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Fuel 242 (2019) 673–686

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Potential of acetone-butanol-ethanol (ABE) as a biofuel T


a a a a,⁎ b,⁎
Yuqiang Li , Wei Tang , Yong Chen , Jiangwei Liu , Chia-fon F. Lee
a
School of Energy Science and Engineering, Central South University, Changsha, Hunan 410083, China
b
Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, IL 61801, USA

A R T I C LE I N FO A B S T R A C T

Keywords: Biobutanol has demonstrated to be a superior alternative biofuel in internal combustion engine (ICEs). Acetone-
Biofuel butanol-ethanol (ABE) fermentation engineering is a typical technique for biobutanol production. However, the
Acetone-butanol-ethanol high costs and extra energy consumption in recovery process of biobutanol from intermediate fermentation
Production solvent (i.e. ABE mixture) has obstructed its large-scale application. It is gaining increasing attention to in-
Combustion
vestigate ABE as a potential alternative biofuel. ABE production and ABE combustion in ICEs have been widely
Internal combustion engines
studied, but these studies are rarely reviewed to favor understanding and popularization for ABE so far. In this
work, the updated progress of ABE fermentation techniques is first summarized from the aspects: (i) selection of
suitable strain; (ii) availability of cheaper substrates; (iii) development of fermentation engineering. Then, the
research on ABE combustion in ICEs are concluded from the aspects: (i) physicochemical properties and tests in
ICEs of ABE components; (ii) substitute for diesel in compression ignition engines; (iii) substitute for gasoline in
spark ignition engines. These studies demonstrate that ABE is a better alternative for gasoline or diesel fuel due
to the environmentally benign manufacturing process and the potential to improve energy efficiency and reduce
pollutant emissions. However, ABE has not been intensively studied when compared to conventional alternative
fuels (e.g. ethanol, butanol, biodiesel, etc.), for which considerable numbers of reports are available. Therefore,
some challenges and future research directions are outlined in the end. This review is helpful for finding op-
portunities to make ABE as a feasible alternative biofuel in near future.

1. Introduction received more attention due to its renewability, less toxic, higher en-
ergy density, etc., therefore, ethanol is the most common alternative
Due to the continuous worldwide energy consumption with tech- fuel for internal combustion engines (ICEs) in United States, Brazil and
nology development and human progress, the extensive use of fossil South Africa [18–20]. Recently, much attention has been paid on bu-
fuels has led to numerous social, economic and environmental issues, tanol belonged to higher alcohol due to its several advantages over
such as energy security, climate change and human diseases [1–5]. lower alcohols [21–23]. For instance, butanol has a lower auto-ignition
Hence, the search for renewable energy sources has grown con- temperature and thus it can be burned easier. Butanol can be blended
siderably. Biofuel, produced through biological process, has drawn with base fuel without phase separation, allowing it to be transported
great attentions from the world due to its environment-friendly feature and distributed using the existing fuel supply infrastructure. Besides,
[6–10]. For instance, the Biofuels Research Advisory Council of Eur- butanol is less corrosive and evaporative and can releases more energy
opean Union proposed that the fraction of biofuels usage in transpor- per unit mass.
tation fuel consumption has to increase to 25% in 2030 [11]. The En- One major drawback of biobutanol is its high price caused by the
ergy Independence and Security Act of USA mandated the renewable low production efficiency [23–25]. The production rate of bioethanol
fuel used in transportation need to grow to 36 billion gallons in 2022 from biological process is 10–30 times higher than biobutanol yielded
[12]. The National Energy Administration of China announced the from acetone-butanol-ethanol (ABE) fermentation process. The pro-
production of ethanol and biodiesel should reach 4.0 and 2.0 million duction economics of ethanol and butanol was compared by Tao et al.
tons by 2020, respectively [13]. [26] in detail. The production costs of ethanol and n-butanol from corn
Currently, primary alcohols including methanol, ethanol and bu- was estimated to be $1.53 and $1.96 per gallon, respectively. Pfromm
tanol, are common biofuels [14–16]. Methanol is generally made from et al. [27] predicted the prices of ethanol and butanol from 2007 to
coal or methane [17]. In comparison with methanol, ethanol has 2027 based on historical data and certain assumptions, as shown in


Corresponding authors.
E-mail addresses: jiangweiliu@csu.edu.cn (J. Liu), cflee@illnois.edu (C.-f.F. Lee).

https://doi.org/10.1016/j.fuel.2019.01.063
Received 11 October 2018; Received in revised form 4 January 2019; Accepted 9 January 2019
Available online 18 January 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
Y. Li et al. Fuel 242 (2019) 673–686

2. Production of ABE

In order to make ABE fermentation engineering sustainably and


economically feasible, research points are mainly focused on strains
screen, substrates selection and fermentation techniques innovation,
which are introduced in this section.

