1.

1 PROCESS BACKGROUND/SELECTION
1.1.1 INTRODUCTION

Propanol is a chemical compound with the molecular formula of C3H7OH. There are two
isomers for propanol which are 1-propanol and 2-propanol. 1-propanol is also known as
propyl alcohol and normal propanol while 2-propanol is known as isopropyl alcohol.
Naturally, propanol occurs in crude fusel oils and also as fermentation and
decomposition products of vegetables (Papa, A.J., 1993).

The formal name of an alcohol indicates the number of hydroxyl (-OH) groups
and the number of carbon atoms in the molecule, the names of any other atoms, and
the attachment of the atoms in the molecule. Most simple alcohols end with the -ol
suffix, added to the name of the molecule that had the same number of carbon atoms,
but with a hydrogen atom in place of the hydroxyl group. The two isomers of propanol
exist because the hydroxyl group can be attached either at the end or in the middle of
the three-carbon-atom chain. Alcohols with two hydroxyl groups on adjacent carbon
atoms are called glycols or diols.

The task is to design equipments and processes for the large-scale chemical
industry to produce propanol. It is aimed to obtain high-productivity process in safe and
economic ways with minimum production rate of 100,000 matrix tonne per year. The
total cost of whole plant should not exceed RM200 million.

1.1-1
1.1.2 PHYSICAL PROPERTIES

Propanol is colorless and flammable liquid with slightly odor like ethanol. Propanol is
completely mix together with water to form homogenous solution and readily soluble in
various solvents such as ethers and esters. Table 1.1.1 shows the list of physical
properties for propanol such as boiling and melting point, critical temperature and
pressure, liquid density and viscosity at 20C, as well as values of various heat types
and acidity.

Table 1.1.1: Physical properties of 1-propanol

Name 1-Propanol
Chemical structure

Chemical formula C3H7OH

Formula weight 60.1 g/mol
Synonyms n-propanol, propan-1-ol, n-propyl alcohol
CAS no. 71-23-8
Appearance Colorless
Behaviour Flammable liquid
Boiling point 97°C
Melting point -127°C
Critical temperature 60.096°C
Critical pressure 263.65 kPa
Liquid density at 20°C 1.3837 kg/m3
Water solubility Completely soluble
Form Colorless liquid
Stability Stable, but highly flammable

1.1-2
Viscosity at 20°C 2.256 mPa.s
Critical density 0.275 g/cm3
Heat capacity, liquid at 25°C 141 J/(mol.K)
Heat of vaporization at 25°C 47.53 kJ/mol
Heat of combustion, liquid at 25°C 2033 kJ/mol
Heat of formation, vapour at 25°C -254.7 kJ/mol
Electrical conductivity at 25°C 2 x 108 S
Odour Wine-like odor
Flash point 15°C
Autoignition temperature 370.85°C
Explosive limits 2.1% - 12%
Acidity pKa ~16
(Source: Unruh J. D. & Pearson, D., 1993)

1.1.3 CHEMICAL PROPERTIES

Since propanol is hydroxyl group therefore the characteristic reactions are based on
hydroxyl group include dehydrogenation (oxidation), esterification, amination and
dehydration.

Partial oxidation of 1-propanol with air can be obtained to produce propanal and
propionic acid in presence of catalysts. In addition to that, reaction with strong oxidizing
agents such as nitric acid would form products with complex compositions.

The propanol can be reacted with organic or inorganic acids to forms propyl
esters in the presence of mineral acid catalyst through esterification process. Through
the direct esterification process with suitable alcohols, propanol can converted to n-
propyl acetate or isopropyl acetate in the presence of sulfuric acid, p-toluenesulfonic
acid and methanesulfonoic acid as a catalyst.

Propanols also can be reacted with ammonia and lower amines to produced
propylated amines derivatives. This reaction is run under the pressure of 1.0-10.0MPa

1.1-3
and temperature of 190-250oC (Papa A. J., 1993). Nickel, aluminium, cobalt,
molybdenum and or chromium are used as catalyst.

