OPTIMAL PROCESS FLOW

PRODUCTS :

OPTIMAL OLEFINS (MALAYSIA) SDN BHD

Products Capacity (kTa) Market Applications

Ethylene 600 Feedstock for Olefins Derivatives,

Polyethylene and Ethylene Oxide

Glycol

Propylene 95 Butanol and Derivatives

Pyrolysis Gasoline 35 Aromatics

OPTIMAL GLYCOLS (MALAYSIA) SDN BHD

Products Capacity (kTa) Market Applications

Mono-Ethylene Glycol 365 Resins for Fibers and PET

containers/bottles, Antifreeze as well

as Electronic applications

Di-Ethylene Glycol 20 Unsaturated Polyester Resins (used

for fiberglass) and Brake Fluid

Formulation

Re-Distilled Ethylene 140 Derivatives

Oxide

OPTIMAL CHEMICALS (MALAYSIA) SDN BHD

Products Capacity (kTa) Market Applications

A. Performance Chemicals

Ethanolamines 75 Personal Care Products, Electronics,

Taurine and Glyphosate

Gas Treating Fluids 10 Oil & Gas Processing

(UCARSOL™

Solvents)

Nonyl Phenol 25 Detergents, Household, Industrial &

Ethoxylates Institutional Cleaners and Emulsion

(TERGITOL™ Polymerization

surfactants)

Octyl Phenol 5 Specialty Surfactants, Paints and

Ethoxylates Emulsion Polymerization

(TRITON™

surfactants)

Polyalkylene Glycol 10 Metal Quenchants, Hydraulic Fluids,

(UCON™ Fluids) Compressor Lubricants and

Metalworking Fluids

Polyethylene Glycol 15 Pharmaceuticals, Cosmetics and

(CARBOWAX™) Personal Care Products

B. Chemicals

Brake Fluids DOT-3 3 Automotive Brake Fluids

(UCON ™ E-360)

Butanol / Iso butanol 140 Butyl Derivatives for Solvents, Paints &

Inks, Coatings and Adhesives

Butyl Acetate 50 Paint, Printing Ink, Leather and

Coating markets

Butyl Glycol Ethers 60 Coatings, Hard Surface Cleaners and

(CELLOSOLVE ™ & Electronics

CARBITOL™ Butyl

Glycol Ethers)

Production

ETHYLENE

Ethylene is produced in the petrochemical industry by steam cracking. In this process,

gaseous or light liquid hydrocarbons are heated to 750–950 °C, inducing numerous free
radical reactions followed by immediate quench to freeze the reactions. This process
converts large hydrocarbons into smaller ones and introduces unsaturation. Ethylene is
separated from the resulting complex mixture by repeated compression and distillation. In
a related process used in oil refineries, high molecular weight hydrocarbons are cracked
over zeolite catalysts. Heavier feedstocks, such as naphtha and gas oils require at least
two "quench towers" downstream of the cracking furnaces to recirculate pyrolysis-
derived gasoline and process water. When cracking a mixture of ethane and propane, only
one water quench tower is required.[9]

The areas of an ethylene plant are:

1. steam cracking furnaces;

2. primary and secondary heat recovery with quench;
3. a dilution steam recycle system between the furnaces and the quench system;
4. primary compression of the cracked gas (3 stages of compression);
5. hydrogen sulfide and carbon dioxide removal (acid gas removal);
6. secondary compression (1 or 2 stages);
7. drying of the cracked gas;
8. cryogenic treatment;
9. all of the cold cracked gas stream goes to the demethanizer tower. The overhead
stream from the demethanizer tower consists of all the hydrogen and methane that
was in the cracked gas stream. Different methods of cryogenically treating this
overhead stream results in the separation of the hydrogen and the methane. This
usually involves liquid methane at a temperature around −250 °F (−156.7 °C).
Complete recovery of all the methane is critical to the economical operation of an
ethylene plant. Often one or two Turboexpanders are used for Methane recovery
from the demethanizer overhead stream.
10. the bottom stream from the demethanizer tower goes to the deethanizer tower. The
overhead stream from the deethanizer tower consists of all the C2,'s that were in
the cracked gas stream. The C2's then go to a C2 splitter. The product ethylene is
taken from the overhead of the tower and the ethane coming from the bottom of
the splitter is recycled to the furnaces to be cracked again;
11. the bottom stream from the deethanizer tower goes to the depropanizer tower. The
overhead stream from the depropanizer tower consists of all the C3's that were in
the cracked gas stream. Prior to sending the C3's to the C3 splitter this stream is
hydrogenated in order to react out the methylacetylene and propadiene. Then this
stream is sent to the C3 splitter. The overhead stream from the C3 splitter is
product propylene and the bottom stream from the C3 splitter is propane which
can be sent back to the furnaces for cracking or used as fuel.
12. The bottom stream from the depropanizer tower is fed to the debutanizer tower.
The overhead stream from the debutanizer is all of the C4's that was in the cracked
gas stream. The bottom stream from the debutanizer consists of everything in the
cracked gas stream that is C5 or heavier. This could be called a light pyrolysis
gasoline.[9]

