National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
Production of Activated Carbon from Spent Lubricating Oils by
Chemical Treatment
Ammar A. Hamdon
Dept. Chem.,/ College of Education, University of Mosul
(NJC)
(Received on 25/1 /2005)
(Accepted for publication on 22/ 6/2005)
Abstract
In this work activated carbon of a good quality prepared from spent lubricating
oils using oxidation condensation process. The oxidation of the spent lubricating oils
conducted using 2% (wt%) of (CoCl2, ZnCl2 & FeCl3) and in the presence of a stream
of air or oxygen. The reaction mixture was heated at 350C for (12, 24 & 36) hr, this
followed by removal of uncarbonized materials under reduced pressure. The
carbonization and activation was conducted at 55025C for 3 hrs and the ratio of the
feedstock to NaOH (1:2). After the carbonization was completed, the reaction mixture
was subjected to purification by treatment with distilled water, 10% HCl and distilled
water till it gives neutral test to litmus paper. The samples were dried at 120C for 24
hr and its physical properties were determined, the research work indicated that a
good quality activated carbon was obtained when the oxidation of sample was
conducted using 2% FeCl3 for 36 hr.
‫الخالصة‬
‫يتضمن البحث تحضير الكاربون المنشط من الزيوت المستتللكة عتن طريتج اجتراء عمليتة اكستد تكاثفيتة‬
‫ و‬24 ،12 ‫ لمتتد‬350 ‫) وام ترار تيتتار متتن الل تواء عنتتد‬FeCl3 ‫ و‬ZnCl2 ،CoCl2 ‫ وزن تان متتن‬%2 ‫باستتتادا‬
‫ يلي ذلت عمليتة ا ازلتة للمتواد ايتر الم ربنتة باستتادا التقطيتر الف اراتي بمتد ذلت يتت مفاعلتة مالفتات‬،‫ ) ساعة‬36
‫ م ت تتاد اولي ت تتةد يدرو س ت تتيد ال ت تتوديو عن ت تتد‬،)2:1
‫التقطي ت تتر الف ارا ت تتي م ت تتو زي ت تتاد م ت تتن يدرو س ت تتيد ال ت تتوديو‬
‫ ستتاعات يتتت تنقيتتة المتتاد الناتجتتة عتتن طريتتج القستتل بالمتتاء المقطتتر لحتتين التمتتاد ومتتن ث ت‬3 ‫ لمتتد‬25550
‫ يلي ذل‬، ‫ حامض الليدرو لوري وباستادا عملية الت ميد الحراري لمد ساعة واحد‬%10 ‫المماملة مو محلو‬
،‫ ستاعة‬24 ‫ لمتد‬120 ‫تجفف النماذج عند‬
‫عملية ترشيح للماد الكاربونية واسللا بالماء المقطر لحين التماد‬
‫يلي ذل عملية تحديد موا فات الكاربون المنشط المحضتر ومقارنتلتا متو تاربون منشتط تجتاري متن انتتاج شتر ة‬
B.D.H
216
National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
by heating the feedstock under vacuum
Introduction
Activated carbon, also called
to produce a “char”. The char is then
charcoal, is greatly involved in recent
activated by exposure to an extremely
civilization. It is employed in the
hot gas, usually at about 800-1000C,
production of many products of great
which may help to open the pores of
need every day; to remove impurities
all its type, by reaction with unrequired
that cause an objectionable colour,
atom in the structure. The feedstock
taste,
from
selected plus the manner in which it’s
drinking water and nutrients. Removal
carbonized and activated, determines
of leathal gas in the chemical ware fare
the characteristics of the finished
(gas masks) and to separate/purify
activated carbon product and its cost.
products
and
There are dozens. Of different kinds of
pharmaceutical industries. Activated
activated carbon produced; of these
carbon covers a family of materials
only a handful will be well valuable to
made from carbon which have the
any particular application(1).
odour,
in
heavy
the
metals
chemical
ability to attract and hold certain
The literature contains many
substance on the carbon surface. This
research work concerning activated
ability is called “adsorption”. The
carbon, which may include source of
adsorption process is an example of
the feedstock, nature of carbonization
what is termed “chemical filtration”,
processes, type of activation methods
where certain dissolved substance are
and texture of the product activated
removed from the water. Filter floss,
carbon which is given as follow;
on
the
other
hand
O’Grady
performs
and
Wennerbery,
“mechanical filtration” by trapping
prepared
solid particles suspended in the water.
