Process Design For The Production of Ethylene From Ethanol

Department of Chemical & Biomolecular Engineering
Senior Design Reports (CBE)

University of Pennsylvania Year 2012
Process Design for the Production of
Ethylene from Ethanol
Gregory Cameron Linda Le
University of Pennsylvania University of Pennsylvania
Julie Levine Nathan Nagulapalli
University of Pennsylvania University of Pennsylvania
This paper is posted at ScholarlyCommons.
http://repository.upenn.edu/cbe sdr/39
Process Design for the
Production of Ethylene from
Ethanol

Design Project By:
Gregory Cameron
Linda Le
Julie Levine
Nathan Nagulapalli

Presented To:
Professor Leonard Fabiano
Dr. Raymond Gorte

April 10, 2012
Department of Chemical and Biomolecular Engineering
University of Pennsylvania
School of Engineering and Applied Science
April 10, 2012
Professor Leonard Fabiano
Dr. Raymond Gorte
University of Pennsylvania
School of Engineering and Applied Science
Department of Chemical and Biomolecular Engineering

Dear Professor Fabiano and Dr. Gorte,

We would like to present our solution to the Ethylene from Ethanol design project suggested by
Mr. Bruce Vrana. We have designed a plant, to be located in So Paulo, Brazil, which will
produce one million tonnes of polymer-grade ethylene (99.96% pure) per year from a 95%
ethanol feed. The ethanol will be dehydrated using fixed-bed, adiabatic reactors filled with
gamma-alumina catalyst. The products of the dehydration will then be separated using flash
distillation, adsorption over a zeolite packing, and cryogenic distillation. This method of
ethylene production presents an alternative to the popular hydrocarbon cracking technique that is
presently widely used.

This report contains a detailed description of the plant process equipment and operating
conditions. Our plant is expected to be complete in 2015 and has an anticipated life of 20 years.
It will require an annual ethanol feed of 2,300,000 tonnes of 95% purity ethanol. Because we
will be operating in Brazil (where ethanol is only produced nine months out of the year), we
expect to operate 280 days per year (including 30 days of operating from on site storage). This
design is expected to meet the required one million tonnes of 99.96% purity ethylene per year.

Additionally, this report discusses our decision to locate the plant in So Paulo and the technical
and economic implications of operating in Brazil. We will present a comparison of the details of
operating in the United States and Brazil which led us to make this choice. Additionally, we will
discuss the economics of building and running the plant and its potential profitability. As it
stands, current ethylene and ethanol prices do not allow this plant to be profitable. However,
prices for which this plant can be successful are not far off.

Sincerely,

_______________ _______________ _______________ _______________
Gregory Cameron Linda Le Julie Levine Nathan Nagulapalli

Ethylene From Ethanol Process: Cameron, Le, Levine, Nagulapalli

4


5

Table of Contents
Section Page
I. Abstract 7
II. Introduction 9
III. Customer Requirements 13
IV. Process Flow Diagram and Material Balances 17
V. Process Description 29
VI. Energy Balance and Utility Requirements 37
VII. Economic Discussion and Market Analysis 41
VIII. Location 55
IX. Safety and Other Considerations 59
X. Equipment List and Unit Descriptions 63
XI. Specification Sheets 75
XII. Conclusions and Recommendations 107
XIII. Acknowledgements 109
XIV. Bibliography 111
XV. Appendix 115


6


7

Section I
Abstract


8

This project considers using ethanol dehydration as a means to mass-produce ethylene. 2.3MM
tonnes of a 95% ethanol / 5% water feed will be converted into 1MM tonnes of 99.96% pure
ethylene per year using a series of adiabatic, fixed-bed catalytic reactors operating at 750F and
600psi. The catalyst is gamma-alumina in the form of 1cm diameter spherical pellets. After the
dehydration process, the product will be purified using two flash separation units, an adsorption
unit with zeolite 13X sorbent, and finally a cryogenic distillation unit. The plant will be located
in So Paulo, Brazil. Because ethanol production in Brazil is seasonal, the plant will operate
only 280 days per year at a very high capacity. This includes 30 days worth of on-site feed
storage. After conducting an analysis of the sensitivity of the plants Net Present Value and
Internal Rate of Return to ethylene and ethanol prices, it was determined that while profitability
is not attainable in the current market (which prices ethanol at $0.34/lb and ethylene at $0.60/lb),
profitability is attainable should ethylene prices rise to $0.64/lb and ethanol prices fall to
$0.305/lb.


9

Section II
Introduction


10

Background
The purpose of this project is to design a plant that efficiently converts liquid ethanol into high
purity ethylene gas using an alumina catalyst. Ethylene is currently the most consumed
intermediate product in the world. In 2009 it was estimated that the world demand for ethylene
was over 140 million tons per year, with an approximate yearly increase of 3.5%. One of the
most important uses of ethylene is the production of polyvinyl chloride (PVC). PVC currently
serves over 70% of the construction market. This includes plastics, dominating pipe and fittings,
widows, siding, decking and fencing. In addition, PVC serves 60% of the wire and cable plastics
market and 25% of the coatings market.
Ethylene was first obtained from ethanol in the 18
th
century, when ethanol was passed over a
heated catalyst. The plastics industry gave rise to several ethanol dehydration units which
operated from the 1930s up until the 1960s. The advent of naptha (liquefied petroleum gas)
cracking rendered these dehydration units defunct. Naptha cracking involves a liquid feed of
saturated hydrocarbons diluted with steam and heated to extreme temperatures in the absence of
oxygen. The functionality of this process reversed industrial trends, turning ethylene into a raw
material for ethanol, as opposed to a derivative of it.
However, with increasing global demand for hydrocarbons and increasingly stricter
environmental regulations, this process for ethylene production has proven to become very
costly. Therefore, a cheaper process of creating ethylene is highly sought in todays economy,
and the original production method of ethanol dehydration is being reconsidered.
Process Goals
This project focuses on using the dehydration of ethanol as an alternative to cracking for
producing ethylene. This report details a plant that produces 1MM tonnes of 99.96% pure
ethylene per year from approximately 2.19MM tonnes of 95% ethanol, along with a thorough
economic analysis. US Patent 4,396,789 has been used as the basis for the plant design, with
several modifications and optimized design decisions put in place.


11

Reaction
The dehydration reaction of ethanol to yield ethylene is shown below.
C
2
H
5
OH H
2
O + C
2
H
4

This reaction is zero-order and endothermic, having a standard heat of reaction (H
RXN
) of
approximately 401BTU/lb. In addition, the reaction does not progress to completion under
standard temperature and pressure (298K and 1atm) and exhibits an equilibrium that favors
ethanol formation.
A high temperature reactor operating at 750F is needed in order to shift the equilibrium toward
product formation and efficiently produce ethylene with a high conversion. Additionally, the
reaction over -Alumina yields a number of byproducts that must be removed through the
separations train. The side reactions that produce these byproducts are listed in approximate
order of decreasing prevalence.
2C
2
H
5
OH H
2
O + (C
2
H
5
)
2
O
C
2
H
5
OH H
2
+ CH
3
COH
C
2
H
5
OH + 2H
2
H
2
O +2 CH
4

C
2
H
5
OH + H
2
O 2H
2
+ CH
3
COOH
C
2
H
5
OH + H
2
H
2
O + C
2
H
6
Due to the high purity of ethylene product required (99.96 %), nearly all of the byproducts must
be removed from the final product stream. These two factors form the basis of this plant design:
a high temperature reactor and an intricately designed separations train with product purity as the
main goal.


