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J. Chem. Chem. Eng.

7 (2013) 175-180

D DAVID PUBLISHING

Characterization and Modification of Indonesian Natural


Zeolite for Hydrocracking of Waste Lubricant Oil into
Liquid Fuel Fraction
1* 1 2
Wega Trisunaryanti , Akhmad Syoufian and Suryo Purwono
1. Department of Chemistry, Faculty of Mathematics and Natural Sciences, Gadjah Mada University, Yogyakarta 55281, Indonesia
2. Department of Chemical Engineering, Faculty of Engineering, Gadjah Mada University, Yogyakarta 55281, Indonesia

Received: December 06, 2012 / Accepted: December 28, 2012 / Published: February 25, 2013.

Abstract: Modification and characterization of natural zeolite under some various methods for hydrocracking catalyst of waste
lubricant to gasoline and diesel fractions have been conducted. Natural zeolite from Klaten was activated using hydrothermal
o
treatment at temperature 500 C for 6 h (produced ZAAHd), the ZA sample was treated with hydrothermal followed by Microwave
o
(produced ZAAHdM), the ZA sample was treated with HCl 3 N at temperature of 90 C for 30 min (produced ZAAH), the ZAAH
sample was heated in to microwave (produced ZAAHM), the ZAAHM was treated hydrothermal (produced ZAAHMHd), the
ZAAHMHd sample was heated in to microwave (produced ZAAHMHdM), soaking of natural zeolit activated by HCl-microwave-
hydrothermal-microwave in NH4NO3 1 N which was stirred using stirer at room temperature for 24 h (produced ZAAHMHdMN)
and the ZAAHMHdMN sample was heated into microwave (ZAAHMHdMNM). The heating process by microwave was conducted
at 550 watt for 15 min. Catalyst characterization involved determination of the number of total acid sites using gravimetric method
with vapour adsorption of NH3 and pyridine, catalyst crystallinity by XRD (X-ray diffraction) and TO 4 (T= Si and Al) site by infra
red spectrophotometer (IR). Hydrocracking of waste lubricants oil was performed in a fixed bed reactor of stainless steel at
o
temperature of 450 C, H2 flow rate of 15 mL/min., feed/catalyst ratio of 5. Liquid products of the hydrocracking were analyzed
using GC (gas chromatography). The characterization results showed that various modification of natural zeolite increased acidity
and dealumination degree of the catalysts. Products of the hydrocracking were liquid, coke, and gas fractions. Liquid products
consisted of gasoline fraction (C5-C12), diesel fraction (C12-C20), and heavy oil fraction (> C 20).The conversion of liquid products
was increased with the increase of catalyst acidity. The greatest liquid product conversion was produced by the ZAAHMHdMNM
catalyst, i.e., 56.80%, with selectivity towards gasoline, diesel, and heavy oil fractions was 88.37%, 8.61% and 3.02%, respectively.
The increase of catalyst acidity increased the selectivity of gasoline fraction.

Key words: Natural zeolite, characterization, modification, hydrocracking, waste lubricant oil.

1. Introduction e.g., acid dealumination [1-3].


On the other hand, there are widespread, abundant
Zeolites play highly important roles as acidic solid
resources of natural zeolites in Indonesia. Their
catalysts in petroleum refining and petrochemical
utilization as catalysts, however, has been little explored,
industry, including cracking, hydrocracking and
in spite of the fact that their potential effectiveness may
isomerization of hydrocarbon and hence, various
methods have been developed to modify their acid contribute to reduce industrial production costs.

properties and to improve their catalytic performance, Synthetic zeolites were used in a wide range as catalysts.
However, the synthetic zeolite was expensive and still
* imported by Indonesia. In spite of the fact that Indonesia
Corresponding authors: Wega Trisunaryanti, Processor,
research fields: materials and catalysis. E-mail: have abundant natural zeolites spread out in Java,
wegatri@yahoo.com.
Celebes, Sumatra and Timor.
176 Characterization and Modification of Indonesian Natural Zeolite for
Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction

Indonesian natural zeolites produced in West Java until no chloride ion could be detected by test using
(Bayah and Cipatuja), Center of Java (Wonosari, AgNO3 solution, after which it was dried at 120 ºC for
Yogyakarta) has been known contains large portion of 3 h and calcined at 450 ºC for 3 h. This sample was
mordenite. The zeolites showed better performance in coded as ZAAH. The ZAAH sample was then heated
crystallinity and acidity after treated with HCl [1-2]. in a microwave at 550 watt, 90 ºC for 15 min
The treatment of waste lubricant oil was an important produced the ZAAHM sample. The ZA sample was
concern of modern society to protect the environment. hydrothermally treated for 6 h produced the ZAAHd
The thermal and catalytic treatment of waste lubricant oil then followed by heating in a microwave under the
into fuel or chemical feedstock is one of the best same condition produced the ZAAHdM sample. For
methods for preserving valuable petroleum resources in modification of zeolite treatment, the ZAAHM sample
addition to protect the environment. The recycling of
was hydrothermally treated for 6 h produced the
waste lubricant oil from automobile industry was found
ZAAHMHd sample. The ZAAHMHdM was the
to be best alternative to incineration. Bhaskar [4] carried
sample of ZAAHMHd heated in a microwave. The
out the recycling of waste lubricant oil by thermal and
catalytic desulphurization over supported iron oxide ZAAHMHdM was then immersed in 1 N NH 4NO3
solution for 24 h at 30 ºC while mild stirring. After the
catalysts such as Fe/SiO 2, Fe/Al 2O3 and Fe/SiO2-Al2O3
treatment the sample was then filtered and washed
o
catalysts at 400 C. The results showed that Fe/SiO 2 with deionized water, after that it was dried at 120 ºC
catalyst facilitated the formation of lower hydrocarbons for 3 h. The resulting sample was coded as
by cracking higher hydrocarbons (about C40) present in ZAAHMHdMN and followed by microwave produced
the ZAAHMHdMNM.
waste lubricant in a small portion.
2.2 Catalyst Characterization
In an attempt to utilized Indonesian natural zeolite
as catalysts, in the present the authors undertaken The effect of modified treatments towards
characterization and modification of natural zeolite dealumination (TO4 sites) as well as acid sites in the
produced in Klaten, Indonesia, which have appeared natural zolite was analyzed by FT-IR
to consist mainly of mordenite type crystalline matter, spectrophotometer (Shimazu). Total acid site amount
and its modifications by treating with an aqueous HCl on zeolite samples was determined gravimetrically
solution, and/or hydrothermal followed by microwave using ammonia and pyridine base vapour adsorption.
treatment. Their properties to hydrocrack waste Crystallinity changed of zeolite samples was analyzed
lubricant oil collected from automotive industry in by XRD (Shimazu), and their surface perform was
Indonesia were then evaluated. The results described observed using SEM (scanning electron microscope)
in the following section. connected with EDAX-Hitachi.
2. Experiments 2.3 Catalytic Activity Test

2.1 Treatment of Zeolite Catalytic activity test was carried out in


hydrocracking process of waste lubricant oil. The
ZA (natural zeolite) produced in Klaten, Indonesia
process was conducted in a semi flow reactor system
was ground and sieved to < 100 mesh particles before
use. About 5 g of natural zeolite sample in 3 N HCl using H2 gas at flow rate of 15 mL/min.; for 60 min;
o
3 reaction temperature 450 C, feed/catalyst weight ratio
(125 cm ) was heated at 90 ºC for 30 min while
= 5 (the feed was a waste lubricant oil). The liquid
magnetically stirred. After the HCl treatment, the
sample was filtered and washed with deionized water product was analyzed by GC. Oxidation of the used
Characterization and Modification of Indonesian Natural Zeolite for 177
Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction
o shifted of the wave number from 1,064.71 to 1,072. 42
catalyst was conducted at 500 C for 1 h to determine
-1
the amount of coke. Gas product (wt.%) was cm . The successive treatment caused the increase of
quantitatively calculated by means of [(the initial dealumination. The acid treatment leached Al
weight of waste lubricant oil-coke-liquid products) framework of Indonesian natural zeolites as shown by
( initial weight of lubricant oil)] 100%. research undertaken by Trisunaryanti et al. [5].
Microwave treatment enhanced the dealumination
3. Results and Discussion
caused by the wave that activated the movement of Al
3.1 Zeolites Acidity out from the zeolite framework. The hydrothermal
treatment was also leached Al from zeolite framework.
Table 1 showed total acid amount of the zeolite
samples determinated by ammonia or pyridine base
vapour adsorption. It can be seen that the acid amount
determined by ammonia was higher than that of pyridine.
This phenomena caused by the facts that ammonia was a
stronger base than that of pyridine and pyridine has
bigger molecular size than ammonia thus pyridine can
only adsorbed in the outer surface of the zeolite.
Ammonia with smaller molecular size can be adsorbed
on outer and inside the zeolite surfaces. It can also be
seen that the total acid amount of the zeolite samples
increased by the treatment orders. These may be caused
by the dissapear of impurities in the zeolite.

