Chapter

I
 Chapter one
Introduction

1.1.Overview

Vinyl acetate, also known as vinyl acetate monomer (VAM), is a crucial industrial chemical used primarily in the
production of polyvinyl acetate and polyvinyl alcohol, which are key components in adhesives, coatings, and
various polymers. The production of vinyl acetate involves a well-established industrial process that primarily
utilizes ethylene, acetic acid, and oxygen as raw materials.
The dominant method for producing vinyl acetate is through the vapor-phase reaction of ethylene and acetic acid
over a palladium catalyst. This process can be broken down into three main stages:

1. Reaction: Ethylene, acetic acid, and oxygen are fed into a reactor where they react in the presence of a
palladium catalyst. The reaction typically occurs at temperatures between 175–200°C and pressures of 5–9 bar¹⁴.

2. Separation: The reaction mixture contains vinyl acetate, unreacted ethylene, acetic acid, and by-products such
as water and carbon dioxide. This mixture is then subjected to a series of separation processes, including
distillation, to isolate vinyl acetate from other components¹.

3. Purification: The crude vinyl acetate is further purified to remove any remaining impurities, resulting in high-
purity vinyl acetate suitable for industrial applications.

The production of vinyl acetate is a critical process in the chemical industry due to its wide range of applications.
The efficiency and optimization of this process are essential for meeting the growing demand for vinyl acetate-
based products while minimizing environmental impact and production costs.
1.2.Problem statement

The production of vinyl acetate faces several challenges, including optimizing reaction conditions to maximize
yield and selectivity, managing by-products and waste, and developing more effective catalysts. Additionally, the
process must address the environmental impact associated with the use of acetic acid and ethylene, as well as the
high energy consumption required for the reactions
Proposed Solutions:
To address these challenges, this project will focus on:
1.Catalyst Improvement: Investigating and developing more efficient catalysts to enhance reaction rates and
selectivity.
2.Process Optimization: Fine-tuning reaction conditions such as temperature, pressure, and reactant ratios to
maximize yield and minimize by-products.
3.Waste Management: Implementing strategies to reduce and recycle by-products and waste materials.
4.Energy Efficiency: Exploring methods to lower energy consumption, such as heat integration and alternative
energy sources.
By tackling these areas, the project aims to improve the overall efficiency and sustainability of the vinyl acetate
production process.

1.3.Objectives of the project

The objective of this project is to give a fully explained process and a design of vinyl acetate production plant
with related calculations , this can be accomplished by the following subobjectives :
1. To give full idea about vinyl acetate production process.
2. To illustrate all the raw material required for the process with their properties.
3. To carry out material and energy balances.
4. To carry out primary design calculations for the equipments.
5. To introduce control calculations ,measures , and design .
6. To determine cost estimations for the process.
7. To study the effect of the products on the environment
1.4.Scope of the project

This project encompasses a comprehensive analysis and enhancement of the vinyl acetate production process. The
scope includes:
1.Catalyst Development: Researching and synthesizing new catalysts, followed by testing their performance in the
vinyl acetate production reaction.
2.Process Optimization: Conducting experiments to determine the optimal reaction conditions, including
temperature, pressure, and reactant ratios, to maximize yield and minimize by-products.
3.Environmental Impact Assessment: Evaluating the environmental impact of the production process, including
emissions and waste management. Proposing methods to reduce the environmental footprint.
4.Economic Analysis: Performing a cost-benefit analysis to determine the economic feasibility of the proposed
enhancements. This includes calculating the return on investment (ROI) and payback period
5.Safety and Compliance: Ensuring that the production process adheres to industry safety standards and regulatory
requirements. This involves conducting risk assessments and implementing necessary safety measures.
6.Pilot Plant Design: Designing a pilot plant to test the optimized process on a smaller scale before full-scale
implementation. This includes layout planning, equipment selection, and process simulation.
1.5.Project organization
This project includes the following :
- Chapter one introduces the reader to the project , this chapter includes overview about the process, problem
statement with solution , objective of the project ,scope of the project , and project organization .

- Chapter two Is the literature review section, which describes the chemistry of the reactants and products,
the kinetics, the type of catalysts used, and different alternatives have been studied.

- Chapter three of this project is the mass and energy balance. In this part, a detail mass and energy balances
were performed using hand calculation. The flow of energy around each equipment was calculated using
the concept of energy balance.

- Chapter four of this project is the detail design of process equipment. This part has been divided into 6
main parts. The first part is designing the reactor which is the heart of most chemical engineering
processes.. Then, flash drum is designed. After that, absorber and distillation towers were designed.
Furthermore, heat exchangers, pumps and piping and plant layout were designed.

- Chapter five is the cost and economy analysis. In this section, the profitability of vinyl acetate production
process is analyzed. First the profit margin was calculated for the raw material which are ethylene, and
acetic acid. Cost of raw material for ethylene, acetic acid . , Then the cost of operating labor was
calculated based on the number of equipments. Then, CAP-COST analysis was used to find the discounted
payback period, revenue, rate of return and the other parameters for the process.

- Chapter six explains control and instrumentation where we will design control for each unit in the plant .

- Chapter seven is the safety, environment & HAZOP. This small part that illustrate HAZOP analysis. The
aim of this chapter is some possible scenarios for major equipment’s, such as decrease in the feed and try
to give quick actions to overcome those unwanted changes.

- Chapter eight is the conclusion and recommendations .

Chapter
II
 Chapter two
Literature review
2.1 Vinyl acetate
2.1.1 Introduction:
Vinyl Acetate (also known as acetic acid ethenyl ester, acetic acid ethylene ether,
acetoxyethene, 1-acetoxyethylene, ethenyl ethanoate, ethenyl acetate, and acetic acid vinyl ester)
is a flammable, colorless mobile liquid that is partly soluble in water. It has a sharp sweet smell
that can become irritating at higher levels. It has the formula CH3COOCH=CH2 and is considered
slightly toxic and is completely soluble in organic liquids and its vapors are heavier than air. Vinyl
Acetate (VA) is solely used as a key raw material in the production of chemicals which are then
used to manufacture a wide variety of consumer and industrial products. Vinyl acetate is a man-
made compound that was first prepared by Fritz Klatte in 1912 as a by-product in the synthesis of
ethylidene diacetate [3]. Currently, according to the Journal of Catalysis the manufacturing
process most widely used to produce vinyl acetate is the vapor phase ethylene reaction process.
An oxidative reaction in which ethylene is bubbled through acetic acid in the presence of
palladium catalyst [2].
Several companies in the United
States, Japan, Germany, and the
United Kingdom have modified the
vapor phase ethylene process by using
different types of catalysts in the
reaction. The catalyst is usually
palladium or its salt, the advantage of
these processes is that the catalyst lasts
longer and undergoes less corrosion. Figure 1: Chemical structure of Vinyl acetate

