Article

~
ROLE OF SOLVENT DEASPHALTING IN PROCESSING
PETROLEUM RESIDUES IN REFINERIES
'* G.S. Dang & B.S. Rawat

Solvent Oeasphalting (SOA) is basically a liquid-liquid extraction process. The

conventional applications are in producing extra heavy viscosity grade lube oils called
bright stock/cylinder oils and in upgrading bottom of barrel by recovering incremental/
additional feedstocks from vacuum residues for secondary conversion units like Fluid
CatalyticCracking/Hydrocracking.Some newer applicationsinclude making of quality
bitumen from waxy crudes, low sulpher fuel oils etc. Industrially,propane, butane and
pentane (C3-CJ solvents, either alone or there combinationsfor greater flexibility,are
being used widely. To improve the process economics, novel features like supercritical
solvent recovery, better counter current columns, etc. are being incorporatedin existing
and new grass-root deasphalting plants. The SOA process in combination with thermal
cracking processes etc. is further contributing in reducing the availability of short/vacuum
residues in refineries.
INTRODUCTION refinery. When propane is used as solvent, the process is
Refineries are being faced currently with need to called propane deasphalting (PDA) (Figure-1) and it
produce more and more light and middle distillates and produces DAO which is finished into extra heavy viscosity
less of residue/residual fuel oil due to changing product grade lube oil (bright stock, viscosity 35 cst at 1000C &
demands world wide. This need coupled with increasing CCR below 2.0%).
supply of relatively heavier crude oils in world market PDA operating conditions are optimised for each
presents a major challenge to the refiner. To meet this feedstock to obtain desired quality of DAO. In general, the
challenge together with "bottom of barrel" processing i.e. operating conditions(1) with respect to temperature and
converting residual stock to lighter and middle distillates, pressure lie between 50 to aoocand 27 to 37 kg/cmz
the solvent deasphalting (SDA) process has gained respectively. Solvent to feed (S/F) ratio varies from 6 to
considerable importance, like any other carbon rejection 10 by vol. Counter current extraction columns, ROC or
or hydrogen addition residue upgrading process. baffled tray, are in use industrially. In conventional PDA
SDA traditionally is in use for producing extra units all the solvent is separated from the DAO and asphalt
heavy viscosity lubricating oil, generally called bright stock streams in a series of progressively lower pressure flashes
and for producing feedstocks for secondary conversion and the remaining traces of solvent are stream stripped
r units like Fluid Catalytic Cracking (FCC) and Hydrocrack- from the oil. The solvent is condensed and recycled in the
ing (HC) from vacuum/short residues. It is basically a process.
liquid-liquid extraction process using a number of light For vacuum residues not suitable for producing
hydrocarbon solvents mainly propane, butanE and pen- bright stocks, SDA is used to recover incremental or
tane, either alone or their appropriate combinations like additional feedstock for FCC/HC units. These conversion
propane-butane o~ butane-pentane depending upon na- processes enhance the yield of lighter and middle
ture of the feedstock and the desired end product distillates in the refinery. Since the uses of propane
quality. precipitated asphalt are limited, the short residues are
extracted/deasphalted deeply, using heavier and less
SOLVENT DEASPHAL TING (SDA) selective paraffinic solvents Le. C4-C,z' Commercially
Vacuum residue also referred as short residue is butane and pentane and to some extent hexane have
generally the feedstock for deasphalting units. Alternative- found wider applications. While still he~vier soivents like
ly depending upon suitability, it goes either for bitumen heptane, etc. have been used for separating asphaltenes
manufacture or is blended with other lighter oil fractions . at laboratory or pilot plant scale. With butane and pentane,
to produce heavy fuel oil, for which the demand is the yield of DAO or demetallised oil (DMO) is increased
continuously decreasing. Solvent deasphalting, as stated by a factor of 2 to 3 as compared to propane DAO yield
earlier, utilizes light hydrocarbon solvents and produces
valuable extract product, called deasphalted oil (DAO) and ItMr. G.5. Dang and Mr. B.S. Rawat are associated with Indian Institute
thus reduces the net availability of vacuum residue in a of Petroleum, Dehrsdun.

CHEMICAL ENGINEERING WORLD 85 , Vol. XXX No.9, September '.95

Article .:::.

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'
OIL

!
:
fEED A 1 ~f
PROPANE
!! , I
STRIPPER

,-1!\OPANE EVAPORATORS I
:
DAO
CONTACTING
TOWER r-~ ,
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PROMN!
ASPHAcr
STRlftPER ~

