RESEARCH PROPOSAL

CULTIVATION OF POLYETHYLENE AND

POLYPROPYLENE PLASTIC LOW-DENSITY PLASTIC
MIXED OIL WITH CATALYS
HIERARCHICAL H-ZSM-5

BAGAS RIMAWAN
F1C116027

CHEMICAL STUDY PROGRAM

DEPARTMENT OF MATHEMATICS AND NATURAL SCIENCE

FACULTY OF SCIENCE AND TECHNOLOGY

JAMBI UNIVERSITY
2020
 RESEARCH PROPOSAL

CULTIVATION OF POLYETHYLENE AND

POLYPROPYLENE PLASTIC LOW-DENSITY PLASTIC
MIXED OIL WITH CATALYS
HIERARCHICAL H-ZSM-5

Proposed as one of the requirements in conducting research in the

context of writing a thesis in the Chemistry Study Program

BAGAS RIMAWAN
F1C116027

CHEMICAL STUDY PROGRAM

DEPARTMENT OF MATHEMATICS AND NATURAL SCIENCE

FACULTY OF SCIENCE AND TECHNOLOGY

JAMBI UNIVERSITY
2020
 RESEARCH PROPOSAL

CULTIVATION OF POLYETHYLENE AND POLYPROPYLENE PLASTIC LOW-

DENSITY PLASTIC MIXED OIL WITH CATALYS
HIERARCHICAL H-ZSM-5

By:
BAGAS RIMAWAN
F1C116027

Approved :

Main Guide Companion Advisor

Dr. Lenny Marlinda, ST, MT Heriyanti, ST., M.Sc., M.Eng

NIP. 197907062008122002 NIP. 198405022014042001

Known :

head of the study program

Heriyanti, ST., M.Sc., M.Eng

NIP. 198405022014042001

i
 TABLE OF CONTENTS
Page
TABLE OF CONTENTS.......................................................................................ii
LIST OF TABLES .............................................................................................. iii
LIST OF PICTURE............................................................................................. iv
I. PRELIMINARY................................................................................................1
1.1 Background................................................................................................. 1
1.2 Problem Identification and Formulation...................................................3
1.3 Hypothesis............................................................................................... 4
1.4 Research purposes...................................................................................4
1.5 Benefits of Research.................................................................................4
II. THEORETICAL BASIS....................................................................................5
2.1 Plastic...................................................................................................... 5
2.2 Conversion of Plastic Waste into Oil Fuel..................................................9
2.3 Liquid Fuels............................................................................................ 11
2.4 ZSM-5 catalyst........................................................................................13
2.5 Testing of Liquid Product Characteristics.................................................15
2.6 Instrumentation......................................................................................16
III.RESEARCH METHODOLOGY.......................................................................21
3.1 Place and time.........................................................................................21
3.2 Materials and Equipment.........................................................................21
3.3 Research methods...................................................................................21
3.4 Data analysis..........................................................................................23
REFERENCES.................................................................................................. 25

ii
 LIST OF TABLES
Table Page
1. Types of plastics, codes and their use............................................................6
2. The heating value of plastic...........................................................................7
3. Thermal Properties of Plastics........................................................................9
4. Hydrocarbon Components in Fuels..............................................................10
5. Standard Solar or Biosolar..........................................................................12
6. Density of various fluids..............................................................................16
7.Previous Research Studies of Catalytic Cracking...........................................20
8.Previous Research Studies ZSM-5 Zeolite ............................................23

iii
 LIST OF PICTURE

Picture Page
1. Plastic Code Number.....................................................................................5
2. LDPE Polypropylene.......................................................................................6
3. Formula........................................................................................................ 8
4. Saturn CP-3800 / 2200MS variant GC-MS instrument................................17
5. SEM-EDX instruments................................................................................18
6. Mechanism of Action of SEM.......................................................................19
7. Bomb Calorimeter.......................................................................................20

iv
 APPENDIX LIST

Attachment Page
1. Work procedures.........................................................................................47

v
 I. PRELIMINARY

1.1 Background
Plastic is the material most widely used in everyday life. However, the
result of using excess plastic has a negative impact, in the form of plastic waste
accumulation. Several types of plastics are the biggest contributor to plastic
waste, such as LDPE (Low Density Polyethylene) and PP (Polypropylene). A type
of LDPE plastic that has excellent water resistance, which is used by
manufacturers as plastic for frozen meat wrappers, food wrappers and plastic
bags. LDPE waste accumulates as one of the biggest contributors to plastic
waste in Indonesia (Sharuddin et al. 2016).
The type of polypropylene (PP) plastic which is generally used as plastic
beverage cups, plastic bottle caps and instant noodle packaging contributes
around 16% in the plastic waste category, which is the second largest amount of
plastic after LDPE. These two types of plastic are types of plastic that cannot
biodegrade naturally because of their long average carbon content, and there is
an accumulation of waste from both types of plastic. So a solution is needed to
overcome the amount of plastic waste (Trisunaryanti, 2018).
One alternative method is the conversion of plastic waste into fuel through
pyrolysis of long chain molecules into small hydrocarbon fragments in the
absence of oxygen (Wong et al. 2017). However, pyrolysis still has disadvantages,
such as expensive operating costs and oil products formed in high hydrocarbon
bond chains. Catalytic cracking has the potential to reduce energy costs and
increase selectivity in product yields by operating at lower temperatures.
Catalytic cracking is one of the most popular processes used by the petroleum
refining industry to break down and convert large hydrocarbon molecules into
smaller and lighter ones (Castro el at. 2004).
The catalytic cracking with different solid catalysts, such as amorphous
silica-alumina, FCC (Fluid Catalytic Cracking) catalysts, clays, zeolites and
structured mesopores, have attracted particular attention to the scientific
community in recent years. (Figueiredo et al. 2016). The ability of the catalyst to
be able to break down and convert these hydrocarbons is due to the
characteristics of the catalyst caused by the acid site of the catalyst which helps
the formation of large numbers of unstable molecular fragments at lower
temperatures. The properties of porosity, acidity and crystal size play important
roles for catalytic conversion due to their high viscosity, large molecular volume,
and complex conversion pathways (Mastral et al. 2006).

1
 One of the most widely applied zeolites as catalysts in the petrochemical
industry is the ZSM-5 zeolite in isomerization, alkylation and aromatization
processes. ZSM-5 has a Si / Al mole ratio ranging from 10 to 100, and has a
high degree of thermal stability, acid stability, and high selectivity. Zeolite ZSM-5
is an important component of FCC (fluid catalytic cracking) which functions to
increase the octane number of material products. burn. However, the main
obstacle in using zeolite ZSM-5 as a catalyst is the micropore itself (Hartati et al.
2019).
The zeolite ZSM-5 micropore which is relatively small (0.55 nm) causes
molecular diffusion inhibition, both in the reactants and products to reach the
active site of the catalyst and the maximum bond breaking. Therefore, a greater
porosity, namely mesoporous (2-50 nm) is needed to facilitate molecular
diffusion. Zeolites that have both micropore and mesoporous are called
hierarchical zeolites (Mukaromah et al. 2016).
The combined micro and mesoporous ZSM-5 Zeolites have been shown to
be hydrothermal stable to at least 799oC, thus allowing form selective operation
with enhanced intracrystalline transport properties (Sartipi el at, 2013), even
under extreme conditions. Introducing mesoporous in H-ZSM-5 desilication
provides it with sufficient mesoporous surface area to be used as a catalyst
support in the FTS (Fischer – Tropsch synthesis) process. Application of this
bifunctional catalyst in FTS results in high selectivity to the liquid fraction and
reduces wax production (C20-C40).
PP and LDPE plastics have a large calorific value of 46.4 MJ / kg and 46.3
MJ / kg compared to other types of plastic materials that can be used as
alternative energy sources (Rijani and Rangkuti, 2016). Research on the use of
various plastic waste into liquid fuel by pyrolysis is still being developed at this
time, such as research conducted by Miandad et al (2016), which explains that
pyrolysis of a mixture of PP and LDPE can increase the production of aliphatic
compounds such as alkanes, alkenes and alkenes.
Jing et al (2013), also explained about the interaction of LDPE and PP
during the thermal cracking process in a closed batch reactor which was carried
out with various variations in the LDPE: PP ratio (70%: 30%), there was a
decrease in viscosity and a decrease in temperature then with the ratio of LDPE:
PP (50 %: 50%) gives a higher yield of gas products, whereas with a ratio of
LDPE: PP (30%: 70%) more aromatic compounds are found in liquid products.
According to Mastral et al. (2006) HDPE plastics were catalytically
degraded using a laboratory fluidized bed reactor to obtain high yield gas
fractions at mild temperatures, between 350 and 550 C. The catalyst used was