Vinyl acetate monomer is mainly used in the production of polyvinyl acetate (PVA) and polyvinyl
alcohol (PVOH or PVA). In fact, Industry statistics estimate that 80 % of all the global VA
produced in the world is used to manufacture these two chemicals. Polyvinyl acetate is used in
paints, adhesives, paper coatings and textile treatments, while polyvinyl alcohol is used in the
production of adhesives, coatings, and water-soluble packaging, and textile warp sizing [1].
 Moreover, VA is also used to make polyvinyl butyral (PVB) which is used in laminated safety
glass for cars and buildings.
Ethylene-vinyl acetate (EVA) resin is also made from VA and is used in the manufacture of packaging
film, heavy-duty bags, extrusion coating, wire and cable jacketing, hot-melt adhesives and cross-linked
foam. Other products made from VAM are ethylene-vinyl alcohol (EVOH) resins which are used as a gas
barrier in multi-layered food and beverage packages, and as a barrier layer in automobile tanks. Vinyl
acetate is also copolymerized as a minor raw material for vinyl chloride and ethylene to form commercial
polymers and acrylic fibers.

2.1.2 Applications

Application Uses
VA is widely used to make food contact materials used in
Food
adhesives, paper and paperboard coatings, and printing inks.
VA is used in the manufacture of plastics.
Plastics

VA is broadly used in coating formulations as well as in water-

Coatings
based coatings.

Adhesives VA is raw material for various adhesive products.

Chemical Intermediates VA is used as monomer for different types of polymers.

Textiles Fabric treatments, pigments

 2.1.3 Physical and chemical properties :
Physical properties:

Compound Name Vinyl Acetate

Chemical Formula C4H6O2

Role in Process product

Phase & Color colorless liquid

Molecular Weight (g/mol) 86.09

Melting Point (oC) -92.8

Boiling Point (oC) 72.9

Density (kg/m3)
933.7
“normal conditions”

Viscosity (cP)
0.41
“normal conditions”
Specific Gravity 0.9336

Critical Pressure (bar) 39.55

Critical Temperature (oC) 245.8

Critical Volume (cm3/mol) 270

Heat of Formation (kJ/mol) -313.6 (l)

Heat of Combustion (kJ/mol) -1950 (l)

Heat Capacity, Cp (gas) (J/mol K) 129.025

Heat Capacity, Cp (liquid) (J/mol K)

169.5
Chemical properties :
Reactivity: Vinyl acetate is reactive due to the presence of a carbon-carbon double bond, making
it prone to addition and polymerization reactions
Hazards: It is flammable, mildly toxic, and classified as a Class 2B carcinogen by the
International Agency for Research on Cancer (IARC)

2.2 Ethylene :
2.2.1 introduction:
Ethylene is a colorless gas with the chemical formula C₂H₄ , It's a hydrocarbon and the simplest
alkene, widely used in the chemical industry as a building block for various products ,In the
production of vinyl acetate, ethylene plays a crucial role as commonly the limiting reactant . The
most common industrial method for producing vinyl acetate involves reacting ethylene with
acetic acid and oxygen in the presence of a palladium-based catalyst.
2.2.2 Applications:
Ethylene is incredibly versatile and is used in various industries ,Some of its primary
applications include:
1. Polyethylene Production: The most common use of ethylene is in the production of
polyethylene, a widely used plastic for packaging, containers, and insulation.
2. Ethylene Oxide: Ethylene is converted to ethylene oxide, which is then used to produce
ethylene glycol (antifreeze) and polyester fibers.
3. Vinyl Chloride: Ethylene is used to produce vinyl chloride, which is polymerized to make
polyvinyl chloride (PVC) used in pipes, siding, and medical devices.
4. Ripening Agent: Ethylene is used in agriculture to promote the ripening of fruits.
5. Other Chemicals: It serves as a starting material for producing ethanol, acetaldehyde, and
other chemicals.
Ethylene is often referred to as the "world's most important chemical" due to its widespread use
and essential role in the production of various materials.
2.2.3 Physical and chemical properties :
Physical properties :

Compound Name Ethylene

Chemical Formula C2H4

Role in Process reactant (feed)
Phase & Color colorless gas
Molecular Weight (g/mol) 28.054
Melting Point (oC) -169.18

Boiling Point (oC) -103.7

Density (kg/m3)
1.138
“normal conditions”
Viscosity (cP)
0.01032
“normal conditions”
Specific Gravity 0.975
Critical Pressure (bar) 50.6
Critical Temperature (oC) 9.2
Critical Volume (cm3/mol) 131

Heat of Formation (kJ/mol) +52.47 (g)

Heat of Combustion
-1410.99(g)
(kJ/mol)
Heat Capacity, Cp (gas)
55.89
(J/mol K)
Heat Capacity, Cp (liquid)
67.4
(J/mol K)
Chemical properties :
Solubility: Slightly soluble in water, more soluble in organic solvents.
Reactivity: Highly reactive due to the carbon-carbon double bond, making it prone to addition
reactions.
2.3 Acetic acid
2.3.1 Introduction:
Acetic acid, also known as ethanoic acid, is a colorless liquid organic compound with the
chemical formula CH₃COOH. It is the main component of vinegar when diluted and has a
pungent smell and sour taste ,Acetic acid is a key raw material in the production of vinyl acetate.
2.3.2 Applications:
1. Vinyl Acetate Production: Used to produce polyvinyl acetate, which is used in adhesives,
paints, and coatings.
2. Food Industry: As a preservative and flavoring agent in the form of vinegar.
3. Pharmaceuticals: Used in the production of various drugs and chemicals.
4. Textiles: Used in the production of cellulose acetate for making photographic films and
textiles .
5. Solvents: Used as a solvent in the production of resins, paints, and lacquers
2.3.3 physical and chemical properties :
Physical properties :
Compound Name Acetic Acid
Chemical Formula C2H4O2
Role in Process Reactant (feed)
Phase & Color colorless liquid
Molecular Weight (g/mol) 60.05
Melting Point (oC) 16.6
Boiling Point (oC) 118.2
Density (kg/m3)
1049
“normal conditions”
Viscosity (cP)
1.155
“normal conditions”
Specific Gravity 1.049
Critical Pressure (bar) 57.8
Critical Temperature (oC) 320
Critical Volume (cm3/mol) 171
Heat of Formation (kJ/mol) -431.9 (g)
 Heat of Combustion
-919.73 (g)
(kJ/mol)
Heat Capacity, Cp (gas)
83.23
(J/mol K)
Heat Capacity, Cp (liquid)
123.1
(J/mol K)

Chemical properties :
Solubility: Miscible with water, ethanol, and ether.
Acidity (pKa): 4.76.

