Synthesis of activated carbon using mixed

vacuum residue and castor oil

Cite as: AIP Conference Proceedings 2062, 020052 (2019); https://doi.org/10.1063/1.5086599
Published Online: 25 January 2019

Dijan Supramono, and Arif Hendrawan

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AIP Conference Proceedings 2062, 020052 (2019); https://doi.org/10.1063/1.5086599 2062, 020052

© 2019 Author(s).
 Synthesis of Activated Carbon Using Mixed Vacuum
Residue and Castor Oil
Dijan Supramono 1a) and Arif Hendrawan2)
1,2
Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Depok 16424, Indonesia
a)
Corresponding author : dsupramo@che.ui.ac.id

Abstract. Petroleum refinery produces vacuum residue in a vacuum distillation unit as waste. Mixture of the vacuum
residue and a conjugated double bond compound can be used as feedstock to produce activated carbon because the
compound forms a stable mesophase at high temperature to allow polymerization of aromatic compounds in vacuum
residue. Castor oil, which is available in tropical forest in Indonesia, can be dehydrated to form conjugated double-bond
compounds. Polymerization can form a pitch with different extents of aromatization so that high surface pore area of
the activated carbon can be achieved. The subsequent process was carbonization of the pitch to form activated carbon,
where oligomerization and cracking of side chains occurred. The purpose of this study is to investigate effect of
addition of dehydrated castor oil on aromatic growth during polymerization and voidage of activated carbon precursor
and on carbon content and pore surface area of activated carbon. Co-pyrolysis to prepare activated carbon precursor
improved aromatic content compared to the mixture without co-pyrolysis, but with short holding time at maximum
temperature during co-pyrolysis, the addition of dehydrated castor oil of 10 and 15% gave small improvement. SEM-
EDX analysis upon activated carbon indicates that only addition of dehydrated castor oil to vacuum residue of 15%
exhibited very few voids in the activated carbon, which means that the aromatization growth filled nearly the whole
voidage of activated carbon to form pores. BET analysis shows that increasing addition of dehydrated castor oil
improved pore surface area from 733 to 1208 m2/g. SEM-EDX analysis of activated carbon shows that increasing
addition of dehydrated castor oil increased carbon content from 74% to 85%.

INTRODUCTION

Activated carbon is the most commonly used adsorbent in the adsorption system, because the activated
carbon has a large surface area and adsorption power. Thus, activated carbon is suitable as an adsorbent to absorb
color, odor and taste of pollutants [1]. Today, activated carbon is widely used for filtration of drinking water,
purification, gas adsorption, dry cleaning, alcoholic beverages, and solvent purification [2].
Activated carbon need increases along with the development of the industrial world. This is indicated by the
increasing number of industries of activated carbon producers in Indonesia from 13 producers in 2000 to 19
producers in 2006. Based on the data, the need for activated carbon in Indonesia reached 35,942 tons per 2007 and
Indonesia's activated carbon import reached ± 6,000 tons [3]. Increasing need for activated carbon due to the
development of the industrial world encourages innovation to optimize the performance of activated carbon. This
can be done by increasing the surface area of the activated carbon pores so that the adsorption quality is better. The
surface area of activated carbon from biomass raw materials tends to be low, whereas activated carbon can be made
from other raw materials that are rich in carbon, such as petroleum, coal etc.
Research to increase the pore surface area have been carried out by utilizing coal tar pitch which is the final
product as residue in destructive distillation of coal. Zeng, et al., 2013 [4] produced activated carbon from coal tar
pitch with maximum surface area reaching 2800 m2/gram. The synthesis of this activated carbon was carried out
through pyrolysis and aromatization processes of mixture of coal tar pitch and rosin. In addition, rosin was added to
provide conjugated double bonds to decrease the pitch melting point and free radicals to initiate polymerization of
the pitch [5].
In Indonesia, coal tar pitch is not available because there is no coal destructive distillation unit, whereas
vacuum residue (VR) is widely available because Indonesia has petroleum refineries in various regions. Both coal

The 10th International Meeting of Advances in Thermofluids (IMAT 2018)

AIP Conf. Proc. 2062, 020052-1–020052-8; https://doi.org/10.1063/1.5086599
Published by AIP Publishing. 978-0-7354-1790-8/$30.00

