KKEK4281

DESIGN PROJECT
SEMESTER 1, SESSION 2015/2016
FEASIBILITY REPORT

G6

Synthesis of Highly Reactive Polyisobutylene (HR-PIB) Using BF3/methanolalumina Catalyst System in Fixed Bed Reactor
Prof. Dr. Wan Mohd Ashri Bin Wan Daud
Group Facilitator
How Seow Wah
KEK120011
Group Members
Ahmad Farid Bin Yahaya
KEK120002
Khor Suet Fenn
KEK120016
Nurshafikah Binti Abdul Rahim
KEK110043
Aravend A/L Kumaresan
KEK120004
29 October 2015
Submission Date

Acknowledgement
Hereby, our group would like to express our highest gratitude to everyone who has provided us
guidance and supervisions throughout the composure of this feasibility report.

Prof. Dr. Wan Mohd Ashri WAN DAUD (Group Facilitator)

Thank you for your guidance and advices on the progress of our group on weekly basis,
we are really grateful for your assistance in answering our doubts so far.

Dr. Nur Awanis HASHIM / Professor Ir. Dr. Mohd Azlan HUSSAIN (Course
Coordinators)
We are thankful for your relentless effort in coordinating the project and groups to ensure
all the groups are on the right track. Special thanks for arranging various industrial talks to
widen our horizon in chemical industries.

Friends and family members

Our heartfelt gratitude to all of our friends and family members for their mental support
and assistance, especially to all of our course mates for your encouragements despite being
in different groups.

Table of Contents
No.

1.0

2.0

3.0

4.0

5.0
6.0

7.0
8.0
9.0

Items
Acknowledgement
Table of Contents
List of Figures and Tables
Identification of Raw Materials and Products
1.1 Brief Introduction of Highly Reactive Polyisobutylene (HR-PIB)
1.2 Raw Materials Considered
1.2.1 Isobutane
1.2.2 C4-Raffinate
1.2.3 Pure Isobutylene
Identification of Process Routes
2.1 Cationic Polymerization
2.2 Selection of Raw Material
2.3 Selection of Catalyst
2.4 Selection of Reactor
Market Survey
3.1 Latest Industrial Development
3.2 Demand of HR-PIB
3.3 Applications
3.4 Capacity
Preliminary Economic Analysis
4.1 Capital Cost
4.2 Production Cost
4.3 Estimated of Generated Revenue
4.4 Cash Flow Analysis
4.5 Payback Period and ROI
Location
5.1 The Plant Location Survey
Safety Considerations
6.1 Location
6.2 Raw Material (Isobutylene)
6.3 Processes
6.4 Product (HR-PIB)
6.5 Hazard Mitigation Methods
Environmental Considerations
Novelty
References
Appendix

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List of Figures and Tables

Items
Figure 1: The scores for each location based on the 11 criteria
Figure A1: Cationic polymerization of isobutylene
Figure A2: The cash flow analysis in 20 years with and without interest
Figure A3: Preliminary process flow diagram (PFD) of the proposed HR-PIB plant
with operating parameters of major equipment
Table 1: Countries with major HR-PIB producers
Table 2: Comparison of cumulative cash flow with and without interest rate
Table 3: Summary of economic feasibility study of HR-PIB plant
Table A1: Comparison between raw materials
Table A2: Comparison between catalysts
Table A3: Comparison between loop reactor and fixed bed reactor
Table A4: Inside battery-limits (ISBL) equipment (inclusive of delivery cost)
Table A5: Total Fixed Capital Investment Preliminary Estimation (Peters and
Timmerhaus Method)
Table A6: Consumables and utilities
Table A7: Total estimation of production cost
Table A8: Estimated Annual Revenue
Table A9: Cash flow analysis with cumulative for with and without interest rate
Table A10: Comparison of three candidate locations with the assessing criteria
Table A11: Preliminary mass balance of the proposed HR-PIB plant at 50 kMT
(equivalent to 6315 kg/h)

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A8
A12
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A3
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A5
A6
A6
A7
A7
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A11

iii

1.0 Identification of Raw Materials and Products

1.1 Brief Introduction of Highly Reactive Polyisobutylene (HR-PIB)
HR-PIB is a type of polyisobutylene that has greater than 80% of terminal vinylidene group,
this property allows the HR-PIB to be refined into fuel additives due to their high reactivity.
HR-PIB usually has a lower range of molecular weights, ranging from 500 to 5000 Dalton.
The further processed HR-PIB is ideal in improving automobile engine performance. Hence,
production of HR-PIB has a globally lucrative market because automobile vehicles are
omnipresent, these additives can significantly reduce the detrimental impacts of engine
operation on the environment.
1.2 Raw Materials Considered
1.2.1 Isobutane
Industrial production of isobutane can be acquired by processing and fractionating field
NGLs, it can be also procured as a by-product of refinery cracking and distillation
processes. However, isobutane, which is available locally, though not of high purity can be
isomerized into isobutylene. Isobutane is inherently inert and does not adsorbed onto the
solid surface. Also, the solubility of isobutane in aqueous medium is extremely limited.
Thus isobutane can be concurrently found with Light Petroleum Gas (LPG), or where
natural gas and petroleum are present.
1.2.2 C4-Raffinate
Raffinate-1 is one of the co-products produced from a steam cracker in the manufacturing
of ethylene and propylene (PT Chandra Asri Petrochemical Tbk, 2014). Many of the main
players in PIB industries utilize C4-Raffinate as the feedstock due to its cost-effectiveness.
However, one of the drawbacks is that the percentage of isobutylene can be as low as 30%
by weight of the whole stream. The Raffinate-1 contained in C4-Raffinate consists of
isobutylene, n-butenes, along with other trace quantities of butanes and other compounds.
Among these components, isobutylene and n-butene have similar boiling points and small
relative relativity (Derouane et al, 2005), thus the separation of the two aforementioned
components are not economically viable. Therefore, the presence of n-butene acts as
diluent of the reaction and must be purged out from the system to avoid unwarranted
accumulation.
1.2.3 Pure Isobutylene
Isobutylene of high purity (>90% wt) can be obtained with the combination of MTBE
synthesis and cracking (Kalakkunnath, 2012). In addition, separating isobutylene from 1butene by direct fractionation is almost impossible. Therefore, in integrated SnamprogettiYarsintez process, isobutylene is stripped out using MTBE. Hence, the high purity
isobutylene with MTBE enters the polymerization process requires constant purging of
recycled stream into reactor in order to maintain the composition of the feed stream.
1

