Originally appeared in:
September 2012, pgs 79-85.
Used with permission.
Special Report
Bio-isobutanol: The next-generation biofuel
The success of any new industry lies in its ability to innovate
and grow. Future growth in renewable fuels may require an
evolution from first-generation products, such as ethanol and
biodiesel, to next-generation products, such as isobutanol.
Isobutanol, a form of biobutanol, has many outstanding
characteristics that allow it to be used in a variety of ways:
• “As is”—i.e., as a solvent or as a gasoline blendstock
• Converted, through known processes, to a variety of
hydrocarbons for use in the petrochemical and/or refining
industries
• In existing production, distribution, marketing and end-
user assets.
This article highlights the technology, feedstocks and
market growth opportunities for isobutanol, with a focus on
potential new market offerings in 2012.
Technology pathway for bio-isobutanol. The specialized
production process for bio-isobutanol is fermentation paired
with an integrated separation technology. This approach,
developed over the past seven years, has been successfully
proven at bench scale, at a pilot plant, and at a 1 million-
gallon-per-year (MMgpy) demonstration plant. In May 2012,
the world’s first commercial, bio-based isobutanol production
plant was started up in Luverne, Minnesota, with a capacity of
18 MMgpy.
Bio-isobutanol fermentation is very similar to the existing
ethanol process. Ethanol plants can be repurposed to make
Fig. 1. Conversion of a fermentation ethanol plant to an isobutanol plant in Luverne, Minnesota.
HYDROCARBON PROCESSING September 2012
Refining Developments
R. Kolodziej, Wood Group Mustang, Houston, Texas;
and j. Scheib, Gevo Inc., Englewood, Colorado
isobutanol relatively easily and cost-effectively, with two
key modifications:
1. Modified biocatalyst. Isobutanol is a naturally
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
innovations in microbiology and biochemistry, traditional
yeasts have been modified, making possible a much higher
selectivity in producing isobutanol—i.e., turning up the yeast’s
ability to make isobutanol while also limiting the ethanol
production pathway.
2. Unique proprietary separation. As the isobutanol is
produced, a stream is taken from the fermentation broth where
the isobutanol is removed, and the remaining broth is returned
for further conversion. This has the effect of keeping the
isobutanol concentration below the biocatalyst toxicity level,
but it allows for improved conversion.
With these two additions to existing facilities, it is clear how
theprojectcompletiontimeand CAPEXtomakebio-isobutanol
can be significantly lower than those for the construction of a
greenfield plant. A plant conversion can nominally be 20%–
40% of the CAPEX of a greenfield bio-isobutanol plant. As
fermentation ethanol plants have been shut down or under-
utilized due to recent poor economics (e.g., the US ethanol
subsidy has been repealed, and the regulation “blend wall” has
effectively been reached), the ability to repurpose these plants
to isobutanol becomes an attractive opportunity.
 Refining Developments