2.4 Oxygen
2.4.1 introduction :
Oxygen (O₂) is a colorless, odorless, and tasteless diatomic gas that is essential for life on Earth.
It is the most abundant element in the Earth's crust and makes up about 21% of the Earth's
atmosphere.Oxygen is a key reactant in the production of **vinyl acetate**. The process
involves the catalytic oxidation of ethylene and acetic acid with oxygen, typically in the presence
of a palladium catalyst.
2.4.2 Applications :
1. Medical: Used for respiratory therapy and in life support systems.
2. Industrial: Involved in metal cutting, welding, and smelting processes.
3. Chemical Production: Used in the synthesis of chemicals like ethylene oxide and vinyl
acetate.
4. Environmental: Employed in water treatment processes to improve the efficiency of
pollutant degradation.
5. Aerospace: Essential for rocket propulsion systems.
Oxygen’s reactivity and abundance make it essential for numerous industrial, environmental, and
medical applications.
2.4.3 Physical and chemical properties :
Compound Name Oxygen
Chemical Formula O2
Role in Process Reactant (feed)
Phase & Color Colorless gas
Molecular Weight (g/mol) 31.998
Melting Point (oC) -218.4
Boiling Point (oC) -182.96
Density (kg/m3)
1.429
“normal conditions”
Viscosity (cP)
0.0275
“normal conditions”
Specific Gravity 1.1
Critical Pressure (bar) 49.7
Critical Temperature (oC) -118.75
Critical Volume (cm3/mol) 73.4
Heat of Formation (kJ/mol) -
Heat of Combustion
-
(kJ/mol)
Heat Capacity, Cp (gas)
30.35
(J/mol K)
Heat Capacity, Cp (liquid)
55.174
(J/mol K)

Chemical properties :
Solubility: Slightly soluble in water.
Reactivity: Highly reactive, forms oxides with most elements, supports combustion.
2.5 Ethan
2.5.1 introduction:
Ethane (C2H6) can be used as an inert diluent in the production of vinyl acetate monomer
(VAM). In industrial chemical processes, inerts are non-reactive substances added to the reaction
mixture to help control temperature, pressure, and reaction rates without participating in the
chemical reaction itself.
In the VAM production process, which involves the catalytic reaction of ethylene, acetic acid,
and oxygen, ethane serves as an inert diluent. Its presence helps to manage the exothermic nature
of the reaction by absorbing some of the heat generated, thereby preventing the reactor from
overheating. This control is crucial to maintaining optimal reaction conditions and ensuring the
efficiency and safety of the production process.
Chemically, ethane is a simple hydrocarbon with a molecular formula of C2H6. It is a non-polar
molecule, making it relatively inert under the conditions of the VAM production process. Its
physical properties, such as being a gas at room temperature, make it suitable for use as a diluent
in gas-phase reactions.
2.5.2 Applications:
Applications of ethane extend beyond its role as an inert in VAM production. In the
petrochemical industry, ethane is a primary feedstock for the production of ethylene through
steam cracking. Ethylene, in turn, is a precursor for various plastics, including polyethylene.
Additionally, ethane is used as a refrigerant in cryogenic applications and plays a role in natural
gas processing.
2.5.3 Physical and chemical properties:
Compound Name Ethane

Chemical Formula C2H6

Role in Process Inert (feed)
Phase & Color colorless gas
Molecular Weight (g/mol) 30.07
Melting Point (oC) -182.8
Boiling Point (oC) -88.6
Density (kg/m3)
1.212
“normal conditions”
Viscosity (cP)
0.0094
“normal conditions”
Specific Gravity 1.047
Critical Pressure (bar) 48.72
Critical Temperature (oC) 32.17
Critical Volume (cm3/mol) 145.5
Heat of Formation (kJ/mol) -84.67 (g)
Heat of Combustion
-1559.9 (g)
(kJ/mol)
Heat Capacity, Cp (gas)
68.58
(J/mol K)
Heat Capacity, Cp (liquid)
68.44
(J/mol K)
2.6 Carbon dioxide
2.6.1 introduction:
Carbon dioxide (CO2) is a critical component in the chemical industry, playing a versatile role in
various processes, including the production of (VAM). In the context of vinyl acetate production,
CO2 can be emerged as a by product particularly when the ethylene is oxidized . while co2 is not
a primary reactant in VAM production managing it effectively is important to ensure process
efficiency and minimize environmental impact .
2.6.2 Applications :
Applications of CO2 in the industry extend beyond vinyl acetate production. It is used in the
food and beverage industry for carbonation, in the pharmaceutical industry for the production of
certain drugs, and in enhanced oil recovery techniques in the energy sector.
2.6.3 Physical and chemical properties :
Physical properties :

Compound Name Carbon Dioxide

Chemical Formula CO2
Role in Process product
Phase & Color colorless gas
Molecular Weight (g/mol) 44.01
Melting Point (oC) -56.6
Boiling Point (oC) -78.5
Density (kg/m3)
1.98
“normal conditions”
Viscosity (cP)
0.0147
“normal conditions”
Specific Gravity 1.5189
Critical Pressure (bar) 73.77
Critical Temperature (oC) 30.98
Critical Volume (cm3/mol) 94
Heat of Formation (kJ/mol) -393.5 (g)
Heat of Combustion (kJ/mol) -
Heat Capacity, Cp (gas) (J/mol K) 42.35
Heat Capacity, Cp (liquid) (J/mol
128.3
K)
Chemical properties :
Chemically, CO2 is a linear molecule consisting of one carbon atom double-bonded to two
oxygen atoms (O=C=O). It is a non-polar molecule with a relatively low boiling point, which
makes it a gas at room temperature. CO2's chemical properties make it a useful feedstock in
various chemical reactions, including the synthesis of organic compounds, where it can act as a
carbon source.