2.0 Identification of Process Routes

2.1 Cationic Polymerization
The main product, highly reactive polyisobutylene is made by the cationic polymerisation of
isobutylene. Cationic polymerization is a type of chain growth polymerization in which a
cationic initiator transfers charge to a monomer which then becomes reactive. There are three
main steps in cationic polymerization in this process as shown in Figure A1.
Step 1: Initiation step (I)
The catalyst will be associated with the isobutylene monomer to provide the initial
carbocation.
Step 2: Propagation step (P)
Additional monomer is added to initial carbocation in order to generate a new carbocation
at the end of the grow chain. The chain of propagation will continue until a desired molecular
weight is reached.
Step 3: Termination step (T)
Catalyst residue is reacted with the carbocation reacts and consequently a double bond is
being generated. Polyisobutylene that consists of alpha vinylidene and beta trisubstituted
molecules are produced.
Lower molecular weight polymer is produced at higher reaction temperature, while higher
molecular weight is produced at lower reaction temperatures. This is because of the polymer
molecular weight is inversely proportional to reaction temperature, where the propagation step
(P) is favored at lower reaction temperatures, while termination step is favored at higher
reaction temperatures (U.S. Patent No. 8,816,028 B2, 2014).
2.2 Selection of Raw Material
From Table A1, it is obvious that the pure isobutylene route is the best among all other routes
as raw material. The high purity isobutylene does not require extra equipment to purify the
component or product form, results in lower plant facilities and capital cost. This raw material
can be obtained from MTBE plant in Gebeng. Instead of import from other country, it is more
preferable that to obtain the raw material locally in short distance. Furthermore, the use of
isobutane requires the dehydrogenation unit to convert isobutane to isobutylene, while C 4raffinate requires the larger design of distillation column for stripping process to remove the
mixture, results in higher production cost. Therefore, pure isobutylene is the most suitable for
the production of HR-PIB among the other raw materials. By using pure isobutylene, the
conversion is up to 94% (U.S. Patent No. 6,562,913, 2003).
2.3 Selection of Catalyst
Catalyst plays an important role in cationic polymerization in order to give free radical of
carbocation. The common use of catalyst is Lewis acid catalyst, typically included AlCl 3, BF3
in liquid phase or gas phase. There are few potential catalysts listed in Table A2 in appendix.
2

Boron trifluoride/methanol catalyst complex with alumina support is chosen in this process
because of few reasons. This catalyst complex embedded in a -alumina support exists in a
solid phase, which allows the heterogeneous reaction to take place in the reactor and easier for
separation after polymerisation reaction if compare to the traditional processes which use a
liquid polymerisation catalyst. In conventional designs of HR-PIB production facility, the
homogenous reaction with the use of BF3 as liquid catalyst require special handling systems
and procedures such as the use of washing water to neutralise the toxic and hazardous liquid
catalyst, making undesirable wastes produced.
In addition, the use of boron trifluoride/methanol catalyst complex reduces the capital
investment and low operating cost in comparison to other conventional catalyst. BF3/methanol
catalyst complex in alumina support have long catalyst life span in comparison to conventional
BF3 catalyst. This is because the solid catalyst can be reused until the catalyst is deactivated,
while the conventional design of catalyst cannot be recycled after polymerization. Moreover,
the very high feed-to-catalyst ratio requires only 1-2% of the present catalyst used (U.S. Patent
No. 8,816,028 B2, 2014), which significantly reduces the catalyst use in the results of more
cost-effective. Whereas, AlCl3 catalyst has almost the same properties with BF3/methanol
catalyst complex in alumina support, yet it requires the larger diameter fluid duct leading from
reactor, results in higher capital cost is required (U.S. Patent No. 2,957,930 A, 1960).
Therefore, BF3/methanol catalyst complex in alumina support is preferred to be chosen in the
reactor instead of AlCl3 catalyst.
In conclusion, BF3/methanol catalyst complex in alumina support is selected for this process
because of its highly catalytic, stable, have a long life span and it does not require post-reaction
catalyst removal section. Catalyst injection and handling system are not required since the
catalysts are contained within the reactor. All these factors translate into reduced health and
environmental hazards apart from reducing capital investment and subsequent operating cost.
2.4 Selection of Reactor
The design and types of reactor are also important to produce HR-PIB instead of conventional
polyisobutylene. The common reactors for polymerization technology are loop reactor, CSTR,
and fluidized bed (Cheremisinoff, 1989). The comparison between loop reactor and fixed bed
reactor are listed as Table A3 in Appendix.
It is best to carry out continuous polymerization with fixed bed catalysts, where the hassles of
separating the catalyst from the reaction mixture is eliminated (U.S. Patent No.
US2011/0218362 A1, 2011). This saves the equipment utilization since no additional
equipment for separation is needed. Besides, the catalyst consumption of fixed bed process is
less than the loop process (Suyenty et al, 2007). It is also possible to control the production
rate as well as the product selectivity through continuous fixed bed reaction technology.
3