Upon fermentation plant conversion, the plant capacity
will be approximately 80% on a volumetric product-yield
basis (compared to ethanol), but comparable on an energy-
equivalent basis (isobutanol contains more energy than
ethanol). Therefore, the utility requirements and OPEX
are comparable to ethanol production (which, again, limits
CAPEX requirements).
There is over 20 billion gpy (Bgpy) of existing fermentation
ethanol capacity in the world, located mostly in North
and South America. A leading company in bio-isobutanol
is converting some of these ethanol plants to isobutanol
production. That company’s business model is based on the
flexibility to buy ethanol plant assets, form a joint venture with
the current plant owner for the conversion, or to license the
isobutanol production technology to ethanol plant owners.
lilustrates a isobutanol plant conversion. The “before”
Fig. 1n
photo shows a facility in Luverne, Minnesota as a 22-MMgpy
ethanol plant. The “after” photo depicts the plant as it was
repurposed to produce up to 18 MMgpy of isobutanol.
Feedstock. One company’s proprietary fermentation process
is designed to convert feedstocks of all types: grain, sugarcane,
cellulose and/or nonfood-based materials. Almost anything that
can be converted into a fermentable sugar can be used, whether
it is a traditional C6usgchar, s as glucose, or a C5 sugar, such as
pentose. The issue of feedstock selection is one of economics,
but technology can be put into yeasts to allow them to digest C6
or C5 sugars. In fact, at bench scale, these yeasts have produced
cellulosic isobutanol using a mixed stream of C5 and C6 sugars.
Bio-isobutanol has versatility. One of the main reasons
that converted plants have such good projected economics is
that bio-isobutanol is versatile as a platform molecule. In the
chemicals arena, it can be sold as a solvent product (e.g., paints)
Table 1. Gasoline blendstock comparison: Ethanol vs. isobutanol
ethanol isobutanol alkylate
blend octane (R + M) ÷ 2 112 102
blend RVP (psi) 18–22 4–5
O2 content 34.7 21.6
Net energy (% of gasoline) 65 82
Fungible in infrastructure No Yes
and/or converted into materials such as butyl rubber, paraxylene
(PX) and other derivatives for use in market applications such
as tires, plastic bottles, carpets and clothing. (This conversion
is accomplished through dehydration to isobutylene.) For fuels
applications, isobutanol can be blended as a low-vapor-pressure
gasoline component and/or used as feedstock to make other
transportation fuels (e.g., iso-paraffinic kerosine for use as biojet)
or other renewable products (e.g., renewable heating oil).
Bio-isobutanol as a gasoline blendstock. Bio-isobutanol’s
properties as a gasoline blendstock can best be understood
by comparing some of the blending properties to ethanol and
alkylate. Table 1uosme arizes s key aspects in the comparison.
Compared to ethanol, isobutanol has a much lower Reid
vapor pressure (RVP) and about a 30% higher energy content.
The blend octane of isobutanol is high as well (although
slightly lower than ethanol). Isobutanol also has a lower
oxygen (O2) content than ethanol, so more isobutanol can be
blended into gasoline for a given O2 content. Greater blend
volume, plus higher energy content, means more renewable
identification number (RIN) generation. See Table 2 for a
RIN comparison summary.
Unlike ethanol, which is fully miscible in water, isobutanol
has 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 refinery and shipped in pipelines to fuel terminals
via existing infrastructure, which prospectively eliminates
the need for segregated tankage or pipelines. This also
affords refiners the opportunity to once again produce a
finished-specification gasoline vs. a sub-octane blendstock
for oxygenate blending.
Isobutanol overcomes the regulation “blend wall” limitation
of ethanol blending. Isobutanol blended into gasoline up to
12.5 vol% produces a substantially similar gasoline at a 2.7% O2
content. For refiners, this is a conservative first step for blending,
and it generates 16.25 RINs per gallon of finished product. E10
has 3.5 vol% O2, which is the currently accepted limit of O2
95 content by automobile engine manufacturers. For this same 3.5
4–5 vol% O2 n,SaviU
ronEmental Protection Agency (EPA) waiver
0 (211b) exists that would potentially allow isobutanol blending
95 of up to 16.1 vol%, yielding 20.93 RINs, or more than twice the
number of RINs as E10 for an equivalent O2 content.
Yes

2.5
Domestic ethanol
Table 2. Gasoline blend RIN generation summary Brazilian ethanol
2.0 Biodiesel
RiN-gal per
Pyrolysis oil, FT liquids, green diesel
Million barrels per day

Volume in 100 gal of EISA renewable

1.5
gasoline O2 content finished product EISA advanced
e10 10% 3.5% 10 1.0
e15 15% 5.2% 15
0.5
isobutanol 12.5% 2.7% 16.25
(substantially similar
0.0
to gasoline) 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021 2022
Year
isobutanol 16.1% 3.5% 20.93
(ePa waivers allowing
O2 content of 3.5 wt%) Fig. 2. Projected RIN-gallons vs. EISA targets.

