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The Polyolefin

Industry

Jomari O. Magadan
BS Chemical Engineering
University of the Philipipnes Diliman

The Polyolefin
Industry

In Partial Fulfilment of the Requirements for Chemical Engineering 140:


Chemical Process Industries

Jomari O. Magadan
2010-46743
BS Chemical Engineering
May 2015

Table of Contents
Industry and Market Profile .......................................................................................................................... 3
Industry Overview .................................................................................................................................... 3
Philippines Market .................................................................................................................................... 4
Global Market ........................................................................................................................................... 9
Manufacturing Process................................................................................................................................ 10
Raw Materials ......................................................................................................................................... 10
Manufacturing Process............................................................................................................................ 10
Health, Safety, and Environment ................................................................................................................ 19
Occupational Safety ................................................................................................................................ 19
Process Safety ......................................................................................................................................... 19
Quality Assurance ................................................................................................................................... 20
Waste Management ................................................................................................................................. 21
Product Development and Process Development ................................................................................... 22
References ................................................................................................................................................... 22

Industry and Market Profile


Industry Overview
The polyolefins industry is one of the fastest growing industries because of its key role in
manufacturing and packaging industry. What makes polyolefins such a competitive market is that
despite their wide use, they are made up of simple hydrocarbon monomers. Polyolefins compose
the largest group in thermoplastics and are polymers of olefins, non-aromatic hydrocarbons more
commonly known as alkenes where a carbon atom is double-bonded to an oxygen atom. They are
generally non-polar, non-porous, and have low energy surfaces which makes it hard for inks and
prints to adhere under normal conditions. Polyethylene (PE) and polypropylene (PP) are the two
most important polyolefins because of their low cost and wide range of applicability.
Polyethylene was accidentally discovered in 1931 at the research laboratory of Imperial
Chemical Industries while observing a different reaction. Further examination of the polyethylene
showed that it had promising properties which could be used in an array of applications.
Polypropylene production and studies were also started in the mid 1950s. Nowadays, feed stocks
for polyolefin production come from petroleum refineries. Several studies are also being done on
catalysts used in the polymerization process.
Polyethylene can be divided into three types based on its properties and are given as
follows: low density (LDPE), linear low density (LLDPE), and high density (HDPE). LDPE and
LLDPE are most commonly used in film packaging and electronic cables. HDPE is used for
making more rigid containers, drums, industrial packaging, and pipes. Figures 1 and 2 illustrate
how PE is divided in the market based on its application.

Polyethylene Production per Grade

LDPE
18%
HDPE
46%
LLDPE
36%

Figure 1. Market segmentation of polyethylene based on grade

HDPE Applications

Blow moulding
41%

Injection
moulding
24%
Film
16%
Pipe
14%

Others
5%

Figure 2. Market segmentation of HDPE based on use

LDPE/LLDPE Applications
4%

7%

5%

Film
Extrusion coating

8%

Injection moulding
Wire and cable

76%

Others

Figure 3. Market segmentation of LDPE and LLDPE based on use

Philippines Market
The Philippine economy is improving as seen in Figure 1 which is a general trend among
ASEAN nations. More industries and foreign investors are brought in the country and contribute
to this increase in GDP. In 2014, it had a GDP of 272.02 billion USD, accounting for 0.44% of the
world economy and growing at an annual GDP growth rate of 6.9%. Compared to Thailands
387.25 billion USD and Singapores 297.94 billion USD, the Philippines has a relatively weaker
economy but still belongs to the more competent economies in Asia.

Figure 4. Philippines GDP (billion USD) compared to Thailands GDP (billion USD)
This improving economy is brought about by the increase in foreign investments,
expansions of some manufacturing companies, and the improving status of the petroleum industry.
Because of the wide applicability of polyolefins and their importance as raw materials in
packaging, the polyolefins consumption in the Philippines is also seen to be stable as illustrated in
Figure 4. Despite the expansions and developments in the construction and manufacturing
industries, legislations against the use of plastic products also played a part in controlling the
markets growth. The presence of petroleum refineries also mean that raw materials for polyolefin
production are also available within the country. However, still, bulk of the raw materials used are
still imported from other countries. Polyolefins play a wide role in the manufacturing and
construction industries and as such, the local demand for polyolefins is also seen to keep up with
the
improving
manufacturing
and
construction
industries.