3.0 Market Survey

3.1 Latest Industrial Development
Most of companies that specialized chemical products announced that it has commenced
engineering to expand production capacity of HR-PIB. The need for a capacity is driven by
the growing demand for HR-PIB due to upcoming changes in automotive engine oil standard
that favor HR-PIB based dispersants, as well as increasing demand for wide variety of other
uses of HR-PIB (Fuelsandlubes.com, 2013).
3.2 Demand of HR-PIB
The versatility in applications of HR-PIB offers a bright prospect. Nowadays, HR-PIB are
produced in numerous countries worldwide as shown in Table 1. There is no reliable up-todate data regarding the global production of HR-PIB available free of charge. The projected
demand for HR-PIB is expected to reach 1.3 million tons per annum by the end of 2018
globally, making the production of HR-PIB a highly lucrative business (King, 2013).
Table 1: Countries with major HR-PIB producers
Country
Company Name
Korea
Daelim
USA
Lubrizol, Chevron Oronite,TPC
Belgium INEOS, BASF
Germany BASF
China
Linan Euro-China, Zhejiang-Shunda
India
Kothari Petrochemical
3.3 Applications
Highly reactive polyisobutylene (HR-PIB) is an important intermediate product in the
manufacture of premium quality fuel additives. The base oils used to synthesize hydrocarbon
lubricants can be classified into five groups (Group I, II, III, IV and V) (Noria Corporation,
2012). The first three groups are non-synthetic while the latter two are synthetic. The lubricants
derived from HR-PIB fit into Group V. Apart from that, PIB succinimides is widely used as
dispersants to disperse dirt, sludge and varnish particles in engine lube oil matrix for
subsequent filtration. PIB succinic anhydrides (PIBSA) is also well-known oil in water
emulsifier for lubricants so that it provides high heat capacity apart from lubrications.
3.4 Capacity
The plant capacity is determined at 50 kMT per year to supply the demand for Asia Pacific
region. All the produced HR-PIB will be exported to countries within the Asia Pacific region
where the HR-PIB can be further processed into fuel additives. It is estimated that the plant
will generate RM300 millions of export revenue per annum for Malaysian economy (Sharidan,
2015).
4

4.0 Preliminary Economic Analysis

4.1 Capital Cost
One of the major aspects to determine the overall economic viability of a chemical process is
by determining the capital cost. A preliminary economic analysis usually has an accuracy
30% according to The Association for the Advancement of Cost Estimating International
(AACE International). Total Plant Fixed Capital Investment, TFC is estimated by the sum of
ISBL (Inside Battery Limits) and OSBL (Outside Battery Limits) fixed capital investment is
used in preliminary estimation. ISBL Fixed Capital Investment Preliminary Estimation (Peters
and Timmerhaus method) is the total cost that associated with construction the plant. This cost
includes site remediation, purchasing process equipment, design, developing infrastructure,
contingency chargers, raw material cost and also labor. It starts with the Inside Battery-Limit
(ISBL) Equipment as stated in Table A4 where the total equipment cost inclusive of delivery
cost is RM 28,316,000.00.
The ISBL Fixed Capital Investment Preliminary Estimation can be further categorized into
direct and indirect cost. Direct costs are referring to labor, material expenses related to product
and production. In other words, costs such as administrative and depreciation expenses are
considered as indirect costs. The sum of these two components the Total ISBL Fixed Capital
Investment.
OSBL (Outside Battery-Limits) fixed capital investment or known as off-site costs is the costs
that are associated with off-site developments that are required for plant to run. OSBL costs
are initially estimated as a percentage of the ISBL costs. A rule of thumb is to use 40% of the
ISBL costs as an estimate for OSBL (Chandel et al., 2014). Hence, the Total Plant Fixed
Capital Investment is RM 19,147,2792.00. The calculations are represented in Table A5. The
total fixed capital investment (TFC) finally sums up to RM 191,472,792.00.
4.2 Production Cost
Estimate annual production cost is also divided to direct and indirect cost. Consumption rate
is based on average 3000kg of catalyst in the reactor with 4 replacements each year. While the
catalyst price is based on USD1000/ton of BF3-methanol complex, USD1500/ton alumina
support, USD500/ton catalyst processing cost. These are shown in Table A6 and Table A7
where the estimate annual production cost is RM 215,164,520.94.
4.3 Estimation of Generated Revenue
There are 3 major products produced from the plant which are main product, HR-PIB and byproduct which are C8 Oligomers and C12-C16 Oligomers. The products price are estimated
according to the current petrochemical price (Platts, 2015). Based on these products price the
Estimated Annual Revenue that can be generated is RM 259,155,000.00 as stated in Table A8.

