Optimization of Production of Next Generation Biofuels from Camelina Oil using a Low Energy Chemical Process
The Bio-Energy Center found the optimum reaction conditions for converting camelina oil to bio-jet fuel using a low energy chemical process. The project accelerated knowledge generation and will lead to rapid commercialization of the process.
Funding: Economic Development Administration
Pilot-Scale Evaluation of a Low Energy Chemical Process for the Production of Advanced Fuels from Camelina
Researchers at the Center discovered a low energy chemical process that converts camelina oil to jet fuel. Bench-scale experiments successfully demonstrated that significant fractions of jet fuel can be produced from camelina using this process. Like every technology developed in the laboratory, the process needs to work as well in large scale in order to be commercialized. Thus, we will explore a pilot-scale production of bio-jet fuel from camelina oil. The goal of the project is to process 100 gallons of camelina oil to bio-jet fuel.
Funding: Economic Development Administration
Engine Performance, Exhaust Emissions and Fuel Properties of Cineole Blends
Cineole, a cyclic ether organic compound, has the potential to be a fuel blend for jet fuel and diesel. A few studies have showed cineole’s capability to be a cloud point depressant and reduce hydrocarbon exhaust emissions for single cylinder diesel engines. However, these limited studies do not fully portray cineole’s potential as a bio-based fuel. Therefore, a comprehensive fuel characterization, engine performance and exhaust emission analysis of cineole blends on a heavy-duty diesel engine was conducted.
USP Grade Eucalyptol (also known as 1,8-cineole or cineole), purchased from The Lebermuth Company, Inc. (South Bend, IN), was used in this study. Winter grade No. 2 ultra-low-sulfur diesel (ULSD) was purchased from Ezzie’s Wholesale Inc, Havre, MT. Three blends of cineole, specifically, 5, 10 and 20% by volume, were prepared and its fuel performance properties determined. The fuel characterization study also included analysis of a 20% cineole-jet fuel blend utilizing Jet-A fuel with anti-freeze additive obtained from the Havre Airport, Havre, MT.
Fuel characterization results showed that blending cineole with ultra-low-sulfur diesel (ULSD) improved cold filter plugging point (CFPP), cetane number and oxidative stability in comparison to those of 100% winter grade ULSD. Sulfur and aromatic content were lower for cineole blends.
The results of tests conducted on a cineole-jet blend showed that cineole did not significantly alter Jet-A’s fuel properties. The changes in the distillation characteristics for Jet-A blended with 20% volume of cineole were insignificant compared to pure Jet A fuel that the T90 of the pure Jet A and cineole-Jet A blend were the same.
The study included heavy duty diesel engine performance testing utilizing an alternating current engine dynamometer and a 2007 emissions compliant on-highway Cummins ISL engine. The test cell includes exhaust emissions analysis equipment.
Results of engine performance testing showed exhaust emissions, C10 (ULSD blended with 10% by volume of cineole) resulted in a significant reductions in particulate matter, total hydrocarbon and carbon monoxide exhaust emissions. Other emission species, like formaldehyde and isocyanic acid, were also significantly reduced for C10. However, this resulted in a tradeoff whereby NOx exhaust emissions slightly increased. It is noteworthy to mention that this inversely proportional relationship between particulate matter and NOx exhaust emissions is a characteristic of most diesel engines. Finally, the test engine consumed more fuel (weight basis) when operated with C10 than 100% winter grade ULSD. There were no significant changes in the exhaust emission and engine performance between C5 (5% blend) and 100% winter grade ULSD.
Funding: Economic Development Administration and Department of Environmental Quality, State Energy Office, Renewable Energy Program
Effects of Contaminants in Canola Biodiesel to Diesel Engine Exhaust Emissions
Biodiesel positively affects the lubricity of petrodiesel and significantly lower harmful exhaust emissions, like particulate matter and unburnt hydrocarbons, compared to petrodiesel. Although, poor processing and refining practices during production could lead to a fuel with deficient properties and could result to engine problems. For example, carbon residue increases as more unconverted oil is in a biodiesel. Carbon residue is the tendency of a fuel to form carbon deposits when under high temperature and inert atmospheres. Carbon deposits can accumulate in injector nozzles thus, decreases engine performance.
