7

Solvent Extraction in the Oil Industry

Thierry Hombourger
Lu C COil ::;iell

PUll/ Mikitl'lIlw
Pascal HOI/fils

In this chapter we are going to examine three important applications of the

extraction process in the oil industry:
extraction of aromatic compounds from lube oil stocks in order to pro-
duce lubricants;
deasphalting of distillation residues, used to produce both deasphalted
oils and asphalts, with the possibility of deasphalted oils undergoing the
extraction operation mentioned above;
extraction of aromatic compounds from lighter stocks, gasolines or
kerosines, in order to comply with present and future regulations con-
cerning motor fuels and other combustion products.
In the last part of the chapter we will review the different types of extrac-
tion equipment.

7.1 Eliminating Aromatic Compounds from

Lube Oil Stocks to Produce Lubricants
The viscous feed used in lube oil stocks production units comes either from
vacuum distillation or from propane deasphalting.
It is called ”distillate”when it comes from vacuum distillation and “DAO” or
deasphalted oil when it comes from the propane deasphalting unit.
The hydrocarbon families that make up the feed are:
paraffins (straight or branched chains),
naphthenics with one or two rings,
polynaphthenics (with more than two rings),
aromatics.
360 Chapter 7. SOLVENT EXTRACTION IN THE O I L INDUSTRY

The relationship between the properties and structures of the hydrocar-

bons found in the cuts for lube oil stocks is indicated in Table 7.1.