2
nanocrystalline zeolite H-ZSM-5. The high yield butene (25%) is found in the gas
fraction, which consists mostly of olefins. The wax consists entirely of linear and
branched paraffin, with components between C10 -C20.
Huang et al. (2010) studied several types of catalysts such as ZSM-5
zeolite, ultrastable Y (USY), mordenite (MOR), silica-alumina 71 (ASA) and MCM-
41 for polymer waste pyrolysis (LDPE / HDPE / PP / PS) in 360 ° C, obtained
higher gas yields than ZSM-5 (93.1%), USY (87.5%), MOR (90.2%), ASA (85.6%)
and MCM-41 (87.3 %). In addition, Lopez et al. (2011) studied the comparison of
zeolite ZSM-5 and Red Mud in Catalytic Cracking. The two catalysts were
characterized; zeolite ZSM-5 shows weak and strong acid sites and BET surface
area (412.0m2 g-1), while Red Mud contains lower acidity, with also weak and
strong acid sites, meso-macropores and BET surface area (27, 49m2 g-1). Both
catalysts were tested with mixed plastic waste at temperatures of 440 and 500 C
in a 3.5dm3 semibatch reactor. It has been demonstrated that ZSM-5 has a
strong effect on product characteristics and distribution on yield. Red sludge
requires a higher temperature than ZSM-5 zeolite to exert a catalytic effect, since
a yield similar to that obtained without a catalyst is obtained at 440 C, whereas
at 500 C it gives a product with a higher gas content and a higher aromatic
proportion. greater in the obtained liquid.
So that in this study using H-ZSM-5 catalysts and Hierarchical H-ZSM-5
catalysts and using liquid fuels that have been carried out in previous studies by
Ulfa et al. (2019), LDPE and PP plastic pyrolysis obtained results in the form of
liquid fuel. The PP / LDPE variations used are PP (100%), PP / LDPE (75/25%),
PP / LDPE (50/50%), PP / LDPE (40/60%), PP / LDPE (25 / 75%), LDPE
(100%). From this variation, the PP / LDPE ratio was selected (75/25%). This
variation was chosen because it has the highest heating value of 46,955 MJ /
Kg, a density of 7.02 gr / mL and a viscosity of 0.55 mm2 / s. The results of GC-
MS analysis show PP plastic pyrolysis oil, a mixture of PP: LDPE and LDPE
belonging to the type of diesel fuel that has a C12-C24 carbon chain.
Referring to this, in this study the author takes the title "PLASTIC LOW-
DENSITY POLYETHYLENE AND POLYPROPYLENE MIXED PIROLYSIS OIL
CREATION WITH H-ZSM-5 HIERARCHICAL CATALYSIS"
1.2 Problem Identification and Formulation
In the research that has been done, the pyrolysis of LDPE and PP plastics
was obtained in the form of liquid fuel. The PP / LDPE variations used are PP
(100%), PP / LDPE (75/25%), PP / LDPE (50/50%), PP / LDPE (40/60%), PP /
LDPE (25 / 75%), LDPE (100%). From these variances were selected by
comparison (25/75%). This variation (25/75%) has the highest heating value of

3
46,955 MJ / Kg, density of 7.02 gr / mL and viscosity of 0.55 mm2 / s. The
results of GC-MS analysis show PP plastic pyrolysis oil, a mixture of PP: LDPE
and LDPE belonging to the type of diesel fuel that has a C12-C24 carbon chain.
(Ulfa et al. 2019).
With the addition of ZSM-5 and Hierarikal ZSM-5 catalysts, it is hoped
that it can break the chain of bonds in oil yield, so that it is expected to produce
liquid fuel equivalent to gasoline with gasoline chain linkages (C8-C10).
Based on the description above, the problem formulation in the research
is as follows:
1. What are the characteristics of Hierarchical H-ZSM-5 (hHZSM-5) obtained
from the desilication process of H-ZSM-5 with 1 M NaOH?
2. How is the effect of the volume ratio of mixed plastic oil (PP / LDPE) and
the weight of the hH-ZSM-5 catalyst on the hydrocarbon composition of the
cracked oil?
3. How does the volume ratio of mixed plastic oil (PP / LDPE) and the weight
of the hH-ZSM-5 catalyst affect the quality of the oil?
4. How is the quality of the cracked oil with the hHZSM-5 catalyst compared
to the H-ZSM-5 catalyst?
1.3 Hypothesis
The hierarchical form of HZSM-5 can improve the quality of the pyrolysis
oil from a mixture of Polypropylene (PP) and Low-Density PolyEthylene (LDPE)
through a catalytic cracking process into a liquid fuel equivalent to gasoline
(C8-C10).
1.4 Research purposes
The objectives of this study are as follows
1. Knowing the Hierarchical characteristics of H-ZSM-5 (hHZSM-5) obtained
from the desilication process of H-ZSM-5 with 1 M NaOH.
2. Knowing the effect of the volume ratio of mixed plastic oil (PP / LDPE) and
the weight of the hH-ZSM-5 catalyst on the hydrocarbon composition of
the cracked oil.
3. Knowing the effect of the volume ratio of mixed plastic oil (PP / LDPE) and
the weight of the hH-ZSM-5 catalyst on oil quality.
4. Knowing the quality of the cracked oil with the h-HZSM-5 catalyst if
compared with the H-ZSM-5 catalyst.
1.5 Benefits of Research
The benefits expected from this research are:
1. Can determine the effect of PP: LDPE oil ratio and ZSM-5 catalyst on oil
quality.

4
2. Can know the characteristics of the oil from the catalytic cracking of
plastic types PP: LDPE with the addition of the ZSM-5 catalyst.
3. Can know the effect of adding a hierarchical ZSM-5 catalyst on oil quality.

5
 II. THEORETICAL BASIS
2.1 Plastic
Plastics are long-chain polymer compounds of atoms that bind to one
another. This chain is formed by many repeating molecular units, or monomers
(Kadir, 2012). Plastics are a type of macromolecule formed by a polymerization
process. Plastics are polymer compounds whose main constituent elements are
Carbon and Hydrogen. In the plastic manufacturing process, one of the raw
materials that is often used is Naphta, which is a material produced from the
refining of petroleum or natural gas. (Kumar et al., 2011).
Plastics in general can be grouped into two types, namely thermoplastic
and thermosetting. Thermoplastic is a plastic material which when heated to a
certain temperature, will melt and can be reshaped into the desired shape.
Meanwhile, thermosetting is plastic which, if it has been made in solid form,
cannot be melted back by heating it. Based on the properties of the two groups
of plastics above, thermoplastic is the type that allows it to be recycled. The
types of plastic that can be recycled are coded in the form of a number to make
it easier to identify and use.

Image 1. Plastic Code Number (Surono, 2013)

Table 1. Types of plastics, codes and their use

No. Type Use
Code Plastic
1 PET mineral water bottles, oil bottles
fry, juice, chili sauce bottles, medicine
(PolyethyleneTerephth bottles, and cosmetic bottles
alate)
2 HDPE (High- liquid milk bottles, lubricating jerry cans,
densityPolyethylene) and cosmetic bottles
3 PVC water hoses, toys, plastic tablecloths,
shampoo bottles and chili bottles.
(PolyvinylChloride)
4 LDPE (Low- bag crackle, Lid plastic, plastic
densityPolyethylene) meatpacking frozen, and
various other kinds of thin plastic.
5 PP (Polypropylene or plastic cups, plastic bottle caps, children's
Polypropene) toys, and margarines
6 PS (Polystyrene) box CD, glass Plastic, or place
Styrofoam food, and transparent plastic
containers

6
 7 Other (O), other types bottle milk, Plastic packaging, gallon
of plastic apart from water drinking, household appliances,
no.1 to 6 computers, electronic devices, toothbrushes,
and lego toys
(Surono, 2013)
Plastics have many applications in everyday life, but plastic also has
negative impacts such as plastic waste. Plastic waste creates problems in the
environment. The main factor is due to the nature of the plastic which cannot
decompose naturally in the soil. One solution is to recycle plastic waste.
However, this method is not very effective. Only about 4% can be recycled, while
the rest of the waste will return to the landfill. Processing plastic plastic waste
into plastic bags again or other lower grade plastic products is one effort to
overcome the problem of plastic waste (Santoso, 2010).
Polypropylene / Polpropylene (PP)
Polypropylene (Polypropylene) is a polymer plastic that is easily formed
when heated, the molecular formula for polypropylene is (-CHCH3-CH2-) n,
which is flexible, hard and resistant to fat. Polypropylene is derived from
propylene monomer which is derived from petroleum refining. The molecular
structure of propylene and polypropylene can be seen in Figure 2.
s (a) (b)

Figure 2. Structure of (a) Propylene and (b) Polypropylene

Polypropylene has a density of 0.90-0.92 g / cm3, a conductivity of 0.12

W / m, and a melting point of 160oC (320oF) as determined by the Differential
Scanning Calorimetry (DSC) method (Andarini and Purwo, 2009). Polypropylene
is a crystalline polymer produced from the polymerization process of propylene
gas. Polypropylene has a glass transition (Tg) which is quite high (190⁰C –
200⁰C), while the crystallization point is between 130⁰C– 135⁰C.
Low thermal conductivity (0.12 w / m), low surface tension, high impact
strength, resistance to organic solvents, inorganic chemicals, water vapor, oil,
acids and alkalis, good insulator but can be damaged by nitric acid
concentrated, and easily flammable by a slow flame are properties possessed by
polypropylene plastics.
The chemical properties of polypropylene are very good resistance to non-