Figure 5. Philippine Housing Index (PhP/m2)

Figure 6. Building Permits Issued in the Philippines


Cost of housing is seen to be decreasing and at an all-time low since 2012. This means that
families are now more likely to afford building their own homes, giving construction a boost. After
reaching its peak during the second quarter of 2014, the number of Philippine building permits
decreased by around 30% but is still stable around 29,000. However, looking at previous trends, a
sudden drop might be expected to arise any time soon.

Figure 7. Philippines Consumer Spending


The packaging and manufacturing industry is also expected to improve in the near future
as local consumer spending is seen to be steadily increasing. The Philippine GDP per capita PPP
is also at its peak at 6,324.58 USD. All of these points to suggest that the spending power of the
Filipinos is steadily increasing.

Philippines Polyolefins Consumption


800,000

Gross Weight (MT)

700,000
600,000
500,000

PVC

400,000

PS
PP

300,000

PE

200,000
100,000
0
2009

2010

2011

2012

2013

Figure 8. Local Polyolefins Consumption from 2009 to 2013


Polyethylene and polypropylenes dominance is perfectly demonstrated in Figure 4, where
PE alone contributes to almost half of the total consumption of the country. Looking at the import
and exports of polyolefins in the country. We can see that the Philippine polyolefins industry has
been depending more on imported products than locally produced ones. This can be inferred from
the decrease in exports (Figure 6) and the increase in imports (Figure 5) in the country. Figure 11
also compares the local demand of PP and PE, showing how the demand for PE is nearly twice as
that of PP.

Philippine Polyolefins Import (GK)


600,000,000.00

Gross Weight (kgs)

500,000,000.00
400,000,000.00
300,000,000.00

Polypropylene, others

200,000,000.00

Polyethylene

100,000,000.00
2010

2011

2012

2013

2014

Year

Figure 9. Polyolefins Import in the Philippines (2010-2014)

Philippine Polyolefins Export (GK)


Gross Weight (kgs)

140,000,000.00
120,000,000.00
100,000,000.00
80,000,000.00
60,000,000.00
40,000,000.00
20,000,000.00
2010

2011

2012

2013

2014

Year
Polyethylene

Polypropylene, others

Figure 10. Polyolefins Export in the Philippines (2010-2014)

PE vs PP Consumption
400,000
350,000
300,000

MT

250,000
PE

200,000

PP

150,000
100,000
50,000
0

2009

2010

2011

2012

2013

Figure 11. PE vs PP consumption in the Philippines


In the Philippines, the major players in the polyolefins industry are JG Summit
Petrochemical, Corp., Petron Polypropylene Inc., and NPC Alliance Corporation. JG Summit
Petrochemical produces around 200,000 MT of polyethylene while almost 180,000 MT of
polypropylene annually. NPC Alliance Corporation also produces 250,000 MT/yr of polyethylene
resin.
Petron Polypropylene Inc., (PPI) is the polypropylene plant subsidiary of the Petron
Corporation located within the PNOC-AFC Industrial Park in Mariveles, Bataan. It was
established in 1997 as a response to the increasing demand of petrochemical products. It currently

runs at an annual plant capacity of 160,000 MT but can be expanded to 225,000 MT/year upon
operation of their second reactor. PPI produces different grades of polypropylene resins for
different applications. The raw feedstock in their production process is propylene which is directly
sent by the Petron refinery in Bataan. They make use of the Novolen process from Germany which
can be summarized into three basic operations reaction, polymer-gas separation, and extrusion
and degassing.

Global Market
The global polyolefin market has been seen to be growing at an annual average growth rate
of 4.9% (LDPE 3.1%, HDPE 5.0%, LLDPE- 6.5%, PP 5.1%) with strong demand growth in
Asia, Europe, Brazil, and Middle East-Africa. Global capacity is seen to be growing at 4% while
the global demand grows at 5%. Several expansions are also to be expected across different
regions. Global polypropylene demand was also seen to be growing annually at an average of
2.95MMT from 2011 to 2015. Although PP expansions in the Middle East and Africa are limited,
China is undergoing several expansions and is expected to achieve 25.9MT/yr of PP capacity. As
the Asia-Pacific market continues to grow faster than the others and acquiring as much as 45% of
the global market, the Asia-Pacific polyolefin market is expected to increase its exporting
capability and reduce its dependency on imports.
Table 1. Annual Production of polyethylene in million tons (2011)
LDPE
HDPE
23.3
25.5
World
6.7
5.1
Europe
3.5
6.5
US
Total 1.4
Russia
1.9
Middle East
3.5
1.4
China
4.3
6.4
Rest of Asia

