Emerging Technologies

Received: 6 September 2010 Revised: 8 October 2010 Accepted: 11 October 2010 Published online in Wiley Online Library: 9 December 2010

(wileyonlinelibrary.com) DOI 10.1002/jctb.2540

The role of butanol in the development of sustainable fuel technologies

Benjamin G. Harvey and Heather A. Meylemans
Abstract
OVERVIEW: The development of innovative methods to efciently convert biomass to fuels and industrial chemicals is one of the grand challenges of the current age. n-Butanol is a versatile and sustainable platform chemical that can be produced from a variety of waste biomass sources. The emergence of new technologies for the production of fuels and chemicals from butanol will allow it to be a signicant component of a necessarily dynamic and multifaceted solution to the current global energy crisis. IMPACT: The production of butanol from biomass and its utilization as a precursor to a diverse set of fuel products has the potential to reduce petroleum use worldwide. In concert with other emerging renewable technologies, signicant reductions in greenhouse gas emissions may be realized. The rapid incorporation of renewables into the world fuel supply may also help to offset predicted increases in transportation fuel prices as the supply of oil declines. APPLICATIONS: Recent work has shown that butanol is a potential gasoline replacement that can also be blended in signicant quantities with conventional diesel fuel. These efforts have transitioned to research focused on the development of viable methods for the production of an array of oxygenated and fully saturated jet and diesel fuels from butanol. The technologies discussed in this paper will help drive the commercialization and utilization of a spectrum of butanol based sustainable fuels that can supplement and partially displace conventional petroleum derived fuels. Published 2010 by John Wiley and Sons, Ltd. Keywords: Butanol; renewable jet fuel; biodiesel; sustainable chemistry; biorenery

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

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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.

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CONVERSION OF BIOMASS TO BUTANOL

While there is renewed interest in the use of butanol as a transportation fuel, the major pathway by which it is produced has been known for over a century. In 1862 Louis Pasteur was the rst to report the fermentation of glucose to butanol using a grampositive Clostridium anaerobe.13 Since then this fermentation method has become known as the ABE process, which stands for acetone, butanol and ethanol, the three major products. Even today, members of the Clostridium genus, specically Clostridium acetobutylicum (CA) and Clostridium biejerinckii (CB), continue to be the most widely used organisms for butanol fermentation. The typical ABE process produces a 6 : 3 : 1 ratio of butanol : acetone : ethanol.14 Despite the maturity of this process, overall yields of solvent production are only on the order of 12% due to the toxicity of the products to the bacteria. In the case of butanol, this toxicity is known to come from damage to the cell membrane. The membrane loses its integrity and becomes more permeable, allowing introduction of everything from ADP and ions, to the solvent itself, leading to cell death. Attempts to improve processes that utilize Clostridia bacteria have focused on specic goals including decreasing the solvent toxicity, improving the overall butanol yield, and decreasing the yield of by-products. Some success has been achieved with Clostridia strains that have been engineered to increase butanol production above the practical maximum of 13 g L1 produced by CA. Papoutsakis and co-workers have created a mutant of CA-ATCC 824 which has been shown to produce 40% more butanol than the wildtype species with nal concentrations as high as 18.5 g L1 . In addition, active metabolism in this strain lasted between two and three times longer than in the wild type.15 Another high yielding strain developed by Blaschek and co-workers, CB-BA101,16 showed butanol concentrations up to 20.9 g L1 , representing the highest yield reported in the literature for a batch fermentation process.17 Perhaps the most important factor for increasing butanol yield in batch fermentation processes is organism resistance to butanol. In the wild-type strain of CA, 1% butanol signicantly inhibits cell growth and fermentation and at a concentration of 1.6%, these processes are arrested.18 The greatest increase in butanol resistance was observed in the CA-ATCC 824 mutant created by Papoutsakis and co-workers.15 The mechanism for this increased resistance and subsequent improvement in the production of butanol is not yet fully understood, but this result provides a benchmark for future studies. Another important factor that limits the efcacy of the ABE process is the production of by-products. Recovery of butanol from fermentation broths can be difcult due to low yields of solvent in the batch process and the need to separate the butanol from acetone and ethanol. The creation of knockout species and inhibition of certain genes has been explored to reduce both acetone and ethanol production. To date, most attempts at optimizing butanol yield over ethanol and acetone have focused on the butanol/acetone ratio as ethanol is a minor component of the mixture. In a recent study Papoutsakis and co-workers were able to increase the ratio of butanol to acetone from two to almost ve, however, the overall yield of butanol was lower than that of the control strain.19 Other studies in this area have seen similar decreases in yield when trying to inhibit one of the two products.

