Chemical Engineering

Department,Faculty of
Technology and
Engineering,The Maharaja
Sayajirao University of
Baroda.
Project report on

1-PROPANOL

Submitted by:

Jignesh suva
Guided by: Roll No. :828
Mr. Rahul sharma
Exam No. :801028
 Certification
This is to certify that Mr. Jignesh suva, student of BE-IV Chemical Engineering,
MSU,Roll number 828, Exam number 801028, has satisfactorily completed his project
report on "1-Propanol" under my guidance and here with submit his project in partial
fulfilment of degree of BE Chemical forthe year 2020-2021

Guide:

Mr.Rahul sharma Dr.Nitin Bhate

(Assistant Professor) (Head of Chemical Engineering

Department,MSU)

Date:

Place:
 Acknowledgement

I am very thankful to Dr. Nitin Bhate (Head of chemical engineering

department, MSU)forproviding me theopportunity forthisproject.

I would like to express my sincere gratitude to my guide, Mr.Rahul

sharma(Assistant Professor) for their valuable guidance. He has been very
concerned and helped me to explored this topic.

A special thanks to all the faculties.Education and knowledge, I get from them
project.I would also like to thank my friendss fort heir help and suggestions.

Jignesh suva
 Abstract

1-Propanol is a primary alcohol with the formula CH3CH2CH2OH and sometimes

represented as PrOH or n-PrOH. It is a colorless liquid and an isomer of
2propanol. It is formed naturally in small amounts during many fermentation
processes and used as a solvent in the pharmaceutical industry, mainly for resins
and cellulose esters, and, sometimes, as a disinfecting agent.

Table of Content
Chap. Title Page
No. No.

1 INTRODUCTION TO 1-PROPANOL
1.1 Basic Introduction
1.2 Physical and chemical properties
1.3 Applications 3-4
2 LITERATURE REVIEW 5-14
2.1 History and Market sizing 5-10
2.2 Preliminary process synthesis 10-13
2.2.1 Fischer Esterification 10-11
2.2.2 Dehydrogenation reaction 11-13
2.3 Process selection 13-14
3 MATERIAL AND ENERGYBALANCE 15-41
3.1 Block flow diagram Process overview 15-16
3.2 Process flow diagram and lock description 17-21
3.2.1 Reactive distillation (RD)(C-101) 18-19
3.2.2 Hydrogenation reactor (R-100) 19-20
3.2.3 Distillation column(C-102) 20
3.2.4 Stripper(C-100) 20
3.2.5 Molecular sieve(S-100) 20
3.2.6 Flash heat exchanger(E-103) 20-21
3.3 Material Balance 21-29
3.3.1 Basis 21
3.3.2 Material balance across Reactive distillation column 21-23
(C -101)
3.3.3 Material balance across the Stripper(C-100) 23-24
3.3.4 Material balance across the Molecular sieve(S-100) 24-25
 3.3.5 Material balance across the Splitter (S-101) 25
3.3.6 Material balance across the Mixer(M-100) 25-26

