Upgrading Petroleum Residues with Solvent Deasphalting Technology

AK Jain and SJ Chopra

Research & Development Centre
Engineers India Limited, Gurgaon
It is imperative to upgrade petroleum residues to recover valuable products and improve the overall
economics of petroleum refining. Solvent deasphalting technology is one such technology, being
utilized by refineries to upgrade residues, for the production of lube bright stocks and as
incremental feedstock to other secondary processes such as FCC and hydro cracking.
Solvent deasphalting is essentially a solvent extraction process. Light paraffins such as propane,
butane or their mixtures are used as the solvent. Light liquid paraffin solvent partially or completely
dissolves the constituents of low degree of aromaticity, which causes asphaltenes and resins to
precipitate. The dissolved components, known as deasphalted oil, are recovered from solvent in
flash column and stripper. The major process variables are temperature, pressure, solvent to oil
ratio and solvent type. Pressure and temperature are both variables because the solvent power of
light hydrocarbon is approximately proportional to the density of the solvent. Higher temperature
always results in decreased yield of deasphalted oil. On the other hand, increasing solvent to oil
ratio increases the recovery of deasphalted oil with increase in viscosity. However, for the given
product quality which can be maintained with change in temperature, solvent to oil ratio increases
the yield of deasphalted oil. It has been shown that solvent power of paraffin solvent increases with
increase in solvent molecular weight. The higher DAO yield is accompanied with higher viscosity,
specific gravity. CCR etc.
To make the overall process energy efficient, it is necessary that energy conservation measures
are taken. Some of these measures are multistage solvent recovery and recovering solvent from
deasphalted oil from extraction column above the critical temperature of the solvent. It has been
shown that such measures reduce energy consumption in a propane-deasphalting unit by about
30%.
Engineers India Limited along with Indian Institute of Petroleum (IIP), Dehradun have developed
the technology for solvent deasphalting. The technology is energy efficient and utilizes the
multistage solvent recovery technique. The technology has been successfully applied for designing
two grassroot units and revamping an existing unit. The grassroot units were commissioned in
1994 and since then, are providing satisfactory service. EIL/IIP have carried out numerous
experiments and a detailed understanding have been developed in the areas of thermodynamics of
the process, feed characterization, estimation of physical properties, prediction of liquid liquid and
vapour liquid equilibria. In addition, capabilities have been developed to design the various
equipment used in the process.
The process can be efficiently used for producing additional feedstock to existing FCC and hydro
cracking units. The technology is being further improved upon and can be applied to meet specific
needs.

Upgrading Petroleum Residues with Solvent Deasphalting Technology

AK Jain and SJ Chopra
Research & Development Centre
Engineers India Limited, Gurgaon
The petroleum refining industry has to deal with the bottom residues. The residue is a mixture of
oils, resins and asphaltenes. Resins and asphaltenes are poor in hydrogen but rich in sulphur,
nitrogen, nickel and vanadium. For a typical Arab Heavy vacuum residue, the hydrogen to carbon
ratio is 1.06 for asphaltenes, 1.33 for resins and 1.41 for vacuum residue (for comparison, H/C ratio
for diesel 1.9-2.2 and for methane 4.0). It is imperative to upgrade residues to recover valuable
products, as economically as possible. The basic technologies for residue upgrading can be
classified under three categories.

Hydrogen Addition (Hydro treating, Residue Hydrodesulphurisation)

Carbon Rejection (RFCC, Delayed Coker, Visbreaker)
Physical Separation (Solvent Deasphalting, Deep vacuum Distillation, Short Path
Distillation)

