Bioethylene Production from Ethanol:
A Review and Techno-economical Evaluation
Abas Mohsenzadeh[1], Akram Zamani[1], Mohammad J. Taherzadeh[1],*
Abstract
Manufacturing of bioethylene via dehydration of
bioethanol is an alternative to the fossil-based
ethylene production and decreases the environmen-
tal consequences for this chemical commodity. A
few industrial plants that utilize 1st generation
bioethanol for the bioethylene production already
exist, although not functioning without subsidiaries.
However, there is still no process producing
ethylene from 2nd generation bioethanol. This
study is divided into two parts. Different ethanol
and ethylene production methods, the process
Keywords: Bioethanol, Bioethylene, Process design, Techno-economic analysis
Received: October 25, 2016; revised: February 22, 2017; accepted: February 24, 2017
DOI: 10.1002/cben.201600025
1 Introduction
Concerns about global warming and climate change due to
greenhouse gas emissions encourage making use of renewable
energy and materials instead of fossil fuels. The polymer mar-
ket is not an exception [1, 2], where bio-based polymer produc-
tion capacity is estimated to be tripled from 5.7 million t in
2014 to 17 million t in 2017 [3]. The current global market size
for ethylene accounts for 127 million t which is by far the larg-
est commercial chemical produced by volume [4].
Ethylene or ethene (CH2=CH2) is the first member of the
alkenes. It is a colorless gas with a normal boiling point of
103.7 C and is slightly soluble in water and alcohol. This
compound is highly active and reacts easily when added to
many chemical reagents. For instance, addition of water to
ethylene produces ethyl alcohol or ethanol. Ethylene is a good
starter molecule to build on due to its simple chemical formula
combined with the double bond. It is also the raw material for
the production of different grades of polyethylene and other
bulk and base chemicals [5, 6]. Straight chain olefins can be
produced by the oligomerization of ethylene through a process
developed by Shell called the Shell higher olefin process
(SHOP). These higher chain hydrocarbons (a-olefins) are used
primarily as comonomers to produce linear low-density poly-
ethylene and to manufacture detergents and synthetic lubri-
cants as well as gasoline, diesel, and jet blend stocks [58]. For
example, ethylene oxide, produced by oxidation of ethylene, is
a key raw material in the production of surfactants and deter-
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specifications and current technologies are briefly
discussed in the first part. In the second part, a tech-
no-economic analysis of a bioethylene plant was
performed using Aspen plus and Aspen Process
Economic Analyzer, where different qualities of
ethanol were considered. The results show that im-
purities in the ethanol feed have no significant effect
on the quality of the produced polymer-grade
bioethylene. The capacity of the ethylene storage
tank significantly affects the capital costs of the
process.
gents. Another major chemical intermediate obtained by
alkylation of ethylene is ethylbenzene which is precursor for
styrene production. Styrene is utilized for manufacturing of
polystyrene for insulation, packaging, rubber for tires, and
footwear [5, 6].
In petrochemical industries, ethylene is produced mainly by
cracking of naphtha [5]. One of the relatively old applications
of ethylene was its hydration to produce synthetic ethanol. This
technology had a high share of ethanol market in 19th century
[9]. However, due to the rapid expansion of bioethanol or fer-
mentative ethanol production from sugar and grains since
1980s, the share of synthetic ethanol in the market dropped
rapidly. In addition, it opened up production of bio-based
ethylene or bioethylene using the reverse process of producing
bioethylene from bioethanol [10]. Bioethylene can be used by
existing equipment since bioethylene and ethylene are chemi-
cally identical [11].
[1]
Dr. Abas Mohsenzadeh, Dr. Akram Zamani,
Prof. Mohammad J. Taherzadeh (corresponding author)
Swedish Centre for Resource Recovery, University of Bors, SE
501-90 Bors, Sweden.
E-Mail: mohammad.taherzadeh@hb.se
This is an open access article under the terms of the Creative Com-
mons Attribution-NonCommercial-NoDerivs License, which permits
use and distribution in any medium, provided the original work is
properly cited, the use is non-commercial and no modifications or
adaptations are made.
ChemBioEng Rev 2017, 4, No. 2, 7591 75
 According to a 2013 joint brief by the International Renew-
able Energy Agency [11] and the Energy Technology Systems
Analysis Programme (ETSAP), 0.3 % of the global capacity of
ethylene is produced from bioethanol. There are commercial
facilities producing bioethylene located in Brazil and India, and
also several production plants are under construction or
planned (e.g., in China). The largest bioethylene producer is
located in Brazil with a production capacity of 200 kt a1 of
bio-ethylene [11].
Although commercial processes are currently running
[1219], there are questions that arose in several research
studies. Several studies have investigated the production of
ethylene from ethanol [10, 12, 2022]. Morschbacker [10]
reviewed bioethanol-based ethylene as raw material for the
production of bioplastics, e.g., polyethylene, with the focus on
the aspects relative to the ethanol manufacture in Brazil, using
sugarcane as feedstock. He concluded that ethanol conversion
and the reaction selectivity have a direct impact on the yield,
and consequently, on the costs of the process. He also discussed
that bioethanol-based polyethylene can be an alternative to
plastics that have come to the end of their life. It can be
recycled mechanically or by incineration since it releases a
non-fossil carbon dioxide that will be equivalent to the quantity
absorbed by the sugarcane crop at the beginning of the cycle.
Zhang et al. [12] also reviewed the process of ethanol to ethyl-
ene, mainly focused on the reactor design, the reaction mecha-
nism, and the catalyst. They concluded that a fluidized bed
reactor with an efficient and stable catalyst and deep under-
standing of the reaction mechanism will be the focus of future
research. This will promote the development of the process
and provide strong support for the market competiveness. A
techno-economic assessment of potential processes for bio-
ethylene production was done by Haro et al. [20]. They
assessed production of ethylene via dehydration of bioethanol
and conversion of bio-dimethyl ether into olefins. Further-
more, they studied different cases regarding the origin of bio-
ethanol and showed that two of those case studies including
Brazilian ethanol and ethanol via indirect synthesis from syn-
gas (carbon monoxide and hydrogen rich synthesis gas) led to
cost-competitive production of ethylene at market prices in
2013. They also reported that, except for the case of bioethanol
from biochemical processing, all cases would be profitable if
bioenergy with carbon capture and storage (BECCS) was taken
into account.
This review deals with a summary of different processes for
the production of ethanol and ethylene, their operating param-
eters and current technologies as well as the techno-economic
evaluation of the effect of impurities on ethylene production
from bioethanol.
2 Ethanol Production
Ethanol can be produced by catalytic hydration of ethylene,
fermentation of sugars and from lignocellulosic materials.
These methods (Fig. 1) are discussed briefly in this section.
More discussions on the technical readiness level and commer-
cial plants for ethanol production can be found elsewhere
[2326].
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Figure 1. Schematic diagram of different methods for produc-
ing ethanol.
2.1 Ethanol Production from Ethylene
In the petrochemical industry, ethanol is produced via direct
and indirect hydration of ethylene. Catalytic direct ethylene
hydration was first introduced by Shell in 1947. In this process,
ethanol is produced by a reversible exothermic reaction
between ethylene and water vapor. The process consists of
three different steps including reaction, recovery and purifi-
cation [9, 27]. The ethylene is mixed with steam with a molar
ratio of 0.6 at 250300 C and 7080 bar and then passes over
an acidic catalyst in a fixed bed reactor. The water-to-ethylene
ratio should be less than one to avoid catalyst losses. The ethyl-
ene conversion is about 425 % and it is recycled. The ethanol
selectivity is 98.5 mol % [12, 2830]. Phosphoric (V) acid coat-
ed onto a solid silicon dioxide has been used mainly as the
catalyst. Several impregnated metal phosphates (metal: Ge, Zr,
Ti, and Sn) were also studied, showing slightly higher conver-
sions compared with phosphoric acid on silica [31, 32].
A simple process diagram of direct hydration of ethylene is
presented in Fig. 2. The feed stream (ethylene and water) pre-
heated by effluent is heated up to 300 C in the furnace. There-
after, it enters into a packed bed catalytic reactor at 70 bar.
Phosphoric acid is used as catalyst and conversion is 425 %.
Acetaldehyde is produced as a by-product, which can either be
sold or further hydrogenated to produce ethanol. The un-
reacted reactants are separated from the outlet vapor mixture
of the reactor in a high pressure separator and then scrubbed
with water to dissolve the ethanol. The recycled vapor from the
scrubber contains ethylene, and the molar ratio of water to
ethylene is maintained as 0.6:1. The bottom streams of the
scrubber and the separator are then fed to the hydrogenator,
where acetaldehyde is converted into ethanol on a nickel-
packed catalyst. In the acetaldehyde separator column, the
unreacted acetaldehyde is removed and recycled to the hydro-
genator, and the bottom stream is fed to the light and the heavy
(purifier) columns to increase the ethanol concentration [6]. It
should be noted that the ethanol-water mixture forms an azeo-
trope mixture which needs special distillation techniques which
eventually increase the costs of the plant [33].
As mentioned before, the share of synthetic ethanol in the
market has decreased significantly since 1980s due to the in-
crease of bioethanol or fermentative ethanol production from
sugar and grains [9, 10]. According to the global statistics in
ChemBioEng Rev 2017, 4, No. 2, 7591 76
Figure 2. Simple process diagram of the direct hydration of ethylene.
2010, only 7 % of ethanol was produced using hydration of
ethylene by a few multinational companies such as Sasol in
Europe and South Africa, Equistar in the USA, and SADAF in
Saudi Arabia [34, 35].
Furthermore, this process is not economically feasible be-
cause ethanol is a cheaper chemical than ethylene. Also, it is
non-renewable if the ethylene is produced by hydrocracking
petroleum feedstocks.
2.2 Ethanol from Sugar and Starchy Materials
Microorganisms such as yeast can be employed to produce
ethanol via fermentation of sugars. The 1st generation bioetha-
nol is the ethanol produced from sources where the sugars are
more easily obtainable [36]. The sugars are either directly
extracted from sources such as sugarcanes and sugar beet juices
or obtained via hydrolysis of starchy materials such as corn
and grains. Starch consists of long chain polymers of glucose
and cannot be fermented directly to ethanol by conventional
bakers yeast. Therefore, the macromolecular structure of
starch should first be depolymerized into glucose by enzymes.
Microorganisms are then employed for the production of etha-
nol via fermentation. There are three different categories of
these microorganisms including yeast (e.g., Saccharomyces