2.1. Selection of suitable strain

The screen of strain is crucial to produce ABE since it determines


fermentation performance and influences methods for feedstock pre-
treatment/hydrolysis and solvent recovery. Many strains being capable
of ABE fermentation are currently recognized and can mainly be cate-
gorized as genus Clostridium strains (e.g. Clostridium Acetobutylicum (C.
Acetobutylicum), C. beijerinckii, C. saccharoperbutylacetonicum, C. sac-
charobutylicum) and non-Clostridium strains (e.g. Escherichia coli,
Fig. 1. Predicted price of ethanol and butanol based on historical data and
Lactobacillus brevis, Pseudomonas putida, Lactobacillus buchneri,
expected future market trends [27].
Saccharomyces cerevisiae), as listed in Table 1. Fig. 2 shows the scheme
of ABE fermentation pathway employed by C. acetobutylicum. The
Fig. 1. It is seen that butanol has a much higher price than ethanol. products during fermentation engineering can be categorized into three
Therefore, ethanol still being the most widely used alternative fuel in types: (i) solvents (acetone, ethanol and butanol); (ii) organic acids
ICEs. (acetate and butyrate); (iii) gases (CO2 and H2) [30]. Compared to
Besides the low production rate, the separation of butanol from ABE genus Clostridium strains, non-Clostridium strains can reduce or elim-
mixture requires extra money and energy. Based on traditional direct inate the major byproducts of acetone and ethanol from synthetic
distillation method, the process requires 18.4 MJ/kg accounting for biology [31].
54% combustion heat value of butanol [28]. These issues could be It is known that genus Clostridium strains are capable of utilizing
eliminated if the intermediate fermentation solvent (i.e. ABE) could simple and complex carbohydrates, such as glucose, sucrose, cellulose
become a fuel for clean combustion. It motivates many researchers to [32]. Among vast variety of genus Clostridium strains, C. acetobutylicum
consider ABE as an alternative biofuel in ICEs and investigate com- [33], C. beijerinckii [34], C. saccharoperbutylacetonicum [35] and C.
bustion and emissions characteristics of ICEs fueled with ABE-fossil fuel saccharobutylicum [36] can produce solvent with relatively high yields
blends. Qureshi and Blaschek [29] performed an economic assessment during fermentation under appropriate conditions. The performance of
of ABE fermentation, and forecasted price of ABE (0.27 $/kg) was close ABE fermentation using wild-type Clostridium strains is severely limited
to the price of gasoline (0.22 $/kg). by weak solvent tolerance, sluggish growth and low cell density during
As fermentation engineering develops, ABE could become an eco- the solventogenic phase of Clostridium growth. Mutagenesis, evolu-
nomically feasible potential biofuel. Therefore, progress in the pro- tionary engineering and molecular engineering have been considered to
duction and application of ABE in ICEs was reviewed in this study. The address these problems [37]. In the mutagenesis engineering, mutagens
recent advances in ABE fermentation and the improved methods of ABE (e.g. N-methyl-N-nitro-N-nitrosoguanidine (MNNG), hydrogen peroxide
fermentation are first described. Then, the fundamental combustion and nalidixic acid) is used to activate the mutation of genus Clostridium
experiments in some burning reactors and the investigations of com- strains, among which direct acting MNNG seems to work best. The
bustion, performance and emissions characteristics of spark ignition mutant C. beijerinckii BA101 was generated from C. beijerinckii NCIMB
engine or compression ignition engine fueled with ABE are summarized 8052 through the treatment with MNNG [38]. Evolutionary en-
to discuss the applications of ABE as a biofuel in ICEs. It is expected that gineering, following a principle “Mutagenesis followed-by Selection”,
this review is helpful: (i) for researchers and engine manufacturers to can also be employed to further improve solventogenic performance. C.
develop the further researches related to optimize and readjust ICEs acetobutylicum T64 was obtained from C. acetobutylicum D64 through
fueled with ABE and its relevant systems; (ii) for governments to design artificial simulation of bio-evolution [39]. As a more rational strategy,
new energy policies to impel the use of ABE in the light of environ- molecular engineering modifying strains through inactivated and/or
mental costs; (iii) for private users to understand profits for using ABE, overexpressed genes, was expected to be able to solve the issues of te-
and enhance consciousness of environmental protection. dious and instability related to mutagenesis and evolution engineering.
Moreover, several genes encoding metabolic enzymes were knocked
out/down (e.g. buk, ptb and ack) and/or overexpressed (e.g. aad, adhE

Table 1
Strains utilized in ABE fermentation engineering.
Type Strain Substrate Main solvent product Production titer (g/l) Refs

Clostridium C. acetobutylicum ATCC 824 Macroalgae Acetone, butanol, ethanol 6.1 [33]
C. beijerinckii P260 Switchgrass Acetone, butanol, ethanol 14.6 [34]
C. saccharoperbutylacetonicum N1-4 Potato Acetone, butanol, ethanol 16.0 [35]
C. saccharobutylicum DSM 13864 Sago Starch Acetone, butanol, ethanol 9.1 [36]
C. beijerinckii BA101 Synthetic medium Acetone, butanol, ethanol 8.8 [38]
C. acetobutylicum T64 cornmeal Acetone, butanol, ethanol 15.3 [39]

Non-Clostridium E. coli Glucose Butanol, propanol 2.0 [41]


L. brevis Glucose Butanol, ethanol 0.303 [42]
P. putida Glucose Butanol, ethanol 0.12 [43]
L. buchneri Glucose Butanol 0.066 [44]
S. cerevisiae Glucose Butanol 0.0025 [45]

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Y. Li et al. Fuel 242 (2019) 673–686

Fig. 2. Metabolic pathway of ABE fermentation employed by C. acetobutylicum [30,31].

and thiL) in genus Clostridium strains to alter the concentration, yield, fermentation using low-cost soy molasses through C. beijerinckii BA101.
and ratios of solvents [40]. Solventogenic genes (e.g. adhE1, adhE2 and Huang et al. [47] successfully used corn in ABE fermentation by C.
bdhB) of clostridia were extracted for heterologous expression of non- acetobutylicum ATCC 55025 immobilized in a fibrous bed bioreactor.
Clostridium strains. Escherichia coli (E. coli) [41] is well-established non- Corn and cornstarch (after removal of corn oil and protein) are the
Clostridium strains although other organisms such as Lactobacillus brevis major substrates used in Chinese ABE fermentation plants [48]. Because
(L. brevis) [42], Pseudomonas putida (P. putida) [43], Lactobacillus cassava is able to grow in poor soils and is not the staple food in some
buchneri (L. buchneri) [44] and Saccharomyces cerevisiae (S. cerevisiae) countries, Tang et al. investigated ABE batch fermentation of cassava
[45] are also under development. The progress in heterologous ex- using C. saccharoperbutylacetonicum N1-4 [49]. Jerusalem artichoke
pression of butanol pathway in non-Clostridium strains is exciting, containing oligomeric fructans gives an excellent solvent yields after
however, butanol concentrations for the non-Clostridium strains were being hydrolyzed with a chemical or enzyme process [50]. Among the
much lower than those for genus Clostridium strains. More compre- traditional substrates, the use of corn and Jerusalem artichokes conflict
hensive and deep studies on how to control the expressions of genes and with its nutritional purpose, especially in areas concerned with poten-
enzymes are still needed. tial food shortages. Moreover, the prices of cassava and molasses, have
also been pushed up because they do not suffice to fulfill the growing
demand for biofuels intended. The exploration of inexpensive and
2.2. Availability of cheaper substrates
nonfood substrates for ABE fermentation have been driven by these
concerns.
As listed in Table 2, traditional substrates such as: sucrose and
Considerable efforts in recent years have been made to utilize cost-
starch-based carbohydrates have been utilized in ABE fermentation at
effectively sustainable substrates for ABE fermentation. As one of most
industrial scale production. Qureshi et al [46] evaluated ABE

