FACULTY OF ENGINEERING

BACHELOR OF TECHNOLOGY IN CHEMICAL ENGINEERING

BELLVILLE CAMPUS

PROJECT TITLE: MANUFACTURE OF ETHANOL FROM

ETHYLENE AND STEAM

Group Members: Emmanuel Kongolo 212064509

Jonathan Kabamba Katende 211066192

Due Date: 13 February 2015

Lecturer: Mr. Taffy Madzimbamuto

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List of symbols

Symbol Description Units

N Steam to ethylene ratio in the feed to the reactor Mol/mol

V Volume m3

M Mass kg

P Pressure in the reactor atm

R Recycle to purge ratio Mol/mol

K Equilibrium constant Dimensionless

f Scale up factor based on assumed basis Dimensionless

F Scale up factor based on actual flow rate Dimensionless

ξ Extent of reaction Mol

Nab Mol flow rate or number of moles in stream a of kmol/h

component b

ρ density kg/m3

2
 1. Introduction

A new ethanol producing plant wants to have an output of 5 million gallons of 95% by volume ethanol
per year. Using pure steam and 99% ethylene combined with 1% ethane are to be used as raw material.
The tasks at hand consists in using a simplified model to estimate the costs involved in the production
of ethanol and calculate the profit. 3 parameters: the reactor pressure, the steam to ethylene reactor feed
and the recycle to purge ratio were varied in order to obtain optimum conditions which result in
maximum profits or minimum losses.

2. Mass Balance Calculations

Different approaches are used in various textbooks in mass balance calculations. Coulson and
Richardson used the modular approach whilst Felder and Rousseau used the equation oriented method.
The latter method was used for these calculations.
Simplifying Assumptions:
 The process is run in steady state conditions
 In the flash separation unit, a perfect separation has been achieved meaning the gases leaved
the column by the overhead stream and the liquids at the bottom.
 There is a negligible quantity ethanol in the bottom product of the distillation column
 Equilibrium conditions have been reached in the reactor
 There is no side reaction occurring

The mass balance calculations are summarized on the excel spreadsheet. A simplified flowsheet of the
process has been included in the appendix. To determine the various flow rates, expressions written in
terms of known values were derived for each stream. From the derived expressions, the flow rates were
calculated.
A basis of 100 kmol was assumed for the overhead product from the distillation column. Given the
specific gravity and the volume fractions of ethanol and water in the product stream, their respective
mole fractions were calculated making use of density and molar masses. From the total mol flow and
the fractions, the flow rates of individual components were determined. Since there were insufficient
information on the distillation column to proceed further, the balances on the reactor were done.
Assuming the reaction has reached equilibrium, the principles given in chemical equilibrium were used
to derive an expression function of the pressure in the reactor and the steam to ethylene feed ratio to
which enabled us to determine the extent of reaction. It tells us how much of the reactant has been
consumed and how much product has been generated. The extent calculated for the reactor was done
assuming 1 mole of ethylene in the feed to the reactor. Using the quantity of ethanol obtained from the

1
assumed basis and the extent of reaction, a scale up factor was determined. This factor was used to
calculate the flow rates of all various streams.
In the spreadsheet, this factor is referred to as scale up factor based on basis. Using the ethanol quantity
from the assumed basis and the actual volume of ethanol produced, a new scale up factor was
determined. From that scale up factor, the actual feed and all other stream flow rates were determined.
The costs were given in terms of $/lb; they were converted to $/kg. From the masses obtained the various
operating costs were determined. Some costs calculations required the stream’s total molar flow rate.
Knowing the total mass flow rates, mol compositions and molar masses of the components in each
stream, the average molecular mass was determined and the flow rate calculated.
The parameters that can be varied are highlighted in very light blue on the left hand side of the
spreadsheet. The capacity is also a value that can be varied. The cost associated will be calculated
automatically. The given data were also included on the left hand side. In the middle of the spreadsheet
the various mass and mole flow rates and the compositions were calculated. The values (except for the
inerts) depend on the extent of reaction which is a function of pressure and steam to ethylene ratio (N).
The costs are on the right hand side of the sheet. The fuel gas and ethanol cost are considered as sources
of income for the process and all the other costs are considered as expenses. From the given information
it was not clear to the students whether the pressure drop across the condenser should be multiplied by
the cost per kmol fed to the unit and the number of moles to get the total compression cost. That is what
was done since the pressure change across the compressor are believed to have a direct effect on the
costs involved. The difference of the income and expenses gives the loss/profit.

