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Energy & Fuels 1994,8, 788-792

788

Utilization of Refinery Sludge for Lighter Oils and


Industrial Bitumen
A. P. Kuriakose* and S. Kochu Baby Manjoorant
Department of Polymer Science and Rubber Technology, Cochin University of Science and
Technology, Kochi 682 022, India
Received November 24, 1993. Revised Manuscript Received February 28, 1994

This paper reports the data obtained in an attempt to utilize the waste sludge of the Cochin
Refineries Ltd., Kochi, India. About 17% of a lighter oil fraction can be recovered from this sludge
and the characteristics of the lighter oil are such that it can be used as diesel fuel by blending with
other appropriate refinery streams. An attempt was also made to convert the residue left after the
removal of the lighter oils into different grades of industrial bitumen. This residue, obtained after
vacuum distillation, was heat treated without and with different catalysts. The change in softening
point:penetration ratio when heat treated without any catalyst was not enough to meet the specifications
of any industrial bitumen. Catalysts like sulfur, FeC13, and P205were able to bring down the penetration
sharply but failed to increase the softening point which is a requirement for the different grades of
industrial bitumen. AlC13 was found to bring about the different reactions required in the vacuum
residue and converted it into some useful grades of industrial bitumen, viz., 65125,75130,85125,and
90115. Possible reaction mechanism involved is also postulated. The optimum conditions of
temperature, heating duration, and amount of catalyst required for these different grades was
determined.

Introduction
In petroleum refineries, a lot of sludge accumulates a t
the bottom of tanks where crude oil is stored. This is
taken out during periodic tank cleaning and dumped
separately in ponds. Also, the bottom portion left behind
in furnace oil tanks, LSHS (low sulfur heavy stock) tanks,
asphalt tanks, etc. is also taken out at the time of their
periodic cleaning and dumped in the above-mentioned
ponds. Whatever heavy oil spillages occur during the
operation of this petroleum refinery is also dumped into
the ponds. About 8000-10000 tonnes of oily sludge is
accumulated in the quarry pond of Cochin Refineries Ltd.
a t Ambalamugal in Kerala, India. This sludge is an
accumulation from the last 20 years and has been exposed
to the atmosphere in all seasons. It is likely to increase
further by 500-1000 tonnes per annum.
A study of the constituents of this sludge has shown
that it contains approximately 25 9% water, 5 % inorganic
solids, and about 70 % hydrocarbons. The hydrocarbon
part is reported to contain 7.8 wt % of asphaltenes and
has a gross calorific value of about 10 300 kcallkg. The
ash content is 4.8% and percentage weight of the different
elements in the ash is Fe 23.49; A1 10.57; Ca 1.64; Na 0.57;
K 0.46; Ni 0.12; V 0.23; Mg 0.65; Zn 0.21; Ti 0.53; and Mn
0.10, The different methods for the disposal of the sludge
considered are (1) burning in a rotary incinerator, (2)
burning in a step furnace type incinerator, (3) microbial
treatment to convert the hydrocarbons to combustible
gases, (4) using in a delayed coker, and (5) separation of
water and sediments at elevated temperature using
diluents and emulsifiers and subsequent burning.

* Author to whom correspondence should be addressed.

Address for communication: Dept. of Quality Control, Cochin


Refineries Ltd., Kochi, India.
Abstract published in Advance ACS Abstracts, April 1, 1994.
(1)Report on sludge disposal at Cochin Refinery. Indian Oil
Corporation R&D Report, May 1988, No. 88042.
t

0887-0624/94/2508-0788$04.50/0

The above methods help mainly by disposing of the


sludge and not by effective utilization. So it was thought
worthwhile to see whether this sludge can be utilized as
a source of light oils and industrial bitumen. The raw
materials used a t present for industrial bitumen are
somewhat costly. Industrial bitumen of various grades
are manufactured in India2 from the vacuum residue of
some imported crudes like Arab mixed, Suez Blend, etc.
by air blowing in the presence of catalysts at temperatures
of 200-275 O C . It has been shown3 that dehydrogenation
and polymerization are involved in air blowing and that
only a minor amount of oxygen is added to the asphalt.
It is also reported that naphthene aromatics are converted
into polar aromatics and then to a~phaltenes.~The
following are reported to be the reactions occurring during
air blowing of the raw material.5