nH\NM;E

ASPHALT
FIG. 1- PROPANE DEASPHALTING

of 20 to 50%, depending upon nature of the feedstock and stream units like FCC/HC. Typicallimitations(3) of contam-
the operating conditions used. Solvent blends like C3-C4 ination in feed to above conversion units are given in
and C4-CS'etc. have also been used and are claimed to Table-1. Generally the level of impurities Le. Sulphur,
provide more flexibility with respect to temperature of nitrogen, metals and CCR in DAO/DMO is higher and
operation. Low boiling lighter petroleum fractions/ therefore it is hydrotreated (HDl). The HOT processes aim
gasolines(2)(b < 65°C), free from aromatics, are also being to improve one or more proporties depending upon the
used to produce DMO. objective Le. hydrodesulphurization (HDS), hydro-
The propane solvent rejects both resins and demetallisation (HDM) and hydrodenitrification (HDN). The ~
asphaltenes whereas heavier solvents reject mainly HDT of DAO/DMO is comparatively much easier and r
asphaltenes and a part of resins depending upon the economical than direct residue hydrotreating.
operating conditions of the process. The operating . Asphalt/asphaltics obtained as SDA bottoms is
conditions are so selected that asphalten'3s in the utilized in several ways. It forms a component for making
conversion feedstocks are reduced below 0.05 wt% pavinu !~rade bitumen. It also serves as feed (4)to partial
because they carry catalyst poisons like metals, sulphur, oxidation units to make hydrogen rich gas. It may be
nitrogen, etc. and are main source of coke formation/ blended with visbreaker feed(5). Any remaining asphalt
deposits leading to de-activation of catalysts. Nitrogen which cannot be disposed off, as above, can be blended
compounds neutralize the acidic function of the catalyst with catalytic cycle oil/distilled fuel to make bunker fuel oil
and metals more specifically influence the life of catalyst. or finally can be used as refinery fuel.
Deasphalting process using propane or other
PRODUCT UTILISATION
solvents employs relatively larger S/F ratios hence in
As stated earlier, the DAO obtained through PDA conventional units appreciable energy. is consumed for
is used for producing heavy viscosity lube oil called bright solvent evaporation, compression and condensation for its
stock/cylinder stock. The DAO/DMO obtained through recycle in the process. In an attempt to conserve energy
heavier solvent deasphalting forms the feedstock for FCC/ (mainly utilities) and improve process economics, the
HC units along with vacuum gas oil (VGO). DAO/DMO are solvent mcovery mainly from solvent-DAO mixture is now
blended with VGO in such proportions that the blend increasingly being done under supercritical conditions of
characteristics meet the feedstock requirements of down-
solvent. Under these conditions, the solvent loses solubility
CHEMICAL ENGINEERING WORLD 86 Vol. XXX No.9, September '95
Article

for oil (virtually insoluble) and a phase separation occurs. CRUDE OIL CONSUMPTION
About 85% of associated solvent is thus separated forming The deasphalting unit, as stated before, also
upper phase and is utilized for heat exchange within the produces additional cracking feedstock which on conver-
process before being recycled. The major benefits(6) sion increases the overall availability of lighter and middle
claimed in "ROSE" (Figure-2) and "DEMEX" processes distillates from a given quantity of crude oil. This increase
following this approach are: utility savings of the order of of desirable distillates is at the cost of less needed residue.
about 40% and savings in capital investment for grassroot Therefore instead of adding refining capacity in a refinery
units, approximately form 15 to 25%. The relative cost(7) another option is to reduce crude run while producing a
of energy for above two techniques is compared below: constant quantity of cracking unit feedstock. Figure-3
shows the relationship between UOP's DEMEX extraction
Solvent recovery technique Relative cost level and relative crude requirements to produce a
constant quality of conversion. unit charge form light
Single effect evaporation 280 Arabian vacuum residue. At a DMO yield of 40 vol. %, the
Double effect evaporation 170 crude requirement with DEMEX is only 84%. At this
Triple effect evaporation 150 extraction level, the VGO-DMO blend contaminant levels
"ROSE" 100 are not significantly affected by the DMO addition. At the
highest extraction level, the crude requirement has been
Owing to the above projected advantages, the reduced to 73% of that without DEMEX(9\.
C new grassroot units are generally based on supercritical
r approach and the existing units are also increasingly being PROCESSING OF HEAVIER CRUDES
converted to this approach. Off late 8 of existing PDA units Heavier solvent deasphalting mainly using pen-
have been converted to ROSE scheme by MIs. Kerr tane may soon find application in upgading heavier
McGee Corp, USA (8). crudes(IO).The process separates asphaltenes, the least
valueable components, from heavier crude oils. Such
CONTRIBUTION OF DEASPHAL TING PROCESS IN process units may be located in or near oil production
REFINING fields. The deasphalted petroleum exhibits higher fluidity
In addition to above mentioned application of than the original crude and is then transported and refined
producing bright stock, the SDA has following emerging in conventional ways. The separated' asphaltenes can be
applications: burned to produce steam for steam flooding, etc.

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SOlYENT I
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ASPHALTENES
IltESINES
FIG. 2- ROSE PROC E S5 OILS

CHEMICAL ENGINEERING WORLD 87 Vol.

