CHAPTER # 01

Introduction
1.1 Introduction
Ethanal, CH3CHO is an important intermediate in industrial organic synthesis. Acetic acid,
acetic anhydride, n-butanol, and 2-ethylhexanol are the major products derived from
acetaldehyde. Smaller amounts of acetaldehyde are also consumed in the manufacture of
pentaerythritol, trimethylolpropane, pyridines, peracetic acid, crotonaldehyde, chloral, 1,3-
butylene glycol, and lactic acid. It has structural formula:

Figure 1.1: Structure of Ethanal

1.2 History
Ethanal is one of the oldest known aldehydes and was first made in 1774 by Swedish
chemist Carl Wilhelm Scheele by the action of manganese dioxide and sulfuric acid on
ethanol. Its structure was not completely understood until 60 years later, when Justus von
Liebig determined the constitution of ethanal, described its preparation from ethanol, and
gave the name of aldehydes to the chemical group. The formation of acetaldehyde by the
addition of water to acetylene was observed by Kutscherow in 1881.
Ethanal was first used extensively during World War I as an intermediate for making
acetone from acetic acid. Ethanal (acetaldehyde) is the name of the shortest carbon chain
aldehyde. It has a central carbon atom that has a double bond to an oxygen atom (the
carbonyl group), a single bond to a hydrogen atom, and a single bond to another carbon
atom connected to three hydrogen atoms (methyl group). Its chemical formula is written as
CH3CHO.
1.3 Natural occurrence
Ethanal is a simple, naturally occurring, organic chemical present in many ripe fruits,
apples, grapes, and citrus fruits (up to 230 ppm). It is produced during the fermentation of
sugar to alcohol, and is a natural constituent of butter, olives, frozen vegetables, and
cheese. It forms in wine and other alcoholic beverages after exposure to air (up to 140
ppm). It even occurs as an intermediate in the metabolism of sugars in the body and hence
can be found in human blood.
 Ethanal is listed as an approved food additive and is used to enhance citrus flavors, helping
to create natural, fruity tastes and fragrances. As a flavor ingredient, it can be found in ice
creams, sweets, baked goods, chocolates, rum, and wine.
In nature Ethanal is found in oak and tobacco leaves, in the fruity aromas of apple,
raspberry, strawberry, pear and pineapple. It is also found in the distillation waters of orris,
cumin, chenopodium, essential oils of Magnolia grandijlora, rosemary, clary sage, daffodil,
bitter orange, camphor angelica, fennel mustard, whiskey, rose wine and rum.
Ethanal is a natural component of, broccoli, coffee, grapefruit, grapes, lemons, mushrooms,
onions, oranges, peaches, pears, pineapples, raspberries, and strawberries. It has been
detected in the essential oils of alfalfa, rosemary, balm, clary sage, daffodil, bitter orange,
camphor, angelica, fennel, mustard, and peppermint.
Acetaldehyde (systematically ethanal) is an organic chemical compound with the formula
CH3CHO, sometimes abbreviated by chemists as Me-CHO (Me = methyl). It is one of the
most important aldehydes, occurring widely in nature and being produced on a large scale
industrially. Acetaldehyde occurs naturally in coffee and bread and is produced by plants
as part of their normal metabolism. It is also produced by oxidation of ethylene and is
popularly believed to be a cause of hangovers from alcohol consumption through drinking
spirits. Pathways of exposure include air, water, land or groundwater as well as drink and
smoke.

1.4 Physical Properties of Ethanal

Table 1.1: Physical Properties of Ethanal
Properties Ethanal

Chemical Formula C2H4O

Melting point °C -123.5

Boiling point °C 20.2

Density kg/m³ 788

Appearance Colorless liquid

Critical temperature °C 181.5

Critical pressure, atm 63.2

Freezing point °C -123.5

 Flash point, closed cup, °C -38

Ignition temperature in air, °C 165

Heat of vaporization, kJ/mol 25.71

Heat of combustion of liquid at constant
11867.9
pressure, kJ/mol c
Heat of formation at 273 K, kJ/mol c -165.48

Viscosity at 20 °C 0.295

Relative density d t4 = 0.8045 – 0.001325t (t in ◦C)

Refractive index ntD = 1.34240 – 0.0005635t (t in ◦C)

Specific volume of the Vapor at 20.16 °C 0.531m3/kg

Specific volume of the Vapor at 25.0 °C 0.541m3/kg

Surface tension γ at 20 °C 21.2×10−2 mNcm−1

Latent heat of fusion 3246.3 J/mol

Cubic expansion coefficient per K (0-
0.00169
20◦C)
Entropy for gaseous acetaldehyde at 25
265.9 Jmol−1 K−1
°C
Entropy for liquid acetaldehyde at 20.16
172.9 Jmol−1 K−1
°C
First ionization potential 10.5 eV

Entropy of vaporization at 20.16 °C 91.57 Jmol−1 K−1

Dissociation constant at 0 °C 0.7×10−14 mol/L

Thermal conductivity of liquid at 20 °C 0.174 Jm−1 s−1 K−1

Thermal conductivity of vapor at 25 °C 1.09×10−2 Jm−1 s−1 K−1

Table 1.2 Vapor pressure of Ethanal

 Temperature (oC) Vapor Pressure (mm Hg)
-50 19
-20 123
0 330
5 411
10 508
15 622
20 755
20.16 760
30 1069
50 3096
70 3696
100 3607

1.5 Chemical properties

Ethanal is a highly reactive compound showing all the typical aldehyde reactions as well as
those of an alkyl group in which hydrogen atoms are activated by the carbonyl group in the
position. When heated above 420°C acetaldehyde decomposes into methane and carbon
monoxide.
1.5.1 Addition Reaction
With water, acetaldehyde forms an unstable hydrate; isolable solid hydrates are known
only with chlorinated acetaldehydes. Alcohols add to acetaldehyde giving hemiacetals,
which form acetals with additional alcohol in the presence of acids by removal of water.
Diols give cyclic acetals; for example, 2-methyl-1,3-dioxolane is obtained from ethylene
glycol and acetaldehyde, and 2-methyl1,3-dioxane from 1,3-propanediol.
Aqueous sodium bisulfite solution and acetaldehyde give a crystalline adduct from which
acetaldehyde can be liberated. Dry ammonia forms crystalline acetaldehyde ammonia.
Acetaldehyde and hydrocyanic acid react to give lactonitrile(a-hydroxypropionitrile), a
possible intermediate in acrylonitrile production.

