Professional Documents
Culture Documents
Received: 6 September 2010 Revised: 8 October 2010 Accepted: 11 October 2010 Published online in Wiley Online Library: 9 December 2010
INTRODUCTION
As originally delineated by Malthus, an increase or even the maintenance of the world population is necessarily limited by the means of subsistence.1 Although this argument has traditionally been related to the availability of food, in the modern era, the perpetuation of our more advanced societies and the emergence of new industrial powers rely on the availability of energy. This fundamental and ubiquitous resource is used to light, cool, and heat homes; power automobiles, trucks, aircraft, and ships; and to provide electricity for televisions, laptops, cell phones and a host of other electronic gadgets. Unlike food which is a renewable resource, energy in the form of conventional fossil fuels is not, necessitating a denitive shift by the world economy to sustainable alternatives.2 For renewable energy sources to be considered sustainable, they must not affect global food production in light of the ethical ramications of competing energy and food use.3 Complex energy feedstocks such as municipal waste, crop and forestry residues, and other lignocellulosic waste materials4 represent a vastly underutilized renewable power source. These materials can be harnessed to produce a variety of products, from fuels to custom chemicals, while drastically reducing net carbon emissions and providing for a sustainable future. A variety of techniques including, but certainly not limited to thermochemical biomass processing (pyrolysis, liquefaction, gasication),5 fermentation,6 chemical hydrolysis,7 hydrotreating,8 and FischerTropsch catalysis9 have been developed for the conversion of biomass to fuels. The selection of biofuel candidates and promising technologies to produce them
is a challenging proposition. Two key factors to address in any comprehensive approach to biofuel development are the ability to utilize a diverse range of feedstocks and to produce fuels through the application of carbon efcient processes. Ideally, direct biomass products or daughter products will be suitable not only for a diverse set of fuels (gasoline, diesel, jet fuel), but also as feedstocks for both polymers and commodity chemicals. This type of biorenery approach holds great promise for efcient biomass utilization. It is generally agreed that an eclectic approach to biofuel development will be necessary to address current challenges, i.e. there is no one solution to the problem.2 A recent resurgence in the study of biobutanol has shown that it has the potential to play a signicant role in a sustainable, non-petroleum-based, industrial system. In regard to overall biomass utilization, butanol has a key advantage over ethanol, the most established biofuel, as butanol can be produced from both ve and six carbon sugars without organism modication.10 In addition to cellulose, this allows for the efcient use of hemicellulose, which accounts for 2040% of biomass.11,12 This paper will discuss recent technological advances that have revealed the versatility of butanol as a standalone fuel,
Correspondence to: Benjamin G. Harvey, 1900 N. Knox Rd. Stop 6303, China Lake, CA 93555, USA. E-mail: benjamin.g.harvey@navy.mil United States Navy-Naval Air Systems Command (NAVAIR), Naval Air Warfare Center, Weapons Division (NAWCWD), Research Department, Chemistry Division, China Lake, California 93555, USA
www.soci.org
Role of butanol in the development of sustainable fuel a valuable component of fuel mixtures, and as a precursor to saturated, full performance hydrocarbon fuels.
www.soci.org
Another strategy for reducing by-products employs a twostage method20,21 that utilizes two different Clostridia strains for butanol production (Fig. 1). In the rst stage, Clostridium tyrobutyricum selectively produces butyric acid. The butyric acid is then transferred to the second stage where a CA strain is used to convert butyric acid to butanol. By selectively producing butyric acid, acetone and ethanol are not produced in signicant quantities, allowing for the easy isolation of butanol. Another important aspect to the design is that it can be run as a continuous fermentation process by immobilization of the organisms on a polymer support. While much of the current work on increasing butanol production has focused on modication of the ABE process, other researchers have attempted to incorporate the butanol fermentation pathway from the Clostridia genus into the hardier E. coli bacteria.22 While initial efforts have shown that butanol production in E. coli is possible, these species exhibit poor resistance to butanol and produce it in low yield. Additionally, indepth studies to determine the overall effect of butanol production on E. coli have yet to be done. The fermentation pathway of CA is fairly complex with ve separate intermediates and four moles of NADH required to produce one mole of butanol. This pathway requires the transcription and expression of six different genes from CA, which each have the potential to disturb a native process in the E. coli species.17 Signicant research still needs to be conducted to determine if E. coli will be a viable option for butanol production. With regard to sustainability, some novel feedstocks for butanol production have recently been explored. For example, Clostridium pasteurianum has been shown to produce butanol from glycerol at conversions up to 31%.23 Glycerol is a convenient, renewable feedstock produced as a by-product of biodiesel, bioethanol and oleochemical production.24 Although this approach is promising, high yields of butanol with the C. pasteurianum species are only seen after very long fermentation times, on the order of weeks, which makes this process currently impractical for commercial production. In a completely different approach, Arp and co-workers have shown that butane can be converted to butanol using a monooxygenase enzyme found in the gramnegative bacteria Pseudomonas butanovara, among others. For P. butanovara, in particular, 1-butanol conversion from butane
wileyonlinelibrary.com/jctb
www.soci.org
BG Harvey, HA Meylemans
Table 1. Key performance indicators for alcohol and conventional fuels Fuel Gasoline Methanol Ethanol n-propanol n-butanol biodiesel Diesel No. 2
a b
Net heat of combustion Anti-knock index Figure 2. Graph of cetane number vs chain length for linear alcohols.