3.2 Dealumination of Zeolites

Effect of the modified treatment towards


dealumination of zeolite framework was analyzed by
IR (infra red spectroscopy) based on the wave number
-1
of TO4 (T = Si or Al) site at 1,250-950 cm . The
result was shown in Fig. 1.
Fig. 1 showed that the acid treatment caused Fig. 1 Infra red spectra of: (a) ZA, (b) ZAAH, (c) ZAAHM,
dealumination of the zeolite sample indicated by the (d) ZAAHMHd, (e) ZAAHMHdM and (f) ZAAHMHdMN.

Table 1 Total acid amount in zeolite.

Sample Ammonia (mmol/g) Pyridne (mmol/g)


ZA 1.67 0.57
ZAAH 1.73 1.11
ZAAHd 1.00 0.35
ZAAHdM 1.62 1.10
ZAAHM 2.02 0.95
ZAAHMHd 2.04 1.10
ZAAHMHdM 2.05 0.87
ZAAHMHdMN 2.07 0.66
ZAAHMHdMNM 2.54 1.14
178 Characterization and Modification of Indonesian Natural Zeolite for
Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction

This fact can be described by the fact that the


3.3 Zeolites Crystallinity
treatments removed some impurities from the zeolite
It can be seen from Fig. 2 that the successive surface and pore that caused the increase of acidity
treatment to the natural zeolite did not caused the and crystallinity, thus, produced clean surface zeolite.
crystal defect. The mordenite content of the natural The phenomena increased the catalytic activity in
zeolite was about 75% (marked by M in Fig. 2). This producing liquid fraction and decreased the gas
indicated that the natural zeolite has high stability fraction production.
towards the acid and thermal treatment. Table 3 showed the distribution of the liquid fraction
that consisted of gasoline (C5-C12), diesel (C13-C20) and
3.4 Hydrocracking Result
heavy oil (> C20). The gasoline fraction was predominant
The activity of catalysts on hydrocracking of for all catalysts. The successive treatments increased the
lubricant oil was showed in Table 2. It was seen that gasoline production. The phenomena indicated that the
the successive treatment increased the liquid product. catalysts were selective
Table 2 Product distribution of hydrocracking of lubricant oil.
Catalyst Produk distribution (wt.%)
Liquid Gas Coke
ZAAHd 10.70 87.92 1.38
ZAAH 12.96 85.36 1.68
ZAAHdM 31.18 67.85 0.97
ZAAHM 37.73 61.23 1.04
ZAAHMHd 43.50 54.37 2.13
ZAAHMHdM 48.02 49.84 2.14
ZAAHMHdMN 50.15 47.42 2.43
ZAAHMHdMNM 56.80 40.48 2.72

Fig. 2 Difractogram of: (a) ZA, (b) ZAAH, (c) ZAAHM, (d) ZAAHMHd, (e) ZAAHMHdM and (f) ZAAHMHdMN.

Table 3 Product distribution of liquid fraction.