Significant advances have been made in these technologies over the past two decades and
numerous residue-processing schemes are currently available. A wide range of catalytic processes
have been developed using a variety of reactor designs and configurations such as multireactor
fixed bed systems, ebullated reactors, fluidized reactors and moving bed reactors (Halabi, 1997).
The current developments focus on the catalyst processing of the heavy feedstocks due to the
presence of heavy molecules and other metal components. These high CCR and metal bearing
compounds lead to deposition of coke and metals on the catalyst, direct inhibition of active sites by
molecules rich in sulphur and nitrogen, etc, thus, limiting the life of the catalyst. However, the noncatalytic carbon rejection processes like delayed coking and visbreaking are widely used in
refineries to upgrade residues. Complex schemes involving combinations of two or more
processes, such as HDS/Delayed Coking, HDS/deasphalting/partial oxidation or
visbreaking/hydrotreating have also been introduced for processing medium and heavy crudes.
Deep vacuum distillation has become a feasible process over the last decade due to availability of
low-pressure drop structured packings. Another process employing principles of molecular
distillation, Short Path Distillation is still being explored and commercial scale units using this type
of technology may come into operation in future.
Solvent deasphalting is essentially a solvent extraction process. The required solvent is usually
available with in the refinery. The process separates oil from carbon rich components, resins and
asphaltenes and makes it available to convert it to lube stock or as feedstock for other secondary
processing facilities. Feed impurities such as sulphur and metals get concentrated in the
asphaltene phase. The flexibility, inherent in the process, allows wide variation in product quality to
meet specific downstream process needs. The process continues to play a significant role, as one
of the key process units of the modern refinery complex. Installed capacity for solvent deasphalting
units worldwide is now over 20 million tonnes per annum (Dickenson, 1997). In India, solvent
deasphalting units have been installed at Haldia Refinery, Madras Refinery and HPCL's Mumbai

Refinery. One unit at HPCL Vizag refinery, which was used to provide additional feedstock to FCC
unit, is not in operation. Two more solvent deasphalting units have been proposed for Cochin
Refinery and Bina Refinery.
Like all refining processes, deasphalting is an evolving process. Major advances are taking place
towards improved energy efficiency, application of better internals, use of heavier solvent,
development of appropriate process simulation model and adequate tools for estimation of physical
properties.
Engineers India Limited in association with Indian Institute of Petroleum, Dehradun has developed
capabilities for designing commercial scale propane-deasphalting process. The technology has
been successfully applied for designing two grassroot units and revamping an existing unit. Figure
1 shows the photo of a commercial PDA unit in an operating refinery. The grassroot units,
commissioned in 1994 to produce the desired yield and quality of bright stock (capacity 100,000
TPA), are optimised towards energy consumption compared to the earlier units, operating in the
country. These units employ a double effect evaporator system, for the DAO + Propane mix and
saves about 40-45% of energy as compared to single effect evaporation system. The other
features of this process include precise temperature control at the top of the extractor and water
content of propane. The process is being further upgraded to include supercritical solvent recovery
configuration and currently available high capacity extraction column internals.
Process Description
A typical flow scheme of a solvent deasphalting process is given in Figure 2. The process involves
four basic steps

Extraction
Solvent Recovery from Deasphalted oil-solvent mix
Solvent Recovery from Asphaltene-solvent mix
Solvent recirculation

The heart of the process is the extraction column, which controls the product yield and quality. The
extraction
operation
is
carried out counter currently
in an extraction column with
suitable internals for efficient
liquid/liquid contact. Part of
the solvent is premixed with
feed before it enters the
Steam
DAO
extraction column to maintain
desired viscosity. Pressure is
normally maintained above
the bubble pressure of the
solvent at the temperature
used.
Normally,
a
temperature gradient is Feed
Steam
Asphalt
Figure 2 Typical Flow scheme of a Solvent Deasphalting Process