Besides, 1-propanol could also react with ethylene oxide, propylene oxide or
both to form glycol ethers group. This reaction involves catalyst, alkali hydroxide. The
dehydration of 1-propanol would produce di-n-propylether with presence of cation-
exchangeable layered clay catalyst containing titanium or zirconium operated at 180C
(Papa A. J., 1993). Table 1.1.2 shows the summarized chemical properties according to
chemical reactions.

Table 1.1.2: Chemical properties of 1-propanol

Reactions Products
Oxidation with air (partially) Propionic acid, propanal
Esterification (with organic and inorganic Propyl esters
acids)
Reaction with ammonia and amines Propylated amine derivatives
Etherification and dehydration Glycol ether
(Source: Papa, A. J., 1993)

1.1.4 USES

There are many uses of propanols according to their solvent properties, high water
miscibility, and their potential to introduce propyl group into chemical intermediates.

1-propanol is used mainly as a solvent and as a chemical intermediate. In

solvent applications 1-propanol has been used either directly or commercially to
produce in form of acetate ester or glycol ether derivatives which is principally used in
printing inks, paint, cosmetics, pesticides, and insecticides (Papa, A.J., 1993). Glycol
ether is a liquid substance, derived from organic chemistry, characterised by particular
properties, which lead to its use as a solvent in various industrial and domestic
applications.

1.1-4
 Chemical intermediate is any chemical substance produced during the
conversion of some reactant to a product. Most synthetic processes involve
transformation of some readily available and often inexpensive substance to some
desired product through a succession of steps. All the substances generated by one
step and used for the succeeding step are considered intermediates.

The largest uses are as a specialty solvent in flexographic printing inks

particularly for printing on polyolefin and polyamide film. Besides that, 1-propanol also
improves drying rates, reduces foaming and controls viscosity at constants solids levels
in water- based printing inks. It is also used to produce n-propylamines that are
herbicide intermediates, glycol ethers and as ruminant feed supplement. These
intermediates are characterized by dual functionality, which imparts high solvency,
chemical stability, and water compatibility.

In addition, 1-propanol has minor uses as a flavor and fragrance in foods and as
a solvent or cosolvent in pesticide formulations. 1-propanol is also used as as a reaction
medium in making low density polyethylene (LDPE) and as an alkylating agent in
organic synthesis. 1-propanol is also used to prepare propionic acid, propionic
aldehyde, propyl acetate, propylamine and to manufacture pesticides and surface-
active substances.

1.1.5 PROCESS BACKGROUND

The production process of 1-propanol involves two methods:

(a)Two step oxo which consists of hyrdoformylation and hydrogenation

(b)Homologisation of methanol

1.1-5
1.5.1.1 Hyrdoformylation and Hydrogenation

Hydroformylation

The production of 1-propanol by hydroformylation or oxo technology is a two- step

processes in which ethylene is first hydroformylated to produce propanal. The resulting
propanal is then hydrogenated to 1-propanol. C3H8O

CH2 = CH2 + CO + H2  CH3CH2CHO (1.1.1)

(ethylene)(carbon monoxide)(hydrogen) (propanal)

Typical oxo conditions employed in the low- pressure rhodium catalyzed oxo
process are 90-130 °C, < 2.8 MPa total pressure, with CO at <380 kPa, H2 at < 1.4MPa,
and <500ppm rhodium (Papa A. J., 1993). In this process, hydrogen, carbon monoxide,
catalyst and water is introduced into a hydroformylation reactor. The water content fed
to the reactor is held between 0.1 and 10.0 percent.

The rhodium-tryphenylphosphine catalyst system is normally used in

hydroformylation because it gives higher reaction rates, greater stability, lower
operation pressure, and lower by-product. Rhodium content in the reactor is maintained
at about 50 ppm. The reaction is conducted at temperatures of from about 90°C to
about 160°C. The temperature should not be permitted exceed 160°C as catalyst
decomposition will begin at that point. The effluent from the reactor is cooled and
passed through conventional successive high and low pressure separators to recover
the unreacted gases. The liquid material form the final separator is introduced into an
azeotropic distillation column operated at a base temperature of from about 60 to about
100°C. The overhead from this distillation column is separated in a decanter. The
product aldehydes are recovered as the organic layer from the decanter. The water
layer may be recycled to the distillation column temperature and inhibits high boiler
formation. The base stream from the distillation column contains water, organic high
boilers such as glycols, acids, some aldehydes and the catalyst. This base stream is
introduced into a separator where the water is separated for recycle to the reactor. The

1.1-6
organic stream from the separator is fed to a gas stripping column. Temperature in the
column is maintained below 160°.

