio-oil, which was higher for the high-ash residue oils. Lower moisture content in the starting biomass was consistent with lower sulfur content in bio-oil. Yields and properties of hydrotreated fuel products showed minimal deference among the bio-oils.

Klinger, Jordan↗

Pilot Scale Testing of Lignite Adsorption Capability and the Benefits for the Recovery of Rare Earth Elements from Dilute Leach Solutions

Naturally occurring organic materials containing humic acids show a strong affinity towards rare earth elements (REE) and other critical elements. Leaching experiments on lignite coal waste produced from construction sand production revealed that the contained REEs were associated with the organic matter. Furthermore, adsorption studies revealed that the lignite waste was capable of extracting REEs from a model solution and increased the REE content of the lignite waste by more than 100%. As such, this study aimed to utilize the lignite waste to adsorb REEs from pregnant leach solutions and acid mine drainage sources having low REE concentrations and subsequently leach the lignite material to produce pregnant leach solutions containing relatively high amounts of REEs, which benefits the performance and economic viability of downstream separation and purification processes. An integrated flowsheet was developed based on this concept and tested at a pilot scale. The pregnant leachate solution (PLS) was generated from a heap leach pad containing 2000 tons of Baker seam coarse refuse. The pilot scale circuit was comprised of aluminum precipitation, adsorption using the waste lignite, and rare earth-critical metal (RE-CM) precipitation stages in succession. The results indicated that the aluminum precipitation stage removed over 88% and 99% of the Al and Fe, respectively. The adsorption stage increased the REE content associated with the waste lignite from 457 ppm to 1065 ppm on a whole mass basis. Furthermore, the heavy REE (HREE) content in the feedstock increased by approximately 250%, which raised the percentage of HREE in the REE distribution by 19 absolute percentage points. In addition to the REEs, concentrations of other critical elements such as Mn, Ni, and Zn also improved by 75%, 37%, and 250%, respectively. Bench-scale tests revealed that increasing the solids concentration in the waste lignite and PLS mix from 1% to 20% by weight enhanced the adsorption efficiency from 32.0% to 99.5%, respectively. As such, a new flowsheet was proposed which provides significantly higher REE concentrations in the PLS that can be fed directly to solvent extraction and/or oxalic acid precipitation and, thereby, enhancing process efficiency and economics.

58 GEOSCIENCES↗