020052-1
tar pitch and VR contain similar compounds, i.e. alkane, asphaltene, resin and aromatics [6]. An original Indonesian
product that can be used as a substitute for rosin to provide free radicals and conjugate double bonds is castor oil but
it requires dehydration [7]. Petroleum refinery disposes residues in the distillation unit. The disposal of these low
economic residues emanates a huge problem for petroleum industry because direct combustion of these residues will
pollute the air and also contribute to serious environmental problems such as CO2 and NOx emissions [8]. The
utilization of VR will diminish the burden of the disposal.
In the present wok, it was proposed to make activated carbon from VR obtained as the bottom product of a
distillation vacuum unit. The residue is rich in aromatic compounds and the addition of DCO containing carboxylic
acid was expected to improve polymerization of aromatics of VR and of conjugated double bonds of DCO. The aim
of the present work is to investigate effect of addition of DCO on aromatic growth during polymerization and
voidage of activated carbon precursor and on carbon content and pore surface area of activated carbon.

EXPERIMENTAL

Materials

VR was obtained from a refinery company in Cilacap, castor oil was obtained from extraction from Jatropha
plantations in Lampung.

Methodology

The study was carried out in three stages [4]. The first was the dehydration process of castor oil. This stage
was carried out to form conjugated double bonds. The bonds were generated by heating castor oil with NaHSO4
catalyst as much as 1% in a stirred tank reactor until the temperature of 230oC to form dehydrated castor oil (DCO).
The second stage was the manufacture of activated carbon precursors. In this stage, VR was mixed with DCO in a
stirred tank reactor with variation of 0%, 5%, 10%, and 15% added DCO until the temperature of 150Ԩand
maintained for 30 minutes under nitrogen flow of 600 ml/min. Then, co-pyrolysis of the mixed feed was carried out
with increasing temperature until temperature of 390Ԩ and held at this temperature for 30 minutes to form carbon
precursors. The last stage was the manufacture of activated carbon. In this stage, carbon precursor was mixed with
KOH solution at a ratio of 1: 5 for 60 minutes before carbonization. This stage was carried out in a tubular reactor
with increasing temperature until 650Ԩ and maintained at this temperature for 60 minutes until activated carbon was
formed. After activated carbon was formed, the sample was neutralized with 0.5M HCl, washed with aquadest, dried
in an oven and ground to small particles. All stages are described in Figure 1.

FIGURE 1. Experiment Diagram

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 The chemical bonds of DCO were tested with UV-Vis (ultra violet – visible) spectroscopy to detect the
presence of conjugated double bonds. The sample of the mixture obtained from the stirred tank reactor was tested by
TGA (thermo-gravimetric analysis) to determine final temperature of co-pyrolysis. H-NMR (proton-nuclear
magnetic resonance) spectroscopy was carried out on carbon samples before and after carbonization to see the
changes of contents of monoaromatics, diaromatics and polyaromatics. SEM-EDX (scanning electron microscopy –
energy dispersive X-ray) analysis was carried out on activated carbon samples to see the surface morphology of
activated carbon and carbon content in each sample. The last test was BET (Brunauer-Emmet-Teller) analysis to see
the surface area of the activated carbon.

RESULTS AND DISCUSSION

UV-Vis Analysis of Dehydrated Castor Oil

10
9
8
% absorbance

7
6
5
4
3
2
202.5 209 214.5 222.5 230 237 243.5 252 257.5 264 270.5
wavelength (nm)

FIGURE 2. UV-Vis Analysis of DCO

Castor oil contains mostly ricinoleic acid (89.5%) containing one hydroxyl group and one double bond.
Conjugated double bonds exist in linoleic acid comprising 4.5% weight of castor oil. (Mubofu, 2016). Dehydration
of ricinoleic acid in castor oil removes hydroxyl group to form a new double bond and form a new conjugated
double bond [9]. By dehydration, the composition of linoleic acid increases. Linoleic acid with conjugated double
bonds can be detected in the wavelength between 220-300nm [10]. In Figure 2 the presence of linoleic acid of castor
oil is presented by peaks within this wavelength range. This shows the existence of conjugated double bonds of
linoleic acid compounds in the DCO obtained in the present work.

Activated Carbon Precursor

TGA of Activated Carbon Precursor

TGA measurement was conducted on samples of the mixture of VR and DCO prior to co-pyrolysis of the
mixture. Based on TGA measurement, DTG (differential thermal gravimetry) analysis was conducted to determine
the final temperature of co-pyrolysis. TGA curves of VR, VR with 5, 10, and 15% DCO are shown in Figure 3. It
can be seen that the initial mass reduction occurred at a temperature of 130-149 qC and more castor oil content
added shifted the initial temperature of the mass reduction from 149 to 130 qC. About 490qC, VR and its mixtures
lost about 95% of the initial mass. DCO contains double bonds, conjugated double bonds and carboxyl groups.
However, DCO with its carboxylic acid and conjugated double bond content has the ability to initiate
polymerization of VR and polymerize with VR [5].

