Department of Chemical Engineering

M.S. THESIS PROPOSAL

INVESTIGATION OF CO HYDROGENATION
CATALYSTS FOR PRODUCING ETHANOL and
HYDROCARBON OXYGENATES

by
Didem Bra Kabak

Supervisors
Prof. ZEYNEP LSEN NSAN
Assoc. Prof. AHMET KERM AVCI

Date of Submission: 12/02/2013

Boazii University
Bebek, Istanbul

Chemical concepts used for engineering purposes

M. E. Dry
Catalysis Research Unit, Department of Chemical Engineering,
University of Cape Town, Rondebosch, 7701, South Africa

1. INTRODUCTION

1. STOICHIOMETRY
A promising alternative to petroleum-derived fuels and chemicals is the utilization of
Thenatural
term stoichiometry
is commonly
used tofor
describe
the way of
in alcohols
which theand
coal,
gas, and biomass
to make syngas
the production
components in a chemical reaction combine to form products. Thus in the case

hydrocarbons.
Indeed, large-scale
facilities
for the isproduction
of methanol
of the Fischer-Tropsch
process the
stoichiometry
primarily concerned
withand
the ratio of consumption
of continue
hydrogentoand
carbon
monoxide
and [1].
in some cases
FischerTropsch
hydrocarbons
be built
around
the globe

also carbon dioxide. In this context, the H2 to CO consumption ratio (or simply
the consumption ratio); the H2 to CO usage ratio (or simply the usage ratio) and
the stoichiometric
ratio (incanthebeabsence
CO2 reaction)
are synonyms.
The
Fischer-Tropsch
technology
briefly of
defined
as the means
used to convert
simple terminology of the usage ratio is preferred in this text.
synthesisWhen
gas containing
monoxide
to hydrocarbon
CO2 is a hydrogen
reactant, and
the carbon
stoichiometric
ratio
i.e. the ratioproducts.
in whichFor
are consumed,
will'hydrocarbons'
involve CO2. includes
The H2 tooxygenated
CO usage ratio
may still be
thereactants
above definition
the term
hydrocarbons
such
of interest but it is then no longer synonymous with the stoichiometric ratio.
as alcohols.
chemistry
taking
place
a Fischer-Tropsch
reactor
is complex
The The
chemistry
taking
place
in ainFischer-Tropsch
reactor
is complex
butbut
simplified
following
chemical
reactions"
cancan
be be
simplified
intointo
the the
following
chemical
reactions
[2]:
methane
CO + 3H2 ---* CH4 + H20

(1)

heavier hydrocarbons
nCO + 2nil2 ~ (-CH2-)n + nH20

(2)

alcohols
nCO + 2nil2 ~

(3)

CnH2n+ 2 0 +

(n - 1) H 2 0

water gas shift (WGS)

CO + H20 ~

CO2-k- H2

(4)

The synthesis of higher alcohols from syngas by direct catalysis was recognized in
1923 by Frans Fischer and Hans Tropsch. They reported that a mixture of alcohols,
aldehydes, ketones, fatty acids, and esters were formed when the reaction between CO
and H2 was performed at pressures ranging from 10 to 14 MPa and at temperatures of
400500 C in the presence of an alkalized iron oxide catalyst. Variations on this
synthesis pathway were soon to follow for the selective production of methanol,
mixed alcohols, and isosynthesis products [3,4].
The hydrogenation of synthesis gas to oxygenates is a field of renewed interest due to
their properties as gasoline blends and the necessity of finding alternative automotive
fuels to meet legal requirements. Among the potential end products ethanol is
particularly attractive since it serves as a clean alternative fuel, a gasoline blend, and a
hydrogen carrier. In addition, ethanol has been considered as a feedstock for the

