1. Value-Addition by Copper-based Catalysts in Biomass Derived and Shale-Gas
Derived Chemicals’ Syntheses
Shingo Watanabe,a
* Jeanette Simpson,b
Aalbert Zwijnenburgc
a
Johnson Matthey - Chemical Catalysts, Oakbrook Terrace, IL, 60181, U.S.A.
b
Johnson Matthey - Chemical Catalysts, Royston, Herts, SG8 5HE , U.K.
c
Johnson Matthey - Chemical Catalysts, Emmerich am Rhein, D-46446, Germany
*Corresponding author: shingo.watanabe@matthey.com
Abstract: Applications utilizing heterogeneous copper-based catalysts are discussed in the area of biomass
derived and shale-gas derived chemicals’ syntheses. Methanol, ethanol and glycerol were chosen as platform
molecules, and their hydrogenation, hydrogenolysis, dehydrogenation, dehydration and condensation were
reviewed along with the properties of copper-based catalysts.
Keywords: copper, hydrogenolysis, condensation, biomass, sustainable, shale gas, methanol.
1. Introduction
Biomass-derived and shale-gas derived chemicals received unprecedented attention in North and
South America due to environmental concern. Traditional biomass based chemicals are synthesized from
sugars and vegetable oils, and these materials are still major feeds in recent biomass-based chemicals’
research and development. Sugars and vegetable oils are often converted to ethanol, fatty acids and glycerol,
and are used in various industrial chemical applications. Shale gas, on the other hand, has recently been
more attractive in North America due to its more affordable cost and growing availability. By utilizing such
low cost shale gas as a feedstock, methanol production has been significantly increasing in the US.1
In
addition, methanol can be produced from bio-syngas. As a result, methanol, ethanol and glycerol are
becoming very important chemical intermediates, however in order to realize the hydrocarbon value from
these oxygenates the oxygen content must first be reduced.
In industrial chemical processes, Cu-based catalysts are used in various applications, especially those
related to selective hydrogenation, hydrogenolysis and dehydrogenation.2
Copper is known to be less
thermally, mechanically and chemically stable in heterogeneous catalysis by comparison with precious
metals.3
However, copper offers beneficial intrinsic catalytic characteristics, especially when considering its
higher affinity towards oxygen. Through the use of promoters, supports, dopants and synthesis methods, we
can take advantage of these beneficial characteristics. Industrial Cu-based catalysts, for example copper
chromite, play an important role in the area of carbonyl reduction and hydrogenolysis of FAME in biomass-
derived chemicals. However, due to the toxicity of Cr, an enormous effort has been devoted to develop more
environmentally friendly Cr-free Cu catalysts.4
In this paper, synthesis routes for biomass-derived and shale-gas derived chemicals are discussed
along with the properties of the copper-based catalysts. The different synthesis of approaches for biomass-
derived and shale-gas derived chemicals are introduced and discussed based upon a literature review of
heterogeneous Cu catalysis.
2. Discussion
Sugar, ethanol, glycerol and methanol are chemical intermediates with the potential to bring
economic and environmental advantages to industrial chemical synthesis. The average price of sugar,
ethanol, glycerol and methanol were recently reported as approximately ¢30/kg,5
¢30/L,5
¢8/kg6
and ¢40/kg,1
respectively. In particular, 2nd
generation ethanol and shale gas-derived methanol are, seen to
have particular price advantages. Various different chemicals can be synthesized from these compounds.
Acrylonitrile and butadiene, for example, can be produced from these low cost oxygenates, and they are
seen as very economically attractive due to the high value of the finished product. At the end of 2012

2. acrylonitrile and butadiene were reported as $18/kg and $16/kg7
offering approximately 50-fold price
differential from raw material to finished product. The associated chemical modification of the oxygen
containing functionality required for such a conversion is often conducted by Cu-based catalysts.
Figure 1. Representative reactions using Cu-based catalysts in bio-renewable-based and shale-gas related applications.8
Typical industrial Cu-based catalysts are Cu/ZnO, Cu-Chromite, Cu/SiO2, Cu/Al2O3 and Cu/MgO and
their promoted analogues. Examples of their use in the conversion of methanol, ethanol and glycerol are
shown in Figure 1. Cu/ZnO, for example, has been employed for methanol synthesis from syngas, CO2
hydrogenation to methanol and alcohol dehydrogenation. Due to the intrinsic catalytic property of Cu,9
oxygenated species selectively adsorb to the Cu surface The addition of ZnO to Cu catalysts can enhance
their properties through improved stability and Cu dispersion. It is important to note, however, that these
types of effects from supports and promoters may not always electronically influence Cu.10
A detailed study
of each support, promoter and catalyst preparation method can aid successful catalytic process design in new
applications such as biomass and shale gas derived chemicals.
Various Cu-based catalysts are commercially available and would add value to chemical syntheses
from biomass-derived and shale-gas derived oxygenates. In contrast, biological conversion, such as
fermentation, is still facing the economic challenges in biomass-derived chemical synthesis due to the cost
of enzymes. Comparing the different approaches it can be seen that selective chemical catalysis could offer
commercially realistic options for conversion of these important new feedstocks.
4. Conclusions
Ethanol, glycerol and methanol, particularly those which are biomass-derived and shale gas-derived,
are important raw materials for chemical synthesis in North and South America. Cu-based catalysts could
convert such oxygenates to more valuable molecules. Further understanding of the effects of promoters
supports and dopants for supported Cu catalysts would lead to success in the development of cost effective
and/or environmentally friendly chemical processes.
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