2.7 Water
2.7.1 Introduction :
Water (H2O) plays an indispensable role in the chemical industry, including the production of
vinyl acetate monomer (VAM). This exothermic reaction generates water as a byproduct along
with vinyl acetate. The presence of water in the reaction mixture can influence the efficiency and
yield of the production process. Efficient removal and management of water are crucial to
optimize reaction conditions and ensure the quality of the final product.
2.7.2 Applications:
Water’s applications extend far beyond its role as a byproduct in VAM production. It is a
universal solvent, playing a critical role in countless industrial processes, including chemical
synthesis, cooling, and cleaning. In the biological context, water is vital for life, facilitating
biochemical reactions and maintaining cellular structure. In everyday life, water is used for
drinking, sanitation, agriculture, and recreation
2.7.3 Physical and chemical properties:
Physical properties :

Compound Name Water

Chemical Formula H2O
Role in Process product
Phase & Color clear liquid
Molecular Weight (g/mol) 18.02
Melting Point (oC) 0
Boiling Point (oC) 100
Density (kg/m3)
999.98
“normal conditions”
Viscosity (cP)
0.890
“normal conditions”
Specific Gravity 1
Critical Pressure (bar) 220.64
Critical Temperature (oC) 373.9
Critical Volume (cm3/mol) 55.9
Heat of Formation (kJ/mol) -241.84 (l)
Heat of Combustion (kJ/mol) -
Heat Capacity, Cp (gas) (J/mol K) 34.51
Heat Capacity, Cp (liquid) (J/molK)
75.338

Chemical properties :
Chemically, water is a polar molecule, consisting of two hydrogen atoms covalently bonded to
an oxygen atom (H-O-H). Its polarity makes it an excellent solvent, capable of dissolving many
ionic and polar substances. Water’s physical properties include a high specific heat capacity,
surface tension, and its ability to exist in three states—solid, liquid, and gas—under normal Earth
conditions.
2.8 Alternative production processes
Vinyl acetate can be produced in more than one route. Along with the route used
in this project which is the reaction of ethylene, acetic acid and oxygen. There are
two main alternative routes to produce VA, they are:

1) reaction of acetic acid and acetylene.

2) Acetaldehyde and acetic anhydride.

These routes are different in terms of reactants, catalysts, operating conditions

and number of reactions. Each route or method has its own advantages as well as
its disadvantages. In the following, these two alternative methods will be
discussed:

2.8.1 Reaction of acetic acid and acetylene:

In 1912, Fritz Klatte accomplished the first production of Vinyl acetate using the
reaction of acetic acid and acetylene with mercury as a catalyst. The reaction was
initially carried out in the liquid phase with mercury catalysts at 60−100 °C, but
this approach was later replaced by a gas-phase process and Zinc catalyst was
used . In this method, acetylene conversion varies from 60% to 70%, and the
selectivity of acetylene, acetic acid is more than 93% each . The reaction of this
method is as following:

HC≡CH + CH3COOH → H2C=CH-O-(CO)CH3

(Acetylene) (Acetic acid) ( Vinyl acetate)

However, this process is less utilized due to an economical reason. The

cost of acetylene as a raw material is considerably high. Generally, it is
economically less beneficial than the case of ethylene instead of acetylene .
2.8.2 Reaction of acetaldehyde and acetic anhydride (Synthesis gas method):

The second alternative route for producing vinyl acetate involves the reaction of acetaldehyde
with acetic anhydride. This reaction proceeds with the formation of EDA Ethylenediamine, an
intermediate chemical compound. Then EDA is reacted to produce Vinyl acetate.
These two reversible reactions are held in the presence of a Bronsted acid
catalyst at a temperature of 800C. The reactions are as follows:

CH3CHO + (CH3CO)2O → CH3CH(CH3CO2)2

(Acetaldehyde) (Acetic anhydride) ( EDA)

CH3CH(CH3CO2)2 → H2C=CH-O-(CO)CH3 + CH3COOH

(EDA) (Vinyl acetate) (acetic acid)

Even though the raw materials are not expensive which is an advantage for this method but the
capital cost for the utilities used in this process is higher than the other methods.
2.9 Main production process
The route for Vinyl acetate production in this project is the reaction of acetic
acid, ethylene and oxygen. It is economically the most profitable method to
produce vinyl acetate . Nowadays, this process has dominating position in the
Vinyl acetate production. This process contains of two reactions, and these
reactions occur in gas phase:

Desirable reaction :

C2H4 + CH3COOH + 0.5O2 → H2C=CH-O-(CO)CH3 + H2O

(Ethylene) (Acetic acid) (Oxygen) (Vinyl acetate) (Water)

Undesirable reaction :

C2H4 + 3O2 → 2CO2 + 2H2O

(Ethylene) (Oxygen) (Carbon dioxide) (Water)

Even though, the synthesis of vinyl acetate from ethylene, acetic acid and oxygen
over a palladium catalyst is a very important industrial process, but its selectivity
is affected by the production of CO2 due to the combustion of the ethylene.
Various other factors affect the synthesis of vinyl acetate, like for example, the
dispersion of Pd catalyst, partial pressures, and contact time. These reactions are
highly exothermic, and the heat of reactions must be removed by generating vapor
in the shell section of the tubes [1]. The temperature must be below 200ºC because
at this temperature the catalyst suffers irreversible damages. The recommended
operation pressure is between 8 and 10 atm because higher pressures favor the
productivity but affect negatively the selectivity due to the adsorption of the
ethylene.
Acetic acid, oxygen, and ethylene are provided as fresh feeds separately where
they are combined in mixer to create a mixture of those three components. It is
important to note that ethylene and oxygen are fed in the gas phase while acetic
acid is fed in the liquid phase where it vaporized using a superheated steam at the
vaporizer before entering the mixer. The stream coming out of the Mixer is then
directed into a feed Preheater and then the feed is directed in to the reactor. These
exothermic vapor-phase reactions then occur in a tubular reactor containing tubes
packed with a metal catalyst such as palladium on a silica support. Since the
composition of the reaction is two phase (gas reaction mixture, solid catalyst) the
type of reactor must be heterogeneous .

