CHAPTER 1

INTRODUCTION

POLYETHER:
Polyether, any of a class of organic substances prepared by joining together or polymerizing many
molecules of simpler compounds (monomers) by establishing “ether” (-R-O-R-) links between
them. Polyethers, which may be either chainlike or network like in molecular structure, comprise
an unusually diverse group of polymers.
These polymers find an extensive use in a wide array of applications. As flexible foams they are
used as construction materials in products ranging from furniture and bedding, to car interiors, to
insulation. As rigid foams, they are found in packaging and refrigeration. Furthermore, depending
on their specific properties, polyethers may also be used as synthetic lubricants,used as synthetic
lubricants, adhesives and sealants, surface active agents, elastomers, castings,specialty coatings,
defoamers, and inks. These have been used as impression materials in dentistry.

The phenyl ether polymers are a class of aromatic polyethers containing aromatic cycles in their
main chain: Polyphenylether(PPE) andPoly(p-phynelene oxide) (PPO).

Polyethers are formed through a polymerization reaction that adds a small oxirane
monomer, such as PO or ethylene oxide (EO), to the end of a growing chain via a ring-opening
anionic polymerization mechanism by alkaline catalysed addition of petrochemical base units
(epoxides). With the aid of further cationic catalysed synthesis, additional heterocyclic oxides can
be incorporated (eg THF) .‘Chain regulators’ such as alcohols, amines, carboxylic acids and other
materials are used to control the formation of the chain.
Anionic polymerization using SN2 mechanism.
Monomers PO and EO may be added in certain ratios, as block copolymers or alternating polymers,
or as caps to a block polymer to tune the properties of the final product to a desired specification.
Polyethers are typically manufactured at a desired molecular weight and sold as a mixture of
alcohols called polyols. Polyether polyols are most commonly used for reaction with poly-
isocyanates to form polyurethane foams, with the size of the polyurethane product directly

proportional to the size of the polyether.

PHYSICAL PROPERTIES:
(1)Solubility in water/water & moisture resistant : The capacity of the various polyethers to
absorb water is dependent on the content of ethylene oxide in the polyether molecule, the degree of
polymerisation, and the temperature. Higher-molecular weight (mol.wt. -2,000) PO polyethers
absorb quantities of water of only <5% by weight, independent of their functionality. In contrast,
polyethers with a relatively small proportion of EO absorb approximately 35% by weight.
Polyethers with an EO content >40% by weight are clearly miscible with water in every ratio.
The capacity to absorb water of polyether types with limited water miscibility decreases with
increasing molecular weight. Polyethers with unlimited water miscibility exhibit a temperature
where a separation of phases may occur while heating the aqueous solutions. These segregation
temperatures are dependent on structure and concentration: as a rule, they lie between 45°C and
>100 °C. Mineral oil-soluble types of polyethers absorb no water at all.
Polyethers have excellent hydrolytic stability.
(2) Solubility in mineral oils : The solubility of polyethers in mineral oil is influenced by type,
quantity and arrangement of the epoxide units incorporated in the molecule. Ethylene
oxide/propylene oxide-polyethers propylene oxide-polyethers as well as EO/PO tetrahydrofuran
polyethers are not soluble in mineral oils. Butylene oxide-polyethers are soluble in mineral oils over
a limited temperature range (from approximately +lO°C). If the polyether molecule, however,
contains sufficient quantities of long-chain epoxides (>C8), the polyethers are clearly soluble over
the tribologically interesting temperature range (ie from the cloud point of the mineral oil to the
decomposition temperature) in mineral oils of the most varied origin as well as in polyalphaolefins
(3) Viscosity : The viscosity indices increase with increasing ethylene oxide proportions in the
polyether molecule.
Compared with mineral oils, the viscosity-temperature curves of polyethers are essentially flatter.
Also, Viscosity-pressure curves are flatter with increasing ethylene oxide content or incorporation
of tetrahydrofuran, than the VP curves of pure propylene oxide polyethers.
(4) Low temperature flexibility: Polyethers are also clear liquids at low temperatures (<O°C) if
their ethylene oxide-content does not exceed 50% by weight. The pour points of the polyether types
considered in tribological areas of appli- cation are, as a rule, between -3OOC and -50°C according
to structure and molecular weight. Upon reaching the pour point they solidify as clear as glass. All
elastomers (rubbers, urethanes, silicones, etc.) get harder and less flexible as temperatures drop and
will eventually reach a temperature at which they become brittle.Polyethers are less effected by cold
temperatures

