POLYETHER POLYOL

PRODUCTION
Implementation of Inherently Safer Design

35030 Chemical Engineering in Global Business

Anissa Nurdiawati

13M53170

INTRODUCTION
Process safety is a fundamental component of process design. From famous historic disasters such
as Flixborough and Bhopal to recent events, the process safety in chemical process design becomes
more important. Inherently safer design (ISD) is a philosophy for addressing safety issues in the
design and operation of facilities that use or process hazardous chemicals. ISD should be considered
throughout the process life cycle, from initial conception through R&D, plant design, construction,
and operation.
Polyether polyols serve as important raw materials in the urethane industry, which represents
roughly 5% of the worldwide polymer consumption (Ionescu, 2005). A polyol is an alcohol containing
multiple hydroxyl groups which can be classified as a polyether polyols and polyester polyols.
Polyether polyols are used in the preparation of polyurethanes: flexible polyurethane foam, rigid
polyurethane foam, and CASE (coatings, adhesives, sealants, elastomers). Polyether polyols are
manufactured by ethoxylation/propoxylation of a polyhydric alcohol in the presence of a catalyst.
Polyether polyols are produced by anionic ring opening addition polymerization of ethylene oxide or
propylene oxide. The reaction is highly exothermic so that the temperature control becomes very
critical. The raw material such as propylene oxide is a flammable substance containing hazard to the
process. Moreover, the process is batch mode so that the operation procedure will be very
important with regard to process safety. By applying for inherently safer concepts to this

process and procedures, its expected to make less hazardous operations.

MAIN PROCESS DESCRIPTION - REACTIONS
The anionic polymerization of PO for the production of a polyether polyol involves the successive
reaction of an organic oxide with an initiator compound containing active hydrogen atoms. This
requires the addition of the alkylene oxide through anionic (basic) catalysis or cationic (acidic) to the
initiator molecule. Commercial production is usually using a base such as KOH which catalyses the
ring opening and oxide addition which is continued until a required molecular weight is achieved.
The mechanism for the polymerization process is shown in Figure 1 and 2. Since the epoxide
monomers and polyether polyols are easily oxidized, air is excluded from the manufacturing process.
In the given case, polyether polyol is produced from initiators, which contains hydroxyl functions
such as glycerin, sorbitol and sucrose, cauterized with alkaline materials such as alkaline metals (e.g.
Sodium, Potassium hydroxide) amines with addition polymerization with propylene oxide at about
115oC.

Figure 1 Base Catalyst Production of Poly(propylene oxide)

Figure 2 Mechanism of Base Catalyzed Ring Opening Polymerization

PHYSICAL-CHEMICAL CHARACTERISTIC
Propylene oxide is a stable material that will not decompose under normal conditions of
temperature and pressure. Propylene oxide is a colorless, low-boiling and highly volatile liquid with a
sweet, ether-like odor. It is highly flammable and reactive, and storage and unloading areas must be
appropriately designed and monitored. Table 1 shows the physical and chemical property of
propylene oxide.

Table 1 Property of Propylene Oxide

Property
Physical State
Color
Boiling Pt.
Molecular Wt.
Vapor Density (Air =1.0)
Heat of Combustion, Liquid @25oC
Flash Point
Autoignition Temperature
Upper Explosion Limit
Lower Explosion Limit

Value
Liquid
Colorless
34.2oC
58.08
2.0
-426.745 kcal/mol
-37.2oC
449oC
42 vol%
1.6 vol%
3

By identifying the property of PO, it can be described that the hazards of processing propylene oxide
include:
-

Propylene oxide is an extremely flammable liquid

A gas phase explosion hazard related to the flammability of PO in the presence of air or
oxygen
A runaway reaction hazard when PO is reacted with other chemicals in propoxylation
processes, if PO is allowed to accumulate in reaction vessels, due to improper operating
conditions. Also concentrated PO solutions may self-heat and runaway if the
temperature is not controlled. Dow's Fire & Explosion Index Hazard Classification Guide
1987-published via the American Institute of Chemical Engineers in Appendix B Example
problem 4 on page 58 suggests that 15 percent unreacted propylene oxide is a "worst
case reaction mixture" for a polyol batch process reactor operating at a maximum
reaction temperature of 120 C.
A toxic hazard since PO is highly toxic and may cause cancer.

