project on propylene oxide

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PROJECT ON PROPYLENE OXIDE MAHATMA GANDHI MISSION’S COLLEGE OF ENGINEERING & TECHNOLOGY KAMOTHE, NAVI MUMBAI. ACADEMIC YEAR: 2011-2012. PROJECT REPORT ON MANUFACTURE OF “PROPYLENE OXIDE” UNDER THE GUIDANCE OF Prof.: CYRUS K MISTRY SUBMITTED BY- MIKHIL MOHAN VINEET G. NAIR 1 MGM COLLEGE OF ENGINEERING AND TECHNOLOGY

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Page 1: Project on Propylene Oxide

PROJECT ON PROPYLENE OXIDE

MAHATMA GANDHI MISSION’S

COLLEGE OF ENGINEERING & TECHNOLOGY

KAMOTHE, NAVI MUMBAI.

ACADEMIC YEAR: 2011-2012.

PROJECT REPORT

ON

MANUFACTURE OF “PROPYLENE OXIDE”

UNDER THE GUIDANCE OF

Prof.: CYRUS K MISTRY

SUBMITTED BY-

MIKHIL MOHAN

VINEET G. NAIR

1MGM COLLEGE OF ENGINEERING AND TECHNOLOGY

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Department of Chemical Engineering

MAHATMA GANDHI MISSION’S

COLLEGE OF ENGINEERING & TECHNOLOGY

KAMOTHE, NAVI MUMBAI.

CERTIFICATE

This is to certify that the following students,

MIKHIL MOHAN

VINEET G. NAIR

have successfully completed the project report entitled “PROPYLENE OXIDE” during

the prescribed period in the academic year 2011-12. This Project report is submitted in

the partial fulfillment of “BACHELOR OF CHEMICAL ENGINEERING” of Mumbai

University.

GUIDE EXTERNAL EXAMINER

HEAD OF DEPARTMENT PRINCIPAL

2MGM COLLEGE OF ENGINEERING AND TECHNOLOGY

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ACKNOWLEDGEMENTS

This project would never have seen the light of the day if it hadn’t been for support and

encouragement of multitude of very exemplary people.

We would like to sincerely thank my guide & Head of Chemical Engineering Department Dr.

CYRUS K MISTRY who is the driving force behind this project and discussion with him

proved to be enlightening.

We express our sincere gratitude toward our principal Dr. GEETHA JAYARAJ, for

providing us with the opportunity to chose this project. We would be failing our duty if we do

not acknowledge the help extended by professors of Chemical Department of MGM’S

college of engineering and technology. Our heartfelt gratitude to library and their staff

member.

MIKHIL MOHAN

VINEET G. NAIR

3MGM COLLEGE OF ENGINEERING AND TECHNOLOGY

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4MGM COLLEGE OF ENGINEERING AND TECHNOLOGY

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Sr. No. Topic Page No.

1 Introduction 4

2 Physical and Chemical Properties

2.1 Physical Data

2.2 Chemical Reactions

7

3 Manufacturing Processes

3.1 Chlorohydrin Process

3.2 Hydroperoxide Process

12

4 Process Selection And Description

4.1 Raw Materials Used

4.2 Flowsheet and Process Description

16

5 Manufacturers of Propylene Oxide in

India

23

6 Applications And Uses

6.1 Derivatives

25

7 Material Safety Data Sheet

7.1 Hazard Identification

7.2 Primary Routes of Exposure

7.3 Signs and Symptoms of Over Exposure

7.4 Acute Health Effects

7.5 Chronic Health Effects

7.6 First Aid Measures

7.7 Handling and Storage

7.8 Disposal Considerations

29

5MGM COLLEGE OF ENGINEERING AND TECHNOLOGY

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Chapter 1

Introduction

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Introduction of Propylene Oxide

Propylene Oxide (PO) is a highly reactive chemical used as an

intermediate for the production of numerous commercial materials. It reacts

readily with compounds containing active hydrogen atoms such as alcohols,

amines and acids.

Its main derivatives include polyether polyols, propylene glycol (PG) and

propylene glycol ethers but it has many other outlets. Propylene oxide is used in

the production of poly-ethers (the primary component of polyurethane foams)

and propylene glycol. 

