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Article history:
Received 25 June 2014
Accepted 22 October 2014
Available online 15 December 2014
Bio-ethanol, as a clean and renewable fuel, is gaining increasing attention, mostly through its major
environmental benets. It can be produced from different kinds of renewable feedstock such as e.g. sugar
cane, corn, wheat, cassava (rst generation), cellulose biomass (second generation) and algal biomass
(third generation). The conversion pathways for the production of bio-ethanol from disaccharides, from
starches, and from lignocellulosic biomass are examined. The common processing routes are described,
with their mass and energy balances, and assessed by comparing eld data and simulations. Improvements through 5 possible interventions are discussed, being (i) an integrated energy-pinch of condensers
and reboilers in the bio-ethanol distillation train; (ii) the use of Very High Gravity (VHG) fermentation;
(iii) the current development of hybrid processes using pervaporation membranes; (iv) the substitution
of current ethanol dewatering processes to >99.5 wt% pure ethanol by membrane technology; and (v)
additional developments to improve the plant operation such as the use of microltration of the
fermenter broth to protect heat exchangers and distillation columns against fouling, or novel distillation
concepts.
Whereas the benets of introducing these techniques are recognized, extensive research is still needed
to scientically and economically justify their application. The paper nally presents a tentative economic assessment, with production costs not only depending on the extent of applying process improvements, but also on the raw material used in the process.
2014 Elsevier Ltd. All rights reserved.
Keywords:
Bio-ethanol
Characteristics
Environmental aspects
Raw materials
Energy saving
Hybrid process
Anhydrous ethanol
Aspen Plus V8.2
Contents
1.
2.
3.
* Corresponding author. Beijing University of Chemical Technology, College of Life Science and Technology, Key Lab of Bioprocess, Beijing, China. Tel.: 86 1015210645421;
fax: 86 1064794689.
E-mail address: kangqian1985@gmail.com (Q. Kang).
http://dx.doi.org/10.1016/j.pecs.2014.10.003
0360-1285/ 2014 Elsevier Ltd. All rights reserved.
4.
5.
6.
7.
61
3.6.
The problem of ethanol-inhibition in the first generation feedstock fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
Traditional processing routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.1.
Integrated saccharification/fermentation processes versus two-step processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.
Basic data and energy requirement of the process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.2.1.
Fermentation broth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.2.2.
Simulation in Aspen Plus of the basic concept (no internal energy recycle) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Process improvements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.1.
Energy integration within the current production processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.2.
The use of VHG fermentation: principles and application results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.2.1.
Introduction of very high gravity (VHG) fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.2.2.
Effect of implementing VHG on the distillation thermal requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
5.3.
The development of hybrid (pervaporation) systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.3.1.
Introduction of hybrid operations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.3.2.
Effect of implementing pervaporation on the distillation thermal requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.4.
Overall assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
5.5.
The process of final ethanol dewatering to fuel grade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.5.1.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.5.2.
Major processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.5.3.
Production of anhydrous ethanol using hydrophilic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5.6.
Additional developments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
5.6.1.
Cross-flow microfiltration of bio-ethanol fermentation broth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
5.6.2.
Novel distillation concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
5.6.3.
The improved bio-ethanol production plant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Preliminary economic assessment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
Table 1
Primary properties of ethanol.
Boiling point
Flash point
Auto-ignition temperature
Heat of combustion
351.37 K
289.6 K
698 K
26,800 kJ/kg
62
Fig. 2. Schematics of the processes for bio-ethanol production (a) As currently applied; (b) With potential membrane applications (DDGS: Distillers Dried Grains with Solubles;
123: cellulosic materials; 23: starch or carbohydrate rich materials).
The ash point of pure ethanol is 289.6 K only, lower than the
ambient temperature [6]. The ash points of ethanolewater solutions are shown in Fig. 1 [7].
Ethanol for industrial synthesis reactions or as a solvent is
mainly produced petrochemically through the acid-catalyzed hydration of ethylene [8]:
C2 H4 H2 O/CH3 CH2 OH
The catalyst is most commonly phosphoric acid [9,10], absorbed
onto a porous carrier such as silica gel or diatomaceous earth.
Ethanol for use in alcoholic beverages, and the vast majority of
ethanol for use as bio-fuel [9,10], is produced by fermentation.
Certain species of yeast (e.g., Saccharomyces cerevisiae) or bacteria
(e.g. Zymomonas mobilis) metabolize sugars in oxygen-lean conditions and produce ethanol and carbon dioxide. The chemical reactions for glucose/fructose and for sucrose as respective raw
materials are given below:
(1.1)
(1.2)
; for sucrose
The general ow sheet of the fermentative bio-ethanol production, including the starting fermentation and successive process
steps, is illustrated in Fig. 2.
