ROSE PROCESS OFFERS EIIIERGY SAVINGS FOR SOLVEft En'RACTIOR

J. A. Gearhart and S. R. Nelson

Kerr-McGee Refining Corporation
Oklahoma City, Oklahoma
ABSTRACT
Kerr-McGee has developed and commercialized an
energy-efficient solvent extraction process
known as ROSE (Residuum Oil Supercritical
Extraction) in which the solvent is
recovered as a supercr i tical flu id. The energy
requirement for supercritical solvent recovery
is substantially lower than for conventional
solvent processes using evaporation, compression
and condensation. The ROSE technology is
applicable to a wide variety of both organic and
inorganic solvents. Energy savings of forty to
fifty percent have been demonstrated
commercially with ROSE compared to traditional
solvent recovery. The dollar value of the
savings is related to the solvent-to-feed ratio
employed in the process and the cost of steam,
fuel and electr ici ty. Kerr-McGee has a bench
scale pilot plant available for feedstock
evaluation. Four commercial ROSE units and a
large pilot plant have been placed into
operation during the past five years. Two
additional units are under construction and
others are in various stages of design.
This paper descr ibes the ROSE process and
illustrates its flexibility with respect to the
types of feedstocks and variety of solvents
which are utilized.
IN'!'RODUCTION
Conventional solvent extraction has been
utilized for more than half a century to
separate the more valuable constituents from
heavy oils and residuals while rejecting the
less des irable mater ials. For example, propane
deasphalting rejects high molecular weight
viscous asphaltic and resinous materials from
residuals while producing premium quality lube
oil stocks and FCC and hydrocracker feedstocks.
The ROSE process produces identical products
more efficiently through the use of super
critical solvent recovery.
Solvent recovery in conventional solvent
extraction processes consists of evaporating all
of the solvent in a series of progressively
lower pressure flashes, followed by steam
stripping to produce a virtually solvent-free
product. After the solvent has been vaporized
it must be condensed and pumped from the
condensing pressure back to the pressure
required for extraction. It is well known that
the quality of the oil extracted from petroleum
residues can be improved by increasing the
solvent-to-charge ratio. This requires an
increased energy demand in the solvent recovery
system proportional to the increase in the sol
vent-to-oil ratio.
The excessive energy requirements of conventional
solvent recovery techniques had little punitive
impact until the cost of crude oil, and con
sequently the cost of energy, increased drama
tically du ring the past decade. The increased
cost of both raw rna ter ial and energy has
aged the refining and chemical process
to explore every conceivable technique for redue
ing raw material requirements and
energy.
The oil embargo of 1974 and subsequent rapid
increase in the cost of crude, and hence energy,
were not anticipated twenty years ago when Kerr
McGee's Research and Development group
the experimental work which led to the develop
ment of ROSE (Residuum oil Supercritical Extral:
tion). The initial objectives were not
conserve energy, but rather to explore tre
potential of recovering more valuable products
from the heavy non-distillable portion of a
barrel of crude. From this early work
developed a work ing knowledge of the
products that could be produced through solvent
extraction.
The three basic products are referred to as
Asphaltenes, Resins, and Deasphalted Oil (DAO).
Asphaltenes are the heaviest, highest mOlecular
weight, most viscous and most hydrogen-deficient
type of hydrocarbon found in crude petroleJm.
Asphaltenes are precipitated from
residues when the peptizing agents in
residues are dissolved in solvents such as
pentane. Other solvents can be used, though the
asphaltene yield and properties will vah.
Asphaltenes may be described as dark brownito
black friable solids that have Ring and B 11
softening points ranging from 70
0
to 200: C.
Elemental analyses of asphaltenes show
high carbon to hydrogen ratios ranging from
to 11.6 by weight. Because of the complex
compact lattice-type molecular structure :of
asphaltenes, it is extremely difficult to tdd
hydrogen, or to remove sulfur, nitrogen or
from asphaltenes. Rydrotreating and cracking
catalysts are rapidly coked, de-activated and
poisoned by the contaminants present in
asphaltenes.
Resins may be classified as an intermediate
fraction, lighter than asphaltenes but heavier
than deasphal ted oi 1. In the absence of these
intermediate components, asphaltenes can be
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
insoluble in the oil fraction. Resins, there
fore, can play an impor tant role in the manu
facture of asphalt because of their peptizing
action which permits the asphaltenes to be
solubilized in the oil medium to produce a homo
geneous colloidal petroleum asphalt sOlution.