Table 2. Selected properties of alcohol fuels Alcohol Methanol Ethanol n-propanol n-butanol Boiling point ( C) 64.7 78.4 97.1 117.2
Flashpoint ( C) 12 13 15 29
has been reported with yields up to 90%.25 The drawback of this process is that P. butanovara does not produce butanol as an end product. Instead the 1-butanol is subsequently converted to butyraldehyde, and 2-butanol is converted to butanone through an alcoholdehydrogenase induced reaction.26 In order to make this a viable option for butanol production, further exploration is necessary.
to note that this effect is even more pronounced for ethanol and methanol as they have much higher AKIs and require even lower air/fuel ratios.30,32 Testing of butanol/gasoline mixtures in a direct injection spark ignition engine revealed that butanol rich mixtures exhausted more unburned hydrocarbons, primarily in the form of alcohols, formaldehyde and acetaldehyde, than neat gasoline mixtures.33 In contrast, other researchers have reported that less hydrocarbons are emitted.28 These disparate results are probably a result of the use of different analytical techniques and engine congurations. The lack of a consensus in the open literature on the relative benets of neat and blended alcohol fuels has made it clear that a variety of properties need to be evaluated to adequately compare these fuels. In particular, the NHOC, although an important parameter, is insufcient for fully describing the relative superiority of a sustainable fuel. Other important paramaters include fuel conversion efciency, the amount and type of emissions produced, and the compatibility of a given fuel with existing infrastructure. The use of multiple parameters for fuel evaluation is especially important when fuels of vastly different composition are compared.
wileyonlinelibrary.com/jctb
www.soci.org
MeOH R O KOH R
C O + O HO OH OH
H2C
BuOH KOH
C R O
O + OH
OH
acid cat.
O DBE
+ H2O
for the 20% butanol blend compared to conventional diesel fuel both in a hot start urban cycle and steady state (highway driving) cycle, whereas conversion efciency was decreased in a cold start cycle, probably due to the higher autoignition temperature of butanol. The 40% butanol blend performed poorly under both cold start and hot start urban cycles, with 12 and 10% lower fuel conversion efciency, respectively, but had virtually identical conversion efciency to diesel fuel in the highway driving cycle. These results show that signicant amounts of butanol can be blended into diesel fuel while maintaining suitable performance characteristics. Engines specically modied for these blends are likely to provide improved performance data.
butyl esters such as heat of combustion, viscosity, lubricity, and cloud point have not yet been reported, it is expected that these fuels will have higher net heats of combustion, as well as higher viscosities and cloud points than traditional biodiesel fuels. Oxygenates have been shown to have a dramatic effect on decreasing the amount of particulates and soot present in diesel exhaust. Traditional gasoline oxygenates such as methyl and ethyl tert-butyl ether are unsuitable for incorporation into diesel fuel due to their low cetane numbers (2.5 for ETBE). Incorporation of low cetane number additives can decrease the overall cetane number of a fuel, leading to diminished performance. An intriguing alternative is 1,1-dibutoxyethane which can be synthesized from renewable acetaldehyde and butanol with the aid of a heterogeneous acid catalyst (Scheme 2).39 Perhaps the most promising butanol-derived, oxygenated diesel fuel product is dibutyl ether (DBE). DBE, which has a cetane number of approximately 100, can be synthesized directly from butanol using an acid catalyst (Scheme 3).40,41 Fuels consisting of a mixture of butanol, dibutyl ether, and a lubricant (e.g. biodiesel, jojoba oil) have recently been tested in a diesel engine.42 Although hydrocarbon emissions increased from 5 ppm to 39144 ppm depending on the mixture, with increasing mass fraction of butanol leading to higher emissions, NOx emissions decreased signicantly, particularly for blends with higher mass fractions of butanol. Fuel consumption was about 16% higher than for petroleum diesel which matches well with biodiesel consumption. Given that butanol and dibutyl ether have net heats of combustion 26 and 19%, respectively, lower than conventional diesel fuel, it is interesting that the reduction in efciency was only 16%. This result suggests that the combustion properties of the oxygenated fuels resulted in improved fuel conversion efciency.
