Refining biofeedstock

innovations
Analysis of processing routes for producing renewable diesel, gasoline and olefins with
feedstocks that include vegetable oil, pyrolysis oil and biomass. Biorenewable integration
in refineries is evaluated along with work to commercially produce green diesel

Jennifer Holmgren, Chris Gosling, Keith Couch, Tom Kalnes, Terry Marker,
Michael McCall and Richard Marinangeli
UOP-Honeywell

CO2
Feedstocks Products

Sugars Fermentation Dehydration Ethanol

C6 sugars

Distiller’s
C5/C6 sugars

H2O
grain
Optional
Starches
petroleum

Acid or enzyme Green

hydrolysis gasoline

Direct
Lignin, conversion
cellulose
and
hemicellulose Pyrolysis/thermal Bio-oil
depolymerisation Hydrotreating

Lights H2O
Syngas
Fischer
Gasification Green
Tropsch
diesel
H2O

Alcohol synthesis

FCC

Natural
oils Hydrotreating

H2O
Co-feed

FAME or FAEE
Transesterification
Optional
petroleum Glycerine

Figure 1 Overview of biofuel production

T
he production of renewable fuels
has been expanding worldwide,
driven by increasing petroleum
prices, government mandates and
incentives, as well as commitments to
Green House Gas reduction. Despite this
growth in renewable fuels, there has been
little integration of renewable fuels with
petroleum refineries. This segregation
of renewable fuel increases the cost
of production, since it does not take
advantage of any existing infrastructure
for the production and distribution
of fuels. Renewable fuels would find
greater application in meeting the
increasing demand for transportation
fuels if economical opportunities for
blending or co-processing in traditional
petroleum refineries could be identified
and developed.
In order to evaluate profitable refining

www.eptq.com PTQ Q3 2007 119

 and correlations to estimate commercial
performance. From these estimates, the
60 000 potential business value of biorenewable
Consumption Feed potential integration in conventional refineries
was evaluated. Government subsidies
50 000
were required to make some of the
processes economically attractive, but
40 000
several of the options were favourable
without subsidies. All options become
kpsd

30 000 more attractive with high crude

oil prices.
20 000 A schematic showing several options
for biofuel production from different
10 000 biomass sources is shown in Figure 1.
Some of the routes are already in
0 commercial practice, such as ethanol
id e ne el e l ol ls t e from the fermentation of corn or sugar
qu ls lin se es es an oi as
Li fue aso o Di od
i
et
h bl
e w cane, or biodiesel production from oils.
t G er Bi o- ta si
c
p or et/k Bi ge lo
Other less developed technology, such
J e l u
ns V l as the deoxygenation of plant oils to
tra Ce
produce a green diesel fuel, will soon be
a common renewable fuel. Several
Figure 2 Global potential for biofuels 1,2,3,4,5,6,7 routes have a considerable longer time
frame for commercialisation due to the
technical challenges required for
economic conversion to fuels.
Application Feed Process Product
Biofuel and biofeedstock
sources
Methanol Biodiesel (FAME)
Figure 2 compares the global volume of
Biodiesel petroleum-based liquid transport fuels
Biodiesel
and the current biofuels; bioethanol
Vegetable oil from starches and sugars; and biodiesel
and grease Glycerol from vegetable oils. The potential supply
of these fuels is small relative to the
H2 global demand for transportation fuels.
Vegetable oil About 13% of US corn production was
and grease used to supply ethanol for 2% of the US
Green Diesel gasoline market in 2005. In addition,
Diesel/green diesel
diesel hydrotreater
vegetable oils and greases could only
Diesel replace a very small fraction of
transportation fuel. The large supply of
lignocellulosic biomass could supply a
Vegetable oil high percentage of future liquid
Green and grease
Catalytic transport fuels if commercial processes
gasoline Gasoline
cracker were available to convert these feeds.
One such process evaluated in this study
VGO was fast pyrolysis. The quantity of
pyrolysis oil is currently very low, since
Vegetable oil there is little commercial production
Green and grease due to a lack of demand.
olefins Catalytic The study took into account both
Light olefins
cracker
feedstock costs and the projected prices
VGO of potential products. Current prices of
raw vegetable oils, greases and pyrolysis
oils were used in the economic
assessment. The costs ranged from $16/
Figure 3 Processing routes for vegetable oils and grease bbl for pyrolysis oil to greater than $75/
bbl for raw vegetable oils. Each economic
processing options for biologically Many options were found, including analysis was based on a West Texas
derived feedstocks, UOP partnered with the production of liquid transport fuels Intermediate (WTI) crude price of $40
the US Department of Energy (DOE), the through co-processing and standalone per barrel, a level considerably lower
National Renewable Energy Laboratory production plants. Processes to convert than the recent greater than $60/bbl
(NREL), Pacific Northwest National Lab these feedstocks into chemicals, price. The cost of each potential biofuel
(PNNL) and Michigan Tech University hydrogen and power production were was compared to this crude price after
(MTU) to commercialise a process to also considered. Details of promising incorporating a number of factors that
produce green diesel, a high-cetane fuel, processing options were defined after included capital costs, transportation
from vegetable oil. During this study, completing proof-of-principle experi- costs, CO2 credits, subsidies, and cetane
options for integrating biorenewable ments in batch and continuous pilot and octane numbers. Most of the
feeds and fuels into existing refineries plants with online analysis of products. feedstocks looked promising when
were identified. The data were used to develop models current US subsidies were applied.