Table 2
Substrates utilized in ABE fermentation engineering.
Type Substrate Strain Production titer of ABE (g/l) Refs

Traditional substrates: Soy molasses C. beijerinckii BA101 10.7 [46]


Sucrose and starch Corn C. acetobutylicum ATCC 55025 12.5 [47]
Cassava C. saccharoperbutylacetonicum N1-4 21.0 [49]
Jerusalem artichoke C. acetobutylicum IFP904 9.1 [50]
Cost-effectively sustainable substrates: Corn stove C. beijerinckii P260 16.0 [53]
Lignocellulosic biomass Corn fiber C. beijerinckii BA101 9.0 [54]
Wheat straw C. beijerinckii P260 22.2 [55]
Rice bran C. saccharoperbutylacetonicum N1-4 12.1 [56]
Micro-algae Wastewater algae C. saccharoperbutylacetonicum N1-4 5.2 [58]
Arthrospira platensis C. acetobutylicum 8.2 [59]
Dunaliella tertiolecta C. acetobutylicum 12.7 [59]
Nannochloropsis C. acetobutylicum 15.4 [59]
Glycerol Glycerol C. pasteurianum ATCC 6013 18.3 [60]
Syngas Syngas C. carboxidivorans P7T 0.009 [61]

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Y. Li et al. Fuel 242 (2019) 673–686

abundant renewable resource on the earth, lignocellulosic biomass properties of enzyme have encountered impressive developments in the
considered as a potential renewable substrate for ABE fermentation has last years including microbiology, protein engineering, chemistry of
been a key research topic since the late 20th century [51]. In China, proteins, etc. [76–79]. The formed or released inhibitors during pre-
nearly 830 million tonnes of lignocellulosic biomass per year are pro- treatment and hydrolysis steps can cause the decrease of fermentation
duced directly from straw, wood residues, rice busk and bagasse [52]. yields and productivity, thereby the detoxification operation is needed
Using C. beijerinckii P260, hydrolyzed corn stover can produce 16.0 g/l [80]. Palmqvist and Hahnhägerdal reviewed various detoxification
solvents after removing inhibitors [53]. Similarly, after removal of the methods involving biological, physical and chemical detoxifications
inhibitors of corn fiber hydrolysate with XAD-4 resin through the [81]. Among them, ion exchange resins are considered to be relatively
treatment of sulfuric acid, 9.3 g/l solvents were produced in ABE fer- effective one and are simple to operate [82].
mentation by C. beijerinckii BA101 [54]. Wheat straw was hydrolyzed The midstream of ABE fermentation engineering can be performed
by alkaline peroxide and hydrolytic enzymes and then employed in ABE under batch, fed-batch or continuous modes. In general, batch mode is
fermentation by C. beijerinckii P260 [55]. Al-Shorgani et al. [56] ex- more suitable for small scale production, while fed-batch or continuous
amined the ABE fermentation of de-oiled rice bran by C. sacchar- modes are good selections at large scale [83]. In order to make fer-
operbutylacetonicum N1-4. Micro-algae have recently got much attention mentation process to be more productive and cost-competitive, much
as an attractive renewable substrate for ABE fermentation. Compared to efforts have been placed on the development of advanced fed-batch and
terrestrial biomass, the usage of micro-algae does not only saves culti- continuous fermentation strategies. PH-stat fed-batch fermentation and
vation land to grow food crops to feed the world’s increasing popula- pH-controlled fed-batch fermentation techniques were examined by
tion, but also saves fresh water due to the high growth rate of algae in Tashiro et al. [35] and Wu et al. [84], respectively. It has been proved
seawater and wastewater [57]. Ellis et al. completed the ABE fermen- that the pH-controlled fed-batch fermentation lead to lactic acid con-
tation using acid/base pretreated wastewater algae biomass as the sumption acceleration and productivity increase. In comparison with
substrate by C. saccharoperbutylacetonicum N1-4 [58]. Efremenko et al. typical fed-batch fermentation, continuous fermentation can reduce
demonstrated the highly efficient conversion of various preheated mi- reactor volume and operational period. Cell immobilization or cell re-
croalgae, including arthrospira platensis, dunaliella tertiolecta and cycling technique are used in continuous fermentation to solve the
nannochloropsis for ABE fermentation by C. acetobutylicum cells im- problem of cell wash-out [85]. Under cell immobilization continuous
mobilized into poly cryogel [59]. Glycerol and syngas were also used as fermentation, cells were mainly immobilized by adsorption [86], en-
substrates in the ABE fermentation by C. pasteurianum ATCC 6013 and trapment [87] and covalent bond formation [88]. Among the reports
C. carboxidivorans P7T, respectively [60,61]. related to cell recycling continuous fermentation, Jang et al. presented
a high solvent production of 32.5 g/l using C. acetobutylicum BKM1
[89]. Membrane fouling is a major obstacle in cell recycling continuous
2.3. Development of fermentation engineering
fermentation, and thus more superior membranes need to be developed
[90]. Another effective technique for improving continuous fermenta-
A typical ABE fermentation engineering contains the following main
tion productivity is to use multi-stage continuous fermentation system.
units: upstream, midstream and downstream, as shown in Fig. 3. Se-
An overall 25.32 g/l ABE solvent was produced from a two-stage con-
lected substrates determine the type and number of required steps in
tinuous fermentation with integrated solvent removal using C. acet-
upstream progress. Generally, noncellulosic substrates need hydrolysis
obutylicum B5313, which is higher than that from the single stage fer-
and detoxification steps, while lignocellulosic substrates need an extra
mentation (15.98 g/l) [91].
pretreatment step to remove structural and compositional barriers to
In situ product recovery (ISPR) technique is employed in the
hydrolysis [62]. Physical, physic-chemical, chemical and biological
downstream of ABE fermentation to alleviate solvent toxicity for the
pretreatment techniques have been introduced in Refs. [63–67]. Steam
microorganisms [92]. Liquid-liquid, perstraction, pervaporation, ex-
explosion [68], liquid hot water [69], dilute acid [70], lime [71], am-
traction, and gas stripping are most important ISPR techniques. Usage
monia [72] and ionic liquid [73] pretreatments have been potentially
of liquid-liquid, perstraction and pervaporation based ISPR in ABE
considered cost-effective methods. Both acid and enzymatic treatments
fermentation was reviewed in Refs. [93–95], respectively. Although the
are mainly used to carry out the hydrolysis step. Compared to the en-
encouraging results can be obtained by pervaporation and liquid-liquid
zymatic hydrolysis, acid hydrolysis can penetrate lignin without pre-
based ISPR, the issues of membrane fouling, extractant formation and
treatment, and thereby the hydrolysis is faster, but some generated by-
extractant loss are still common and the process is relatively costly to
products (e.g. acetic acid, formic acid and furfural) are toxic to strains
operate. Literatures suggested gas stripping based ISPR was simple,
[74]. Because enzymes are highly specific in the catalytic reactions, by-
cost-effective and advantageous over others because it has no negative
products formation in acid hydrolysis is avoided and waste treatment
effect on fermentation, expensive or harmful membrane and extractants
costs are reduced [75]. Several available techniques improving critical