~ ~

Main properties
Families Typical structure
Favorable Unfavorable

Straight chain High viscosity High pour

paraffins index point

Branched Good to high

paraffins viscosity
and paraffins
with few rings Good resistance
to oxidation

~~~

Vaphthenics r‘
0
Good resistance Low viscosity
to oxidation index

Low pour
point
J
0

4romatics Generally low- Low viscosity

pour point- index

Very poor
resistance to
oxidation
Table
Characteristicproperties of chemical Families of hydrocarbons Found in lube oil
stocks.

One of the main characteristics of a lube oil is its ability to maintain its vis-
cosity at engine operating temperatures.
The VI (viscosity index) is used to measure this characteristic, a number
that characterizes the variation in kinematic viscosity of a petroleum cut ver-
s u s the temperature on a conventional scale. The higher the VI, the less the
viscosity varies with temperature.
The VIs of hydrocarbon families in the petroleum cuts used to produce
lube oil stocks coming from conventional solvent based processes are indi-
cated hereafter:
Chapter 7. SOLVENT EX7RACTION IN THE OIL lNDUSTRY 361

Paraffins 140 to 180

Raffinates 105 to 120
Dewaxed oils 95 to 105
Distillates 75 to 95
Naphthenic oils 40 to 65
Extracts from aromatics extraction
by selective solvent < 30
In order to produce high quality lube oils, the paraffinic hydrocarbons with
a high viscosity index must be separated from the naphthenic and aromatic
hydrocarbons with a low viscosity index. The different hydrocarbons have
neighboring boiling points and can not be separated by distillation.
The process used to separate paraffinic from aromatic hydrocarbons is a
liquid-liquid extraction by means of a selective solvent. The operation is car-
ried out in an extraction column.
The high added value product with a high viscosity index is called the
"raffinate". The product with a very low viscosity index containing aromatic
molecules is called the "extract".
The distillates coming from the vacuum distillation unit or the deasphalted
oil coming from the deasphalting unit make up the feed of the column.
The solvent is placed in contact with the feed in the column (or extractor)
where the feed/solvent mixture divides up into three zones:
the upper zone (above the interface), which is made up of mixed raffinate
containing approximately 15 to 20% solvent:
the extraction zone (included between the feed inlet and the solvent
inlet), which is made up of mixed extract (95%) and mixed raffinate (5%);
the lower zone (below the feed inlet), which is made up of mixed extract,
whose composition is approximately 80 to 85% solvent and 15 to 20%
extract.
The extraction process causes contact to occur between a dispersed phase
and a continuous phase. The column is partially filled with a liquid (continu-
ous phase) that the other liquid moves through in the form of drops (dis-
persed phase).
The drops come together in a homogeneous layer separated from the con-
tinuous phase by an interface. Depending on the position of the interface,
either the heavy phase or the light phase or both can be dispersed (see
Fig. 7.1: Operation of an extraction column depending on the position of the
interface).
The position of the interface is governed by the type of products in contact
with one another (polarity, interfacial tension, etc.) and by the type of extrac-
tion column used (see Section 7.1.1.1.b:Choice of the extractor).
The solvent contained in the mixed raffinate and extract is separated by
distillation and recycled to the extractor. The solvent-free raffinate is stored in
tanks before undergoing the other processes required to obtain a lube oil
362 Chaoter 7. SOLVENT IN THE OILINDUSTRY
EXTRACTION

Light phase out

Heavy phase in

Light phase in

1
-
Figure
7.1 Position of the interface.

stock. The solvent-free extract can be sold as is for specific applications

(mainly in the tire manufacturing industry), is sent to the fuel oil pool or is
used as cracking feed.
Extraction yield varies between 50 and 85%volume of the feed depending
on the solvent, the type of feed processed in the extractor and the severity of
the process.
Table 7.2 gives typical characteristics for distillates, raffinates and extracts.
The table illustrates how the extract phase is enriched in aromatics com-
pared to the raffinate phase (84% aromatics in the extract and 25% in the raf-
finate). Product aromaticity is measured by the aniline point (the lower the
measurement the more aromatic the product is).
The raffinate and the extract are also different from one another in the fol-
lowing ways:
Specific gravity: the extract gravity is close to 1.0 (the extract is recov-
ered at the bottom of the column); the raffinate gravity is approximately
0.85.
Viscosity: the raffinate is mainly made up of paraffinic chains, which are
less viscous than the complex aromatic rings in the extract.
Pour point: the paraffins that make up the raffinate have a high pour
point.
Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY 363

Sulfur: the raffinate sulfur content is lower than that of the extract, with
sulfur-bearing molecules of the benzothiophenic type.
Color: the raffinate is yellow while the extract is dark green.
By eliminating aromatics, solvent extraction significantly improves the
quality of the products that serve as a basis for producing lube oils.

Products
Distillate (feed) Raffinate Extract

d’4“ 0.927 0.875 1.005

Viscosity at 100°C (mm2/s) 8.74 6.98 15.91
Flash point (“C) 240 240 242
Pour point (“C) 34 39 17
Sulfur %
(! wt) 2.6 0.8 4.9
Aniline point (“C) 83 106 33
KUOP 11.7 12.7 10.5
Conradson carbon (% wt) 0.14 < 0.01 0.59
ASTM color 3 1 6
Yield (96 vol) 100 60 40
Table
Characteristicso f the feed, raffinateand extract.

7.1.1 Furfural Extraction

As we will indicate later on, extraction solvents are numerous. Among the
range of available solvents, only a few, among which furfural, meet the target
criteria adequately.
We will examine the different variables of the system by dividing them into:
external variables:
- choice of solvent,
- choice of extractor,
- feed composition,
- extraction efficiency.
internal variables:
- solvent ratio,
- extraction temperature,
- temperature gradient,
- extractor feed flow rate,
- solvent purity.
364 ChaDter 7. SOLVENT EXTRACTION
IN THE O I L /NOUSTRY

7.1.1.1 External Variables

a. Choice of Solvent
The essential characteristics of a good extraction solvent are its selectivity
and its solvent power, or solvent capacity.
Selectivity corresponds to the solvent’s affinity for one substance rather
than another, so that it will be able to extract this compound preferentially
from the hydrocarbon mixture making up the feed of the extraction unit.
The solvent power, or capacity, is expressed by the amount of feed oil that
can be dissolved per unit of volume or weight of solvent.
A good extraction solvent for aromatics must therefore have high selectiv-
ity for aromatics molecules and good solvent power in order to perform the
extraction with a small volume of solvent.
Besides these two characteristics, the following points also enter into con-
sideration in the choice of a solvent:
high extraction temperature for good mass transfer:
easy recovery, if possible simply by flash:
low vapor pressure to make high pressure equipment unnecessary:
high specific gravity for rapid separation of the oil and solvent phases;
no emulsion for rapid separation of the oil and solvent phases:
stability, i.e. no thermal and/or chemical degradation:
adaptability to a wide range of feeds:
availability at a reasonable cost:
noncorrosive toward conventional construction metals:
non-toxic for the environment and on-the-job safety.
Table 7.3 lists the most widely used solvents in the industry for different
liquid-liquid extraction processes. Because they meet the requirements for a
good aromatics extraction solvent best, the most often chosen are as follows:
Furfural
Phenol
N-methyl-2-pyrrolidone, or NMP.
Table 7.4 shows to what extent the different solvents have been used in the
last fifty years.
Environmental and toxicity criteria have taken on increasing importance in
recent years, and this explains why the phenol process, which was very widely
used in 1937, has remained static.
Table 7.5 establishes a comparison between the three main solvents and
shows that furfural and NMP meet the requirements of a good aromatics
extraction solvent, as defined earlier, quite well.
Chapter 7. SOLVENT EXTRACTION IN THE O I L INDUSTRY 365

Solvent Formula ipecific gravity (di5) I Boiling point (“C)

Benzene 0.884 80.1

Sulfur dioxide 1.397 -10
Cresol 1.045 186
Propane 0.51 1 -44.5
Dichloroethylether 1.230 178
Furfural 1.162 162
Nitrobenzene 1.207 21 1
Phenol 1.072 182
Aniline 1.022 184
NMP 1.030 202

Table

LY Extraction solvents.

1937 1992 1992

Capacity PA) Capacity (%) I Number of sites

Furfural 28 40 20
Phenol 25 28 12
Duosol @henol/propane) 26 14 7
Liquid SO, J 5 3
NMP 0 11 3
Others 18 2 2
Total 100 100 47

I 7.4 1 Variations in extraction units worldwide since 1932

Characteristics I Furfural NMP Phenol

Relative cost 1.o 1.5 0.36

di5 1.162 1.04 1.08
Boiling point (“C) 162 202 182
Vaporization enthalpy
at 60 mmHg (kJ/kg) 45 1 493 479
Selectivity Excellent Very good Good
Solvent power Good Excellent Very good
Stability Good Excellent Very good
Biodegradability Good Good Good
Toxicity Moderate Low Severe
1 Table
Comparison between furfural, NMP and phenol
366 Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY

We will now examine the characteristics of furfural more particularly.

Furfural is an aldehyde whose developed chemical formula is:

In addition to the characteristics already listed in Table 7.5, the following

points should also be mentioned as they are useful in understanding the
extraction flow scheme:
Water and furfural form a heteroazeotrope (see Fig. 7.7).
The mutual solubility of water and furfural are not negligible (see Fig. 7.7)
even at low temperature.
The solvent power of furfural with respect to oil increases when the tem-
perature increases. This effect varies with the type of feed processed.
Generally speaking, the solvent power decreases when the molecular
mass increases. The solvent power is expressed by the amount of oil that
can be dissolved by unit of weight or unit of volume of solvent.
The selectivity of furfural toward aromatics decreases when the temper-
ature increases, more particularly in the neighborhood of the miscibility
temperature. Selectivity corresponds to the solvent's affinity for one sub-
stance rather then another, so that it can extract the substance more or
less from the feed oil mixture.
Furfural is a chemical compound that is sensitive to oxidation, acids and
temperature.
This last point deserves particular attention, Certain inhibitors such as