species), bacteria (e.g., Zymomonas species), and molds (e.g.,
Mucor species). The produced ethanol is then separated by dis-
tillation [3638]. More details about the ethanol fermentation
technologies from sugar and starch feedstocks can be found
elsewhere [37, 39, 40].
The two major world ethanol producers are the United
States and Brazil with nameplate capacities of 56 and
30 billion L a1 in 2016. These countries produce more than
83 % of the ethanol globally supplied. China, Canada, and
European countries are other big ethanol producers. Corn
starch, sugarcane, and wheat starch are the most important
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feedstock for production of American, Brazilian, and European
ethanol, respectively [41, 42].
Ethanol production from starch feedstock can be performed
through two different processes, i.e., dry milling and wet mill-
ing. In the wet milling process which is not the most popular
method in industrial ethanol production, different ingredients
of the grain (corn or wheat) such as protein and oil are sepa-
rated prior to enzymatic hydrolysis of starch. Therefore, nearly
pure starch is employed for ethanol production. However, the
majority of the big ethanol production processes use the dry
milling process where the whole grain is subjected to the etha-
nol production process. In this process the residue of the grains
as well as the yeast cells produced during the fermentation are
recovered as a protein-rich co-product called DDGS (dried dis-
tiller grains with solubles). This co-product brings a high posi-
tive economic impact to the ethanol process and is sold, e.g., as
animal feed. Typically, 1/3 kg ethanol, 1/3 kg carbon dioxide,
and 1/3 kg DDGS are produced from 1 kg of grain (corn or
wheat) [43]. More details of the ethanol process have been
presented elsewhere [37, 39, 40].
2.3 Ethanol from Lignocellulosic Materials
Lignocellulosic materials, such as woody crops and agricultural
residues can be used to produce 2nd generation bioethanol.
Lignocellulosic materials have three main components includ-
ing cellulose, hemicellulose, and lignin [36, 38, 44]. The hydro-
lysis of lignocellulosic material is more difficult compared to
starch due to their recalcitrance structure. Lignin forms a pro-
tective barrier for the cellulose microfibrils, which makes the
cellulose hydrolysis to glucose difficult. In addition, the linkage
between lignin and hemicellulose hinders the degradation of
hemicellulose to pentose and hexose sugars [38, 45]. The pro-
cess of ethanol production from lignocellulosic biomass
consists of four main steps, namely, pretreatment, hydrolysis,
ChemBioEng Rev 2017, 4, No. 2, 7591 77
fermentation, and distillation [46]. In the pretreatment step,
the lignocellulosic structure is opened up via physical, chemi-
cal, physicochemical, or biological methods [45]. Hydrolysis is
the second step where the cellulose and hemicellulose mole-
cules are degraded into monosaccharides by cellulolytic
enzymes or acids [46]. The sugars are then fermented to etha-
nol in the third step. Many microorganisms have the potential
of being used in the fermentation process. Among those, the
normal bakers yeast (Saccharomyces cerevisiae) is well estab-
lished in large-scale production, has a high ethanol tolerance
and relatively good resistance against inhibitors formed in the
process. However, it does not naturally ferment pentoses
[31, 46]. Purification of the fermentation broth is the last step,
which is mainly done by distillation.
After distillation, most of the formed by-products and other
impurities are removed, leaving only traces behind. It should
be mentioned that distillation is one of the most energy-inten-
sive units and has a major impact on the overall energy
demand of the process. Furthermore, the ethanol-water mix-
ture forms an azeotrope mixture. Consequently, simple distilla-
tion techniques cannot change the composition of this mixture.
This eventually increases the cost of the plant [33]. Using mo-
lecular sieves is another ethanol purification technology which
has become more attractive for industries since it has a lower
energy consumption compared to other methods such as azeo-
tropic distillation. Also, there is no need to use other chemicals
in this process. This eliminates the chance of contamination
and the cost of the usage of such chemicals [47]. More details
about the developments in the technology for ethanol produc-
tion from lignocellulosic materials can be found elsewhere
[44, 48, 49].
2.4 Ethanol from Waste Materials
A potential source of fermentable sugars that can be used to
produce bioethanol is the waste biomass in the form of ligno-
cellulosic or starch-based materials. This type of waste can be
in the form of lignocellulosic materials or starch-based origin
such as food waste, municipal solid waste, agricultural waste
and paper waste. The overall process of bioethanol production
from waste biomass is shown in Fig. 3. However, the terminol-
Figure 3. General process scheme for bioethanol production from waste materials [50].
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ogy of the process steps differs based on the type of feedstock
used. The major steps can be categorized as feedstock prepara-
tion, pretreatment, release of free fermentable sugars, fermenta-
tion, and purification [50].
The new-generation bioethanol production processes have
been greatly improved by new technologies. However, several
challenges still remain, such as developing more efficient pre-
treatment technologies, developing and maintaining stably
performing microorganisms, and integrating the attained opti-
mal components into the economics of ethanol production
systems [51].
Another process is to utilize organic wastes in the anaerobic
digestion plants to produce methane. In the anaerobic diges-
tion process, the carbonaceous matter of wastes is degraded in
natural environments. In general, the feedstock is harvested or
collected, coarsely shredded, and placed into a reactor contain-
ing active inoculum of microorganisms required for the meth-
ane fermentation. The produced methane in this process can
be used to manufacture ethanol via methane reforming to
syngas [21, 52].
2.5 Ethanol from Thermochemical Conversion
Processes
One of the benefits of thermochemical processes is that a wide
variety of biomass feed stocks can be utilized irrespective of
their sugar and lignin contents. This method involves the gasi-
fication of biomass to syngas and then either fermentation of
syngas to ethanol or catalytic conversion of the syngas to etha-
nol and other mixed alcohols. In the context of gas fermenta-
tion, syngas is fermented by acetogenic microorganisms to pro-
duce ethanol or other hydrocarbons that can be used as a fuel
or chemical feedstock. The catalytic conversion syngas into
ethanol can be direct or indirect. In the direct method, syngas
is converted into ethanol (or other alcohols) in a single catalytic
reaction. The indirect synthesis proceeds via dimethyl ether
(DME) hydrocarbonylation to produce ethanol from syngas.
The indirect synthesis has a higher efficiency and better
economics since the direct synthesis has low selectivity that
reduces the efficiency of the ethanol production [20, 21, 53, 54].
ChemBioEng Rev 2017, 4, No. 2, 7591 78
 Several techno-economic analyses have investigated thermo-
chemical conversion processes and showed that the biomass-
derived ethanol by this method has the potential to be cost-
competitive due to higher yields of ethanol per ton of biomass,
as well as lower ethanol selling prices than their fermentation
counterparts [21, 5355].
3 Ethylene Production
Ethylene can be produced in plants and microorganisms or via
synthetic methods such as pyrolysis of naphtha or ethane and
catalytic dehydration of ethanol (Fig. 4). These methods are
discussed briefly in this section.
Figure 4. Schematic diagram of different methods for produc-
ing ethylene.
3.1 Ethylene from Petrochemicals
In the petrochemical industry, ethylene is mainly produced via
steam cracking (pyrolysis) of naphtha in which feed streams
are preheated and then mixed with steam with a 1:1 ratio at
750850 C for a short period of time (less than 0.5 s). The yield
of ethylene depends on the type of feedstock used in the pro-
cess. For instance, the yield of ethylene produced is about 35 %
for naphtha and 80 % for ethane as feedstock [5]. Using ethane
as feedstock has increased since it can be extracted from natu-
ral gas. During the last decade, availability of natural gas has
increased because of the development of hydraulic fracking
technologies, where the gas is extracted using drilling, sand,
high pressure water, and chemical solutions [56]. The increase
in availability of ethane has considerably decreased the ethyl-
ene raw material price. However, studies have revealed that the
hydraulic fracking method can result in environmental conse-
quences such as methane contamination of drinking water [57]
and increased seismic activities [58]. Besides, the traditional
ethylene production processes are one of the most energy-in-
tense chemical processes [59].
3.2 Ethylene Production by Plants
In nature, ethylene is involved in controlling events throughout
the lifecycle of plants, and it is known as the plant hormone
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that can be sensed and produced by plants [60]. Two key
enzymes including ACC (1-aminocyclopropane-1carboxylic
acid) synthase and oxidase (ACS and ACO, respectively) are
involved in the ethylene biosynthetic pathway, where ACS con-
verts the methionine derivative SAM (S-adenosyl methionine)
into ACC and methylthioadenosin. The methylthioadenosin is
then recycled and produces SAM via the Yang cycle, and the
ACC is degraded by ACO into ethylene, CO2, and HCN
[6063] (Fig. 5).
Figure 5. Ethylene biosynthesis pathways in plants [61, 63].
3.3 Ethylene Production by Microorganisms
Several bacterial and fungal ethylene producers have been re-
ported since the discovery of microorganisms able to produce
ethylene in the mid-1900s [6366]. Two main pathways are
involved in the ethylene production in these microorganisms.
The first one is called the L-methionine-dependent KMBA
(2-keto-4-methylthiobutyric acid) pathway. In this pathway,
L-methionine is converted into KMBA and then oxidized to
ethylene via a complex reaction and formation of hydroxyl rad-
icals [67]. The second pathway is the 2-oxoglutarate-dependent
EFE (ethylene forming enzyme) pathway where 2-oxoglurta-
rate is a key substrate [68]. More details about the ethylene
pathways can be found elsewhere [69].
The ethylene producing cyanobacteria has recently been
shown to increase photosynthesis more than wild type cyano-
bacteria. Xiong et al. [70] demonstrated that ethylene can be
sustainably and efficiently produced from the cyanobacterial
tricarboxylic acid (TCA) cycle of the recombinant cyanobacte-
rium.
During the last decade, the biochemical area has expanded
immensely, and nowadays a vast variety of materials are pro-
duced based on biotechnological methods [71]. Thus, bio-
ethylene production using microorganisms would be of great
interest in the future as alternative for the traditional petroleum
based processes, which are highly energy demanding and major
CO2 producer (Fig. 6). A techno-economic analysis of the
ethylene production from cyanobacteria has been done by
Markham et al. [72]. They reported that the productivity of
ethylene has the largest effect on costs and that the synergistic
improvements in productivity, reactor design, and separation
technologies are of great importance for reducing the costs in
ChemBioEng Rev 2017, 4, No. 2, 7591 79

