Bio-based Isobutanol a versatile,

viable next generation biofuel

T
he success of any new industry is its ability
to innovate and grow; relative to renewable
fuels, future growth may require the evolu-
tion away from frst-generation products, such
as ethanol and/or biodiesel, to next-generation
products, such as isobutanol.
Isobutanol, a form of biobutanol, has many
outstanding characteristics that allow it to:
Be used as Is, as either a solvent or as a gaso-
line blendstock
Be readily converted, through known
processes, to a variety of hydrocarbons for use in
the petrochemical and/or refning industries
Be effciently and effectively used in existing
production, distribution, marketing and end-
user assets
This article will highlight the technology, the
feedstocks and the market-growth opportunities
for isobutanol, by reviewing Gevo, Inc. a
company bringing isobutanol and/or its deriva-
tives to market beginning in 2012.
Technology Pathway Bio-isobutanol via an
integrated fermentation/separation process
The pathway to make bio-isobutanol is via
fermentation, paired with using an integrated
separation technology to optimise production.
This approach, developed over the past seven
years, has been successfully proven at bench
scale, at a pilot plant and a 1.0 MMGPY demon-
stration plant. In May 2012, Gevo announced
that it started up the worlds frst commercial
bio-based isobutanol production plant in
Luverne, Minn, a planned 18 MMGPY facility.
Bio-isobutanol fermentation is quite similar to
Richard Kolodziej Wood Group Mustang
Jeff Scheib Gevo, Inc.
the existing ethanol process; ethanol plants can
be repurposed to make isobutanol relatively easily
and cost effectively with two key modifcations:
1. Modifed Biocatalyst Isobutanol is a natu-
rally occurring product of the fermentation
process, found in many items such as bread and
scotch whiskey; however, its commercial use to
date has been limited. However, through innova-
tions in microbiology/biochemistry, traditional
yeasts have been modifed, which make possible
a much higher selectivity in producing isobu-
tanol (i.e., turn up the yeasts ability to make
isobutanol while also limiting the ethanol
production pathway).
2. Unique Proprietary Separation As the isobu-
tanol is produced, a stream is taken from the
fermentation broth where the isobutanol is
removed and the remaining broth returned for
further conversion. This has the effect of keeping
the isobutanol concentration below the biocata-
lyst toxicity level, but allows improved
conversion.
With mainly just these two additions to exist-
ing facilities, one can see how the project
completion time and CAPEX to make bio-isobu-
tanol can be signifcantly lower than having to
build a greenfeld plant. A plant conversion can
nominally be 20-40% of the CAPEX of a green-
feld bio-isobutanol plant. As fermentation
ethanol plants have been shutdown or underuti-
lised due to recent, poor economics (i.e. the
ethanol subsidy is now gone, and the regulation
blend wall has effectively been reached), the
ability to re-purpose these plants to isobutanol
becomes an attractive opportunity.
www.digitalrening.com/article/1000899 January 2014 1
From fuel blendstock to operations to infrastructure compatibility, Isobutanol is
a cost effective, drop-in renewable alternative with broad optionality for use in
fuel and chemicals
Upon fermentation plant conversion, the plant
capacity will be ~80% on a volumetric product
yield basis (compared to ethanol), but compara-
ble on an energy equivalent basis (isobutanol
contains more energy than ethanol). So, the util-
ity requirements and OPEX are comparable to
ethanol production (which again, limits CAPEX
requirements.)
There is over 20 BGPY of existing fermenta-
tion ethanol capacity in the world, mostly in
North and South America. Gevo is a leading
company in bio-isobutanol, and its plans for the
foreseeable future are to convert ethanol plants
to make isobutanol. Gevos business model is
based on the fexibility to buy the ethanol plant
assets, JV with the current plant owner for the
conversion or license the isobutanol production
technology to ethanol plant owners.
Figure 1 illustrates the isobutanol plant
conversion. The before picture is a photo of
Gevos Luverne, Minn. facility while it was a 22
MMGPY ethanol plant. The after picture is
photo of the plant as it has been repurposed to
make up to 18 MMGPY of isobutanol. Gevos
proprietary separation package addition (the
second required addition noted above) is trade-
marked as GIFT, which stands for Gevo
Integrated Fermentation Technology, a modu-
lar unit which ties into the fermentation and
distillation processes.
Feedstock
Gevos fermentation process is designed to
convert feedstocks of all types: grains, sugar
2 January 2014 www.digitalrening.com/article/1000899
cane, non-food-based materials and/or cellu-
losics. Basically, anything that can be converted
to a fermentable sugar can potentially be used,
whether it be a traditional C
6
sugar, such as
glusoce, or a C
5
sugar, such as pentose. The issue
of feedstock selection is one of economics, but
Gevos isobutanol pathway technology can be
put into yeasts that can digest C
6
or C
5
sugars. In
fact, at bench scale, they have produced cellu-
losic isobutanol, using a mixed stream of C
5
and
C
6
sugars.
Bio-isobutanol has Versatility
One of the main reasons that converted plants
have such good projected economics is that
bio-Isobutanol is so versatile as a platform mole-
cule. In the chemicals arena, it can be: sold as
solvent product itself (e.g., paints) and/or,
through dehydration to isobutylene, converted
into materials such as butyl rubber and parax-
ylene and other derivatives for use in market
applications such as tires, plastic bottles, carpets
and clothing. For fuels applications, isobutanol
can be blended in as a low vapour pressure gaso-
line component, and/or used as feedstock
to make other transportation fuels (e.g., iso-
paraffnic kerosene for use as bio-jet) or
other renewable products (e.g., renewable heat-
ing oil).
Bio-isobutanol the Gasoline Blendstock
Bio-Isobutanols properties as a gasoline blend-
stock can best be understood by comparing some
of the blending properties to ethanol and