Resins affect the penetration, viscosity,
ductility and stability of asphalts. Resins can
be hydrotreated, hydrocracked, thermally cracked
or even coked to produce more valuable products.
Resins are less viscous, lower in metals, sulfur
and carbon as well as less hydrogen-deficient
than asphaltenes.
The recovered deasphalted oil (DAO), on the
other hand, is a relatively clean product con
taining substantially lower metals and carbon
residue than either asphaltenes or resins. The
DAO can be directed to such downstream processes
as hydrotreating, hydrocracking or catalytic
cracking without having to suffer the severe
penalties imposed by the high metals and carbon
residue contained in the asphaltenes and resins.
Kerr-McGee's research efforts and experimental
work during the late 1950's were surprisingly
successful and led to a significant breakthrough
in solvent extraction technology. Not only were
the asphaltenes, resins and oils separated by
the newly developed techniques, but the revolu
tionary discovery was made that one could
utilize the supercritical properties of the
e x t r ~ c ~ i ~ n solvent to improve the efficiency and
flexlblllty of extraction processes. The ROSE
process recovers 85 to 93% of the extraction
solvent as a supercri tical flu id, thereby con
suming a fraction of the thermal energy required
for. evapora tive recovery. OVerall energy
savlngs of 40 to 50% compared to conventional
solvent recovery techniques have been demon
strated commercially. The economic magnitude of
the potential savings is directly related to the
solvent-to-feed ratio employed by the process
and the cost of steam, fuel and electricity.
In solvent extraction it is recognized that
increasing the extraction temperature yields
progressively greater amounts of insoluble
material. In the ROSE process the yields from
the asphaltene and resin separators in a 3-stage
unit or the combined asphaltenelresin (AIR)
separator yield in a 2-stage unit are controlled
by adjusting the separators' operating tempera
tures. The oil separator, operating at super
cri tical tempera ture and pressure, is str ictly a
solvent recovery device. The DAO yield is set
by the Resin (3-stage) or AIR (2-stage)
separators temperature. The beauty of the ROSE
process is that 85 to 93% of the extraction
solvent is recovered in the oil separator with
out evaporation. Further, the recovered solvent
is recycled through exchangers which recover a
major portion of the energy necessary to achieve
supercritical conditions. The energy required
for supercritical solvent recovery is substan
tially lOwer than that required by any other
method including conventional evaporation.
Solvent losses also tend to be minimized with
this solvent recovery technique.
PROCESS DBSCRIP'l'IOII
The simplicity of operation of the ROSE process
is illustra ted schematically in Figure 1. The
flow sequence follows: The feedstock, wh ich may
be either long or short residuum, or a blend
thereof, is charged thru a mixer M-l, where it is
contacted with several volumes of light
hydrocarbon solvent at elevated temperatures and
pressures. The mixture passes to the asphal tene
separa tor V-I, where the heavy asphal tene frac
tion is withdrawn as a liquid on level control
from the bottom and passes thru a heater H-l to a
flash tower T-l where the contained solvent is
flashed and stripped from the asphaltene product.
The solvent-res in-oil phase flows from the top of
V-I thru heat exchanger E-l, where it is heated
by the recycle solvent before entering the resin
separator V-2. As a result of the increased
temperature, with a corresponding decrease in
solubility, a second phase separation takes place
yielding an intermediate "resin" fraction. The
resin fraction is withdrawn on level control from
the bottom of the second separator vessel V-2 and
stripped of its solvent in tower T-2.
The remaining solvent-oil solution proceeds
overhead from V-2 thru heat exchanger E-4 where
it is heated by the recycle solvent before flow
ing thru heater H-2, in which the temperature is
elevated above the critical temperature of the
solvent.
At this increased tempera ture, there is a
decrease in the solubility of the oil in the
solvent and a resultant phase separation occurs
in the oil separator V-3. The oil phase is
withdrawn from the bottom of V-3 and stripped of
its solvent in tower T-3. The substantially oil
free supercri tical solvent phase flows overhead
from V-3 thru exchangers E-4 and E-l, giving up
heat to the solvent-oil solution from V-2 and the
solvent-res in-oil solution from V-I, before being
further cooled in exchanger E-2 for recycling
back thru the process via the recycle solvent
pump P-l. In many applications E-2' s duty is
negligible.