exceptionally high surface area over
2500
The Feedstock most commonly
activated
m2/gm
and
carbon
having
extraordinary
used to produce the carbon are coal,
adsorptive capacities. The carbon is
petroleum residue and asphaltenes,
made by a direct chemical activation in
peat, lignite, wood and other plants
which petroleum coke and other
harvesting products. These feedstock
carbonaceous sources are reacted with
containing recognizable amount of
excess KOH at 400-600C(2). Gercia et.
carbon.
other
al., prepared activated carbon from
unrequired components are driven of
mixing pine wastes with KOH in a
The
hydrogen
and
217
National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
pilot gasifier, without any previous
with (5%) NHCl and finally with
treatment.
different
distilled water till neutral litmus paper
alkali/char ratios varied from 1:1 to 1:4
is indicated. Then the sample dried at
at 725-800C. After the activation
110C for 24 hr(3). Ceren and Meral,
process, the sample was cooled under
prepared Activated Carbon as given
N2 and washed sequentially five times
below(4);
They
employ
Char Coal
Crushing
Cooling
Purification
by
1-10%HCl
2-D.W.
3-0.5NHCl
4-Hot D.W.
5-Cold D.W.
Activated with ZnCl2 (24 hr, R.T.)
Carbonization
at
500,600&700C
for
1 hr.
Drying (105C)
Drying (105C)
Grinding (0.125-0.250mm)
Sieving
Chipofy
and
McConnachie
area and pore volumes as high as 2900
from
m2/gm and 1.7 cm3/gm, respectively
agricultural waste. Production involved
with high yields of approximate 30%
carbonization of set quantity of the
Wt(6). Kobayashi et. al., prepared
precursors in stainless steel trays that
activated carbon from brown coal and
were in turn placed in a stainless steel
weathered coal with a relatively large
box and heated in a steam atmosphere
quantities of sodium hydroxide or
at 600, 650, 700, 750 and 800C, 
potassium hydroxide (alkali ratio to
10C for 30 minutes. Steam was
coal 2-2.5) under low temperature
generated by pumping water from a 20
(500-700)C than the conventional
liter jar into the steel box at different
steam activated (900-1000)C. For
feed rates(5). Teng and Weng, prepared
instance, active carbon with specific
activated carbon from mesophase pitch
surface area of more than 1000m2/gm
powders by heat treatment and KOH
were
etching at temperature 427C. The
(33-36%), when weathered coal was
activated carbon obtained has a surface
activated by NaOH (ratio 2.5-3.0) at
prepared
activated
carbon
218
obtained
with
high
yield
National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
700C. the effect of alkali could be,
of air or oxygen at 350C for 3 hrs.
improved significantly by pre-heating
The carbonization and activation was
at 500C of coals, affording the active
conducted at 55025C for 3 hrs using
carbon with higher values of specific
excess NaOH(10). Al-Ghanam, et. al.,
surface area (1300m2/gm) at 550C(7).
prepared activated carbon from (Heet
Aweed, prepared activated carbon
asphalt) using several percentage of
from residual petroleum products such
poly ethylene in the presence of air at
as that of qaiyarah heavy crude oil (S
350C for 3 hrs and then complete the
about 7.45%) by employing direct
carbonization
oxidation with and/or by using certain
55025C using excess NaOH(11). Al-
type of catalysts (CoCl2, ZnCl2 and
Ghanam, et. al., prepared activated
FeCl3) at 350C. Activation of the
carbon from heavy petroleum residue
carbon after oxidation carried out at
using chemical treatment. The activity
about 55025C by using different
of carbon was performed through
percentage of KOH. Catalysts used in
adsorption of acids in aqueous(12).
the research (CoCl2 & ZnCl2) give a
Experimental
good result but not as the same as that
1-
and
Treatment
activation
of
at
Spent
(8)
of FeCl3 .
