PRODUCTION OF PROPYLENE

OXIDE
BY
HPPO TECHNOLOGY
 WORK PLAN

SELECTION OF PRODUCT
LITERATURE
 PHYSICAL AND CHEMICAL PROPERTIES
 INDUSTRIAL USES
 EXPLORED ALL POSSIBLE METHODS OF PRODUCTION
LISTED OUT LIMITATIONS OF PROCESSES
 BYPRODUCT FORMATION AND ITS USES
 DISPOSAL PROBLEMS
 COSTS INVOLVED
COME UP WITH BEST METHOD OF PRODUCTION
FLOW SHEETING
MASS AND ENERGY BALANCES
 INTRODUCTION

Propene oxide (PO) is an important building block in industry,

with a demand that grows continuously.
Propylene oxide serves as an important chemical
intermediate.
It is a building block to a diverse number of products such as
polyether polyols, propylene glycols, and propylene glycol
ethers.
Approximately 70% of it is used as polypropylene glycol
in the raw materials for urethane, and the remainder is
used as propylene glycol in the raw materials for
unsaturated polyesters, food and product additives.
Propylene oxide is also an intermediate in the
manufacture of cosmetics, pharmaceuticals, household
detergents, textiles, and many other products
Propylene oxide is among the top 50 chemicals
produced (by volume) in the world.
INDUSTRIAL USES
 MARKET ANALYSIS OF PROPYLENE OXIDE
Traditionally, Europe has been dominant in the propylene oxide
market, but the market share is expected to shift to North America
and the Asia-Pacific region due to technological advances and
rapidly growing economies in those regions.
Asia-Pacific region dominated the global market share in 2018.
Robust growth of construction sector and increasing automotive
production are some of the factors driving the demand for
propylene oxide market in the region.
One restricting factor in the growth of the propylene oxide
market is fluctuating raw material prices.
The major factors driving the growth of market studied are the
rising demand for polyether polyols for polyurethane production,
and wide ranging downstream applications of propylene glycol.
.
 PROPYLENE OXIDE-PHYSICAL PROPERTIES
• Propylene oxide is a colorless, low-boiling,
highly volatile liquid with a sweet, ether-
like smell.
Chemical Safety:
• Propylene oxide is Flammable, Acute
Toxic, irritant and health hazard
• Propylene oxide is readily biodegradable
and photodegrades rapidly in the
atmosphere.
 PROPYLENE OXIDE-CHEMICAL PROPERTIES

Propylene oxide molecule contains an asymmetrical carbon

atom, being able to carry out many chemical reactions.
 Ring Opening: The epoxide ring of propylene oxide
may open at either of the C-O bonds.In anionic
(basic) catalysis the bond preferentially opens at the
least sterically hindered position, resulting in mostly
(95%) secondary alcohol products . Cationic (acidic)
catalysts provide a mixture of secondary and primary
alcohol products.
 With Water:
Hydrolysis reaction can generate propylene glycol with
etherification reaction leading to the formation of alcohol
ether. Under the action of catalyst, it can produce
polyether polyol.
 METHODS OF PRODUCTION

 CHLOROHYDRIN PROCESS
 ORGANIC PEROXIDE PROCESSES
i. TERT-BUTYL HYDROPEROXIDE PROCESS
ii. ETHYLBENZENE HYDROPEROXIDE PROCESS
iii. CUMENE HYDROPEROXIDE PROCESS
iv.HYDROGEN PEROXIDE TO PROPYLENE OXIDE
PROCESS(HPPO)
 BRIEF HISTORY OF PREVIOUS TECHNOLOGIES
Propylene oxide has traditionally been produced using
chlorohydrin processes. This process creates a large volume of
chlorinated side products that are difficult to separate and
then have to be sold as well.
Other processes have been created to avoid using chlorine
including epoxidation reactions. However, this process
produces 2.25 times more styrene than it does propylene oxide,
which leads to greater economic volatility as the price of
styrene fluctuates. Additionally, this process also has a high
capital cost.
More recently, companies have aimed to develop
processes that can produce propylene oxide while
minimizing the amount of side products produced.
Propylene can be reacted with hydrogen peroxide to
produce propylene oxide and water.
So far, no one has been able to develop and scale up
a process to directly oxidize propylene, reducing both
material and capital costs while making almost no side
products.
COMPARISION OF DIFFERENT PRODUCTION METHODS OF
PROPYLENE OXIDE
 CHLOROHYDRIN TERT-BUTYL ETHYLBENZENE CUMENE HYDROGEN
PROCESS HYDROPEROXIDE HYDROPEROXIDE PROCESS. HYDROGEN PEROXIDE TO
PROCESS. PEROXIDE PROPYLENE OXIDE
(HPPO) PROCESS
RAW Propylene, Chlorine Isobutane, Oxygen, Catalyst Ethyl benzene, Air, Cumene, Ti based Propylene ,Hydrogen
MATERIALS organo metal Propylene, Catalyst-Mo,W epoxidation catalyst, peroxide
Oxygen

