Final Project Updated 2

PRODUCTION OF ACETALDEHYDE
Submitted in partial fulfillment of the requirements for the award of the degree of
BACHELOR IN
CHEMICALENGINEERING
Submitted By:
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TABLE OF CONTENTS
ACKNOWLEDGEMENT................................................................................................................I
TABLE OF CONTENTS...............................................................................................................II
LIST OF TABLE AND FIGURE...................................................................................................IV
LIST OF SYMBOLS AND ABBREVIATIONS USED............................................................VII
ABSTRACT................................................................................................................................VIII
CHAPTER ONE..............................................................................................................................1
INTRODUCTION.......................................................................................................................1
ACETALDEHYDE FORMULA................................................................................................1
STRUCTURE OF ACETALDEHYDE.....................................................................................2
PHYSICAL PROPERTIES.......................................................................................................2
CHEMICAL PROPERTIES......................................................................................................3
USES OF ACETALDEHYDE..................................................................................................6
ASPECTS OF THE ENVIRONMENT....................................................................................7
CHAPTER TWO.............................................................................................................................8
LITERATURE REVIEW............................................................................................................8
GLOBAL ACETALDEHYDE MARKET OVERVIEW............................................................8
GLOBAL ACETALDEHYDE MARKET: SEGMENTATION ANALYSIS................................9
1. ACETALDEHYDE MARKET, BY PROCESS. ...............................................................10
2. ACETALDEHYDE MARKET, BY DERIVATIVE........................................................10
3. ACETALDEHYDE MARKET, BY APPLICATION.....................................................11
4. ACETALDEHYDE MARKET, BY GEOGRAPHY......................................................12
METHODS OF MANUFACTURE.........................................................................................13
1. PRODUCTION OF ACETALDEHYDE FROM OXIDATION OF ETHYL ALCOHOL. 13
2. PRODUCTION OF ACETALDEHYDE FROM DEHYDROGENATION OF ETHYL

ALCOHOL.......................................................................................................................... 14
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3. PRODUCTION OF ACETALDEHYDE FROM OXIDATION OF ETHYLENE............14
4. PREPARATION METHOD OF ACETALDEHYDE FROM ACETYLENE .................16
5. PRODUCTION OF ACETALDEHYDE FROM SYNTHESIS GAS............................17
6. FROM ACETIC ACID...............................................................................................17
7. PRODUCTION OF ACETALDEHYDE FROM SATURATED HYDROCARBONS.. .18
SELECTION OF PROCESS.................................................................................................18
DESCRIPTION OF THE PROCESS....................................................................................19
THE INFORMATION REQUIRED IN THE ASPEN HYSYS MODEL:............................20
CHAPTER THREE.......................................................................................................................22
MATERIAL BALANCE............................................................................................................22
1) MATERIAL BALANCE ON MIXING OF ETHANOL FEED WITH RECYCLE IN

MIXER -100....................................................................................................................... 24
2) MATERIAL BALANCE ON THE REACTOR PFR-100, PFR-101 AND PFR-102......25
3) MATERIAL BALANCE ON THE SEPARATOR V-100..............................................28
5) MATERIAL BALANCE ON THE MIXER-102............................................................30
6) MATERIAL BALANCE ON THE DISTILLATION COLUMN T-101...........................31
7) MATERIAL BALANCE ON THE DISTILLATION COLUMN T-102...........................32
8) SUMMARY OF MATERIAL BALANCE....................................................................33
CHAPTER FOUR.........................................................................................................................34
ENERGY BALANCE...............................................................................................................34
1) ENERGY BALANCE ON MIXER -100.....................................................................34
2) ENERGY BALANCE ON FEED PUMP P-100..........................................................35
3) ENERGY BALANCE ON HEATER E-100................................................................35
5) ENERGY BALANCE ON THE REACTOR PFR-100................................................37
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8) ENERGY BALANCE ON COOLER E-102...............................................................39
9) ENERGY BALANCE ON COOLER E-103...............................................................39
10) ENERGY BALANCE ON THE SEPARATOR V-100................................................40
11) ENERGY BALANCE ON THE ABSORPTION COLUMN T-100...............................41
13) ENERGY BALANCE ON MIXER -102.....................................................................42
14) ENERGY BALANCE ON THE DISTILLATION COLUMNT-101...............................43
15) DISTILLATION COLUMN T-101 CONDENSER AND RE-BOILER..........................44
16) ENERGY BALANCE ON THE DISTILLATION COLUMNT-102...............................44
17) DISTILLATION COLUMN T-102 CONDENSER AND RE-BOILER..........................45
18) ENERGY BALANCE ON THE PUMP P-101............................................................46
19) SUMMARY OF ENERGY BALANCE.......................................................................46
1. DESIGN OF ETHANOL DEHYDRATION REACTOR............................................47
2. DISTILLATION COLUMN DESIGN T-101...............................................................59
3. HEAT EXCHANGER DESIGN...................................................................................62
CHAPTER SIX..............................................................................................................................64
REFERENCES.............................................................................................................................69
List Of Table And Figure
Figure 1.1:Structure Of Acetaldehyde........................................................................2
Figure1.2: Derivatives Of Acetaldehyde.....................................................................7
Figure 2.1: The Global Acetaldehyde Market By Process (Usd Million)..................10
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Figure 2.2: The Global Acetaldehyde Market By Derivative (Usd Million)...............11
Figure2.3: The Global Acetaldehyde Market By Geography (Usd Million)..............12
Figure 2.4: Process Flow Diagram Of Acetaldehyde Production Plant...................21
Figure 3.1: Ethanol Feed And Ethanol Recycle Mixer -100.....................................24
Table 3.1: The Material Balance Of Mixer-100, Calculation And Result..................25
Figure 3.2: Reactor Pfr-100, Pfr-101 And Pfr-102...................................................26
Table 3.2a: The Material Balance Of Reactor Pfr-100, Calculation And Results....26
Table 3.2b: The Material Balance Of Reactor Pfr-101, Calculation And Results....27
Table 3.2c: The Material Balance Of Reactor Pfr-102, Calculation And Results....27
Table 3.3: The Material Balance On Separator V-100, Calculation And Results....28
Table 3.4: The Material Balance On Absorber Column T-100.................................29
Table 3.5: The Material Balance On Mixer-102, Calculation And Results...............30
Table 3.6: The Material Balance On Distillation Column T-101, Calculation And
Results......................................................................................................................31
Table 3.7: The Material Balance On Distillation Column T-102...............................32
Table 3.8: The Summary Of Material Balance.........................................................33
Table 4.1: The Energy Balance On Mixer -100, Calculation And Results...............34
Table 4.2: The Energy Balance On Feed Pump, Calculation And Results.............35
Table 4.3: The Energy Balance On Heater E-100, Calculation And Results...........36
Table 4.4: The Energy Balance On Heater E-101, Calculation And Results...........36
Table 4.5: The Energy Balance Reactor Pfr-100, Calculation And Results............37
Table 4.8: The Energy Balance On Cooler E-102, Calculation And Results...........39
Table 4.9: The Energy Balance On Cooler E-103, Calculation And Results...........40
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Table 4.10: The Energy Balance On The Separator V-100, Calculation And Results
40
Table 4.11: The Energy Balance On The Absorption Column T-100, Calculation
And Results..............................................................................................................41
Table 4.12: The Energy Balance On Heater E-104, Calculation And Results.........42
Table 4.13: The Energy Balance On Mixer -102, Calculation And Results.............42
Table 4.14: The Energy Balance On The Distillation Column T-101, Calculation And
Results......................................................................................................................43
Table 4.15: The Energy Balance On The Distillation Column T-101 Condenser And
Re-Boiler, Calculation And Results..........................................................................44
Table 4.16: The Energy Balance On The Distillation Column T-102, Calculation And
Results......................................................................................................................45
Table 4.17: The Energy Balance On The Distillation Column T-102 Condenser And
Re-Boiler, Calculation And Results..........................................................................45
Table 4.18: The Energy Balance On The Pump P-101, Calculation And Results...46
Table 4.19: The Summary Of Energy Balance........................................................46
Table 5.1: The Reaction Conversation With Reaction Rate Results.......................48
Figure 5.1: The Graph Between Xa And 1/-Ra........................................................49
Table 5.2: The Wall Thickness Of Vessels With A Corrosion Allowance Of 2 Mm. 55
Table 5.3: Heads Of Various Shapes Close The Ends Of A Cylindrical Vessel......56
Figure 5.2: Bracket...................................................................................................57
Table 5.4: Pfr Reactor Specification Sheet..............................................................58
Figure 5.3: Distillation Column (T-101)....................................................................60
Table 5.5a: Distillation Column Design Summary Results.......................................60
Table 5.5b: Distillation Column Design Summary Results.......................................61
Table 5.5c: Distillation Column Design Summary Results.......................................62
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Table 5.6: Shell And Tube (E-103) Design And Summary Results.........................62
Table 5.7: Heat Exchanger Specification Sheet.......................................................63
Table 6.1: Feed Stream And Product Stream Price.................................................68
Table 6.2: Summary Of Capital Cost Obtained By Aspen Hysys V.11...................68
List of Symbols and abbreviations used
Msteam Mass flow rate of steam.

∆Hsteam Enthalpy of steam.
E Mass flow rate of ethanol.
A Mass flow rate of acetaldehyde.
H Mass flow rate of hydrogen.
Cp Specific heat capacity.
F Molar flow rate of Feed, kmol/hr.
D Molar flow rate of Distillate, kmol/hr.
W Molar flow rate of Residue, kmol/hr.
XF Mole fraction of Acetaldehyde in liquid/Feed.
YD Mole fraction of Acetaldehyde in Distillate.
XW Mole fraction of Acetaldehyde in Residue.
MF Average Molecular weight of Feed, kg/kmol
MD Average Molecular weight of Distillate, kg/kmol
MW Average Molecular weight of Residue, kg/kmol
Rm Minimum Reflux ratio
R Actual Reflux ratio
Q Thermal condition of Feed