(5) Thermal stability/heat resistant :Perform well at elevated temperatures. The thermal loading
capacity of polyether molecules increases with an increasing proportion of ethylene oxide. By
incorporating tetrahydrofuran and/or long-chain epoxides into the polyether molecule, thermal
stability increases thermal stability of polyethers can be basically improved by suitable stabilisers,
but onIy up to the pyrolysis temperature, which is approximately 24O°C to 250°C for polyethers
which are well-stabilised. Polyethers cannot be used above this temperature limit.
 (6)Shock abrasion resistant : Excellent impingement abrasion resistance which makes it the
choice for sandblast curtains and bumpers that get hit head-on.

(7)Hardness properties : Polyethers can be made to any hardness from marshmallow soft to
bowling ball hard.

(8)Rebound properties : Polyether provide much higher rebound and therefore is the choice for
skate wheels and high speed rollers.

CHEMICAL PROPERTIES :

Oxidation stability: Polyethers should basically only be used in oxidation-stabilised form for
tribological applications. Like all base fluids for lubricants, polyethers are also oxidisable in the
presence of oxygen. The oxidation of polyethers which are stabilised well is however different, for
example when compared with mineral oils, and is especially slow under comparative conditions.
The oxidation of stabilised polyethers is influenced by the structure of the polyether as well as by
the oxidation inhibitors used for stabilisation. Besides these, the operational temperature and the
oxygen supply play a decisive role in the process of oxidation, In a number of oxidation studies, it
has been determined that the stability of polyethers with the same highly effective stabiliser-
combination improves with increasing ethylene oxide-content as well as with tetra- hydrofuran
and/or long-chain epoxides incorporated in the molecule. Phenylene diamine derivatives, combined
with sterically-hindered phenols, phenothiazines and metal de-activators have proved to be highly
effective antioxidants for polyethers. However, as polyether oils are frequently used in high-
temperature applications, it should be ensured that the antioxidants are also sufficiently
temperature-stable over long periods. As a rule, an essentially higher dose of antioxidants is
required with polyethers than with mineral oils due to the usually higher operational temperatures.

DEMAND FOR POLYETHER: In recent years, the global market for polyethers has seen rapid
expansion due to the growth of the construction, automobile, and foam industries. Polyethers are
principally sold to polyurethane plants to produce a wide range of flexible and rigid foams that are
used in a widerange of applications from automotive upholstery to inks. Consequently, the process
for manufacturing polyethers is extremely vital to the consumer goods market and for maintaining
the quality of life to which many people have grown accustomed.
MARKET ANALYSIS : Polyether polyols account for nearly 25 percent of the total polyol
production. The global market size for polyether polyols is expected to grow at a CAGR of 3.5 - 4
percent to reach $ 8.8 billion by 2020. Higher production cost and eroding margins due to higher
feedstocks costs has resulted in increased polyol prices on a global scale. The Asia Pacific region
has dominated the regional market and accounts for nearly 30 percent share in the global polyester
polyol market. The U.S. has excessive production of polyols due to the presence of multiple
domestic producers and meets the excessive requirement for polyols by importing from regions
such as China and Korea. The demand for aromatic polyester polyol has witnessed growth in
regions such as Europe and North America, which is mainly driven by the increasing demand for
high-quality thermal insulation
 DRIVERS :-

Consumer sentiment has shifted from purchasing long lasting goods to short-life low cost goods.
Periodic changes in daily use materials such as electronics, furniture and fittings, automotive
accessories etc., has become the approach of younger demography, across the world.