The crude propanal is eliminated by vapour stripping with excess synthesis gas
and by vapor stripping with excess synthesis gas and the rhodium-triphenylphosphine
catalyst is recycled. Traces of carbon monoxide are removed in a stripping column from
the crude, and condensed propanal before hydrogenation to prevent poisoning of the
hydrogenation catalyst in the second step. The higher selectivity and milder conditions
of the rhodium-catalyzed process provide crude 1-propanol for hydrogenation
containing fewer impurities, such as higher aldol- condensation products and aldehyde
trimers.

Hydrogenation

Hydrogenation of propanal is conventionally carried out as a heterogeneous process in

either vapor or liquid process using a variety of metal catalysts. The process conditions
of heterogeneous vapor- phase are effective at 110-150°C, and 0.14-1.0 MPa at a 20:1
mole ratio of hydrogen to propanal (Papa A. J., 1993). Reductions are accomplished in
excess hydrogen, and the heat of reaction is removed by circulating the vapor through
external heat exchangers or by cooling the reactor internally. Hydrogen efficiencies are
>90% with aldehyde conversions as high as 99.9% and alcohol yields >99%. The
commonly used commercial hydrogenation catalysts include combinations of copper,
zinc, nickel, and chromium compounds. Major impurities at vapor phase are dipropyl
ether, ethane and propyl propionate. Furthermore, to reduce zinc oxideand copper
oxide catalysts, selectivity enhancers such as alkali and transition metals can be added
to significantly reduce the formation of esters and ethers. In addition, adding 1-10%
water to the reactor feed also suppresses ether formation. The propyl propionate
byproduct formed in the catalytic hydrogenation can be separated and hydrogenolyzed
in the presence of reduced CuO-ZnO catalyst at 75-300°C and 9.8 kPa- 9.8MPa to give
1-propanol as the major product.

CH3CH2CHO + H2  CH3CH2CH2OH (1.1.2)

(propanal) (hydrogen) (propanol)

1.1-7
1.1.5.2 Homologisation of Methanol

This method allows the production of higher homologous alcohols to be produced from
methanol by introducing into the molecule one or more methylene groups. This method
uses methanol and synthesis gas to produce ethanol and / or n-propanol. A suitable
feed stock is synthesis gas or methanol produced therefrom. The synthesis gas can be
obtained from coal or natural gas by various well known, reliable, and efficient
processes. The reaction is carried out in the presence of a water soluble cobalt catalyst
at elevated temperatures and pressures and proceeds according to the following
equation.

CH3OH + CO + 2H2 C2H5OH + H2O

(1.1.3)
(methanol) (carbon monoxide) (hydrogen) (ethanol) (water)

Furthermore, there is some formation of higher alcohols in relatively small

amounts. This proceeds in accordance with the equation:

CH3OH + n(CO + 2H2) CH3(CH2)n OH + nH2O

(1.1.4)
(methanol) n(carbon monoxide + hydrogen) n(ethanol) (water)

The conversion process is carried at elevated pressures and temperatures to

obtain ethanol and n-propanol from methanol, carbon monoxide and hydrogen. The
catalyst used contains a cobalt compound, a ruthenium compound, iodine or an iodide,
and a bi-dentate organic phosphine or phosphate to enhance the process. The reaction
temperature is 150° to 250° C while the pressure is 200 to 600 bars (20-60 MPa) and
there is 5 to 25% by weight of water present, based on the methanol. This addition has
been found to increase the conversion rate. There will be only slight effect to conversion
when increase amounts of water while smaller amounts have either a slight effect or
none at all. The water can be conveniently added with the methanol directly into the
reactor. The molar ratio of cobalt to methanol is 1:30 to 1:2,000. The cobalt and
phosphine or phosphate is used in a molar ratio of 1:1 to 1:5. The atomic ratio of cobalt
to ruthenium is 1:0.05 to 1:0.1. Cobalt and iodine are used in atomic ratio of 1:0.1 to 1:1.
The foregoing ratios have been found to be advantageous in the carrying out this
reaction. In order to obtain better results, the carbon monoxide/ hydrogen mixture
1.1-8
should contain no impurities such as sulfur which will affect the catalyst’s activity.
Impurities such as carbon dioxide and nitrogen in amounts of 5% by volume based on
the total mixture are harmless.

