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Introduction
Nowadays the society we are living in is experiencing high oil prices and global warming threats, which are
mainly caused by extensive use of traditional fossil fuels such as coal and crude oil. In the future, renewable
and environmental friendly sources of energy would be more and more attractive. Synthesis gas (also called
as syngas, which is a mixture of mainly CO and H2) could potentially play a significant role in addressing the
above mentioned problems. Basically it can be derived from any carbon containing raw material: coal,
biomass such as straw and wood or even wastes. Provided that a sustainable and effective way of
electrochemical conversion is found, even CO2 and H2O could serve as initial materials for syngas
production. (Electrochemical fixation of CO2, CASE project). Then, syngas can be converted to various liquid
fuels such as methanol, Fisher-Tropsch oil (FT oil, a mixture of hydrocarbons) and higher alcohols (Figure 1).
Alcohols are widely used in our society as solvents, pharmaceuticals, and starting materials for synthesis of
various chemicals, including fuels or fuel additives.1,2,3. The scope of this project is to develop catalysts for
the direct conversion of syngas to alcohols, either methanol (low pressure synthesis) or higher alcohols.
Methanol Synthesis
Introduction
Synthesis of methanol from syngas (a mixture of carbon monoxide and hydrogen with small amounts of
carbon dioxide) in an industrial scale is typically carried out at elevated temperatures and pressures (up to
2500C and 100 bar respectively 4), which requires high operational and investment costs. The only
commercially used catalyst for methanol production is Cu/ZnO/Al2O3, which is optimized to operate under
conditions mentioned above.
Synthesis of methanol from synthesis gas at lower temperature and pressure are desirable if sustainable
fuel methanol is to be synthesized in decentralized units following biomass gasification or synthesis gas
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production by electrolysis. The «Dream Carbon Cycle» is schematically illustrated in the picture below:
carbon dioxide and water are electrochemically converted to syngas (a mixture of CO and H2), which is then
converted into methanol at low pressure and temperature over a catalyst that needs to be developed.
Finally, methanol can be used as a fuel.
High pressure processes not only contribute significantly to the total process cost of chemical engineering
plant, but also add up certain degree of complexity to the equipment used, thus increasing the investment
costs. Consequently, low pressure process would make methanol a more sustainable fuel, both
economically and environmentally.
From thermodynamic point of view, one has to go down in temperature in order to produce methanol from
syngas with reasonable conversion at low pressures, as it can be seen from the figure below (assuming
stoichiometric amounts of CO and H2 and no water-gas shift activity; the same trends apply for CO2
containing mixtures):
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It is clear that at lower temperatures thermodynamic yield of methanol is sufficiently high even at low
pressures. However, at present no catalyst is known to activate the process at such low temperatures.
The main objective of the research is to validate DFT calculations by synthesizing, testing and
characterization of several most interesting alloyed catalysts. Depending on the progress of the research,
one of the catalysts should be optimized
Currently, higher alcohols such as ethanol are mainly produced according to two processes. The first
process is essentially fermentation of sugars that are derived from sugarcane or corn; 2,8 the second one is
hydration of ethylene produced from petroleum. However, Crutzen et al. 9 found that corn-ethanol
production process can emit nitrous oxide that contributes to global warming as well. Moreover, food
shortage problems might come up if materials such as sugarcane and corn are utilized for fuel production.
Therefore, an alternative way to produce higher alcohols from syngas is favorable.
Syngas can be converted into alcohols in a two step process: first a mixture of CO and H2 is
thermochemically produced by gasification of biomass, and then syngas is converted into higher alcohols
catalytically.
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The catalysts and process for the higher alcohol synthesis (HAS) can be divided into four catagories
10,11,12:
Table 1 illustrates that the higher alcohol synthesis typically takes place at 250-325 °C, 50-200 bar, H2/CO =
1 mol/mol and GHSV = 2000-10000 h-1. In comparison the dedicated methanol synthesis operates at a
lower temperature and pressure (225 °C - 275 °C, <100 bar) with a more hydrogen rich feed (often 80-90
vol% H2), and typically also with a higher space velocity 13,14,15.
10,16
Table 1: Typical operating conditions for various higher alcohol synthesis processes reported in the literature .
T P Feed CO2 GHSV CO conv.
