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Critical quality parameters from BQ-9000 member companies were analyzed for calendar year 2018. The National Biodiesel Board provided blinded and randomized data sets on 14 critical metrics for biodiesel quality. This report summarizes the results of the parameters and found that overall, biodiesel readily met the ASTM D6751 specification limits in 2018.
Crystallization or gel formation of normal paraffins in diesel fuel under cold weather conditions leading to fuel filter clogging is a common problem. Cold weather operability of biodiesel (B100) and blends with diesel fuel presents additional complexity because of the presence of saturated monoglycerides (SMGs) and other relatively polar species. Currently, the cloud point measurement (a measure of when the first component crystallizes out of solution) is used to define the lowest temperature at which the fuel can be used without causing cold weather issues. While filter plugging issues have declined, there still remain intermittent unexpected problems above the cloud point for biodiesel blends. Development of a fundamental understanding of how minor components in biodiesel crystallize, gel, and transform is needed in order to prevent these unexpected issues. We have found that SMGs, a low level impurity present in B100 from the production process, can crystallize out of solution and undergo a solvent-mediated polymorphic phase transformation to a more stable, less soluble form. This causes them to persist at temperatures above the cloud point once they have some out of solution. Additionally, we have found that SMGs can cause other more soluble, lower melting point minor components in the B100 to co-crystallize and come out of solution. Monoolein, another minor component from the production process is an unsaturated monoglyceride with a much lower melting point and higher solubility than SMGs. It is able to form a co-crystal with the SMGs and is found together with the SMGs on plugged filters we have analyzed in our laboratory. An observation of isolated crystals in the lab led us to believe that the SMGs may also be forming a gel-like network with components of the B100 and diesel fuel. During filtration experiments, we have noted that in some cases a solid layer of crystals forms and blocks the filter completely, while in other cases this does not occur. Because SMGs are polar and can form layered networks once a sufficient amount of crystals have come out of solution, we recently began investigating the ability of SMGs to form a gel network with fuel components as well as with other minor polar components in the fuel in order to obtain a fundamental understanding of the mechanism of formation. It has been well established that this type of phenomena occurs in sub-sea pipelines where a chief crystallizing component begins to crystallize out of solution. Once a sufficient amount of crystals exists, a volume spanning network of solid crystals can trap liquid crude oil and form a solid-like gel network. We are investigating whether this type of phenomena can occur with SMGs and both fatty acid methyl esters from the B100 and normal paraffins from diesel fuel. Additionally, SMGs are well known to incorporate water into their layered crystal structure. Water is often used to stabilize less stable polymorphic forms of SMGs, therefore water was another minor component of interest. Also of interest is glycerin which has been found on clogged filters in our laboratory.
Secondary organic aerosol (SOA), formed in a process of photooxidization of diesel fuel, biodiesel fuel, and 20% biodiesel fuel/80% diesel fuel mixture, are prepared under high-NOx conditions in the presence and absence of sulfur dioxide (SO2), ammonia (NH3), and relative humidity (RH). The composition of condensed-phase organic compounds in SOA is measured using several analytical techniques including aerosol mass spectrometry (AMS), high-resolution nanospray desorption electrospray ionization mass spectrometry (nano-DESI/HRMS), and ultra high resolution and mass accuracy 21T Fourier transform ion cyclotron resonance mass spectrometry (21T FT-ICR MS). Results demonstrate that sulfuric acid and condensed organosulfur species formed in photooxidation experiments with SO2 are present in the SOA particles. Fewer organosulfur species are formed in the high humidity experiments, performed at RH 90%, in comparison with experiments done under dry conditions. There is a strong overlap of organosulfur species observed in this study with previous field and chamber studies of SOA. Many mass spectrometry peaks of organosulfates (R–OS(O)2OH) in field studies previously designated as biogenic or of unknown origin might have originated from anthropogenic sources, such as photooxidation of hydrocarbons present in diesel and biodiesel fuel.
The production of biodiesel has notably increased over the past decade. Currently, plant oil is the main feedstock for biodiesel production, but, due to concerns related to the competition with food production, alternative oil feedstocks have to be found. Oleaginous yeasts are known to produce high amounts of lipids, but no integrated process from microbial fermentation to final biodiesel production has reached commercial realization yet due to economic constraints. Therefore, growth and lipid production of red yeast Rhodotorula glutinis was tested on low-cost substrates, namely, wastewaters from potato, fruit juice, and lettuce processing. Additionally, the production of carotenoids as high-value by-products was examined. All evaluated wastewaters met the general criteria for microbial lipid production. However, no significant increase in lipid content was observed, probably due to lack of available carbon in wastewaters from fruit juice and lettuce processing, and excess of available nitrogen in potato processing wastewater, respectively. During growth on wastewaters from fruit juice and lettuce processing the carotenoid content increased significantly in the first 48 hours. The relations between carbon content, nitrogen content, and carotenoid production need to be further assessed. For economic viability, lipid and carotenoid production needs to be increased significantly. Lastly, the screening of feedstocks should be extended to other wastewaters.