The function of the different process steps, and the difference
between 1st, 2nd and 3rd generation raw materials will be discussed in Section 1.2. The possible introduction of membrane
separations is also indicated in the ow sheet, and will be detailed
in Section 5 of this paper.
The liquid waste of the fermenter (stream 8) and the stillage
recovered from the distillation (stream 5) of Fig. 2 are valuable
sources for anaerobic treatment. These streams contain moderate
concentrations of glucose and starch, respectively 1e20 g/L and up
to 200 g/L [11]. The waste water production exceeds 8 m3/ton bioethanol, providing sufcient substrate for an efcient anaerobic
digestion. The biogas produced (~670 Nm3/ton bio-ethanol) has a
sufcient energy content to make a CHP (Combined Heat and Power) application viable, generating sufcient electricity to partly
power the whole bio-ethanol plant, whilst also providing hot water
(~353 K) to be used in the boiler.
The CO2 production of fermentation nearly equals the bioethanol yield. The CO2 produced is recovered, cleaned, and
Bio-ethanol General;
Fuel-Application;
Simulation and
63
Table 2
Literature (>2010) about rst generation bio-ethanol in general, and cassava in particular.
Reference
Objectives
Main results
[19]
[20]
[21]
[22]
[18,23e25]
- Produced ethanol at 91% and 80% of theoretical yield from 5% to 10% cassava pulp
(K7G strain fermented starch and glucose).
- S. cerevisiae CHY1011 and CHFY0901 have potential use in industrial bio-ethanol
fermentation processes.
- The reaction was completed within 48.5 h at 303 1 K.
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
64
Table 3
Literature (>2010) about second generation bio-ethanol production.
Reference
Objectives
Main results
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
Lignin and silica from the black liquor generated during the production
of bio-ethanol from rice straw
[54]
[55]
[56]
[57]
[58]
[59]
[60]
[61]
[62]
[63]
[64]
65
Table 3 (continued )
Reference
Objectives
Main results
[65]
Combined use of gamma ray and dilute acid for bio-ethanol production
[66]
[47]
[67]
66
Table 4
Literature (>2010) about algal bio-ethanol.
Reference Objectives
Main results
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
MJ/L
MJ/kg
17.9
21.2
25.2
25.3
26.8
33.5
~19.5
19.9
26.8
33.2
~55
50
46.8
33.7
34.8
47.1
44.4
38.6
45.4
RON
108.7
108.6
105
100/130
(lean/rich)
93/94
Min. 91
Max. 104
25
Table 6
Common ethanolepetrol mixtures.
Code
Composition
Countries
Comments
E5
Western Europe,
India
USA, Europe, China,
India, South Africa
USA, cars >2000,
South Africa
Brazil
Blends for
regular cars
USA, Europe
Flexefuel
vehicles
E10
E15
E25
E85
E100
Brazil
67
as the ethanol lower evaporative pressure (as compared to gasoline) causes problems when cold starting the engine at temperature
below 288 K. For this reason, both pure ethanol and exefuel vehicles are built with an additional small gasoline reservoir inside
the engine compartment to help in starting the engine when cold
by initially injecting gasoline. Once started, the engine is then
switched back to ethanol. An improved exefuel engine generation
was developed to eliminate the need for a gasoline tank by
warming the ethanol during starting and allowing them to start at
temperatures as low as 268 K. The use of ethanol blends in conventional gasoline vehicles is restricted to low mixtures, as ethanol
is corrosive and can degrade some of the materials in the engine
and fuel system. The hygroscopicity of ethanol should moreover be
considered in colder and humid climates, due to the possible
plugging of fuel lines by ice crystals, and due to the lower ashpoints at higher water contents.
Due to its low cetane number, ethanol does not burn efciently
by compression ignition. Moreover, ethanol is not easily miscible
with diesel fuel. To improve the use of ethanol in CI vehicles,
measures can be taken, such as the addition of an emulsier in
order to increase the ethanolediesel miscibility; or the addition of
ethylhexylnitrate or diterbutyl peroxide in order to enhance the
cetane number. Most blends of ethanol and diesel (E-diesel) are
limited to 15% ethanol and 5% emulsiers [88].
Alternative solutions are either a dual fuel operation in which
ethanol and diesel are introduced separately into the cylinder, or
the modication of diesel engines in order to adapt their characteristics of auto-ignition and make them capable to use high blends,
up to 95% ethanol [89].
2.2. The uses of bio-ethanol as fuel and feedstock in chemicals'
synthesis
The uses of bio-ethanol as a fuel or as raw material for the
chemical synthesis of other products have been dealt with in
numerous publications, some of the relevant and recent ones
(>2010) being summarized in Table 7.