RH

+ 0,

+ RH RRH
RRH + RH
R

+ HOO

(RH = unsaturated compound)

disproportionation

RRHRH

stable products

As a result of the comparatively low concentration of


hydrocarbon radicals, there is small probability of their
recombination (2R
R-R) and the interaction of the
radicals with oxygen takes place to a smaller extent as
follows:

(2) Joseph Francis, D.; Antony, T. P. Ind. J. Technol. 1988,26,579-

582.
( 3 ) Corbett, L. W.; Swarbrick, R. E. Proc. Assoc. Asphalt Pauing
Technol. 1960, 29, 104.
( 4 ) Rossi, Albert0 Manufacture of blown asphalts-their physical and
chemical variations. Bol. Inform. Petr. (Buenos Aires) 1942,19, 37.
(5) Antony, T. P. Ph.D. Thesis, Cochin University of Science and
Technology, 1989.

0 1994 American Chemical Society

Utilization of Refinery Sludge for Lighter Oils


R'
ROO'

- +
- +
- +
- +
- +

+ 0,

ROO'

+ R'H

ROOH

ROOH

RO'

+ *OH
RH + HOO'
R"H

H,O,
R'H

+ *OH

R'*

'OH

R"'

H,O

R'

H,O,

2 'OH
R"

H,O

Various catalysts and oxidizing agents have been


proposed for augmenting the air-blowing process of the
vacuum residue to give a product having a higher
penetration for a given softening point.6 They include
~ u l f u rP
, ~z O and
~ ~ F e c l ~ .Since
~
the agents used here
cannot be recovered as such, technically they might better
be termed chemical reactants than catalysts. In any event,
the general effect is to reduce blowing time as well as to
change the softening point-penetration relationship.
Reduction of blowing time is an economic incentive,
whereas the change in the flow properties permits the
manufacture to specifications. In his studies, Grunderm a n d o has shown that metal chlorides act as catalysts a t
relatively low temperatures and without air blowing,
causing condensation and polymerization reactions similar
to those obtained in air blowing. He has shown that the
best catalyst is AlC13 which converted naphthenic aromatic
asphalts by treatment a t 150 "C for 3 h into asphalts of
medium to high hardness.
In view of the fact that the refinery sludge mentioned
earlier contains many useful hydrocarbons and that it
accumulates in large quantities in the refinery creating a
disposal problem, it was thought worthwhile to study the
possibility of converting this sludge into some useful raw
material like industrial bitumen without the air-blowing
process. In the present study, an attempt was also made
to separate the lighter oil fractions from the sludge,
characterize them, and see whether they can be blended
with appropriate refinery streams. Keeping this view in
mind, the sludge obtained was first purified and dehydrated. This was then subjected to vacuum distillation to
separate the light oils. About 17% of the dehydrated
sludge was recovered as light oil. The residue left was
treated with varying amounts of catalysts like sulfur,FeCl3,
P2O5, and
a t different temperatures ranging from
200 to 275 "C, for time periods varying from 1to 3 h. The
products obtained were tested for different parameters
and the results compared with different grades of industrial
bitumen.

Experimental Procedure
Sludgewas collected from the quarry pond of CochinRefineries
Ltd., Ambalamugal, Kerala, India. Sulfur, FeC13, P&,, AlC13
(anhydrous),and carbon disulfide used in the study were all of
(6) Hoiberg, A. J. Catalysts for use in blowing asphalts. R o c . Assoc.
Asphalt Paving Technol. 1950,19, 225.
(7) Brooks,B. T. The oxidation of mineral oils by air. Ind.Eng. Chem.
1917,9, 746.

( 8 ) Shearon,W. H. Catalytic asphalt-PhosphorousPentoxideasphalts.


Ind. Eng. Chem. 1953,45, 2122.
(9)Hampton, W. H.US Patent, August 16 (1949),No. 2479235.
(10)Crundermann, Erich Deut. Akad. Wiss.,Leipzig, GerErdoel Kohle
1965, 18(10)780-7.