Abstract Presence of free fatty acids along with glycerides poses a technical difficulty for biodiesel production. This work used a Taguchi L9 design to optimize the solvent‐free enzymatic process to result in the esterification of oleic acid with glycerol. Under optimal conditions the esterification reaction temperature of 60°C, enzyme dose of 5 wt%, glycerol: oleic acid molar ratio of 5:1, and reaction time of 3 h, a 75.235 ± 2.19% conversion of oleic acid to esters was achieved. With the addition of molecular sieves, the conversion increased to 86.73% ± 1.09%. However, using the parameters predicted by Taguchi design (60°C, 5 wt%, 5:1, and 4.5 h), 88.5% ± 1.11% of oleic acid could be converted to esters derivative. Diglycerides were the major product, and the reaction equilibrium was attained after 4 h. The immobilized enzyme could be used up to seven times with only a 10% reduction in the conversion. Thus, the process can efficiently reduce the free fatty acid content of oil to make it suitable for biodiesel production.
Ethylic transesterification process for biodiesel production without any chemical or biochemical catalysts at different subcritical thermodynamic conditions was performed using wet animal fat, soybean and palm oils as feedstock. The results indicate that 2 h of reaction at 240 °C with pressures varying from 20 to 45 bar was sufficient to transform almost all lipid fraction of the samples to biodiesel, depending on the reactor dead volume and proportions between reactants. Conversions of 100%, 84% and 98.5% were obtained for animal fat, soybean oil and palm oil, respectively, in the presence of water, with a net energy ration values of 2.6, 2.1 and 2.5 respectively. Finally, these results indicate that the process is energetically favorable, and thus represents a cleaner technology with environmental advantages when compared to traditional esterification or transesterification processes.
We demonstrated production of a superior performance biodiesel referred to here as fatty acid fusel alcohol esters (FAFE) – by reacting fusel alcohols (isobutanol, 3-methyl-1-butanol, and (S)-(-)-2-methyl-1-butanol) with oil (glyceryl trioleate) using lipase from Aspergillus oryzae. Reaction conditions corresponding to a molar ratio of 5:1 (fusel alcohols to oil), enzyme loading of 2% w/w, reaction temperature of 35 °C, shaking speed of 250 rpm, and reaction time of 24 h achieved >97% conversion to FAFE. Further, FAFE obtained from reacting a fusel alcohol mixture with corn oil were evaluated for use as a fuel for diesel engines. FAFE mixtures showed superior combustion and cold-flow properties, with the derived cetane numbers up to 4.8 points higher, cloud points up to -6 °C lower, and the heat of combustion up to 2.1% higher than the corresponding FAME samples, depending on the fusel mixture used. This represents a significant improvement for all three metrics, which are typically anti-correlated. Finally, FAFE provides a new opportunity for expanded usage of biodiesel by addressing feedstock limitations, fuel performance, and low temperature tolerance.
Commercial biodiesel blends were aged at 43 degrees C while monitoring stability. The oxidation stability -- or oxidation reserve expressed as Rancimat induction period (IP) -- gradually decreased from its initial value. At a predetermined IP threshold, an antioxidant was used to restore IP to the ASTM D7467 specification minimum of 6 h, referred to as re-additization. At lower IP values, the amount of antioxidant required increased significantly, and the effectiveness tended to be reduced. Once IP fell to essentially zero, the acid content increased to above the allowable limit and insoluble material was also detected. Storage life was increased relative to the as-received fuels as evidenced by longer time to produce acids. Experience in the field may vary based on storage conditions; however, these results indicate re-additization can significantly increase storage life of biodiesel blends when used with regular monitoring of IP and acid number. An assessment of the storage stability of the as-received fuels showed that the initial IP did not predict storage behavior, although fuels above the specification minimum remained stable for >12 weeks accelerated aging (1 year simulated).
