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PAMANTASAN NG LUNGSOD NG MAYNILA

University of the City of Manila


Intramuros, Manila

Petrochemicals
In partial fulfilment of the course
CHE Elective I
Submitted by:
Raymundo, Karl Joshua

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Submitted to:
Engr. Milagros R. Cabangon
OUTLINE:
Introduction
Physical Characteristics
Uses of Propylene Oxide
Production Plants of Propylene Oxide in the Philippines

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Process involving Propylene Oxide


Reactions from Propylene to Propylene Oxide
Chlorohydrin process
Hydrogen Peroxide process
Safety Procedures and Practices for Propylene Oxide
Exposure Potential
Measures in the event of a release of Propylene Oxide

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Measures in the event of a Fire


Personal protection
First aid and medical treatment
Storage & Handling of Propylene Oxide
INTRODUCTION

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Propylene oxide is a colorless low-boiling and highly volatile liquid with a sweet ether-like
smell. It is highly flammable and reactive. Propylene oxide reacts readily with alcohols, amines,
and acids. Propylene oxide also reacts with water to form Propylene Glycol.
Physical Characteristics
Molar Mass
Melting Point @ 101.3 kPa
Boiling Point @ 101.3 kPa
Flash Point
Critical Temperature

58.08 g/mol
-111.9C
34.2C
-37C
209.1C

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Critical Pressure
Critical Density
Critical Compressible Factor
Auto ignition temperature in air at
101.3 kPa
Heat of combustion (25C 101.3
kPa)
Heat of Polymerization
Heat of fusion
Heat of solution in water at 25C

4920 kPa
312 kg/m^3
0.2284
449C
-33035 kJ/kg
-1500 kJ/kg
112.6 kJ/kg
-45 kJ/kg

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Heat of formation of the ideal gas


(25C)
Heat of formation of liquid
Propylene Oxide (25C)
Standard enthalpy (298.15K)
Standard entropy (298.15K, 1
atm.)
Free energy of formation (25C,
101.3 kPa)

-1600 kJ/kg
-2080 kJ/kg
248 kJ/kg
4.94 kJ/kg -1 K-1
459 kkJ/kg

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Solubility of Propylene Oxide in


water at 20C
Solubility of water in Propylene
Oxide at 20C
Density g/cm^3 at 20C
Vapour pressure (kPa at 20C)
Saturation concentration at 20C
Minimum ignition energy

40.5 wt%
12.8 wt%
0.83
57.7
1360 g/m^3
0.13 mJ

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Flamability Diagram and Triangle of Propylene oxide

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Product Uses
Propylene oxide is an intermediate used in
the manufacture of a wide variety of important
chemical products such as:

Polyether
polyols
(polyglycol
ethers),primarily used to make
flexible and rigid polyurethane
foams and surface active agents

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Propylene glycols used in the manufacture of unsaturated polyester resins,


pharmaceuticals, cosmetics, food, heat transfer fluids, antifreeze, and aircraft
deicing fluids
Propyleneglycol ethers used in solvents and as coupling agents in paints and in
the production of coatings, inks, resins, and cleaners
Polyglycols and other propoxylated derivatives produce flame retardants,
solvents, metal-working fluids, cosmetics, resins, coatings, varnishes, floorings,
automotive parts,and many other products in the construction, paint, food, and
pharmaceutical industries.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Production Plants of Propylene Oxide in the


Philippines
JG Summit Petrochemicals Group
Naphtha Cracker Plant

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

JGSOCs $700 million Naphtha Cracker Plant uses Lummus Technology (a CB&I
company) which is one of the more widely applied processes for the production of
polymer-grade ethylene and propylene. This plant is designed to produce 320 KTA of
ethylene and 190 KTA of propylene.
Features of JGSOCs ethylene process as adopted from Lummus Technology are:

Use of Short Residence Time (SRT) pyrolysis furnace for high olefins yield, high
thermal efficiency, long run-length, feed flexibility