Before
After
Figure 1 Luverne, Minn. Fermentation Ethanol Plant Conversion to Isobutanol Plant
2 January 2014 www.digitalrening.com/article/1000899
alkylate. Figure 2 summarises some key aspects
in the comparison.
Compared to ethanol, isobutanol has a much
lower RVP and about 30% more energy content.
The Blend Octane of isobutanol is high as well
(although slightly lower than ethanol).
Isobutanol also has less oxygen content than
ethanol, so more isobutanol can be blended into
gasoline for a given oxygen content. And, more
blend volume plus more energy content means
more renewable identifcation number (RIN)
generation. See Figure 3 for a RIN comparison
summary.
Unlike ethanol that is fully miscible in water,
Isobutanol has very limited water solubility
(about 8.5%). Isobutanol also does not cause
stress corrosion cracking in pipelines. These
factors result in major advantages in terms of
blending logistics. Isobutanol can be blended as
a drop-in renewable fuel at the refnery and
shipped in pipelines to fuel terminals via exist-
ing infrastructure which prospectively eliminates
the need for segregated tankage or pipelines.
This also affords refners the opportunity to once
again produce a fnished spec gasoline vs. a
sub-octane BOB.
Isobutanol overcomes the regulation blend
wall limitation of ethanol blending. Isobutanol
is substantially similar to gasoline at a 2.7
vol.% oxygen content (or up to 12.5 vol.% blend).
This is a conservative frst step for blending for
refners, and generates 16.25 RINs per gallon of
fnished product. E10 has 3.5 vol. % oxygen,
which is the currently accepted limit of oxygen
content by automobile engine manufacturers.
For this same 3.5 vol.% oxygen, a U.S. EPA
211(b) wavier exists that would allow isobutanol
blending to 16.1 vol.%, yielding 20.93 RINs,
more than twice the RINs as E10 for equivalent
oxygen content.

Bio-isobutanol can be an Advanced Biofuel
To account for the relative amounts of renewable
energy beneft, each biofuel generates a RIN,
based on its energy content. There are basically
four types of RINs: renewable (e.g., frst genera-
tion corn ethanol), biomass-based diesel,
cellulosic and advanced. Advanced RINs are
generated with the production of advanced
biofuels with an approved U.S. EPA pathway
(i.e., rated as having at least a 50% reduction
in greenhouse gas footprint vs. baseline
www.digitalrening.com/article/1000899 January 2014 3
hydrocarbon fuel). Since bio-isobutanol has a
higher energy content than ethanol, bio-isobu-
tanol generates 1.3 RINs/gallon (vs. frst
generation ethanols 1.0). In addition, whereas
todays corn ethanol is precluded from qualifying
as an advanced biofuel, bio-isobutanol, produced
with a green energy source (e.g., biomass-fred
combined heat and power) has the potential to
qualify for advanced RIN status.
Figure 4 here summarises the Renewable Fuel
Standard (RFS) projected gallons for imple-
mented renewable and advanced biofuels as
compared to the requirements as stated by the
Energy Independence and Security Act (EISA) of
2007.
As can be seen, there is a projected shortfall of
advanced biofuels. Bio-isobutanol offers some
fexibility for meeting the RFS2 targets with
domestically produced renewable fuels as
opposed to relying on sugar-cane ethanol
imports from Brazil the main biofuel pathway
currently approved by U.S. EPA for advanced
status.
Gasoline Blendstock Comparison: Ethanol vs Isobutanol
Ethanol Isobutanol Alkylate
Blend Octane (R+M)/2 112 102 95
Blend RVP (psi) 18-22 4-5 4-5
Oxygen Content 34.7 21.6 0
Net Energy (% of gasoline) 65 82 95
Fungible in Infrastructure No Yes Yes
Figure 2