Highlights: • ZnAl{sub 2}O{sub 4} spinel was synthesized by the microwave hydrothermal method in only 15 or 30 min. • The powders show high specific surface area. • ZAT{sub b}15 showed activity of 52.22% for the conversion of soybean oil into biodiesel. - Abstract: Zinc aluminate is a material with high thermal stability and high mechanical strength that, owing to these properties, is used as a catalyst or support. In this work, zinc aluminate spinel was synthesized by the microwave hydrothermal method in only 15 or 30 min at a low temperature (150 °C) without templates, using only Al(NO{sub 3}){sub 3}·9H{sub 2}O, Zn(NO{sub 3}){sub 2}·6H{sub 2}O, and urea as precursors and applied in the transesterification of soybean oil. X-ray diffraction analysis showed that ZnAl{sub 2}O{sub 4} had a cubic structure without secondary phases. The nitrogen adsorption measurements (BET) revealed a high surface area (266.57 m{sup 2} g{sup −1}) for the nanopowder synthesized in 15 min. This powder showed activity of 52.22% for the catalytic conversion of soybean oil into biodiesel by transesterification.
A rotor-stator spinning disk reactor for intensified biodiesel synthesis is described and numerically simulated. The reactor consists of two flat disks, located coaxially and parallel to each other with a gap ranging from 0.1 mm to 0.2 mm between the disks. The upper disk is located on a rotating shaft while the lower disk is stationary. The feed liquids, triglycerides (TG) and methanol are introduced coaxially along the center line of rotating disk and stationary disk, respectively. Fluid hydrodynamics in the reactor for synthesis of biodiesel from TG and methanol in the presence of a sodium hydroxide catalyst are simulated, using convection-diffusion-reaction species transport model by the CFD software ANSYS©Fluent v. 13.0. The effects of upper disk’s spinning speed, gap size and flow rates at inlets are evaluated.
Commercial biodiesel blends representative of the U.S. market were aged following procedure ASTM D4625, Standard Test Method for Middle Distillate Fuel Storage Stability at 43°C (110°F), with periodic monitoring of fuel properties indicative of oxidation. The oxidation stability—or oxidation reserve expressed as Rancimat induction period (IP)—gradually decreased from its initial value, as expected. At a predetermined IP threshold, an antioxidant was used to restore IP to the ASTM D7467 specification minimum of 6 six hours, referred to as re-additization. At lower IP values, the amount of antioxidant required increased significantly, and the effectiveness tended to be reduced. Once IP fell to essentially zero, the acid content increased to above the allowable limit. Insoluble material was detectable after the acid number increased out of specification. Storage life was increased with re-additization relative to the as-received fuels, as evidenced by longer time to produce acids. Experience in the field may vary based on storage conditions; however, these results indicate re-additization can significantly increase the storage life of biodiesel blends when used with regular monitoring of IP and acid number. An assessment of property changes during long-term storage showed the initial IP did not predict storage behavior, although fuels above the specification minimum remained stable for greater than 12 weeks of D4625 accelerated aging (1 one year simulated).
Biodiesel producers in the United States and Canada can voluntarily participate in the industry's BQ-9000 quality assurance program. This is the fourth in a series of reports documenting biodiesel quality from participating producers. Participants in the BQ-9000 program were requested to voluntarily provide data to a third-party team. This team anonymized and randomized the data prior to providing to the National Renewable Energy Laboratory (NREL) for analysis and reporting. The critical quality parameters analyzed are: sodium and potassium, calcium and magnesium, phosphorus, flash point and alcohol control, water and sediment, cloud point, acid number, free and total glycerin, monoglycerides, sulfur, oxidation stability, and cold soak filterability test (CSFT). The statistical analysis for these parameters is presented in Table ES-1.
This is the fifth in a series of reports documenting the quality of biodiesel from U.S. and Canadian-based producers that participate in the BQ-9000 program, the biodiesel industry voluntary quality assurance program. Participants agreed to provide monthly data on critical quality parameters for calendar year 2021. The quality data was provided to a team of experts, who removed any identifying company information and provided anonymized and randomized data to the National Renewable Energy Laboratory (NREL) for statistical analysis. The critical quality parameters analyzed were: sodium and potassium (Na+K); calcium and magnesium (Ca+Mg); phosphorus (P); flash point and alcohol control; water and sediment; cloud point; acid number; free and total glycerin; monoglycerides; sulfur; oxidation stability; and cold soak filterability test (CSFT). The data was not weighted for production volume.
This is the sixth in a series of reports documenting the quality of biodiesel from U.S. and Canadian-based producers that participate in the BQ-9000 program, the biodiesel industry voluntary quality assurance program. Participants agreed to provide monthly data on critical quality parameters for calendar year 2022. The quality data was provided to a team of experts, who removed any identifying company information and provided anonymized data to the National Renewable Energy Laboratory (NREL) for statistical analysis.