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Quick Quencher Transfer Line Exchanger (TLE) for low pressure drop and short
residence time resulting in minimum yield degradation
TLE decoking technology for reduced maintenance, longer tube life and less
emissions
Low pressure chilling train for energy efficiency and lower investment cost
Hydrogenation process for acetylene/diene towards higher selectivity,
minimization of green oil production and reduction of energy consumption
Tertiary refrigeration that results in lower investment cost, enhanced reliability
and simplified maintenance

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Polymers Plant
Commissioned in 1998, JGSSPCs Polymer Plant was constructed in a 27.9hectare lot by Mitsubishi Heavy Industries as turnkey contractor and with EEi, DMCI and
Cape East as subcontractors. The Group initially invested $350 million to build the
Polymer Plants. Another $100 million were spent for its expansion which was completed
in 2014.
The JGSPC Plant has the following facilities:

Two reactors for Polyethylene with 320 KTA combined capacity

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

One reactor for Polypropylene with 190 KTA per annum capacity
Central Control Room with Distributed Control System (DCS) Technology by
Honeywell-Yamatake
Tank Farm with cryogenic and ambient storage tanks and Flare Facilities
Laboratory with state-of-the-art instruments for Quality Control, Quality Assurance,
Product Applications and Technical Services
Closed-loop Cooling Water System, with heat exchange to sea water
Jetty that can accommodate 54,000 DWT vessels

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Three-hectare covered warehouse for storing up to 37,000 tons of packaged


products. It includes a packaging facility for loading products into 25kg, 750kg, and
1,000kg bags, as well as in-house heavy duty bag-making equipment.

PROCESS INVOLVING PROPYLENE OXIDE


The process of getting propylene oxide starts with the cracking of naphtha. After that the
long carbon chained carbon will enter the quench tower in gas state going to the compressor. It
will then enter into different processes of distillation such as the depropanizer, demethanizer

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

and deethanizer. After that, the products will go to the propylene splitter to produce a
condensate of propylene and a distillate of propane which will be used to supply the fuel source
of the whole plant.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Reactions from Propylene to Propylene Oxide


The two manufacturing processes used by Dow to produce propylene oxide
commercially are the chlorohydrin process and the hydrogen peroxide process. In the
chlorohydrin process, propylene is reacted with hypochlorous acid to form propylene
chlorohydrin, which is subsequently reacted with sodium or calcium hydroxide to form propylene
oxide and sodium or calcium chloride. In the hydroperoxide process, propylene reacts with
hydrogen peroxide producing propylene oxide and water, with no significant co-products.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Chlorohydrin process
The main method to obtain propylene oxide is chlorohydrination followed by epoxidation.
This older method still holds a dominant role in propylene oxide production. Chlorohydrination is
the reaction between an olefin and hypochlorous acid. When propylene is the reactant,
propylene chlorohydrin is produced. The reaction occurs at approximately 35C and normal
pressure without any catalyst.
Approximately 87-90% yield could be achieved. The main by-product is propylene
dichloride (6-9%). The next step is the dehydrochlorination of the chlorohydrin with a 5%
Ca(OH)2 solution:

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Propylene oxide is purified by steam stripping and then distillation. Byproduct propylene
dichloride may be purified for use as a solvent or as a feed to the perchloroethylene process.
The main disadvantage of the chlorohydrination process is the waste disposal of CaCl2. Figure
8-3 is a flow diagram of a typical chlorohydrin process/2
The second important process for propylene oxide is epoxidation with peroxides. Many
hydroperoxides have been used as oxygen carriers for this reaction. Examples are tbutylhydroperoxide, ethylbenzene hydroperoxide, and peracetic acid. An important advantage of
the process is that the coproducts from epoxidation have appreciable economic values.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Epoxidation of propylene with ethylbenzene hydroperoxide is carried out at


approximately 130C and 35 atmospheres in presence of molybdenum catalyst. A conversion of
98% on the hydroperoxide has been reported. The coproduct a-phenylethyl alcohol could be
dehydrated to styrene.
Ethylbenzene hydroperoxide is produced by the uncatalyzed reaction of ethylbenzene
with oxygen.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Hydrogen Peroxide process

