ISSN 2070-0504, Catalysis in Industry, 2016, Vol. 8, No. 2, pp. 152–167. © Pleiades Publishing, Ltd., 2016.

Original Russian Text © I.S. Yakovleva, S.P. Banzaraktsaeva, E.V. Ovchinnikova, V.A. Chumachenko, L.A. Isupova, 2016, published in Kataliz v Promyshlennosti.

BIOCATALYSIS

Catalytic Dehydration of Bioethanol to Ethylene

I. S. Yakovleva, S. P. Banzaraktsaeva, E. V. Ovchinnikova, V. A. Chumachenko, and L. A. Isupova
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
e-mail: irga@catalysis.ru, sardana_b@catalysis.ru, evo@catalysis.ru, vachum@catalysis.ru, isupova@catalysis.ru
Received July 14, 2015

Abstract—This review presents an up-to-date analysis of the scientific and patent literature concerning etha-
nol dehydration catalysts and ethylene synthesis processes, taking into consideration the specific features of
utilizing biological raw materials.

Keywords: bioethanol, bioethylene, dehydration, catalysts, reactors

DOI: 10.1134/S2070050416020148

CONTENTS 800–1200°C, consuming much energy, and emit mil-

Introduction
1. Outlooks for the use of bioethanol and some exam-
ples of commercial ethanol dehydration to ethylene
2. Some conceptions of the mechanism of ethanol
dehydration to ethylene
3. Catalysts for ethanol dehydration to ethylene
3.1. Acid-based catalysts
3.2. Catalysts based on molecular sieves
3.3. Oxide catalysts for ethanol dehydration to ethylene
4. Technological features of the process and reactor
types
4.1. Fluidized-bed reactors
4.2. Tubular fixed-bed reactors
4.3. Adiabatic fixed-bed reactors
Conclusions
References
INTRODUCTION
Ethylene is among the key products of the petro-
chemical industry. According to recent estimates [1],
approximately 75% of the petrochemical products are
obtained using ethylene. These include polyethylene,
α-olefins, acetaldehyde, ethylene oxide, ethylene gly-
col, ethylbenzene, ethyl chloride, vinyl chloride, eth-
ylene dichloride, and vinyl acetate. The annual world
production of ethylene is about 156 million tons [2, 3],
and over 95% of the product is obtained by the pyrol-
ysis of liquid raw materials (naphtha and gas oil) and
gases (propane and liquefied associated gas). These
large-scale processes yield, along with ethylene and
propylene, considerable amounts of by-products,
which are separated out and then used. However, the
pyrolysis processes take place at high temperatures of
lions of tons of carbon dioxide into the atmosphere
[4]. For this reason, it is still important to find alterna-
tive methods of ethylene production.
In recent years, there have been extensive studies
on the possibility of obtaining ethylene from natural
gas and renewable resources. Although ethylene pro-
duction by the oxidative condensation of methane [5, 6]
and by the oxidative dehydrogenation of ethane [7] has
been widely discussed, these methods have not been
commercialized. Note the process developed by Dow
Co. To produce olefins from synthesis gas via the
Fischer–Tropsch reaction over molybdenum catalysts
and the technology developed by Mobil Co. for
obtaining ethylene by methanol dehydration over zeo-
lite-containing catalysts (MTO process). In most
studies on methanol conversion into light (С2–С4)
olefins, the process has been carried out over zeolite
catalysts, mainly over H-ZSM-5 and various types of
SAPO. The activity of the zeolite catalysts in the MTO
process is attributed to the narrowness of the zeolite
channels and the presence of acid–base sites of certain
strength [8]; however, although there has been 30-
year-long research in this area, the process has not
been commercialized yet. An example of scaling up
this process is the UOP/HYDRO MTO pilot plant
(Norsk Hydro Co., Norway), which produces eth-
ylene and propylene using SAPO-34. The rapid deac-
tivation of the zeolite catalysts because of their coking
and the short interregeneration service life of the cata-
lysts, which does not exceed 3–5 min, are the main
problems in putting the MTO process into practice.
Brazil, India, the United States, and other coun-
tries possessing large vegetable biomass resources are
developing enzymatic technologies for converting bio-
mass into bioethanol followed by obtaining ethylene.
The process of ethylene production by the catalytic