LLDPE
7.4
1.1
2.8

1.6
1.8

Countries such as Thailand, Malaysia, and Singapore are also looking to increase capacity
to meet increasing demands and to improve exports to China. The ASEAN Free Trade Agreement
also paves the way for better trade options within the region as it accompanies the increase in
demand. Polyethylene demand in Southeast Asia is expected to increase from 4.89 million MT/yr
in 2011 to 6.17 million MT/yr in 2016 while production is also expected to increase from 6.28
million MT/yr to 9.29 million MT/yr within the same period because of several new plants that
are to start running. Majority of the polyolefins produced in the region are exported to China, the
largest producer and consumer of polyolefins the world.
Thailand is the biggest exporter of polyolefins to China, owing to its large natural gas
reserves and the polyolefin plants located near the sea which makes for strategic trade locations.
Besides China, there are also other Asian countries which import polyolefins, providing other
countries with trade opportunities. Vietnam, for example, cannot satisfy its local demand for
polyolefins which has been growing at an average of 15% annually over the last decade.

Manufacturing Process
Raw Materials
Polyolefins are generally produced from steam cracking of either natural gas or naphtha.
In high purities, ethylene or propylene monomers are directly piped from the petroleum refinery
to a polymerization plant. Feedstocks may also be delivered by naval freight and trucks. In more
recent trends, polyolefins may also be derived from methanol. Methanol is produced from
synthesis gas and is further processed to obtain high purity ethylene and propylene. Bio
petrochemicals can also be a source of polyolefins as in the case of ethanol dehydration to produce
ethylene.
In the production of polypropylene, the main feedstock is polymer grade propylene having
at least 99.5% purity by weight. Impurities in the feed may either be inerts or copolymerizable
components, such as ethylene and butenes, where the latter may affect the final polymer properties
at a certain degree. Inerts are mainly propane, ethane, methane, nitrogen, and other higher saturated
hydrocarbons. These, on the other hand, act as diluent and reduces the final polymer yield. Other
impurities such as acetylene, dienes, CO, CO2, O2, water, alcohols, H2S, COS, arsine, and other
sulphur-containing components act as catalyst poisons.
Different catalysts are used in the production of polyolefins and may affect the polymer
properties and yield accordingly. In low pressure polymerization of polyethylene, three types of
catalysts may be used Ziegler/Natta, Cr/Mo oxide, or metallocene. In polypropylene production,
they also use the Ziegler/Natta catalyst or titanium tetrachloride with magnesium chloride support
and is present either as dry powder or in slurry form with solvent or mineral oil. Co-catalysts are
also used in conjunction with the main catalyst in the polymerization process. For example, in
polypropylene production, tri-ethyl aluminium (TEA) is also used to activate the titanium catalyst.
Cyclohexyl methyl dimethoxy silane (CMMS, silane) controls the isotacticity index of the polymer
and acts as a stereomodifier.
Hydrogen acts as the terminating agent in the polymerization reaction and controls the melt
flow rate (MFR) of the polymer powder. For slurry reactors, heptane is used as a solvent in the
catalyst slurry. It is also used as a diluent in the silane solution and for flushing catalyst, TEA, and
silane lines. Pure nitrogen (99.999% purity) is used in the process for inerting of vessels, lines, and
equipment, and blanketing flammable and pyrophoric compounds such as TEA, silane, and
heptane. Hydrogen and nitrogen are both delivered by trucks into the plant facility.

Manufacturing Process
The processing of polyolefins may be divided in three steps upstream, midstream, and
downstream. Upstream processes involve processes that lead to the extraction of olefins (ethylene
and propylene) from petroleum and natural gas. Midstream processes include processing of olefin
monomers to yield synthetic polymer resins. Finally, downstream processes deals with processing
of synthetic resins to produce finished plastic products. In this study, we will only tackle only the
midstream processes on the manufacturing of polyolefins.