ρL Density of Liquid, kg/m3.
ρV Density of Vapor, kg/m3.
qL Volumetric flow rate of Liquid, m3/s
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qV Volumetric flow rate of Vapor, m3/s
μL Viscosity of Liquid, cP.
TL Temperature of Liquid, K.
TV Temperature of Vapor, K
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ABSTRACT
This study illustrates the production of acetaldehyde using different production
methods, market research, literature review and selection of the appropriate
method. our chosen production method is ethanol dehydrogenation. During this
process, hydrogen is produce as a by-product that can be used to generate heat.
More conversion occurs in the dehydrogenation process compared to other
processes with use of three reactors to final reaction conversion, the total
reaction conversion in three PFR reactors is 92.21% and 7.79% of ethanol is
separated from product and recycle to feed. A mass balance is carried out for the
various units involved in the production of acetaldehyde using the ethanol
dehydrogenation method. We also prepared an energy balance for each device
to determine the usefulness of the heat and the amount of auxiliary fluids needed
in the heat supply. In terms of design, we designed a PFR reactor, distillation
column and heat exchanger, that meets the design requirements of a specific
plant. Cost estimates are also done with benefit studies that show the required
investment, return and payback period.
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CHAPTER ONE
INTRODUCTION
Acetaldehyde is also known as ethanal. It is a chemical compound that has the
formula ch3cho. Acetaldehyde is a very significant aldehyde. It is manufactured
on a big scale in a variety of sectors. It is found in a variety of foods, including
coffee, bread, and ripe fruit, and is produced by plants. It also contributes to the
cause of hangovers after consuming alcohol. Acetaldehyde exposure can
occur through the air, water, soil, or groundwater, as well as through drink and
smoking. Acetaldehyde dehydrogenase is inhibited by disulfiram use. It is the
enzyme that is responsible for acetaldehyde metabolism.
Acetaldehyde dissolves quickly in naphtha, gasoline, xylene, ether, turpentine,
alcohol, and benzene. it’s a colorless, flammable liquid with a stifling odor.
Although acetaldehyde is non-corrosive to many metals, its narcotic impact
might provoke mucosal irritation.
ACETALDEHYDE FORMULA
Acetaldehyde has the chemical formula CH 3CHO or C2H40. 44.053 g ml-1 is the
molar mass. the acetaldehyde molecule contains the normal functional group of
an aldehyde H-C=O linked to a methyl group (-CH 3), making it the second
simplest aldehyde after formaldehyde. Furthermore, the c atom from the
aldehyde has a hybridization sp2, whereas the methyl group has sp 3, resulting in
a molecule with planar-trigonal and tetrahedral geometry.
STRUCTURE OF ACETALDEHYDE
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The Structure Of Acetaldehyde Is Given Below. [1]
Figure 1.1:Structure Of Acetaldehyde.
PHYSICAL PROPERTIES
Clear colorless fuming liquid with a pungent, fruity odor. The vapors are heavier
than the air and can travel long distances and cause flashbacks from the
combustion source. It will emit acrid smoke and toxic fumes of carbon monoxide
and carbon dioxide when it is heated to decomposition.
Specific gravity: 0.778 at 20°C
Melting point: -123.5°C
Boiling point: 21°c
Vapor pressure: 400 mm Hg at 4.9°c: 760 mm Hg at 20.2°C
Flashpoint: -40°C
100% volatile by volume. [2]
CHEMICAL PROPERTIES
Acetaldehyde has chemical characteristics comparable to formaldehyde. It is
used as an electrophile precursor in organic synthesis.
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Condensation reactions provide intermediates such as pentaerythritol, which can
be utilized in chemical synthesis. It may also be used to make hydroxyethyl
derivatives via a reaction with a grignard reagent. acetaldehyde is a building
block used in the production of heterocyclic compounds such as imines and
pyridines.
Acetaldehyde is a highly reactive compound exhibiting the general reactions of
aldehydes,under suitable conditions, the oxygen or any hydrogen can be
replaced.
Acetaldehyde undergoes numerous condensation, addition, and polymerization
reactions. [3]
1. DECOMPOSITION
At temperatures above 400°c, acetaldehyde decomposes mostly into
methane and carbon monoxide. The pyrolysis process has an activation
energy of 97.7 kj/mol (408.8 kcal/mol). Many studies have been conducted
on the photolytic and radical-induced breakdown of acetaldehyde and
deuterated acetaldehydes.
2. THE HYDRATE AND ENOL FORM
Acetaldehyde occurs in equilibrium with the hydrate, CH3CH(OH)2, in
aqueous solutions. An equation developed by Bell and Clunie can be used
to calculate the degree of hydration. The mean heat of hydration is -21.34
Kj/mol (89.29 kcal/mol).Hhydration is due to hyper conjugation. Vinyl
alcohol (CH2 = CHOH), an Enol form, is in equilibrium with acetaldehyde
to the amount of around one molecule per 30,000. Vinyl acetate is formed
by acetylating acetaldehyde Enol with ketene.
3. OXIDATION
acetaldehyde is easily oxidized with oxygen or air to produce acetic
acid, acetic anhydride, and peracetic acid (see acetic acid and
derivatives). Acetic acid is commercially produced by liquid-phase
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oxidation of acetaldehyde at 65°C with cobalt or manganese acetate
dissolved in acetic acid as a catalyst. Liquid – phase oxidation of
acetaldehyde in the presence of mixed acetates of copper and cobalt
yields acetic anhydride.
4. REDUCTION
acetaldehyde is easily reduced to ethanol. By used of suitable catalysts
for vapor-phasehydrogenation are supported nickel and copper oxide.
Studied the kinetics of the hydrogenation of acetaldehyde over a
commercial nickelcatalyst by oldenberg and rose.
5. POLYMERIZATION
Paraldehyde,2,4,6- trimethyl – 1,3,5 – trioxan, a cyclic trimer of
acetaldehyde is formed when a mineral acid, such as sulfuric,
phosphoric, or hydrochloric acid, is added to acetaldehyde.
Paraldehyde can also be formed continuously by feeding acetaldehyde
as a liquid at 15 - 20°c over an acid ion – exchange resin.
Depolymerization of paraldehyde occurs in the presence of acid
catalysts. After neutralization with sodium acetate, acetaldehyde and
paraldehyde are recovered by distillation. Paraldehyde is a colorless
liquid, boiling at 125.35 °c at 101 kpa (1 atm).
6. REACTIONS WITH ALDEHYDES AND KETONES

The base catalyzed condensation of acetaldehyde leads to the dimmer,
Acetaldol, which can be hydrogenated to form 1,3 butandiol or
dehydrated to form crotonaldehyde. Crotonaldehyde can also be made
directly by the vapor-phase condensation of acetaldehyde over a
catalyst. Crotonaldehyde was formerly an important intermediate in the
production of butyraldehyde, butanol, and 2-ethylhexanol. However, it
has been replaced completely with butyraldehyde from the oxo process.
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A small amount of crotonaldehyde is still required for the production of
crotonic acid. Acetaldehyde forms aldols with other carbonyl
compounds containing active hydrogen atoms.
7. REACTIONS WITH AMMONIA AND AMINES
Acetaldehyde readily adds ammonia to form acetaldehyde ammonia.
Diethyl amineis obtained when acetaldehyde is added to a saturated
aqueous or alcoholic solution of ammonia and the mixture is heated to
50-750C in the presence of a nickel catalystand hydrogen at 1.2 MPa
(12atm).
Pyridine and pyridine derivate are made from paraldehyde and aqueous
ammonia in the presence of a catalyst at elevated temperatures;
acetaldehyde may also be used by the yields of pyridine are generally
lower than when paraldehyde is the staring material.
Levy and Other have studied the vapor- phase reaction of
formaldehyde,
acetaldehyde, and ammonia at 3600C over oxide catalysts; a 49% yield
of Pyridine and Picolines was obtained using an activated silica-alumina
catalyst. Brown polymers result when acetaldehyde reacts with
ammonia or amines at a PH of 6-7and temperature of 3-250C. With
acetaldehyde, a primary amine can be condensed to Schiff bases:
CH3CH=NR, the Schiff base rivets to the starting materials in the
presence of acids.
8. REACTIONS WITH ALCOHOLS AND PHENOLS
Alcohols add readily to acetaldehyde in the presence of a trace of
mineral acid to form acetals; eg, ethanol and acetaldehyde form diethyl
acetal. Similarly, cyclic acetals are formed by the reactions with glycols
and other polyhydroxy compounds; eg, there action of ethylene glycol
and acetaldehyde gives 2 – methyl – 1,3 – dioxolane.
5
9. REACTIONS WITH HALOGENS AND HALOGEN COMPOUNDS
Halogens readily replace the hydrogen atoms of the methyl group: eg,
chlorine reacts with acetaldehyde or paraldehyde at room temperature
to give chloro acetaldehyde; increasing the temperature to 700-8000C
gives dichloro acetaldehyde; and at a temperature of 80-900C chloral is
formed. The catalytic chlorination with an antimony powder or aluminum
chloride ferric chloride has been described.
USES OF ACETALDEHYDE
To manufacture other chemicals, acetic acid is used to a large extent. In the
manufacture of acetic acid, it is used. In the manufacture of polymers, it's
applied. it is applied for the manufacture of disinfectants, pharmaceuticals,
and fragrances. It is used to produce polyvinyl acetate.
It is used to make pyridine derivatives, crotonaldehyde, and pentaerythritol.
Moreover, acetaldehyde is used in the manufacture of wine, yeasts, and
various products as a preservative for fruit and fish. As a solvent, It is used in
several manufacturing processes which include paper making, tanning, and
rubber production. It is also used in the manufacture of n-butyraldehyde. It is
used as an alcohol denaturant in fuel mixtures and as a hardener for gelatin
fibers, glues, and casein products in the tanning of leather. [4]
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Figure1.2: Derivatives of Acetaldehyde
ASPECTS OF THE ENVIRONMENT
Acetaldehyde is toxic when exposed to the skin for an extended length of
time, an irritant, and a possible carcinogen. It is a kind of air pollution
produced by burning, such as automobile exhaust and tobacco smoke.
Acetaldehyde is used to make acetic acid, acetic anhydride, ethyl acetate,
peracetic acid, pentaerythritol, chloral, glyoxal, alkyl amines, and pyridines.
During World War I, acetaldehyde was widely employed as an intermediary in
the production of acetone from acetic acid.
CHAPTER TWO
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LITERATURE REVIEW
In 1774, Scheele first produced acetaldehyde through the action of manganese

dioxide and sulfuric acid on ethanol. [6].
In 1835, Liebig established the structure of acetaldehyde Pure samples were

prepared by oxidation of ethanol with chromic acid. [7]
From the Latin words translated as al (alcohol) dehyd (rogenated), Liebig gave
the compound the name "aldehyde". In 1881, Kutscherow observed the addition
of water to acetylene resulting in the formation of acetaldehyde. [8]
The following are commercial methods for producing acetaldehyde: the addition
of water to acetylene, the partial oxidation of hydrocarbons, the direct oxidation of
ethylene, and the oxidation or dehydrogenation of ethanol. Wacker Hoechst
processes were used by 29 companies in 1976, accounting for more than 82% of
the world's 2.3 megatons per year plant capacity for direct ethylene oxidation.[10]
GLOBAL ACETALDEHYDE MARKET OVERVIEW
The Global Acetaldehyde Market is primarily driven by rising demand for

acetaldehyde as an intermediary in the manufacturing of commodity chemical
compounds, which are used in a variety of end-use sectors such as food and
beverage, rubber, paper and pulp, and others. Furthermore, increased demand
for polymer resins and basic dyes made with this chemical is expected to drive
the acetaldehyde sector forward in the future years. Furthermore, the product is
employed in the crystallization of gelatin, which drives demand for the product in
the photographic, pharmaceutical, and cosmetic sectors. Additionally, increased
R&D investment and changing consumer consumption behaviors are boosting
the Acetaldehyde Market growth.
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However, the growth of the Acetaldehyde Market is restrained by the use of
methanol in the production of acetic acid. Additionally, propylene is being used
as a replacement for ethanol in the manufacturing of butyraldehyde. Also,
according to the International Agency for Research on Cancer, it is determined to
be carcinogenic to humans. Thus, these factors are negatively affecting market
growth to some extent. Nevertheless, variety in the end-user industry is expected
to create new lucrative opportunities for the Acetaldehyde Market during the
forecast period of 2020- 2027.
However, the usage of methanol in the manufacturing of acetic acid limits the
expansion of the Acetaldehyde Market. Furthermore, propylene is being utilized
to replace ethanol in the production of butyraldehyde. Furthermore, the
International Agency for Research on Cancer has established that it is
carcinogenic to humans. As a result, these issues have a negative impact on
market growth to some level. Nonetheless, variation in the end-user industry is
likely to provide new attractive prospects for the Acetaldehyde Market between
2020 and 2027. Other important aspects driving the Acetaldehyde Market growth
are changing consumer consumption trends.
GLOBAL ACETALDEHYDE MARKET: SEGMENTATION ANALYSIS
The Global Acetaldehyde Market Segmented based on:
 Acetaldehyde Market, By Process

 Acetaldehyde Market, By Derivative,
 Acetaldehyde Market, By Application
 Acetaldehyde Market, By Geography.
1. ACETALDEHYDE MARKET, BY PROCESS. [5]
 Oxidation of Ethylene (Hoechst-Wacker Process)

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 Oxidation of Ethanol
 Dehydrogenation of Ethanol
 Others
Figure
2.1:
The
Global
Acetaldehyde Market by Process (USD million).