152
 CATALYTIC DEHYDRATION OF BIOETHANOL TO ETHYLENE
Table 1. Ethanol production from different raw materials
Crop yield, Carbohydrate
Culture
t/ha content, %
Sugarcane 65 Sugar 15
Corn kernels 4.9 Starch 65
Wheat grains 2.8 Starch 55
Potato tubers 20 Starch 20
Sunchoke tubers 40 Sugar 22
Cow parsnip (Herácléum) 50–200 Sugar 10–31
dehydration of ethanol has been known since 1913 [9].
Studies in this area were performed in the 1960s–1980s
as well, but they were fundamental ones, aimed at,
e.g., elucidating the mechanism of the reaction [10].
In recent decades, interest in this process has risen [11]
owing to the increasing demand for ethylene for poly-
mer production and due to modern enterprises being
oriented to renewable biological raw materials, such as
bioethanol [12] (Bioethanol-to-Ethylene, B.E.T.E.).
The number of publications on the catalytic dehydra-
tion of ethanol to ethylene increased from about 200 in
1998 to 1200 in 2010 [13]. There have been reviews
dealing with ethanol dehydration to ethylene (see,
e.g., [14]).
Note that the large-scale production of bioethylene
may be strongly limited both by ethical considerations
associated with the depletion of grain resources and by
economic problems of processing bioethanol as an
excisable good. For the Russian Federation, a possibly
more promising approach is the use of inedible plants
provided that their high-productivity species have been
developed. A real technological niche is creation of
large- and medium-scale bioethylene industries ori-
ented towards the production of specialty polymers,
carbon nanotubes, polymer–carbon composites, and
other high-added-value materials.
This review presents an up-to-date analysis of the
scientific and patent literature concerning ethanol
dehydration catalysts and processes for obtaining eth-
ylene, taking into consideration the specific features of
utilizing biological raw materials.
1. OUTLOOKS FOR THE USE OF BIOETHANOL
AND SOME EXAMPLES OF COMMERCIAL
ETHANOL DEHYDRATION TO ETHYLENE
Bioethanol has become widely known primarily
owing to its usability as a biofuel and the possibility of
preparing bioethanol-based antiknock additives for
motor fuels [15–19]. In recent years, a number of
reviews have been published on bioethanol conversion
into various organic products, including ethylene, eth-
ylbenzene, toluene, divinyl, isobutene, 1-butanol, and
acetic acid [20–22].
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
153
Ethanol yield, Ethanol yield, Cultivated area,
kgethanol/t kgethanol /ha ha/tethylene
55.2 3590 0.5
315.6 1546 1.1
268.3 751 2.3
90.7 1894 0.9
79.7 3188 0.5
37–114 1973–22881 0.89–0.08
Bioethanol can be derived from any vegetable feed-
stock containing considerable amounts of sugar,
starch, and cellulose. Table 1 lists characteristics of
some cultures used in bioethanol production. The
guiding criterion in selecting a raw material is the eth-
anol yield from 1 ha, an integrated characteristic com-
bining the crop yield and the ethanol capacity of the
culture, the latter depending on its sugar or starch con-
tent [23]. The last column of Table 1 indicates, for
each culture, the cultivated area necessary for obtain-
ing 1 t of ethylene at an ethanol consumption rate of
1.75 t/t [24].
Due to high cropping capacity and sugars/starch
content and the abundance of sugarcane in Brazil and
corn in the United States, these countries account for
the greater part of the global production of ethanol
from biological raw materials. In Russia, promising
raw material for bioalcohol production are sunchoke
[25] and cow parsnip [23]; under cool weather condi-
tions, these are Russian silver-grass waste from agri-
cultural processing of cellulose-containing raw mate-
rials, for example, rice husks and wheat straw [26, 27].
Extensive discussions of the prospects of chemical
processes consuming renewable resources have
brought up the issue of whether it is ethical to use food
raw materials in the production of biofuels and organic
synthesis products [28] and whether it is efficient and
environmentally appropriate to use lands for this pur-
pose [29, 30]. From this standpoint, chemical pro-
cesses utilizing the products from the processing of
high-yielding and readily available non-food raw
materials, including agricultural waste, are preferable
[27, 31, 32]. Some inorganic impurities that appear in
biomass after its pretreatment can exert an adverse
effect on the catalyst, thus reducing the product yield
and the catalyst’s service life [33]. Nevertheless, the
issue of the effects of impurities in biomass and
bioethanol on their further processing are not usually
considered, likely because the processing technology
includes feedstock pre-purification stages. At the
same time, the expensiveness of biomass processing
and the large contribution from bioethanol pretreat-
ment to the bioethylene cost are keenly discussed [1,
11, 29, 30, 35–37].
154 YAKOVLEVA et al.
Table 2. Biggest producers of ethylene from bioethanol
Production
Company Location
capacity, KTPA
Braskem Triumfo, Brazil 200
Solvay Indupa* Santa André, 60
Brazil
Petrobras Maceió, Brazil 60
Dow Chemical United States 190
(Mitsui) (Japan)
Jilin Zhongxin China 90
Chemical Group Co**
Greencol Taiwan 100
(Toyota)**
Oswal Petrochemical** India 58
*Process developed by Halcon/SD (Chematur International AB).
**Process developed by GI Dynamics (Petron Scientech).
The economic efficiency and appropriateness of
bioethylene production from bioethanol was consid-
ered in a number of works [11, 29, 30, 34, 35, 37].
Studies in this field demonstrated that bioethylene
production by bioethanol dehydration has the follow-
ing advantages over petrochemical ethylene produc-
tion processes [11, 36]: (1) bioethylene is purer than
petrochemical ethylene; (2) bioethanol is a renewable
raw material, and is possible to organize a closed-loop
production system; (3) the technology and equipment
are simple; (4) product separation and ethylene pro-
cessing are inexpensive processes; (5) the process
needs only small investments and a short facility con-
struction time and provides a quick payback. The eco-
nomic efficiency of bioethylene production from
bioethanol was demonstrated by comparing the
investments in the dehydration of wood-derived
bioethanol and the thermal cracking of hydrocarbons
[34, 36]. A detailed technological analysis of bioetha-
nol and bioethylene production demonstrated that,
irrespective of the bioethanol synthesis method, the
main factors in the economic efficiency of bioethylene
production from bioethanol are the availability of the
biological raw material and combining the biomass
processing, bioethanol production, and bioethylene
synthesis stages at one plant in order to avoid paying
excise duty on alcohol [37]. According to some
authors [19, 37], the most efficient way of obtaining
bioethylene is its synthesis from bioethanol via a tech-
nology developed by the Brazilian company Braskem
and the low cost of bioethanol and biopolyethylene,
which are produced in one technological complex, is
due to the availability and high crop yield of the vege-
table raw material, namely, sugarcane.
Note that the terms biopolyethylene and green eth-
ylene have not been rigorously defined in the litera-
ture. The authors of a recent review [38] think that the
term green applies only for biodegradable materials.
The prefix bio may be used to distinguish the products
whose application or production at any stage involves
elements of a biotechnology, whether it be use of
renewable vegetable raw materials and bio-enzymes in
the synthesis, or the presence of bacteria in the final
product, and to indicate that the synthesized product
is biodegradable [39]. Possibly based on these consid-
erations, Braskem applies the term green ethylene to
the bioethanol dehydration product derived from
renewable plant raw materials.
The bioethanol-to-ethylene process flowsheet
(Fig. 1), irrespective of the kind of catalyst and reactor
unit type, includes a feedstock preparation and dosage
module, an ethanol dehydration module, and an eth-
ylene purification module [9, 40, 41]. After being pre-
evaporated, the ethanol-containing feedstock is fed
into the ethanol-to-ethylene dehydration reactor. The
product mixture leaving the reactor is washed with
water in a column and then with an alkali in another
column. Next, the mixture enters a drying column and
is then separated into light and heavy fractions in dis-
tillation columns. Polymer-grade ethylene is obtained
as a result. The process is generally conducted in a gas
phase with a high ethanol content of 95 vol % at a tem-
perature of 200–500°С and an hourly space velocity of
0.5–3 h–1 and is characterized by high bioethanol con-
version and target-product selectivity values of 95–
99.5%. As a rule, the catalyst needs to be regenerated
with a steam–air mixture at 1–12 month intervals [24,
42–46].
Catalytic bioethanol dehydration has been com-
mercialized in many countries. The American Hal-
con/Scientific Design Company, Brazilian National
Petrobras, and other big companies license their own
ethanol/bioethanol dehydration technologies (Table 2).
The first industrial ethanol dehydration process
was implemented in 1913 by Elektrochemische Werke
GmbH (Bitterfeld, Germany) in an isothermal tubular
reactor over an alumina catalyst [9]. The first large-
scale production of ethylene from ethanol with an out-
put capacity of 200000 TPA was started by Braskem
Co. in Triunfo (Brazil). This company claims that
their bioethylene compares in characteristics with the
product derived from petrochemical feedstocks. Since
2010, the journal Focus on Catalysts has been publish-
ing reports about putting this plant into operation [47].
For a plant of Solvay Co., Halcon/SD Co. designed its
first ethanol-to-ethylene process (1960), which is car-
ried out in a multilayer adiabatic reactor and uses an
А12О3–MgO/SiO2 mixed catalyst (SynDol) [43]. The
Petrobras Co. (Brazil) has developed an ethanol-to-
ethylene technology involving several parallel adia-
batic reactors with a fixed bed of an aluminosilicate
catalyst [46]. This technology made it possible to raise
the ethanol conversion to 98% to exceed the 93% con-
version level attained with a similar tubular isothermal
reactor. Dow Chemical Co. (United States) in collab-
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
 CATALYTIC DEHYDRATION OF BIOETHANOL TO ETHYLENE 155

Evaporation Heating Crude

ethylene Light
Ethanol components
Water NaOH
Polymer
Technical
Initial ethylene grade
Steam ethylene ethylene
(A) Heating agent
(H)
Waste Caustic Heavy
water waste
components
Reactor Quenching Purification Drying Distillation
and stripping

Fig. 1. Flowsheet for ethylene production from bioethanol [9].