Fig. 3. Processes of ABE fermentation engineering.

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Y. Li et al. Fuel 242 (2019) 673–686

are not required, and there is no loss of nutrients and intermediates butanol and acetone is lower than that of gasoline and diesel, and thus
[96]. Integration of gas stripping based ISPR with batch, fed-batch, and more fuel required for the same power output; (4) Ethanol and acetone
continuous fermentation processes has resulted in a highly improved have higher octane number than gasoline and are able to withstand
productivity and yields, which was reviewed by Qureshi et al. [97]. A more compression before detonation; (5) The lower cetane number of
novel two-stage gas stripping ISPR was used for solvent recovery from ethanol and n-butanol than diesel could cause a longer ignition delay
ABE fermentation using C. acetobutylicum JB200 immobilized in a fi- and an increase of premixed-phase of combustion and result in a higher
brous bed bioreactor [98]. The fermentation got a highly concentrated combustion efficiency due to more fuel burned under constant volume
product containing 195.9 g/l ABE. ABE fermentation integrated with conditions; (6) Ethanol, n-butanol and acetone have higher latent heat
gas stripping ISPR has caught the attentions to scale up ABE fermen- than gasoline and diesel and need to absorb more heat from in-cylinder
tation. environment to evaporate; (7) Ethanol, n-butanol and acetone do not
contain mono-aromatic and poly-aromatic hydrocarbons which are
2.4. Summary and perspectives harmful to environment and health; (8) Ethanol, n-butanol and acetone
have a higher flashing point and auto-ignition temperature than gaso-
In this section, the update progress in ABE fermentation was re- line and diesel, and thus their usage at high temperatures are more
viewed from three aspects, including selection of suitable strain, safer; (9) The lower saturation pressure of ethanol and n-butanol
availability of cheaper substrates, and development of fermentation compared to that of gasoline decreases the chance of cavitation and
engineering. Recent advances in Clostridium and non-Clostridium strains vapor lock problem and eliminates the usage of very special blends
indicates that, in addition to the use of conventional mutagens and during hot day in summer and cool day in winter; (10) Although the
evolution, molecularly modified strains through inactivated and/or miscibility of ethanol in diesel at low temperatures may cause phase
overexpressed genes are employed to improve the performance of separation and then leads to serious consequences on engine operation,
strains based on the principles of efficient use of alternative substrates, n-butanol and acetone can be as a co-solvent additive of ethanol to
improvement of solvent yields, alteration of solvent ratios, enhance- ensure solubility of the blend in diesel; (11) The higher laminar flame
ment of end product tolerance and solvents concentrations, and su- propagation of ethanol, n-butanol and acetone than gasoline makes
perior performance and productivity in advanced fermentation process. combustion process finish earlier being beneficial of improvement of
Problems associated with cost-effectiveness and non-availability of thermal efficiency.
conventional substrates are one of the challenges of ABE fermentation The potential of improving combustion efficiency and reducing
in current age. The research should focus on looking for the least ex- pollutant emissions has driven researchers to consider ethanol, n-bu-
pensive and most abundant materials, reducing the risk of food scarcity tanol and acetone as alternative fuels in ICEs. The usage of ethanol in SI
and drought and soil infertility, and addressing the problems of inter- and CI engines has gained great interests since the 1970s energy crisis,
mediate compounds inhibiting strain growth and ABE production. since then, a comprehensive research has been performed as shown in
Recently, the successful utilization of cheap and renewable cellulosic Fig. 4. Due to the addition of ethanol to gasoline and diesel, the change
materials as substrates has opened new possibilities to achieve eco- of some key properties associated with the proper operation of ICEs,
nomical ABE production. including blend stability [105], materials compatibility [106], viscosity
Developments in the field of process technology are also able to [107], lubricity [108], flammability [109], biodegradability [110],
result in improvements in numbers of aspects of ABE fermentation et al., were examined. Through the investigation of combustion char-
engineering, including improvement in the processing of lignocellulose acteristics [111–116], engine performances and emissions [117–122],
and other feedstocks to yield fermentable sugars, optimization of pro- the political, economic and environmental problems of blending
cess control through the application of on-line monitoring and using ethanol have been clarified, such as: Will ethanol addition reduce air
microprocessors, development of cheap and efficient systems for the pollutant emissions and greenhouse gas emissions? What is the energy
continuous production of solvents, and improvement of by-product efficiency of ethanol? What is the impact of ethanol added into gasoline
utilization. and diesel on soil and groundwater contamination? Is ethanol addition
Given that academic and industrial research work towards eco- sustainable? The studies related to ICEs fueled with ethanol-fossil fuels
nomically bio-based solvent production will continue, ABE fermenta- blends were summarized and discussed by Masum et al. [123] and
tion industries would have a bright future. Ribeiro et al. [124]. The advances of high energy content, cetane
number and viscosity, etc., make butanol preferable than ethanol to be
3. Application of ABE as a biofuel in ICEs alternative fuel of ICEs. With the improvement of butanol productivity,
increasing studies on the usage of butanol on ICEs have been carried out
ABE has attracted attention as a biofuel due to its various ad- in recent years, including fundamental combustion [125–128] and
vantages. Investigations of ICEs fueled ABE-fossil fuel blends have re- chemical kinetics [129–132] in some burning reactors, performance
cently been carried out from the following three aspects: (1) ABE and emissions of butanol-fossil fuels blends in SI engines [133–136] and
components’ physicochemical properties and tests in ICEs; (2) substitute CI engines [137–140]. The evolutions of production technology and
for diesel in compression ignition (CI) engines; (3) substitute for gaso- application research in ICEs of butanol as a biofuel have been reviewed
line in spark ignition (SI) engines. by No [141] and Jin et al. [24]. Acetone (a colorless, somewhat aro-
matic and flammable liquid) is often referred to as a good solvent for
3.1. Physicochemical properties and tests in ICEs of ABE components some synthetic fibers and plastic materials and important orga-
nic synthesis for producing epikote, medicine, pesticide, etc.
The physicochemical properties directly affect the combustion [142–145], and has higher energy density, heating value, octane
quality of fuel and performance and emissions characteristics of ICEs. number and lower latent heat vaporization than ethanol. It can be
Some key physicochemical properties of gasoline, diesel and ABE produced through oxidation of isopropyl alcohol, cumene process and
components (i.e. ethanol, butanol and acetone), such as energy density, fermentation process, etc. [146–148]. Acetone has been considered an
lower heating value and laminar flame speed, etc., are listed in Table 3 alternative fuel of ICEs [149–154], however, less research was done on
[99–104]. The comparative features of these fuels are presented below: the effect of blending acetone on combustion and emission character-
(1) The oxygen contained in ethanol, n-butanol and acetone is bene- istics compared to ethanol and n-butanol.
ficial for combustion quality; (2) The lower C/H atom ratio of ethanol
and n-butanol compared to that of gasoline and diesel reduces the
adiabatic flame temperature; (3) The energy density of ethanol, n-

