A Perspective On Oxygenated Species in The Refinery Integration of Pyrolysis Oil

Green Chemistry
CRITICAL REVIEW
Cite this: Green Chem., 2014, 16,
407
Received 18th September 2013,
Accepted 25th November 2013
DOI: 10.1039/c3gc41951g
www.rsc.org/greenchem
A perspective on oxygenated species in the
renery integration of pyrolysis oil
Michael S. Talmadge,
a
Robert M. Baldwin,
a
Mary J. Biddy,
a
Robert L. McCormick,
b
Gregg T. Beckham,
a,c
Glen A. Ferguson,
a
Stefan Czernik,
a
Kimberly A. Magrini-Bair,
a
Thomas D. Foust,
a
Peter D. Metelski,
d
Casey Hetrick
d
and Mark R. Nimlos*
a
Pyrolysis oers a rapid and ecient means to depolymerize lignocellulosic biomass, resulting in gas,
liquid, and solid products with varying yields and compositions depending on the process conditions.
With respect to manufacture of drop-in liquid transportation fuels from biomass, a potential benet
from pyrolysis arises from the production of a liquid or vapor that could possibly be integrated into exist-
ing renery infrastructure, thus osetting the capital-intensive investment needed for a smaller scale,
standalone biofuels production facility. However, pyrolysis typically yields a signicant amount of reactive,
oxygenated species including organic acids, aldehydes, ketones, and oxygenated aromatics. These oxyge-
nated species present signicant challenges that will undoubtedly require pre-processing of a pyrolysis-
derived stream before the pyrolysis oil can be integrated into the existing renery infrastructure. Here we
present a perspective of how the overall chemistry of pyrolysis products must be modied to ensure
optimal integration in standard petroleum reneries, and we explore the various points of integration in
the renery infrastructure. In addition, we identify several research and development needs that will
answer critical questions regarding the technical and economic feasibility of renery integration of pyro-
lysis-derived products.
1. Introduction
There is significant, worldwide interest in converting renew-
able biomass sources to liquid transportation fuels, with the
overall aim to develop a more sustainable and diverse trans-
portation fuel economy. Lignocellulosic biomass, derived from
plant cell walls, oers a significant pool of renewable carbon
that can be upgraded to a wide range of fuels and
chemicals.
13
To date, there are multiple technologies being
considered for producing biofuels from lignocellulosic
biomass, which can quite broadly be categorized as biochemi-
cal and thermochemical conversion routes. Standard
biochemical conversion routes typically include a mild ther-
mochemical pretreatment step intended to make the plant cell
wall more amenable to hydrolysis of the most recalcitrant
biomass fractions to soluble sugars by enzymes. The resulting
sugars can then be upgraded catalytically
4,5
or biologically.
6
Conversely, thermochemical conversion uses significantly
harsher conditions to depolymerize biomass, either via pyro-
lysis (400 C600 C)
7
to a mixture of vapor, liquid, and solid,
or to synthesis gas via gasification
8,9
at much higher tempera-
tures (750 C950 C).
Ethanol can readily be produced from either biochemical
conversion through fermentation
10
or via thermochemical con-
version through gasification, followed by catalytic upgrading to
mixed alcohols.
11
In the current gasoline market, ethanol pro-
duced by fermenting sugar from grains or sugarcane has been
widely accepted as a gasoline blendstock in some parts of the
world. However, there are significant technical challenges to
expanding the use of ethanol, such as its incompatibility with
existing vehicles at higher blends and its inability to be trans-
ported in the fungible fuel distribution system.
In contrast to ethanol, producing infrastructure-compatible
hydrocarbon fuels from biomass has distinct benefits in that
these materials can be tailored to be chemically similar or
identical to existing gasoline, jet, and diesel fuels. Producing
hydrocarbon fuels from lignocellulosic biomass will undoubt-
edly require an even broader range of research and develop-
ment activities far beyond the significant eorts to
demonstrate ethanol production at scale, as the slate of hydro-
carbon molecules to be produced for broader fuel pools is
Electronic supplementary information (ESI) available. See DOI:
10.1039/c3gc41951g
a
National Bioenergy Center, National Renewable Energy Laboratory,
15013 Denver West Parkway, Golden, CO 80401, USA. E-mail: mark.nimlos@nrel.gov
b
Transportation and Hydrogen Systems Center, National Renewable Energy
Laboratory, 15013 Denver West Parkway, Golden, CO 80401, USA
c
Department of Chemical Engineering, Colorado School of Mines, Golden, CO 80401,
USA
d
BP Refining and Marketing Research & Technology, Naperville, Illinois, USA
This journal is The Royal Society of Chemistry 2014 Green Chem., 2014, 16, 407453 | 407
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necessarily more expansive. To accomplish this goal, conver-
sion pathways using biochemical, thermochemical, and
hybrid thermochemical/biochemical processes are being
considered.
12
A particularly attractive technology for producing hydro-
carbon fuels from biomass is fast pyrolysis. Slow pyrolysis for
the production of charcoal has been utilized for centuries,
while over the past 30 years the focus has been on fast pyro-
lysis to produce both pyrolysis oils as well as chemicals and
fuels.
7,13
Fast pyrolysis can produce a liquid carbonaceous
material in high yield in a relatively inexpensive process.
7
Because of the advantages of this technology, it has been
extensively studied for many decades and recently the process
has advanced to commercial scale.
13
With the approval of
ASTM D7544, which defines the required specifications for
pyrolysis oil for use in fuel-burning combustors, and the estab-
lishment of environmental policies and societal focus through-
out the world to reduce utilization of fossil fuels, pyrolysis oil
is being strongly considered as a fuel oil replacement. There
are currently several demonstration plants being operated
worldwide producing pyrolysis oil as boiler feed for electricity
generation.
13
Hydroprocessing of pyrolysis oil is a newer area
of research focus with the goal of producing infrastructure-
compatible hydrocarbon fuels and/or refinery intermediates
and blendstocks. While work was begun in the 1980s in these
eorts, there has been a resurgence in this research area over
the past 5 years with the bulk of the research focusing on pro-
cessing at the bench and pilot scale.
14
One advanced pyrolysis
process for producing transportation fuels involves generating
fast pyrolysis oil, often called bio-oil, and upgrading the bio-oil
into hydrocarbon fuels using hydrotreating or hydroproces-
sing. Converting pyrolysis oil directly to a fuel using this tech-
nology requires a significant capital investment for a
standalone biorefinery as well as an external, readily available
source of hydrogen. Because of significant biomass transpor-
tation costs, production capacity for a single biorefinery is
limited, and thus cannot take full advantage of economies of
scale for capital equipment costs.
Though hydrotreating of pyrolysis oil has been extensively
investigated, there are limited studies in the literature on
using pyrolysis oil in existing petroleum refineries, which is
the subject of this perspective. The advantages of using bio-oil
in refineries are significant:
Integrating pyrolysis oil into the refinery could signifi-
cantly reduce the cost of producing fuels from biomass. Tril-
lions of dollars have been invested in petroleum refineries,
and if bio-oil can be upgraded in these facilities, many of the
capital expenses associated with building a new plant to
handle bio-oil alone could be avoided.
Processing bio-oil with petroleum in a refinery could
produce a fuel that is indistinguishable from existing gasoline,
jet, and diesel fuels. As a result, there would not likely be
requirements for extensive, time consuming, and expensive
engine and acceptance testing.
Biomass fast pyrolysis produces a suite of hundreds to
thousands of chemical compounds and modern refineries
have been optimized to use complex and varying feedstocks to
produce transportation fuels at a profit.
In this perspective, we discuss various options for integrat-
ing pyrolysis oil into a standard petroleum refinery. Specifi-
cally, we first review the pyrolysis process for lignocellulosic
feedstocks and the composition of resulting bio-oils in light of
physical property requirements for petroleum refinery inte-
gration. We then discuss options for upgrading pyrolysis oil to
meet these requirements. In section 4, we discuss standard
petroleum refinery unit operations and examine associated
quality metrics for each. Section 5 describes several options for
integrating pyrolysis oil into refinery unit operations. Lastly,
section 6 outlines some potential fuel molecules and their
associated physical and chemical properties that may result
from the oxygenated feedstocks in a refinery.
2. Pyrolysis and composition of
pyrolysis oil
Fast pyrolysis is an attractive process for deconstructing
biomass into smaller carbonaceous molecules that could
potentially be used as intermediates in refinery unit oper-
ations. Using typical heating rates of 1000 K s
1
, carbon con-
versions greater than 70% into a liquid product can be
obtained. This high conversion is essential because of the
high feedstock costs associated with the collection and delivery
of biomass. In addition, pyrolysis reactors are relatively small
and of low capital cost due to the short residence time
required, and they are typically easy to operate. Reactor con-
figurations such as fluidized bed, circulating bed, and
entrained flow are ideally suited to fast pyrolysis; these have
been widely used for more than 60 years in the refining and
petrochemical industry and are commercially available.
Finally, the relatively low temperature required for biomass
pyrolysis (400 C600 C) means that inexpensive materials
can be used for reactor construction.
If the fast pyrolysis process is conceptually ideal for prepar-
ing refinery intermediates, the reality is that the composition
of the resulting bio-oils is far from ideal from the perspective
of the refining industry. Typically, biomass pyrolysis oil has
many undesirable physical characteristics that make its use in
a refinery problematic. These include thermal instability,
immiscibility in hydrocarbons, high viscosity, high water
content, and corrosivity. These properties are directly related
to the chemical composition of the bio-oil and in particular,
the oxygen content of the products formed from the pyrolysis
of the biopolymers found in plant cell walls. In this section,
the conversion of biomass into pyrolysis oil products and the
eects of the pyrolysis oil composition on physical properties
will be discussed in detail.
2.1 Biomass composition and yields of oils
Biomass is composed of three main biopolymers, cellulose,
hemicellulose, and lignin; and the decomposition of these
three materials is largely responsible for the observed solid,
Critical Review Green Chemistry
408 | Green Chem., 2014, 16, 407453 This journal is The Royal Society of Chemistry 2014
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liquid, and gaseous products. As can be seen in Fig. 1, these
materials contain a significant amount of oxygen, which trans-
lates into 30 wt%60 wt% oxygen in the oil. Cellulose is a
simple linear polymer consisting of repeat units of cellobiose
with a degree of polymerization (dp) often exceeding 2000. In
plant cell walls, several chains of cellulose are held together in
microfibrils that provide the strength to the plants. Hemicellu-
lose is a branched biopolymer that contains a backbone poly-
saccharide, which is commonly a repeat of xylobiose.
Other sugars, such as manose, arabinose, glucose and
galactose, and sugar acids branch o from this backbone; and
there is a high degree of acetylation. The anhydrosugars in
these biopolymers typically have the atomic formula of
C
6
H
10
O
5
for hexoses and C
5
H
8
O
4
for pentoses, which shows
the source of much of the oxygen in pyrolysis oil. Lignin is a
complex polymer of propylaromatic subunits originally con-
structed from the lignol monomers, p-coumaryl, coniferyl, and
sinapyl alcohol (shown below), which have molecular formulas
of C
9
H
10
O
2
, C
10
H
12
O
3
, and C
11
H
14
O
4
. This polymer does not
contribute as much to the oxygen content of the pyrolysis
oil due to its lower atomic oxygen-to-carbon ratio. The
organization of these polymers in cell walls is the subject of
intense research, but it is clear that cellulose microfibrils form
what appears to be a mat that provides the structure and
strength for plant cell walls and the hemicellulose and lignin
are arranged around the cellulose microfibrils. Although these
biopolymers in biomass largely determine the yields and com-
position of the observed products in biomass pyrolysis oil,
small levels of inorganic constituents also aect the product
yields.
1517
Lignols:
The composition of biomass varies significantly from
woody to herbaceous materials. Data on the composition of
several feedstocks for biofuels manufacture is available at the
Fig. 1 Typical products formed from the pyrolysis of the biopolymers in plant cell walls.
Green Chemistry Critical Review
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U.S. Department of Energys Alternative Fuels Data Center
(http://www.afdc.energy.gov/biomass/progs/search1.cgi). Typical
compositions are shown in Table 1 for some important species
covering hard and soft woods ( poplar and pine), potential
energy crops (switch grass), and agricultural residue (corn
stover). Notice that the woody materials typically have lower
ash, extractives, and hemicellulose and more lignin than the
herbaceous species. The extractives, materials that can be
removed from the biomass using solvents, are fatty acids,
lipids, fatty alcohols, terpenes, resin acids, and terpenoids
18
for woody materials and free sugars, sugar oligomers, alditols,
organic acids, and inorganic ions
19,20
for herbaceous feed-
stocks. Extractives can have a major influence the properties
of pyrolysis oil
18,21,22
and pretreatment of the biomass can
often aect these materials resulting in changes in bio-oil
composition.
During fast pyrolysis, the biopolymers found in plant cell
walls are converted into non-condensable gasses, liquids, and
solid char. The gasses are primarily CO
2
, CO, CH
4
, H
2
, and
some light hydrocarbons. The liquids contain 15%30% water
in an emulsion with hydrophobic and hydrophilic organic
compounds, some suspended solid material, and alkali and
alkaline earth metal compounds that are present as inorganic
matter in the feed biomass. Depending upon the temperature
of pyrolysis, the char is primarily carbon, which can be used
for process heat. Though the light gases may serve as a source
of hydrogen, the liquids are most suitable for refinery oper-
ations. The organic compounds in these liquids typically
contain a wide variety of oxygen functional groups, which
impart undesirable physical and chemical properties to bio-
oil.
Determining the yields of char, gas, and liquid is very
important for assessing the viability of dierent feedstocks for
production of bio-oil. An interesting hypothesis has been
oered, which suggests that these yields can be estimated
from the biopolymer content of the biomass. Perhaps the most
compelling work was conducted by Qu et al., who studied
product yields in a bench-scale tubular reactor in which the
biomass was heated to pyrolysis temperatures (350 C650 C)
within one second.
27
They measured the product yields from
the individual biopolymers as shown in Table 2 and used
these data to predict the formation of products from biomass
pyrolysis based upon the measured biopolymer content. The
reported compositions are consistent with other literature
values,
2831
and Fig. 2 shows a comparison of the predicted
(calculate) product yields to experimental values for rice
straw pyrolysis. Similar results were obtained for corn-stalk
and peanut vine, a woody biomass. If this hypothesis is true,
the carbohydrates will be the dominant source of liquids. As
shown in Table 1, carbohydrates make up roughly 70% of the
biopolymers and have liquid yields of 50%60%, while lignin
makes up 20%30% of the biopolymers and only produces
40% liquid. Thus, the carbohydrates contribute 3 to 4 times as
much liquid as does lignin in biomass pyrolysis.
It should be pointed out that there are studies suggesting
that this component analysis hypothesis is incorrect.
32,33
Of
particular concern are the eects of inorganic materials. For
instance, Oassma et al. measured the pyrolysis yields for
several feedstocks and showed that the organic materials in
Table 2 Products from the fast pyrolysis of select biopolymers at
500 C
24
Yields Cellulose Hemicellulose Lignin
Gas 20% 26% 13%
Char 18% 23% 47%
Liquid 62% 50% 40%
Products in gas
CO
2
48% 60% 32%
CO 47% 30% 25%
CH
4
4% 7% 42%
Fig. 2 Predicted yields compared to measured yields for the products
from rice straw pyrolysis. Taken from ref. 27. Reprinted with permission
from T. Qu, W. Guo, L. Shen, J. Xiao, K. Zhao, Industrial & Engineering
Chemistry Research, 2011, 50, 1042410433. Copyright 2011 American
Chemical Society.
Table 1 Typical biomass composition
a
Species Extractives Ash Lignin Hemi-cellulose Cellulose
Hybrid Poplar
b
3.6 0.9 23.3 (24.6) 27.8 (29.3) 43.7 (46.1)
Monterey Pine
c
2.7 0.3 25.9 (28.6) 23.0 (25.4) 41.7 (46.0)
Switchgrass
d
17.0 5.8 17.4 (23.1) 27.3 (36.1) 30.8 (40.8)
Corn Stover
e
7.6 6.8 17.2 (21.1) 26.3 (32.5) 37.8 (46.4)
a
Given in weight percent. Values in parenthesis are ash and extractive free.
b
Ref. 23.
c
Ref. 24.
d
Ref. 25.
e
Ref. 26.
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the liquids were directly related to the amount of ash in the
feedstock, as shown in Fig. 3. Alkali metals present in the ash
are known to increase the yields of char, water, and gases
during pyrolysis
17,3437
and this could lead to lower yields of
liquid organic compounds. Potassium is known to be particu-
larly active.
3842
In the study of Qu et al., the ash (inorganics)
were treated as inert materials that only add to the char
yields.
27
This appears to be dierent from a significant body of
literature, which shows that the presence of alkali metals dra-
matically influences the yields and composition of pyrolysis
oils.
2.2 Oxygen content
As mentioned above, oxygen in bio-oil is responsible for some
of the physical and chemical properties that make it unsuita-
ble for introduction into refineries. There are a significant
number of studies that report on the elemental composition of
biomass fast pyrolysis oils; some of these data are shown in
Table 3. In this table, the elemental composition is reported in
the absence of water, which makes up roughly 20% of the oil.
Another study of note is a round robin campaign
43
conducted
in 2000 for the IEA, in which four pyrolysis samples were ana-
lyzed by twelve laboratories. The standard deviations of the
measurements were 1%3% for carbon and 3%5% for hydro-
gen. Oxygen was determined by dierence. The larger vari-
ations shown in Table 3 may be because of variations in the oil
preparation and the feedstock composition. As can be seen,
the amount of oxygen varies from 32 wt% to 48 wt%, and sig-
nificant variations are found between each species. The table
Fig. 3 Organic compound yields in the condensable liquids from fast
pyrolysis as a function of ash content of biomass. From ref. 16. Reprinted
with permission from A. Oasmaa, Y. Solantausta, V. Arpiainen,
E. Kuoppala, K. Sipil, Energy & Fuels, 2010, 24, 13801388. Copyright
2010 American Chemical Society.
Table 3 Elemental composition of fast pyrolysis oil on a dry basis
Feedstock
Weight percent ppm
C H O
a
N S
b
KNa
b
Cl
b
Pine
VTT
44
55.8 5.8 38.2 0.1 0.02 20 30
Dynamotive
44
52.6 7.53 39.52 0.09 0.0197
BTG
44
53.7 6.0 40.0 0.3
Fortum
44
57.1 6.4 36.4 0.1
PNNL
45
51.2 7.5 41.1 0.1 10
PNNL
46
53.0 6.4 40.5 0.1 0.003
Poplar
NREL
47
57.3 6.3 36.2 0.18 0.02 10 8
NREL
47
60.5 6.7 32.6 0.23 0.02 12 8
Waterloo
48
54.7 6.7 38.3
Waterloo
49
51.8 6.7 41.3
Waterloo
50
57.3 6.29 36.4
Oak
Dynamotive
44
47.2 4.5 48.0 0.12 0.022
PNNL
45
56.0 6.8 37.2 57
NREL
51
59.6 6.0 34.2 0.11 0.01 100
Corn Stover
UMinn
52
60.66 7.70 2.2 0.15
USDA
53
53.97 6.92 37.94 1.18
Iowa St
54
58.4 5.2 30.9 0.5
Straw
VTT
44
55.3 6.6 37.7 0.4 0.05 2 330
Waterloo
50
55.55 6.39
CHEC 37 7.7 52 1.1 0.1
Switchgrass
NREL
44,50
55.8 6.9 36.3 0.79 0.03 128 1900
PNNL
45
46.6 8.0 45.4 165
USDA
55
46.0 6.7 42.6 0.3
a
By dierence.
b
Some of the studies did not report sulfur, alkali and chloride.
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also shows the nitrogen and sulfur levels, where determined.
As discussed later in this paper, fuel standards require low
levels of sulfur in finished fuels and both elements can be
catalyst poisons. Also shown in this table are measurements of
potassium, sodium, and chloride. These elements can also be
catalyst poisons; chloride can also contribute to corrosion.
2.3 Molecular composition
Numerous studies
16,43,44,5662
have measured the products of
biomass pyrolysis; and the list of measured compounds
includes carboxylic acids, esters, ethers, alcohols, ketones,
aldehydes, diols, hydroxylated ketones and aldehydes, furans,
sugars and anhydrosugars, phenolic compounds, and hydrocar-
bons. Oxygen is present in most of more than 300 compounds
that have been identified by GC/MS.
63
Typically, the concen-
tration of any particular compound is less than 10 wt% though
there is a large variability in the measurements of individual
molecular species in the products. The IEA round robin study,
43
where the same oils were measured by dierent laboratories,
highlighted the diculty in measuring these compounds.
To some degree, the observed molecular products can be
related to the plant cell biopolymers as shown in Fig. 1 which
highlights the product distribution from the pyrolysis of the
dierent biopolymers. Most of the aliphatic and furanic oxyge-
nated hydrocarbons are formed from cellulose and hemicellu-
lose,
64,65
while the phenolic compounds arise from pyrolysis of
the lignin component.
66
As with total organic yield, the mole-
cular composition of pyrolysis oil is also aected by the
amount of alkali and alkaline earth metals in the biomass.
The products from cellulose and hemicellulose are particularly
sensitive.