Since the production of ethylene is energy intensive, much effort has been dedicated
recovering heat from the gas leaving the furnaces. Most of the energy recovered from the
cracked gas is used to make high pressure (1200 psig) steam. This steam is in turn used to
drive the turbines for compressing cracked gas, the propylene refrigeration compressor,
and the ethylene refrigeration compressor. An ethylene plant, once running, does not need
to import any steam to drive its steam turbines. A typical world scale ethylene plant
(about 1.5 billion pounds of ethylene per year) uses a 45,000 horsepower (34,000 kW)
cracked gas compressor, a 30,000 horsepower (22,000 kW) propylene compressor, and a
15,000 horsepower (11,000 kW) ethylene compressor.

When starting an ethylene plant it is important to start the cooling systems in the proper
order. The cooling systems consist of Cooling Tower Water (CTW); propylene
refrigeration with four or five different levels or stages. Each level corresponds to a
particular pressure and temperature; and three or four stages of ethylene regfrigeration.
The CTW must be started first because the propylene system needs it to condense
propylene and the ethylene refrigeration systems needs it to desuperheat high pressure
ethylene. The propylene system must start next because the ethylene system needs high
pressure propylene for desuperheating the high pressure ethylene stage and the low
pressure propylene stage for condensing the high pressure ethylene. While the ethylene
plant is running, the plant can continue to run for a time if the ethylene refrigeration
compressor shuts down. However, if the propylene compressor shuts down the whole
plant must be shut down immediately

ETHYLENE GLYCOL

Ethylene glycol is produced from ethylene, via the intermediate ethylene oxide. Ethylene
oxide reacts with water to produce ethylene glycol according to the chemical equation

C2H4O + H2O → HOCH2CH2OH

This reaction can be catalyzed by either acids or bases, or can occur at neutral pH under
elevated temperatures. The highest yields of ethylene glycol occur at acidic or neutral pH
with a large excess of water. Under these conditions, ethylene glycol yields of 90% can
be achieved. The major byproducts are the ethylene glycol oligomers diethylene glycol,
triethylene glycol, and tetraethylene glycol.

This molecule has been observed in space.[2]

EtHYLENE OXIDE

Ethylene oxide is produced by oxidation of ethylene with oxygen at circa 250 °C over a
catalyst comprising metallic silver supported on alumina[4]. Typically, promoters such
as chloride are also included. Pressures used are in the region of 1-2MPa. The overall
chemical equation is:

7 H2C=CH2 + 6 O2 → 6 C2H4O + 2 CO2 + 2 H2O

The mechanism involves binding of ethylene and oxygen (O2) to the catalyst. Per
molecule of oxygen, one atom is inserted into ethylene affording ethylene oxide. The
other oxygen atom remains strongly absorbed on the catalyst and must be burnt off before
the next productive catalytic cycle can take place. This consumes one extra molecule of
ethylene for every six molecules of ethylene oxide produced. The extra molecule of
ethylene undergoes combustion to carbon dioxide and water presumably via
acetaldehyde:

6 H2C=CH2 + 6 O2 → 6 C2H4O + 6 O (bound to catalyst)

O (bound to catalyst) + H2C=CH2 → CH3CHO (bound to catalyst)
CH3CHO (bound to catalyst) + 5 O (bound to catalyst) → 2 CO2 + 2 H2O

Hence, the yield of the process is limited to 6/7 (85.7%). The yield under industrial
conditions stands at 83-84%. The high yield is due to extensive research by big
producers, driven by enormous cost savings potential: With approximately 15 million
tonnes of ethylene oxide being produced annually[1] every percent of yield increase saves
95,500 tonnes of ethylene worth $67 million.

Ethylene oxide can be produced in the laboratory by the action of an alkali hydroxide on
ethylene chlorohydrin.[5]

HOH2CCH2Cl + NaOH → C2H4O + NaCl + H2O

PROPENE

Propene is the raw material for the production of polypropylene, a versatile polymer
widely used in several different grades for packaging. Most propene is polymerized
using Ziegler-Natta catalysis, which produces isotactic polypropylene. Along with
benzene, propene is a key feedstock in the cumene process, a reaction carried out on
industrial scales to produce acetone and phenol. Propene is also used during the
production of many other chemical products such as isopropanol (propan-2-ol),
acrylonitrile, and propylene oxide (epoxypropane).[1]

Oxosynthesis reactions

The oxosynthesis process (also called hydroformylation) involves the reaction of syngas
(CO and H2) with olefinic hydrocarbons to form an isomeric mixture of normal- and iso-
aldehydes. The basic oxosynthesis reaction is highly exothermic and is
thermodynamically favorable at ambient pressures and low temperatures (Whyman,
1985). The reaction proceeds only in the presence of homogeneous metal carbonyl
catalysts. One of the more important factors in oxosynthesis is the normal to branched
isomeric ratio (n/i). The normal (straight chain) isomer is the desired product, as shown
in the equation below.