amines can protect it during storage against the action of oxidizing agents, but
they are difficult to use in a unit in operation. Metals such as copper acceler-
ate the oxidation process. Oxidation causes acids to form and they in turn
make furfural break down into resins. The rate of degradation is proportional
to the concentration in hydrogen ions. As a result, water itself can also affect
furfural.
Furfural also has a tendency to break down with temperature. At 230°C, 5%
is degraded in 80 hours. Above this temperature degradation becomes expo-
nential with the formation of resins that are insoluble in aromatics. Moreover,
furfural may not be inert toward some components of feeds treated in extrac-
tion processes, thereby giving rise to complex polymers.

b. Choice of the Extractor

Figure 7.2 sums up the relative performance of the main extraction methods in
terms of final viscosity index (Vr) achieved.
The diagram clearly shows that the countercurrent extraction method is
superior, and this is why it is so popular with a majority of operators.
Chapter 7. SOLVENT EXTRACTION
IN THE OIL /NDUSTRY 367

Countercurrent
Multiple addition
105
100
95
VI 90
85
80
75
..,
7n
100 200 300 400
Solvent ratio

1Figure
7.2 Viscosity index versus solvent ratio and extraction method.

There are different types of extraction columns. Given their operating prin-
ciple and the technological constraints of construction and cost, they perform
more or less well as characterized by the number of theoretical extraction
stages.
Figure 7.3 shows the most widely used extractors in the industry.
The former generation of furfural extraction columns were of the packing
type, with 1 to 2' ceramic saddles (often varnished to reduce the rate of foul-
ing by resins).
The present-day trend is to use the high efficiency RDC (Rotating Disc
Contactor) column, which offers a large number of advantages compared to
other extractors:
High number of theoretical stages (up to 10 compared with 5-7 for con-
ventional columns).
Very clear-cut raffinate/extract interface.
Raffinate yield 3 to 5% higher than with packing-type extractor columns.
Possibility of optimizing extraction quality depending on the type and
flow rate of the feed by using rotating discs (which cause one of the solu-
tions to be dispersed in the other, with drop size depending on the rotor
speed).
The RDC type extractor has a high cost, but its performance gives great
adaptability to different feeds, thereby allowing access to a larger number of
crudes and making the refining margin easier to optimize. Figure 7.4 illustrates
this. For example, for an Arabian Light crude an extraction column with 5
368 Chapter 7. SOLVENT EXJRACTION IN THE OIL lNDUSTRY

q
Mixer-settler Packed tower Sieve tray column
Raffinate Raffinate

Furfural

$.
Extract Extract Extract

Rotating disc contactor

Raffinate

Centrifugal extractor

Furfural

Extract

--
Figure
7.3 Extractor types. In practice in the industry only rotating disc contactors and
packing type columns are used. Mixer-settlers and centrifugal extractors are

0 Arabian light North Sea

80

h
75
2 70
65
2
60
pal 55
5
a:
50
45
40
1 2 3 4 5 6 7 8
Number of stages

1Figure
7.4 RaFFinate yield versus the number of stages and the type OF crude.
Chapter 7. SOLVENT EX~RACTION
IN THE OIL /NOUSTRY 369

theoretical stages gives perfectly satisfactory results in terms of the raffinate

yield/viscosity index compromise. Meanwhile a North Sea type crude in the
same column will have a yield 15 to 20% lower than with an RDC.
Figure 7.5 shows the outside of an industrial RDC in the foreground.

hml!=
Figure
"RDC" type of extraction column with the mixed
extract furnace in the background.

c. Type of Feed
The type of feed is crucial for extraction results. As a general rule for feeds of
the distillate type, the more viscous the feed and the higher the specific grav-
ity, the more difficult extraction will be. This can be explained by the fact that
viscous feeds contain more complex ring molecules than low viscosity cuts.
370 Chapter 7. SOLVENT EXTRACTION
IN THE O I L lNDUSTRk'

Additionally, the gravity of heavy cuts is close to that of furfural and conse-
quently the rate of separation between the oil and solvent phases is slower.
Accordingly, for a solvent ratio of 290% volume in relation to the feed and
an identical extraction temperature, the following results are obtained:
20 mm2/s at 40°C VI = 110
60 mm2/s at 40°C VI = 107
140 mm2/s at 40°C VI = 97

d. Extraction Efficiency
Under identical extraction conditions (solvent ratio and temperature), effi-
ciency is directly related to the number of theoretical stages in the extraction
column. For example, a column with 5 theoretical stages will achieve a viscos-
ity index 2 to 3 points higher than a column with 3 theoretical stages. For cer-
tain types of crude and heavy cuts, extraction may not be possible.
Consequently, it is extremely important to guard against fouling, which causes
a decrease in the number of theoretical stages.
Degradation of furfural causes formation of resins which have a relatively
high fouling capacity. An extractor of the packed column type is very sensitive
to fouling. It can be so detrimental to extraction quality that the extractor
exhibits results comparable to a column with two or three fewer theoretical
stages, and this can occur in a very short time.

7.1.1.2 Internal Variables

a. Solvent Ratio
The solvent ratio is defined in % volume of the extractor feed flow rate. The
higher the solvent ratio for a feed of given quality, the more extraction is in
progress, with the following results:
an increase in the viscosity index, due to a decrease in naphthenic and
aromatic molecules in the raffinate;
a decrease in raffinate yield;
an increase in extract aromaticity (which is measured by the aniline
point).
Table 7.6 illustrates this.
Figure 7.6 shows that the increase in solvent ratio causes a decrease in the
volume of recovered raffinate, but with improved quality. Table 7.6 corrobo-
rates this observation by means of the viscosity index values achieved, which
rise rapidly at the beginning of the increase in solvent ratio, then show an
asymptotic increase at a very high solvent ratio.
In practice it is often advantageous to minimize the solvent ratio, given the
energy cost of solvent recovery. It must be pointed out, however, that there is
a minimum solvent ratio, lower than this the process should not operate what-
ever the severity of the other operating variables. The minimum solvent ratio
used by lube oil stock producers is greater than the figure obtained by the
Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY 371

Solvent Raffinate yield Specific gravity Conradson carbon

(% vol) VI (“Awt)
(“Avol) (di5>
0 100 0.925 65 2.9
300 75.2 0.900 84.7 1.1
600 62.6 0.895 88.6 0.9
900 53.3 0.892 91.0 0.8
1200 47.1 0.891 93.2 0.7
-
Table
7.6 Effecto f the proportion o f solvent (93% furfural) on raffinateyield and qualiw.

Paraffins I I n Raffinate

1
Naphthenics
mono + di

Polynuclear
naphthenics
Aromatics
mono + di

Polynuclear Extract
aromatics

Increase in solvent ratio

Figure
7.6 Yield and selectivity versus solvent ratio.

theoretical extraction calculation and depends on the degree of quality

desired for the end product (oxidation resistance, etc.).
b. Extraction Temperature
The increase in extraction temperature, which increases the solubility of aro-
matic molecules in furfural, has the same effects as the increase in solvent
ratio. However, the higher temperature has a less selective action than the sol-
vent ratio, and this means a lower raffinate yield for an identical viscosity
index.
372 Chapter 7. SOLVENT EXTRACTION IN THE OIL /NOUSTRY

Figure 7.7 gives a simplified illustration of the cuts obtained according to

the temperature used in the extraction process.
It is interesting to compare Figures 7.6 and 7.7. In Figure 7.7, the slope of the
borderline between the extract and the raffinate increases much more quickly
when the extraction temperature increases than when the solvent ratio
increases in Figure 7.6. This shows the lesser selectivity of furfural when the
temperature is raised. The very accentuated slope on the third extraction dia-
gram in Figure 7.7 illustrates the fact that the closer we approach miscibility
temperatures, the more furfural selectivity decreases.

Paraffins I I n Raffinate

Naphthenics

Aromatics

Extract

b
Increase in temperature
I

I I 7-7
Yield and selectivity versus temperature.

The increase in temperature is limited by the raffinate's miscibility in fur-

fural. When the miscibility temperature is reached there is only one phase in
the extractor, which of course makes any extraction impossible. The closer we
get to this temperature, the more the proportion of furfural increases in the
raffinate, and this allows the phenomenon to be fairly easily detected in an
industrial unit. The miscibility temperature, approximately 120 to 145"C,
depends on the type of feed (type of crude, viscosity).
Since the effects of increasing the solvent ratio and the temperature are the
same, these two operating variables will need to be optimized somewhere
between the following two extreme cases:
Chapter 7. SOLVENT EXTRACTION
IN THE OIL /NDUSTRY 373

High temperature/ Low temperature

low solvent ratio high solvent ratio

Use when: Use when:

- the volume of solvent - the volume of solvent
circulated in the extrac- circulated in the extrac-
tion unit is a bottleneck tion unit is not the first
in the series of lube oil bottleneck encountered
stock treatments
- feed availability is - distillate availability
in excess is limited
Results Results
Lower extraction yield High extraction yield
High feed flow rate Low unit load
Low energy consumption Greater energy consumption

c. Temperature Gradient
The temperature gradient between the bottom and the top of the extractor
usually allows considerably improved efficiency in a column of given height.
Experience will indicate the gradient that should be used depending on the
type of feed and the solvent ratio.
The basic rules are as follows:
High temperature at the top of the column is used t o eliminate low VI
components from the raffinate. This can be explained by the increase in
furfural solubility toward naphthenic and aromatic molecules.
Low temperature at the bottom of the column serves to release compo-
nents with the proper VI from the extract, because furfural’s selectivity
toward aromatic molecules rises when the temperature decreases.
Extraction temperatures vary widely depending on the crudes, the viscos-
ity of the extractor feed and the quality required. They can range from 100°C
at the top and 60°C at the bottom for an Arabian Light light distillate, to 135°C