ASTM D6751, also known as the “Standard Specification for Biodiesel Fuel Blend Stock (B100) for Middle Distillate Fuels”, lists the required properties of the biodiesel for use as a blend component of a diesel fuel. It is our understanding that ASTM D6751 rational are to ensure a good quality fuel blend stock is sold to consumers, to warrant successful operation of engines using the fuel, and to protect engines from damage and premature wear and tear. But, it is still not clear if a biodiesel that does not meet the standard properties in the ASTM will result to poor engine emissions. Thus, this project is aimed to investigate the effects of contaminants, such as, unconverted oil, methanol and free fatty acids, in the biodiesel to diesel engine’s exhaust emissions.
As expected, results of the fuel characterization of the different fuels showed that the addition of contaminants affected some of the properties. Kinematic viscosity of biodiesel contaminated with unconverted oils is higher than the biodiesel that passed total and free glycerin test. Addition of methanol to the biodiesel significant decreased both kinematic viscosity and flash point.
For the exhaust emissions, all the biodiesel samples tested, including biodiesel samples with unconverted oil (5% by weight), methanol (3% by weight) and high free fatty acids resulted in significant reduction in particulate matter (PM) and carbon monoxide (CO) exhaust emissions in comparison with ULSD. Although, we observed an increase in CO exhaust emission for biodiesel contaminated with methanol compared to the biodiesel meeting ASTM specification. Similarly, particulate matter emissions were also higher in biodiesel contaminated with methanol and free fatty acids.
As common to biodiesel, this reduction resulted to a tradeoff whereby NOx exhaust emissions were significantly higher for biodiesel and contaminated biodiesel than for ULSD. It is noteworthy to mention that there were no significant changes in NOx emissions among the different biodiesel tested.
In conclusion, canola biodiesel with specifications slightly outside the ASTM D6751 standards, specifically total glycerin, methanol content and acid number, are unlikely to produce more harmful emissions than using petrodiesel.
Funding: Department of Energy, Office of Energy Efficiency & Renewable Energy
Evaluation of Multi-Catalyst System in Hydro-thermochemical Processing of Glycerol
Converting crude-glycerol from biodiesel production to 1,2-propanediol, a valuable chemical, is a promising solution to solve glycerol’s increasing surplus. Although, conventional hydrogenolysis has been effectively used, the process needs external supply of hydrogen to work. Consequently, requires an expensive hydrogen storing facility which is unappealing to biodiesel producers. Hydro-thermochemical processing of glycerol to 1,2-propanediol has the potential in bringing new opportunities to the biodiesel industry. The hydrogen needed to produce 1,2-propanediol is generated in situ during hydro-thermochemical process. Previous research conducted by Dr. He and Dr. Maglinao showed that 1,2-propanediol can be produced in high yields from glycerol using a batch set up. Though, it is still unknown whether this process can be translated to a continuous mode. This collaborative project between University of Idaho and Montana State University-Northern aimed to evaluate the continuous hydro-thermochemical processing of glycerol using a multi-catalyst system. The experiments were carried out using a bench-scale two-stage tubular reactor using BASF Cu-0860 ERL and BASF Ni-3298E catalysts, arranged in series. The reaction temperature, reaction pressure and liquid hourly space velocity (LHSV) were varied to determine their effects on the conversion of glycerol to 1,2-propanediol and hydroxyacetone, the intermediate compound of the process. Results showed that hydroxyacetone and 1,2-propanediol were the major compounds in the products. Up to 20.13% and 6.34% wt. of hydroxyacetone and 1,2-propanediol were produced in the liquid stream, respectively. Reaction temperature, reaction pressure and LHSV affected the amount of hydroxyacetone and 1,2-propanediol. In the 24-hours of continuous operation, Cu-0860 ERL disintegrated into clay-like substance after 17 h and blocked the flow of liquid. Using crude-glycerol as feedstock, the reactor stopped flowing much earlier (seven hours). The main reason for the clog was due to the impurities present in the crude glycerol. Despite Cu-0860 catalyst’s instability for this process, its activity and Ni-3298 remain consistent throughout the experiment.