12

Plant Location
In the United States, ethanol is produced from corn, which is grown year-round. In Brazil,
ethanol is produced from sugar cane, which is only available nine months per year. However,
the cheaper Brazilian ethanol prices and greater costal access for shipping purposes allow for a
more cost-effective process. Therefore, a plant situated in and around the Sao Paulo area is the
most fiscally sensible plan. For a more detailed discussion regarding the choice to locate in
Brazil, please refer to Section 8)
Safety
Both ethanol and ethylene are potentially dangerous materials if handled incorrectly. Section 9
contains a detailed discussion of safety considerations. Additionally, MSDS reports for all
materials handled in this process are supplied in the appendix.

13

Section III
Customer Requirements


14

Figure 3.1
15

Voice of the Customer
The main customers for this plant are plastic companies that require ethylene for polymerization
into products such as high-density polyethylene (HDPE), low-density polyethylene (LDPE),
polystyrene, ethylene glycol, or polyvinyl chloride (PVC). Ethylene demand is generally
demand and classified as fitness-to-standard, based upon the existing characteristics of ethylene
produced by cracking of fossil fuels. Figure 3.1 shows an innovation map, which illustrates the
relationship between customer values and the two main ethylene production processes (ethanol
dehydration and hydrocarbon cracking). Most customers require their ethylene to be polymer-
grade, or 99.96% pure. In general, an environmentally friendly process with low carbon
emissions and waste is desired. It has been projected that by 2030, the demand for ethylene in
the United States alone will be about 5MM tonnes /year. Most industrializing countries, such as
Brazil, have a growing market for plastics, and resultantly, an increasing demand for ethylene.

16

17

Section IV
Process Flow Diagram and
Material Balances

18

Figure 4.1: Reactor Section 100

R101-A/B
P101 A/B
SEP
HX101
F101
FUEL-1
F102
FUEL-2
S104 S105
R102-A/B
F102
FUEL-3
S107
S106
FLUE-1
S103
R-103-A/B
S110
FLUE-2 FLUE-3
RECYCLE
S109
FEED
S108
P102 A/B
S102
19

Stream ID FEED S102 S103 S104 S105 S106 S107 RECYCLE
Temperature (F) 77.0 78.8 572.0 752.0 590.0 752.0 590.0 96.9
Pressure (psi) 14.7 602.5 595.4 618.0 584.2 580.2 582.7 2.0
Vapor Fraction 0.00 0.00 1.00 1.00 1.00 1.00 1.00 1.00
Volume Flow (ft
3
/h) 11,485 11,502 209,159 256,490 394,244 471,246 445,761 208
Enthalpy (BTU/h) -1.621E+09 -1.620E+09 -1.259E+09 -1.196E+09 -1.080E+09 -1.025E+09 -1.029E+09 -3.846E+07
Mass Flow (lb/hr)
Ethanol 5.499E+05 5.499E+05 5.499E+05 5.499E+05 1.615E+05 1.615E+05 4.382E+04 9.998E+03
Water 2.894E+04 2.894E+04 2.894E+04 2.894E+04 1.800E+05 1.800E+05 2.257E+05 3.155E+03
Ethylene 0.000E+00 0.000E+00 0.000E+00 0.000E+00 2.344E+05 2.344E+05 3.052E+05 8.562E+02
Diethyl-Ether 0.000E+00 0.000E+00 0.000E+00 0.000E+00 2.212E+03 2.212E+03 3.187E+03 4.395E+02
Methane 0.000E+00 0.000E+00 0.000E+00 0.000E+00 3.830E+01 3.830E+01 7.205E+01 8.831E-02
Acetaldehyde 0.000E+00 0.000E+00 0.000E+00 0.000E+00 4.207E+02 4.207E+02 5.288E+02 1.169E+03
Ethane 0.000E+00 0.000E+00 0.000E+00 0.000E+00 3.589E+01 3.589E+01 4.644E+01 5.715E+01
Acetic Acid 0.000E+00 0.000E+00 0.000E+00 0.000E+00 1.792E+02 1.792E+02 2.108E+02 6.111E-02
Hydrogen 0.000E+00 0.000E+00 0.000E+00 0.000E+00 2.406E+01 2.406E+01 2.618E+01 2.309E-02
Total Mass Flow (lb/h) 5.788E+05 5.788E+05 5.788E+05 5.788E+05 5.788E+05 5.788E+05 5.788E+05 1.568E+04
Stream Table for Reactor Section 100
Stream ID S108 S109 S110 SEP
Temperature (F) 591.1 752.0 590.0 179.3
Pressure (psi) 582.7 577.3 581.2 577.3
Vapor Fraction 1.00 1.00 1.00 0.47
Volume Flow (ft
3
/h) 454,243 541,479 473,540 127,545
Enthalpy (BTU/h) -1.067E+09 -1.011E+09 -1.049E+09 -1.409E+09
Mass Flow (lb/hr)
Ethanol 5.383E+04 5.383E+04 1.027E+04 1.027E+04
Water 2.289E+05 2.289E+05 2.458E+05 2.458E+05
Ethylene 3.061E+05 3.061E+05 3.323E+05 3.323E+05
Diethyl-Ether 3.627E+03 3.627E+03 3.952E+03 3.952E+03
Methane 7.214E+01 7.214E+01 9.276E+01 9.276E+01
Acetaldehyde 1.701E+03 1.701E+03 1.747E+03 1.747E+03
Ethane 1.037E+02 1.037E+02 1.107E+02 1.107E+02
Acetic Acid 2.108E+02 2.108E+02 2.214E+02 2.214E+02
Hydrogen 2.621E+01 2.621E+01 2.597E+01 2.597E+01
Total Mass Flow (lb/h) 5.945E+05 5.945E+05 5.945E+05 5.945E+05
Section 100 Cont.
Stream ID FUEL-1 FUEL-2 FUEL-3
Type Natural Gas Natural Gas Natural Gas
Temperature (F) 70 70 70
Pressure (psi) 14.7 14.7 14.7
Volume Flow (SCF/h) 60,106 52,908 53,734
Duty (BTU/h) 6.311E+07 5.555E+07 5.642E+07
Utilities Table for Reactor Section 100
Table 4.1

Table 4.2 Table 4.3
20

Figure 4.2: Flash Separation 200

FL201
S204
SEP
HX201
FC
S202 S203
FL202
HX202
FC
S206 S207
CW201
CW202
V201
S205
CRYO-OUT
PRODUCT
V202
S208
ADSORB
DISTILL
21

Stream ID CRYO-OUT PRODUCT ADSORB DISTILL
Temperature (F) -35 52 39 122
Pressure (psi) 275.6 275.6 455.6 455.6
Vapor Fraction 1.00 1.00 1.00 0.00
Enthalpy (BTU/h) 2.452E+08 2.578E+08 2.448E+08 -1.694E+09
Volume Flow (ft
3
/h) 141,716 202,904 100,528 4,391
Mass Flow (lb/h)
Ethanol 7.443E-11 7.443E-11 7.320E-04 3.876E-02
Water 8.816E-19 8.816E-19 2.606E-04 9.506E-01
Ethylene 9.996E-01 9.996E-01 9.863E-01 3.319E-03
Diethyl-Ether 1.219E-07 1.219E-07 1.045E-02 1.704E-03
Methane 2.804E-04 2.804E-04 2.758E-04 3.424E-07
Acetaldehyde 4.917E-08 4.917E-08 1.711E-03 4.533E-03
Ethane 8.322E-05 8.322E-05 1.591E-04 2.215E-04
Acetic Acid 7.519E-18 7.519E-18 2.315E-07 8.561E-04
Hydrogen 7.852E-05 7.852E-05 7.721E-05 8.951E-08
Section 200 cont.
Stream ID CW201 CW202
Type Cooling Water Cooling Water
Temperature (F) 100 120
Pressure (psi) 14.7 14.7
Mass Flow (lb/h) 903,320 903,320
Duty (BTU/h)
Utilities Table for Flash Section 200
-1.436E+09
Stream ID SEP S202 S203 S204 S205 S206 S207 S208
Temperature (F) 179.3 122 122 122 122 57 39 39
Pressure (psi) 577.3 574.3 573.1 573.1 573.1 569.3 455.6 455.6
Vapor Fraction 0.47 0.46 0.00 1.00 1.00 1.00 0.00
Enthalpy (BTU/h) 1.275E+05 -1.436E+09 -1.686E+09 -1.686E+09 2.498E+08 2.371E+08 -7.662E+06 -7.662E+06
Volume Flow (ft
3
/h) -1.409E+09 107,996 108,259 4,306 103,952 78,294 141,740 24
Mass Flow (lb/h)
Water 2.458E+05 2.453E+05 2.453E+05 2.443E+05 1.044E+03 1.044E+03 1.044E+03 9.563E+02
Ethylene 3.323E+05 3.316E+05 3.316E+05 8.357E+02 3.308E+05 3.308E+05 3.308E+05 2.046E+01
Methane 9.276E+01 9.256E+01 9.256E+01 8.640E-02 9.248E+01 3.534E+03 9.248E+01 1.911E-03
Ethane 1.107E+02 1.105E+02 1.105E+02 5.673E+01 5.377E+01 3.534E+03 5.377E+01 4.149E-01
Acetic Acid 2.214E+02 2.209E+02 2.209E+02 2.200E+02 9.218E-01 3.534E+03 9.218E-01 8.441E-01
Hydrogen 2.597E+01 2.592E+01 2.592E+01 2.285E-02 2.589E+01 3.534E+03 2.589E+01 2.367E-04
Stream Table for Flash Section 200
Table 4.4