020052-3
 1.2
100%VR
1
5%DCO
0.8 10%DCO

Mass, wt%
15%DCO
0.6

0.4

0.2

0
0 100 200 300 400 500 600
Sample Temperature, oC

FIGURE 3. TGA Curve of VR and Its Mixture with DCO

Sample Temperature, oC
0.5
Mass Derrivative, wt%/min

0
0 100 200 300 400 500 600
-0.5

-1

-1.5
100%VR
-2 5%DCO
10%DCO
-2.5
15%DCO
-3

FIGURE 4. DTG Curve of VR and Its Mixture with DCO

Figure 4 shows that DTG curves have peaks of derivative weight in the samples at 348 oC for VR with
added 15% DCO and increasing to 383oC for VR. The mass reduction prior those peaks mainly occurred due to mild
alkane evaporation [11]. Beyond those peaks, the mass reduction was caused by cracking of heavy fractions such as
asphaltene and resin [11] and the removal of gases produced by cracking reactions occurred during the pyrolysis
process [5]. Figure 4 demonstrates that mass loss in VR sample occurred with higher rate compared to other
samples, thus expectedly causing the smallest yield of carbonization. For all mixtures, co-pyrolysis was carried out
up to temperature of 390oC where cracking of heavy fractions occurred.

H-NMR Analysis of Vacuum Residue

H-NMR characterization was applied to the samples of VR already mixed with 0%, 5%, 10%, and 15%
DCO obtained prior to co-pyrolysis and after co-pyrolysis. The former samples (prior to co-pyrolysis) were named
VR0%, VR5%, VR10%, and VR15%, respectively, while the latter named VR-390-0%; VR-390-5%; VR-390-10%;
and VR-390-15%, respectively. This analysis can quantify how polymerization progressed featured by H abundance
bound to aromatic rings at different mixtures of VR and DCO.

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 TABLE 1. H-NMR Integration Data

H NMR VR0% VR-390- VR5% VR-390- VR10% VR-390- VR15% VR-390-

0% 5% 10% 15%
Har(poly) (%) 10,29 12,06 10,14 12,12 10,73 11,02 10,28 10,91
Har(di) (%) 14,02 17,28 13,58 17,28 14,57 15,34 13,80 16,29
Har(mono) (%) 7,10 8,52 6,96 8,61 7,33 7,88 7,07 7,74
Har (%) 31,41 37,87 30,69 38,02 32,64 34,25 31,15 34,95
Hα (%) 23,75 27,76 10,68 27,50 25,00 25,80 24,10 26,19
Hβ (%) 34,00 26,04 35,74 26,13 32,94 30,73 34,49 29,67
Hγ (%) 10,82 8,31 22,87 8,33 9,40 9,21 10,24 9,18
Hal (%) 68,58 62,12 69,30 61,97 67,35 65,74 68,84 65,04
Har/Hal 0,458 0,137 0,100 0,138 0,108 0,119 0,102 0,119
Notes: Har(mono) is the H abundance in monoaromatic rings, Har(di) is the H abundance in diaromatic rings, Har(poly) is
the H abundance in polyaromatic rings, HD is the H abundance in CD to aromatic rings, HE is the H abundance in CE
to aromatic rings, HJ is the H abundance in CJ to aromatic rings, Hal is the H abundance in aliphatic chains, Har is the
H abundance in aromatic rings.

Table 1 indicates that VR prepared prior to polymerization contained mostly aliphatic chains. During
thermal treatment the aliphatic chains reduced by producing active free radicals which reduced the activation energy
of polymerization [8]. Aromatic rings were polymerized to provide large size of aromatic molecules. The mesophase
pitch resulting from mixture of VR and DCO gave high impact on polymerization featured by Harr/Hal ratio on the
mixture containing 5% DCO where the ratio was high. It seems that the duration of co-pyrolysis at peak temperature
needs to be extended to allow more time for polymerization. In all mixtures, monoaromatic, diaromatic and
polyaromatic ring compositions in samples obtained after co-pyrolysis were larger than those before undertaking co-
pyrolysis. contains aromatic protons (Har), which corroborate the finding by Kumar and Srivastava [8]. Different
compositions of monoaromatic, diaromatic and polyaromatic ring during polymerization enhances high pore surface
area [12].
Table 1 shows that the content of Hβ and Hγ in the samples reduced as a result of polymerization. This
illustrates that the pyrolysis process was the removal of Hβ and Hγ and this removal promoted polymerization to
form more aromatic rings, which are more stable than aliphatic chains [13]. During polymerization, DCO has a
cycloparaffin function group, conjugated double bonds, and carboxyl, which eventually disappears during thermal
treatment. These compounds increase the degree of aromatization as temperature increases [5].