As a result consumption for polyols in foams and elastomers for packaging, furnish and cushions,
coatings in electronics and automobiles is expected in crease, particularly in China and India, which
are not only the most populated nations but with more than 60 percent of the population being in the
age group of 16-35

Global polyether polyol production capacity has expanded significantly over the past 5 years, by 2.8
million metric tons, while demand growth, primarily led by the bedding, automotive and
construction industries, has only achieved less than half of this amount, increasing by only 1.1
million metric tons from 2010-2015. Most capacity growth has taken place in China, far in excess
of domestic demand, which has led to a global oversupply situation. This has depressed polyols
prices significantly.

Most polyether polyols are produced for polyurethane applications; however, other end uses range
from synthetic lubricants and functional fluids to surface-active agents.

The following pie chart shows world consumption of polyether polyols for urethanes in 2017:
 CHAPTER 2

PROCESSES FOR MANUFACTURE

DIFFERENT POLYMERISATION TECHNIQUES :

Aliphatic polyethers generated by the ring-opening polymerization (ROP) of the epoxide monomers
ethylene oxide (EO),propylene oxide (PO), and, to a lesser extent, butylene oxide(BO) are a highly
established and important class of polymers that are commercially used for an immense variety of
applications. The characteristic properties of polyether-based materials are due to their unique
backbone, in particular its high flexibility leading to low glass transitions below−60°C, and its
hydrophilicity due to the C−O−C bond. These properties cannot be matched by a carbon-based
backbone, as it is present in polyolefins or other vinyl polymers.Although generally three- to five-
membered cyclic ethers can be polymerized to generate polyethers by ROP, epoxides clearly
represent the most versatile class of monomers for polyether synthesis, since they can be
polymerized by different mechanisms, and EO and PO are readily available in industry in large
quantities directly from the oxidation of the respectivealkenes. The driving force for the ROP is the
high ring strain ofepoxides, which is on the order of 110−115 kJ/mol for ethyleneoxide.This enables
polymerization of epoxide (IUPAC:oxirane)monomers in three ways: (i) base-initiated, (ii) acid-
initiated, and (iii) by coordination polymerization.Other classes of epoxide monomers, such as
epichlorohydrine,longer alkylene epoxides, a large variety of glycidyl ethers, and glycidyl amines,
play an increasing role in academia and are highly promising as comonomers for specialty
applications in thefuture.

Oxyanionic polymerization :
The anionic polymerization of EO is based on nucleophiles as initiators. The widely applied
standard method is the controlled addition of EO to water or alcohols as initiators in the presence
of alkaline catalysts. In most cases alkali metal compounds with high nucleophilicity are employed
for this purpose. For higher molecular weights, alkali metal hydrides,alkyls, aryls, hydroxides,
alkoxides, and amides can be employed for the living anionic polymerization of EO in an inert
solvent. As in all ionic polymerizations, the counterion plays a key role and should exhibit low
Lewis acidity and preferentially little or nointeraction with the chain end. Solvents employed for the
anionic polymerization of epoxides must be polar and aprotic.