maintained. The extract containing deasphalted oil and majority of solvent is obtained from top of
the extraction tower and raffinate-containing asphaltene with balance solvent is the bottom product.
Extract and raffinate are sent for solvent recovery. The recovered propane is condensed and
recycled. Oil & asphalt, after stripping off the solvent are sent to storage for subsequent down
stream processing.
.
Chemistry of Solvent Deasphalting
Petroleum residua can be characterized as a mixture of various hydrocarbon classes including
saturates, aromatics and asphaltenes (Johnson, 1955). It is postulated that asphaltenes exist in
residue as the center of a colloidal particle or miscelle. The structure of the miscelle is such that the
central part consists of a high molecular weight, highly branched aromatic structure, surrounded by
constituents with low degree of aromaticity. When the entire miscelle system contains sufficient
constituents for the formation of the semi continuous outer region, the asphaltenes are fully
peptized or solubilised by this outer ring. Light liquid paraffin solvent partially or completely
dissolves these peptizing agents and asphaltenes precipitate. As the molecular weight of the liquid
paraffin solvent decreases, the solubility of the resins and of some of the heavier and more
aromatic hydrocarbon in the paraffin solvent decreases. Thus, lower molecular weight paraffin
solvent precipitates a tacky material consists of asphaltenes, resins, other aromatics and some
saturates. Clarified oil, consisting of lighter aromatics and saturates, get dissolved in the paraffin
solvent and is recovered as deasphalted oil.
Extraction Section
Process Variables
The variables of the process for the given feed are temperature, pressure, solvent to oil ratio and
solvent type.
Temperature and Pressure
Pressure and temperature are both variables because the solvent power of light hydrocarbon is
approximately proportional to the density of the solvent. That is, decreasing temperature or
increasing pressure will increase the average molecular weight of hydrocarbons soluble in solvent
rich phase. For propane solvent, at temperature below 80 C and pressure above the vapour
pressure of propane, temperature is the most important factor in determining solubility. At
temperature near critical region, pressure is also an important factor, as properties of liquid
propane approach those of a gas.
Higher temperature always results in decreased yields of deasphalted oil. This is accompanied with
the decrease in viscosity and molecular weight range of deasphalted oil (DAO). The Table 1
shows the typical effect of temperature on DAO yield and viscosity (Smith, 1957).

Table 1 Effect of Temperature on DAO Yield and Quality

Temperature, C

DAO Yield, wt%

97.8
92.8
88.9

23.9
50.6
58.1

DAO viscosity @100C, DAO API Gravity

cst
6.2
31.4
8.0
29.9
9.0
29.1

Generally the control of plant becomes difficult when rapid changes in temperature occur especially
near critical region. The loss of control or instability occurs because at conditions close to critical
point, the rate of change of solubility is very large. For practical applications, the lower operating
temperature is set by the viscosity of the asphaltene phase. The upper limit is to stay below the
critical temperature while maintaining desired DAO yield and stable operation.
Some time, a temperature gradient is also maintained along the length of the column. Higher
temperature at the top of the column generates an internal reflux by precipitation of dissolved
heavier material. This improves DAO quality significantly. However, high rate of internal reflux
limits the capacity of the extraction column.
Solvent to Oil Ratio
In general, increasing solvent to oil ratio increases the recovery of deasphalted oil with increase in
viscosity. Table 2 shows effect of solvent to oil ratio on yield and quality of deasphalted oil derived
from long residue of viscosity 25 cst @ 100C.
Table 2 Effect of Solvent to Oil ratio on DAO yield and quality (Poddar, 1995)
Solvent to Oil Ratio, DAO Yield, vol%
v/v
2.8
37.5
3.9
50.6
11.4
76.0

Gravity API
30.1
29.9
28.8

Viscosity @ 100C,
cst
7.5
8.0
10

DAO yield can be further adjusted with other variables like solvent type or the temperature. At
higher Solvent to Oil ratio, DAO quality can be regained by increasing the extraction temperature
with small decrease in DAO yield. For case III in Table 2, increasing temperature reduces viscosity
of DAO from 10 cst to 7.5 cst @ 100 C while reducing DAO yield from 76.0 to 72.0 vol% at the
constant solvent to oil ratio (11.4 by vol) (Hood, 1994). Thus, increasing solvent to oil ratio from 2.8
to 11.4, DAO yield increases from 37.5% to 72.0% at the constant DAO viscosity. Solvent to oil
ratio is important from the standpoint of solvent selectivity. The extent of yield advantage at a given
product quality at higher solvent ratio varies from crude to crude and need to be estimated.
However, higher solvent to oil ratio results in higher solvent circulation rate thereby increasing the
utility cost to recover solvent and may require higher equipment sizes.