the long-term projection scenario. It should be noted that this
technology is in the early stages.
3.4 Catalytic Dehydration of Ethanol to Ethylene
Catalytic dehydration of ethanol is an alternative route for pro-
duction of ethylene. The first report on catalytic dehydration of
ethanol to ethylene was published in the literature in 1797 [73].
However, the first commercial plant was started in the begin-
ning of the 20th century. In the industry, the alcohol dehydra-
tion mainly occurs in the vapor phase of two-catalyst systems,
i.e., supported phosphoric acid and activated alumina. Most
old technologies used phosphoric acid while the activated alu-
mina became predominant later [10].
The ethanol dehydration is an endothermic reaction (requir-
ing 1632 J g1 or 390 cal g1 of ethylene formed). Therefore, the
reaction temperature affects the yield of ethylene. The highest
selectivity towards ethylene is obtained at 300500 C (Eq. (1)).
Higher temperatures shift the reaction towards acetaldehyde
production (Eq. (2)), while lower temperatures result in pro-
duction of diethyl ether (Eq. (3)). Isothermal and adiabatic
modes of operations have been suggested for the dehydration
of ethanol to ethylene, while the latter is more economically
feasible [10, 12, 30, 74].
cat
C2 H5 OH C2 H4 H2 O (1)
cat
C2 H5 OH C2 H4 O H2 (2)
cat
C2 H5 OH C2 H5 2 O H2 O (3)
3.4.1 Reaction Conditions
The dehydration reaction occurs in the vapor phase inside
fixed or fluidized-bed reactors with catalyst. The process in the
fixed-bed reactor can be either isothermal or adiabatic, while it
is usually adiabatic in the fluidized bed reactor.
3.4.1.1 Isothermal Fixed-bed Reactor
Since the early stages of the technology, the isothermal process
was mainly used in ethanol dehydration. Usually in this pro-
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Figure 6. Ethylene biosynthesis
pathways in microorganisms
[63].
cess, a multi-tubular fixed-bed arrangement is used with the
catalyst placed inside the tubes. A hot stream circulates in the
shell side to provide the needed heat for the endothermic reac-
tion and to maintain the temperature of the catalysts within a
specific range. The operating temperature range is 330380 C
with a liquid hourly space velocity (LHSV) of about 0.2 to
0.4 h1. The conversion of ethanol is 9899 % and the molar
selectivity ethylene is between 9599 %. A frequent regenera-
tion of catalyst is necessary due to the coke deposition. An air-
diluted with steam is used for this purpose, and it is done every
16 months depending on the catalyst and the process condi-
tion. It is more difficult to control the temperature of bigger
tubes. Thus, the possibility to scale up to large capacities is lim-
ited [6, 10, 74, 75].
3.4.1.2 Adiabatic Fixed-bed Reactor
In this process, a series of fixed-bed reactors, packed with cata-
lyst, are used. The heat needed for the reaction is supplied by
an inert heat-carrying fluid. Intermediate furnaces are used to
reheat the feed stream, which enters into the next reactor. The
steam to ethanol weight proportion in the feed stream is typi-
cally 2:1 to 3:1. Ethanol make-up streams are added between
each stage. The inlet temperature is 450500 C with a LHSV of
about 0.15 to 0.5 h1. The conversion is higher than 99 % and
the ethylene molar selectivity is 9799 %. The catalyst regenera-
tion cycle is between 6 to 12 months since steam is used and
coke formation is lower [10, 12, 74, 75].
3.4.1.3 Fluidized-bed Reactor
A nearly quantitative ethanol conversion with very high selec-
tivity to ethylene can be achieved in the fluidized-bed reactor.
It also allows an optimum temperature control with minimized
by-product and coke formation. The conversion of ethanol is
99.5 % at 400 C with a molar selectivity of 99.9 % to ethylene.
No external heating of the reactor is needed since the hot feed
and the heated catalyst (recycled from the catalyst regenerator)
provide the endothermic heat for the reaction [10, 12, 75].
3.4.2 Catalysts
The dehydration of ethanol is an acid-catalyzed reaction. There
are four main categories that can be used as catalyst in such a
ChemBioEng Rev 2017, 4, No. 2, 7591 80
process including phosphoric acid, oxides, molecular sieves,
and heteropoly acid catalysts [12].
3.4.2.1 Phosphoric Acid Catalysts
Phosphoric acid was first used as catalyst in the 1930s by load-
ing phosphate on clay or coke. The ethylene produced from the
ethanol dehydration reaction with this type of catalyst has high
purity. However, the deposition of coke leads to catalyst deacti-
vation and the regeneration takes about a month. Therefore,
such catalysts have no longer been used since the 1950s
[12, 76].
3.4.2.2 Oxide Catalysts
The oxide catalyst is the typical representative of activated alu-
mina-based catalysts, which are currently used in the industrial
equipment for dehydration of ethanol. Alumina can be used as
both catalyst and catalyst carrier for many important chemical
reactions such as the alcohol dehydration, isomerization, alky-
lation, and catalytic cracking. The activated alumina-based cat-
alyst is stable and the purity of the produced ethylene is high.
However, the concentration of ethanol should not be too low,
otherwise higher temperature and lower space velocity are
needed in the presence of this catalyst, which leads to higher
energy consumption [12, 29, 7780].
3.4.2.3 Molecular-Sieve Catalysts
Molecular sieves are materials with regular pore structure,
unique acid-base properties, and large specific surface area.
Molecular sieves can be utilized as catalyst, adsorbent, and
ion-exchange materials in many fields such as environmental
decontamination, petrochemical, and detergent industry, etc.
[81]. Molecular sieves, such as ZSM-5 type, the Si-Al-phos-
phate (SAPO) type, A type, and AM-11 type, have been applied
as catalyst for dehydration of ethanol since the 1980s. The ac-
tivity of ethanol dehydration reaction for different types of mo-
lecular sieves is not very high. To increase the catalytic activity,
molecular sieves were modified by modulating the surface acid-
ity and pore size [8285]. Compared to the activated alumina-
based catalysts, the modified molecular sieves have higher
activity, operate at lower temperatures, and are able to catalyze
the ethanol aqueous solution of low concentration. However,
they are very costly, require a complicated preparation process,
are less stable, and can be deactivated easily. Thus, they are not
applicable in large-scale industrial production [12].
3.4.2.4 Heteropoly Acid Catalysts
Heteropoly acid is an oxygen-containing multi-acid, which
consists of a central atom (such as P, Si, Ge, Fe, and Co) and a
ligand atom (such as Mo, W, V, Nb, and Ta). Heteropoly acids
can be utilized as the acid or the oxidation-reduction catalyst,
both in the homogeneous or nonhomogeneous reactions [86].
They have been studied as catalysts for ethanol dehydration. It
was found that the catalysts have high activity and selectivity
and low reaction temperature, although they showed relatively
low ethanol conversion rate. Usually, this type of catalyst
should be loaded onto the carrier, which leads to serious loss
and high preparation costs [8789].
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3.4.3 Potential By-products Formed in the Ethylene
Process
A range of by-products is formed during the catalytic dehydra-
tion process. Acetic acid, ethyl acetate, acetone, methanol,
methane, ethane, propane, propylene, butane, butylene iso-
mers, hydrocarbons with five carbons or more, carbon monox-
ide, and carbon dioxide are some examples of these by-prod-
ucts. The feedstock ethanol may also contain impurities, e.g.,
methanol [10, 31].
3.4.4 Product Purification
Nowadays, a major part of petrochemical ethylene is used for
the production of plastics. To perform a successful polymeriza-
tion reaction, a very high purity polymer-grade ethylene is re-
quired since the presence of impurity in ethylene has negative
effects on the polymerization [90]. The produced raw ethylene
in the dehydration unit goes through different purification
operations depending on the impurities. The process typically
starts with cooling of the stream, followed by a quench tower
to eliminate most of the formed water and the condensable
polar substances including small quantities of acetaldehyde and
acetic acid as well as the non-reacted ethanol. To remove traces
of carbon dioxide, the ethylene stream is caustic-washed in a
scrubbing tower. The stream is then compressed and passed
through a desiccant drying bed with molecular sieves. The ob-
tained ethylene after this unit has a chemical grade with purity
higher than 99 %. The ethylene stream can be fractionated in a
cryogenic distillation/stripping system to eliminate heavy and
light contaminants and to produce polymer-grade ethylene
adequate for most catalytic polymerization systems. The com-
ponents in the effluent streams from the quench and the scrub-
bing tower can be removed by stripping [10, 12, 30].
3.5 Current Technologies and Industrial Plants
Several commercial processes are currently in operation, devel-