at the top and 105°C at the bottom for a North Sea heavy distillate.
Optimization needs to be carried out to determine the temperature profile in
the column.
d. Extractor Feed Flow Rate
The feed flow rate affects extraction results by its impact on the velocity of flu-
ids inside the column, which in turn modifies the size of solvent/product
droplets in contact with each other. This action is very slight in the normal
operating range of the extractor and grows exponentially when the flow rate is
either extremely low or higher than the column’s design rate. When the feed
flow rate is too low, the contact between feed and solvent is insufficient to
ensure good extraction. On the contrary, when the feed flow rate is too high,
374 Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY

it will cause formation of overly fine droplets and result in the existence of a
continuous phase in the extractor (no interface). The extractor is then said to
be flooded.
In RDC type columns the rotation speed of the rotor is adjusted to attenu-
ate an overly low feed flow rate. The faster it rotates, the smaller the droplet
size. An overly high rotation speed will have the same effect as an overly high
feed flow rate. In practice, it is difficult to optimize the rotor speed because it
is also related to other operating variables such as temperatures, solvent ratio
and type of feed handled. It is useful to know the flooding limit versus the feed
flow rate and the rotor rotation speed for an RDC type extractor and a given
feed quality. The profile of this limit is represented in Figure 7.8 and shows
that:
the higher the extractor feed flow rate, the lower the admissible rotor
speed before flooding occurs;
the higher the viscosity of the extractor feed, the lower the authorized
feed flow rate for the same rotor rotation speed.

8 000
7 000
h

U
2 6000
2
v E 5000
(I)
c
!! 4000
3
3000
-0
(I)
IL" 2000

1 000

0
0 0.6 1.2 1.8 2.4 3
Rotor speed (mk)
J
Figure
7.8 Flooding in an RDC extractor versus the feed flow rate and the rotor speed.

e. Solvent Purity
The solvent may be contaminated mainly in two ways:
by water (traces) coming from the feed and from the stripping steam
used in the solvent recovery process;
Chapter 7, SOLVENT EXTRACTION
IN THE OIL INDUSTRY 375

by oily compounds, often resulting from mechanical carryover in extract

or raffinate/solvent separation towers.
Even in very small amounts, these contaminants degrade extraction qual-
ity significantly. For example, 3 to 4% water in furfural can cause a VI loss of 4
to 6 points and identical proportions of hydrocarbons bring about a drop of 2
to 3 points. It should also be noted that the presence of hydrocarbons in fur-
fural makes it break down into resins faster.

f. Assessment of Extraction Results

The result of an extraction operation is measured by the viscosity index
achieved for the base stocks.
The VI is measured on the lube oil exiting the dewaxing units, i.e. a rela-
tively long time between any action on an operating variable in the extraction
unit and its result. To minimize this disadvantage, it is possible to regulate the
extractor on the basis of its yield. In effect, for a feed of given nature, the
desired VI is directly related to extraction yield, which can be obtained by a
balance using feed, raffinate and extract specific gravity or their refractive
index. The refractive index measurement is more precise than that of the spe-
cific gravity, and moreover it characterizes the feed better (for the same VI
value, refractive indices can be very different depending on the crude feed).
The technology of continuous refractive index analyzers has evolved signifi-
cantly and their accuracy today allows them to be used industrially to detect
any extraction column malfunction in real time.

7.1.2 Flow Scheme of a Furfural Extraction Unit

The complete flow scheme of a furfural extraction unit is given in Figure 7.9.
The following parts can be seen:
Feed deaeration
Extraction
Recovery of solvent in the raffinate
Recovery of solvent in the extract
Water removal and azeotropic distillation section
Drainage system.

7.1.2.1 Feed Deaeration

The distillate or the DAO from storage is pumped to the deaeration tower C,
after having been heated to approximately 100°C by exchange with the extract
exiting the unit. Tower C, is connected to the unit’s vacuum system and works
at an absolute pressure of 50 mmHg. Its purpose is to eliminate the moisture
and air contained in the feed (because furfural is sensitive to oxidation and to
the presence of water, which significantly lower extraction performance).
0
-l
Q,
Raffinate
I
u

I I

To column C,
Extract 1 To drum 6,
r

Steam

I 1 To column C9

w Aromatics extraction unit using furfural.Flow scheme (Source: Mobil).

Chapter 7. SOLVENT EXTRACTIONIN THE O I L /NDUSTRY 377

7.1.2.2 Extraction Tower C,

The extractor C2 works under pressure (6 bar at the top) so that it is unnec-
essary to use pumps to evacuate the mixed raffinate (mixed, because it con-
tains solvent) to the section where furfural is removed from the raffinate. The
extractor’s operating pressure is determined only on the basis of hydraulic
parameters and has practically no influence on liquid-liquid extraction quality.
The feed is sent to the bottom of the extraction zone (specific gravity close
to 0.85). The solvent is sent to the top of the same zone (specific gravity =
1.1598 at 20°C). Its temperature conditions that of the top of the column.
Because of the difference in specific gravity, the furfural flows downward in
the column and comes into contact with the rising lube oil stream, dissolving
part of the oil.
The feed temperature is adjusted by means of the exchanger EI8 which can
be used alternatively as a heater (calories are provided by condensation of low
pressure steam) or a cooler (calories are evacuated by process water).
In addition, a mixed extract side stream is drawn off under the feed inlet,
cooled in exchanger EI5 and sent back to the tower. This recirculation allows
the desired temperature to be regulated at the bottom of the column.
The top/feed/bottom temperature gradient is regulated by a complex con-
trol loop whose set points are the temperature of the top of the column and
the different gradients required between the top and the feed, then between
the feed and the bottom.
An interface control loop regulates the separation level between the mixed
raffinate and the mixed extract. The pressure available at the bottom of the
extractor (6 bar + the height of the liquid column, i.e. approximately 10 bar)
allows the mixed extract to be evacuated without using a pump.

7.1.2.3 Recovering the Solvent from the Raffinate

The mixed raffinate is sent to furnace F, via exchangers E,, (exchange between
mixed raffinate and raffinate exiting the unit). It is heated to approximately
200°C at the furnace outlet to vaporize practically all the furfural in the flash
zone of tower Cs. The solvent is recovered in drum B, (called the dry drum).
The last traces of furfural are eliminated in the C, steam stripping zone. Tower
C, is connected to the unit’s vacuum system and works at a pressure of around
0.2 bar absolute at the top. The furfural impregnated with water coming from
the C, steam stripping zone is sent to drum B, (called the wet drum).
The simplicity of the process can be explained by the small amount of fur-
fural carried over by the raffinate (from 10 to 15%),which does not warrant
high investments to reduce energy consumption.

7.1.2.4 Recovering the Solvent from the Extract

Compared to the raffinate circuit, the extract circuit is relatively complex
because of the attempt made to reduce the energy consumption involved in
378 ChaDter 7. SOLVENT IN THE OILINDUSTRY
EXTRACTION

vaporizing furfural. In this connection, the extract circuit is made up of four

consecutive vaporization stages and ends with steam stripping.
The mixed extract, containing approximately 85 to 90% furfural, is evacu-
ated from the bottom of the extractor by gravity. It is heated to approximately
165°Cby heat recovery from the overhead vapors of the flash tower C,, before
undergoing flash at atmospheric pressure in tower C,. The furfural vapors at
the top of C, are only partially condensed in Eg and are then sent to the bot-
tom of the furfural tower C,. When they finish condensing in C,, the furfural
vapors provide the calories required to vaporize the azeotrope (see the sec-
tion on azeotropic distillation).
Approximately 20% of the furfural contained in the mixed extract is recov-
ered in C,.
The mixed extract at the bottom of C, is then pumped to furnace F, where
it is heated to around 225°C to undergo a flash in tower C, working at 3.5 bar
abs.
The solvent vapors at the top of C, are condensed and sent to the furfural
tower C,.
About 60% of the furfural contained in the initial mixed extract is recovered
at the top of C,.
The mixed extract at the bottom of C, is then flashed in C, which is con-
nected to the unit’s vacuum system. Its overhead pressure is some 0.3 bar abs.
The temperature in C, is approximately 185°C (decrease in temperature in
C, due to furfural vaporization).
The furfural collected at the top of C, (about 10%) is sent after condensa-
tion to drum B, to be used as a reflux in the furfural tower C9.
The recovery of furfural from the extract ends in c6, whose design and
operation are the same as for tower C, (raffinate). The furfural vapors from the
c6 flash zone are sent to drum 9, after condensation. The vapors impregnated
with water coming from the c6 steam stripping zone are condensed and col-
lected in drum 9,.

7.1.2.5 Water Removal and Azeotropic Distillation Section

The furfural recovered at the top of steam stripping towers is contaminated by
water due to water/furfural partial solubility. Since water present in furfural
has a negative effect on extraction quality, it should be separated from the sol-
vent and eliminated. This objective becomes more complex subsequent to for-
mation of a furfural/water azeotrope.
The simplified flow diagram of furfural/water separation is shown in
Figure 7.10 and completed by the furfural/water vapor-liquid equilibrium
(Fig. 7.11).
The solvent in 9, that needs to be regenerated, whose composition is
approximately 95% furfural and 5% water, is distilled (upper part of C, in the
process flow scheme). The pure furfural is recovered at the bottom of the
tower. At the top of the column, the azeotrope (furfural 35%/water 65%) is
Chapter 7 SOLVENT EXTRACTION IN THE OIL /NOUSTRY 379

T
(90%)

Y To water
treatment

To C, extractor

-
Figure
7.10 Simplified flow diagram of the azeohopic distillation system.

cooled and condensed (temperature around 40°C) before settling in drum B,.
The furfural phase coming out of B, is sent as a wet reflux to the upper part