As it was stated above by Dimian and Bildea [4] that the typical operating
conditions for the reactor are as follow: Pressure 5-12 atm and Temperature
below 200 ⁰C. These ranges are as follows because the reactions are highly
exothermic, and it is desirable to operate the reactor in isothermal conditions. it
is Therefore, to control the temperature an inert gas such as ethane (used in this
project) or nitrogen is used. Since the reactor is a fixed-bed tubular-reactor with
tube and shell, the generating heat from the reactions are removed by generating
steam on the shell side of the tubes. Also, the reactor is design to achieve a low
conversion of ethylene by each pass 9%.

Another important reason for this temperature range is that the activation energy
of the undesirable reaction is greater than the activation energy of the desirable
reaction, so high temperature will affect the selectivity of Vinyl acetate which
must be 90% and purity of 95%. The exit stream from the reactor is then cooled
by passing through a heat exchanger, where the cold stream is the gas recycled.
From the heat exchanger the mixture passes through a phase separator which
separates condensable components water, vinyl acetate and unreacted acetic acid
from the remained no condensable gas of unreacted ethylene, carbon dioxide and
oxygen. The vapor stream from the separator goes to the compressor and the
liquid stream from the separator becomes a part of the feed to the azeotropic
distillation column.

The gas from the compressor enters the bottom of an absorber, where the
remaining vinyl acetate is recovered. A liquid stream from the base is recirculated
through a cooler and fed to the middle of the absorber. Liquid acetic acid that has
been cooled is fed into the top of the absorber to provide the final scrubbing. Part
of the overhead gas exiting the absorber enters the carbon dioxide removal system.
The gas stream minus carbon dioxide is split, with part going to the purge for
removal of the inert ethane from the process. The rest combines with the large
recycle gas stream and goes to the feed-effluent heat exchanger.

The liquid bottom acetic acid from the absorber combines with the liquids from
the separator as the feed stream to the distillation column. In this part of the
process, the main objective is to separate the acetic acid (bottoms) form the water
and vinyl acetate mixture (distillate).

The overhead product is condensed with cooling water and the liquid goes to a
decanter, where the vinyl acetate and water phases separate. The heavier of the
two phases is recycled back in to the distillation column and the other passes on
to the purification process to obtain the vinyl acetate, while the other is mainly
water.

Vinyl acetate forms the organic phase and water goes to the aqueous phase; Vinyl
acetate product is discharged as organic product from the decanter. While
unreacted acetic acid is discharged from the bottom and recycled after being
cooled to both the vaporizer and the absorber. The gaseous acetic acid obtained
is mixed with the recycle gas, oxygen and ethylene to form the feed to the reactor.
Figure 3: An initial block diagram of Vinyl production process
Figure 4: BFD of Vinyl Acetate Production
Chapter
III
 Chapter three
Material and energy balance

It is important to apply the laws of physics in to gain useful quantitative information from a system. The
most fundamental physical laws (for our purpose here) are conservation of mass which means mass
neither be produced nor destroyed and conservation of energy that states energy can't be created or
destroyed; it changes from on form into another. These two laws are widely applied in engineering and
science fields.

The general mass balance equation applicable to any system can be stated as:

Input + Generation – Consumption – Output = Accumulation.

The general energy balance equation applicable to any system can be formulated as:

Kinetic Energy + Potential Energy + Internal Energy = Work +Heat

Thus, mass balances are used extensively in engineering and environmental analyses. For instance, mass
balance theory is used to design chemical reactors, to analyze alternative processes to yield chemicals,
also to model pollution dispersion and other processes of physical systems. In this report, the balance of
the material and energy are described around all the equipment used in oxyacetylation of oxygen, acetic
acid and ethylene to produce vinyl acetate.
 1) Material balance :
The aim of this project is to produce 35000 tons a year of Vinyl Acetate. By converting to SI
unit per hour basis, it becomes :
(35000 tons/year) *(1000kg/1ton)*(1year/365days)*(1day/24h)*(1kmol/86kg)*(1/0.93)
≈50kmol/hr

3.1 Reactor (R-101) :

We implement our calculation for material balance with the reactor since the degree of freedom
is equal to zero after assuming a basis of 50 kmol vinyl acetate/h as production and then using
the conversion and selectivity was found that the ethylene feed to reactor is 617.33 kmol /h.
Using the ratio from source [2], the feed compositions entering to the reactor were found.

Equations :

Assumptions:
- Steady state.
- The selectivity is equal to 90%
- The single pass conversion is 9% of ethylene.
- The process is carried out isothermally.
 C2H4 + CH3COOH + 0.5O2 → H2C=CH-O-(CO)CH3 + H2O
(Ethylene) (Acetic acid) (Oxygen) (Vinyl acetate) (Water)

Desired chemical reaction equation:

Undesired chemical reaction equation:

C2H4 + 3O2 → 2CO2 + 2H2O

(Ethylene) (Oxygen) (Carbon (Water)

dioxide)

The overall mass balances

𝑛𝑖 𝑜𝑢𝑡 = 𝑛𝑖 𝑖𝑛 + ∑ 𝑣𝑖𝜉𝑖
Where:

𝑛 is the molar flow rate (kmol/h).

𝜉𝑖 is the extent of the reaction (kmol/h).

𝑣𝑖 is the reaction coefficient.

From the extent of reaction, the following was determined:

𝐼𝑛𝑝𝑢𝑡 −𝑂𝑢𝑡𝑝𝑢𝑡
1. Single pass conversion for E 𝑥 100 = 9 %
𝐼𝑛𝑝𝑢𝑡

2. Selectivity, σ= ( ξ1 )/(ξ1 +ξ2)=0.9

 3. For Ethylene, 𝑛 𝑜𝑢𝑡 = 𝑛 𝑖𝑛 − 𝜉1 − 𝜉2
4. For Vinyl Acetate, 𝑛 𝑜𝑢𝑡 = 𝜉1
5. For Oxygen , 𝑛 𝑜𝑢𝑡 = 𝑛 𝑖𝑛 − 0.5𝜉1 + 3𝜉2
6. For Carbon Dioxide, 𝑛 𝑜𝑢𝑡 = 𝑛 𝑖𝑛 + 2𝜉2
7. For Acetic Acid, 𝑛 𝑜𝑢𝑡 = 𝑛 𝑖𝑛 − 𝜉1
8. For Water, 𝑛 𝑜𝑢𝑡 = 𝑛 𝑖𝑛 + 𝜉1 + 2𝜉2
Calculation :
From the final vinyl acetate mass balance equation number (4):