oration with Mitsui (Japan) started the construction of
an integrated enterprise in Brazil for producing
bioethanol-based biopolyethylene. This enterprise
will include a plant producing 240 million liters of
bioethanol per year from sugarcane and a plant pro-
ducing 350000 t of biopolyethylene per year [48].
Characteristics of industrial processes used by various
companies are presented in Table 3.
Although there has been an extensive discussion of
the possibility of employing zeolite catalysts in fluid-
ized-bed reactors in the literature (see section 3.2),
industrial application data were found only for the
Chinese zeolite catalyst NKC-03А (Table 3). Most of
the ethanol-to-ethylene dehydration processes known
today employ alumina catalysts and are carried out in
a tubular or adiabatic fixed-bed reactor (Table 3) [56].
Lummus Co. reported that the process was also car-
ried out in a fluidized-bed reactor, but there is infor-
mation that the process was later changed to tubular
reactors.
Thus, the bioethanol-to-ethylene process has good
development prospects, and will be economically
more attractive than ethylene production from petro-
chemical feedstocks in the case of optimal prodcution
organization. Obviously, because of the specific fea-
tures of plant-based raw materials, bioethylene pro-
duction cannot totally replace the petrochemical pro-
duction of ethylene. However, present-day research
and development in process organization and catalyst
improvement make it possible to create biopolyeth-
ylene plants that are independent of petrochemical
raw materials. The latter is particularly promising for
the expanding production of various polymer com-
posites [35].
2. SOME CONCEPTIONS OF THE MECHANISM
OF ETHANOL DEHYDRATION TO ETHYLENE
Ethanol dehydration is an endothermic reaction
occurring at elevated temperatures [24, 40]. Over an
alumina catalyst, ethylene can be formed via parallel
and consecutive reactions both directly from ethanol

Table 3. Characteristics of industrial ethanol-to-ethylene dehydration processes

Ethanol,
Company Reactor Catalyst T, °С P, atm WHSV**, h–1 X/S, %
vol %
Braskem Adiabatic А12О3–
[42, 43, 49] (four layers) MgO/SiO2 450 – 0.56 95 99/97
(Syndol)
Solvay Indupa Adiabatic Syndol
200–400 5.9–6.4 0.33–0.43 95 99/97
(Halcon/SD) [44]
Lummus [50] Adiabatic γ-Al2O3 400 0.66 – 49.75 99/95
Lummus [43, 45, 51] Fluidized bed γ-Al2O3 400 0.66 – 49.75 99.6/99.9
Petrobras [46] Cascade of parallel Al-Si
300–440 0.84–7 0.03–0.7 – 99/98
adiabatic reactors
China* Tubular HZSM-5
260 – 2.4 98/99
[52–55] (NKC-03A)
*Reactor designed by Shanghai Engineering Co Ltd; catalyst developed by Nankai University [54, 55].
**WHSV is feed weight hourly space velocity.

CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016

156 YAKOVLEVA et al.
as a result of monomolecular dehydration (reaction (1))
and via the dehydration of an intermediate product,
namely, diethyl ether (reaction (3)), which results
from bimolecular ethanol dehydration (reaction (2)):
C2H5OH ⇒ C2H4 + H2O + 45 kJ/mol, (1)
C 2H 5OH ⇒ 0.5C 2H 5OC 2H 5
(2)
+ 0.5H 2O − 12 kJ mol ,
C2H5OC2H5 ⇒ 2C2H4 + H2O + 115 kJ/mol. (3)
The assumption that diethyl ether (DEE) is formed
as an intermediate product [24] is consistent with ear-
lier data indicating that the ether adsorbed on the cat-
alyst surface turns into an intermediate as the tem-
perature is raised and this intermediate than yields
ethylene [57]. It was demonstrated [24] that the con-
tribution from the consecutive route of ethylene for-
mation through intermediate DEE over the alumina
catalyst is much larger than the contribution from the
parallel route and depends only slightly on the reac-
tion temperature. At the same time, it was noted in
earlier works [58, 59] that it depends considerably on
the reaction temperature whether the consecutive or
parallel ethanol dehydration route is dominant.
The possible major by-products are DEE (reac-
tion (2)) and acetaldehyde (reaction (4)) formed from
from ethanol, as well as butylenes, which result from
ethylene dimerization (reaction (5)) [24]:
C2H5OH ⇒ C2H4O + H2 + 184 kJ/mol, (4)
C2H4 ⇒ 0.5C4H8 – 52 kJ/mol. (5)
Other possible products of ethanol dehydration are
methane, ethane, propylene, СО2, СО, Н2, etc. [60].
The mechanism of ethanol dehydration to ethylene
is widely discussed in the literature, and there have
been reviews systematizing information concerning
alcohol dehydration mechanisms [14, 22]. Depending
on processing conditions and catalyst type—alumina
[61–64], magnesium oxide [65], molecular sieve [66],
or heteropoly acid [67]—various mechanisms and
routes are hypothesized for catalytic ethanol dehydra-
tion [14]. Because the proportion of by-products in
this reaction us small, most researchers discuss only
the DEE formation mechanism. The most important
issue here is whether ethylene is formed directly from
ethanol via the parallel route or from DEE via the con-
secutive route or both the parallel and consecutive
routes take place. The intermediates in ethylene for-
mation are alkoxides [14] and ethoxy groups [68]. An
earlier study [69] provided an explanation for the
dynamic phenomenon of ethanol dehydration rate
growth (so-called stop effect), which was observed
when the ethanol feed was periodically replaced with
an inert gas stream [70, 71]. It was hypothesized that
there are three surface compounds on the γ-Al2O3 sur-
face, namely an ethylene precursor bound to acid sites,
an process inhibitor that is bound to basic sites and
desorbs readily under the action of a flowing inert gas,
and a compound that accumulates slowly on the cata-
lyst surface during the reaction and is removable only
above 400°С.
The monomolecular and bimolecular ethanol
dehydration to ethylene and DEE, respectively, is cat-
alyzed by acid sites, while ethanol dehydration to acet-
aldehyde is catalyzed by basic sites [72]. It was
reported [73] that the bimolecular dehydration of eth-
anol to DEE may be favored by weak and medium-
strength acid sites, while strong acid sites are possibly
favorable for undesired ethylene polymerization fol-
lowed by coke formation and catalyst deactivation. It
was demonstrated [74] that the presence of strong acid
sites increases the alcohol conversion. The highest
alcohol dehydration rate is reached at the maximum
possible Brønsted-to-Lewis acid site concentration
ratio [75]. Studies of the acid properties of individual
and mixed aluminum and titanium oxide systems by
titration with amines demonstrated the concentration
of acid sites is a more significant factor in the rate of
the dehydration reaction than their strength [76]. It
was concluded [77] that alcohol dehydration is cata-
lyzed by weak electron acceptor sites.
The investigation of the effect of sodium traces on
the catalytic activity of alumina catalysts in alcohol
dehydration demonstrated that sodium exerts an effect
on the composition of acid and basic surface sites of
the oxides [78] and markedly reduces the activity of
the catalysts.
Another significant factor in the activity of ethanol
dehydration catalysts and in ethylene selectivity is
porous structure. It was demonstrated, using zeolites
with narrow channels as an example, that catalysts
with a developed porous structure are favorable for
ethylene formation, since ethanol dehydration over
such catalysts proceeds via the monomolecular mech-
anism [79]. In catalysts with a large pore size, in which
there are no steric limitations for ethanol dimeriza-
tion, the bimolecular dehydration of ethanol to DEE
takes place.
An in-depth mechanistic analysis of the reaction is
beyond the scope of this review. At the same time, it
follows from the literature that a catalyst should have
optimum proportions of acid and basic surface sites
and a developed microporous structure. The process-
ing temperature and pressure, the hourly space veloc-
ity, the water content of the ethanol/bioethanol feed-
stock, and other operating parameters have to be set
according to the catalytic system chosen.
3. CATALYSTS FOR ETHANOL DEHYDRATION
TO ETHYLENE
Ethanol dehydration to ethylene belongs to acid-
catalyzed reactions. The compounds that catalyze this
group of reactions and are used for this purpose
include clays, alumina, silicon dioxide, magnesium
oxide, zirconium dioxide, phosphates (including cal-
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
 CATALYTIC DEHYDRATION OF BIOETHANOL TO ETHYLENE
cium phosphates), zinc aluminates, polyoxometa-
lates, and molecular sieves. According to the classifi-
cation suggested in the literature [80], these catalysts
can be divided into three main categories: acid-based
catalysts, molecular sieves, and various oxides.
3.1. Acid-Based Catalysts
The catalyst based on phosphoric acid, which was
among the first catalysts to be used in the industrial
synthesis of ethylene by catalytic ethanol dehydration,
was prepared by impregnating clay or carbon with
phosphoric acid [81]. Ethylene obtained with this cat-
alyst was very pure, but the catalyst was undergoing
rapid coking. Nevertheless, the latest studies have
demonstrated the effectiveness of adding phosphates
to oxide catalysts for increasing the rate and selectivity
of the reaction.
The catalysts based on heteropoly acids. Heteropoly
acids (HPA’s) are strong, polybasic, Brønsted acids
and are anionic complexes, whose inner coordination
sphere contains anions of an inorganic isopoly acid
(molybdic, tungstic, or, less frequently, vanadic, nio-
bic, or another acid) as ligands [82]. The possibility of
employing various heteropoly acid and their salts pos-
sessing Brønsted acidity in alcohol dehydration was
analyzed in a number of works [67, 83–86].
Varisli et al. [85] studied the activity of phospho-
tungstic, silicotungstic and phosphomolybdic acids in
ethanol dehydration. The catalysts were tested at 140–
250°C in a flow reactor at atmospheric pressure.
Phosphotungstic acid demonstrated the highest eth-
ylene selectivity, 75%, which was reached at optimal
values of temperature, residence time, and ethanol
concentration in the carrier gas. Other conditions
being equal, increasing the amount of HPA in the
reactor did not enhance the ethylene selectivity.
Therefore, the olefin selectivity depends weakly on the
residence time. The catalytic activity of the HPA’s
decreases in the following order: phosphotungstic >
silicotungstic > phosphomolybdic. This activity order
can be explained by the fact that phosphotungstic and
silicotungstic acids are more stable in reductive media
above 200°C.
Haber et al. [83] studied the effect of К+ and Ag+
cations on the catalytic activity of phosphotungstic
acid H3PW12O40 in ethanol dehydration. It was found
that an increase in the К+ content decreases the cata-
lytic activity and, as a consequence, the potassium
phosphotungstates K2H1PW12O40 and K3PW12O40 are
inactive in the dehydration reaction; at the same time,
the addition of Ag+ made the catalyst more active. No
ethylene selectivity data for the potassium and silver
salts of the HPA’s were presented.
Phosphomolybdic and phosphotungstic acids sup-
ported on SiO2 were tested in the liquid-phase dehy-
dration of 96 wt % ethanol [86]. The activity of these
catalysts at 20°С over 72 h was assessed as satisfactory.
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
157
Centrifugal separation of the catalyst from the reaction
products made it possible to employ the catalyst many
times, and no radical structural difference between the
used and fresh catalysts was revealed.
A literature analysis demonstrates that the HPA-
based catalysts are very active in ethanol dehydration
at low temperatures, but, because of their low thermal
stability in reductive media, they cannot be used above
250°С. Their ethylene selectivity at 250°С does not
exceed 75% and depends weakly on the residence
time. In addition, the HPA’s are expensive are deacti-
vated in the presence of water, so it is irrational to use