oped by Braskem, Chematur, British Petroleum (BP), and
Axens together with Total and IFPEN. The process by BP is
called Hummingbird. In this process, a heteropoly acid is used
as catalyst, and the reactor operates at 160270 C and
145 bar. The unreacted ethanol in recirculated to the reactor.
The process developed by Axens is called Atol. Two fixed bed
adiabatic reactors, operating at 400500 C, are used in this
process which produces 50 000400 000 t a1 ethylene. Chema-
turs process operates with four adiabatic tubular reactors with
a capacity of 5000200 000 t a1 ethylene. Syndol catalysts, with
the main components of Al2O3-MgO/SiO2, are employed in
this process that was developed by American Halcon Scientific
Design, Inc. in the 1980s [1217]. The Braskem (Brazil) etha-
nol to ethylene plant, which started in 2010, produces
200 000 t a1 ethylene from sugarcane based feedstock. In this
process, the adiabatic reactor feed is diluted with steam to a
large extent. The patent reveals limited information [18, 19].
ChemBioEng Rev 2017, 4, No. 2, 7591 81
4 Bottlenecks and Possible Solutions:
A Case Study
The cost of ethylene production by ethanol dehydration tech-
nology mainly depends on the ethanol price as feedstock [91].
The pure ethanol is relatively expensive (Fig. 7) and the price of
the ethylene produced from ethanol is not compatible with pet-
rochemical ethylene. The current price of ethanol is 0.42 kg1
(or US$ 1.41 per gallon) [92] while production of petrochemi-
cal ethylene costs about 0.541.17 kg1 (6001300 US$ t1), as
reported by the International Renewable Energy Agency in
2009 [11].
If biomass is used as feedstock for bioethanol production, it
accounts for about 60 % of the costs. In turn, the bioethanol
cost accounts for about 6075 % of the bioethylene production
cost, depending on the region [11].
The production costs of bioethylene are very low in Brazil
and India (from sugarcane, 1200 US$ t1 bioethylene), while the
costs are higher in United States (from corn, 2000 US$ t1) and
in European Union (from sugar beets, 2600 US$ t1). The cost
of Chinese bioethylene production from sweet sorghum is
somewhere in between (about 1700 US$ t1) [11].
Using ethanol grades with lower purity as feedstock might
be considered as an alternative to reduce the production costs.
Thus, it is important to see how ethanol impurities would affect
the process from a technical and economical point of view. This
was investigated using an Aspen simulation.
4.1 Process Description
Ethanol dehydration for ethylene production consists of three
major steps: reaction, ethylene recovery, and ethylene purifica-
tion. In the reaction step, ethanol is brought to reaction condi-
tions and sent to catalytic reactors (with a SynDol catalyst) to
be converted into ethylene. Besides ethylene, water is also pro-
duced as a main by-product of reaction. Moreover, there will
be some unreacted ethanol left in the product stream. Nearly
all of ethanol and water must be removed to be able to produce
a polymer-grade ethylene. This is performed in recovery step.
1400
Ethylene (EUR/tonne)
1300
Ethylene price (EUR/tonne)
Ethanol (UDS/GAL)
1200
1100
1000
900
800
700
600
Figure 7. Ethylene and ethanol price evolution from 2006 to 2016; data taken from [92, 93].
www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA
Carbon dioxide is the other main component removed in this
step. Finally, in the purification step, the polymer-grade ethyl-
ene is obtained by removing the remaining impurities
[10, 12, 30, 74]. It should be noted that the overall simulated
process in this step is similar to the process used by Chematur
and has been revised by experts in this company.
4.1.1 Reaction Step
The process flow diagram of the reaction step is presented in
Fig. 8. The process can either be performed diluted or undi-
luted. In the diluted process, the reactor feed is to a large extent
diluted with steam, while in the undiluted process, no steam is
injected to the feed and the feed is heated between different
reactors [74]. The undiluted process was used in the simulation
since the diluted process does not seem to be economically
attractive [21]. The suitable pressure for ethanol dehydration
reaction is about 15 bar. As the main reaction is an equilibri-
um reaction, higher pressures would shift the equilibrium back
to ethanol. Therefore, even though a higher pressure is re-
quired in the purification step, ethanol is only pressurized to
4.5 bar in the reaction step. The ethanol feed is then preheated
to 82C in a preheater. The next step is the complete evapora-
tion of ethanol. Ethanol vapor then passes through a knockout
drum before entering the first furnace to ensure that no liquid
will enter the furnace system. In the furnace, the temperature is
increased to 425 C. Then, ethanol feed enters the first fixed-
bed catalytic reactor. Under adiabatic conditions, the progress
of the reaction is accompanied by a reduction in temperature.
The reaction mixture is taken out from Reactor 1 before the
temperature decreases to 310 C. Thereafter, it is sent to the
second furnace to heat up the mixture back to 425 C before
reaching Reactor 2. A total of four adiabatic reactors, in series,
are used in this process. The temperature of output in the last
reactor is set to be higher than 370 C. This stream has a very
high heating capacity and is therefore used for steam produc-
tion in a steam generator. The obtained steam is then used for
evaporation of the ethanol feed. The temperature of the reac-
tion mixture is decreased to 144 C in the steam generator. This
stream still has a rather high heating capacity and can therefore
5
Ethanol price (USD/GAL)
4
3
2
1
ChemBioEng Rev 2017, 4, No. 2, 7591 82
Figure 8. Process flow diagram of the reaction step of ethylene production from ethanol.
be utilized for preheating of the ethanol feed. The temperature
of the reaction mixture finally reaches 90 C.
4.1.2 Recovery Step
One of the main purposes of this step is to remove the carbon
dioxide, water, and the unreacted ethanol from the product.
Some other impurities are also removed in this step (Fig. 9).
The big difference between the boiling point of water and
ethylene makes the separation process easy. The product is first
cooled to 50 C in a heat exchanger and then enters into a
quench tower. Water at 40 C is sprayed at the top of this col-
umn where the water vapor is condensed and separated from
the ethylene column. Part of the condensed water is cooled and
reused in the quench tower (Fig. 9). The ethylene that leaves
the quench tower contains 92.1 wt % ethylene as well as
5.2 wt % water, 1.4 wt % ethanol, and 1603 ppm carbon dioxide.
The CO2 concentration should be decreased to 5 ppm to ful-
fil the requirements for polymer-grade ethylene. Before CO2
removal, the ethylene stream is pressurized to 27 bar using
compressors (three stages). This pressure is required in the
purification step. Between the compressors, the ethylene stream
is cooled down to 15 C to condense some more water. The
condensed water is separated in the knockout drums. Carbon
dioxide removal is performed by dissolution in sodium hydrox-
ide solution (in a caustic wash column). A water washing col-
umn is also used in this process to remove any possible drops
of alkali solution that have been carried by the ethylene stream.
Concentration of the carbon dioxide in the remaining stream is
less than 2 ppm. Before entering the final purification section,
it is necessary to completely remove the water. This is because
www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA
the purification is performed at very low temperatures (cryo-
genic condition), and presence of water would damage the in-
struments. Final water removal is performed by molecular
sieves. An ethylene stream with 99.2 wt % ethylene is sent to
the final purification stage.
4.1.3 Ethylene Purification Step
Cryogenic distillation is used in this section to remove the
remaining impurities from the ethylene product. A process
flow diagram of this section is presented in Fig. 10.
In the beginning, the ethylene stream is cooled to 23 C.
Then, it passes through an expansion valve, which reduces the
temperature further to 28 C by dropping the pressure from
27 to 22 bar. Cryogenic distillation is performed in two col-
umns, i.e., ethylene column and stripper column. The former
removes the heavy impurities from ethylene, namely propylene,
butadiene, diethyl ether, acetaldehyde, and ethane. The latter
removes light impurities, i.e., hydrogen and methane from ethyl-
ene. The two columns have a joint condenser (Fig. 10). An ethyl-
ene stream with a purity of 99.97 wt % is obtained at the end. The
impurity profile of this product fulfils the requirements for poly-
mer grade ethylene (Tab. 1). Finally, ethylene is warmed up to
10 C by exchanging heat with the impure ethylene that enters
the purification section (Fig. 10).
4.2 Simulation Hints
Aspen plus 8.6 and Aspen Process Economic Analyzer 8.6
were used to simulate the process. Due to presence of polar
ChemBioEng Rev 2017, 4, No. 2, 7591 83
Figure 9. Process flow diagram of the recovery step of ethylene production from ethanol.