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Acute (short-term) exposure of humans and animals to propylene oxide

has caused eye and respiratory tract Irritation. Dermal contact, even with dilute

solutions, has caused skin irritation and necrosis in humans. Propylene oxide is

also a mild Central Nervous System (CNS) depressant in humans. 

Inflammatory lesions of the nasal cavity, trachea, and lungs and neurological

effects have been observed in animals chronically (long-term) exposed to

propylene oxide by inhalation.  Propylene oxide has been observed to cause

tumors at or near the site of administration in rodents, causing forestomach

tumors following ingestion via gavage (experimentally placing the chemical in

the stomach) and nasal tumors after inhalation exposure.  EPA has classified

propylene oxide as a Group B2, probable human carcinogen.

Other applications for PO include hydroxypropyl acrylates used in UV

curable resins, inks, coatings and varnishes; iso-propanolamines employed as

solvents in natural gas purification, metal working fluids and cosmetics; and

propylene glycol alginates made with sea weed (kelp) for use as food grade

thickeners, emulsifiers and stabilisers.

Global demand for PO had been growing at 4-5%/year. Growth in Europe

and the US had been around 3-4%/year while Asia, in particular China, had

seen the strongest growth at 7-8%/year.

In addition, growth came to an abrupt halt when markets collapsed in the

second half of 2008 due to the economic crisis. Overall sales were said to be 5%

down in 2008 compared to 2007 and a further decline of 5% is expected in

2009. As a result much capacity has been temporarily idled in this period.

Markets are not expected to return to pre-crisis growth levels until 2011,

according to some market sources.

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Chapter 2

CHEMICAL AND

PHYSICAL

PROPERTIES

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2.1 Physical Properties

Propylene oxide is a colorless, low-boiling (34.2 °C) liquid. Table 1 lists

general physical properties. Table 2 provides equations for temperature

variation on some thermodynamic functions. Vapor-liquid equilibrium data for

binary mixtures of propylene oxide and other chemicals of commercial

importance are available. References for binary mixtures include 1, 2-

propanediol, water, 1,2-dichloropropane, 2-propanol, 2-methyl-2-pentene),

methyl formate, acetaldehyde, methanol, propanal, 1-phenylethanol, oxygen,

nitrogen, and tertiary butanol. Reference 27 provides liquid-liquid equilibrium

data for propylene oxide, water, and 1,2-dichloropropane.

Physical Data

Property Value

Molecular Weight 58.08

Boiling Point at 101.325 kPa 34.2 oC

Freezing Point -111.93 oC

Critical Pressure 4.92 MPa

Critical Temperature 209.1 o C

Critical Volume 186 cm3/mol

Flash Point -37 oC

Heat of Fusion 6.531 kJ/mol

Heat of Vapourisation (1 atm.) 27.8947 kJ/mol

Heat of Combustion 1915.6 kJ/mol

Specific Heat at 20 oC 122.19 J/(mol-K)

Refractive Index at 25 oC 1.36335

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2.2. Chemical Properties

Propylene oxide is highly reactive owing to the strained three-membered

oxirane ring. The C-C and C-O bond lengths have been reported as 147 pm and

144 pm, respectively, while the C-C bond for the substituted methyl group is

152 pm. Although some reactions, such as those with hydrogen halides or

ammonia, proceed at adequate rates without a catalyst, most reactions of

industrial importance employ the use of either acidic or basic catalysts.

Recovery of optically active propylene oxide from a mixture of enantiomers is

accomplished by the action of micro-organisms.

2.2.3 Reactions

2.2.3.1 Water

Propylene oxide reacts with water to produce propylene glycol,

dipropylene glycol, tripropylene glycol, and higher molecular weight

polyglycols. This commercial process is typically run with an excess of water

(12 to 20 mol ater/mol propylene oxide) to maximize the production of the

mono-propylene glycol.

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2.2.3.2 Hydroxy-Containing Organics

Propylene oxide reacts with the hydroxyl group of alcohols and phenols

to produce monoethers of propylene glycol. Suitable catalysts include sodium

hydroxide, potassium hydroxide, tertiary amines, potassium carbonate, sodium

acetate, boron trifluoride, and acid clays. Further addition of propylene oxide

yields the di-, tri-, and poly (propylene glycol) ethers. Multiple hydroxyls

(glycol, glycerol, glucose, etc) on the organic reactant lead to the polyether

polyols discussed earlier. Propylene oxide and carboxylic acids in equimolar

ratios produce monoesters of propylene glycol. In the presence of basic catalysts

these monoesters can undergo trans-esterification reactions that yield a product

mixture of propylene glycols, monoesters, and diesters.