Table 4.5 Table 4.6

22

Figure 4.3: Distillation 300

D301
S303
HX302
AC301
P301 A/B
S308
S310
C301
DISTILL
HX301
REBOIL-OUT
TO-REBOIL
S304
FC
S302
V301
S309
STEAM301
STEAM302
S305
S306
S307
P302 A/B
S311
TREAT
RECYCLE
FROM-COOL
S312
23

Stream ID DISTILL S302 S303 S304 S305 S306 S307 S308
Temperature (F) 121.7 122.1 221.7 206.4 206.4 206.4 206.4 206.4
Pressure (psi) 455.6 30.9 29.5 29.4 29.4 29.4 28.0 29.4
Vapor Fraction 0.00 0.00 1.00 0.54 1.00 0.00 0.00 0.00
Volume Flow (ft
3
/h) 4,391 10,794 - - 109,081 - - -
Enthalpy (BTU/h) -1.694E+09 -1.694E+09 -9.379E+08 -1.029E+08 -4.139E+07 -6.153E+07 -6.153E+07 -6.153E+07
Mass Flow (lb/h)
Water 2.457E+05 2.457E+05 9.922E+03 9.922E+03 3.161E+03 6.760E+03 6.760E+03 6.760E+03
Ethylene 8.580E+02 8.580E+02 8.588E+02 8.588E+02 8.580E+02 8.367E-01 8.367E-01 8.367E-01
Methane 8.850E-02 8.850E-02 8.852E-02 8.853E-02 8.850E-02 2.541E-05 2.541E-05 2.541E-05
Ethane 5.727E+01 5.727E+01 6.201E+01 6.201E+01 5.727E+01 4.743E+00 4.743E+00 4.743E+00
Acetic Acid 2.213E+02 2.213E+02 4.650E-01 4.650E-01 6.124E-02 4.037E-01 4.037E-01 4.037E-01
Hydrogen 2.314E-02 2.314E-02 2.314E-02 2.314E-02 2.314E-02 4.290E-06 4.290E-06 4.290E-06
Stream Table for Distillation Section 300
Stream ID S309 S310 S311 TREAT RECYCLE
Temperature (F) 252.4 252.6 252.6 252.6 634.4
Pressure (psi) 31.1 31.2 31.1554114 45.9 599.6
Vapor Fraction 0.00 1.00 0.00 0.00 1.00
Volume Flow (ft
3
/h) - - 4350.76317 4,351 8,028
Enthalpy (BTU/h) -1.958E+09 -2.970E+08 -1.612E+09 -1.612E+09 -4.139E+07
Mass Flow (lb/h)
Ethanol 5.459E+00 3.996E+00 1.486E+00 1.486E+00 1.002E+04
Water 2.947E+05 5.244E+04 2.426E+05 2.426E+05 3.161E+03
Ethylene 1.953E-42 1.964E-42 6.070E-46 6.070E-46 8.580E+02
Diethyl-Ether 8.149E-25 8.148E-25 4.791E-27 4.791E-27 4.404E+02
Methane 7.363E-52 7.404E-52 9.732E-56 9.732E-56 8.850E-02
Acetaldehyde 8.445E-05 7.106E-05 1.380E-05 1.380E-05 1.172E+03
Ethane 4.494E-06 3.744E-06 7.715E-07 7.715E-07 5.727E+01
Acetic Acid 2.473E+02 2.619E+01 2.212E+02 2.212E+02 6.124E-02
Hydrogen 3.883E-52 3.905E-52 5.683E-56 5.683E-56 2.314E-02
Total Mass Flow (lb/h) 2.950E+05 5.247E+04 2.428E+05 2.428E+05 1.571E+04
Section 300 cont.
Stream ID REBOIL-OUT FROM-COOL TO-REBOIL STEAM301 STEAM302
Type Cooling Water Cooling Water Cooling Water Steam Steam
Temperature (F) 100 100 120 298 298
Pressure (psi) 14.7 14.7 14.7 50 50
Mass Flow (lb/h) 49,342 209,162 258504 54267 54267
Duty (BTU/h) 9.063E+06 49469600
Utilities Table for Distillation Section 300
Table 4.7
Table 4.8

Table 4.9

24

Figure 4.4: Adsorption Sequence 400

AD401 A
S410
V407
V402
S404
NITROGEN
S402
S403
V401
FC
FC
FC
V403
FC
TO HEAT
AD401 B
V405
S407
S405
S406
V404
FC
FC
V406
FC
TO HEAT
ADSORB
CRYO
V408
FC
S409 S408
C401
25

Stream ID ADSORB CRYO NITROGEN S408 TO HEAT
Temperature (F) 39.0 39.6 80.0 350.0 352.0
Pressure (psi) 455.6 441.0 15 41 26.3
Vapor Fraction 1.00 1.00 1 1 1.00
Enthalpy (BTU/hr) 2.448E+08 2.459E+08 2.632E+03 2.603E+05 2.608E+05
Volume Flow (ft
3
/h) 100,525 100,854 67,506.0000 36,171.0000 38,210
Mass Flow (lb/hr)
Ethanol 3.315E+05 3.315E+05 0.000E+00 0.000E+00 0.000E+00
Water 2.460E+02 0.000E+00 0.000E+00 0.000E+00 0.000E+00
Ethylene 6.770E+01 0.000E+00 0.000E+00 0.000E+00 0.000E+00
Diethyl-Ether 3.511E+03 3.511E+03 0.000E+00 0.000E+00 0.000E+00
Methane 4.204E+01 4.204E+01 0.000E+00 0.000E+00 0.000E+00
Acetaldehyde 2.609E+02 2.609E+02 0.000E+00 0.000E+00 0.000E+00
Ethane 1.180E+01 1.180E+01 0.000E+00 0.000E+00 0.000E+00
Acetic Acid 3.500E-02 3.500E-02 0.000E+00 0.000E+00 0.000E+00
Hydrogen 0.000E+00 0.000E+00 0.000E+00 0.000E+00 0.000E+00
Nitrogen 0.000E+00 0.000E+00 4.070E+03 4.070E+03 4.070E+03
Total Mass Flow (lb/h) 3.353E+05 3.350E+05 4.070E+03 4.070E+03 4.070E+03
Stream Table for Adsorption Section 400
Table 4.10
*Note: The 400 section is designed such that at a given time the only active streams are ADSORB and CRYO,
which are run through one column. The other streams are used for hot Nitrogen purge gas, which cleans the
sorbent.
26