7
oxidizing inorganic chemicals, detergents, alcohol and so on. But polypropylene
can be degraded by oxidizing agents such as nitric acid and hydrogen peroxide.
Its high crystallinity nature causes high tensile strength, stiffness and hardness
(Adoe et al., 2016).
Polypropylene is widely used in various applications, including for plastic
bags, plastic cups, buckets and bottles. Polypropylene is more heat resistant,
hard, flexible and can be translucent. Polypropylene can undergo chain
degradation when exposed to ultraviolet radiation. These types of PP and PET
plastics are usually found in glass and mineral water bottles (Nugraha et al.,
2012). The calorific value of polypropylene plastic is shown in Table 2.
Table 2. The heating value of plastic
Material Calorific value (MJ / Kg)
Polyethylene 46.3
Polypropylene 46.4
Polyvinyl 18.0
chloride 41.4
Polysterine 24.3
Petrol Coal 44.0
Diesel 43.0
Heavy fuel oil 41.1
Light fuel oil 41.9
LPG 46.1
Kerosen 43.4
e
(source; Rijani and Rangkuti, 2016)
Low Density Polyethylene (LDPE)
Polyethylene is a transparent, white thermoplastic material which has a
melting point of between 110-137⁰C. Generally, polyethylene is resistant to
chemicals. At room temperature, polyethylene is insoluble in organic and
inorganic solvents. (Landi and Arijanto, 2017) Polyethylene is the result of
polymerization from ethene (C2H4), so that the molecular formula (C2H4) is n.

Several types of polyethylene include: Low Density Polyethylene (LDPE),

High Density Polyethylene (HDPE). LDPE is a hydrocarbon polymer that has
branched carbon chains which results in weaker intermolecular strength, and
thus lower tensile strength. Low Density Poly Ethylene (LDPE) plastic is a
thermoplastic made from petroleum. First produced by Imperial Chemical
Industries (ICI) in 1933 using high pressure and free radical polymerization.

8
 Figure 3. Polyethylene Formula
LDPE is characterized by a density between 0.910 -0.940 g / cm³ and is
not reactive at room temperature, except by strong oxidizing agents and some
solvents that can cause damage. LDPE can withstand temperatures of 90ºC for a
relatively short time.
The melting point of this plastic is 248 ° F or 120 ° C with a tensile
strength of 1700 psi and a specific gravity of 0.92. Chemically, LDPE is similar
to HDPE, but physically LDPE is more flexible and has a smaller density than
HDPE. LDPE is used to wrap food. In order, this plastic has a triangle logo
numbered 4.
This type of plastic is usually used for soft food containers and bottles.
Plastics made from this material are recyclable and good for items that require
flexibility but are strong. LDPE-based plastics are practically indestructible, but
they are still good for food. The advantages of LDPE as a wrapping material are
its low price, flexible nature, and easy manufacturing process (Budiyantoro,
2010).

Characteristics of Plastic Oil from Pyrolysis

The thermal characteristics of the type of plastic are an important factor
in the process of making and recycling plastics. Thermal properties such as
melting point (Tm), transition temperature (Tg) and decomposition temperature.
The transition temperature is the temperature at which the plastic is stretched
structure so that there is a change from being rigid to being more flexible. Above
the melting point, the plastic undergoes an increase in volume so that the
molecules move more freely, which is indicated by the increase in flexibility.
Melting temperature is the temperature at which the plastic begins to
soften and turn into a liquid. The decomposition temperature is a limitation of
the liquefaction process. If the temperature is raised above the melting
temperature, the plastic will easily flow and the structure will decompose.
Decomposition occurs because the thermal energy exceeds the energy binding
the molecular chains. In general, polymers will decompose at temperatures
above 1.5 times the transition temperature. Important thermal properties data in
the plastic recycling process can be seen in Table 3 as follows:
Table 3. Thermal Properties of Plastics

9
 Type Tm Tg Max working
materi (° (° temperature
al C) C) (° C)
PP 168 5 80
HDPE 134 -110 82
LDPE 330 -115 260
PA 260 50 100
PET 250 70 100
ABS - 110 85
PS - 90 70
PMMA - 100 85
PC - 150 246
PVC - 90 71
(Surono, 2013)
2.2 Conversion of Plastic Waste into Oil Fuel
Plastic pyrolysis is a process of waste thermal degradation in the absence
of oxygen / air. Pyrolysis is used as an alternative method of disposing of plastic
waste by converting plastic waste into liquid fuels such as gasoline and diesel. In
the pyrolysis process, the polymer material is heated to a high temperature, so
that its macromolecular structure is broken down into smaller molecules,
forming various hydrocarbons. This pyrolytic product can be divided into non-
condensed gas fraction, liquid fraction (consisting of paraffin, olefins,
naphthenic and aromatic), and solid residue (Scheir, 2006).
Catalytic Cracking
Converting plastic waste into fuel oil includes tertiary recycling.
Converting plastic waste into fuel oil can be done by a cracking process.
Cracking is the process of breaking polymer chains into compounds with lower
molecular weight. The results of this plastic cracking process can be used as a
chemical or a fuel.
The pyrolysis concept of plastic waste looks simple. However, thermal
cracking often results in a mixture of low-value hydrocarbons (cocktails) which
have a wide range of hydrocarbons, typically formed from light alkane gases to
coke (Figure 4). So it is necessary to find the optimal pyrolysis conditions and /
or the most optimal catalysts to obtain commercial products (diesel or gasoline)
from plastic waste. Catalytic degradation results in a much narrower
distribution of the product carbon atomic number and reduces the reaction
temperature. Such a hydrocarbon mixture can be used as a transportation fuel.

10
 Figure 4. The schematic shows the difference in yield and length
distribution of carbon for thermal cracking and catalytic cracking (Scheir, 2006).
Catalytic Crackingis the cracking process of high molecular mass
polymers in the absence of oxygen and produces low molecular mass
compounds with the addition of a catalyst. Catalytic cracking is one of the most
popular processes used by the refining industry, breaking down and converting
large hydrocarbon molecules into smaller, lighter ones. Compared to
conventional thermal cracking, catalytic cracking has the potential to reduce
energy costs and increase selectivity and product yield by operating at lower
temperatures (Castro el at. 2004).
This characteristic occurs due to the acid site of the catalyst which helps
the formation of a large number of unstable molecular fragments at lower
temperatures. It was found that porosity, acidity and crystal size are very
important for the catalytic conversion of polyolefins due to their high viscosity,
large molecular volume and complex conversion pathways. Thus, catalytic
cracking of different solid catalysts, such as amorphous silica-alumina, FCC
catalysts, clays, zeolites and structural mesoporous, has attracted particular
attention to the scientific community in recent years (Figueiredo et al. 2016).
Combustion at low temperatures will produce toxic substances that are
harmful to health (Surono, 2013). In this condition, the main chain (CC) of the
plastic will break so that it becomes a shorter chain and eventually becomes

11
liquid and gas hydrocarbons at room temperature. The main chain can be
broken by random decomposition and depolymerization.
The addition of a catalyst is expected to reduce the temperature in the
decomposition process, accelerate the rate of decomposition, and modify the
product. Catalytic framing has been carried out considering a wide variety of
catalysts with little emphasis on the reactor design, with only simple adiabatic
batches and fixed bed reactors used. The following is a table of hydrocarbon
compounds in fuels in general:
Table 4. Hydrocarbon Components in Fuels

Fuels LPG Petrol Kerosen Diesel Heavy fuel

e oil

Hydrocarbon C3-C4 C4-C12 C12-C15 C12-C24 C12-C70

s
(Salamah and Aktawan, 2016).
The main products of pyrolysis that can be produced are charcoal, oil
and gas. The charcoal formed can be used for fuel or used as activated carbon.
Meanwhile, the oil produced can be used as an additive or mixture in fuel. While
the gas that is formed can be burned directly (Santoso, 2010).
According to Endang (2016) the pyrolysis method can convert plastic
waste into pyrolytic oil and coking solids. Some of the advantages of pyrolysis
include:
1. Low energy consumption (for example, only about 10% of the total
energy of plastic waste is used to convert pieces of plastic waste into
petrochemical products).
2. The process operates without the need for air or a hydrogen mixture
and involves no pressure.
3. Pollutants and impurities from the pyrolysis process are concentrated
in a solid residue from the process.
The cracking is carried out in a closed system, so that no pollutants can
escape. Plastics are polymers whose molecular weights cannot be determined, or
calculated. Therefore, the speed of a decomposition reaction is based on the
change in mass or mass fraction per unit time. Factors that Can Affect the
Pyrolysis Process are:
1. Time. Time affects the product to be produced because the longer the
pyrolysis process takes place, the products it produces (solid residue,
tar, and gas) will increase.