components, e.g., water and ethanol, the NRTL activity coeffi-
cient model was used in the reaction section. For the caustic
wash unit, a modified version of NRTL, i.e., ELECNRTL was
chosen. For the purification step where the non-polar compo-
nents are dominant, the Peng-Robinson equation was used.
For the steam (utility), the steam table was employed. Eight
parallel reactions were considered in this simulation. Stoichio-
metric calculations were used to model the process. Selectivity
of each reaction is presented in Tab. 2 [94].
In each of the adiabatic reactors, the conversion was set at a
level where the temperature of the product was above 310 C. For
the last reactor, it was 377 C. Ethanol conversions were 28.7,
40.2, 67.0, and 87.0 % for reactors 1 through 4, respectively.
The overall ethanol conversion in this process was 98.2 %.

Figure 10. Process flow diagram of the purification step of ethylene production from ethanol.

www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2017, 4, No. 2, 7591 84
Table 1. Specification of polymer grade ethylene and results of 4.3.1 Pure Ethanol as Feed
simulation.
The process simulation was performed for a product formation
Required for Simulation results of 180 kt a1. Flow rate and composition of the main streams
the polymer grade for 180 kt a1 are presented in Tab. 3. The pure ethanol (95 %) feed stream
represents the ideal case that was obtained from an ethanol fac-
Ethylene [mol %] 99.9 99.97
tory with starch as feed (1st generation ethanol).
Maximum impurities [mol ppm]

