Originally appeared in:

February 2010, pgs 35-38.

Used with permission.

Clean fuels

SpecialReport

Consider new methods for bottom

of the barrel processingPart 1
Advanced methods use molecule management to upgrade heavy ends
M. Motaghi, KBR, Houston, Texas; and K. Shree and S. Krishnamurthy, KBR,
New Delhi, India

arge price differentials between light, sweet crudes vs. heavy,

sour crudes have created strong incentives for refiners to lower
costs by incorporating as much heavy crude blends into the
refinery processing in scheme as it can tolerate. Several refineries
have little or no bottoms processing capabilities, thus yielding large
volumes of high-sulfur fuel oil (FO). New bunker-fuel legislation
and pending carbon-footprint initiatives create the need to further
upgrade refinery resid products, both for expansion and enhancement
reasons. Several case histories will cover the staggered investment
options to produce premium road asphalt and solid fuels (Fig. 1).

Changing crude diet. Recent economic and geopolitical global

uncertainties are factors in the steep rise in crude prices, thus affecting refinery operations worldwide. Refiners are finding themselves
faced with the difficult quest to search for crude blends to maximize margins. While refinery margins will continue to be dictated
by processing heavier, more sour crudes, the dramatic increase in
residuum content from 10% in light sweet crudes to 50% in extra
heavy crudes poses interesting challenges, while presenting some
unique opportunities. The bulk of the global operating refineries
have little or no residuum processing capabilities and produce large
volumes of high-sulfur FO (HSFO) and bunker fuel.
As demand shifts to natural gas, FO demand is expected to
drop adversely, thus affecting FO prices in the future (Fig. 2). This
situation is only expected to worsen as refiners face regulatory
pressures ranging from new maritime bunker fuel specifications

to carbon dioxide cap-and-trade and carbon footprint limitations.

As the world moves towards cleaner bunker fuels, finding alternative means to upgrade bottom of the barrel streams will become
increasingly important.
In parallel, the demand for jet fuel and diesel is expected to
grow, and many refiners are actively focused on shifting demand
from motor gasoline to diesel, while still analyzing all available
options. The price differential between diesel and gasoline is likely
to be sustained over the long-term and is validated by the billions
of dollars of investment announcements by the major international and national oil companies toward dieselization. In markets
dominated by fluid catalytic cracking (FCC)-based refineries, this
need to increase distillate production has taken on a new dimension that will impact long-term refining margins.
Changes in C/H ratios. In its simplest form, refining is
the process of changing the carbon-to-hydrogen (C/H) ratio of
naturally occurring crude oils. Thus, at the molecular level, the
operation of all 650 refineries in the world is essentially targeted at
converting high C/H ratio feedstocks into high hydrogen to carbon ratio for transportation fuels. This ratio change between the
crudes and products can only be accomplished through two broad
processing routes: carbon rejection and hydrogen addition.
While profitability can only be sustained by economically converting the large volumes of residuum into high-value transport
fuels, these objectives must be accomplished in a difficult business
climate that mandates applying low-investment solutions while
optimizing usage of existing refinery resources.

FO crack margin, $/bbl

-10

-20
2000

2004

Source: Singapore margins w.r.t. Dubai crude from Platts

Fig. 1

The residuum oil supercritical extraction unit at the

Navaho Refinery.

Fig. 2

FO cracking margins 2000 to 2008.