Therefore,tetrahydrofuran (THF), dioxane, dimethyl sulfoxide (DMSO),and

hexamethylphosphoramide (HMPA) are often used. Furthermore, polymerization in the bulk
monomer is possible,if low molecular weights are targeted, albeit at the expense of a higher
polydispersity. The addition of complexing agents, such as crown ethers suitable for the respective
cation can strongly accelerate epoxide polymerization. Proton exchange isextremely rapid, and
therefore the combination of alkoxide withthe respective alcohol is employed as initiator system in
mostinstances, particularly in the synthesis of polyether polyols (i.e.,PPO or PPO/PEG star
polymers) to retain solubility of the respective multihydroxyfunctional initiator.
The oxyanionic polymerization of EO in solution relies on the oxygen atom at the charged end of
the growing chains as the active center, where the negative charge is localized. Depending on the
counterion, solvated contact ion pairs may be present. In addition, the active chain ends can be
highly associated even in dilute solution. In solvents oflow or medium polarity, alkali metal
alkoxides of sodium show a strong tendency to aggregate, which leads to complex polymerization
kinetics. Commonly the reaction rate of the alkoxide-initiated polymerization is slow but can be
accelerated to a certain extent by raising temperature and also by a small excess of the respective
alcohol.
Therefore, oxyanionic polymerization of EO is characterized by (i) tight ion pairs with low
dissociation constants (10−8−10−12mol L−1) in THF; (ii) the presence of ion triplets and higher
associates; (iii) competitive interaction of the growing chains with monomer unit sequences and
most likely also with the EO monomer. This complex nature of the active center presents a
fundamental problem in the anionic polymerization of EO, but also for PO and other oxiranes in
solution. An upper limit of 50 000 g/mol for the attainable molecular weights has been reported for
this common approach.
COORDINATION POLYMERISATION : PEO with molecular weights exceeding 100 000
g/mol is of great interest for hydrogels, PEO fibers, mechanically strong films and for surface
modification, albeit preparation by oxyanionic polymerization is not possible. The coordination of
the epoxide results in two main effects: (i)activation of the monomer for the polymerization, and
(ii)generation of a specific orientation of the reacting molecules that may lead to stereo specific
polymerization of PO or longer alkylene oxides. The currently established most effective initiators
are derivatives of divalent and trivalent metals, e.g.,Ca, Zn, and Al. It is obvious that metals used
for this purposeshould exhibit Lewis acidity. In industry, mostly calcium andzinc/aluminum-based
catalysts are used. Zhang and Shen67usedalkaline-earth carbonate, [(RO)2Al−O−Zn-Al(OR)2],
trialkyl aluminum-water-zinc acetylacetonate, trialkylaluminum-water,and rare earth metal
acetylacetonate as catalysts to obtain high-MW PEO.
The synthesis of high molecular weight copolymers of ethylene oxide and other epoxides with polar
functional groups via the coordination methods remains an interesting challenge.Polar epoxide
monomers may undergo various side reactions involving either cationic or anionic polymerization,
making the propagation process complex.

Phosphazene Bases: Metal-Free Initiators :Another metal-free polymerization technique relies

on the use of phosphazene bases as deprotonation or complexation agents. Phosphazene bases, also
known as“Schwesinger Bases”,belong to the family of neutral Bronsted“super”bases, which are
highly basic but only weakly nucleophilic (selected phosphazenebases .Despite their exceptional
structure,phosphazene bases are commercially available, chemically and thermally stable, and
soluble in nonpolar and moderately polar organic solvents (e.g., hexane, toluene, and
THF).Nevertheless, the commercially available phosphazene bases may contain their respective
isomers as impurities, which could have an influence on their reactivity. The salient feature of
phosphazene bases and especiallyt-BuP4for epoxide ROP is that they are metal-free and thus
alternative deprotonation agents to common alkali hydroxides. After deprotonation, the bulky
phosphazenium cation [t-BuP4]H+represents a soft counterion with low tendency for ion-pair
association. Consequently, high polymerization rates also in nonpolar solvents under mild reaction
temperatures can be observed, as the chain end is highly reactive
In 2012, Carlotti and co-workers combined t-BuP4with the activated monomer technique for the
rapid polymerization of PO at room temperature. PPO with molecular weights up to 80 000
g·mol−1was obtained. However, the authors reported the occurrence of unsaturated chain ends
indicating the occurrence of transfer reactions despite the high molecular weight; consequently the
combination of both methods did not lead to a significant improvement of the common activated
monomer technique.