Acetylene 2 0
4.3.2 Effect of Ethanol Impurities on the Quality
Methane 200 194 of Produced Ethylene
Ethane 200 129
In this section, the impact of the impurities of the bioethanol
Oxygen 2 0 feed was investigated. Different types of ethanol streams can be
Carbon monoxide 1 trace considered as feed for the ethylene production process. In this
work, four different streams were studied including E95, E100,
Carbon dioxide 5 less than 1.3 E87, and E87cellulose. E87 is the ethanol stream from the top of
Total sulfur 2 0 aldehyde column. E87cellulose represents lignocellulosic ethanol
that contains three additional impurities including furfural,
Propylene 10 0
acetic acid, and acetone, which are typical volatile compounds
C4+s 10 0 for lignocellulosic ethanol with organosolv pretreatment [95].
The specifications of the E95, E100, and E87 streams taken
Water 2 0
from an industrial ethanol plant are presented in Tab. 4 togeth-
Hydrogen 5 0 er with the E87cellulose stream, which is fabricated based on E87
data. The Aspen model developed in previous parts was
Methanol 5 0
employed to investigate the impact of the impurity profile on
Total chlorine 2 0 the quality of the final ethylene. The results are summarized in
Other compounds 5 0
Tab. 5. It can be seen that the impurity profile of ethanol feed
does not have a significant effect on the quality of the obtained
bio ethylene.
Table 2. Parallel reactions assumed to occur in the adiabatic
reactors [94].
4.4 Economic Evaluations
Product name Reaction Selectivity
The process of ethylene production from ethanol was modelled
Ethylene C2 H5 OHC2 H4 H2 O 0.988 in details and the economic calculations were performed as-
suming an n-th plant design, i.e., the design was based on the
Diethyl ether C2 H5 OHC2 H5 2 O H2 O 0.00052
technologies which have already been used in commercial
Acetaldehyde C2 H5 OHC2 H4 O H2 0.002 plants and are well understood. Annual working hours were
considered to be 8000 h in this study and the project life was
Ethane 2C2 H5 OH H2 2C2 H6 2H2 O 0.0027
assumed to be 20 a. The cost estimations were performed using
Propylene 3C2 H5 OHC3 H6 3H2 O 0.0006 Aspen Process Economic Analyzer version 9. Pricing was based
Butadiene 2C2 H5 OHC4 H6 2H2 O 0.005 on first quarter of 2015. A tax rate of 25 % and discount rate of
10 % was considered in the calculations.
Carbon 2C2 H5 OHCO CH4 H2 0.00007 The prices of the major equipments in the process are pre-
monoxide sented in Tab. 6. A ten days supply for the ethanol feed has
Carbon C2 H5 OH H2 OCO2 CH4 H2 0.0011 been considered to estimate the price of an ethanol storage
dioxide tank (US$ 2 million). The equipment in the reaction, recovery,
and purification steps have a purchase cost of US$ 2.2, 4.7, and
4.3 million, respectively. These values are in agreement with
the values reported by Haro et al. [20].
4.3 Simulation Results The price of an ethylene storage tank (a sphere tank) consid-
erably varies with the ethylene storage time. If there would be
The simulation of the process was done for two cases. In the the possibility of direct consumption of the ethylene in another
first case, a pure ethanol 95 wt % stream was used as feed, while unit (e.g., a polymerization unit) a short residence time of 2 h
in the second case a feed of ethanol containing different impur- seems to be reasonable. For this residence time, the price of the
ities was investigated. ethylene storage tank is about US$ 0.86 million. For longer
storage times however, the price of the storage tank would be