Catalyst H2/CO [mol/mol]
[°C] [bar] [vol%] [h-1] [mol%]
Modified methanol synthesis catalysts exhibit the highest selectivity and activity for alcohols in term of CO
conversion; however, methanol is the predominant alcohol product. The selectivity for the formation of C2+
alcohols is limited by the kinetics of chain growth. The C1 (methanol) to C2 (ethanol) step is the rate
determining step for HAS. Noble metal catalysts such as Rh showed highest higher alcohols selectivity;
however, they are limited in availability, higher cost and lower activity, which make them unattractive for
commercial application.
Modified Mo-based (MoS2) catalysts exhibit relatively high selectivity and activity for higher alcohols, which
has been studied by Christensen et al. 17,18 at CASE Process Lab.
Modified F-T synthesis catalysts are one of the most promising candidates for HAS via syngas. It has
moderate alcohol selectivity and activity for alcohols, but relatively high activity for higher alcohols. Wu et
al. (CASE Process Lab) is working on the Cu/Ni and Cu/Co catalyst systems. The current work is focused on
changing the catalytic selectivity of the catalysts towards ethanol and higher alcohols by trying different
supports and modifying basicity of the catalysts with alkali and other promoters.
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Challenges
• Catalysts with high selectivity towards higher alcohols.
• Sufficiently active catalysts.
• Cheap catalysts, i.e. based on abundant elements.
• Chemical stability in synthesis gas.
Approaches
• Design of catalysts using both density functional theory (DFT) and literature-based prediction.
• Synthesis of catalysts by different methods such as co-precipitation and flame spray pyrolysis.
• High pressure testing of catalysts for activity and selectivity.
• Characterization techniques: BET (DTU KT), H2-TPR (DTU KT), XPS (DTU Fysik), ICP (Haldor Topsøe
A/S), and XRD (DTU Fysik).
• In-situ characterization like TEM (DTU Cen), XAS (ANKA-KIT, Inst. for chem. technol. and polymer
chem. at Univ. Karlsruhe), and XRD (DTU Fysik).
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Titan ETEM
This machine is an Environmental Transmission Electron Microscope (ETEM). It features the full capability
of a monochromated, image Cs
aberration corrected TEM with the
possibility to study specimens in a gas
atmosphere and at elevated
temperatures. It is still possible to get
atomic resolution at these conditions
20. Within CASE, this microscope is
mainly used for dynamic studies of
the catalysts focusing on the crystal
structure, particle sizes and other
effects on the nm to Å scale. The
electron microscopes are located at
the Center for Electron Nanoscopy
(DTU Cen).
During the catalytic process the catalyst undergoes structural changes. In this case it is
CuSn catalyst particles that sinter and get deactivated during the process.
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In-situ XRD
This is an X-ray diffractometer equipped with a gas handling system and an in-situ
cell to study specimens in gas atmosphere and at elevated temperatures. The XRD
reveals the crystal structure and changes thereof during the exposure to the gas
and heat. Libraries allow identifying different phases in a mixture and during
changes. In the future it will be possible to treat and investigate the same sample
in the XRD and transfer it over to the TEM for further investigation
This XRD system is also part of DTU Cen.
High pressure fixed-bed continuous-flow reactor Diagram illustrating the catalyst testing setup.
(maximum 110 bar and 600 °C) at Department of BFM: Bubble Flow Meter; MF(P)C: Mass Flow
Chemical Engineering (DTU KT) (Pressure) Controller; P: Manometer. Heat
traced tubing is indicated by sinusoidal curves.
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BET-Autosorb-iQ2 (Quantachrome Instruments) H2-TPR on NETZSCH STA-449 at Department of
at Department of Chemical Engineering (DTU KT) Chemical Engineering (DTU KT)
Institute for Synchrotron Radiation (ISS – ANKA, Karlsruher Institut für Technologie , Germany)
List of participants
Name Affiliation
Anker Degn Jensen DTU KT
Qiongxiao Wu DTU KT
Jakob Munkholt Christensen DTU KT
Jakob Birkedal Wagner DTU Cen
Christian Danvad Damsgaard DTU Cen
Linus Daniel Leonhard Duchstein DTU Cen
Søren Dahl DTU Fysik
Irek Sharafutdinov DTU Fysik
Christian Fink Elkjær DTU Fysik
Jens Kehlet Nørskov Dep. of Chemical Engineering at Stanford University
Jan-Dierk Grunwaldt Inst. for chem. technol. and polymer chem. at Univ. Karlsruhe
Burcin Temel Haldor Topsøe A/S
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References