Figure 3 Gasoline Blend RIN Generation Summary
Bio-Isobutanol Renewable Feedstock
for Bio-jet
Taking the bio-isobutanol and processing it
further to iso-paraffnic kerosene (IPK) bio-jet
has now been demonstrated at Gevos hydrocar-
bon plant in Silsbee, Texas. The process is
outlined in Figure 5:
To make IPK bio-jet from bio-isobutanol
involves three sequential steps:
1. Dehydration of the renewable isobutanol to
mainly isobutylene
2. Oligomerisation of the isobutylene to mostly
trimers/tetramers to produce C
12
and C
16
molecules
3. Hydrogenation of olefns to iso-paraffnic
kerosene (IPK) bio-jet
These processes present opportunities for
retrofts of existing underutilised refning/petro-
chemical assets in some cases and
commercialisation and integration into an exist-
ing process plant should be straightforward.
Depending upon economics, the overall
process also has the fexibility to make more or
less iso-octene and/or iso-octane byproduct
streams (which make good renewable gasoline
blending components). It should be noted that
both renewable gasoline blendstocks (isobutanol
and iso-octene) are not tied to crude oil process-
ing, so these are not likely to have crude oil
volatility effects. And again, isobutylene, iso-oc-
tene, and iso-octane can also be drawn off for
production into other renewable petrochemical
products (i.e. paraxylene, which is noted later).
This bio-jet process has been demonstrated in
a small 10,000 gal/month (feedstock design
capacity) unit for many months now. The alco-
hol-to-Jet (ATJ) product has been sold to the
U.S. Air Force as part of the Alternative Fuel
Certifcation Division (AFCO) process. Figure 6
is a picture of the demonstration plant located at
South Hampton Resources in Silsbee, Texas.
A look at each of the three steps for the entire
IPK process:
4 January 2014 www.digitalrening.com/article/1000899

Figure 4 Project RIN-Gallons versus EISA Targets

Figure 5 Isobutanol to IPK Jet Process Block Flow Diagram
Dehydration
Step 1 is the Dehydration of isobutanol to isobu-
tylene and water. The reaction is endothermic,
with a relatively low operating pressure (<200
psig) and temperatures around 550-650F. The
operating requirements are similar to semi-re-
generative catalytic reforming, older technology
which has been since upgraded in refneries and
petrochemical plants. So, idled semi-regen
reformers are possibilities for retrofts to develop
the dehydration step. The catalyst for the dehy-
dration has been fully commercialised in similar
applications, and thus is known.
The dehydration reaction can be effciently
designed to almost complete conversion, mini-
mising the downstream complexities of the
separation of the butylene and water, and the
effuence of the water.
It should be noted that isobutylene can be a
hydrocarbon feedstock for other refning/petro-
chemical processes, and this isobutylene is
renewable so any resulting RINs would carry
forward to any hydrocarbon product covered by
RFS2.