When specically discussed in the respective publications, the
environmental effects of using bio-ethanol as fuel are also included
in the summaries. From the literature survey, it appears that the
main reasons of the success of bio-ethanol are the following: (i) its
use as renewable energy to partially substitute oil and increase
security of supply; (ii) its use as octane enhancer in unleaded
gasoline to replace metyl-tert-butylether (MTBE); (iii) its use as
oxygenated compound for clean combustion of the gasoline, thus
reducing the tailpipe emissions and improving the ambient air
quality and (iv) its use as renewable fuel to reduce CO2 emissions
and its contribution to a reduced effect on climate change.
In addition to the few publications concerning the conversion of
bio-ethanol to H2, there is a recent revival of its conversion into
various organic chemicals with either a higher number of carbonatoms in their molecules, or/and with an added-value. Fig. 4 summarizes the different options.
Although these conversion pathways offer possibilities to
upgrading bio-ethanol, their investigation is at an early stage of
research.
Specic recent literature about environmental effects has been
listed in Table 8.
The environmental advantages of using ethanol as a fuel are
recognized since it reduces harmful tailpipe emissions of carbon
monoxide, particulate matter, and nitrogen oxides. Argonne National Laboratory analyzed the greenhouse gas emissions of
different engine and fuel combinations. Comparing ethanol blends
with gasoline alone, they showed reductions of 8% with the biodiesel/petrodiesel blend known as B20, 17% with the conventional
68
Table 7
Literature (>2010) concerning the applications of bio-ethanol.
Ref.
Objectives
Bio-ethanol as fuel
[90]
Investigation of using blends of diesel and ethanol
[91]
[92]
[93]
[94]
[95]
[96]
[97]
[98]
[99]
[100]
[101]
[102]
[103]
[104]
[105]
[106]
[108]
[109]
[110]
[111]
Main results
- Engine power increases (up to 8.5%);
- Fuel consumption increases (low caloric value of ethanol);
- Unburned hydrocarbon combustion emissions decrease.
- High injection pressure needed;
- Low tendency to soot formation.
- Modeling density;
- Recommendations on suggested blends.
- Reduced HC and CO emissions;
- Premixed combustion phasing decreases when bioethanol fraction increases.
- Biodiesel: reduction of NOx;
- Bioethanol: engine tolerance to exhaust gas recycle (EGR) was extended.
- E20 recommended;
- With increasing bioethanol, CO deceases, cylinder pressure and temperature
increase.
- The spark ingnition (SI) engine efciency and power performance increase by
using bioethanol;
- CO, HC, and NOx emissions decrease for bioethanol used in supercharged engine.
- Bioethanol: CO2 and smoke decrease;
- Diesel fuel (DF) and Rapeseed Methyl Ester (RME): NOx and CO2 decreases;
- Ethanol fraction in both fuels reaches 50%.
- Linear optimization model used to consider the economic cost of distributing
ethanol;
- Cassava, sweet potato, sweet sorghum and sugar beet are promising feedstocks for
bioethanol expansion.
- Low emissions and substantial fuel exibility obtained in lean, premixed, prevaporized (LPP) combustion with ethanol;
- NOx emission reduction from gas turbines.
- The closed loop combustion control (CLCC) adoption enables the performance
improvement with the blend.
- Lignocellulose-to-ethanol is the most viable pathway (environmental view).
- Brazilian ethanol has the lowest environmental performance.
- The kinetic modeling gave an overall good representation of the experimental
results.
- Ethanol exhaust 2.14 times as much as gasoline exhaust;
- The pollution contributing to smog is 1.7 for ethanol.
- High stability bioethanol/gas oil emulsion produced with 5.0 v/v% biodiesel and
4.0% new chemical structure additive (20 C) in the 5.0 vol% water containing
ethanol.
- Torque with E50 and E85 found to be higher than E0;
- The engine torque, power and fuel consumption increase; CO, NOx and HC
emissions decrease with ethanol;
- Compression ratio (CR) without knock occurrence increases with ethanol
egasoline blends
- Maximum hydrogen product;
- The total amount of VFA/ethanol and the proportion of acetic acid in the VFA
increase with the increase of pH.
- High hydrogen plant efciency and a highly efcient heat integration obtained
with typical ethanol feed.
- An improvement of the cell performance with an increase in temperature
(enhanced kinetics and electrolyte conductivity);
- The E/W weight ratio (0.25e0.5) was found to be suitable;
- Ethanol crossover currents increases with the temperature and the E/W;
- This cell can tolerate the use of the renewable bio-ethanol.
- Bioethanol-based processes have better cost saving and less global warming
potential;
- Bioethanol-based processes have great potential in ethyl acetate production.