DMC CATALYSTS FOR EPOXIDE POLYMERISATION:

An increasingly important method, yet currently only employedfor specialty polyols in industry,
particularly for high molecularweight polyalkylene ether polyols is based on the so-called“double
metal cyanide catalysts”(DMC). Highpolymerization temperatures, elevated pressures, and a
complexcatalyst preparation procedure, followed by difficult character-ization of the actual catalyst
structure render this approach lessattractive for scientific purposes. However, the DMC method
isapplicable to large scale processes. The formation of unsaturatedimpurities is suppressed, and
high molecular weight polyalkyleneether polyols can be achieved. Especially in the
industrialproduction of polyols based on PPO, where mainly potassiumhydroxide (KOH) is applied
as a deprotonating agent and metalsalts have to be removed after polymerization, the DMC
catalystcan be a suitable alternative, enabling a continuous process withno need for further
purification steps. Nevertheless, the DMCmethod includes various challenges and limitations DMC
is a heterogeneous catalyst with the general structure ofM1u[M2(CN)6]v·xM1Xw·yL·zH2O, where
M1= Zn, M2= Co, Fe.L is an organic complexing agent, such astert-butyl alcohol,diglym. Detailed
analysis of the DMC structure is difficult, which is due to its insoluble character and the strong
dependence of the crystal structure on the preparation procedure

CATIONIC RING OPENING POLYMERISATION(CROP):

The CROP is rarely used for thepolymerization of EO or PO, since the formation of
considerableamounts of cyclic polyether byproducts cannot be avoided,which is due
to“backbiting”processes, i.e., intramolecular chaintransfer. The active species in CROP are
typically secondary or tertiaryoxonium ions, and two fundamentally different mechanisms have to
be considered .The activatedchain-end mechanism (ACE) that is based on a tertiary oxoniumion
located at the chain and as an active center. A nucleophilicattack of the oxygen atom in the cyclic
monomer at a carbon atom in α-position to the oxygen bearing formally the positivecharge leads to
propagation. However, since nucleophilic oxygenatoms are also present in the polymer chains
formed, both inter-as well as intramolecular chain transfer can occur. In the intramolecular case
cyclic byproducts are formed, e.g., 1,4-dioxane or crown ether structures in the case of EO
polymerization. The chain transfer to polymer is a typical and inavoidable feature of the CROP, if it
is dominated by the ACEmechanism.
In contrast to the ACE mechanism, the“activated monomermechanism”(AM) permits considerably
better control overmolecular weights and permits to circumvent the issues related tocyclization. n
case ofthe AM mechanism, the active centers, i.e., the cationic chargesare located on the monomer
(Figure 6), and the polymer chain isneutral, which strongly reduces the occurrence of
backbiting.233Suitable conditions for a controlled AM-type polymerization ofEO in the presence of
an alcohol-initiator ROH can be created, ifrather high ratios [EO]/[ROH] are chosen, however,
keepingthe instantaneous monomer concentration low. These conditions can be implemented by
slow addition of the epoxidemonomer to the reaction mixture. Unfortunately, this on theother hand
may lead to prolonged reaction times
In summary, the CROP under AM conditions offersinteresting options for the synthesis of
telechelic polymers,macromonomers and several copolymers.However, EO, PO,and BO are mostly
polymerized with other techniques describedabove that offer better control over molecular weights
as well asend groupfidelity and permit to avoid cyclic side products.
 PROCESS DESCRIPTION
The process laid out in this report has been designed to manufacture a 3,000 mol. wt.
polyether product using glycerin as an initiator, potassium hydroxide (KOH) as a catalyst, and
PO as the backbone monomer. We utilize a semi-batch process to produce 100 million pounds of
polyether annually, assuming 330 days of operation every year. With a batch time of 24 hours (8
hour cycle time), each batch will produce approximately 101,000 pounds of product in order to
meet our yearly goal of 100 million lb/yr.
The process consists of five main steps: activation, PO addition, PO reaction,
purification, and stabilization. The activation step allows the glycerin molecules to initiate the
polymerization reaction upon PO addition and is accomplished by heating solid KOH with
glycerin at 250ºF. In this step, a hydrogen atom from the glycerin reacts with the hydroxide
anion of KOH, producing water, and the positive potassium cation is attracted to the revealed
negative charge on the terminating oxygen of the glycerin molecule. The water produced in this
step will be removed using evaporation, since water can prematurely terminate the growing chain
during the reaction phase as well as degrade the final polyether.
The addition phase involves adding PO to the activated glycerin. As soon as PO is
introduced into the reactor, an exothermic reaction is initiated, resulting in the formation of
polyether chains. After the PO addition is complete, the reaction phase occurs, and the
concentration of the monomer gradually decreases as it is incorporated into the growing polymer.
Both of the reactors will have their own addition and reaction phases during operation. Due to
the exothermic nature of epoxide ring-opening, these steps generate a large amount of heat, and
external heat exchangers will be used to control the temperature of the reactor contents.
The purification step consists of removing unreacted PO from the reaction mixture and
separating the potassium catalyst from the crude polyether to meet industrial product purity
4
specifications. Separation of PO is performed in the second reactor and is accomplished by
decreasing the pressure in the vessel so that liquid PO vaporizes and is removed by opening a
pressure relief valve. A water wash performs the dual function of terminating the reaction and
extracting the potassium ions from the nonpolar polymer product. A gravity decantation process
follows where the water, carrying most of the catalyst, is separated from the polyether. Washing
and decantation will be performed three times to reach the desired purity level of less than 5
ppm.
Lastly, it should be noted that auto-oxidation is a phenomenon commonly observed in
ethers, in which diatomic oxygen from air is incorporated into the ether as a peroxide or
hydroperoxide to form a highly explosive product. Failure to control ether auto-oxidation has
been cited as a cause of several industrial accidents, including a 2004 explosion at Sterigenics
International Facility in California1. Thus, to avoid this safety hazard, our packaging step will
consist of loading the polyether into a large storage tank and adding 0.05 wt% of Irganox(r)
1010, an antioxidant.
APPLICATIONS:

 Construction,automobile & foam industries

 Panel insulation
 Pipe section insulation
 Used in manufacturing fishing net floats
 Used in insulating thermoware containers
 Used in high density applications
 Used in insulating refrigerators,solar water tanks
 Used in making boat hulls,spray insulation
 Upholstery and PU inks
 Furniture,bedding,car interirors
 Depending on specific properties,they may be also used as synthetic lubricants,adhesives
and sealants,surface active agents,elastomers,castings,speciality coatings & defoamers.

OBJECTIVE:

POLYETHER synthesis -design options using glycerine initiator,KOH catalyst,Propylene oxide

monomer which produces 125 tons per day of 3000g/mol polyether product

PURITY OF PRODUCT: 0.9 ppm w.r.t potassium with 90% catalyst removal

PROFITABILITY ANALYSIS : NPV & ROI

RISKS:

PO is highly reactive and flammable

PROCESS includes 5 major steps:

1. Reaction
2. Initiation
3. Addition of PO monomer
4. Elongation of chain
5. Purification and stabilization of product

Major equipment:

 1 reactor for activating glycerine initiator

  2 reactors in series for polymerization
 Continuous gravity decanter for catalyst removal

SAFETY:

 To avoid leaks and maintain PO in liquid phase

PROCESS

 Polyethers are formed by addition of small oxiranes like EO or PO at the end of growing
chain through ring opening anionic polymerization reaction mechanism.
 A variety of polymers may be formed based on length and composition of constituent
monomers EO/PO.
 EO & PO can be added as block co polymers to tune the properties of desired final product
to desired specifications.

STEP 1- ACTIVATION

 Glycerine initiates the reaction on addition of PO by heating itself with solid KOH at 2500F.
 In this step,’H’ from glycerine reacts with ‘OH’ of KOH and thereby producing water
molecule.’K’ is attracted to the negative charge on terminating oxygen of glycerine.
 Water produced in this step is removed by evaporation.Removal of water is necessary as it
can prematurely stop the growth of polymer chain & can degrade the final quality of
polyether.

STEP 2-INITIATION

 This initiation phase involves addition of PO to activated glycerine.An exothermic reaction

is initiated as soon as PO is introduced into the reactor,resulting in the formation of
polyether chains.
 External heat exchangers are used to control the temperature of reactor contents.

STEP 3-REACTION

In this step,concentration of monomer gradually decreases as it is getting incorporated into the

growing polymer.