The small amount of solvent associated with the
heavy phases wi thdrawn from vessels V-I, v-2 and
V-3 (between 7 and 15% of the total extraction
solvent) is recovered by conventional stripping
in T-l, T-2 and T-3 and condensed in E-3. The
recovered solvent is then collected in the
solvent surge drum S-1. This relatively small
volume of solvent is pumped by the make-up
solvent pump P-2 into the large volume of high
pressure solvent upstream of the recycle solvent
pump, P-l. The recycle solvent pump P-l develops
only the differential pressure necessary to
overcome the separator system pressure drop.
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
An al terna te and somewhat simpler configura tion
of a ROSE unit, a 2-stage instead of a 3-stage
unit, may be all that is required in some
applications. By simply leaving out V-2, .E-4
and T-2, as shown wi thin the dashed boundanes,
one may combine the asphal tenes and res ins into
a single product, which is withdrawn from the
bottom of asphal tene/res in separator V-l. The
deasphalted oil fraction is then recovered from
the oil separator V-3. This 2-stage configura
tion can also be operated to produce asphaltenes
in V-l and reject all or any portion of the
resins overhead from V-l to combine them with
the deasphaltened oil product from V-3.
m'ILITY REQUlREMEIftS
The utility requirements of the ROSE process are
relatively insensitive to variations in either
solvent-to-charge ratio or solvent selection
(rang ing from propane thru pentane). For
example, increasing the solvent-to-charge ratio
from 5 to 1 up to 10 to 1 results in an insig
inificant increase of about 10% in the elec
trical power requirement with no significant
change in the other utili ties. By way of com
parison with conventional extraction in which
all of the solvent is vaporized, doubling the
solvent-to-charge rat io results in s ignif icantly
higher utility requirements, both in electrical
load and heater duty.
Figures 3 and 4 illustrate why the ROSE process
has these inherent advantages:
Figure 3: In conventional solvent recovery, all
of the solvent used to extract the DAO leaves
the extractor as a liquid at a relatively low
temperature and high pressure (Point A). This
material (solvent plus MO) is heated and
flashed, to some point, labeled E, in the vapor
region of the solvent's enthalpy diagram. At
Point E virtually all of the extraction solvent
is vaporized, leaving a small amount of solvent
to be stripped. This remaining solvent is
stripped, with steam at a higher temperature and
a much lower pressure (Point F).
Figure 4: In the ROSE process, the extraction
solvent and DAO start out at the same tempera
ture and pressure as was used in the conven
tional case (Point A). To make the comparison
easily understood a 2-stage ROSE unit is used.
The DAO plus Solvent flow from the extractor (V
I) (see Figure 1) through exchanger E-l, gaining
heat from the recycle solvent. The DAO plus
solvent leave E-l at Point B. Heater H-2
provides the energy necessary to heat the DAO
plus solvent from Point B to Point C. At Point
C, 85 to 93% of the solvent is recovered as a
supercri tical fluid, ready to recycle back
through exchanger E-l, heating the DAO plus
solvent from Point A to Point B. As the recycle
solvent heats the DAO plus solvent, it is in
turn cooled from Point C to Point D. The
recycle solvent is cooled from Point D to Point
A by a combination of mixing with the cold
recovered solvent from the product stripping
section (T-l and T-3) and trim cooling which is
provided by E-2.
The residual solvent in the DAO from V-3 is
recovered by flashing and
stripping, in a like
manner as that presented for the conventional
case. In the ROSE case,
only 7 - 15% of the
extraction solvent is heated to Point E, compared
with heating 100% of the solvent in the
conventional case.
Knowing that horizontal distance in Figures 3 and
4 is proportional to change in the solvent's
enthalpy and that only 0.5% of the extraction
solvent must be steam stripped in both cases
(Point E to Point F); further, assuming the worst
case, tha t only 85% of the solvent is recovered
in the DAO separator, it can be seen that
supercr it ical solvent recovery requires only 34%
of the heat energy required for evaporative
recovery.
A comparison of overall utility requirements is
shown in Table 1 for a ROSE unit versus a con
ventional propane deasphalter (PDA) . Total
utility requirements for the ROSE process are
substantially less (approximately one-third) than
those required for a conventional PDA unit at
normal solvent-to-charge ratios of 10 or 12 to 1.
The unique solvent recovery system, which was
discussed above, makes the utility reduction
possible. Plant acceptance test runs, conducted
on a licensee's commercial solvent extraction
unit, before and after conversion to the ROSE
process, have demonstra ted these savings in
utilities.