Oligomerisation
Step 2 is the oligomerisation of the isobutylene
to dimers (iso-octene), trimers (C
12
olefns), and
tetramers. There is some measure of fexibility in
the amount of each olefn produced. Since IPK
jet fuel primarily requires C
12
-C
16
olefns, dimers
are recycled to yield more trimer/tetramer
product.
Oligomerisation is an exothermic reaction,
with operating conditions, heats of reaction, and
catalysts that closely resemble MTBE Production
Units and/or Catalytic Polymerization Units. So,
these units are possible retroft candidates for
this oligomerisation step. In fact, after MTBE
was banned here in the U.S., many MTBE units
were already converted to make iso-octene
(dimer). These units could be used with a minor
retroft. And again, Cat Poly units are also good
candidates for retroft. But, in any case, this step
is a known process, so integration into a refn-
ery/petrochemical plant, and other aspects:
catalyst preparation, unit startup, and unit oper-
ations, etc., all should be straightforward.
Depending upon economics, the dimer could be
a byproduct for gasoline blending and/or further
processing options.
Hydrogenation
Step #3 is the saturation of the olefns product
from the oligomerisation section. This is also a
well-known and practiced operation in refneries
and petrochemical plants. The main reaction is
conversion of the trimers/tetramers to iso-par-
affnic kerosene (IPK). The operating conditions
are mild and have relatively low operating pres-
sure and temperature and modest space velocity
requirements. The hydrogenation reaction is
exothermic and with the hydrogen consumption
in the rocess, so some recycle and cooling design
details are correlated with the reactor bed design
to ensure proper heat removal and control of the
reaction.
Olefn hydrogenation is well known and prac-
ticed, so again, there may be an opportunity to
retroft existing assets, as lower pressure hydro-
genation units have sometimes been idled, as
hydrogenation requirements have become more
severe. And again, the operations learning curve
here is already somewhat established, as per
catalyst preparation, unit startup, and normal
plant operations, etc.
Bio-jet Properties
This iso-paraffnic kerosene (IPK) bio-jet
product has some properties that enhance its
value. The Freeze Point is low: -80C; while
Oxidation Stability is high. Starting from
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Figure 6 IPK Bio-jet Demonstration Plant
isobutanol a renewable IPK would also generate
RINs at the rate of 1.6/gallon based on the
process. The current specifcation limit for a
jet blend with synthetic blending components is
a maximum of 50%, so, for a 1:1 blend with
petroleum jet, 80 RINs are generated for every
50 gallons of IPK that are used to produce 100
gallons of blended jet product.
Scoping Economics of Bio-jet
One important aspect of understanding how
bio-isobutanol can be a versatile alternative
biofuel is to understand the nominal economic
incentives for its conversion to jet fuel.
Preliminary scoping economics were developed
by Mustang Engineering for making bio-jet from
renewable isobutanol feedstock. Although a
retroft of existing units would help the econom-
6 January 2014 www.digitalrening.com/article/1000899


Figure 7 Bio-Jet Plant Financial Summary Analysis
6 January 2014 www.digitalrening.com/article/1000899
ics, retrofts may not be possible in all cases.
Therefore, a new unit was used as the basis for
this scoping evaluation.
In addition to CAPEX and effciencies associ-
ated with the possible retroft of some existing
assets, the other sensitivity in scoping economics
is the value and use of established RIN
(Renewable Identifcation Number) and other
tax credit incentives as allowed.
The CAPEX through put basis was a nominal
3,000 BSD Grass Roots Plant. The unit was
assumed with all new equipment (no retroft or
surplus or idled equipment). All Inside Battery
Limit (ISBL) equipment was sized, specifed, and
budget estimated. The CAPEX was determined
by applying factors to the equipment pricing to
account for commodity materials and labour.
Allowances were also made for engineering,
escalation, and contingency. A 30% allowance for
offsites was also assumed and added.
As per the Jet Fuel Prices Basis, a relatively
conservative $2.60-3.40 per gallon price range
was assumed, although the price could be higher.
Sensitivities for this price range were included in
the scoping economic study.
With the advent of the jet fuel carbon tax on
international fights landing in the European
Union, the airline industry and fuel suppliers
have been looking for cost effective renewable
alternatives to petroleum jet fuel. The cost of this
EU carbon tax is subject to change, but has been
estimated to be about $0.40/gal. A scoping
sensitivity of including this tax credit or not is
shown in Figure 7.
As can be seen, the EU tax credit has a signif-
cant effect on the scoping economics. And, as
one might expect, the RIN value has a signifcant
effect as well. In summary, not to imply any
actual economics for such a project, this nominal
3,000 BSD bio-jet plant study illustrated some
positive scoping economics, even at conservative
jet fuel prices.
Bio-Isobutanol to make renewable PX for PET
Once the renewable hydrocarbon is made, as
noted already, there is the chance to make
renewable hydrocarbon products via traditional
or even newer processes. For example, Gevo has
developed a new process that can take iso-octene
to make paraxylene (PX), which then can be
made into PTA, and then into renewable PET via
traditional methods. (Of course, plastic bottles
are a major market that uses PET, and thus, this
process generates a renewable plastic.) A pilot
plant is being designed for this new process,
which yields PX at a very high selectivity versus
other xylenes. High selectivity eliminates the
need for xylene isomerisation, separation, and
recycle steps. Plus, as shown in Figure 8, the PX
can be integrated with the rest of Biofuels plant.
Depending upon the relative amounts of each
renewable product, even the hydrogen made in
the PX plant can be used in the bio-jet
Hydrogenation Unit.
www.digitalrening.com/article/1000899 January 2014 7