wileyonlinelibrary.com/jctb
www.soci.org
BG Harvey, HA Meylemans
cis-2-butene
Scheme 4. Dehydration of n-butanol to a mixture of isomers.
n
Scheme 5. Conversion of 1-butene to oligomers with a metallocene based Ziegler-Natta catalyst.
acid cat.
the production of these fuels typically requires one or more deoxygenation steps. For example, pyrolysis oils derived from biomass must be hydrotreated at elevated temperature in the presence of a late transition metal catalyst.43 Additional steps such as reforming, alkylation, metathesis, and oligomerization may also have to be performed in order to produce fuels that can be used in specic applications (gasoline, jet, and diesel fuels).44 In the case of alcohol fuels, the deoxygenation step proceeds through a dehydration process that can be carried out at modest temperatures using abundant and cheap metal oxide catalysts. The feasibility of such an approach has been demonstrated by the recent development of a process for the conversion of sugarcane derived ethanol to ethylene for the production of high density polyethylene.45 Low density polyethylene has also been produced on a pilot plant scale by the incorporation of biobutanol derived 1-butene as a comonomer.46 In both cases, the olens were produced through dehydration of the alcohols using a -alumina catalyst in a xed bed reactor. In addition to polymers, renewable ethylene has been oligomerized with zeolite catalysts to produce a gasoline range product (predominantly C5C10 oligomers).47 Unlike the selective dehydration of ethanol to ethylene, the low temperature dehydration of butanol results in a mixture of 1- and 2-butene (Scheme 4). When catalysts of low acidity ( -alumina) are used as the catalyst, about 80% 1-butene is produced.48 Although the dehydration of both butanol and ethanol requires only a modest amount of energy, 0.93 and 1.49 MJ L1 , respectively,
butanol dehydration is clearly a more favorable process. Only 3.4% of the NHOC of the product butene must be incorporated from external sources, while 6.6% or almost double the percentage of the nal NHOC is required for ethylene. Although this added energy is reected in the higher gravimetric heat of combustion of the products, any heat loss in the process will be nearly doubled for ethanol dehydration.49 The oligomerization of butene to produce fuels has been well studied. Small and medium pore zeolites such as ZSM-5, -12, and -23 produce short chain oligomers (trimers and tetramers) with modest branching that allows for a diesel fuel cut with an excellent cetane number.50 The use of amorphous silico-aluminas, cation exchange resins, large pore zeolites, polyphosphoric acid, and similar catalysts produce oligomers with signicant branching and thus low cetane numbers. Depending on the distribution, these catalysts can produce gasoline or jet fuel range hydrocarbons. Synthetic titaniumaluminumsilicalite zeolites have been shown to convert butene at 230 C and 45 bar to fuel mixtures with about 70% selectivity to C12C20 hydrocarbons and with cetane numbers >50.51 In a recent report by Dumesic and co-workers, Amberlyst-70, a cation exchange resin, and HZSM-5 were shown to be efcient catalysts for the conversion of butene, derived from the decarboxylation of -valerolactone, to jet fuel range hydrocarbons. The highest yield of C12/C16 hydrocarbons in their work was 54%.52 Although solid acid catalysis has been shown to be an effective method for the production of fuels from butenes, recent work has shown that methylaluminoxane (MAO) activated metallocenes are perhaps the most selective and elegant catalysts for the synthesis of jet and diesel fuels.53 Cp2 ZrCl2 /MAO catalysts produce almost exclusively 1,2 insertion products upon reaction with 1-butene (Scheme 5). No stereochemical control is exerted by this catalyst system, which allows for fuel diversity through the presence of diasteriomers. The regular degree of branching coupled with the designed complexity of the product greatly reduces the freezing point of these mixtures. This in turn allows for the incorporation of some heavier oligomers (i.e. >C20), which can improve lubrication values and overall density without signicantly affecting the low temperature properties of the mixture. The distribution of the oligomers can be further tuned through catalyst design. For example, a homogenous catalyst system produces a relatively broad oligomer distribution, whereas a slurried catalyst system produces a narrow distribution consisting of primarily C12 and C16 isomers. One drawback to this approach is the production of signicant amounts of the dimer, 2-ethyl-1hexene. The hydrogenated dimer product, 3-methyl-heptane, has a ashpoint of only 7 C, which signicantly limits the amount that can be incorporated in jet fuels. To efciently use all of the oligomerization products, a method has been developed that utilizes heterogeneous acid catalysts to selectively dimerize
wileyonlinelibrary.com/jctb
www.soci.org
H2 cat.