3.3.7 Material balance across the Hydrogenation reactor 26-27

(R 100)
3.3.8 Material balance across the Flash heat 27-28
exchanger(E103)
3.3.9 Material balance across the Distillation column 28-29
(C102)
3.3.10 Overall material balance 29
3.4 Energy balance 30-41
3.4.1 Energy balance across the Reactive distillation’s 30-32
column(C-101)
3.4.2 Energy balance across the Stripper (C-100) 32-33
3.4.3 Energy balance across the Molecular sieve (S100) 33
and Splitter (S-101)
3.4.4 Energy balance across the Mixer(M-100) 34-35
3.4.5 Energy balance across the Hydrogenation reactor (R 36-37
100)
3.4.6 Energy balance across the Heat exchanger (E-102) 37
3.4.7 Energy balance across the Flash heat exchanger 38-39
(E103)
3.4.8 Energy balance across the Distillation column 39-41
(C102)
3.4.9 Energy balance across the Heat exchanger (E-106) 41
3.4.10 Energy requirements 41
4 PROCESSANDMECHANICALDESIGNOFEQUIPMENTS 42-80
4.1 Design of Hydrogenation reactor(R-100) 42-52
4.1.1 Process design of hydrogenation reactor 42-45
4.1.2 Mechanical design of hydrogenation reactor 46-52
4.2 Design of distillation column(C-102) 52-70
4.2.1 Process design of distillation column 52-63
4.2.2 Mechanical design of distillation column 64-70
4.3 Design of process heat exchanger (E-102) 70-
4.3.1 Process design of heat exchanger 70-74
4.3.2 Mechanical design of heat exchanger 74-80
5 PLANTLOCATION ANDLAYOUT 81-87
5.1 Plant location 81-85
5.1.1 Raw material availability 81
5.1.2 Markets 82
5.1.3 Energy availability 82
 5.1.4 Climate 82
5.1.5 Transportation 82-83
5.1.6 Water supply 83
5.1.7 Waste Disposal 83
5.1.8 Labour 83
5.1.9 Taxation and Legal restrictions 84
5.1.10 Site Characteristics 84
5.1.11 Flood and Fire protection 84
5.1.12 Community factor 84-85
5.2 Plant layout 85-87
6 COSTESTIMATION 88-93
6.1 Estimation of total purchase equipment cost 88-90
6.2 Estimation of total capital investment 90
6.3 Estimation of total product cost 91-92
6.4 Profitability analysis 93
References i-ii
Appendix:1Streamresulttable iii-iv
Appendix: 2Dewpoint and Bubble point calculations v-ix
Appendix: 3Materialsafetyand datasheet (MSDS) x-xxxix

List of Figures

Figure Title Page

No. No.

1.1 Structure of Ethyl acetate 2

2.1 Global EtAc production by country 7
2.2 ChinaEtAc prices 8
2.3 Overall reaction pathway to for methyl acetate from raw materials 10
2.4 By-product Reactions in Novel Reaction Pathway 12
3.1 First proposed plant schematic (BFD) 15
 3.2 Second proposed plant schematic (BFD) 16

3.3 Process flow diagram 17

4.1 Graphof1/-rbutanalvsxbutanal 45
4.2 Temperature profile aroundE-102 71
5.1 Plant layout 86

List of Tables

Table Title Page

No. No.

1.1 Physical properties of ethyl acetate 2

2.1 European ethyl acetate capacity 5
2.2 North American ethyl acetate capacity 6
2.3 Asia ethyl acetate capacity 7
2.4 Ethyl acetate plant comparison 14
3.1 Keyto process flow diagram 18
3.2 Energy requirements 41
4.1 Rate of reaction calculations 44
4.2 Tray specification sheet 63
5.1 Keyto plant layout 87

6.1 Estimation of total purchase equipment cost 88

6.2 Estimation of total capital investment 90
6.3 Estimation of total product cost 91
6.4 Profitability analysis 93
Note: Tables of material balance, energy balance and equipment design calculations are not
numbered nor listed in list of tables.

Nomenclature
Symbol Caption
Keq Equilibrium rate constant
D Distillate rate
W Bottom product rate
m Flowrate
Cp Specific heat
∆t Temperature difference
∆Hreac Heat of reaction
I/P&O/P Input and Output
Qc Condenser duty
Qb Reboiler dusty
λ Latent heat
∆Hs Heat of solution
-rbutanal Rate of reaction (Rate of disappearance of butanal)
k Rate constant
ko Pre-exponential factor/frequency factor
E Activation energy/Modulus of elasticity
R Gas constant /Reflux ratio
V Volume
Fo Molar flowrate
x Conversion
Vo Volumetric flowrate
P Pressure

f Maximum Allowable stress

J Joint efficiency
Di/ di Inside diameter
Do/ do Outside diameter
L Length
CA Corrosion allowance
MA Mechanical allowance
ti Thickness
Ri/ri Radius
N Number
G Mean gasket diameter
A Area
α Relative volatility