Catalyst Product distribution (wt.%)
Gasoline Diesel oil Heavy oil
ZAAHM 73.44% 12.62% 13.94%
ZAAHMHd 78.98% 10.18% 10.84%
ZAAHMHdM 80.46% 12.36% 7.18%
ZAAHMHdMN 88.37% 8.61 % 3.02%
Characterization and Modification of Indonesian Natural Zeolite for 179
Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction

Fig. 3 Chromatograms of: (a) waste lubricant oil, hydrocracking product of the lubricant oil using: (b) ZAAH, (c) ZAAHd,
(d) ZAAHM AND (e) ZAAHDM catalyst.

to the gasoline fraction. This may be due to the pore size 4. Conclusions
of the catalyst that similar to the gasoline molecularsize.
Modifications of Indonesian natural zeolite
The data was support by chromatogram of the product
produced in Klaten and their characterizations for
fractions showed in Fig. 3. It can be seen from Fig. 3 that
hydrocracking of waste lubricant oil have been carried
the heavy hydrocarbons (C40) in the waste lubricant oil
out.
was converted to the lighter hydrocarbons (C 5-C20). The The characterization results showed that various
performed zeolites showed high catalytic activity in modification of natural zeolite increased acidity and
hydrocracking of a heavy hydrocarbon feed. This result dealumination degree of the catalysts. Products of the
was in line with the result showed by Bhaskar, et al. [4]. hydrocracking were liquid, coke, and gas fractions.
Liquid products consisted of gasoline fraction (C 5-
Bhaskar et al. used Fe/SiO2 catalyst at 400 ºC and
C12), diesel fraction (C12-C20), and heavy oil fraction (>
showed only a small portion of high molecule
C20). The conversion of liquid products was increased
hydrocarbons converted into lighter hydrocarbons. In the
with the increase of catalyst acidity. The greatest liquid
present study, the modified Indonesian natural zeolites product conversion was produced by the
showed better performance in converting the high ZAAHMHdMNM catalyst, i.e., 56.80%, with selectivity
hydrocarbons to lower hydrocarbons in the range of towards gasoline, diesel, and heavy oil
gasoline fraction.
180 Characterization and Modification of Indonesian Natural Zeolite for
Hydrocracking of Waste Lubricant Oil into Liquid Fuel Fraction

fractions was 88.37%, 8.61% and 3.02%, respectively. Properties for Hydrocracking of a Paraffin. J. Jpn. Petr.
Inst. 1996, 1, 20-25.
The increase of catalyst acidity increased the [2] Trisunaryanti, W.; Syoufyan, A.; Purwono, S.; Izul, F. I.;
selectivity of gasoline fraction. Padi, P. In The Effect of Hydrochloric Acid Solution
Treatment towards Characters of Indonesian Natural
Acknowledgments Zeolite, Proceeding of the 2nd International Conference
on Chemical Sciences, Yogyakarta, 2010.
The authors thank the Ministry Office of Indonesian
[3] Trisunaryanti, W. In Effect of Sulfuric Acid Treatment
Culture and Education (DP2M-DIKTI) and the towards Indonesian Natural Zeolite for Catalytic
Lembaga Penelitian dan Pengabdian Kepada Cracking of N-Hexane, Proceeding of the National
Masyarakat Universitas Gadjah Mada (LPPM-UGM) Seminar of Chemistry, Yogyakarta, Indonesia, 2006.
[4] Bhaskar, T.; Md, U. A.; Akinori, M.; Yusaku, S. Recycling
for the financial supported under The Research
of Waste Lubricant Oil into Chemical Feedstock or Fuel
Program of HIBAH KOMPETENSI 2010. Oil over Supported Iron Oxide Catalysts. Fuel 2004, 83,
9-15.
References [5] Trisunaryanti, W.; Triyono, P. S.; Dewi, K. Characteristics
[1] Trisunaryanti, W.; Shiba, R.; Miura, M.; Nomura, M.; of Metals Supported-Zeolites Catalysts on Steam
Nishiyama, N.; Matsukata, M. Characterization and Reforming of Bioethanol. J. Materiala Science and
Modification of Indonesian Natural Zeolites and Their Engineering 2011, 5, 239-246.