1.1-9
 Table 1.1.3: Comparisons of operating conditions between hydroformylation and hydrogenation and homologisation methods

Hydroformylation and hydrogenation

Methods Hydroformylation Hydrogenation Hydrogenation Homologisation

(vapor phase) (liquid phase)

Raw material(s)  Ethylene, carbon  Propanal, hydrogen  Methanol, hydrogen,

monoxide, hydrogen carbon monoxide

Conditions  Temperature:90-  Temperature: 110-  Temperature:95-  Temperature:150-250°C

130°C 150°C 120°C  Pressure: 200 – 600 bars
 Total Pressure: <2.8  Pressure: 0.14-1.0  Pressure: 3.5MPa (20-60 MPa)
MPa MPa
 Carbon monoxide  Mole ratio of
pressure: <380 kPa hydrogen to
 Hydrogen pressure: propanal:20:1
<1.4MPa
Catalyst  Rhodium pressure:  Combinations of  Nickel and copper  Cobalt compound, a
<500 ppm copper, zinc, based catalysts ruthenium compound,
nickel, and containing iodine or an iodide
chromium molybdenum, compound, a bi-dentate
compounds manganese and organic compound
sodium promoters phosphine or phosphite

1.1-10
By-product  Higher aldol-  Dipropyl ether,  Methane, ethane, propane,
condensation ethane, and propyl ethers, methyl acetate,
products, aldehyde propionate ethyl acetate, propyl
trimers acetate, acetaldehyde-
dmethyl-acetal,
acetaldehyde-methyethyl
acetal, acetaldehydediethyl
Advantage(s)  Lower operation  Lower operation  Conversions of  The gas can be obtained
pressure pressure >99.9% from coal or natural gas
 Fewer impurities  Conversions of by various well know,
 Gives higher >99% reliable, and efficient
reaction rates process
 Greater stability
 Lower by- product
production
Disadvantage(s)  Carbon monoxide  Higher operation  Undesired by- products of
and pressure the reaction are very large
triphenylphosphine  High cost in order to isolate
poison the the desired fractions from
hydrogenation the numerous and varied
catalysts impurities to commercialize
the process

1.1-11
1.1.6 PROCESS SELECTION

In this project, two step methods, hydroformylation of ethylene and hydrogenation of propanal
will be used in manufacturing of 100,000 tonnes per year of 1-propanol based on the process
descriptions. And Table 1.3 shows the comparisons between hydroformylation and
hydrogenation process and homologisation. The stated process has been the principal process
to commercial manufacture of 1-propanol compared to homologisation process. Besides that, it
is also an important and most commercialize industrial process in producing 1-propanol.

The selection of this process is also based on the operating temperature condition which
for two step oxo, lower temperature, range from 90 to 150 ⁰C, compared to homologisation
method which is the higher temperature is required, range from 150 to 250 ⁰C. And while the
total pressure required for production of 1-propanol is less than 2.8 MPa which is also low
compared to homologisation process, 20-60 MPa. Therefore, the process condition for two-step
oxo is much safer than homologisation in terms of low temperature and low pressure.

In addition, two-step oxo process produces fewer impurities and fewer by-products
compared to homologisation process. By-product production is avoidable since it will decrease
the conversion of the product. It costs a lot of money to isolate the desired fractions from the
numerous and varied impurities from the homologisation process. This process is believed to
operate in safe and economic ways.

1.1.7 RAW MATERIALS

Raw materials are important since they required producing new product. For n-propanol
production, the main reactants are ethylene, carbon monoxide and hydrogen. These chemical
are used in such amount and conditions in order to get high product percentage.