To demonstrate that this newly discovered tech
nology could be practiced on a commercial scale,
a 120 m
3
/SD plant was constructed by Kerr-McGee
in 1954. This plant operated successfully over a
six-year period processing feedstocks ranging
from 85-100 penetration asphalt to a topped crude
with only the naphtha fraction removed.
Feedstock gravities ranged from 9
0
to 18
0
API,
and DAO yields ranged from 56 to 93 volume per
cent of charge. Typical results from this
operation were reported earlier (Gearhart and
Garwin, 1976).
Since then the ROSE process has been utilized by
four domestic refiners to produce a wide spectrum
of products including lube oils, a variety of
asphalt products, incremental feedstocks for
downstream processing in catalytic crackers,
together wi th seve ral specialty products. Two
additional commercial ROSE units are in the
engineering design and construction stage. An 8
m
3
/SD ROSE pilot plant has been in operation in
Japan since early 1982.
A propane deresining un i t was converted to the
ROSE process in the latter part of 1979 for a
licensee whose plan t produces lube oil and resin
from Pennsylvania crude residues. The conversion
resulted in a significant capacity
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
increase and a substantial reduction in utility
requirements. Feedstock and product analyses
from a test run in the converted plant are
summarized in Table 2.
A grass roots 795 m
3
/SD 2-stage pentane ROSE
unit was constructed at one of Kerr-McGee's
refineries in 1979 to produce asphalt and cat
cracker feedstock from either atmospheric or
vacuum residue. This unit has been modified
recently to produce asphaltenes from the first
stage and a resin-oil fraction from the second
stage. Kerr-McGee is conducting a series of
exploratory tests to develop commercial uses for
the asphaltenes and asphaltene-resin blends.
Typical results for this ROSE unit are shown in
Table 3.
A third commercial ROSE unit was completed and
placed into operation in January 1981. This 3
stage 510 m
3
SD grass roots ROSE unit is capable
of utilizing isobutane, normal butane or pentane
solvent. The feedstock is a waxy vacuum residue
from a variety of crudes. The products are
asphalt blend stocks and deasphalted oil (DAO).
The DAO is charged directly to a fluid catalytic
cracker without further treatment. This plant
has opera ted well above design charge rates for
extended periods. Operating results are shown
in Table 4.
The installation and commissioning of a fourth
ROSE unit was completed in December 1981. This
plant, a 3-stage 715 m
3
/SD grass roots facility,
was initially designed to use normal pentane
solvent to produce 163
0
c Ring and Ball softening
point asphaltenes, resins and DAO. The inherent
flexibility of the ROSE process made it possible
to start up this plant on normal butane solvent
instead of the pentane for which it was
designed. This unit currently produces asphalt
blending stocks and DAO for catalytic cracking
feedstock. Operating results are listed in
Table 5.
construction is in progress on the fifth com
mercial ROSE unit, a 1908 m
3
/SD 3-stage pentane
unit with completion and start-up due shor tly.
This plant will be capable of producing high
softening point asphaltenes, which will be
flaked and marketed as supplemental fuel for
coal-fired boilers. The resins will either be
blended to fuel oil or combined with the DAO for
catalytic cracking feedstock.
The process des ign has been comple ted and
detailed engineering is in progress on a sixth
ROSE unit. This will be a 795 m
3
/SD 2-stage
unit designed to use normal butane solvent
initially, but will have the flexibility to use
either isobutane or normal pentane. The asphal
tene-resin product will be blended into fuel
oil, and the recovered DAO will be charged to a
catalytic cracking unit.
FEKDSTOClt EVALUATION PACILI'!'IES
A 0.16 m
3
/SD bench-scale ROSE pilot plant
facili ty is available at Kerr-McGee I s Technical
Center in Oklahoma City, Okla., to evaluate feed
stocks for potential licensees as well as to set
the design basis for commercial ROSE units. This
facility is also used for continued research and
development to find further improvements and
utili za tions of ROSE technology. The choice of
solvent is dictated by the nature of the
feedstock and the desired specifications for the
materials to be produced.
In addi tion to residual feedstocks der ived from
crude petroleum, oil from tar sands and oil
shales, pyrolysis tar residues and tall oil have
been processed in the ROSE pilot plant. Experi
mental work has been planned for upgrading very
heavy crudes. Deasphal tening in the field would
result in a lower-viscosity crude with improved
transportation and processing Characteristics.
This upgrading technique would be applicable to
many domestic as well as foreign crudes.