17,64
The molecular composition and the concentration of these
individual compounds also depend on process severity (temp-
erature, residence time, and heating rate profiles). Elliott
67
and
Evans and Milne
15
found that highly oxygenated aliphatic and
aromatic primary pyrolysis vapors (oils) form at 400 C. Many
of these compounds crack at temperatures above 550 C and
produced pyrolysis vapors that are less oxygenated and more
aromatic. As a result, oils produced at elevated temperatures
include more phenolic compounds.
The chemical composition of bio-oils produced from
process conditions that maximize liquid yields is very complex,
and complete analysis of those oils requires the combined use
of several analytical techniques. A precise description of bio-
oil composition has not yet been achieved and even with con-
siderable analytical eorts, about 20% of the composition still
remains unknown. According to Meier,
68
water is the single
most abundant component of bio oil, accounting for 15 wt%
30 wt% of the whole oil. Other major components include:
40 wt% GC-detectable organic compounds; 15 wt% non-vola-
tile HPLC detectable compounds; and 15 wt%25 wt% of high-
molecular-weight compounds. Major organic compounds
classes identified in bio-oil are hydroxyaldehydes, hydroxy-
ketones, sugars, carboxylic acids, and phenolics,
69
with most
of the phenolic compounds present as oligomers with mole-
cular weights ranging from 900 to 2500 AMU.
66,70
A comprehensive approach to bio-oil analysis has been pro-
posed by the VTT research group
44
in which water content is
determined by Karl-Fischer titration: the high-molecular-
weight, water insoluble compounds collectively termed pyro-
lytic lignin are precipitated by mixing small amounts of bio-
oil with water and measuring the subsequent precipitate
weight. The pyrolytic lignin is a fraction composed of many oli-
gomeric fragments originating from the biomass lignin. The
most extensive studies on characterization and analysis of this
material were done by the Institute of Wood Chemistry in
Hamburg.
7174
GC/MS analysis has been used extensively to identify and
quantify the volatile components of bio-oils. The most compre-
hensive results are those published by Branca et al.,
58
Garca-
Prez et al.,
75
and Azeez et al.
76
Azeez quantified 80 com-
pounds that accounted for 36.3 wt% of beechwood bio-oil and
44.0% of corn cob bio-oil. Piskorz et al.
69
used HPLC analysis
of water-soluble fractions to determine types and amounts of
varied carboxylic acids, hydroxyaldehydes, ketones, and carbo-
hydrates that were not quantified by gas chromatography. The
most abundant organic components of bio-oils that have been
reported in these studies are generally hydroxyacetaldehyde,
acetic acid, formic acid, acetol, glyoxal, levoglucosan, and
cellobiosan.
A simplified approach to bio-oil characterization uses func-
tional group analysis. Radlein
77
provided the results shown in
Table 4 obtained by Nicolaides
78
for the primary functional
group content of bio-oils produced from dierent feedstocks
using appropriate chemical analysis methods.
Interesting information on bio-oil composition was also
obtained from
13
C NMR analysis that provides data on bio-oil
carbon distribution between dierent types of functionalities.
Table 4 Group distribution in bio-oils produced from dierent feedstocks
75
Feedstock
Moles functional groups per kg organic liquid
Carboxyl Carbonyl Hydroxyl
a
Phenolic Methoxy
Maple 2.1 5.7 0.92 2.8 2.1
Wheat straw 1.4 5.3 1.40 3.0 1.1
Poplar-Aspen 2.1 6.2 0.77 2.8 1.6
Peat moss 1.2 3.0 1.30 1.8 0.7
a
Hydroxyl contents may be underestimated as the phthalic anhydrate method used here is not very reliable for analyzing hydroxyl groups
attached to adjacent carbon atoms.
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Ingram et al.
79
gathered the results in Table 5 for several bio-
oils produced in an auger pyrolyzer. These data show a signifi-
cant dierence in the composition of bio-oil obtained from
wood and from bark, especially for carbonyl and aliphatic
compound content.
Because of the extensive variation in bio oil chemical pro-
perties, several fractionation methods have been used to facili-
tate the chemical analysis of these complex liquids. One
successful approach is based first on solvent extraction using
water followed by dierent polarity organic solvents such as
ether and dichloromethane. Oasmaa et al.
22
analyzed bio-oils
produced from forest residues using this method in which
seven distinct fractions were obtained consisting of:
1. High-molecular-weight lignin
2. Low-molecular-weight lignin
3. Extractives
4. Sugars
5. Water
6. Aldehydes, ketones, and lignin monomers
7. Acids, alcohols, other volatiles.
Based on currently available analyses of bio-oils, Radlein
77
presented the bio-oil composition considering both compound
class and associated size of molecules as shown in Table 6.
Two-dimensional gas chromatography coupled with time of
flight mass spectrometry (2D GCxGC/TOFMS) and two-dimen-
sional flame ionization detection (2D GCxGC/FID) have been
recently applied to more comprehensively characterize bio-oil.
The ability to spatially separate polar from nonpolar com-
pounds with selective detection expands the range of volatile
oil compounds that are analyzable with this technique.
Other recent work characterizes chemical changes via func-
tional groups in raw bio-oils using both 2D GCxGC/TOFMS
and 2D GCxGC/FID. As shown in Fig. 4,
80
major functional
groups can be identified using these techniques comprising
sugars, aromatics, phenols, aldehydes, ketones, furans and
benzenediols. The combined method provides both quantitat-
ive (FID) and qualitative (TOFMS) information on raw and
treated oils for 150 discrete peaks that comprise more than
80% of the total peak area. Further work on raw and hydro-
deoxygenated (HDO) pyrolysis oils using 2D GCxGC/TOFMS
identified 250 and 350 analytes, respectively, for the raw and
treated oils that described greater than 75% of total peak area.
These GC techniques give promise for the rapid determination
of the composition of both raw and upgraded pyrolysis oils
and are potentially very useful tools for exploratory catalyst
research and for reaction mechanism and kinetic studies.
81
In summary, because of the chemically complex nature of
fast pyrolysis bio-oils, comprehensive compositional analysis
remains a very challenging task that requires application of
multiple analytical techniques. Despite significant progress,
about 20% of the bio-oil composition is still unknown. Based
on the behavior of this material (non-volatile, water insoluble,
ether insoluble), it is likely the unidentified fraction is mostly
comprised of polyols derived from the thermal decomposition
of polymeric carbohydrates. However, no direct evidence cur-
rently exists to confirm this hypothesis. The emerging two-
dimensional GC techniques are rapidly changing how bio-oils
are characterized and, when used with other analytical tech-
niques, may provide powerful new tools for comprehensive
chemical characterization of these unique and complex renew-
able materials.
2.4 Properties of oils
Several physical and physico-chemical properties of raw
biomass pyrolysis oil make it unsuitable for use in petroleum
refineries; for the most part these undesirable properties are a
result of the high oxygen content and the particular oxygen
functionality present in bio-oil. In particular, many of the com-
ponents of pyrolysis oil are not soluble in organic solvents,
Table 5 Distribution in bio-oils produced in an auger reactor
Type of carbon
Carbon content (% of all bio-oil carbon)
Pine wood
oil
Pine bark
oil
Oak wood
oil
Oak bark
oil
Carbonyl 11.8 0.5 18.1 2.4
Aromatic 48.4 43.9 40.1 35.3
Carbohydrate 5.8 1.4 10.3 2.1
Methoxy/hydroxy 16.1 20.8 16.1 12.5
Alkyl 17.9 33.4 15.5 47.7
Table 6 Compound classes in bio-oil
Compound Class
Composition range
Wt% of organic
bio-oil fraction
C
1
compounds (formic acid, methanol,
formaldehyde)
510
C
2
C
4
linear hydroxyl and oxo
substituted aldehydes and ketones
1535
C
5
C
6
hydroxyl, hydroxymethyl and
oxo substituted furans, furanones,
and pyranones
1020
C
6
anhydrosugars and
anhydrooligosaccharides
610
Water soluble carbohydrate derived
oligomeric and polymeric material
of unknown composition
510
Monomeric methoxyl substituted
phenols
615
Pyrolytic lignin 1530
Fig. 4 Group type analysis of the crude bio-oil.
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which is a potential barrier to co-processing with petroleum.
Of additional concern are the following:
1. High water content.
2. Pyrolysis oil contains a significant amount of particulate
matter that can foul catalysts.
3. The pyrolysis oils are reactive, particularly at elevated
temperatures, which results in increased viscosity.
4. Raw pyrolysis oils can have high viscosity, which as noted
can increase during storage and handling. This can lead to
poor flow characteristics and plugging, particularly in distilla-
tion units.
5. Pyrolysis oils have low volatility, leading to high amounts
of residue upon fractional distillation.
6. Pyrolysis oils are more corrosive than petroleum feed-
stocks and can damage the reactors and transfer lines.
Table 7 shows some of the specifics of pyrolysis oil properties
that are relevant to introduction into a refinery;
16,18,43,44,8190
these properties are discussed in more detail below.
2.4.1 Water content. Water is the most abundant com-
pound in biomass pyrolysis oil with typical loadings of 15 wt%
to 30 wt%. At these loading ranges, the pyrolysis oil does not
separate into aqueous and oil phases, but remains as a single-
phase pseudo-emulsion. This emulsion is thought to be facili-
tated by hydrogen bonding due to the oxygen content of most
of the organic species in pyrolysis oil. The oxygen-containing
functional groups on these compounds can form hydrogen
bonds to water molecules and facilitate the formation of a
stable emulsion. Imaging
91
has shown that 510 m aqueous
droplets are found in these emulsions. At weight loadings
greater than 30%, separation of water and oil occurs and two
phases are seen. The water in the bio-oil results from moisture
in the biomass plus water formed by dehydration reactions
occurring during pyrolysis. The impact of water content on
refinery integration is a key issue that needs to be investigated.
Water in the pyrolysis oils will decrease the viscosity of bio-oil,
but the presence of water can be damaging to some of the cata-
lysts used in the downstream unit operations used for upgrad-
ing bio-oil Phase separation and water extraction may be an
approach for reducing water in the oil phase, but will likely
remove a significant amount of the organic material and will
increase the waste water clean-up demands.
2.4.2 Solids. Particulate matter is generated by pyrolysis
and in spite of attempts to filter this material with cyclones,
some of the solid material is carried into the pyrolysis
oil.
44,51,87,88,91,92
In addition, there is evidence that particulate
matter is formed during bio-oil condensation
66
and aging of
pyrolysis oil. Particles found in pyrolysis oil vary from nan-
ometer to micrometer sizes. Fig. 5 shows three measurements
of size distribution in pyrolysis oil
87
for particles greater than
1 m. The nanometer-sized particles have been observed in
imaging studies of pyrolysis oil and are thought to be an
important component of the micro-emulsion. The solids could
be from char formed during pyrolysis, sand or other heat
transfer material, polymerized pyrolysis products, or inorganic
material from the biomass. The presence of these materials is
problematic because:
1. They can facilitate aging and polymerization of the pyrol-
ysis oil.
51
2. They increase viscosity.
3. They can plug transfer lines and damage pumps.
4. They can deactivate catalysts.
A recent study by the National Renewable Energy Laboratory
has shown that application of hot gas filtration to pyrolysis
vapors prior to condensation is eective for producing a bio-
oil with very low particulate content, and with very low concen-
trations of alkali and alkaline earth metals.
48
The stability of
the hot gas filtered oil was also found to be greatly improved
when compared to unfiltered oil as discussed in the following
section.
2.4.3 Stability and aging. Bio-oil is not a product of ther-
modynamic equilibrium during pyrolysis, but is produced
with short reactor times and rapid cooling or quenching from
the pyrolysis temperatures. This produces a condensate that is
also not at thermodynamic equilibrium at storage tempera-
tures. Bio-oil contains many oxygenated organic compounds
with a wide range of molecular weights, typically in small per-
centages. During storage, the chemical composition of the bio-
oil changes toward thermodynamic equilibrium, resulting in
changes in the viscosity, molecular weight, and co-solubility of
its many compounds.
Table 7 Properties of biomass pyrolysis oil
Property Notes
Water 15 wt%30 wt%
Viscosity 1380 cSt @ 50 C
Solids content 0.01 wt%1 wt%
Miscibility in
organic solvents
Poor
Stability Oil components polymerize,
particularly at elevated temperatures
Corrosivity pH 2.03.7, TAN 100
Distillation 30%50% residue
81,89
Density 1.2 g cm
3
Fig. 5 Three measurements of particle sized greater than 1 mm from
the pyrolysis of forest residue.
87
Reprinted with permission from
A. Oasmaa, C. Peacocke, A guide to physical property characterisation of
biomass derived fast pyrolysis liquids, VTT Publications, 2001, vol. 450,
pp. 1102. Copyright 2001 VTT Publications.
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The aging of biomass pyrolysis oil has been extensively
studied and has important implications for its use in refi-
neries. These studies have shown that chemical reactions in
the oil lead to increased water content, the evolution of light
gasses, greater tendency towards phase separation, increased
molecular weight, and increased viscosity. The rate of aging is
strongly dependent upon temperature,
9294
which also has
important implications for introduction into refinery unit
operations. Fig. 6 shows a plot of the viscosity and molecular
weight of pyrolysis oil. As can be seen, the viscosity increases
by roughly 50% in 80 days at 37 C, while the viscosity doubles
in 15 hours at 90 C. The concomitant increase in molecular
weight shown in this plot suggests that polymerization reac-
tions are occurring during aging. This type of increase in vis-
cosity and molecular weight has been observed by several
laboratories
9597
and was the subject of a recent round robin
study.
98
Most projected uses of bio-oil require that it retain these
initial physical properties during storage, shipment, and use.
However, some bio-oils rapidly become more viscous during
storage. Fig. 7 shows this increase for three bio-oils made from
three hardwoods using dierent pyrolysis conditions after
aging 3 months at 35 C to 37 C. These three bio-oils exhibit
very dierent initial viscosities and rates of viscosity increase.
The eect of aging on viscosity is greater at lower measure-
ment temperatures.
99
Because the viscosity change rates may be represented as
Arrhenius exponential functions of the inverse of absolute
temperature, chemical reactions appear to be involved. Fig. 8
shows that the bio-oils must be cooled quickly after being pro-
duced and then stored at low temperatures to maintain their
low viscosity.
In addition to simple viscosity increases, the bio-oil emul-
sion can separate into various tarry, sludgy, waxy, and thin
aqueous phases during aging. Tarry sludges and waxes still in
suspension have caused rapid plugging of fuel filters. They can
form during storage in previously filtered bio-oils and in
aqueous phases. Bio-oils seem to be more unstable during
storage than are petroleum-derived fuel oils, although there
appear to be many similarities in their mechanisms.
The reactions that occur in pyrolysis oil largely involve the
oxygen functionalities. Diebold discussed several types of reac-
tions
100
including:
Esterification: the reaction of organic acids with alcohols
to form esters and water.
Condensation reactions involving aldehydes and ketones
and water or alcohols.
Condensation reactions of aldehydes with phenols.
Condensation reactions involving furfurals.
Many of these reactions can also be catalyzed by solid
material in the bio-oil, such as inorganic material from the
biomass. Studies where the solids are filtered out show much
slower changes in viscosity.
51
These reactions reduce the
amounts of carbonyls and alcohols; increase the molecular
weight; and, with dehydration reactions, lead to water for-
mation. An increase in water concentration has been
observed,
93
and although increased water has been shown to
reduce viscosity,
88
this eect is overwhelmed by an increase in
molecular weight. Fig. 9 shows a plot of the observed trends in
pyrolysis oil,
98
which are consistent with the reactions dis-
cussed by Diebold
100
and which show that most of the aging
occurs during the first 3 months.
The reactivity of pyrolysis oil can be particularly proble-
matic for distillation operations. Polymerization and molecular
Fig. 8 Rate of viscosity increase with temperature during oil storage.
Fig. 6 Changes in the viscosity and molecular weight of pyrolysis oil
generated from oak in a vortex reactor.
93,94
Fig. 7 Aging of bio-oils at 35 C to 37 C.
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weight growth during distillation leads to the formation of
solid residue, particularly as the distillation pot is heated to
drive o dierent components. This eventually leads to the for-
mation of nonvolatile solid materials that form a solid residue.
This can result in up to 50% of the starting material remaining
as solid residue.
90
2.4.4 Viscosity. The viscosity of bio-oil as produced can
vary from as low as 25 cP to as high as 1000 cP (measured at
40 C) or more depending on the feedstock, the water content
of the oil, the amount of light ends that have been collected,
and the extent to which the oil has aged. Other researchers
have found that polymerization reactions that lead to viscosity
increases are accelerated at higher storage temperatures, and it
has been shown that the rate of change in viscosity can
increase from 0.009 cP per day when stored at 20 C to more
than 300 cP per day at 90 C.
101
Bio-oil is more viscous than crude oil at room temperature;
however, its viscosity is very similar to that of crude oil in a
temperature range of 35 C45 C.
102105
To transport the bio-
oil in pipelines, the temperature of the pipeline should be
maintained in the range of 35 C45 C to keep the viscosity
similar to that of crude oil.
104,105
Bio-oil produced from P.
indicus and F. mandshurica had a kinetic viscosity of 70350 cP
and 1070 cP separately. Bio-oil produced from rice straw had
a minimum kinetic viscosity of about 510 cP, which is mainly
due to the rice straws high water content.
106
The lignin content of the original feedstock has a positive
influence on the molecular weight and viscosity of bio-oil.
34
Recently, Ertas and Alma
107
compared the average molecular
weight and molecular weight distribution of laurel extraction
residues bio-oil (664 g mol
1
and 1.52) and found they were
very close to those of switchgrass bio-oil of 658 g mol
1
and
1.49, respectively.
108
Simple methods such as adding polar solvents, diesel, or
other fuels can address some of the undesired bio-oil charac-
teristics described in this section. Polar solvents, such as
methanol or ethanol, can improve the volatility and heating
value and decrease the viscosity and acidity. Adding ethanol
improves the volatility, stability, and heating value and
decreases the viscosity, acidity, and corrosivity.
109
Blending
diesel or other fuels can positively impact oil viscosity.
110
Finally, application of hot gas filtration prior to condensation
oers a relatively simple method to produce a bio-oil with low
particulate content (essentially zero ash) and improved stabi-
lity with respect to increases in viscosity.
2.4.5 Corrosivity. The corrosivity of pyrolysis oil is primar-
ily due to its acidity, which is derived mainly (60%70%) from
the volatile acids and phenolic compounds. Measurements of
total acid number (TAN) of bio-oil samples show that values in
the 90100 range are fairly common, with a pH typically in the
range 23; TAN values of 150200 are not uncommon. The pK
a
values for the acids are the lowest of all the compounds in the
liquid, and this is the reason for the good correlation between
the TAN and the amount of acids as shown in Fig. 10. There
are also other groups of compounds in fast pyrolysis liquids
that influence acidity, like phenolics (5%10%) and fatty and
resin acids (<5%). The acidity of the sugar fraction, mainly
due to hydroxy acids, covers about 20% of the total acidity.
111
This level of acidity has been shown to cause corrosion pro-
blems for many materials. In particular, high corrosion rates
for carbon steel (AISI01) have been observed,
44,92
which would
be problematic for many refining operations. Further, the cor-
rosivity increases significantly at higher temperatures.
112
Several metal and polymer materials have been tested
113117
for resistance to corrosivity from pyrolysis oil and Table 8 col-
lects the result from one of the studies.
Fig. 9 Observed trends in compound classes during the aging of pyro-
lysis oil.
98
Reprinted with permission from D. C. Elliott, A. Oasmaa,
F. Preto, D. Meier, A. V. Bridgwater, Energy & Fuels, 2012, 26, 37693776.
Copyright 2012 American Chemical Society.
Fig. 10 Correlation of TAN with volatile acids, determined by capillary
electrophoresis (CE), in pyrolysis liquid.
111
Reprinted with permission
from A. Oasmaa, D. C. Elliott, J. Korhonen, Energy & Fuels, 2010, 24,
65486554. Copyright 2010 American Chemical Society.
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Keiser et al.
118
reported corrosion rates of structural
materials obtained with pyrolysis oils from varied feedstocks
and with varied TAN and carboxylic acid content. All three
samples contained significant concentrations of formic and
acetic acids as well. Metallic specimens were immersed in the
oil as well as in the vapor space above the oil with the oil at a
temperature of 50 C, which was considered to be the
maximum temperature the bio-oil would reach during storage
and transport. Weight change calculations showed significant
weight loss occurred in carbon steel and the 2
1
4
Cr-1 Mo
samples, and a hydrated iron formate corrosion product was
identified on the surface of these specimens. Calculated cor-
rosion rates for these alloys were much more than could be tol-
erated in any system that was expected to last for years. The
stainless steel specimens showed minimal weight change.
They also reported that stress corrosion was likely an active
mechanism for the lower chrome content steels. This result
emphasizes the need to control bio-oil TAN as storage and
pipeline material needs must be similar to materials currently
in use.
Technologies like hydrogenation, hydro-deoxygenation, and
other similar conventional processes address the high acidity
problem; however, they require large-scale plants and capital,
and exhibit substantial yield losses (up to 50%) mainly due to
the use of hydrogen. Torrefying the biomass feedstock has
resulted in 25% less acetic acid in the produced oil although
as mentioned previously torrefaction results in a loss of
carbon eciency.