Based on the Process, the market is bifurcated into the Oxidation of Ethylene,
Oxidation of Ethanol, Dehydrogenation of Ethanol, and Others. Oxidation of
Ethylene accounted for the largest market share in 2021. Acetaldehyde is
obtained on a large scale using the oxidation of ethylene, with ethylene as a raw
material.
2. ACETALDEHYDE MARKET, BY DERIVATIVE. [5]

 Acetic Acid
 Ethyl Acetate
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 Pyridine & Pyridine Bases
 Pentaerythritol
 Others
Figure 2.2: The Global Acetaldehyde Market by derivative (USD million)
Based on derivate, the Global Acetaldehyde Market has been segmented into
Pyridine & Pyridine Bases, Pentaerythritol, Ethyl Acetate, Acetic Acid, and
Others. Pyridine & Pyridine Bases accounted for the largest market share in
2021. Pyridine & pyridine bases are the major derivatives of acetaldehyde. They
are highly soluble in alcohol, water, benzene, and ether. These derivatives act as
scavengers and are used as catalysts in several reactions.
3. ACETALDEHYDE MARKET, BY APPLICATION

 Chemicals
 Plastics & Synthetic Rubber
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 Food & Beverage
 Paints & Coatings
 Pharmaceuticals & Cosmetics
 Others
Based on Application, the Global Acetaldehyde Market has been segmented into
Food & Beverage, Chemicals, Paints & Coatings, Plastics & Synthetic Rubber,
Pharmaceuticals & Cosmetics, and Others. Food & Beverage accounted for the
largest market share in 2021. Acetaldehyde is widely used in food & beverage
applications as a preservative for fruits, and fish, and as a flavoring agent.
4. ACETALDEHYDE MARKET, BY GEOGRAPHY. [5]

 North America
 Europe
 Asia Pacific
 Latin America
 Rest of the World
Figure2.3: The Global Acetaldehyde Market by Geography (USD million).
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Based on Geography, the Global Acetaldehyde Market is classified into North
America, Europe, Asia Pacific, and the Rest of the world. Asia-Pacific is expected
to hold the largest market share of Acetaldehyde over the forecast period
followed by North America. APAC is emerging as a leading consumer of
acetaldehyde because of the increasing demand from domestic as well as
international markets.
METHODS OF MANUFACTURE
The economy of the commercial processes depends essentially upon prices

and the availability of raw materials.
Raw materials that have been used for the production of acetaldehyde are:
1) Ethanol from the fermentation of carbohydrates or hydration of ethylene
2) Acetylene
3) Ethylene
4) Lower hydrocarbons
5) Carbon monoxide and hydrogen
6) Methanol
1. PRODUCTION OF ACETALDEHYDE FROM OXIDATION OF ETHYL
ALCOHOL
The oxidation is carried out by passing alcohol vapors and warmed air over a
silver catalyst at 4800 degrees Celsius. Conversions of 74-82% per pass may be
produced with a multi-tubular reactor while producing steam that can be used
elsewhere in the process. [6]
REACTION
CH3CH2OH + ½ O2  CH3CHO + H2O, ΔH = 242 kJ/mol (57.84 kcal / mol)
Temperature: 4800C
Catalyst: silver
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2. PRODUCTION OF ACETALDEHYDE FROM DEHYDROGENATION OF
ETHYL ALCOHOL
REACTION
C2H5OH → CH3CHO + H2
Catalyst: Cu -Co-Cr2O3
Temperature: 280 – 350 °C.
PROCESS DESCRIPTION
The feedstock material of ethanol is vaporized and the vapors so generated
are heated in a heat exchanger to the reaction temperature by hot product
stream. The product stream is cooled to the required temperature (280 –
350°C) and in doing it; all unreacted ethanol and acetaldehyde are
condensed. The outgoing gaseous stream, containing hydrogen mainly, is
scrubbed in a scrubber with dilute alcohol (alcohol + water) to remove
uncondensed products and the undissolved gas. The remaining pure
hydrogen (98%) is used for heat generation. The heated vapors are passed
through the converter. The product stream is first cooled in the heat
exchanger and then in condensers using water and liquid ammonia. This
condenses most of the unreacted ethanol and the acetaldehyde formed in the
reactor. The escaping gas, which is almost pure hydrogen, is scrubbed by
ethanol to remove all the traces of the product. The liquid stream consisting of
mainly ethanol and acetaldehyde is distilled in the distillation column to get
acetaldehyde. [10]
3. PRODUCTION OF ACETALDEHYDE FROM OXIDATION OF ETHYLENE.
REACTIONS
C2H4+PdCl2 + H2O CH3CHO +Pd +2HCl
Pd + 2CuCl2  PdCl2 +2CuCl
2CuCl+1/2 O2 + 2HCl 2CuCl2 + H2O
An aqueous solution of PdCl2 and CuCl2 serves as the catalyst. F.C. Phillips
14
discovered acetaldehyde by reacting ethylene with an aqueous palladium
chloride solution in 1894. As a result, ethylene is continually oxidized by a
succession of oxidation-reduction reactions.
Overall Reaction:
C2H4 + ½ O2  CH3CHO
There are two processes for the production of acetaldehyde by the oxidation
of Ethylene. [5]
3.1. ONE-STAGE PROCESS DEVELOPED BY FARBWERKE HOECHST

Under little pressure, ethylene, oxygen, and recycling gas are delivered
to a vertical reactor for contact with the catalyst solution in the one-
stage process. The heat generated by the reaction is absorbed by the
water that evaporates throughout the reaction, and make-up water is
given as needed to maintain the catalytic solution concentration. The
gases are washed with water, and the resultant acetaldehyde solution
is put into a distillation column, yielding acetaldehyde. [10]
3.2. TWO-STAGE PROCESS DEVELOPED BY WACKER CHEMIE

In the two–stage process ethylene and oxygen (air) react in the liquid
phase in two stages. In the first stage, ethylene is almost completely
converted to acetaldehyde in one pass in a tubular plug-flow reactor
made of titanium. The reaction is conducted at 125-1300C and 1.13
Mpa (150 psig) palladium and cupric chloride catalysts.
Acetaldehyde is removed from the reaction loop by adiabatic flashing in
a tower in the first reactor. The flash stage also reduces the reaction's
heat. The catalyst solution is recycled from the flash-tower base to the
second stage (or oxidation) reactor, where the air is used to oxidize the
cuprous salt to the cupric state. TheBefore venting, high-pressure off-
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gas from the oxidation reactor, primarily nitrogen, is separated from the
liquid-catalyst solution and cleaned to remove acetaldehyde. The light
above feeds a distillation system, which removes water for recycling to
the reactor system and separates organic contaminants, including
chlorinated aldehydes, from the purified acetaldehyde output. [10]
4. PREPARATION METHOD OF ACETALDEHYDE FROM ACETYLENE
REACTION
H2C = CH2 + H2O CH3CHO
Temperature: 70-900C
Pressure: 103.4 KPa
PROCESS DESCRIPTION
Fresh catalyst is fed to the reactor periodically; the catalyst may be added in
the mercuries form. The excess acetylene sweeps out the dissolved
acetaldehyde which is condensed by water and refrigerated brine and
scrubbed with water; the crude acetaldehyde is purified by distillation and the
unreacted acetylene is recycled. The catalytic mercuric ion is reduced to
catalytically inactive mercurous sulfate and metallic mercury; this sludge,
consisting of reduced
catalyst and tars is drained from the reactor at intervals and resulfated.
Adding ferric or other salts to the reaction solution can reduce the rate of
catalyst depletion. In one variation, acetylene is completely hydrated with
water in a single operation at 68-730C using the mercuric iron salt catalyst.
The acetaldehyde is partially removed by vacuum distillation and the mother
liquor is recycled to the reactor. The aldehyde vapors are cooled to about
350C, compressed to 253 KPa, and condensed. It is claimed that this
combination of vacuum and pressure operations substantially reduces heating
and refrigeration costs.
Fresh catalyst is supplied into the reactor regularly; the catalyst might be in
16
the mercuries form. The dissolved acetaldehyde is condensed by water and
chilled brine and washed with water; the crude acetaldehyde is refined by
distillation, and the unreacted acetylene is recycled. The catalytic mercuric ion
is reduced to catalytically inactive mercuries sulfate and metallic mercury; this
sludge, consisting of reduced catalyst and tars, is drained and re-sulfated at
regular intervals from the reactor. By adding ferric or other salts to the
reaction solution, the rate of catalyst depletion can be slowed. Using the
mercuric iron salt catalyst, acetylene is thoroughly hydrated with water in a
single operation at 68-730C. Vacuum distillation is used to remove some of
the acetaldehyde, and the mother liquor is recycled back into the reactor. The
aldehyde vapors are cooled to around 350 degrees Celsius, compress to
253KPa, and condensed. This combination of vacuum and pressure
operations is substantially reducing heating and refrigeration costs. [7,8]
5. PRODUCTION OF ACETALDEHYDE FROM SYNTHESIS GAS

REACTION
CO + H2 → CH3CHO + other products
Catalyst: Rhodium
Temperature: 3000C
The process is a single step comprising passing synthesis gas over 5%
rhodium on SiO2 at 3000C and 2.0 Mpa (20 atm). The principal co-products
are acetaldehyde, 24% acetic acid, 20%; and ethanol, 16%.[7]
6. FROM ACETIC ACID
REACTION
CH3 COOH + H2 → CH3 CHO + H2 O ΔG300° C. = +0.8 kcal/mole
Catalyst: Iron oxide containing 2.5-90 wt% Pd
Temperature: 250-400 °C
PROCESS DESCRIPTION
Hydrogen and acetic acid are fed to a reactor in hydrogen to acetic acid ratio
17
of 2:1 to 25:1.The hydrogenation of acetic acid produces a partially gaseous
product, and acetaldehyde is absorbed from the partially gaseous product
with a solvent containing acetic acid. The gas remaining after the absorption
step contains hydrogen, and this gas is recycled for the hydrogenation of
acetic acid. The absorbed acetaldehyde is distilled. After acetaldehyde is
isolated from unreacted acetic acid and the other products via distillation, the
unreacted acetic acid is separated from the other products using azeotropic
distillation. Water is contained in the other products, and the azeotrope is an
azeotrope of ethyl acetate and water. The unreacted acetic acid is separated
into a column, and the column is controlled to contain an ethyl acetate-rich
azeotrope of ethyl acetate and water.[9]
7. PRODUCTION OF ACETALDEHYDE FROM SATURATED
HYDROCARBONS
Acetaldehyde is formed as a co-product in the vapor–phase oxidation of
saturated
hydrocarbons, such as butane or mixtures containing butane, with air or in
higher yield oxygen. Oxidation of butane yields acetaldehyde, formaldehyde,
methanol, acetone, and mixed solvents as major products; other aldehydes,
alcohols, ketones, glycols, acetals, epoxides, and organic acids are formed in
smaller concentrations. It has almost no chance to be used as a major
process.
SELECTION OF PROCESS
For the manufacture of acetaldehyde, ethyl alcohol dehydrogenation is used.