Lubricating Oils
Prinsloo and Jiger, prepared
Exactly weighed (100gm) from
activated carbon by the chemical and
spent lubricating oils were treated with
physical activation. Coke precursors
2% (Wt%) of (CoCl2, ZnCl2 & FeCl3).
(uncalcined) produced from waxy oil
The mixture was heated gradually till
and medium temperature pitch were
350C and kept for a period of 12,24 &
activated between 0.5 & 9 base coke
ratio,
600-800C
heat
36 hr. Air was continuously passes
treatment
during the heating period. The product
temperature (HTT) and 1.5 and 12 hr
heat
treatment
time
(HTt).
from the oxidation was allowed to cool
All
to room temperature. Unreacted part of
activation and cooling cycles were
the spent lubricating oils were removed
carried out under a constant flow of
nitrogen(9).
Rhamadhan
et.
by distillation under vacuum. The
al.,
residual materials left behind were
prepared activated carbon from (Beje
used as a feedstock for the activated
asphalt) using several percentage of
carbon preparation.
V2O5 and in the presence of a stream
219
National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
2- Carbonization of The
4- Activated Carbon
Oxidized Spent Lubricating
Measurements:
Oils
A- Measurement of Density
The materials from above step
The density of the prepared
were mixed with twice its weight of
activated carbon were determined by
the carbonizing agent (Ca: NaOH) and
weighing 10 cm3 of the carbon sample
(30-50) ml of distilled water. The
using graduated cylinder(20).
mixture was heated gradually with
B- Determination of Ash
continuous stirring till a thick bulk of
Content
the oxidized product were obtained.
The
heating
was
continued
The ash content was measured
at
by heating burning one gram of the
55025C for a period of 3 hrs. The
prepared activated carbon sample in a
product
room
porcelain crucible using an electrical
temperature and purified as in the next
furnace for five hours at temperature of
step.
1000-1100oC. the remained residue
3- Purification of The
was considered as the ash content.(21)
Carbonized Product
C- Measurement of Humidity
was
cooled
to
The carbonized materials were
One gram (exactly weighed) of
crushed carefully and washed with
the activated carbon was heated in an
large amount of distilled water till it
oven at 150oC for 3hr. The difference
gives neutral test for litmus paper. The
in weight before and after heating
carbonized materials were mixed with
operation was calculated as H2O
a sufficient amount of 10% HCl
vapour in the sample(22).
solution. The mixture was heated
D- Determination of Carbon
under reflux for 1 hr, cooled, filtered
Activity by Methylene Blue
and washed with distilled water. The
Adsorption Method
washing continued till a negative
litmus
paper
was
indicated.
An exactly weight (0.1 gm) of
The
the prepared activated carbon sample
sample obtained was dried at 120C
was added to an aqueous solution of 20
for 24 hr and kept for property
ppm methylene blue pigment in a
measurements.
conical
flask.
The
solution
was
shacked by an electrical shaker for 24
220
National Journal of Chemistry, 2005, Volume 18,216-225
hr at a temperature of 25oC till
standardized 0.1 N iodine
solution to the flask.
5- Immediately stopper flask and
shake the contents vigorously
for 30 minute.
6- Filter by gravity immediately
after the 30 minute shaking
period through filter paper.
7- Mix the filtrate in the beaker
with a stirring rod and pipette
50 ml of the filtrate into 250
ml Erlenmeyer flask.
adsorption of methylene blue from its
aqueous solution was completed a state
of equilibrium was reached. The
absorbance
determined
of
the
using
solution
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
was
(UV-Visible
Spectrophotometer) at max 665 nm.
The procedure was carried out for the
different types of the prepared samples
for comparison purposes. The final
concentration of methylene blue value
8- Titrate the 50 ml sample with
for each activated carbon sample was
standardized 0.1N sodium
thiosulfate solution until the
yellow color has almost
disappeared. Add about 1 ml
of starch solution and continue
titration until the blue indicator
color just disappears. Record
the
volume
of
sodium
calculated as the number at milligrams
of methylene blue adsorbed by one
gram of carbon(23).
E- Determination of Carbon
Activity by Iodine Adsorption
Method
The iodine number (In), which
is the amount (in milligrams) of iodine
adsorbed from its aqueous solution by
one gram of activated carbon. The
method involve:
1- One gram of the dried
activated carbon transferred to
250 ml Erlenmeyer flask.