119
Modifying raw bio-oils to reduce TAN and acid content has
been demonstrated by deoxygenating fast pyrolysis oils
via reaction with recycled product gas
120
in which a two-fold
reduction in oil oxygen content was achieved. These types of
recent improvements in reducing bio-oil acidity are needed
to reduce corrosivity and ensure infrastructure compatibility
as potential renewable hydrocarbon fuels and fuel
intermediates.
3. Upgrading biomass pyrolysis oil
As detailed in the previous section, biomass pyrolysis oil (bio-
oil) has many undesirable properties that make it unsuitable
for direct use as a fuel or as a feedstock for fuel manufacture.
Technologies and technical pathways for upgrading biomass
bio-oil into a more useful material can generally be broken
down into two categories:
1. Vapor-phase processes operating at low (atmospheric)
pressure using crystalline aluminosilicate catalysts.
2. High pressure catalytic hydrotreating.
Research on these two processing options is reviewed in the
following sections.
3.1 Ex-situ vapor-phase catalytic upgrading of whole bio-oil
Vapor-phase upgrading of whole bio-oil can be carried out via
either in situ or ex-situ processes. Catalytic fast pyrolysis, where
release of the primary pyrolysis vapors is accomplished in a
bed of catalytic material, is an example of the in situ upgrading
mode, while contacting of pyrolysis vapors resulting from
thermal fast pyrolysis with catalysts in a separate reactor is an
example of the ex-situ upgrading mode. This latter mode of
operation has several advantages, including the potential for
operating the upgrading reactor at dierent reaction con-
ditions (temperature, space time, reactive gases, etc.) than the
pyrolysis reactor. It also aords the opportunity to protect the
upgrading catalysts from deleterious alkali and alkaline earth
metals by using a solids separation step such as hot gas fil-
tration.
51
The ex-situ mode gives more flexibility in operation
and provides opportunities to optimize the process by tuning
the reaction conditions and improving thermal eciencies by
close-coupling of the pyrolysis and upgrading steps. The
remainder of this section will examine results of investigations
concerning ex-situ upgrading.
At temperatures of 350 C to 500 C with zeolite catalysts,
oxygenated organic compounds undergo cracking, dehy-
dration, decarboxylation, aromatization, alkylation, conden-
sation, and polymerization reactions. Dehydration is the
dominant mechanism when using acidic catalysts such as
ZSM-5; the product obtained while the catalyst is active is a
mixture of aromatic hydrocarbons and low molecular weight
olefins. The general scheme for upgrading bio-oil using cata-
lysts like ZSM-5 is shown in Fig. 11.
Ex-situ vapor-phase catalytic upgrading of whole oil and
model compounds representing the major oxygenated moi-
eties present in bio-oil produced by thermal pyrolysis has been
studied by several investigators.
121128
In a series of seminal
studies, Adjaye and Bakshi investigated bio-oil cracking in a
fixed-bed microreactor in a range of temperatures from 290 C
to 410 C
121123
over several dierent catalysts including
HZSM-5, H-Y zeolite, H-mordenite, silicalite, and amorphous
silica-alumina. These studies showed that hydrocarbon yields
ranged from a high of 27.9 wt% with HZSM-5 to only 5 wt%
with silicalite. At the higher temperatures studied, coke on
catalyst was significant ranging from a low of 15 wt% for
HZSM-5 to as much as 29 wt% for amorphous SiAl catalyst.
Table 8 Weight loss for materials stored in pyrolysis oil
90
Material Weight loss (wt%)
Polymers
Teflon 0.000
Steels
AISI01 0.823
AISI316 0.000
AISI420 0.191
HASTELLOY X 0.012
NIMONIC 80A 0.002
HAYNES 188 0.000
ARCLOK 0.006
Metals
Copper 0.000
Chromium 0.000
Nickel 0.004
Alloys
NIKROTAL 0.005
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These high levels of coke-make severely impact the carbon
eciency of ex-situ cracking strategies. Other studies have con-
firmed that zeolites such as ZSM-5 are moderately eective in
transforming model compounds representative of biomass
pyrolysis vapors to hydrocarbons.
122,129
Chang et al.
130
showed
that adding hydrogen-rich compounds with a high eective
hydrogen index could radically reduce the coke-make
observed during ex-situ catalytic upgrading while simul-
taneously improving the hydrocarbon yield over crystalline alu-
minosilicate catalysts. A dierent approach to vapor-phase
catalytic upgrading of bio-oil was reported by Vispute et al.,
who describe an integrated hydroprocessing plus ex-situ cata-
lytic upgrading scheme.
128
Their approach involves increasing
the eective hydrogen index of bio-oil by hydroprocessing first
followed by subsequent catalytic upgrading over zeolites.
Several studies have been conducted on model compounds
to elucidate which of the oxygenated molecules in bio-oil are
challenging to upgrade using this technical pathway. Using a
fixed bed of HZSM-5 catalyst, high conversions (>90%) were
obtained for alcohols, aldehydes, ketones, acids, and esters
while phenols and ethers remained mostly unchanged. Alco-
hols and ketones reacted to produce high yields of aromatic
hydrocarbons.
124127,131
Acids and esters were mostly con-
verted to gas, water, and coke with low hydrocarbon yield. The
hydrocarbon production was the lowest and coke formation
the highest for oxygenated organic compounds with a low
eective hydrogen index.
3.2 Catalysts for ex-situ vapor-phase upgrading of bio-oil
When zeolites are used to deoxygenate biomass pyrolysis oils,
hydrocarbon yields of 10 wt% to 30 wt% have generally been
reported; however, high coke production and rapid catalyst de-
activation were also observed,
131133
which is consistent with
the hydrogen deficiency of bio-oil (eective hydrogen index of
ca. 0.3). Results of laboratory investigations for upgrading
whole bio-oil on a suite of catalysts with varying acidity includ-
ing HZSM-5, H-Y zeolite, mordenite, silicalite, and amorphous
silicaalumina have been reported by a number of investi-
gators.
122,134,135
NREL pioneered an integrated process in
which vapors from a biomass pyrolyzer were fed to a catalytic
reactor containing HZSM-5 and converted to aromatic and ole-
finic hydrocarbons.
136,137
Using a pilot-scale vortex reactor in
series with a fixed bed of commercial Mobil MCSG-2 catalyst at
450 C, a total hydrocarbon yield of 12.7 wt% based on wood
feedstock was achieved, which is about one third of the theore-
tical yield. Excessive coking was observed due to the high
acidity of the HZSM-5 catalyst, which enhanced dehydration
reactions. The presence of transition metals has been shown
to aect the mode of oxygen rejection by producing more
carbon oxides and less water, thus making more hydrogen
available for incorporation into hydrocarbons.
138
3.3 Hydroprocessing
Bio-oil can be converted to a gasoline- or diesel-like liquid by
catalytic hydroprocessing using catalysts and conditions that
are similar to those used in petroleum hydrodesulfurization,
hydrotreating, and hydrocracking processes.
139
Several
Fig. 11 Pyrolysis of biomass and upgrading of bio-oil using ZSM-5.
Defined as (H/C)
e
= (H 2O)/C, where H, C, and O represent the number of
moles of hydrogen, carbon, and oxygen per unit mass sample.
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excellent reviews highlight the history, current status, and
technical challenges associated with hydroprocessing bio-
oil.
139143
Elliott reported that hydroprocessing whole bio-oil
in a single-stage hydrotreater gave rise to severe product loss
due to coking; hence, a two-stage process was developed. In
this improved process, the oil was stabilized at a lower tempera-
ture (150 C280 C) before it was fed to a high temperature
reactor (350 C400 C) where the majority of the oxygen removal
took place. Standard petroleum industry hydrotreating catalysts
were used including both nickel-molybdenum (NiMo) and cobalt-
molybdenum (CoMo) on a -alumina support; the upgraded
product represented 30 wt%50 wt% of the crude bio-oil.
144
Several, detailed economic studies have been published for
this process
145148
assumed the bio-oil was produced in a cir-
culating fluidized bed at a feed rate of 2000 bone-dry metric
tons per day of wood chips at a cost of $50.7 per ton. The oil
was then upgraded in two stages at temperatures of 240 C
370 C and 20152500 psig pressure to produce 44 wt% hydro-
treated oil containing 1.5 wt% oxygen. Hydrogen consumption
was assumed to be 5 wt% of the feed. This product oil was
then hydrocracked as necessary and separated into gasoline
and diesel streams. The projected minimum fuel-selling price
was $2.04 per gal ($1.34 per gal ethanol equivalent). This
could be reduced to $1.74 per gal ($1.14 per gallon ethanol
equivalent) by co-locating the plant with a petroleum refinery
to take advantage of the refinerys low-cost hydrogen and
large-scale hydrocracking capacity. While these projections are
promising, other studies have concluded that the process was
too expensive to compete with conventional crude oil because of
the large amount of hydrogen consumed, low product yields,
low quality products that would require further upgrading in a
refinery, and the corrosivity of the raw oil.
149
A recent technoeco-
nomic analysis for hydroprocessing of bio-oil produced by mild
catalytic pyrolysis
146
suggested that the most probable fuel
price for transportation fuels was $3.03 per gal for this pathway.
Another recent study was carried out to obtain an assess-
ment of the process economics in light of incremental
improvements to the bio-oil catalytic hydrodeoxygenation
process, changes in refining requirements ( particularly
increased hydrodesulfurization requirements), and changes in
petroleum prices. This report suggested that costs could be sig-
nificantly reduced by mildly hydrotreating the bio-oil and then
co-processing the partially deoxygenated products with pet-
roleum-derived material in a refinery.
150
The authors rec-
ommended reducing the severity of HDO to leave about 7 wt%
oxygen in the bio-oil, thus avoiding hydrogenating aromatics
while reducing hydrogen consumption, catalyst costs, and
hydrotreater capital costs. The residual acidity of the oil could
then be accommodated by diluting with crude oil or an
internal refinery stream (naphtha, gas oil, etc.).
Various blending strategies could be employed, with
material derived from mild hydroprocessing of bio-oil blended
and co-processed with petroleum-derived material using exist-
ing refinery unit operations to carry out additional deoxygena-
tion required to maintain acceptable product quality for the
final fuels. For this strategy to work, a number of important
criteria must be met by the products from mild hydrotreating:
(1) the acidity of the bio-oil must be reduced from the typical
TAN value of over 100 to about 15, assuming that hydrotreated
bio-oil would be blended in a 1 : 8 ratio (acidity of blend less
than 2 mg KOH per g oil
150
). (2) The hydrotreated bio-oil must
be completely miscible with hydrocarbons. (3) The hydro-
treated bio-oil must be suciently volatile so that it is amen-
able to fractional distillation (some high-boiling residue is
acceptable). If hydrotreated bio-oil is to be co-processed in the
refinery, information on the composition and concentration of
oxygenates in the bio-oil-derived hydrotreated products is criti-
cal to ensure that product quality is maintained.
Other studies have highlighted the relationship between
total oxygen, oxygen functional groups, acidity (TAN), hydro-
carbon miscibility, and hydroprocessing severity for a bio-oil
that had been hydroprocessed to various levels of oxygen
content;
151,152
these results are reviewed in section 5 of this
document. Co-processing bio-oil with petroleum in refinery unit
operations such as the FCC and hydrotreaters is also reviewed in
section 5 (below). Mild hydrotreating and mild HDO of bio-oil
has also been investigated by Venderbosch et al., who rec-
ommend a multi-stage reaction scheme for upgrading bio-oil.
153
3.4 Bio-oil hydroprocessing catalysts
Many studies have been carried out concerning the impact of
catalyst formulation on hydroprocessing and hydrodeoxygena-
tion of whole bio-oil and model compounds representative of
the major oxygenated moieties in bio-oil. Mortensen et al.
139
have recently summarized the important findings for a broad
range of standard and novel hydroprocessing catalysts. Several
investigations have been carried out using industrial pet-
roleum hydroprocessing catalysts such as Co-MoS
2
and Ni-
MoS
2
on a -alumina support.
154156
Wildschut et al.
157
reported that catalyst formulations containing Pt, Ru, and Pd
supported on carbon gave superior results for HDO of whole
bio-oil, while maintaining high yields of upgraded products
when compared to standard cobalt- and nickel-moly sulfide
catalysts. Other novel catalytic materials have been recently
reported for hydroprocessing bio-oil and HDO of representa-
tive oxygenated model compounds including WO
3
, NiCu/CeO
2
,
and phosphides of nickel, cobalt, iron, tungsten, and molyb-
denum supported on SiO
2
.
158160
The impact of the support on bio-oil hydroprocessing cata-
lysts has also been investigated. Standard petroleum refining
catalysts normally utilize alumina (Al
2
O
3
) as the support
material, but this is unsuitable for bio-oil upgrading as
alumina is unstable in high water environments. As alterna-
tives to alumina, zirconia (ZrO
2
), silica (SiO
2
), and ceria (CeO
2
)
have been identified as promising stable carriers for transition
metals used in hydroprocessing bio-oil.
161,162
Other investi-
gations have focused on the use of carbon as a support
material.
163,164
Since carbon is relatively neutral (in compari-
son to the more acidic alumina, zirconia, or ceria materials),
the tendency to promote coke-on-catalyst is reduced when
carbon is used as the support. However, regeneration of
carbon-supported catalysts can be problematic as techniques
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based on oxidation of poisons cannot be used for these
materials.
3.5 Problems and issues associated with upgrading bio-oil
Upgrading bio-oil produced by thermal fast pyrolysis of
biomass to a more useful hydrocarbon-like product essentially
involves removing organic oxygen, reducing the average mole-
cular weight, and increasing the atomic hydrogen-to-carbon
ratio. Water produced by dehydration reactions occurring
during pyrolysis also needs to be removed. Reducing organic
oxygen will lower the acidity of the upgraded bio-oil and will
also improve the volatility of the product towards fractional
distillation. When oxygen is removed by catalytic cracking, the
primary oxygen rejection mechanisms are dehydration
accompanied by significant decarboxylation and decarbonyla-
tion (loss of oxygen as CO
2
and CO, respectively). These reac-
tions result in poor carbon eciency with respect to carbon in
the feed being translated into carbon in the upgraded product
and a hydrogen-deficient product with low quality (low H/C
ratio). Typical carbon eciencies for catalytic cracking of
whole oil are approximately 15 wt%20 wt% for upgraded oil,
with 20 wt%30 wt% of the feed carbon going to light gases
and the remainder to coke. Hydroprocessing removes organic
oxygen primarily as water, giving better carbon eciencies but
at the expense of the necessity of providing gas-phase mole-
cular hydrogen. Carbon eciencies for hydroprocessing are
approximately 30 wt% to 50 wt% for converting carbon in the
feed to carbon in the upgraded oils. Approximately 10 wt%
30 wt% of the carbon in the bio-oil is converted to gaseous
products during hydrotreating, with the remainder lost as
coke.
While carbon eciencies are important metrics for bio-oil
upgrading processes, capital and operating costs for the
upgrading operation must also be considered. Catalytic vapor-
phase upgrading of bio-oil is typically carried out at ambient
pressure, at relatively low temperatures (300 C500 C), and in
the absence of added gas-phase molecular hydrogen. Some
researchers have suggested that adding hydrogen-rich and/or
hydrogen transfer molecules can improve the carbon eciency
of catalytic vapor-phase upgrading,
130
but this will increase
cost and add additional complexity to the operation due to
consumption of added chemicals and/or the need to recover
and re-use the hydrogen shuttlers. Hydroprocessing, on the
other hand, is done at moderate temperatures (350 C450 C)
but at high pressure (>100 atm.) and in the presence of gas-
phase molecular hydrogen. Hydrogen consumption during
bio-oil hydroprocessing varies widely with operating severity
and the source of the bio-oil; a comparison of hydroprocessing
parameters for bio-oil and various petroleum fractions is
shown in Table 9. Reported hydrogen consumptions for hydro-
treating bio-oil vary widely and will depend largely on the
degree of deoxygenation required for the final product.
153
All of these factors result in significant additional costs for
hydroprocessing due to high capital costs associated with the
upgrading reactors and (especially) hydrogen manufacture. A
recent study
150
by the Global Energy Management Institute on
upgrading bio-oil concluded that upgrading costs for hydro-
processing would be in the range of $25 to $40 per BBL
depending on the oxygen content for the final product for a
single stand-alone upgrading facility processing the output of
one pyrolysis plant (Fig. 12). Finally, upgrading by either
vapor-phase or hydroprocessing technologies will involve
rapidly deactivating catalysts, which must be regenerated fre-
quently to maintain activity. Regeneration of vapor-phase
upgrading catalysts can be accomplished readily using recircu-
lating reactor/regenerator technology as is currently practiced
in the fluid catalytic cracking of gas oil in the petroleum refin-
ery. Costs associated with regenerating fixed-bed bio-oil hydro-
treaters would be expected to be particularly high; moving-bed
reactor technology may have to be applied to maintain accepta-
ble hydrotreating activity.
150
4. Standard renery needs and
quality metrics and impact of bio-oil
4.1 Petroleum hydrocarbon chemistry
A brief introduction to petroleum hydrocarbon chemistry is
helpful before initiating discussions on crude oil and pet-
roleum refinery operations. This section of the report focuses
on
165
identifying the various types of hydrocarbons present in
petroleum refineries and
166
general trends of hydrocarbon
bulk properties. This section also includes a discussion of the
eects of bio-oil constituents on these bulk properties.
There are four major types of hydrocarbons present in the
feedstocks to or intermediate streams found in a petroleum
refinery, following the acronym PONA as follows:
Table 9 Hydroprocessing conditions for dierent feedstocks
153
Feed
Severity T (C) : P (bar) :
LHSV (h
1
)
H
2
Consumption
(Nm
3
m
3
feed)
Naphtha 260350 : 1535 : 25 210
Light oil 290400 : 1735 : 25 1550
Heavy oil 350425 : 70140 : 13 70170
Residuum 350425 : 70140 : 0.151 100200
Bio-oil 350450 : 100170 : 0.11 200800
Fig. 12 Eect of plant size on hydrotreating cost.
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Parans: normal and iso-parans (or alkanes) are naturally
occurring molecules in crude oil.
Olefins: olefins (or alkenes) are not naturally occurring in
crude oil, but they are formed in several conversion processes
of a typical petroleum refinery.
Naphthenes: naphthenes (or cyclo-parans/cyclo-alkanes)
are naturally occurring molecules in crude oil.
Aromatics: aromatic compounds do not naturally occur in
petroleum, but are formed during processing.
In addition to the major categories of chemical species
found in the petroleum refinery, it is also important to under-
stand the major trends in physical properties among these
species as functions of carbon number, the number of carbon
atoms present in a particular molecule.
The first of these trends is boiling point, which is presented
in Fig. 13 for a wide range of hydrocarbon compounds includ-
ing normal parans, naphthenes, and aromatics, as a func-
tion of carbon numbers. The trend clearly shows that boiling
point closely correlates with a carbon number. The scatter
associated with the data, around C10 single-ring aromatics for
example, represents the impact of structural variations
between molecules of the same carbon number on the boiling
points. For example, the boiling point of isobutylbenzene
(173 C) is lower than its isomer with the same molecular
formula, 1,2,3,4-tetramethylbenzene, which boils at 205 C.
As will be discussed below, much of the processing in a
refinery is based upon the boiling point of the cut that is
being processed. As Fig. 13 shows, the hydrocarbon molecules
in a particular boiling range have essentially the same number
of carbon atoms. However, the boiling points for oxygen-con-
taining organic molecules that are typical of those found in
pyrolysis oil are considerably higher than the hydrocarbons.
Therefore, a boiling point cut containing oxygenated com-
pounds from pyrolysis oil will necessarily contain molecules
with shorter carbon chains than is typical for hydrocarbons.
Another important trend to identify is that between carbon
number (or boiling point) and density for the various types of
hydrocarbons present in the refinery. Fig. 14 presents density
trends (as API gravity) for n-parans, naphthenes and single
ring aromatics. The two most important observations from
Fig. 14 are that density increases with (1) increasing carbon
number for similar chemical structures, and (2) decreasing
hydrogen to carbon ratio.
The trend of increased hydrocarbon density with decreasing
hydrogen-to-carbon ratio is also shown with the C
6
compounds
below. The lowest density compound, n-hexane, contains the
highest H/C ratio, while the highest density compound,
benzene, has the lowest H/C ratio. Understanding this
phenomenon is critical to the refining industry as product
sales are on a volumetric basis (barrels or gallons). Equal
masses of n-hexane and benzene will represent significantly
dierent volumes of the respective compounds. For example,
1 kilogram of n-hexane equals approximately 1.5 liters of
product while 1 kilogram of benzene equals only 1.1 liters of
product.
Fig. 13 Boiling points of hydrocarbons versus carbon number.
167
The
plot also contains the boiling points of 57 oxygen-containing organic
molecules that are typical of those found in biomass pyrolysis oil. A list
of these molecules and their properties is provided in the supplemental
material.
Fig. 14 API gravities of hydrocarbons versus carbon number.
167
The
gravity for the 57 representative oxygen-containing compounds are
shown in the black squares. Several of these oxygenated compounds as
well the compound classes are called out. DME = dimethyl ether, MEE =
methylethyl ether, DEE = diethyl ether, MTBE = methyl tert-butyl ether,
FA = formic acid, AA = acetic acid, PA = propionic acid, Fur = furfural,
DEGly = diethylene glycol, TEGly = tetraethylene glycol, PGly = propy-
lene glycol, PhOH = phenol.