STEPS 1.Chlorohydrination 1.Liquid phase air oxidation 1.Oxidation of Ethylbenzene 1.Oxidation 1.Reaction With
INVOLVED 2.Epoxidation of isobutene to TBHP 2.Epoxidation Reaction 2.Epoxidation hydrogen peroxide
3.Product 2.Reaction of TBHP with 3.Distillation 3.Hydrogenation 2.Recycle
Purification Propylene 3.Purification
3.Final Purification
BYPRODUCTS Crude propylene TBA,TBHP acetophenone, Cumyl alcohol Propylene glycol and
Dichloride,Nacl Brine or 1-phenylethanol,and organic acids, water
Cacl2 brine, Styrene
Epichlorohydrin
LIMITATIONS Effluent water Extractive distillation needs Use of energy Epoxidation reaction is Excess amount of
Treatment to be employed to remove intensive distillation process for an exothermic reaction hydrogen peroxide is
impurities or byproducts purification used in the reaction to
increase the formation
of
propylene oxide
USE OF Epichlorohydrin can be MTBE is used as gasoline Styrene is used to make Cumyl Propylene glycol is used
BYPRODUCTS used in epoxy additive latex,synthethic rubber,plastic alcohol is as drug solubiliser,stabili
resins packaging,disposa used as a ser for vitamins and as a
ble cups and free radical water miscible cosolvent
containers initiator for
acrylate and
methacrylate
monomers
 HYDROGEN PEROXIDE TO PROPYLENE OXIDE PROCESS(HPPO)
In the reaction unit, the catalytic epoxidation of propene is carried out
in the presence of a titanium silicalite catalyst using hydrogen
peroxide (H2O2) in methanol as the solvent. The propene cycle of the
PO plant is totally closed and the surplus propene recovered is
returned to the reaction section.

The crude PO contains some impurities which are removed in the PO

purification section by state-of-the-art 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.
BLOCK DIAGRAM OF HPPO PROCESS
Reaction

In the PO reaction process, the reaction of propene (C3H6) and

hydrogen peroxide (H2O2) takes place in a methanol/water
mixture using a fixed-bed reactor with a special titanium
silicalite catalyst (TS-1 type).
The process is characterised by mild process conditions with
temperatures below 100°C leading to low formation of by-products.
The pressure in the reaction unit is about 30 bar.
Due to the optimised process parameters, a high propene-based PO
selectivity of more than 95% can be obtained.
The heat of the highly exothermic reaction is removed by an
integrated cooling system. After reaction, the product mixture
containing mainly methanol, water, propene and PO is withdrawn
from the reactor and depressurised to a pressure slightly above
atmospheric pressure.
 Propylene Recycling:

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
 PO Purification:

The depressurised liquid product mixture is then transferred to the

pre-separation section where PO and dissolved propene are
separated from 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
are taken off in the bottom product. The PO distillate meets the
highest quality standards.
Methanol Processing:
The methanol in the methanol/water mixture withdrawn from the
bottom of the pre-separation column and from 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 water and small amounts
of high-boiling by-products, is delivered to the battery limits.
 ADVANTAGES OF HPPO PROCESS:
•Co-product-free process

•Epoxidation reactor specially designed for highly exo-thermic

reaction conditions combines an efficient heat transfer with an
almost ideal plug-flow characteristic

•High-performance catalyst with a long lifetime

•The process is free of chlorine

•Lower capital investment and energy consumption
•High specific yields resulting in low feedstock
consumption

•Stand-alone technology: no market dependency on

co-products
•Totally closed solvent and feedstock cycles

•Valuable by-product are recovered from the waste

water (approx. 37 kg propylene glycol per ton of PO)
References:
1. https://pure.tue.nl/ws/files/4013323/784812
2. ICIS. http://www.icis.com/chemicals/channel-info-chemicals-a-z/
3. Mengke Lu, Xuan Zhao, Jinghong Zhou, Gang Qian, Xuezhi Duan, Weikang Yuan,
Xinggui
Zhou. Solvent Screening and Process Optimization for Separating Propylene Oxide from
Direct Propylene Epoxidation with H2 and O2. Industrial & Engineering Chemistry
Research 2019, 58 (1) , 395-402. DOI: 10.1021/acs.iecr.8b05407.
4. https://www.researchgate.net/figure/Schematic-scheme-of-Evonik-TKISs-
HPPOprocess_fig2_287346684

5. P. Bassler, H.-G. Göbbel and M. Weidenbach, "The new HPPO Process for Propylene
Oxide: From," Chemical Engineering Transactions, vol. 21, pp. 571-576, 2010.
6. V. Russo, R. Tesser, E. Santacesaria and M. Di Serio, "Chemical and Technical Aspects
of
Propene Oxide Production via Hydrogen Peroxide (HPPO Process)," Industrial and
Engineering Chemistry Research, pp. 1168-1178, 2013.
7. S. B. Shin and D. Chadwick, "Kinetics of Heterogeneous Catalytic Epoxidation of
Propene
with Hydrogen Peroxide over Titanium Silicalite (TS-1)," Industrial & Engineering
Chemistry Research, vol. 49, pp. 8125-8134, 2010.
THANK YOU