2- To the flask, add 10 ml of 5%
HCl and swirl until the carbon
thiosulfate solution used(24).
Iodine number =
X
m
D
Where:
m = is the weight of the
activated carbon in grams
X = A – [2.2 Bx ml of
thiosulfate solution used]
A = N1  1269.0
B = N2  126.93
is wetted.
3- Place the flask on a hot plate,
bring the contents to a boil and
allow to boil for exactly 30
minute.
4- Allowing the flask and
contents to cool to room
temperature add 100 ml of
N1 = normality of iodine
solution.
N2 = normality of sodium
thiosulfate solution.
D = correction factor.
221
National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
Production of activated carbon
Lubricants  resins 
Asphaltenes
The results of using Zinc
usually carried out by carbonization of
Chloride for different period of times
any organic compound that have high
using the same feed stock showed little
carbon
routine
effect which could be explained in
carbonizing method or modified ones.
term of low activity of ZnCl2 as lewis
The
for
acid in the presence of lubricant
carbonization processes is of a vital
addatives. The polymerization and
important to the uses and application
oxidation reactions could be poisoned
since activated carbon is used in the
by side reactions and no increase in the
removal of pollutants and support for
carbon content as recognized. This
catalysts, therefore in this research
appeared little change of the density
work liquid spent lubricating oils
and adsorptive properties.
Results and Discussion
content
choice
by
of
a
feedstock
which have no economical value has
On the other hand when Cobalt
been used. Lubricating oils contain a
Chloride substituted Zinc Chloride for
large molecules and various molecular
the same period of times and the same
structure that may include aromatic,
amount
naphthenic in a free form or condense
improvement
and in some cases waxes is present.
especially in the Iodine number and
The
was
slight reduction in the density which
conducted by direct oxidation of the
may refer to a certain polymerization-
material
The
oxidation reaction took place. The
condensation process was conducted
results also indicated a slight intensity
by
in the feed stock after treatment.
carbonization
till
using
process
solidification.
catalysts
of
different
of
lubricant,
was
a
certain
recognized
molecular weight and ions. Application
However application of Ferric
of the catalysts aimed to increase the
Chloride as lewis acid in the presence
molecular weight (condensation and
of oxygen gave a great polymerization-
oxidation
oxidation process which is recognized
increase
the
oxygen
functionality).
Condensation
by the low density and high adsorptive
oxidation
of
for Iodine number and Methylene blue.
lubricant as given by other worker may
In
processed throw the the following
reaction
addition
the
ability
of
condenseation and oxidation using
(18)
:
different lewis acids is greatly affected
222
National Journal of Chemistry, 2005, Volume 18,216-225
‫المجلد الثامن عشر‬-2005-‫المجلة القطرية للكيمياء‬
by the molecular size of the cation and
the effective charge (i.e. FeCl3 > CoCl2
> ZnCl2).
The results of the investigation
were given in table below.
Table: Properties of the Prepared Activated Carbon
Sample
Cat.
Time
Density
Ash
Humidity
hr
g/cm3
%
%
Iodine
Methylene
Number
Blue
mg/g
Mg/g
1
-
12
0.441
1.610
0.821
150
15
2
-
24
0.440
1.521
0.800
200
19
3
-
36
0.440
1.512
0.790
225
22
4
ZnCl2
12
0.432
1.471
1.101
450
60
5
ZnCl2
24
0.431
1.521
1.001
525
63
6
ZnCl2
36
0.431
1.621
1.231
575
65
7
CoCl2
12
0.421
1.521
1.521
475
65
8
CoCl2
24
0.401
1.550
1.201
560
68
9
CoCl2
36
0.400
1.561
1.761
625
70
10
FeCl3
12
0.322
1.521
1.201
750
73
11
FeCl3
24
0.321
1.501
1.810
880
85
12
FeCl3
36
0.301
1.536
0.981
950
93
B.D.H
-
-
0.345
3.200
0.800
908
90
Publ. ACS, Washington D.C., USA, pp.
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National Journal of Chemistry, 2005, Volume 18,216-225
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225
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