www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2017, 4, No. 2, 7591 85
Table 3. Properties of the main streams (180 kt a1).

Stream P T Flow rate Ethylene Water Ethanol CO2 Other

[bar] [C] [kg/h] [wt%] [wt%] [wt%] [ppm] [wt%]

Reaction Step

EtOH feed 1 25 42 194 0 5 95 0 0

EtOH vapor 4.5 121.4 42 194 0 5 90 0 0

Outlet of reactors 1.4 377.1 42 194 56.11 41.3 0 980 0.75

Ethylene stream to step 2 1.4 90.4 42 194 56.11 41.3 0 980 0.75

Recovery Step

Quench outlet 1 41.6 25 449.7 92.1 5.2 1.4 1603 1.1

High pressure ethylene 27 25 23 579.2 98.7 0.028 0.14 1730 1

stream to Caustic wash

CO2-free ethylene stream 27 28.3 22 665.4 99.2 0.053 0 0.4 0.775

Dried ethylene stream to step 3 27 15 22 637.9 99.2 0 0 0.4 0.768

Purification Step

Ethylene and light products 22 25.7 22 218 99.87 0 0 0.45 0.125

Heavy products 22 16 419.9 65.2 0 0 0 34.8

Light products 22 40 342.4 93.5 0 0 0 6.5

Polymer grade ethylene 22 25.6 21 875.7 99.97 0 0 0.45 0.03

Final ethylene product 22 10 21 875.7 99.97 0 0 0.45 0.03

Table 4. Composition of different ethanol feeds. Concentrations are presented in g/g. E87 represents the etha-
nol stream from the top of aldehyde column while E87cellulose represents lignocellulosic ethanol.

Composition E95 E100 E87 E87cellulose

Ethanol 0.926400 0.986900 0.871584 0.871584

Methanol 0.000045 0.000065 0.000500 0.001150

Acetaldehyde 0.000026 0.000055 0.001100 0.001100

Propanol 0.000130 0.000340 0.000049 0.000049

Diethylamine 0.000010 0.000000 0.000000 0.000000

Ethylacetate 0.000009 0.000020 0.003406 0.003406

Isobutanol 0.000068 0.000390 0.000044 0.000044

1-butanol 0.000006 0.000018 0.000008 0.000008

2-pentanol 0.000160 0.000000 0.000006 0.000006

Isoamyl alcohol 0.000055 0.000720 0.000913 0.000910

2-methyl 1-butanol 0.000048 0.000220 0.000469 0.000469

Water 0.073042 0.011272 0.121910 0.117754

Furfural 0.000000 0.000000 0.000000 0.001150

Acetone 0.000000 0.000000 0.000000 0.001150

Acetic acid 0.000000 0.000000 0.000000 0.001150

www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2017, 4, No. 2, 7591 86
Table 5. Expected composition of ethylene obtained from different ethanol streams. The negative profit margin indi-
cates that the process is not pro-
Ethanol feed Ethylene Water Ethanol CO2 Other fitable with the above prices for
[wt%] [wt%] [wt%] [ppm] [wt%] raw materials and products. Ac-
E95 99.92 0 0 0.45 0.08
cordingly, at current prices, the net
present (NPV) value of the project
E100 99.92 0 0 0.48 0.08 will be negative. Tab. 9 presents the
E87 99.92 0 0 0.43 0.08 minimum required price of the
product or the maximum required
E87cellulose 99.92 0 0 0.34 0.08 price of the raw material which re-
sult in NPV = 0. For example, when
the ethylene storage time is 2 h, an
Table 6. Summery of the costs for the major equipments in the process.
ethylene price of 1.8606 US$ kg1 is
required to achieve NPV = 0, which
Description Major equipment Price [US$]
means the project would give a
Ethanol storage tank 10 day supply of ethanol to the process 2 006 500 10 % rate of return on investment.
Alternatively, with the current price
Reaction step Reactors 229 500
of ethylene, reduction of the etha-
Furnaces 1 829 400 nol price to 0.4814 US$ kg1 is re-
quired to get NPV = 0 (Tab. 9).
Other equipment 139 300
It should be noted that the bio-
Recovery step Quench system 265 100 energy with carbon capture and
Compression system 4 245 700 storage (BECCS) for the ethanol
feedstock is not included in the
Caustic and water wash system 90 200 economic calculations of this case
Dehydration system 72 500 study. If BECCS is taken into
account for the case studies, the re-
Purification step Ethylene column 3 811 500 sults may be substantially enhanced
Stripper column 152 800 as reported by Haro et al. [20].
They studied five different poten-
Other equipment 395 000 tial processes to produce ethylene
Ethylene storage tank 2 h storage 860 500 from biomass and concluded that
two cases (Brazilian ethanol and
24 h storage 39 877 000
the estimated price of ethanol via
48 h storage 80 808 000 the indirect synthesis of syngas)
would enable the cost-competitive
production of ethylene. However,
significantly higher with respect to other equipment. The price all cases, except for the case of bioethanol from biochemical
of the ethylene storage tank represents 6, 72, and 83 % of the processing, would be profitable if BECCS is taken into account.
total purchase costs of the equipment for residence times of 2, Another solution to lower the production costs and to save
24, and 48 h, respectively. Therefore, building the ethylene pro- energy in the process is the integration of the ethylene produc-
duction plant next to the plant that consumes ethylene will sig- tion unit with a 1st and 2nd generation ethanol production
nificantly reduce the investment costs and improve the econo- unit. In this scheme, the produced ethanol after initial
my. The details of the projects capital costs for different purification steps can be used as the feedstock for the ethylene
ethylene storage times are presented in Tab. 7. According to the production. The techno-economic study of such a plant as well
results, the total project costs are significantly affected by the as sensitivity analysis remains as a future work.
ethylene storage time. However the annual operating costs are
not significantly affected by the ethylene storage time (Tab. 8).
The main raw material is 95 wt % ethanol. This is considered 5 Concluding Remarks
to be supplied from an ethanol plant, e.g., in Sweden with a
cost of 0.85 US$ kg1. A transportation cost of 0.08 US$ kg1 is Ethylene is one of the most important chemical intermediates
added to the price of ethanol for a typical 400 km distance produced by steam cracking of petroleum liquids and natural
between the ethanol supplier and the ethylene plant. Therefore, gases. Catalytic dehydration of bioethanol is an alternative
a value of 0.93 US$ kg1 ethanol is considered for economic route for production of ethylene, which reduces the greenhouse
calculations. The current price of fossil based ethylene is gas emissions and dependency on limited fossil fuels. First and
1.01 US$ kg1. The difference between the revenue from the second generations of bioethanol can be used as the feedstock
sales of the product (1.77 108 US$ a1) and the cost of the raw for manufacturing of ethylene. However, the contaminants in
materials (3.14 108 US$ a1) is considered the profit margin, the second generation of bioethanol may have an impact on
here 1.8 108 US$ a1 for a production capacity of 180 kt a1. the process. Results showed that the impurities in the ethanol