Because hydrogen is produced as a byproduct in this process, it can be utilized
elsewhere or to create heat. In comparison to other procedures, the
dehydrogenation process involves higher conversion. The dehydrogenation
catalyst has a long life but must be reactivated regularly. Because there are
18
fewer products in the dehydrogenation process, separating acetaldehyde from
other compounds is not a difficult problem.
DESCRIPTION OF THE PROCESS

PRODUCTION OF ACETALDEHYDE BY DEHYDROGENATION OF ETHYL
ALCOHOL
A PFD of Acetaldehyde production plant is shown in figure 1, Ethanol feed
stream mixing with water feed stream as 85%wt of Ethanol and 15% water at 1
bar and 25°C The mixed product is pumped to 6.5 bar and mixed with Ethanol-
water recycle stream ( 85% Ethanol,15%water), then pumped in P-100 to 9 bar
to To avoid pressure losses in heat exchangers and reactors due to the catalyst
and heating by Heat Exchangers E-100 & E-102 to 300 °C before being fed to
reactor PFR-100, an isothermal, catalyst, the packed bed is Cu/SiO2, where the
ethanol is dehydrogenated to product Acetaldehyde.[11]
The flowing reaction occurs during the dehydrogenation of ethanol to produce

acetaldehyde in reactors flowing:
CH3CH2OH  CH3CHO + H2 (1), conversion 51.88% in PFR-100
In PFR-101is conversion 58.8% and in PFR-102 is conversion 55.95 %
The total reaction conversion in three PFR reactors is 92.21%. with Ignoring side
reactions. The reactor product is then cooled in E-102 and E-103. The resultant
two-phase stream is then separated in separator V-100, the vapor stream,
stream 9 is sent to the absorption column T-100 where it is contacted with water
from stream 10 which absorbs the acetaldehyde and ethanol from hydrogen in
the vapor stream, and the product stream is stream 11 (hydrogen 98.7%mol.)
this stream sent to anther processing and recovery of hydrogen or used for fuel.
19
The absorber liquid product is stream 12 mixed with stream 14 the liquid product
of V-100 after heating and sent to distillation column T-101, the acetaldehyde
product from the top of T-101 with purity 99.95%wt.The bottom product of T-101
is ethanol unreacted with water and waste is sent to distillation column T-102 to
separate ethanol and water with ( ethanol 85% and water 15% and trace by
acetaldehyde 2.7%wt) in stream 18 in top product from wastewater in the bottom
product, the top product sent to mixer mix-100 to mixing with ethanol feed and
pumped to process. The wastewater from T-102 and stream waste from bottom
T-102 are sent to the wastewater treatment plant.
THE INFORMATION REQUIRED IN THE ASPEN HYSYS MODEL
We use in aspen hysys model
1- The chemical components and UNIQUAC-Ideal Thermodynamics.

2- Chemical reactions with reaction rate constant A (6*10^6 L/hr.gm of cat.)
and activate energy (55 Kj./mol.) for the reaction above. [12]
3- The specifications of catalyst Cu/SiO2 are particle diameter (5mm), particle
density (3596.5 Kg/m3), void fraction (0.45), and Particle Sphericity (0.94).
[12]
20
Figure 2.4: Process Flow Diagram of Acetaldehyde production plant
21
CHAPTER THREE
MATERIAL BALANCE
Material balance (also called mass balance) is an application of conservation of

mass to the analysis of physical systems. The law of conservation of mass states
that mass can neither be created nor destroyed. Material balances are the basis
of process design.
A material balance taken over the complete process will determine the quantities
of raw materials required and the products produced. Balances over individual
process units set the process stream flows and compositions. For any process
system, the material balance is summarized as follows:
INPUT-OUTPUT + GENERATION – CONSUMPTION = ACCUMULATION
EQ(3.2)
The consumption and generation terms are peculiar to systems in which
chemical reaction(s) takes place. They account for reactant consumption and
product formation respectively. However, when the system is assumed to
operate at a steady-state (e.g. as in distillation columns), the accumulation term
would be equal to zero. It is with this background that the analysis of the material
balance Acetaldehyde production plant.
FEED STREAMS
Ethanol and water with percentage 85%wt ethanol and 15%wt water.
ASSUMPTIONS
Let us assume an annual production of acetaldehyde 90000 tons per year.
It is assumed that the plant works for 300 days in a year.
Amount of acetaldehyde produced per day =300 tons per day
22
BASIS: One hour of operation.
Amount of acetaldehyde to be produced = 300 TPD = 12500kg/h.
Molecular weight of ethanol = 46.07 kg/kmol.
Molecular weight of acetaldehyde = 44.054 kg/kmol.
Molecular weight of hydrogen = 2.016 kg/kmol.
Therefore, amount of acetaldehyde to be produced = 295.0924 kmol/h.
The conversion be of ethanol to acetaldehyde is 91.21% molar conversion. From

kinetics reaction and catalyst data in reference [13].
Taking into account the losses let, the acetaldehyde produced to be some
extra.
Let acetaldehyde to be produced = 13000 kg/h.
Amount of ethanol required for 91.21% molar conversion = 323.5307Kmol/hr. *

46.07 kg/kmole.= 14905.06 Kg/hr
Amount of ethanol required for 100% molar conversion =295.0924 Kmol /hr.
*46.07 kg/kmol. =13594.91 Kg/hr.
the Ethanol feed with recycle = 14905.06 Kg/hr.
the water feed with recycle = 2630.305 Kg/hr.
the total feed with recycle = 17535.37 Kg/hr.
23
MATERIAL BALANCE ON UNITS
1) Material balance on mixing of Ethanol feed with recycle in Mixer -100
Material balance for mixer (Mixer -100)
Assumption
1- Steady state
2- No reaction, material generation or consumption
Figure 3.1: Ethanol feed and

Ethanol recycle Mixer -100
Inlet = outlet
The streams inlet is three stream and one stream is outlet
Inlet = m1 +m2, Outlet = m3, m1 +m2 = m3
m1 = Ethanol feed, m2 = Ethanol Recycle, m3 = stream 1
the material balance, calculation and result in table 3.1
24
Table 3.1: the material balance of mixer-100, calculation and result
Stream Feed Product
Stream Name Ethanol 18 1
Vapor 0.00 1.00 0.00
Temperature [C] 25.00 134.41 56.26
Pressure [bar] 6.50 6.50 6.50
Molar Flow [kgmole /h] 430.35 38.30 468.65
Mass Flow [kg/h] 16056.16 1479.21 17535.37
Mass Fractions
Ethanol 0.8388 0.8500 0.8398
H2O 0.1505 0.1235 0.1481
Hydrogen 0.0000 0.0000 0.0000
Acetaldehyde 0.0107 0.0265 0.0121
total 1.0000 1.0000 1.0000
2) Material balance on the Reactor PFR-100, PFR-101 and PFR-102.
After mixing of ethanol feed with ethanol recycle and pumped to 9 bar and
heating in heat exchangers to 300 °C enter to reactor PFR-100
The material balance on reactor PFR-100 where is reaction of Ethanol to product
Acetaldehyde in reactor with conversion
For aspen hysys model we use conversion reactor for the flowing reactions
CH3CH2OH  CH3CHO + H2 (1), conversion 51.88% in PFR-100
In PFR-101, conversion 58.8%.
In PFR-102, conversion 55.95 %
The total reaction conversion in three PFR reactors is 92.21%. with Ignoring side
reactions. the material balance, calculation and result in table (3.2A,2Band3.2C)
25
Figure 3.2: Reactor PFR-100, PFR-101 and PFR-102
Table 3.2A: the material balance of Reactor PFR-100, calculation and results
Stream Feed Product
Stream Name 4 6
Vapor / Phase Fraction 1.00 1.00
Temperature(°C) 300.00 350.00
Pressure (bar) 8.40 8.38
Molar Flows (kmol/hr.) 468.65 634.47
Mass Flows (kg/hr.) 17535.37 17535.39
Mass Fractions
Ethanol 0.8398 0.4041
H2O 0.1481 0.1481
Hydrogen 0.0000 0.0191
Acetaldehyde 0.0121 0.4287
total 1.0000 1.0000
Table 3.2B: the material balance of Reactor PFR-101, calculation and results
Stream Feed Product
Stream Name 6 6A
26
Mass Flows (kg/hr.) 17535.39 17535.40
Mass Fractions
Ethanol 0.4041 0.1665
H2O 0.1481 0.1481
Hydrogen 0.0191 0.0295
total 1.0000 1.0000
Table 3.2C: the material balance of Reactor PFR-102, calculation and results
Stream Feed Product
Stream Name 6A 6B
Mass Flows (kg/hr.) 17535.40 17535.40
Mass Fractions
Ethanol 0.1665 0.0733
H2O 0.1481 0.1481
Hydrogen 0.0295 0.0335
total 1.0000 1.0000
3) Material balance on the Separator V-100
27
The product of reactors is cooling in heat exchangers (E-101, E-102 and E-103)
and enter the separator V-100.
Material balance on Separator V-100
Assumption
1- Steady state
Inlet = outlet
Inlet = m1, outlet =m2+ m3  m1 = m2+m3 ,
m1 = stream (8A), m2 = stream (9), m3= stream (13)
the material balance, calculation and result in table 3.3.
Table 3.3: The Material balance on Separator V-100, calculation and results
Stream Feed Product
Stream Name 8A 13 9
Vapor 0.63 0.00 1.00
Temperature [C] 60.00 59.77 59.77
Pressure [bar] 5.83 5.77 5.77
Molar Flow [kgmole/h] 760.36 284.44 475.93
Mass Flow [kg/h] 17535.40 9146.03 8389.37
Mass Fractions
Ethanol 0.0733 0.1310 0.0105
H2O 0.1481 0.2597 0.0265
Hydrogen 0.0335 0.0000 0.0701
Acetaldehyde 0.7450 0.6093 0.8929
total 1.0000 1.0000 1.0000
4) Material balance on the absorber Column T-100
28
The vapor product stream of V-100 enters to absorber ColumnT-100 with the
absorption solvent of water in stream 10 to purity of hydrogen from other
component (Ethanol, Acetaldehyde and waste water), the hydrogen product in
stream 11 with purity 98.7% mol. The other component with solvent water
product in stream 12.
Assumption
1- Steady state
Inlet = outlet , Inlet = m1+ m2 outlet = m3+ m4  m1+ m2 = m3+ m4.

m1 = stream (10), m2 = stream (9), m3= stream (11), m4 = stream (12)
Table 3.4: The Material balance on absorber Column T-100.

Stream Feed Product
items 15 16 17
Vapor / Phase Fraction 0.04 1.00 0.00
Temperature(°C) 108.89 72.66 151.02
Pressure (bar) 5.47 5.40 5.47
Molar Flows (kmol/h) 2465.01 296.15 2168.86
Mass Flows (kg/h) 52906.87 13027.79 39879.08
Mass Fractions
Ethanol 0.0243 0.0000 0.0323
H2O 0.7288 0.0005 0.9667
Hydrogen 0.0000 0.0000 0.0000
Acetaldehyde 0.2469 0.9995 0.0010
total 1.0000 1.0000 1.0000
5) Material balance on the Mixer-102
The mixer-102 is mixing of stream 12(bottom product of absorber T-100)
29
and stream 14 (bottom product of separator V-100 after heating in heat
exchanger to 130C by LP. Steam.) to product stream 15.
Assumption
1- Steady state
Inlet = outlet
Inlet = m1, outlet = m2+ m3  m1 = m2+ m3 ,
m1 = stream (12), m2 = stream (14), m3= stream (15)
Table 3.5: The Material balance on Mixer-102, calculation and results

Stream Feed Product
items 12 14 15
Temperature(°C) 69.48 130.00 108.89
Pressure (bar) 5.50 5.47 5.47
Mass Flows (kg/h) 43760.84 9146.03 52906.87
Mass Fractions
Ethanol 0.0020 0.1310 0.0243
H2O 0.8269 0.2597 0.7288
Hydrogen 0.0000 0.0000 0.0000
Acetaldehyde 0.1711 0.6093 0.2469
total 1.0000 1.0000 1.0000
6) Material balance on the Distillation Column T-101
The Distillation Column T-101 is separated of acetaldehyde from top product with
higher purity (99.95%wt.)And bottom product is content ethanol and waste water
30
Assumption
1- Steady state
Inlet = outlet
Inlet = m1, outlet = m2+ m3  m1 = m2+ m3 ,
m1 = stream (15), m2 = stream (16), m3= stream (17)
Table 3.6: The Material balance on Distillation Column T-101, calculation and
results
Stream Feed Product
items 15 16 17
Temperature(°C) 108.89 72.66 151.02
Pressure (bar) 5.47 5.40 5.47
Mass Flows (kg/h) 52906.87 13027.79 39879.08
Mass Fractions
Ethanol 0.0243 0.0000 0.0323
H2O 0.7288 0.0005 0.9667
Hydrogen 0.0000 0.0000 0.0000
Acetaldehyde 0.2469 0.9995 0.0010
total 1.0000 1.0000 1.0000
7) Material balance on the Distillation Column T-102
The Distillation Column T-102 is recovery of ethanol unreacted from waste water
The ethanol is recovered from top in stream 18 and waste water in bottom
product.
31
Assumption
1- Steady state
Inlet = outlet , Inlet = m1, outlet = m2+ m3  m1 = m2+ m3 ,

m1 = stream (17A), m2 = stream (waste water), m3= stream 18
(Acetaldehyde)
the material balance, calculation and result in able 3.7.
Table 3.7: The Material balance on Distillation Column T-102.