120 PTQ Q3 2007 www.eptq.com

Several were economically attractive
without subsidies. Vegetable oils were
not attractive without subsidies until
crude prices exceeded $70/bbl.
The properties of biorenewable
feedstocks were compared to petroleum,
as shown in Table 1. The biggest
difference between biorenewable and
petroleum feedstocks is oxygen content.
Biorenewables have oxygen levels
ranging from 10–40%. Petroleum has
essentially none. These feedstocks are
often more polar, and some easily entrain
water and can therefore be acidic. All
have very low sulphur levels and many
have low nitrogen levels, depending on
their amino acid content. Bio-derived
feedstocks are incompatible with typical
refinery operations due to the acidity and
alkali content, so processes were
identified to pretreat many of these feeds
before entering refinery operations.
Opportunities for vegetable
oils and greases
Options were identified for processing
vegetable oils and greases in refineries,
as shown in Figure 3. One option is to
produce gasoline or olefins in an FCC
unit. These oils could also be
deoxygenated using hydroprocessing
technology to produce a high-cetane
green diesel product. Different fits for
the production of biodiesel in refineries
were also evaluated.
Catalytic cracking of vegetable oils
and greases was identified, and one
example is shown in Figure 4. A
pretreatment unit is required to remove
catalytic poisons such as alkali metals
and other problem components such as
water and solids. The pretreated feed can
then be introduced as a co-feed with
virgin gas oil (VGO) to produce gasoline
and other products. A modified catalytic
cracking process can produce high-value
products such as ethylene and
propylene.
Estimated yields for each processing
option are shown in Tables 2 and 3,
which compare standalone processing
of the vegetable oils to VGO. Co-
processing experiments are in progress.
Vegetable oil and greases produce
gasoline yields similar to VGO, with
reduced yields of heavier and often
undesirable products such as light cycle
oil (LCO) and clarified slurry oil (CSO).
Such processing also produces a
significant amount of water and/or COx
as a consequence of feedstock
deoxygenation in the FCCU. Results
were similar for olefins production,
where vegetable oil and greases can
produce competitive yields of ethylene
and propylene with reduced amounts of
gasoline, LCO, and CSO. RON values are
slightly higher for processing vegetable
oils in both catalytic cracking schemes,
while coke yields are slightly higher for
gasoline production. In either case, the
122 PTQ Q3 2007 www.eptq.com
Typical properties of petroleum and biorenewable feedstocks
Petroleum Biorenewable
Crude typical Resid Soy oil Yellow grease Pyrolysis oil
% C 83–86 84.9 77.6 76.4 56.2
%H 11–14 10.6 11.7 11.6 6.6