1.5.2 Derivatives of Aldol Addition

Two molecules of acetaldehyde combine in the presence of alkaline catalysts or dilute
acids at room temperature or with moderate heating to form acetaldol
CH3CH(OH)CH2CHO. At increased temperatures, water is cleaved easily from this
acetaldol, forming crotonaldehyde. Further condensation under more stringent conditions
to form aldehyde resins (e.g., synthetic shellac) now has no industrial importance.
Urea and acetaldehyde condense in the presence of H2SO4 to form crotonylidenediurea (6-
methyl-4-ureidohexahydropyrimidin-2-one which is used as a long-term nitrogen fertilizer.
Acetaldehyde is also an intermediate in the butadiene synthesis starting from acetylene and
proceeding via acetaldol and its hydrogenation product, 1,3-butanediol. This process was
introduced around 1918 and is still carried out on a commercial scale in some Eastern
European countries.
Acrolein is obtained by aldol condensation of acetaldehyde and formaldehyde and
subsequent water elimination, analogous to the formation of crotonaldehyde. This method
is also without commercial importance today, whereas the production of pentaerythritol
from acetaldehyde and a fourfold amount of formaldehyde in the presence of Ca(OH)2 or
NaOH is very important industrially.
1.5.3 Reaction with Nitrogen Compounds
With primary amines, Schiff bases, CH3CH=NR, are formed. Nitrogen compounds such as
hydroxylamine, hydrazine, phenylhydrazine, and semicarbazide react with acetaldehyde to
give easily crystallizable compounds that are used for the analytical determination and
characterization of aldehydes. Many other aldehydes and ketones can be characterized in
the same way because their analogous derivatives generally have sharp melting points.
The synthesis of pyridine and pyridine derivatives is of increasing importance. 5-Ethyl-2-
methylpyridine is obtained in the presence of fluoride ions by the reaction of aqueous
ammonia with acetaldehyde (or with paraldehyde, which slowly releases the monomer). In
the added presence of formaldehyde or acrolein, mixtures of pyridine and alkylpyridines
formed.
1.5.4 Oxidation
The major part of the acetaldehyde produced commercially is used for manufacturing
acetic acid by oxidation with oxygen or air. Acetaldehyde monoperacetate is formed as an
intermediate and decomposes into peracetic acid and acetaldehyde at elevated temperatures
and in the presence of catalytic amounts of iron or cobalt salts. In the presence of 𝑀𝑛+2
salts, acetic acid is obtained from acetaldehyde monoperacetate, and in the presence of
𝐶𝑜+2 and 𝐶𝑢+2 salts, acetic anhydride can be formed.
 Figure 1.2: Oxidation of Ethanal

1.5.5 Reduction
Acetaldehyde is hydrogenated readily to ethanol. Prior to 1939, that is, before
petrochemically produced ethylene became available in Europe, this reaction was used
industrially to produce ethanol from acetaldehyde and, therefore, from acetylene. Mono-,
di-, and triethylamine can be produced from acetaldehyde, ammonia, and hydrogen in the
presence of a hydrogenation catalyst.
1.5.6 Reaction with Ammonia and Amities
Acetaldehyde readily adds ammonia to form acetaldehyde ammonia. Diethyl amine is
obtained when acetaldehyde is added to a saturated aqueous or alcoholic solution of
ammonia and the mixture is heated to 50-75°C in the presence of a nickel catalyst and
hydrogen at 1.2(12atm) Pyridine and pyridine derivatives are made from paraldehyde and
aqueous ammonia in the presence of a catalyst at elevated temperatures.
1.6 Uses
Acetaldehyde is used in a wide range of industrial applications; it is the most commonly
used raw material in the organic chemical industry. As a raw material, it is used in the
manufacturing of paint binders, plasticizers, and super absorbents that are used in baby
nappies. It is also used in the manufacture of various types of building materials, synthetic
lubricants, fire protection paints, and explosives. In the pharmaceutical industry, it is used
in the production of vitamins, sleeping aids, and sedatives. It is also often used as an
intermediate in the chemical synthesis of acetic acid. Moreover, acetaldehyde chemical is
infused in various types of perfumes and can further be used in decorative cosmetics,
fragrances, shampoos, soaps, and oral care products as well as in household cleaners and
detergents.
The global acetaldehyde market by application has been segmented into chemicals, plastics
& synthetic rubber, food & beverages, paints & coatings, pharmaceutical & cosmetics,
paper & pulp, and others. The acetaldehyde market for the paints & coatings application is
projected to grow at the fastest pace over the forecast period. Acetaldehyde is used as a
binder in paints and coating substances for the modification of gloss and rheology. It is
used as a raw material for the manufacturing of pentaerythritol, which is used in the
synthesis of Alkyd resins, fatty acid resin, and tall oil esters; it is also used as intumescents
in flame retardant paints. It is used in wooden varnished, laminate, linoleum, and cork/pine
flooring. The chemical also finds applications in plastic water-based and matt emulsion
paints used for wood ceilings, and wooden, particle board, plywood, pinewood, and
chipboard furniture. Therefore, the elevating use of acetaldehyde in the paints and coating
application is projected to boost the demand for this compound over the forecast period.
Acetaldehyde plays a vital role in wastewater treatment owing to its disinfectant properties.
Acetaldehyde is used for the treatment of wastewater from various industries and
manufacturing plants. The demand for acetaldehyde from the water treatment application is
gaining momentum due to rising environmental impact, such as degradation of freshwater
bodies and aquatic life by untreated wastewater, increasing population, and concerns about
pollution.
 CHAPTER # 02
Market Analysis and Capacity Selection
2.1 World Wide Statistic
The global acetaldehyde market accounted for US$ 1,329.4 Mn in 2018 and is expected to
grow at a CAGR of 6.7% during the forecast period 2019 - 2027, to account for US$
2,367.0 Mn by 2027.
APAC accounted for the largest share of the global acetaldehyde market. The growth of
the market in this region is primarily attributed to the growing manufacturing industry in
countries such as China, India, Japan, and South Korea. India also offers huge market
potential due to emerging players in the chemicals, plastics and synthetic rubber, food &
beverages, paints and coatings, and pharmaceuticals and cosmetics industries. Moreover, in
the agriculture industry, acetaldehyde is used in the production of methomyl. The chemical
is also used to make acetaldoxime, which is used as an insecticide. The Asia Pacific region
has a well-established agriculture sector, and the demand for insecticides is growing over
the past few years. This factor is projected to propel the demand for acetaldehyde. In the
pharmaceutical industry, acetaldehyde is used in the production of sedatives and
tranquilizers. Therefore, the growth of this industry in India is projected to boost
the acetaldehyde market over the forecast period

Figure 2.1 Demand forecast of Ethanal

The acetaldehyde market in the Asia Pacific region is projected to grow at the highest
CAGR during the forecast period, which can be attributed to the easy availability of raw
materials used for the manufacture of acetaldehyde. The Asia Pacific is a strategic location
for acetaldehyde manufacturers, as an overall slowdown in the global economic scenario
has encouraged many established manufacturers to expand their manufacturing facilities in
this region and, thus, increase their sales. The growth of the Asia Pacific market is
expected to be primarily driven by China, India, and Japan. Key manufacturers of
acetaldehyde are focusing on expanding their bases in the Asia Pacific region to increase
their market shares and enhance profit margins.
In 2019, the world imports of "Ethanal (acetaldehyde)" exceeded $58 million (according to
external trade statistics of 91 countries).
The world's largest importers of this commodity group in 2019:
 France - 25% of the world imports ($15 million)
 Spain - 23% ($13.5 million)
 Germany - 19.4% ($11.3 million)
 Switzerland - 7.38% ($4.32 million)
 Italy - 3.95% ($2.31 million)

Figure 2.2 Major importers of Ethanal

The Acetaldehyde market in the U.S. is estimated at US$387.3 Million in the year 2020.
The country currently accounts for a 27.08% share in the global market.
 China, the world second largest economy, is forecast to reach an estimated market size of
US$439.9 Million in the year 2027 trailing a CAGR of 8.6% through 2027.
Among the other noteworthy geographic markets are Japan and Canada, each forecast to
grow at 2.8% and 4.9% respectively over the 2020-2027 period.
Within Europe, Germany is forecast to grow at approximately 3.4% CAGR while Rest of
European market (as defined in the study) will reach US$439.9 Million by the year 2027.