Figure 1. Two-stage conversion of sugar feedstocks to butanol.

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

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Table 1. Key performance indicators for alcohol and conventional fuels Fuel Gasoline Methanol Ethanol n-propanol n-butanol biodiesel Diesel No. 2
a b

NHOCa (MJ L1 ) 32.3 15.6 21.1 24.6 26.8 32.9 36.0

Density (g mL1 ) 0.74 0.79 0.79 0.80 0.81 0.88 0.85

AKIb 87 120 113 104 87 15-25

NHOC/NHOCgas a 1.00 0.48 0.65 0.76 0.83 1.02 1.11

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

Water solubility Miscible Miscible Miscible (7.7 g)/100 mL

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.

BUTANOL AS A GASOLINE SURROGATE

The most direct application of butanol as a transportation fuel is predicated on its utility as a gasoline replacement. In this respect, butanol has a number of advantages over other common alcohol fuels such as ethanol and methanol. The net heat of combustion of butanol (NHOC) is roughly 83% that of gasoline (Table 1) compared with 65 and 48% for ethanol and methanol, respectively.27 Butanol is far less hygroscopic than methanol, ethanol, and propanol. These lower alcohols are fully miscible with water, whereas butanol has only a modest water solubility of 7.7 g per 100 mL water (Table 2). The solubility of water in butanol is signicant (20 g per 100 mL butanol), but limited. This allows butanol/water mixtures to form a heterogeneous azeotrope boiling at 93 C that separates into two phases upon condensation, allowing for a low energy intermediate purication step.21,28 The lower hydrophilicity of butanol also makes it an excellent candidate for energy efcient separation techniques such as pervaporation.29 Butanol is less corrosive than ethanol, can be transported in existing pipelines and is much safer to work with than lower alcohols based on its relatively high boiling point of 117 C and ashpoint of 29 C. With regard to fuel performance, butanol has an anti-knock index (AKI-dened as (research octane number + motor octane number)/2) of 87 which compares favorably with gasoline.30,31 Butanol also requires a lower air/fuel ratio than conventional gasoline which promotes improved fuel conversion efciency, particularly under high power output conditions. Its important

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.

DIESEL FUEL BLENDS

Unlike shorter chain alcohols, butanol not only has the potential to perform well as a gasoline surrogate, but also has a moderate cetane number which allows for incorporation of signicant amounts into diesel fuel. The cetane number of butanol has been reported as high as 25,34 however based on the available data, the actual number is probably closer to 20 in line with the cetane ratings of other normal alcohols (Fig. 2).35,36 This is in contrast to ethanol and methanol which can only be added in minor amounts before they adversely affect the cetane number of the fuel. For comparison purposes, the cetane number for petroleum diesel ranges from about 4245, while straight chain alcohols do not have comparable cetane numbers until n-octanol with a cetane number of 40. Although butanol is not suitable as a direct diesel replacement, the use of butanol as a signicant component of diesel fuel has been explored in detail. Blends of 20 and 40% butanol in diesel fuel have recently been evaluated in a commercial diesel engine.37 The cetane numbers of these blends were determined to be 38.6 and 35.2, respectively. As expected, the blends had lower fuel economy than the pure diesel, primarily due to the reduced heating value of the blend. However, the fuel conversion efciency was higher

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Role of butanol in the development of sustainable fuel

O O C H2C HC O O C R O C O
Scheme 1. Conversion of triglycerides to methyl and butyl esters via microwave irradiation.

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MeOH R O KOH R

C O + O HO OH OH

H2C

BuOH KOH

C R O

O + OH

acid cat. O O 1,1-dibutoxyethane

Scheme 2. Synthesis of 1,1-dibutoxyethane from acetaldehyde and butanol.

OH

acid cat.

O DBE

+ H2O

Scheme 3. Partial dehydration of butanol to di-butyl ether.

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.

DIESEL FUEL OXYGENATES

In addition to blending, butanol can be chemically incorporated into diesel fuel in a manner similar to the well established procedure for converting triglycerides to biodiesel. Biodiesel has been shown to be an excellent replacement for traditional diesel and is typically synthesized from triglycerides and methanol to produce fatty acid methyl esters (FAME). Methanol is used in this process due to its low cost and rapid reaction rate, but is typically derived from non-renewable natural gas. Recent work has shown that butanol can be substituted for methanol under moderate conditions using microwave irradiation as the heating source (Scheme 1).38 Instead of relying on conduction currents, microwave heating allows for direct transfer of energy into the sample. Using this approach, FAME can be produced in quantitative yield (oil : methanol 1 : 6, 1 wt% KOH, 50 C, 1 min). A butyl version can be prepared in 93% yield by a moderate increase in the temperature (120 C, oil : butanol 1 : 6, 2 min). The reaction can also be catalyzed by an acid catalyst (5 wt% H2 SO4 ), which may have advantages in an industrial process as base catalysis can lead to soap formation, particularly when free fatty acid and water concentrations are high. Although the key properties of these

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.

