Carbon Monoxide

Carbon monoxide (CO) is a colourless, odourless toxic gas that can be produced
naturally or as a result of human activities. It is considered one of the main
contaminants of the air. In Europe, the production and processing of metals is the
source of 16% of CO emissions (European Commission report).
As a raw material, it is mainly used as reducing agent for the production of metals, in
the production of hydrogen (by water-gas shift reaction) and for the synthesis of
organic intermediates. Furthermore, mixtures of hydrogen (H2) and CO known as
synthesis gas: syngas - are used as feedstocks of growing importance for the large-scale
production of several chemicals. Thus, the applications of carbon monoxide can be
classified in: purified CO and CO as a component of Syngas. A summary of some
possible pathways to produce chemicals from both approaches is shown on figure X.
Water gas shift

Hydrogen

Phosgene synthesis

Phosgene

Purified

Methyl Formate
Carbonylation of
methanol

Carbon Monoxide

Acetic Acid

Carbonylation of
ethylene

Propionic Acids

Waxes

Fischer-Tropsch
synthesis

Gasoline/Diesel

Light Olefins

As component of
Syngas

Oxosynthesis

Butanal

Methanol synthesis

Methanol

Ethanol and alcohols

2,3-butanediol
Acetogens bacteria
fermentation
Carboxylic acids

Acetone

CO as a component of syngas
Products obtained through Fischer-Tropsch synthesis
The Fischer-Tropsch (FT) synthesis is a chemical catalytic process that converts syngas a mixture of CO and H2 - into hydrocarbons. It includes a large number of consecutive
and parallel transformations which derive on the production of a wide range of
hydrocarbon products of various molecular weights. The product distribution is
influenced by the feed composition (H2-CO ratio), temperature, pressure and catalyst
type, yet this process is usually classified by the applied temperature.
The products related to the Low temperature FT (220-250C) are commonly waxes
and/or diesel fuels, while the ones related to the High temperature (330-350C) synthesis
are gasoline and light olefins such as ethylene, propylene, pentene and hexene -.
Furthermore, for the Low temperature process Cobalt-based catalyst are preferred
whereas Iron-based materials are commonly used for the High temperature FT [1].
Nevertheless, catalyst involving Ruthenium and Nickel are used as well.
The FT process offers a wide variety of economically attractive products to synthesize,
being a technology that has been used at an industrial scale since 1938 [2]. However,
its competitiveness with petroleum processes is usually hindered by the presence of
impurities on the feed stream since compounds as NH3, HCN, H2S and COS have to be
removed to concentrations below 1ppmV in order to avoid severe damage on the
catalyst [3]. Moreover, temperature control of the process due to the large amounts of
heat released during the reaction also represents a technical challenge for its industrial
application.
Considering this, the following products have been taken as the most relevant
examples for further research on the use of the steel mill off-gasses:
FT waxes
Gasoline, Diesel fuels
Ethylene or Propylene
The specific information of each product (estimated market, yield, reaction, etc.) can
be found on Table X.
Oxosynthesis
Butanals (butyraldehydes) are saturated aliphatic C4 aldehydes present in two isomers:
n-butanal - being the straight chain -, and the branched one called isobutyraldehyde.
Due to its high reactivity and availability, butanals are important feedstocks, typically
involved on the production of solvents and plasticizers[4].
They are produced by the oxosynthesis process (also known as hydroformylation). This
involves the reaction of syngas with unsaturated hydrocarbons Alkenes to produce a

mixture of aldehyde isomers. In general, oxosynthesis products range from C3-C15, yet
butanals have the largest produced volume [5]. Currently, butanal production by the
hydroformylation of propene uses Rhodium based catalysts at 70150C and 1.55 MPa.
As in the case of other metallic catalysts, poisoning of the active sites can occur when
in contact with strong acids HCN, H2S, COS, O2 and dienes [5].
Methanol
This alcohol is one of the most important chemical raw materials, one of the top ten
chemicals produced globally. Despite its properties as fuel, about 85% of the methanol
production is used on industry as a starting material or solvent for synthesis[6]. As energy
source, methanol can be used to fire rapid-start combustion turbines and to substitute
for or blend with gasoline to power vehicles. As commodity it is used mainly for the
production of Formaldehyde, Methyl tert-butyl ether, Acetic Acid and Dimethyl Ether
which derive on a wide variety of plastics, coatings, pharmaceutical precursors, etc.
Nowadays, Methanol is produced exclusively by catalytic conversion of synthesis gas
according to the reactions shown on Table X. This exothermic process is carried out at
200-300C and 5-10MPa with catalysts based on CuZnOAl2O3 or Cr2O3 with different
additives and promoters. This materials can actively last from two to five years,
however, deactivation can occur if the operation conditions are not selected properly
and because of the presence of poisons on the streams. It is well known that Sulphur
components usually H2S and COS can block the active sites on metal catalysts.
Hence, sulfur is removed before the methanol synthesis on a gas cleaning stage or in
the watergas shift step.
What else?
Products obtained through biochemical synthesis
Research on syngas fermentation for the production of multicarbon compounds has
strongly increased since 2006 (Drzyzga paper). Naturally, this recent interest responds to
the environmental and economic requirements to replace petrochemical routes of
production with more sustainable pathways. These researches have demonstrated the
ability of acetogens bacteria to convert C1 mixtures with hydrogen into fuels and
chemicals such as acetate, butyrate, alcohols and fatty acids, among others. Syngas
fermentation can also produce monomers useful for biopolymers synthesis or directly
biopolymers(Kopke, Do YS). Furthermore, genetic engineering techniques have been
and are currently applied to gas fermenting organisms in order to increase the
productivities and to obtain different and more valuable chemicals.
Some of the advantages for the use of biological conversions over the thermochemical
pathways for syngas processing are (Drzyzga paper and Commercial biomass
syngas.):