2.2 Raw Material & Product Price

Raw Material:
Ethylene = 1471.58$/MTON
Product:
Ethanal = 6570$/MTON

2.3 Capacity Selection

Pakistan Import Data

Figure 2.3 Pakistan import data for

Ethanal
The product has CAGR of 21% as per average growth rate of the product and by extra
plotting results for next ten years keeping constant increment growth we will get the
following results

Table 2.1 Extra plotted growth data of Ethanal

 Year Weight (ton/year) Increment in capacity

2019 6629 0.21

2020 8154 0.21

2021 10030 0.21

2022 12337 0.21

2023 15174 0.21

2024 18664 0.21

2025 22957 0.21

2026 28237 0.21

2027 34732 0.21

2028 42721 0.21

Capacity on the basis of average growth rate= 42721 ton/year

=117.04 ton/day
We are contributing 100 MT/DAY of Ethanal.
 CHAPTER # 03
Manufacturing Processes and Process
Selection
3.1 Processes for Ethanal Production

Raw materials that have been used for the production of Ethanal are:

1. Ethanol from fermentation of carbohydrates or from hydration of ethylene

2. Acetylene

3. Ethylene

4. Lower hydrocarbons

5. Carbon monoxide and hydrogen

6. Methanol
The economy of the commercial processes depends essentially upon prices and the
availability of raw materials. In highly industrialized countries maintaining high prices for
ethanol by fiscal measures or where petrochemical ethanol was not available, as in
Germany or Japan before 1939, acetylene was the favored starting material for
acetaldehyde. The acetylene process is still operated in some Eastern European countries
and also by companies where cheap acetylene is available. Petrochemically produced
ethanol, however, was the favored raw material in the other countries, whereas ethanol
made by fermentation was and still is used on a small scale in countries with less chemical
industry.
In Western countries, including Japan, all these processes have now been almost
completely replaced by the direct oxidation process developed in the late 1950s by
Wacker-Chemie and Hoechst. This is because ethylene is available at a lower price than
acetylene. Even the two- stage processes using ethanol from ethylene as starting material
are no longer competitive because of the decreasing importance of acetaldehyde as an
organic intermediate.
Generally, all processes based on acetylene, ethylene, and ethanol are more selective than
the oxidation of saturated hydrocarbons. This is because, in the latter case, other oxidation
products are formed in addition to acetaldehyde. Because of the great expense of
separating the product mixture, such processes are economical only in large units and when
all main and secondary products obtained in the process are utilized.
3.1.1 Production from Ethanol
For the production of Ethanal, ethanol can either be dehydrogenated or oxidized in the
presence of oxygen. Between 1918 and 1939, dehydrogenation took precedence over
oxidation because of the simultaneous production of hydrogen. Later, however, the
catalytic vapor-phase oxidation of ethanol became the preferred process, probably because
of the long catalyst life and the possibility of recovering energy.
Dehydrogenation of Ethanol
In the first work on ethanol dehydrogenation, published in 1886, ethanol was passed
through glass tubes at 260 ◦C.
CH3CH2OH(l) → CH3CHO(l) + H2(g) ΔH = + 82.5 kJ/mol
Improved yields are obtained in the presence of catalysts such as platinum, copper, or
oxides of zinc, nickel, or cobalt. In later patents, zinc and chromium catalysts, oxides of
rare earth metals, and mixtures of copper and chromium oxides have been reported. The
lowest amounts of decomposition products are obtained using copper catalysts. Frequent
regeneration of the catalysts is required, however.
Ethanol vapor is passed at 260 – 290 ◦C over a catalyst consisting of copper sponge or
copper activated with chromium oxide in a tubular reactor. A conversion of 25-50 % per
run is obtained. By washing with alcohol and water, acetaldehyde and ethanol are
separated from the exhaust gas, which is mainly hydrogen. Pure acetaldehyde is obtained
by distillation the ethanol is separated from water and higher-boiling products by
distillation and flows back to the reactor. The final acetaldehyde yield is 90 %. Byproducts
include butyric acid, crotonaldehyde, and ethyl acetate.
Oxidation of Ethanol
Oxidation of ethanol is the oldest and the best laboratory method for preparing
acetaldehyde. In the commercial process, ethanol is oxidized catalytically with oxygen (or
air) in the vapor phase. Copper, silver, and their oxides or alloys are the most frequently
used catalysts.
CH3CH2OH(g) + 1/2O2 (g) → CH3CHO(l) + H2O(l) ΔH = - 242.0 kJ/mol
Ethanol is mixed with air and passed over a silver catalyst at 500 – 650 ◦C (c). The
temperature depends on the ratio of alcohol to air and the flow rate of the gas through the
catalyst. Alcohol conversion varies between 50 and 70 % and the yield is between 97 and
99 % depending on the reaction conditions. Acetaldehyde and unreacted alcohol are
removed from the waste gas by washing with cold alcohol and separated by fractional
distillation after concentration the alcohol returns to the reactor. Heat formed in the
reaction is utilized for steam production using a waste-heat recovery system immediately
after the reaction zone. The waste gas consists mainly of nitrogen, hydrogen, methane,
carbon monoxide and carbon dioxide; it is burned as lean gas with low calorific value in
steam generators. Small amounts of acetic acid are obtained as a by-product.
3.1.2 Production from Acetylene

The most important catalysts for the industrial water addition (hydration) are mercury
compounds:
C2H2(g) + H20(l) CH3CHO(l) ΔH = - 138.2 kJ/mol