2. Temperature. Temperature greatly affects the product produced

because in accordance with the Arhenius equation, the higher the

12
 thermal decomposition constant, the greater the consequence that the
pyrolysis rate increases and the conversion increases.
3. Particle size. The particle size affects the yield, the larger the particle
size, the smaller the surface area per unit weight, so the process
becomes slower.
4. Particle weight. More and more materials are added, causing the
yield of liquid fuel (tar) and charcoal to increase.
5. Catalyst.With the addition of a catalyst can reduce the activation
energy so that it can accelerate the rate of bond breaking reaction
Based on the analysis conducted by the Oil and Gas Institute (Lemigas),
oil from used plastics has unsaturated properties. That is, the ratio between
carbon and hydrogen is not balanced so that there are links that are not filled
in. The oil is brownish yellow, but it can be used as fuel for stoves or torches
(Ani and Sumarni, 2008).
ZSM-5 Zeolite Catalyst
The ZSM-5 catalyst, Zeolite Socony Mobil-5 (MFI frame type of ZSM-5
(five)), is a zeolite aluminosilicate belonging to the zeolite pentacyl family which
was patented by Mobil Oil Company in 1975. The chemical formula is
NanAlnSi96 – nO192 · 16H2O (0 <n <27). This zeolite is manydIt is used in the
petroleum industry as a heterogeneous catalyst for hydrocarbon isomerization
reactions (Kumar et al. 2015).

Figure 5. (A) Pentasil building units;

(B) ZSM-5 zeolite lattice structure (Source: Fyfe et al. 1988)
ZSM-5 in Fig. 4B, is the best known of the entire family of lattice
structures based on pentacyl units (Fig. 4A), and has unique and highly
selective absorption and catalytic properties. ZSM-5 consists of several pentacyl
units connected together by oxygen bridges to form a pentacyl chainas shown in
Figure 4.

13
 Figure 6.The enlargement of the portion of the pentacyl layer (100) shows the
angle of SiOSi in ORTHO (top) and MONO (bottom) (Koningsveld et
al. 1990)
Si atoms are numbered at the intersection of the lines. The oxygen atom
is about halfway between the Si atoms. The circled Si atoms are in the
neighboring chain and link the chain to the (010) layer. Space groups, elements
of symmetry, and unit cell axis orientations are included in the Tlo ring of the
sinusoidal tract (Koningsveld et al. 1990)
One pentasil unit consists of eight five-membered rings. In this ring, the
knot is Al or Si and O is assumed to be tied between the knots. The pentacyl
chains are connected to each other by oxygen bridges to form a corrugated sheet
with 10-ring holes. Like the pentacyl unit, each 10-ring hole has Al or Si as a
knot with O assumed to be tied between each vertex (Čejka et al. 2007).
Each corrugated sheet is connected by an oxygen bridge to form a
structure with a 10-ring channel running parallel to the wave and a 10-ring
sinusoidal channel perpendicular to the sheet. The adjacent sheet layers are
related to the point of inversion. is 5.4-5.6 Å.
The ZSM-5 crystallographic unit cell has 96 T sites (Si or Al), 192 O sites,

14
and a number of compensating cations depending on the Si / Al ratio, which
ranges from 12 to infinity. The structure is orthorhombic (Pnma space group) at
high temperatures, but the phase transition to the monoclinic space group P21 /
n.1.13 occurs on cooling below the transition temperature, which lies between
300 and 350 K.
The ZSM-5 catalyst was first synthesized by Argauer and Landolt in
1969. A moderately porous zeolite with a channel defined by ten-membered
rings. Synthesis involves three different solutions. The first solution is a source
of alumina, sodium ions, and hydroxide ions; in the presence of excess base,
alumina will form dissolved Al (OH) 4 sol ions. The second solution has a
tetrapropylammonium cation which acts as a templating agent. The third
solution is a source of silica, one of the basic building blocks for zeolite frame
structures. Mixing the three solutions gives the superaturated
tetrapropylammonium ZSM-5, which can be heated to recrystallize and produce
a solid (Mobil Oil Corparation, US Patent, 1972).
Hierarchical Catalyst
Currently, hierarchically structured zeolites are considered to have
potential in heterogeneous catalysis, adsorption and separation, so hierarchical
zeolites have become the subject of intensive research for such applications.
Compared with conventional zeolite, this hierarchical zeolite can overcome pore
size limitations, has the ability to break large molecules.
The general synthetic approach to hierarchical zeolites previously relied
on endotemplating or exotemplating routes, such as molecules, supramolecules,
colloid crystal templates, latex ball beads, carbon fiber, mesoporous silica balls,
ceramic foam, and wood cells. However, they have the disadvantages of limited
mechanical stability and controlled morphology (Sartipi et al. 2013).
ZSM-5 is a synthetic zeolite, closely related to ZSM-11. There are many
ways to synthesize ZSM-5; general methods are as follows:

SiO2 + NaAlO2 + NaOH + N (CH2CH2CH3) 4Br + H2O → ZSM-5 +analcime

+ alpha-quartz

(Lermer et al. 1985).

ZSM-5 is usually prepared at high temperature and high pressure in a
Teflon coated autoclave and can be prepared using various ratios of compounds
containing SiO2 and Al. The catalytic conversion of polyolefin plastic waste to
fuel over a solid acid catalyst is one technology that is gaining increasing
attention due to the attractive products obtained (gasoline, diesel, fuel, etc.).
This fact has led to the development of several processes on a pilot plant

15
scale or even at a commercial level. The success of the process depends largely
on the catalyst used as they allow the working temperature to decrease and
products that have a narrow molecular size distribution can be obtained
(Schmidt et al. 2013).
Due to this, the amount of work studying the performance of different
catalysts (zeolites, silica-alumina and mesostructuring materials) in the catalytic
cracking of polyolefins is sufficient. From these works, it is concluded that, the
need to use catalysts containing highly accessible acid sites due to the large
nature of plastic waste usually leads to steric barriers or diffusion constraints
eg. in zeolite micropores. This can be overcome by using mesostructured
catalysts (Al-MCM-41, Al-SBA-15) with mesopore sizes in 2.0-30.0 nm,
nanozeolites with high external surface area (above 100 m2g − 1) (Dyer, Alan.
1988)
Desilication Mechanism
Desilication is a method of reducing or removing silica (Si) on a Zeolite
framework using an alkaline solvent (Hartati et al. 2019). The desilication
process is used to modify the zeolite framework so that it can increase thermal
stability by controlling the Al / Si ratio of the zeolite.
Releasing Si on the zeolite framework using an alkaline solution. The
desilication process shows the best results in modifying the zaolites that
havehigh Si content, such as ZSM-5. So that it can form extra-porosity on the
zeolite ZSM-5 framework (Groen et al. 2005).
Desilication is used as a method to convert the pores in the HZSM-5
structure into a hierarchical pore structure through a washing process with an
alkaline solution (alkaline treatment) such as with NaOH solution. According to
Yoo et al (2012), during desilication the solute contains silicates,
aluminosilicates, and ZSM-5 crystal fragments (Figure 6). After the desilication
process, HZSM-5 is expected to have a mesoporous structure in addition to a
micropore structure.
Desilication via alkaline treatment gives H-ZSM-5 a pore size and volume
similar to that of amorphous SiO2 (conventional carrier), while acid treatment
removes the extraframework aluminum produced and increases FTS catalyst
activity. The acid-catalyzed reaction model and deactivation induced by zeolite
acid sites confirm that hydrocracking of primary FTS hydrocarbons on zeolites
greatly increases selectivity against C5-C11 (gasoline fraction) (Sartipi et al.
2013).
The reaction mechanism for the formation of the Hierachical H-ZSM-5
catalyst is as follows:

16
 NH4-ZSM-5 H-ZSM-5 + NH3 (calcination 550 oC, 5 hours)

HZSM-5 + NaOH Na-ZSM-5 (hierarchical) + H2O (desilication)

Na-ZSM-5 + NH4NO3 NH4-ZSM-5 + NaNO3 (ion exchnage)

NH4-ZSM-5 + HNO3 acidiy Increase

NH4-ZSM-5 hH-ZSM-5 + NH3

The zeolite frame contains more silicon than aluminum and it is easier to
create micro and meso interconnecting networks during silicon removal. In this
context, Groen et al (2004) demonstrated the formation of mesopores for the MFI
type zeolite using a desilication process in an alkaline medium (Figure 6). The
optimal Si / Al ratio in the 20-50 range results in a pore range of 5-20 nm. At a
Si / Al ratio ≤ 15, pore formation is limited and almost no mesoporous is created
because the Al atom will prevent the extraction of Si atoms. While the Si / Al
ratio ≥200, too much Si is lost and causes the pore size to increase (meso-
macropore).