Stream Feed Product
items 17A 18 waste water
Temperature(°C) 151.05 134.41 161.90
Pressure (bar) 6.60 6.50 6.50
Mass Flows (kg/h) 39879.08 1479.21 38399.87
Mass Fractions
Ethanol 0.0323 0.8499 0.0008
H2O 0.9667 0.1231 0.9992
Hydrogen 0.0000 0.0000 0.0000
Acetaldehyde 0.0010 0.0270 0.0000
total 1.0000 1.0000 1.0000
8) Summary of material balance
The summary of material balance in table 3.8

Table 3.8: The summary of material balance
32
CHAPTER FOUR
ENERGY BALANCE
The first law of thermodynamics we can write as fallow
The input of Energy - Output Energy = Accumulation of energy in the process
33
Δ U + ΔE p + ΔE k = Q + W eq. (4.1)
first law of thermodynamics. [3]
assumption:
Steady-state: Accumulation = zero

Rate of energy input = Rate of energy output
The calculated ofenergy balance by aspen hysys V.11 program.
1) Energy balance on Mixer -100

The feed stream is stream (Ethanol) and recycle stream (18)
The outlet stream is stream(Mix)
energy inlet = energy outlet,The energy balance on Mixer -100 in table 4.1
Table 4.1: the energy balance on Mixer -100, calculation and results
Stream Feed Product
items Units Ethanol 18 1
Temperature C 25.00 134.32 56.79
Pressure bar 6.48 6.48 6.48
Mass Flows kg/h 16031.55 1503.82 17535.37
Mass Enthalpy kcal/kg -1790.13 -1412.18 -1757.71
Mass Enthalpy kJ/kg -7489.89 -5908.57 -7354.27
Heat flow KJ/h -128959911.35 -128959911.35
2) Energy balance on feed pump P-100

Assumptions:
1- Incompressible fluids
Work W = P2 V2- P1V1 eq. (4.2)
34
where V1 = V2
Work = V(P2-P1) = ΔH*mass flow. The energy balance of pump in table 4.2.
Table 4.2: The energy balance on feed pump, calculation and results
Stream Feed Product
items Units 1 2
Temperature C 56.79 56.90
Pressure bar 6.48 9.00
Mass Enthalpy Kcal/h -1757.71 -1757.61
Std Ideal Liq Vol Flow cum/h 21.38 21.38
Mass Flows kg/h 17535.37 17535.37
Mass Enthalpy change ΔH =(H2-H1) KJ /kg 0.415
power required W =ΔH*mass KW 2.019
pump efficiency 75.00 %
Total power required KW 2.692
3) Energy balance on heater E-100

The stream (RCY) heated from 56.9°C to 250°C in heater E-100, By HP-Steam
at feed temperature 400 °C and mass flow rate 9710.60 kg/h and heat transfer
from tube side to shell side is Q = -7072.28 Kw. The energy balance on heater E-
100in table 4.3.
Table 4.3: the energy balance on heater E-100, calculation and results
Tube side Shell side
Stream
Feed Product Feed Product
items Units HPS-in HPS-out RCY 3
35
Temperature C 400.00 150.00 56.90 250.00
Pressure bar 20.00 19.50 9.00 8.70
Mass Flows kg/hr 9710.60 9710.60 17535.37 17535.37
Mass Enthalpy kcal/kg -3026.72 -3653.37 -1758.06 -1411.04
Enthalpy change kJ/h -25460206.63 25460206.63
Heat transfer Q = m*ΔH Kw -7072.28 7072.28

The stream (3) heated from 250 C to 300°C in heater E-101
By cooling of product stream (6B) from Reactor PFR-102, heat transfer from tube
side to shell side is Q = -528.44 Kw.
The energy balance of on heater E-101 in table 4.4
Stream
items Units 6B 7 3 4
Temperature C 350.00 305.03 250.00 300.00
Pressure bar 7.13 6.63 8.70 8.40
Mass Flows kg/h 17535.40 17535.40 17535.37 17535.37
Mass Enthalpy Kcal/kg -1062.04 -1087.97 -1411.04 -1385.11
Mass Enthalpy change kJ/h -1902380.49 1902380.49
5) Energy balance on the Reactor PFR-100

The feed stream of reactor is stream (4) at300 °C and chemical reactions is
endothermic we use heater to heating of reactor and save outlet temperature
at350 °C to higher of conversion in reactor. And heat required Q = 3982.50 Kw.
36
The energy balance of Reactor PFR-100 in table 4.5
Table 4.5: the energy balance Reactor PFR-100, calculation and results
Stream Feed Product
items Units 4 6
Mass Flows kg/h 17535.37 17535.39
Mass Enthalpy kcal/kg -1385.12 -1189.70
Mass Enthalpy kJ/kg -5795.33 -4977.72
Heat required Q =m*ΔH =(H2-H1)*m kJ/h 14336983.44
Heat transfer Q = m*ΔH Kw 3982.50

The feed stream of reactor is stream (6) at350 °C and chemical reactions is
The energy balance of Reactor PFR-101 in table 4.6.
Stream Feed Product
items Units 6 6A
37
Mass Flows kg/h 17535.39 17535.40
Enthalpy kJ/kg -4977.72 -4594.05
Heat required Q =m*ΔH =(H2-H1)*m kJ/h 6727805.16

The feed stream of reactor is stream (6A) at350 °C and chemical reactions is
The energy balance of Reactor PFR-102 in table 4.7
Stream Feed Product
items Units 6A 6B
Mass Flows kg/h 17535.40 17535.40
Mass Enthalpy kJ/kg -4594.05 -4443.57
Heat required Q =m*ΔH =(H2-
kJ/h 2638673.10
H1)*m
8) Energy balance on Cooler E-102

The product of reactor PFR-102 is cooling in heat exchanger E-102 by heating
feed of reactor PFR-100 and cooling and cooler E-102, The stream (7) cooled
from 305°C to 120°C in Cooler E-102
38
By water cooler with mass flow rate is 16101.15 Kg/h and heat transfer from gas
stream to water cooler stream is Q = -1977.51Kw to cooled stream
The energy balance on Cooler E-102 in table 4.8
Table 4.8: the energy balance on Cooler E-102, calculation and results
Stream
items Units W.C-IN W.C-Out 7 8
Temperature C 25.00 130.00 305.03 120.00
Pressure bar 5.00 4.50 6.63 6.33
Mass Flows kg/h 16101.15 16101.15 17535.40 17535.40
Enthalpy change kJ/h 7119077.47 -7119033.93
Heat transfer Q = m*ΔH Kw 1977.52 -1977.51
9) Energy balance on Cooler E-103

The stream (7) after cooling in E-102 to 120 C is cooled from 120°C to 60 °C in
Cooler E-103 By water cooler with mass flow rate 46172.77 kg/h and heat
transfer from gas in tube side to water in shell side is Q = -3242.23 Kw to cooled
stream.
The energy balance on Cooler E-103 in table 4.9
Table 4.9: the energy balance on Cooler E-103, calculation and results
Stream
items Units 8 8A W.C2-IN W.C2-Out
39
Temperature C 120.00 60.00 20.00 80.00
Pressure bar 6.33 5.83 5.00 4.70
Mass Flows kg/h 17535.40 17535.40 46172.77 46172.77
Mass Enthalpy change kJ/h -11672039.56 11671714.76
10) Energy balance on the Separator V-100

The feed stream (8) at 60 °C and 5.83 bar.
The product stream (9 and 13) at 59.77°C and 5.77 bar
Energy balance
Enthalpy Inlet = Enthalpy outlet
The energy balance on the Separator V-100 in table 4.10
Table 4.10: the energy balance on the Separator V-100, calculation and results
Stream Feed Product
items Units 8A 13 9
Temperature C 60.00 59.77 59.77
Mass Flows kg/h 17535.40 9146.00 8389.40
Mass Enthalpy kJ/kg -5623.67 -7421.14 -3664.09
Change Enthalpy KJ/h -98613267.52 -98613267.52
11) Energy balance on the absorption Column T-100

The Solvent feed stream (10) at 40.00°C and 5.77 bar and gas feed stream 9 at
59.77°C and 5.77
40
The gas product stream (11) in top product of absorber at 40.04°C and 5.70 bar,
the absorber bottom product is solvent with components its removal from gas
stream (12) at 69.48 °C and 5.50 bar
Energy balance
Inlet = outlet
The energy balance on the absorption Column T-100 in table 4.11
Table 4.11: the energy balance on the absorption Column T-100, calculation and
results
Stream Feed Product
items Units 10 9 11 12
Temperature C 40.00 59.77 40.04 69.48
Pressure bar 5.77 5.77 5.70 5.50
Mass Flows kg/h 36030 8389 659 43760.84
Mass Enthalpy kcal/kg -3765 -876 -292 -3263
Enthalpy kJ/h -598245138 -598245100
Enthalpy KW -166179.21 -166179.19

The stream (13) heated from 59.77°C to 130.00°C in heater E-104
By MP steam with mass flow rate 4449.51 Kg /h heat Q = -2950.84Kw.
The energy balance of on heater E-104in table 4.12
Table 4.12: the energy balance on heater E-104,calculation and results
41
Stream
items Units MPS-in MPS-out 13 14
Temperature C 250.00 130.00 59.77 130.00
Pressure bar 15.00 14.50 5.77 5.47
Mass Flows kg/h 4449.51 4449.51 9146.03 9146.03
Enthalpy change kJ/h -10623016.81 10623016.81
13) Energy balance on Mixer -102

