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CHAPTER I

PRODUCT DESCRIPTION

I. INTRODUCTION

Acrylic esters make the main product derived from acrylic acid and traditionally
produced by using propylene as raw material. They account for 55% of global demand. About
half of the crude acrylic acid is processed to purified (glacial) acrylic acid, which is further
processed both on-site (captive use) and by external downstream users. The other half of crude
acrylic acid is transformed into various acrylate esters at the production sites. Identical to
glacial acrylic acid, these acrylic esters serve as commercial products, which are further
processed both on-site and by external downstream users.Currently, the trend of using
sustainable materials for production is increasing in popularity due to the changes in global
climate and as fossil sources for hydrocarbons run short. For this reason, the production of fuel
from renewable sources such as biodiesel production is developing fast. In the biodiesel
industry, the biodiesel is produced through the transesterification of natural oils where one
mole of such oil yields three moles of hydrocarbon chains and one mole of glycerol. The
hydrocarbon chains are used as biodiesel fuels and the by-product is glycerol. Due to the
increasing awareness of climate change, these industries are projected to increase, thus
increasing in the glycerol production. However, the demand for glycerol is not increasing with
the same tendency. This causes the price for glycerol to decrease, making it an interesting
carbon source for intermediates. It is known that crude oil price is increasing. In connection to
that, the propylene price increases as well, since it is mainly crude oil based. This can lead to
increasing prices for acrylic acid production. On the other hand, glycerol prices are decreasing.
The reason: Glycerol is not an important intermediate. It is mostly used in small amounts for
cosmetics and for the food industry. Global glycerol demand is not increasing so fast as the bio-
diesel production. The use of glycerol produced during the bio-diesel process has potential to
be an environmentally carbon source for the production of acrylic acid. Moreover, the
economical valorisation of glycerol makes the bio-diesel production more attractive. Replacing
propylene by glycerol would be an indirect step for improving the sustainability in
environmental care. The manufacturing process of acrylic acid from glycerol involves first the
dehydration of glycerol to acrolein in phase gas, in the presence of solid catalysts such as
sulfated zirconia has been developed. These catalysts deactivate slowly so as to permit long
reaction cycles and low reactor volumes. The dehydration of glycerol to acrolein takes place in
the gas phase and can be expressed as:
That means, for each mole of glycerol, one mol of acrolein and two moles of water (steam) are
formed. In the case of the dehydration of glycerol, the reaction is carried out in the presence of
a solvent. The reaction takes place in a catalyst fix bed, heated up by an oven with a heat
homogenization system to assure the heat homogenization. The gaseous products coming out
from the reactor are condensed in a glass reflux heat exchanger. The liquid is collected in a
continuously glass cooled double-coated flask. A sample can be taken for the analysis, or the
condensate can be transferred to the product flask. The next process is the oxidation of acrolein
which produces the product, acrylic acid. This takes place in another catalyst fixed bed. The
catalyst used is vanadium-molybdenum oxide.

Technical Grade Acrylic Acid which usually has a purity of about 95%. Technical acrylic acid is
suitable for the production of commodity acrylate esters. Acrylic Acid and its esters (which
include methyl, ethyl, n-butyl, and 2-ethylhexyl acrylate) are among the most versatile
monomers for providing performance properties to a wide variety of polymers. Major markets
for the commodity esters include surface coating, adhesive and sealants, textiles, plastic
additives, and paper treatment.

Acrylic esters may also be used in solutions and emulsions; the ethyl ester is used in water-
based paints and binders in non-woven fabrics; methyl ester as the copolymer component of
acrylic fibres; the butyl ester in the water-based paints and adhesives; and the 2-ethylhexyl
ester, used like the butyl ester as well as for stick-on labels and sealants. Co-polymers and
blends of methyl methacrylate, butyl acrylate and ethyl hexyl acrylate are used in acrylic gloss
paints where the acrylates typically represent between 20 and 30 percent (dry basis) of the
formulation.

II. PRODUCT PROFILE


Acrylic acid and its esters have served, for more than 30 years, as an essential building block in
the production of some of our most commonly used industrial and consumer products. One of
its esters, ethyl acrylate, is used in the production of polymers including resins, plastics, rubber,
and denture material. It is a clear liquid with an acrid penetrating odor. The human nose is
capable of detecting this odor at a thousand times lower concentration than is considered
harmful if continuously exposed for some period of time. Acrylic acid and its esters readily
combine with themselves or other monomers which are used in the manufacture of various
plastics, coatings, adhesives, elastomers, as well as floor polishes, and paints.