This is the seventh in a series of reports documenting the quality of biodiesel from U.S.- and Canadian-based producers that participate in the BQ-9000 program, the biodiesel industry’s voluntary quality assurance program. Participants provided monthly data on critical quality parameters for calendar year 2023 with quality data provided to a team of experts, who removed any identifying company information and provided anonymized data to the National Renewable Energy Laboratory (NREL) for statistical analysis. New for 2023, data on kinematic viscosity, sulfated ash, distillation temperature, carbon residue, and cetane were collected, as well as individual levels of sodium, potassium, calcium, and magnesium. Critical quality parameters analyzed are listed in Table ES-1 with descriptive statistics.
This is the eighth in a series of reports documenting the quality of biodiesel from U.S.- and Canadian-based producers that participate in the BQ-9000 program, the biodiesel industry's voluntary quality assurance program. Participants provided monthly data on critical quality parameters for calendar year 2024 with quality data provided to a team of experts, who removed any identifying company information and provided anonymized data to the National Renewable Energy Laboratory (NREL) for statistical analysis. Similar to 2023, data on kinematic viscosity, sulfated ash, distillation temperature, carbon residue, and cetane were collected, as well as individual levels of sodium, potassium, calcium, and magnesium.
A single-cylinder diesel engine was used to investigate the impact of biodiesel-based Na on emissions control components using specially blended 20% biodiesel fuel (B20). The emissions control components investigated were a diesel oxidation catalyst (DOC), a Cu-zeolite-based NH{sub 3}-SCR (selective catalytic reduction) catalyst, and a diesel particulate filter (DPF). Both light-duty vehicle, DOC-SCR-DPF, and heavy-duty vehicle, DOC-DPF-SCR, emissions control configurations were employed. The accelerated Na aging is achieved by introducing elevated Na levels in the fuel, to represent full useful life exposure, and periodically increasing the exhaust temperature to replicate DPF regeneration. To assess the validity of the implemented accelerated Na aging protocol, engine-aged lean NO{sub x} traps (LNTs), DOCs and DPFs are also evaluated. To fully characterize the impact on the catalytic activity the LNT, DOC and SCR catalysts were evaluated using a bench flow reactor. The evaluation of the aged DOC samples and LNT show little to no deactivation as a result of Na contamination. However, the SCR in the light-duty configuration (DOC-SCR-DPF) was severely affected by Na contamination, especially when NO was the only fed NO{sub x} source. In the heavy-duty configuration (DOC-DPF-SCR), no impact is observed in the SCR NO{sub x} reduction activity. Electron probe micro-analysis (EPMA) reveals that Na contamination on the LNT, DOC, and SCR samples is present throughout the length of the catalysts with a higher concentration on the washcoat surface. In both the long-term engine-aged DPF and the accelerated Na-aged DPFs, there is significant Na ash present in the upstream channels; however, in the engine-aged sample lube oil-based ash is the predominant constituent.
Combustion in direct-injection diesel engines occurs in a lifted, turbulent diffusion flame mode. Numerous studies indicate that the combustion and emissions in such engines are strongly influenced by the lifted flame characteristics, which are in turn determined by fuel and air mixing in the upstream region of the lifted flame, and consequently by the liquid breakup and spray development processes. From a numerical standpoint, these spray combustion processes depend heavily on the choice of underlying spray, combustion, and turbulence models. The present numerical study investigates the influence of different chemical kinetic mechanisms for diesel and biodiesel fuels, as well as Reynolds-averaged Navier-Stokes (RANS) and large eddy simulation (LES) turbulence models on predicting flame lift-off lengths (LOLs) and ignition delays. Specifically, two chemical kinetic mechanisms for n-heptane (NHPT) and three for biodiesel surrogates are investigated. In addition, the RNG k-{epsilon} (RANS) model is compared to the Smagorinsky based LES turbulence model. Using adaptive grid resolution, minimum grid sizes of 250 {micro}m and 125 {micro}m were obtained for the RANS and LES cases respectively. Validations of these models were performed against experimental data from Sandia National Laboratories in a constant volume combustion chamber. Ignition delay and flame lift-off validations were performed at different ambient temperature conditions. The LES model predicts lower ignition delays and qualitatively better flame structures compared to the RNG k-{epsilon} model. The use of realistic chemistry and a ternary surrogate mixture, which consists of methyl decanoate, methyl 9-decenoate, and NHPT, results in better predicted LOLs and ignition delays. For diesel fuel though, only marginal improvements are observed by using larger size mechanisms. However, these improved predictions come at a significant increase in computational cost.