1.3.1.

Raw Material Analysis

1.3.1.1. Coal
Indonesia has three largest coal mines, in South Sumatera, South
Kalimantan, and East Kalimantan. In Indonesia, South Sumatera is the largest coal
resources and reserves than South Kalimantan and East Kalimantan. The
following is a table of coal resources and reserves in Indonesia
Resources Reserves
Places
(million tonnes) (million tonnes)
South Sumatera 11,208 3,851
South Kalimantan 8,115 1,845
East Kalimantan 10,558 2,161
Source: Coal Map of Indonesia 2014
According to the table above, we plan to use South Sumateras coal. In
South Sumatera, PT. Bukit Asam is the largest coal corporation with resources of
7,290 million tonnes and reserves of 1,990 million tonnes [ CITATION Coa14 \l
1033 ]. By 2014, the average selling price of coal and Bukit Asams component at
the mines that produce each of the three main types of coal:
Component Lignite Sub-Bituminous Bituminous
Price ($/ton) 19.44 14.72 59.10
Fixed Carbon (%) 29 31 56
Total Sulphur (%) 1.2 1.6 0.66
Moisture (%) 12 15 10
Ash (%) 6 6 4
Calorific Value
< 4,900 4,900 6,400 > 6,400
(kcal/kg adb)
Calorific Value
< 4,400 4,400 5,800 5,800 7,950
(kcal/kg ar)
Availability
5,342 6,373 335
(million tonnes)
Source: Coal Prices and Outlook 2014, Bukit Asam Product 2016
From the table above, the most promising coal for our process seems to be
bituminous coal. Though the price is the most expensive, but according to our
process, bituminous is more efficient than others because coal with a low carbon
content and high water content will produce olefin in a very low yield. So, olefin
production using lignite and sub-bituminous need more coal when compared to
olefin production with bituminous coal. In addition, it will actually save storage
space and transport costs since less coal is needed.
 Of three coals, bituminous has the lowest sulfur content, lowest moisture
content, and the highest fixed carbon content. With low sulfur content, there will
be less acid gas to be removed during the acid gas removal process. Since it has
the highest fixed carbon content, it also will be able to produce the most synthesis
gas and the production cost will decrease.
Another factor taken into consideration is the sulfur content in the coal. The
bituminous coal is found to have the lowest percentage of sulfur content, 0.66% as
compared to 1.2% and 1.6% of lignite and sub-bituminous respectively. In high
temperature process, all sulfur components in the feed are converted to H2S which
are undesirable components and require acid gas removal technology to be
treated. Thus, with less sulfur content, it will be easier to remove sulfur based
compounds. Another advantage of using this bituminous coal is the lowest
moisture content (10%) and the lowest ash content at 4%.
Considering the coals price and composition, bituminous coals are selected.
Bituminous coals have composing components with the following composition
and physical properties.
Parameter Range Typical
Total Moisture (TM) (%, ar) 13.00 17.00 14.00
Proximate Analysis
3.00 7.00 5.00
Inherent Moisture (%, adb)
Ash Content (%, ar) 4.00 8.00 6.00
Volatile Matter (%, ar) 33.00 40.00 34.00
Fixed Carbon (%, ar)
42.00 49.00 46.00
Calorific Value (CV)
Gross Calorific Value (kcal/kg, ar) 6300 6500 6400
Gross Calorific Value (kcal/kg, adb) 6959 - 7180 7070
Total Sulphur (TS) (%, adb) 0.40 1.20 1.20 Max
Ultimate Analysis (%, adb)
66.55 74.45 68.74
Carbon (C)
Hydrogen (H) 3.14 6.91 4.41
Nitrogen (N) 0.75 1.48 1.11
Oxygen (O)
8.83 20.74 12.79
Ash Analysis (%, adb in ash)
Silicon Dioxide (SiO2) 44.97 78.88 61.31
Aluminum Oxide (Al2O3) 13.64 37.20 24.02
Iron Oxide (Fe2O3)
 1.66 7.55 4.34
0.08 1.49 0.71
Calcium Oxide (CaO)
Magnesium Oxide (MgO) 0.03 0.92 0.48
Titanium Oxide (TiO2) 0.43 1.35 0.89
Potassium Oxide (K2O)
0.12 0.59 0.36
Phosphorus Pentaoxide (P2O5)
Sodium Oxide (Na2O) 0.16 0.94 0.55
Manganese Oxide (Mn3O4) 0.00 0.70 0.25
Sulphur Trioxide (SO3)
0.04 0.04 0.04
0.10 0.77 0.43
Ash Fusion Temperatures (Reducing/Oxidizing) (oC)
1389 1500 1466
Deformation
Spherical 1447 1500 1488
Hemisphere 1452 1500 1491
Flow
1461 1500 1493
Handgrove Grindability Index 55 65 60
Source: PT. Bukit Asam (Persero) Tbk.
Physical Properties Data
Ignition Temperature 260 F 365oF
o

