HEAT EFFECTS ANALYSIS IN THE ETHANOL INDUSTRY

In Partial Fulfilment of the Requirements for the Course

Chemical Engineering Thermodynamics 1

Submitted By:
LAPUEBLA JEREMY C.
MAMBA, RHEA D.
OBILLO, ANA ROSE S.

Submitted To:
ENGR. CAESAR P. LLAPITAN

MAY 2017
Table of Contents
Abstract
I. Introduction .................................................................................................................. 1
II. Ethanol Production Processes ...................................................................................2-6
A. Ethanol Production by Catalytic Hydration .............................................................
B. Ethanol Production by Indirect Hydration ............................................................. 6
C. Ethanol Production by Fermentation ...................................................................... 6
III. Energy balance in the Reactor .................................................................................... 10
IV. Conclusion .................................................................................................................. 15
V. References ................................................................................................................. 16
 HEAT EFFECTS ANALYSIS IN THE ETHANOL INDUSTRY

Abstract: Ethanol plays an important role in human life, it is used in the production of
beverages and an important component in the production of fuel. In producing ethanol, four
processes can be applied but the commonly used processes are the catalytic hydration of
ethylene and the fermentation processes. In using catalytic hydration process in a mole of
ethylene gas at 320°C the resulting product is one mole of ethanol with a temperature of 25°C,
heat effects occur during the production; it starts from the furnace moving to the reactor, so
that to get the amount of heat transfer energy balance from the system must be done and the
resulting heat is equal to Q= -155.563 KJ which means that as the process move from furnace
to the reactor heat loss occur.

I. Introduction
The world ethanol production has recently seen an incremental growth mainly due to
economic and environmental security concerns, worldwide. Ethanol or ethyl alcohol
(CH3CH2OH), a colorless liquid with characteristic odor and taste; commonly called grain
alcohol has been described as one of the most exotic synthetic oxygen-containing organic
chemicals because of its unique combination of properties as a solvent, a germicide, a beverage,
an antifreeze, a fuel, a depressant, and especially because of its versatility as a chemical
intermediate for other organic chemicals. Ethanol has been recognized as an important
renewable and sustainable fuel source for modern industries. For example, it can be used as a
replacement of gasoline for many internal combustion engines, and it can be mixed with
gasoline to any concentration. Most existing car engines can run on blends of up to 15% bio-
ethanol with petroleum/gasoline, thus it can significantly reduce the dependence on crude oil.
Ethanol produced has three major applications: fuel ethanol, beverage ethanol, and
industrial ethanol. Fuel ethanol is blended with gasoline for use as motor fuel. Beverage ethanol
is used to produce beer, wine, and other spirits. Industrial ethanol is a chemical feedstock
typically used to produce pharmaceutical products and polymers.
Ethanol production had an extreme requirement globally as a fuel additive as 1.02 ×
1011 liters were produced in 2010. Most of the ethanol produced is used as motor fuel or an
additive in gasoline to improve its octane level. As a liquid fuel, ethanol has long-term
advantages. Ethanol has good properties for spark ignition with the motor octane number and
research octane number of 90 and 109, respectively that is much greater than regular gasoline
which is 88.
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II. Ethanol Production Process

Catalytic
Ethylene Ethanol
Hydration

Sugar Fermentation

Starchy Hydrolysis
Material

Lignocellulosic
Pretreatment
Material

Figure 1.0-Schematic diagram of some of the different methods for production of ethanol

The economic competitiveness of ethanol has been heightened by concerns over prices
and availability of crude oil as well as greenhouse gas emissions which have stimulated interest
in alternatives to crude oil to provide for automotive power and also by the use of bioethanol
in the production of hydrogen for fuel cells. Therefore, there is the need to explore ways of
producing ethanol at competitive costs by the use of energy efficient processes. Some of the
processes involved in producing ethanol are shown in Figure 1.0.
Some of the several ways to produce ethanol production includes fermentation of
ethanol, indirect hydration (esterification-hydrolysis) process and direct hydration of ethylene.
Ethanol is produced by petrochemical through direct and indirect hydration as well as via
biological processes by fermenting sugars with yeast. Most of the industrial processes were
done by fermentation process but the output was not reliable.

