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BELLVILLE CAMPUS

ETHYLENE AND STEAM

1

List of symbols

V Volume m3

M Mass kg

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.

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.

2.1.1. 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 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

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

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 -

3

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)

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

4

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

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

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

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

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.

6

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

The given cost was 0.35 USD per lb.

0.35USD 1lb

Cost1 21473328kgfreshfeed 16569182USD

lb 0.453953kg

The given cost was 0.03 USD per lb.

0.03USD 1lb

Cost 2 94165663kgsteam 6227984USD

lb 0.453953kg

The given cost was 0.18 USD per lb.

0.18USD 1lb

Cost 3 12753557kgsteam 5061013USD

lb 0.453953kg

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

7

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.

Cost 5 5

676440USD

lbmol 0.453953kgmol MW lbmol 0.453953kgmol 23

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

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

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

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.

8

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.

10

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

11

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