Figure 8 Bio-isobutanol to: PX, Gasoline blendstock, and/or Bio-Jet
Summary
Isobutanol has gasoline blending, chemical and
usage advantages versus ethanol, which results
in positive economics for the conversion of exist-
ing ethanol facilities to bio-isobutanol
production. Compared to other transportation
fuel blendstocks, bio-isobutanol is a better envi-
ronmental alternative (e.g., low vapour pressure,
meaning lower volatility in fnished fuel). And,
being made by fermentation of sugars (via
normal or cellulosic biomass), these renewable
fuels are not tied to crude oil price or supply
fuctuations.
The process confguration for bio-isobutanol to
IPK Bio-Jet Fuel involves three sequential steps
that are straightforward. The process operates at
moderate operating conditions, and is similar to
some existing idled or underutilised refnery/
petrochemical units. So, revamps are possible,
reducing the CAPEX and construction time.
Projected RIN Values and EU Carbon Tax
Incentives would provide additional upside on
the project economics. This 3-step process has
been demonstrated at a 10,000 gallon per month
(feedstock design capacity) hydrocarbon plant at
South Hampton Resources in Silsbee, Texas.
On-spec product is being made and sold to the
US Air Force for the military certifcation
process.
Bio-isobutanol has numerous process and
product platforms that can be employed as
economics dictate including but not limited to
solvent sales, use as a gasoline blendstock,
conversion to bio-jet or as feedstock for renewa-
ble PX. Bio-isobutanol has the versatility to
allow multiple different options at the same
time. For example, marine and small engine
fuels are niche options that can be addressed
and renewable diesel is also an option.
Gevos pathway for bio-isobutanol via fermen-
tation is established and the business model
makes economic sense to revamp idled or
underutilised fermentation ethanol plants.
Gevos production of bio-isobutanol at demon-
stration scale was proven in 2009, and recently
a commercial scale 18 MMGPY plant has begun
start-up operations. Further, bio-isobutanol has
versatility and environmental and economic
advantages when compared to ethanol.
Bio-isobutanol has the capability to provide
signifcant impact as an advanced gasoline
blendstock or used as feedstock to make other
advanced fuels or products and therefore should
be considered as a high potential, next- genera-
tion biofuel.
Richard Kolodziej, Process Technology Manager, Wood Group
Mustang, has thirty plus years experience in process/project
engineering and development roles serving the: rening,
petrochemicals, chemicals, polymers and gas processing
industries. Rick has been involved with several newer technology
development projects, including several such bio-related
projects. Most recently Rick has been involved with Gevo and
their projects for renewable isobutanol to various petrochemicals.
Rick is also responsible for Process Plant project development
for Wood Group Mustang in the Far East. Rick has a U.S.be and
International patent in hydro-treatment. Rick has B.S. Engineering
(Chemical Engineering) from the University of Illinois in Chicago
and an MBA in Finance from DePaul University and is a registered
Professional Engineer in the State of Illinois.
Jeff Scheib, as Vice President of Fuels for Gevo, oversees
sales, marketing and business development activities for
commercialising isobutanol into fuels markets, including
rening, bio-jet, gasoline distributors and marketers, marine
and small engine applications. Jeff has over 20 years of fuels and
biofuels leadership expertise, having worked 17 years within the
petroleum sector with ARCO and BP followed by four years in the
renewable energy arena with Cilion and Chromatin, prior to joining
Gevo in 2011. Jeff holds a Master of Business Administration from
UCLA and a Bachelor of Science in Industrial Engineering from
Northwestern University.
8 January 2014 www.digitalrening.com/article/1000899

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