RCH=CH2 + CO + H2 → RCH2CH2CHO + R(CH3)CHCHO

(normal) (branched)
Usually a 1:1 H2 to CO syngas mixture is required for oxosynthesis. The overall reaction
rate has first-order dependence on the hydrogen partial pressure and inverse-first order
dependence on CO partial pressure making the reaction rate essentially independent of
total pressure (Pruett, 1979). Higher CO partial pressures are usually required, however,
to maintain the stability of the metal carbonyl catalysts. The reaction is also first order in
olefin and metal concentration at the higher CO partial pressures.

The first step in the oxosynthesis process is to remove the CO from the
organometallic catalyst making the catalyst deficient in electrons. The double bond
in the olefin attaches to the metal atom at this site (the M-H bond) resulting in an
alkyl metal carbonyl complex. A CO molecule is then inserted into the complex at
the C-M bond followed by insertion of hydrogen at the same point to yield an
aldehyde. The general reaction mechanism is shown in figure 2 (Whyman,
1985).

Oxosynthesis catalysts

Oxosynthesis generally uses soluble cobalt or rhodium catalysts. Three

complimentary catalytic hydroformylation processes have been developed and
commercialized. The choice of catalyst depends of the particular starting olefin or
desired product.

The first hydroformylation catalysts were cobalt carbonyls, specifically, HCo(CO)4 in

equilibrium with Co2(CO)8. Cobalt metals and most cobalt salts will form cobalt
carbonyl under hydroformylation conditions. The cobalt catalyzes both double bond
isomerization and oxosynthesis. Undesired competing side reactions such as the direct
hydrogenation of the starting olefin and the condensation of product aldehydes to high
boiling products are generally avoided in the Co-catalyzed process. For cobalt carbonyl
catalysts, a normal to branched isomeric ratio (n/i) of 4:1 can be achieved with catalyst
concentrations of 0.1-1% metal/olefin at 200-300 atm and 110-200°C with a 1:1 H2/CO
ratio. Lower process temperatures and higher CO partial pressures favor the formation of
the straight chain isomer, however, the overall conversion efficiency decreases. Cobalt
carbonyl catalysts are not very stable at high temperatures and tend to deposit on reactor
walls decreasing their activity and reducing recovery of the catalyst.

Phosphine-modified cobalt catalysts were developed by Shell Oil Company in the

1960’s, and are used for the production of higher (detergent range) alcohols. The addition
of a phosphine ligand to Co results in a trialkylphosphine-substituted cobalt carbonyl
catalyst [HCo(CO)3P(n-C4H9)3]. It shows high selectivity for straight-chain aldehydes
(n/i = 7:1) and has improved thermal stability compared to the unsubstituted cobalt
catalysts. The improved thermal stability allows for lower process pressures but higher
process temperatures (50-100 atm and 160-200°C with H2:CO = 1). Even though this
catalyst has improved thermal stability, it has a lower hydroformylation activity than
cobalt carbonyl catalysts, hence the higher reaction temperature. The higher temperatures
also increase the competing olefin hydrogenation reaction. Shell has optimized the
process to produce detergent range alcohols (C11-C14) in a single step by capitalizing on
the conversion of terminal olefins to alcohols by hydrogenating the aldehyde
hydroformylation products. A high n/i ratio results from increased isomerization rates
concurrently with hydroformylation.

Phosphine-modified rhodium catalysts are composed of triphenylphosphine rhodium

(HRh(CO)(PPh3)3). These catalysts function under significantly lower operating
pressures and temperatures (7-25 atm; 60-120°C; n/i ratio of 8-12:1) and demonstrate
increased selectivity to linear products compared to other oxosynthesis catalysts. Rh-
based catalysts are used mainly for the hydroformylation of lower olefins (e.g.,
propylene to butyraldehyde) and are typically not used for higher olefins because of their
thermal instability at the high distillation temperatures required to separate the product
and the catalyst. Rh-based hydroformylation catalysts are also expensive relative to other
catalysts, and the availability of rhodium is low. The high cost of rhodium, however, is
offset by lower equipment costs, increased activity, and higher selectivity and efficiency.
The development of water-soluble Rh-based catalysts avoids some of these issues.
Rhone-Poulenc commercialized an oxo process based on a water-soluble Rh catalyst in
1984 (Billig, 2000).

Catalyst lifetimes are significantly reduced by poisoning from strong acids, HCN,
organosulfur, H2S, COS, O2, and dienes (Bahrmann, 2000).

Butyl acetate
Butyl acetates are commonly manufactured by the esterification of a butanol isomer and
acetic acid with the catalytic presence of sulfuric acid. [1]