- The pore size of SBA-15-100 is optimum for the ETB catalyst.
- Selectivity to H2 and CO on NiAlZn was lower than on CoAlZn (673e773 K), but the
selectivity trend reversed (>873 K);
- ZnAl2O4 spinel was less active in ethanol conversion and much less selective to H2
and CO;
- NiAlZn is a better catalyst.
3. Bio-ethanol production
3.1. Major raw materials
Bio-ethanol can be produced from a large variety of carbohydrates (mono-, di-, polysaccharides). Monosaccharides (e.g. xylose,
69
Table 8
Literature (>2010) about the environmental effects.
Reference Objectives
[112]
[95]
[113]
[114]
[115]
[116]
[117]
[118]
[119]
[120]
[121]
[90]
Main results
70
(3.1)
Wastes
Investment
Physical or physico-chemical
Mechanical
Steam explosion
Ammonia ber explosion (AFEX)
Carbonic acid
Low
High
Moderate
Very high
Very low
Low
Very low
Very low
Low
High
High
Low
Chemical
Dilute acid
Concentrated acid
Alkaline extraction
Wet oxidation
Organosolv
Very high
Very high
Very high
High
Very high
High
High
High
Low
Low
Moderate
High
Low
Low
Very high
Carbonic acid and alkaline extraction have the best performance. However, the most common methods are steam explosion
and dilute acid pre-hydrolysis, which are followed by enzymatic
hydrolysis. Sulphuric acid or carbon dioxide are often added in
order to reduce the production of inhibitors and improve the solubilization of hemicellulose [131]. Steam explosion has a few limitations since the ligninecarbohydrate matrix is not completely
broken down; degradation products are generated that reduce the
efciency of hydrolysis and fermentation steps; and a portion of the
xylan fraction is destroyed.
The use of dilute sulphuric acid (0.5e1%; 433e463 K for 10 min)
has the preference of the US National Renewable Energy Laboratory
[134,135]: hemicellulose is largely hydrolysed releasing different
simple sugars (xylose, arabinose, mannose and galactose) but also
other compounds of the cellulosic matrix, that can however inhibit
the enzymatic hydrolysis and fermentation. Part of the acetic acid,
much of the sulphuric acid and other inhibitors produced during
the degradation of the materials need to be removed, and
neutralization is performed before fermentation.
Enzymatic hydrolysis of cellulose is achieved using cellulases,
usually a mixture of groups of enzymes such as endoglucanases,
exoglucanases and b-glucosidases acting in synergy for attacking
the crystalline structure of the cellulose, removing cellobiose from
the free chain-ends and hydrolysing cellobiose to produce glucose.
Cellulases are produced by fungi, mainly Trichoderma reesei, besides
Aspergillus, Schisophyllum and Penicillium. High concentrations of
cellobiose and glucose inhibit the activity of cellulase enzymes and
reduce the efciency of the saccharication. One of the methods
used to decrease this inhibition is to ferment the reduced sugars
along their release. This is achieved by simultaneous saccharication and fermentation (SSF), in which fermentation using yeasts (S.
cerevisiae) and enzymatic hydrolysis are achieved simultaneously
in the same reactor. The fermentation of the xylose released from
the pre-hydrolysis process can be carried out in a separate vessel or
in the SSF reactor using a genetically modied strain from the
bacterium Z. mobilis that can convert both glucose and xylose. The
latter method is named simultaneous saccharication and cofermentation (SSCF).
Compared to the sequential saccharication and fermentation
process, SSCF exhibits several advantages like lower requirement of
enzyme, shorter process time and cost reduction due to economy in
fermentation reactors (only one reactor compared to the multiple
sets). Disadvantages include the difference between optimal temperatures for saccharication (323e333 K) and fermentation
(303 K), inhibition of enzymes and yeast by ethanol and the
insufcient robustness of the yeast in co-fermenting C5 and C6
sugars. The efuent from the distillation column that contains most
of the lignin and other non-fermentable products is sent to a
71
(3.2)
(3.3)
S. cerevisiae, a facultative anaerobic yeast, and Z. mobilis, a gramnegative bacterium are commonly used to convert C6 sugars. Both
are adapted to ethanol fermentation, with a high ethanol tolerance,
and amenability to genetic modications. Both are however unable
to ferment C5 sugars. Other yeasts and bacteria are under investigation to ferment xylose and other pentoses into ethanol, with
Candida shehatae and Pichia stiplis yeasts offering a good potential,
despite a low tolerance to ethanol, a low ethanol yield and inactivity at low pH. Pachysolen tannophilus and Escherichia coli, both
gram-negative bacteria, are able to use both pentose and hexose
sugars. Kluveromyces marxianus, a thermophilic yeast, is able to
grow at a temperature above 325 K; and is capable to ferment a
broad spectrum of sugars. Excess of sugars affect its alcohol yield. It
has however a low ethanol tolerance and poor xylose fermentation
yield. Thermophilic bateria, e.g. thermoanaerobacterium sacchaarolyticum, thermoanaerobacter ethanolicus, clostridium thermocellum, are extreme anaerobic bacteria, resistant to an
extremely high temperature of 343 K. These bacteria can ferment a
variety of sugars, display cellulolytic activity, but exhibit a low
tolerance to ethanol.