2008

SpecialReport

Clean fuels

Carbon rejection. Carbon rejection is favored by low crude

prices and high hydrogen prices, when it is economical to reject the

residuum as petroleum coke, while producing the required transport fuel volumes by incremental crude oil processing. During these
processes, the bulk of feed contaminants are rejected with the carbon into the coke, rather than into the liquid products. Traditional
carbon rejection techniques include FCC, resid fluidized catalytic
cracking (RFCC), delayed coking (DC) and visbreaking (VB).
FCC and RFCC in combination are widely used carbon rejection technologies to convert the high-boiling, high-molecular weight
hydrocarbon fractions into more valuable gasoline, olefinic gases
and other products. However, due to the nature of the process, they
are limited in processing lighter, low-metals, low-sulfur residues.
Visbreakers are essentially a means of improving viscosity of the
residuum so as to minimize the addition of valuable distillate boiling
range cutter stock to meet FO specifications. In addition, with the
increasing shift in product demand from motor gasoline to diesel
and jet fuels, these technologies will no longer be the first choice.
Residues from heavy crude oils contain high concentrations of
sulfur, complex hydrocarbons and heavy metals such as nickel and
vanadium. Due to the nature of these residues, delayed coking
technology is the most commonly used carbon-rejection technology.
However, this process produces highly hydrogen-deficient, unstable
products that require further processing and yields coke residuea
high C/H ratio molecule, as a byproduct.
Although, coking is a mature technology with low implementation risks, in a carbon footprint future, this technology is likely
to face stiff environmental and regulatory resistance even in the
face of lower crude prices. High-sulfur petroleum coke prices are
distressed and as is evident in the Canadian inland environment,
coke is just being piled up in large quantities with no real economic outlet. This trend cannot be sustained in the long run.

Hydrogen addition. Conversely, hydrogen addition is favored

by high crude prices and low hydrogen prices when it is more

economical to upgrade the residuum to transport fuels, while
maximizing the transport fuels production from the base crude
capacity. Thus far, residue-hydrogen addition technologies have
focused on fixed-bed hydrocracking as against ebullated-bed
hydrocracking and slurry-phase hydrocracking, the former requiring periodic shutdowns to regenerate catalyst.
Ebullated-bed processes are continuous and produce higher
levels of liquid fuels (no coke). But they are unable to achieve complete resid conversion and still produce 20%30% of heavy-resid
product. Ebullated beds have also been prone to high operating
costs, and have sometimes been plagued with poor operability. The
quality of liquid products, although improved over coking, still
requires secondary processing to produce clean fuels. The inability
to achieve near complete conversion requires further processing
of unconverted resid. As a result, ebullated-bed technologies have
not achieved huge deployment, which, when coupled with the
high capital cost, makes them the least robust at low-oil price
scenarios.
Slurry-phase hydrocracking. The recent flurry of activities
indicates the advent of slurry-phase hydrocracking into the market
place. This technology adopts high operating pressures and can
achieve near complete conversion of the residuum while producing finished saleable products. While the projected economic
conditions of high crude prices and low gas prices are ideal for
investment in these high-pressure/high conversion technologies,
the capital investment requirements may have some dampening

effect for immediate widespread adaptation.

Principles of molecule management. In the background
of high volatility within the markets, which is expected to continue, the optimal solution may require most refiners to adopt a
combination of carbon rejection and hydrogen addition processes.
This is especially true in an environment of uncertain refining margins where the size of capital investment can come under a higher
scrutiny over traditional project return on investment criteria. It
is in this context that a staggered investment option involving the
ability to achieve partial benefits at lower initial investments, while
preserving options for incremental benefits with higher investment
in the future, gains increasing importance.
Refiners are often constrained by the need to convert a defined
crude slate to a set product slate without realizing the change required
at the molecule level and the cost associated with such conversion.
Refiners can also be blinded by the compelling need to produce traditional refinery products such as transport fuels and petrochemical
feedstock from every barrel of crude, often expending substantial
capital in the process, while ignoring economic synergistic opportunities that may exist with other nontraditional industrial applications.
The principles of molecule management dictate that the best economics are derived by capturing the highest value of every molecule
present in naturally occurring crude oils at every point in the process.
When viewed in this context, it is evident that it will be prudent to
analyze the residuum fraction not only by the traditional barometers
of boiling range and gravity, but by molecular speciation.
While distillation based separation schemes for the virgin
crude fractions are economical and adopted almost universally, in
almost all cases, the volume and quality of the residuum is essentially determined by the quality of the vacuum gasoil (VGO) fraction and the ability to process this fraction through conventional
hydroprocessing or catalytic cracking conversion units.
In most cases, the limiting factor is the metals content or the
Conradson Carbon Residue (CCR) in the GO. The residuum volume and quality is, by balance, a reject defined by GO quality, and
is characterized as black oil. By conventional wisdom, this stream is
either removed as FO or asphalt, or is subject to thermal conversion
processes for upgrading.
While it is a well-established fact that hydro or catalytic conversion of the heavy gasoil (HGO) fractions will result in substantially better yields and qualities of transport fuels (gasoline, jet fuel
and diesel) than thermal conversion processes, and the incentive to
maximize this fraction of the crude exists, operating economics are
substantially influenced by the incremental concentration of impurities (metals and CCR) in the feed due to their impact on conversion
unit catalysts.
When analyzing the residuum at a molecular level, it will be
evident that a substantial volume of higher boiling range white oil
molecules worthy of effective catalytic upgrading are present in
this fraction, which by conventional methods, are rejected as black
oil products or subjected to thermal conversion processes. This
phenomenon is essentially caused by limitations in distillationbased separation processes where the lowest boiling point species
of the undesirable impurity is the determining factor in the volumes of the GO and residuum derived. This impacts the refinery
product slate and economics negatively.
It is, therefore, essential to look at supplemental alternate
separation technologies to effectively extract these higher boiling
white oil molecules from the residuum. The options become obvious when analyzing these molecular species, and it is clear that