Energy & Fuels, Vol. 8, No. 3, 1994 789


Table 1: Characteristics of Dehydrated Sludge and
Vacuum Rssidue of Sludge
vacuum
test
dehydrated residue
characteristic
method
sludge
of sludge
specific gravity at 27 O C BS 2000182
1.014
1.017
softening point ("C)
IP 58/65
46
52
penetration (1/10nm)
IP 49/76
230
41
ductility (cm)
IP 32/55
32.5
48
flash point ("C)
IP 34/75
>200
>200
solubility in CS2 (wt %) B.S. 4600
99.81
99.78
loss of heating (wt %)
IP 45/58
0.93
0.10
kinematic viscosity
IP 71/60
474
1500
at 100 O C (cS)
total sulfur (wt W )
IP 61/65
3.43
2.1
Table 2 Data of Vacuum Distillation
temp on
conversionto
press.
atm press.
temp
recovery in
volume (%)
("C)
(mm)
(760mm) ( O C P
5
10
15
20
25
30
4

149
193
216
235
249
270

0.6
0.9
0.8
0.8
0.8
1.75

347
397
430
455
414
481 (cracking starts)

initial boiling point = 295 "C.

L.R. grade. To removewater, inorganic materials, etc. the sludge


(150 kg) was heat treated in a barrel of 200 L capacity fitted
inside with steam coils. It was maintained at 110 f 10 OC for 12
h at which time the sludge was fully dehydrated (tested as per
IP 291173). The remaining hot oil was then passed through
strainers (60and 40 mesh) to remove solid impurities. The oil
thus obtained was highly viscous and solid at room temperature.
Its characteristics are given in Table 1. A 163-gsample of this
dehydrated sludge was taken in a round-bottomed flask and
subjected to vacuum distillation. Hot water was circulatedround
the condenser and the receiver so that the waxy distillate coming
out as vapour did not stick to the sides of the condenser. The
lighter oil fraction thus recovered from the sludge amounts to
17% (see Table 2 for data of vacuum distillation). The residue
obtained after vacuum distillation was tested for different
parameters. These results are also given in Table 1.
According to Bureau of Indian Standards (IS 702-1961)there
are 10 different grades of industrial bitumen depending upon
the softening point-penetration relationship. They are 65/25,
75/15,75/30,85/25,85/40,90115,105120, 115115, 135110,and
15516. The first figure represents the softening point and the
second one penetration. A grade 65/25should have the softening
point between 59.5 and 70.5 and penetration between 21 and 29.
Attempts to convert the vacuum residue of the sludge to some
of the above grades of industrial bitumen were carried out as
follows.
A 250-g portion of this vacuum residue was heated without
any catalyst in a cylindrical can (16.5cm height and 9 cm dia)
at 250 "C for 3 h with periodical stirring. The sample was then
taken out and tested for the different parameters (Table 3).The
above experiment was repeated adding 2 5% each of sulfur, FeCls,
Pz05and AlC13. From the results (Table 3) it is seen that AlC13
can bring about appreciable variation in the softening pointpenetration ratio while the other catalysts used were not able to
bring about such a significant variation. To determine the
optimum concentration of AlC13 and the optimum time and
temperature required, the experimentwas further repeated with
different percentages of AlCb ranging from 1 to 2.75% and
temperatures ranging from 200 to 275 OC for periods varying
from 1-3 h (see Figures 1-4). The samples were taken out at
definite intervals and tested.
The softening point reported in this paper was determined by
the ring and ball method according to IP 58/65. Here a steel ball

Kuriakose and Manjooran

790 Energy & Fuels, Vol. 8, No. 3, 1994

Table 3 Data on Heat Treatment of Vacuum Residue at 250 OC without and with Different Catalysts for 3 h
catalyst
specific
softening
penetration
ductility
flash
matter soluble in
loss on
(2%)
gravity
point ( O C )
(1/10 mm)
(cm)
point ( O C )
carbon disulfide (wt %)
heating (wt %)
>300
99.76
1.020
55.0
31
20.5
0.07
Nil
1.028
58.5
23
13.0
>300
99.70
Sulfur
0.05
FeC13
1.024
58.0
26
17.5
>300
99.72
0.05
P2O6

AlC13

56.0
83.0

1.021
1.030

29
20

>300
>300

19.0
5.0

99.74
99.64

0.06
0.04

0 2030c
e 225'C
A 2 50*C
A 275'C

0 1 % AlCg

~*/.AIcI~
A 2.5%AIC13
A 275%AlC13

20

25
PENETRATION, 1 /lOmm

30

90

15

20

PENETRATION. 1/10"

25

30

Figure 1. Effect of different percentages of aluminum chloride


on properties of vacuum residue of sludge.