Many natural products, eg, sugars, starches, and cellulose, contain hydroxyl

groups that react with propylene oxide. To yield a variety of ether and ester

products.

2.2.3.3 Ammonia and Amines

Isopropanolamine is the product of propylene oxide and ammonia in the

presence of water. Propylene oxide reacts with isopropanolamine or other

primary or secondary amines to produce N- and N, N-disubstituted

isopropanolamines. Propylene oxide further reacts with the hydroxyl group of

the alkanolamines to form polyether polyol derivatives of tertiary amines or of

secondary amines in the presence of a strong base catalyst.

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2.2.3.4 Carbon Dioxide

Propylene oxide and carbon dioxide react in the presence of tertiary

amine, quaternary ammonium halides, anion exchange resins having a

quaternary phosphonium group, or calcium or magnesium halide catalysts to

produce propylene carbonate. Use of catalysts derived from diethylzinc results

in polycarbonates.

2.2.3.5 Polymerization to Polyether Polyols

The addition polymerization of propylene oxide to form polyether polyols

is very important commercially. Polyols are made by addition of epoxides to

initiators, i.e., compounds that contain an active hydrogen, such as alcohols or

amines. Some of the simplest polyols are produced from reaction of propylene

oxide with propylene glycol and glycerol initiators. Polyether diols and

polyether triols are produced, respectively.

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Chapter 3

MANUFACTURING

PROCESSES

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Propylene oxide is produced by one of two commercial processes: the

chlorohydrin process or the hydroperoxide process. The 1999 global propylene

oxide capacity was estimated at about 5.78 × 106 t/yr, with about half came

from each of the two processes. The chlorohydrin process involves reaction of

propylene and chlorine in the presence of water to produce the two isomers of

propylene chlorohydrin. This is followed by dehydrochlorination with caustic or

lime to Propylene Oxide and salt. The Dow Chemical Company is the only

practitioner of the chlorohydrin process in North America. However, several

companies practice the chlorohydrin process at more than 30 locations in

Germany, Italy, Brazil, Japan, Eastern Europe, and Asia.

3.1. Chlorohydrin Process

The chlorohydrin process is fairly simple, requiring only two reaction

steps, chlorohydrination and epoxidation, followed by product purification.

Propylene gas and aqueous chlorine solution in which HCl and HOCl are in

equilibrium are reacted at a temperature of 35-50 oC and a pressure of 2-3 bar. It

results in the formation of 4-6 % mixture of α- and β-propylene chlorohydrin

(9:1 ratio) and a small amount of chlorinated organic co-products, chiefly 1, 2-

dichloropropane. Epoxidation, also called saponification or

dehydrochlorination, is accomplished by treatment of the chlorohydrin solution

with an excess of alkali e.g. 10% lime water or dilute sodium hydroxide

solution from NaCl electrolysis).

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Propylene oxide and other organics are steam-stripped from the resulting

sodium chloride or calcium chloride brine. The brine is treated, usually by

biological oxidation, to reduce organic content prior to discharge. The

propylene oxide is further purified to sales specifications by removal of lights

and heavies via distillation.

3.2. Hydroperoxide Process

The hydroperoxide process to propylene oxide involves the basic steps of

oxidation of an organic to its hydroperoxide, epoxidation of propylene with the

hydroperoxide, purification of the propylene oxide, and conversion of the co-

product alcohol to a useful product for sale. Incorporated into the process are

various purification, concentration, and recycle methods to maximize product

yields and minimize operating expenses. Commercially, two processes are used.

The co-products are tert-butanol, which is converted to methyl tert-butyl ether

(MTBE), and 1-phenyl ethanol, converted to styrene. The co-products are

produced in a weight ratio of 3–4:1 tert-butanol/propylene oxide and 2.4:1

styrene/propylene oxide, respectively. These processes use iso-butane and ethyl

benzene, respectively, to produce the hydroperoxide. Other processes have been

proposed based on cyclohexane where aniline is the final co-product, or on

cumene with α-methyl styrene as the final co-product.