Figure 6. Schematic depiction showing the preparation of meso-zeolite materials

with desilication (top right) and desilication / re-assembly
processes (bottom right) (Yoo et al, 2012)

17
 Al prevents the
Si / Al 15 extraction of Si

Aluminum Mesoporous
 Silicon formation is
limited

Optimal Si / Al
range
Si / Al =
25-50 Mesopores are
formed in the 5-
20 nm range

Eliminating lots
of Si
Si / Al  Large meso-and
200 macropores are
formed

Figure 7. Illustration of Si / Al ratio to MFI zeolite desilication with NaOH

treatment and the mechanism of pore formation (Groen et al., 2004)

2.3 Liquid Fuels

Liquid fuel is a combination of hydrocarbon compounds obtained from
nature or artificially. Generally, liquid fuel comes from petroleum. In the future,
the possibility of using liquid fuel derived from oil shale, tar standard, coal and
biomass will increase. Petroleum is a natural mixture of liquid hydrocarbons
with a small amount of sulfur, nitrogen, oxygen, very few metals and minerals
(Murni, 2013).
Some of the advantages of liquid fuels compared to solid fuels include:
- Cleanliness of the combustion
- Using a more compact combustion tool
- Handling is easier.
One of the drawbacks of this liquid fuel is that it has to use a fairly
complex refining process.
According to (Adoe et al., 2016), Diesel fuel is also commonly called
debgan light oil or diesel, which is a mixture of hydro-carbon that has been
distilled after gasoline and kerosene from crude oil at a temperature of 200 ° C

18
to 340 ° C . This type of fuel or commonly referred to as diesel fuel is mostly
used to drive Diesel engines. Diesel fuel has the following main properties:
- Colorless or slightly yellowish and smelly.
- It is thin and does not evaporate below normal temperature.
- High flash point (40 ° C to 100 ° C).
- Burns spontaneously at 350 ° C, slightly below gasoline.
- Specific gravity 0.82 to 0.86.
- Generates large heat (10,500 kcal / kg).
- Has a sulfur content greater than gasoline.
Based on the Minister of Energy and Mineral Resources Regulation No.
25 of 2013 concerning the supply, utilization and trading system of biofuels as
other fuels for diesel or biodiesel specifications, it has the following standard
limits:
Table 5. Standard Solar or Biosolar
Parameter Unit Limitation
Density at 15 ° C (kg / m3) 815 - 860
Kinematic Viscosity at 40 ° C mm2/ 2.0 - 4.5
Flash Point (° C) sec (° C) Min. 52
Pour Point (° C) (° C) Max. 18
Water content mg / Max. 500
kg
Source: Ministry of Energy and Mineral Resources Regulation No. 25 of
2013.
Among the many properties of diesel fuel that affect engine
performance, there are 3 main parameters that need to be considered related
to fuel consumption, namely density, viscosity, water content and heating
value.
According to (Adoe et al., 2016), the requirements for using diesel as
fuel must pay attention to the quality of diesel, including the following:
1. Flammable, meaning that the combustion delay time must be short
or short, so that the engine is easily started. Solar should allow gentle engine
operation with minimal knocking.

2. Keep it thin at cold temperatures (not easy to freeze), indicating that

diesel fuel must remain liquid at low temperatures so that the engine will be
easy to turn on and turn gently
3. Lubrication power, meaning that diesel fuel also functions as fuel
and lubricant for injection pumps and nozzles. Therefore it must have good
lubrication properties and power.
4. Viscosity, related to lubrication requirements, in the sense that the
diesel fuel must have a good thickness so that it is easy to spray by the

19
injector.
5. Sulfur content, a characteristic of sulfur that can damage the use of
engine components, requires that the sulfur content of diesel fuel be as small
as possible (<1%).
6. Cetane number, that is, a way to control diesel fuel in the ability
to prevent knocking, a larger level has a better capability.
2.4 Testing Characteristics of Viscosity Pyrolysis Oil
Internal friction in a fluid is expressed in terms of viscosity or viscosity
in units of poise. Viscosity can also be defined as the ability of a substance to
flow in a particular medium.
One way to measure the value of the viscosity of a liquid is to use an
oswald viscosimeter. The method of measurement using the oswald
viscosimeter is by comparing two types of fluids, namely aquadest with other
liquids, each with a thickness of ηa and ηx, both of which have the same
volume and flow through pipes of the same size. Because the two flow
substances have the same volume but different viscosity, the discharge of the
two is also different, for example Qa and Qx. Thus the time needed to drain
the aquadest and the liquid with the same volume is also different, for
example ta and tx. Thus:
In this study, viscosity was measured at room temperature conditions. Where :

Ƞx = Ƞa
Information : Ƞa = water viscosity

Ƞx = viscosity ta =
liquid flow time tx =
water flow time
a = density of water
x = density of the liquid

Density
Density is a measurement of the mass per unit volume of an object. The
higher the density of an object, the greater the mass per volume. The average
density of an object is the total mass divided by its total volume. An object that
has a higher density will have a lower volume than an object with the same
mass which has a lower density The SI unit of density is kg / m3. Density serves
to determine a substance because each substance has a different density. The
formula for determining density is:
m
ρ=
v
Information : ρ = density (kg / m3)

20
 m = mass (kg)
v = volume (m3)
Table 6. Density of various fluids
No. Type of Oil Density (kg / m3)
1. Fuel 0.68
2. Alcohol 0.79
3. Alkil 1,025
4. Sea water 13.6
5. Mercury 1
6. Air Blood 1.05
7. Water 1.29
8. Oil 0.78-0.81
Source: Giancoli, 1997
2.5 Previous Research Studies

Table 7.Previous Research Studies of Catalytic Cracking

N Research / Year Title Methods and Results

o.
Malhatul Ulfa, Utilization of PP PP and LDPE plastic waste is cut
1.
Sutrisno, and LDPE Type into small pieces, then put into
Heriyanti / 2019 Plastics into Liquid the reactor as much as 4 kg with
Fuels through the a variation of the LDPE ratio of
Pyrolysis Method 100%, (PP: LDPE) 75%: 25%,
50%: 50%, 40%: 60%, 25 %:
75%, S PP 100%. Furthermore, it
is heated using 12 kg of LPG gas
fuel at a temperature range of 60-
1800C for 2-4 hours. The results
obtained areThe best ratio of
mixed pyrolysis is PP: LDPE
(75:25)% with the highest heating
value of 46,955 MJ / Kg, density
7.02 gr / mL and viscosity of 0.55
mm2 / s.The results of GC-MS
analysis show PP plastic pyrolysis
oil, a mixture of PP: LDPE and
LDPE belonging to the type of
diesel fuel that has a C12-C24
carbon chain.

21
 Priyatna, et al / Catalytic Cracking Fly ash (FA) samples originating
2.
2015 of Polypropylene from Indonesian coal are used as
(Pp) Plastic Waste raw material for the catalytic
into Oil Fuel Using zeolite synthesis. The
Zeolite A Catalyst physicochemical properties of FA
and zeolite A are characterized by
atomic absorption spectroscopy
(AAS) and X-ray diffraction (XRD).
The fuel oil fraction obtained by
using a catalyst of 1.5% Zeolite A
and a temperature of 350oC is
32.56% gasoline and a kerosine-
diesel mixture of 29.07%. Using a
catalyst of 1.5% Zeolite A and a
temperature of 400oC is 36.28%
gasoline and 34.51% kerosine-
diesel mixture. The use of a
catalyst of 1.5% Zeolite A and a
temperature of 450oC is 43.97%
gasoline and 31.03% kerosine-
diesel mixture. And without a
catalyst at 450oC is 39.80%
gasoline and a kerosine-diesel
mixture of 32.56. %.
Juwono, et al / Catalytic Hydrocarbon fuel (C8-C12) from
3.
2019 Conversion of propylene plastic waste (PP) has
Polypropylene been successfully synthesized
Plastic Waste with through the catalytic conversion
Silica Alumina method using an Al-MCM-41
Ceramic Catalyst catalyst of 11.18 grams, the use
to Produce of the catalyst was also repeated
Alternative Fuels of three times, namely with sample
Hydrocarbon code A, B, and C. The results
Fraction showed that A, B, and C each
produced hydrocarbon fuel (BBH)
with a gasoline fraction
composition (C8-C12) of 92.76;
91.92; and 90.58%. The repeated