of cg.
The water phase from drum B, containing around 8%furfural is sent to the
water removal tower C, to be distilled. The azeotrope coming from the top of
C, settles out in B, in the same way as the one coming from Cg.The furfural-
free water (less than 25 ppm) coming from the bottom of C, is discharged into
the sewer. C, operates at approximately 100°C and atmospheric pressure.
The temperature of drum B, is crucial, it must be low enough for furfural
and water to settle out properly. The quality of the water/furfural interface
level measurement in B, is also very important. In fact sending the water phase
t o the furfural tower causes pollution of the solvent, resulting in a degradation
in extraction conditions (not to mention the risks of sudden water vaporiza-
tion in tower Cg). Sending the furfural phase t o C, automatically means furfural
is present in the wastewater coming from the bottom, which is detrimental t o
the environment (pollution of refinery wastewater by furfural).

7.1.2.6 Drainage System

The presence of furfural in refinery wastewater causes a rapid increase in the
water’s chemical oxygen demand (COD). As a result, it is essential to keep
380 Chapter 7. SOLVENT EXTRACTION
IN THE OIL /NDU.STRY

62
15C

00

5c

0 10 20 30 40 50 60 70 80 90 10,
Furfural (% wt)

Phase diagram of the water-furfuralsystem. P = 760 mmHg. % wt.

Reference for the liquid-liquidequilibrium:S~irensenet al. (1979).
Reference for the vapor-liquidequilibrium: Gmehling et al. (1981).
Published with the kind permission of Dechema (Dr R. Sass, 5/07/1996).

furfural discharges to the sewer at a minimum. In this connection, a furfural

extraction unit is equipped with a drainage system to recover all the occur-
rences of solvent leakage (e.g. from mechanical pump gear and seals) and
purges (sample taking, equipment cleaning, etc.).
The drainage system generally works by gravity, i.e. all the leaks and
purges are collected in funnels and flow by gravity to a collector drum located
underground. The drum is kept under inert gas blanketing (see Section 7.1.2.7)
to prevent oxidation of furfural by contact with air.
The product recovered in the drainage system collector drum is pumped to
an intermediate settling drum where the water plus furfural phase is separated
from the hydrocarbon phase. The water plus furfural phase is sent to the unit's
azeotropic distillation system through the water/furfural settling drum. The
hydrocarbon phase is pumped to the extract circuit steam stripping tower to
Chapter 7, SOLVENT EXTRACTION IN THE OIL /NDUSTRY 381

recover the furfural it contains. However, when the hydrocarbons are very
light fractions, it is preferable to send them to the refinery’s fuel oil pool.
Because of their volatility, any attempt at recovery in the unit would pollute
the solvent.

7.1.2.7 Inert Gas System

Since furfural is a compound that is sensitive to oxidation, any and all air
influxes into the unit should be prevented, especially in storage facilities and
drums working at atmospheric pressure. Accordingly, vessels are placed
under inert gas (oxygen-free) blanketing at a slight overpressure (approxi-
mately 30 mbar rel.). A drop in pressure in these vessels (caused for example
by a decrease in the liquid level) will be offset by introduction of inert gas. A
gas holder could be installed to attenuate variations in pressure in the system.
The inert gas can be nitrogen (nitrogen can be produced by separation of
the 0, - N, in the air with a membrane process) or can come from stoichio-
metric combustion of propane.

7.1.3 Operating a Furfural Extraction Unit

The main points to be routinely monitored when operating a furfural extrac-
tion unit are:
extractor operation;
solvent quality;
temperatures and pressures in furfural recovery sections (energy con-
sumption);
azeotropic system operation;
furfural consumption;
corrosion risk equipment (related to degradation of furfural into acids).

7.1.3.1 Extractor Operation

This point has been thoroughly covered in the section on internal variables.
From a practical standpoint, the operator in charge of running the unit
should pay particular attention to the following points:
precision of the solvent ratio, easily checked by a material balance of the
extractor;
temperature profile in the extractor;
furfural content in the mixed raffinate (indicating an overhead tempera-
ture lower than the solubility temperature of the raffinate in furfural and
therefore a sign of proper extraction);
a clear-cut interface in the extractor, proof of good quality extraction:
382 Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY

extraction yield, evidence of proper extractor operation and required

quality;
specific gravity or refractive index of the raffinate, which should be con-
stant.
Any significant variation in these parameters for a feed of given quality
means there is some malfunction in the extraction operation.

7.1.3.2 Maintaining Solvent Quality

The solvent should be monitored with the naked eye, completed by laboratory
analyses regularly.
As mentioned earlier, the pollutants to be detected are water and hydro-
carbons. The water content should be less than 0.1% and hydrocarbons
should be at less than 0.4% (for light bases) and 0.2% (for heavy bases).
Hydrocarbon pollution of the solvent can be easily seen with the naked eye
and whether it comes from the extract circuit (green) or raffinate circuit
@rown/yellow) can even be distinguished.
The total acidity or TAN should be measured regularly as furfural degrada-
tion can be detected in this way. The solvent’s acidity should be lower than
0.15 mg KOH/ml.

7.1.3.3 Temperatures and Pressures

in the Furfural Recovery Circuits
Vaporizing furfural in order to recycle it to the extractor consumes huge
amounts of energy. Accordingly, operating temperatures and pressures in the
different vaporization stages should be checked to be sure they comply with
the unit’s design features.
For example, if the temperature at the top of C5 (see the unit process flow
scheme, Fig. 7.9) is too low, there will not be enough calories to vaporize the
normal amount of furfural in C,. This in turn will give a greater amount of fur-
fural to be vaporized in the furnace F2, and therefore higher consumption of
fuel oil burned in the furnace.

7.1.3.4 Azeotropic Distillation Operation

The crucial point to monitor is the settling quality in drum B,. Inadequate set-
tling yields a furfural phase containing too much water (detrimental to extrac-
tion quality due to solvent contamination). Meanwhile, the water phase has
too much furfural to be distilled properly in tower C, (which causes pollution
of refinery wastewater by furfural).
The reliability of the automatic interface level in B, is of prime importance
and it should frequently be checked to see if it agrees with the reading on B,’s
level gauge.
Chapter 7. SOLVENT EXTRACTION IN THE OIL /NOUSTRY 383

7.1.3.5 Furfural Consumption

There are two basic reasons why furfural is consumed: degradation (thermal
or oxidation) and losses to the sewer.
In addition to the significant financial impact (1 kg of furfural cost approxi-
mately 6 FF in 1992), these two types of consumption also have consequences
on the environment (losses to the sewer) and on safety (degradation), since
furfural degradation causes serious corrosion in equipment (see Section
7.1.3.6).
Consequently, furfural consumption should be closely monitored and no
effort should be spared to reduce it.
The methods to control degradation by oxidation are as follows:
proper deaeration of the feed (vacuum tower C, upstream from the
extractor);
effective inert gas blanketing on furfural storage and on drums working
at atmospheric pressure;
regular monitoring of circuits working under vacuum conditions (mea-
surement of oxygen content at the vacuum pump outlet, pressure testing
before starting up the unit, etc.).
In order to prevent thermal degradation, the main point is to avoid tem-
perature peaks of over 235°C.
The furnace temperature should be regulated very precisely with great
care, more particularly the mixed extract furnace FZ,whose outlet temperature
is some 225°C. Furnaces should be designed to avoid temperature peaks inside
the furnace, caused by excessive pressure drop in the tubes. Care must also
be taken that through velocities are sufficiently high in equipment working at
high temperatures (exchangers).
Since furfural breakdown invariably causes formation of acids, the simplest
means of detection is the measurement of total acidity (TAN) of the solvent
and of the final raffinate and extract products.
In order to lessen losses to the sewer, the main points that need to be
checked are:
proper working of the gravity drainage system (no plugging):
furfural content in wastewater coming from the water removal tower C,,
which should be less than 25 ppm.

7.1.3.6 Corrosion Related to Furfural Degradation

Corrosion is mainly of the "acid" type, due to the acids from furfural degrada-
tion as mentioned earlier.
It can be extremely rapid and intense, and can have serious consequences
on the safety of the unit (for example, sudden failure of a furnace tube). It is
more severe in equipment containing furfural in the presence of water (for
384 Chapter 7. SOLVENT EXTRACTION
IN THE OIL INDUSTRY

example, the whole azeotropic system), which should be made of suitable

materials (steel alloys).

7.1.4 Operating Costs of a Furfural Extraction Unit

7.1.4.1 Energy Costs
Energy consumption costs can be broken down as follows:
fuels consumed in raffinate and extract furnaces (80%);
steam used in heaters, pipe tracing and flame atomization in furnaces
(10%);
electricity (pumps) (10%);
Total = 50 FF/m3 of feed processed (1993 value).
Solvent vaporization accounts for most of the energy consumption in the
unit. Given the costs mentioned above, it is easy to see why it is advantageous
to minimize the solvent ratio in the process.

7.1.4.2 Furfural Consumption Cost

A modern furfural extraction unit consumes (mainly by oxidation and thermal
degradation) approximately 0.2 kg of furfural per m3 of distillate fed into the
extractor, i.e. a cost of about 1.2 FF/m3 of distillate handled.

7.1.5 NMP Extraction

7.1.5.1 Characteristics of NMP
N-methylpyrrolidone, whose major physical characteristics are indicated in
Table 7.5, has the following developed chemical formula:

2HC- CH2
I I
2HC c
\N/ \\
0
I

In comparison with furfural it has the following advantages:

better stability,
better oxidation resistance,
less carryover in the raffinate and the extract,
higher solvent power toward aromatics,
lower process temperature,
less toxicity,
Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY 385

but also the following drawbacks:

lower specific gravity,
less selectivity,