SATURATED HYDROCARBON FUELS FROM BUTANOL

Although oxygenated fuels can be used in place of traditional petroleum distillates, the loss in performance due to the decrease in volumetric heat of combustion makes these fuels unsuitable for certain applications. To address this shortcoming, fully saturated hydrocarbon fuels can be produced from biomass. However,

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trans-2-butene cat. HO n-butanol 1-butene + H2O

cis-2-butene
Scheme 4. Dehydration of n-butanol to a mixture of isomers.

[Zr] n [Zr] =Cp2ZrCl2/MAO H2 cat. n = 0-4

n
Scheme 5. Conversion of 1-butene to oligomers with a metallocene based Ziegler-Natta catalyst.

acid cat.

C16H32 isomers H2 cat. C16H34 isomers

Scheme 6. Dimerization of 2-ethyl-1-hexene.

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

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Role of butanol in the development of sustainable fuel

O CO/H2 cat. H

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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.

Figure 3. Oil prices 1986present.

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%

n-Butyl Acetate 14%

Solvent 7%

Glycol Ethers 24%

Figure 4. Distribution of industrially important chemicals derived from butanol.

Acrylates 49%

7
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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).

Figure 5. Butanol as a platform chemical.

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

Published 2010 by John Wiley and Sons, Ltd.

J Chem Technol Biotechnol 2011; 86: 29

Role of butanol in the development of sustainable fuel

31 Graboski M, An analysis of alternative for unleaded petrol additives for South Africa. Report for the United Nations Environment Programme (2003). 32 Abu-Zaid M, Badran O and Yamin J, Effect of methanol addition on the performance of spark ignition engines. Energy Fuels 18:312315 (2004). 33 Wallner T and Frazee R, Study of regulated and non-regulated emissions from combustion of gasoline, alcohol fuels and their blends in a DI-SI engine. SAE Internal 10SFL-0085 (2010). 34 The cetane number of butanol has been reported as 25 in the popular press. Avaliable: http://peswiki.com/index.php/directory:butanol [28 October 2010]. 35 Lujaji F, Bereczky A, Novak CS and Mbarawa M, Cetane number and thermal properties of croton oil, biodiesel, 1butanol, and diesel blends. Proceedings World Congress Engineering 3:24242428 (2010). 36 Murphy MJ, Taylor JD and McCormick RL, Compendium of experimental cetane number data. NREL/SR-54036805 (2004). 37 Miers SA, Carlson RW, McConnell SS, Ng HK and Wallner T, Drive cycle analysis of butanol/diesel blends in a light-duty vehicle. SAE Internal 2008012381 (2008). 38 Leadbeater NE, Barnard TM and Stencel LM, Batch and continuousow preparation of biodiesel derived from butanol and facilitated by microwave heating. Energy Fuels 22:20052008 (2008). 39 Graca NS, Pais LS, Silva VMTM and Rodrigues AE, Oxygenated biofuels from butanol for diesel blends: synthesis of the acetal 1,1dibutoxyethane catalyzed by Amberlyst-15 ion-exchange resin. Ind Eng Chem Res 49:67636771 (2010). 40 Olah GA, Cleaner burning and cetane enhancing diesel fuel supplements. US Patent 5520710 (1996). 41 Olah GA, Iyer PS and Prakash GKS, Peruorinated resinsulfonic acid (Naon-H). Catalysis in synthesis. Synthesis 1986:513531 (1986). 42 Wright ME, Harvey BG and Quintana RL, New navy fuels from biobutanol. Prepr Pap-Am Chem Soc, Fuel Div 53:252253 (2008). 43 Czernik S and Bridgewater AV, Overview of applications of biomass fast pyrolysis oil. Energy Fuels 18:590598 (2004). 44 Olah GA and Moln r A, Hydrocarbon Chemistry 2nd edn. John Wiley & a Sons, Hoboken, NJ (2003). 45 Morschbacker A, Bio-ethanol based ethylene. Polym Rev 49:7984 (2009).

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.

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