22
 use of the catalyst caused a
decrease in the composition of
the hydrocarbon fraction (C8-
C12) as evidenced by the TON
(Turn Over Number) value which
increased from 0.075% / gram to
0.156% / gram). Based on the
physical tests that have been
carried out, including boiling
point, flash point, density,
viscosity, and calorific value, it
can be proven that hydrocarbon
fuel A,
Wahyudi, et al / Processing of The catalyst is used as a catalyst
4.
2016 Polypropylene (PP) for cracking plastic waste
Plastic Waste into because it contains crystals
Oil Fuel with the contained in the standard zeolite
Catalytic Cracking X, namely Faujasit. The highest
Method Using yield (%) was obtained at a
Synthetic Catalysts temperature variation of 450oC
and a catalyst / plastic ratio of
1.5%, which was 76.09%. The
resulting calorific value is 10,884
cal / g or the equivalent of 45.56
MJ / kg and the product density
is in the range of gasoline,
kerosene and diesel fuel. From
the results of GC-MS analysis,
the product contains fuel
fractions of gasoline, kerosene
and diesel fuel of 60.46% and
7.48%. For further research, it is
necessary to separate the product
fraction and upgrade it to obtain
the desired type of fuel.
Table 8.Previous Research Studies ZSM-5 Zeolite
Design Of Hierarchical Desilication in alkaline media
1. Verboekend
Zeolite Catalysts By has become a widely applied
and Ramı´rez
Desilication preparation method for

23
 adapting this modified zeolite,
/ 2011
due to the optimal combination
of efficiency and simplicity. This
review presents the latest
developments that have
broadened general
understanding and made this
top-down treatment highly
flexible, controllable and
scalable. The design aspects of
mesoporous zeolites for catalytic
applications are emphasized,
including the formation of the
synthesis-property-function
relationship. The base
treatment is a key step in
strategic combination with other
post-synthesis modifications
towards superior zeolite
catalysts.
Desilication was carried out in a
2. Sadowska et Desilication of highly
NaOH solution and a mixture of
al / 2017 siliceous zeolite ZSM-5
NaOH and TBAOH
with NaOH and NaOH /
(tetrabutylamine hydroxide) at
tetrabuty amine
338 and 353 K for 0.5 hours.
hydroxide
100 ml of the solution were
added to 3.0 g of zeolite. If the
desilication is carried out with
only NaOH solutions, 0.1, 0.2,
and 0.5 M are used. The
NaOH / TBAOH mixture has
concentrations of 0.2 and 0.5
M. For the 0.2 M ratio of the
TBAOH / (NaOH + TBAOH)
mixture (denoted immediately
as R) is 0.1 and 0.4, for a
solution of R the ratio is 0, 5 M
is 0.1. After desilication, the

24
 suspension is cooled in an ice
bath and filtered. At this stage,
the collected filtrate sample is
taken for analysis. The
structured zeolite is
hierarchically washed with
water to a neutral pH.
Subsequently, a fourfold ion
exchange with 0.5 M NH4NO3
was carried out at 333 K for 1
hour. Finally, the zeolite is
filtered again, washed, and
dried at room temperature. The
results obtained are the results
of chemical analysis and XPS
analysis showed that the
desilication of ZSM-5 highly
silica from Si / Al = 164 was
more effective in the surface
zone than in bulk zeolite. For
lower Si / Al zeolites = 31.6
more effective desilication than
bulk, what is explained by
excess Al at the surface and
protection of neighboring Si
atoms with negative AlO4
charge against OH attack.
Zeolite beta crystals (Si / Al =
3. Groen et al / Mesoporous beta zeolite
35) synthesized in fluoride
2008 obtained by Desilication
medium were treated in 0.2 M
NaOH solution for mesoporous
formation by selective extraction
of silicon skeleton. The 16-
parallel reactor was used to
study the effect of treatment
time and temperature on the
physico-chemical properties of
zeolites, which were

25
 characterized by the adsorption
of ICP-OES, XRD, N2 at 77 K,
SEM, TEM, DRIFTS, and ATR-IR
in situ. As a result, this is
derived from substantial
mesoporosity and possibly
improved transport, but
negatively impacts the micro
and acid properties of the
resulting sample. As a result,
the alkaline treated beta zeolite
exhibits lower catalytic activity
in acid-catalyzed liquid phase
benzene alkylation than the
micropore pure parent material.
Hierarchical H-ZSM- The mesostructure is made in
4. Sartipi et al /
5supported cobalt for the crystallite H-ZSM-5 by
2013
direct synthesis of demetalation through
subsequent alkaline and acid
gasoline-range
treatment. Desilication via
hydrocarbons from
alkaline treatment gives H-ZSM-
syngas: Advantages,
5 a pore size and volume similar
limitations, and
to that of amorphous SiO2
mechanistic insight.
(conventional carrier), while acid
treatment removes the
extraframework aluminum
produced and increases the
activity of the FTS catalyst. The
acid-catalyzed reaction model
and the induced deactivation of
the zeolite acid sites confirm
that hydrocracking of primary
FTS hydrocarbons on zeolites
greatly increases selectivity to
C5-C11 (gasoline fraction). On
the other hand, the strong Co-
zeolite interactions as expressed
by TPR (H2) resulted in lower

26
 stabilization of the Co-
coordinated sites (as expressed
by IR-assisted CO adsorption)
and in higher selectivity to
methane.
2.6 Instrumentation
Gas Cromathography Mass Spectrometry (GC-MS)
GC-MS is a method of separating organic compounds which uses two
methods of compound analysis, namely gas chromatography (GC) to
quantitatively analyze the number of compounds and mass spectrometry (MS) to
analyze the molecular structure of the analyte compound. The use of gas
chromatography can be combined with mass spectroscopy. The combination of
the two can produce more accurate data in identifying compounds that are
accompanied by their molecular structure (Skoog et al., 1991).
GC-MS consists of two parts, namely gas chromatography (GC) and mass
spectrometry (MS), each of which has a different function. GC serves to separate
the compounds in the sample. Separation occurs in the column. The principle of
separation is based on the difference in the volatility of the compounds and also
on the interaction with the stationary phase. The temperature and holding
gradient applied to the column to optimize the separation process of the
compounds.
The compounds that have been separated on the GC column will enter
MS. MS consists of three parts, namely an ion source, a mass analyzer and a
detector. Compounds that enter MS will undergo ionization and fragmentation
into fragment ions. ionization occurs due to the presence of electrons from the
ion source. The fragment ions will enter the mass analyzer and will be separated
based on their m / z value. Fragment ions that have a small m / z value will
enter the detector faster than fragment ions that have a large m / z value. The
output from the detector is a diagram of the relationship between the m / z
value and the relative intensity of the fragment ions of a compound. Each
compound has a different m / z pattern, so that we can identify a compound by
comparing it with the spectral patterns in the literature.

27
Figure 7. GC-MS Instrument Saturn Variant CP-3800 / 2200MS (Surono, 2013)
In the GCMS (Gas Chromatography mass spectrometry) analysis method
is to read the spectra contained in the two combined methods. In the GC
spectra, if there is that the sample contains many compounds, it can be seen
from the number of peaks in the GC spectra. Based on known retention time
data from the literature, it can be seen which compounds are present in the
sample.
Next is to enter the suspected compound into the mass spectroscopy
instrument. This can be done because one of the uses of gas chromatography is
to separate compounds from a sample. After that, the results obtained from
mass spectroscopy on different charts. The information obtained from these two
techniques combined in the GC / MS instrument is none other than the result of
each spectra. For GC spectra, the most important information obtained is the
retention time for each compound in the sample. As for the MS spectra,
information can be obtained about the relative molecular masses of the sample
compounds (Skoog et al., 1991).
Calorimeter Bomb
The calorific value of the fuel can be determined using a calorimeter. The
fuel to be tested for its heating value is burned using a coil of wire electrified in a
chamber called a bomb and immersed in water. Fuel that reacts with oxygen will
produce heat, this causes the calorimeter temperature to rise. To keep the heat
generated from the fuel reaction with oxygen from spreading to the outside
environment, the calorimeter is coated with an insulating material (Wibowo,
2011).
The calorific value is a number which expresses the amount of heat /
calories generated from the process of burning a certain amount of fuel with
air / oxygen. Mahmud (2010), defines the calorific value as the calorific energy
contained in each unit of fuel. This calorific value analysis is determined using
the Bomb Calorimeter instrument. The sample has a calorific value that comes
from the energy released during the sample combustion process.

28
 The calorific value is the heat produced by the complete combustion of 1
unit weight of solid or liquid fuel or 1 unit of volume of gas fuel in the raw state.
The gross heating value is the heat produced when all the water that was
originally liquid after combustion condenses into liquid again. The lower calorific
value (net heating value) is equal to the upper heating value minus the heat
required by water contained in the fuel and water formed from combustion of
fuel which evaporates at 25oC at a constant pressure. The following is an image
of the bomb calorimeter which can be seen in Figure 7.

Figure 8. Bomb Calorimeter (Handayana, 1994)

X-Ray Diffraction (XRD)
One technique used to determine the structure of a crystalline solid is the
powder X-ray diffraction method (X ray powder diffraction) as shown in Figure 6.
The sample is a solid powder crystalline which has a small size with a grain
diameter of about 10 7-10 4 m is placed on a glass plate. X rays are obtained
from electrons which exits the hot filament in a vacuum at high tension, at high
speed striking a metal surface, usually copper (Cu).
The X-rays shoot the crystalline solid sample, then diffract the rays in all
directions by complying with Bragg's Law. The detector moves at a constant
angular velocity to detect the X-ray beam being diffracted by the sample. A
sample of a powder or a crystalline solid has lattice planes arranged randomly
with various possible orientations, as well as the crystal particles contained
therein. Each set of lattice planes has some specific angular orientation angle, so
X-ray diffraction satisfies Bragg's Law:
n λ = 2 d sin θ (1) with; n : diffraction order (1,2,3,…); λ: Length of X ray;d : Grid
spacing θ : Diffraction angle.