API gravity or API = 141.5/specific gravity 131.5.
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Fig. 14 also shows the API gravity for the 57 compounds
that are representative of oxygenates in biomass pyrolysis oil.
As can be seen, the ethers have gravities similar to
naphthenes; aldehydes, ketones and alcohols have gravities
between aromatic compounds and naphthenes; and the gravi-
ties for esters and acids are smaller than aromatic compounds.
Several of the compounds, such as polyols, phenols, and fur-
fural are significantly lower than hydrocarbons. This shows
that the oxygenates will require significant upgrading (hydro-
treating) to reach the gravities of paranic fuels.
Another important aspect of hydrocarbon chemistry is the
increasing number of existing isomers, dierent hydrocarbon
structures with the same molecular formula, as a function of
carbon number. For example, the number of C
5
paran
isomers is 3, the number of C
8
paran isomers is 18, the
number of C
11
paran isomers is 159, and so on. Crude oil
and petroleum refinery streams contain compounds up to the
C
40
range, representing a very large number of dierent hydro-
carbon compounds.
This ability to profitably process complex mixtures of
organic molecules suggests that refineries are well suited to
handle bio-oil mixtures. However, the oxygen content of the
bio-oil will introduce uncertainty into existing refiner oper-
ations. The existing oxygenated compounds in petroleum are
typically furans, quinone, phenols, and some carboxylic acids
and are present in concentrations under 1 wt%. The oxygen in
petroleum crude is treated as a contaminant that is removed
during hydrotreating.
4.2 Refinery overview
The simplified process flow diagram presented in Fig. 15 rep-
resents a typical, high-conversion U.S. petroleum refinery to be
referenced throughout the following discussions. The term
high-conversion, applied to the configuration in Fig. 15,
refers to the presence of all major conversion processes fluid
catalytic cracker or FCC, coker, and hydrocracker. Not all refi-
neries possess each of these process units and a refinerys con-
version capabilities are measured on the processing capacities
of these conversion units relative to the crude fractionation
capacity of the refinery. The fact that the refinery is noted as a
U.S. refinery is also important. A refinery is designed to meet
a specific product market distribution based on demand and
available crude oils in that region. The European product
demand is very dierent than that of the United States and,
therefore, typical refinery configurations are dierent as well.
As shown in Fig. 15, the major processing steps of a typical
U.S. petroleum refinery are as follows:
4.2.1 Fractionation. The first major processing step in the
petroleum refinery is the fractionation of the crude oil into
various petroleum fractions or cuts. Fractionating the crude oil
is accomplished by distillation in the Atmospheric Distillation
and Vacuum Distillation columns as shown in Fig. 15. In these
two distillation columns, the crude oil is fractionated into five
major cuts as follows:
(1) Butanes and lighter: the stream labeled Gas from the
Atmospheric Distillation column in Fig. 15 represents the
butanes and lighter materials from the crude oil. This fraction
of the crude oil includes a mixture of C
4
hydrocarbons
(butanes, butenes), C3 hydrocarbons ( propane, propene), and
any other light ends (ethane, methane). The C3s and C4s are
often recovered and are referred to as LPG, or liquefied pet-
roleum gas.
(2) Naphthas: represented by the Light Naphtha and
Heavy Naphtha streams from the Atmospheric Distillation
column, the naphtha materials include C
5
hydrocarbons
through boiling points of approximately 165 C, corresponding
roughly to C
10
hydrocarbons. Light Naphtha includes C
5
hydro-
carbons up to boiling point of 75 C while Heavy Naphtha
includes hydrocarbons in the 75 C to 165 C boiling range.
Naphtha materials typically contribute to gasoline products
after processing in the refinery.
(3) Middle distillates: the middle distillate materials from
the crude oil include the Jet Fuel Kerosene and Diesel Oil
fractions from the Atmospheric Distillation column.
Kerosene: the kerosene cut includes hydrocarbons in the
boiling range of 165 C to 250 C, corresponding roughly to
hydrocarbons in the C
10
to C
14
range. The kerosene cut from
the crude unit can contribute to jet fuel, gasoline, and diesel
fuel products after refinery processing.
Diesel: the diesel cut includes hydrocarbons in the boiling
range of 250 C to 340 C, corresponding roughly to hydrocar-
bons in the C
14
to C
20
range. The diesel cut from the crude
unit can contribute to diesel fuel or heating oil products after
refinery processing.
(4) Gas oils: the term Gas Oil applies to hydrocarbons in
the boiling range of 340 C and 540 C. The gas oil fraction as
defined for this discussion includes the Atmospheric Gas
Oil, Light Vacuum Gas Oil, and Heavy Vacuum Gas Oil
streams from Fig. 15.
(5) Residue: the term Resid applies to hydrocarbons
boiling above 540 C. This stream is identified as Vacuum
Resid in Fig. 15.
Gas oils and resids contain materials that are too heavy
(high molecular weight, high boiling points) to contribute to
the typical refinery products like gasoline and diesel. These
materials must be processed in the refinery to reduce the
molecular weights in order to produce intermediates that boil
in the range of streams used for production of fuels.
The term cut point refers to the distillation temperature
at which one petroleum fraction ends and another begins. For
example, the cut point between heavy naphtha and kerosene
in this discussion is 165 C. The cut points between the
various petroleum fractions vary from one refinery to the next
depending on product slate and refinery capabilities.
After crude oil fractionation, each fraction or cut is sent to
an appropriate destination for further processing.
4.2.2 Treating/finishing processes. Treating and finishing
processes are generally designed to improve a specific physical
property of a stream or remove impurities from a stream. The
light fractions from the crude oil butanes and lighter,
naphthas, and middle distillates are the streams that typi-
cally enter the treating and finishing steps after fractionation.
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The treating and finishing processes of a typical petroleum
refinery are described briefly as follows:
Gas processing: these processing steps include light hydro-
carbon separation and product recovery through multiple dis-
tillations (deethanizer, depropanizer, debutanizer, butane
splitter, etc.). Typically, the C
4
(butanes and butenes) and
lighter streams are separated into several saleable products
like propane, propylene, iso-butane, mixed butanes and
butenes (C
4
olefins), and LPG. The light gases C
2
and lighter
generally contribute to refinery fuel gas.
Hydrotreating: hydrotreating operations fall into a broader
category of hydroprocessing, which will be described in detail
in later sections of the report. The major objective of a hydro-
treating process is to remove impurities in hydrocarbon
streams like sulfur, nitrogen, and oxygen. These impurities
must be removed from the hydrocarbons to meet product
blending specifications and to minimize undesired catalyst
poisoning in various locations of the refinery.
4.2.3 Conversion processes. The hydrocarbons present in
the heavy petroleum fractions like gas oils and residue are
much too high in molecular weight to contribute to high-value
products like gasoline and diesel fuel. These heavy petroleum
fractions are also typically hydrogen-deficient relative to the
hydrogen-to-carbon ratios of gasoline and diesel. Therefore,
the conversion processes in the refinery are designed to
165
reduce the molecular weight of the feedstocks and
166
increase
the hydrogen-to-carbon ratio of the feedstocks by carbon rejec-
tion (coking) or hydrogen addition (hydrogenation). The major
conversion processes in a typical petroleum refinery are as
follows:
Fluid catalytic cracking: fluid catalytic cracking (FCC) is a key
conversion technology for the U.S. refining industry as it
Fig. 15 Overview of typical U.S. petroleum renery conguration. https://upload.wikimedia.org/wikipedia/commons/6/60/ReneryFlow.png.
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produces a significant yield of high-octane gasoline blendstock
from high molecular weight feedstocks like gas oils from
crude oil fractionation. The FCC reduces molecular weight by
catalytic cracking of carboncarbon bonds and increases the
hydrogen-to-carbon ratio by coke extraction.
Coking or visbreaking (thermal cracking): the coking and vis-
breaking processes utilize thermal energy (heat) to non-cata-
lytically crack heavy hydrocarbons in the vacuum residuum
stream to lighter molecules and increase hydrogen-to-carbon
ratio by coke extraction.
Hydrocracking: hydrocracking falls into the broader category
of hydroprocessing, which will be described in detail in later
sections of the report. The major objective of hydrocracking
processes is to catalytically crack carboncarbon bonds and
increase hydrocarbon-to-carbon ratio by hydrogenation under
high hydrogen partial pressures. Typical feedstocks for the
hydrocracker are virgin gas oils from the atmospheric and
vacuum columns and heavy cracked intermediates from the
FCC and thermal cracking processes.
Table 10 summarizes the total U.S. operating capacities for
crude oil distillation/fractionation and the major conversion
processes including FCC, thermal cracking (coking and vis-
breaking), and hydrocracking.
4.2.4 Other catalytic processes. Several other processes in
the refinery are designed for catalytic conversion of specific
refinery streams for maximizing gasoline production and
improving the properties of gasoline streams specifically the
octane number. These catalytic processes are as follows:
Catalytic reforming: the two major purposes of catalytic
reforming processes are (1) to convert virgin naphtha streams,
containing high concentrations of parans and naphthenes,
into higher octane products by reforming parans into
naphthenes and aromatics and naphthenes into aromatics;
and (2) to generate a hydrogen supply for hydroprocessing unit
operations in the refinery. A simple example of a reforming
reaction is shown below in the conversion of methylcyclo-
hexane to toluene and hydrogen.
Depending on product market pricing, a refiner may also
recover valuable aromatic compounds from the reformer
product stream (reformate) like benzene, toluene, and xylenes
for sale as individual products prior to blending the reformate
stream into gasoline. Catalysts used in catalytic reforming pro-
cesses are typically highly promoted precious metals (i.e. plati-
num, rhenium) on a silicaalumina support.
Isomerization: another means of increasing octane values of
refinery streams is through an isomerization process. The
objective of isomerization in petroleum refining is to convert
straight-chain parans into branched parans, which are
higher-octane molecules relative to their straight-chain equi-
valents. Isomerization for gasoline blending is commonly
applied to light naphtha streams from crude fractionation,
which contains high concentrations of C
5
and C
6
parans.
Alkylation: alkylation processes in the U.S. petroleum refin-
ery context are typically closely coupled with the FCC and
thermal cracking processes, which yield substantial volumes
of light olefins (butenes) and branched parans (e.g. iso-
butane). The alkylation reaction example below shows the
conversion of isobutene and isobutane to form 2,2,4-trimethyl-
pentane or isooctane, a high-value gasoline blending com-
pound (blending octane number of 100).
Refinery alkylation units are typically designed to utilize a
circulating inventory of acid solution, either sulfuric acid
(H
2
SO
4
) or hydrofluoric (HF), which serves as the acid catalyst
for alkylation reactions.
4.2.5 Ancillary processes. There are several ancillary pro-
cesses in the petroleum refinery that are designed to minimize
environmental emissions. These environmental control unit
operations are as follows:
Wastewater treatment: the wastewater treatment plant is
another environmental set of operations focused on minimi-
zing emissions of hydrocarbons, salts, solids, and other impu-
rities from water streams emitted from the refinery.
4.3 Crude oil
Typical refinery feedstocks consist of various blends of pet-
roleum crude oils. Crude oils are raw and complex mixtures of
hydrocarbons with constituents ranging from light gases like
methane and ethane to long-chained hydrocarbons like those
found in asphalt. The types and concentrations of dierent
hydrocarbon species in crude oils can vary significantly
depending on the source/location of the material. Simple com-
positional examples of two dierent crude oils Brent Crude
and Cold Lake Crude are presented in Fig. 16 relative to
average European and United States product market demands
for major crude-derived products.
Fig. 16 demonstrates two very important facts. First,
dierent crude oils can have very dierent compositions, pro-
perties, and qualities. Second, typical compositions of crude
oil are not consistent with the distribution of products
demanded. The fraction of heavy hydrocarbons (gas oil and
Table 10 U.S. capacities for crude distillation and major conversion
processes
168
Refinery operation
Total U.S. operating
capacity (10
6
Bbl per day)
Atmospheric distillation 17.86
Vacuum distillation 8.94
Fluid catalytic cracking (FCC) 6.17
Thermal cracking 2.88
Hydrocracking 2.08
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resid) generally present in crude oils are significantly higher
than the demand for these materials. This discrepancy
between crude supply compositions and product demand
defines the need for petroleum refining. The two major objec-
tives of petroleum refining are to
165
recover the naturally occur-
ring hydrocarbons that can be blended with minimal
processing from the crude oil (naphtha, kerosene/jet fuel,
diesel/heating oil) and
166
convert the heavy, less-valuable
hydrocarbon compounds like gas oil and resid through
various refinery conversion processes to increase the yields of
higher-value products.
Crude oils are characterized through compilations of
analytical results called assays. Simplified assays for several
crude oils of varying qualities are presented in Table 11, and
the corresponding complete assays are provided in the ESI.
165
The analytical data from the assays provides a refiner with
essential information to assess the suitability of a particular
crude oil for a refinery or various refineries with dierent con-
figurations. The major categories of information provided in
the crude oil assays are discussed below. The discussions refer
to the simplified process flow diagrams of a typical U.S. pet-
roleum refinery configuration in Fig. 15.
Theoretical fractionation volumes: the first process step in a
petroleum refinery is to fractionate the crude oil by distillation
into multiple cuts based on boiling point. The volume frac-
tion breakdowns for five dierent crude oils of varying qual-
ities are provided in Table 11 and displayed graphically in
Fig. 17. As the data in the table and figure shows, dierent
crude oils can have widely varying contents of the major hydro-
carbon fractions. The heavy crude (Cold Lake Blend) possesses
much less light material (diesel and lighter) and much more
heavy material (gas oil and residue) relative to the lighter
crudes like Gippsland Blend and Brent Blend.
Another method for refiners to identify the volumes of
each fractionation range present in crude oils or refinery
intermediates is to plot the cumulative fractionated volume of
the material as a function of the distillation temperature, an
analysis known as a crude oil distillation or boiling point
curve. An example of this type of analysis is presented in
Fig. 18 for two dierent crude oil types. The color schemes on
the plot represent each of the major petroleum fractions
defined previously naphtha and lighter, kerosene and diesel,
gas oil and resid. A refiner can look at the distillation curves
for the whole crude oils and quickly identify the dierences in
cut volumes. For example, the Gippsland Blend distillation
curve crosses the naphtha/kerosene cut-point of 165 C at
approximately 43 vol% of the distilled crude oil, while the
Hungo Blend distillation curve crosses the same cut-point at
only 18 vol% of the crude oil. These values correspond to the
sums of the butane and lighter, light naphtha, and heavy
naphtha volumes presented in Table 11 for Gippsland Blend
and Hungo Blend crudes, the sums equating to 42.56 vol%
(0.44 + 6.32 + 35.80) and 17.86 vol% (1.33 + 4.24 + 12.29),
respectively.
Data provided by crude oil assays also provide refiners with
very useful information regarding impurities in the various
cuts of petroleum fractions. For example, Fig. 19 presents the
sulfur contents of each crude oil cut from kerosene to residue
for five dierent crude oils. Most product blends like gasoline,
jet fuel, heating oil, and diesel fuel have a maximum sulfur
content specification, which means that refiners must reduce
sulfur contents of applicable blending components to meet
the fuel sulfur specifications. The information presented in
Fig. 19 can provide a refiner with insight on how much proces-
sing is required to meet such specifications and if the refinery
has the capabilities to meet them. For example, a refiner must
consider available SRU capacity if a high-sulfur crude is being
evaluated. Note that the sulfur contents of these crudes are
typically higher than 0.1 wt% and are significantly higher than
biomass pyrolysis oils as shown in Table 3. Thus, bio-oil will
not adversely contribute to the sulfur content of the fuel and
in fact may be used to reduce sulfur with an appropriate blend-
ing strategy.
Other important specifications for refiners to consider in
evaluating crude oils are Conradson carbon (Concarbon) and
metals contents, which are typically concentrated in the heavy
fractions like gas oils and resid. Conradson carbon is a
measurement of the tendency of the hydrocarbon stream to
leave carbon deposits (coke) when processed at elevated temp-
eratures. Metals like nickel and vanadium are present in many
refinery feedstocks as organometallic compounds; these
materials are severe poisons for refinery catalysts like those in
the FCC and hydroprocessing units and will contribute to
accelerated reduction of catalyst activity. Concarbon and
metals contents of the gas oil and resid fractions for each of
the crude oils are presented in Fig. 20a (gas oils) and Fig. 20b
(resids). A refiner must consider the impact of Concarbon and
metals contents of petroleum fractions when determining the
appropriate processing unit. As the figures below clearly show,
Concarbon and metals contents can vary drastically from one
crude oil to another. The potential contribution of bio-oils to
Fig. 16 Benchmark crude oil compositions compared with major
market demands.
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Table 11 Simplied crude oil assays
165
Crude oil name Gippsland blend Brent blend Alaskan North slope Hungo blend Cold Lake blend
Origin Bass Strait, Australia North Sea Alaska, USA Angola Alberta, Canada
Whole crude oil (200 F to 1499 F)
API gravity 49.00 38.50 31.40 28.30 19.71
Sulfur (wt%) 0.0140 0.4060 0.9580 0.6410 3.8177
Concarbon (wt%) 0.2200 2.1800 4.8600 5.6400 11.6900
Total nitrogen (ppmw) 57.0 970.0 1800.0 2640.0 0.0
Total acid number (TAN), mg/g 0.050 0.090 0.200 0.470 1.018
ASTM distillation type D-1160 D-1160 D-1160 D-1160 Est. from Cut D-86
Initial boiling point (F) 118.1 9.0 32.0 17.8 33.5
5 vol% (F) 173.8 102.0 98.8 151.5 98.9
10 vol% (F) 207.4 157.4 158.3 228.2 124.1
30 vol% (F) 277.7 316.3 377.8 457.3 552.2
50 vol% (F) 371.7 508.4 582.1 666.5 836.2
70 vol% (F) 476.4 716.7 814.4 882.1 1088.6
90 vol% (F) 613.9 970.3 1085.9 1135.7 1342.4
95 vol% (F) 692.6 1107.3 1216.2 1258.2 1400.8
End boiling point (F) 958.2 1389.2 1398.6 1414.4 1,423.0
Butane & lighter (200 F to 60 F)
Total cut liquid volume% 0.44 2.55 2.53 1.33 0.65
API gravity 117.28 118.54 113.65 121.03 113.01
Carbon (wt%) 82.6 82.5 82.6 82.4 82.7
Hydrogen (wt%) 17.4 17.5 17.4 17.6 17.4
Light naphtha (60 F to 165 F)
API gravity 79.57 82.04 83.77 79.73 89.21
Parans (volume%) 93.8 85.6 84.7 83.9 93.8
Naphthenes (volume%) 6.2 12.9 14.3 15.9 5.9
Heavy naphtha (165 F to 330 F)
API gravity 60.34 56.07 55.02 55.05 57.80
Parans (volume%) 64.9 47.1 43.3 42.5 52.9
Naphthenes (volume%) 34.1 38.5 43.0 49.8 35.6
Aromatics (volume%) 1.0 14.5 13.7 7.7 11.5
Kerosene (330 F to 480 F)
API gravity 47.73 42.88 41.10 41.02 37.88
Sulfur (wt%) 0.0006 0.0327 0.0929 0.0781 0.6814
Aromatics (volume%) 6.28 14.92 21.24 15.53 12.87
Freeze point (F) 39.1 48.0 52.1 58.9 96.9
Smoke point (mm) 29.4 20.7 21.5 24.0 20.1
Diesel (480 F to 650 F)
API gravity 35.53 34.80 31.39 32.65 26.07
Sulfur (wt%) 0.0185 0.2585 0.5304 0.3126 1.9316
Cloud point (F) 20.0 20.0 7.0 12.0 42.0
Pour point (F) 13.0 10.0 2.0 4.0 51.0
Cetane index 1990 (D4737) 55.6 55.8 48.1 51.0 37.8
Gas oil (650 F to 1000 F)
API gravity 25.39 24.86 21.24 21.20 15.27
Sulfur (wt%) 0.1054 0.6079 1.2117 0.7550 3.2888
Pour point (F) 88.0 100.0 88.0 89.0 34.0
Concarbon (wt%) 0.0600 0.2300 0.5200 0.4700 0.8500
Nickel (ppmw) 0.30 0.00 0.00 0.10 0.10
Vanadium (ppmw) 0.00 0.00 0.00 0.00 0.40
Residue (1000 F to 1499 F)
API gravity 0.08 10.81 6.87 7.77 1.14
Sulfur (wt%) 0.4991 1.3673 2.3438 1.3325 6.0816
Pour point (F) 109.0 97.0 121.0 108.0 124.0
Concarbon (wt%) 33.63 15.50 21.76 21.82 27.88
Nickel (ppmw) 76.50 9.50 51.50 71.50 155.80
Vanadium (ppmw) 12.00 43.10 118.70 59.60 384.30
Asphaltene (wt%) 7.60 2.30 7.30 3.60 19.90
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the Concarbon content is unclear. As discussed in section 2,
crude pyrolysis oils are reactive and will coke when heated.
Though this has not been quantified, coke formation from
heating pyrolysis oil is likely to be significant.