Melting Point 750oF

Average Specific Gravity 1.43
%, Volatility by Volum Negligible
Vapour Density N/A
Solubility in Water Non-soluble
Source:

1.3.1.2. Mono Ethanol Amine (MEA)

Mono Ehanol Amine (MEA) is supplied from PT. the function of MEA is absorp
acid gas, such as carbon dioxide (CO2), sulphur oxide (SOx), sulfide acid, and
another acidic gas. MEA is used in absorption process is technical grade with
purity of 99,5%. Specifications mono ethanol amine used in the absorption acid
gas are as follows:
No. Parameter Value
1 Grade Technical
2 Phase Colorless Liquid
3 Purity 99,5%
4 Specific Gravity 1.018
5 Vapor Pressure 0.1 kPa (@ 20oC)
6 Boiling Point 170.8oC
 7 pH 10 [Basic]

1.3.1.3. Copper (Cu) - Zinc Oxide (ZnO) - Aluminum Oxide (Al2O3) Catalyst
Copper (Cu), Zinc Oxide (ZnO) and Aluminum Oxide (Al 2O3) are catalyst
system that is used for convert synthesis gas (CO 2, CO, and H2) to methanol
(CH3OH). In this catalyst system, the active site consists of Cu steps decorated
with ZnO, all stabilized by a series of well-defined bulk defects and surface
species that need to be present jointly for the system to work.

Source: https://suncat.stanford.edu/theory/news/active-site-methanol-synthesis-catalysts
Industrial Cu/ZnO based catalyst are prepared by a coprecipitation method
that creates porous aggregates of Cu and ZnO nanoparticles, with molar
composition of Cu and Zn near 70:30. The industrial system is a bulk catalyst
characterized by a high Cu:Zn ratio with >50 mol% Cu (metal base),
approximately spherical Cu Nanoparticles of a size around 10 nm, and ZnO
Nanoparticles that are arranged in an alternating fashion to form porous
aggregates. These aggregates expose a large Cu surface area of up to ~40 m 2g-1.
Furthermore, industrial catalysts contain low amounts of a refractory oxide as
structural promoter, in most cases up to ~10% Al 2O3. Omitting any of the
constituting elements drastically reduces the performance of the system.
One important key to high performance is a large accessible Cu surface
area, which has been observed to scale linearly with activity for sample. Different
qualities of Cu surfaces can be prepared that vary in the activity of their active
sites and/or in the concentration of these site. ZnO functions as a physical spacer
between Cu nanoparticles and helps disperse the Cu phase in the course of catalyst
preparation and is thus responsible for the high Cu surface areas of industrial
catalysts. However, the presence of ZnO increases the intrinsic activity of Cu-
based methanol synthesis catalysts, an effect known as the Cu-ZnO synergy (3,
12, 13), and has led to many different (and conflicting) mechanistic models (14
20). This situation is partially the result of some models mainly having their bases
in results from simplified samples, ranging from Cu single crystals to Cu
Nanoparticles supported on highly crystalline ZnO with a low loading, that have
compositions and microstructure that strongly deviate from that of the industrial
catalyst described above.