ρ Density
μ Viscosity /Poisson ratio
σ Surface tension
η Efficiency
F Feed
Ln/Lm Liquid load
Vn/Vm Vaporload
DLK Diffusivity of light key
∆P Pressure drop
z Section modulus
U Overall heat transfers co-efficient
Kw Thermal conductivity of wall material
hi/ ho Heat transfers co-efficient
 CHAPTER :1. INTRODUCTION TO 1PROPANOL

1.1 Basic Introduction

Propanol is a clear, colorless liquid with alcohol odor, it is also miscible in water, and organic
solvent such as ethyl ether and alcohols. It can forms azeotrope with water appearance. It is
consist of three carbons, eight hydrogens and one oxygen with the molecular formula of

C3H7OH. In addition, it is a primary alcohol that‘s also known as 1-propanol, 1-propyl alcohol,
n-propyl alcohol, n-propanol, or simply propanol. It has an isomer called 2-propanol which also
known as isopropanol (IPA). n-propanol is not considered a hazardous air pollutant (HAP)
solvent by the U.S. Environmental Protection Agency.

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1.2 Physical and chemical properties

Figure: 1.1 Structure of 1-Propanol

Table 1.1 Physical properties of 1-propanol

Property Description

Molecular Formula C3H8O

Molar Mass 60.1 g/mol

IUPAC Name Propan-1-ol

Other Name 1-propanol propyl

alcohol n-propanol

n-propyl alcohol

propanol

Form Liquid

Colour Colourless

Adour Alcoholic

pH 7

Melting Point Temperature -126.2oC

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 Boiling Point Temperature 97.2 °C

Flash point 15 °C; closed cup

23 °C; open cup

Vapour Pressure 27.998 kPa; 25 °C

Density 805 kg/m3

Water Solubility completely miscible

Viscosity 2.170 MPa.s

A number of physical and chemical properties of 1-propanol are listed in table 1.1.the
chemistry of 1 -propanol is typical of low molecular weight primary alcohols. Biologically
1propanol is easily degraded by activated sludge and is the easiest alcohol to degrade.

1.3 Applications

n-propanol is not sold for direct consumer use. The major use of n-propanol is as a
solvent which used as carrier and extraction solvent for natural products, such as
flavourings, vegetable oils, resins, waxes, and gums, and as a solvent for synthetic
polymers, such as polyvinyl butyral, cellulose esters, lacquers, and PVC adhesives. Other
solvent applications include the use of n-propanol in the polymerization and spinning of
acrylonitrile, in flexographic printing inks, and in the dyeing of wool. npropanol is used
for both its solvent and antiseptic properties in drugs and cosmetics, such as lotions,
soaps, and nail polishes. It is a chemical building block for the manufacture of chemical
intermediate of esters, amines, and halides such as in the manufacture of propanal,
1bromopropane, O,O- dipropylphosphoro-dithioic acid, npropyl amines, esters (propyl
acetate, propyl carbamate), alcoholates, and xanthates.

Other than that, n-propanol is used in a broad range of applications, including

coatings, dispersing agents, pesticide formulations, metal degreasing fluids, adhesives
polishing compounds (window cleaners, floor polishes), and brake fluid, as coupling and
as a ruminant feed supplement. Because of its relative inertness and low odor, this
material is also used for packaging and food-contact applications. In the current usage of
engines, the characteristic of n-propanol from the aliphatic alcohols group has the
potential to use as a liquid fuel due to its characteristics which improves the water
tolerance of motor fuels.

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 CHAPTER: 2 LITERATURE REVIEW

2.1 History and Market sizing

The global propanol market size was valued at USD 4.21 billion in 2019 and is expected to
grow at a compound annual growth rate (CAGR) of 6.5% from 2020 to 2027. It is colorless
alcohol that exists in the form of 2 isomers: n-propanol and isopropyl alcohol. The product
demand is driven by rising utilization in the pharmaceutical and chemical intermediate
manufacturing industries.

Figure: 2.1 U.S. propanol market demand

N-propanol and isopropyl alcohol have different properties, despite having similar chemical
structures. Their unique chemical properties have positioned the building blocks of a large
number of chemicals that are currently being used in the pharmaceutical and plastics industries.
These chemicals are majorly manufactured using the hydrogenation reaction. However, the
price of n-propanol is generally higher than that of isopropyl alcohol owing to high raw material
costs and its application as a solvent.