Funding: Economic Development Administration and Idaho State Board of Education
Performance of Locomotive Engine Fueled with Biodiesel Blend
Biodiesel is a well-recognized and government-approved biomass-based alternative to petrodiesel. In the past decade, the production and use of biodiesel in the United States have been growing exponentially and in fact, close to a billion gallons of biodiesel was produced in 2012. The Burlington Northern Santa Fe Railway Company (BNSF Railway), the second-largest freight railroad in North America, uses between 70,000 to 80,000 gallons of diesel each day for every refueling station. Havre, Montana where one of the BNSF Railway’s refueling stations is located, is an ideal place for producing and marketing biodiesel. With this huge demand for diesel, this could fuel Havre’s and near-by town’s economic growth, both in the biofuels industry and agricultural sector. Hill county, where Havre is located, and its surrounding counties, Blaine, Liberty, Chouteau, Glacier, Phillips, Toole and Valley, has the potential to provide over 30 million gallons of biodiesel per year.
Oilseed crops such as canola and safflower has been proven to produce biodiesel that is suited to Montana’s cold weather. However, using these oils for fuel production raises concerns in the food versus fuel dilemma because these oils can also be used for food applications such as culinary oils. Camelina (Camelina sativa), on the other hand, has the potential to produce fuel without any of the food versus fuel concerns. Camelina can be used as a rotational crop for Montana’s wheat which erases the question of using land for just fuel production and it is also a dedicated energy crop which eliminates the dilemma to use it for food. Camelina biodiesel has excellent cold flow properties, perfect to Montana’s cold winter, but it also has its deficiencies. Camelina contains high amount of omega-3 fatty acids which has positive effects to human health when consumed but contributes to its susceptibility to oxidative degradation when used as a fuel. In short, camelina have relatively shorter shelf life compared to other biodiesels.
With the feedstock versatility of biodiesel and camelina’s potential as an ideal feedstock for biofuels, having a biodiesel industry in Havre is a promising driver for economic growth. However, it is vital to demonstrate to the agricultural and transportation industry the proven benefits of using biodiesel and increase public awareness of biodiesel’s positive economic and environmental impacts to the community. Opportunity Link of Havre, Montana (OL), Montana State University-Northern Bio-Energy Center (BEC) and BNSF Railway worked on a demonstration project to address these concerns. The one-year project entitled “Developing Railway Markets for Montana Biodiesel” aimed to (a) demonstrate to Montana’s railway market the proven advantages of biodiesel in fueling locomotive engines and (b) provide information, assistance and planning to local oilseed producers and refiners, businesses, governments and railroad industry in anticipation of increased industrial demand for biodiesel in Montana. Specifically, BEC’s participation was to evaluate the biodiesel’s performance in locomotive switcher engines and analyze the fuel properties of biodiesel produced during the course of the study in accordance with ASTM standards. This section reports the highlights of the results of the tests conducted by BEC on locomotive switcher engine emissions and biodiesel properties.