Figure 4.4: Cryogenic Distillation 500
D501
S504
HX503
AC501
P501 A/B
S509
S511
CRYO-IN
HX502
R501
R502
S505
S510
S512
REBOIL-OUT
S506
S508
PURGE-2
CRYO-OUT
S507
HX501
S502 S503
V501
TO-REBOIL
TO-COOL
27

Table 4.11

Table 4.12

Stream ID CRYO-IN S502 S503 S504 S505 S506 S507 S508 S509
Temperature (F) 39.61 6.80 -35.11 -67.15 -67.54 -67.54 -67.54 -67.54 -67.54
Pressure (psi) 455.6 452.5 279.2 279.3 279.2 279.2 279.2 238.2 279.2
Vapor Fraction 1.00 1.00 1.00 1.00 0.57 0.00 1.00 0.00 0.00
Volume Flow (ft
3
/h) 100,864 80,797 139,354
- - -
102,938
- -
Enthalpy (BTU/h) 2.460E+08 2.394E+08 2.394E+08 4.177E+08 3.613E+08 1.228E+08 2.386E+08 2.386E+08 2.386E+08
Mass Flow (lb/h)
Ethanol 8.716E-07 8.716E-07 8.716E-07 2.460E-05 2.460E-05 3.090E-26 2.460E-05 3.090E-26 3.090E-26
Water 3.103E-07 3.103E-07 3.103E-07 7.312E-10 2.009E-06 2.009E-06 2.913E-13 2.009E-06 2.009E-06
Ethylene 1.174E+04 1.174E+04 1.174E+04 5.781E+05 5.739E+05 2.436E+05 3.303E+05 2.436E+05 2.436E+05
Diethyl-Ether 1.244E+02 1.244E+02 1.244E+02 1.600E+01 3.544E+03 3.544E+03 4.028E-02 3.544E+03 3.544E+03
Methane 3.284E+00 3.284E+00 3.284E+00 1.038E+02 9.970E+01 7.035E+00 9.267E+01 7.035E+00 7.035E+00
Acetaldehyde 2.038E+01 2.038E+01 2.038E+01 4.261E+00 6.204E+02 6.204E+02 1.625E-02 6.204E+02 6.204E+02
Ethane 1.894E+00 1.894E+00 1.894E+00 8.621E+01 1.311E+02 1.036E+02 2.750E+01 1.036E+02 1.036E+02
Acetic Acid 2.757E-03 2.757E-03 2.757E-03 1.532E-07 5.665E-03 5.665E-03 2.485E-12 5.665E-03 5.665E-03
Hydrogen 9.194E-01 9.194E-01 9.194E-01 2.616E+01 2.607E+01 1.205E-01 2.595E+01 1.205E-01 1.205E-01
Total Mass Flow (lb/h) 1.190E+04 1.190E+04 1.190E+04 5.783E+05 5.783E+05 2.479E+05 3.305E+05 2.479E+05 2.479E+05
Stream Table for Cryogenic Distillation Section 500
Stream ID S510 S511 PURGE-2 CRYO-OUT
Temperature (F) -66.59 -21.20 -21.15 -35.44
Pressure (psi) 280.0 272.0 279.8 275.6
Vapor Fraction 0.00 1.00 0.00 1.00
Volume Flow (ft
3
/h) - - 122 141,716
Enthalpy (BTU/h) 8.236E+07 1.379E+08 -6.496E+06 2.386E+08
Mass Flow (lb/h)
Ethanol 5.156E-67 7.499E-69 5.081E-67 2.460E-05
Water 8.935E-06 1.792E-07 8.756E-06 2.914E-13
Ethylene 1.918E+05 1.907E+05 1.124E+03 3.303E+05
Diethyl-Ether 5.209E+03 1.697E+03 3.511E+03 4.028E-02
Methane 2.378E-02 2.374E-02 4.273E-05 9.267E+01
Acetaldehyde 1.133E+03 5.583E+02 5.751E+02 1.625E-02
Ethane 1.131E+03 1.105E+03 2.596E+01 2.750E+01
Acetic Acid 7.816E-02 3.482E-04 7.781E-02 2.485E-12
Hydrogen 1.292E-07 1.292E-07 2.089E-11 2.595E+01
Section 500 cont.
28

Table 4.13

Stream ID TO-REBOIL TO-COOL REBOIL-OUT R501 R502
Type Water Water Water Propylene Propylene
Temperature (F) 100 100 120 -78 -78
Pressure (psi) 14.7 14.7 14.7 - -
Mass Flow (lb/h) 258,504 49,342 49342 420000 420000
Duty (BTU/h) N/A
Utilities Table for Distillation Section 500
-5.637E+07 4.904E+07
29

Section V
Process Description

Figure 6.1
30

Overview
The above illustration (Figure 6.1) provides a brief introduction to the specifics of the process.
Each item mentioned will be described in more detail in the sections immediately following. In
addition, the exact specifications for each process unit are provided in Section X. The process
begins with a 1MM gallon feed storage tank. A tank of this size can hold a one month supply of
ethanol. The feed is then pumped to a high pressure, vaporized, and passed through a series of
three adiabatic reactors. Just after leaving the second reactor, it is combined with a recycle
stream. The reaction products are sent through a separation train designed to purify the ethylene
product to a polymer-grade level of 99.96%. The ethylene product stream is sent directly into
the customers barge or, if necessary, into one of the two on-site spherical storage tanks
available. A plant operating at this capacity is capable of filling a 3000 ton barge in 18 hours.
The separation train also produces a waste stream of mostly water, which is sent directly to an
off-site waste treatment facility.
Ethanol
Storage
Vessel
Reactor
Section
Separation
Train
Purge (entirely basedon stoichiometry)
Total 248,300 lb/hr
Water 246,000 lb/hr
Other 2,300 lb/hr
Product
Total 330,470 lb/hr
Ethylene 330,321 lb/hr
Methane 93 lb/hr
Hydrogen 26 lb/hr
Recycle
Total 15,700 lb/hr
Ethanol 10,020 lb/hr
Water 3,161 lb/hr
Ethylene 860 lb/hr
Other 1,660 lb/hr
Feed
Total 578,800 lb/hr
Water 23,800 lb/hr
Reactor Outlet
Total 578,800 lb/hr
Water 245,800 lb/hr
Ethylene 332,300 lb/hr
Byproducts 6,153 lb/hr
1MM gal
588 psi 572 F 752 F
752 590 F, 585psi
180 F 585psi
31

Feed Storage
A 95% solution of ethanol (5% water) feed is stored at atmospheric pressure and
temperature in a 1MM gallon, floating-roof storage tank. This volume is large enough to hold a
one month supply of ethanol and will be replenished by the ethanol plants located conveniently
in the area. The large volume of storage allows the plant to continue operation for one month
into the rainy season when Brazilian ethanol plants cease production and the price of ethanol
increases. In addition, it provides flexibility in scheduling feed replenishment and helps ensure
consistent production. In the future, it might be of value to install a direct piping route from one
of those plants; however, for now it is assumed that all feed ethanol arrives via railcars and
barges and is pumped directly into the storage tank.
Reactor Section
The reactor section of this process is shown in Figure 4.1 and details regarding the conditions
and contents of the streams in this section are included in Tables 4.1, 4.2, and 4.3. Two, three-
staged pumps in parallel (P101 A/B and P102 A/B) are used to increase the pressure of the feed
stream to 603 psi. This very high pressure is used to obviate subsequent compression that would
be needed in the separation train. At the high flow rates at which this plant operates, the
economic difference between pumping here and compressing later is on the order of
$12MM/year.
The stream is then passed through a shell and tube heat exchanger (HX101) which is used to
preheat the feed to 572
o
F. HX101 uses the heated reactor effluent stream (S110) to reduce the
energy required to raise the feed to temperatures. A furnace (F101) is necessary to heat the feed
stream the rest of the way to the desired reactor inlet temperature of 752
o
F. Furnace F101 will
require about 60,000SCF/h of natural gas to supply enough energy and impart this temperature
increase.
A series of three adiabatic, fixed-bed reactors follows (R101, R102, and R103) in which the
overall reaction of ethanol to water, ethylene, diethyl-ether, methane and the other byproducts
takes place. The reactors are sized progressively to accommodate the increasing volume of fluid
and ensure adequate overall conversion of ethanol. R101 is 224 ft
3
, R102 is 256 ft
3
, and R103 is
32