U.S. is one of the major markets for propanol. The presence of a large number of manufacturing
facilities, coupled with steady growth in end-use industries, is aiding the product consumption.
The market is largely driven by rising demand for isopropyl alcohol as it is majorly used in
pharmaceuticals and chemical intermediate manufacturing. The chemical is majorly used for
its antiseptic properties and as a solvent in pharmaceutical formulations. The n-propanol market

4|Page
is expected to witness steady growth as it is majorly used as a solvent and in the production of
specialty chemicals.

The pharmaceutical industry is growing rapidly over the past few years on account of product
innovation and increased healthcare spending by governments in emerging economies. The rise
in chronic diseases has prompted a large-scale innovation in the pharmaceutical industry. With
the rising pandemic caused by COVID-19, demand for hand sanitizers and personal protective
equipment has witnessed a rise. Isopropyl alcohol is one of the major ingredients used in
sanitizer formulations. The growing trend of preventive healthcare will benefit market growth
as sales of sanitizers and other associated products are expected to increase rapidly over the
next few years.

N-propanol and isopropyl alcohol are among the largest industry solvents consumed globally
in the manufacturing industries. They are used in applications ranging from paints and inks,
adhesives, cosmetics, plastics, and rubber to heavy industries, such as automotive and industrial
machinery. Their miscibility with water and low reactivity towards the majority of commodity
chemicals makes them an efficient solvent. Rising infrastructure spending in emerging
economies globally is expected to play a major role in driving demand for products, such as
paints and coatings, adhesives, and industrial machinery. The growth in these highvalue sectors
is expected to have a positive ripple effect on the consumption of propanol.

As the majority of the propanol is sourced from petrochemicals, the pollution concerns
surrounding its application have impacted the market growth. Petrochemical solvents are now
being replaced by green solvents in the majority of the applications. Product innovation in the
green solvent industry is happening rapidly and it can hamper the demand for propanol. Solvent
recycling can be a game-changer in the industry as it can maintain the demand for propanol and
also help in reducing the environmental impact caused by propanol. Companies can also look
at new chemical intermediates that can be developed using the recovered propanol so that it can
open up new growth avenues.

Product Insights:
Isopropyl alcohol was the largest product segment with a revenue share of 63.2% in 2019 and
is anticipated to witness the fastest growth over the forecast period. The major application
areas of isopropyl alcohol are an antiseptic and astringent, cleaning agent, solvent, chemical
intermediate, and others. The antibacterial properties and low chemical reactivity exhibited by
isopropyl alcohol have boosted the demand for isopropyl alcohol.

5|Page
Demand for cleaning agents is growing at a steady pace as it is one of the essential products
that is used in all households. Cleaning agents are witnessing significant growth in the
emerging economies as manufacturers have adopted product differentiation and innovation
strategies. Rising disposable incomes have also benefitted the growth of these products.
Isopropyl alcohol forms an important component of these cleaning formulations and with
rising importance about hygiene in the home, the application segment is expected to grow at a
steady pace.

Figure: 2.2 Global n-propanol market demand share

N-propanol is a specialized solvent that is majorly used in the production of chemical
intermediates. The behavior of n-propanol as primary alcohol is driving the demand for
npropanol. It is majorly used in the manufacturing of alkyl halides and acetylated chemicals.
These chemicals are further used in industries, such as pharmaceuticals and specialty
chemical manufacturing.

Regional Insights :
Asia Pacific dominated the industry with a volume share of 42.9% in 2019 and is anticipated to
witness the fastest growth over the forecast period. Rapid growth in countries such as China,
India, and South Korea is driving the demand for propanol and its derivatives. Rising spending
on infrastructure, coupled with the presence of a robust pharmaceutical industry ecosystem, is
one of the major factors driving consumption. Governments are also working towards boosting
production to increase the production of sanitizers to combat the COVID 19 virus.
Demand in Europe is on a rising trend due to increased application in the pharmaceutical and
specialty chemicals industries. The consumption is increasing rapidly since the start of 2020
due to the rising demand for sanitizers. Isopropyl alcohol is being consumed in large quantities,
resulting in a shortage of the chemicals. Many companies in the region are streamlining their
raw material supply to efficiently manufacture isopropyl alcohol.
Germany is one of the leading countries in Europe in the production of propanol. Companies
such as INEOS and Oxea Gmbh are increasing their production capacities to cope with the
increasing demand. N-propanol production has been ramped up to support the production of
disinfectant products.