The final crude oil quality metric presented in this discus-
sion is the TAN, which is a measure of a crude oils acidity as
determined by titration with potassium hydroxide. The
amount of potassium hydroxide required to neutralize the
acids present in the crude oil (typically naphthenic acid) serves
as the metric for TAN. The TAN values are used to determine
the relative corrosivity of crude oils on equipment encountered
by the crude oil (tankage, piping, preheat, and crude oil frac-
tionation). TAN values for various crude oils are presented in
Fig. 21, which shows that ranges of TAN values vary signifi-
cantly between crude oils. A refiner must consider the impact
of TAN on the refinerys impacted metallurgy. If a crude oil has
a TAN value that is deemed too high for a refinerys current
metallurgy (materials of construction), the refiner is faced with
the decision to avoid purchasing and processing that particu-
lar crude oil or invest in a capital project to upgrade the metal-
lurgy of the impacted equipment. The impact of bio-oil on
TAN will clearly be significant. As discussed in section 2,
Fig. 17 Theoretical fractionations based on crude oil assay cut
volumes.
Fig. 18 Theoretical fractionations based on crude oil distillation curves.
Fig. 19 Sulfur contents of crude oil fractions based on crude oil assay.
Fig. 20 (a) Concarbon and metals contents of gas oil fraction of crude
oil. (b) Concarbon and metals contents of residue fraction of crude oil.
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bio-oil can have TAN values in excess of 100 mg g
1
, often
ranging to as much as 200.
4.4 Refinery unit operations and refinery intermediates
The following discussions focus on more detailed information
on (1) the major unit operations found in a typical petroleum
refinery, and (2) the refinery intermediates that are produced
from these processes. The major unit operations discussed in
the following sections are crude fractionation, FCC, thermal
cracking (coking and visbreaking), and hydroprocessing
(hydrotreating and hydrocracking) units.
4.4.1 Crude oil fractionation unit. The overall objective of
this process unit is to fractionate the crude oil entering the
refinery into major petroleum distillation cuts while achieving
satisfactory product quality (cut-point overlap), maximizing
product recovery, and minimizing energy consumption.
A simplified process flow diagram for crude fractionation is
provided in Fig. 22. The processing steps typically included in
the crude fractionation unit in a petroleum refinery are listed
and discussed below. Typical ranges for operating parameters
(temperature and pressure) for each processing step in the
crude fractionation unit are summarized in Table 12.
Desalting raw crude oil: the first major processing step
within a typical crude fractionation unit is the desalter, which
utilizes a water wash to remove inorganic salts from the crude
oil that may negatively impact downstream systems such as
poisoning catalyst systems in conversion reactors. The desalter
is also eective at removing suspended solids such as sand,
clay, and particulates from metallurgical corrosion from the
crude oil. The crude oil is first pumped to an operating
pressure above the crude oil vapor pressure, typically in the
range of 100 psig150 psig, and pre-heated to an operating
temperature range of 95 C150 C. The crude oil is then con-
tacted with wash water at a volumetric flow rate of approxi-
mately 3% to 10% of the crude oil volumetric flow;
170
the salts
enter the aqueous phase. The washed oil and aqueous solution
then enter an electrostatic charged liquid/liquid separation
vessel where electric current assists in the phase separation
between the aqueous phase and the crude oil. The brine wash-
water is sent to the wastewater treatment plant and the
desalted crude oil is sent to the next processing step, the crude
oil preheat system.
Crude preheat: after the desalter, the crude oil enters the
crude preheat system, which consists of a series of heat
exchangers and a fired-furnace to vaporize the gas oil and
lighter fractions and a portion of the resid fraction (10%
20%).
170
These unit operations provide heat required for frac-
tionation in the atmospheric distillation column. The heat
exchangers increase the crude temperature from desalter con-
ditions to approximately 290 C and the fired-furnace heats
the crude oil up to the optimal inlet temperature for the
atmospheric distillation column, typically in the range of
400 C410 C.
Atmospheric distillation: the preheated crude oil then enters
the flash zone of the atmospheric distillation column. The
vapor (gas oil and lighter plus a portion of the resid) travels up
the column and is contacted with internally condensed and
refluxed resid, commonly referred to as overflash. Steam is
also added to the column in the flash zone to assist in strip-
ping gas oil molecules from the heavy resid. Throughout the
column, liquid circulation and cooling loops called pump-
arounds draw liquid from an internal collection tray and rein-
troduces the cooled liquid to the column as reflux for
improved eciency. A portion of the liquid can be drawn from
the pumparound as a crude oil cut. The atmospheric distilla-
tion column and associated equipment separate the crude oil
Fig. 21 Total acid number (TAN) of crude oil (mg g
1
).
Fig. 22 Simplied process ow diagram for crude oil fractionation
unit.
169
Table 12 Typical operating conditions for processing steps in crude oil
fractionation
170173
Processing step
Temperature
(C)
Pressure
(barg
a
)
Desalter 95150 6.910.3
Crude preheat 400410 1.72.1
Atmospheric distillation Overhead 150200 1.72.1
Bottoms 340400 Overhead P + DP
Atmospheric
bottoms preheat
400430 0.030.10
Vacuum distillation Overhead 65120 0.030.10
Bottoms 400410 Overhead P + DP
a
Represents gauge pressure in bar (100 kPa). Gauge P = Absolute P
Atmospheric P.
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into multiple cuts ranging from the C
4
and lighter stream to
the atmospheric tower bottoms (ATB). The ATB streams are
further fractionated in the vacuum distillation column while
the other fractionated crude oil streams proceed to the appro-
priate processing steps in downstream refinery units. Atmos-
pheric bottoms preheat: the ATB stream from atmospheric
distillation enters the vacuum preheat system, which includes a
second fired-heater to increase the temperature of the ATB to
temperatures near 430 C. Similar to the atmospheric column,
the fired-heater provides heat for fractionation in the vacuum
distillation column. Adding steam to the ATB stream in the
fired-heater helps control thermal decomposition and coking in
the heater tubes by reducing the hydrocarbon partial pressure.
Vacuum distillation: the preheated ATB enters the vacuum
distillation column, which operates at pressure below atmos-
pheric to prevent the heavy fractions of crude oil from under-
going undesired decomposition by thermal cracking and
coking. Stripping steam is added to the bottom of the column
to assist in feed vaporization and to minimize coking. Typical
operating pressures in the vacuum tower range from 10 to
40 mmHg, depending on the crude and desired intermediate
products. The vacuum distillation column and associated
equipment separate the ATB stream into light vacuum gas oil,
heavy vacuum gas oil, and resid.
The various intermediate streams produced through crude
oil fractionation are sent to dierent areas of the refinery for
further processing prior to product blending. The following
discussion summarizes the common destinations for each
fractionated stream from the crude unit.
Butanes and lighter: this mixture of light hydrocarbons is
most commonly sent to a gas processing plant where it is
further split into C
4
hydrocarbons, C
3
hydrocarbons and other
light ends (ethane, methane). After amine scrubbing to remove
the H
2
S, the light ends are generally burned as refinery fuel
gas for heat and power. After mercaptan removal, the C
3
stream is blended into a propane product or LPG. The C
4
stream is also treated for mercaptan removal and then
blended into a mixed butanes product or sent as feed to the
alkylation unit.
Light naphtha: the light naphtha stream is sent to a mild
hydrotreating unit if necessary to meet gasoline product sulfur
specifications. The stream can then serve as a direct gasoline
blendstock or as isomerization unit feed to increase the octane
value prior to gasoline blending.
Heavy naphtha: the heavy naphtha stream is sent to the
catalytic reformer hydrotreating unit to reduce sulfur and
nitrogen contents to protect the catalytic reformer catalyst
from nitrogen poisoning and to meet gasoline product sulfur
specifications. After hydrotreating, the stream then serves as a
direct gasoline blendstock or as catalytic reformer unit feed to
increase the octane value prior to gasoline blending. The
decision on whether or not to catalytically reform the heavy
naphtha is an economic one, which depends on the market
value of high octane gasoline versus low octane blends and the
refinerys hydrogen balance (since the reformer is a net produ-
cer of hydrogen).
Kerosene: the kerosene cut is sent to a sulfur reduction
process like mercaptan treating or hydrotreating. The stream
then serves as a blendstock for jet fuel or ultra-low-sulfur
diesel (ULSD). Kerosene blending strategy is another economic
decision that depends on the relative market values of jet fuel
and ULSD.
Diesel oil: the diesel oil cut is sent to a hydrotreating unit to
reduce the sulfur content to levels consistent with product spe-
cifications. Most refiners reduce the sulfur content of the
diesel oil for ULSD blending (<15 ppmw sulfur), however refi-
ners can also produce marine diesel (<500 ppmw sulfur) and
home heating oil (<2000 ppmw sulfur).
Atmospheric gas oil and light vacuum gas oil: the atmospheric
gas oil and light vacuum gas oil streams most commonly serve
as FCC feedstock. The FCC converts the gas oil range hydrocar-
bons to light gases, naphtha, and diesel range products. FCC
units normally have a hydrotreater upstream which impacts
the FCC product quality and yield structures as a function of
degree of hydrotreating.
Heavy vacuum gas oil: this stream can either be sent to the
FCC, coker, or hydrocracker. The appropriate destination for
this stream depends on product quality (metals content), avail-
able unit operations and capacities at the refinery, and relative
yield structures for the stream in each of the possible unit
operations.
Residue: the resid material from the crude fractionation
unit is most commonly sent to the coker unit to yield naphtha
and diesel range hydrocarbons by thermal cracking. Some refi-
ners co-feed resid in low concentrations (<5%) to the FCC as
the yields of fuel-range products are more favorable relative to
the coker. Refiners have also constructed grass-roots FCC units
designed to process high concentrations of resid feedstocks.
Resid materials can also be sold as asphalt if the economics
and market demand are favorable.
4.4.2 Fluid catalytic cracking (FCC) unit. The overall objec-
tive of the FCC process is to catalytically convert heavier pet-
roleum molecules, primarily from the gas oil fractions, to
salable products like gasoline and diesel blending
components.
A simplified process flow diagram for a fluid catalytic crack-
ing unit is provided in Fig. 23. The processing steps included
in the FCC unit are listed and discussed below.
Fig. 23 Simplied process ow diagram for uid catalytic cracking
unit.
169
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Feed preheat: the FCC feed enters the crude preheat system,
which consists of a series of heat exchangers similar to the
configuration in the crude fractionation unit to increase the
gas oil temperature to approximately 290 C through heat
transfer with process streams being cooled from the down-
stream main fractionator.
Catalytic cracking in reactor: the preheated feed is injected
into the reactor where it meets hot regenerated catalyst from
the regenerator. The hot catalyst vaporizes the oil, and crack-
ing reactions take place in the riser reactor at temperatures
ranging from 510 C565 C and at a residence times generally
ranging from 0.1 to 1 s. The principal reactions in FCC units
are presented in Fig. 24. Carbon (coke) from the cracking reac-
tions is deposited on the catalyst surface lowering its conver-
sion activity; catalyst exiting the riser typically contains about
1 wt% carbon. However, this value can vary depending on
feedstock quality and operating conditions. The deactivated or
spent catalyst is recovered through the vapor/solids disenga-
ging equipment (rough cut separator and cyclones) and flows
through the stripping section where residual hydrocarbons are
stripped from the catalyst surface with steam. The fluidized
spent catalyst then flows from the reactor to the regenerator.
The cracked vapor products are separated from the circulating
catalyst through the vapor/solids disengaging equipment and
sent to the main fractionator.
Coke combustion in regenerator: coke is burned from the
spent catalyst at temperatures ranging from 650 C760 C. Air
is supplied to the regenerator from the air blower through the
air distributor (air grid). The combustion of coke in the regen-
erator provides the heat required in the reactor for feed vapori-
zation and catalytic cracking reactions (overall endothermic
reactions). The cracking reactor and catalyst regenerator are
typically operated in heat balance where the energy required
for the reactor to vaporize feed plus endothermic cracking
reactions equals the energy supplied by coke combustion in
the regenerator (sensible heat to catalyst).
Flue gas is separated from the catalyst through disengaging
systems similar to the FCC reactor. The flue gas from the
regenerator enters a power recovery turbine to generate power
and/or a series of heat exchangers to recover heat energy.
Product fractionation: the product vapors from the FCC are
sent to the main fractionator for distillation into cuts, similar
to the fractionation of crude oil in the atmospheric distillation
operation.
Gas oil crackers are the most common types of FCCs in the
United States. These units are generally straightforward to
keep in heat balance. Resid crackers are less common but
attractive for the United States as FCCs provide better yield
structures over thermal cracking processes like cokers. It is
more challenging to maintain heat balance due to excessive
coke make from Concarbon and regenerator design limit-
ations. Specific design aspects are required for resid FCCs to
control the heat balance such as catalyst coolers to reduce the
temperature of regenerated catalyst and control the catalyst-to-
oil ratio.
The major refinery intermediates produced by the FCC unit
are fuel gas, C
3
s, C
4
s, cracked naphthas, light cycle oil, heavy
cycle oil, slurry oil, and coke, which is not recovered as it is
burned in the regenerator. Typical yield structures are primar-
ily a function of feed conversion, which is calculated as 100%
(LCO vol% + HCO vol%). The major unit operating para-
meters that impact feed conversion are catalyst type and
activity, reactor operating temperature, contact time/reactor
residence time, and catalyst-to-oil ratio. A simple example of
how the yield structure is impacted by conversion is presented
in Fig. 25.
The various intermediate streams produced through the
FCC unit operation are sent to dierent areas of the refinery
for further processing prior to product blending. The following
discussion summarizes the common destinations for each
FCC intermediate stream.
sent to the FCC gas processing plant where it is further split
into C
4
hydrocarbons, C
3
hydrocarbons, and other light ends
(ethane, methane). After amine scrubbing to remove the H
2
S,
Fig. 24 Summary of uid catalytic cracking reactions.
174
Fig. 25 Typical yield structure for FCC.
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the light ends are generally burned as refinery fuel gas for heat
and power. The C
3
stream is typically blended into a propane/
propylene product. The C
4
stream, which is high in olefin
content, is sent to the alkylation unit for conversion to a high
octane gasoline blendstock through reaction with isobutane
molecules from other refinery processes.
FCC cracked naphtha(s): the FCC naphtha streams are highly
aromatic and represent high octane materials that are desir-
able as gasoline blendstocks. These intermediates are typically
sent to a hydrotreating unit that uses a catalyst specifically
designed to selectively reduce sulfur while minimizing aro-
matic saturation, which will minimize the octane loss associ-
ated with saturation of aromatics to cycloparans. After
desulfurization in the FCC naphtha hydrotreater, the stream
serves as a direct gasoline blendstock.
FCC light cycle oil (LCO): the FCC LCO stream is a highly
aromatic diesel range intermediate. Raw LCO from the FCC is
a low-quality diesel blendstock because its high aromatic
content makes its cetane number very low. Therefore, to
improve the diesel blending properties of the LCO intermedi-
ate, it is typically sent to a high-pressure hydrotreater to satu-
rate the aromatics and improve the cetane value, while
simultaneously reducing the sulfur content to levels appropri-
ate for ultra-low sulfur diesel (ULSD), marine diesel, or home
heating oil. If a refinery produces ULSD and higher sulfur pro-
ducts (marine diesel and heating oil), the LCO will be prefer-
entially blended in the higher sulfur blends due to the high
hydrogen consumptions associated with removing sulfur down
to ULSD specifications. The LCO can also serve as a hydro-
cracker feed to produce C
3
s, C
4
s, naphtha, and ULSD blend-
stocks, depending on the relative economics of gasoline and
diesel and refinery processing capabilities and capacities.
Heavy cycle oil (HCO): depending on available processing
units in the refinery, the FCC may yield a heavy cycle oil (HCO)
intermediate, consistent with the boiling range of light atmos-
pheric gas oil. This stream is also highly aromatic. If a refiner
has the available hydrocracker capacity to process HCO, it can
be converted to C
3
, C
4
, naphtha, and diesel products in the
hydrocracker.
FCC slurry oil: the heavy residual material from the FCC is
called slurry oil because, in addition to the highly aromatic
and high boiling point molecules present in the stream, sus-
pended catalyst fines from reactor carry-over may also be
present in the liquid. The slurry oil is sometimes sent to the
coker if the material does not negatively impact the quality of
coke product. The stream can also be blended as lower value
bunker fuel or blended as asphalt.
FCC catalysts: FCC catalysts have evolved over the past 70
years to allow for flexibility in terms of variations in process
configurations and conditions as well as changes in FCC feed
characteristics. Modern FCC catalysts are amorphous silica
aluminas or rare earth exchanged Y-zeolites; desirable catalyst
properties include high thermal and hydrothermal stability
(>850 C), high attrition resistance, high activity, high activity
for the desired selectivity to C
5
C
10
fractions and low coke
yield.
175177
A major driver associated with the economics of
an FCC unit is the required make-up rate for replacing the
spent catalyst, with current rates being cited at <1 wt%.
175
The
make-up rate also eects the composition of the catalyst such
that the circulating FCC catalyst is a mixture of newer, highly
active catalyst and older catalyst with reduced activity. In
industrial terms, this mixture is often referred to as equili-
brium catalyst or E-Cat.
178
Additives to the FCC catalyst are
also included to improve overall yields and fuel properties as
well as to help control emissions from the FCC unit. ZSM-5 is
often included either by incorporating it into the FCC catalyst
matrix or as a separate catalyst to boost the octane of the gaso-
line product and promote light olefin production.
175,178
The
addition of ZSM-5 reduces gasoline yields; a 1-unit increase in
octane roughly results in a 2 vol% reduction in gasoline yields
due to cracking losses.
175
Additives are also utilized to reduce
sulfur content in the gasoline fraction. Metal passivators, such
as antimony or bismuth help to improve catalyst lifetimes and
reduce coke formation, specifically when processing heavier
resids that may contain significant amounts of metal por-
phyrins.
175,177
Additives in the catalysts are also often employed
to help control emissions from regeneration, particularly SO
x
and NO
x
, as well as promote the oxidation of CO.
175177
4.4.3 Thermal cracking unit(s). The overall objective of
thermal cracking processes is to thermally convert heavy pet-
roleum molecules, primarily from the resid fraction, into
salable products or blendstocks like gasoline and diesel blend-
ing components. A comparison of thermal reaction types rela-
tive to catalytic cracking reaction types is presented in
Table 13. Simplified process flow diagrams for three types of
thermal crackers visbreaker, delayed coker, and fluid coker
are presented in Fig. 2628. Although the process configur-
ations dier in each of the thermal processes, the major pro-
cessing steps are similar. The major steps for each process
configuration are discussed below.
Table 13 Comparison of thermal cracking and catalytic cracking
reactions
179
Hydrocarbon
type Thermal cracking Catalytic cracking
Normal
parans
High gas production
(C
3
and lighter)
High yield of LPG and
naphtha range compounds
High yield of normal
-olefins
Low yield of normal
-olefins above C
4
Low yield of branched
aliphatics (non-
aromatics)
High yield of branched
aliphatics (non-aromatics)
Low yield of aromatics High yield of aromatics
Olefins Low degree of skeletal
isomerization
High degree of skeletal
isomerization
H-transfer is minimal H-transfer is extensive
Rate of cracking is
roughly equal to that
of parans
Rate of cracking is much
higher than that of
parans
Naphthenes Rate of cracking is less
than that of parans
Rate of cracking is roughly
equal to that of parans
(with equivalent structural
groups)
Alkyl
aromatics
Cracked within alkyl
side-chain
Cracked alkyl side-chain at
ring
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Visbreaker
Feed preheat: the first process step in visbreaking is feed
preheat, which consists of a series of heat exchangers and
fired furnaces to increase the resid temperature to above
430 C. The thermal cracking and viscosity reduction reactions
initiate in the process heater and continue in the downstream
operations.
Thermal cracking: the preheated feed is injected into an
optional soaking drum, which provides residence time for the
thermal reactions to take place.
Product fractionation: the hot liquid from the fired-heater/
soaking drum is quenched with recycled fractionator bottoms
and enters the atmospheric fractionator. The products from
the visbreaker include C
4
and lighter gases, naphtha, gas oil,
and bottoms/tar.
Delayed coker
Feed fractionation: the delayed coker process configuration
is unique in that the heavy oil (resid) feed enters the fractiona-
tor prior to the reactor system to remove any light products
that may be present in the resid. The fractionator bottoms
stream is recycled to extinction through the downstream fired-
furnace and reactor system.
Bottoms preheat: from the fractionator, the heavy bottoms
stream is preheated in a series of heat exchangers and a fired-
furnace to increase the resid temperature to above 480 C. The
thermal cracking and coking reactions initiate in the process
heater and continue to the downstream coke drum. Steam is
typically added to the process side of the furnace to control the
buildup of coke deposits in the heater tubes.
Thermal cracking: the thermal cracking reactions continue
from the furnace to the coke drum where coke is collected
until the drum is filled to a controlled level. As coke deposits
in the drum, the cracked vapor products exit the top of the
drum and enter the fractionator for product recovery and sep-
aration. Once the operating coke drum is full, it is taken out of
service and the second coke drum takes its place. The full coke
drum is then decoked (the coke is removed from the drum)
through a labor intensive series of coke cutting and cooling
steps. Once the coke is cooled and broken into small pieces,
the coke is dumped from the bottom of the drum and sold as
product or burned as fuel. The empty coke drum is then pre-
pared to enter operating service again.