2.1. Detailed Calculations

2.1.1. Balances around distillation column

The composition of the overhead was given in terms of volume fractions. In material balance
calculations involving a reactor in the process, it is much simpler to work with moles. Making
use of the given specific gravity, the density of water at 25⁰C obtained from Chemical
engineering Perry and the molar masses of the components, the mole fractions were determined.

Assuming a basis of 100 m3 in the overhead stream (this basis was only used for volume to mol
fraction conversion purpose):

2
  water  997.045 Kg
m3
Vwater  5m 3
VEthanol  95m 3

 m water    V  5  997.045  4985.225Kg

m water  m Ethanol 4985.225  m Ethanol
SG    75714.795Kg
Vwater  VEthanol 5  95
98
46
Ethanol 
x13  0.855  x13
water  0.145
93.8 6.2

46 18
 x water  1  0.855  0.145
13

Assume 100 kmol leaving the overhead of the distillation column

 N ethanol
13
 x13
Ethanol  N
13
 0.855  100  85.5Kmol
13
N water  xW13ater  N 13  0.145  100  14.5Komol

Since the amount of ethanol coming in the Distillation column was assumed to be coming out
only in stream 12, it can therefore be said that the ethanol recovered in stream 12, is equal to
the amount of ethanol fed to the column in stream 9 which is equal to the amount of ethanol
leaving the reactor in stream 5, passed through the valve in stream 6 and fed to the flash in
stream 7.

12
N Ethanol  N Ethanol
9
 N Ethanol
5
 N Ethanol
6
 N Ethanol
7
 85.5kmol

2.1.2. Mass balance around the Reactor

Assuming a basis of 1 kmol of ethylene fed to the reactor and N, the steam to ethylene ratio,
chemical equilibrium expressions were used to determine the extent of reaction.

C2 H 4  H 2 O  C2 H 5OH

Initial: 1 N -

Final: 1-  N-   sum = 1+ N - 

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The equilibrium constant expression was derived using partial pressures since the reactor is
gas phase.

PEthanol
K
PEthelene  PW ater
 1 N 
PEthanol  PT ; PEthelene  PT ; PW ater  PT
1 N  1 N  1 N 


PT
1 N   1  (1  N   )
K  K
1 N  (1   )( N   ) PT (1   )( N   )
PT  PT PT
1 N  1 N  1 N 
 KPT (1   )( N   )   (1  N   )
 KPT ( N    N   2 )    N   2
 KPT N  KPT   KPT N  KPT  2    N   2
 ( KPT  1) 2  ( KPT  1)( N  1)  KPT N  0
Note : P  PT
( KP  1)( N  1)  [( KP  1)( N  1) 2  4( KP  1)( KPN )
 
2( KP  1)

For N=1; P = 10 atm:

(0.01306  10  1)(1  1)  [(0.01306  10  1)(1  1) 2  4(0.01306  10  1)(0.01306  10  1)

  0.0595kmol
2(0.01306  10  1)

The extent of reaction was calculated for 1 kmol of ethylene fed to the reactor. It corresponded
to the amount of ethanol leaving the reactor. The assumed value and the extent of reaction were
used to determine a scale up factor “f”’ used to determine the values based on the initial basis
assumed on the distillation column.
12
N Ethanol 85.5
f    1436
 0.0595

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 STREAM 4 :
4
N Ethylene  f  1436kmol
N W4 ater  Nf  1  1436  1436kmol
4
N Ethane  N Ethane
3

 STREAM 5 :
5
N Ethanol    f  85.5kmol
5
N Ethylene  (1   )  f  (1  0.0595)  1436  1350kmol
N W5 ater  (1   )  f  (1  0.0595)  1436  1350kmol
5
N Ethane  N Ethane
4

 N 6  N 7  N 5  N Ethanol
5
 N Ethane
5
 N W5 ater  N Ethylene
5

2.1.3. Mass balance around flash separator

It was assumed that all the gases came out of the unit via the overhead stream and the liquid via the
bottom stream.

7
N Ethanol  N Ethanol
9
 85.5kmol
7
N waterl  N water
9
 1350kmol
7
N Ethylene  N Ethylene
8
 1350kmol
7
N Ethane  N Ethane
8

2.1.4. Mass Balance around SPLITTER

The first R value used for the calculations was 10

N 8  N 10  N 11
N 11
10
 R  N 11  RN 10
N
 N 8  N 10  RN 10  N 8  (1  R) N 10

Component Balance:

The compositions of streams 8, 10 and 11 were the same since stream 8 is split into streams 10 & 11.
The compositions of the same component in different streams were used interchangeably.