A.PRODUCT IDENTIFICATION

PRODUCT NAME ETHYL ACRYLATE


IUPAC ETHYL PROPENOATE
Molecular Formula C5H8O2
Molecular Weight 100.12 g/mole
Specific gravity 0.922 (20°C)
Melting point -72°C
Boiling point 99.5 °C
Viscosity 0.55 Pa⋅s (25 °C)
Surface tension 25.2 mN/m (20°C)
Vapor pressure 29.3 mmHg (20°C
Vapor density 3.45
Solubility in water 1.5 g/100g (25 °C)

B. PRODUCT COMPOSITION

SUBSTANCE CONCENTRATION BY WEIGHT


Ethyl acrylate 98%
Acrylic acid 1%
Ethanol 1%

C. HAZARD IDENTIFICATION

Physical State and Appearance Liquid

color Colorless to Light Yellow

Odor Non-corrosive in presence of glass

Incompatibility with various Product may react violently with water


substances to
emit toxic gases or it may become self
reactive under conditions of shock or
increase in temperature or pressure.

Corrosivity Non-corrosive in presence of glass.

stability Stable

D. PRODUCT TRANSPORT, HANDLING AND STORAGE

Keep locked up Keep container dry. Keep


away from heat. Keep away from sources
of ignition. Keep away from direct sunlight
Handling or strong incandescent light. Ground all
equipment containing material. Do not
ingest. Do not breathe
gas/fumes/vapour/spray. Never add water
to this product Avoid shock and friction. In
case of insufficient ventilation, wear
suitable respiratory equipment. If ingested,
seek medical advice immediately and show
the container or the label. Avoid contact
with skin and eyes.
Storage
Flammable materials should be stored in a
separate safety storage cabinet or room.
Keep away from heat. Keep away from
Storage sources of ignition. Keep container tightly
closed. Keep in a cool, well-ventilated
place. Ground all equipment containing
material. A refrigerated room would be
preferable for materials with a flash point
lower than 37.8°C (100°F).

E. APPLICATION

Use as main raw material in production of acrylic latex paint


III. RAW MATERIALS PROFILE

• GLYCEROL

Glycerol is the common name of propane-triol. It is a sweet tasting, highly viscous


colorless and odorless liquid with no known toxic properties. Glycerol has many direct
utilization fields, such as cosmetics, lubricants or explosives, and other applications. Glycerol is
a side-product of bio-diesel production. Natural oils are triglycerides. The transesterification of
one mole of such an oil yields three moles of hydrocarbon chains and one mole of glycerol. The
hydrocarbon chains are used as bio-diesel fuels. Due to the developments in the bio-diesel
industry, the glycerol production is also increasing. Since the demand for glycerol is not
increasing with the same tendency, the glycerol price is decreasing, which makes it an
interesting carbon source for intermediates.

A.RAW MATERIAL IDENTIFICATION

Raw Material Name Glycerol


Synonyms 1, 2, 3-propanetriol
Glycerine
Glycol alcohol
Chemical Family Alcohol
Molecular Formula C3H5(OH)3
Structural Formula

Molecular Weight 92.10 g/mol


Density 1.261 g/cm³
Specific gravity 1.261
Melting point 17.8 °C (64.2°F
Boiling point 290 °C (554°F)
Solubility Partially soluble in water
Appearance Clear oily liquid
Color colorless
Odor odorless

B. RAW MATERIAL COMPOSITION

SUBSTANCE CONCENTRATION BY WEIGHT


Glycerol <60%
Water >40%
C. HAZARD IDENTIFICATION

Physical State Liquid (viscous)

Stability stable
Flammability Slight
Incompatibility Reactive with oxidizing agents

D. STABILITY AND REACTIVITY

Stability Stable under ordinary conditions of use and


storage.
Hazardous Decomposition Toxic gases and vapor may be released if
Products involved in a fire. Glycerin decomposes
upon heating above 290°C, forming
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corrosive gas (acrolein).
Hazardous Polymerization Will not occur.
Incompatibilities Strong oxidizers. Can react violently with
acetic anhydride, calcium oxychloride,
chromium oxides and alkali metal
hydrides
Conditions to Avoid Heat, flames, ignition sources and
incompatibles.