HYDROCARBONPROCESSING february 2010

SpecialReport

Clean fuels
these undesirable impurities are essentially asphaltenic or resinic
in nature and can be separated by solubility driven processes.

Easier to process downstream

applying the solubility-based physical separation process, solvent

deasphalting (SDA), wherein the saturates can be effectively separated
from the resinic and asphaltenic molecules contained in the residuum.
SDA uses a paraffinic solvent, which by molecular structure (like dissolves like) preferentially dissolves paraffinic and naphthenic molecules
while rejecting the aromatic-rich molecules in the pitch (Fig. 3).
Although light-paraffin solvent-based deasphalting is often referred
to as a metals or CCR rejection process, in essence, it is an aromaticsrejection technology. The reject contains complex aromatic molecules
that are the least soluble in paraffinic solvents, are highly hydrogen
deficient and contain a majority of polars (metals and CCR) that are
least desirable when fed to a hydro or catalytic conversion unit.
Conversely, the extract or the deasphalted oil (DAO) contains
essentially the saturates, with very low metals and CCR, making
this a white oil ideal for conversion processes. Also, the top barrel of DAO derived from the residue via solvent extraction by all
measures, will always represent a superior conversion feedstock
to any secondary unit when compared to the last barrel of VGO
derived from a distillation process.
When examining the suitability of feedstocks to a conversion
process, the inherent molecular content (as opposed to boiling
range) and their impact on conversion unit performance will
become obvious. For example, a close examination of the Watson
K factors of feeds derived from GO fractions and resids from
staple Arabian crudes to an FCC unit will reveal that the DAO
derived from a solvent extraction process brings in resid boiling
range white oil molecules that are not otherwise achievable by
conventional distillation based processes (Table 1).
The DAO, rich in paraffins and saturates, is an excellent feed
to the FCC. Also, due to the inherent nature of the aromatic rejection associated with solvent-based separation processes, the DAO
will always have a higher Watson K than the corresponding VGO
from the same crude.
As listed in Table 2, the FCC yields and product qualities derived
from a DAO based feed (Mid Continent) is very similar to the
VGO yields from the same crude in spite of processing heavier
molecules derived from the resid boiling range. The alternate option
would be to reject these valuable resid white oil molecules to lower
value black oil products, or to process through a lower yield thermal
conversion process while reprocessing the derived coker GOs in
the FCC. The understanding of the value of these high hydrogen
content resid molecules and their disposition is a critical data point
in determining refinery yields and economics.
An understanding of the metals and CCR content in the DAO
stream and their impact on conversion unit catalysis is critical to
determining the extractable volume of white oil molecules contained in the residuum. While metals are inherently addressed
by demetalization catalysis in a hydrocracker, or by FCC catalyst
consumption, and the economics are easy to calculate, the understanding of the CCR is more complicated (Table 2).
Notice that the CCR content of DAO is nearly 10 times higher
than the VGO, yet the yields and product qualities and coke make
are still comparable. The obvious inference is that the CCR in
this case does not impact the conversion simply by virtue of the
molecules that contribute to it.
In its simplest form, CCR is the residue derived from a test
wherein a heavy hydrocarbon is subject to a temperature-time

Feed

Bottom-of-the-barrel

White oil molecule management. The solution involves

DAO

Asphaltene

Asphaltenes w/CCR, metals,

nitrogen, etc.
Fig. 3

Solvent de-asphalting process and product streams.