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Key Companies & Market Share Insights:
Companies are investing in R&D activities to explore new applications of propanol. Stringent
regulatory norms in North America and Europe are expected to boost demand for bio-based
chemicals. Market players are investing in integrated facilities to manufacture end-use
products. Some industry participants are also adopting forward integration strategies by
collaborations to reduce production costs. Some of the prominent players operating in the
global propanol market include:
• Dow Chemical Company
• BASF SE
• Royal Dutch Shell Plc
• Eastman Chemical Company
• Mitsui Chemicals Inc.
• China National Petroleum Corporation
• Zhejiang Xinhua Chemical Co Ltd.
• LG Chem Ltd.
• Oxea GMBH
• LCY Chemical Corp.
• ISU Chemical Co Ltd.

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8|Page
 9

2.2 Reaction Mechanism

There are two steps involves on the production. The first step is hydroformylation
reaction and the process is then proceeding with the second step which is
hydrogenation process after the complete reaction in the previous step.

2.2.1 Hydroformylation Reaction :

This reaction is a reaction mixtures that produce substantial amounts of aldehydes
and alcohols due to rection between olefins with syngas which were carbon monoxide
and hydrogen at elevated temperature and pressure in the presence of catalyst. In
order to produce n-propanol, the type of olefin will be ethylene. It will react with carbon
monoxide and hydrogen gas at specific order to produce propionaldehyde at certain
temperature and pressure.

2.2.2 Hydrogenation Reaction :

A process where aldehyde is converted into alcohol in the addition of hydrogen gas
with the presence of certain catalyst as an additive to the reaction. The reaction took
part in the desired temperature and pressure condition. The propionaldehyde
produced from hydroformylation will be then undergo second reaction with hydrogen
to produce n-propanol.
 10
Mechanics of ethylene hydroformylation and hydrogenation can be shown as below

Source from: Journal of Molecular Catalysis A: Chemical 138 _1999. 155–176

2.3 Side Reaction and By-product

2.3.1 Hydroformylation Reaction

Minor by-products from this process include propionaldehyde, ethane, and some
heavy ends. The composition of these by-products produced will be depending on the
condition of the process itself and the catalyst used.

2.3.2 Hydrogenation Reaction

The main product in this reaction will be n-propanol. However, certain impurities tend
to be formed from the adol condensation of the propanal such as n-propyl propionate,
dipropylether (DPE) and also 2-methylpentenal. The synthesis of C6 aldehydes from
propanal via aldol condensation reaction occur in ionic liquid media with NaOH as a
catalyst. NaOH is used as the activated agent in preparing the dicobalt octacarbonyl
catalyst. The production and composition of these by-products also depend on the
 11
catalyst used. Different chose of catalyst resulting in different composition of
byproduct produced.

Journal of Molecular Catalysis A: Chemical 278 (2007) 135–144

2.4 Process Background

2.4.1 Method Selection

There are three processes that have commercially being used in the industrial in order
to produce n-propanol. They were the oxo process, glycerol conversion and also
homologisation process. Each of this process has their own benefits due to raw
material, catalyst and equipments used. Below are the general descriptions for all the
processes.
 8

Table 2.1 : Process Descriptions of Methods in Producing n-propanol.