Figure 2. Effect of temperature on properties of vacuum residue


of sludge containing 2.5 % aluminum chloride.

(9.5 mm diameter) of specified weight (3.5 g) is placed upon a


disk of sample contained within a metal ring of depth 6.4 mm;
inside diameter at bottom and top 15.9and 17.5mm, respectively,
and outside diameter 20.6 mm. The assembly is heated at a
constant rate and the softening point is taken as the temperature
at which the sample becomes soft enough to allow the ball
enveloped in bitumen to fall the specified distance (25 mm). To
determine softening point below 80 O C , a water bath was used
for heating while for those above 80 O C a glycerinebath was used.
Penetration was determined as per IP 49/76. A penetrometer
made by Precision Scientific Co., USA, was used for the purpose.
The experiment was conducted at 25 O C for 5 s with a total moving
weight of 100 g. The distance in tenths of a millimeter that a
standard needle (50 mm long and 1.02 mm diameter) vertically
penetrates the sample is reported as penetration.
Ductility was determined as per IP 32/55 at 27 "C and at a rate
of pull of 50 mm/min. A ductility meter manufactured by
Humboldt Manufacturing Co., U.S.A.,was used. The density of
water in the bath was adjusted by adding sodium chloride so that
the bitumenous thread formed during the test did not touch the
bottom of the bath at any time during the test. The distance in
centimeters by which a standard briquet having the following
dimensionscan be elongated before the thread breaks is reported
as ductility (total length = 75 mm, distance between clips = 30
mm, width at mouth of clip = 20 mm; and width at minimum
cross section = 10 mm). Flash point was determined by the
Pensky-Martens closed method as per IP 34/75, at a heating
rate of 5 "C/min and with a stirrer speed of 60 rpm. The
temperature at which the vapor above the sample can ignite with

a distinct flash inside the cup on the application of the test flame
is reported as flash point.
Solubility in carbon disulfide was determined as per IP 47/74
using 2 g of the dry material and 100 mL of carbon disulfide. Loss
on heating was determined as per IP 45/58 in a stabiltherm oven
(BLUE M Electric Co., USA). A 50-g portion of the sample in
the sample container was placed near the circumference of the
revolving shelf which is made to rotate at a rate of 5-6 rpm, the
temperature being maintained at 163 "C for 5 h after the sample
was introduced. Density of the samples was determined as per
IP 160/68 usinga hydrometer of range 0.85490g/mL. Recovery
was determined as per IP 123/78. A 100-mLvolume of the sample
was distilled, and the total volume of the distillate collected in
the receiver at 366 O C was recorded as the recovery. Kinematic
viscosity was determined as per IP 71/60. The time was measured
for a fixed volume of oil to flowthrough the capillaryof a calibrated
glass viscometer at 38 "C. The kinematic viscosity of the oil was
then calculated from the measured flow time and the calibration
constant of the viscometer obtained using freshly distilled water
as the primary standard.
The diesel index was determined as per IP 21/53. It was
calculated using the formula GA/100 where G is the API gravity
and A is the aniline point in O F . The aniline point was determined
as per IP 2/78. Pure aniline (5 mL) and sample (5 mL) were
placed in a tube and mixed mechanically. The mixture was heated
at a controlled rate until the two phases became miscible. The
mixture was then cooled at a controlled rate and the temperature
at which the two phases separated was recorded as the aniline
point. Ramsbottom carbon residue was determined as per IP

Energy & Fuels, Vol. 8, No. 3, 1994 791

Utilization of Refinery Sludge for Lighter Oils

Chart 1
density at 15 "C (g/mL) (IP I60/68)
recovery at 366 O C (vol % (mL))(IP 123/78)
flash point (PMC)("C)(IP 34/75)
kinematic viscosity at 38 O C (cS) (IP 71/60)
diesel index (IP21/53)
carbon residue (Ramsbottom) (wt % ) (IP 14/65)
aniline point (OC)(IP 2/78)
total sulfur (wt % ) (IP63/65)
pour point ("C)(IP 15/67)

A 1% Atcis
0 2 % AlClj

A 25%A C l j
0 Z?T/.AlC13

56

64

72
SOFTENING POINT'C

80

88

Figure 3. Effect of duration of heat treatment with varying

percentages of aluminum chloride.