1.1-12
1.1.7.1 Ethylene

Ethylene, also called ethane (H2C––CH2) is the simplest alkene. Since ethylene contains a
carbon-carbon double bond it is classified as an unsaturated hydrocarbon. Ethylene is the
lightest olefin. It is a colorless, flammable gas with a slightly sweet odor.

Ethylene is a very reactive intermediate, and hence it involves in many chemical

reactions. Its double bond reacts readily to form saturated hydrocarbons. Besides
hydroformylation, ethylene is also used in polymerization, oxidation, halogenations, alkylation
and niche process.

In oxidation, ethylene is used to produce ethylene oxide which used to produce

detergent in ethoxylation process. Meanwhile ethylene is used in alkylation, to produce
ethylbenzene, precursor to styrene.

Ethylene is produced mainly from petroleum-based feedstock by thermal cracking. In

thermal cracking, valuable by products including propylene, butadiene, and benzene are also
produced.

1.1.7.2 Carbon Monoxide and Hydrogen

Carbon monoxide and hydrogen are usually comes together that can also be called synthesis
gas. This synthesis gas is combustible and need a good handle. It can be obtained from oil
companies such as Shell Berhad and Petronas Berhad.

Carbon monoxide is used for hydroformylation process, meanwhile hydrogen is used for
both hydroformylation and hydrogenation process. The preferred molar ratio of carbon
monoxide to hydrogen is 2:1 to 1:1 (Papa A. J., 1993). This ratio leads to increase the selectivity
in producing alcohol and decrease selectivity to the alkane product.

1.1-13
1.1.8 BY-PRODUCTS

For first reaction which is hydroformylation process, there is one by-product chosen that is
ethane. That is because ethane tends to form when ethylene reacts with hydrogen.

C2H4 + H2  C2H6 (1.1.5)

Ethylene + Hydrogen  Ethane

For second reactor which is hydrogenation process, there is one by-product chosen that
is dipropyl ether. That is because the most significant impurities are only dipropyl ether and
propyl propionate. However, since cobalt is used as the catalyst, the amount of propyl
propionate is very low that can be ignored. Therefore, the considered by-product is dipropyl
ether.

2C3H8O  C6H14O + H2O (1.1.6)

Propanol  Dipropyl ether + Water

1.1.9 CATALYSTS

In propanol production, there are two process involve which are hydroformylation/oxo and
hydrogenation process. Catalyst plays important role for both process. For oxo reaction,
transition metal carbonyls such as Co, Fe, Ni, Rh and Ir are already use to catalyze the process.
But, cobalt and rhodium are the most cost-effectively applied by industry.

1.1.9.1 Hydroformylation Process

The rhodium-triphenylphospine catalyst system is most usually applied for hydroformylation

than cobalt because it properties will gives higher reaction rates, greater stability, and lower by-
product production. Rhodium carbonyls are 100-1000 times more reactive than cobalt carbonyls
although operating pressure slightly higher than cobalt. Although high operating pressure for
this process, it will produce more propanal because of it’s reaction rates. Reaction rate will
automatically increases monotonically until the triphenylphospine : rhodium mole ratio reaches
20:1 to 50:1.

1.1-14
 Rh-catalyzed hydroformylation can be carried by using a ligands. Ligands is an ion, or
molecule that binds to a central metal-atom to form a coordination complex. The bonding
between metal and ligand generally involves formal donation of one or more of the ligand's
electron pairs. The nature of metal-ligand bonding can range from covalent to ionic.

For rhodium catalyst, ethylene hydroformylation process operate at ratio 1:1-3:1 for
H2:CO. Rhodium can get from any sources except those contain halogen because halogen
have very low hydroformylation activity. Lower concentrations may be used, such as 0.4-5ppm
by weight relative to the olefin feed. However, a limitation of the process is the coupling of
reaction and separation conditions. It used to separate catalyst from the product that had been
produce. Stripping requires a combination of high temperature and low pressure to decrease the
selectivity, lower linearity and more paraffin produced. For propanol production, paraffin
(ethane) produced by side reaction between ethylene and hydrogen gas.