Solvent Type
Light hydrocarbons such as propane, butane, isobutene, and pentane can be used. The solvent
power of light hydrocarbons increases with increased molecular weight. When the lowest practical
temperature is reached with a particular solvent, it is necessary to use higher molecular weight
solvents in order to recover maximum of DAO. The increased DAO yield with higher molecular
weight solvent is accompanied with higher viscosity, specific gravity, CCR etc. The typical
maximum DAO yield for each solvent is shown in Table 3 (Sprague, 1986). However, maximum
DAO yield with a particular solvent is highly dependent on the feedstock and desired product
quality.
Table 3 Typical Maximum DAO Yields
Solvent
n Pentane
n Butane
I Butane
Propane

Max DAO Yield, wt%

84
74
66
50

Bright stock manufacture using conventional processing route (solvent extraction, solvent
dewaxing) requires DAO with a viscosity of about 40 cst at 100 C, essentially zero metals and CCR
of about 2 wt%. These properties require solvent deasphalting unit to be operated with propane.
When DAO is routed as a incremental feedstock to other secondary conversion processes, the
quality of DAO is dictated by the gas oil quality and tolerance limit of catalyst. Normally, in these
cases, it has been possible to use higher MW solvent such as isobutene, n butane or their mixtures
like LPG.
Solvent deasphalting units need to have flexibility to operate with different solvents. Factors such
as market supply and technology of downstream processes can change during the operating life of
a solvent deasphalting unit in a refinery. The development in catalysts may allow higher metal and
CCR in feedstock to conversion processes. The solvent flexibility in a solvent deasphalting unit
needs to be inbuilt during design stage.
Solvent Recovery
Since, majority of solvent from extraction column is with DAO stream, energy conservation
measures are focused on solvent recovery from this stream. Conventionally, solvent recovery from
deasphalted oil is carried out in multistage evaporative flash columns. However, the present day
deasphalting units ensure recovery of maximum solvent at high temperature using the supercritical
phenomena. The heat from the recovered supercritical solvent is used efficiently in the process
configuration making the process highly energy efficient. The operating conditions for supercritical
solvent recovery shall satisfy the following requirements

Low oil Content ( less than 0.5%) in recovered solvent

Low solvent content (less than 30%) in DAO from bottom of the supercritical flash column

Solvent recovery from asphaltene solvent mix stream is carried out conventionally. The mix stream
is heated in a furnace and is flashed in a medium pressure flash column. Since, the solvent vapour
quantity is relatively small, asphaltene entrainment in solvent vapour need to be prevented. Bottom
is routed to steam stripper for removal of last traces of solvent.
Changeover Of Conventional Solvent Recovery Scheme To Incorporate Super Critical
Solvent Recovery Scheme
The conventional solvent recovery scheme can be retrofitted with supercritical solvent recovery
scheme to reap benefits of higher energy efficiency. The inhouse studies carried out with short
residue derived from 80:20 Arab Mix and the present configuration of two stage solvent recovery
from DAO mix stream, shows that 95% of solvent can be recovered in supercritical flash drum. The
bottom from supercritical flash drum contains about 28.0% wt propane, which is recovered in
downstream flash drum by lowering pressure. Last traces of solvent are recovered in steam
stripping column. The energy savings due to the changed configuration is given in Table 4.
Table 4 Energy Savings due to changeover to supercritical solvent recovery
Utility
Steam
Fuel
Cooling Duty

% Savings (Savings/existing utility)

12.5
33.0
29.3

In addition, lower solvent losses are expected as most of the solvent is recovered and recycled in a
single step. During changeover, the new major equipments, which may be required, are

DAO mix- Supercritical Propane exchanger

Supercritical DAO mix preheater
Solvent Cooler
Supercritical Flash Drum
DAO mix Booster pump

In addition, the existing exchangers, columns and other equipments need to be evaluated for their
new duties. The compressor duty is expected to fall and need to be evaluated in a new
configuration.
Design Philosophy
To optimise the overall process for a cost effective design, a detailed understanding of the process
variables and their interaction is very important. This requires understanding the thermodynamics
of the process along with development of tools for feed characterisation, accurate estimation of
physical properties, prediction of liquid liquid and vapour liquid equilibria besides critical equipment
design capabilities.