This method only succeeds industrially when the polymerization and condensation
products of acetaldehyde formed in the acid medium are eliminated. To achieve this, the
Consortium fur electrochemist Industries in 1912 proposed a process using excess
acetylene at an elevated temperature and removing the acetaldehyde product immediately
from the reaction liquid. At the same time, the heat of reaction is removed by distilling an
appropriate amount of water. Secondary reactions, such as the oxidation of acetaldehyde to
form acetic acid and carbon dioxide, result in reduction of Hg2+ to metallic mercury. In
Western countries, acetaldehyde production from acetylene has now been discontinued.
Wet Oxidation Process (Hoechst)
The wet oxidation process avoided direct handling of the toxic mercury compounds. It was
operated, among others, by Wacker-Chemie until the changeover to ethylene as the starting
material in 1962. In this method, iron (III) sulfate is added to re-oxidize the mercury metal
to the mercury (II) salt, thus ensuring sufficient concentrations of active catalyst. The
acetylene reacts at 90 – 95◦C with the aqueous catalyst solution; between 30 and 50 % of
the injected acetylene reacts in one run. The gas emerging from the reactor is cooled;
mainly water and traces of mercury are separated and returned to the reactor. Acetaldehyde
and water are condensed in additional coolers and the acetaldehyde finally is washed out
with water from the cycle gas which has been cooled to 25 – 30 ◦C. An 8-10% aqueous
acetaldehyde solution is obtained. Nitrogen is introduced with the feed gas while carbon
dioxide is formed as a byproduct; to avoid excessive accumulation, these gases are
removed by withdrawing a small stream of the cycle gas. Iron (II) sulfate is formed in the
reaction and is oxidized in a separate reactor with 30 % nitric acid at 95 ◦C. Pure
acetaldehyde is obtained by fractional distillation of the aqueous solution at about 200 kPa.
Chisso Process
The Chisso process also uses sulfuric acid/mercury sulfate solution as a catalyst. The
acetylene reacts completely with the catalyst solution at 68 – 78 ◦C and a gauge pressure of
140 kPa. A combination of pressure and vacuum process stages at low temperature and
without excess acetylene are used; pure acetaldehyde can be isolated and distilled by
utilizing the heat of the reaction. As in the Hoechst process, the catalyst can be regenerated
with nitric acid. Production of acetaldehyde by this method was discontinued at Chisso
Corp more than a decade ago.
3.1.3 Production via Ethylidene Diacetate
Addition of acetic acid to acetylene in the presence of mercury (II) salts yields ethylidene
diacetate CH3CH(OCOCH3)2, which decomposes into acetaldehyde and acetic anhydride
at 130-145 ◦C in the presence of acid catalysts (ZnCl2). This process was developed by the
Societe Chimique des Usines du Rhone on an industrial scale in 1914 but is now without
importance.
3.1.4 Direct Oxidation of Ethylene
Ethylene is now the most important starting material for the production of acetaldehyde.
Most of the present capacity works by the direct oxidation of ethylene (Wacker process).
This process was developed between 1957 and 1959 by Wacker-Chemie and Hoechst.
Formally, the reaction proceeds as follows:
C2H4 + 1/2O2 → CH3CHO ΔH =− 244 kJ/mol
An aqueous solution of PdCl2 and CuCl2 is used as catalyst. Acetaldehyde formation had
already been observed in the reaction between ethylene and aqueous palladium chloride.
This reaction is almost quantitative:
C2H4 + PdCl2 +H2O → CH3CHO + Pd + 2HCl
In the Wacker-Hoechst process, metallic palladium is re-oxidized by CuCl2, which is then
regenerated with oxygen:
Pd + 2CuCl2 → PdCl2 + 2CuCl
2CuCl + 1/2O2 + 2HCl → 2CuCl2 + H2O
Therefore, only a very small amount of PdCl2 is required for the conversion of ethylene.
The reaction of ethylene with palladium chloride is the rate-determining step.
One-Stage Process
In One-Stage Process Ethylene and oxygen are charged into the lower part of the reaction
tower the catalyst is circulated. Reaction conditions are about 130 ◦C and 400 kPa. An
acetaldehyde– water vapor mixture, together with unreacted gas, is withdrawn from the
separating vessel; from this mixture the reaction products are separated by cooling and
washing with water; unreacted gas is returned to the reactor. A partial stream of catalyst is
heated to 160 ◦C to decompose byproducts that have accumulated in the catalyst. Crude
acetaldehyde obtained during washing of the reaction products is distilled to get the
purified product

Two-Stage Process
In Two-Stage Process Tubular reactors are used for both “reaction” and “oxidation”. The
gases react almost completely in the presence of the catalyst. Reaction of ethylene takes
place at 105– 110 ◦C and 900 – 1000 kPa. Catalyst solution containing acetaldehyde is
then expanded in a flash tower by reducing the pressure to atmospheric level. An
acetaldehyde –water vapor mixture distills overhead while catalyst is sent via the pump to
the oxidation reactor, in which it reacts with oxygen at about 1000 kPa. As oxidation and
reaction are carried out separately, no high-purity starting gas is required. Acetaldehyde –
water vapor mixture from the flash tower is preconcentrated in column to 60 –
90%acetaldehyde by utilizing the heat of reaction. Process water discharged at the bottom
of is returned to the flash tower to maintain a constant catalyst concentration. A portion of
the process water is used for scrubbing exhaust air (nitrogen from the “oxidation” and
exhaust gas (inert gas from the “reaction”) in free of acetaldehyde. Scrubber water then
flows to the crude aldehyde column. A two-stage distillation of the crude acetaldehyde
follows.
3.1.5 Production Directly from Synthesis Gas
Acetaldehyde is formed with low selectivity and a yield of 30 % from synthesis gas,
together with acetic acid, ethanol, and saturated hydrocarbons, mainly methane. Catalysts
are cobalt and rhodium compounds activated by iodine compounds or magnesium chloride
and supported on a silicate carrier. There is so far no industrial use of this process.
3.1.6 Production via Methanol, Methyl Acetate, or Acetic Anhydride
Hydroformylation of methanol with CO/H2 has been well known since the discovery of
the oxo process. It takes place in the presence of hydroformylation catalysts, such as
cobalt, nickel, and iron salts (CoBr2, CoI2) or the corresponding metal carbonyls, at
increased temperature (180- 200 ◦C) and high pressure (30 – 40MPa). An acetaldehyde
selectivity of 80 % or more has been claimed using an iron – cobalt carbonyl or
alternatively a cobalt – nickel catalyst in the presence of tertiary amines, phosphines, or
nitriles as the catalyst.
Similarly, high selectivity has been claimed for the hydrocarbonylation of methyl acetate
with palladium or rhodium catalysts in the presence of tertiary phosphines and iodine
compounds as well as cobalt – ruthenium catalysts in the presence of methyl and sodium
iodides.

3.1.7 Production from Hydrocarbons

Acetaldehyde is a byproduct of the production of acrolein, acrylic acid, and propene oxide
from propene. It is also formed in the oxidation of saturated hydrocarbons (e.g., propane or
butane) in the gas phase as operated by Celanese in the United States.
3.2Process Comparison
 Processes Dehydrogenation of Oxidation of Production from Direct oxidation of Direct oxidation of
Ethanol Ethanol Acetylene Ethylene
Ethylene (one
(two stage)
stage)
Temperature 260-290 C֯ 500-650 C֯ 90 – 95◦C 130-160 ◦C 105 – 110 ◦C

Pressure 1 atm 1 atm 200 kPa 400 kPa 900 – 1000 kPa

Cost High price High price High price but lower Low price Low price
than ethanol

Catalyst Copper sponge or Silver Iron (III) sulfate is An aqueous solution An aqueous solution of
copper activated with added to re-oxidize of PdCl2 and CuCl2 PdCl2 and CuCl2 is used
chromium the mercury metal to is used as catalyst
the mercury (II) salt as catalyst
Yield 90% 97 Pure 95% 95%

Conversion 20-50% 50% 30 and 50 % 75% Per Pass 75% Per Pass

By Products Butyric acid, Acetic acid Carbon dioxide Carbon dioxide and Carbon dioxide and
Crotonaldehyde, and Acetic acid Acetic acid
Ethyl acetate