A 2dC
0 225Oc

A 256C
27dC

0.8923
73
>80
10.6
45
0.29
86.6
1.3
+ 21

over CaClz for 20 min and weighed again. The percentage weight
of carbon residue was then calculated and reported as Ramsbottom carbon residue. Total sulfur was determined as per IP
61/65. A0.6-g portion of the sample was subjected to combustion
using a firing wire of length 100 mm in a bomb of capacity 300
mL containing oxygen at 35 atm pressure. The interior of the
bomb and the cup were then washed with distilled water and the
washings were collected. The washings were then heated to
boiling and 10 mL of barium chloride solution was then added
dropwise. Boiling was continued for 5 min more and the sample
was then cooled. The supernatant liquid was then filtered
through a filter paper (Whatman No. 40) and the precipitate was
washed until free from chloride. The paper and the precipitate
was then transferred into a weighed crucible and ignited until
the residue was white in colour. The crucible was then allowed
to cool to room temperature and weighed. The percentage weight
of total sulfur was then calculated using the formula 13.73(A/B),
where A is weight in grams of barium sulfate and E is weight in
grams of the sample taken for test.
Pour point was determined as per IP 15/67. The sample was
heated in a water bath without stirring to a temperature of 45
OC. The test jar containing the sample was then placed in a
vertical position in the cooling bath. At each multiple of 3 O C ,
the test jar was taken out carefully from the cooling bath and
tilted to ascertain whether there is a movement of the oil in the
test jar. The complete operation of removal and replacement
was done within 3 s. The test was continued until the oil in the
test jar showed no movement when the test jar was held in a
horizontal position for exactly 5 s. The reading of the test
thermometer was recorded as the pour point.
Results and Discussion

75

79

63
SOFTENING POINT * C

87

Figure 4. Effect of duration of heat treatment at varying


temperatures with 2.5% aluminum chloride.
14/65. A 5-g portion of the sample was introduced into the cocking
bulb by means of a hypodermic syringe and the bulb was
reweighed. The coking bulb was then placed in the furnace at
550 "C for 20 min. It was then taken out and placed in a desiccator

The initial part of the study demonstrates that about


17% of lighter oils can be isolated from this refinery sludge.
Characteristics of the recovered oil (Chart 1)show that it
can be blended with other refinery streams to make it
useful as high-speed diesel.
The catalytic effect on the heat treatment of the vacuum
residue of the sludge was also investigated. The results
of the action of sulfur, FeCl3, PzOS,
and AlC13 on the heat
treatment a t 250 "C and a t a catalyst ratio of 2 % for 3 h
are shown in Table 3. It is seen that sulfur, FeCl3, and
Pz05 are successful in bringing down the penetration
sharply but fail to bring up the softening point. But AlC13
not only brought down the penetration sharply but was
also able to bring up the softening point to the required
level.
The pronounced catalytic effect of AlC13 in such
polymerization reactions involving olefins can be explained
by means of the following ionic mechanism. Since AlC13
has an incomplete octet, it, when added to the olefin,
polarizes it to such an extent that it is capable of adding
further monomers.l1 At high temperatures, AlC13 can also
(11)Rieche, Alfred Outline of Industrial Organic Chemistry;

Butterworth: London, 1964;Chapter 11, p 394.

Kuriakose and Manjooran

792 Energy & Fuels, Vol. 8, No. 3, 1994

Table 4: Data on Heat Treatment of Vacuum Residue at 250 OC with Different Percentages of AlClJ for Varying Durations
amount of
duration of heat
specific
softening
flash
matter soluble
loss on
AlC13 (5%)

treatment (h)

gravity

point

penetration

1.0
1.5
2.0
2.5
3.0
1.0
1.5
2.0
2.5
3.0
1.0
1.5
2.0
2.5
3.0
1.0
1.5
2.0
2.5
3.0

1.023
1.023
1.024
1.026
1.026
1.025
1.026
1.028
1.030
1.030
1.028
1.028
1.029
1.032
1.034
1.028
1.030
1.031
1.032
1.033