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Y. Li et al. Fuel 242 (2019) 673–686

Table 3
Physicochemical properties of conventional fossil fuels and ABE components.
Parameter Gasolinea Dieselb Ethanolc n-Butanold Acetonee

Chemical formula C4 ∼ C12 C12 ∼ C25 C2H5OH C4H9OH C3H6O


Oxygen content (wt%) – – 34.8 21.6 27.6
C/H atom ratio 0.44 (octane) 0.44 (n-heptane) 0.33 0.40 0.50
Density (kg/m3) at 20 °C 715 ∼ 765 820 ∼ 860 795 813 791
Lower heating value (MJ/kg) 43.4 42.7 26.8 33.1 29.6
Energy density (MJ/l) 31.0 ∼ 33.2 35.0 ∼ 36.7 21.3 26.9 23.4
Octane number 88 ∼ 99 20 ∼ 30 100 96 117
Cetane number 0 ∼ 10 40 ∼ 55 5.0 ∼ 8.0 25 –
Latent heat at 298 K (kJ/kg) 380 ∼ 500 270 904 582 518
Auto-ignition temperature (K) ∼300 ∼210 434 343 465
Flash point (°C) −45 ∼ −38 65 ∼ 88 13 35 −20
Flammability limits (vol.%) at 25 °C 0.6 ∼ 8.0 1.5 ∼ 7.6 3.5 ∼ 15.0 1.4 ∼ 11.2 2.6 ∼ 12.8
Stoichimometric AFR 14.7 14.3 9.0 11.2 9.5
Saturation pressure (kPa) at 38 °C 31.0 1.9 13.8 2.3 52.5
Solubility in water (g/l) at 25 °C Immiscible Immiscible Miscible 73 Miscible
Laminar flame speed (cm/s) ∼33f – ∼39f ∼48g ∼34h

Note: aProperties of gasoline are from [99,100]. bProperties of diesel are from [103]. cProperties of ethanol are from [99,102]. dProperties of n-butanol are from
[103,104]. eProperties of acetone are from [101]. fp = 1 atm, T = 325 K. gp = 1 atm, T = 343 K. hp = 1 atm, T = 298 K.

600 oxygen extended sooting index (OESI). Results showed that the high H/
Ethanol and engine as search topics in Web of Sience
Butanol and engine as search topics in Web of Sience C ratio and oxygen content of ethanol and butanol had a positive effect
500 Acetone and engine as search topics in Web of Sience on reducing soot emission, while unsaturation degree of acetone had a
negative effect. A multi-component evaporation model was built to
Total publications

400 accurately predict the evaporation evolution of ABE-diesel blends, and


the model was validated by the experimental results of droplet fiber-
suspension evaporation [165].
300
In order to study the effect of acetone content in ABE on combustion
characteristics in CI engine, Wu et al. [166,167] tested the combustion
200 of 20 vol% ABEs with various components volumetric ratio (A:B:E of
3:6:1, 6:3:1 and 0:10:0) blended with diesel (i.e. ABE(6:3:1)20, ABE
100 (3:6:1)20 and ABE(0:10:0)20) in CVC. In comparison with diesel, ABE
(6:3:1)20 presented similar shape and peak value of both pressure trace
0 and heat release rate (HRR), shorter ignition delay and combustion
20