Table 3.1 Process comparison

3.3 Process Selection
From the above comparison of processes, we have selected the oxidation of
ethylene through one stage process for the production of acetaldehyde.
3.4 Process Description
3.4.1 Pre-treatment
Ethylene and oxygen are separately compressed to 400 kPa and then separately
pass-through heat exchangers to raise the temperature up to the 403 K to achieve
the desire temperature conditions.
3.4.2 Reactor
After passing through heat exchangers ethylene and oxygen enters the reactors
through separate streams and reaction take place at the 400 kPa and 403 K and the
aqueous solution of palladium chloride and copper chloride is recirculated which
acts as a catalyst.
Reactor gives the 75% single pass conversion with the 95% yield of acetaldehyde.
3.4.3 Separating vessel
Product in gaseous phase along with the liquid catalyst are sent to the separating
vessel where the separation of the catalyst takes place and then it is recirculated
back to the reactor.
3.4.5 Cooler
The gaseous product after passing through the separating vessel is at 403 K and
then it is passed through a cooler to lower the temperature up to the 342.13 K.
3.4.6 Scrubber
After cooler the product is passed to the scrubber in which water is used as a
solvent and it absorbs the acetaldehyde completely and ethylene and oxygen
which are not soluble in water are collected from top of tower and then recycled
back to the reactor.
3.4.7 Distillation column
The bottom product from the scrubber is sent to the distillation column in which
further separation takes place and acetaldehyde is collected from the top of column
with the 99% purity.
3.5 Process flow diagram

Figure 3.1 Process flow diagram

 CHAPTER # 04
Material Balance
4.1 Reactor
Assumption
 Process is isothermal.

 Steady State Process (No Accumulation)

General Mass balance Equation for Chemical Reaction
Input − Output + Generation − Consumption = Accumulation
For steady state:
Input − Output + Generation − Consumption = 0
Now,
ϑℇ
f=-
L.Rin

Here,

𝑓 = fractional conversion

ℇ = extent of reaction

𝖯 = stoichiometric coefficient
Component Mass Balance:
No of final moles = initial moles + stoichiometric coefficient *(extent of reaction)
𝒏𝒇 = 𝒏𝒊 + ℇ𝝑

Basis: 100 MTPD or 4166.67 kg/hr of Ethanal Produced

Main Reaction:

C2H4(g) + ½O2(g) CH3CHO(g) ΔHr = -244 kJ/kmol

By Product Reactions:
C2H4(g) + O2(g) CH3COOH(g) ΔHr = -1421.18
kJ/kmol
C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(g) ΔHr=-537.03 kJ/kmol
 CH3CHO
CH3COOH
H2O
CO2
O2
C2H4
C2H4
O2

O2
C2H4
Figure 4.1 Schematic diagram of reactor

For 1st Reaction (Main Reaction)

Amount of Ethylene for 1st reaction = Yield * FxC2H4
Amount of Ethylene for 1st reaction = 0.95 * 3723.84
Amount of Ethylene for 1st reaction = 3537.648 kg/hr of C2H4
= 126.12 kgmol/hr of C2H4
so,
ε1 = -(0.75*126.12)/-1
ε1 = 94.59 moles reacting
For 2nd Reaction (side Reaction)
Amount of Ethylene for 2nd reaction = Yield * FxC2H4
Amount of Ethylene for 2nd reaction = 0.032 * 3723.84
Amount of Ethylene for 2nd reaction = 119.16 kg/hr of C2H4
= 4.25 kgmol/hr of C2H4
so,
ε2 = -(0.75*4.25)/-1
ε2 = 3.188 moles reacting
For 3rd Reaction (Side Reaction)
Amount of Ethylene for 3rd reaction = Yield * FxC2H4
Amount of Ethylene for 3rd reaction = 0.018 * 3723.84
Amount of Ethylene for 3rd reaction = 67.03 kg/hr of C=H4
= 2.39 kgmol/hr of C2H=
so,
ε3 = -(0.75*2.39)/-1
ε3 = 1.793 moles reacting
 Final moles = Initial moles + (Extent of reaction * stochiometric coefficient)
nf = ni + εv
For CH3CHO:
nf = ni + ε1v = 94.59 kgmol/hr
For CO2:
nf = ni + ε2v = 6.38 kgmol/hr
For HO2:
nf = ni + ε2v = 6.38 kgmol/hr
For CH3COOH:
nf = ni + ε3v = 1.739 kgmol/hr
For O2:
nf = ni + ε1v + ε2v + ε3v = 7.70 kgmol/hr
For C2H4:
nf = ni + ε=v + ε2v + ε3v = 33.19 kgmol/hr

Table 4.1 Reactor material balance

Input Output

Molecular Moles Mass Moles Mass

Component
Weight (kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr)

C2H4 28.05 132.76 3723.84 33.19 930.98

O2 32 66.35 2124.12 7.70 246.4

CH3CHO 44.05 94.59 4166.67

CO2 44 6.38 280.72

H2O 18 6.38 114.84

CH3COOH 60 1.793 107.58

Total 199.11 5847.96 150.033 5847.21

For Single Pass Conversion

fsp = -vAε/nAreactor

Here,
f = single pass conversion
 ε = extent of reaction
nAreactor = moles of A fed to the reactor
vA = stochiometric coefficient of A
For Ethylene:
nC2H4Fresh + nC2H4Recycle = Σ−vε/ fsp
Here,
nC2H4Recycle = nC2H4Product
nC2H4Recycle = 33.19 kgmol/hr
so,
nC2H4Fresh + 33.19 = - [(-1) (94.59) + (-1) (3.188) + (-1) (1.793)]/0.75
nC2H4Fresh + 33.19 = 132.76
nC2H4Fresh = 99.57 kgmol/hr
Now,
F + R = F’
F = 199.11 – R (1)
Here,
F = fresh feed
R
R = recycle feed
F F’
F’ = reactor feed
Ethylene Balance, Figure 4.2 Schematic diagram of reactor

RxC2H4 + FxC2H4 = F’xC2H4 feed

RxC2H4 = F’xC2H4 - FxC2H4 xC2H4 = 33.19/ [33.19 + 7.70]

R = [F’xC2H4 – FxC2H4]/ xC2H4 xC2H4 = 0.812
R = [132.76 – 99.57]/0.812
R = 40.87 kgmol/hr
From 1
F = 199.11 – 40.87
F = 158.24 kgmol/hr
Now Recycle Ratio to Fresh Feed:
R/F = 40.87/158.24
R/F = 0.26
 Fresh Feed Recycle Feed Reactor Feed Reactor Out

Molecular Moles Mass Moles Mass Moles Mass Moles Mass

Component
Weight (kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr)

C2H4 28.05 99.69 2796.34 33.19 930.98 132.76 3723.84 33.19 930.98

O2 32 58.5 1873.56 7.70 246.4 66.35 2124.12 7.70 246.4

CH3CHO 44.05 94.59 4166.67

CO2 44 6.38 280.72

H2O 18 6.38 114.84

CH3COOH 60 1.793 107.58

Total 158.24 4669.9 40.89 1177.38 199.11 5847.96 150.033 5847.21

Table 4.2 Reactor material balance including recycle

4.2 Scrubber
Assumptions:
 Steady State Process (No Accumulation)
 No Reaction involved (No Generation and Consumption)
 Ethanal is completely miscible with water in all proportions.
 20% excess water is used.
Overall Material Balance Equation:
G1 + L 2 = L 1 + G2
Component Material Balance Equation:
YiG1 + XiL2 = XiL1 + YiG2
Here,
Li = liquid Absorbent in
Lo = liquid solution out
Vi = Gaseous mixture in
Vo = Gaseous Mixture Out
O2