Activated Carbon

Analysis of SEM-EDX and BET were conducted upon activated carbon. The former analysis was used to
observe the image of activated carbon samples to see whether carbonization occurred over the whole part of
activated carbon. Improper carbonization is seen by many large pores in which the growth of aromatization does not
fill some voids in activated carbon. BET analysis was used to measure the pore surface area, whether the addition of
DCO gives significant effect on the area.

020052-5
 SEM-EDX Analysis

A B

C D

FIGURE 5. Activated Carbon Surface Morphology of (A) VR, (B) VR+5% DCO, (C) VR+10% DCO, (D)
VR+15% DCO

Figure 5 shows surface morphologies of activated carbon samples obtained from carbonization originated
100%VR (sample A), VR added with 5%DCO (sample B), VR added with 10%DCO (sample C), and VR added
with 15%DCO (sample D). Samples A, B and C exhibit some large pores (featured by large black images), while
sample D exhibit more homogeneous small pore size. It demonstrates that only mixture with 15%DCO addition
exhibited polymerization growth to fill all voids in the mixture.

TABLE 2. EDX Data of Activated Carbon

VR + 5% VR + 10% VR + 15%
Comp VR
DCO DCO DCO
(wt%) (sample A)
(sample B) (sample C) (sample D)
C 74,43 74,91 76,97 85,12
O 8,77 13,25 12,25 4,28
Al 0,21 0,30 1,69 -
Ca 0,99 1,12 - 0,31
Zn 1,08 - 0,79 -
Cu 0,93 - - 0,70
K 0,76 0,59 0,42 0,21
Cl 0,34 0,28 0,22 0,20

Based on EDX analysis which excluded hydrogen composition, Table 2 shows that with the assumption
that hydrogen contents were similar, DCO added to the VR promoted carbon content in activated carbon samples.
Among samples B, C and D, more DCO added imparted more removal of oxygen through pyrolysis, which means
that the addition of DCO facilitated more free radicals to initiate polymerization.

020052-6
 BET Analysis

Table 3 shows that the addition of castor oil has high impact on increasing pore surface area of the
activated carbon. It accounts for from 733 to 1208 m2/g with addition from 0 to 15% DCO. DCO contains
cycloparaffins, conjugated double bonds and alkene. Carboxylic acids are mostly of 18-carbon chains. Maher (2008)
identified that stearic acid (C18 carboxylic acid) cracks in the temperature range of 390-450oC. By carrying out co-
pyrolysis at maximum temperature of 390oC, it can be expected that most of carboxylic acids were partly cracked
while at the time aromatic rings polymerized to form solid phase. The cracking offered some voids in the activated
carbon which constituted as pores and increased the pore surface area. Moreover, the cracking allowed the formation
of free radical to initiate polymerization.

TABLE 3. Pore Surface Area of Activated Carbon based on BET Analysis

No Sample Surface Area

(m2/g)
1 VR 733
2 VR + 5% DCO 891
3 VR + 10% DCO 1044
4 VR + 15% DCO 1208

CONCLUSIONS
This study has demonstrated that the co-pyrolysis improved aromatic content compared to the mixture without
co-pyrolysis, but with short holding time at maximum temperature during co-pyrolysis, the addition of DCO of 10
and 15% gave small improvement. SEM-EDX analysis shows that only addition of DCO of 15% to VR exhibited
very few voids in the activated carbon, which means that the aromatization filled the whole voidage of activated
carbon to form small pores. BET analysis shows that increasing addition of DCO improved pore surface area from
733 to 1208 m2/g. SEM-EDX analysis of the activated carbon shows that increasing addition of DCO increased
carbon content from 74% to 85%.

ACKNOWLEDGMENTS

The authors would like to express their gratitude to Universitas Indonesia for its financial support through PITTA
(Publikasi Terindeks Internasional Untuk Tugas Akhir Mahasiswa) scheme contract no.
2417/UN2.R3.1/HKP.05.00/2018 for the budget year 2018.

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