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

In the reaction unit, the catalytic epoxidation of propene/ propylene is carried out in the
presence of a titanium silicate catalyst using hydrogen peroxide (H2O2) in methanol as the
solvent. The focal point of the development was the epoxidation reactor for the synthesis of PO
using a fixed bed reaction system which operates at elevated pressure and moderate
temperature. The special design combines an intense heat transfer, with almost ideal plug-flow
characteristics, resulting in a high PO selectivity.
The quality and characteristics of the hydrogen peroxide have a substantial influence on the
process parameters. The propene cycle of the PO plant is totally closed and the excess
propene recovered is returned to the reaction section.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

The crude PO contains some impurities which are removed in the PO purification section by
rectification under moderate conditions. Water and small amounts of by-products are removed
in the methanol processing section and the purified solvent is recycled to the reactor.

Reactor Section.
The process is characterized by mild process conditions with temperature below 100C
leading to low formation of by-products. The pressure in the reaction unit is 30 bar. More than
95% can be obtained here.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

The exothermic heat is removed by integrated cooling system. After the reaction, the
product mixture containing mainly of methanol, water, propene and PO is withdrawn from the
reactor and depressurized to a pressure slightly above atmospheric pressure.
Propene recycling Section.
The product mixture leaving the reaction unit is decompressed and heated, resulting in a
propene-rich gas phase which is compressed, condensed and returned to the reaction section.
The off gas, which mainly contains inert compounds and a small quantity of oxygen from
the decomposition of the hydrogen peroxide, is withdrawn and delivered to the battery limits

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PO Purification Section.
The depressurized liquid product mixture is then transferred to the pre-separation
section where PO and dissolved propene are separated from the methanol and water. A C3
stripper removes the remaining C3 hydrocarbons from the PO/methanol mixture.
The PO distillate is purified in the PO column and the remaining methanol and water as
well as the small quantities of impurities ar taken off in the bottom product. The PO distillate
meets the highest quality standards.
Methanol Processing Section.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

The methanol/water mixture withdrawn form the bottom of the PO column is separated
from the water in the methanol processing section. The emanating overhead methanol stream is
returned to the PO reaction section.
The bottom product from the methanol column, which contains the water and small
amounts of high-boiling by-products, is delivered to the battery limits.
Purification of Chemical-grade Propene.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

The column increases the propene concentration in the overhead product while the
bottom product accounts for the propane balance. The bottom product is sent to the battery
limits while the propene stream is returned to the PO reaction section.

SAFETY PROCEDURES AND PRACTICES FOR PROPYLENE OXIDE


Exposure Potential

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Propylene oxide is used in the production of industrial and consumer products. Based on the
uses for this product, the public could be exposed through:
Workplace exposure Exposure can occur either in a facility that manufactures
propylene oxide or in the various industrial or manufacturing facilities that use propylene
oxide. It is produced, transported, stored, and consumed in closed systems. Those
working with propylene oxide in manufacturing operations could be exposed during
maintenance, sampling, testing, or other procedures. Each manufacturing facility should
have a thorough training program for employees and appropriate work processes,
ventilation, and safety equipment in place to limit exposure.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Consumer exposure to products containing propylene oxide Propylene oxide is a


raw material used to produce finished goods for consumers such as polyurethane
foams, paints, cosmetics, and lubricants. Propylene oxide is consumed in the reaction to
produce these products and would not be considered to present a risk to consumers.
Environmental releases In the event of a spill, the focus is on containing the spill to
prevent contamination of soil, surface water, or groundwater. Respiratory protection is
necessary for cleaning up spills and leaks. Eliminate all sources of ignition immediately.
For small spills, wash the spill site with large quantities of water. Do not use absorbents.
When released to soil, propylene oxide will quickly evaporate. Once in the atmosphere, it