C
C2H4
CO2

H2O B

CH3CHO
CH3COOH A CH3CHO
O2 D
CH3COOH
C2H4
H2O
H2O
CO

Figure 4.3 Schematic diagram of scrubber

Table 4.3 Scrubber material balance
Inlet Outlet

A B C D
Molecular
Component Moles Mass Moles Mass Moles Mass Moles Mass
Weight
(kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr) (kgmol/hr) (kg/hr)

C2H4 28.05 33.19 930.98 33.19 930.98

O2 32 7.70 246.4 7.70 246.4

CH3CHO 44.05 94.59 4166.67 94.59 4166.67

CO2 44 6.38 280.72 5.86 257.88 0.51 22.50

H2O 18 6.38 114.84 5000.004 277.78 284.16 5114.84

CH3COOH 60 1.793 107.58 1.793 107.58

Total 150.033 5847.21 5000.004 2277.78 46.79 1436.31 381.05 9411.59

4.3 Distillation Column
Assumptions:
 Steady State Process (No Accumulation)
 No Reaction involved (No Generation and Consumption)
General Mass Balance:
F=D+W
Component Mass Balance:
Fxf = Dxd + Wxw
Separation Basis
CO2: Lighter than Light Key 100% in Top
CH3COOH: Heavy Key 99% in Bottom
CH3CHO: Lighter Key 99% in Top
H2O: Heavier than Heavy Key 100% in Bottom

CH3CHO
CH3COOH
Top CO2

CH3CHO
Feed
CH3COOH
H2 O
CO2

Bottom CH3CHO
CH3COOH
H2O
Figure 4.4 Schematic diagram of Distillation
Table 4.4 Distillation column material balance
Outlet

Inlet
Top Bottom
Molecular
Component
Weight Mass Mass Mass
Moles (kgmol/hr) Moles (kgmol/hr) Moles (kgmol/hr)
(kg/hr) (kg/hr) (kg/hr)

CH3CHO 44.05 94.59 4166.67 93.64 4125.00 0.95 41.67

CO2 44 0.51 22.50 0.51 22.50

H2O 18 284.16 5114.84 284.15 5114.71

CH3COOH 60 1.793 107.58 0.018 1.08 1.77 106.64

Total 381.05 9411.59 94.17 4148.58 286.87 5263.01

CHAPTER # 05
Energy Balance
5.1 Introduction
First law of thermodynamics:
“The First Law of Thermodynamics is a statement of energy conservation. Although energy
cannot be created or destroyed, it can be converted from one form to another.”
For example, internal energy stored in molecular bonds can be converted into kinetic energy,
potential energy can be converted too kinetic or too internal energy, etc. Energy can also be
transferred from one point to another, or from one body to a second body. The general energy
balance for a process can be expressed as
Accumulation of Energy in System = Energy input to System – Energy Output from System
Energy
“Energy is the ability to do work.”
Energy comes in different forms:
 Heat (thermal)
 Light (radiant)
 Motion (kinetic)
 Electrical
 Chemical
 Nuclear energy
 Gravitational
Energy is often categorized as:
 Kinetic Energy
 Potential Energy
 Internal Energy
Kinetic Energy
A system’s kinetic energy is associated with directed motion (e.g., translation, rotation) of the
system. Translation refers to straight line motion. The kinetic energy Ek of a moving object of
mass “m” and travelling with speed “v” is given by,
𝐸𝑘=1/2𝑚𝑣2
Potential Energy
“Potential energy of a system is due to the position of the system in a potential field.”
This energy can be calculated as
𝐸=𝑚𝑔ℎ
 Where “m” is the mass of object, “g” is the gravitational acceleration and “h” is the height of the
object from the reference position.

Internal Energy
All the energy associated with a system that does not fall under the above definitions of kinetic or
potential energy is internal energy. More specifically, internal energy is the energy due to all
molecular, atomic, and subatomic motions and interactions. The internal energy will be
represented by the symbol U.
5.2 Specific Heat Capacity Constants and Formulas
Constants for specific heat for vapours/Gas:
Table 5.1 Perry constants for vapor heat capacity
Components C1 C2 C3 C4 C5

H2O 33360 26790 2610.5 8896 1169

O2 29100 10040 2526.5 9360 1153.8

CO2 29370 34540 1428 26400 588

CH3COOH 40200 136750 1262 70030 569.7

CH3CHO 44510 106870 1614.1 61350 737.8

C2H4 33380 94790 1596 55100 740.8

Formula for Cp:

= C1 + C2[(C3/T)/Sinh(C3/T)] ^2 + C4[(C5/T)/Sinh(C5/T)] ^2

Here,
Temperature is in Kelvin
And we will get the
Cp units are in J/kmol K
Constants for specific heat for Liquid:

Table 5.2 Perry constants for liquid heat capacity

Components C1 C2 C3 C4 C5

H2O 276370 -2090 8.125 -0.014166 0.00000937

 O2 175430 -6152.3 113.92 -0.9328 0.0026963

CO2 -8304300 104370 -433.33 0.60052 0

CH3COOH 139460 -320.8 0.8985 0 0

CH3CHO 115100 -433 1.425 0 0

C2H4 247390 -4428 40.936 -0.1697 0.00026816

Formula for Cp:

= C1 + C2T + C2T2 + C3T2 + C4T3 + C5T4
Cp units are in J/kmol K
Temperature is in Kelvin
5.3 Compressor [C-101]
298 K 310.49 K
101 kPa 410 kPa

Figure 5.1 Schematic figure of C-101

For Inlet Stream
Tin = 298 K
Tref = 298 K
Table 5.3 Specification of inlet stream of C-101
Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate fraction
Oxygen 1876.66 1 0 0.917 0

So,
Qin = m*Cp* ΔT
Qin = 0 kW
For Outlet Stream
Tin = 310.49 K
Tref = 298 K

Table 5.4 Specification of outlet stream of C-101

Mass Flow Mass fraction ΔT Cp Xi*Cp* ΔT
 Component rate
Oxygen 1876.66 1 12.49 0.919 11.48
So,
Qout = m*Cp* ΔT
Qout = 5.98 kW
Now,
Q = 5.98 kW
5.4 Compressor [C-102]
298 K 305.93 K
101 kPa 410 kPa

Figure 5.2 Schematic figure of C-102

For Inlet Stream
Tin = 298 K
Tref = 298 K
Table 5.5 Specification of inlet stream of C-102
Mass Flow Mass
ΔT Cp Xi*Cp* ΔT
Component rate fraction
Ethylene 2792.88 1 0 1.53 0

So,
Qin = m*Cp* ΔT
Qin = 0 kW
For Outlet Stream
Tin = 305.93 K
Tref = 298 K
Table 5.6 Specification of outlet stream of C-102
Mass Flow Mass
ΔT Cp Xi*Cp* ΔT
Component rate fraction
Ethylene 2792.88 1 7.93 1.56 12.37