%S 0–4 (1.8 avg) 4.2 0.0006 0.04 –
%N 0–1 (0.1 avg) 0.3 0.0011 0.03 0.3
%O – – 10.4 12.1 36.9
H/C 1.8–1.9 1.5 1.8 1.8 1.4
Density 0.86 (avg) 1.05 0.92 0.89 1.23
TAN <1 <1 2 30 78
ppm alkali metals 60 6 100 100 100
Heating value, kJ/kg 41 800 40 700 37 200 37 200 15 200
Table 1
Light ends
Gasoline
VGO Catalytic
cracker LCO
CSO
Vegetable oil
Pretreater
and grease
Remove alkali metals,
solids and water
Figure 4 Processing approach for catalytic cracking of vegetable oil
Estimated green gasoline yields Estimated green olefins yields
VGO Vegetable VGO Vegetable
oil/grease oil/grease
C2= 1.5 1.9 C2P+ methane 4.1 4.0
C3P 0.7 0.8 C2= 8.6 8.6
C3= 4.0 4.5 C3P 2.0 2.0
C4s 7.9 6.5 C3= 22.0 22.2
Gasoline 45.5 44.9 C4s 15.0 13.4
LCO 17.5 11.3 Gasoline 27.3 22.7
CSO 19.5 12.7 LCO 9.5 4.9
Coke 3.4 4.5 CSO 5.0 3.0
Water/COX (Est.) 0 12.7 Coke 6.5 6.5
RON of gasoline 92.1 94.8 Water/COX (Est.) 0 12.7
RON of gasoline 94.8 96.8
Table 2 Table 3
use of vegetable oils and greases in not readily scaled down. This modular
catalytic cracking units is feasible. green diesel unit could be constructed
at an existing refinery or at a remote
Green diesel production location. The paraffinic product could
The use of existing hydroprocessing be blended with the hydrotreated
technology was evaluated for the diesel or could serve as a high-quality
deoxygenation of vegetable oils and diesel fuel on its own.
greases to produce a paraffinic diesel This modular approach is attractive
fuel through two promising processing for feedstocks containing high
options. As with catalytic cracking, co- percentages of free fatty acids or when
processing in existing units requires a transportation of the feedstock is
pretreatment unit to remove alkali prohibitively high, since construction
metals and hydrogenate units of near the feedstock source and the choice
unsaturation on the fatty acid chains. of proper metallurgy will solve both
The pretreated feed is then fed to an these issues. Generally, separate
existing hydrotreater. We prefer to processing in a modular unit has the
produce the green diesel in a separate following advantages:
unit, where processing conditions are — Optimisation of the processing
optimised for the vegetable-oil-based conditions and catalyst for conversion
feedstock. FCC processing in a modular of the biofeedstock
unit is not feasible, since these units are — Minimisation of the use of
 Performance estimates for green
diesel process

Products
Vol% naphtha <1–10%
Vol% diesel 88–98+%
Cetane number 80–100
ppm S <10

Table 4

Performance estimates for the

production of naphtha and diesel
from pyrolysis oil
Feed wt% bpd
Pyrolytic lignin 100 2250
H2 4–5 –
Products – –
Lt ends 15
Naphtha 30 1010
Figure 5 NPV comparison of biofuels and chemicals 8,9,10,11 Diesel 8 250
Water, CO2 51–52 –