This hazard identification of related chemical substance then should be considered in the process
design of polyether polyol production.

ANALYSIS OF EXISTING PROCESS POTENTIAL HAZARD IDENTIFICATION

Original procedure is
1. Charge pre-catalyzed initiator at about 5% of reactor volume
2. Charge PO with required amount (about 80% of reactor volume)
3. Mix well
4. Bring reactor temperature to the reaction temperature to react.
5. Cool reactor to remove heat of polymerization
6. Digestion 3 hours and transfer to the rundown tank for catalyst removal

Inert Gas
Propylene Oxide

Reaction System

Polyether Polyols

Initiator

Heating/Cooling

PO, having a low boiling point (bp = 33.6oC), is volatilized spontaneously by the simple contact with
the hot reaction mass at 100-125oC and generates a pressure. If all PO is reacted directly, without

continuous cooling process, it is possible that it leads to a very strong exothermal reaction
impossible to control (runway reaction). This process is inherently unsafe and experienced runaway
batch with some unexpected problem takes place. To identify and evaluate possible hazard scenario
in polyethers production, What-if analysis was conducted as presented in Table 2 below. What-If
Analysis technique is prefered here (rather than other hazard evaluation technique) since it does not
require detailed information of the plant design and has broad flexibility for identifying and
evaluating hazards
Table 2 Potential Hazard Scenarios for Polyether Polyols Production
What if?
There is no flow of gas inert

Initiating Cause
Valve for inert gas fails open

There is no coolant circulation (loss

of cooling)

Cooling water pump fails

Recirculating pump fails
Failure of heat exchanger

There is higher pressure in the

reactor

Runaway reaction lead to higher

temperature

Theres no agitation

External fire in the process area

Gas inert regulator fails
Agitator motor fails

Theres higher temperature in the

reactor

EO accumulation

Consequence
In the presence of air and high
temperature, oxidation of alcohol
groups may be occured resulting in
product degradation. Moreover,
PO is flammable and in the
presence of air is explosive
mixture.
Reactor overheating may lead to
overpressure , possible reactor
rupture, loss of product, and
personnel injury due to exposure
Leading to possible reactor
rupture, release of flammable
material to the atmosphere and
personnel injury due to exposure
PO accumulation lead to runaway
reactions may result in higher
temperature and ovepressure.
Leading to overpressure , possible
reactor rupture, loss of product,
and personnel injury due to
exposure

INHERENTLY SAFER CONCEPT IMPLEMENTATION

Application of Inherently Safer Strategies to the Hazard and Process Design

It is extremely important to maintain reaction parameter constants, not only for the quality of the
resulting polyethers, but for the safety as well. As an immediate consequence, inherently safer
design is applied to the process, such as control of PO addition, automation of cooling system and
the other process design and control which explained below.
Table 3 Inherently Safer Design Choices for Design Application
Hazard Scenario
Loss of inert gas flowing

Process Operation
Operating a reactor
under inert gas pressure

Loss of cooling (higher

temperature)

Circulate coolant in
jacket and external heat
exchanger

Overpressure

Operating a reactor
under inert gas pressure
Filling a reactor with a
pump

Potential Upset Case

Failure of inert gas
opening valve leading to
product degradation and
may lead to explosive
condition.
Failure of pump/heat
exchanger leading to
overheating and
overpressure. Runaway
reaction may lead to
explosive condition.
Failure of inlet gas
regulator leading to
overpressure.
Overpressure by pump
deadhead due to overfill

Inherently Safer Design

Stop the flow of PO
under this circumstances

Provide reactor with

active safeguard (rupture
disc, automatic water
spray)
Stop PO Flowing to
maintain the amount of
unreacted oxide

External Fire

Operating a reactor
under inert gas

Overpressureand may
lead to rupture of the
reactor

No agitation

Mix the material inside

the reactor

Underpressure

Draining an elevated
process vessel by gravity

Failure of agitation/ loss

of power supply causes
PO to accumulate and
leading to runaway
reaction
Blocked vent leading to
vacuum pulled during
draining

Filling PO to the reactor

Stop PO Flowing to
maintain the amount of
unreacted oxide

Vessel design pressure

greater than inert gas
supply pressure
Vessel design pressure
greater than pump
deadhead pressure

1.