So,
Qout = m*Cp* ΔT
Qout = 9.59 kW
Now,
 Q = 9.59 kW
5.5 Pre-Heater [HX-101]
403 K
310.49 K
410 kPa 400 kPa

Figure 5.3 Schematic figure of HX-101

For Inlet Stream
Tin = 310.49 K
Tref = 298 K
Table 5.7 Specification of inlet stream of HX-101

Mass Flow Mass

ΔT Cp Xi*Cp* ΔT
Component rate fraction
Oxygen 1876.66 1 12.49 0.919 11.48

So,

Qin = m*Cp* ΔT

Qin = 5.98 kW

For Outlet Stream

Tin = 403 K

Tref = 298 K

Table 5.8 Specification of outlet stream of HX-101

Mass Flow Mass

ΔT Cp Xi*Cp* ΔT
Component rate fraction
Oxygen 1876.66 1 105 0.941 98.91

So,
Qout = m*Cp* ΔT
Qout = 51.51 kW
Now,
Q = 45.53 kW
5.6 Pre-Heater [HX-102]

305.93 K 403 K

410 kpa 400 kpa

Figure 5.4 Schematic figure of HX-102

For Inlet Stream
Tin = 305.93 K
Tref = 298 K
Table 5.9 Specification of inlet stream of HX-102

Mass Flow Mass

ΔT Cp Xi*Cp* ΔT
Component rate fraction
Ethylene 2792.88 1 7.93 1.56 12.37

So,

Qin = m*Cp* ΔT

Qin = 9.59 kW

For Outlet Stream

Tin = 403 K

Tref = 298 K
Table 5.10 Specification of outlet stream of HX-102

Mass Flow Mass

ΔT Cp Xi*Cp* ΔT
Component rate fraction
Ethylene 2792.88 1 105 1.91 200.55

So,
Qout = m*Cp* ΔT
Qout = 155.59 kW
Now,
Q = 145.99 kW
5.7 Reactor [R-101]
 Reactants at 403 K ΔHrxn (T) Products at 403 K
(1) (4)
ΔH1

ΔH2 ΔHreactants ΔH4

ΔHproducts

Reactants at 298 K ΔH3 Products at 298 K

(2) ΔHrxn (298K) (3)

Figure 5.5 Schematic figure Reactor energy balance

route
Reaction 1 (Main Reaction):
C2H4 + ½ O2 CH3CHO ΔH = -244 kJ/mol
Reaction 2 (Side Reaction):
C2H4 + 3O2 CO2 + H2O ΔH = -1421.18 kJ/mol
Reaction 3 (Side Reaction):
C2H4 + O2 CH3COOH ΔH = -537.03 kJ/mol
Formulas:
ΔHr2 = ΔHr1 – (H2 -H1)reactnts + (H2 – H1)products
ΔH r2 (T) = ΔHr1 (298K) + ΔHreactnts + ΔHproducts
Now:
ΔHreactnts = (n * cp * ΔT)reactants
Also:
ΔHproducts = (n * cp * ΔT)products

Table 5.11 Specific heat capacities of component involved in reactor energy balance
Components Temperature (K) Cp kJ/kmol K
C2H4 403 53.47
O2 403 30.09
CH3CHO 403 66.86
CH3COOH 403 79.99
CO2 403 41.76
H2O 403 32.27
For 1st Reaction (Main Reaction):
ΔHr1 at 403K = (n*Cp*ΔT)reactants + ΔHr1 at 298K + (n*Cp*ΔT)products
= -23080133.1 KJ/hr
= -6411.148 kW
For 2nd Reaction (Side Reaction):
ΔHr2 at 403K = (n*Cp*ΔT)reactants + ΔHr2 at 298K + (n*Cp*ΔT)products
= -4532694.655 KJ/hr
= -1259.08 kW
For 3rd Reaction (Side Reaction):
ΔHr3 at 403K = (n*Cp*ΔT)reactants + ΔHr3 at 298K + (n*Cp*ΔT)products
= -961660.286 KJ/hr
= -261.127 kW
Now:
Q = -7937.357 kW
Coolant Flow rate:
Tin = 298 K
Tout = 313 K
Also:
Q = m*cp*ΔT
And:
Q = 7937.357 kW
Now:
m = 455733.461 kg/hr
5.8 Cooler [HX-103]

403 K 342.13K

Figure 5.6 Schematic figure of HX-103

For Inlet Stream

Tin = 403 K

Tref = 298 K
 Table 5.12 Specification of inlet stream of HX-103
Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

H2O 114.84 0.0196 105 1.904 3.927

O2 246.4 0.0421 105 0.941 4.163

CO2 280.72 0.0480 105 0.949 4.784

CH3COOH 107.58 0.0184 105 1.333 2.575

CH3CHO 4166.67 0.7126 105 1.518 113.580

C2H4 930.98 0.1592 105 1.906 31.864

Total 5847.19 1 160.894

So,
Qin = m* Σxi∗Cp∗ΔT
Qin = 261.327 kW

For Outlet Stream

Tin = 342.13 K
Tref = 298 K
Table 5.3 Specification of outlet stream of HX-103
Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

H2O 114.84 0.0196 44.13 1.878 1.628

O2 246.4 0.0421 44.13 0.925 1.720

CO2 280.72 0.0480 44.13 0.894 1.894

CH3COOH 107.58 0.0184 44.13 1.179 0.957

CH3CHO 4166.67 0.7126 44.13 1.366 42.956

C2H4 930.98 0.1592 44.13 1.688 11.860

Total 5847.19 1 61.016

So,
Qin = m* Σxi∗Cp∗ΔT
Qin = 99.103 kW
Now,
Q = -162.224 kW
Coolant Flow rate:
Tin = 298 K
Tout = 308 K
Also:
Q = m*cp*ΔT
And:
Q = 162.224 kW
Now:
m = 13971.4 kg/hr
5.9 Scrubber [S-101]

O2
C2H4
T = 315 K CO2

Q2
H2O

T = 298 K

CH3CHO Q1
Q4
CH3COOH CH3CHO
H2O T = 324.13 K CH3COOH
CO2 T = 327 K H2 O
O2
C2H4
Figure 5.7 Schematic figure of S-101
For Stream 1
Tin = 342.13 K
Tref = 298 K
Table 5.14 Specification of gas stream of S-101
Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

H2O 114.84 0.0196 44.13 1.878 1.628

O2 246.4 0.0421 44.13 0.925 1.720

CO2 280.72 0.0480 44.13 0.894 1.894

CH3COOH 107.58 0.0184 44.13 1.179 0.957

CH3CHO 4166.67 0.7126 44.13 1.366 42.956

C2H4 930.98 0.1592 44.13 1.688 11.860

Total 5847.19 1 61.016

So,
Q1 = m* Σxi∗Cp∗ΔT
Q1 = 99.103 kW
For Stream 2
Tin = 298 K
Tref = 298 K
Table 5.15 Specification of solvent stream of S-101
Mass Flow Mass
Component rate(kg/hr) fraction ΔT Cp Xi*Cp* ΔT

