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Pathapati Bioprocessing Symposium 2011
1. Catalytic Conversion of Tall Oil to Renewable Diesel and Biodiesel University of Louisiana at Lafayette Chemical Engineering Department Kiran Pathapati, Stephen Dufreche, Rakesh Bajpai, Mark Zappi
15. Transfer Line (200˚C) He ˉ40 – 350˚C RX-1MS Column 50 - 400˚C ˉ40 - 300˚C Sample Injector Catalyst Bed Split Flow 1 mL/min 15 mL/min 14 mL/min Purge gas for column change MS-OpenSplit System He, H 2
As of 2008, transportation share of the U.S. petroleum consumption is 71%. The U.S transportation sector is 97 percent reliant on oil, with 60 percent of this oil imported. In 2008, the U.S. used over 45 billion gallons of petroleum diesel fuel and 140 billion gallons of gasoline. Mobile sector greenhouse gas emissions are projected to increase 37 percent over the next 25 years.
This dependence on oil to meet our growing demand for travel leaves our economy vulnerable to price increases. In October 2003, oil was $25 a barrel. Recently, the cost has been as high as $100 a barrel, a fourfold increase. We are likely to see continued price fluctuations and increases due to rising costs associated with growing world oil demand, historic low capacities in oil-producing countries, refinery outages, and political instability in oil-rich nations and regions. The transportation sector dominates demand for liquid fuels, which grows from a 69-percent share of total consumption in 2007 to a 75-percent share in 2030.
The importance of bio-fuels for transport has become more and ,more important in the past years and this trend is expected to continue environmental Issues: Petroleum fuels have exacted a heavy environmental toll on the planet, and their impact is likely to worsen as “dirtier” energy supplies, such as heavy oil and coal, are tapped. As an alternative, biofuels offer the opportunity to reduce the emissions of both greenhouse gases (GHGs) and urban air pollutants energy security : Petroleum is a highly concentrated energy resource, and the world’s current transportation systems are almost completely dependent on it. As a result, the world economy is (or could be) at risk if oil supplies are disrupted in any of the relatively few countries that are significant oil exporters. As a result of concentrated wealth, social tensions, and inadequate political institutions, many of these countries are less-than-secure suppliers of the world’s most vital commodity. Biofuels promise to bring a much broader group of countries into the liquid fuel business, diversifying supplies and reducing the risk of disruption. And because they can be produced in most regions of the globe, the risks inherent in transporting these fuels over long distances will be reduced as well. In the long run, this is likely to help stabilize fuel prices. Economy : Oil imports account for almost half the U.S. trade deficit, which has an enormous impact on our economy and the creation of new jobs. A high trade imbalance from dependence on foreign oil also leaves our economy vulnerable to price hikes from supply disruptions. eveloping a stronger market for domestically produced biofuels in the United States will help alleviate the negative implications of our trade deficit and contribute to positive economic trends in the U.S. transportation sector.
The feedstock is the fundamental building block for a transportation fuel. One of the big debates in the emerging Bio-Economy involves the tradeoffs between growing agricultural crops for human consumption and animal feed versus biomass feedstocks for alternative fuels. : (i) deposits throughout the fuel and combustion systems, (ii) problems related to the poor cold-flow properties of FAME, (iii) low stability towards heat and oxidation, (iv) prone towards water absorption, (v) higher emissions of NOx relative to fossil type diesel and (vi) shortening of engine oils lifetime, The impediments to significant expansion in the ethanol and biodiesel industries are the identification of additional economically viable alternative feedstocks The impediment to the use of hydrogen in the transportation sector is the high cost of production, the availability of supply infrastructure.
increasing demand from developing economies. alternative, lower cost, non-food feedstocks.
tall oil is a dark. odorous liquid that is one of the two commercially imp by product from the sulfate process of paper manf. it is obtained by chemically treating the cooking liquor used in the operation of pulping wood for paper. Its name comes from the swedish word for pine, tall.
The principal components of CTO include saturated and unsaturated C18 FFA, free resin acids and other non-acidic compounds tall oil supplies about two thirds of the fatty acids used in the US for industrial purposes.
the exact comp of cto can vary widely. while the time of year the wood was harvested has little effect on the cto comp, the geographic location, wood type, and age have temendous effect.
the cto is upgraded by distillation to produce five major fractions. heads product consists of the lower boiling fractions such as palmitic acid, and some neutral compounds, whitle pitch fraction consists of mostly the higher boiling or nonvolatile unsaponifiable products. the dto contains a mixture of fatty acids and resin acids that can vary in conc. the main fractions TOFA and TOR consist almost entirley of the respective fatty and resin acids.
Price is driving the growth of renewable diesel markets worldwide. The second defining characteristic of renewable diesel is the way it is processed. Compared with biodiesel, which combines virgin vegetable ils with alcohol, renewable diesel uses traditional refinery processes to produce clean biofuels The third defining characteristic lies in the chemical properties of the fuel.
Biodiesel from tall oil gives good yield percentage from TOFA fraction. Catalytic cracking may convert other fractions of CTO along with TOFA effectively. Effect of Tall Oil on the commercial catalyst.
Has high Si to Al ratio The heterogenous catalyst chosen for this project was Silica/Alumina zeolite catalyst called zsm-5. it is higly ordered, small pore zeolite catalyst, which has been well characterised by industrial and academic sources.