The feed of mixer are streams (12 and 14)
The outlet is stream (15)
inlet = outlet
The energy balance on Mixer -102 in table 4.13
Table 4.13: the energy balance on Mixer -102, calculation and results
Stream Feed Product
items Units 12.00 14.00 15.00
Temperature C 69.48 130.00 108.89
Mass Flows kg/h 43760.84 9146.03 52906.87
kcal/
Mass Enthalpy -3263.00 -1496.09 -2957.56
kg
Enthalpy kJ/h -654691494.21 -654691494.21
Enthalpy Kw -181858.75 -181858.75
14) Energy balance on the Distillation columnT-101
42
The feed stream (15) at 108.89 °C and 5.47 bar
The top product stream (16) is acetaldehyde with purity (99.95%wt.) at 72.66°C
and 5.40 bar and bottom product stream (19) is mixture of waste water and
unreacted ethanol at 151.02 °C and 5.47 bar and sent to Distillation Column T-
102 to recovery of ethanol.
Energy balance overall
Enthalpy for input stream with re-boiler duty = -181858.75 Kw. + 7672.253788Kw
= -174186.5 Kw
Enthalpy for output stream with condenser duty = -178992.23 Kw +
4805.693431Kw
= -174186.5 Kw
The total energy input = total energy output.
The energy balance on the Distillation Column T-101 in table 4.14
Table 4.14: the energy balance on the Distillation Column T-101, calculation and
results
Stream Feed Product
items Units 15.00 16.00 17.00
Temperature C 108.89 72.66 151.02
Mass Flows kg/h 52906.87 13027.79 39879.08
Enthalpy kJ/h -654691494.21 -644372011.33
Enthalpy Kw -181858.75 -178992.23
Change Enthalpy ΔH kJ/h 2866.52
Condenser Duty 4134917.87 kcal/h 4805.693431 kw
Re-boiler Duty 6601365.592 kcal/h 7672.253788 kw
15) Distillation Column T-101 Condenser andRe-boiler
43
The condenser and re-boiler specifications and Heat duty in table 4.15
Table 4.15: the energy balance on the Distillation Column T-101 Condenser and
Re-boiler, calculation and results
Condenser T-101 Re-boiler T-101
Type Total reflux Units Type Regular Units
Temperature 72.66 °C Temperature 151.02 °C
Pressure 5.40 bar Pressure 5.47 bar
4134917.8
Duty kJ/h Duty 6601365.59 kJ/h
7
kgmol/
Reflux Flowrate 740.37 Outlet Flowrate 2168.86 kgmol/h
h
16) Energy balance on the Distillation columnT-102

The feed stream (17A) at 151.05°C and 6.60 bar
The top product stream (18) is Ethanol recovery to recycle with concertation
(85%wt.) at 134.41 °C and 6.50 bar and bottom product stream (19) is waste
water with concertation (99.92%wt.) at 161.90 °C and 6.50 bar and sent to waste
water plant.
Energy balance overall
Enthalpy for input stream with re-boiler duty = -165693.63Kw. + 3902.611405 Kw
= -161791.02 Kw
Enthalpy for output stream with condenser duty = -164854.15 Kw +3063.1778Kw

= -161790.97 Kw
The total energy input = total energy output.

The energy balance on the Distillation Column T-102 in table 4.16
44
Table 4.16: the energy balance on the Distillation Column T-102, calculation and
results
Stream Feed Product
items Units 17A 18 waste water
Temperature C 151.05 134.41 161.90
Mass Flows kg/h 39879.08 1479.21 38399.87
Enthalpy kJ/h -596497069.15 -593474922.49
Enthalpy Kw -165693.63 -164854.15
Change Enthalpy ΔH kJ/h 839.49
Condenser Duty 2635621.47 kcal/h 3063.177847 kw
Re-boiler Duty 3357887.442 kcal/h 3902.611405 kw
17) Distillation Column T-102 Condenser and Re-boiler

The condenser and re-boiler specifications and Heat duty in table 4.17
Condenser T-102 Re-boiler T-102
Type Total reflux Units Type Regular Units
Temperature 134.41 °C Temperature 161.90 °C
Pressure 6.50 bar Pressure 6.50 bar
Duty 2635594.66 kJ/h Duty 3357877.01 kJ/h
kgmole/ kgmole/
Reflux Flowrate 316.16 Outlet Flowrate 2130.56
h h
45
18) Energy balance on the Pump P-101
The feed of pump p-101 is Distillation Column T-101 bottom product stream (17)
at 151.02 and 5.47 bar to pumped to 6.6 bar is required in Distillation Column T-
102 to higher efficiency of column separation.
The fluid is pumped to 6.6 bar and power required W = 2.81 Kw at pump
efficiency 75%
Table 4.18: the energy balance on the Pump P-101, calculation and results
Stream Feed Product
items Units 17 17A
Mass Enthalpy -3575.00 -3574.96
Std. Ideal Liq. Vol Flow cum/h 40.30 40.30
Mass Flows kg/h 39879.08 39879.08
Mass Enthalpy change kJ/kg 0.168
power required W =ΔH*mass KW 1.860
pump efficiency 75.00 %
Total power required KW 2.480
19) Summary of energy balance

The summary of Energy balance in table 4.19
46
Table 4.19: The summary of Energy balance
47
CHAPTER FIVE
DESIGN OF ACETALDEHYDE PLANT
1. Design of Ethanol dehydration reactor
The reactor used in the process is a fixed bed of plug flow reactor.
Performance equation for the reactor:
The performance equation for the fixed bed plug flow reactor is:
XA
W d Xa
=∫
F Ao 0 −r A
Where W is the weight of the catalyst. F Ao is the flow rate of the Ethanol .−r A is
the rate of the reaction. The weight of the catalyst found in this performance
equation.
Since the rate equation of reaction is
−r E=K C E [16]
In the form of conversion, the rate equation becomes
−r A =K C Ao
( 1− X A
1+∈ A X A )
Where
K= K o exp [ ]
−E a
RT
ℜ=K o exp [ ]
−Ea
RT
CE
Kmol
Kg. catalyst . s
With Ea = 55 KJ/mol.
Ko = 6x106 (L/h. g.cat.). = 1666.67 m3/kg.s [17]
48
CE has units of Kmol/m3.gas
εA = (number of moles if completely reacted – number of moles initially)/ number

of moles
initially= (634.47- 468.65)/ 468.65 ) = 0.353819154
R =8.31447*10-3 kj/k.mol., CE = 0.033378kmol/m3 at conversion Xa= 51.88%
K = 0.040788531 m3/Kg.h
By putting the values of conversion from 0 to 1 in the rate equation we obtain the
values of−r A . From this, we find the values of 1/ −r A . Plot the graph between Xa
and 1/−r A , the weight of the catalyst can be calculated. In Table 5.1 of X A , −r A
and 1/−r A and figure 5.1
From the rate equation:
Table 5.1: The reaction conversation with reaction rate results.
Xa −r A 1/−r A
0.050 0.00458 218.45

0.100 0.00426 234.60
0.150 0.00396 252.64
0.200 0.00366 272.94
0.250 0.00338 295.95
0.300 0.00310 322.24
0.350 0.00284 352.58
0.400 0.00258 387.98
0.450 0.00233 429.81
0.500 0.00208 480.00
0.550 0.00185 541.35
0.600 0.00162 618.04
49
700.00
1/-ra V.S Xa
600.00
500.00
400.00
1/-ra
300.00
200.00
100.00
0.00
0.000 0.050 0.100 0.150 0.200 0.250 0.300 0.350 0.400 0.450 0.500 0.550 0.600 0.650
Conversion Xa
XA
Figure 5.1: the graph between Xa and 1/-rA

From figure(5.1), the area under the curve = 147.6
So
XA
dX
∫ −r A =147.6
0 A
1.1. Weight of catalyst
Weight of catalyst = W = F Ao× 147.6 = 319.64× 147.6= 47178.86 kg
1.2. Volume of catalyst
Kg
Density of copper particles with SiO 2= ρ=3596.5
m3
W 47178.86 3
Volumeof catalyst bed =V cat = = =13.12 m
ρ 3596.5
From the gas feed flow rate Vo = 2658.695189 m3/h
50
the concentration of Ethanol E CAo = No/Vo = C Ao=¿ 0.1202 kmol /m3
1.3. Space-time
The time needed to treat the one reactor volume is called the space-time.
W C Ao 47178.86∗0.1202 kg . hr
τ= = =17.74
F Ao 319.64 m3
Catalyst particles size
The following shapes of catalyst were frequently used in applications:
 20-100 µm diameter spheres for fluidized-bed reactors.

 0.3-0.7 mm diameter spheres for fixed-bed reactors.
 0.3-1.3 cm diameter cylinders with a length-to-diameter ratio of 3-4.
 Up to 2.5 cm diameter hollow cylinders or rings.
The void fractions for the spherical particles are between 0.3 to 0.45
The diameter of the copper particles selected (from the literature) = 5 mm with
the void fractions (Porosity = φ) of 0.45
1.4. Volume of reactor
V cat
Volume of reactor =V r =
1−φ
13.12 3
Volume of reactor =V r = =23.855 m
1−0.45
1.5. Number of tubes
The preferred lengths of the tubes (according to the TEMA standard) should be is
6ft, 8ft, 12ft, 16ft, 20ft and 24ft.
So Length of tube selected = 28 ft = 8.534 m
To calculate tube diameter
51
As we know that to prevent deviation from plug flow assumption
Dt
>15
Dp
Where Dt =diameter of tube ∧D p=diameter of particle
Assuming the Diameter of the tube = 300 mm = 12 “inches
Dt 300
= =60 >15
Dp 5
π 2 π 2 3
Volume of one tube= D L= ( 0.300 ) ×8.534=0.6033 m
4 4
Total volume 23.855

Number of tubes= = =39.54=40 tubes
Volume of one tube 0.6033
1.6. Height of reactor (Shell)
The allowance of the reactor height is 20% - 50% of the shell height.
For our system, assuming the allowance for shell is 20% of the tube height.
So
Shell height=8.534 +0.20 ( 8.3534 ) =10.24 m
1.7. Diameter of reactor
Diameter of the shell calculated by using the Harvey equation. Harvey equation
is:
NT =
[ ( D −K ) ]−P ( D −K ) ( nK
s 1
2
t s 1 1 + K 4)
2
1.23 ( Pt )
Where N T =Number of tubes=40
Ds =Diameter of shell=?
52
Tube out diameter = 12.75 inches = 323.85 mm
PT =Pitchof tube=1.25 × Tube diameter=404.8 mm = 15.938 inch
The tubes used in triangular form. For triangular form
K 1=1.08 , K 2=−0.9 , K 3 =0.69 , K 4=−0.8
n=Number of passes=1
By putting all these values in the Harvey and solving, we have
Ds =Diameter of shell=122 inch=10.17 ft=3.0988 m
1.8. Verification of the assumptions
All the values assumed can be verified from the length to diameter ratio of the
given reactor and the pressure drop calculations. If the value of length to
diameter ratio and pressure drop lies within the limit of the fixed bed plug flow
reactor then the design is accepted, otherwise we have to perform the
calculations again with the different assumptions.
1.9. Length to diameter ratio
For the plug flow reactor, the length to diameter ratio lies between 3-5.
For the desired reactor
Length = 10.24 m
Diameter = 3.0988 m
10.24
Length to diameter ratio for desired reactor = = 3.304
3.0988
For the desired reactor the length to diameter ratio is 3.304 lies between the
allowable limit. So the design is satisfactory.
1.10. Pressure drop calculation
53
For the fixed bed reactor to operate economically the pressure drop along the
length of the reactor should be less than the 10% of the operating pressure.
The pressure drop along the length of the packed bed calculated by using the
Ergun equation. The Ergun equation is:
∆P −G 1−ɸ 150 ( 1−ɸ ) µ

= ( )[ +1.75G]
ΔL ρ. gc . Dp ɸ 3 Dp
Where
∆ P=Pressure drop along thelength of reactor =? pa
L=Length of reactor=10.24 m
kg
μ=Viscosity of the gasseous feed=1.4477 CP=1.4477 x 10−3
m.s
π 3.142∗(0.300)2
Area Ac = ∗D2= =¿ 0.0707m2
4 4
Mass flow mo = 17535.37 kg /hr =4.871 kg/s
m°
G=Mass velocity= = 4.871 /(0.0707 X40)= 1.722 kg/m2.s
Ac . Nt
ρ=Feed density =6.595 Kg /m 3
D=Diameter of the particle=5 mm=0.005 m
∈=φ= porosity=0.45
gc=conversion factor=1∈SI unit .
By putting all the values in the Ergun equation:
∆ P=74359 Pa=0.74359 ¯¿
The operating pressure is 8.4 bars.
The pressure drop along the length of the reactor is less than the 10% of the
operating pressure. So the design is accepted.
54
1.11. Volume of tubes
In plug flow reactor where the reacting fluid is inside the tubes, the volume of
tubes should be greater than the volume of the reactor. So
In the desired reactor
Number of tubes=40
Length of tube=10.24 m
Diameter of tube=300 mm
π 2 π 2 3
Volume of one tube= D L= ( 0.300 ) ×10.24=0.7239 m
4 4
3
Total volume of tubes=28.956 m
This is greater than the reactor volume. So all the conditions are satisfied and the
design is accepted.
1.12. Mechanical design of the reactor