these catalysts in ethanol/bioethanol dehydration.
3.2. Catalysts Based on Molecular Sieves
Molecular sieves, which have a developed porous
structure, unique acid–base properties, and a large
specific surface area, are widely employed as adsor-
bents and catalysts [87]. Use of various types of zeo-
lites as catalysts in the dehydration of alcohols to ole-
fins has been the subject of numerous studies. There
have been reports on the use of natural zeolites and
clays [88, 89], as well as synthetic zeolites, both bulk
ones (NaX [75], SAPO-34 [90], H-ZSM-5 [4, 91–
96]) and supported ones (H-ZSM-5/TiO2, H-ZSM-
5/SiC [97, 98]). The molecular sieves that have been
most profoundly studied in the hydrogenation of eth-
anol to ethylene are those based on SAPO and ZSM-5.
This is most likely due to their developed microporous
structure, the high concentration of Brønsted acid
sites, and the possibility of tuning their acid properties
by the introduction of various elements. Owing to
these features, zeolite-based systems are active and
selective in alcohol dehydration even at moderate tem-
peratures.
Pure zeolite ZSM-5 employed in the dehydration
of a 20% ethanol solution to ethylene at 400°С
afforded an ethanol conversion of ≈99% and an eth-
ylene selectivity of 80%; on passing to 298°С, the con-
version decreased to approximately 42% and the eth-
ylene selectivity decreased to ≈72% [99].
Zhang et al. [90] compared the catalytic activities
of alumina and SAPO-34, Ni-substituted SAPO-34,
and H-ZSM-5 (Si/Al = 25) zeolites. The most active
catalyst was H-ZSM-5, and the least active one was
alumina. In prolonged tests of the H-ZSM-5 catalyst,
the ethanol conversion began to decrease dramatically
in about 60 h, which might be due to catalyst coking.
The activity of the catalyst could be restored by peri-
odically regenerating it with air, hydrogen, or an inert
gas.
It was demonstrated [92] that adding water to eth-
anol enhances the stability of the H-ZSM-5 catalyst
and the ethylene selectivity possibly by reducing the
acidity of catalytic sites; in turn, this diminishes the
deactivation of the catalytic caused by coking. Thus,
water hampers carbon deposition on the catalyst and
158 YAKOVLEVA et al.
increases its activity. For this reason, alcohol dehydra-
tion and olefin synthesis over zeolites are mainly car-
ried out in the presence of a large excess of water [94],
even though considerable catalyst deactivation was
observed in this case and it was recommended that the
process should be conducted at elevated temperatures
[92]. For solving these problems, zeolite ZSM-5 was
modified by treating it with hot water, ion exchange,
impregnation, and other methods.
Le Van Mao et al. [100] suggested a direct single-
step method for converting ethanol into ethylene
(B.E.T.E.) over zeolite H-ZSM-5 without a fine puri-
fication stage. At an ethanol concentration of 15% and
a temperature of 400°С, the ethanol conversion was
96% and the ethylene selectivity was 49%. Le Van Mao
et al. [93] demonstrated that the introduction of zinc
and magnesium cations into the H-ZSM-5 catalyst
enhances its olefin selectivity. A similar effect is pro-
duced by modifying the H-ZSM-5 catalyst with phos-
phoric acid [4], as is indicated by the selectivity being
proportional to the amount of phosphoric acid intro-
duced.
The stability of H-ZSM-5 catalysts with a crystal-
lite size of 50–100 nm and 1–3 μm was investigated by
Bi et al. [94]. The catalytic tests were carried out in a
flow reactor at atmospheric pressure and a tempera-
ture of 240°C. The feed consisted of 45 vol % ethanol
and 55% water, and the weight hourly space velocity
was 0.8 h–1. The ethanol conversion and ethylene
selectivity for the catalyst with a crystallite size of 50–
100 nm remained practically invariable for 320 h, and
those for the catalyst with a crystallite size of 1–3 μm
decreased steadily during the process.
Modifying zeolite H-ZSM-5 by ion exchange [52,
53] made it possible to create the commercial catalyst
NKC-03A. With this catalyst in an industrial tubular
reactor at 260°С and an ethylene hourly space velocity
of 2.3 h–1, the ethanol conversion is 98% and the eth-
ylene selectivity is 98–99%.
A study of solid acid catalysts, including mor-
denite, zeolite ZSM-5, zeolite Н-β, and a Si–Al com-
pound [101], demonstrated that the activity of a cata-
lyst in ethanol dehydration to ethylene is determined
by the number of acid sites. Mordenite showed the
highest catalytic activity in dehydration. Jia et al. [102]
studied ethanol dehydration over lanthanum-modi-
fied zeolite ZSM-5. Over 950 h, the ethanol conver-
sion and ethylene selectivity were higher than 98%.
In 1984, Union Carbide Co. [103] developed
molecular sieves based on Si–Al phosphates (SAPO-n,
where n is the modification number). The composi-
tion of this series of molecular sieves can be varies in a
wide range, and the silicon content is also variable,
depending on the synthetic conditions. A comparison
of the ethylene dehydration activities and stabilities of
the H-ZSM-5, NiAPSO-34 (Si/Al = 25), SAPO-34,
and γ-Al2O3 catalysts [90] demonstrated that the most
stable catalysts over 100 h are SAPO-34 and NiAPSO-34.
Zeolites of the SAPO-34 series, which have a
chabazite structure and an effective pore diameter of
0.43–0.50 nm showed a high activity in the methanol
dehydration (MTO) process [104]. Ethanol dehydra-
tion over SAPO-34 [105] carried out at 220–320°С
and a liquid ethanol hourly space velocity of 2 h–1
demonstrated that, under these conditions, the activ-
ity of SAPO-34 is higher than the activity of zeolite
ZSM-5. Above 260°С, the ethanol conversion was
90% and the ethylene selectivity was 99%; below
260°С or at higher space velocities, the ethylene selec-
tivity decreases because of the increasing proportion of
DEE in the products.
The pretreatment of SAPO-34 with propylene was
demonstrated to increase the ethylene yield at 400°С,
an ethanol-to-water weight ratio of 1, a mixture pressure
of 0.4 MPa, and an hourly space velocity of 16.7 h–1
[106]. Under these conditions, there are no diffusion
limitations in the dehydration of ethanol to ethylene.
Use of SAPO-11/HZSM-5-type composite cata-
lysts with an increased acidity makes it possible lower
the reaction temperature by 60°С relative to the reac-
tion temperature required for the individual zeolites
HZSM-5 and SAPO-11 and to raise the ethanol con-
version to 99.19% and the ethylene selectivity to
98.77% at an ethanol concentration of 99.7%, a tem-
perature of 240°С, an hourly space velocity of 1.2 h–1,
and a pressure of 0.1 MPa [107].
An analysis of the literature concerning the uses of
various types of zeolites demonstrated that, on the
whole, cheap natural zeolites and clays show only a
low activity in dehydration reactions. SAPO-type cata-
lysts are rather expensive for this process and are only
slightly superior in activity and selectivity to individual alu-
minum oxides at long operation times [90]. H-ZSM-5,
the most common zeolite, is highly active and highly
selective in olefin formation, but, because it is rapidly
deactivated as a consequence of coking, it is also inap-
propriate for industrial applications and can be used
only for dilute ethanolic mixtures. However, modifi-
cation of zeolites and preparation of composite sys-
tems provide means to increase the number of surface
acid sites and the pore size. According to the latest
studies, modified molecular sieves and related com-
posites are more active at low temperatures than alu-
mina catalysts and can be operated in mixtures that are
richer in ethanol.
The newest catalysts based on modified ZSM-5
molecular sieves are characterized by a high catalytic
activity and a high selectivity and are easy to regenerate
when they are used in the dehydration of feedstocks
with a low ethanol content. When operated continu-
ously for a long time in a fixed-bed reactor, modified
ZSM-5 performs stably at 400°С, affording a high eth-
anol conversion of, 98% and an ethylene selectivity of
94–98% or above [108]. The zeolite is modified with
soluble salts of Li, Na, К, Mg, Ca, Sr, Ba, La, Ce, Cr,
Mn, Fe, Co, Ni, Pd, Cu, Zn, Pr, Ti, Zr, Cd, Sb, Ru,
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
 CATALYTIC DEHYDRATION OF BIOETHANOL TO ETHYLENE
Pt, and Rh; the weight fraction of a modifier is 0.5–4%
of the catalyst weight. The catalyst also contains 2–
10 wt % solid HPA’s (P–Mo, P–W). A method of pre-
paring an SAPO-34 catalyst modified with Со, Ni,
Zn, Cu, and Fe nitrates was described [109]; the cata-
lyst is very stable and affords a high ethanol conversion
(98%) and an ethylene selectivity of 95% at ethanol
concentrations of 10–90%, high flow rates, and low
temperatures of 280–350°С.
There is a patent describing an ethanol-to-ethylene
dehydration catalyst based on solid superacids with
molecular sieving properties [110]. According to this
patent, the catalyst can operate at various ethanol con-
centrations and the conversion can be fairly high
(98.4%) at a low temperature (220°С).
An important place in present-day research is
occupied by mesoporous systems. There is a patent
suggesting a mesoporous Zr–Ti catalyst for the syn-