Table 1. Watson K of FCC feed fractions

Feedstock Atmospheric
source
resid
VGO

Propane
DAO

Butane
DAO

Coker GO

Arabian light

11.60

11.68

11.81

11.74

11.4

Arabian heavy

11.44

11.62

11.86

11.78

11.4

Table 2. FCC yields from Mid-Continent VGO/DAO

and CGO

100% DAO

100% VGO

100% CGO

API

19.2

24.7

19.0

S, wt%

0.79

0.75

CCR, wt%

3.9

0.39

Less than 1

Ni + V, PPM

16

Less than 1

Conversion

80.3

81.05

63.2

C2

4.86

3.65

1.49

Total C3s

6.37

6.80

4.60

Total C4s

10.30

11.76

8.87

Total gasoline

48.98

52.12

40.16

Total cycle oil

19.70

18.95

35.78

Coke

9.79

6.72

6.00

FCC yields, wt%

exposure. While the temptation to use CCR as a parameter to

establish conversion unit performance exists, a molecular level
examination will highlight significant differences. In short, all
CCRs are not the same. While the heptane insolubles have an
almost direct permanent deactivation effect on downstream process catalysts, the other CCR molecules have a far less telling
effect.
The CCR derived from a distillation-based separation process will contain substantial C7 insolubles, while that in a DAO
derived from a solvent extraction, by definition, should be nondetectable. This distinction can be clearly demonstrated by operating performance differences between units processing atmospheric
or vacuum resids and those processing DAOs with identical CCR
content. This difference is often not well understood by refiners
while correlating the impact of CCR on their unit performance.

HYDROCARBONPROCESSING february 2010

SpecialReport

Clean fuels

Table 3. Commercial data for conversion

After conversion to residuum
Supercritical SDA oil supercritical extraction
Feed rate, bpsd

7,000

10,000 (up to 15,000)

Solvent ratio vol/vol

4.56

56

Energy MMBtu/bbl

99

69

6575

7085

Deasphalted oil quality

Yield, LV%

Asphaltene, (C7 insols) ppmw 200800

< 25

CCR, wt%

1213

911

With trays

With advanced intervals

With mesh pad

With advanced intervals

High pressure vessels

Extractor
DAO separator

While the DAO must theoretically contain no C7 insolubles,

an examination of the DAO derived from conventional SDA
processes would often indicate levels ranging from 3001,000
ppmw. This can only be explained by the phenomenon of entrainment. With the advent of state of the art structured-packing based
internals into the solvent deasphalter separator vessels in 1995, the
level of C7 insolubles is now controlled at or below 100 ppmw
in most deasphalting units and below 25 ppmw in several high
performing units. As an added benefit, the process unit can now
operate at about twice the phase rates of conventional separators
and provides about twice the mass transfer efficiency of conventional extraction contacting devices.

Table 3 lists commercial data published by a US refiner that

shows the before and after conversion of a non-supercritical SDA
unit to an advanced residuum oil supercritical extraction technology
with advanced internals. As evident from the data, the addition of
new internals and adoption of residuum oil supercritical extraction
methods achieved a higher throughput, higher yield and a better
DAO product quality. All this was achieved at similar operating
conditions with significantly lower specific energy consumption.
Note, the decrease in asphaltene content of the DAO to nearly
below detectable limits, conforming the assertion that the presence
of C7 insolubles in the DAO is an artifact of entrainment that can
be controlled by good technology and internal design features. HP
Next month. In Part 2, the authors discuss new supercritical
extraction methods that can be applied to optimize molecule
management of residuum.
Mitra Motaghi is an associate with the KBR refining technology business unit
in Houston Texas, with specific focus on resid and hydroprocessing technologies. She
holds an MS degree in chemical engineering from Texas A&M, Kingsville, Texas.

Kanu Shree is an associate with the KBR refining technology business unit in
New Delhi, India, with specific focus on resid and hydroprocessing technologies. She
holds a BS degree in chemical engineering from the Indian Institute of Technology,
New Delhi, India.
Sujatha Krishnamurthy is an associate with the KBR refining technology
business unit in New Delhi, India, with specific focus on resid and hydroprocessing
technologies. She holds a BS degree in chemical engineering from Anna University,
Chennai, India.