56
59
62.5
64
65
69
75
78
81
83
76
81
84
88
89
80
84
86
88
89

30
29
27
25
25
25
23
22
21
20
24
22
20
17
16
22
21
20
18
17

2.5

2.75

ductility
11
9

6.5
6.3
6.25
6.0
5.75
5.5
5.0
5.0
5.3
5.0
4.5
3.75
3.5
5.1
4.5
4.25
4.0
4.0

point
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300
>300

in CS2 (wt % )
99.76
99.72
99.70
99.68
99.65
99.74
99.72
99.70
99.67
99.64
99.72
99.69
99.64
99.60
99.59
99.68
99.65
99.62
99.60
99.60

heating (wt 5%)


0.08
0.06
0.05
0.03
0.03
0.06
0.06
0.05
0.05
0.04
0.05
0.04
0.04
0.03
0.03
0.04
0.04
0.03
0.03
0.03

Table 5: Data on Heat Treatment with 2.5% AlC13 at Varying Temperatures and Duration
temp
PC)

duration of heat
treatment (h)

specific
eravitv

softening
Doint ("C)

penetration
(1/10 mm)

ductility
(cm)

flash
Doint ("C)

matter soluble
in CS2 (wt % )

loss on
heating (wt % )

275

1.0
1.5
2.0
2.5
3.0
1.0
1.5
2.0
2.5
3.0
1.0
1.5
2.0
2.5
3.0

1.025
1.026
1.028
1.030
1.032
1.026
1.028
1.029
1.034
1.036
1.025
1.026
1.026
1.028
1.028

78
80
83
86
87
76
83
86
89.5
90
75
79
81
83.5
84.5

25
23
21
19
18
25
22
18
15
14
29
27
26
25
25

6.0
5.75
5.5
5.0
4.0
5.4
4.75
4.25
3.5
3.0
6.0
5.8
5.75
5.0
5.0

>300
>300
>300
>300

99.74
99.72
99.70
99.64
99.61
99.70
99.67
99.65
99.59
99.56
99.72
99.70
99.67
99.64
99.63

0.06
0.06
0.05
0.04
0.04
0.05
0.04
0.03
0.02
0.02
0.06
0.06
0.05
0.05
0.05

225

200

bring about Friedel-Crafts arylation (Sholl reaction).'*


Intramolecular Sholl reaction can also take place.
Table 4 gives the effect of different percentages (ranging
from 1to 2.75%) of A1C13a t 250 "C on the heat treatment
of the vacuum residue of sludge for periods ranging from
1 to 3 h (Figure 1). The results show considerable
improvement in the softening point-penetration relationship upto a catalyst level of 2.5% and duration of 2.5 h.
With higher percentages, the improvement is not significant. Table 5 reports the data obtained when the heat
treatment was carried out a t other different temperatures
ranging from 200 to 275 "C for varying periods keeping
the catalyst level at 2.5% (Figure 2). The results show
that a high temperature of 275 "C as well as a lower
temperature of 200 "C did not give a better softening point(12)March, Jerry Advanced Organic Chemistry-Reactions, Mechanisms and Structure; International Student edition; McGraw-Hill
Kogakusha Ltd. Tokyo, 1968; Vol. 11, p 412.

>300

>300
>300
>300
>300
>300

>300
>300
>300

>300
>300

penetration relationship. The best result was obtained at


the temperature of 225 "C and duration of 2.5 h. This can
be taken to be the optimum conditions for preparing grades
of industrial bitumen of lower penetration and higher
softening point like 90115.
The results show that only four of the 10 different grades
of industrial bitumen can be prepared by the methods
used in the present study. Heat treatment of the vacuum
residue a t 250 "C for 2.5 h with 1% AlC13 is sufficient for
preparing the 65/25 grade. The 75/30 and 85/25 grades
can be obtained by heat treatment at 200 "C with 2.5%
AlC13 for 1 and 3 h, respectively. Similarly, 90115 grade
can be prepared by heat treatment at 225 "C for 2.5 h with
2.5 % AlC13. For the remaining grades, the softeningpointpenetration specifications were found difficult to meet by
the methods used in this study, probably due to the low
asphaltene content in the vacuum residue of sludge.