ROSE PROCESS VERSUS DELAYED COt!NG
Tradi tionally, cokers have been destined to the
role of "garbage can" for refiners who process
heavy crudes and have an excess of asphal t or
heavy residual fuel production. When no satis
factory or profitable market existed for these
materials, a coker was considered to- be the
obvious answer because it served a dual purpose:
First, a coker affords a means of increasing the
value of the products made from a barrel of
crude. Second, a coker removes the limitation on
crude runs imposed by the excess residuals such
as asphalt or fuel oil. Delayed cokers also play
an important role in the production of specialty
products, such as electrode coke for the
metallurgical industry.
Many residuals contain excessive contaminants
(sulfur and metals) , thereby producing an
inferior quality coke which is unsuitable for
many applications. The coker gas oil, coker
naphtha and sour gas are difficult products to
utilize in most refineries, and less desirable
for downstream processing than uncracked or
virgin material. Furthermore, a significant
portion of the gas oil contained in the residual
feedstock to a coker is cracked, producing gas
and coke.
The ROSE process offers numerous advantages over
coking: (1) ROSE yields a higher liquid recovery
of virgin gas oil, which is a better feedstock
than coker gas oil for downstream processing in
hydrotreaters, cat crackers or hydrocrackers; (2)
no sour naphtha or sour gas is produced; and (3)
the capital investment and operating costs are
significantly less for ROSE than for a coker.
Table 6 illustrates the comparative utility costs
for a delayed coker versus ROSE.
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
Based on vacuum residuum from Arabian Light
crude as a feedstock, product yield and quality
estimates have been developed for a delayed
coker and a ROSE unit. ROSE unit yields and
produc t quali ties are shown for both n-pentane
and n-butane solvents. The delayed coker data
is summarized in Table 7A and the ROSE data is
shown in Table 7B. By utilizing n-pentane sol
vent the asphaltene yield from a ROSE unit only
20 wt% while a coker would produce 32.8 wU
coke. If cleaner OAO is required, progres
sively lighter solvents can be utilized as is
demonstra ted in Table 7B for n-butane. OAO can
be processed in a fluid catalytic cracker or
hydrocracker, yielding products which do not
require the extensive upgrading that coker
products necessitate.
POTRN'rIAL USES FOR ROSE PRODUCTS
Asphaltenes can be burned either as a liquid or
as a solid fuel like coke or coal. Other
potential uses for asphaltenes are: as a sub
stitu te for coke in metallic ore reduction and
in cement manufacture 1 as a blending component
in asphal t manufacture 1 as either a solid or
liquid fuel for fluidized bed combustionl as
feedstock for partial oxidation to produce
synthetic fuel gas which, in turn, can be con
verted to hydrogen, ammonia or methanoll and as
an additive in drilling mud. Asphaltenes
typically have Ring and Ball softening points
ranging from 70
0
to 200
0
C and a heating value of
39,500 kilojoule/kilogram. Their ash content is
nil. Asphaltenes are very friable, having a
Hardgrove Gr indabili ty Index of 120+, compared
to about 50 to 60 for coal and 40 to 60 for
delayed coke. A typical asphaltene contains 60
70 wt% volatile and 30-40 wt% fixed carbon.
Resins can be used as coker feedstock to produce
premium quality anode grade coke for the
aluminum industry, provided the sulfur and
vanadium content is not excessive. This utili
zation has been demonstrated on a pilot-plant
scale. Resins are a valuable ingredient in
asphalt, providing ductility and viscosity as
well as improved homogeneity. Resins and
asphaltenes can be blended in a variety of com
binations to produce binders, protective coat
ings, asphalt cements, etc.
OAO can be produced in a wide range of specifi
cations by the ROSE process to manufacture
lubricating oils as well as incremental feed
stock for either hydrocracking or cat cracking.
The ROSE process can also be used to separate
OAO into multiple fractions.
CSD PROCESS - BRIEF AND
As an ou tgrowth of ROSE technology, Ker r-McGee
has developed another critical solvent extrac
tion process for separating solids (mineral
matter and unreacted coal) from coal liquids as
well as for removing solids from shale oil and
tar sands. This process operates near the
critical point of the extraction solvent and is
called the Critical Solvent Oeashing process, or
CSO.