Vessel designed for

full vacuum
2. Liquid drain lined
sized to be self
venting
Continuous feedingcontrolling PO rate

The improvement plans for achieving inherently safer design based on above analysis:

Reducing the amount of hazardous material present at any one time. Rather than charging all
PO in a one time as in the initial procedure, the PO will continuously added to the reactor.
Therefore, the process becomes semibatch mode. New proper operating procedure is explained
in the next subchapter.

In the no inert gas flow, no agitation, and loss of cooling scenario, the hazard can be controlled
and prevented by control the flow of PO. Reactor temperature, pressure or unreacted oxide in the
reactor can be an indicator for maintaining a safe process. Therefore, adequate instrumentation
and control system should be added to the process design. Active safeguard should be provided
especially for medium to high level hazard.It will be further explained in the next subchapter.

In the overpressure and underpressure scenario, good engineering design for reactor, heat
transfer equipment and the other process equipment are required to prevent those hazard
possibilities.

Application of Inherently Safer Strategies to the Design of Layers of Protection

The maintenance of the reaction parameter constants is really important for the process safety.
There are two main control loops:
1. Pressure Control Loops
In addition, the reactor is equipped with a high-high pressure switch, taking a signal from the
rupture disk burst detector. The rupture disk is provided and set below the MAWP.
2. Temperature Control Loops
To monitor the temperature and alert the operator if the temperature is not being
controlled, the reactor has a temperature controller with a high temperature switch and
audible alarm. In addition, the reactor is equipped with an independent temperature sensor
and hgh-high temperature switch interlocked with an isolation valve in the PO feed line. This
interlock will shut off the PO feed to the reactor in the event of a high-high temperature,
and the heat of reaction will drop quickly. The cooling water supply line to the reactor jacket
is backed up by an interconnection to the city water system, which can be manually turned
on by the operator should the cooling water system fail.

Piping and Instrumentation Diagram of Batch Reactor

Initiator
KOH

N2
Temperature
Interlock

M
TIC

FIC

TT

PI

FI

TI

Interlock
System

PO

PSV

FT
LT

CI

TT

PO
Composition
Interlock

Hot/Cooling Fluid Supply

LIC
To Purification unit

Improved Semibatch Procedure for Polyether Polyol Production

The process which implements inherently safer concept can be carried out by the following
procedure.
1. Catalyst, initiator compound are introduced into a reaction vessel and then brought to the
desired reaction temperature.
2. The reactor is purged with nitrogen to displace air and nitrogen as gas inert is continuously
flow to the reactor.
3. Subsequently, the desired quantity of propylene oxide is dosed continuously into the
reaction vessel by means of a controlled diaphragm pump.
4. The reactor jacket is switched from heating to cooling service. Cooling process is
continuously maintained by the cooling jacket and more efficiently by external heat
exchanger to remove heat of reaction. Temperature inside reactor is controlled within the
required range by the flow rate of coolant and in emergency case (superior limit
temperature) PO flow should be stopped and begun again when the parameter once again
within the required value.
5. Agitation should be kept during the process to ensure that no overaccumulation unreacted
oxide and improve heat exchanger effectiveness. In case of no agitation, the control loop will
stop the PO addition to prevent the unreacted oxide over the set point.
6. At digestion step, the reaction of unreacted monomer is occurred by maintaining the
reaction condition (temperature) under continuous stirring and recirculation of the reaction
mass. Since the PO addition has been stopped at this stage, pressure will gradually
decreased so that, the pressure is control during this process. Moreover, unreacted oxide
should be analyzed and maintain within acceptable range to ensure the quality of the final
product. To remove the last traces of unreacted oxide, degassing process may be
introduced.

7. In the final step, removal of KOH is required to purify the final product. Purification of the
product can be performed by various methods such as neutralisation with acids, adsorption,
extraction or ion exchange.

REFERENCES

Ionescu M. Chemistry and Technology of Polyols for Polyurethanes. Rapra Technology, 2005.
Nie Y, Biegler L. Reactor Modeling and Recipe Optimization of Polyether Polyol Processes:
Polypropylene Glycol. AIChE, 2013.
Seay JR, Eden MR. Incorporating Risk Assessment and Inherently Safer Design Practices into
Chemical Engineering Education. ASEE, 2008.
U.S. Pat. 6,093,793. (Jul.25, 2000). Process for the production of polyether polyols. Hofmann J,
Gupta P, Pielartzik H (to Bayer Aktiengesellschaft).