Product fractionation: the hot product vapors from the coke
drum enter the fractionator column where they are separated
into C
4
and lighter gases, naphtha, and gas oil intermediate
streams.
Fluid coker
The fluid coker process configuration is similar to the FCC
process in that a circulating fluidized solid material serves as
the heat transfer media between the reactor and burner
vessels. Coke produced from the reactor is sent to the burner
for combustion. The coke combustion in the burner provides
heat to the reactor for heating the feed and for the endother-
mic coking reactions. However, instead of the catalyst used for
FCC unit operations, the fluid coker utilizes coke particles as
the heat transfer media.
Feed pre-heat/scrubbing: in the fluid coker process configur-
ation, the feed is pumped into the vapor scrubber section on
top of the reactor. The vapor scrubber serves several purposes
including preheating the feed by direct contact with the hot
reactor vapors from the coker reactor and flashing any light
products present in the feed. The heavy resid feed flows down
through the contacting media and reaches a liquid draw tray at
the bottom of the scrubber. The liquid then flows from the
scrubber section to the reactor through one or several injection
points.
Thermal cracking: the preheated feed from the scrubber is
injected into the reactor where it meets hot circulating coke
particles. The hot coke particles heat the residual oil and
Fig. 26 Simplied process ow diagram for visbreaker unit.
170
Fig. 27 Simplied process ow diagram for delayed coker unit.
170
Fig. 28 Simplied process ow diagram for uid coker unit.
170
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thermal cracking reactions take place in the reactor at tempera-
tures in the range of 510 C540 C. Carbon (coke) from the
cracking reaction mechanisms is deposited on the surface of
the circulating coke particles. The coke particles from the
reactor are recovered through the vapor/solids disengaging
equipment (cyclones) and flows from the reactor to the regen-
erator. The cracked vapor products are separated from the cir-
culating catalyst through vapor/solids disengaging equipment
and sent to the vapor scrubber and fractionator.
Coke combustion in burner: coke accumulated on the circu-
lating coke particles is burned by partial oxidation in the
burner. Air is supplied to the burner from an air blower
through the air distributor (air grid). Coke combustion pro-
vides the heat required in the reactor for feed vaporization and
the endothermic thermal cracking reactions. The flue gas is
separated from the catalyst through disengaging systems
similar to the reactor. The partially oxidized vapor from the
burner typically serves as fuel for a downstream CO boiler,
where the CO is combusted to CO
2
. The flue gas from the CO
boiler can then enter a power recovery turbine to generate
power and/or a series of heat exchangers to recover heat
energy.
Vapor scrubber and product fractionation: the reactor vapors
flow from the reactor, through the cyclones where residual
solids are removed, and enter the vapor scrubber. The scrub-
ber cools the vapors through direct contact with cold feed and
knocks out residual solids or heavy hydrocarbon droplets
carried over from the reactor. The vapors then flow from the
vapor scrubber to the fractionator for distillation into cuts,
similar to the fractionation of crude oil in the atmospheric dis-
tillation operation. The cuts typically obtained from the fluid
coker are C
4
and lighter gases, naphtha, and gas oil intermedi-
ate streams. The heavy bottoms stream is recycled to
extinction.
The major refinery intermediates from the thermal cracking
processes include fuel gas, C
3
s, C
4
s, cracked naphthas, and
cracked gas oil. The coker also yields a coke product while the
visbreaker yields a heavy unconverted bottoms/tar stream.
Typical yield structures are primarily a function of feed quality,
specifically the Conradson carbon content. A simple example
of how the yield structure from the coker is impacted by feed
quality is presented in Fig. 29.
The various intermediate streams produced through the
thermal cracking unit operations are sent to dierent areas of
the refinery for further processing prior to product blending as
summarized below.
typically sent to a gas processing plant where it is further split
into C
4
hydrocarbons, C
3
hydrocarbons, and other light ends
(ethane, methane). After amine scrubbing to remove H
2
S, the
light ends are generally burned as refinery fuel gas for heat
and power. The C
3
stream is typically blended into a propane/
propylene product. The C
4
stream, which is high in olefin
content, is sent to the alkylation unit for conversion to a high
octane gasoline blendstock through reaction with isobutane
molecules from other refinery processes.
Thermally cracked naphtha(s): these naphtha streams are
high in olefins and possess moderate octane values. Since
these naphthas can also be high in sulfur content, the inter-
mediates are typically sent to the cracked naphtha hydrotreat-
ing unit with the FCC naphtha streams. After desulfurization
in the cracked naphtha hydrotreater, the stream serves as a
direct gasoline blendstock.
Thermally cracked gas oil: the gas oil streams from thermal
cracking processes are lower quality intermediates relative to
raw gas oils recovered from crude fractionation due to their
high aromatic and olefin content. However, the cracked gas
oils can serve as feedstocks for other process units where
further conversion can yield high-value products like naphtha
and middle distillates for product blending. The most
common destinations for the thermally cracked gas oils are
the FCC (typically one with a feed hydrotreating unit upstream)
or a high pressure hydrocracker.
Bottoms/tar oil: the heavy residual material from visbreaking
processes is blended as lower value bunker fuel or as asphalt.
Coke: coke recovered from the delayed coker process can be
sold into various markets including carbon anode production
(needle coke). The coke from the delayed coker and purged
coke particles from the fluid coker can also be used as feed-
stocks for gasification processes to produce synthesis gas for
downstream conversion or to produce heat and power.
4.4.4 Hydroprocessing units. The term hydroprocessing
as it relates to the petroleum refining industry represents a
diverse variety of chemical processes in which catalytic hydro-
genation is used to manipulate the molecular composition of
a petroleum-derived refinery intermediate. The overall purpose
of hydroprocessing is to maximize the value of products from
the petroleum refinery (finished fuel sales) relative to the cost
of the hydrogen ( purchased or manufactured on-site) con-
sumed in the hydroprocessing unit operations.
A simplified process flow diagram representing the most
common configuration of a hydroprocessing unit found in a
U.S. refinery is provided in Fig. 30. The major processing steps
included in the configuration are listed and discussed below.
Feed pre-heat: the feed to the hydroprocessing unit is heated
in a series of feed/euent exchangers and a fired-furnace up
Fig. 29 Typical yield structure for coker units.
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to the appropriate reactor inlet temperature, which is specific
to the service/purpose of the hydroprocessing unit operation.
Reactor(s): the preheated feed from the pre-heat system is
mixed with fresh and recycled hydrogen streams and enters
the reactor system, which can consist of a single vessel or a
multi-reactor configuration. The ratio of hydrogen to feed,
operating pressure, and operating temperature in the reactor
system depends on the hydroprocessing service. There are two
major categories of reactions that take place in hydroproces-
sing units; hydrotreating reactions, which are summarized in
Fig. 31a, and hydrocracking reactions, summarized in
Fig. 31b. The unit purpose and design, operating conditions,
and catalyst dictate the types of reactions that take place in the
reactor(s). Typically, sulfur and nitrogen removal (hydrotreat-
ing) reactors will utilize supported cobalt-molybdenum
(CoMo) or nickel-molybdenum (NiMo) catalysts while hydro-
cracking reactors will possess an acidic zeolite catalyst to favor
molecular weight reduction reactions. The reactor euent
stream leaves the reactor system and enters the euent
cooling section of the unit.
Euent cooling and vapor/liquid separation: the hot reactor
euent stream enters the feed/euent heat exchangers and
downstream coolers to reduce the temperature and condense
the hydrocarbon products. Once cooled, the hydrogen-rich
recycle gas is removed from the euent mixture in the first-
stage separator vessel. The hydrogen-rich recycle gas is com-
pressed and sent back to the reactor inlet while the liquid is
sent to the second-stage separator, which typically operates at
a lower pressure relative to upstream operations, allowing light
hydrocarbons to flash and exit in the vapor stream. The light
hydrocarbons from the second-stage separator generally serve
as fuel gas for heat and power. The liquid from the second-
stage separator enters the product stripper or fractionator for
product recovery/separation.
Product fractionation: the liquid from the vapor/liquid separ-
ation system flows to the product stripper or fractionator vessel
for product separation and recovery. A product stripper is
usually present for hydrotreating operations where molecular
weight reduction reactions are minimal. A product fractionator
is required in hydrocracking services where significant
conversion reactions result in a diverse product distribution.
The product slates for hydroprocessing units vary widely
depending on the feed and function of the unit.
As Fig. 15 shows, a typical U.S. refinery possesses many
dierent hydroprocessing unit operations that serve dierent
roles in processing a diverse array of refinery intermediate
streams. The most common hydroprocessing unit operations
found in U.S. petroleum refineries are summarized in the
descriptions below. The operations are grouped together in
three major categories Naphtha Hydroprocessing, Distillate
Hydroprocessing, and Gas Oil and Resid Hydroprocessing. The
descriptions include typical feedstock(s), processing objectives,
and ranges of typical operating parameters associated with
each respective hydroprocessing unit operation.
Naphtha hydroprocessing. The two major sources of the
naphtha intermediates that feed hydroprocessing units in the
refinery are (1) the crude fractionation units and (2) the FCC
and coker. The unprocessed or virgin naphthas from crude
Fig. 30 Simplied process ow diagram for hydroprocessing unit.
170
Fig. 31 (a) Summary of metal catalyzed hydrotreating reactions. (b)
Summary of acid catalyzed hydrocracking reactions.
180
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fractionation units are generally high in paran (alkane) and
naphthene (cycloalkane) contents. The cracked naphthas from
the FCC and coker units are generally high in olefin (alkene)
and aromatic contents. Since virgin naphthas possess high
levels of hydrogen saturation relative to cracked naphthas, the
virgin materials generally consume significantly less hydrogen
than cracked naphthas in hydroprocessing units. Table 14 pre-
sents a comparison of operating conditions for typical
naphtha hydrotreating services found in U.S. refineries.
Virgin naphtha/reformer feed hydrotreating
This relatively mild hydrotreating operation processes
virgin ( previously unprocessed) naphtha streams recovered
from the raw crude oil during crude fractionation. Hydro-
treated products from virgin naphtha units either serve as
gasoline blendstock or feed to the naphtha reformer unit,
which increases octane value by yielding single-ring aromatics
and hydrogen for use in other hydroprocessing units in the
refinery. The primary processing objectives for naphtha hydro-
treating units are (1) desulfurization, if the product is used for
gasoline blending, to meet gasoline blending specifications;
and (2) denitrogenation, if the product feeds a reformer unit,
as nitrogen is a poison for the reformer catalyst. Cobalt-molyb-
denum catalysts are most commonly employed in these units.
Cracked naphtha hydrotreating
The primary feeds to this higher-severity naphtha hydro-
treating service are cracked naphthas from the FCC and coker
units. These cracked materials generally possess higher octane
values relative to virgin materials due to higher olefin and aro-
matic contents. The major objective of hydrotreating these
materials is desulfurization to meet finished fuels specifica-
tions while minimizing (1) octane loss by hydrogen saturation
of carbon chains and rings and (2) minimizing naphtha losses
to light ends by cracking reactions. Cobalt-molybdenum and
nickel-molybdenum catalysts are most common in these units.
Distillate hydroprocessing. Similar to the naphtha intermedi-
ates, the two major sources of distillate (kerosene/jet fuel and
diesel) intermediates feeding hydroprocessing units are (1) the
crude fractionation units and (2) products from the FCC and
coker. The unprocessed or virgin distillates from crude frac-
tionation units include the kerosene/jet fuel and virgin distil-
late. The cracked distillates from FCC, light cycle oil (LCO) and
coker distillates contain molecules that are significantly less
saturated in hydrogen relative to their virgin boiling-range
equivalents. Therefore, virgin distillates generally consume sig-
nificantly less hydrogen than cracked distillates in hydropro-
cessing units. Table 15 presents a comparison of operating
conditions for typical distillate hydroprocessing services found
in U.S refineries.
Deep desulfurization distillate hydrotreating capacity in the
United States has increased significantly in recent years due to
increasingly challenging sulfur specifications for on-road
ULSD diesel (S < 15 wppm).
Kerosene/jet fuel hydrotreating
This relatively low-severity hydrotreating unit operation per-
forms desulfurization on the virgin kerosene/jet fuel cut from
the crude oil fractionation units. The treated product will typi-
cally serve as a blendstock for either jet fuel or ULSD. The des-
tination for the product depends on a refinerys ability to
produce jet fuel and the relative economics of jet fuel versus
ULSD. Cobalt-molybdenum catalysts are most common in
these units.
Virgin distillate hydrotreating
This processing unit performs desulfurization on the virgin
distillate cuts from the crude oil fractionation units. The
treated product will serve as a blendstock for ULSD, marine
diesel, or heating oil depending on the refinerys capabilities
and market demands for each product. Product from this unit
will preferentially enter the lower-sulfur finished fuel blends
since the virgin distillates are less challenging for deep desul-
furization relative to the cracked distillates. Cobalt-molyb-
denum catalysts are most common in these units.
Cracked distillate hydrotreating
This processing unit performs desulfurization on the
cracked distillate materials from the FCC (FCC LCO) and coker
(coker distillate). Like the virgin distillate unit, the treated
product will serve as a blendstock for ULSD, marine diesel, or
Table 14 Typical operating conditions for naphtha hydrotreating
units
153,169,170,173,180
Process parameter
Virgin naphtha/
reformer
feed hydrotreating
Cracked
naphtha
hydrotreating
Feed gravity (API) 5065 3050
Temperature (C) 230340 230340
Pressure (psia) 300450 6501000
H
2
partial pressure (psia) 100150 200650
LHSV (h
1
) 310 15
H
2
consumption (SCF/Bbl) 40200 200500
H
2
to oil ratio (SCF/Bbl) 300600 15003000
Table 15 Typical operating conditions for distillate hydrotreating units
153,169,170,173,180
Process parameter
Kerosene/jet
hydrotreating
Virgin distillate
hydrotreating
Cracked distillate
hydrotreating
Distillate
hydrocracking
Feed gravity (API) 4050 3045 1530 1530
Temperature (C) 290370 310400 3407400 340450
Pressure (psia) 7001000 7001500 10002500 10002500
H
2
partial pressure (psia) 500900 5001200 8001800 8002300
LHSV (h
1
) 36 14 12 0.52
H
2
Consumption (SCF/Bbl) 150500 300700 7001700 5002000
H
2
to oil ratio (SCF/Bbl) 6002500 12003000 20007000 20008000
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heating oil. However, product from this unit will preferentially
enter the higher-sulfur finished fuel blends since the cracked
distillates are significantly more challenging for deep desulfur-
ization relative to the virgin distillates. Most of the recent
hydroprocessing investments in the United States have
focused on desulfurization of cracked distillates to maximize
ULSD production. Cobalt-molybdenum and nickel-molyb-
denum catalysts are most common in these units.
Distillate hydrocracking
Hydrocracking processes add another objective
beyond desulfurization and denitrogenation namely molecular
weight reduction or cracking. A distillate hydrocracker is
capable of processing both virgin and cracked distillate
materials, yielding a product slate that commonly favors
naphtha-range compounds. Hydrocracking units typically are
accompanied by upstream hydrotreating units that utilize
cobalt-molybdenum and/or nickel-molybdenum catalysts for
sulfur and nitrogen removal to protect the zeolite hydrocrack-
ing catalysts.
As demand for diesel fuel increases relative to gasoline, dis-
tillate hydrocracking economics become less attractive com-
pared to desulfurization-only units, which yield higher
volumes of USLD blendstock relative to naphtha. Units orig-
inally designed for distillate hydrocracking can often be modi-
fied by catalyst-loading strategies and operating conditions to
favor higher distillate yields.
Gas oil and resid hydroprocessing. The sources of gas oil and
resid intermediates feeding hydroprocessing units are (1) the
crude fractionation units and (2) the FCC and the coker. The
unprocessed or virgin cuts from crude fractionation units typi-
cally include the atmospheric gas oil (AGO), light vacuum gas
oil (LVGO), heavy vacuum gas oil (HVGO) and resid from the
vacuum tower bottoms. The cracked gas oils and resids that
are candidates for hydroprocessing are the FCC heavy cycle oil
(FCC HCO), coker light gas oil (CLGO) and coker heavy gas oil
(CHGO). Table 16 compares operating conditions for typical
gas oil and resid hydroprocessing units in U.S. refineries.
Gas oil/FCC feed hydrotreating
This unit operation provides desulfurization, denitrogena-
tion, and mild hydrogen saturation to FCC feedstocks, which
can include AGO, LVGO, HVGO, and, in some cases, small
volumes of resid. The gas oil/FCC feed hydrotreating service
provides significant yield benefits in FCC products and also
reduces the required desulfurization severities for hydrotreat-
ing FCC products like FCC naphtha, LCO, and HCO. Cobalt-
molybdenum and nickel-molybdenum catalysts are most
common in these units.
Cracked gas oil hydrocracking
An alternative and often economically preferred processing
strategy for upgrading coker gas oils is high-severity hydro-
cracking to produce high distillate yields for ULSD blending.
In addition, challenging FCC products like HCO (and LCO dis-
tillate) can be processed in the hydrocracker to produce diesel
and gasoline blendstocks. The penalty for converting these
hydrogen-deficient intermediates in the hydrocracker is that
they consume significant amounts of hydrogen.
Resid hydrocracking
This high severity hydrocracker is designed to process
heavy virgin fractions like HVGO and resid to produce higher-
value products for product blending or further downstream
processing. Based on literature,
173
these heavy oil hydrocrack-
ers are typically designed as ebullated catalyst bed systems
with supported nickel-molybdenum or zeolite hydrocracking
catalysts. Like cracked gas oil hydrocrackers, these units also
consume significant amounts of hydrogen.
4.5 Refinery products
The typical U.S. petroleum refinery markets a variety of fin-
ished products ranging from propane (LPG) to asphalt. Some
of the common refinery products and associated specifications
are discussed below.
Liquefied petroleum gas (LPG): LPG products consist of mix-
tures of the C
3
and C
4
hydrocarbon streams. Some common
LPG products are described below.
Propane products are commonly comprised of the C
3
hydrocarbons from the crude fractionation unit and various
hydroprocessing unit operations due to the low propylene
content of the streams. Propane products normally have speci-
fications on the amounts of other materials present in the
mixture. For example, HD5 consumer grade propane must
have a minimum propane content of 90% and a maximum
propylene content of 5%.
Propylene products can also be sold from a refinery. Typi-
cally, propylene is sold as a polymer precursor for polypro-
pylene production. The specifications on propylene typically
vary depending on agreements established with the purchas-
ing company, however, commodity specifications exist for pro-
pylene materials as well. For example, polymer grade
propylene must have a minimum purity of 99.5%.
Butanes can be sold as products if the refinery has excess
material that is not being utilized in the alkylation unit, the C
4
isomerization unit, or blended into gasoline products to adjust
the vapor pressure (Reid vapor pressure, Table 17). Minimum
purity specifications of 95% on isobutane and normal butane
products are common.
Gasoline: gasoline products are created by blending the
various naphtha streams from the refinery into a mixture
Table 16 Typical operating conditions for gas oil and resid hydrotreat-
ing units
153,169,170,173,180
Process parameter
Gas oil or
FCC feed
hydrotreating
Cracked gas oil
hydrocracking
Resid
hydrocracking
Feed gravity (API) 1525 020 (10)15
Temperature (C) 340430 340450 400450
Pressure (psia) 8001200 15003000 24003000
H
2
partial pressure
(psia)
6001000 12002700 19002700
LHSV (h
1
) 0.51 0.52 0.51
H
2
consumption
(SCF/Bbl)
5001000 12003500 12003500
H
2
to oil ratio
(SCF/Bbl)
15004000 400010 000 400010 000
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meeting all applicable fuel specifications. A refinery typically
produces several gasoline products with varying average octane
numbers. Specifications for gasoline products can vary
depending on location, ambient temperature, and specific cus-
tomer requirements. An example of how individual naphtha
blending components compare to properties of a typical fin-
ished gasoline fuel blend is presented in Table 17.
Jet fuel: the most significant contributor to jet fuel pro-
duced by a refinery is the straight-run kerosene stream from
the crude fractionation unit. However, hydrotreated and hydro-
cracked refinery intermediates with comparable boiling ranges
may also contribute to jet fuel products. The straight-run kero-
sene is normally upgraded by mercaptan treating, clay treating,
or hydrotreating before it can be sold as jet fuel.
181
Specifica-
tions for jet fuel products vary depending on the requirements
of the service and customer. Table 18 presents a summary of
major fuel property specifications for civilian jet fuels.
181
If a
refiner does not produce jet fuel products, the kerosene-range
blendstocks can be used to contribute to USLD, another highly
valued product.
Diesel fuels and heating oil: diesel fuel products are
created by blending the various middle-distillate streams
(virgin and cracked kerosenes and diesel oils) from the refinery
into a mixture meeting all applicable fuel specifications. An
example of how individual middle-distillate blending com-
ponents compare to properties of a typical finished diesel fuel
blend is presented in Table 19.