4.4 Cash Flow Analysis

The cash flow analysis is one of the most important financial statements for a project where
the company is able to check the cash into and out of the project. This can be a projection of
future flows of cash which involved both amount of the cash flows and timing of the flows.
Cash flow analysis for this project are using present worth basis with 3 years of construction
period and plant life time estimation for about 20 years. The information is tabulated in Table
A9 which take into consideration constant 5% interest rate annually. The cumulative cash flow
with and without interest for 20 years are RM 344,716,928.30 and RM 688,336,789.20
respectively. Based Figure A2, the amount of capital generated is higher without interest which
is linear. The breakeven point for cumulative cash flow with interest is approximately half a
year later than that for without interest rate. The interest rate causes the net cash inflow to the
company to diminish on annual basis, thus the curve for cumulative cash flow with interest
rate exhibits a curve of decreasing gradient.
Table 2: Comparison of cumulative cash flow with and without interest rate
Cumulative Cash Flow (20 years)
Without Interest
With Interest

RM 344,716,928.30
RM 688,336,789.20

4.5 Payback Period and ROI

The payback period is the initial capital investment that is expected to recovered back from the
income which is generated. Equation involve payback period is:
Initial capital cost
=
(Eq. 1)

As the initial capital cost is RM 19,147,2792.00 and the annual cash inflow is RM
43,990,479.06. The payback period of 4.3 years is favorable for investors as it is less than 5
years.
The ROI is the expected profit divided by the total cost and expressed in the percentage form.
Expected profit
(%) =
(Eq. 2)

ROI obtained for this project is 22.97% which are under the low risk
Table 3: Summary of economic feasibility study of HR-PIB plant
Payback Period
Return-onInvestment
(ROI)

4.3 years
23%

5.0 Location
5.1 The Plant Location Survey

Figure 1: The scores for each location based on the 11 criteria

Based on the comparison above, the criteria used to select the most suitable plant location are
marketing area, raw materials, transportation, labor availability, utilities, total land available,
climate, land topography, local community, project execution immediacy and incentives given by
government. Based on these criteria, Kerteh is very strategic for project execution as there are
many raw lands that can be developed in the future. However, Kerteh is in close proximity to local
residential area while the HR-PIB plant has to be operated at least 5 km away from residential
areas, making Kerteh IPC a not so desirable candidate. For Pengerang IPC, the scores for
availability of raw material and utilities such as electricity are poor because the IPC is still an ongoing project by PETRONAS. Factors such as high living cost further deteriorate its scores as high
living cost tends to decrease labor availability despite having attractive incentives. On the other
hand, Gebeng has an excellent marketing area and raw material is readily available from nearby
MTBE plant, the utilities are also well equipped. All these factors favors Gebeng IPC as the place
for the project execution although the land availability is inferior to Pengerang IPC. Besides that,
Gebeng IPC has a well-developed transportation system of chemical materials with promising
incentives by government as it is located within the East Coast Economic Corridor (ECER).
In conclusion, Kerteh IPC and Gebeng IPC are among the best but Gebeng IPC is chosen because
it is technically more feasible as we can get pure raw material of isobutylene from MTBE plant
which can significantly reduce cost of feed preparation, such as isobutane dehydrogenation or even
n-butane isomerization into isobutane.
7

6.0 Safety Considerations

6.1 Location
Plant should be located 5km apart from residential area and preferably away from other
petrochemical plants to minimize the impact of explosion risk caused by HR-PIB plant. A
runaway polymerization would be catastrophic, including the propagation of high-pressure
shock wave, secondary damage caused by missile projection of torn equipment parts and
massive release of highly-flammable hydrocarbons into atmosphere.
6.2 Raw Material (Isobutylene)
Isobutylene is a highly flammable liquid. After ignition, isobutylene fires can be extinguished
by shutting off the source of the gas. Alternatively, water spray or a foam agent can be applied
to cool fire-exposed containers, structures, and equipment.
In addition, isobutylene is a toxic chemical. High concentrations of this gas can cause an
asphyxiating environment. Individuals breathing such an atmosphere may experience medical
symptoms which include headaches, ringing in ears, dizziness, drowsiness, unconsciousness,
nausea, vomiting, and depression of all the senses. Under some circumstances death is
plausible if overexposed. Therefore, trained personnel should be readily available to administer
supplemental oxygen and/or cardiopulmonary resuscitation when situation demands.
Besides that, physical contact with compressed liquid or rapidly expanding gases may cause
frostbite. Symptoms of frostbite include change in skin color to white or grayish-yellow. The
pain after such contact can quickly subside. Place the frostbitten body part in warm water. If
warm water is not available, or is impractical to use, wrap the affected parts gently in blankets
and seek for medical attention immediately.
6.3 Processes
The solid catalyst is not hazardous under normal operating condition. However once the BF3methanol complex is leached, the resultant reaction mixture will become toxic and requires
special handling methods. The catalyst might hydrolyze into acids which can severely corrode
the equipment.
Polymerization of isobutylene into HR-PIB may cause explosion if the process is poorly
controlled up to the extent where runaway reaction occurs. Therefore, mild cryogenic operating
conditions have to be maintained for the reactor to suppress the reaction and prevent
uncontrolled release of heat of reaction.
6.4 Product (HR-PIB)
Physical contact with HR-PIB may cause eye and skin irritation, rinse the affected body parts
using copious amount of flowing water with soap if irritation occurs on skin. Apart from that,
8