synthesis of variety of chemicals, fuels and polymers. Different catalytic systems can
be used for synthesizing higher alcohols from synthesis gas. Product distributions are
influenced by temperature, feed gas composition (H2/CO), pressure, catalyst type, and
catalyst composition [5].
Currently, ethanol is mostly produced via fermentation of biomass-derived sugars . At
least three methods are known in the literature for the catalytic conversion of syngas
to ethanol and higher alcohols: (i) Direct conversion of syngas to ethanol, wherein
selective hydrogenation of CO occurs on a catalyst surface to produce ethanol
directly. (ii) Methanol homologation, which involves reductive carbonylation of
methanol over a redox catalyst surface to produce ethanol. (iii) A multistep ENSOL
process, wherein syngas is first converted to methanol over a commercial methanol
synthesis catalyst followed by methanol carbonylation to acetic acid in the second
step and, then, subsequent hydrogenation of acetic acid to ethanol [6].
There are currently no commercial plants producing ethanol or higher alcohols from
syngas as an end product. It is well known that syngas conversion to C2+ oxygenates
is often limited by the formation of methane and methanol. Low yield and poor
selectivity for ethanol production from syngas stand as the major obstacles associated
with the use of known catalysts. In order to make this catalytic conversion route
commercially attractive, it is necessary to develop more effective catalysts [5,6].
The catalysts for the production of ethanol and other light alcohols from syngas can
be grouped broadly into 4 categories: (i) Rh-based catalysts, (ii) modified hightemperature and low temperature methanol synthesis catalysts based on ZnO/Cr2O3
and Cu/ZnO/Al2O3, respectively, (iii) modified FischerTropsch catalysts based on
Co, Fe, and Ru, and (iv) modified unsulfided and sulfide Mo-based catalysts. A
growing consensus regarding ethanol synthesis from syngas is that supported Rh has a
great potential for the reaction, but suitable supports and promoters are needed to
enhance the reactivity of Rh and the current high cost of Rh may hinder its
commercial utilization [7].

2. LITERATURE SURVEY
Recently, there is a growing worldwide interest in the conversion of syngas to higher
alcohols, with an emphasis on ethanol. Significant improvements in catalyst design
need to be achieved to make this conversion commercially attractive [6]. Substantial
research work has been carried out for ethanol and higher alcohols production via CO
hydrogenation.
Mei et. al. [8] investigated the reaction kinetics of ethanol synthesis from CO
hydrogenation over SiO2-supported Rh/Mn alloy catalysts. They found that Mn
promoter can exist in a binary alloy with Rh and has a critical role in improving the
selectivity toward ethanol and other C2+ oxygenates, although the barrier toward
methane formation is not changed. Then, the effects of various promoters (M = Ir, Ga,
V, Ti, Sc, Ca, and Li) on the CO insertion reaction over Rh/M alloy nanoparticles
were investigated. They also found alloying the promoters with the electro negativity
difference, between the promoter (M) and Rh leads to higher selectivity to ethanol.
In another study, Haider et. al. [1] explored the influences of support (silica or titania)
and loading of Fe promoter on the activity and selectivity of Rh-based catalysts for
the synthesis of ethanol from syngas. Promotion of 2 wt% Rh/SiO2 by 1 wt% Fe
produced a catalyst that exhibited 22% selectivity to ethanol, with methane being the
primary side-product. Addition of Fe to 2 wt% Rh/titania also improved the
selectivity to ethanol with the highest selectivity being 37% for a sample 5 wt% Fe.
In the study of Subramanian et. al. [9] CO hydrogenation to ethanol over
Rh(1.5)/SiO2 promoted with La and/or V oxides. The effects of reaction conditions
temperature, H2/CO ratio, space velocity, and pressure are examined on the activity
and selectivity of these catalysts. An ethanol selectivity of 51.8% (close to the highest
literature value) at a CO conversion of 7.9% was achieved with a corresponding
methane selectivity of 15.4% at 270 C, 14 bar and H2/CO = 2 over the Rh
La/V/SiO2 catalyst. Combined La/V promotion reduces methane selectivity and
increases C2+ oxygenates selectivity compared to the singly promoted catalysts by
increasing the rate of CO insertion.