Figure 2 is a simplified CSo flowsheet. Vacuum
bottoms feed and the extraction solvent are mixed
and fed to a first-stage settler. The heavy
phase, a slurry containing 10-20 wt% of the coal
liquids plus deashing solvent, along with
essentially all of the coal solids, is "let-down"
to about atmospher ic pressure. The deashing
solvent is flashed and recovered, and the
remaining solids leave the system as a dry
flowable powder called Ash Concentrate. The
light phase, which contains the remaining 80-90
wt% of the coal liquids, is heated and passed to
a second-stage settler. The heavy phase is
let-down to flash off deashing solvent and
produce SRC (solvent refined coal). The pressure
of the light phase is reduced, and it passes to a
third-stage settler. The heavy phase, after
flashing off the deashing solvent, becomes Light
SRC, which either becomes a product for sale or
is recycled back to the coal liquefaction step to
become a part of the coal-dissolving solvent.
As a result of the successful demonstration of
the CSO process in the SRC pilot plant at
Wilsonville, Ala., and in subsequent bench-scale
development work, International Coal Refining
Company has licensed the CSo process as the
solids-removal method for the proposed 5,500
metric ton/day SRC-I demonstration plant.
In addition to the pilot plant, Kerr-McGee has
bench-scale facilities for evaluating samples for
potential CSO licensees to test not only coal
liquids slurry samples but also shale oil or tar
sands oil samples.
caiCLOSIONS
The ROSE process has emerged as a competitive,
well established and commercially proven solvent
extraction process. No other solvent extraction
process offers greater flexibility, either in
choice of solvent, in ability to process as many
different types of feedstocks, or in potential
recovery of higher-quality products with more
attractive market values. ROSE has the addi
tional advantages of lower capital investment and
substantially lower operating costs when compared
with conventional solvent extraction processes.
Evaporative type solvent recovery systems can be
readily converted to utilize ROSE technology with
a resultant reduction in energy requirements.
The energy-efficient ROSE process offers an
economical and effective method for rejecting
metal containing carbonaceous and highly viscous
components from heavy residual or low-gravity
crude oil feedstocks that are destined for
downstream hydrotreating, hydrocracking or
catalytic cracking. Each of these downstream
processes is very catalyst-sensitive to such
contaminants because of their adverse effect on
catalyst life and activity.
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
The flexibility of the ROSE process can be
utilized by refiners to improve their processing
capabilities and profitability. These appli
cations include: debottlenecking or replacing
cokers; relieving overloaded vacuum units;
producing premium qual i ty lubricating oils;
manufacturing paving, roofing and specialty
asphalts; substantially reducing or eliminating
heavy fuel oil produc tion; and recover ing
incremental feedstocks for hydrocracking or cat
cracking.
In summary, the poten tial advan tages offered by
the ROSE process are:

Lower capital investment

Lower utility costs

Lower maintenance costs
Wide range of solvent selection

Maximum yield and quali ty of recovered
oil
Ability to process a wide range of
feedstocks
Easy conversion of conventional
solvent extraction units
The advantages offered by the ROSE process and
their economic impact can be readily evaluated
for your particular refinery configuration. With
the continuing decline in average crude gravity,
coupled with higher sulfur content of the crude,
it is imperative that more effective processing
of the residual portion of crude petroleum be
employed to remain competitive.
Gearhart, J.A., and Garwin, Leo, "ROSE process
improves resid feed", Hydrocarbon Processing