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A. Ethanol production by catalytic hydration

Light Product

Water Hydrogen

Hydrogenerator
Light Distillation
Pump Column
Scrubber Acetaldehyde
separator
Separator

Feed

Pump Furnace
`
Feed
Preheater
Pump
Reactor
Purifier

Figure 2.0-Process flow diagram for catalytic hydration of ethylene

Ethanol can be manufactured industrially by reacting ethane with steam. This reaction
is reversible and the formation of ethanol is exothermic. At normal conditions, the equilibrium
is positioned to the left and the amount of ethanol formed is quite small, therefore, to
significantly increase the yield of ethanol, the reaction is carried out at 300C and about 60-70
atmospheric pressure using catalyst compounds such as phosphoric acid (H3PO4) which acts as
the catalyst. The reaction for the process is
CH 2  CH 2 ( g )  H 2 ( g )  C2 H 5OH ( g ) (H  45 kj / mol )

In the petrochemical industry, ethanol is produced via direct and indirect hydration of
ethylene. Catalytic direct ethylene hydration was first introduced by Shell in 1947. In this
process, ethanol is produced by a reversible exothermic reaction between ethylene and water
vapor. The process consists of three different steps including reaction, recovery and
purification. The ethylene is mixed with steam with a molar ratio of 0.6 at 250–300 ºC and 70–
80 bar and then passes over an acidic catalyst in a fixed bed reactor. The water-to-ethylene
ratio should be less than one to avoid catalyst losses. The ethylene conversion is about 4–25%
and it is recycled. The ethanol selectivity is 98.5mol%. Phosphoric acid coated onto a solid
silicon dioxide has been used mainly as the catalyst.

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 A simple process diagram of catalytic direct hydration of ethylene is presented in Figure
2.0. The feed stream (ethylene and water) preheated by effluent is heated up to 300 ºC in the
furnace. Thereafter, it enters into a packed bed catalytic reactor at 70 bar. Phosphoric acid is
used as catalyst and conversion is 4–25%. Acetaldehyde is produced as a by-product, which
can either be sold or further hydrogenated to produce ethanol. The unreacted reactants are
separated from the outlet vapor mixture of the reactor in a high pressure separator and then
scrubbed with water to dissolve the ethanol. The recycled vapor from the scrubber contains
ethylene, and the molar ratio of water to ethylene is maintained as 0.6:1. The bottom streams
of the scrubber and the separator are then fed to the hydrogenator, where acetaldehyde is
converted into ethanol on a nickelpacked catalyst. In the acetaldehyde separator column, the
unreacted acetaldehyde is removed and recycled to the hydrogenator, and the bottom stream is
fed to the light and the heavy (purifier) columns to increase the ethanol concentration.

a. Reactors used in catalytic hydration

The reactor used in this process is a fixed bed reactor in which a stationary solid catalyst
is used to carry out reactions whereby the reactant is in mobile fluid phase that takes place on
the surface of the catalyst. The reactant diffuses, adsorbs and reacts on the active surface of the
catalyst. Catalytic fixed bed reactors are the most widely used reactor for gas phase reactants
as well as in the production and synthesis of large scale basics chemicals and intermediates.
Fixed bed reactor is usually modelled and optimised using the continuum models that are
grouped in two categories namely; pseudo-homogeneous and heterogeneous model. If the
differences between the fluid and solid phase conditions are significant, heterogeneous model
has to be considered in spite of the pseudo-homogeneous model with average properties. The
pseudo-homogeneous model does not take into account explicitly for the presence of the
catalyst in contrast to heterogeneous model which, in turns leads to the separate conservation
equations for fluid phase in the catalyst pores.

b. Catalysts used in catalytic hydration

The direct hydration of the ethylene has been carried out since about 60 years ago in
the chemical industry over catalyst consisting of the silica gel with a high loading of phosphoric
acid. Catalyst is characterised as the supported liquid phase and the catalytic active bound on
a carrier as the concentrated liquid acid. Phosphoric acid on silica gel is more resistant to
leaching than the acid on metal phosphate. The Silica gel-supported phosphoric acid catalyst
(H3PO4/SiO2) is used in the industry as it has high selectivity in excess ethylene. The ethanol
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production rate increases remarkably with increasing phosphoric acid loadings. Phosphoric
acid present in liquid like form on silica gel has a pure acidic nature. The higher condensed
phosphates take longer time to be hydrolysed.