𝑛 𝑜𝑢𝑡 = 𝜉1

35∗10−6 𝐾𝑚𝑜𝑙
𝜉1 = ≈ 50
8400∗86 ℎ𝑟

From the selectivity equation (2)

ξ1 𝜉1
𝜎= = 0.9 =
𝜉1 +𝜉2 50+𝜉2

Therefore, the extent of the undesired reaction is

𝐾𝑚𝑜𝑙
ξ2 = 5.56
ℎ𝑟
From Ethylene mass balance equation (3):

𝑛 𝑜𝑢𝑡 = 𝑛 𝑖𝑛 − 𝜉1 − 𝜉2
since the conversion of ethylene is 9%, then 𝑛 𝑜𝑢𝑡 = 0.91 𝑛 𝑖𝑛

0.91 𝑛 𝑖𝑛 = 𝑛 𝑖𝑛 − 𝜉1 − 𝜉2
Therefore,𝑛 𝑖𝑛 = 617.33 (𝑘𝑚𝑜𝑙/ℎ𝑟) , and 𝑛 𝑜𝑢𝑡 = 561.77 (𝑘𝑚𝑜𝑙/ℎ𝑟)
It was stated that the fraction of the feed composition will be:

O2 = 0.075,

CO2 = 0.007,

C2H4 = 0.583,
 C2H6 = 0.216,

VAM= 0,

H2O = 0.009,

AcOH= 0.110

The total flow can be found using the composition of ethylene entering:

Total flowrate = ethylene feed/ composition of ethylene in total flow= 617.33/0.583

= 1058.885 kmol / hr
Using equations (5) through (8), the following table was created :

Table 5: Material Balance around the reactor

Component Reactor Feed (kmol/hr) Reactor out(kmol/hr)

Vinyl Acetate 0 50

Oxygen 79.416 37.736

Ethylene 617.330 561.77

Ethan 228.719 118.719

Acetic Acid 116.477 66.477

Water 9.530 70.65

Carbon Dioxide 7.412 18.532

Total (kmol/hr) 1058.885 1033.884

3.2Flash drum (V-101) :
The main purpose of this flash drum is to separate the light key components from the reactor
effluent. A multicomponent flash distillation can be performed in this case to calculate vapor and
liquid flowrates and composition.

Equations :

Solving by Richford – Rice Equation:

𝑁
𝑍𝑖 𝐾𝑖
∑ =1
𝑉
𝑖=1 1 + ∗ (𝐾𝑖 − 1)
𝑓

Since the F and Zi are known, the objective is to calculate V/F

from the iterative procedure. The K-value can be calculated
from the Rault's law as follow,

𝑃𝑖𝑠𝑎𝑡
𝐾𝑖 =
𝑃 Figure 6: Flash Drum (V-101)

However, since this not an ideal solution, modified Roult's

law should be used:

𝑃𝑖𝑠𝑎𝑡 ∗𝑦
𝐾𝑖 =
𝑃
K-value have been taken from ChemiCad .

Calculations:
By trial and error, V/F was obtained to be 0.8604. As F = 1033.884 kmol/h and V/F = 0.8604, V
=889.503 kmol/h
L = F – V =144.381 kmol/h.

xi = zi/(1+(ki-1) (V/F)) and yi = ki xi

By substituting the values of z and k, the values of x and y were obtained.

 Table 6: z and k (from ChemCad) values and calculated x and y:

FeedIn(k Vapor Out Liquid Out

Component Zi Ki Xi yi
mol/hr) (Kmol/hr) (Kmol/hr)
Oxygen 0.036499 281.42 0.000151 0.042399 37.736 37.71425 0.021753
Vinyl Acetate
0.048361 0.12889 0.193032 0.024879 50 22.12986 27.87014

Water 0.068335 7.44E-02 0.335567 0.024958 70.65 22.20042 48.44958

Acetic Acid 0.064298 5.85E-03 0.444402 0.002601 66.477 2.313641 64.16336

Ethylene 0.543359 38.577 0.016303 0.628909 561.77 559.4162 2.353837
Carbon Dioxide
0.017925 23.968 0.000863 0.020694 18.532 18.40734 0.124661
Ethane 0.221223 26.393 0.009683 0.25556 228.719 227.321 1.398015
3.3Absorber(T-101):
A key aspect in an absorption system is the contact
between the gas and liquid phase. The main function is
to absorb a specific material in vapor phase using a
proper solvent, at an appropriate temperature and by
countercurrent contact, in which this vapor phase
material is highly soluble in that solvent.

Figure 7: Absorber (T-101)

Equations:
Some assumptions were proposed to make material balance calculations around
the absorber easier, where these assumptions are summarized as follows:

- Vapor stream (V7) is totally consisted of ethylene, oxygen, carbon dioxide and
 ethane.
- Liquid stream (L8) has a high recovery of Vinyl acetate 99.9% and 98% for
acetic acid.
- Water completely condense and leaves liquid stream (L8).
- Acetic acid enter liquid stream (L18) with a flow rate of 45 kmol/hr.

Employing these assumptions, mass balance will be done by a straight forward

computation using the following equation:

Overall Mass Balance:

𝐿𝑖𝑛 + 𝑉𝑖𝑛 = 𝐿𝑜𝑢𝑡 + 𝑉𝑜𝑢𝑡

𝐿18 + 𝑉6 = 𝐿8 + 𝑉7
Calculations :

Vinyl Acetate Mole Balance

𝑥𝑉𝐴𝑀,18𝐿18 + 𝑦𝑉𝐴𝑀,6𝑉6 = 𝑥𝑉𝐴𝑀,8𝐿8 + 𝑦𝑉𝐴𝑀,7𝑉7

0 𝑥 (45) + 0.02488 𝑥 (889.503) = 0.99 𝑥 [0.02488 𝑥 (889.503)] + 𝑦7 (𝑉7)

𝑦𝑉𝐴𝑀,7 (𝑉7) = 0.22129

Acetic Acid Mole Balance

𝑥𝐴𝐶𝑂𝐻,18𝐿18 + 𝑦𝐴𝐶𝑂𝐻,6𝑉6 = 𝑥𝐴𝐶𝑂𝐻,8𝐿8 + 𝑦𝐴𝐶𝑂𝐻,7𝑉7

1 𝑥 (45) + 0.002610 𝑥 (889.503) = 0.98 𝑥 [1 𝑥 (45) + 0.002610 𝑥 (889.503)] + 𝑦7 (𝑉7)