thesis of ethylene from ethanol and describing the
method of preparing this catalyst [111]. With this cat-
alyst at a weight hourly space velocity of 1.2 h–1, a tem-
perature of 300°С, and an ethanol concentration of
60%, the process is characterized by a high ethanol
conversion (99.6%) and a high ethylene yield (99.3%).
The catalyst has a long service life and is usable at var-
ious ethanol concentrations in the feed. Another pat-
ent [112] presents a method of preparing a
macro/mesoporous aluminosilicate composite cata-
lyzing ethanol dehydration.
There are a number of works making good use of a
size effect. For example, there is a patent describing
the preparation of zeolite ZSM-11 with a crystallite
diameter no larger than 5 μm as an ethanol dehydra-
tion catalyst [113].
Use of composite systems based on a molecular
sieve makes it possible to decrease the reaction tem-
perature and to enhance the stability of the catalyst. A
composite catalyst consisting of titanium dioxide sup-
ported on molecular sieve 4A affords an increase in
ethanol conversion and ethylene yield at a lower tem-
perature [114]. A similar effect was observed with a
composite consisting of the ZSM-5 catalyst deposited
on titanium dioxide nanotubes prepared by the hydro-
thermal method [115]. According to the authors of
that study, this effect arises from the increase in the
effective concentration of acid sites on the surface due
to the electron-accepting properties of TiO2. A com-
posite catalyst based on a molecular sieve modified
with a compound of Р, Fe, Zn, K, Ce, La, Sr, Ba, Ca,
Mg, Mo, or Mn [116],in addition to being highly active
and highly selective at fairly low temperatures of 220–
300°С, is characterized by a high mechanical strength,
hydrothermal stability, a long service life over the wide
ethanol concentration range from 20 to 100%.
Thus, the zeolite catalysts are the focus of present-
day studies of ethanol dehydration to ethylene, even
though only a single example of industrial application
of a zeolite catalyst is known with an ethylene yield of
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
159
about 97% at 260°C. Despite that zeolite catalysts are
conventionally assigned to medium- or low-tempera-
ture ones, most likely because the reaction onset tem-
perature is ≈200°С, the best results in most tests of
these catalysts are obtained near 400°С. Some draw-
backs of individual zeolites, namely, their rapid deac-
tivation and their ability to operate only in dilute etha-
nol–water mixtures can be eliminated by modifying
the zeolites and/or by preparing zeolite-based com-
posite systems. Nevertheless, the complexity and
expensiveness of the zeolites restrict prevent them
from being widely employed in the production of eth-
ylene from ethanol.
3.3. Oxide Catalysts for Ethanol Dehydration to Ethylene
There have been many publications on ethanol
dehydration to ethylene over various oxide catalysts,
including the following ones: titanium dioxide [76,
117]; magnesium oxide [72, 118]; cobalt oxide [119,
120]; chromium oxides [121]; iron and manganese
oxides [122]; mixed or supported oxide systems
Fe2O3/Al2O3 [123], Na2O–Mn2O3/Al2O3 [124],
FeOx/Al2O3 [125]; Fe2O3, CoO, or NiO/clay [126];
alumina and aluminosilicate systems [127].
Studies of transition metal oxides [122] demon-
strated that the total ethanol conversion increases as
the reaction temperature is elevated from 200 to
500°С, the major products of the dehydration reac-
tions are ethylene and DEE, and the process also
yields small amounts of acetaldehyde and ethane as
by-products. For example, it was shown that, on pass-
ing to 500°С, the total yield of dehydration products
increases from 19.2 to 71.2% for individual Fe2O3 and
to 55.1% for MnO2. In the testing of a Fe2O3–MnO2–
Al2O3–SiO2 catalyst, the highest yield of dehydration
products was 68.7%, attained at 500°С. Thus highest
ethylene selectivity was shown by individual iron oxide
and by mixed oxides containing iron oxide, but even
with these catalysts the ethylene selectivity did not
exceed 65.4%. An analysis of a large data array on the
use of transition metal oxides in alcohol dehydration
demonstrated that, over iron and manganese oxides,
mixed iron–manganese systems, and iron–manga-
nese–silicon ternary oxides, the reaction suffers from
a low olefin selectivity because of the formation of by-
products such as acetaldehyde and ethane.
It was reported that individual zirconium oxides,
zirconium–silicon mixed oxides, and sulfated zirconia
[128–132] are very active and selective in alcohol
dehydration. However, zirconium oxides (both pure
and modified) are expensive, so it is irrational to
employ them in dehydration reactions on an industrial
scale.
Aluminum oxides, both as such and as a support,
are used in isomerization, alkylation, catalytic crack-
ing [133], and other processes. It is these catalysts that
are mainly used in commercial-scale ethanol dehydra-
160 YAKOVLEVA et al.
tion to ethylene (Table 3). In the 1950s, Asian and
South American countries constructed ethanol-to-
ethylene dehydration plants employing clay or alu-
mina. Alumina catalysts proved more stable than clay-
based catalysts; however, the purity of ethylene
obtained using the alumina catalysts was lower and
was only 96–97% [134]. With the γ-Al2O3 catalyst
from Lummus Co. used in the commercial-scale pro-
duction of ethylene from ethanol, the ethanol conver-
sion is 99% and the ethylene yield is 94% [50]. The
simple γ-Al2O3 catalyst preparation procedure sug-
gested by Roca et al. [136] ensures an ethanol conver-
sion of 95% and an ethylene selectivity of 96% in the
dehydration of 15–100 wt % ethanol at 350–400°С.
Passing from pure alumina systems to mixed sys-
tems, such as Si–Al oxides [136], enhances the stabil-
ity, activity, and selectivity of the catalyst. At the same
time, according to the literature, the addition of sili-
con dioxide to alumina generates stronger acid sites
responsible for skeletal isomerization and double bond
shift [137, 138]. There has been a report [139] on alco-
hol dehydration over γ-Al2O3 modified with KOH and
ZnO, and it was demonstrated therein that this modi-
fication increases the olefin yield over the yield attain-
able with individual aluminum oxides. With the
sodium oxide–doped aluminum–manganese catalyst
(Na2O–Mn2O3/Al2O3), an ethanol conversion of 97%
was reached at 300°C and a low ethanol hourly space
velocity [124].
Studies of aluminum–titanium oxide catalysts
demonstrated that these mixed oxides are more active
in alcohol dehydration than individual alumina [76],
and there is a correlation between catalytic activity and
the surface concentration of acid sites measured by
titration with an amine. Chen et al. [40] studied alumi-
num–titanium oxide catalysts in ethanol dehydration
in a microchannel reactor at atmospheric pressure.
The reaction was carried out in the temperature range
from 300 to 500°С. The feed hourly space velocity was
varied between 26 and 304 h–1, and the ethanol con-
centration in the ethanol–water mixture was varied
between 12 and 100 vol %. The titanium dioxide con-
tent of TiO2/γ-Al2O3 catalyst was varied between 0 to
20 wt %. It was demonstrated that the presence of
water exerts a favorable effect on the selectivity of the
process and the optimum ethanol concentration is
30–50%. With the TiO2/γ-Al2O3 catalyst, a very high
ethanol conversion (99.96%) and ethylene selectivity
(99.4%) were reached in a microchannel reactor.
With the Syndol catalysts (А12О3–MgO/SiO2
mixed oxide systems) developed in the 1980s by the
US company Halcon for industrial fixed-bed reactors,
the ethanol conversion is 97–99%, the ethylene selectivity
is 97%, and the service life of the catalyst is 8–12 months
at 335–445°C and a liquid ethanol space velocity of
0.7 h–1 [140]. According to Kochar et al. [49], an
increase in the temperature of ethanol dehydration
over the Syndol catalyst enhances the ethylene selec-
tivity.
The addition of Cr2O3 raises the activity of the alu-
mina catalyst; with the doped catalyst, the product mix-
ture contains, aside from the target product—ethylene—
and by-products (water and DEE), small amounts of
acetaldehyde and acetone [141–143]. The addition of
calcium, magnesium, or zinc phosphate to alumina
increases the rate of the reaction and the target-prod-
uct selectivity [144].
Modifying alumina with iron, titanium, silicon, or
zirconium oxide provides means to tune the propor-
tions of acid and basic sites on the surface [72–77] and
thereby affect the activity of alumina catalysts [40, 76,
125]. For example, on passing to the FeOx/Al2O3 cat-
alyst, the ethylene selectivity increases and the ethanol
conversion remains unchanged [125]. At the same
time, if an excessively high concentration of strong
acid sites is produced in alumina by adding Fe or Ti
oxide, this will cause undesired changes in catalytic
properties [145]. This inference was made by examin-
ing catalysts prepared by the alkoxide technology or
reprecipitation (VGO-1, A1) and commercial oxides
prepared by thermochemical activation (AOK-63-22,
AOK-78-59, AOK-63-25) [145]. Modification was
carried out at the aluminum hydroxide hydrolysis