Genetically engineered microorganisms [69,137e139] that produce large volumes of cellulase, xylanase, and hemicellulase enzymes, are under investigation. These could convert agricultural
residues (e.g. corn stover, straw, sugar cane bagasse) and energy
crops (e.g. switchgrass) into fermentable sugars [69]. The development of genetically modied fermentative and cellulolytic microorganisms is recommended to increase the ethanol yield and
productivity under the stress conditions of high production bioethanol processes [140].
Genetic engineering has succeeded in altering the conventional
S. cerevisiae's capacity to ferment glucose and pentose sugars
simultaneously [141]. Almaida et al. [142] investigated a modied
S. cerevisiae, capable of co-fermenting saccharides but also generating less furfural inhibitors. Z. mobilis remains an attractive
candidate due to its high ethanol yield and resistance to temperature in the range of 313 K [137]. Numerous genes have been
introduced and heterologous expression has been incorporated
into Z. mobilis to extend its effectiveness toward other substrates
namely, xylose and arabinose [143]. Both the gene engineered
72
Fig. 6. Inhibition of the fermentation (a) and the cell growth (b).
73
Table 10
Literature review of inhibition studies (>2008).
Reference
Objectives
Main results
[147]
[148]
[149]
[150]
[151]
- Obtained both at 408 K, 2.0% H2SO4 and 45 min, and at 408 K, 1.25% H2SO4 and 45 min
showed inhibition in the growth of the tested microorganisms;
- Spiked yeast medium (YM) broths could withstand the highest levels of inhibitors.
- The maximum rate of CO2 production and nal ethanol concentration generated by the
atg32D laboratory yeast mutant were 7.50% and 2.12% higher than those of the parent
strain, respectively;
- The mutant produced ethanol at a concentration that was 2.76% higher
than the parent strain;
- The ethanol yield of the atg32D mutant was increased, although its biomass
yield was decreased.
- Saccharomyces cerevisiae isolate (ISO12) is capable of growing and fermenting the liquid
fraction of non-detoxied spruce hydrolysate at 312 K with an ethanol yield of
0.38 g ethanol/g hexoses;
- ISO12 shows a higher capacity to ferment hydrolysate at 312 K and higher viability
during heat-shock at 325 K than the industrial strain Ethanol Red (ER).
- A range of potential xylanase inhibitors observed in dilute-acid pretreatment slurries
and fermentation broths are dosed into washed insoluble solids (IS) and beechwood
xylan at varied concentrations prior to enzymatic hydrolysis.
- The ethanol yield from corn by simultaneous saccharication and fermentation (SSF)
with TT6 at 309 K was 91.7% of the theoretical yield.
- The contamination of bioethanol fermentations with lactic acid bacteria (LAB) and wild
yeasts is a signicant industrial problem causing production loss of anywhere from 2 to 22%;
- Dekkera bruxellensis has been cited as one of the main contaminant yeasts in
ethanol production.
- Fermentation yield of hydrolysates can be improved signicantly by
increasing pH of hydrolysates;
- For hydrolysates at 25% and 30% total solids, pH of 8.0e9.0 yields optimal fermentation
with almost no bacterial contamination.
- The bioethanol yield in the presence of furfural increased via mutation of a native
strain of Saccharomyces cerevisiae;
- A potent mutant was selected which produced 36.7% more bioethanol than the parent
strain at 0.2 vol% furfural.
- NFRI3225 produced ethanol from potato mash at the fastest rate and in the
highest volume (13.7 vol%), and the maximum productivity and ethanol yields
were 9.1 g L1h1 and 92.3% respectively during the VHG-SSF process.
- NFRI3225 would save cooling energy during the SSF process and heating energy
during distillation.
- Low pH activates the general stress response (GSR), and mainly the heat shock response;
- A ne regulatory protein kinase A (PKA) dependent mechanism might affect the cell
cycle in order to acquire tolerance to an acid environment.
- The volumetric productivities and ethanol yields were attained to 3.26 g L1h1 and
93.5% for brown rice, 2.62 g L1h1 and 90.4% for barley, and 3.28 g L1h1 and 93.7% for
cassava, respectively.