HO n-butanol
Scheme 7. Hydroformylation of propene for the production of butanol.
COMMERCIAL OUTLOOK
The commercialization and widespread use of biobutanol will not initially be driven by its utility as a fuel component or precursor. Petroleum butanol which is produced from propene through hydroformylation (Scheme 7) is a commodity chemical. Its price is dictated by the price of petroleum and in concert with the rapidly changing global economy, has recently been quite volatile (Fig. 3).56 In 2009 when oil peaked at $145/bbl, butanol soared to nearly $8.50/gal compared with its relatively stable price of $4.00/gal in the rst half of the decade. Industrially, butanol is converted to acrylates, ethers, and butyl acetate (Fig. 4), which in turn are utilized in paints, lacquers, and resin formulations.57 These initial lucrative commercial markets may allow for biobutanol to gain a foothold that will then allow for its transition to the fuel market. In particular, economics will favor renewable butanol for fuel consumption as petroleum prices continue to increase.
2-ethyl-1-hexene to a complex distribution of C16 molecules (Scheme 6).54 The combination of these oligomerization and dimerization processes allows for the conversion of 1-butene to jet fuel range oligomers in over 90% yield. The cetane numbers for both the butene oligomer mixtures and the dimerized 2-ethyl-1-hexene mixtures have not yet been determined. However, a calculation utilizing a simple additive method for a hydrogenated butene trimer suggests that mixed oligomer fuels will have moderate cetane numbers (>35).55 This may allow for these mixtures to act as standalone diesel fuels or blending agents with other butanol derived fuels such as dibutyl ether. In the case of the C16 mixtures derived from 2-ethyl-1hexene, the degree of branching (average of three branch sites per molecule) in these fuels suggests that they will be unsuitable as major components of diesel fuels, however, the complex product distribution arising from the acid catalysis allows for excellent cold ow properties, thus making them suitable candidates for jet fuels.
CONCLUSION
Given the complexity of natural feedstocks, any successful approach to the large-scale production of biofuels will probably be centered on a biorenery. These reneries will produce a variety of products including fuels, commodity chemicals, and polymer precursors. In a plant dedicated primarily to the production of butanol, the process would start with raw lignocellulosic materials and proceed to hydrolysis of the hemicellulose fraction, followed by separation of the lignin from the product stream, and hydrolysis of the remaining cellulose. Mixed hemicellulose/cellulose derived sugar solutions would then be converted to butanol. Lignin could be used to power the overall process, be packaged and sold in pellet form for the production of heat or electricity, pyrolyzed to fuels, or converted into phenolic precursors for use in composites. Ethanol and acetone produced as side-products in butanol fermentation would be used as fuels, solvents, and chemical
Plasticizers 2% Miscellaneous 4%
Solvent 7%
Acrylates 49%
7
wileyonlinelibrary.com/jctb
www.soci.org
BG Harvey, HA Meylemans
8 Donnis B, Egeberg RG, Blom P and Knudsen KG, Hydroprocessing of bio-oils and oxygenates to hydrocarbons. Understanding the reaction routes. Topics Catal 52:229240 (2009). 9 Tijmensen MJA, Faaij APC, Hamelinck CN and van Hardeveld MRM, Exploration of the possibilities for production of Fischer Tropsch liquids and power via biomass gasication. Biomass Bioenergy 23:129152 (2002). 10 Angenent LT, Energy biotechnology: beyond the general lignocellulose-to-ethanol pathway. Curr Opin Biotechnol 18:191192 (2007). 11 Yang H, Yan R, Chen H, Zheng C, Lee DH and Liang DT, In-depth investigation of biomass pyrolysis based on three major components: hemicellulose, cellulose and lignin. Energy Fuels 20:388393 (2006). 12 McKendry P, Energy production from biomass (part 1): overview of biomass. Bioresource Technol 83:3746 (2002). 