1.3.1.4. ZSM-5 Catalyst

Zeolite Socony Mobil-5 (ZSM-5) is an aluminosilicate zeolite belonging to
the pentasil family of zeolites. Its chemical formula is Na nAlnSi96-nO192 . 16H2O
with the value of n between 0 and 27. ZSM-5 is patended by Mobil Oil Company
in 1975, it is widely used in the petroleum industry as a heterogeneous catalyst for
hydrocarbon reactions, such as convert methanol to olefins especially ethylene,
propylene, and butane.

https://www.acsmaterial.com/index.php/zsm-5-catalyst-839.html
 ZSM-5 is composed of several pentasil units linked together by oxygen
bridges to form pentasil chains. A pentasil unit consists of eight five-membered
rings. In these rings, the vertices are Al or Si and an O is assumed to be bonded
between the vertices. The pentasil chains are interconnected by oxygen bridges to
form corrugated sheets with 10-ring holes. Like the pentasil units, each 10-ring
hole has Al or Si as vertices with an O assumed to be bonded between each vertex.
Each corrugated sheet is connected by oxygen bridges to form a structure with
"straight 10-ring channels running parallel to the corrugations and sinusoidal 10-
ring channels perpendicular to the sheets.Adjacent layers of the sheets are related
by an inversion point. The estimated pore size of the channel running parallel with
the corrugations is 5.45.6 . The crystallographic unit cell of ZSM-5 has 96 T
sites (Si or Al), 192 O sites, and a number of compensating cations depending on
the Si/Al ratio, which ranges from 12 to infinity. The structure is orthorhombic
(space group Pnma) at high temperatures, but a phase transition to the monoclinic
space group P21/n.1.13 occurs on cooling below a transition temperature, located
between 300 and 350 K.

Source: https://commons.wikimedia.org/wiki/File:Zeolite-ZSM-5-vdW.png
ZSM-5 catalyst was first synthesized by Argauer and Landolt in 1969. It is a
medium pore zeolite with channels defined by ten-membered rings. The synthesis
involves three different solutions. The first solution is the source of alumina,
sodium ions, and hydroxide ions; in the presence of excess base the alumina will
form soluble Al(OH)4ions. The second solution has the tetrapropylammonium
cation that acts as a templating agent. The third solution is the source of silica, one
of the basic building blocks for the framework structure of a zeolite. Mixing the
three solutions produces supersaturated tetrapropylammonium ZSM-5, which can
be heated to recrystallize and produce a solid.
 Specifications ZSM-5 used for convert methanol to propylene are as
follows:
Parameter Value
SiO2 / Al2O3 Molar Ratio 38
Shape Column (pelletized)
Dimension 2 x 2-10 mm
Pore Volume 0.25 ml/g
Bulk Density ~ 0.72 kg/l
Specific Surface Area 250 m2/g
Crushing Strength 98 N/cm2
Attrition < 1 wt.%
Pore Size ~5
Binder Type Pseudo-Boehmite
Binder wt.% 30 wt.%
Source: https://www.acsmaterial.com/index.php/zsm-5-catalyst-839.html

1.3.1.5. Vanadium (V) Oxide (V2O5)-Titanium Oxide (TiO2) Catalyst

Vanadium (V) oxide is the inorganic compound that consists vanadium and
oxygen atom with the formula V2O5, commonly known as vanadium pentaoxide.
In this catalyst, vanadium atom is at the level of the highest oxidation number,
V5+. Because of that, vanadium (V) oxide catalyst is both an amphoteric oxide and
oxidizing agent. From the industrial perspective, it is the most important
compound of vanadium, being principal precursor to alloys of vanadium and is a
widely used industrial catalyst. The mineral form of this compound, shcherbinaite,
is extremely rare, almost always found among fumaroles. A mineral trihydrate,
V2O53H2O, is also known under the name of navajoite.