8
xethylene  xethylene
10
 xethylene
11

8
xethane  xethane
10
 xethane
11

5
 8
N Ethylene  N Ethylene
10
 N Ethylene
11

8
N Ethylene  xethylene
10
N 10  xethylene
11
N 11
8
N Ethylene  xethylene
10
N 10  xethylene
10
RN 10
8
N Ethylene  x10
Ethylene N ( R  1)
10

8
N Ethylene  ( R  1) N Ethylene
10

8 5
N Ethylene N Ethylene
1350
 N Ethylene
10
  
 123kmol
R 1 R 1 10  1
11
Then : N Ethylene  RN Ethylene
10
 10  123  1230kmol

2.1.5. Mass Balance around mixing point 1 (streams 1,14 &3)

Since streams 11 and 14 have the same compositions and flow rates, they were used interchangeably.

N 1  N 11  N 3

Component Balances

3
N Ethylene  N Ethylene
4

0.99 N 1  N Ethylene
11
 N Ethylene
3

3
N Ethylene  N Ethylene
11 4
N Ethylene  N Ethylene
11
1436  1230
N1     210kmol
0.99 0.99 0.99
1
N Ethane  0.01N 1  0.01  210  2.1kmol

2.1.6. Overall Mass Balance

The overall mass balance was done to calculate the number of moles of ethane in the purge stream.
Atomic balances were used.

1
Carbon : 2 N Ethelene  2 N Ethane
1
 2 N Ethylene
10
 2 N Ethane
10
 2 N Ethanol
12

10
N Ethane  N Ethylene
1
 N Ethane
1
 N Ethylene
10
 N Ethanol
12
 (0.99  210)  2.1  123  85.5  2.1kmol

N 10  N Ethylene
10
 N Ethane
10
 123  2.1  125.1kmol
N 11  RN 10  10  125.1  1251kmol
N 8  ( R  1) N 10  11  125.1  1374kmol
8
N Ethane  N 8  N Ethylene
8
 1374  1350  24kmol

These calculations were done for an assumed basis of 100 kmol of overhead product leaving the
distillation column. To upscale them to the actual amounts, a new scale up factor ‘’F’’ was calculated.

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Knowing the specific gravity of the 95% ethanol product, its mass for a 5 million gallon capacity was
5000000 gal
found to be: M 12  V 12 (m 3 )     807kg / m 3  1.53  10 7 kg
gal
264.17 3
m
1.53  10 7 kg
F  3642
85.5kmol  46kg / kmol
To get the actual amount of the components masses in various streams; the various quantities obtained
were converted to masses then multiplied by the scale up factor.

3. Economics

3.1. Ethylene fresh feed cost

The given cost was 0.35 USD per lb.

0.35USD 1lb
Cost1    21473328kgfreshfeed  16569182USD
lb 0.453953kg

3.2. Steam cost

The given cost was 0.03 USD per lb.

0.03USD 1lb
Cost 2    94165663kgsteam  6227984USD
lb 0.453953kg

3.3. Fuel gas cost

The given cost was 0.18 USD per lb.

0.18USD 1lb
Cost 3    12753557kgsteam  5061013USD
lb 0.453953kg

3.4. Distillation cost

The given cost was 0.47 USD per lbmol of feed to the unit.

0.47USD 1lbmol
Cost 4    N9
lbmol 0.453953kgmol
The total mass of the components in stream 9 was determined. To calculate the total number of moles,
the mass was divided by the streams average molecular weight.
Stream 9 molecular weight (MW9) was given by:

MW 9  X water
9
MW water  X ethanol
9
MW water  X ethane
9
MWethane  X ethylene
9
MWethylene
MW 9  0.06 *18  0.94 * 46  0 * 30  0 * 28  19.7kg / kmol

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 0.47USD 1lbmol M9 0.47USD 1lbmol 102885434
Cost 4    9
    5420653USD
lbmol 0.453953kgmol MW lbmol 0.453953kgmol 19.7
3.5. Cooling after reactor cost
A similar approach to the previous cost calculation was used. The only difference is that the stream
leaving the reactor is stream number 5. The given cost was 0.03 USD per lbmol.

0.03USD 1lbmol M5 0.03USD 1lbmol 243174562

Cost 5    5
    676440USD
lbmol 0.453953kgmol MW lbmol 0.453953kgmol 23

3.6. Compression costs

A similar approach to the previous cost calculation was used. The only difference is that the stream
entering the compressor is stream number 11. The given cost was 0.003 USD per lbmol for a pressure
difference of 1 atm. The entry and exit pressures for the first calculation were 5 and 10 atm respectively.
The pressure difference was 5 atm

0.003USD 1lbmol M 11
Cost 5     P
lbmol 0.453953kgmol MW 11
0.003USD 1lbmol 127535571
Cost 5     5  150444USD
lbmol 0.453953kgmol 28