Characteristic Oxo Process Conversion of Glycerol Homologisation

i)Gas dehydration (endothermic)
i)Hydroformylation (exothermic) Temperature = 200-400 oC
o
Temperature = 90-130 C Pressure
Pressure = 0.1-3 Mpa
Process Condition = 2-5 Mpa ii)Hydrogenation
ii)Hydrogenation of acrolein
(exothermic) Temperature = 150-250 oC
(exothermic) iii)Hydrogenation
Temperature = 120 -180 oC Pressure = 20-60 Mpa
of aldehyde
Pressure = 3-5 Mpa
(exothermic)
Temperature = 200-250 oC
Pressure = 5-20 Mpa

Raw Material Ethylene, Hydrogen, Carbon Glycerol, Hydrogen Methanol, Hydrogen, Carbon
Monoxide Monoxide
 Group 8-10 (VIII) metal catalyst in Cobalt catalyst together with organic
the liquid phase and also Group 9 Pt, Ru, Pd and Ni catalysts with and inorganic iodine compouns, and
like cobalt carbonyl(Co), rhodium the support of ion-exchange ammonium or phosphonium
Catalyst
triphenylphosphine (Rh) and Raney resin. compund, as well as a rhuthenium
nickel(Ni). compound as promoters.

Conversion 50%-70% 45%-65%

By Product Ethane gas and heavy carbon Ethylene-glycol, Ethanol, Methane, ethane and propane,
compound from adol condensation Methane, Acetol, 1,2- various ethers as well as methyl

Con‘t

of the propanal such as n-propyl propanediol, 2-propanol acetate, ethyl acetate, propyl
propionate, dipropylether (DPE) and acetate, acetaldehyde-dimethyl-
also 2-methylpentenal acetal, acetaldehyde-methyl-
ethylacetal and acetaldehyde-diethyl-
acetal

Rate of hydroformylation is increase • Low price of raw material Large amount of water increase
Advantages with increasing of hydrogen and • The use of glycerol solution conversion of product.
decreasing in carbon monoxide at the lowest purity which is
partial pressure. at 40 wt% - 60 wt%.
 • Carbon monoxide could cause • High concentrations of • Numerous different individual
poison for the second reaction ethylene-glycol, the main compound occur as undesired by
which is hydrogenation that can side reaction product, product in the large amount.
effect product yield. appear with a selectivity • Expensive industrial process to
Disadvantages isolate hydrogenation,
• Formation of water could value of around 10%.
produce azeotrope with n- saponification and distillation
• Formation of water could from useful product fraction and
propanol which lead to complex
separation produce azeotrope with n- by- products
propanol which lead to
complex separation
From all the processes that already compared in the table above, oxo process is
chosen as a method in producing n-propanol because this process produced fewer
impurities with low industrial process cost.

2.4.2 Catalyst Selection

In order to fasten the reaction, a number of transition- metal carbonyls like cobalt
carbonyl, Raney nickel, rhodium triphenylphosphine, rutherium, and iron is used to
catalyze the oxo reaction. The most commercialized catalysts in the industries
nowadays are cobalt carbonyl and rhodium triphenylphosphine due to their
advantages compared to other catalysts. Catalyst selection also is based on the types
of reactor use in the process because reactor and catalysts using is interrelated.
Besides that, cost of catalyst is also considered in order to choose the best catalyst
for the oxo process. The advantages and disadvantages of each catalyst and price
ratio between them are shown below.

Table 2.2: Comparisons of Catalysts.

Catalyst Advantages Disadvantages

 Cobalt Carbonyl • Economic practical choice. • Thermally unstable.
(Co) • Very cheap/inexpensive. • Easily decompose to
• Highest yield • Longest life cobalt and carbon
monoxide.
time.
• Produce predominantly
linear alkanes.
• Reduce impurities.
• Energy required is low.
• Most reactive in reaction of
synthesis gas.

Raney Nickel (Ni) Large amount of

impurities in no or
presence of water. (di-
n-propylether,DPE and
n-propyl

propionate,prpr).Con‘t
• Makes separation and
purification of n-
propanol difficult
because of binary
azeotrope between
water and n-propanol.
• High energy
consumption.
• Need larger purification
column.

Rhodium • Economic practical choice. Very expensive catalyst.

Triphenylphosphine • High reaction rate.
(Rh) • Greater stability.
• Low operation pressure.
• Lower by product
production.
• More active than cobalt.
• Result in less high boiling
point of by product.
 Table 2.3: Price Ratio Between the Catalysts.