Polymerization techniques for polyolefins generally can be classified either as high


pressure polymerization or low pressure polymerization. High pressure polymerization is
commonly used in the production of LDPE and usually operates at pressures of 800-3000 barg and
temperatures of 80-300 C. It is usually done in autoclave or tubular reactors with free radical
catalysts such as peroxides as initiators. The polymerization reaction occurs in a random manner
and produces a wide distribution of molecular sizes. Polyethylene was discovered via chance
observation in 1933 by an ICI research team of the formation of a waxy polymer formed after
subjecting benzaldehyde and ethylene at 170C and 190 MPa. This was then patented by 1936 and
started small-scale production in 1939. The polymerization produces a white polyethylene solid
from the reaction of ethylene with minute amounts of oxygen.
Autoclave reactors in industrial high pressure polymerization of ethylene can be singlestirred tank reactors, cascades of stirred reactors, or multi-chamber autoclaves. Single-stirred tank
reactors were used in the first generation technologies of polyethylene production. Nowadays,
however, they find use most commonly in low capacity plants or laboratory scale operations. These
reactors are usually made with thick-walled or two-layer shrunk mantle. Typical length to inner
diameter ratios are between one and two with reactor volumes between 1-2 m3.

Figure 12. Process Flow Diagram of High Pressure Polymerization of Ethylene


Low pressure polymerization, on the other hand, uses catalysts to allow the reaction to
proceed even at lower pressures. Operating pressures range only from 10 to 80 barg while

temperatures still run from 70 to 300 C. Low pressure processing produces LLDPE and HDPE
and sometimes makes used of co-monomers such as butene, hexene, and octene.

Low pressure polymerization can still be subdivided into three different processes: (a)
solution process, (b) slurry process, and (c) gas phase process. In the solution process, both the
catalyst and the polymer product remain dissolved in a solvent. Further processing is therefore
needed to isolate the polymer. The polymerization in the solution process takes place in a CSTR.
The slurry process also takes place in a CSTR and sometimes in tubular reactors but in this process,
the catalyst and polymer are suspended in a liquid medium without being dissolved. Finally, in a
gas phase process, there is no solvent used and the monomer feed and catalyst are blown into a
fluidized bed reactor.

Figure 13. Process Flow Diagram for Novolen Process of Polypropylene Production 1

Figure 14. Block flow diagram of a typical polyolefin plant

Generally, polymerization plants may be divided into three sections or units: (a)
polymerization/reaction, (b) degassing and pelleting, and (c) vent recovery. In some cases, vent
recovery or recovery of unreacted gases are within the degassing section while separating the
extrusion or pelleting section. Unreacted gases are mixed with the fresh feed and used as reactants.

Figure 15. Typical process sections in polypropylene plant

In PPI, they divided their process as follows: (a) reaction section, (b) polymer-gas
separation, and (c) extrusion and degassing section.
Olefin monomers are first sent to the plant via naval freight or pipelines from petroleum
refineries. Co-monomers, if used by the process, may also be delivered in a similar manner. These
are then stored in refrigerated and pressurized storage tanks. Fresh feed is mixed with the unreacted
monomer and passes through purification towers.

Figure 16. Purification/safeguard towers


In the purification towers, alumina balls and mole sieves are present for moisture removal,
nickel catalyst trilobes for arsenic and sulphur removal, and copper catalyst for oxygen removal.
The alumina balls also remove CO and CO2 in the incoming feed stream and can be regenerated
using hot nitrogen. The copper catalyst can be regenerated with hot hydrogen while the mole sieve
is also regenerated with hot nitrogen. A nitrogen heater, therefore, heats nitrogen gas up to 230 C
for the regeneration of the catalysts.

Figure 17. Nitrogen gas heater


In the first section, the reaction section, gases hydrogen, ethylene and propylene are fed at
the bottom of a vertical gas phase stirred reactor. Then, the catalyst, co-catalyst, and stereomodifier
is also sent to the reactor. The recycle gas leaving the reactor is then condensed and fed back to
the reactor. The reactor operates at 80-82 C and 28-30 bar. The polymer powder and the carrier
gas leave the top of the reactor and undergoes degassing. The polymer-gas separation section starts
off with a discharge vessel where the reactor product enters the vessel while the unreacted
monomer is vented for recovery. The product then enter a second vessel, the purge vessel, where
nitrogen is used to recover the remaining gases. Polymer powder leaving the bottom of the purge
vessel is then sent to a powder silo using nitrogen as conveying medium. The gas leaving the
reactor also passes through distillation columns to recover unreacted propylene.