stage in the case of VGO-1 and A1 and by incipient-
wetness impregnation for the commercial aluminum
oxides AOK-63-22, AOK-78-59, and AOK-63-25. As
distinct from what was reported in an earlier publica-
tion [144], the introduction of phosphate ions into
catalysts based on the commercial aluminum
oxides/hydroxides exerted practically no effect on cat-
alytic activity [145, 146]. The addition of sulfate ions
increased catalytic activity but made the catalyst less
stable because of rapid coking, and the addition of
chloride ions (4 wt %) enhanced the activity of the alu-
minum oxides in ethanol dehydration [145, 146]. The
discrepancy between the results of modification of
aluminum oxides can be explained in terms of nonad-
ditive changes in the strength and total concentration
of acid and basic sites as a result of modification. For
example, it was demonstrated [145, 146] that modify-
ing alumina with Cl– ions increase the number of
strong acid sites and, to a much greater extent, that of
weak electron-acceptor sites on the alumina surface,
and it was concluded that ethanol dehydration to eth-
ylene mainly involves weak electron-acceptor sites.
Therefore, specific features of the preparation of alu-
minum oxides and those of their modification can
determine the numbers and proportions of acid and
basic sites and, accordingly, the activity of the catalyst.
The hydrothermal treatment of boehmite with
steam for 1–10 h at 300–650°С and modification of
the product with silicon compounds yields an effective
catalyst with an optimum acidity: ethanol dehydration
at atmospheric pressure and a temperature of 350°С
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
 CATALYTIC DEHYDRATION OF BIOETHANOL TO ETHYLENE
[147] leads to an ethanol conversion of 99.95% at an
ethylene selectivity of 99.32%.
Increasing the specific surface area of, and the
number of surface hydroxyl groups in, a catalyst based
on mesoporous Al2O3 with a pore diameter of 1–
20 nm makes it possible to reach an ethanol conver-
sion close to 99% and an ethylene selectivity of 98%
under the following conditions: aqueous solution con-
taining 5–100 wt % ethanol, 250–500°С, space veloc-
ity of 0.1–25 h–1 [148].
Granule shape optimization [149] also improved
the properties of the alumina catalyst, which was
tested at ethanol concentrations of 5–100 wt %, tem-
peratures of 250–500°С, and space velocities of 0.1–
25 h–1. A spherical aluminum oxide-based catalyst
(NC1301) was patented [150], which affords an etha-
nol conversion of 99.53–100% and an ethylene selec-
tivity of 99.57–100%. This catalyst is used by a Chi-
nese chemical plant at 350–440°С, a pressure of up to
0.3 MPa, and a space velocity of 0.3–0.6 h–1. The cat-
alyst is characterized by a long service life of 12–
18 months, requiring one or two regenerations in this
period. The testing of a tubular reactor with a fixed bed
of activated alumina [151] demonstrated that, as the
ethanol concentration is increased from 50 to 100%,
the ethanol conversion increases from 88 to 98% at an
average ethylene selectivity of >98%. The stable per-
formance of the catalyst and the purity of the resulting
ethylene were noted.
Thus, among the catalytic system types considered
above, modified alumina catalysts seem to us most
promising. In industrial ethanol dehydration units,
pure alumina catalysts are operated at relatively higher
temperatures, and this requires considerable energy
inputs. However, the possibility of carrying out the
process at a high ethanol concentration in the feed (at
least 95%) and the high performance stability of the
catalyst are significant advantages of these processes.
Modified or composite oxide systems provide
means to enhance the ethylene selectivity and ethanol
conversion, ensuring an ethylene yield of up to 99%.
Promising data were obtained for the Cr2O3–Al2O3
and MgO–Al2O3/SiO2 mixed oxide systems, for alu-
minum oxides modified with calcium, magnesium,
and zinc phosphates, and for TiO2/γ-Al2O3.
In discussions of application prospects of catalysts,
their production technology should be taken into con-
sideration. Among the individual aluminum oxides,
the most active ones are those which were obtained by
reprecipitation or by the alkoxide method, as was
demonstrated by Zotov [146]. These technologies
minimize the concentration of impurity alkali metals,
which decrease the concentration of active (acid) sites
on the surface. At the same time, modifying alumi-
num oxides prepared by thermal activation methods
(without reprecipitation) provides means to consider-
ably increase the activity of these oxides. The thermal
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
161
activation technologies are simpler and are distin-
guished by the absence of wastewater [153–155], and a
lower cost of the thermal activation products makes
these alumina systems promising for practical use in
ethanol dehydration.
Note that there have been works dealing with cata-
lysts that are uncommon for ethanol dehydration to
ethylene. For example, a phosphorus-doped catalytic
nanocarbon material was suggested for this purpose
[152]. It was reported that, as compared to conven-
tional ethanol dehydration catalysts, this catalytic
material has obvious advantages in terms of hydrother-
mal stability and ethylene formation selectivity.
4. TECHNOLOGICAL FEATURES
OF THE PROCESS AND REACTOR TYPES
The ethanol-to-ethylene dehydration process is
extremely temperature-sensitive. The temperature
range, within which ethylene formation over a γ-
Al2O3-based catalyst takes place, is 320–500°С; at
lower temperatures of 150–300°С, the dominant
product is DEE [9, 40, 46]; above 400–500°С, acetal-
dehyde formation is observed [49, 156]. Continuous
heat supply is necessary for maintaining the required
temperature in the endothermic process of ethanol
dehydration. Each mole of ethanol converted via reac-
tion 1) yields 1 mol of water. The increase in the vol-
ume of the mixture due to the formation of water,
whose heat capacity is 1.5 times higher than that of the
feed, is particularly significant in the case of a high ini-
tial ethanol concentration. At low ethanol concentra-
tions typical for zeolites, the temperature is easier to
regulate and control, but the metal intensity of the
reactor block and the first and operating costs per unit
are higher.
Thus, the problem of ensuring reliable temperature
control for the ethanol dehydration reactor is an
important problem in carrying out the process. This
problem is solved in the following ways: heat carrier
circulation in a tubular reactor, preheating of the feed
and distribution of the ethanol fed into the reactor
among the layers in a multilayer adiabatic reactor,
addition of steam as the heat carrier to the feed, and
supply of a preheated catalyst to the reaction zone of a
fluidized-bed reactor [9, 40–44, 49, 157–161]. Some
temperature regulation schemes will be discussed
below.
4.1. Fluidized-Bed Reactors
High heat and mass transfer rates, a sufficiently
uniform temperature distribution in the reactor space,
and the possibility of continuously withdrawing the
catalyst for regeneration have made the fluidized-bed
reactor promising for large-scale processes suffering
from catalyst deactivation [162, 163]. Heat supply is
ensured by preheating the feed stream and by entering
a hot catalyst, which circulates continuously between
162
Steam
Ethanol
Fig. 2. Multilayer adiabatic reactor with different size layers arranged in (a) one unit and (b) separate units.
the reactor and the regenerator. For the first time, a
fluidized-bed catalytic reactor was suggested for etha-
nol dehydration in the late 1970s [43, 45, 51, 55]. This
way of conducting the ethylene production process
facilitates maintaining the optimum temperature and
minimizes coke deposition and by-product formation.
As a result, ethanol dehydration to ethylene over an
aluminosilicate catalyst at 400°C affords a high etha-
nol conversion of 99.5% and an ethylene selectivity of
99.9% [9, 45, 55, 162]. The reactor designs suggested
to date allow the feed to be distributed among different
zone of the reactor [161]. Nevertheless, this technol-
ogy has not found wide application in bioethanol
dehydration, apparently because of problems associ-
ated with catalyst deactivation and abrasion or because
of the high specific metal intensity of the reactor
block, a feature that is disadvantageous for small-scale
bioethylene plants.
4.2. Tubular Fixed-Bed Reactors
In the chemical industry, tubular reactors are most
widespread at plants with an annual capacity of
20000–340000 t. A typical feature of these reactors is
that the longitudinal temperature profile passes
through an extremum. In most processes, it is this
extremum that is most sensitive to variations of process
parameters [164–166]. Ethanol dehydration, an
endothermic process, is characterized by the existence
of a so-called cold spot [24]. Since the tube diameter
and catalyst grain size determine the efficiency and
parametric sensitivity of the process, these parameters
should be optimized at the reactor design stage by
mathematical modeling. Optimization of the ethanol
dehydration process provides means to decrease the