higher boiling point.
Some refineries have chosen to use NMP in aromatics extraction. Yithout
describing the NMP extraction unit in detail (see Fig. 7.12), we will point out
the differences between furfural and NMP units.

7.1.5.2 Description of an NMP Unit’s Specific Features

a. Feed Inlet
Since NMP is much more stable than furfural, the deaeration section is unnec-
essary and the distillate can directly be let in to the extraction tower with reg-
ulated temperature and flow rate.

b. Solvent Inlet
NMP solvent power is very high toward aromatics, and also considerable
toward paraffins, which consequently lowers the raffinate yield. To attenuate
NMP’s solvent power, a small amount of water (0.8 to 3.2%) is added and the
solvent that circulates in the unit is a mixture of NMP + water. The amount of
water required in the solvent depends on the target level of extraction.
In order to get stable running conditions, the water concentration must be
constant. This means that the water content in the solvent has to be moni-
tored, because the water supplied by the feed ends up in the solvent. A batch
operated drying section is periodically used to remove excess water from the
solvent.
Water’s sensitivity to the solvent also justifies replacing stripping steam by
nitrogen in the NMP recovery sections.
The solvent is injected at the top of the tower with regulated flow rate and
temperature:
Solvent ratios in an NMP unit are significantly lower than for furfural,
thanks to its higher solvent power.
Solvent injection temperatures are lower by 10 to 20°C for the same final
VI and an identical raffinate yield.

c. Solvent Recovery From the Raffinate and the Extract

NMP’s higher boiling point and heat of vaporization make for higher thermal
levels in the solvent recovery sections (310 to 340°C) than for furfural. Energy
consumption is also greater than for furfural recovery.

d . NMP Drying Section (Fig. 7.13)

After cooling to approximately 50°C, NMP containing some 30% water is tem-
porarily stored in a tank. When the tank has become full enough, the dehy-
dration section is started up.
Figure
7.12
Extraction
column

-
Process flow scheme of an NMPextraction unit (mass flow rates) (Source: Esso France).
NMP solvent
+ 2%H20

Raffinate

Nitrogen
To dehydration
section
Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY 387
388 Chapter 7. SOLVENT EXTRACTION
IN THE OIL INDUSTRY

The dehydration section consists mainly of a distillation tower. The feed for
the tower (NMP containing between 15 and 30% water) is preheated to 170°C
to achieve proper separation between the water and the NMP. The water con-
taining a few tens of ppm of NMP is recovered at the top of the tower and the
NMP containing some 15 to 20% water is recovered at the bottom and then
sent back to the storage tank. This explains why the NMP in the wet NMP stor-
age tank can have between 15 and 30% water content. Given the very small
amounts of water (0.1 kg per m3 of distillate handled) and its NMP content
lower than 50 ppm, the water stream is sent to the refinery’s wastewater treat-
ment unit without any significant impact on the COD.
When extra water is needed in the solvent circuit following a variation in
the required extraction level, the solvent-water mixture (NMP containing 30%
water) from the storage tank in the dehydration section is the preferred
source.

7.2 Deasphalting
7.2.1 Purpose and Principle of the Process.
Feed Structure
7.2.1.1 Purpose of the Process
The purpose of a deasphalting unit is to separate out the asphaltenes and
resins from the oily fractions contained in the feed (see Vol. 1, Chapter 1).
The first industrial propane deasphalting unit came into being sometime in
1934 and was designed to produce lubricants. Several decades prior to then
the type of crudes used for lube oils (relatively non-asphaltic crudes from
Pennsylvania) did not require any preliminary step before sulfuric acid refin-
ing. Pennsylvania crudes became scarcer and it became necessary to develop
the vacuum fractionated distillation process with massive injections of super-
heated steam to separate the asphaltic fractions from the oily fractions. The
process eventually did not survive propane deasphalting, because the
required temperature levels (over 400°C) inevitably caused significant thermal
cracking with the formation of unsaturated compounds (olefins to be hydro-
genated later on) and the destruction of the heaviest and most viscous
molecules.
As a supplement to this chapter, a lot of useful information concerning deas-
phalting and related operations can be found in a number of reference works
and magazines listed in the general references at the end of this volume, such
as: Le Page et al. (1990), Chang and Murphy (Vol. 14, Encyclopedia of Chemical
Processing and Design), Sequeira (Vol. 28, Encyclopedia of Chemical Processing
and Design), Anon. (1992) (“Deasphalting“ in Refining Handbook 92 of
Hydrocarbon Processing).
Deasphalting should always be considered as a intermediate refining step
requiring some sort of added value afterward.
Chapter 7. SOLVENT IN THE OIL INDUSTRY 389
EXTRACTION

Accordingly, it can be incorporated in any refining flow scheme as dictated

by the different possible ways of providing this added value for asphaltic and
oily fractions:
Oily fractions:
- production of bright stock and waxes: here deasphalting is an impor-
tant link in the production chain for oils, paraffins and waxes (most
common use today);
- preparation of catalytic cracking feeds with or without an intermediate
hydrorefining step;
- preparation of hydrocracking feeds to increase the production of high
quality middle distillates.
Asphaltic fractions:
- production of road quality bitumens;
- use as components in industrial fuel oil or solid fuels;
- feed for conversion units such as visbreakers, oxyvapogasifiers and
cokers.
a. Deasphalting in the Lubricant Production Process (Fig. 7.14)
Lubricants only account for approximately 2% of the products manufactured
from crude oil. The required properties for lubricants demand highly elabo-
rate production techniques, with a series of five or six operations being car-
ried out between the crude and the end product. The first two operations are
atmospheric and vacuum fractionation. The vacuum residue is then deas-
phalted, a very viscous deasphalted oil is produced which undergoes extrac-
tion (except for cylinder stock production, a low VI product, around 80) to
eliminate aromatics whose lubricant properties are mediocre (furfural or NMP
extraction, to achieve viscosity index specifications, see Section 7.1). After
stripping, the raffinate undergoes solvent dewaxing (with MEK-toluene, for
example, see Chapter 9) to meet pour point specifications. A final low pres-
sure-low temperature hydrofinishing step (40 bar, close to 250°C) allows the
color and odor of the product, viscous lube oil stock, to be adjusted (removal
of impurities: sulfur, oxygen and nitrogen compounds). The produced tar from
deasphalting can serve as a basis for formulating bitumens (mixed with vac-
uum residue and aromatic extract). All types of bitumens can be obtained by
fluxing and oxidation (air blowing).
b. The Deasphalting Process a s an Extra Conversion Unit (Fig. 7.15)
The use of the deasphalting process as an extra conversion unit is bound to
develop in the coming years. Deasphalted oil can in fact be used as feed for
catalytic cracking (FCC) or for hydrocracking (HDC) mixed with straight run
vacuum distillate. Feed specifications for these conversion units may require
an intermediate hydrorefining step for the deasphalted oil depending on deas-
phalting unit operating conditions and the origin of processed crudes.
Feed specifications for a conventional FCC unit:
2 000 ppm mass maximum basic nitrogen content (to protect the cata-
lyst’s acid function),
3
Atmospheric Vacuum Deasphalting Aromatics Solvent Hydrofinishing .”
2
distillation distillation extraction dewaxing Y

-
Crude

Distillate 1
I
Paraffins and waxes
to be hydrogenated

z
3
rn
P

I 7.14 I Incorporation of deasphalting process in the lube oil stock production process.
Chapter 7. SOLVENT E ~ ~ R ~ C TINI O N OIL
THE INDUSTRY 391
t
392 Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY

2% wt maximum Conradson carbon content (coke bottleneck in the unit),

20 ppm mass maximum metals (to limit catalyst consumption),
are such that mixtures of vacuum distillate and DAO from Arabian Light can be
contemplated for use as feeds after propane deasphalting (Table 7.7).
Mixtures of vacuum distillate and DAO that have undergone butane or even
pentane deasphalting would require an FCC unit equipped with systems to
push back the coke bottleneck.
However, it should be borne in mind that hydrotreating of deasphalted oils
is not a very constraining refining step, as long as the deasphalting operation
is properly conducted (limitation of C, asphaltene content to 500 ppm weight).
The operation can be carried out at medium hydrogen partial pressure (8 to
11 MPa). For pentane deasphalted oils which come from crudes with a high
metal content, a demetallization step on a specific catalyst is recommended.
In any case, hydrotreating of deasphalted oils prior to catalytic cracking will
give better FCC yields and products quality.
The growth in demand for good quality middle distillates can make it
advantageous for deasphalted oils to undergo hydrocracking. For a new hydro-
cracking unit, the hydrorefining step should be designed to meet the habitual
feed specifications for the hydrocracking step (maximum basic nitrogen con-
tent several tens of ppm, molecular weight adapted to the zeolitic function of
the hydrocracking catalyst).

- --
Vac. DAO DAO DAO
Vat. Dist. Vac. Dist. Vac. Dist.
Dist. +DAO +DAO + DAO
c3 c4 c5 c3 c4 c5

Yield on crude 19 9.9 15.4 18.7 28.9 34.4 37.7

@ wt)
dl5 0.929 0.933 0.959 0.974 0.930 0.942 0.951
Viscosity at 100°C 6.0 44 66 107 10 14 19
(mm2/s>
Sulfur (% wt) 2.4 2.8 3.3 4.2 2.5 2.8 3.3
Basic nitrogen
@pm mass) 270 280 350 450 273 306 359
Asphaltenes C, 0.2 0.1 0.1 0.3 0.2 0.2 0.3
(% wt)
Asphaltenes C, < 500 < 500 :500 < 500 < 500 < 500 < 500
@pm mass)
Ni @pm mass) <1 <1 2 2 (1 1 1
V @pm mass) <1 <1 3 9 <1 1 5
Conradson carbon 0.9 2.5 5.6 11.0 1.4 3.0 6.0
%
(J wt)
- --
1 Table - 1
Yields and characteristics of deasphalted oils (DAO) h-om Arabian Light com-
pared with those of the vacuum distillate from Arabian Light.
Chapter 7. SOLVENT EXTRACTION
IN THE OIL INDUSTRY 393

Lastly, tars from deasphalting can be excellent feed for medium or deep
(thermal) conversion later on. The great stability of their asphaltenes gives
them higher thermal cracking potential than the vacuum residues that they
come from.

7.2.1.2 Feed Structure

Feed for deasphalting units is made up of a mixture of overflash and residue