Other products: products including heavy fuel oils, asphalt,
lubricant oils, waxes, coke (carbon), elemental sulfur, aro-
matics (benzene, toluene and xylenes), specialty chemicals,
Table 17 Comparison of gasoline blend component properties to nished gasoline product
a 173,182
Property
Finished gasoline
specification
Light cracked
naphtha
Heavy cracked
naphtha
Straight run
naphtha Alkylate Reformate
API gravity Report 70.6 57.2 76.6 71.4 47.6
Distillation (ASTM D86)
10 vol% BP (C) 70 Max 46 57 44 78 66
50 vol% BP (C) 77 Min/121 Max 79 116 70 103 101
90 vol% BP (C) 190 Max 126 146 106 119 180
Final BP (C) 221 Max 150 155 117 188 191
Reid vapor pressure (psia) 7.0 9.1 2.6 9.7 4.5 6.7
Aromatics (vol%) 50 6.6 13.3 3.5 0.7 52.9
Olefins (vol%) 25 44.6 39.0 0.1 0.6
Research octane no. Report 89.6 84.0 55.2 96.0 97.2
Motor octane no. Report 78.5 75.9 55.0 94.0 87.1
Ave. octane no. (R + M)/2 90.0 84.1 80.0 55.1 95.0 92.2
a
Note: the summary presented in the table does not represent a complete set of gasoline specifications.
Table 18 Summary of property specications for major jet fuel products
181
Fuel Jet A Jet A-1 TS-1 Jet B
Specification ASTM D 1655 DEF STAN 91-91 GOST 10227 CGSB-3.22
Acidity (mg KOH g
1
) 0.10 0.015 0.7 (mg KOH per 100 ml) 0.10
Aromatics, % vol. max 25 25.0 22 (% mass) 25.0
Sulfur (mass%) 0.30 0.30 0.25 0.40
Sulfur, mercaptan (mass%) 0.003 0.003 0.005 0.003
Distillation, C: initial boiling point Report 150 Report
10% recovered, max 205 205 165 Report
50% recovered, max Report Report 195 min 125; max 190
90% recovered, max Report Report 230 Report
End point 300 300 250 270
Vapor pressure, kPa, max 21
Flash point, C, min 38 38 28
Density, 15 C, kg m
3
775840 775840 min 774 @ 20 C 750801
Freezing point, C, max 40 47.0 50 (Chilling point) 51
Viscosity, 20 C, mm
2
s
1
, max 8 8.0 8.0 @40 C
Net heat of combustion, MJ kg
1
, min 42.8 42.8 42.9 42.8
Smoke point, mm, min 18 19.0 25 20
Naphthalenes, vol%, max 3.0 3.00 3.0
Copper corrosion, 2 h @ 100 C, max rating No. 1 No. 1 Pass (3 h @ 100 C) No. 1
Thermal stability
Filter pressure drop, mm Hg, max 25 25 25
Visual tube rating, max <3 <3 <3
Static test 4 h @ 150 C, mg per 100 ml, max 18
Existent gum, mg per 100 ml, max 7 7 5
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and many others can be produced by petroleum refineries and
other integrated petrochemical facilities.
5. Integrating pyrolysis oil into
standard reneries
5.1 Introduction
As mentioned earlier, a potentially very attractive option for
introducing biomass-derived materials into the fuels market-
place would be to use bio-oil as a feedstock and/or blendstock
in a standard petroleum refinery, either replacing or supple-
menting fossil-derived materials with biomass-derived
materials. This would, in principle, facilitate the introduction
of renewable carbon into the fuels infrastructure and would
economically advantage the biofuels industry by using the
multi-trillion dollar refining and distribution infrastructure
already in place. As detailed in section 4, from the refiners
perspective when evaluating potential refinery feedstocks,
important properties include the boiling range distribution
obtained from the main crude oil fractionator and the hydro-
carbon types (PONA) and heteroatom (sulfur, nitrogen, oxygen)
contents of each of the resulting primary distillation and
process-derived intermediate fractions. The boiling range dis-
tribution from the main fractionator impacts all of the major
downstream unit operations, which are in turn designed to
optimize the refinery product slate to produce the most profit
per barrel of feedstock.
Using bio-oil as a blendstock and/or feedstock in a conven-
tional petroleum refinery introduces several potential pro-
blems and pitfalls associated with the dierences in physico-
chemical properties of bio-oil relative to petroleum crude oil.
Important properties of bio-oil as they related to refinery feed-
stocks have been reviewed in detail in section 2.5 of this docu-
ment. In addition to these issues, the following points
represent significant barriers to utilization of bio-oil in a
conventional petroleum refinery.
(1) Miscibility: due to its high organic oxygen content and the
presence of highly polar oxygenates, raw or non-upgraded bio-
oil is largely immiscible in aliphatic and aromatic hydrocarbons
typical of petroleum-derived crude oil and crude oil fractions.
This problem can be mitigated by catalytic upgrading of the
bio-oil to reduce oxygen and improve miscibility.
145,146
(2) Acidity: as mentioned previously the acidity of petroleum
crude oil is generally very low (Fig. 21). Acidic components
present in crude oil generally represent naphthenic acids as
measured using copper and silver strip tests (ASTM D130-12,
ASTM D7671). These components are corrosive to mild steel at
high temperatures. The refining industry has long since deter-
mined mechanisms for mitigating the impact of corrosion
imparted by naphthenic acids [http://www.setlaboratories.com/
nac/tabid/79/Default.aspx] including blending (industry stan-
dard is that the TAN of the blend must be <0.6
183
), use of cor-
rosion inhibitors, and upgraded materials of construction. For
a discussion of the impact of TAN of bio-oil on corrosion, see
section 2.5.5.
(3) Presence of organic oxygenates: as outlined in section 4,
most crude oils contain very small amounts of organic oxygen;
in general less than 1 wt% and often less than 0.1 wt%.
184
Accordingly, catalysts and processes used in the refinery unit
operations for hydroprocessing intermediates and upgrading
fossil petroleum to finished fuels are not designed to accom-
modate these materials. The presence of organic oxygenates
and oxygen functional groups can impart very dierent pro-
perties to feedstocks in the refinery when compared to streams
that are predominately hydrocarbon. Physical properties such
as density, viscosity (section 2.5.4), and storage stability
(section 2.5.3) can be altered and oxygenates can also degrade
elastomers used in engine parts. The presence of organic
oxygen leads to changes in volatility, which impacts unit oper-
ations used for separating intermediates or producing final
products. Chemical properties are also altered by the presence
of organic oxygen, which can influence the reaction chemistry
of important conversion and fuels synthesis processes. Cata-
lysts, which are eective for converting crude fractions in the
absence of oxygenates, may function entirely dierently when
oxygenated compounds are present, leading to changes in
activity and selectivity.
Table 19 Comparison of diesel blend component properties to nished diesel product
a 173,182
Property
Finished diesel
specification
Hydrotreated
straight run diesel
Hydrotreated
cracked diesel
Hydrocracker
kerosene
Hydrocracker
diesel
API gravity 33.5 Min/39.0 Max 33.8 35.0 38.0 34.0
Distillation (ASTM D86)
Initial BP (C) 171 Min 267 223 191 285
50 vol% BP (C) 238 Min 291 261 229 321
90 vol% BP (C) 282 Min/338 Max 334 319 267 363
Cetane index 40 Min
Flash point (C) 60 Min
Cloud point (C) 12 Max
Pour point (C) 7 Max
Viscosity (cSt at 40 C) 1.9 Min/4.1 Max
Sulfur (ppmw) 15 Max
a
Note: the summary presented in the table does not represent a complete set of diesel fuel specifications.
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(4) Presence of alkali and alkaline earth metals in the oil:
crude oil has a very small inorganic content, which is generally
comprised of salt and porphyrins of vanadium and nickel.
Salts and suspended solids in crude oil are readily removed in
a de-salting unit operation prior to the initial fractionation
(section 4.4.1). Refiners have developed strategies to mitigate
and/or passivate the impact of vanadium and nickel contami-
nation on refining catalysts, but introducing bio-oil brings a
new suite of potential catalyst poisons from silicon, calcium,
potassium, and other alkali and alkaline earth metals. These
metals could act as poisons for cracking and hydrotreating
catalysts. The eect of these contaminants can be greatly
reduced by using hot gas filtration during the pyrolysis
process,
51
but trace quantities of these metals could still wind
up in downstream unit operations.
5.2 Refinery integration studies
In a comprehensive investigation into incorporating bio-renew-
ables into the petroleum refinery, Marker
183
examined several
opportunities for including bio-oil into standard petroleum
refinery unit operations. In addition to an examination of uti-
lizing waste fats and greases as refinery feedstocks and hydro-
gen production from the aqueous fraction of bio-oil, this study
looked at:
Hydroprocessing pyrolytic lignin to produce aromatics
and gasoline.
Co-processing bio-oil with vacuum gas oil (VGO) in the
fluid catalytic cracker (FCC).
Using a two-step process
46
consisting of catalytic hydrotreat-
ing over a Ru/C catalyst followed by catalytic hydrocracking
over a NiMo/alumina catalyst, hydroprocessing of pyrolytic
lignin was reported by Marker to be successful in producing a
hydrocarbon-like liquid product that represented 32 wt% of
the starting material at 96 wt% oxygen removal. Approximately
80 wt% of the hydrotreated liquid was found to be material
boiling in the naphtha range. Co-processing whole raw bio-oil
and pyrolytic lignin in a laboratory ACE system was carried out
for blends of up to 20 wt% raw bio-oil and/or pyrolytic lignin.
These experiments were accompanied by tests on the catalytic
cracking of a hydrotreated whole bio-oil and for VGO alone.
Results showed that all three biomass-derived oils gave greatly
increased yields of coke (16 wt% and 27 wt% for the bio-oil/
VGO blends) when compared to catalytic cracking of VGO
alone. The bio-oil/VGO blends were found to increase the
crackability of the feedstock when compared to VGO alone
and to increase the yields for light-end products, which is
potentially an economically attractive outcome.
A comprehensive investigation of opportunities for incor-
porating biomass-derived materials in the petroleum refinery
was carried out under the auspices of the BIOCOUP project.
This study concluded that the best insertion point for
bio-oil was the FCC using a partially deoxygenated bio-oil con-
taining up to 20% organic oxygen as the feedstock.
More recently, a team with members from NREL, PNNL,
GEMI, and Valero
185
conducted an investigation on the impact
of upgrading with hydrogen on several of the important
refinery-relevant properties of bio-oil. The objective of this
study was to develop information on changes in acidity,
boiling range distribution, elemental composition (including
total oxygen), and hydrocarbon and oxygenate types in streams
that represent important refinery intermediates, and to corre-
late this information with hydroprocessing severity ( principally
temperature, pressure, liquid hourly space velocity or LHSV)
and total oxygen content of the upgraded oil. Three levels of
hydroprocessing severity were analyzed, consisting of reaction
conditions required to produce an oil with low oxygen content
(LOC; organic oxygen = 0.4 wt% on a water-free basis),
medium oxygen content (MOC; organic oxygen = 4.9 wt% on a
water-free basis), and high oxygen content (HOC; organic
oxygen = 8.2 wt% on a water-free basis). Fig. 32 shows the defi-
nitions that were used in this study for the various boiling
range fractions for the upgraded bio-oils (as determined by
simulated distillation) related to the definitions normally
employed in the refining industry for these same fractions. As
can be seen, the upgraded bio-oil fractions from this study are
considerably wider in boiling range than their petroleum-
derived counterparts; in several cases the T90 point for the
biomass-derived fraction falls outside of the range normally
used for petroleum-derived fractions.
Information on the distillate fractions and elemental analy-
sis of the upgraded bio-oil fractions (as defined in Fig. 32) are
shown in Table 20. As can be seen, hydrotreating results in a
gradual shift of the distillate product slate towards lighter frac-
tions (naphtha + light ends) with a reduction primarily in the
gas oil fraction as hydroprocessing severity increases. For the
HOC and MOC oils, an additional 10 wt% of the starting oil
comprised a non-volatile residue. These data also show that
organic oxygen is concentrated in the lighter distillate frac-
tions for the HOC oil, while the opposite trend is found for the
MOC oil with organic oxygen concentrated in the heavier
Fig. 32 Actual fraction distillation range in comparison to targets (by
simulated distillation).
185
LOC (low oxygen content) = 0.4 wt%. MOC
(medium oxygen content) = 4.9 wt%. HOC (high oxygen content) =
8.2%.
T90 is the temperature at which 90% (by volume) of the fraction has been dis-
tilled into overhead products, and is an important characteristic of refinery
intermediates.
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fractions. For the LOC oil, the organic carbon content of all
fractions was basically the same.
In addition to elemental composition and boiling fraction
distribution, the acidity of the fractions is extremely important
to the refiner. Table 21 presents data on the relationship
between acidity and hydroprocessing severity for each distillate
fraction obtained from this study.
These acidity data are presented in terms of total acid
number (TAN) and carboxylic acid number (CAN). The intent
here was to indicate the relative proportion of strong acids (car-
boxylic acids) in the TAN, as corrosion issues associated with
carboxylic acids are anticipated to be quite problematic. As
shown in the table, for the HOC oil TAN is still very high and
most of the total acids consist of carboxylic acids, indicating
that the weak acids ( phenolics) have been removed by hydro-
treating. At higher hydrotreating severities, the TAN and CAN
are both significantly reduced.
Data on the chemical compound classifications and hydro-
carbon types (PONA) of the lighter distillate fractions as a func-
tion of hydrotreating severity are shown in Fig. 33 and
Table 22, respectively.
Oxygenated compounds were present in all of the HOC frac-
tions represented in Fig. 33. In the light ends and naphtha
fractions, these were primarily C
5
, C
6
and C
7
cyclic and noncyc-
lic ketones, esters of C
6
and shorter carboxylic acids, methyl
substituted tetrahydrofurans, and aliphatic alcohols. Some
acetic acid was present in these fractions. In the jet fraction,
oxygenates were primarily methyl- and ethyl-substituted
phenols, with some methoxy phenols and C
6
and C
7
cyclic
ketones. Ketones in the jet fraction were less than in the
lighter fractions, but phenols were much greater in this frac-
tion. The MOC fractions contained much lower levels of oxyge-
nates compared to the HOC fractions; detected compounds
consisted primarily of alkyl phenols and aryl ethers. Fractions
from the LOC oil contained no oxygenates in the lights and
naphtha (below detection limits), with a small amount of
alkyl-substitute phenols in the jet fraction.
Table 21 Acidity
185
TAN for untreated (raw) oil was approximately 185
HOC MOC LOC
mg KOH g
1
CAN
a
TAN
b
CAN TAN CAN TAN
Lights 102 102 BD
c
14 BD BD
Naphtha 123 123 BD 100 BD 2
Jet 67 154 BD 199 BD 14
Diesel 20 20 BD 0.3 0.1 0.1
Gasoil 9 9 BD BD 0.4 0.4
a
Carboxylic acid number.
b
Total acid number.
c
BD = below detection
limit.
Fig. 33 Chemical composition of the distillate fractions as a function of
hydrotreating severity.
185
Table 20 Elemental analysis of boiling range fractions
185
Oil
sample Fraction
Distillate
fraction C H N S O
% w/w % w/w % w/w % w/w ppm % w/w
HOC Lights 5.3 72.8 11.9 0.01 25 14.2
Naphtha 19.7 73.7 11.5 0.01 19 14.4
Jet 18.7 77.8 11.0 0.03 23 11.9
Diesel 17.2 82.4 10.7 0.09 101 7.5
Gasoil 30.3 84.6 10.4 0.14 354 5.3
MOC Lights 4.6 85.6 13.6 0.02 8 0.5
Naphtha 17.7 84.5 11.9 0.05 8 3.9
Jet 23.1 83.9 10.1 0.14 12 6.6
Diesel 18.3 85.7 10.2 0.32 21 4.4
Gasoil 32.6 87.8 9.9 0.40 116 2.5
LOC Lights 13.9 85.9 14.6 0.01 2 0.3
Naphtha 30.2 86.3 13.3 0.02 2 0.3
Jet 22.0 87.0 12.3 0.02 12 0.7
Diesel 20.6 88.4 11.4 0.02 310 0.5
Gasoil 13.5 88.6 11.5 0.03 243 0.4
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Results for the PONA analysis were determined using the
accepted GC method for petroleum, where the content of
organic oxygen is low. The impact of oxygenates on this
analytical procedure is unknown; accordingly, results for the
HOC and MOC fractions should be treated as approximate. In
general, increasing hydroprocessing severity is found to
decrease aromatics and increase the amount of parans and
naphthenes in the light and naphtha fractions. For the LOC
fraction, the data indicate low aromatic content and moderate
isoparan content leading to the relatively low research (RON)
and motor octane numbers (MON) for these fractions.
Benzene content in the light and naphtha fractions was found
to be below the limits set by the EPA for motor gasoline in all
fractions analyzed.
5.3 Integration of bio-oil in the FCC
The FCC is the single most important unit operation in the
modern petroleum refinery that has been optimized for produ-
cing motor gasoline; accordingly, a great deal of interest has
been focused on investigating production of transportation
fuels by processing bio-oil in the FCC either by itself or as a
blend with petroleum-derived gas oil/vacuum gas oil (usually
known as co-processing). It has been speculated that decarboxy-
lation via FCC could provide a more cost-eective route for
producing transportation fuels from biomass when compared
to deoxygenation by hydroprocessing.
186
Further, the FCC is a
flexible refinery unit operation that can, in principle, be
readily tuned to accommodate dierent feedstocks by modify-
ing catalysts and/or operating conditions. Several potentially
viable strategies exist for integrating bio-oil into the fluid cata-
lytic cracking unit of an existing petroleum refinery. The work
at UOP on co-processing bio-oil in the FCC has been reviewed
above;
183
additional co-processing investigations are reviewed
below.
5.3.1 Co-processing whole bio-oil in the FCC. A simple
and straightforward method for integrating bio-oil into an
existing refinery would be to use whole bio-oil without pre-
treatment or fractionation as a blendstock with petroleum-
derived GO or VGO and direct feed the blend to the FCC. In
one study, mixtures of model oxygenates (acetone, acetic acid,
2-propanol) and iso-octane as a surrogate for gas oil were
cracked over an industrial equilibrium catalyst (E-cat) in a
fixed-bed laboratory reactor.
187
In general, selectivity to light
gases and olefins was reduced and coke dramatically increased
by adding oxygenates. Blends of model oxygenates such as
acetic acid, hydroxyacetone, and phenol with petroleum-
derived gas oil were processed under standard FCC conditions
in a lab-scale reactor using both an E-cat and a mixture of
E-cat and ZSM-5.
188
In general, adding the model oxygenates
increased overall conversion; reduced the coke yield; and
increased the yield of fuel gas, LPG, and gasoline. Conversion
of the gas oil was not significantly altered. It is worth noting,
however, that the model compounds used in many of these
studies are not within the boiling point range that is typical
for upgrading in an FCC. A simulated distillation curve for pet-
roleum-derived gas oil is shown in Fig. 34, along with boiling
points for some of the model compounds that have been
employed. Accordingly, conclusions from model compound
studies may not be completely relevant when applied to co-
processing in the refinery.
Fluid Catalytic Cracking mixtures of petroleum-derived gas
oil with whole bio-oil has been reported. Fogassy et al. investi-
gated co-processing VGO and whole bio-oil over a standard
FCC catalyst, H-Y zeolite, and HZSM-5 in a laboratory reactor
and found that introducing bio-oil resulted in lower rates for
formation of cracked products except for coke and aro-
matics.
189
In a laboratory cracking reactor (ACE system), Agble-
vor et al.
190
were able to produce fuel-range products by co-
processing bio-oil with gas oil in a ratio of 15/85 (wt/wt). The
product yields were almost identical to that for cracking gas oil
alone, and the products were found to contain negligible
amounts of oxygen. Similar results were reported for co-proces-
sing a mixture of 10 wt% bio-oil and 90 wt% vacuum gas oil
using an E-Cat in a laboratory ACE system.
191
Up to 1500 ppm
phenols were found in the liquid products. However, co-pro-
cessing 10 wt% bio-oil and 90 wt% vacuum gas oil in a pilot-
scale reactor system at Petrobras showed substantial dier-
ences in the yields of coke and liquid products and the
products contained significant organic oxygen content.
192
Similar findings were reported by these same researchers
Table 22 PONA analysis of the distillate fractions as a function of
hydrotreating severity
185
Vol%
LOC MOC HOC
Lights Naphtha Lights Lights Naphtha
Parans 28.3 15.4 13.6 7.9 5.9
Isoparans 14.9 26.8 25.9 32.8 38.8
Naphthenes 51.3 46 47.8 31.8 20.3
Aromatics 5.6 11.8 5.2 10.9 27.0
Olefins 0.07 0.01 7.54 16.7 8.3
Benzene 0.5 0.4 0.6 0.3 0.8
RON 64 71 73 79 88
MON 61 68 72 77 87
Fig. 34 Example simulated distillation of petroleum gas oil fraction
(343538 C) compared to model oxygenated compounds used in
recent upgrading studies.
165,167
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when cracking a feedstock containing 100% bio-oil in a labora-
tory ACE unit.
In an important study, Fogassy et al. investigated partition-
ing fossil carbon and biomass-derived carbon in products
from co-processing bio-oil with petroleum gas oil. Using
carbon-14, they were able to determine that both coke and
light gases were richer in
14
C than the gasoline from the FCC,
suggesting that biomass-derived components react preferen-
tially to undesirable products under cat cracking
conditions.
193
Co-processing whole bio-oil with hydrogen-rich materials
other than petroleum has been studied by Chen et al.