1.12.1. The thickness of the reactor:
An estimate of the thickness of the shell is obtained from the diameter of the
shell. The wall thickness of any vessel should not be less than the values given
below; the values include a corrosion allowance of 2 mm in table 5.2:
55
Table 5.2: The wall thickness of vessels with a corrosion allowance of 2 mm
Vessel Diameter (m) Minimum thickness (mm)
1 5
1-2 7
2-2.5 9
2.5-3 10
3-3.5 12
Since the diameter of the vessel is 3.0988m, so from the above table the
thickness of the shell is 12 mm. Thickness of the reactor shell = 12 mm
1.12.2. Head selection and design
Heads of various shapes close the ends of a cylindrical vessel. The principal
types used are:
1. Flat plates and formed flat heads

2. Hemispherical head
3. Ellipsoidal head
4. Tori spherical head
Heads of various shapes close the ends of a cylindrical vessel in table 5.3
56
Table 5.3: Heads of various shapes close the ends of a cylindrical vessel
Flat head Tori spherical head Ellipsoidal head Hemispherical
head
Applicable to low Used up to the operating Above 15 bars Used for very high
pressure pressure of 15 bar ellipsoidal head is pressures
used
Cheapest from all Above 10 bars their cost Economical within Capital cost is high
types should be compared with pressure limits
that of an equivalent
ellipsoidal head
From table 5.3, So the right choice of head is Tori spherical head with working
pressure up to 15 bar. Thickness of head calculated by:
Pi R C C S
e=
2 Jf + Pi ( C s−0.2 )
Where
e=Thickness of shell=?
C S=
1
4 ( √ )
R
3+ C = 1.771
RK
Rc =Crown radius=Diameter of shell=3.0988 m
Rk =Knuckle radius=0.06 R C = 0.1859 m
J=1( for no joints ∈the head )
f =Stress factor=80 ( for carbon steel )
57
So by putting the values of all the variables the value of the thickness of head is:
e=14 mm
1.12.3. Vessel Supports:
The method used to support a vessel will depend on the size, shape, and weight
of the vessel; the design temperature and pressure, and the vessel location and
arrangement.
Types of supports:
 Saddle support (for horizontal vessels)

 Brackets support (for vertical vessels)
 Skirt support (for vertical vessels, particularly where the length is high and
the effect of wind is prominent) For the desired reactor “Bracket supports”
are used.
Figure 5.2: Bracket
58
Table 5.4: PFR Reactor Specification Sheet
Equipment Reactor
Type of reactor Multi-tubular fixed bed reactor
Operating temperature 350 °C
Operating pressure 8.4 bar
Volume of reactor 23.855m3
Volume of catalyst 13.12m3
Weight of catalyst 47178.86 Kg
Number of tubes 40
Shell height 10.24 m
Diameter of shell 3.0988m
Thickness of shell 12 mm
Head type Tori spherical head
Support type Bracket support
59
2. Distillation column design T-101
Distillation Column Design

Consider a single distillation column as shown in below . Short-cut methods have
been developed that allow you to see the splits that can be achieved at different
pressures,with different reflux ratios, and with a different number of stages. It is
often useful to do a short-cut distillation calculation first, before doing the more
rigorous plate-to-plate calculations, because the preliminary calculations give you
an idea of what is reasonable.
The methods are based on the relative volatility of the chemicals and
require you to identify two components that will be essentially separated (to the
extent you specify). If you line up all the components in the order of their boiling
points and draw a line between two of them, the more volatile component is
called the light key and the less volatile component is called the heavy key.
For separation of aced aldehyde from water and unreacted methanol, we choose
the distillation column in the process shown in below Fig. In Aspen hysys you use
the module for the shortcut method Distillation Column; we also use chemical
components and UNIQUAC-Ideal Thermodynamics as the physical property
method, because it is a good one foralcohols and aldehydes with water .The feed
of column is 50143.979 Kg/h from Acetaldehyde as mixed with water and ethanol
unreactedAcetaldehyde with water and ethanol unreacted all composition its
clear in mass balance Table, at 5.47 bar and 108.89 °C. The column operates at
5.47 bar with a reflux ratio of 2.5 (a wild guess initially, confirmed because the
column worked). Remember, the minimum number of stages goes together with
infinite reflux, so if your column doesn’t work, increase the reflux ratio.
We calculated the material and energy balance of the distillation column
(T-101) by Aspen hysys V.11, and summary results are in the below table.
60
Figure 5.3: Distillation Column (T-101)
Table 5.5A: distillation column design summary results
Column internals summary Condenser Re-boiler
Number Of Stages 8 Type Total reflux Type Regular
Temperature
Total Height [m] 4.8768 (°C) 72.6585448 Temperature(°C) 151.0241074
Total Head Loss 865.887844 Pressure
[mm] 8 (bar) 5.4 Pressure (bar) 5.47
Total Pressure Drop 68.8402922 4134917.86
[mbar] 2 Duty (kcal/hr) 6 Duty (kcal/hr) 6601365.592
Number Of
Sections 2 Reflux
Number Of Flowrate 740.372193 Reflux Flowrate
Diameters 2 Kgmol/hr) 3 Kgmol/hr) 2168.863695
61
Table 5.5B: distillation column design summary results
Distillation column design T-101
Section 1 Section 2
Section Starting Stage 1 Main Tower Section Starting Stage 5 Main Tower
Section Ending Stage 4 Main Tower Section Ending Stage 8 Main Tower
Tray Type Sieve Tray Type Sieve
Number Of Passes 1 Number Of Passes 1
Tray Spacing [m] 0.6096 Tray Spacing [m] 0.6096
Section Diameter [m] 1.634933734 Section Diameter [m] 1.294942892
Section Height [m] 2.4384 Section Height [m] 2.4384
Section Pressure Drop [mbar] 31.01152741 Section Pressure Drop [mbar] 37.82876481
Section Head Loss [mm] 427.2700777 Section Head Loss [mm] 438.6177671
section 1 section 2
Tray Type Sieve Tray Type Sieve
Diameter [m] 1.634933734 Diameter [m] 1.294942892
Tray Spacing [m] 0.6096 Tray Spacing [m] 0.6096
Number Of Passes 1 Number Of Passes 1
Hole Diameter [mm] 12.7 Hole Diameter [mm] 12.7
Hole Area to Active Area 0.1 Hole Area to Active Area 0.1
Deck Gauge Thickness 10 Gauge Deck Gauge Thickness 10 Gauge
Deck Gauge Thickness Value
3.4036 Deck Gauge Thickness Value [mm] 3.4036
[mm]
Cross-Sectional Area [m2] 2.10E+00 Cross-Sectional Area [m2] 1.32E+00
Active Area [m2] 1.68E+00 Active Area [m2] 1.02E+00
Net Area [m2] 1.89E+00 Net Area [m2] 1.17E+00
Down comer geometry Down comer geometry
Down comer Clearance (mm) 38.1 Down comer Clearance (mm) 38.1
Down comer Width Top (mm) 255.8272144 Down comer Width Top (mm) 217.9863573
Down comer Width Bottom
255.8272144 Down comer Width Bottom (mm) 217.9863573
(mm)
Down comer Area Top (m2) 2.10E-01 Down comer Area Top (m2) 1.46E-01
Down comer Area Bottom (m2) 2.10E-01 Down comer Area Bottom (m2) 1.46E-01
Weir geometry Weir geometry
Weir Height (mm) 50.8 Weir Height (mm) 50.8
Weir Length (m) 1.187961244 Weir Length (m) 0.969044544
62
Table 5.5C: distillation column design summary results
Vessel Re-boiler Condenser
Diameter [m] 1.192933639 1.192933639
Length [m] 1.789400458 1.789400458
Volume [m3] 2 2
Orientation Horizontal Horizontal
3. Heat exchanger design.
Shell and tube (E-103) design by Aspen Exchanger Design and Rating Shell &
Tube V11 and summary results are in the below table,
Table 5.6: Shell and tube (E-103) design and summary results
Heat exchanger Heater E-103

Thermal Load (Kcal/hr) operating 2845830.3414 tube Outer Diameter (Do is,m) 0.0191
Thermal Load (kW) operating 3307.4873 tube thickness (m) 0.0021
Thermal Load (kW) with add 20% for

3968.9847 tube Inner Diameter (DI, m) 0.0148
safety design
Area (m2) 126.7000 cooler (Utility) Fluid Type water cooler
Heat transfer coefficient overall (kJ/C-h) 417965.5360 Cooler (Utility) Fluid Amount kg/h) 39633.2211
Material Carbon steel pressure drop tube side( bar) 0.0443
Number of tubes per pass (one pass) 367.0000 pressure drop shell side (bar) 0.2706
tube Length (m) 5.8500 LMTD ( °C) 28.3827
63
Aspen Exchanger Design and Rating Shell & Tube V11
TEMA Sheet, Heat Exchanger Specification Sheet in table 5.7.

Table 5.7: Heat Exchanger Specification Sheet
64
CHAPTER SIX
COST OF ACETALDEHYDE PLANT
PLANT COST ESTIMATIONS
The estimate of the purchase costs of the main equipment required for the
process, together with the other costs to be estimated as a factor of the cost of
the equipment, are often used to estimate the cost of the chemical processing
plant. The accuracy of the estimate will be dependent on whether or not a design
stage has been achieved at the time an estimate is carried out, and if available
data regarding equipment costs are reliable. In the later stages of the project
design, when detailed equipment specifications are available and firm quotations
have been obtained, an accurate estimation of the capital cost of the project can
be made.
ESTIMATION OF TOTAL INVESTMENT
For the evaluation of the total investment in a plant, it is possible to perform many
quick estimations using step-counting methods. The cost of the purchased
equipment is used as the basis of the factorial method of cost estimation and
must be determined as accurately as possible. In particular, it should take
account of the recent prices paid for this type of equipment.
THE DIRECT COST ITEMS THAT ARE INCURRED IN THE CONSTRUCTION
OF THE PLANT IN ADDITION TO THE COST OF EQUIPMENT ARE
The installation of equipment, including foundations and repairs to the structure.
A pipe, including insulation and painting. We're looking at electricity, power, and
lights. The instruments, the local, and the control room. Process building and
structures. Ancillary buildings, offices, laboratories, and workshops. Storage, raw
materials, and finished product. The costs related to utility services, for example,
the cost of steam, water, air, etc. Preparation of the site and preparation of the
site.
65
WHERE INDIRECT COST INCLUDES
The design and engineering expenditure covers both the cost of designing a
plant as well as its installation; purchasing, procurement, and construction
supervision. Contractors' fees, which can range between 5 % and 10% of the
direct cost, are added to the overall capacity costs if a contractor is employed.
Contingency allowance, this is a provision added to the capital expenditure
estimates that would be used for Unprecedented events, usually ranging from
5% to 10% of direct costs.
ESTIMATION OF FIXED CAPITAL INVESTMENT