29
 Figure 9. Bragg reflection scheme.

The output form of the diffractometer can be analog or digital data. The
analog data record is a line graph that is recorded per minute synchronous, with
the detector at an angle of 2θ per minute, so that the axis equals an angle of 2θ.
Meanwhile, digital recording informs the intensity of the X-rays against the total
light intensity per second. The resulting diffractogram pattern is a series of
diffraction peaks with varying relative intensities along a certain 2θ value. The
relative intensity of the series of peaks depends on the number of atoms or ions
present, and their distribution in the unit cell of the material. The diffraction
pattern of each crystalline solid is very distinctive, which depends on the crystal
lattice, the parameter units and the wavelength of the X-rays used. Therefore,
BET (Brunauer-Emmett-Teller)
Brunauer-Emmett-Teller (BET) aims to describe the physical adsorption
of gas molecules on solid surfaces and serve as the basis for important analytical
techniques for the measurement of specific surface area of materials. In 1938,
Stephen Brunauer, Paul Hugh Emmett, and Edward Teller published the first
articles on BET theory in the Journal of the American Chemical Society.
The BET theory applies to multilayer adsorption systems and usually
uses a probing gas which does not react chemically with the surface of the
material as an adsorbate to measure specific surface area. Nitrogen is the most
commonly used gaseous adsorbate for investigating surfaces by the BET
method. For this reason, standard BET analyzes are most often performed at the
boiling temperature of N2 (77 K). Further probe adsorbates are also used, albeit
at a lower frequency, allowing measurement of surface area at different
temperatures and measurement scales.
This includes argon, carbon dioxide, and water. Specific surface area is a
scale dependent property, with no single true value of the specific surface area
that can be determined, and thus the amount of specific surface area
determined by BET theory can depend on the adsorbed molecules used and the
adsorption cross section.

30
 The concept of this theory is an extension of Langmuir's theory, which is
a theory for monolayer molecular adsorption, for multilayer adsorption with the
following hypothesis:
1. Gas molecules are physically adsorbed on the solid in layers without
limits;
2. Gas molecules only interact with adjacent layers; and
3. Langmuir theory can be applied to every layer.
4. The adsorption enthalpy for the first layer is constant and greater than
that for the second (and higher) layer.
5. The adsorption enthalpy for the second (and higher) layer is the same
as the enthalpy for liquefaction.
The resulting BET equation is:

W = weight of gas adsorbed

P / P0 = relative pressure
Wm = weight of adsorbate as one color
C = BET constant

Figure 9.The BET model of multilayer adsorption, that is, the random
distribution of sites covered by one, two, three.
Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-
EDS)
Scanning Electron Microscopy (SEM) is a tool that can form surface
shadows. The surface structure of a material to be tested can be studied with an
electron microscope because it is much easier to study the surface structure of
the material directly. Basically, SEM uses signals that are generated by electrons
and reflected, this is called a secondary electron beam. The most common
accessory equipped with SEM is the energy-dispersive x-ray detector or EDX
(sometimes referred to as EDS) (Kroschwitz, 1990).

31
 Figure 10.SEM-EDX instrument (Handayana, 1994).
The characterization results of the SEM-EDX instrument can provide
information about the topography, morphology, and composition of the analyzed
sample (Kroschwitz, 1990). Topography is the ability to analyze surfaces and
textures. Morphology is the ability to analyze the shape and size of the sample
object. Composition is the ability to analyze the composition of an object's
surface quantitatively and qualitatively.
The SEM instrument uses the scanning principle, namely the electron
beam is directed at a point on the specimen surface. The movement of electrons
is directed from one point to another on the specimen surface. If a beam of
electrons is shot on the surface of the specimen, some of the electrons will be
reflected back and part of it will be transmitted. If the surface of specimen 19 is
uneven, there are many curves, folds or holes, then each part of the surface will
reflect electrons with a different number and direction then will be captured by
the detector and will be forwarded to the screen system.

Figure 11.The Working Mechanism of SEM (Abdullah and Khairurrijal,

2009).
The results obtained are a clear picture of the specimen surface in three
dimensions. In surface morphology studies using SEM, its use is very limited
but provides useful information on surface topology with a resolution of about
100 Å (Stevens, 2001).

32
 In SEM, the high-energy electron beam hits the surface of the material.
The reflected electrons and the secondary electrons are re-emitted at an angle
depending on the surface profile of the material. The specific energy X-rays
emitted by each atom in a compound can be detected with Energy Dispersive X-
Ray Spectroscopy (EDX), which is an analytical technique used to analyze
elements or characterize the chemical constituents of a sample. EDX analyzes X-
ray emission by elements in particles (Goldstein et al., 1981).

33
 III. RESEARCH METHODOLOGY

3.1 Place and time

The research was conducted at the Final Project Laboratory of the
Faculty of Science and Technology, Jambi University which was held at June -
October 2020.
3.2 Materials and Equipment
The materials needed, namely oil from pyrolysis of a mixture of PP and
LDPE plastic waste with a comparative variability (75/25)%). This variation was
chosen because the best ratio of mixed pyrolysis was PP: LDPE (75:25)% with
the highest heating value of 46,955 MJ / Kg, density 7.02 gr / mL and viscosity
of 0.55 mm2 / s. The results of GC-MS analysis show PP plastic pyrolysis oil, a
mixture of PP: LDPE and LDPE belonging to the type of diesel fuel that has a
C12-C24 carbon chain. (Ulfa et al. 2019).
Commercial activated carbon, commercial catalyst Zeoilit ZSM-5
Ammonium (NH4-ZSM-5) obtained from AlfaAesar with code
(ALFA45881),NaOH, NH4NO3, HNO3 and aquades.The specifications of the
NH4-ZSM-5 catalyst can be seen in table 9.
Table 9. Specifications NH4-ZSM-5
No. Information Information
1. Product name ZSM-5 Ammonium Zeolite
2. Product Code 45881
3. CAS Number 1318-02-1
4. MDL Number MFCD00132601
5. Chemical Formulas NanAlnSi96 – nO192 · 16H2O (0
<n <27)
(SiO2: Al2O3)
6. Surface area 425 m2 / g
Source: AlfaAesar (https://www.alfa.com/en/catalog/045881/)
In this study, the tools used were a set of glassware (Pyrex or iwaki
brands), cracking reactor and catalytic cracking reactor, magnetic stirrer,
analytical balance, pycnometer, oswald viscometer, thermometer, Gas
Chromatography-Mass Sepectrometry (GC-MS), bomb calorimeter, X-Ray
Diffraction (XRD), SEM EDX, BET (Brunauer-Emmett-Teller)
3.3 Research procedure

This research was conducted in several stages with the scheme as shown in
Appendix 1.
H-ZSM-5 and hH-ZSM-5 catalyst preparation
The hierarchical H-ZSM-5 catalyst preparation method was carried out
according to the procedure carried out by Sartipi, et al (2013). Solid ammonium-

34
ZSM-5 was calcined at 550 oC for 5 hours to obtain the H-ZSM-5 form. Then,
the H-ZSM-5 powder was desilicated with 1 M NaOH solution (vol. Base / weight
= 8.0 cm3 g-1) while stirring at 70oC for 1 hour using reflux. This treatment is
followed by immediate direct cooling in an ice water bath and centrifugation to
separate the zeolite powder from the solution.
The zeolite solid was washed with distilled water to remove the remaining
NaOH until the pH was neutral. To remove Na ions that remained in the pores,
ion exchange was carried out on the zeolite with an excess of 0.1 M NH4-NO3
solution, at room temperature for 15 minutes in three cycles. Each cycle is
separated by a washing process. This solid was stored overnight at 60oC, then
dried at 120oC for 12 hours. Then it was calcined at 550 oC for 5 hours. The
hH-ZSM-5 solid was re-retained with 1 M HNO3 (vol. Acid / weight = 28.6 cm3
g-1) at 70 oC for 2 hours while stirring in an oil bath. After sudden cooling, the
samples were washed with distilled water until the pH was neutral. This solid
was stored overnight at 60oC, then dried at 120oC for 12 hours. Then it was
calcined at 550 oC for 5 hours. The yield obtained is calculated. The zeolite
which was washed with acid is denoted as "hH-ZSM-5". The yield obtained is
calculated.
Catalytic Cracking Process
The catalytic cracking reaction was carried out in the reactor shown in
Appendix 1. For each catalytic cracking reaction test, the variations in the
volume of oil from pyrolysis were 200, 250, 300, 350 and 400 mL and 0.5 g of H-
ZSM-5 catalyst, and 0.5 g of hH-ZSM-5 catalyst was introduced into the reactor
at a reaction temperature of 200 ° C for 60 minutes. The research matrix
showing the research variables can be seen in Table 3.1.
After the reaction time has been reached, the reactor is allowed to cool
down to room temperature. Part of the product gas is condensed and collected in
the erlenmeyer. The remaining liquid product in the reactor is separated from
the catalyst solids by means of a vacuum filter.The liquid product is removed
and distilled. Before being distilled, the liquid product is adsorbed with activated
carbon to remove impurities.
Fractionation of Cracked Liquid Products
The liquid product that has been obtained is first carried out with an
adsorption process with activated carbon according to the previous procedure
(Sylvilia et al. 2009). The adsorption process is carried out by mixing 250 mL of
liquid product with 2.5 g of adsorbent in erlenmeyer (ratio of oil to carbon = 100:
1). then carried out while stirring for 20 minutes at 30oC. After that, the
purification results are deposited for 2-3 hours. Furthermore, the liquid product