HYDROCARBON PROCESSING September 2012

 Refining Developments

Bio-isobutanol can be an advanced biofuel. To account for
the relative amounts of renewable energy benefit, each biofuel
generates a RIN based on its energy content. There are basically
four types of RINs: renewable (e.g., first-generation, corn-based
ethanol), biomass-based diesel, cellulosic and advanced.
Advanced RINs are generated with the production of
advanced biofuels with an approved US EPA pathway (i.e., rated
as having at least a 50% reduction in greenhouse gas footprint vs.
baseline hydrocarbon fuel). Since bio-isobutanol has a higher
energy content than ethanol, bio-isobutanol generates 1.3 RINs
per gallon, vs. first-generation ethanol’s 1.0 RINs per gallon.
In addition, whereas today’s corn ethanol is precluded from
qualifying as an advanced biofuel, bio-isobutanol—produced
with a green energy source (e.g., biomass-fired combined heat
and power) has the potential to qualify for advanced RIN status.
Fig. 2 summarizes the US Renewable Fuel Standard (RFS)
projected gallons for implemented renewable and advanced
biofuels, as compared to the requirements stated by the US
Energy Independence and Security Act (EISA) of 2007. As
can be seen, there is a projected shortfall of advanced biofuels.
Bio-isobutanol offers some flexibility for meeting the RFS2
targets with domestically produced renewable fuels, as
opposed to relying on sugarcane ethanol imports from Brazil,
which is the main biofuel pathway currently approved by the
EPA for advanced status.
Bio-isobutanol as renewable feedstock for biojet.aTking
the bio-isobutanol and processing it further to isoparaffinic
kerosine (IPK) biojet has been demonstrated at a hydrocarbon
plant in Silsbee, Texas. The process is outlined in Fig. 3.
PrKoducing I biojet from bio-isobutanol involves three
sequential steps:
1. Dehydration of the renewable isobutanol to isobutylene
2. Oligomerization of the isobutylene to mostly trimers/
tetramers to produce C12 and C16 molecules
3. Hydrogenation of olefins to IPK biojet.
These processes present opportunities for retrofits of
existing, underutilized refining/petrochemical assets, in some
cases. Commercialization and integration into an existing
process plant should be straightforward.
Depending upon economics, the overall process also has
the flexibility to make more or less isooctene and/or isooctane
product streams, which make good renewable gasoline
blending components. It should be noted that both renewable
gasoline blendstocks (isobutanol and isooctene) are not tied
to crude oil processing, so these are not likely to have crude oil
volatility effects. Again, isobutylene, isooctene and isooctane
can also be drawn off for the production of other renewable
petrochemical products (e.g., PX).
This biojet process has been demonstrated in a small
(10,000-gallon-per-month-capacity) unit for several months.
The alcohol-to-jet (ATJ) product has been sold to the US
Air Force as part of the Alternative Fuels Certification Office
(AFCO) process. Fig. 4 shows a picture of the demonstration
plant in Silsbee, Texas.
isobutylene and water. The reaction is endothermic, with a
relatively low operating pressure (< 200 psig) and temperatures
of around 550°F–650°F. The operating requirements are similar
to semi-regenerative catalytic reforming—older technology
that has since been upgraded in refineries and petrochemical
plants. Therefore, idled semi-regenerative reformers are
possibilities for retrofits to develop the dehydration step. The
catalyst for the dehydration has been fully commercialized in
similar applications.
The dehydration reaction can be efficiently designed to
almost complete conversion, minimizing the downstream
complexities of the separation of the butylene and water, and
the effluence of the water.
It should be noted that isobutylene can be a hydrocarbon
feedstock for other refining and petrochemical processes.
Since the isobutylene is renewable, any resulting RINs would
carry forward to any hydrocarbon product covered by RFS2.
Oligomerization. Step 2 is the oligomerization of the
isobutylene to dimers (isooctene), trimers (C12 olefins) and
tetramers. There is some measure of flexibility in the amount
of each olefin produced. Since IPK jet fuel primarily requires
C12–C16 olefins, dimers are recycled to yield more trimer/
tetramer product.
Oligomerization is an exothermic reaction, with operating
conditions, heats of reaction, and catalysts that closely resemble
MTBE production units and/or catalytic polymerization
units; these units are possible retrofit candidates for this
oligomerization step. In fact, after MTBE was banned in the
US, many MTBE units were converted to make isooctene
Isooctene Isooctane
(if desired) (if desired)
Isobutanol Isobutylene IPK
Dehydration Oligomerization Hydrogenation
Hydrogen
Fig. 3. Isobutanol-to-IPK jet fuel process flow diagram.