The extraction column where the primary separation of DAO and asphalt take place is the most
critical equipment in the PDA process. It is a multistage liquid liquid contacting device wherein
short residue feed is introduced at the top and dispersed into droplets by means of a distributor.
Solvent is introduced at the bottom and travels upward as a continuous phase. During the counter
current contact, low molecular weight component and paraffinic fractions of the feed gets dissolved
in solvent. The dispersed asphaltene phase gets settled at the bottom and provides operating
interface of the column. Solvent enriched with DAO is taken out from top under pressure control
while asphaltene phase from bottom is taken out on level control or flow control.
Many type of extraction equipment are in use in solvent deasphalting process. Earlier units were
employing baffle tray column and Rotating Disc Column (RDC). Baffle tray column used to provide
a trouble free operation because of their open structure. However, baffle tray columns are less
flexible to column throughput and changes in physical properties of the system. RDC has been
widely applied in various solvent extraction unit. However, lately, their application is limited to pilot
scale or low scale operation due to the requirement of the complicated mechanical seal of the
rotating shaft. The present day modern random packings and structured packings, which have
been successfully applied in other solvent extraction processes, are also being attempted in
solvent deasphalting.
The three major properties, which influence the design of extraction column, are interfacial tension,
viscosity and density of phases. Solvent deasphalting extraction column is characterized by low
interfacial tension (0.5 dynes per cm), high viscosities of asphaltene phase (10 to 50 cst) and
reasonably good density difference (0.2-0.3 gms/cm3). Most of the literature correlations for design
of extraction column are valid for medium to high interfacial tension and have been developed with
clean systems. Extension of these correlations for solvent deasphalting applications needs to be
suitably validated.
The asphaltene entrainment and foaming in solvent recovery flash column need to be critically
looked into. The availability of suitable process simulation model is of help to optimize the process
configuration and making the process energy efficient.
DAO as Feed to FCC/Hydrocracking
Since, solvent deasphalting selectively rejects asphaltenes, metals and high molecular weight
aromatics from vacuum bottoms, the resulting DAO can be combined with the vacuum gas oil to
give a greater quantity of acceptable feed to FCC/HC unit. The increased feed to FCC/HC will
increase distillate production. Table 5 compares the yield pattern with and without DAO from
conversion unit (Penning, 1982, Hood, 1993).

Table 5 Yield Pattern from FCC/HC with/without DAO with Arab Light
Conversion Process
Vacuum Gas Oil (vol % of crude)
Vacuum Residue (vol % of crude)
DAO added (vol % of crude)
Product Yields, vol%
LPG
Gasoline
LCO
Diesel

67.8
32.2
nil

FCC
67.8
25.1

Hydrocracking
67.8
67.8
32.2
nil
18.1

19.6
39.7
9.7
-

25.5
50.1
12.7
-

2.9
64.5

4.1
81.5

DAO addition to FCC/HC feed is now a matured configuration. The typical DAO and FCC feed
quality for units feeding DAO is given in Table 6 (NPRA Q&A, 1995). The amount of DAO that can
be added to FCC feed largely depends on the limitation with FCC catalyst and throughput
constraint to FCC.
Table 6 DAO mix feed to FCC unit
Unit
A
B
C
D
E

DAO % of
FCC Feed
20
24
35
20
17

DAO CCR
wt%
4.0
5.5
6.0
5.9
7.0

DAO Ni+V ppm

9
20
8
3
10

FCC Feed,
CCR wt%
1.4
1.0
2.0
1.5
1.0

FCC Feed,
Ni+V, ppm
3
3
4
2
3

Areas of Development
The areas of development in this process are the improvement in extractor tower internals, studies
with higher molecular weight solvent, accurate estimation of physical properties of mix stream,
studies in combination with other processes and firming up design tools for supercritical solvent
recovery configuration.
EIL/IIP along with HPCL have planned to further improve upon the existing capabilities. A pilot
plant facility is being created along side the commercial scale PDA unit to generate design data for
supercritical solvent recovery. Hydrodynamics data have been generated with modern day random
packings with low interfacial tension system in a glass column available at EIL R&D center in
Gurgaon. The high-pressure phase equilibria data for the system of interest is also being
generated.
Acknowledgement
Authors are thankful to the management of Engineers India Limited for permitting the publication of
this paper.