ingestion of the chemical may cause gastric disturbances, loss of consciousness and even death
if left untreated. Seek immediate medical treatment when irritations linked to contact with HRPIB occurs.
It is also possible for HR-PIB to enter a human body by respiratory tract, upon such exposure
with associated difficulty to inhale, immediately exit the confined space and seek further
medical assistances.
6.5 Hazard Mitigation Methods
The discussed hazardous materials are properly isolated and confined as per required by
Department of Safety and Health, this is to ensure safe operations even under minimal human
supervisions. Under circumstances where the unit equipment have to be opened for
maintenance, contact with the hazardous chemicals are extremely probable. Thus, during
handling process use sufficient PPE to properly protect a trained personnel from such contacts.
7.0 Environmental Considerations
Environmental Quality Act 1974 is required to be complied by any production plant in Malaysia.
Thus, it is the companys responsibility to minimize the impact of the production on the
environment. In chemical processes, wastes are unavoidable. The following by-products are the
possible wastes that being generated during the process:
a. Solid wastes may be produced from the deactivated catalyst. The selection of catalyst is
based on highly catalytic, stability and has a long life. The long lasting solid catalyst can
be reused in the reaction in order to save cost and reduce solid waste generated. One way
to get rid of the deactivated catalyst is by sending it back to the supplier for refining, it is
also possible that the supplier provides additional discounts for subsequent catalyst
purchases by doing so.
b. There are some liquid effluents that will be produced from the process, which is C 4s from
the first distillation column, C8 oligomers from second distillation column and C12-C16
oligomers from third distillation column. C4s that included isobutylene and isobutane can
be recycled into the process to convert more raw materials into products in order to save
cost, while C8 oligomers and C12-C16 oligomers can be concentrated and sold.
c. Possible gaseous emission from the process are isobutane, isobutylene and C8 oligomers
vapor. The purge gas, isobutylene will be compressed and used as fuel gas in fired burner
to generate steam for driving steam turbine for electricity generation. This feature makes
the proposed HR-PIB plant a more sustainable petrochemical plant. Excess hydrocarbon
gases such as isobutylene and C8 oligomer vapor that cannot be recovered or recycled in
the process are burnt in the flare system in an environmentally-sound manner, as an
alternative for releasing the vapor directly into the atmosphere. Regular maintenance
should be carried out to prevent the leakage of the harmful gases.
9

8.0 Novelty
The novelty of the design lies in the use of boron trifluoride/methanol catalyst complex with
alumina support, this allows the catalyst complex to be embedded in a -alumina support which
exist as solid catalyst. The use of solid catalyst allows heterogeneous reaction to take place in a
fixed bed reactor and promotes ease of separation after the polymerization reaction. In
conventional designs of HR-PIB production facility where homogeneous reaction is employed,
separation of catalyst complex from the reactor effluent is essential as the presence of BF3 in final
polymer product is highly unfavorable (U.S. Patent No. 8,791,216, 2014). Apart from that, BF 3 is
also hazardous for biological organisms as it can hydrolyze in the presence of moist air or hot
water into boric acid, hydrogen fluoride and fluoboric acid (Center for Disease Control and
Prevention, 2011). In addition, settling tanks and filters are usually applied to allow the precipitated
catalyst complex to settle by gravity. Not only can it pose severe corrosion hazards to the
subsequent separation equipment but also fatal hazards to plant personnel when exposed. The
elimination of such corrosion-proof separation equipment constitutes a major reduction in capital
investment required to construct the aforementioned production.
On the other hand, conventional homogeneous polymerization of HR-PIB requires the use of
organic solvents to dissolve boron trifluoride gas so that a liquid-phase catalyst complex can be
obtained, which is subsequently fed into the reactor. Some typical solvents used for such purpose
include hexane, toluene, dichloromethane or C1-C5 hydrocarbons present in the feedstock (U.S.
Patent No. 2,957,930, 1960). These solvents has to be removed via stripping or distillation column
and represent additional cost for separation. Therefore, with the use of heterogeneous catalyst
complex for polymerization the CAPEX and OPEX for such separation equipment can be saved
and divert to enhance the SHE aspects of the plant as the explosion hazards of HR-PIB production
plant remains unsolved. Furthermore, the mentioned organic solvent is extremely detrimental to
the environment and the safety aspects with regards to transporting such solvents have to be finetuned to near perfection as an effort to mitigate hazards posed by potential leakage.
Besides that, the use of BF3/methanol catalyst complex in alumina support ensures a prolonged
catalyst life span in comparison to conventional BF3/methanol catalyst complex in liquid phase.
This is because solid catalyst allows the catalyst to be reused until the catalyst is deactivated, while
the quenched catalyst for conventional design after polymerization reactor cannot be recycled
unless it is sent back to the supplier for catalyst refining (U.S. Patent No. 8,791,216, 2014). Thus,
fresh BF3 catalyst has to be bought in bulk quantity. Again, this supports the use of BF3/methanol
catalyst complex in alumina support as a more cost-effective and novel method to produce HRPIB.
In short, the present solid catalyst system does not require post-reaction catalyst removal section
and allow BF3/methanol catalyst complex to be used repetitively until the catalyst is deactivated.