Figure 18. Polymer-gas separation section

Figure 19. Propylene recovery section

Finally, in the extrusion section, polymer powder is mixed with additives to further
manipulate the polymer properties. Additives used include stabilizers, primary and secondary antioxidants, chlorine scavenger, slip agent, anti-block agent, anti-static agent, UV stabilizers, and
clarifying agent. As the powder goes through the length of the extruder, it slowly forms into a melt
and passes through a die cutter to produce pellets. Water is added to the freshly cut pellets to hasten
the cooling and hardening process. The pellets are then dried in a centrifugal drier where the water
is recycled in the extrusion process. Dried pellets are then sent to another vessel for desorption
using low pressure steam and nitrogen gas. The final product leaving the desorber can now be sent
to packaging or storage.

Figure 20. Novolen Process for polypropylene production in continuous operation1


The reactor is a 75 m3 vertical gas phase stirred reactor with a helical ribbon impeller. In
some cases, two reactors are operated in series for full product coverage. The extruder is a W&P
ZSK 300 twin screw extruder with an underwater pelletizer. The extruder has a rated capacity of
31 MT/hour and works using a 6.5 MW motor. Product silos have 130 MT capacity and are made
from aluminium. All other equipment in the process may be constructed using carbon steel.
The plant gets its power from the grid at 138 KV. Its electrical system steps it down to
4160 V for motors rated higher than 250 kW, 440 V for low voltage applications, and 220 V for
lighting. It also uses a DCS for process control and is equipped with fire alarms and gas detector
alarms. The plant also uses high pressure (HP) and low pressure (LP) steam as utilities. HP steam
is produced in a HP steam boiler working at 55 bars and producing steam at 1000 kg/hr. LP steam

is also produced by an LP steam boiler working at 3.5 barg and produces 8000 kg/hr of steam. The
boilers use diesel oil as fuel and in some cases off-gas fuel. Demineralized water is produced at 10
m3/hr while the cooling water system uses 4 cooling water pumps at 2900 m3/hr each.

Health, Safety, and Environment


Occupational Safety
As in any chemical manufacturing plant, all personnel are expected to wear personal
protective equipment which comprises of sleeved jackets, long pants, safety shoes, safety goggles,
dust masks, safety helmets, and ear plugs. Because polyolefin plants handle various flammable
and volatile materials, their protective clothing are made from a special fabric which is meant to
prevent skin burns in case of fires. The fabric, when combusted, breaks apart in flakes or fragments
instead of melting. These are also made from a reflective material to prevent accidents at night or
at dark areas in the plant. Strict security is also imposed in the plant facility where authorized
personnel are only given access to certain areas provided that they are wearing their PPEs. The
plant is also divided into certain areas depending on the level of security. Thus, personnel are only
granted access to areas where they are expected to work.
In polyolefin plants, most of the occupational issues such as heat stress, noise stress,
explosion and fire hazards, and dust and volatile material inhalation are addressed by PPEs, placing
safety and warning signages, regular seminars on firefighting, and disaster evacuation trainings.
Material safety data sheets are also available to guide employees in chemical handling. Generally,
there is minimal exposure of the employees to process equipment because of the plants control
systems. Pedestrian lanes are also present in main roads and access roads in the plant to prevent
vehicular accidents.

Process Safety
Table 2. Hazardous Chemicals Used
Chemical
Ethylene, Propylene

Use/Role in process
Raw material

Polyethylene,
polypropylene

Product

Cyclohexyl methyl
Co-catalyst
dimethoxy silane (CMMS)
Tri-ethyl aluminium (TEA) Co-catalyst

Hydrogen

Terminating agent

Health Hazards
- Toxic
- Irritant
- Flammable
- Toxic
- Irritant
- Combustible
- Irritant
- Toxic
- Pyrophoric
- Irritant
- Toxic
- Corrosive
- Explosive
- Flammable
- Asphyxiant