Article copyright 2010 by Gulf Publishing Company. All rights reserved.

Printed in U.S.A.
Not to be distributed in electronic or printed form, or posted on a Website, without express written permission of copyright holder.

Originally appeared in:

March 2010, pgs 55-58.
Used with permission.

Clean fuels

SpecialReport

Consider new methods for bottom

of the barrel processingPart 2
New principles of molecule management dictate
the best economics when upgrading residuum
M. Motaghi, KBR, Houston, Texas; and K. Shree and S. Krishnamurthy, KBR,
New Delhi, India

lobally, refiners are often constrained by the need to convert a defined crude feed slate into a desired finished product slate without realizing the reaction changes required at
the molecule level and associated costs for such conversions. Too
often, refiners can be blinded by the compelling need to produce
traditional refinery products such as transportation fuels and
petrochemical feedstocks from every barrel of crude. Such actions
involve expending substantial capital in the process, while ignoring economic synergistic opportunities that may exist with other
nontraditional processing applications. For example, cost-effective
upgrading of the bottom of the barrel can involve applying new
supercritical extraction technologies that can manage the black
molecules or residuum oil and produce end products other than
transportation fuels.
Black oil molecule management. In Part 1, the merits

of DAO as a valuable feedstock to conversion units were presented. However, the limited outlets for the effective disposition
of the pitch has historically had some dampening effects on the
widespread acceptance of this molecular solution. The commercially practiced solutions, so far, involve using the pitch as
a high-sulfur FO (HSFO) blending component, a road-asphalt
blending component, thermal or delayed coke feedstock, or as a
liquid feed to a gasifier.
Although the blend out to FO will lower the refinery HSFO
production, with the diminishing outlets for FO, the ultimate goal
of a refiner to eliminate this product is not achieved. In addition,
using high-value distillate boiling range cutter stock will have a
negative impact on refinery economics.
As an alternate option, the most obvious solution would be to
direct these black oil molecules to a delayed coker. As the CCR
content of the pitch is essentially a product of a concentration
effect, its inherent limitation in the delayed coker feed and its
impact on coker furnace run length must be considered. In commercial applications, this parameter is closely monitored and is
often limited to about 34 wt%, with the option to go up to 38 wt%
in a grassroots design. This, in turn, means that limitations in coker
feed CCR can sometimes be the controlling factor in the amount
of white oil molecules that can be lifted from the residuum.
In many cases, the asphaltene molecules directly produced
from a traditional SDA process are too hard to be sold as road
asphalt. The production of road asphalt would require the overall

lift of the white molecules from the residuum to be very low, making this entire solution uneconomical.
Road asphalt is often driven by seasonal demand changes, and
refiners address this through direct air blowing of the vacuum
resids (VRs). While air blowing is a solution of convenience, when
viewed through the prism of molecule management, it involves
the downgrading of valuable white oil molecules contained in the
VR to a black oil productan economic negative, not withstanding the implications of the associated environmental control issues
that come with it.
An interesting refinery hydrogen balance can be established
through gasification of the pitch. The liquid feed system lowers the net capital investment requirements, although it can
still be very high when viewed in absolute terms. In addition,
commercial experience suggests a substantial improvement in
reliabilityin some cases, twice as that of traditional solid-fuel
based gasifiers. However, with the projection of depressed natural
gas prices, a cheaper hydrogen source availability in the longterm, refiners may find it difficult to justify large investments in
gasification technologies.
Pitch molecule management. Against this background,

eliminating the pitch at the molecular level will be required to

explore all available options to maximize the benefits of the solubility driven process. The pitch consists of essentially asphaltenic
and resinic molecules. For this exercise, resinic molecules are

C84 H98 N2S2O3

1248 MW
40.4 % Aromatic carbons
80.85 wt % C
7.92 wt % H
2.24 wt % N
5.14 wt % S
3.85 wt % O

O
S

H
N

S
N

Asphaltene materials with complex structures

Precipitated from crude oils by aliphatic solvents. Soluble in benzene.
Mol. wt. 1,0003,000. High in S, N, O and metals ( V + Ni).
Fig. 4

Asphaltene materials with complex structures.