20 5
20
20
20 3
20 6
20
20 8
20 2
20
20 4
20

20
20
20

20
20

duration, and stronger premixed combustion. Meanwhile, ABE-diesel


20

12

16
17
1
14
0
09
03
0
05
0
07

11
01
0

1
10
00

blends showed a relatively lower spatial integrated natural flame lu-


Year
minosity (SNIL, an indicator of soot emission [168]) compared to
Fig. 4. Total publications with ethanol, butanol, acetone and engine as search diesel. Tim et al. [169] tested a CI engine fueled with ABE(3:6:1)10,
topics in Web of Science respectively from 2000 to 2017. ABE(3:6:1)20, ABE(6:3:1)10, ABE(6:3:1)20 and diesel. It was seen that
ABE-diesel blends slightly reduce power output except for ABE(6:3:1)
3.2. Substitute for diesel in CI engines 10, and ABE(6:3:1) blends had a retarded combustion and lower
emissions compared to the ABE(3:6:1) blends.
Investigations of ABE as an alternative fuel in CI engine have been The effect of butanol content on ABE combustion in CI engine was
conducted by several researchers, as listed in Table 4. The effect of ABE studied through comparing pure ABE, n-butanol, and diesel referred to
ratio on combustion characteristics was study by Zhou et al. [155,156], as ABE100, n-B100 and D100, respectively [170]. ABE100 presented a
Wu et al. [157,158] and Lin et al. [159] through the experimental test longer flame lift-off length (FLoL) and a shorter liquid penetration than
of D100, ABE20, ABE50 and ABE80 (0, 20, 50 and 80 vol% ABE with a n-B100 and D100. Therefore, the droplets of ABE100 had more space
typical fermentation product volumetric ratio of A:B:E = 3:6:1 blended and time to evaporate and mix with air. With regards to combustion
with diesel) in a constant volume chamber (CVC) under different am- characteristics, ABE100 generally showed a retarded combustion
bient temperatures and oxygen concentrations, as shown in Fig. 5. phasing and a lower peak HRR than B100 and D100. The peaks of the
ABE50 displayed a combustion characteristic similar with pure diesel. It SINL and the time integrated natural luminosity (TINL) of n-B100 and
was speculated that a critical blend ratio between 50 vol% and 80 vol% D100 were higher than those of ABE100.
could be existed, beyond which the combustion characteristics may be Since the amount of ethanol is usually small (∼10 vol%) in ABE
controlled by ABE. Meanwhile, ABE-diesel blends got a lower natural from the current fermentation process, the investigations concerning
flame luminosity than pure diesel. It means the blends have the po- the effect of ethanol in ABE combustion is rare. However, through
tential to reduce soot emission. Lin et al. [160,161] tested a CI engine comparing the previous results of different ABE compositions and neat
fueled with ABE10 and ABE20. ABE additive retarded the start of auto- butanol, it was indicated that ethanol has a retardation effect on the
ignition, accelerated heat release during CA10 ∼ CA50, reduced power ignition timing of the mixtures due to its low cetane number. Some
output, improved indicated thermal efficiency (ITE), reduced soot researchers have also investigated the application of ethanol-diesel in
emissions, and increased NOx emissions. A phenomenological soot CI engines [171]. Common conclusions included the decreased engine
model considering the oxidation effect on soot density was proposed for torque, the increased brake specific fuel consumption (BSFC) and the
ABE by Zhao et al. [162,163]. Luo et al. [164] used a wick-fed burner to reduced particulate matter (PM) after ethanol addition.
evaluate soot tendency of ABE-diesel blends according to three para- Study on the effect of water containing on ABE combustion in CI
meters including flame height, threshold sooting index (TSI) and engine was performed by Chang et al. [172]. In comparison with diesel,
the ABE20 improved brake thermal efficiency (BTE), increased NOx

678
Y. Li et al. Fuel 242 (2019) 673–686

emissions and reduced PM and toxicity equivalency of PAHs (BaPeq)

[155–159]

[162–164]
[160,161]

[166,167]
emissions, while adding 0.5 vol% water into ABE20 (ABE20W0.5) did

[165]

[170]

[171]

[172]
Refs

not only cause a further increase in BTE and decrease in PM and BaPeq
emissions, but also a decrease of NOx emissions. In order to solve the

Effect of acetone content on spray and combustion of ABE-

Effect of butanol content on spray and combustion of ABE-


Effect of blend ratio on spray and combustion of ABE-diesel

Engine performance, emissions and durability with ethanol-


Effect of blend ratio on combustion and emissions of ABE- problem of the increase of NOx emission after adding biodiesel to diesel,
the usage of water-containing ABE-biodiesel-diesel blends was in-

Effect of ABE and water contents on combustion and


vestigated, and results showed that both PM and NOx emissions of

emissions of water containing ABE-diesel blends


water-containing ABE-biodiesel-diesel blends were simultaneously re-
duced relative to those of diesel [173].
Evaporation model of ABE-diesel blends

3.3. Substitute for gasoline in SI engines


Soot model of ABE-diesel blends

There are also lots of work on ABE as a substitute for gasoline, as


listed in Table 5. Van Geem et al. conducted an experimentally kinetic
modeling study of ABE combustion [174]. In this study, a detailed
mechanism of the pyrolysis and oxidation of ABE was proposed, in
which 350 species and more than 10,000 reactions were contained. The
diesel blends

diesel blends

diesel blends

diesel blends

laminar flame speed (LFS) of ABE was also measured and its value was
Purpose

higher than that of acetone and lower than that of ethanol and butanol.
blends

The complicate interaction between ABE components was clarified by


Zhang et al. [175] based on the analysis of chemical kinetics, stretch
Surface mass fraction, Normalized squared droplet diameter,
Engine power, ITE, BSFC, Ignition delay, CA10-CA50, CA50-

effect and laminar flame speed under various component ratios and
Ignition delay, Combustion duration, Spay structure, Liquid

Ignition delay, Combustion duration, Spay structure, Liquid

equivalence ratios. It was seen the LFSs followed the order of ABE
Spatial distributions of soot and relevant species, Flame

(6:3:1) < ABE(3:6:1) < ABE(1:6:3), and ethanol or n-butanol had a


positive effect on burning velocity enhancement of ABE, while acetone
penetration, Flame structure, FLoL, SINL, TINL

had a negative effect.