194
and
Chang et al.
130
These investigators found that mixing bio-oil (a
hydrogen-deficient material with a low EHI) with a hydrogen-
rich material (such as methanol) dramatically improved the
conversion of bio-oil to hydrocarbons during catalytic cracking
in the vapor phase over HZSM-5. They reported that a mixture
with a combined EHI of 1.0 or greater resulted in a greater
than 300% increase in C5+ hydrocarbon yield accompanied by
a 32 wt% reduction in coke-on-catalyst (water-free basis) when
compared to vapor phase cracking of whole bio-oil alone.
Petrobras has applied this concept to the catalytic cracking of
petroleum-derived hydrocarbons with ethanol to produce
ethylene in high yields.
195
Findings from these studies show that whole bio-oil and
model compounds representing the major oxygenated com-
pounds in whole bio-oil produce large amounts of coke and
light gases when processed over acid catalysts typical of those
used in a conventional FCC unit. Catalyst deactivation was
found to be rapid, and alkali and alkaline earth metals present
in the whole oil caused severe and irreversible poisoning of
the catalysts. Other factors, including the acidity and high
water content of whole bio-oil, make whole bio-oil a particu-
larly dicult feedstock for the cat cracker. FCC units are gener-
ally not made from high alloy steel, and the corrosivity of
whole bio-oil would present severe operational diculties.
Similarly, the high water content of whole bio-oil is deleterious
to catalyst integrity in the FCC unit. Finally, it is unlikely that
production facilities for bio-oil will be able to supply sucient
quantities of product. Typical modern petroleum refineries
process upwards of 200 000 barrels per day of crude; a signifi-
cant fraction of that amount is fed to the FCC. Single bio-refi-
neries based on pyrolysis will initially produce bio-oils at a rate
of only about 8000 BBL per D,k which is insucient to satisfy
the demand for the FCC in even one small- to medium-sized
refinery. Accordingly, integration strategies based on proces-
sing whole bio-oil without blending with refinery feedstocks
and/or intermediates do not appear to be technically or com-
mercially feasible.
142
A blend of up to 10 wt% whole
(untreated) bio-oil was suggested to be a suitable feed for the
FCC unit in a conventional petroleum refinery.
188
5.3.2 Co-processing hydrotreated/HDO bio-oil with VGO in
the FCC. Problems associated with co-processing whole bio-
oil can be partially addressed by upgrading the whole oil prior
to blending with gas oil. Thermal and catalytic hydrotreating
and catalytic hydrodeoxygenation (HDO) of thermal pyrolysis
oil have all been investigated as upgrading strategies to reduce
acidity and improve properties with respect to co-processing of
bio-oil in the FCC. Both low-severity thermal (e.g., non-cata-
lytic) hydrotreating and catalytic hydrotreating have been
investigated by Samolada et al.,
196
who found that the heavy
fraction from thermal hydrotreating could be successfully co-
processed with light cycle oil in the FCC. Coke formation was
less than 1%, and gasoline yields of up to 25% were obtained
using this strategy. Co-processing hydrotreated bio-oil in the
FCC has been studied by several investigators.
197199
Using a
laboratory FCC system, Mercader et al. found that co-proces-
sing HDO bio-oil in the FCC with long residue and light cycle
oil produced products that were almost free of organic oxygen
without excessive coke formation. Fogassy et al. found that
blending HDO bio-oil and VGO at a level as high as 20% gave
comparable yields for the gasoline fraction when compared to
cracking VGO alone. A common thread in many of these
studies is that removing oxygen in the FCC consumes hydro-
gen from the hydrocarbon feedstock, resulting in the pro-
duction of more olefins and aromatics in the products.
5.4 Other strategies
Co-processing partially upgraded bio-oil produced by catalytic
fast pyrolysis (CFP) has been compared to co-processing an
HDO bio-oil by Thegarid et al.
200
This study showed that
product distributions were similar, but that the CFP oil could
eliminate the need for upstream hydrodeoxygenation. Organic
carbon eciency of the CFP/FCC strategy was found to be sig-
nificantly better than the HDO/FCC strategy.
Co-processing upgraded bio-oil in the FCC provides a tech-
nical solution to some of the more problematic issues associ-
ated with using biomass-derived liquids in the refinery.
However, the economics of these strategies are dominated by
the high capital and operating costs associated with hydropro-
cessing and hydrodeoxygenation. These costs are present, in
part, because the strategies being employed involve high-sever-
ity hydrodeoxygenation and then co-processing the whole bio-
oil. This results in high capital costs due to large reactor
volumes and high operating costs due to the high hydrogen
demand for hydroprocessing/deoxygenation of the whole oil.
A dierent strategy, which in principle could circumvent some
of these problems, is shown below. This scheme involves first
mildly hydrotreating the whole bio-oil to the point where the
oil can be distilled followed by fractionation. Hydrotreating
conditions could be adjusted to allow for water removal as a
separate phase during this initial step as mild hydrotreating
has been shown to be eective in facilitating this separ-
ation.
150
Depending on their distillation characteristics and
boiling range, the bio-derived fractions could then be sent to
the appropriate unit operation in the refinery (e.g., bio-
naphtha to the reformer hydrotreater, bio-diesel to the diesel
kAssuming a single bio-refinery processing 2000 metric tons per day ligno-
cellulosic biomass.
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hydrotreater) for blending with petroleum-derived material
and further processing into finished fuels (Fig. 35).
In this scheme, high severity hydroprocessing associated
with the HDO step would be reserved for that fraction of the
bio-oil that requires more severe processing to reduce acidity
and improve miscibility. This would result in improved hydro-
gen utilization eciency and savings in both capital and oper-
ating costs when compared to the whole-oil strategies
discussed above.
This strategy of selective hydrotreating also applies when
the bio-oil is available from CFP. In the context of the scheme
shown above, CFP is used to provide a partially upgraded bio-
oil that can be fractionated, removing the need for hydrotreat-
ing the whole oil prior to fractionation and improving the
overall economics and carbon eciency accordingly. Con-
ditions and catalysts for CFP required to produce a bio-oil that
can be fractionated have not been widely investigated to date.
5.5 Co-processing in hydrotreaters
Co-processing bio-oil with petroleum-derived materials in
hydrotreaters has not been extensively investigated to date. Bui
et al.
201
investigated co-processing straight-run gas oil with
guaiacol as the surrogate for bio-oil in a laboratory hydrode-
sulfurization (HDS) reactor using a standard CoMo/Al
2
O
3
HDS
catalyst. Their results indicated a competition between HDS
and HDO with a decrease in HDS activity under certain con-
ditions. Pinheiro et al.
202
used model oxygenates blended with
straight-run gas oil (SRGO) to investigate the impact of bio-oil
on HDS, HDN, and aromatic ring saturation. These studies
showed no impact of 2-propanol, cyclopentanone, anisole, and
guaiacol on HDS, HDN, or ring saturation; propanoic acid and
ethyldecanoate were found to inhibit all three hydrotreating
functions. In a separate study,
203
these same investigators
found that CO and CO
2
formed during hydroprocessing also
inhibited HDS and HDN for hydrotreating SRGO. One of the
few studies of co-processing authentic bio-oil with petroleum-
derived material in a hydrotreater was conducted by Mercader
et al.
204
These investigators processed HDO bio-oil with SRGO
under typical HDS conditions and also found competition
between HDS and HDO; the product from co-processing con-
tained substantially higher levels of sulfur when compared to
HDS of the SRGO alone. However, catalyst activity for HDS was
not reduced by co-processing with bio-oil as indicated by a
return to the original low sulfur levels in the product when the
bio-derived material was removed from the feed. Product
yields were the same for SRGO and when SRGO was co-
processed with bio-oil.
5.6 Co-processing in other refinery unit operations
While the literature for co-processing in the FCC is substantial,
there is limited information in the open literature on co-pro-
cessing biomass-derived materials with petroleum-derived
materials in other standard refinery unit operations. Studies
on co-processing in the FCC and FCC hydrotreater are cited
above, but similar investigations for co-processing bio-naphtha
with petroleum naphtha in the naphtha hydrotreater (for
example) are missing. Fully integrating bio-oil in the refinery
will require an understanding of the impact of bio-derived
materials on all refining unit operations and the products
from these unit operations including the naphtha hydro-
treater/reformer, the diesel hydrotreater, the hydrocracker, and
the coker. This information needs to be developed and disse-
minated to fully inform eorts to integrate bio-oil into conven-
tional petroleum refineries.
6. Biomass-derived oxygenates in
nished fuels
Because of the high oxygen content of bio-oils, there is a
strong economic incentive to leave much of this oxygen in the
finished fuel product to the extent that government regulations
and product quality standards will allow. As shown
150
by Arbo-
gast, hydrotreating costs are significant for reducing oxygen
content to the 2 wt% to 3 wt% range. These costs increase
exponentially as the oxygen content goes below approximately
2 wt%. Here we examine what is known about the potential for
oxygenates in bio-oil to be components of drop-in-fuels.
As described above, the three components of biomass
(cellulose, hemicellulose, and lignin) produce dierent oxyge-
nated products during pyrolysis. Cellulose and hemicellulose
form low molecular weight (C
4
and smaller) ketones, alde-
hydes, acids, esters, ethers, and alcohols that cannot easily be
directly incorporated into gasoline. Hydrogenation of these
compounds leads to low molecular weight hydrocarbons,
suggesting that some form of oligomerization to increase
molecular weight is necessary if this bio-derived carbon is to
be incorporated into fuel. Cellulose and hemicellulose can
also produce furanic compounds such as furfural, furfuryl
alcohol, and furoic acid that, upon hydrogenation, can yield
methyl furans because of the relative recalcitrance of the furan
ring structure.
205
Sugars and anhydrosugars have also been
observed in the pyrolysis products, with hydrogenation produ-
cing 5- and 6-carbon alcohols. Pyrolysis of lignin, on the other
hand, produces phenols and alkyl phenols, methyl aryl ethers,
and guiacols. Ethers are generally converted to phenolics by
hydrotreating at adequately severe conditions.
The actual oxygenate composition of an upgraded pyrolysis
oil is highly dependent upon the degree of
Fig. 35 Alternate hydroprocessing schemes.
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hydroprocessing.
152,185
Hydroprocessing to 8 wt% to 10 wt%
oxygen yields distillate fractions containing carboxylic acids,
carbonyls, phenols, and ethers. Increasing the hydroproces-
sing severity eliminates carbonyl and carboxyl compounds and
converts aryl ethers to phenols, consistent with model com-
pound studies.
205
The oxygen present also varies with distillate
fraction. At roughly 8 wt% to 10 wt% oxygen the light and
naphtha fractions will primarily contain carbonyl, carboxyl,
and ether groups. The jet and diesel fractions will contain
these functional groups at lower levels, but will also contain
phenolic compounds. Upgrading further, under more severe
conditions, to roughly 5% oxygen leads to fractions containing
almost exclusively phenolic compounds.
6.1 Properties of biomass-derived oxygenates
Certain oxygen functional groups present in pyrolysis oils are
unlikely to be acceptable in fuel products. While carboxylic
acids are used in fuels as corrosion inhibitors at very low
levels,
206
at higher levels they cause corrosion and are poten-
tially poorly soluble in hydrocarbons at cold temperatures.
Aldehydes and ketones may undergo condensation reactions
leading to the formation of gums, although there do not
appear to be published studies showing this occurring. Esters,
ethers, and alcohols have all been used successfully in fuels
(biodiesel, MTBE, and ethanol, respectively) with the caveat
that MTBEs poor biodegradability in ground water ultimately
led to its removal from the US market.
207
Table 23 shows property data for a number of oxygenated
compounds that have been observed in raw and upgraded
pyrolysis oils. For gasoline, the boiling point must be between
about 25 C and the 225 C end point limit in standard specifi-
cations (ASTM D4814). Additionally, the 90% volume boiling
point is limited to 185 C or 190 C, depending on volatility
class (time of year). Therefore, only limited amounts of com-
pounds boiling above about 185 C can be blended. Examin-
ation of the data in Table 23 indicates that the furans, as well
as anisole and methyl anisole boil in the acceptable range,
and also have high octane number and very low water solubi-
lity. Christensen and coworkers
208
describe the properties of
dimethyl furan and 2-methyl furan blends with gasoline; and
these oxygenates have many desirable properties, including
little eect on vapor pressure. Singerman described the use of
methyl aryl ethers as gasoline blend components in the early
1980s.
209
Methyl aryl ethers improved octane number without
degrading other gasoline properties. These molecules may be
viable gasoline blending components if all regulatory require-
ments described below can be met. An important caveat is that
gasoline aromatics have been linked to fine particle emissions
for emerging gasoline direct-injection engines
210
and to the
formation of secondary organic aerosol in the atmosphere.
211
Both types of fine particles have been shown to have negative
health eects, suggesting that environmental regulators could
limit the allowable levels of aromatics in gasoline in the
future. For example, the United States Environmental Protec-
tion Agency currently limits benzene in gasoline to an average
of 0.62 vol%, not to exceed a maximum of 1.30 vol%.
212
It is
unknown if furans or aryl ethers show the same eect on
atmospheric fine particles.
Phenol also has a boiling point just in the acceptable range;
however, it also has high water solubility, poor solubility in
hydrocarbon at cold temperatures, and is corrosive. Other
ethers and phenols have boiling points too high to be used in
gasoline as blend components, although low residual levels
(below roughly 1000 ppm oxygen) may be tolerable.
Diesel fuels boil between either 200 C and 350 C (no.
2 grade) or 145 C to 300 C (no. 1 grade). No. 1 grade or
blends of no. 1 and no. 2 are used predominantly in cold
climate, wintertime environments. Thus, the oxygenates in
Table 23 that boil at too high a temperature for use in gasoline
could be used in diesel fuels based on boiling point. Addition-
ally, as C/O ratio increases, the phenolics become less soluble
in water and more soluble in hydrocarbon. However, because
these oxygenates are all aromatic compounds, they have a very
low cetane number, significantly limiting the amount that
could be economically blended. Their impact on precipitate
formation at cold temperatures is also unknown. Potentially,
these oxygenates could be tolerated in diesel fuels as residual
components up to an oxygen content of roughly 1000 ppm.
Very little research has been published on the potential for
biomass-derived oxygenates to be present in fuels at these low
levels.
Jet engine fuels boil between 180 C and 300 C, and have a
freezing point below 40 C. However, quality standards and
regulatory requirements for jet engine fuels are necessarily
more strict. Jet engines require clean, low soot formation com-
bustion and so the sooting tendency of jet fuels (measured as
smoke number) is limited in ASTM standard D1655. The pres-
ence of aromatic compounds can lead to high sooting ten-
dency, and so the standard also limits aromatics to 25 vol%.
Oxygenated compounds other than specifically approved fuel
additives are not permitted. Given these requirements, pyro-
lysis oil components will need to be fully hydrogenated to
alkanes before their use in jet fuel could be considered.
6.2 Regulatory and commercial requirements
New transportation fuels cannot simply be produced and then
introduced into the fuel market place. In the United States
there are many federal and state regulatory, commercial, and
consequent testing requirements that must be met. The exact
requirements will depend on the chemical makeup of the new
fuel. If it is demonstrably hydrocarbon ( primarily hydrogen
and carbon with less than perhaps 1000 ppm of sulfur, nitro-
gen, and oxygen), then requirements for market introduction
are likely to be less than if the fuel is an oxygenate (such as
ethanol, butanol, or biodiesel).
Clean air act. Compliance with the Act is mandatory and
has two aspects. First, the new fuel must meet the require-
ments for gasoline or diesel fuel that the EPA has already put
in place through rulemaking, such as limits on sulfur content
of diesel and gasoline, or vapor pressure of gasoline. Second,
and more importantly, new fuels have to meet the fuel
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Table 23 Properties of model biomass derived oxygenates
Compound class/name Molecular structure
Research and motor
octane numbers
Boiling
point (C)
Solubility in water
at 20 C (wt%)
Solubility in
hydrocarbon
Furans
2,5-Dimethylfuran 153, 109 94 0.26 Miscible
2-Methylfuran 155, 92 65 0.3 Miscible
Ethers
Anisole Unknown 154 Insoluble Miscible
4-Methylanisole 166, 148 174 Insoluble Miscible
1,2 dimethoxybenzene
(veratrole)
Unknown 206 Insoluble Miscible
Propylanisole Unknown 215 Insoluble Miscible
Phenols
Phenol Unknown 181.7 8.3 Soluble,
not miscible
p-Cresol 153, 149 202 1.9 Miscible
2,4-Xylenol 140, 113 211 0.5 Miscible
Guaiacol Unknown 205 1.7 Soluble,
not miscible
Syringol Unknown 261 1.7 Soluble,
not miscible
4-Propylphenol Unknown 232 Insoluble Miscible
4-Propylguiacol Unknown 250 Insoluble Miscible
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registration requirements of Section 211b of the Clean Air Act,
as implemented in CFR 40 Part 79. These consist of formal
registration with EPA, which includes divulging the compo-
sition of the new fuel, and dierent levels of emission and
animal exposure testing, depending on the fuel. Additionally,
if new fuels are to be used in existing engines designed for
gasoline or diesel, the EPA will require demonstration that the
emissions performance of existing engines/vehicles is not
degraded for the full useful life of the engine/vehicle
(190 000 km for a car, as much as 700 000 km for a heavy duty
truck). Potentially, this could involve testing many vehicles (for
example, testing to support EPA in dealing with the E15 waiver
petition involved testing of at least 80 vehicles).
Commercial acceptance (ASTM standard). Because most, if
not all, new fuels will be blended with petroleum fuels and uti-
lized in existing engines, acceptance of the new fuel by the pet-
roleum and auto/engine industries is critical. If the petroleum
distribution industry refuses to distribute the blended fuel
because they are uncomfortable handling it for safety or
environmental reasons, because it cannot be obtained with
consistent quality, or because they feel they accept too much
liability for engine operating problems, then the new fuel will
not be distributed. While these requirements are not directly
legislated, they are an important aspect of consumer protec-
tion. Primarily, this involves developing data to show that the
new material can be safely handled and that it is compatible
with existing engines and vehicles. This compatibility is
dierent than the emission performance mandated by the
Clean Air Act. The primary way that this is accomplished is
through development of an ASTM specification for the new
fuel, which may take the form of a blendstock specification
(such as exists for ethanol and biodiesel), adding the new fuel
to existing specifications (such as those for gasoline or diesel
fuel), or a new specification for a blended fuel (such as that for
B6 to B20 blends). ASTM specification development requires
data on a variety of issues, and what testing must be done ulti-
mately depends on the properties of the new fuel. But it
should be clear that this is a non-trivial requirement and may
take 2 to 5 years to complete.
Approval of tanks and dispensers for use with new fuel. In the
United States, underground storage tanks are regulated by the
EPA, which requires tanks to be compatible with the liquid
being stored. This can be demonstrated via testing at a third-
party laboratory such as Underwriters Laboratories (UL) or by
warranty approval from the tank manufacturer. Local ocials,
such as fire marshals, regulate the dispensing and handling of
fuels. These ocials are known as Authorities Having Jurisdic-
tion or AHJs. These ocials require that equipment (fuel
tanks, piping, pumps, fuel dispensers, hoses, and nozzles) be
listed by a third party organization as being safe for use with
the fluid being handled or be covered under warranty for use
with the new fuel. In most cases this means that the equip-
ment has been listed by UL for use with the fuel in question.
UL develops test methods and aggressive test fluids to ensure
that equipment passing their tests will be safe for use with the
designated fluid. For a new fuel a UL test fluid will likely not
exist. Development of test methods, fluids, and performance
testing of equipment can take several years.
7. Summary
Introducing biomass pyrolysis oils into existing petroleum refi-
neries oers an opportunity facilitate the introduction of ligno-
cellulosic bio-oils for production of renewable biofuels. As
described in this perspective, raw pyrolysis oils have physical
and chemical properties that make direct insertion into refin-
ery unit operations dicult. Dilution with petroleum streams
is not feasible because of the poor miscibility of pyrolysis oil
and distillation is not practical because of its reactivity. Thus,
it is highly likely that upgrading will be necessary before the
oils can be introduced.
There are several options available for upgrading pyrolysis
oils, some of which are described above. Generally, these
approaches involve upgrading the condensed oil or the pyro-
lysis vapors before they are condensed. In this context, the
appropriate upgrading strategy will depend upon the chemical
and physical properties of the resulting oil, where the oil is
introduced and ultimately the profitability for the refinery.
As shown in this perspective, there is great need for further
research in this area. While some studies have been published
in this area more work is needed to evaluate and compare
dierent upgrading and integration strategies. Any research
program in this area should also include a fundamental under-
standing of the how the upgrading process aects the physico-
chemical properties of the resulting oil and how this in turn
influences how the material can be inserted into the pet-
roleum refinery with minimal impact on existing unit oper-
ations. Research should also include a detailed understanding
of ultimate cost of the upgraded oil and the eects on refinery
profitability.
Acknowledgements
We acknowledge funding from the National Advanced Biofuels
Consortium, funded by the US Department of Energy (DOE)
BioEnergy Technologies Oce (BETO) through Recovery Act
Funds and the US DOE BETO program that supported this
eort. We would like to thank researchers at BP for stimulating
conversations in this area.
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A Perspective On Oxygenated Species in The Refinery Integration of Pyrolysis Oil

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