10

9.0 References
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CDC- NIOSH Pocket Guide to Chemical Hazards - Boron Trifluoride. (2011). Retrieved 23
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TPC to expand production capacity of polyisobutylene. (2013). Retrieved 25 October, 2015,
from http://fuelsandlubes.com/flw/tpc-to-expand-production-capacity-of-polyisobutylene/
. GIFT General Business Guide. (2014). In L. I. B. a. F. Centre (Ed.). Kuala Lumpur: Labuan
International Business and Financial Centre.
Platts: Global Petrochemical Prices Fall to 6-year Low. (2015). Retrieved 25 October, 2015,
from http://www.platts.com/news-feature/2015/petrochemicals/pgpi/index
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Cheremisinoff, N.P. (1989). Handbook of Polymer Science and Technology: Synthesis and
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Coppersmith, J.M., P., Forest, & Peterson, K.C. (1959). U.S. Patent No. 2,918,508. Washington,
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Derouane, E.G., Parmon, V., Lemos, F., & Ribeiro, F.R. (2005). Sustainable Strategies for the
Upgrading of Natural Gas: Fundamentals, Challenges, and Opportunities. NATO Science
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Jackson, W.K. (1960). U.S. Patent No. 2,957,930. Washington, DC: U.S. Patent and Trademark
Office.
Kalakkunnath, S. (2012). High Purity Isobutylene Production by MTBE Cracking (pp. 6). Santa
Clara, CA: IHS Inc.
King, M. (2013, November 13). Polyisobutylene market to reach a total of 1.3 million tonnes by
the end of 2018, Companiesandmarkets.com. Retrieved from
https://uk.finance.yahoo.com/news/polyisobutylene-market-reach-total-1000000906.html
Liu, Q, Wu, Y., Zhang, Y, Yan, P., & Xu, R. (2010). A cost-effective process for highly reactive
polyisobutylenes via cationic polymerization coinitiated by AlCl3. Polymer, 51, 59605969. doi: 10.1016/j.polymer.2010.10.012
Ostgard, D., Olindo, R., Duprez, V., Rder, S., & Berweiler, M. (2011). U.S. Patent No.
US2011/0218362 A1. Washington, DC: U.S. Patent and Trademark Office.

R1

PT, Chandra Asri Petrochemical Tbk. (2014). Expanding to Capture Growth (pp. 164). Jakarta,
Indonesia: PT Chandra Asri Petrochemical Tbk.
Sharidan, M.A. (2015, July 27). Joint venture O&G related plants in Kuantan to cost billions,
The Star. Retrieved from http://www.thestar.com.my/Business/BusinessNews/2015/07/27/JV-plants-to-cost-billion/?style=biz
Soltex. (2014). The Application and Use of Soltex Products in Hydrocarbon Lubricants and
Lubrication Systems - Lubricant Market Segments. Retrieved 25 October, 2015, from
www.soltexinc.com/pdf/Application and Use of Soltex Products-Lubricant Market
Segments.pdf
Suyenty, E., Sentosa, H., Agustine, M., Anwar, S., Lie, A., & Sutanto, E. (2007). Catalyst in
Basic Oleochemicals. Bulletin of Chemical Reaction Engineering and Catalysis, 2(2-3),
22-31. doi: 10.9767/bcrec.2.2-3.6.22-31

R2

Appendix

Figure A1: Cationic polymerization of isobutylene

A1

Table A1: Comparison between raw materials

C4-Raffinate
Type of Raw Isobutane
Material
42-45 wt% of isobutylene,
0.5 wt% of C3, about 4.5
Component
and about 50 to 52 wt% of wt% of isobutane, about
Content
isobutane within the
16.5 wt% of n-butane, about
balance being small amounts 38.5 wt% of 1-butene, about
of C3, normal butanes, 28.3 wt% of
butylenes, and butadiene isobutylene, about 10.2
(U.S. Patent No. 8,816,028 wt% of cis- and trans-20
B2, 2014)
butene, and <0.5 wt% of
butadiene and <1.0 wt of
oxygenates. (U.S. Patent
No. 8,816,028 B2, 2014)
Dehydrogenation unit
Downstream stripping steps
Special
are required to remove inert
Equipment
C3 and n-butane from the
Requirement
mixture
Petronas Gas
Raffinate-1 from Lanxess,
Availability
Berhad, Kerteh
Singapore or BASF, Europe
Mode of
Operation

Difficult
- involved more operation
unit
- particularly suitable for
the production of
polyisobutylene in location
in which the inert isobutane
may be utilized

Difficult
- required larger design of
distillation column
- hard to control the
reaction condition
- preferable for the
production of conventional
polyisobutylene

Pure
isobutylene
>90% purity of
isobutylene

No extra
equipment is
required as its
high purity
Obtained from
MTBE plant,
Kerteh
Medium
- highly
suitable for the
production of
HR-PIB

A2

Type of catalyst

Phases
Operating
Temperature
Reusability
Stability
Post Reaction
Removal
Conversion
Overall Plant
Capital, Operation,
Energy Cost
Remarks

Table A2: Comparison between catalysts

BF3
AlCl3

liquid
-80C to 0C

solid
-43C to 16C

BF3/Methanol
Catalyst Complex in
Alumina Support
solid
-40C to 0C

Cannot
Low
Require

Can
High
No

Can
High
No

75% - 85%
High

60% - 85%
Medium

80% - 95%
Low

- Conventional
- Low reaction
temperatures increase
energy requirements
-require washing step

- Conventional
- Require larger
diameter of the fluid
duct leading from the
reactor
-lab scale only

-no catalyst residues

in crude reaction
mixture
-no
subsequent
washing step
-no require catalyst
injection
and
handling system

A3

Table A3: Comparison between loop reactor and fixed bed reactor
Loop
Fixed Bed
Higher catalyst consumption
Lower catalyst consumption
Catalyst
Consumption
Catalyst is charged into the reactor Renewal of catalyst is difficult due to
Catalyst
from the loop together or the need to take out and replace the
Recovery
separately from isobutylene. solid catalyst bed of a few tons.
Catalyst can be recycled only after
purification.
Need to filter out the spent catalyst No need to filter out the spent catalyst
Filtration
after reaction
after reaction. However, a post-reactor
alumina filter is placed to screen out
the unlikely leached boron content.
Process of synthesizing HR-PIB The solid catalyst is packed to form
Process (U.S.
involving two stages:
stationary, completely contained bed.
Patent No.
i.
Provide a feedstock
Feedstock directly enter the fixed bed
US6562913 B1,
comprising isobutylene
reactor from top. When the
2003)
ii.
Provide catalyst
isobutylene is fed to reactor over the
composition BF3-methanol solid catalyst, the polymerization
system
reaction occur.
The feedstock and catalyst are
introduced and recirculated at first
volumetric flow rate. Then, the
composition is introduced at
combined second volumetric rate.