Metal Price Ratio

Iron 1

Cobalt 230

Nickel 250

Rutherium 31 000

Rhodium 570 000

Source from : Rhodium-Catalyzed Hydroformylation.(2000)

Based on the tables above, cobalt carbonyl has been choosing to be use in the oxo
process. This is because the catalyst is commercialized enough in the chemical
industries and has it own benefits like low cost compared to others. Cobalt carbonyl
will be used in the first reactor at the hydroformylation process and also second reactor
at the hydrogenation process.

2.4.3 Equipment Selection

Besides catalyst selection, reactor selection also plays an important role in the oxo
process to increase the process efficiency. There are different types of reactor that
can be considered for oxo process such as fixed bed reactor, fluidized bed reactor,
slurry reactor, and batch reactor. Catalyst form also affects the selection of reactor.
For the fixed bed, the raw material or reactant of the process must be between liquid
and gas and the catalyst in the form of pellet. This kind of reactor also can react any
two gas phase. Meanwhile for the slurry bed, the reactant is between gas and gas.
Catalyst form is in liquid form. This shown that selection of reactor and catalyst is very
important consideration. Table below shows advantages and disadvantages of each
reactor.

Table 2.4: Reactor Selection

 Types of Reactor Advantages Disadvantages

Fixed Bed Reactor Simple analysis. Poor heat transfer in fixed

High efficiency. bed reactor.
Low cost. Non uniform
Low maintenance.
flow pattern.
Little loss or attrition.
Swelling of the catalyst
High ratio of catalyst and deformation of
reactor.
reactants.
Little wear of catalyst and Regeneration or
to

equipment. replacement of catalyst

Only practical and economical is difficult and need
reactor at high pressure. shutdown. Con‘t
Efficient-long residence time
High pressure drop for
and achieve near complete small beads or pellets.
reaction.

Fluid Bed And Frequent regeneration of the Complicated.

Slurry Reactor catalyst. Extensive
Rapid mixing of solids in beds investment and
means uniform gas high maintenance.
composition. Low residence time and
Efficient temperature control. conversion maybe
Small diameter particles in limited.
fluid minimize pore diffusional Attrition and loss of
catalyst.
resistance.
High heat transfer rates.

2.5 Process Description

Worldwide production of n-propanol has been carried out in two complex reactions which
were hydroformylation of ethylene followed by hydrogenation of
propionaldehyde or propanol, the product of the first reaction
.
By referring to the process PFD at the APPENDIX A, the main equipment processes were
elaborate.
Hydro formulation of Ethylene (slurry Bed Reactor)

C 2H 4
H2
C2H 4
CO
H
2
CO
C H O
3 6
Stream 4 Stream 7 C2H 6
Stream 5
Stream 6

R1

Figure 2.3 First reactor

The oxo process or hydroformylation reaction is a reaction where the

synthesis gas, carbon monoxide and hydrogen react with ethylene to produce
propionaldehyde. Propionalehyde is an aldehyde group that also known as propanal.
Besides that, hydroformylation reaction also produced by product known as ethane.
The formation of propionaldehyde and ethane are shown in below equation.
 Hydroformylation, was carried out initially with a dicobalt octacarbonyl, CO2CO8, catalyst at
temperatures of about 90-130°C and 2-5 Mpa. A breakthrough was the discovery that rhodium
chloride with ligands such as triphenylphosphine allowed the reaction to take place at
temperatures of around 100°C and 1–2.5 Mpa. Chemo selectivity to aldehydes is high for all Rh
catalysts.

Slurry bed reactor is for a gas-liquid contacting accompanied by chemical reaction.

The most attractive technical process is with a slurry reactor due to its heat removal
capability, low investment, and high one-pass conversion. With the raw material of
ethylene, carbon monoxide and hydrogen in gas phase, the use of slurry bed in
contacting the liquid cobalt carbonyl is the ideal reactor where gas solubility is low and
a large liquid holdup is required.