from the vacuum distillation tower. All vacuum residue can be considered as a
colloidal system of high molecular weight compounds classified in three dis-
tinct categories:
a) The oil medium is the lightest part and includes light aromatic, paraffinic
and cycloparaffinic compounds. Its average molecular weight is approximately
700. Its molecules are typically made up of 50 carbon atoms and include sulfur
and nitrogen atoms, without any metals.
b) Resins have a molecular structure made up of condensed aromatic com-
pounds with long cycloaliphatic chains, making them soluble in the oil
medium. The average molecular weight of resins is approximately 1 000. The
molecules are typically made up of 100 carbon atoms and include sulfur, nitro-
gen, nickel and vanadium atoms. The oil medium and resins are generally
grouped together under the term malthenes.
c) Asphaltenes have a very condensed flat aromatic structure, including
between 6 and 20 aromatic rings. Their average molecular weight is approxi-
mately 1 000 to 2 000. They include sulfur, nitrogen and metal (nickel and
vanadium in the form of porphyrins) atoms. Their side chains are too small to
make them soluble in the oil medium, so that they are present in the form of
small particles. However, the particle size is several angstroms and they are
“peptized” (i.e. solubilized) by resins which give them pseudo-solubility in the
oil medium.
A straight run vacuum residue is generally stable, as its asphaltenes are all
peptized. On a macroscopic scale it looks like a perfectly homogeneous solu-
tion which leaves no deposit on being filtered (filters of several microns). A
residue is qualified unstable if some asphaltenes are not peptized. These
asphaltenes are said to be “flocculated” and are present in the form of large
particles whose size can range from several microns to several millimeters.
Asphaltene flocculation is an irreversible phenomenon.

7.2.1.3 Principle of a Deasphalting Operation,

The deasphalting operation is carried out in an extractor where the feed is
placed in contact with a solvent that promotes precipitation of the asphaltic
fraction. The separation between the asphaltic and the oily fraction is accen-
tuated by operating with a temperature gradient between the top and the bot-
tom of the extractor. Liquefied gases of light hydrocarbons and saturated light
hydrocarbons, which are liquid at ambient temperature and atmospheric pres-
sure, are used to precipitate the asphaltic fraction, but in widely different
ways.
394 Chapter 7 SOLVENT EXTRACTION
IN THE OIL INDUSTRY

Propane is well suited to obtaining deasphalted oils for lubricant produc-

tion. Without a deasphalted oil hydrotreating unit, propane and butane are
suited to prepare the feed for cracking (FCC) or hydrocracking (HDC). With a
complementary deasphalted oil hydrotreating unit, pentane can be used to
maximize the yield in oil with potential added value as extra distillate.

7.2.2 Feeds and Products

The fractionation in a deasphalting operation occurs on the basis of structure
rather than temperature or molecular weight. This critical difference com-
pared with a distillation operation is where the advantage lies. In Table 7.8 we
provide a comparison of the properties of cuts obtained by vacuum distillation
(in the laboratory) and by pentane deasphalting of a Kirkuk vacuum residue.
For a given yield (for example 22% wt), the vacuum distillate has much more
impurities (Ni + V = 6 ppm mass; Conradson carbon = 4% wt) than the corre-
sponding deasphalted oil (Ni + V < 1 ppm mass; Conradson carbon = 0.8% wt).
For the same impurity content (for example, Ni + V = 25 ppm mass), the
yield in deasphalted oil is higher by about 50% wt than that of the corre-
sponding vacuum distillate (Fig. 7.16).
We present a comparison of structure analyses obtained by NMR of an
Arabian Light butane deasphalted oil and an Arabian Light vacuum distillate in
Table 7.9. It can be seen that deasphalting concentrates the aliphatic carbons
in the deasphalted oil along with hydrogen, whose content becomes even
higher than that of the vacuum distillate, which is much lighter nevertheless.
Besides its great selectivity, the deasphalting process shows results which
demonstrate its capacity to produce purified oils that can be easily value-
enhanced by conversion processes.
- -
Products Jac. Dist. Vac. Dist rac. Dist. DAO DAO DAO
lac. Res.
1 2 3 1 2 3

Yield on vacuum 100 21.9 35.2 48.3 21.6 48.6 88.2

residue (x wt)
di5 1.019 0.966 0.968 0.975 0.910 0.946 0.970
Viscosity at 100°C 600 33 44 65 22 51 104
(mm2/s)
Refractive index 1.5270 1.5308 1.5322 1.4898 1.5120 I .530 5
at 60°C
Conradson carbon 18.0 4.0 5.6 6.6 0.8 3.4 7.8
(xk wt)
Ni @pm mass) 50 2.0 8.0 17.0 0.2 2.8 13.0
v (PPm mass) 118 4.0 16.0 32.0 0.1 2.6 16.0

Comparison between vacuum distillates and pentane deasphalted oils (DAO)

h-om a Kirkuk vacuum residue.
Chapter 7. SOLVENT EXTRACTION IN THE OIL INDUSTRY 395

50

40

c
h

30
k
Q
v

>
2
z
20

10

25 50 75 100
+
Yield (% wt)
L

Figure
7.16 Comparison of metal content (Ni + V) in vacuum distillates (A) and pentane
deasphalted oils (m) from a Kirkuk vacuum residue.

Vac. Res. Vac. Dist. DAO C,

Yield on crude (55wt) 19 25 10

di5 1.019 0.930 0.945
Viscosity at 100°C (mm2/s) 600 9.8 55
Hydrogen by NMR (% wt) 10.4 11.9 12.1
Saturated carbons (% wt) 65.8 79.8 82.0
Aromatic carbons (% wt) 34.2 20.2 18.0

Table
Comparison of the structure of a vacuum distillate and that of a butane deas-
phalted oil (DAO C4), both from an Arabian Light crude.

Liquid chromatography was applied to feeds and effluents from propane

deasphalting of Arabian Light vacuum residue. The results show the concen-
tration in paraffins, naphthenes and light aromatic structures in the deas-
phalted oil. Meanwhile, the resins and asphaltenes are concentrated in the tar
and give it very great stability, which can be thoroughly exploited in thermal
cracking processes such as visbreaking (Table 7.10 and Fig. 7.17).
396 Chapter 7, SOLVENT EXTRACTION IN THE O I L /NOUSTRY

Products
Vac. Res. DAO C, Tar C,
Properties
Yield on vacuum residue (x vol) 100 28.5 71.5
Paraffins and naphthenes 10 30 2
Mono- and di-aromatics 8 18 4
Tri-aromatics and higher 16 26 12
aromatics
Soft resins 39 24 45
Hard resins 15 2 20
Asphaltenes 12 0 17

Table
Composition of propane deasphalted oils and tars from an Arabian Light vac-
uum residue, by liquid chromatography.

DAO = 28.5%

Paraffins +
naphthenes

Mono +
di-aromatics

Tri-aromatics +
higher aromatics

Vacuum
residue = 100%
Soft resins
I
L
Figure
7.17 Propane deasphalt-
ing of Arabian Light
vacuum residue (the
curve shows the par-
tition between tar
and DAO).

Hard resins

Asphaltenes

Tar = 71.5%
Chapter 7. SOLVENT E ~ ~ R ~ C TINI OTHE
N OIL INDUSTRY 397

7.2.3 Solvent Characteristics

The most important process parameter is the nature of the deasphalting sol-
vent. It is what primarily determines the yield and quality of the extracted oil
phase. The heavier the paraffinic solvent, the higher the yield in malthenic
phase at the corresponding expense of its quality. The influence of the type of
solvent on the process is schematically shown in Figure 7.18.
For example, butane and pentane exhibit solvent power for soft and hard
resins, while ethane precipitates not only asphaltenes and resins but also a
large fraction of the oil medium. Propane proves to be particularly well
adapted to the production of lubricants (Table 7.1 1).

Operating conditions
C, in solvent (% vol) 100 60
C, in solvent (% vol) 0 40
Solvent in feed (% vol) 600 600
Temperature (“C) at the top/feed inlet/bottom 145/110/105 145/115/110
DAO yield (% vol) 38.6 66.8
DAO characteristics
Standard specific gravity 0.925 0.955
Viscosity at 100°C (mm2.s) 37 81
Conradson carbon (% wt) 1.7 7.6

Table

17111 Effects of the type of solvent (butane and propane) on deasphalting an Arabian
Light vacuum residue.

The effect of the type of solvent on the extracted malthenic phase yield is
quantified (Fig. 7.19) for a Poso Creek atmospheric residue and an Arabian
Light vacuum residue (use of ten volumes of solvent at 27°C). The results
would be equivalent for other asphaltic residues.

7.2.4 The Deasphalting Process

7.2.4.1 Extraction Principle
There are three unit operations in the extraction process (Fig. 7.20):
Precipitating the asphaltic phase
Deresining the asphalt
Settling the asphalt.
Malthenic phase yield
("10 wt)
A
kl (n -J
0 VI 0 (n F:
R 1 1 7
I I I I
9 9 e
0 0
0
Chapter 7. SOLVENT ExrRaCTlON IN THE O I L INDUSTRY 399

,Deasphalted,oil

6
Deresining zone
(deasphalted oil
phase quality)

Feed
m
Precipitation
m

Solvent
b D I I .

.-r b
-
1
Asphalt
temperature gradient

-Figure
7.20 Principle of deasphalting extractor operation.

a. Precipitation
Precipitating the asphalts means breaking the equilibrium within the colloidal
system between the malthenic medium and the asphaltic phase (see
Sections 7.2.1.2 and 7.2.1.3).
The most important variables in precipitation are:
the type of solvent (see Section 7.2.3, Solvent characteristics);
the solvent ratio;
the temperatures (gradient and absolute values).
The operating pressure is chosen so that it is higher than the solvent’s crit-
ical pressure.
The influence of operating variables is discussed later on in Section 7.2.4.2.
Contrary to a widespread misconception, the precipitation of asphalts with
C, to C, solvents does not induce asphaltene flocculation. The asphaltenes
400 Chapter 7 SOLVENT EXTRACTION
IN THE OIL INDUSTRY

remain pseudupeptized by the heaviest resins (the asphaltic phase can then
be considered on a macroscopic scale as perfectly stable).
The precipitation zone is generally made up of:
a predilution zone, upstream from the extractor, whose main objectives
are to reduce feed viscosity and to approach feed saturation with the sol-
vent (typical predilution is half a volume of solvent per volume of feed):
the feed inlet to the extractor, where separation takes place between the
deasphalted oil and the tar in contact with the solvent fraction which is
introduced at the bottom of the extractor and tends to rise because of its
low specific gravity.

b. Deresining
Deresining consists in generating an internal reflux that improves the separa-
tion between the oil medium and the resins.
The solvent/oil mixture is heated at the top of the extractor by steam coils.
With the rise in temperature, the resinous fractions are precipitated out and
move downward in the extractor, where the rising countercurrent flow of
solvent/oil mixture redissolves the lightest resinous fractions at a lower tem-
perature. The temperature gradient set in the deresining zone allows the pre-
cipitation-redissolution cycle to be maintained.
The resinous particles in suspension in the solvent/oil medium settle out