B. Ethanol production by indirect hydration

Sodium
Hydroxide Ethyl
Solution Ether
Ethyl
Sulfuric Alcohol
Acid

Ethylene Steam

Absorption Fractionating
Hydrolyzer Stripping Scrubber Ether
tower Column
Column Column
Spent
Water Caustic Water
Diluted
Acid Concentrator

Figure 3.0- Process flow diagram for indirect hydration of ethylene

Gas containing ethylene with a C2H4 percentage variable from 35% to 95% reacts in
adsorption towers at 55-80°C and 10-35 bars with sulphuric acid and H2SO4 percentage varying
from 94 to 98%; eventually, the reaction is catalysed by Ag2SO4. The reaction is exothermic
and gives mono and diethylsulphate. Both esthers are hydrolysed to ethanol in towers with
antiacid coating at 70-100°C. During the hydrolysis at high temperatures, the by-product
diethylether is obtained. The sulphuric acid is later concentrated from 50 to 98%. The process
efficiency is of 86%.
The indirect hydration uses as principal raw material ethylene from different sources:
coke production, cracking gas of ethane/propane mixtures, cracking gas of heavy gasoline or
naphtha. The gases have to be enriched in ethylene and made free from superior olephines. The
natural resources necessary to produce ethylene are: natural gas, petroleum, and carbon. The
others raw materials are sulphuric acid and the sulphur or pyrites. During the process a small
quantity of NaOH and water are used. As far as energy consumption is concerned, it is
necessary to consider the following steps: ethylene production, sulphuric acid production,
concentration of ethylene, heating ethylene and sulphuric acid, compressing ethylene,

5
distillation of ethanol, and concentration of sulphuric acid. The total energy consumption can
be calculated in about 29 MJ/kg.

C. Ethanol production by fermentation

Water
Molasses Water
Condenser
Carbon Dioxide
Sulfuric Aldehydes
Acid Scrubber
Mixing
Tank
Ammonium Fermenter
Aldehhyde Rectifying
Sulfate Column
Fuel Column
Sterilizer Oil
Beer
Yeast Water Water
Tub Beer
Still
Yeast
Culture
Machine Benzene

Slop
Aldehhyde
Column

Ethyl
Alcohol
(absolute)

Figure 4.0- Process flow diagram for catalytic fermentation

A distinction must be made from raw materials. Those which are specifically grown for
ethanol production (sugar substrates such as sugar beet, fodder beet, sugar cane, starch products
such as potatoes) and the residues: industrial and food processing wastes (waste sulphite
liquors, whey, food industry wastes); agricultural and domestic residues. A different treatment
is necessary, of course, to prepare the culture broth with different energetic and environmental
impact. Once the culture broth is prepared, the process is common. The resulting wine, at a
maximum ethanol concentration of about 10% by volume is decanted and centrifuged to
separate the non-fermentable matter and the yeasts. The obtained liquor is distilled, rectified
and dehydrated to obtain absolute alcohol. The scheme of the process is illustrated in Figure
4.0.
The raw materials for ethanol fermentation are various: sugar substrates, starchy
products, cellulose material, and industrial residues. Other materials and utility requirements
are sulphuric acid and ammonium sulphate with a much reduced consumption of natural

6
 sources and water. As far as energy consumption is concerned, the following steps have to be
considered: operation of agricultural machinery, irrigation, chemical products, preparation of
worth, fermentation and distillation. The total energy consumption can be calculated in about
21 MJ/kg.