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3.3 Hydrogen Peroxide Processes

Since each of the commercial processes has issues of effluent treatment,

by-product treatment, co-product sales, and cost, development of alternative

processes that address one or more of these issues is on-going.

A titanium silicalite catalyst (TS-1) is used to produce propylene oxide

from propylene and hydrogen peroxide. Alcohol or alcohol–water mixtures are

used as solvent. Methanol is the preferred alcohol. Yields on peroxide are

quantitative and propylene selectivity is high (95%). TS-1 is a molecular sieve

having an average pore diameter of 0.55 nm and a TiO2 content of 2.6 wt %.

The catalyst deactivates due to polymer formation and is regenerated by

calcining or treatment with hydrogen peroxide solutions. Propylene oxide

selectivity is improved by treating the catalyst with neutral or basic salts, tin, or

metal cations at the expense of catalyst activity. Peroxide decomposition to

water and oxygen is reduced by use of chelating agents, but is increased by Pd

in the catalyst. Fully integrated processes have been proposed that include

hydrogen peroxide production, propylene reaction to propylene oxide, product

purification, and solvent recycle. Peroxide formation can be from catalytic

hydrogen and oxygen reaction in alcohol solvent or the anthraquinone process.

Purification of propylene oxide by extractive distillation using water or

propylene glycol effectively removes impurities such as acetaldehyde.

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Chapter 4

PROCESS

SELECTION AND

DESCRIPTION

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Up until the year 2005, both the Chlorohydrin process and the

Hypoperoxide were used on an equal importance. But the recent technologies

have found it useful to use the Hypoperoxide method. Also this method, Ethyl

Benzene Hypoperoxide method in particular gives Styrene as a co-product.

A continuing trend in the propylene oxide industry is the drive to develop

and commercialize process routes that do not produce sizeable co-product

quantities and do not use chlorine-based chemistry.

The hydroperoxidation routes to propylene oxide that co-produce styrene

monomer (POSM) and t-butyl alcohol (POTBA) are responsible for the

majority of current global production as seen in the figure below.  However,

they require relatively large capital investments and present difficulties in

balancing the markets for propylene oxide and the co-products, leading to

considerable volatility in the economic performance of the operations over

time.  Existing hydroperoxidation plants continue to be operated and

incrementally improved, but new installations are more likely in less-developed

regions.  Although significant propylene oxide capacity is also based on the

chlorohydrin process (CHPO), this route suffers from environmental liabilities

and large capital investment requirements.   Also, inexpensive electric power

must be available for the integrated chloro-alkali facility.

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Ethylbenzene Hydroperoxide Process

4.1 Raw Materials Used

Ethyl Benzene

Ethylbenzene is an organic compound with the formula C6H5CH2CH3.

This aromatic hydrocarbon is important in the petrochemical industry as an

intermediate in the production of styrene, which in turn is used for

making polystyrene, a common plastic material. Ethylbenzene has been used as

a solvent for aluminium bromide in the anhydrous electrodeposition of

aluminium. Ethylbenzene is also an ingredient in some paints, and solvent

grade xylene (xylol) is nearly always contaminated with a few percent of

ethylbenzene.

Although often present in small amounts in crude oil, ethylbenzene is produced

in bulk quantities by combining benzene and ethylene in an acid-

catalyzed chemical reaction:

C6H6 + C2H4 → C6H5CH2CH3

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Approximately 24,700,000 tons were produced in

1999. Catalytic dehydrogenation of the ethylbenzene then gives hydrogen and

styrene:

C6H5CH2CH3 → C6H5CH=CH2 + H2

Properties of Ethylbenzene

Property Value

Appearance Liquid

Odour Sweet, Aromatic

Colour Transparent, Colourless

Molecular Weight 106.17

Density at 20 oC 868 kg/m3

Boiling Point at 1013 hPa 136.2 oC

Freezing Point -95 oC

Kinematic Viscosity at 10 oC 0.9 mm2/s

Dynamic Viscosity at 10 oC 0.78 m-Pas

Critical Pressure 3.701 mPa

Critical Temperature 343.05 oC

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4.2.2 Flowsheet and Process Description:

Figure above shows the process flow sheet for production of propylene

oxide and styrene via the use of ethylbenzene hydroperoxide (EBHP). Liquid-

phase oxidation of ethylbenzene with air or oxygen occurs at 206–275 kPa (30 –

40 psia) and 140 150 oC, and 2–2.5 hrs. are required for a 10–15% conversion to

the hydroperoxide. Recycle of an inert gas, such as nitrogen, is used to control

reactor temperature. Impurities in the ethylbenzene, such as water, are

controlled to minimize decomposition of the hydroperoxide product and are

sometimes added to enhance product formation. Selectivity to by-products

include 8–10% acetophenone, 5–7% 1-phenylethanol, and <1% organic acids.

EBHP is concentrated to 30–35% by distillation. The overhead ethylbenzene is

recycled back to the oxidation reactor. Because the by-product organic acids

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decompose EBHP and decrease epoxidation catalyst activity, an alkali

hydroxide or carbonate wash is used to neutralize the acids.

EBHP is mixed with a catalyst solution and fed to a horizontal

compartmentalized reactor where propylene is introduced into each

compartment. The reactor operates at 95–130◦C and 2500–4000 kPa (360–580

psi) for 1–2 h, and 5–7 mol propylene/1 mol EBHP are used for a 95–99%

conversion of EBHP and a 92–96% selectivity to propylene oxide. The

homogeneous catalyst is made from molybdenum, tungsten, or titanium and an

organic acid, such as acetate, naphthenate, stearate, etc. Heterogeneous catalysts

consist of titanium oxides on a silica support.

After epoxidation, propylene oxide, excess propylene, and propane are

distilled overhead. Propane is purged from the process; propylene is recycled to

the epoxidation reactor. The bottoms liquid is treated with a base, such as

sodium hydroxide, to neutralize the acids. Acids in this stream cause

dehydration of the 1- phenylethanol to styrene. The styrene readily polymerizes

under these conditions. Neutralization, along with water washing, allows phase

separation such that the salts and molybdenum catalyst remain in the aqueous

phase. Dissolved organics in the aqueous phase are further recovered by

treatment with sulfuric acid and phase separation. The organic phase is then

distilled to recover 1-phenylethanol overhead. The heavy bottoms are burned

for fuel. Crude propylene oxide separated from the epoxidation reactor effluent

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is further purified by a series of conventional and extractive distillations to

reduce the content of aldehydes, ethylbenzene, water, and acetone.

The co-product 1-phenylethanol from the epoxidation reactor, along with

acetophenone from the hydroperoxide reactor, is dehydrated to styrene in a

vapor-phase reaction over a catalyst of silica gel or titanium dioxide at 250–280 oC and atmospheric pressure. This product is then distilled to recover purified

styrene and to separate water and high-boiling organics for disposal. Unreacted

1-phenyl ethanol is recycled to the dehydrator.

Acetophenone is separated for hydrogenation to 1-phenylethanol, which

is sent to the dehydrator to produce styrene. Hydrogenation is done over a fixed-

bed copper-containing catalyst at 115–120 oC and pressure of 8100 kPa (80

atm), a 3:1 hydrogen-to-acetophenone ratio, and using a solvent such as ethyl

benzene, to give 95% conversion of the acetophenone and 95% selectivity to 1-

phenyl ethanol.

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Chapter 5

Manufacturers of

Propylene Oxide in

India

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Triveni Interchem Pvt. Ltd. in Vapi, Gujarat, India.

Mulberry Chemicals Pvt. Ltd. in Mumbai, India.

Suyash Herbs Export Private Limited in Surat, India.

Arihant Chemicals in Mumbai, India.

Alpha Chemika in Mumbai, India.

Taj Pharmaceuticals Ltd. in Mumbai, India.

Ksm Intertrade Agencies in Mumbai, India.

Desmo Exports Ltd in Mumbai, India.

N. R. Chemicals Corporation in Dewas, Madhya Pradesh, India.

Chemix Speciality Gases And Equipments in Bangalore, India.

Excel International in Mumbai, India.

Sri Jayalaxmi Traders in Arcot, Tamil Nadu, India.

Intersperse Industries in Ahmedabad, Gujarat, India.

Sunn Chhem in Pune, India.

Bnh Gas Tank in Pune, India.