References
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0

Halabi MA, Stanislaus A and Qabazard H, Trends in catalysis research to meet future
refining needs, Hydrocarbon Processing, Feb, 1997
Johnson PH, Mills KL and Benedict BC, Recovery of catalytic cracking stock by solvent
fractionation, Ind & Eng Chemistry, V47, N8, August, 1955
Poddar SK, Ragsdale R and Hood RL, Application of the ROSE Technology for lube oil
production, Paper presented at International Symposium on production and application of
LOBS, Nov 1995, New Delhi
Hood RL, Importance of Supercritical Solvent Recovery, International Chemical
Engineering, March, 1994
Le Page JF, Chatila SG and Davidson M, Resid and Heavy Oil Processing, IFP, Edition
Technip, 1992
Sprague SB, How solvent selection affects Extraction Performance, Paper presented at
1986 NPRA annual meeting, March, 1986
Dickenson RL, Biasca FE, Schulman BL and Johnson HE , Refiner options for converting
and utilizing heavy fuel oil, Hydrocarbon Processing, Feb 1997
Penning RT, Vickers AG and Shah BR, Extraction upgrades resid, Hydrocarbon
Processing, May 1982
NPRA Q&A 1995 session on Refining and Petrochemical Technology
Smith EE & Fleming CE, Here is data on Propane Fractionationation, Petroleum Refiner,
July 1957.
Hood R and Bonilla J, Residue Upgrading by Solvent Deasphalting and FCC, Fifth Annual
Refining Seminar, Dallas, Texas, October, 1993

Details about the authors

Dr S J Chopra is presently Director Technical and is holding the additional charge as Chairman
and Managing Director of Engineers India Limited, New Delhi.
Dr Chopra is Bachelor in Chemical Engineering from Delhi University (1962) and Doctorate in
Chemical Engineering from IIT, Delhi. Dr Chopra has 36 years of professional experience, 4 years
in operation, trouble shooting of process plants, subsequently in Research and Development of
petroleum refinery processes and development of process design tools, chemical process
equipments, steady state process flow sheet simulator, advanced control of refinery processes etc.
Dr Chopra has been pioneer in developing a very active and healthy relationship with various
Academic Institutes and National Research Laboratories. His efforts have lead to the creation and
operation of different pilot units in operating refineries and successfully carrying out collaborative
research projects. Many of these projects have been commercialized. His efforts have helped in
maintaining EIL's preeminence as Engineering Company.
Dr Chopra is recipient of NRDC Independence Day award during the year 1987 for meritorious
invention entitled " A Solvent Extraction Process for the Production of Pure Aromatics". In addition,
he has received many national awards. The latest among them is the CSIR technology award
(1999) for Development of Propane Deasphalting Technology. His efforts have also lead to EIL
bagging various National Awards like ICMA, Dept. of Petrochemicals, etc.
Dr Chopra has presented various papers at national and international conferences and has also
chaired several sessions at international seminars in India and abroad.

AK Jain is presently Manager in Research and Development Division in Engineers India Limited.
Mr. Jain is Bachelor in Chemical Engineering from Punjab University, Chandigarh (1984) and M.
Tech in Chemical Engineering from IIT, Delhi.
Mr. Jain has 13 years of professional experience in R&D. His specialization is in the area of solvent
extraction processes, phase equilibria and process simulation. He has presented various papers at
national and international conferences.
Mr. Jain is recipient of CSIR Technology Award (1999) for Development of Propane Deasphalting
Technology