Spivey et. al. [10] used silica-supported CoPd catalysts with two different cobalt
loadings: 2 wt% (2Co2Pd) and 10 wt% (10Co2Pd) to investigate activity/selectivity
in CO hydrogenation. The studies showed that the 10Co2Pd catalyst is more active
for CO hydrogenation with high selectivity toward hydrocarbons, while 2Co2Pd
catalyst shows higher selectivity toward oxygenates, but considerably lower overall
activity.
Yong et. al. [11] studied MoCoK sulfide-based catalysts promoted by rare earth
metal salts (La, Ce, and Y). The catalytic performance for the selective synthesis of
ethanol and mixed alcohols from syngas was evaluated and compared with that of the
unpromoted catalyst MoCoK. It was observed that the MoCoK sulfide catalyst
had a much lower CO conversion and ethanol distribution. In this study, also
influence of molar ratio of La/Mo on the CO conversion and amount of ethanol were
performed. Both CO conversion and ethanol distribution increased with the molar
ratio of La/Mo. However, too high a molar ratio of La/Mo led to a decrease in the CO
conversion and ethanol distribution.
In the research [12] investigating the production of alcohols over Zn-Mn promoted
Cu-Fe based catalyst, the results showed that Zn-Mn promoted Cu-Fe based catalyst
had high catalytic activity and high alcohol selectivity. This catalyst can be regarded
as a potential candidate for catalytic conversion of syngas to mixed alcohols. The
maximal CO conversion rate was 72%, and the yield of alcohol and hydrocarbons
were also very high. The mainly hydrocarbon products were olefin and paraffin, and
the CH4 selectivity was relatively low.
Xiangen and coworkers [13] examined the catalytic performance for CO
hydrogenation over a series of silica supported Fe and Ni metal phosphides catalyst.
With the FePx/SiO2 catalysts (x denotes the molar ratio of P to metal), the product was
a mixture of oxygenates containing methanol as the major component. With the
NiPx/SiO2 samples, the liquid product was mainly methanol.
In a recent study [14], Rh-Mn-Li catalysts supported on SiO2, ZrO2 and SiO2-ZrO2
mixed oxides with various molar ratios of Si/Zr were tested for the synthesis of C2+
oxygenates from syngas. Compared with pure SiO2 and ZrO2 supported catalysts,

catalysts supported on SiO2-ZrO2 mixed oxides showed higher activity and C2+
oxygenates selectivity, in which Rh-Mn-Li/SiO2-ZrO2 (molar ratio of Si/Zr=1:3)
exhibited the best yield of C2+-oxygenates. It is found that Rh-Mn-Li supported on
SiO2-ZrO2 mixed oxide improved not only the CO conversion but also the C2+
oxygenates selectivity.

3. PROPOSED WORK
The aim of this study is focused on testing catalysts for ethanol and other C2+
oxygenates by CO hydrogenation. Based on the results of detailed literature search, a
number of catalysts, promoters and supports will be selected to test their catalytic
activities for CO hydrogenation in a fixed-bed reactor. Experimental plan includes a
parametric study of reaction temperature, pressure and contact time (W/FCO) as well
as effects of support material and promoters on CO conversion. The product
distributions will be tested on each catalyst for various feed rates, feed compositions
and temperatures. The Autoclave Engineers' BTRS-Jr-PC reaction system will be
used in the experiments. The system includes a tubular reactor with an internal
diameter of 1/4 inch, liquid metering pumps, mass flow controllers for automated
delivery of reactants and a heated transfer line to gas chromatograph. Also there is
GC-MS for product analysis. A computer equipped with Programmable Logic
Controller (PLC) and HMI software performs data collection and allows for the
remote control of system functions.

REFERENCES
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Catalysts for Direct Conversion of Syngas to Ethanol, Journal of Catalysis, Vol. 261,
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[2] Dry, M. E. and A. Steynberg, 2004, Commercial FT Process Applications, in A.
Steynberg and M. Dry (eds.), Fischer Tropsch Technology, Studies in Surface Science
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[3] Surisetty, V. R., A. K. Dalai, J. Kozinski, 2011, Alcohols as alternative fuels: An
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[11] Yong, Y., W. Yangdong, L. Su, S. Qingying, X. Zaiku, 2007, MoCoK SulfideBased Catalysts Promoted by Rare Earth Salts for Selective Synthesis of Ethanol and
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