Rhodium catalyst formed in solid phase in reactor. So, it will react with feed withough
changes their composition and phase. It also easily to remove this catalyst by separated solid
phase before the reaction involve at second reactor. Operating conditions for this process are
about 100 0 C, 15-20 bar, 300 ppmw Rh, a molar TPP/Rh ratio of 100:200. Ethylene conversion
per pass is low (ca. 30%); unconverted ethylene is recycled with the syn gas and overall
ethylene conversions are in the range of 85-90%, but probably dependent on ethylene quality.

A large synthesis gas compressor is required to generate the gas flows required for
stripping, via syn gas recycling (syn gas recycle/feed ratios of ca. 10). A syn gas bleed is
required to get rid of ethylene gases. Due to syn gas recycling, H2/CO ratios above 10 are
achieved. A large reactor freeboard and a de-mister pad are required to ensure that no
Rhodium exist at second reactor.

1.1.9.2 Hydrogenation Process

Catalyst used for the hydrogenation process of such streams containing saturated or
unsaturated aldehydes or enals, may be based on copper,chrome, cobalt, nickel, molybdenum,
aluminium oxide and combination thereof.

1.1-15
 Catalyst commonly have been used is solid rhodium. It is also well known that the main
aldehyde product of the Oxo-synthesis reaction may be hydrogenated to form alcohols by
having the same number of carbon atoms/molecule. For propanol production, cobalt nickel
usually applied in industry as catalyst because it will react with propanal from hydroformylation
process and hydrogenated to form propanol.

The temperature desired for this operation about 150-2000C and pressure ranges just
about 5 to 100kg/cm2. An amount of the catalyst is selected depending upon a reaction velocity
and an elimination of heat. Temperature and pressure is very importantly because when the
hydrogen pressure is too low, the reaction velocity affected and become too low. Whereas when
it is too high, the special equipment is uneconomically required. Meanwhile, when the
temperature of the hydrogenation is too high, the production of the by-product obtained by it is
highly resulted over the thermal stability.

The reaction mixture obtained by the hydrogenation is kept in stand-still after purging
hydrogen gas to carry out the phase separation into the organic phase and the water phase.
The hydrogenation catalyst is separated by a filtration from the reaction mixture before the
phase separation or the organic phase or the water phase after the phase separation. The
separation is carried out in the absence of oxygen.

1.1-16
1.1.10 PURIFICATION OF PRODUCT ALCOHOL

The product of hydrogenation of propanal is crude n-propanol. Hydrogenation of propanal

occurs after hydroformylation of ethylene with carbon monoxide and hydrogen. Therefore, in
order to make the product suitable for various applications such as solvent for vegetable oils,
waxes, resins, and cellulose esters and others in manufacture of polishing compounds, brake
fluids, and various propyl compounds, the purified n-propanol must contain fewest impurities.
The impurities are ether, aldol condensation, aldehyde trimers, sulfur, and nitrogen but the most
significant amount of impurities is n-propyl propionate (prpr) and di-n-propylether (DPE).

The purification of n-propanol is perform after hydrogenation process by using

fractional distillation column with water added up to 3% base on weight of purification feed but
most likely 0.1 to 1%. The amount of water must be significant regarding the purification process
because the presence of large amount of water makes the purification more difficult to proceed.
This is because n-propanol will forms a binary azeotrope with water having a boiling point of
about 87C, and a ternary azeotrope with water and DPE having a boiling point of about 74C,
which must be withdrawn from the column as different streams from the purified n-propanol
stream that has boiling point of 97C. Therefore, the amount of water is important since large
amount of it would lead to high energy consumption, large fractional distillation column, and
lower production of alcohol.

Normally, the amount of water feed into the distillation column is same as that of
hydrogenation effluent. However, additional water may be added for cooling effect purpose. The
cooling effect may happens in two ways either internal reflux or external reflux. For internal
reflux, it happens when water vapor condenses toward the top of column and flows back down
to where it absorbs heat and revaporized to start again. While for external reflux, water-
containing liquid streams are withdrawn from the column by decantation and liquid water is
returned to a point at the upper portion of the column. Basically, the number of trays in the
column and amount of heat transferred to the material being purified in the column are sufficient
to produce a liquid stream of purified n-propanol with 99.9 wt % of purity.