𝑦𝐴𝐶𝑂𝐻,7 (𝑉7) = 0.94627

Overall Mass Balance for Vapor outlet

 𝑉7 = 𝑦𝑉𝐴𝑀,7 𝑉7 + 𝑦𝐴𝐶𝑂𝐻,7 𝑉7 + 𝑦𝑂2,7 𝑉7 + 𝑦𝐻2𝑂,7 𝑉7 + 𝑦𝐸𝑇𝐻𝑌,7𝑉7 + 𝑦𝐸𝑇𝐻𝐴 𝑉7 + 𝑦𝐶𝑂2,7 𝑉7

𝑉7 = 0.22129 + 0.94627 + 37.71425 +0+ 559.4162 + 227.321 + 18.40734

𝑽𝟕 = 𝟖𝟒𝟒. 𝟎𝟐𝟔𝟑𝟓 𝒌𝒎𝒐𝒍/𝒉𝒓

Overall Mass Balance for Liquid outlet

𝐿18 + 𝑉6 = 𝐿8 + 𝑉7

45 + 889.5027 = 𝐿8 + 844.02635

𝑳𝟖 = 𝟗𝟎. 𝟒𝟕𝟔𝟑𝟓 𝒌𝒎𝒐𝒍/𝒉𝒓

Table 7: Absorber Mass Balance :

Component Name Vapor In, 𝑽𝟔 Liquid In, 𝑳𝟏𝟖 Vapor Out, 𝑽𝟕 Liquid Out, 𝑳𝟖

Oxygen 37.71425 0 37.71425 0

Vinyl Acetate 22.12986 0 0.2212986 21.9085614

Water 22.20042 0 0 22.20042

Acetic Acid 2.313641 45 0.94627282 46.36736818

Ethylene 559.4162 0 559.4162 0

Carbon Dioxide 18.40734 0 18.40734 0

Ethane 227.321 0 227.321 0

Total (kmol/hr) 889.502711 45 844.026361 90.47634958

3.4 Distillation column :

Distillation columns are separation techniques

used to separate liquid mixtures that have
difference in boiling point as a driving force for
separation. Energy and mass balances are
performed around the column to get the
condensers and reboilers duty along with the
component molar flowrate in each stream.

Figure 8: Distillation Column (T-102)

Equations:
The bottom stream from the flash separator is sent to the distillation column unit after mixing
with the outlet absorber.
Assumptions:

- Steady state.
- Since there is no water in gas recycled stream, all of water that entering the
reactor comes from the bottom of the distillation column.
- All vinyl acetate goes to the top stream.
- The 5% impurity in the VAM stream is only acetic acid that comes from top
stream.
- Assume all gases go up to the top.
- Reflux ratio is 0.85.

The overall mass balance:

𝐹=𝐷+𝐵

Solving for the distillate stream:

𝐷 = 𝐹 − 𝐵 = 234.8577 − 117.4408 = 𝟏𝟏𝟕. 𝟒𝟏𝟔𝟗 𝑲𝒎𝒐𝒍/𝒉𝒓

Calculations:
𝑛𝑖,𝑓 = 𝑛𝑖,𝑏 + 𝑛𝑖,𝑡𝑜𝑝 𝑜𝑢𝑡𝑙𝑒𝑡

Where,

𝑛𝑖,𝐹 is the molar flow rate of component i in the feed (kmol/h).

𝑛𝑖,𝐷 is the molar flow rate of component i in the distillate (kmol/h).

𝑛𝑖,𝐵 is the molar flow rate of component i in the bottom (kmol/h).

𝑛𝑖,𝑉𝐴𝑀 is the molar flow rate of component i in the Vinyl acetate product stream (organic product)
(kmol/h).

𝑛𝑖,𝑝𝑢𝑟𝑔𝑒 is the molar flow rate of component i in the purge stream (kmol/h).
𝑛𝑖,aqueous is the molar flow rate of component i in the aqueous product stream (kmol/h).

Component mass balance of oxygen O2:

𝑛̇𝑂2,𝑝𝑢𝑟𝑔𝑒 = 𝑛̇𝑂2,𝐹 = 0.021753 (Kmol/hr)

Component mass balance of vinyl acetate VA:

𝑛𝑉𝐴,𝑉𝐴𝑀 = 𝑛𝑉𝐴,𝐹 = 49.7787 (Kmol/hr)

To check the value of VA, from problem statement, VA production was 35000
ton/year which equals to around 49 kmol/hr.
Component mass balance of vinyl acetate VA:
𝑛𝑉𝐴,𝐷 = 𝑛𝑉𝐴,𝐹 ∗ 𝑓𝑟𝑉𝐴,𝐷

𝑛𝑉𝐴,𝐷 = 49.7787 x 1 = 49.7787 kmol/hr

 To check the value of VA, from problem statement, VA production was 35000
ton/year which equals to around 50 kmol/hr.

Component mass balance of water H2O:

The bottom amount of water is 9.53 kmol/hr which will further recycle back to the

reactor. The water fed to the tower is 70.65 kmol/hr.

Bottom stream of water is: 70.65 - 9.53=61.12 kmol/hr

𝑛𝐻𝑂2,𝐴𝑞𝑢𝑒𝑜𝑢𝑠 = 9.53 (Kmol/hr)

𝑛𝐻𝑂2,𝑏 = 𝑛𝐻𝑂2,𝑓 − 𝑛𝐻𝑂2,𝐴𝑞𝑢𝑒𝑜𝑢𝑠 = 70.65 − 9.53 = 61.12 (Kmol/hr)

Component mass balance of acetic acid AcOH:
Since the product’s impurity is 5%, the acetic acid in the organic products stream:

𝑛𝐴𝑐𝑂𝐻,𝑉𝐴𝑀 = 52.39863 ∗ 0.05 = 2.619932 (Kmol/hr)

The bottom acetic acid: 110.5307 -2.6199 = 107.9108 kmol/hr

𝑛𝐴𝑐𝑂𝐻,𝑉𝐴𝑀 = 𝑛𝑉𝐴𝑀 ∗ 0.05

𝑛𝐴𝑐𝑂𝐻,𝑏 = 𝑛𝐴𝑐𝑂𝐻,𝑓 − 𝑛𝐴𝑐𝑂𝐻,𝑉𝐴𝑀 = 110.5307 − 2.6199 = 107.9108(Kmol/hr)