A4

Table A4: Inside battery-limits (ISBL) equipment (inclusive of delivery cost)

Items
Capacity/Area
Unit Cost (MYR)
Quantity
Total Cost (MYR)
3
2
(m /m )
Heat Exchangers
8
352,000.00
10
3,520,000.00
Pumps
10
276,000.00
7
1,932,000.00
Distillation
20
3,500,000.00
3
10,500,000.00
Column
Trays and
20
1,750,000.00
3
5,250,000.00
Internals
Fixed Bed
15
2,300,000.00
1
2,300,000.00
Reactor
Gas Flare
12
1,500,000.00
1
1,500,000.00
Alumina Filter
15
134,000.00
1
134,000.00
Condenser Pot
20
600,000.00
3
1,800,000.00
Gas-Liquid
18
690,000.00
2
1,380,000.00
Separator

28,316,000.00
Table A5: ISBL Fixed Capital Investment Preliminary Estimation (Peters and Timmerhaus
Method)
DIRECT COST
ITEMS
Description
Factors
Cost (MYR)
1
2
3
4
5
6
7
8
9

Delivered Equipment
Cost
Equipment Installation
Instrumentation and
Controls
Piping
Electrical Connections
Building (Including
Services)
Yard Improvements
Service Facilities
Land

1.00

28,316,000.00

0.47
0.18

13,308,520.00
5,096,880.00

0.66
0.11
0.18

18,688,560.00
3,114,760.00
5,096,880.00

0.10
0.70
0.06

2,831,600.00
19,821,200.00
1,698,960.00
97,973,360.00

Total Direct Plant Cost

INDIRECT COST
11
Engineering and
Supervision
12
Construction Expenses
13
Contractor's Fees
14
Contingency

0.33

9,344,280.00

0.41
0.21
0.42

11,609,560.00
5,946,360.00
11,892,720.00
A5

Total Indirect Plant Cost

TOTAL ISBL FIXED CAPITAL INVESTMENT

38,792,920.00
136,766,280.00

TOTAL OSBL FIXED CAPITAL INVESTMENT (40% OF ISBL)

TOTAL PLANT FIXED CAPITAL INVESTMENT, TFC

54,706,512.00
191,472,792.00

Consumables
Isobutane
Isobutylene
Catalyst*
Utilities
Water
Electricity
Inert Gas (N2)
Cylinder
Rental

Table A6: Consumables and utilities

Consumption Rate
Unit Price (MYR)

Annual Cost
(MYR)

7,260 ton/year
64,350 ton/year
12 ton/year

2600.00/ton

186,186,000.00

12800.00 /ton

153,600.00

150 m3/month
160,000 kWh/month

0.92 /m3
0.34 /kWh

1,440 m3/month

4.00 /m3

1,656.00
647,040.00
69,120.00

160 unit/month

10.50 /unit

20,160.00

Table A7: Total estimation of production cost

DIRECT COST
Type
Consumables
Utilities
Operating Labor (OL)
Operating Supervision (OS)
Quality Control
Maintenance Labor

Factor
0.20*OL
0.20*OL
0.027*TFC

Maintenance Material
0.018*TFC
Operating Supplies
0.0075*TFC
INDIRECT COST
Depreciation
TFC/Plant Life
Property Taxes
0.02*TFC
Insurance
0.01*TFC
Fringe Benefits
0.22*(OL+OS)
Medical Facilities
0.5*(OL+OS)
ESTIMATED ANNUAL PRODUCTION COST

Cost (MYR)
186,339,600.00
737,976.00
1,200,000.00
240,000.00
240,000.00
5,169,765.38
3,446,510.26
1,436,045.94
9,573,639.60
3,829,455.84
1,914,727.92
316,800.00
720,000.00
215,164,520.94

A6

Products

HR-PIB
C8 Oligomers
C12-C16 Oligomers

Table A8: Estimated Annual Revenue

Production
Unit Price (MYR)
Rate
(Ton/Year)
50,000
4,500.00 /ton
5,940
2,750.00 /ton
5,940
3,000.00 /ton

ESTIMATED ANNUAL REVENUE

Revenue (MYR)

225,000,000.00
16,335,000.00
17,820,000.00
259,155,000.00

Table A9: Cash flow analysis with cumulative for with and without interest rate
Without Interest Rate (MYR)
With Interest Rate (MYR)
Cash Flow
Present Value
Cumulative
5%
Present Value Cumulative
Year
(MYR)
Interest
0
-191472792.00 -191472792.00 -191472792.00 1.0000 -191472792.00 -191472792.00
1
43990479.06
43990479.06 -147482312.94 0.9500
41790955.11
-149681836.89
2
43990479.06
43990479.06 -103491833.88 0.9025
39701407.35
-109980429.54
3
43990479.06
43990479.06
-59501354.82
0.8574
37716336.98
-72264092.56
4
43990479.06
43990479.06
-15510875.76
0.8145
35830520.13
-36433572.42
5
43990479.06
43990479.06
28479603.30
0.7738
34038994.13
-2394578.29
6
43990479.06
43990479.06
72470082.36
0.7351
32337044.42
29942466.13
7
43990479.06
43990479.06
116460561.42
0.6983
30720192.20
60662658.33
8
43990479.06
43990479.06
160451040.48
0.6634
29184182.59
89846840.92
9
43990479.06
43990479.06
204441519.54
0.6302
27724973.46
117571814.38
10
43990479.06
43990479.06
248431998.60
0.5987
26338724.79
143910539.17
11
43990479.06
43990479.06
292422477.66
0.5688
25021788.55
168932327.72
12
43990479.06
43990479.06
336412956.72
0.5404
23770699.12
192703026.84
13
43990479.06
43990479.06
380403435.78
0.5133
22582164.17
215285191.00
14
43990479.06
43990479.06
424393914.84
0.4877
21453055.96
236738246.96
15
43990479.06
43990479.06
468384393.90
0.4633
20380403.16
257118650.12
16
17
18
19
20