SpecialReport

Clean fuels

Cooler

those composed of aromatic rings with long side chains, while

asphaltenic molecules are complex aromatic compounds with
relatively shorter side chains (Fig. 4). This observation leads to the
obvious questions associated with the ability to separate the pitch
into two distinct molecular fractions and the refinery benefits that
can be derived by finding economic outlets for these fractions.

Exchanger
Resin
heater

Steam

Resin
separator

Resin
stripper
Resin

Mixer
START

Resid
Solvent
circulation

Condenser

Asphaltene
separator

Solvent
surge

Asphaltene
heater

DAO
stripper

DAO
separator
DAO
heater

Solvent
recycle

Steam

Asphaltene
stripper

Steam

DAO

Asphaltene
Fig. 5

Exchanger

Flow diagram of a residuum oil supercritical extraction

process.

New supercritical extraction methods. In a solubility

driven process, the type of molecular structure is a critical parameter in determining the distribution coefficient of that molecule
between the two liquid phases. Therefore, the expectation of separation between structure-based resinic and asphaltenic molecules
in this process will not be unreasonable (Fig. 5).
In reality, this is practiced in three operating commercial
residuum oil supercritical extraction units where the operating
conditions of the asphaltene separator are adjusted to lift the
resinic molecules in the DAO. The resinic molecules are then
recovered from the DAO by partially expanding the solvent under
supercritical conditions.
The intent is to fractionate the DAO exiting the asphaltene
separator (that contains saturates and resins) into a light DAO
(predominantly saturates) and a resin product. This is accomplished by adjusting the operating conditions of the resin separator so that sufficient expansion of the solvent is realized to
selectively drop out the heavy part of the oil, resulting in solubility
based separation at supercritical conditions. The yield and quality
of the resin may be varied to influence the quality and quantity
of the DAO.
This arrangement will also provide the flexibility to balance the
streams to the downstream processing needs, while consistently
meeting the required DAO quality and exercising other disposition options for the intermediate resin stream.
Resins and road asphalt. Examining the properties of the

Fig. 6

Solid asphaltene pellets are easier to transport and store.

Proprietary
high-capacity
feed distributor
Pelletizer
vessel
Surge
drum

Trim heat
exchanger

Hot liquid
asphaltene

Cooling water
Pellets
and water

resin fraction will reveal that this stream can now manifest into
multiple product outlets. One economic outlet is the direct road
asphalt productionsolely from black oil molecules without
further processing. The resin molecules are lighter than road
asphalt and the required grade of road asphalt can be produced
by selectively blending the asphaltenic molecules in the required
proportion. Due to the dewaxed nature of
these molecules, they exhibit excellent ductility properties at the same penetration not
otherwise achievable by traditional technology options.
Inherent in the process is the ability to
adjust the volume and quality of the resin.
Seasonal demand variations in road asphalt
may be addressed by adjusting the resin
volumes derived and by selectively directing the excess to either the DAO or the
asphaltene fraction.

Feed pump
Solid pellets
to storage

Fig. 7

Conveyor belt
for pellet
transportation

Screen for
dewatering
drying

Water
dump

Solids Cooling Fin-fan or

filter water water cooler
pump

Flow diagram of asphaltene solid pelletizing unit.

HYDROCARBONPROCESSING march 2010

Asphaltenic rejects. While this solution provides an attractive economic option

to produce premium-grade road asphalt, the
challenges associated with dealing with the
residual asphaltenic molecules remain.
The asphaltenic molecules are high in
CCR, metals and sulfur content and are
basically not worthy of upgrading. This