III. Energy Analysis

The region in a catalytic hydration process in which the energy balance was analyze
was is shown below.

Heat Work

Furnace
m0 m1
E0 E1
C0 C1
Reactor Reactor

Figure 5.0- Region in which energy balanced was analyzed

The statement of conservation of energy for this system takes the form

rate of energy  rate of energy 

rate of energy      rate of heat  rate of work 
   entering system  leaving system   
 accumulated  by in flow  by outflow  added to system done on system
   
In terms of the defined variables it is written as,
dE    
 m0 E 0  m1 E 1  Q  W (1)
dt
wherein total work done by the system can be expressed as
   
W  W f W s W b (2)
where

W = total work

W f = flow stream

W s = shaft work

W b = boundary work

7
 
Work done by the flow stream W f can be also expressed in different parameters

W f   0 A0 P0  1 A1 P1 (3)

W f  Q0 P0  Q1 P1 (4)
 P0 P1
W f  m0  m1 (5)
0 1
Therefore the overall work of the system is
    P0 P1  
W  W f  W s  W b  m0  m1 W s W b (6)
0 1
This energy balanced can be applied in the given problem which involved a reactor
section.
Ethylene gas and steam at 320 C and atmospheric pressure are fed to a reaction
process as an equimolar mixture. The process produces ethanol by the reaction:
C2 H 2 ( g )  H 2 O ( g )  C2 H 5OH (l )
The liquid ethanol exits the process at 25 C. What is the heat transfer associated with this
overall process per mole of ethanol produced?
1 mol of C2H4 (g)

Reactor 1 mol of C2H5OH

1 mol of H2O(g)

C 2 H 2 ( g )  H 2 O ( g )  C 2 H 5 OH (l )
Energy balance:

H  Q  H R  H 298

H 298  H C 2 H 5OH  (H C 2 H 4  H H 2 O ) 
H 298   277690  (52510  241818)
H 298  8.838  104 J / mol
Reactant consists of 1 mole each of C2H4 and H2O.

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Constants:
C2 H 2 ( g ) H 2O ( g )

A  1.424 A  3.470
B  14.394  10 3 B  1.450  103
C  4.392  106 C 0
D0 D0
A  ni  Ai 
A  (1) (1.424  3.470)

A  4.894

B  ni  Bi 

B  (1) (14.394  103  1.450  103

B  0.001584

C  ni  Ci 

C  (1) (4.392  106  0)

C  4.392  106

D  ni  Di 

D  (1) (0.121105  0)
D  1.21  104
The general formula for solving H R is

H R  R  M C PHT

Solving for M C PH

B C D
M C PH  A  T0 (  1)  T0 ( 2    1)  2
2 3 TT0

9
 where  :
T

T0
298.15
 
593.15
  0.5
0.0158 (4.392  106 ) 1.21 104
M C PH  4.894  (593.15)(0.5  1)  (593.15)2 (0.52  0.5  1) 
2 3 (0.5)(593.15)2

M C PH  11.12

Plugging in the calculated value of M C PH gives

H R  (8.314) (11.12) (298.15  593.15)

H R  2.727  104 J / mol

Solving for Q
Q  (H R  H 298 ) (n)

Q  (2.727  104  8.838  104 ) (1)

1kJ
Q  115653 J 
1000 J
Q  115.563 kJ

IV. Conclusion
Producing ethanol can be done in different processes, these processes include catalytic
hydration of ethylene, indirect hydration and fermentation. The process of catalytic hydration
is used to logically model and solve a problem. Taking the furnace and the reactor as the system
and relating it to the problem, the energy balance was performed in the region. The problem
involves the reaction as shown below
C2 H 2 ( g )  H 2O ( g )  C2 H 5OH g 
.The problem requires the heat transfer associated with the overall process per mole of ethanol
produced, by doing some energy balance, Q is then computed with a result of 115.63 kJ. It is a
negative heat transfer, thus, the system is transferring heat to the surroundings.

10
V. References

11