Heptane
Nitrogen
Titanisum tetrachloride

Solvent
Inerting agent
Catalyst

Flammable
Asphyxiant
Toxic
Irritant

The process uses several chemicals, each with its own hazard and the corresponding
handling measures. To identify how these chemicals are handled, employees refer to MSDS and
are given safety trainings to understand the process and the risks and hazards involved. Raw
materials and products in polyolefin plants are hydrocarbons which are generally flammable, toxic
and causes mild skin irritation and corrosion. When manually handling these hydrocarbons,
personnel must wear PPE including face masks to prevent inhalation of volatiles.
Chemicals in the process that pose the greatest explosion risks are compressed hydrogen
gas and TEA. TEA is a pyrophoric material which means it reacts explosively upon exposure to
air or water, thus extreme caution is done when handling this compound. Emphasis is given in its
storage and handling to prevent contact with water or air. Storage vessel for TEA must therefore
be explosion-proof and tightly sealed and should be located in isolation from heat and sources of
ignition. Similarly, the same precautions should be done in handling and storage of other explosive
and flammable compounds. Molten polymers in the extrusion section may cause serious skin burns
and as such requires PPE with safety gloves and goggles when working near the extruder.
Process safety is observed in both engineering and administrative sectors of the plant. The
process and engineering departments identify the risks and hazards involved in the process, set
standards and codes in plant operation and construction of pressure vessels and other equipment.
They also set the lower and higher limits for parameters that may trigger alarms for incidents and
emergencies that pose health and safety risks. Engineers also work with the administrative sector
to produce job hazard analyses for their employees and safety studies such as Hazard Operability
study (HAZOP) and Hazard Identification Risk Assessment and Control (HIRAC). These studies
are then used to implement safety interlocks, alarms, and instrumental safety systems. Safety
instrumentation allows the engineers to monitor leaks and potentially dangerous equipment
conditions remotely and call on safety interlocks and automatically shut the plant or sections of
the plant in case of an emergency. In Petron Polypropylene, Inc., they use Safety Instrumentation
Level 3.
The plant also goes into a regular full-scale plant shutdown for a whole month in one year
for maintenance and equipment check-up. The plant may also undergo a two-week emergency
shutdown to close off and repair certain sections in the plant.

Quality Assurance
Polyolefin resins are usually sold as white crystalline pellets. Generally, discoloration
suggests degradation or oxidation of the polyolefin. When exposed to oxygen, polyolefin resins
degrade similarly to rusting in that they form a yellowish brown discoloration and flake away at
the surface. During degradation, the polymer chain is gradually split. As chain length decreases,
the melt flow index also increases and generally, its physical properties also start to deteriorate.

Normally, this can be addressed by adding a number of antioxidants. Primary antioxidants are
added to provide end use product stability while secondary antioxidants are added for color and
stability during pelletizing and extrusion. To identify whether the pellets are within specifications
and are not undergoing significant discoloration, discoloration is measured via spectroscopy to
determine its yellowness index. This value therefore can be compared to standards and used for
determine problems in the process.
Discoloration may also be caused by a phenolic compound within the resin. Generally,
these phenolic compounds are usually the antioxidants themselves. Discoloration may be the effect
of two phenomena: (a) an insufficient amount or incorrect selection of antioxidant needed to
stabilize the resin under normal processing conditions, or (b) presence of chemical interactions
that oxidize phenolic compounds without the application of heat. In this case, discoloration
suggests that the antioxidants have already been used up and the natural degradation of the
polyolefin resin is now more likely to occur. To correct for this negative impression from
discoloration, the most common solution is to simply increase the concentration of the antioxidant
system. Another method is to switch to a more suitable antioxidant additive less susceptible to
coloring based on process conditions and other co-additives. One may also opt to use a second
antioxidant to divide the oxidizing workload between the two additives. Finally, if possible, instead
of using a phenol-based stabilization system, one may also shift to a phenol-free stabilization
system to entirely remove the possibility of antioxidation overoxidation.
Before sending to storage or delivery, pellets undergo several testing procedures to ensure
that the products are within consumer specifications. One of the properties tested in the laboratory
is the melt flow index. This basically is a measure of how fluid or viscous the resins are when
melted. A more viscous melt has a lower melt flow index and suggests longer chain lengths. Chain
length or the molecular weight of the polymer also correlates to the materials strength.
Odor is also a general issue in polymer resins. These may come from several sources, from
possible microbes in the resin, odorous additives or simply excess VOCs trapped in the resin.
Although, generally, it has nothing to do with the resins physical integrity, odors are unwanted
features in plastic products, especially as some of them are used in the medical and food industry.
Odor may be removed by using deodorizers or adsorbers to remove the odorous molecules from
the pellets or in other cases, additives are used to kill microbes, trap, neutralize, or modify odorous
molecules. Furthermore, scent additives may be added to mimic fragrance or mask the odor in the
resins.