. XXX No.9, September '95
Article

BITUMEN MANUFACTURE FROM WAXY CRUDES

MAKEUP KYDROGEN
Short residues from waxy crudes do not make I
HYt)ROG~ ~OOU(,T OIL
quality paving grade bitumen due to higher wax. SDA using
propane or heavier solv~nts precipitate asphalt with much
less wax content, suitable for fluxing with cutter stocks like AS PH A LT'EI£
lube oil extracts and/or asphaltene rich residual stocks, VA C UUt.I
CRACKING
SOA
I'ESIDUE
etc. to make desired penetration grade bitumen. Howmver,
this approach needs economic evaluation. The air blowing
for asphaltene generation mayor may not be needed in EXTINCTION RECYCLE
this scheme.
FlG-4 ABC - SDA COMBINATION PROCESS

1.0
CONCLUSIONS
~ 1) In the present situation crude oil supplies to
8: 0.9
u refineries keep changing and also refiners will have to
D
.. process heavier crudes in future. Under such conditions
8:
one of the options with refiner
. is to use solvent ,""""
50.8
..
8: deasphalting route to upgrade heavier crudes and residues
for producingfeedstocksfor FCC/HC units to maximize
0.7 middle distillates.
0 20 40 60 80
D£MEXun (Vo/.%Of' VACUUMBOTTOMS)
2) With increasing popularity of multigrade auto-
motive crankcase oils, the proportion of bright stock,
FIG-3 EFFECT OF DEM EX ON obtained from DAO is likely to decrease. This situtation
CJiUDE REQUIREMENT may provide spare capacity which can be effectively
utilized to produce high quality feedstocks for downstream
units. In many cases yield of DAO for these purposes can
be incrBased by using C4-CSsolvents or their combina-
tions.
PRODUCTION OF LOW SULPHUR FUEL OILS 3) Indian crude oils being waxy are not suitable for
The ever increasing emphasis on cleaner environ- lubes and bitumen. The deasphalting step therefore can
ment forces the refiners to produce fuel oils which are quite be applied to produce cracking feedstocks and asphalt
low in sulphur. The desulphurization of DAO is easier and having reduced wax content The asphalt production alone
economical(11)than short residue desulphurization directly from such crudes for bitumen making through PDA may
and therefore adoption of deasphalting process is picking not be economically attractive.
up in the refineries to make quality fuel oil by blending 4) The approaches like use of solvent blends""
desulphurisezed DAO with short residue. supercritical solvent recovery and optimum utilization 0,-
products/by-products, etc. are commercially feasible and
PROCESS COMBINATIONS FOR RESIDUE REDUC- therefore should be adopted widely in view of currently
TION high energy costs.
To maximise the conversion of vacuum residue
into lighter products, various conversion processes like ACKNOWLEDGEMENT
Visbreaking, Hydrovisbreaking and Asphaltenic Bottom The authors are grateful to the Director, liP,
Cracking (ABC) are being considered for integration with Dehradun, for his kind permission to publish this paper.
SDA. In such combination processes, the residues are first
REFERENCES
thermally cracked with or without hydrogen and then
subjected to solvent deasphalting. This approach reduces 1) Bland, W.F.& Davidson, A., Petroleum Processing
the asphaltproduction.In processes,like ABC-SDA(2) of Handbook (Mc-Graw Hill Book Co., New York) 1967,
p 3-82.
Chiyoda Chemical Engg. & Const Co., Japan, the
2) Yezhov, B.M., eta!., Proceedings of Eighth World
unreacted asphaltenes separated by SDA are recycled to Petroleum Congress, 4, 1972, P 221.
asphaltene cracking step (Figure-4). The residue ultimate- 3) Literature on Residue Solvent Refining (RSR) Pro-
ly gets converted into DAO. The commercialization of this cess by Lummus Crest.
- process is yet to take place. 4) Olson, RK. & Gembiki, VA, Oil & Gas Journal, 80,

CHEMICAL ENGINEERING WORLD 88 Vol. XXX No.9, September '95

Article
L

25, 1982, P 205. 11) Billon, A., etaL, Oil & Gas Journal, 75, 4, 1977, P 43.
5) Baksi, A.S. & Luft,I.H., Oil & Gas Journal, 84, 7, 1986, 12) Sudoh, J., etaL, IEC Process Des. Dev., 23, 4, 1984,
P 52. P 641.
6) Gearhart, J.A.& Garwin, L., Hydrocarbon Processing,
Table 1
55, 5, 1976, P 125.
7) Nelson, S.R., etaL, Chemical Engineering Progress, Typical Feed Contamination Limits
81, 3, 1985, P 63.
8) Literature from MIs. Kerr McGee, Corp., USA on Feed to CCR, Nitrogen Sulphur Metals
"ROSE" Process, May 1992. unit Wt% Wt% Wt% V+NI,ppm
9) Olson, R., etaL, UOP Process Division Conference -
Proceedings, Sept - Nov., 1982. FCCU 1.5-2.5 0.12-0.2 1.5-2.5 1.0-2.0
10) Nelson, S. & Corbett, R.W., Third International Unitar HCU 0.2-1.5 0.08-0.12 1.5-3.0 1.0-3.0
Conference on Heavy Crude and Tar Sands, July RCCU up to 8 35-70
1985. ***

r
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CHEMICAL ENGINEERING WORLD 89 Vol. XXX No.9, September '95

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