Darshit Impex in Ahmedabad, India.

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Chapter 6

APPLICATIONS

AND USES

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Propylene oxide is a useful chemical intermediate. Additionally, it has

found use for etherification of wood to provide dimensional stability, for

purification of mixtures of organo-silicon compounds, for disinfection of crude

oil and petroleum products, for sterilization of medical equipment and

disinfection of foods, and for stabilization of halogenated organics.

Propylene oxide has found use in preparation of polyether polyols from

recycled poly (ethylene terephthalate), halide removal from amine salts via

halohydrin formation, preparation of flame retardants, alkoxylation of amines,

modification of catalysts, and preparation of cellulose ethers.

6.1 Derivatives:

6.1.1 Polyether Polyols:

Polyether polyols produced by polymerization of propylene oxide on

polyhydric alcohols account for the largest use of propylene oxide. The starting

polyhydric alcohols have from two to eight hydroxyl groups and can be

mixtures of two or more alcohols. Molecular weights of the products range from

about 400 to about 8000. Some of the polyether polyols may be made with

copolymerization of ethylene oxide. The ethylene oxide can either be in blocks

or randomly distributed in the polymer. The products are useful for making

flexible and rigid urethane foams, adhesives, coatings, sealants, and reaction

moldable products.

6.1.2 Propylene Glycol:

Propylene glycol, the second largest use of propylene oxide, is produced

by hydrolysis of the oxide with water. Propylene glycol has very low toxicity

and is, therefore, used directly in foods, pharmaceuticals, and cosmetics, and

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indirectly in packaging materials. Propylene glycol also finds use as an

intermediate for numerous chemicals, in hydraulic fluids, in heat transfer fluids

(antifreeze), and in many other applications.

Dipropylene glycol is produced in the manufacture of propylene glycol

and finds utility as an indirect food additive, in brake-fluid formulations, cutting

oils, soaps, and solvents. Tripropylene glycol also finds use as a solvent, as

textile soaps, and as lubricants.

6.1.3 Poly (propylene glycol):

Polymers of propylene oxide based on reaction with water or propylene

glycol are liquids of 400 to about 4000 molecular weight. Viscosity increases

and water solubility decreases with increasing molecular weight.

Poly(propylene glycol)s find use in cosmetics, as synthetic lubricants, as

metalworking fluids, antifoam agents, heat transfer fluids, nonionic surfactants,

and chemical intermediates.

6.1.4 Glycol Ethers:

Glycol ethers are produced by reaction of propylene oxide with various

alcohols such as methanol, ethanol, butanol, and phenol. The products are

themono-, di-, and tripropylene glycol ethers. These products are used in

protective coatings, inks, textile dyeing, cleaners, antiicing additives for jet fuel,

and as chemical intermediates.

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6.1.5 Isopropanolamines:

Reaction of propylene oxide with ammonia yields mono-, di-, and tri-

isopropanolamines. These products find use as soluble oils and solvents,

emulsifiers, waterless hand cleaners, cosmetics, cleaners, and detergents. In

industrial applications isopropanolamines are used in adhesives, agricultural

products, corrosion inhibitors, coatings, epoxy resins, metalworking, and others.

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Chapter 7

Material Safety Data Sheet

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7.1 Hazard Identification

EMERGENCY OVERVIEW

Clear, colorless liquid with a sweet, ether-like odor. Extremely flammable

liquid and vapor. Vapors may cause flash fire and can form explosive mixtures

with air. May polymerize explosively when involved in a fire or in contact with

incompatible materials. Corrosive in nature. Causes severe eye, skin and

gastrointestinal irritation or burns and respiratory tract irritation with central

nervous system effects. Harmful if swallowed or absorbed through the skin.

Possible chance of cancer and reproductive hazard.

DANGER!

Extremely flammable liquid and vapor. May form explosive mixtures

with air. Causes severe eye and skin irritation with possible burns. May cause

allergic skin reaction. May be harmful if absorbed through the skin. Inhalation

may cause respiratory irritation and central nervous system depression. Harmful

if swallowed. May cause burns to the gastrointestinal tract and central nervous

system depression. Aspiration may cause lung damage. Possible cancer hazard.

May cause cancer based on animal data. Possible reproductive hazard.