13 Duerre P, Fermentative butanol production bulk chemical and biofuel. Ann NY Acad Sci 1125:353362 (2008). 14 Jones DT and Woods DR, Acetone-butanol fermentation revisited. Microbiol Rev 50:484524 (1986). 15 Tomas C, Welker N and Papoutsakis E, Overexpression of groESL in Clostridium acetobutylicum results in increased solvent production and tolerance, prolonged metabolism and changes in the cells transcriptional program. Appl Environ Microbiol 69:49514965 (2003). 16 Chen CK and Blaschek HP, Acetate enhances solvent production and prevents degradation in Clostridium beijerinckii BA1010. Appl Microbiol Biotechnol 52:170173 (1999). 17 Zheng YN, Li LZ, Xian M, Ma YJ, Yang, JM, Xu X, et al, Problems with microbial production of butanol. J Ind Microbiol Biotechnol 36:11271138 (2009). 18 Zhang YHP, Production of biocommodities and bioelectricity by cellfree synthetic enzymatic pathway biotransformations: challenges and opportunities. Biotechnol Bioeng 105:663677 (2010). 19 Tummala SB, Junne SG and Papaoutsakis ET, Antisense RNA downregulation of coenzyme A transferase combined with alcohol-aldehyde dehydrogenase overexpression leads to predomninantly alcohologenic clostridium acetobutylicum fermentations. J Bacteriol 185:36443653 (2003). 20 Lui X, Ying Z and Yang S-T, Butyric acid and hydrogen production by Clostridium tyrobutyricum. Enzyme Microb Technol 38:521528 (2006). 21 Ramey D and Yang S-T, Production of butyric acid and butanol from biomass Final Report (U.S. Department of Energy Contract No.: DE-F-G020ER86106). (2004). 22 Atsumi S, Cann AF, Connor MR, Shen CR, Smith KM, Brynildsen MP, et al, Metabolic engineering of Escherichia coli for 1butanol production. Metab Eng 10:305311 (2008). 23 Taconi KA, Venkataramanan KP and Johnson DT, Growth and solvent production by Clostridium pasteurianum ATCC 6013 utilizing biodiesel-derived crude glycerol as the sole carbon source. Environ Prog Sustainable Energy 28:100110 (2009). 24 Clomburg JM and Gonzalez R, Biofuel production in Escherichia coli: the role of metabolic engineering and synthetic biology. Appl Microbiol Biotechnol 86:419434 (2010). 25 Hamamura N, Storfa RT, Semprini L and Arp DJ, Diversity in butane monooxygenases among butane-grown bacteria. Appl Environ Microbiol 65:45864593 (1999). 26 Arp DJ, Butane metabolism by butane-grown Pseudomonas butanovora. Microbiol 145:11731180 (1999). 27 Chao S and Rossini FD, Heats of combustion, formation, and isomerization of nineteen alkanols. J Chem Eng Data 10:374379 (1965). 28 Ramey DE, Continuous two stage, dual path anaerobic fermentation of butanol and other organic solvents using two different strains of bacteria. US Patent 5753474 (1998). 29 Iz k P, Schwarz K, Ruth W, Bahl H and Kragl U, Increased productivity a of Clostridium acetobutylicum fermentation of acetone, butanol, and ethanol by pervaporation through supported ionic liquid membrane. Appl Microbial Biotechnol 78:597602 (2008). 30 Cooney C, Wallner T, McConnell S, Gillen JC, Abell C, Miers SA, et al, Effects of blending gasoline with ethanol and butanol on engine efciency and emissions using a direct-injection, spark-ignition engine. Proceedings ASME Internal Comb. Eng. Div. Spring Tech. Conf. (ICES200976155) (2009).
precursors for industrial and pharmaceutical applications. The primary product of the process, butanol, could be used directly as a fuel, converted to a wide variety of industrially important chemicals, or converted to diesel and jet fuels (Fig. 5). Although signicant progress has been made, it is clear that the production of butanol from biomass and its use both directly as a fuel and as a precursor to a variety of fuel products is still in its infancy. The rise of butanol as a major component of a sustainable fuel product stream will be dictated by the transition of new and promising technologies to full-scale commercial plants. In the years to come, economic factors conducive to the development of sustainable fuel and chemical platforms are likely to accelerate the adoption of these technologies at an unprecedented rate.