Vol. 55, No. 5 125-8 (1976)
Gearhart, J.A., "Solvent treat resids", Hydro
carbon Processing, Vol. 59, No. 5 150-1
(1980)
TABLE 1
COMPARISON OF UTILITY COSTS
Conventional Propane Units/m
3
Deasphalting of Charge Rate Cost/m
3
Electrical Power, kWh 17.6 $0.050/kWh $ 0.88
Steam, kg 610 $0.018/kg $10.98
Fuel Fired, MJ 910 $0.006/MJ $ 5.46
Cooling Water, m
3
37 $0.013/m
3
~
Total
$17.80
ROSE Process
Electrical Power, klfu 17.6 $0.050/kWh $ 0.88
Steam, kg 34 $0.018/kg $ 0.61
Fuel Fired, MJ 640 $0.006/MJ $ 3.84
Total
$ 5.33
Difference in utility costs/m
3
residuum charge
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
TABLE 2
PENNZOIL ROSE UNIT CHARGE AND PRODUCTS ANALYSES
Vacuum
Residue Resin Oil
Yields, Wt% on Crude 16.9 3.2 13.7
LV% on Crude 15.0 2.7 12.3
Wt% on Vac Resid LOO 18.9 81.1
LV% on Vac Resid 100 17.9 82.1
Specific Gravity, 15C/4C 0.906 0.959 0.895
Nitrogen, Wt% 0.03 0.09 0.02
Sulfur, Wt% 0.08 0.14 0.07
Conradson Carbon, Wt% 2.7 11.2 0.67
Nickel, wppm 0.2 0.8 0.01
Viscosities, mPa'S (cst) 42 @ 99C 109 @ 135C 11.3 @ 135C
208 @ 60C 490 @
99C 27.9 @99C
Strieter Analysis
Asphaltenes, \ ~ t % 0.1 0.5 0
Resins, Wt% 12.1 27.4 8.5
Oils, Wt% 87.8 72.1 91.5
TABLE 3
KERR-McGEE ROSE UNIT CHARGE AND PRODUCTS ANALYSES
Vacuum
Residue Pitch Oil
Yields, Wt% on Crude 18.4 5.9 12.5
LV% on Crude 16.0 4.8 11.2
Wt% on Vac Resid 100 32.0 68.0
LV% on Vac Resid 100 30.1 69.9
Specific Gravity, 15C/4C 0.978 1.041 0.951
Nitrogen, Wt% 0.6 1.0 0.4
Sulfur, Wt% 1.2 1.6 1.0
Conradson Carbon, Wt% 13 27 6.7
Nickel, wppm 60 160 20
Vanadium, wppm 120 320 30
R & B Softening Point, c 24 82
Viscosities, mPa's (cst) 360 @ 99C 1600 @ 149C 260 @82C
iDO @ 127C 190 @ 191C 220 @ 99C
Strieter Analysis, Wt%
Asphaltenes 9.2 27.8 0.5
Res ins 23.4 30.6 20.0
Oils 67.4 41.6 79.5
H29
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
Yields, Wt% on Crude
LV% on Crude
Wt% on Vac Resid
LV% on Vac Resid
Specific Gravity, 15C/4C
Nit ragen, Wt%
Sulfur, Wt%
Conradson Carbon, Wt%
Nickel, wppm
Vanadium, wppm
R & B Softening Point, c
Penetration @ 25C
Viscosities, mPa's (cst)
Strieter Analysis, Wt%
Asphal tenes
Resins
Oils
ROCK
Yields, Wt% on Crude
LV% on Crude
Wt% on Vac Resid
LV% on Vac Resid
Specific Gravity, 15C/4C
Nitrogen, Wt%
Sulfur, Wt%
Conradson Carbon, Wt%
Nickel, wppm
Vanadium, wppm
R & B Softening Point, c
Viscosities, mPa.s (cs t)
Strieter Analysis, Wt%
Asphaltenes
Resins
Oils
PESTER ROSE UNIT
Vacuum
Residue
15.1
13.0
100
100
0.985
0.5
1.5
14
34
86
420 @ 93C
110 @ 121C
12.5
25.0
62.5
ISLAND ROSE UNIT
Vacuum
Residue
7.2
6.1
100
100
1.001
0.6
1.5
18
30
75
38
406 @ 118C
106 @ 149C
15
17
68
TABLE 4
CHARGE AND PRODUCTS
Asphaltene
4.1
3.3
27.2
25.0
1.073
0.9
2.4
35
100
270
102
420 @ 199C
335 @ 204C
40.8
26.8
32.4
TABLE 5
CHARGE AND PRODUCTS
Asphaltene
2.2
1.7
31
28.1
1.104
0.8
2.3
41
90
220
127
1360 @ 210C
390 @ 238c
49
23
28
ANALYSES
Resin Oil
1.6 9.4
1.3 8.4
10.3 62.5
10 .0 65.0
1.014 0.946
0.6 0.3
2.0 1.1
19 4.0
42 4.0
89 5.5
23.5
300 @ 138C 330 @ 66C
126 @ 157C 79 @ 93C
6.5 1.1
54.6 19.4
38.9 79.5
ANALYSES
Resin Oil
0.5 4.5
0.4 4.0
7.0 62
7.0 64.9
1.003 0.956
0.6 0.5
1.4 1.1
17 7.0
18 4
33 6
395 @
118C 440 @ 79C
117 @ 135C 159 @ 99C
1.2 a
27 13
72 87
H30
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Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
TABLE 6
COMPARISON OF UTILITY COSTS
DELAYED COKER VS
Delayed Coker
Units/m
3
of Charge
Electrical Power,
Steam, kg
Fuel Fired, MJ
Total
kWh 5.4
7.4
3085
ROSE Process
Electrical Power,
Steam, kg
Fuel Fired, MJ
Total
kWh 17 .6
34
640
Difference in utility costs/m
3
residuum charge
ROSE
Rate
$O.OSO/kWh
$0.018/kg
$0.006/MJ
$O.OSO/kWh
$0.018/kg
$0.006/MJ
Cost/m
3
$ 0.27
$ 0.13
$18.51
$18.91
$ 0.88
$ 0.61
$ 3.84
U:ll
83]
ESL-IE-83-04-128

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
----------------- --- - ---
TABLE 7A
COMPARISON OF DELAYED COKER AND ROSE YIELDS
FOR ARABIAN LIGHT VACUUM RESIDUUM
Coker Products
Feedstock
Lt. Arab.