Engine power, BTE, BSFC, HC, CO, NOx, PM
Ignition delay, Flame structure, FLoL, SINL

The effect of ABE as alternative fuel on performance and emissions


penetration, Flame structure, FLoL, SINL

of SI engine was preliminarily investigated in Refs. [176,177] through


the tests of ABE-gasoline blends (0–80 vol% ABE blended with gasoline
BTE, BSFC, CO, PM, NOx, BaPeq

referred as G100-ABE80) in a port-fuel-injected (PFI) SI engine. ABE80


had a larger pressure peak and an advanced combustion phasing
compared to gasoline because the high laminar flame speed of ABE
suppressed charge cooling effect. The increase of ABE ratio in the
height, TSI, OESI

Evaporation rate
CA90, NOx, Soot

blends resulted in a steady increased BSFC due to its lower energy


Test parameter

density relative to gasoline, a decreased CO emission due to the en-


hanced oxidization, and an initially increased and then decreased HC
emission due to the competition between the improved combustion
quality and the more injected fuel. With respect to NOx emission, no
major differences were observed among the blends, as shown in Fig. 6.
The effect of the components in ABE on performance and emissions
Diesel engine generator, Diesel

of SI engine was investigated by Nithyanandan et al. [178,179] and Li


et al. [180] through the tests of ABE with different formulations of
A:B:E of 1:8:1, 3:6:1, 5:4:1, et al. It was found that the increase of n-
CVC, Wick-fed burner

engine dynamometer

butanol content caused an advanced combustion phasing due to the


higher flame speed of butanol relative to acetone and ethanol. At each
fuel’s MBT (Maximum Brake Torque), ABE(6:3:1)100 had a higher BTE
Equipment
Summarization of the studies on combustion of ABE-diesel blends.

CI engine

CI engine

and a lower CO and HC emissions than ABE(3:6:1)100 and G100 be-


CVC

CVC

CVC

CVC

cause the more oxygen contained in acetone relative to butanol and


gasoline is favor of the improvement of combustion quality and the
post-flame oxidation of HC and CO emissions [178,179]. At gasoline’s
D100, ABE10, ABE20, ABE30, ABE10W0.5, ABE20W0.5,

MBT, ABE(3:6:1)30 showed a higher BTE than ABE(1:8:1)30 and ABE


D100, ABE5, ABE10, ABE20, ABE30, ABE50, ABE100

(5:4:1)30 due to the more work loss resulted from the advanced com-
D100, ABE(6:3:1)20, ABE(3:6:1)20, ABE(0:10:0)20

bustion phasing of ABE(1 8 1)30 and the longer combustion duration of


ABE(5:4:1)30. Meanwhile, ABE-gasoline blends presented an unstable
variation trend of CO and HC emissions due to the competition between
ABE30W0.5, ABE20W1, ABE30W1
D100, ABE20, ABE40, ABE60, ABE80

the effects of oxygen concentration and combustion temperature [180].


The effect of water containing on ABE-gasoline blends combustion
D100, ABE20, ABE50, ABE80

D100, ABE10, ABE20, ABE30

was investigated through the tests of ABE30, ABE29.5W0.5 and


ABE29W1 (29 vol% ABE, 1 vol% water and 70 vol% gasoline)
D100, ABE100, n-B100

[181,182]. In comparison with ABE30, ABE29.5W0.5 and ABE29W1


Ethanol-diesel blends

presented a longer and shorter 0–10% MFB and 10–90% MFB, respec-
tively, because water additive resulted in the decrease of combustion
temperature, but the increase of OH radicals at the same time.
ABE29.5W0.5 had a similar engine torque with ABE30, while ABE29W1
Table 4

Fuel

had a higher one due to the increased volumetric efficiency and the
catalytic activity of water vapor. ABE29.5W0.5 and ABE29W1 had a

679
Y. Li et al. Fuel 242 (2019) 673–686

Fuel D100, ABE(6:3:1)20,


D100, ABE20, ABE50, ABE80 D100, ABE100, n-B100
ABE(3:6:1)20, ABE(0:10:0)
(Oxy16%,1000K) (Oxy16%,1200K)
Item (Oxy21%,800K)
D100ėABE 20ėABE 50ėABE 80 D100ėABE (6:3:1 )20ėABE (3:6:1 )20ėABE (0:10:)20 D100ėABE 100ėn-B10 0

Flame
Structure

Pressure
and
AHRR

Flame
Lift-off
Length

Integrated
Natural
Flame
Luminosity

Fig. 5. Combustion characteristics of ABE-diesel blends in CVC [158,166,170].

lower CO emission compared to ABE30 as result of the water-gas shift injection strategy, oxygenated fuels increased PM emission and E40 had
mechanism. However, for HC emission, a trend opposite to CO emission the highest increase, followed by ABE40 and B40, with respect to ga-
was found because of the higher amount of fuel got into the crevice soline. Based on the reality that high-level ethanol blend has been used
volumes or absorbed in oil layers and then deposited. Moreover, water in flexible fuel vehicles, a comparative study of neat gasoline and ga-
addition caused a reduced NOx emission due to the decreased com- soline blended with 85 vol% ethanol, butanol and ABE (E85, B85 and
bustion temperature. ABE85) in a PFI SI engine was carried out by Zhang et al. [184]. Among
The comparisons between ABE with conventional alternative fuels the fuels, E85 presented the largest peak of in-cylinder pressure and the
of SI engines were also carried out. Fournier et al. evaluated the most advanced combustion phasing, while B85 presented the smallest
emissions of a direct-injection spark-ignition engine (DISI) fueled with peak of in-cylinder pressure and the most retarded phasing. Both
low concentrations of oxygenated fuel (including ethanol, butanol and 0–10% MFB and 10–90% MFB of the fuels were followed in the same
ABE) and gasoline blends [183]. Oxygenated fuel addition increased sequence: B85 > Gasoline > ABE85 > E85. B85 produced much
the ignition delay and the fully developed turbulent combustion, and higher HC and CO emissions than other fuels due to the incomplete
caused slightly increased CO emission, decreased HC emission, de- combustion caused by poor evaporation of butanol. And in general, the
creased or constant NOx emission with homogeneous injection, and alcohol-containing fuels had slightly lower BTE and NOx emission.
increased HC emission with stratified charge injection. Under homo-
geneous injection strategy, ethanol and butanol-gasoline blends re-
duced PM emission, while PM emission of ABE-gasoline blends re- 3.4. Summary and perspectives
mained unchanged with respect to gasoline. While, under stratified
In this section, the application of ABE as a biofuel are summarized