SpecialReport

Clean fuels
represents the lowest-value true black oil content of the residues,
and the best economics lies in solutions that divert these molecules
away from the refinery to industries or end users outside the refining business that have an incentive to process these streams.
The major challenge here is in the handling and transportation of these molecules. The asphaltene product is produced as
a high-viscosity liquid that solidifies at ambient temperature. A
low-cost, high-capacity solid-pelletization technology is the obvious transport solution and will help refiners to economically store
and move these rejects to a more desirable end use (Fig. 6).
Solid fuel. This represents a simple and cost-effective option
for asphaltene disposition for the cement and steel market where
a large demand for high Btu solid fuel exists.
There are existing commercial technologies that produce solid
fuel from the asphaltene rejects. However, these processes are
generally capacity limited, high in maintenance, low in reliability,
and are manpower intensive. A new solid-pelletizing technology
is an ideal solution to solidify asphaltenes and other heavy hydrocarbons. This method is a low-cost process, easy to operate, and
has a high expected onstream factor.
The produced pellets are resistant to dusting and can be easily
handled, stored, and transported. These pellets are near spherical
with an expected size distribution between 1 mm and 3 mm, and
they have good grindability, storage and transportation characteristics as indicated by the high Hargrove Grindability Index
(HGI), storage test temperature and low friability. The high angle
of repose provides high capacity on conveyors. The small amount
of residual moisture on the pellets helps to minimize dust formation during transport (Fig. 7).
The asphaltene pellets can be used as solid fuel in the cement
kilns, steel industry and in utility industries. The pellets can be
added to fuel-grade coke or coal as additive to enhance combus-

tion characteristics. The heating value, organic carbon, and chemical properties such as sulfur, nickel and vanadium are governed
by the crude properties. The asphaltene pellets have 20%50%
higher heating value than petroleum coke. In view of the superior
heating value, combustion characteristics and ease of grinding, the
asphaltene pellets should demand a higher value per ton when
compared to fuel-grade coke and coal.
Refinery case illustration. In this Base Case, a 200,000

bpsd refinery processes heavy, sour, Middle Eastern crude (API

31.4) producing 6,230 tpd of VR and 8,847 tpd VGO (Fig. 8).
The refinery has no bottoms processing units and is currently
using high-value distillates to cut its VRs to produce large volumes
of low-value HSFO (Tables 4 and 5).
Interim investment option. In this interim option, the
refiner invests in a residuum oil supercritical extraction unit and
asphaltene solid pelletizing unit, essentially eliminating the production of HSFO. The investment in the ISBL portion of the two
units will amount to about US$ 6575 million (Fig. 9).
This combination represents the most ideal short-term solution to allow all the DAO produced to be processed in the existing
FCC units offsetting the equivalent VGO that may be sold. The
change in FCC feed will have a small effect on the FCC yields.
The lower the DAO make, the better quality of the DAO, but
a higher, lighter resin volume must be handled. The higher volume, lighter resin will lead to a higher road asphalt volume make,
and a resultant lower solid fuel production (Table 6).
Final investment option. In this ultimate option, the refiner
invests in a product residuum oil supercritical extraction unit and
Vacuum distillation

Table 4. Interim solution: unit yields, (resin yield 20%,

DAO yield 30%, asphaltene yield 50 wt%)
Feed VR Asphaltene

Products resin

DAO

Yield on VR, tpd

6,230

3,115

1,246

1869

S.G.@ 60F

1.033

1.112

0.984

0.952

Nitrogen, wt%

0.4

0.6

0.3

0.2

Sulfur, wt%

5.5

4.5

3.7

CCR, wt%

24

40

12.5

Nickel, wppm

29

56

0.9

Vanadium, wppm

110

216

7.4

1.7

250

R&B softening pt, F

VR 6,230 tpd

Fig. 8

1,908

2,453

6,869

3,847

S.G.@ 60F

1.033 0.922

1.025

1.112

0.930

0.922

0.4

0.6

0.1

0.1

Nitrogen, wt%

0.4

0.1

Sulfur, wt%

5.5

3.3

5.3

3.4

3.3

CCR, wt%

24

0.9

22.1

40

0.9

Nickel, wppm

29

0.1

21.8

56

0.3

0.1

Vanadium, wppm

110

0.4

79.8

216

0.7

0.4

250

R&B softening pt, F

Base Case refinery processes heavy crude with no bottoms

processing capability.