Comparison of biodiesel and green diesel properties Table 6

Biodiesel (FAME) Green diesel planned for operation in a European

%O 11 0 refinery in early 2009. UOP is currently
Density, g/ml 0.883 0.78 licensing this technology.
Sulphur content <10 ppm <10 ppm Figure 5 summarises the economic
Heating value (lower), MJ/kg 38 44 analysis of biofuels and chemicals
% change in NOx emission +10 0 to -10 production from oils and greases,
Cloud Point C -5 -5 to -30 comparing the NPVs of four products as
Distillation 10–90% pt 340–355 265–320
a function of biofuels feedstock. The
Cetane 50 80–90
NPVs were ten-year NPVs with product
pricing of diesel, gasoline and olefins
Table 5 produced from $40/bbl crude. The
different bars represent different
expensive metallurgy for acidic chain paraffin whose cold-flow renewable feedstocks, including
biofeedstocks and products properties can be adjusted by the subsidised and unsubsidised soy. As can
— Removal of products such as CO, appropriate level of isomerisation. The be seen, the subsidies have a large
CO2 and H2O, which impact the product cetane number can reach as impact on the economics of these
hydroprocessing catalyst high as 80–90. Biodiesel, a fatty acid processes.
— These factors must be weighed methyl ester (FAME), is made by adding
against the advantage of using existing methanol to vegetable oils. FAME Refining opportunities for
processing capacity, particularly if it is contains a significant amount of oxygen pyrolysis oil
underutilised. that lowers its heating value and Fast pyrolysis is a thermochemical
Performance estimates for a green contributes to higher NOx emissions for process with the potential to convert
diesel process are shown in Table 4. concentrated blends. There are some cellulosic biomass into liquid fuels and
Hydrogen requirements are variable, other differences in product properties feeds. Large amounts of cellulosic
depending on both the degrees of not identified in the table. The biomass are available around the globe.
unsaturation on the fatty acid chains production of FAME yields a significant Solid biomass feedstock is injected into
and the deoxygenation mechanism, amount of contaminated glycerol a fluidised bed with high a heat-transfer
which itself depends on the choice of byproduct that needs a commercial capability for short contact times,
catalyst and processing conditions. outlet, while green diesel produces light followed by quenching to condense a
Hydrodeoxygenation produces water hydrocarbons from the triglyceride liquid bio-oil in 50–75% yields, with
and requires one hydrogen molecule backbone. The production of biodiesel gas and char forming the balance. The
for each oxygen removed, while requires a less flexible range of vegetable bio-oil contains the thermally cracked
decarboxylation removes one carbon to oil feedstock, and fatty acids must be products of the original cellulose,
produce CO or CO2. Breaking the removed prior to transesterification. hemicellulose and lignin fractions
triglyceride backbone produces propane Highly unsaturated fatty acids chains present in the biomass. It also contains
or lighter hydrocarbons. The yield of a result in a less stable biodiesel product, a high percentage of water, often as
high-cetane and low-sulphur content since oxidation occurs at the double high as 30%.
green diesel product is greater than 98% bonds when stored for extended periods Table 6 shows an estimated biofuel
on a volumetric basis. of time. Green diesel has several product distribution for hydroprocessed
Green diesel is an oxygen-free property advantages over biodiesel and pyrolytic lignin bio-oil based on
paraffinic feed and has several will likely be preferred by vehicle experimental results. These estimates
advantages over biodiesel, also produced manufacturers. were used as a basis for economic
from vegetable oil, as shown in Table 5. Green diesel technology development calculations. The naphtha and diesel are
Green diesel is a high-cetane, straight- has already been completed and a unit is produced along with a large amount of

www.eptq.com PTQ Q3 2007 123

 water and CO2 due to water removal and
deoxygenation. As with the vegetable
oil, hydrogen consumption and the
yield of CO/CO2 will vary, depending on
the mechanism of deoxygenation.

Vegetable oil processing

options
Points

A life cycle analysis (LCA) of the various

vegetable oil processing routes was
conducted at Michigan Technological
University using the proprietary
Simapro LCA program. LCA is a method
to determine and compare the
Petroleum Biodiesel Green Green environmental impact of alternative
diesel diesel gasoline products or processes from “cradle-to-
grave”. In this case, the scope of the
Figure 6 LCA — single environmental impact score analysis was from extraction through
combustion. For analysis purposes, it
was assumed that all fuels have the
same performance in transportation
use. The primary focus of the analysis
was on fossil energy consumption and
emission of greenhouse gases, although
other impact categories are included.
The results of the analysis are shown
in Figure 6. In general, the green
products have much lower total
environmental impact scores than
petroleum diesel, primarily because of
significantly lower production of
climate-active CO2. Of the biofuels,
green diesel and green gasoline (from
the catalytic cracking of vegetable oil)
have the lowest environmental impact
and CO2 production. The environmental
impact of biodiesel production is higher
due to the methanol requirement,
which is produced from natural gas
through an energy-intensive process
with a strong environmental burden.