The fixed capital investment is the total amount of money that is invested in a
fixed asset such as land, plant, buildings, and equipment which are bought only
once at the beginning of the project and remain with a decreasing value
(depreciation) until the plant life goes to the end. Based on Turton’s method., a
plant can normally live up to 20 years. For the purpose of calculating capital
costs, the purchased costs for the main equipment in the plant (CP), the material
of construction factor (FM), the pressure factor (FP), the temperature factor (FT),
and the bare module factor (FBM) must be evaluated. In this literature, there are
no special considerations to be made on temperature factors (FT) and pressure
factor (FP) which is approximately equal to 1. Because no specific considerations
have been taken with regard to these two cases Operating conditions indicate
the effect of changing temperatures and pressures on them. The whole process
is small and cannot be taken into account for costs. [20]
Note: All equations used are from reference[20]
After calculating the purchased costs for the main equipment (CP), the bare
module cost is calculated by:
CBM = CP  FBM
The purchased costs for the main equipment (CP)
66
The bare module factor (FBM)
The total bare module (CTM) cost is obtained by:
CTM = CBM + 0.18 CBM
Finally, the grassroots cost (CGR) is obtained by:

CGR = CTM + 0.5 CBM
Where CBM is the base cost at normal T, P & CS as the MOC (Material of
Construction).
Cost of Manufacturing
The manufacturing costs are needed to convert the raw materials to products.
The cost of manufacturing is classified into three types of costs; direct costs,
fixed manufacturing costs, and general manufacturing expenses.
DIRECT COSTS
Costs that vary with the production rate of the plant or might slightly depend on
the production rate suchas maintenance:
1. Cost of raw material CRM
2. Cost of waste treatment CWT
3. Cost of utilities CUT
4. Cost of operating labor COL
5. Cost of direct supervisory = 0.18 COL
6. Cost of maintenance = 0.06 FCI
7. Cost of operating supplies = 0.009 FCI
8. Cost of laboratory charges = 0.15 COL
9. Cost of patents and royalties = 0.03 COM
The Total Direct manufacturing cost (TDMC) is obtained by:
TDMC =CRM + CWT + CUT + 1.33 COL + 0.069 FCI + 0.03 COM
67
FIXED MANUFACTURING COST
Independent of changes in production rate and are charged at a constant rate
even when the plant is notoperating:
1. Plant overhead costs = 0.708 COL + 0.036 FCI
2. Local taxes insurance = 0.032 FCI
3. Depreciation = 0.1 FCI
The Total fixed manufacturing cost (TFMC) is obtained by:
TFMC =0.708 COL + 0.068 FCI +0.1 FCI
General Manufacturing Expenses

The overhead burden that is necessary to carry out business functions which
seldom vary with the productionrate.
1. Administration = 0.177 COL+ 0.009 FCI
2. Distribution and selling costs = 0.11 COM
3. Research and development = 0.05 COM
The general manufacturing expenses are obtained by:
General manufacturing expenses =0.177 COL + 0.009 FCI +0.16 COM
THE TOTAL COST OF MANUFACTURE
The total cost of manufacturing (COM) =

Direct manufacturing cost + fixed manufacturing cost + general manufacturing
expense
THE PLANT PRODUCTION CAPACITY = 300TPD.

We assume that the working hours per day are 24 hours, and the number of
working days during the year is 330 days.
The Capital Cost obtained by Aspen Hysys V.11 after input feed stream and
product stream costin table 6.1.
Table 6.1: feed stream and product stream price.

ethanol price 1300 $/m3
68
hydrogen price 6740 $/ton
acetaldehyde price 1430 $/ton
Pure water feed price 1030 $/m3
Table 6.2: Summary of Capital Cost obtained by Aspen Hysys V.11
Summary
Total Capital Cost [USD] 2935960
Total Operating Cost [USD/Year] 233925000
Total Raw Materials Cost [USD/Year] 215673000
Total Product Sales [USD/Year] 199003000
Total Utilities Cost [USD/Year] 79864.8
Desired Rate of Return [Percent/'Year] 20
Equipment Cost [USD] 1464600
Total Installed Cost [USD] 4144300
69
REFERENCES
1- Https://Www.Geeksforgeeks.Org/Acetaldehyde-Formula-Structure-Properties-
Uses-Sample-Questions.
2- Https://Www.Dcceew.Gov.Au/Environment/Protection/Npi/Substances/Fact-
Sheets/Acetaldehyde.
3- Ullmann’s, A Ullmann's Encyclopedia Of Industrial Organic Chemistry Edition
7page No.90
4- Ullmann’s, A Ullmann's Encyclopedia Of Industrial Organic
Chemistry Edition7, Page No.8
5- Https://Www.Verifiedmarketresearch.Com/Product/Acetaldehyde-Market
6- James M.Church And Hanamant K.Joshi-Chemical Engineering Department,
Columbia University, New York, N.Y. Acetaldehyde By Dehydrogenation Of Ethyl
Alcohol, Research Article.
7- Jiang-Jen Lin And John F. Knifton, Acetaldehyde Production From Synthesis Gas,
Publication Us4525281 A, Jun 25, 1985.
8- Graham A. Renberg, Production Of Acetaldehyde, Publication Us 3291839 A,
Dec 13, 1966.
9- Gerald C. Tustin, Leslie S. Depew, Nick A. Collins, Hydrogenating Acetic Acid
Using Iron Oxide Catalyst That Contains Palladium, Absorbing Acetaldehyde
From The Gaseous Product Using Solvent Containing Acetic Acid, Publication Us
6121498 A, Sep 19, 2000.
10- The Columbia Electronic Encyclopedia, Columbia University, Wacker Process.
11- Https://Richardturton.Faculty.Wvu.Edu/Files/D/C3e16aec-58ec-41c6-95eb-
42764d491197/Acetaldehyde.Pdf
12- Petr Chládek. Catalytic Separation Of Pure Hydrogen From Synthesis Gas By An
Ethanol Dehydrogenation /Acetaldehyde Hydrogenation Loop. Waterloo, Ontario,
Canada, 2007.
70
13- Https://Richardturton.Faculty.Wvu.Edu/Files/D/C3e16aec-58ec-41c6-95eb-
42764d491197/Acetaldehyde.Pdf
14- Petr Chládek. Catalytic Separation Of Pure Hydrogen From Synthesis Gas By An
Ethanol Dehydrogenation /Acetaldehyde Hydrogenation Loop. Waterloo, Ontario,
Canada, 2007.
15- G. Towler R. Sinnott.Chemical Engineering Design Principles,
Practice, And Economics Of Plant And Process Design. Elsevier (2008).
Isbn 13: 978-0-7506- 8423-1
16- A.Peloso, M.Moresi, C.Mustachi, B.Soracco, Kinetics Of The Dehydrogenation Of

Ethanol To Acetaldehyde On Unsupported Catalysts ,Institute Of Science And
Technology , Genova,
17- , Yau-Jen Tu,Chiuping Li And Yu-Wen Chen, Effects Of Chromium Promoter On
Copper Catalyst In Ethanol Dehydrogenation,Department Of Chemical
Engineering, National Central University, Chung Li 32054, Taiwan, J. Chem.
Tech. Biotechnol, 1994, 59, 141-147
18- Https://Www.Mt.Com/Sg/En/Home/Applications/L1_Autochem_Applications/
Process-Safety.Html
19- Https://Www.Deskera.Com/Blog/Impact-Of-Chemical-Manufacturing-On-The-
Environment
20- R. Turton, R. C. Bailie, W. B. Whiting, J. A. Shaeiwitz, D. Bhattacharyya,
“Analysis, Synthesis, And Design Of Chemical Processes”, (2013), 4th Edition,
Pearson Education, Inc.
71

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PRODUCTION OF ACETALDEHYDE

LIST OF TABLE AND FIGURE...................................................................................................IV

LIST OF SYMBOLS AND ABBREVIATIONS USED............................................................VII

ASPECTS OF THE ENVIRONMENT....................................................................................7

GLOBAL ACETALDEHYDE MARKET OVERVIEW............................................................8

GLOBAL ACETALDEHYDE MARKET: SEGMENTATION ANALYSIS................................9

1. ACETALDEHYDE MARKET, BY PROCESS. ...............................................................10

2. ACETALDEHYDE MARKET, BY DERIVATIVE........................................................10

3. ACETALDEHYDE MARKET, BY APPLICATION.....................................................11

4. ACETALDEHYDE MARKET, BY GEOGRAPHY......................................................12

1. PRODUCTION OF ACETALDEHYDE FROM OXIDATION OF ETHYL ALCOHOL. 13

2. PRODUCTION OF ACETALDEHYDE FROM DEHYDROGENATION OF ETHYL

4. PREPARATION METHOD OF ACETALDEHYDE FROM ACETYLENE .................16

5. PRODUCTION OF ACETALDEHYDE FROM SYNTHESIS GAS............................17

6. FROM ACETIC ACID...............................................................................................17

7. PRODUCTION OF ACETALDEHYDE FROM SATURATED HYDROCARBONS.. .18

DESCRIPTION OF THE PROCESS....................................................................................19

THE INFORMATION REQUIRED IN THE ASPEN HYSYS MODEL:............................20

1) MATERIAL BALANCE ON MIXING OF ETHANOL FEED WITH RECYCLE IN

2) MATERIAL BALANCE ON THE REACTOR PFR-100, PFR-101 AND PFR-102......25

3) MATERIAL BALANCE ON THE SEPARATOR V-100..............................................28

5) MATERIAL BALANCE ON THE MIXER-102............................................................30

6) MATERIAL BALANCE ON THE DISTILLATION COLUMN T-101...........................31

7) MATERIAL BALANCE ON THE DISTILLATION COLUMN T-102...........................32

8) SUMMARY OF MATERIAL BALANCE....................................................................33

1) ENERGY BALANCE ON MIXER -100.....................................................................34

2) ENERGY BALANCE ON FEED PUMP P-100..........................................................35

3) ENERGY BALANCE ON HEATER E-100................................................................35

4) ENERGY BALANCE ON HEATER E-101................................................................36

5) ENERGY BALANCE ON THE REACTOR PFR-100................................................37

6) ENERGY BALANCE ON THE REACTOR PFR-100................................................37

8) ENERGY BALANCE ON COOLER E-102...............................................................39

9) ENERGY BALANCE ON COOLER E-103...............................................................39

10) ENERGY BALANCE ON THE SEPARATOR V-100................................................40

11) ENERGY BALANCE ON THE ABSORPTION COLUMN T-100...............................41

12) ENERGY BALANCE ON HEATER E-104................................................................41

13) ENERGY BALANCE ON MIXER -102.....................................................................42

14) ENERGY BALANCE ON THE DISTILLATION COLUMNT-101...............................43

15) DISTILLATION COLUMN T-101 CONDENSER AND RE-BOILER..........................44

16) ENERGY BALANCE ON THE DISTILLATION COLUMNT-102...............................44

17) DISTILLATION COLUMN T-102 CONDENSER AND RE-BOILER..........................45

18) ENERGY BALANCE ON THE PUMP P-101............................................................46

19) SUMMARY OF ENERGY BALANCE.......................................................................46

1. DESIGN OF ETHANOL DEHYDRATION REACTOR............................................47

2. DISTILLATION COLUMN DESIGN T-101...............................................................59

3. HEAT EXCHANGER DESIGN...................................................................................62

List Of Table And Figure

Figure 1.1:Structure Of Acetaldehyde........................................................................2

Figure1.2: Derivatives Of Acetaldehyde.....................................................................7

Figure 2.1: The Global Acetaldehyde Market By Process (Usd Million)..................10

Figure2.3: The Global Acetaldehyde Market By Geography (Usd Million)..............12

Figure 2.4: Process Flow Diagram Of Acetaldehyde Production Plant...................21

Figure 3.1: Ethanol Feed And Ethanol Recycle Mixer -100.....................................24

Table 3.1: The Material Balance Of Mixer-100, Calculation And Result..................25

Figure 3.2: Reactor Pfr-100, Pfr-101 And Pfr-102...................................................26

Table 3.4: The Material Balance On Absorber Column T-100.................................29

Table 3.5: The Material Balance On Mixer-102, Calculation And Results...............30

Table 3.7: The Material Balance On Distillation Column T-102...............................32

Table 3.8: The Summary Of Material Balance.........................................................33