STEP 4-PURIFICATION

 This step deals with removal of unreacted PO from reaction mixture & separating potassium
calalyst from crude polyether to meet industrial product purity specifications.
 Separation of PO is performed in second reactor by decreasing pressure using PRV(Pressure
relief valve) so that liquid PO vaporizes.
  Water wash performs the dual role of terminating the reaction and extraction of potassium
ions from nonpolar polymer product.
 This is followed by gravity decantation where water carrying most of the catalyst is
separated from polyether.
 Washing & decantation are performed 3 times to reach the desired purity level of less than 5
ppm.

STEP 5-STABILISATION

 Ethers have a tendency for auto oxidation in which they combine with atmospheric oxygen
and turn into explosive peroxide/hydroperoxide.
 Failure to control ether auto oxidation may be fatal and destructive.
 To avoid this safety hazard,polyether is loaded into large storage tank and 0.05% of an
antioxidant is added to it.

PROCESS SPECIFICATIONS

Based on standards for manufacturing & sale of polyethers the following specifications have been
choosen:

 Molecular weight(g/mol) - 2900-3100g/mol

 Maximum catalyst(ppm) - 5ppm
 Maximum water(wt%) - 1wt%
 Stabilizer(ppm) - 300-500ppm

Temperature operates between 2120F ,under which there is not enough energy to continue the
reaction and 2600F ,over which the polymer degrades due to high temperatures.

The maximum PO concentration must be below 20wt% in order to control the reaction rate and
avoid non-uniformity in the reactor which would otherwise lead to variations in the product.

PRELIMINARY CONSIDERATIONS FOR REACRTOR CONFIGUARTION

1. Reactors and heat exchangers configuration that would optimize reaction conditions to
minimize capital costs and produce a final polyol mixture with narrow polydispersity
2. To decide the type & size of vacuum pump required to remove water generated during
catalyst activation step
3. Different alternatives of separation systems to extract potassium catalyst
PLANT DESIGN:

The design configuration has a

Pre-reactor: It is outfitted with a heating jacket and it contains component mixture of glycerol and
KOH. After half an hour the activated mixture will be transferred to reactor 1

Reactor 1: Here the water formed in the initiation step is stripped through vacuum evaporation then
PO is added to the reactor for about 7 5 hours after which the contents of the reactor will be
transferred to reactor 2

Reactor 2: Here PO addition is continued for another 99 minutes and the reaction mixture stays in
reactor 2 till desired molecular weight polymer is achieved

Heat exchangers: Each reactor is associated with a heat exchanger which carries cooling water at
750F to remove the heat generated during polymerization

Liquid ring vacuum pump: This is used along with a pre condenser to remove water formed
during catalyst activation step in the beginning

Further the product is transferred to downstream processes for purification & packaging

Alternatives for separation of catalyst from potassium:

Ion exchange resins

Toluene as a separating agent

Crown ether sequestration

Filtration with magnesol

Extraction using water wash & decantation

SEPARATION OPTImISATION:

1. Batch decanter with liquid holdup for the entire polyol/water mixture
2. Three smaller continuous decanters in series
3. One small decanter with recycle loop

A small decanter with recycle is used for purification and separation of polyether from potassium

A mixing vessel is filled with polyol contents from reactor 2 and cleaning water which passes
through a heat exchanger
After mixing the mixture will be pumped through a continuous gravity decanter at a slow rate for
adequate separation between the immiscible liquids

After going to the decanter the water will be sent to waste and the polyol may be recycled back to
the mixing vessel for successive separations

Conditions:

Minimum temperature of polyol for decantation is 1800F

Ratio of water to polyol in a mixing vessel : 0.75:1

Catalyst recycled from decantation is step is discarded as waste water treat ment costs more than the
virgin KOH

REACTION KINETICS:

Rate of polymerization as a function of reactant concentration would determine batch time and
amount of heat generated as a function of reaction rate would determine the required size of heat
exchangers

The following kinetic equations describing the polymerization of PO were provided by Dr.
P.C. Gopalratnam.