Waste Management
Chemical wastes in polyolefin plants are minimal and mainly comprise of wastewater and
excess additives. The process involves several hydrocarbons and other volatile compounds that are
usually found as off-gases in the polymerization and gas-separation sections. These off-gases are
collected and sent to a flare. Based on their emission tests, their exhaust gases contain 1% of the
allowed limit by DENR. This waste gas comprises 90% of the fuel they use in the plant, with 10%
coming from low sulphur diesel. Failed batches or polymer pellets that do not meet the desired
specifications are simply recycled back into the extrusion process. Other more harmful chemicals
such catalysts and additives are recovered and sent for a third-party waste disposal. The process

also uses water for steam generation, underwater extrusion, and domestic use. Wastewater in
polyolefin plants contain a low BOD that it can already be released into the environment without
further treatment. Monthly testing has shown that their effluents contain only 3-5 ppm of BOD
compared to maximum limits of 30 ppm. Their wastewater is then sent to the Manila Bay for
discharge.

Product Development and Process Development


Polyolefins are widely used in the packaging, construction, and even the automobile
industry where customers demand a wide variety of polymer grades in different applications.
Furthermore, the constant effort to reduce and remove VOCs, phthalates, and sulphur compounds
in the polymers is still observed in polyolefin manufacturing plants. Nowadays, studies on new
sources of feedstocks and more efficient catalysts are being done to improve product outputs and
the overall process performance.
Polyolefins with novel properties for specific applications are also being developed. These
include low-cost anti-bacterial polyolefins, anti-static polyolefins, high purity polypropylene, and
self-cleaning polyolefins for washing machines and anti-mould protection. Other than the
conventional gas-phase process for PP production, there are also studies exploring this gas phase
process for polyethylene and high-temperature gas-phase process for PP. Generally, we also see
plants operating in multi-modal process, series of reactors are used to produce a wider product
coverage or more diverse range of molecular sizes. Regular polyolefin plants only use one to two
reactors in series, but further studies encourage the use of more reactors in series. New catalysts
are also being used to achieve the low phthalate and ash content in the products and for more
versatile applications as in multimodal operation. Similarly, as high temperature processes are
being explored, special catalysts for these operations are also being made.
The propylene to ethylene price ratio has also been seen to be decreasing within the past
three years thus prompting the slight shift of feedstocks from ethylene to propylene. Relative price
ratios between natural gas and crude oil are also seen to be in favour of natural gas as a source of
raw material. There are also new studies and undertakings in developing polyolefin production
using shale gas and coal. Shale gas also is seen to boost the production of polyolefin resins in U.S.
and Canada as availability of cheaper raw materials is also increased.

References
[1] Bertucco, A., Vetter, G., High Pressure Process Technology: Fundamentals and
Applications. Elsevier, 2001.
[2] Lepoutre, Priscilla., The Manufacture of Polyethylene, Transpak Industries, Ltd.
[3] National Statistics Office, Value and Volume of Philippine Imports (2010-2014)
[4] National Statistics Office, Value and Volume of Philippine Exports (2010-2014)
[5] Petron Polyproylene Inc., Petron Corporation

Online Sources
[1] http://www.sciencelab.com/msds.php?msdsId=9925270
[2] http://avogadro.chem.iastate.edu/MSDS/nitrogen.pdf
[3] http://avogadro.chem.iastate.edu/MSDS/hydrogen.pdf
[4] http://www.lookchem.com/msds/2011-06%2F1%2F29463(17865-32-6).pdf
[5]
http://www.oshc.dole.gov.ph/UserFiles/oshc2010/file/occupational_safety_and_health_standards
.pdf
[6] http://www.sciencelab.com/msds.php?msdsId=9924237
[7] http://www.petroleum-economist.com/pdf/andreaborruso.pdf
[8] http://www.nasdaq.com/markets/natural-gas.aspx
[9] http://www.wraconferences.com/sites/default/files/8%20-%2015.50pm%20%20Sun%20Junnan.pdf
[10]
https://www.academia.edu/4066905/POLYETHYLENE_PRODUCTION_TECHNOLOGIES.
[11] http://www.essentialchemicalindustry.org/polymers/polypropene.html.
[12]
http://base.intratec.us/home/chemical-processes/polypropylene/polypropylene-via-gasphase-polymerization
[13] http://www.tradingeconomics.com/philippines/gdp
[14] http://www.essentialchemicalindustry.org/polymers/polyethene.html
[15] http://www.americanchemistry.com/2009-year-in-review
[16] http://www.ptonline.com/articles/additive-masterbatches-make-polyolefins-degrade
[17] http://www.ampacet.com/faqs/yellowing-and-pinking-white-pe-pp/