HAZARD RATINGS: (0=minimum, 4=maximum)

HMIS Rating: Health = 3*

Flammability = 4

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Reactivity = 2

Personal Protection Code = (Consult your supervisor or standard operating

procedures for special handling directions.)

NFPA Rating: Health = 3

Flammability = 4

Reactivity = 2

TWA (8-hr) STEL (15-min)

OSHA 100 ppm None

Exposure Limits: ACGIH 2 ppm None

7.2 PRIMARY ROUTES OF EXPOSURE: Inhalation, eye, skin

contact/absorption, ingestion.

7.3 SIGNS AND SYMPTOMS OF OVEREXPOSURE

Effects include severe eye, skin and respiratory irritation or burns, skin

rash, blistering. Effects of central nervous system depression include

excitement, headache, dizziness, incoordination, narcosis, drunkenness, nausea,

vomiting, collapse, coma and respiratory arrest.

Effects from swallowing may include severe irritation and burns to the

gastrointestinal tract, nausea, vomiting, diarrhea, central nervous system

depression and difficulty breathing.

7.4 ACUTE HEALTH EFFECTS:

INHALATION : Inhalation of vapors or mists may cause mucous membrane

or upper respiratory tract irritation with central nervous system depression.

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Symptoms include headaches, dizziness, coughing, narcosis, drunkenness,

incoordination, nausea, vomiting, and collapse. High vapor concentrations

may cause unconsciousness, coma or death.

EYE CONTACT : Vapors and liquid may cause severe eye irritation with

redness, tearing, burning, swelling of the conjunctiva and corneal burns.

Damage may be permanent.

SKIN CONTACT : Contact may cause severe irritation with redness, pain

and severe burns or blisters. Propylene oxide may be absorbed through the

skin in harmful amounts causing systemic effects similar to those listed

under ingestion and inhalation. Propylene oxide is a skin sensitizer and may

cause an allergic skin reaction. Dilute solutions may be more irritating than

undiluted materials.

INGESTION : Swallowing may cause severe burns to the mouth, throat and

stomach with nausea, vomiting and diarrhea. May cause central nervous

system depression with headache, dizziness, drowsiness, drunkenness and

collapse. May be fatal due to respiratory failure. Aspiration may occur

during swallowing or vomiting resulting in lung damage.

7.5 CHRONIC HEALTH EFFECTS:

SKIN CONTACT: Prolonged or repeated exposure may cause delayed

secondary burns, ulcers or superficial scarring.

EYE CONTACT: No data on chronic effects is available.

INHALATION: Studies with animals have shown chronic effects such as

growth depression, lung and slight liver injury.

INGESTION: Studies with animals have shown chronic effects such as loss

of body weight, gastric irritation and slight liver injury.

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7.6 FIRST AID MEASURES

EYE CONTACT: Immediately flush eyes thoroughly with large amounts of

water for at least 15-20 minutes, occasionally lifting upper and lower lids.

Get immediate medical attention.

SKIN CONTACT: Remove contaminated clothing and shoes. Immediately

wash exposed area with large amounts of mild soap and water. Flush with

lukewarm water for at least 15 minutes. Get prompt medical attention.

Launder contaminated clothing before reuse.

INHALATION: Remove exposed person to fresh air. If breathing has

stopped, give artificial respiration then have qualified personnel administer

oxygen, if needed. Get immediate medical attention.\

INGESTION: If patient is conscious and responsive, give 4 – 8 ounces of

water or milk to dilute. DO NOT INDUCE VOMITING. Keep head lower

than hips to avoid aspiration, should vomiting occur. Get immediate medical

attention. Do not give anything to an unconscious or drowsy person.

MEDICAL CONDITIONS AGGRAVATED BY EXPOSURE: Persons

with pre-existing skin, kidney, liver and respiratory disorders may be at

increased risk from exposure to this substance.

NOTE TO PHYSICIANS: Propylene oxide is an irritant that may cause

coughing, dyspnea, noncardiogenic pulmonary edema, or chemical

pneumonitis. Cyanosis has occurred. Lung injury has been observed in

experimental animals. Respiratory effects may be delayed. Evaluate for

respiratory distress. Consider oxygen administration. If a chemical burn is

present, decontaminate skin and treat as any thermal burn. No specific antidote

is known; however, consider gastric lavage and administration of a charcoal

slurry.