The reacting feed gas (mixed with recycle) is introduced through sparger. It bubbles
through the column, keeping the catalyst in suspension, aerating the liquid and
supplying the agitation necessary for mass transfer as it reacts. Because of the
reaction is highly exothermic, cooling coils are provided in the reaction zone.

Condenser

The highly exothermic hydroformylation reaction (28-35 kcal/mol) requires sufficient

cooling area. The condenser also needed in order to condensate the vapor propanal
into liquid phase.
 Stripper

CO

C3H6O
C2H4
H2
CO
C2H6

C3H6O
C2H4
C2H6
H2

Figure 1.3 Stripper

After condensation, the propanal is sent to a carbon monoxide-stripping column to

remove traces of carbon monoxide prior to hydrogenation. Carbon monoxide is then
recycle back to the reactor to reduce the feedstock. Carbon monoxide need to be
drawn out because it could cause poison for the second reaction.
Hydrogenation of aldehyde (fixed Bed Reactor)

Stream 15 C3H8O
C2H4
Vapor C6H14O
liquid C3H6O
mixture C2H6
C3H6O H2O
Stream 12 H2
H2
C2H4
C2H6

Stream 14

Figure 2.5: Second reactor

Hydrogenation of the aldehyde to the alcohol takes place with a dicobalt octacarbonyl
at 0.2-0.3 Mpa at about 120 – 180°C and hydrogen pressure of about 3-5 Mpa, a
catalyst loading of about 2 to about 20 wt% preferably about 8 to about
10 wt% based on the weight of the feed in the liquid feed. The equation is as follow

In addition the liquid feed should contain for example, either substantially no water, or
an amount of water, for example up to about 3 wt% preferably about 0.0 to about 1.0 wt%
based on the weight of crude hydrogenation reaction product. Substantially no water, means
that no water is added to the hydrogenation reactor or in the fractionating column and the
only water present in the reactor and optionally in column is that form during the
hydrogenation itself and in the hydroformylation reactions.
The reactor used in this reaction was fixed bed reactor. The liquid propanal is fed from
the top of the column counter current with the hydrogen gas from the bottom of the
reactor. With the pellet physical of the dicobalt octacarbonyl make the liquid and gas
interphase in the fixed bed. Undesirable certain impuritiy tend to be form in the little or
no water as a result of side reaction of the hydrogenation form adol condensation
which is dipropylether

Two Tower Purification System

H2
C2H4
C6H14O
C2H6

C3H8O
H2
C2H4
C3H6O
C6H14O
H2O
C2H6

C3H8O
C3H6O
H2O
Figure 2.6: First distillation column

The crude n-propanol (after hydrogenation) is purified in a standard two-tower

purification system. By using a dicobalt octacarbonyl in the hydrogenation process,
the components that have higher boiling point are drawn out at the bottom of the
distillation column. Hydrogen and ethane will be then separated by other compound
by using the gas separator into different storage tank. At certain time both gases will
be recycle back into stream process to avoid waste.
Recovery Column

C6H14O
C2H6

C3H8O
C6H14O
C2H6

C3H8O

Figure 2.7 : Second distillation column

Purification of the n-propanol from the hydrogenation zone is carried out by fractional
distillation is the presence of small quantity of water. No addition of water into the
system is needed because water presence will formed azeotrope with the product.
The amount of water that produce in both hydroformylation and hydrogenation is up
to 3 wt% preferably about 0.1 to about 1 wt%, based on the weight feed to the
fractionating column is already enough. The amount of water entering the column is
generally the same as in the hydrogenation effluent, desired to the column for its
cooling effect. Most of the water are drawn out at the bottom. n- propanol is collected
at the bottom of the column while the impurities are drawn out. Liquid recycle is
necessary to avoid waste. The amount of heat entering the column from the reboiler
and with the feed must equal the amount heat removed by the overhead condenser
and with the products.
CHINESE JOURNAL OF CATALYSIS .Volume 30, Issue 8, August 2009 U.S.
Pat. 5,8667,725 (Feb. 2, 1999), J.D. Unruh and D.A. Ryan (to Celanese
International Corporation)