BEC pressed Montana-grown canola and safflower seeds and converted the extracted oil to biodiesel using a batch biodiesel reactor located at its facility. BEC provided a total of 1,073 gallons of canola and safflower biodiesel and Earl Fisher Biofuels (Chester, MT) added around 9,431 gallons of camelina biodiesel for this study. The canola, safflower and camelina biodiesel was mixed during the study. BNSF Railway stored the biodiesel produced periodically to 330 gallon storage tanks and a 1,000 gallon tank. Samples were collected and tested for fuel properties in accordance with ASTM D6751. The biodiesel was then blended with No. 2 diesel at 20% biodiesel and 80% No. 2 diesel by volume to produce B20. Throughout the study, the B20 would sit only three weeks before being dispensed. This study used two identical EMD SD40-2 switch engines equipped with computer control units to monitor engine problems to conduct a comparative study between B20 and No. 2 diesel. Samples were also collected right after blending and periodically from the locomotive engine fuel tank. The fuel characteristics of the samples were determined according to ASTM D7467.
The results of this study provided information that the biodiesel (B100) and biodiesel blend (B20) derived from Montana-grown oilseeds could be a viable source of alternative biomass-based fuel for locomotive engines. The biodiesel produced in this study met most of the criteria set by ASTM D6751. The sulfur content, which contributes to acid rain when exhausted as sulfur oxide during combustion, was only 2.01 ± 0.74 ppm, way below to the set limit of 15 ppm. The flash point was 159 ± 46.56°C, high enough to classify the biodiesel as a non-flammable product and without requiring producers to buy expensive explosive-proof tankers to transport it. The biodiesel, however, exhibited Oxidative Stability Index (OSI) values lower than the set standard. This means that there is no guarantee that the biodiesel will not degrade when stored for six months. Fortunately, the B20 in this study was stored no longer than three weeks but, it is still important to address the low OSI value of the biodiesel. Based on the results, this led to the conclusion that adding anti-oxidants to the neat biodiesel is a necessary step.
Blending biodiesel with No 2. diesel has proven to improve biodiesel’s fuel properties like carbon residue, acid number and cold flow properties. It was observed that Cold Flow Plugging Point of biodiesel statistically improved from -4.69 ± 2.05°C to -22.93 ± 5.49°C (or from 23.56 ± 3.69°F to -9.27 ± 9.88°F) when blended at 20% by volume. The good fuel properties of the B20 resulted to the smooth operation of the locomotive engine throughout the study. It is noteworthy that BNSF Railway did not experience any operational problems even on days when the outside temperature was at -37°C (-35°F).
In conclusion, biodiesel that is properly processed and meets ASTM standards can be used on locomotive engines without any concerns of engine malfunction. Camelina biodiesel is an ideal feedstock for Montana but it is important to address its low oxidative stability. Further work on finding the right anti-oxidants or other solutions like chemical modification of the biodiesel is necessary to improve camelina’s deficiencies. Lastly, using B20 as a locomotive fuel can promote economic growth in agricultural areas such as Montana.
Funding: Department of Energy, Energy Efficiency & Renewable Energy
Supercritical Alkene Metathesis of Camelina FAME using Different Catalysts
Abstract: Alkene metathesis of unsaturated FAME with ethylene is a powerful synthesis reaction to produce terminal alkenes which can be used for synthesis of polymers and other valuable compounds. Although commercial metathesis catalysts have been proven to be efficient in converting pure FAME, this process has not been used effectively in a mixture of methyl esters like biodiesel. Moreover, there has been no study in the literature that has used supercritical ethylene in alkene metathesis. We anticipate to minimize mass transfer limitations with the use of supercritical ethylene during metathesis with FAME.
In this study FAME derived from camelina oil, which contains as much as 90% unsaturated components, was allowed to react with supercritical ethylene at room temperature in the presence of Grubbs catalyst. A high pressure syringe pump is used to deliver 750 psi of ethylene and the reaction is performed in a 500 mL high pressure and high temperature reactor for 4 hours. Different commercial first and second generation Grubbs catalysts were tested. Depending on the nature of the catalyst, self metathesis of FAME, isomerization and cyclization were observed as well at varying degrees as evidenced by GC/MS analyses. Percent conversion of unsaturated FAME as high as 87% was obtained.
Funding: Department of Energy, Office of Energy Efficiency & Renewable Energy