𝑟=𝑑𝐶0𝑑𝑡=−𝑘𝐶(Equation 1)

𝑘=9.84×1011𝑒−15099(Equation 2)

𝑑𝑄𝑅𝑑𝑡=(𝑊𝑡𝑜𝑡𝑎𝑙)(−∆𝐻𝑅)(−𝑟)(Equation 3)

In reaction 1-Ck & Co represent concentrations of potassium ion and PO in reaction mixture
respectively

“r” has the units of POUNDS total/POUNDS potassium *hour

Units of temperature are in rankine

In equation 3 Wtotal represents the total weight of reaction mixture in pounds

–ΔHrxn represents heat of polymerization at reaction temperature in BTU/lb

In this project, weight fraction, rather than mole fraction, was used because in polymerization
reactions, the moles of the product (polymer) is constant throughout the entire reaction. Instead of
moles of product being formed, the existing product merely increases in molecular weight. The use
of weight fraction is also the established practice within the polymer industry. The specific method
in which we used the equations above to describe the progress of our reaction at every point in time,
including example calculations,are explained in detail in Appendix A. The heat of polymerization
of propylene oxide was found from a 1950 paper entitled Heats of Polymerization: A Summary of
Published Values and Their Relation to Structure21and was determined to be 700 BTU/lb of PO at
25 ºC.

CHEMICAL PROPERTIES:

MATERIAL MOLECULAR HEAT DENSITY IMPORTANT

WEIGHT{g/mol} CAPACITY{BTU/lb*R} {lb/gallon} NOTES
Glycerine 92.09 0.49 10.5 -
KOH 56.1 0.28 21.2 Can cause
corrosion in case
of skin or eye
contact
Propylene Oxide 58.08 0.50 6.8 Highly
flammable
oxygen sensitive
harmful if
ingested
Polyether Polyol 3000 0.49 8.5 -

UTILITY PROPERTIES:

These are needed to determine amount of water required to be circulated through the heat exchangers to
safely remove the heat of reaction as well as the quantity of stea m necessary to be circulated through the
jacket of pre-reactor to raise its contents to the reaction temperature

Assumption : Heat capacity of cooling water remains independent of temperature at a constant value
of 0.998 BTU/lb*R.This is a safe assumption because the true heat capacity over the temperature range
used varies only between 0.9985 to 0.9975 BTU/lb*R
 MATERIAL SUPPLY HEAT CAPACITY LATENT HEAT OF
TEMPERATURE{0F} {BTU/lb*R} FUSION{BTU/lb}
Cooling water 75 0.998 -
5 psig steam 297.7 - 912.1

PROCESS FLOW DIAGRAM:

 Mixer 1: Glycerine is pumped and Solid KOH is added to mixer 1.Jacketed mixer heats
contents to 2500F.Contents are pumped to reactor 1.
Reactor 1: (1)At the start of the batch, reactor is cleaned by spray nozzle showers and
drained.It is inerted by pressurisation purges with nitrogen and releases purged air through a
valve .(final pressure after purge – 14.8 psia). (2) Vessel is pressurised to 165 psia
 Heat exchanger 1 :
 Vacuum pump :
 Condenser 1 :
 Heat exchanger 2 :
 Reactor 2 :
 Heat exchanger 2 :
 Condenser 2 :
 Heat exchanger 3 :
 Mixer 2 :
 Decanter :
MATERIAL BALANCE:

CHEMICAL REACTION:

Solid KOH
+ + H2O
2120F-2600F

(Glycerine) (PO) (Polyether)

ME
CHANISM OF CHAIN TRANSFER REACTION TO THE MONOMER IN PO POLYMERISATION

OVERALL BALANCE:

Basis : 125 tons per day of 3000g/mol polyether INLET OUTLET

product (TON/BATCH) (TON/BATCH)
Given:
Purity of product: 0.9 ppm wrt potassium with
90% catalyst removal
Conversion:95%
Glycerine
K+ 0.0005
PO 25
Water formed 0 12.5
Nitrogen
Stabiliser(Irganox 1010-0.05wt%) 0.05
Polyether 0 125