ethanol consumption rate, to increase the productivity
of the catalyst, and to reduce the energy consumption
and the production cost [14, 24, 167].
YAKOVLEVA et al.
Steam
Ethanol
At present-day Chinese ethanol-to-ethylene plants,
the tubular reactor is the most common reactor type
[54, 55] (Table 3). There have been reports that the
Japanese corporation JGC, which is part of Mitsui &
Co., uses, in ethylene production from ethanol, a
tubular reactor to which heat is supplied by a circulat-
ing heat carrier salt. Doheim et al. [24] have designed
and optimized a tubular fixed-bed reactor for ethanol
dehydration to ethylene over an alumina catalyst with
a production capacity of 60000 TPA. It is recom-
mended that the process be conducted at 330–450°C
with a nitrite–nitrate melt as the heat carrier. The
heating system using molten salts in the intertubular
space proved efficient in many processes, but, in its
operation, there can be problems arising from the
crystallization of the heat carrier in cooling zones.
Authors describing a tubular reactor employed in eth-
anol dehydration to ethylene often use the term iso-
thermal [9]. This is done to underline the efficiency of
evaporative cooling in the intertubular space of the
reactor. A typical problem associated with tubular
reactors is the necessity of using a sufficiently stable
catalyst because of the fact that catalyst regeneration
during the process involves certain difficulties. On the
whole, tubular reactors provide a basis for technologi-
cally flexible small-scale reactor units for ethanol
dehydration.
4.3. Adiabatic Fixed-Bed Reactors
In an adiabatic reactor, heat supply and tempera-
ture control can be carried in different ways, including
dosing of steam as the heat carrier, heating the reac-
tion mixture in the interlayer space of a multilayer
reactor, and optimal feed distribution among the cata-
lyst layers or among parallel adiabatic reactors.
Catalyst layers can be arranged in several serially
connected reactors between which furnaces for inter-
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
 CATALYTIC DEHYDRATION OF BIOETHANOL TO ETHYLENE
mediate heating of the stream are placed [46], or they
can be mounted in a single reactor body [160].
In the Chematur process, heat is supplied using
adiabatic catalyst layers with intermediate heat
exchangers [49, 168]. The Petrobras process is carried
out in a system of parallel reactors, with fresh ethanol
and steam as the heat carrier simultaneously intro-
duced at the inlet of each layer [162]. The introduction
of ethanol together with steam into the reactor reduces
coke deposition, extends the service life of the catalyst,
and increases the ethylene yield [162]. At an inlet tem-
perature of 450–500°C and a liquid ethanol space
velocity of 0.15–0.5 h–1, the ethanol conversion is above
99% and the ethylene selectivity is 97–99% [9, 168].
There is a patent [160] describing an original three-
layer adiabatic reactor (Fig. 2) whose layers differ in
diameter and catalyst volume. After laboratory-scale
testing of this reactor, operating conditions were sug-
gested for carrying out the process over an alumina
catalyst in a three-zone reactor: at the inlet of each
subsequent zone, the temperature should be decreased
by 10–20 deg, the degree of dilution of ethanol with
the inert component should be increased by a factor of
1.5, and the gas hourly space velocity should be invari-
able. It was reported that this reactor design allows for
the marked increase in the mixture volume during eth-
anol dehydration and the separate introduction of the
raw material and inert component and the heating of
the reaction mixture in the interlayer space makes it
possible to optimize the temperature regime in each
layer. It was also reported that 100% ethanol conver-
sion and 100% ethylene selectivity are attained in this
way [160].
CONCLUSIONS
Present-day studies of catalysts and bioethanol-to-
ethylene dehydration processes are aimed at under-
standing the mechanism of the reaction, at developing
stable, inexpensive, and efficient catalysts, and at
designing optimal processes for producing certain
amounts of bioethylene. In many cases, technical and
economic assessments demonstrate that the bioetha-
nol-to-ethylene process provides a real alternative to
petrochemical processes of ethylene production; how-
ever, there are many macroeconomic and social fac-
tors in making decisions.
Alumina, zeolite, and heteropoly acid systems
employed in ethanol dehydration to ethylene can he
assigned to high-, medium-, and low-temperature
catalysts, respectively.
The catalysts that are most commonly used in
commercial-scale bioethanol dehydration units based
on fixed-bed reactors are high-temperature, alumina-
based ones, which can be operated at ethanol concen-
trations of about 95% and afford an ethylene yield of
over 92–97%. The best catalysts of this type are cata-
lysts prepared by reprecipitation or via the alkoxide
CATALYSIS IN INDUSTRY Vol. 8 No. 2 2016
163
technology owing to their very low alkali metal con-
tent.
Modified and composite oxide systems provide
means to increase the ethylene yield to 99%, enhanc-
ing both the ethylene selectivity and ethanol conver-
sion. Promising results were obtained with Cr2O3–
Al2O3, MgO–Al2O3/SiO2, and TiO2/γ-Al2O3 mixed-
oxide systems and with aluminum oxides prepared via
the conventional reprecipitation or thermal activation
technology but modified with calcium, magnesium,
or zinc phosphate or phosphoric or hydrochloric acid.
Along with the chemical composition of the catalyst,
the grain shape and size, porous structure, and prepa-
ration method are significant factors in catalytic prop-
erties.
Since maintaining a high temperature for carrying
out an endothermic process needs a large energy
input, researchers are actively seeking efficient cata-
lysts than can ensure a high ethylene yield at low tem-
peratures and high ethanol concentrations. Recent
advances in composite systems based on a molecular
sieve or zeolite open up the way to catalysts that are
active under these conditions. However, these cata-
lysts are insufficiently resistant to coking. Develop-
ment of these catalysts is now at the laboratory
research stage.
In addition to improving the existing catalysts,
researchers are developing engineering and techno-
logical approaches to realization of optimal tempera-
ture conditions in catalytic reactors as a means of
enhancing the process efficiency. These approaches
include the following ones:
⎯Temperature regulation by circulating a heat car-
rier in tubular reactors, intermediate heating of the
reactants in the interlayer space of multilayer adiabatic
reactors, and distributed feeding of ethanol in these
reactors;
⎯Development of conventional reactors whose
design allows for changes in the reaction mixture volume;
⎯Addition of steam as the heat carrier to the reac-
tion mixture;
⎯Decreasing the initial concentration of ethanol
by diluting it with an inert gas; and
⎯Carrying out the process in a fluidized catalyst
bed in which near-isothermal conditions can be estab-
lished owing to the high heat and mass transfer rates.
The above-listed approaches and some other ones
make it possible to enhance the temperature control
reliability and to diminish the coking of the catalyst,
but they suffer from certain limitations. Therefore, for
developing an efficient ethanol-to-ethylene dehydra-
tion process, it is necessary to take into account the
physiochemical properties of catalysts and the specific
features of the reactor unit. The choice of a reactor is
often governed by the product demand: large-scale
plants with an ethylene capacity of over 100000 TPA
should be based on fluidized-bed apparatuses or mul-
164 YAKOVLEVA et al.
tilayer adiabatic reactors; at small production capaci-
ties of 30–80 TPA, tubular reactors may be more eco-
nomical.
Taking into account the specific features of Rus-
sia’s raw material resources for bioethanol production,
the most promising way of producing bioethanol is by
processing of relatively cheap inedible biomass. How-
ever, developing such technologies is now at its initial
stage. Applications of bioethanol as a product of pro-
cessing renewable plant-based raw materials are
steadily widening, ranging from motor fuel additives to
polymer-grade olefins and other organic compounds.
A promising application of bioethylene is the produc-
tion of bioethylene-based plastics and polymer–car-
bon composites for various purposes. Relatively small
ethylene production units with a capacity of about
10000–40000 TPA that will not need main petro-
chemical raw materials can be constructed in practi-
cally any region. The economic efficiency of bioeth-
ylene and bioethylene-based final products produc-
tion would be increased by organizing integrated
plants with a closed processing loop including conver-
sion of a biological feedstock into bioethanol and cat-
alytic ethanol dehydration to ethylene.
ACKNOWLEDGMENTS
This work was supported by the Ministry of Educa-
tion and Science of the Russian Federation (unique
project identifier RFMEFI60714X0046).
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