Export VGO
3,847 tpd
VGO
VGO
8,847 tpd 5,000 tpd

VR 6,230
tpd

Solid fuel
2,453 tpd

Fig. 9

Pelletizing
technology

FCC feed
6,869 tpd
DAO
1,869 tpd

Vacuum
distillation

FCC

Virgin Road Solid
feed
VGO

VR VGO asphalt fuel
blend export
6,230 8,847

FO 9,811 tpd

Base Case refinery

Table 5. Overall material balance, interim solution

Yield on VR, tpd

Cutter
3,581 tpd

Residuum oil
supercritical
extraction

Asphaltenes
2,453 tpd

Resin
1,246 tpd

Asphaltenes
662 tpd

Road asphalt
1,908 tpd

Interim solution

Base Case refinery processes heavy crude with residuum

oil supercritical extraction unit and solid asphaltene
pelletizing unit.

HYDROCARBONPROCESSING march 2010

SpecialReport

Clean fuels
Table 6. Overall material balance, final solution

VGO
8,847 tpd

Hydrocracker feed
10,716 tpd
DAO
1,869 tpd

Vacuum
distillation
VR 6,230
tpd

Solid fuel
2,453 tpd

Fig. 10

Pelletizing
technology

Residuum oil
supercritical
extraction

Asphaltenes
2,453 tpd

Resin
1,246 tpd

Asphaltenes
662 tpd

Road asphalt
1,908 tpd

Final solution

VR

Virgin
VGO

Road Solid
asphalt
fuel

HC
feed

Yield on VR, tpd

6,230

8,847

1,908

2,453

10,716

S.G.@ 60F

1.033

0.922

1.025

1.112

0.928

Nitrogen, wt%

0.4

0.1

0.4

0.6

0.1

Sulfur, wt%

5.5

3.3

5.3

3.3

CCR, wt%

24

0.9

22.1

40

1.6

Nickel, wppm

29

0.1

21.8

56

0.3

Vanadium, wppm

110

0.4

79.8

216

0.6

250

R&B softening pt, F

Table 7. Hydrocracker yields

Base Case refinery processes heavy crude with residuum

oil supercritical extraction unit and solid asphaltene
pelletizing unit with hydrocracking unit to upgrade extra
DAO product.

an asphaltene solid pelletizing unit, essentially eliminating HSFO

production. The higher volume of conversion feedstock available
will have to be processed in a hydroprocessing unit.
The required conversion can vary from a nominal 20% that
is associated with a traditional catfeed hydrotreater to a nominal
65% conversion achievable in a once-through conversion unit.
The design and operating pressure of the hydrocracker can
be adjusted to vary the conversion from 15%55% by varying
the operating conditions of the hydrocracker beds. This, in turn,
will provide the refiner with the additional flexibility to vary the
gasoline-to-diesel ratio derived from the two conversion units,
while eliminating the production of fuel oil altogether. The
cost of this investment for a large hydrocracker can vary from
$400600 million and can be differed until economic conditions
warrant (Fig. 10).
In the low-conversion mode, the FCC will be at its maximum
capacity, and the yields and quality are expected to be better than
current operations (Table 7). In the high conversion mode, the
FCC will be at low throughput and out of heat balance, prompting the need for a small bypass DAO or resin feed to be sent
directly to the FCC.
Molecule management summary. When adopting the
principles of molecule management, it is clear that the best value
is derived by directing the selected residuum molecule to the

Case Low conversion

High conversion

Pressure, psig

1,960

1,960

H2 circulation, scf/bbl

6,000

6,000

Temperature F

Base

Base +25

650F+ conversion

15

53

H2 consumption

825

1,530

Naphtha, C5-180F

0.2

7.2

Kerosine, 180F330F

1.8

17

Diesel, 330F650F

14.6

39.9

FCC feed

85.2

47.5

Yields, vol%

appropriate end user. The optimal solution will involve adopting

unique means of integrating the principles of carbon rejection and
hydrogen addition while maintaining a keen recognition of the
prevalent investment climate.
The combination of SDA and asphaltene pelletizer technologies represents an economic low-cost solution to eliminate FO
production and can be implemented at a fraction of the cost of all
other resid processing options. The DAO is an excellent feedstock
and can be easily processed in the refinery FCC or hydrocracker
units. Premium road asphalt can be derived from the pitch, and
the reject solid asphaltene pellets can be sold to the cement, steel
and power industries. HP
End of series: Part 1. February 2010.

www.kbr.com/refining

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