Summary
A number of opportunities were
identified for the integration of
biorenewable feedstocks and biofuels in
petroleum refineries, particularly for
two promising feedstocks:
— Vegetable oils/greases to produce
green diesel, gasoline or chemicals
— Pyrolysis oil to produce green
gasoline.
Vegetable oil can be processed in the
short term using commercially available
refining technology, but will be
restricted to producing a small fraction
of liquid transport fuels due to a limited
amount of feedstock. Pyrolysis oil
processing requires more commercial
development and is also limited by the
availability of pyrolysis oil, since
commercial production is still in its
infancy. In the long term, however, the
focus must be on the effective utilisation
of cellulosic biomass.

Acknowledgements
We would like to acknowledge the US
Department of Energy for partially
funding this study (DOE Project DE-FG36-
05GO15085), S Czernik from National

124 PTQ Q3 2007 www.eptq.com


“Vegetable oil can be
processed in the short term
using commercial refining
technology, but will be
restricted to producing
a small fraction of liquid
transport fuels due to a
limited feedstock”
Renewable Energy Laboratory, D Elliott from
Pacific Northwest National Laboratory and
D Shonnard from Michigan Technological
University.
References
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7 Lynd L R, Liquid transportation fuels,
World Congress on Industrial Biotech
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8 National Biodiesel Board, Tax Incentive
Fact Sheet, 2004.
9 Radich A, Biodiesel performance, costs, and
use. Energy Information Administration,
2004. www.eia.doe.gov/oiaf/analysispaper/
biodiesel.
10 Schnepf R, Stallings D, Trostle R, Wescott
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Jennifer Holmgren is the director of the
renewable energy and chemicals business
for UOP LLC in Des Plaines, Illinois, USA.
Holmgren holds a BSc in chemistry from
Harvey Mudd College, a PhD in inorganic
materials synthesis from the University of
Illinois at Urbana-Champaign and an MBA
from the University of Illinois at Chicago.
Email: jennifer.holmgren@uop.com
Chris Gosling is a senior manager
of UOP’s refining conversion process
development in Des Plaines, Illinois, USA.
Gosling holds a BS and a MS in chemical
engineering from Michigan Technological
University. Email: chris.gosling@uop.com
Keith Couch is senior manager of FCC and
treating technologies for UOP’s refining
conversion development department in
Des Plaines, Illinois, USA. Couch holds a
BS in chemical engineering from Louisiana
Tech University.
Email: keith.couch@uop.com
Tom Kalnes is a senior R&D associate in
process design and development at UOP
LLC in Des Plaines, Illinois, USA. Kalnes
holds a BS in chemical engineering from
University of Illinois at Chicago and a MS
in environmental engineering from Illinois
Institute of Technology.
Email: tom.kalnes@uop.com
Terry Marker is a senior hydroprocessing
specialist and development team leader
at UOP LLC in Des Plaines, Illinois, USA.
Marker holds a BS in chemistry from the
University of Illinois and a MS in chemical
engineering from Illinois Institute of
Technology. Email: terry.marker@uop.com
Michael McCall is a research specialist
in exploratory and fundamental research
for UOP LLC in Des Plaines, Illinois, USA.
McCall holds a BSc in chemistry from
Illinois State University and an MS in
chemistry from the University of Michigan.
Email: michael.mccall@uop.com
Richard Marinangeli is manager
of renewable energy and chemicals
development for UOP LLC in Des Plaines,
Illinois, USA. Marinangeli holds a BS
in chemical engineering from Notre
Dame University and a PhD in chemical
engineering from Princeton University.
Email: richard.marinangeli@uop.com
PTQ Q3 2007 125