H2O 5000.004 1 0 1.878 0

So,

Q2 = m*Cp* ΔT

Q2 = 0 kW
For Stream 3
Tin = 315 K
Tref = 298 K
Table 5.16 Specification of top stream of S-101
Mass Flow Mass Xi*Cp*
Component rate(kg/hr) fraction ΔT Cp ΔT

O2 246.46 0.172 17 0.921 2.69

CO2 257.88 0.179 17 0.866 2.65

C2H4 930.98 0.649 17 1.591 17.54

Total 1435.31 1 22.88

So,
Q3 = m* Σxi∗Cp∗ΔT
Q3 = 9.12 kW
For Stream 4
Tin = 327 K
Tref = 298 K

Table 5.17 Specification of bottom stream of S-101

Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

H2O 5114.84 0.543 29 4.183 65.93

CO2 22.5 0.0024 29 11.063 0.78

CH3COOH 107.58 0.011 29 2.178 0.723

CH3CHO 4166.67 0.443 29 2.858 36.69

Total 9411.45 1 104.11

So,
Q4 = m* Σxi∗Cp∗ΔT
Q4 = 272.17 kW
Now,
 Heat of solution of Ethanal in water = 6926 kJ/kg
Qsolution = 181.979 kW
Now,
Q1 + Q2 + Qsolution = Q3 + Q4
281.289 kW = 281.083 kW
5.10 Compressor [C-103]
315 K 319.53 K
235 kPa 410 kPa

Figure 5.8 Schematic figure of C-103

For Inlet Stream

Tin = 315 K
Tref = 298 K
Table 5.18 Specification of inlet stream of C-103
Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

O2 246.4 0.209 17 0.921 3.28

C2H4 930.98 0.791 17 1.591 21.39

Total 1177.36 1 24.66

So,

Qin = m* Σxi∗Cp∗ΔT

Qin = 8.07 kW

For Outlet Stream

Tin = 319.53 K

Tref = 298 K

Table 5.19 Specification of outlet stream of C-103

 Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

O2 246.4 0.209 21.53 0.921 4.15

C2H4 930.98 0.791 21.53 1.607 27.36

Total 1177.36 1 31.56

So,
Qout = m* Σxi∗Cp∗ΔT
Qout = 10.30 kW
Now,
Q = 2.24 kW
5.11 Heater [HX-104]
319.53 K 403 K

410 kPa 400 kpa

Figure 5.9 Schematic figure of HX-103

For Inlet Stream

Tin = 319.53 K
Tref = 298 K
Table 5.20 Specification of inlet stream of HX-103
Mass Flow
Component Mass fraction ΔT Cp Xi*Cp* ΔT
rate(kg/hr)

O2 246.4 0.209 21.53 0.921 4.15

C2H4 930.98 0.791 21.53 1.607 27.36

Total 1177.36 1 31.51

So,
 Qin = m* Σxi∗Cp∗ΔT
Qin = 10.30 kW
For Outlet Stream
Tin = 403 K
Tref = 298 K

Table 5.21 Specification of outlet stream of HX-103

Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

O2 246.4 0.209 105 0.941 20.68

C2H4 930.98 0.791 105 1.906 158.25

Total 1177.36 1 178.93

So,
Qout = m* Σxi∗Cp∗ΔT
Qout = 58.52 kW
Now,
Q = 48.21 kW
5.12 Distillation Column [DC-101]

 Bubble Temperature of Feed: 327 K

 Dew Temperature of Feed: 396.3 K

 Bubble Pressure of Feed: 280 kPa

 Dew Pressure of Feed: 19.8 kPa

5.12.1 Condenser Heat Duty

Sensible Heat of Vapors

Tin = 323 K

Tref = 298 K

Table 5.22 Specification of vapor stream of DC-101

 Mass Flow Mass
Component ΔT Cp Xi*Cp
rate(kg/hr) fraction

CO2 22.5 0.0054 25 0.875 0.0047

CH3COOH 1.08 0.00026 25 1.129 0.0029

CH3CHO 4125.01 0.994 25 1.137 1.131

Total 4148.59 1 1.136

So,

QV = m* Σxi∗Cp∗ΔT

QV = 32.72 kW

Sensible Heat of Liquid

Tin = 296.5 K

Tref = 298 K

Table 5.23 Specification of liquid stream of DC-101

Mass Flow Mass
Component ΔT Cp Xi*Cp
rate(kg/hr) fraction

CO2 22.5 0.0054 -1.5 6.258 0.034

CH3COOH 1.08 0.00026 -1.5 2.096 0.0005

CH3CHO 4125.01 0.994 -1.5 2.648 2.63

Total 4148.59 1 2.67

So,

QL = m* Σxi∗Cp∗ΔT

QL = -4.61 kW
Latent Heat

Table 5.24 Latent heat of components at the top of DC-

101 Mass Flow
Component Mass fraction λ Xi*λi
rate(kg/hr)

CO2 22.5 0.0054 -484.77 -482.02

CH3COOH 1.08 0.00026 0 0

CH3CHO 4125.01 0.994 -393.31 -0.102

Total 4148.59 1 -482.12

So,
QLatent = mλ
QLatent = - 555.58 kW
Now,
Qc = Qv + Qlatent + QL
Qc = -527.48 kW
Coolant Flow rate:
Tin = 298 K

Tout = 308 K

Also:

Q = m*cp*ΔT

And:

Q = 527.479 kW

Now:

m = 30285.853 kg/hr

5.12.2 Reboiler Heat Duty

Enthalpy of Feed

T = 327 K

Tref = 298 K

Table 5.25 Specification of feed stream of DC-101

 Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

H2O 5114.84 0.543 29 4.183 65.93

CO2 22.5 0.0024 29 11.063 0.78

CH3COOH 107.58 0.011 29 2.178 0.723

CH3CHO 4166.67 0.443 29 2.858 36.69

Total 9411.45 1 104.11

So,
QF = m* Σxi∗Cp∗ΔT
QF = 272.17 kW
Enthalpy at Bottom
T = 433.1 K
Tref = 298 K
Table 5.26 Specification of bottom stream of DC-
101 Mass Flow Mass
Component ΔT Cp Xi*Cp* ΔT
rate(kg/hr) fraction

H2O 5114.84 0.972 135.1 4.336 569.69

CH3COOH 106.64 0.020 135.1 2.280 7.67

CH3CHO 41.67 0.008 135.1 4.183 4.69

Total 5263.01 1 581.65

So,
QW = m* Σxi∗Cp∗ΔT
QW= 850.34 kW
Enthalpy of Distillate
Tin = 323 K
Tref = 298 K
Table 5.26 Specification of distillate stream of DC-
101
 Mass Flow Mass
Component ΔT Cp Xi*Cp
rate(kg/hr) fraction

CO2 22.5 0.0054 25 0.875 0.0047

CH3COOH 1.08 0.00026 25 1.129 0.0029

CH3CHO 4125.01 0.994 25 1.137 1.131

Total 4148.59 1 1.136

So,
QD = m* Σxi∗Cp∗ΔT
QD = 32.72 kW
Now,
QB = Qc + Qw + QD – QF
QB = 1138.365 kW
Steam Flow rate:
m = 13729.034 kg/hr