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

is photo-chemically degraded by hydroxyl radicals. When released into water, propylene


oxide will tend to remain dissolved.
In case of fire Deny any unnecessary entry into the area and consider the use of
unmanned hose holders. Use water-sprayer fog, carbon-dioxide or dry-chemical
extinguishers, or foam to fight the fire. Use of a direct water stream may spread the fire.
Firefighters should wear positive-pressure, self-contained breathing apparatus (SCBA)
and protective firefighting clothing. The public should be warned of downwind vapor
explosion hazards. Vapors are heavier than air and may travel a long distance and
accumulate in low-lying areas.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Measures in the event of a release of Propylene Oxide


Shut off all potential ignition sources and leaks, if without risk

No open flames
Keep upwind
Isolate area and deny entry
Do not get into eyes
Avoid contact with skin
Avoid breathing vapor.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Dilute liquid spills with large amounts of water


Use water spray to reduce the extent of vapour
Avoid the use of clay-based absorbents
Dike larger spills and recover
Prevent entry into sewers and/or natural waters
If substance has entered a water course or sewer, inform/advise Authorities.

Measures in the event of a Fire

Do not put out any fire until leak is shut off. The reason is to prevent re-flash.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Cool containers exposed to heat / fire with water, to prevent overpressure / bursting.
Use dry chemical or carbon dioxide (CO2).
Use water spray, fog or alcohol foam.
If massive fire:
o Use unmanned hose holders or monitor nozzle
o Consider letting the fire burn out
o Dike liquid run-off
o Prevent entry into sewers and/or natural waters.

Personal protection

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Eye protection: Use chemical resistance safety goggles.


Normal working clothes should be worn during routine handling.
Clothing for spill and fire:
o Wear full protective clothing PO resistant gloves under gauntlet type Nitriles
rubber gloves, rubber safety boots and approved positive pressure breathing
apparatus
o Remove contaminated clothing immediately, preferably under safety shower / fire
hose spray, and wash before re-use
o Destroy contaminated shoes and leather items

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

First aid and medical treatment


Never give fluids or induce vomiting if patient is unconscious or is having convulsions.
Inhalation. Remove to fresh air. If not breathing, give artificial respiration. If breathing is
difficult, oxygen should be administered by qualified personnel. Call a physician or
transport to medical facilities for immediate medical advice.
Skin contact. In case of contact, immediately flush skin with plenty of water for at least
15 minutes while removing contaminated clothing and shoes. Call a physician if irritation
persists. Wash clothing before reuse. Destroy contaminated shoes. Seek medical
attention immediately.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

Eye contact. Immediate and continuous irrigation with running water for at least 15
minutes is imperative. Prompt medical consultation is essential. Seek medical attention
immediately.
Ingestion. If swallowed, rinse mouth and go immediately to hospital. Inducement of
vomiting to be indicated by a doctor only.
Note to physician. Causes central nervous system depression. If burn is present, treat as
any thermal burn, after decontamination. Treat symptomatically. No specific antidote.
Supportive care. Treatment based on judgement of the physician in
response to reactions of the patient.

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

STORAGE AND HANDLING OF PROPYLENE OXIDE

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

1. Pressure Safety Valve


2. Tank Support
3. Tank Drain
4. Safety Railing
5. Manway
6. Level Transmitter with Output Gauge
7. Outlet Line
8. Approved Ground
9. Filter

11. Pressure Gauge with Diaphragm Seal


12. Pressure Controller (Split Range)
13. Pressure Control Valve
14. NFPA Identification Code
15. Block Valve
16. Check Valve
17. Containment Dike
18. Temperature Indication
19. Level Transmitter

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

10. Pump

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

1. Tank Frame
2. Tank Shell In Stainless Steel with Insulation
and Aluminum Cladding Protection
3. Male Bottom Discharge
4. Data Plate
5. Ladder
6. Walkway
7. Steam Heating (Not Used for P.O. Service)
8. Thermometer
9. Safety Relief Valves (2) with Tank

16. Check Valve


17. Pressure Relief Valve
18. Pressure Control Valve
19. Filter
20. Pump
21. Pressure Gauge with Diaphragm Seal
22. Ground Wire
23. Flexible Hose Assembly
24. DOT Classification Number
25. Pressure Gauge

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila

PAMANTASAN NG LUNGSOD NG MAYNILA


University of the City of Manila
Intramuros, Manila