3.7. Wastewater treatment cost

The treatment cost was 100 dollars for 1000 m3.
100USD M 13 USD 87609444 m 3
Cost 7    0.1   8769USD
1000m 3  m 3 999.045kg / m 3

3.8. Operating costs

The fixed operating costs were assumed to be 0.30USD per gallon of ethanol produced.
For 5 million gallons the cost was given by: 0.3*5000000 = 1500000USD
3.9. Total Operating Cost (TOC)
It is the sum of all various costs involved except the cost of fuel gas and ethanol produced.
TOC = Cost 1 + Cost 2 + Cost 4 + Cost 5 + Cost 6 + Cost 7 + Cost 8 = 30553642 USD

3.10. Profit / Loss

Profit/Loss = Cost of ethanol + cost of fuel gas – TOC = 14.5 million + 5.1 million – 30.6 million
The loss obtained amounts to approximately 11 million USD.

Note: 1. It should be noted that these sample calculations were done using a calculator and that the
values obtained might slightly differ from the ones in the spreadsheet since the latter takes into
consideration all the decimals involved while in the former method a lot of rounding off has been done.
2. The costs estimations shown in this document were not for optimum conditions. The spreadsheet
presents the results to be expected for optimum conditions.

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 4. Discussion

The project was about investigating the technical and economic feasibility of ethanol manufacture from
ethylene and water. Three important parameters namely: the reactor pressure, the water to ethylene feed
ratio to the reactor and recycle to purge streams ratio were varied from minimum to maximum acceptable
value in order to get optimum conditions resulting in maximum profit. To calculate the profits generated,
the value the costs involved for the production of ethanol and the selling price of the product combined
to the cost of fuel gas were determined varying different parameters one by one while keeping the others
constant. The first parameter investigated was the steam to ethylene ratio which was varied from 1 to 1
to 1 to 5. The pressure was 10 atm and stream to urge ratio 10 mol/mol. As the ratio increased, the losses
also increased. The more steam added to the process, the higher the quantity of wastewater generated
which resulted in an increase of treatment costs. More money had to be put towards purchasing the
steam and the reactor effluent cooling costs were increased as well. The optimal conditions were
observed when for each mole of steam fed to the reactor, one mole of ethylene was charged onto the
unit. The second parameter investigated was the recycle to purge ratio. As the ratio increased, the value
of the losses decreased. As more unreacted reactant is recycled to the unit, less raw material would be
needed which decreased the cost attached to the purchase of fresh feed to the process (Felder &
Rousseau, 2005). The optimal value was 50 to 1. The reactor pressure was varied from 10 to 40 atm
while keeping the other parameters at their optimal values. It was the parameter which had the most
impact on the profit or loss observed. A reactor is at the heart of any reactive process. The other
operations involved stem from the results obtained from the reactor (Smith, 2005). The trend observed
was that as the pressure increased, the profits observed increased as well. From the derived equilibrium
expression, it could be seen that the pressure had a direct effect on the conversion of reactants to
products. The pressure and conversion followed the same trend. Higher conversion resulted in higher
profits. The profit found at optimum conditions was 2.1 million dollars.

5. Conclusion

This mini project was about studying the feasibility of a new ethanol plant. Simplifying assumptions
were made to give us a rough idea of what to expect when the detailed design. The mass balance
calculations were used to determine the flow rates in each individual stream and the amount of fresh
feed required to yield the desired quantity of products. A basis was assumed to simplify the calculations
and the flow rates were scaled up with respect to the basis and the desired flow rates. From the various
flow rates the operating costs were determined and profits calculated. The optimum conditions obtained
from the investigated parameters were 40 atm for the reactor pressure, 1 to 1 for the steam to ethylene

9
ratio feed to the reactor and 50 to 1 from recycle to purge ratio. The profits were found to be 1.75 million
USD.

6. References

Felder, M. R. & Rousseau, W. R. 2005. Elementary Principles of Chemical Processes. 4th Ed. New
Jersey: Wiley and Sons.

Smith, R. 2005. Chemical Process Design and Integration. New Jersey: John Wiley & Sons.

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 7. Appendix

N11C2H6 N10C2H6
N11C2H4 N10C2H4

N1C2H4
N1C2H6
N8C2H6
N8C2H4

N2H2O
Flash
Separator N12C2H5OH
N4C2H6 N7C2H5OH N12H2O
N4C2H4 N7C2H6
N4H2O N7C2H4
N7H2O

Reactor
N9C2H5OH
N9H2O Distillation
N5C2H5OH Column
N5C2H6
N5C2H4
N5H2O

N13H2O

Figure 1 Unit 200 used for ethanol production Block Flow Diagram

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