ACKNOWLEDGEMENTS
The authors would like to thank Dr. Michael Wright for helpful discussions and the Ofce of Naval Research In-House Laboratory Independent Research Program for funding this work.
REFERENCES
1 Malthus TR, An Essay on the Principle of Population (1798), ed. by Winch D. Cambridge University Press, Cambridge (1992). 2 Ragauskas AJ, Williams CK, Davison BH, Britovsek G, Cairney J, Eckert CA, et al, The path forward for biofuels and biomaterials. Science 311:484489 (2006). 3 Rathmann R, Szklo A and Schaeffer R, Land use competition for production of food and liquid biofuels: an analysis of the arguments in the current debate. Renewable Energy 35:1422 (2010). 4 Somerville C, Youngs H, Taylor C, Davis S and Long SP, Feedstocks for lignocellulosic biofuels. Science 329:790792 (2010). 5 Huber GW, Iborra S and Corma A, Synthesis of transportation fuels from biomass: chemistry, catalysts and engineering. Chem Rev 106:40444098 (2006). 6 Qureshi N and Ezeji C, Butanol, a superior biofuel production from agricultural residues (renewable biomass): recent progress in technology. Biofuels, Bioprod Bioref 2:319330 (2008); H gerdal BH, a Galbe M, Gorwa-Grauslund MF, Liden G and Zacchi G, Bio-ethanolthe fuel of tomorrow from the residues of today. Trends Biotechnol 24:549556 (2006). 7 Tong X, Ma Y and Li Y, Biomass into chemicals: conversion of sugars to furan derivatives by catalytic processes. Appl Catal A: Gen 385:113 (2010).
wileyonlinelibrary.com/jctb
www.soci.org
46 Morschbacker A and de Castro LR, Integrated process for the production of ethylene-butylene copolymer, and ethylene-butylene copolymer and the use of ethylene and 1butylene, as comonomer sourced from renewable natural raw materials. WIPO Patent WO 2009/070858 (2009). 47 Amin NAS and Anggoro DD, Dealuminated ZSM-5 zeolite catalyst for ethylene oligomerization to liquid fuels. J Nat Gas Chem 11:7986 (2002). 48 Lu M, Xiong G, Zhao H, Cui W, Gu J and Bauser H, Dehydration of 1butanol over -Al2 O3 catalytic membrane. Catal Today 25:339344 (1995). 49 These values were calculated using the heats of formation from Ref. 27 in conjunction with: Prosen EJ, Maron FW and Rossini FD, Heats of combustion, formation, and isomerization of ten C4 hydrocarbons. J Res NBS 46:106112 (1951); and Chase MW, NISTJANAF Thermochemical Tables, 4th edn. J. Phys. Chem. Ref. Data, Monograph 9 (1998). 50 Hellring SD, Huss A, Landis ME, Marler DO, Teitman GJ, Timken HKC, et al, Process for producing low aromatic diesel fuel with high cetane index. US Patent 5639931 (1997). 51 Flego C, Perego C and Marchionna M, Process for obtaining a diesel cut fuel by the oligomerization of olens or their mixtures. US Patent 6914165 (2005). 52 Bond JQ, Alonso DM, Wang D, West RM and Dumesic JA, Integrated catalytic conversion of -valerolactone to liquid alkenes for transportation fuels. Science 327:11101114 (2010). 53 Wright ME, Harvey BG and Quintana RL, Highly efcient zirconiumcatalyzed batch conversion of 1butene: a new route to jet fuels. Energy Fuels 22:32993302 (2008). 54 Harvey BG and Quintana RL, Synthesis of renewable jet and diesel fuels from 2ethyl-1hexene. Energy Environ Sci 3:352357 (2010). 55 DeFries TH, Indritz D and Kastrup RV, Prediction of cetane number by group additivity and carbon-13 nuclear magnetic resonance. Ind Eng Chem Res 26:188193 (1987). 56 http://tonto.eia.doe.gov/dnav/pet/hist/LeafHandler.ashx?n=PET&s= RWTC&f=D Accessed 08/16/2010. 57 http://www.icis.com/Articles/2006/01/30/2012283/chemical-prolen-butanol.html. Accessed 08/16/2010.
9
wileyonlinelibrary.com/jctb