E. HANDLING AND STORAGE

Handling Crude glycerol is shipped to


refiner/manufacturing plants in standard
tank cars or tank wagons.
Storage Glycerol solidifies at lower temperatures,
and should be kept warm during
transportation and storing. Large storage
tanks should contain a heated loop from a
boiler or other heat source. Also, the boiler
room should be heated to prevent the
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glycerol from gelling in the fuel lines, fuel
filters, and the boiler itself.
F. APPLICATION

Glycerol is used as the major raw material for the manufacture of acrylic acid and thus
converting the acrylic acid to ethyl acrylate.

• AIR

Air is mainly composed of nitrogen, oxygen, and argon, which together constitute the
major gases of the atmosphere. The remaining gases are often referred to as trace gases. Dry
air contains roughly (by volume) 78.09% nitrogen, 20.95% oxygen, 0.93% argon, 0.039% carbon
dioxide, and small amounts of other gases. Air also contains a variable amount of water vapor,
on average around 1%. While air content and atmospheric pressure varies at different layers,
air suitable for the survival of terrestrial plants and terrestrial animals is currently only known
to be found in Earth's troposphere and artificial atmospheres.

A.RAW MATERIAL IDENTIFICATION

Raw Material Name Air


Appearance and Odor Colorless and odorless ga
Vapor Density @ 70°F 1.2 kg/m3 (0.0749 lb/ft3
Specific Gravity Not applicable
Molecular Weight 28.97
Solubility in Water (v/v) 0.0292
Vapor Pressure Gas, ambient
Freezing Point -216.2°C (-357.2°F)
Boiling Point (1 atm) -194.3°C (-317.8°F)
Specific Volume (ft3/lb): 13.8 (for Nitrogen)

B. RAW MATERIAL COMPOSITION

COMPONENT COMPOSITION BY MOLE


Nitrogen 79%
Oxygen 21%

C. HANDLING AND STORAGE

Handling Protect cylinders against physical damage.


Store in cool, dry, well-ventilated, fireproof
area, away from flammable or combustible
materials and corrosive atmospheres. Store
away from heat and ignition sources and
out of direct sunlight. Do not allow area
where cylinders are stored to exceed 52°C.
Storage Use only DOT or ASME code containers.
Store containers away from heavily
trafficked areas and emergency exits.
Cylinders should be stored in dry, well
ventilated areas away from sources of heat.
Cylinders should be stored upright and be
firmly secured to prevent falling or being
knocked over.

D. APPLICATION

Air serves as a reactant in the process of converting acrolein to acrylic acid (oxidation
process)..

E.CATALYST:

TUNGSTATED ZIRCONIA

Tungstated Zirconia is a heterogeneous catalyst which is composed of Zirconium Oxide


(Zirconia) and Tungsten Oxide. Zirconia serves as the carrier of the Tungsten Oxide which is the
more active component in the system. This catalyst will be used in the dehydration process of
glycerol.

APPLICATION:

Tungstated Zirconia serves as a catalyst in the process of dehydration of glycerol to


acrolein.

VANADIUM-MOLYBDENUM OXIDE

Vanadium-Molybdenum Oxide Catalyst is a type of heterogeneous catalyst which is


composed of Vanadium (IV) Oxide and Molybdenum Trioxide. This catalyst will be used for the
oxidation process of acrylic acid.

APPLICATION

Vanadium-Molybdenum Oxide Catalyst serves as a catalyst in the process of oxidation


of acrolein to acrylic acid.
Basis for Calculation:

Plant Capacity: 5,700 MT/yr

Production Rate: 19,000 kg/day

Working days: 300 days/yr

Conversion:

Dehydration Reactor: 90% conversion of glycerol to acrolein

Oxidation Reactor: 98% conversion of acrolein to acrylic acid

Esterification Reactor: 99% conversion of acrylic acid to ethyl acrylate

Assumptions for losses:

Absorption Column: 1.5% acrolein is found at the bottom stream of the unit

Glycerol Requirement
MASS BALANCE PER EQUIPMENT

GLYCEROL PREHEATER

Crude Glycerol Vaporized Crude Glycerol


T = 280 °C

B-1
T = 25°C T = 280 °C

Glycerol 20,400.00 kg

Water 13,600.00 kg

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Total 34,000.00 kg