IPK process steps.rheeTre a three steps in the IPK

production process. Fig. 4. IPK biojet demonstration plant.
Dehydration. Step 1 is the dehydration of isobutanol to
HYDROCARBON PROCESSING September 2012
 Refining Developments
40
Return on investment, % rate of return
35
30
25
20
15
10
5 $3.40 jet
0 economics, retrofits are not possible in all cases. Therefore, a
1.10 1.20 1.30 1.40 1.50
Isobutanol advanced RIN value, $
Fig. 5. Biojet plant financial summary analysis.
Source: Mustang Engineering
Corn
Isobutanol
Sugarcane retrofitted ethanol plant
Agricultural
residue
Wood
Fig. 6. Bio-isobutanol to paraxylene, gasoline blendstock and/or biojet.
(dimer). These units could be used with a minor retrofit.
Depending upon economics, the dimer could be used for
gasoline blending and/or further processing options.
Hydrogenation. Step 3 is the saturation of the olefin
product from the oligomerization section. This is also a well-
known and practiced operation in refineries and petrochemical
plants. The main reaction is the conversion of the trimers/
tetramers to IPK. The operating conditions are mild, and
they have relatively low operating pressure and temperature,
and modest space velocity requirements. The hydrogenation
reaction is exothermic and occurs with hydrogen consumption
in the process, so some recycle and cooling design details are
correlated with the reactor bed design to ensure proper heat
removal and control of the reaction.
Olefin hydrogenation is well-known and practiced, so there
may be an opportunity to retrofit existing assets, since lower-
pressure hydrogenation units have been idled as hydrogenation
requirements have become more severe. The operations
learning curve is somewhat established already, as per catalyst
preparation, unit startup, normal plant operations, etc.
Biojet properties.iPoIKjet b has some properties that
enhance its value. The freeze point is low (–80°C), while
oxidation stability is high. Starting from isobutanol, a
renewable IPK would also generate RINs at the rate of 1.6 per
gallon, based on the process. The current specification limit
for a jet fuel blend with synthetic blending components is a
maximum of 50%. For a 1:1 blend with petroleum jet fuel, 80
RINs are generated for every 50 gallons of IPK that are used to
produce 100 gallons of blended jet product.
Scoping economics of biojet. One important aspect
of understanding how bio-isobutanol can be a versatile
alternative biofuel is the nominal economic incentive for its
$2.60 jet
$2.80 jet conversion to jet fuel. Preliminary scoping economics were
$3.00 jet developed for making biojet from renewable isobutanol
$3.20 jet
feedstock. Although a retrofit of existing units would help the
1.60 1.70 1.80 1.90 2.00 2.10
new unit was used as the basis for this scoping evaluation.
In addition to CAPEX and efficiencies associated with the
possible retrofit of some existing assets, the other sensitivity
in scoping economics is the value and use of established RIN
and other tax credit incentives, as allowed.
The CAPEX throughput basis was a nominal 3,000-barrels-
Fuels markets per-stream-day (bpsd) grassroots plant. The unit was
Low-carbon assumed with all new equipment (no retrofit or surplus or
gasoline, jet
or diesel idled equipment). All inside-battery-limit (ISBL) equipment
was sized, specified and budget-estimated. The CAPEX was
Isooctene determined by applying factors to the equipment pricing to
or C12 account for commodity materials and labor. Allowances were
also made for engineering, escalation and contingency. A 30%
Paraxylene allowance for offsites was assumed and added.
For the jet fuel price basis, a relatively conservative
Chemicals markets
$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
flights landing in the EU, the airline industry and fuel suppliers
have been looking for cost-effective, renewable alternatives to
petroleum jet fuel. A scoping sensitivity examining this tax
credit is shown in Fig. 5.
As can be seen, the EU tax credit has a significant effect on
the scoping economics. As one might expect, the RIN value
also has a considerable impact. In summary, this nominal
3,000-bpsd biojet plant study illustrated some positive
scoping economics, even at conservative jet fuel prices.
Bio-isobutanol for renewable PX for PET. Once the
renewable hydrocarbon is made, there is the chance to make
renewable hydrocarbon products via traditional or even newer
processes. One new process uses isooctene to make PX, which