Source: http://www.fhi-berlin.mpg.de/~hermann/Balsac/pictures.html
 TiO2 as a heterogeneous catalyst, can improve the performance of catalyst,
allowing the modulation of catalytic activities for many reactions, including
dehydrogenation, hydrodesulphurization, water gas shift and thermal catalytic
decomposition. There are also some obvious drawbacks in using TiO2 as a
heterogeneous catalysis. The limitations included small specific surface areas, low
quantum efficiency, and low adsorption abilities Furthermore, both costs and
difficulties in the separation of catalyst from the reaction media and inadequacy
for continuous processing limited the applications of TiO2 as a heterogeneous
catalyst in large scale industries. Despite these drawbacks, a number of studies
have focused on catalytic reaction with TiO2 as a support material. The inuences
of TiO2 support on heterogeneous catalysts aect electronic eects and bi-
functional mechanism. TiO2, as a catalyst support, enforces an electronic eect
where the hypo-d-electronic Ti3+ promotes electrocatalytic features of hypered-
electronic noble catalyst surface atoms [42]. Tis, in turn, decreases the adsorption
energy of CO intermediates, while enhancing the mobility of CO groups. At the
same time, the adsorption of OH species on TiO2 tends to facilitate the conversion
of the catalytically toxic CO intermediates in CO2, thus improving the durability
of the heterogeneous catalyst. Both factors indirectly assist the dispersion and
anchor of the heterogeneous catalyst particle. Further improvement in the catalytic
stability and activity of the heterogeneous catalysts involves modifying the TiO2
support material with semiconductor metal oxides.
TiO2 as a support in heterogeneous catalysis are known to have excellent
properties, due to TiO2 nanoparticles high chemical and thermal stability. TiO2
based catalyst supports have outstanding resistance towards corrosion in dierent
electrolytic media. TiO2 can be regarded as a support for heterogeneous catalysts
which guarantees stability in electrochemical environment and commercial
availability. Meanwhile, strong interactions between the catalytic particles and
mesoporous TiO2 have been recorded, which, in the end, resulted in both
improved catalytic stability and activity. TiO2 as a catalyst support material also
indicated a certain degree of proton conductivity, which may potentially enhance
the regime of the triple phase boundary for catalytic reactions.
 In V2O5/TiO2 heterogeneous catalyst, V2O5 is a main catalyst and TiO2 is
a support catalyst. Furthermore, V2O5/TiO2 heterogeneous catalyst found another
promising application in the dehydrogenation of alkanes and selective oxidation
of alcohols/alkanes. It was applied for the o-xylene oxidation to phthalic
anhydride reaction. Ten, the potential of V2O5/TiO2 was recorded in the pollution
abatement of NO with NH3 process [163, 164]. Thus, V2O5/TiO2 is one of the
most efficient catalysts in the oxidative dehydrogenation of propane, with only a
few byproducts [165]. A stable deposit of TiO2 in V2O5/TiO2 heterogeneous
catalyst system was established with dip coating of V2O5 in an aqueous
suspension of titanium isopropoxide

References
Argauer, R. J. et al., 1972. Crystalline Zeolite ZSM-5 and Method Of Preparing the Same.
United States, Patent No. 3702886.

Bagheri, S., Julkapli, N. M. & Hamid, S. B. A., 2014. Review Article-Titanium Dioxide as a
Catalyst Support in Heterogeneous Catalysis. The Scientific World Journal, 14
October.Volume 2014.

Behrens, M. et al., 2012. The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3
Industrial Catalyst. Science, 18 May, Volume 336, pp. 893-897.

Cejka, J., 2005. Zeolites and Ordered Mesoporous Materials: Progress and Prospects,
Volume 157. 1st ed. Prague: Elsevier.

Coaltrans, 2014. Coal Map of Indonesia - Coaltrans Conferences. [Online]

Available at: www.coaltrans.com/pdfs/Coal_Map_Indonesia.pdf
[Accessed 31 August 2017].

Grau-Crespo, R., Acuay, E. & Ruiz-Salvador, A. R., 2002. A free energy minimisation study
of the monoclinicorthorhombic transition in MFI zeolite. hemical Communication, pp.
2544-2545.

Hay, D. G., Jaeger, H. & West, G. W., 1984. Examination of the Monoclinic/Orthorhombic
Transition In Silicalite Using XRD and Silicon NMR. The Journal of Physical Chemistry,
89(7), pp. 1070-1072.

PT. Bukit Asam (Persero) Tbk, 2016. Our Business | PT Bukit Asam. [Online]
Available at: http://www.ptba.co.id/id/about/business
[Accessed 1 September 2017].