- The diffusion inside the biocatalyst particles avoids the inhibitory effects;
- The obtained values of Vmax and K0 m were found to be higher than those under
ethanol inhibition, but lower than those without inhibitory phenomena.
[152]
[153]
[154]
[155]
[156]
[157]
[158]
formed during hydrolysis and include mostly furfural from pentoses and 5-hydroxymethylfurfural (HMF) from hexoses.
The use of a detoxication methodology for a specic feedstock
is mandatory for attaining good results in 2nd generation bioethanol production.
4. Traditional processing routes
4.1. Integrated saccharication/fermentation processes versus twostep processes
Fig. 5 of Section 3.2 illustrated the successive steps of the overall
process, including the different enzymatic activities during
saccharication and fermentation. Whereas some processes, e.g.
Lurgi [162] separate both steps, other processes, e.g. Cofco [24]
combine the dual enzymatic activity within the fermenter solely.
Despite this difference, fermentation yields obtained are nearly
equal, and hence not affecting the subsequent bio-ethanol purication train and/or waste treatment. The fermentation yield depends upon the conversion of starch or monosaccharides content in
the rst place (mostly 60e70%, as function of the rst generation
74
Fig. 7. Mass balance of the rst generation Cofco process of cassava-based bio-ethanol.
Fig. 9. The distillation process of Lurgi (C1501-Crude column; C1502-the polishing column).
75
Table 12
Operating parameters of each column.
Column
Number
of trays
Feed tray
number
Reux
ratio
Top pressure
(kPa)
Bottom
pressure (kPa)
C1501
C1503
C1502
15
30
40
6
20
30
0.3
33.3
189.3
600.4
51.3
215.3
636.7
3.1
(4.1)
For a stream feed at 443 K and the different reboiler temperatures, a conservative average sensible and latent enthalpy of steam
is taken at 2300 kJ/kg steam. For a total production of 25375 kg/h of
pure ethanol, the steam requirements are:
(4.2)
(5.1)
At the average steam enthalpy of 2300 kJ/kg, the energy consumption of the integrated reboiler-condenser solution is
Table 11
Composition of the Cassava-fermentation broth.
Components
wt%
Water
Ethanol
Acetaldehyde
Methanol, isoamylalcohol, isobutanol,
propanol, butanol, pentanol, isopropanol
Methyl and ethyl acetate, ethyl formate
Ethyl isobutyrate
Succinate
Acetic, lactic, butyric, formic acid and propionic acid
Glycerol
C20H16
81.40
11.55
0.005
0.1249
0.0055
0.0005
0.25
0.26
0.4
6
(5.2)
In the current Cofco operation, this reboiler-condenser integration is largely applied, with steam duties cited as ~1.3 kg steam/
kg bio-ethanol, in fair agreement with the Aspen-simulated results.
5.2. The use of VHG fermentation: principles and application results
5.2.1. Introduction of very high gravity (VHG) fermentation
In traditional starch fermentation, Saccharomyces cerevisiae is
used as yeast, however with the drawback of inhibition at ethanol
concentrations in excess of ~12 vol%. The use of specic yeasts or
76
Table 13
Comparison of simulation results with real industrial production data.
C1501
Plant value
Top temperature/K
Bottom temperature/K
Ethanol concentration of side stream (wt%)
Final ethanol concentration (wt%)
Heat duty (kW)
Reboiler
Condenser
329.10
355.70
16
C1502
Simulation value
326.99
355.16
16.9
Plant value
368.60
396.30
C1503
Simulation value
367.88
395.61
Plant value
404.20
432.90
93e94
9000
5694
11,604
11,575
Simulation value
404.93
434.37
93.2
18,222
16,944
(5.3)
kg bio ethanol
(5.4)
Table 14
Literature review of VHG studies (>2010).
Reference
Objectives
Main results
[166]
[168]
Construction of Saccharomyces
cerevisiae yeast strains for VHG fermentation
SSF of sweet potato for the production of
ethanol under VHG conditions
VHG ethanolic brewing and fermentation
[169]
[170]
[167]
[171]
[172]
[173]
77
Table 15
Heat duty of the distillation when using VHG fermentation.
VHG conditions
15 vol%
19 vol%
C1501
C1502
C1503-1
5343
2264
15,094
14,356
18,163
C1503-2
C1501
C1502
C1503-1
10,062
9412
14,512
18,144
4163
2266
C1503-2
14,186
(5.5)
(5.6)
kg bio ethanol
(5.7)
78
Table 16
Literature review (>2010) of applying pervaporation in Bio-ethanol production.
Reference
Objectives
Main results
[178]
[179]
[180]
[181]
[182]
[183]
[184]
[185]
[186]
[187]
[188]
[189]
Table 17
Permeate ux and ethanol concentration at different temperature.