according to Stokes' law:

with:
VR settling velocity of resinous particles (m/s)
R
r radius of resinous particles (m)
ksH viscosity of the solvent + oil medium (Pas)
pR density of resinous particles (kg/m5,
pSH density of the solvent + oil medium (kg/m5,
g acceleration of gravity (9.81 m/s?
As indicated by Stokes' law, settling of resinous particles is promoted by an
increase in the solvent ratio and temperature (lowering the viscosity of the sol-
vent/oil medium).
The design of this zone must give due consideration to:
a minimum residence time for the solvent + oil + resins medium to allow
even the smallest resinous particles to separate out:
a maximum rising velocity for the solvent + oil mixture to allow even the
smallest resinous particles to settle out.
Along with the constraints of maximum extraction column diameter, the
two rules listed above limit deasphalting capacity to 0.6 to 0.7 Mt/year for a
Chapter 7, SOLVENT EXTRACTION IN THE OIL /NDUSTRY 401

vertical extractor. When a conversion capacity of some 2 Mt/year is sought,

the choice may be a horizontal extractor (deresining zone) rather than costly
replication of a number of parallel extractor trains.

c. Settling
Settling the asphalt consists in washing the asphalt emulsion in the solvent +
oil mixture with a countercurrent flow of pure solvent.
The settling zone is located between the feed inlet and the bottom of the
extractor. Stripping of the asphalt is promoted by an increase in the solvent
ratio (i.e. replacing the solvent + oil environment with a pure solvent environ-
ment), at the lowest possible temperature (increasing the solvent specific
gravity and consequently increasing the solubility of resinous fractions in the
solvent).
In contrast to the deresining zone, the idea here is to minimize the internal
reflux so as to promote settling of the asphalt alone. The temperature at the
bottom of the extractor should consequently be as close as possible to the
feed inlet temperature. The typical recommended gradient (to be adjusted
depending on deasphalted oil and tar specifications as well as on feed type) is
indicated in Figure 7.20. It must allow the overhead reflux in the column to be
maximized in order to improve the quality of the deasphalted oil and promote
asphalt stripping in the bottom of the extractor.
The minimum temperature at the bottom of the settling zone is the result
of the maximum admissible viscosity for the tar. The efficiency of the asphalt
stripping zone can be significantly modified depending on the choice of con-
tacting equipment technology.

7.2.4.2 Operating Variables in the Deasphalting Process

a. Feed Composition
Besides the type of feed, its degree of stripping is the first operating variable.
For the same operating conditions (temperature gradient in the extractor,
type and, especially, ratio of solvent), an increase in the light fraction content
of a residue causes an increase in deasphalted oil yield at the expense of its
quality (the volume of solvent versus the volume of deasphalted oil decreases
for the same solvent ratio). Tables 7.12 and 7.13 illustrate the increase in
Conradson carbon content in the deasphalted oil in this case. Under-stripping
in vacuum fractionation consequently requires an increased solvent ratio for
the same quality of deasphalted oil, though there is no need to operate with
the same volume of solvent per volume of deasphalted oil.

b. Type of Solvent
The choice of deasphalting solvent is instrumental in determining the yield
and quality of the extracted oil phase (see Section 7.2.3).
In Table 7.14 we indicate the performance to be expected from pure
propane and pentane for feeds with an asphaltene content ranging between 1
402 Chapter 7. SOLVENT EXTRACTION
IN THE O I L INDUSTRY

Feed
Arabian Light
Yield on crude (% vol) 18.2 16.5
“MI 8.5 7.4
Conradson carbon (% wt) 16.2 18.0
Deasphalting
Type of solvent c3 c3
Solvent ratio (% vol) 700 700
Temperature:
TOP (“C) 68 68
Feed (“C) 49 49
Bottom (“C) 46 46

Yield on feed (% vol) 38 27

“API 22.1 22.4
Viscosity at 100°C (mm2/s) 31.5 33.5
Conradson carbon (% wt) 1.3 0.8
1
Table
7.12 Effectof residue “length”on its deasphalting.

Overflash (% vol) 33 100

Specific gravity 1.009 0.960
Conradson carbon (% wt) 17.2 6.3

Solvent type c3 c3
Solvent ratio (% vol) 700 700
Temperature:
TOP (“C) 68 68
Feed (“C) 49 49
Bottom (“C) 46 46
I Deasphalted oil
Yield on feed (% vol) 42 90
Viscosity at 100°C (mm2/s) 33.5 32.5
Conradson carbon (% wt) 1.4 2.7

Table
7.13 Effectof per cent of residue overflash on its deasphalting.
Feed

Murban Arabian Light Kuwait Buzurgan Boscan

Position on crude (% wt) 90- 100 79-100 72-100 48-100 22-100

Yield on crude (% wt) 10 21 28 52 78
Specific gravity di5 0.982 1.003 1.02 1 1.051 1.037
Viscosity at 100°C (mm2/s) 195 345 1105 3 355 5 250
Sulfur (% wt) 3.03 4.05 5.35 6.20 5.90
Nickel (ppm mass) 17 19 33 76 133
Vanadium (ppm mass) 26 61 87 233 1264
Nitrogen (ppm mass) 3 200 2 900 3850 4 500 7 900
Conradson carbon (% wt) 12.9 16.4 15.4 22.5 18.0
Asphaltenes (% wt) 1.2 4.2 5.2 18.4 15.3
I

c5

Deasphalted oil
Yield on feed (% wt) 54 93 45 86 29 78 31 64 33 64
Specific gravity di5 0.924 0.970 0.933 0.974 0.937 0.986 0.945 0.985 0.953 0.987
Viscosity at 100°C (mm2/s) 38 124 35 105 46 20 1 30 78 33 135
Sulfur (% wt) 1.80 2.85 2.55 3.65 2.70 4.70 3.60 4.80 4.70 5.30
Nickel (ppm mass) <1 8 1.0 7 1.0 12 2 12 6 36
Vanadium (pprn mass) <1 9 1.4 16 2.0 28 4 26 10 270
Nitrogen (ppm mass) 800 1600 1200 2 200 1300 2 100 950 2 400 1600 4 300
Conradson carbon (% wt) 2.0 9.0 1.7 7.9 1.9 8.9 2.0 7.4 1.8 6.4
Asphaltenes (% wt) < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05 < 0.05
I

Penetration at 25°C 3 0 11 0 0 0 0 0 0 0
Softening point (“C) 63 165 60 155 72 143 103 165 101 168

Table
7 < A IXC--.-C--I ..--.&.--
404 Chapter 7. SOLVENT EXTRACTION
IN THE O I L INDUSTRY LIVE GRAPH
Click here to view

and 18%wt. As mentioned earlier, the heavier the deasphalting solvent, the
higher the oil yield at the corresponding expense of its quality. The typical dis-
tribution of sulfur, nitrogen, Conradson carbon and metals according to the
type of feed is indicated in Figure 7.21, with in particular deasphalting’s very
good selectivity toward metals. The more closely bonded the metals are to the
asphaltic structures in the form of porphyrins, the better this selectivity is.
This is generally not the case for residues with Ni/V 9 1 which may exhibit a
high “free” nickel content (example: KolC vacuum residue).

10 20 30 40 50 60 70 80 90 100

DAO/feed yield (?
wt)/.

- Figure
7.2 1 Component distribution in deasphalted oil.

The choice of solvent dictates the minimum operating pressure (slightly

higher than the solvent’s critical pressure, i.e. 30/40 bar for C& and 20/40 bar
for C,/C& which since it is fixed is not an operating variable (little effect on
separation selectivity).

c. Solvent Ratio
The selectivity of the deasphalting operation can be significantly improved by
increasing the solvent ratio: this is the main variable allowing an improvement
in oil quality. Generally speaking, when the solvent ratio is increased, the oil
yield decreases to a value compatible with a settling step, then grows until it
reaches an asymptotic value (Fig. 7.22). An increase in oil yield causes harder
asphalt to be produced (significant rise in tar softening point).
Chapter 7. SOLVENT EXrRaCTlON IN THE OIL INDUSTRY 405

Figure
7.22 Effect of increased sol-
- vent ratio on deas-
phalted oil yield.

-7
Solvent ratio (arbitraty units)

The influence of the solvent ratio on extraction selectivity is schematically

shown in Figure 7.23.

C
tu, point with
low solvent ratio

C
tu, point at
high solvent ratio
Figure
Influence of solvent 7.23
ratio on extraction
Cut point at
selectivi@.
infinite solvent ratio
406 Chapter 7. SOLVENT EX7RACTlON IN THE O I L INDUSTRY

d. Temperature
The effect of the operating temperature on extraction selectivity is the result
of the change in solvent power. Whatever feeds and solvents may be consid-
ered, a higher operating temperature causes a decrease in the solvent’s sur-
face tension and solvent power (the effect is schematically shown in Fig. 7.24).

Cut point at
high temperature

Cut point at
medium temperature
Figure
Cut point at 7.24 Influence of oper-
low temperature ating temperature
on extraction
selectivity

For a given solvent and feed, an increase in operating temperature causes

softer tar to be produced (precipitation of increasingly light resinous frac-
tions) along with lighter, lower yield deasphalted oil. As the supercritical
domain is approached, complete precipitation of the oil medium can be
obtained. Supercritical conditions consequently set the maximum admissible
operating temperature for a given solvent. As previously discussed in
Section 7.2.4.1, optimization of extraction selectivity means adopting a tem-
perature gradient such that:
a significant internal reflux exists in the deresining zone: here the idea is
to increase the deasphalted oil yield while maintaining the same quality
(a temperature difference of > 20°C between the top and the feed is rec-
ommended);
the temperature of the settling zone is at a minimum and close to that of
the feed: here the idea is to promote asphalt stripping (a temperature dif-
ference of < 5°C between the feed and the bottom is recommended).
Next Page

Chapter 7 SOLVENT EXTRACTION IN THE OIL /NOUSTRY 407

Table 7.15 illustrates the effect of operating temperature on extraction

selectivity for a long Rospomare residue with an unchanged solvent ratio.

Operating conditions
Solvent c5 c5 c5
Top temperature (“C) T T-10 T-20
Bottom temperature (“C) T-40 T-50 T-60
Deasphalted oil
Yield on feed (% wt) 100 54.7 56.9 58.5
Specific gravity di5 1.055 0.995 0.999 1.ooo
Viscosity at 100°C (mm2/s) 4 180 38 47 49
Sulfur (% wt) 8.10 6.04 6.20 6.24
Nickel @pm mass) 76 7 8 10
Vanadium @pm mass) 274 50 59 61
Asphaltenes (% wt) 25.2 0.05 0.06 0.11
Tar
Specific gravity d i 5 1.143 1.145 1.149
Softening point (“C) 159 167 169

Table

e. Other Variables
Feed flow rate: the feed flow rate affects yields and qualities of deasphalted
products only to the extent that the extractor’s maximum capacity is exceeded
(flooding with carryover to deasphalted oil).
Operating pressure: the operating pressure must be kept at a value higher
than the critical pressure of the solvent used.
Solvent injection: feed predilution is an effective means of reducing vis-
cosity and approaching saturation. Injection position in the extraction column
can be optimized depending on the type of feed processed.
Table 7.16 shows the usual domain of deasphalting operating conditions for
different solvents.
Table 7.17 recapitulates the influence of solvent ratio and extraction tem-
perature for a general case.