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7.7 HANDLING AND STORAGE

HANDLING AND STORAGE PRECAUTIONS

Wear all recommended protective clothing and devices when handling

this material. Wash thoroughly after handling. Use only in well ventilated

areas. Do not get in eyes, on skin or on clothing. Do not ingest on inhale. Do

not eat, drink or smoke in work areas. Shower, dispose of outer clothing and

change into clean garments at the end of the shift. Avoid cross-

contamination of street clothes. Keep product away from heat, sparks, flames

and all other sources of ignition. Ground and bond containers when

transferring material. Use non-sparking tools and equipment, including

explosion proof ventilation. Empty containers retain product residues and

can be dangerous. Do not pressurize, cut, weld, braze, solder, drill, grind or

expose empty containers to heat, sparks or open flames. Have established

handling and emergency response procedures in place prior to use.

ENGINEERING CONTROLS

All electrical devices used in area processing and handling must be

engineered and designed to all applicable local electrical and/or fire codes.

Safeguards can include designing electrical devices as explosion-proof

and/or intrinsically safe.

ATTENTION

Propylene oxide vapors are colorless and odorless above the OSHA

PEL. An air monitoring system is recommended to determine airborne

exposure limits.

STORAGE SEGREGATION

Store propylene oxide in a cool, dry well-ventilated area, away from

incompatible chemicals and ignition sources. Store only in tightly closed

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containers. Protect against physical damage. Storage and use areas should be

No Smoking areas. Outside or detached storage preferred.

INCOMPATIBILITIES

Avoid acids, bases, peroxides, oxidizing agents, clay-based

absorbents, polymerization catalysts, epoxy resins, anhydrous metal

chlorides, copper and copper alloys, brass, bronze and other acetylide

forming metals.

7.8 DISPOSAL CONSIDERATION

WASTE MANAGEMENT/DISPOSAL

Contaminated solids should be landfilled only at properly permitted

disposal sites using registered contractors. Concentrated liquid waste may be

incinerated (if safety precautions are taken because of very low flash point) in

compliance with applicable air pollution control regulations. It is recommended

that contaminated product, soil or water intended for disposal be handled as

hazardous waste due to potentially low flashpoint. Disposal should be in

accordance with applicable local, state and federal regulations. Return used

containers to manufacturer only.

BIBLIOGRAPHY:

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“Propylene Oxide” under “Ethylene Oxide,” in ECT 1st ed., Vol. 5, pp.

922–923, by R. S. Aries, Consulting Chemical

Engineer, and H. Schneider, R. S. Aries & Associates; “Propylene Oxide”

in ECT 2nd ed., Vol. 16, pp. 595–609, by L. H.

Horsley, The Dow Chemical Co.; in ECT 3rd ed., Vol. 19, pp. 246–274,

by R. O. Kirk and T. J. Dempsey, The Dow Chemical Co.; “Propylene

Oxide” in ECT 4th ed., Vol. 20, pp. 271–302, by D. L. Trent, The Dow

Chemical Company; “Propylene Oxide” in ECT (online), posting date:

December 4, 2000, by D. L. Trent, The Dow Chemical Company.

Dietmar Kahlich, Uwe Wiechern, Jörg Lindner “Propylene Oxide”

in Ullmann's Encyclopedia of Industrial Chemistry, 2002 by Wiley-VCH,

Weinheim. doi:10.1002/14356007.a22_239Article Online Posting Date:

June 15, 2000

"Summary of Sumitomo process from Nexant Reports". Retrieved 2007-

09-18.

"New BASF and Dow HPPO Plant in Antwerp Completes Start-Up

Phase". Retrieved 2009-03-05.

Alex Tullo (2004). Dow, BASF to build Propylene Oxide. 82. pp. 15.

"Usage of proplyene oxide, from Dow Chemical". Retrieved 2007-09-10.

See The FDA Guidance Document For More Info

Agricultural Marketing Service, USDA (30 March 2007). "Almonds

Grown in California; Outgoing Quality Control

Requirements" (PDF). Federal Register 72 (61): 15,021–15,036.

Archived from the original on 2007-09-28. Retrieved 2007-08-22.

"Safety data for propylene oxide".

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