Temperature (K)
Permeate ux (g/m2s)
310
318
328
334
28.7
33
33
34
0.32
0.91
1.24
1.61
79
Table 18
Simulation results of the hybrid operation mode.
Ethanol (wt%)
To column
PV permeate
16
Product
11.6
30
<108
<104
91.7
C1501
C1502
C1503-1
8676
5410
18,222
16,944
15,390
C1503-2
15,081
Table 19
Summary results of the Cofco distillation process.
Adsorption on molecular sieves takes advantage of the difference of the molecular size of ethanol and water molecules to
adsorb water molecules in a selective way and allowing ethanol
separation. The use of e.g. synthetic zeolite in pellet form, can
selectively adsorb water from the 95.6% ethanol solution. The
zeolite can be regenerated an unlimited number of times by drying.
Although a variety of plant-derived sorbents, including cornmeal,
straw, and sawdust can also absorb water, they cannot readily be
regenerated, but where ethanol is made from corn, cornmeal is
available at low cost.
In addition to these major technologies, other alternatives are
drawing increased attention, i.e:
the use of vacuum distillation: the composition of the ethanolewater azeotrope shifts to ethanol-rich mixtures at pressures below atmospheric pressure, whilst the azeotrope
disappears at pressures below 9.333 kPa, making it possible to
distill absolute ethanol from an ethanolewater mixture. Such
high vacuum operation is presently not economical.
applying pressure-swing distillation: in this technique, a
reduced-pressure distillation rst yields an ethanolewater
mixture of more than 95.6% ethanol. Then, fractional distillation
of this mixture at atmospheric pressure distills off the 95.6%
azeotrope, leaving anhydrous ethanol at the bottom.
using membranes to separate ethanol and water: since membrane separations are not subject to the limitations of the
watereethanol azeotrope because separation is not based on
vaporeliquid equilibria, the selective permeation of one of the
components is possible by using either hydrophobic membranes
(ethanol permeates) or hydrophilic membranes (water
System
Steam consumption
(kg steam/kg ethanol)
Basic
Integrating reboilers and condensers
VHG (15%)
VHG (19%)
Pervaporation
2.50
1.18
1.17
0.94
1.13
Fig. 11. The mass balance of basic process and different improvements: (a) traditional process with energy recovery; (b) VHG fermentation; and (c) partial pervaporation.
80
81
Table 20
Illustration of properties and characteristics of common Molecular Sieves.
Type [205]
Form
Pore diameter ()
Moisture (%)
3
5
13X
Bead
Bead
Bead
8e12 mesh
8e12 mesh
8e12 mesh
3
5
10
720e736
704
688
1.5
1.5
1.5
21
21.7
29.5
448e533
473e588
473e588
For the desiccation of e.g. 200,000 ton/year of ethanol, the investment of the molecular sieve unit exceeds 1 MV, including 160
ton of 3 molecular sieve. The annual steam consumption will be
96,000 ton, requiring ~7000 ton of fuel in the steam boiler. For the
membrane application, the investment including feeding pump,
vacuum pump and condenser, is estimated at ~0.3 MV [214,215].
Since no steam is required (the feed is delivered between 333 and
363 K after the nal watereethanol distillation column), only
~50 kWh needs to be accounted for as operating costs, representing
a signicant energy saving in comparison with the current molecular sieve unit.
It is clear that hydrophilic membranes can be a valid alternative,
without steam addition and with a minimum electrical power
required to overcome the transmembrane pressure and create the
permeate vacuum.
5.6. Additional developments
5.6.1. Cross-ow microltration of bio-ethanol fermentation broth
Table 21
Mass and energy balance of the molecular sieve process.
Mass balance
Feed water concentration (wt%)
Product water concentration (wt%)
Total feed ow rate (kg/h)
Feed ethanol ow rate (kg/h)
Product mass ow rate (kg/h)
Water absorption (kg/h)
5.6
0.8
27,160
25,638
25,845
1314
Absorption column
Absorption column
Regeneration column
Regeneration column
Total steam (kg/h)
(kg steam/kg ethanol)
Table 22
Permeate characteristics as function of operating time.
Temperature (K)
Energy balance
Evaporator heat
868
2061
23,563,127
11,434
1,452,207
705
12,139
0.48
Time (min)
30
295
318
323
335
60
90
120
150
EF
PF
EF
PF
EF
PF
EF
PF
EF
PF
51
42
43
44
1.01
2.59
3.78
6.30
51
40
44
45
0.84
2.72
4.15
6.98
51
42
45
44
0.83
2.44
3.96
6.77
51
44
45
44
0.77
2.48
3.61
7.62
51
44
44
45
0.82
2.58
3.83
8.13
82
Table 23
Characteristics of enhanced surface ltration medium.