then can be made into purified terephthalic acid (PTA), and
then into renewable polyethylene terephthalate (PET) via
traditional methods.
A pilot plant is being designed for this new process, which
yields PX at a very high selectivity vs. other xylenes. High
selectivity eliminates the need for xylene isomerization,
separation and recycle steps. Additionally, the PX can be
integrated with the rest of the biofuel plant, as shown in Fig.
6. Depending on the relative amounts of each renewable
product, even the hydrogen made in the PX plant can be used
in the biojet hydrogenation unit.
Takeaway. Isobutanol has gasoline blending, chemical
and usage advantages vs. ethanol, which result in positive
economics for the conversion of existing ethanol facilities to
HYDROCARBON PROCESSING September 2012
 Refining Developments
bio-isobutanol production. Compared to other transportation
fuel blendstocks, bio-isobutanol is a better environmental
alternative (e.g., low vapor pressure, meaning lower volatility
in finished fuel). Also, being made by fermentation of sugars
(via normal or cellulosic biomass), these renewable fuels are
not tied to crude oil prices or to petroleum supply fluctuations.
The process configuration for bio-isobutanol to IPK biojet
fuel involves three sequential, straightforward steps. The
process operates at moderate operating conditions, and it
is similar to some existing refinery and petrochemical units
that have been idled or underutilized. Revamps are possible,
and they would reduce the CAPEX and construction time.
Projected RIN values and EU carbon tax incentives would
provide additional upside on the project economics. This
three-step process has been demonstrated at a 10,000-gallon-
per-month-capacity hydrocarbon plant in Silsbee, Texas. On-
spec product is being made and sold to the US Air Force for
the military certification process.
Bio-isobutanol has numerous process and product
platforms that can be employed as economics dictate. These
include, but are not limited to, solvent sales, use as a gasoline
blendstock, conversion to biojet or use as a feedstock for
renewable PX. Bio-isobutanol has the versatility to allow
multiple options at the same time. For example, marine and
small-engine fuels are niche options that can be addressed.
Renewable diesel is another option.
The pathway for bio-isobutanol via fermentation has
been established, and the business model makes economic
Article copyright ©2012 by Gulf Publishing Company. All rights reserved. Printed in U.S.A.
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Wood Group Mustang
16001 Park Ten Place
Houston, Texas 77084
www.mustangeng.com
sense to revamp idled or underutilized fermentation ethanol
plants. One company’s production of bio-isobutanol at
demonstration scale was proven in 2009. More recently, a
commercial-scale, 18-MMgpy plant was started up.
Furthermore, bio-isobutanol has versatility and
environmental and economic advantages when compared to
ethanol. Bio-isobutanol has the capability to provide significant
impact as an advanced gasoline blendstock, or as a feedstock to
make other advanced fuels or products; therefore, it should be
considered a high-potential, next-generation biofuel.
RIdczk kol
o IEj is a process technology manager at Wood Group Mustang.
He has over 30 years of experience in process and project engineering and
development in the refining, petrochemicals, chemicals, polymers and gas
processing industries. Mr. Kolodziej has been involved with several new
technology development projects, including several bio-related projects.
Most recently, Mr. Kolodziej was involved with Gevo’s projects in renewable
isobutanol and various petrochemicals. He is also responsible for process plant
project development for Wood Group Mustang in the Far East. Mr. Kolodziej
has US and international patents in hydrotreatment technology. He holds a BS
degree in chemical engineering from the University of Illinois (Chicago) and an
MBA degree in finance from DePaul University, and is a registered professional
engineer in the state of Illinois.
jEff SchEIb is vice president for fuels at Gevo Inc., overseeing sales, marketing
and business development activities for isobutanol-into-fuels markets, including
refining, biojet, gasoline distributors and marketers, marine and small-engine
applications. He 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 an MBA degree from the University of California (Los
Angeles) and a BS degree in industrial engineering from Northwestern University.