310 ft
3
. The large increase in volume between R102 and R103 is due to the addition of the
ethanol recycle stream (RECYCLE). The high pressure and temperature conditions at which
these reactors operate result in an overall ethanol conversion of 98% and an ethylene yield of
98%.
The three reactors are filled to capacity with -alumina catalyst in the form of 1cm diameter
spherical pellets. The total weight of catalyst required is 126,260lb. Every 90 days it is
necessary to discard and replace all of the catalyst. Regeneration is not feasible because the loss
of catalytic activity is due directly to irreversible damage caused by constant exposure to the
high temperature and pressure conditions in the reactors. It was deemed economical to have a
separate, identical reactor train running in parallel. For a 1% (~$600,000) increase in the total
permanent investment (Table 7.2), the cost of 3 additional reactors (Table 7.1), the plant can run
consistently and not have to shut down every 90 days. This investment pays for itself in under 3
years. If it takes 2 days to replace the catalyst, the plant would lose approximately $250,000 in
net revenue without the spare reactors.
Between each reactor is a furnace (F102 and F103) that heats the stream from 590F back to the
desired 752
o
F. The intermittent heating steps serve to negate the temperature reduction caused
by the endothermic dehydration reaction and maintain the driving force toward ethylene
production. These furnaces require about 53,000SCF/hr of natural gas.
Upon leaving the reactor, the products enter HX101 which lowers their temperature to 179
o
F. It
is desirable to remove as much heat as possible from this stream since the separation train
requires low temperatures. In addition, the stream that is being heated requires additional
heating after this step. Thus, this heat exchanger was designed to transfer as much heat as
possible by specifying the temperature of the stream going into the reactors (S103 above) at the
maximum it can possibly reach without violating a minimum approach temperature of
40F. Having a minimum approach temperature helps to increase heat exchanger efficiency and
keeps the necessary surface area for transfer from growing out of control. The reactor effluent
stream then enters the separation train.
Separation Train
33

After the reactor effluent stream (S110) passes through HX101 and is cooled by the feed stream,
it enters the separation phase of the process. The separations section is designed to bring the
ethylene product to a 99.96% purity using as little equipment and as few utilities as possible. It
can roughly be broken into 4 sections as shown in the flow diagrams above: a flash section that
removes the high boiling components (Figure 4.2), a distillation section (Figure 4.3) that
removes most of the water from the process so that the unreacted ethanol can be recycled without
causing reactor volume to grow too large, a drying section (Figure 4.4) in which adsorption is
used to remove any remaining water and ethanol, and a cryogenic distillation section (Figure 4.5)
in which very low temperatures are used to finally achieve the needed purity of ethylene. A
more detailed run down of each step follows.
Upon passing through HX101, the stream goes through a cooler, HX201, to further reduce the
temperature. This cooler is designed so that it can use cooling water as its utility. It requires
approximately 903,000 lb/h of cooling water (Table 4.4) to achieve the necessary heat transfer.
Next, the stream is throttled to the desired pressure of 558.4psi and fed into a flash drum, FL201.
This first of two flash vessels (FL201, FL202) serves to remove the bulk of the water and
unreacted ethanol and to lighten the duty of the intermediate heat exchanger (HX202). The
bottom stream (S204) is sent to a distillation tower (D301) and the top stream (S205) is sent to
the intermediate cooler (HX202).
The top stream (S205) is cooled to 57F, throttled to 455psi, and fed into the second flash drum
(FL202). The vapor product is then passed through an adsorption unit (AD401A) and the liquid
product is fed along with the previous product into the distillation tower (D301). This vessel was
designed with the purity of the top stream in mind rather than the flow rate of ethylene. It was
deemed more important to remove as much water and ethanol as possible from this stream, even
though some ethylene must be sent to the distillation tower (D301) to do so. If the flash
specifications are modified so that 50% of the ethylene that exits through the bottom stream now
exits through the top, it takes about 2646lb/h of water and ethanol with it (this is likely due to
solubility). This is a 400% increase from what the design currently specified and results in a
roughly $3.5MM increase in capital cost to cover the much larger adsorption column
34

dimensions. In contrast, increasing the ethylene flow rate into the distillation tower does not
change capital costs appreciably and has hardly any effect at all on annual utilities.
The combined liquid streams from the flash vessels are then fed into a 26 stage distillation
column (D301). The main purpose of this column is to strip away most of the water so that a
more concentrated ethanol stream can be returned to the reactors. The detailed specifications of
the column are included in Section X.
Care was taken to ensure that almost no ethanol was purged. The partial condenser utilizes
cooling water and requires approximately 260,000 lb/hr to achieve the necessary heat transfer.
The reboiler uses 50psi steam and requires approximately 54,000 lb/hr. The distillate stream
(S305) is fed into a compressor (C301) where it is returned to roughly 600psi and recycled into
the reactors. The bottoms (TREAT) is purged and pumped to an off-site waste treatment facility.
When designing this column, additional consideration was paid to finding the best pressure at
which to operate. It was determined from economic analysis that throttling the feed all the way
down to 14.7 psig and then compressing the reflux back to 600psi reduces annual costs
considerably. This is because the utility costs for the reboiler greatly diminish as the column
pressure decreases. If the column is operated at the column feed streams pressure of 455 psi,
the temperature of the bottoms stream is 440F. This high temperature requires 450psi steam
and accounts for roughly $6.2MM/yr in operating costs. When compared to the cost of the
reboiler, the $33,000 annual cost of compression disappears in the rounding. Throttling to
14.7psig reduces the reboiler temperature to 256F which can easily be achieved with only 50psi
steam. While the cost of compression does skyrocket all the way to $360,000 /yr, the reboiler
cost decreases to only $1.4M/yr for a net 73% utilities cost.
The vapor stream from the second flash vessel (ADSORB) then enters stage 4 of the separation
train: the drying stage. In this stage, the vapor is fed through an adsorption column (AD401A)
packed with zeolite 13X particles. This step is critical in ensuring that absolutely no water or
ethanol remains in the stream that will next be fed into the cryogenic distillation tower. If any of
either of those two components remains, the cryogenic conditions could cause them to freeze and
damage the column.
35