i.
ii.
iii.
iv.
v.

Milder operation conditions: temperature 30-60C and pressures close to

atmospheric;
Exceptional feedstock flexibility since the process is less sensitive to the H2/CO
ratio (one of the main constrains on FT synthesis);
Despite the bacteria usually prefers carbon monoxide as carbon source,
H2/CO2 mixtures can also be used
Bacteria are less susceptible than metal based catalysts to trace contaminants
commonly present on syngas streams - char, tar, ash, chlorine and sulphure ;
Biological catalysts are in general more selective than FT catalysts leading to
simplified downstream processing of the product;

Additionally, since only very few microorganisms are capable of living in the presence
of - or using CO, the hazard of microbial contamination is not a problem for this kind
of fermentation.
Currently, a few companies are already applying syngas fermentation for the
production of commodities at pilot or industrial scale. They are mainly focusing on
obtaining
alcohols
(especially
ethanol),
however,
also
fatty
acids,
polyhydroxyalkanoates (footnote with what are these) and 2,3-butanediol are being
produced (Drzyzga paper).
A particularly attractive case is the one of Lanzatech Inc., which is currently producing
ethanol and 2,3butanediol (23BD) (http://www.lanzatech.com/23-butanediol-biobased-23-bdo-set-for-2014-sales/) through the acetogens fermentation of effluent
waste gases from steel mills and coal producers. Having met the production millestones
at the demonstration facilities built in China (see Table X), Lanzatech has formed a joint
venture with the steel corporations to start the construction of a 50,000 Mton/year
facility at the end of 2015, with the objective to further scale it up to a 100,000
Mton/year
plant
(http://www.lanzatech.com/china-steel-corporation-approvesinvestment-lanzatech-commercial-project/).
Based on this, we consider ethanol and 23BD as the most relevant examples for the
biochemical approach to obtain high value compounds form steel mill off-gasses.
Ethanol

Demand for ethanol is driven primarily by its use as a blending ingredient for gasoline.
Non-fuel consumption in the U.S. was only 269 million gal/yr in 2001 (Davenport et. al. 2002).

2,3-Butanediol (23BD)

is a high value chemical used as a precursor in the manufacture of industrial

solvents such as methyl ethyl ketone (MEK) and 1,3-butadiene. Its downstream products
have a global
market of approximately $43 billion per annum, and it is traditionally
producedpetrochemically
2,3 BDO is currently available as a laboratory chemical and is being sold as a smallvolume intermediate for certain niche applications such as in food flavoring additives.
In the past, 2,3 BDO was used as a feedstock to make butadiene for synthetic rubber,
before it was abandoned in favor of a more costeffective naphtha-based BD.
We think we can separate and convert 2,3 BDO cheaply enough to justify using this as
a bulk intermediate, said Holmgren. Weve done quite a bit of work and if we are
right, since its our same organism and reactor, we could commercialize very, very
quickly, she added. (http://www.lanzatech.com/23-butanediol-bio-based-23-bdo-setfor-2014-sales/)

1.
Dancuart, L.P. and A.P. Steynberg, Fischer-Tropsch based GTL Technology:
a New Process?, in Studies in Surface Science and Catalysis, B.H. Davis and M.L.
Occelli, Editors. 2007, Elsevier. p. 379-399.
2.
Dry, M.E., The FischerTropsch process: 19502000. Catalysis Today, 2002.
71(34): p. 227-241.
3.
Boerrigter, H. and R. Rauch, Review of applications of gases from biomass
gasification, in Handbook Biomass Gasification, E. Biomassa, Editor. 2005.
4.
Raff, D.K., Butanals, in Ullmanns Encyclopedia of Industrial Chemistry.
2012.
5.
Spath , L. and C. Dayton, Technical and Economic Assessment of Synthesis
Gas to Fuels and Chemicals with Emphasis on the Potential for Biomass-Derived
Syngas. 2003, National Renewable Energy Laboratory.
6.
Ott, J., et al., Methanol, in Ullmanns Encyclopedia of Industrial Chemistry.
2012, John Wiley and Sons.