Component mass balance of ethylene:

𝑛𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒,𝑝𝑢𝑟𝑔𝑒 = 𝑛𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒,𝑓 =110.5307(Kmol/hr)

Component mass balance of ethane C2H6:

𝑛𝐶2𝐻6,𝑝𝑢𝑟𝑔𝑒 = 𝑛𝐶2𝐻6,𝑓 = 1.398015 kmol/hr

The top stream can be found after using the total mass balance:
𝑛𝑂2,𝑡 = 𝑛𝑂2,𝑓 = 0.021753 (Kmol/hr)

𝑅𝑒𝑓𝑙𝑢𝑥 = 0.85 ∗ 52.39863 = 44.53884(Kmol/hr)

𝑛𝑉𝐴,𝑡 = 𝑛𝑉𝐴,𝐹 + 𝑅𝑒𝑓𝑙𝑢𝑥 ∗ 0.95

𝑛𝑉𝐴,𝑡 = 49.7787 ∗ 1 + 𝑅𝑒𝑓𝑙𝑢𝑥 ∗ 0.95 = 49.7787 ∗ 1 + 44.53884 ∗ 0.95 = 92.0906(Kmol/hr)
𝑛𝐻𝑂2,𝑡 = 𝑛𝐻𝑂2,𝐴𝑞𝑢𝑒𝑜𝑢𝑠 =9.53(Kmol/hr)

𝑛𝐴𝑐𝑂𝐻,𝑡 = 𝑛𝐴𝑐𝑂𝐻,𝑉𝐴𝑀 + 𝑅𝑒𝑓𝑙𝑢𝑥 ∗ 0.05 = 2.619932 + 44.53884 ∗ 0.05 = 4.846874(Kmol/hr)

𝑛𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒,𝑡 = 𝑛𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒,𝑓 = 110.5307 kmol/hr

𝑛co2,t =𝑛co2,f = 0.124661(Kmol/hr)

𝑛̇𝐶2𝐻6,𝑡 = 𝑛̇𝐶2𝐻6,𝑓 = 1.398015 kmol/hr

Table 8:Summary of the streams in the distillation Column

Distillation column

Dis Feed Bottom Top Reflux

Mole Flows 234.8577 117.4408 161.955736 44.53884

(kmol/hr)
Oxygen 0.021753 0 0.021753 0

Vinyl Acetate 49.7787 0 92.0906 42.3119

Water 70.65 9.53 61.12 0

Acetic Acid 110.5307 107.9108 4.846874 2.226942

Ethylene 2.353837 0 2.353837 0

Carbon Dioxide 0.124661 0 0.124661 0

Ethane 1.398015 0 1.398015 0

 3.5Decanter (V-103) :
Is a vessel that is used to hold the decantation of a
liquid to separate a small volume of liquid, containing
the sediment, mainly acetic acid in this process, from
a larger volume of "clear" liquid, which is free of such.

Equations :
Assumptions:
• Steady state.
• The impurity with VA is only acetic acid.
• All the vapor is getting out from the purge
(Ethylene, Ethane, CO2, O2).
• Aqueous product contains only pure
water.
• Assume the reflux ratio (L/D) is 0.85

Table 9: Mass balance around the Decanter

Decanter
Organic aqueous
Stream number Dis Top Purge Reflux
product product
Total Molar Rate 161.955736 3.898266 52.398632 61.12 44.53884
Oxygen 0.021753 0.021753 0 0 0
Vinyl Acetate 92.0906 0 49.7787 0 42.3119
Water 61.12 0 61.12 0
Acetic Acid 4.846874 0 2.619932 0 2.226942
Ethylene 2.353837 2.353837 0 0 0

Carbon Dioxide 0.124661 0.124661 0 0 0

Ethane 1.398015 1.398015 0 0 0

3.6 Purge and recycle :

Recycle is process stream that returns material from downstream of a process unit back to the
process unit to be use again in the reaction and integrate energy effectively. While, the purge
is a stream bled off to remove an accumulation of inert or unwanted materials that might
otherwise build up in the recycle stream.

Equations :

Assumption:

- The efficiency of CO2 Removal is 95%.

- The fraction of stream that enter the CO2 removal is the same as the
out-vapor stream from absorber.
- As stated in [2], the ratio between the fresh feed to the reactor
feed for ethylene is 7.405%, so the fresh feed for ethylene is 48.228
kmol/hr.
- The impurity in ethylene fresh feed is 0.1% which the same amount
that leave in the purge.

The amount of CO2 removed = vapor out from the absorber ‫ ــ‬the amount of CO2 enter
reactor.

➢ Since the amount of CO2 that enter the reactor was found to be 7.412 kmol/hr,
the amount removed is equal to (18.407 - 7.412) = 10.995 kmol/hr.
➢ As the CO2 removal is 95%, the amount of CO2 that enter the CO2 removal
unit will be 10.995/0.95=11.574 (Kmol/hr)

➢ Then to find the purge stream, from the assumption it can be said that the
ethane enter
from fresh feed will be 0.048228 (Kmol/hr)
 ➢ Since the fraction of the purge stream is known, the total molar flow of gas
purge stream will be 0.17516 (Kmol/hr)

Recycle stream = vapor out from the absorber ‫ ــ‬CO2 purge stream ‫ ــ‬the gas purge
Calculations were done, and the results are tabulated in table (7):

Table 10:Summary of mass balance for the Purges and Recycle streams
Absorber CO2
CO2 Gas Purge Vap. Recycle
Streams Vap. Out Removal in
Purge (kmol/hr) (kmol/hr)
(kmol/hr) (kmol/hr)
(kmol/hr)
Total Molar
844.026 530.701 10.995 0.175 832.635
Flows (kmol/hr)
Oxygen 37.714 23.714 0 0.008 37.706
Vinyl Acetate 0.221 0.139 0 0.221 0
Water 0 0 0 0 0
Acetic Acid 0.946 0.595 0 0 0.946
Ethylene 559.416 351.746 0 0.119 559.298
Carbon Dioxide 18.407 11.574 10.995 0 7.412
Ethane 227.321 142.933 0 0.048 227.273