In order to have a continuous process, it is necessary to run two units in parallel, with one unit
processing the stream while the other unit is undergoing regeneration of the sorbent. It was
recommended that our design incorporate a daily cycle where each column is active for a day,
then regenerated for a day with that cycle repeating. This recommendation proved to give
reasonable column sizes and capital costs.
The dried stream (CRYO) passes through a heat exchanger (HX501) where the stream is cooled
to 6.8F by exchanging with the final product stream (S507). Then it is throttled one last time.
This step reduces the temperature all the way to -35F by dropping the pressure to 279psi, a
suitable temperature to perform cryogenic distillation.
The ethylene-rich stream is then fed into the cryogenic distillation unit (D501). D501 has 8 sieve
trays and operates with a condenser pressure of 279.2psi. The partial condenser (HX502)
operates at -67.54F and requires 5.637e7 BTU/hr of refrigeration to achieve the necessary reflux
ratio of 0.75. For temperatures in this range, propylene was selected as an appropriate refrigerant
and it was determined that 420,000 lb/hr are required to achieve this degree of refrigeration.
The reboiler (HX503) operates at -35F and therefore only requires cooling water to heat.
49,342 lb/hr of cooling water are needed to achieve the required heat transfer of 4.904e7 BTU/hr.
The cooling water used for this heat exchanger is piped directly from that used to cool the
condenser in the recycling distillation section (HX301). Following the path of the cooling water
(stream S312 in Figure 4.3), first it enters HX301 at 90F. It exchanges with the top stream of
D301 and exits at 120F (stream TO-REBOIL). From there (moving to Figure 4.5), it splits into
two fractions (S512 and TO-COOL). TO-COOL is sent directly to the cooling tower and
recycled to the process. Stream S512 is sent to the reboiler of the cryogenic column (HX503).
The split fraction was set so that the amount of cooling water that flows through HX503 allows
for a temperature change from 120F to 90F. In this way, 49.342 lb/h of cooling water is both
heated and cooled within the process and can be considered a close to free utility.
Distillation column (D501) removes ethane and the other heavy impurities to the bottom (S510)
and leaves the 99.96% pure ethylene product in the top (S504). This stream is then passed
through two heat exchangers in series (HX501 then HX202) to fully utilize its cooling ability.
First it pre-cools the feed to D501 by exchanging with CRYO-IN. Then it exchanges with S205
36

to cool the feed to the second flash vessel (FL202). After exiting these two exchangers, the
ethylene product stream (PRODUCT) is at a temperature if 52F.
The 1MM tonnes of ethylene product coming from HX202 is fed directly into the customers
barges for transportation to plastic plants around the world. Anticipating a maximum barge
capacity of 3000 tons, our plant will require barges to cycle every 18 hours. To maintain reliable
production and hopefully be able to run continuously throughout the dry season, 2MM gallon
tanks are included in the design to store approximately 3 hours worth of ethylene in case of
unforeseen delays in the transportation. Any more than that results in simply too great of a
capital and land strain.

37

Section VI
Energy Balance and Utility Requirements

38

The major heating requirements of the ethanol processing plant lie mainly in the three fired
heaters (F101, F102, and F103) intermittently placed between the three adiabatic reactors.
Together these three furnaces account for 175,000,000 BTU/hr. The various pumps and
compressors necessary to move the liquid/vapor streams through the process contribute relatively
little to overall energy requirements of the process. The other major heating/cooling
requirements lie in the heat exchangers. HX301 and HX302 function as the condenser and
reboiler of distillation column D301, respectively. HX502 functions as the condenser of the
cryogenic distillation column D501. Meanwhile, HX203 is the only standalone heat exchanger
that contributes a heat duty to the process, utilizing cooling water to achieve the remaining
cooling of the reactor effluent.
Additionally, various other heat exchangers are present throughout the process, such as HX202,
HX501, and HX503, which do not contribute a heat duty to overall process. This is a result of
efficient stream matching, coupling necessary hot and cold streams within the process with each
other to achieve the desired result. HX202 and HX501 each utilize the distillate stream, S507, of
D501 to respectively cool the vapor product of the flash vessel FL201 and the input to D501.
HX503 similarly uses the exit cooling water of HX301 to reboil the bottoms stream of D501.
Table 6.2 shows a complete list of all utilities that are necessary. Cooling water, low pressure
steam (50 psig), natural gas, and propylene are needed to achieve the proper heating and cooling
within the process. Also shown in Table 6.2 are the electrical power requirements of each piece
of equipment.

39

Table 6.1

Equipment Description
Duty
(BTU/hr) Source
Section 100
F101 Fired Heater 63,111,000 Natural Gas
P101 AB Pump 839,261 Electricity
P102 AB Pump 839,261 Electricity
176,763,072 Net Section 100
Section 200
HX201
Heat
Exchanger -27,014,000
Cooling
Water
-27014000 Net Section 200
Section 300
P301 Pump 1,356 Electricity
HX301
Heat
Exchanger -39,976,822
Cooling
Water
HX302
Heat
Exchanger 49,469,600
Steam (50
psig)
C301 Compressor 2,936,625 Electricity
12,447,185 Net Section 300
Section 400
C401 Compressor 295,482 Electricity
AD401
Adsorbtion
Column 113,400 Electricity
408,882 Net Section 400
Section 500
HX502
Heat
Exchanger -56,357,300 Propylene
-56,320,734 Net Section 500
106,284,405 BTU/HR
ENERGY REQUIREMENTS OF PROCESS
Total Net Energy
Required
40

Table 6.2

Electricity kW
Equipment List Description Usage Cost ($)
P101AB 230 129,367
P102AB 230 129,367
P301 0.4 160
P302 4.81 1,941
C301 860 452,562
C401 86.6 45,457
AD401 33.2 10,000
P501 10.7 4,321
Cooling Water lb/hr
HX201 901,425 55,068
HX301 253,085 24,100
Steam (50 psig) lb/hr
HX302 54,266 1,091,736
Natural Gas SCF/hr
F101 60,106 2,176,170
F102 52,908 1,915,565
F103 53,734 1,945,465
Refrigeration lb/hr
HX502 Propylene 420,000 5,368,643
Cleaning lb/hr Cost ($)
Equipment List Description Usage
C401 Nitrogen 91,800
UTILITIES REQUIREMENT OF PROCESS
41

Section VII
Economic Discussion and
Market Analysis

42

One major difficulty with this project is that the selling price of ethylene relative to ethanol is too
low for the plant to be profitable, given 1.73lb ethanol are required to produce 1lb ethylene. An
evaluation of current markets (discussed later) suggests that the selling price of ethylene in 2014
should be around $0.60/lb, while the price of ethanol is expected to fall around $0.34/lb. With
these values, sales of ethylene will not cover operating and raw material costs, and the Net
Present Value of the venture will become increasingly negative over time. However, a
sensitivity analysis of the response of NPV and Internal Rate of Return to ethanol and ethylene
prices does provide some hope; should the prices of these commodities fall around $0.64/lb
ethylene and $0.305/lb ethanol, the plant will become profitable.
Additionally, in an attempt to cut costs, the same analyses were conducted under the condition
that Research and Development (a variable cost previously equal to 4.8% of sales) was shut
down completely. With this change, the potential profitability of the plant increases
considerably. Realistically, it is unwise to entirely scrap all R&D; however it is interesting to
consider the potential value of shrinking the department.
The following section details the various costs of the plant, and shows the aforementioned
sensitivity analysis. Additionally, there is a discussion of other important economic
considerations.

43

Summary of Costs
The following cost analysis is based on selling prices of $0.60/lb ethylene and $0.34/lb ethanol.
It was determined that the total equipment cost for the plant will be $40MM (Figure 7.1). The
Direct Permanent Investment will be $49MM and the Total Permanent Investment will be
$65MM. The Total Depreciable Capital will be $58MM (Figure 7.2). The plants total capital
investment will be around $78MM (Figure 7.5). At the current market prices for ethylene and
ethanol, the Internal Rate of Return for the project will be negative (Figure 7.7), which is
obviously undesirable. Later in this section, the conditions for a positive IRR and Net Present
Value are discussed in more detail.