www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2017, 4, No. 2, 7591 87
Table 7. Details of the project capital costs.

Cost item Cost [US$] of the process for different ethylene storage times

2h 24 h 48 h

Purchased equipment 14 223 601 55 271 100 97 430 112

Equipment setting 155 146 155 146 155 146

Piping 4 594 580 7 233 566 10 218 564

Civil 2 338 493 4 221 064 5 969 494

Steel 216 330 617 920 12 505 832

Instrumentation 2 886 514 3 482 904 3 771 301

Electrical 2 084 340 2 088 153 2 089 465

Insulation 1 071 763 1 454 079 1 671 084

Paint 202 131 203 677 207 494

Other 9 638 200 12 505 101 15 975 900

G and A overheads 965 688 2 447 508 3 982 042

Contract fee 1 323 328 2 476 161 3 697 020

Contingencies 7 146 020 16 588 148 26 355 276

Adjusted total project costs 51 357 006 119 215 670 189 410 047

Table 8. Details of the project operating costs with the exception of the raw material cost.

Cost item Operating costs [US$ a1] of the process with different ethylene storage times

2h 24 h 48 h

Operating labor cost 1 240 000 1 240 000 1 240 000

Maintenance cost 518 000 1 990 000 3 550 000

Operating charges 310 000 310 000 310 000

Plant overhead 897 000 1 615 000 2 395 000

G and A cost 24 672 514 24 849 392 25 036 592

Total Utility costs 9 763 874 9 766 850 9 766 850

feed do not affect the quality of the produced bioethylene, sig- Acknowledgment
nificantly. Therefore, it is not necessary to perform all the puri-
fication steps in an ethanol plant to get a proper feed for ethyl- This work was financed by the Swedish Research Council (For-
ene production. Economic evaluation showed that the process mas), Sweden. We appreciate Chematur Engineering AB for
is not profitable with the current prices for raw materials and providing consulting services in this study.
products. Taking into account the BECCS for the feedstock eth-
anol may change the profit margins and, consequently, enable The authors have declared no conflict of interest
the cost-competitive production of ethylene. The ethylene pro-
duction unit can also be integrated into 1st and 2nd generation
ethanol production units where the ethanol feed stock is the Abbreviations
product of the ethanol plant before the final purification steps.
These studies remain as future work. ACC 1-aminocyclopropane-1carboxylic acid
ACO ACC oxidase
ACS ACC synthase
BECCS bioenergy with carbon capture and storage

www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2017, 4, No. 2, 7591 88
Table 9. Net present value (NPV) of the project considering different prices for ethylene and ethanol.

Ethylene storage time Ethanol price [US$ kg1] Ethylene price [US$ kg1] NPV [US$]

2h 0.93 1.01 1.62 109

0.4814 1.01 0

0.93 1.8606 0

24 h 0.93 1.01 1.67 109

0.4546 1.01 0

0.93 1.9093 0

48 h 0.93 1.01 1.74 10-9

0.4251 1.01 0

0.93 1.9627 0

DDGS dried distiller grains with solubles

DME dimethyl ether Akram Zamani received her
EFE ethylene forming enzyme Ph.D. in Biotechnology from
KMBA 2-keto-4-methylthiobutyric acid Chalmers University of Tech-
LHSV liquid hourly space velocity nology, Sweden, in 2010. She
NPV net present value then worked as an assistant
SAM S-adenosyl methionine professor at Isfahan University
SAPO Si-Al-phosphate of Technology in Iran for three
SHOP Shell higher olefin process years. In 2014, she joined the
TCA cyanobacterial tricarboxylic acid Swedish Centre for Resource
recovery and since then, she is
working as a senior lecturer at
Abas Mohsenzadeh received
the University of Bors, Swe-
his B.Sc. in Chemical Engi-
den. Her research mainly deals
neering from Isfahan Univer-
with the development of
sity of Technology (IUT), Iran,
different biopolymer-based products (e.g., super-absorbents
in 2007. From 2008 to 2015, he
and bioplastics) as well as process simulations using Aspen
worked for his M.Sc. in Indus-
plus.
trial Biotechnology and his
Ph.D. within the Resource Re-
Mohammad J. Taherzadeh,
covery area at the Swedish
received his Ph.D. in Bios-
Center for Resource Recovery
ciences in 1999 from Chalmers
at the University of Bors,
University of Technology in
Sweden. Since 2015, he is post-
Sweden after having obtained a
doctoral researcher at the Uni-
B.Sc. and M.Sc. in Chemical
versity of Bors working with-
Engineering. He worked at dif-
in computational modelling, combustion and thermal
ferent universities and compa-
processes as well as biotechnology groups. His scientific
nies on bioprocess develop-
interests include molecular modeling and computational
ment, until in 2004, he became
simulation of chemical processes from micro to macro
professor in Bioprocess Tech-
levels.
nology at the University of
Bors, Sweden. He is currently
the head of the research school
at the Swedish Centre for Resource Recovery. With more
than 200 publications in scientific journals and books and
patents, he is developing bioprocesses to convert wastes and
agricultural residuals to value added products in form of
energy and materials.

www.ChemBioEngRev.de 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA ChemBioEng Rev 2017, 4, No. 2, 7591 89
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