35
is centrifuged and filtered to separate the remaining adsorbent. The liquid
product is then distilled according to the previous method (Serrano et al. 2017).
The liquid product is then distilled at a distillation temperature of 210oC
to produce 2 separate products, namely the light fraction (C5-C14) and the
heavy fraction (C10– C40). Products heavier than C40 are expected not to be
detected. Analysis of the liquid hydrocarbon composition of the light and heavy
fractions was carried out using the GC-MS instrument. Product selectivity is
expressed by considering four groups of hydrocarbons: gas (C1-C4), gasoline (C5
- C12), light diesel (C13 - C18) and heavy diesel (C19 - C40). The measurement
of the physical properties of each fraction including heating value, density and
viscosity was also carried out.

Figure 3.1 Pyrolysis reactor and catalytic cracking of plastic oil

Catalyst Characterization

XRD (X-Ray Diffraction)

To observe the crystal phase changes in H-ZSM 5 before and after the
desilication process was carried out.
SEM (Scanning Electron Microscope) EDX
To observe and describe the surface area of the ZSM-5 catalyst and serve
as the basis for an important analytical technique for measuring the surface
area of the ZSM-5 catalyst.
BET (Brunauer-Emmett-Teller)
To observe and explain the physical adsorption of gas molecules on the
surface of the ZSM-5 catalyst and serve as the basis for an important analytical
technique for the measurement of the surface area of the ZSM-5 catalyst.

Characterization of Cracked Liquid Products

Analysis of the Composition of Hydrocarbons

For the determination of the chemical compounds of Cracked Liquid

36
Products and the percentage distribution of the carbon number of chemical
compounds, it was carried out using the Gas Chromatography-Mass
Sepectrometry (GC-MS) instrument.
Determination of Calorific Value
Parr Calorimeter and Water Handling ensure that it is filled with water
before use. The Parr Calorimeter and Water Handling are turned on by pressing
the "On" button on the rear of the machine. Then the "Heating and Pump"
button is pressed in the "On" condition. The equipment is left until it reaches a
stand-by condition, which is indicated by an illuminated “Start” button. The set
sample is prepared on the oxygen bomb. The prepared oxygen bottle gas stream
was opened with oxygen pressure at 450 atm for 1 minute. The bucket is filled
with water from water handling. After the Parr Calorimeter is ready (stand by),
the bucket that has been filled with water is inserted into the Parr Calorimeter.
1.0000 ± 0.0001 gram sample GA sized coal was weighed and put into oxygen
bomb from the calorimeter meter. Start the analysis process by pressing the
start button and waiting for it to finish. Remove the oxygen bomb from the parr
calorimeter and exhaust the gas using the outlet hose. The oxygen bomb is
washed, dried and ready to use for further analysis. The water in the bucket is
replaced with new water from water handling. Then a print out of the analysis
was carried out, following the correction data: fuse, acid, total sulfur. Turn off
the parr calorimeter and water handling by pressing the "OFF" button on the
rear of the machine after the GCV analysis is complete.
Determination of Plastic Oil Viscosity
The viscosity of plastic oil can be done according to Sylvilia (2009), using
an Ostwald viscometer. Oswald Viscometer for measuring samples that are thin
or less viscous. In this study, viscosity was measured only at room temperature
(30 ° C).
Determination of Plastic Oil Density
The pycnometer is cleaned and weighed to determine the empty weight.
The pycnometer is then filled with pyrolysis oil, filling is carried out until the
sample in the pycnometer overflows and there are no air bubbles in it. After
closing, the pycnometer was immersed in a water bath at 15o C for a few
minutes then removed and dried then weighed the pycnometer and its contents.
Data analysis
The pyrolysis oil of PP / LDPE plastic mixture (25:75)% was obtained
from the results of pyrolysis that had previously been done (Ulfa, 2019). Table
3.1 is a research matrix that shows the number of variables worked on in this
study.

37
 Table 3.1 Research Matrix

Cracking Liquid Product Analysis

PP /
Weight Weight
LDPE
No. H-ZSM-5, hH-ZSM-5
plastic Hydrocarbon
(g) (g)
oil, (mL) Composition Calorific
Viscosity Density
(C5-C14) and / or Value
(C15-C40)
1. 200 0.5 0

2. 250 0.5 0
3. 300 0.5 0
4. 350 0.5 0
5. 400 0.5 0
6. 200 0 0.5
7. 250 0 0.5
8. 300 0 0.5
9. 350 0 0.5
10. 400 0 0.5
Cracking Liquid Product Analysis

38
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41
Annex 1. Methodology

1. Hierarchical H-ZSM-5 Catalyst Synthesis (hH-ZSM-5)

Ammonium ZSM-5 (AlfaAesar)

 Calcined at 550 oC for 5 hours to obtain the H-ZSM-5 form.

 Desilicate H-ZSM-5 powder with 1 M NaOH solution (vol. Base /
weight = 8.0 cm3 g-1)
 Stir at 70oC for 1 hour in oil bath. Do direct cooling suddenly in
an ice water bath.
 Centrifuged to separate zeolite powder from solution.

Solution Residue

 Washed with distilled water to remove the remaining

NaOH until the pH is neutral.
 Zeolite ion exchange was carried out with an excess of 0.1
M NH4-NO3 solution, at room temperature for 15 minutes
 The washing process is carried out.
 Conducted in 3 cycles
 Stored overnight at 60oC,
 Dried at 120oC for 12 hours.
 Calcined at 550 oC for 5 hours

Solution Residue

 Retractable solid hH-ZSM-5 with 1 M

HNO3 (vol. Acid / weight = 28.6 cm3 g-1)
 Stir at 70 C for 2 hours in an oil bath.
 After cooling suddenly, the samples were
washed with distilled water until the pH
was neutral.
 Stored overnight at 60oC,
 Dried at 120oC for 12 hours.
 Calcined at 550 oC for 5 hours.
 denoted the acid washed zeolite as `` hH-
ZSM-5 ''.
 The yield obtained is calculated

h-H-ZSM-5

42
 2. Catalytic Cracking Process Work Procedure

H-ZSm-5 catalyst, hH-ZSm-5,

PP plastic liquid products: LDPE (75:25)%

 The autoclave reactor was calibrated for 60 minutes.

 The catalytic cracking reaction was carried out with a
stainless steel autoclave reactor
 The feed for this reactor consists of mixed hydrocarbon
oil (C9-C40) derived from the thermal cracking of the PP
/ LDPE plastic mixture.
 Performed testing on each variation of liquid products
with variable volume; 100, 150, 200, 250 and 300 mL.
 0.5 g of H-ZSM-5 catalyst was added to each volume
variation of the liquid product.
 The catalytic cracking process was carried out at a
reaction temperature of 200 oC for 180 minutes.
 Cooled and separated the liquid product from the
catalyst residue with a vacuum filter
 The process was repeated with 0.5 g of hH-ZSM-5
catalyst.

Residue Solution

 Yield
It's dried
catalyst  Separated the volatile product into
 Labeled gas and liquid fractions through a
catalytics cracking condenser,
 Saved
 Stored liquid products with an
erlenmeyer
 The adsorption process is carried out
Liquid product from
with activated carbon to remove
impurities.
catalytic cracking
 The distillation process is carried out

43
3. Fractionation of Cracked Liquid Products

Liquid Products from Catalytic Cracking

(100, 150, 200, 250, 300 mL)

The adsorption process was carried out by mixing 250 mL

of liquid product with 2.5 g of adsorbent in erlenmeyer.
Performed while stirring for 20 minutes at 30oC.
It is deposited for 2-3 hours.
Centrifuge
Filtered to separate the remaining adsorbent.

Residue Solution

Distilled at a distillation temperature of 210oC to

produce 2 separate products, namely light fraction
(C5-C14) and heavy fraction (C10– C40).
The hydrocarbon composition analysis was carried
out using the GC-MS instrument.
The physical properties of each fraction were
measured including heating value, density and
viscosity.

Liquid product resulting

from catalytic cracking

44