44

Figure 7.1

Equipment Description Bare Module Cost
P101 A/B Process Machinery $129,000
HX101 Fabricated Equipment $860,000
F101 Fabricated Equipment $4,022,000
R101-A/B Fabricated Equipment $192,000
FL201 Fabricated Equipment $252,000
FL202 Fabricated Equipment $179,000
D301 Fabricated Equipment $809,000
AC301 Fabricated Equipment $32,000
C301 Fabricated Equipment $4,634,000
C401 Fabricated Equipment $290,000
AD401 Fabricated Equipment $729,000
AD402 Fabricated Equipment $729,000
D501 Fabricated Equipment $720,000
HX502 Fabricated Equipment $9,464,000
AC501 Fabricated Equipment $268,000
FEED TANK Fabricated Equipment $1,820,000
PRODUCT TANK Fabricated Equipment $4,257,000
PRODUCT TANK Fabricated Equipment $4,257,000
P101 A/B Fabricated Equipment $129,000
P102 A/B Fabricated Equipment $129,000
$27,000
$33,000
$192,000
$250,000
Total $40,233,000
45

Figure 7.2

Investment Summary
Bare Module Costs
Fabricated Equipment 43,956,199 $
Process Machinery 334,964 $
Spares - $
Storage 558,300 $
Other Equipment - $
Catalysts - $
Computers, Software, Etc. - $
Total Bare Module Costs: 44,849,463 $
Direct Permanent Investment
Cost of Site Preparations: 2,242,473 $
Cost of Service Facilities: 2,242,473 $
Allocated Costs for utility plants and related facilities: - $
Direct Permanent Investment 49,334,409 $
Total Depreciable Capital
Cost of Contingencies & Contractor Fees 8,880,194 $
Total Depreciable Capital 58,214,603 $
Total Permanent Investment
Cost of Land: 1,164,292 $
Cost of Royalties: - $
Cost of Plant Start-Up: 5,821,460 $
Total Permanent Investment - Unadjusted 65,200,355 $
Site Factor 1.00
Total Permanent Investment 65,200,355 $
46

Figure 7.3

Fixed Cost Summary
Operations
Direct Wages and Benefits 364,000 $
Direct Salaries and Benefits 54,600 $
Operating Supplies and Services 21,840 $
Technical Assistance to Manufacturing - $
Control Laboratory - $
Total Operations 440,440 $
Maintenance
Wages and Benefits 2,619,657 $
Salaries and Benefits 654,914 $
Materials and Services 2,619,657 $
Maintenance Overhead 130,983 $
Total Maintenance 6,025,211 $
Operating Overhead
General Plant Overhead: 262,215 $
Mechanical Department Services: 88,636 $
Employee Relations Department: 217,897 $
Business Services: 273,295 $
Total Operating Overhead 842,043 $
Property Taxes and Insurance
Property Taxes and Insurance: 1,164,292 $
Other Annual Expenses
Rental Fees (Office and Laboratory Space): - $
Licensing Fees: - $
Miscellaneous: - $
Total Other Annual Expenses - $
Total Fixed Costs 8,471,987 $
47

Figure 7.4

Figure 7.5

Variable Cost Summary
Variable Costs at 100% Capacity:
General Expenses
Selling / Transfer Expenses: 39,872,544 $
Direct Research: 63,796,071 $
Allocated Research: 6,645,424 $
Administrative Expense: 26,581,696 $
Management Incentive Compensation: 16,613,560 $
Total General Expenses 153,509,295 $
Raw Materials $0.595680 per lb of Ethylene $1,319,515,398
Byproducts $0.000000 per lb of Ethylene $0
Utilities $0.006222 per lb of Ethylene $13,783,367
Total Variable Costs 1,486,808,060 $
Working Capital
2015 2016 2017
Accounts Receivable 49,157,931 $ 24,578,966 $ 24,578,966 $
Cash Reserves 823,143 $ 411,572 $ 411,572 $
Accounts Payable (49,313,790) $ (24,656,895) $ (24,656,895) $
Ethylene Inventory 6,554,391 $ 3,277,195 $ 3,277,195 $
Raw Materials 3,253,600 $ 1,626,800 $ 1,626,800 $
Total 10,475,275 $ 5,237,637 $ 5,237,637 $
Present Value at 15% 6,887,663 $ 2,994,636 $ 2,604,032 $
Total Capital Investment 77,686,686 $
48

Year
Percent
Capacity
Product
Unit
Price
Sales Sales Capital Costs
Working
Capital
Var Costs Fixed Costs Depreciation Taxible Income Taxible Income Taxes Net Earnings Cash Flow NPV
2012 0% - - - - - - - - - - - - -
2013 0% - - (65,200,400) - - - - - - - - (65,200,400) (56,696,000)
2014 0% - - - - - - - - - - - - (56,696,000)
2015 0% - - - (10,475,300) - - - - - - - (10,475,300) (63,583,600)
2016 45% $0.60 598,088,164 598,088,200 - (5,237,600) (669,063,600) (8,472,000) (11,642,900) (91,090,370) (91,090,400) 33,703,400 (57,386,900) (50,981,700) (92,732,500)
2017 68% $0.60 897,132,246 897,132,200 - (5,237,600) (1,003,595,400) (8,472,000) (18,628,700) (133,563,854) (133,563,900) 49,418,600 (84,145,200) (70,754,200) (127,909,900)
2018 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) (11,177,200) (161,600,117) (161,600,100) 59,792,000 (101,808,100) (90,630,900) (167,092,100)
2019 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) (6,706,300) (157,129,235) (157,129,200) 58,137,800 (98,991,400) (92,285,100) (201,785,500)
2020 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) (6,706,300) (157,129,235) (157,129,200) 58,137,800 (98,991,400) (92,285,100) (231,953,700)
2021 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) (3,353,200) (153,776,074) (153,776,100) 56,897,100 (96,878,900) (93,525,800) (258,539,500)
2022 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (281,964,300)
2023 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (302,333,700)
2024 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (320,046,300)
2025 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (335,448,500)
2026 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (348,841,700)
2027 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (360,487,900)
2028 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (370,615,100)
2029 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (379,421,400)
2030 90% $0.60 1,196,176,327 1,196,176,300 - - (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (94,766,400) (387,079,000)
2031 90% $0.60 1,196,176,327 1,196,176,300 - 20,950,500 (1,338,127,300) (8,472,000) - (150,422,913) (150,422,900) 55,656,500 (94,766,400) (73,815,900) (392,265,700)
Cash Flow Summary

Figure 7.6

49

Figure 7.7

Profitability Measures
The Internal Rate of Return (IRR) for this project is Negative IRR
The Net Present Value (NPV) of this project in 2012 is (392,265,700) $
ROI Analysis (Third Production Year)
Annual Sales 1,196,176,327
Annual Costs (1,346,599,240)
Depreciation (5,216,028)
Income Tax 57,586,408
Net Earnings (98,052,533)
Total Capital Investment 86,150,905
ROI -113.81%
50

Ethylene/Ethanol Price Sensitivity (With Research and Development)
The following figures (Figure 7.8, 7.9) show how the NPV and IRR vary with the prices of
ethylene and ethanol. Notice that the plant will only be profitable with relatively high ethylene
prices ($0.63/lb) and low ethanol prices ($0.32/lb).
Figure 7.8