43990479.06
43990479.06
43990479.06
43990479.06
43990479.06

43990479.06
43990479.06
43990479.06
43990479.06
43990479.06

512374872.96
556365352.02
600355831.08
644346310.14
688336789.20

0.4401
0.4181
0.3972
0.3774
0.3585

19361383.00
18393313.85
17473648.16
16599965.75
15769967.46

276480033.12
294873346.97
312346995.13
328946960.88
344716928.34

A7

800000000.00
700000000.00

Cumulative Cash Flow (MYR)

600000000.00
500000000.00
400000000.00
300000000.00
Without Interest Rate (MYR)

200000000.00

With Interest Rate (MYR)

100000000.00
0.00
0

10

15

20

-100000000.00
-200000000.00
-300000000.00

Year

Figure A2: The cash flow analysis in 20 years with and without interest

A8

Table A10: Comparison of three candidate locations with the assessing criteria
Location
Kerteh IPC
Gebeng IPC
Pengerang IPC
No existing HR-PIB
BASF plant of HRNo existing HR-PIB
Marketing
plant. Marketing area
polyisobutylene is under plant. Marketing area
Area
encompasses Asia
construction and
encompasses Asia
Pacific region.
estimate to operate on
Pacific region.
2017. Marketing area
encompasses Asia
Pacific region.
Available; Kerteh Gas
Available; MTBE plant Not available; C4Raw
Processing Complex
with readily available
raffinate can be
Material
isobutylene feedstock.
imported from
Availability produces LPG which
can be used to
Singapore or piping the
synthesize isobutylene.
isobutane from Kerteh.
Near the Kerteh airport
Near Kuantan port for
Near Senai airport and
Transport
and Kuantan port which the export of HR-PIB.
port for feedstock
is easy for the export of
import and HR-PIB
HR-PIB.
export.
Significant job
Significant job
Availability Significant job
opportunities to
opportunities to
opportunities to
of Labor
community.
community.
community.
Electricity and water are Electricity and water are Electricity still under
Utilities
available.
available.
construction.
Vacant land available
Vacant land available
Vacant land available
Total Land
Available
Tropical climate,
Tropical climate,
Tropical climate,
Climate
affected by northeast
affected by northeast
affected by northeast
monsoon season
monsoon season
monsoon season
Coastal area (flat), RM5 Coastal area (flat),
Coastal area (flat),
Land
RM16/ft2, leasehold
RM26-37/ft2, freehold
Topography 10/ft2, leasehold
and Pricing
Paka residential areas in Balok residential areas
Residential in close
Local
in close proximity to
proximity to industrial
Community close proximity to the
industrial estate
industrial estate
estate
Yes
Yes
No
Project
Execution
Immediacy
Income tax exemption
Income tax exemption
3% flat tax charge rate
Incentives
of 100% for 10 years
of 100% for 10 years
income
commencing from the
commencing from the
A9

year company derives

statutory income
Import duty and sales
tax exemption on raw
materials, components,
machinery, equipment,
spare parts and
consumables that are not
produced locally and
used directly in the
activity.

year company derives

statutory income
Import duty and sales
tax exemption on raw
materials, components,
machinery, equipment,
spare parts and
consumables that are not
produced locally and
used directly in the
activity.

50% exemption on gross

employment income for
non-Malaysian
professionals, staffs
including traders
5 years blanket approval
Flexibility to operate
anywhere in Malaysia.

A10

Table A11: Preliminary mass balance of the proposed HR-PIB plant at 50 kMT (equivalent to 6315 kg/h)
Stream

10

922.42
8013.35
0.00
0.00
0.00

959.13
833.23
0.00
0.00
0.00

871.94
757.48
0.00
0.00
0.00

1009.61
8770.83
0.00
0.00
0.00

1009.61
877.08
789.37
789.37
6315.00

959.13
833.23
0.00
0.00
0.00

50.48
43.85
789.37
789.37
6315.00

47.96
41.66
749.91
0.00
0.00

47.96
41.66
0.00
0.00
0.00

0.00
0.00
749.91
0.00
0.00

11

12

13

14

15

16

2.52
2.19
39.47
789.37
6315.00

2.40
2.08
37.50
749.91
0.00

2.40
2.08
37.50
0.00
0.00

0.00
0.00
0.00
749.91
0.00

50.35
43.74
37.50
0.00
0.00

0.13
0.11
1.97
39.47
6315.00

Components

Isobutane
Isobutylene
C8 Oligomers
C12-C16 Oligomers
HR-PIB
Stream
Components

Isobutane
Isobutylene
C8 Oligomers
C12-C16 Oligomers
HR-PIB

*All values are displayed with the unit kg/h, refer to Figure A3 for stream identification

A11

Figure A3: Preliminary process flow diagram (PFD) of the proposed HR-PIB plant with operating parameters of major equipment
A12