Type
SFM
SFM
SFM
SFM
SFM
SFM
1.3
1.5
2.3
4.3
5.7
6.4
Fiber
diameter (mm)
Thickness
(mm)
Weight
(g/m2)
Porosity (%)
Air permeability
(l/dm2min)
1.25
1.57
2.28
4.31
5.70
6.35
0.1
0.12
0.12
0.12
0.28
0.12
400
400
400
400
900
400
50
60
60
60
60
60
2.47
6.6
7
27
29
57
removed to as low a concentration as possible. The current mechanical separation (belt lter or centrifuge) can only
remove 10 mm particles representing about 90% of the total solids
content. The remaining 10% is usually recovered in the bottom
stream of the rst distillation column, and forms the stillage. To
avoid fouling and even eliminate the rst distillation column where
the ethanol fraction is only increased from 12% (feed) to 16% (top), a
better solids removal is required. The sintered metal ber (SFM)
eeces are highly efcient for microltration and the removal of
suspended solids largely exceeds 99% [216]. Properties of SFM lters are illustrated in Table 23, indicating the range of very ne bers used, the low thickness of the eece, and the fair to excellent
permeability.
The major applications of microltration are situated at different
levels, i.e. (i) in the harvesting and pre-treatment of algal biomass,
hence in item 1 in Fig. 2 [217]; (ii) to ltrate the broth before the
Table 24
Literature about advanced distillation.
Reference Objectives
Main results
[227]
[228]
- Lower investment and operating costs, and reducing the equipment and
carbon footprint;
- Energy savings of 10e20%.
- Savings in total annual cost (32%) for a feed stream with 22 wt% ethanol
[229]
[230]
[231]
- Only one column shell is used in combination (one condenser and two
reboilers);
- Savings on energy total investment and annual costs are about 17%.
- Energy savings of 10e20% and less equipment units.
- DWC as the key separation unit for large scale dehydration of pre-concentrated
bioethanol;
- Energy savings of 10e20%, and less equipment units.
83
84
This work was supported by the National Basic Research Program of China (973 program) (2013CB733600, 2012CB725200), the
National Nature Science Foundation of China (21436002,
21390202), the National High-Tech R&D Program of China (863
Program) (2012AA021404, 2014AA021903, 2014AA021904), and
Key Projects in the National Science & Technology Pillar Program
during the 12th Five-year Plan Period (2011BAD22B04).
References
Fig. 15. Cost calculations for a 200,000 tpa plant (with internal energy recovery), and
economic impact of Molecular Sieve (MS) substitution and using VHG ( : Cost of feedstock; Pre-treatment of feedstock; : Treatment of residues; : Depreciation, Plant
Overherads and insurance, etc; : Labour; : Cost of electricity; : Cost of heavy fuel oil).
based) have been well documented and are largely applied, the
second and third generation of bio-ethanol processes (cellulose- or
algae-based) need further research and development since bioethanol yields are still too low to be economically viable. Applications of bio-ethanol mostly target the combined use with petrol.
The conversion pathways for the production of bio-ethanol from
disaccharides, from starches, and from lignocellulosic biomass
were analyzed. The yield of the fermentation xes the total energy
needed during the downstream separation processes, mostly by
distillation. Mass and energy balances of the common processing
routes were presented. To compare eld data with common engineering design simulations, the software Aspen Plus V8.2 was used.
Field and simulation results showed an excellent agreement.
Without energy recovery, 2.5 kg steam/kg ethanol are required.
Possible energy improvements through 5 modications were
examined and demonstrated that an internal energy re-use, the
application of VHG, or the application of a hybrid operation mode
(pervaporation) could reduce the steam use per kg of bio-ethanol to
1.18, 1.17, 0.94 and 1.13 kg steam/kg bio-ethanol for options of
energy-pinch, VHG (15%), VHG (19%) and pervaporation, respectively. A further energy saving can be achieved in the ethanol
dewatering to fuel grade. Whilst molecular sieves are now
commonly used, the use of hydrophilic membranes was highlighted and conrmed by literature and experimental results,
yielding a signicant energy saving in comparison with the molecular sieve units. Additional technologies to improve the operation of the ethanolewater separation, include microltration of the
broth before the distillation (and pervaporation, in a hybrid system), and membrane distillation. Whereas the benets of introducing these techniques are recognized, extensive research is still
needed to scientically and economically justify their application. A
tentative economic assessment demonstrated that the application
of process improvements can lead to production cost savings of
~11%. Further research of the different alternatives, preferably on
pilot or large scale, appears economically and technically justied.
Acknowledgments
The assistance of Jannis Huybrechts (MEng) during experimental research and Aspen Plus simulation is greatly appreciated.
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