680
Y. Li et al. Fuel 242 (2019) 673–686

from three aspects, including physicochemical properties and tests in

[178–180]
[176,177]

[181,182]

[183,184]
ICEs of ABE components, substitute for diesel in compression ignition
[174] engines, and substitute for gasoline in spark ignition engines. The
Ref

properties indicate ABE has a potential to be a suitable alternative fuel

emissions of water containing ABE-gasoline blends


Effect of blend ratio on combustion and emissions
as it is biodegradable, less detrimental to environment, oxygen con-

Comparison between ABE, ethanol and butanol


taining, etc. compared to gasoline and diesel, and has a higher energy
Effect of ABE components on combustion and

Effect of water content on combustion and


density, less ignition problems, better intersolubility, etc., compared to
ethanol. Based on the fundamental combustion experiments in reactors,
Detailed mechanism for ABE oxidation

the detailed mechanism for the oxidation of ABE was developed. The
emissions of ABE-gasoline blends

tests in CVC, burner and CI engines showed ABE-diesel blends can in-
crease ignition delay, decrease combustion duration, improve com-
bustion efficiency, and reduce soot emission. In SI engines, studies of
of ABE-gasoline blends

ABE-gasoline blends also revealed a decreased combustion duration and


an improved combustion efficiency. However, there were inconsistent
-gasoline blends

trends for HC, CO and NOx emissions of ABE-gasoline blends due to the
different tested engines, operating conditions, or measurement techni-
Purpose

ques and instruments. The water contained in ABE can not only lead to
a further increase in combustion efficiency, but also a decrease in NOx
emission.
Butanol conversion, Yields of acetone, ethanol, methane, ethene, propene, butane,
hydrogen, major oxygenated species and minor heavier species, Laminar burning

Based on the above studies, several challenges are faced in the area
of ABE application in ICEs. The effect of ethanol on the combustion and
0–10% MFB, 10–90% MFB, 50% MFB location, BTE, BSFC, CO, HC, NOx

emissions characteristics of ABE-diesel blends and ABE-gasoline blends


should be further validated. The optimized blend ratio of ABE-gasoline
blends and ABE-diesel blends can be obtained in favor of the power,
0–10% MFB, 10–90% MFB, SFC, BTE, BSFC, CO, HC, PM, NOx

economy and emissions of ICEs. Numbers of key physicochemical


properties of ABE-gasoline blends and ABE-diesel blends being essential
to the proper operation of ICEs need to be evaluated. There is a need for
0–10% MFB, 10–90% MFB, BTE, BSFC, CO, HC, NOx

0–10% MFB, 10–90% MFB, BTE, BSFC, CO, HC, NOx

more optical experimental studies and more detailed chemical kinetic


models, which is important to the development of computational
combustion dynamics for ABE-gasoline blends and ABE-diesel blends.
The single-factorial design of experiment is difficult because the change
of one component of ABE mixture will surely affect the other two,
which makes the conclusions indefinite and obstructs the quantitative
analysis. The methodology and the instrumentation used for should be
improved to fulfill the measurements of ABE in ICEs.

4. Conclusions and future research directions


Test parameter

4.1. Conclusions
velocity

Global energy crisis and limited fossil-fuel resources have rekindled


the worldwide focus towards the usage of biofuel. Given that the issues
DISI engine and PFI SI

related to the low yields and the high cost of butanol would be avoided
if ABE could be directly used for clean combustion, the interest in ABE
as a biofuel has dramatically increased recently.
PFI SI engine

PFI SI engine

PFI SI engine
Summarization of the studies on combustion of ABE-gasoline blends.

The development of ABE fermentation techniques is firstly re-


Equipment

Reactor

viewed, and related work in the areas of stains screen, substrates se-
engine

lection and fermentation engineering innovation to increase production


efficiency are introduced in detail. Improvements in these areas, in-
G100, ABE(6:3:1)100, ABE(3:6:1)100, ABE(5:14:1)100, ABE

G100, E10-E40, B10-B40, ABE10-ABE40, E85, B85, ABE85

cluding the application of various novel genome sequence and genetic


modification tools, the use of fermentation substrates derived from
waste- and lignocellulose-based feedstocks, the optimization of fed-
batch and continuous fermentation processes, the manipulation of
growth and production conditions, etc., have improved ABE yields and
(1:8:1)30, ABE(3:6:1)30, ABE(5:4:1)30

making ABE an economically viable biofuel.


G100, ABE30, ABE29.5W0.5, ABE29W1
G100, ABE20, ABE40, ABE60, ABE80

Next, applications of ABE as the alternative fuel in ICEs are sum-


marized from the physical and chemical properties and the substitutes
Acetone, ethanol, butanol, ABE

for gasoline and diesel in combustion. The properties indicate ABE has
the potential to overcome some drawbacks brought by gasoline, diesel
and ethanol in combustion. The studies of ABE-diesel blends revealed
some common characteristics, including an increased ignition delay, a
decreased combustion duration, a better atomization and evaporation
processes, an increased fuel consumption, an improved combustion
efficiency and a reduced soot emission. In the studies of ABE-gasoline
Table 5

Fuel

blends, a decreased combustion duration, an advanced combustion


phasing, an increased fuel consumption and an improved combustion

681
Y. Li et al. Fuel 242 (2019) 673–686

Fuel Gasoline, ABE(3:6:1), ABE0/Gasoline,


Gasoline, E85, B85, ABE85,
ABE(6:3:1), ABE(5:14:1), Butanol ABE30, ABE29.5W0.5
(Gasoline MBT)
Item (Fuels MBT) (Gasoline MBT)

0 - 10% MFB

10 - 90% MFB

BTE

CO

HC

NOx

Fig. 6. Combustion, performance and emissions characteristics of engine fueled with ABE-gasoline blends [177,179,181,184].

682
Y. Li et al. Fuel 242 (2019) 673–686

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