1.1-17
1.1.11 EQUIPMENT SELECTION
1.1.11.1 Slurry Bed Reactor

The hydroformylation process can be carried out in multiphase reactors. The most common
multiphase reactors in this process are slurry bed reactor (gas lift reactor).

The air-lift reactor has wide application in the fields of both chemical technology and
biotechnology because it offers simple and effective mixing in three-phase processes involving
gases, liquids and solids. The air-lift principle offers advantages of no moving parts, high gas
absorption efficiency, good heat transfer characteristics and rapid mixing which are applicable in
a range of industrial processes.

Specifically in the production of propanol, the air-lift reactor has the most advantages
compare with other reactor. The rector provided with cooling coils, heat exchanger for the
temperature control and it is preferred that the materials be introduced at the bottom of the
reactor and are taken primarily at the top of the reactor. The cost of production is much lower
compare with other reactor such as continuous strirred tank reactor (CSTR).

The hydroformylation process is process of reaction of ethylene, carbon monoxide and

hydrogen with the presence of catalyst to produce propanal. This reaction can be range from
90°C -130°C and pressure inside the reactor lower than 2.8 MPa . The two main groups of air-
lift reactor, baffled vessels and external loop reactors, have four main component parts in
common, the riser, the downcomer, the base and the gas separator, all of which have distinct
characteristics. The performances of these four components are influenced to flow
configurations, fluidization of suspended solids and mass transfer.

1.1.11.2 Fixed Bed Reactor

The hydrogenation process can be carried out in multiphase reactors. Two most common
multiphase reactors are slurry and fixed-bed (trickle-bed) reactors. From Table 1.3 shows the
comparisons between these reactors.

Based on the table, it can be seen that slurry reactor has the most advantages and the
least disadvantages compared to the fixed bed reactor. According to Unruh and Pearson

1.1-18
(1993), one of the main advantages of slurry reactors is that the temperature control and heat
recovery are easily achieved. In addition, constant overall activity can be maintained by the
addition of small amounts of catalyst.

Hydrogenation of propanal is conventionally carried out as a heterogeneous process in

either vapor or liquid process using a variety of metal catalysts. This process proceeds readily
and is highly exothermic as reaction above. From equilibrium stand point, the reaction
temperature should be in the range of 110°C -150°C and 0.14-1.0 MPa at a 20:1 mole ratio of
hydrogen to propanal.

As a result of these thermodynamic considerations, temperature control of the reaction

which can be provided by slurry reactor is critical to obtaining essentially complete conversion of
propanol. Reductions are accomplished in excess hydrogen, and the heat of reaction is
removed by circulating the vapor through external heat exchangers or by cooling the reactor
internally.

In this design of slurry reactor, gaseous s propanal and gaseous hydrogen are fed to
the gas-phase reactor which contains slurry of finely cobalt catalyst. To reduce the significant
amount production of side reaction, the crude propionaldehyde feed the hydrogenation reaction
when cobalt is employed as the hydrogenation catalyst.

1.1-19
 Table 1.1.4: Comparisons between slurry reactor and fixed-bed reactor

Slurry Reactor Fixed-Bed Reactor

i) Due to high heat capacity of i) Catalysts are held in the

liquid, uniform temperature
control is easy to achieve for
highly exothermic reaction.
ii) Uses continuous catalyst make-
up for catalyst replacement
Advantages
iii) The amount of catalyst is only
0.01-1% of the liquid volume.
iv) Cooling surface requirement is
less than a quarter than that in a
fixed-bed reactor
v) Simpler construction
i) Difficulty in separating the
catalyst from the product
ii) Due to lower catalyst loading, it
reactors and do not need to
be separated.
ii) More catalyst can be loaded
into a given volume
iii) Absence of an agitator which
permits operation at very high
pressures in reactors
i) Runs at lower conversion and
reaction rates due to larger
size of catalyst

Disadvantages requires greater reaction ii) Requires periodic shutdown

volume for catalyst replacement
iii) 50-60% of the volume is
occupied by catalyst

1.1-20