l85-343
Vac. Resid H
2
S
~
C
5
/C
6
C
r
185C c 343C+ Coke
Wt% Yield 100 0.4 10.3 3.1 10.8 26.0 16.6 32.8
Vol% Yield 100 4.8 14.3 30.2 18.2
API Gravity 6.9 82 52 29.4 21
Sulfur, Wt% 4.0 0.8 0.9 2.4 3.8 6.9
Nitrogen, wppm 3100 50 1050 2100 7500
Con. Carbon, Wt% 20.8
K 11.4 11.3 11.1
Nickel, wppm 23 70
Vanadium, wppm 75 229
TABLE 7B
ESTIMATED ROSE YIELDS
FOR ARABIAN LIGHT VACUUM RESIDUill1
ROSE Products
Feedstock
Lt. Arab.
n-Pentane n-Butane
Vac. Resid. Asphaltene DAO Asphaltene DAO
\olt% 100 20.0 80.0 32.8 67.2
Vol% 100 17 .8 82.2 30.2 69.8
API Gravity 6.9 - 7.4 10.7 - 7.4 12.3
K 11.4 11. 7 11. 7
Sulfur, lolt% 4.0 5.7 3.6 5.4 3.3
Nitrogen, wppm 3100 fi600 2200 5800 1800
Can. Carbon, Wt% 20.8 52 13 43 10
Nickel, wpprn 23 87 7 65 2
Vanadium, wpprn 75 290 22 214 8
R & B Softening Point,
c
177 135
832
ESL-IE-83-04-128

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
I I
I I
I I
I
I
I
I
FIGURE 1
;-------1
I
,
I
I
I
1
I
I
I "'---"-1----.
START
1 _
ASPHALTENES RESINS OILS
H33
ESL-IE-83-04-128

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
FIGURE 2
THREE STAGE CRITICAL SOLVENT DEASHING UNIT
VACUUM TOWER BOTTOMS
FEED
ALTERNATE
FEED
SURGE
TANK
MIXER
FEED
PUMP
HIGH PRESS
SOLVENT PUMP
1ST 2ND 3RD
STAGE STAGE STAGE
SETTLER SETTLER SETTLER
DEASHING
SOLVENT
PUMP
DEASHING DEASHING DEASHING
SOLVENT SOLVENT SOLVENT
SEPARATOR SEPARATOR SEPARATOR
NO.1 NO.2 NO.3
ASH SRC LIGHT
CONCENTRATE PRODUCT SRC
PRODUCT
834
ESL-IE-83-04-128

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
Figure 3
CONVENTIONAL SOLVENT RECOVERY
SOLVENT ENTHALPY DIAGRAM
ISOTHERMS
INCREASING TEMPERATURE
\ \ \
LIQUID
~ - - A - EXTRACTOR V-1
E FLASH
~ - - - F STRIPPER
::> 1---------------;
(/)
VAPOR
w
a:
(/)
w
a:
Q..
~
Z
(/)

w
a:
U
Z
INCREASING ENTHALPY
83'>
ESL-IE-83-04-128

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983
Figure 4
SUPERCRITICAL SOLVENT RECOVERY
SOLVENT ENTHALPY DIAGRAM
ISOTHERMS
INCREASING TEMPERATURE
...
VAPOR
\ \ \
Y--- A - EXTRACTOR V-'
B H-2 INLET
1'----- C DAO SEPARATOR -----10
D RECYCLE
SOLVENT EX E-' --....
E-FLASH
1---- F STRIPPER
LIQUID
w
ex::
::> I---------------j
(J)
(J)
w
ex::
a
t=)
Z
(J)
<X:
w
ex::
U
Z
INCREASING ENTHALPY
836
ESL-IE-83-04-128

Proceedings from the Fifth Industrial Energy Technology Conference Volume II, Houston, TX, April 17-20, 1983