Figure 7.9

$0.62 $0.63 $0.64 $0.65 $0.66 $0.67
$0.360 (505,735,700) (429,816,500) (391,857,000) (353,897,400) (315,937,800) (277,978,300)
$0.355 (467,878,300) (391,959,200) (353,999,600) (316,040,000) (278,080,500) (240,120,900)
E $0.350 (430,020,900) (354,101,800) (316,142,200) (278,182,600) (240,223,100) (202,263,500)
T $0.345 (392,163,500) (316,244,400) (278,284,800) (240,325,300) (202,365,700) (164,406,100)
H $0.340 (354,306,100) (278,387,000) (240,427,400) (202,467,900) (164,508,300) (126,548,800)
A $0.335 (467,878,300) (240,529,600) (202,570,100) (164,610,500) (126,650,900) (88,691,400)
N $0.330 (278,591,400) (202,672,200) (164,712,700) (126,753,100) (88,793,600) (50,834,000)
O $0.325 (240,734,000) (164,814,900) (126,855,300) (88,895,700) (50,936,200) (12,976,600)
L $0.320 (202,876,600) (126,957,500) (88,997,900) (51,038,400) (13,078,800) 24,880,800
$/LB $0.315 (165,019,200) (89,100,100) (51,140,500) (13,181,000) 24,778,600 62,738,100
$0.310 (127,161,900) (51,242,700) (13,283,200) 24,676,400 62,636,000 100,595,500
$0.305 (89,304,500) (13,385,300) 24,574,200 62,533,800 100,493,300 138,452,900
$0.300 (51,447,100) 24,472,000 62,431,600 100,391,200 138,350,700 176,310,300
ETHYLENE $/LB
Net Present Value for Varied Ethanol and Ethylene Prices
$0.62 $0.63 $0.64 $0.65 $0.66 $0.67
$0.360 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR
E $0.350 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR
T $0.345 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR
H $0.340 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR
A $0.335 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR
N $0.330 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR 2%
O $0.325 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR 12%
L $0.320 Negative IRR Negative IRR Negative IRR Negative IRR 12% 19%
$/LB $0.315 Negative IRR Negative IRR Negative IRR 12% 19% 25%
$0.310 Negative IRR Negative IRR 12% 19% 25% 30%
$0.305 2% 12% 19% 25% 30% 34%
$0.300 12% 19% 25% 30% 34% 38%
Internal Rate of Return for Varied Ethanol and Ethylene Prices
ETHYLENE $/LB
51

Ethylene/Ethanol Price Sensitivity (Without Research and Development)
The following figures (Figure 7.10, 7.11) show the same analysis except with no expenses for
research and development. Notice that the plant becomes profitable at lower prices of ethylene
and higher prices of ethanol. Since prices are ethylene over $0.62 are unlikely, this option for
cutting costs is recommended. Realistically, it is prudent to only downsize R&D spending,
rather than cutting it altogether. This analysis merely illustrates the sensitivity of profitability to
R&D spending.
Figure 7.10

$0.62 $0.63 $0.64 $0.65 $0.66 $0.67
$0.360 ($323,125,700) ($282,833,100) ($242,540,400) ($202,247,800) ($161,955,100) ($121,662,500)
$0.355 ($285,268,300) ($244,975,700) ($204,683,000) ($164,390,400) ($124,097,800) ($83,805,100)
E $0.350 ($247,410,900) ($207,118,300) ($166,825,700) ($126,533,000) ($86,240,400) ($45,947,800)
T $0.345 ($209,553,500) ($169,260,900) ($128,968,300) ($88,675,600) ($48,383,000) ($8,090,400)
H $0.340 ($171,696,200) ($131,403,500) ($91,110,900) ($50,818,300) ($10,525,600) $29,767,000
A $0.335 ($133,838,800) ($93,546,100) ($53,253,500) ($12,960,900) $27,331,800 $67,624,400
N $0.330 ($95,981,400) ($55,688,800) ($15,396,100) $24,896,500 $65,189,100 $105,481,800
O $0.325 ($58,124,000) ($17,831,400) $22,461,300 $62,753,900 $103,046,500 $143,339,200
L $0.320 ($20,266,600) $20,026,000 $60,318,600 $100,611,300 $140,903,900 $181,196,500
$/LB $0.315 $17,590,700 $57,883,400 $98,176,000 $138,468,600 $178,761,300 $219,053,900
$0.310 $55,448,100 $95,740,800 $136,033,400 $176,326,000 $216,618,700 $256,911,300
$0.305 $93,305,500 $133,598,100 $173,890,800 $214,183,400 $254,476,000 $294,768,700
$0.300 $131,162,900 $171,455,500 $211,748,200 $252,040,800 $292,333,400 $332,626,100
Net Present Value for Varied Ethanol and Ethylene Prices Without R&D
ETHYLENE $/LB
52

Figure 7.11

Historical Ethylene Prices
Figure 7.12

As it is clearly seen in figure 7.12, the price of ethylene is hardly stable. This in mind, it is not
unreasonable to assume that prices may rise adequately to make this plant profitable.

$0.62 $0.63 $0.64 $0.65 $0.66 $0.67
E $0.350 Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR Negative IRR
T $0.345 Negative IRR Negative IRR Negative IRR Negative IRR 2% 13%
H $0.340 Negative IRR Negative IRR Negative IRR Negative IRR 13% 20%
A $0.335 Negative IRR Negative IRR Negative IRR 12% 20% 26%
N $0.330 Negative IRR Negative IRR 12% 20% 26% 31%
O $0.325 Negative IRR 11% 19% 25% 30% 35%
L $0.320 10% 19% 25% 30% 35% 39%
$/LB $0.315 18% 25% 30% 34% 38% 42%
$0.310 24% 30% 34% 38% 42% 45%
$0.305 29% 34% 38% 42% 45% 48%
$0.300 34% 38% 41% 45% 48% 51%
Internal Rate of Return for Varied Ethanol and Ethylene Prices Without R&D
ETHYLENE $/LB
0
20
40
60
80
100
Oct-06 Apr-07 Nov-07 Jun-08 Dec-08 Jul-09 Jan-10 Aug-10 Feb-11 Sep-11 Apr-12
E
h
y
l
e
n
e

P
r
i
c
e

(
$
/
l
b
)
Date
53

Market Considerations
Ethylene is a high demand product because it is an essential raw material in the production of
plastics, in particular low and high density polyethylenes and PVC. In the US alone, the yearly
demand is approximately 5MM tonnes of ethylene. Traditionally, ethylene is produced by
cracking of heavy hydrocarbons from fossil fuels. In fact, in the 1960s this process was so
profitable that ethylene was used to produce ethanol in the reverse of the process used by this
plant. However, a worldwide oil crisis in 1973 raised petroleum prices making cracking a much
less economically reasonable method of ethanol production. Since plastics remain in high
demand, ethylene production via ethanol is being explored again.
The major benefit of using ethanol as the raw material for ethylene production instead of fossil
fuels is that ethanol is renewable; it can be produced from fermentation of feedstocks such as
corn or sugar cane. If the demand for ethylene remains high while the supply of fossil fuels is
diminished, the selling price of ethylene may be driven up, making this process profitable.
Additionally, as environmental awareness becomes more socially prevalent, governments are
encouraging companies to move away from fossil fuels because they are non-renewable and
have high carbon emissions. Government support of this greener, renewable process may
further impact ethylene costs and also investment and operating costs for the plant.
Comparison to Traditional Ethylene Plants
According to Seider, Seader, Lewin, and Widago, the typical total depreciable capital associated
with a traditional ethylene plant (naphthalene cracking) is $681MM. The total depreciable
capital for this plant is $58MM (Figure 7.5) which is far less. The total permanent investment
for a traditional cracking plant is $855MM, while the total permanent investment for this plant is
$65MM (Figure 7.2), again far less.
The values were generated with the following assumptions: Land cost is typically 2% of the
C
TDC
. The cost of plant start-up is typically 10% of the C
TDC
. However, since the process is
well-known, the figure can be estimated around 9%. The total permanent investment can be
estimated as 8% of the C
TDC
, and is corrected to a site factor which is now 1.0 for Brazil.

54

Additional Economic Considerations
Transportation of Materials
Transportation of the ethylene product is generally the responsibility of the buyers, who may use
barges docked near the plant. Ethylene can thus be piped directly from the plant onto the barges
at minimal cost. Because there are many ethanol vendors near the plant location, it may be
possible to pipe ethanol directly to the plant at minimal cost. If not it can be transported cheaply
by rail.
With efforts by the Brazilian government to reduce transportation costs in Brazil, it is safe to
assume a low price for shipping the ethylene product to a nearby port, such as Rio de Janeiro, so
that buyers do not have to come to So Paulo to pick up the ethylene.
Cyclic Ethanol Availability
Since the sugar cane ethanol price increases dramatically during the winter months (because
sugar cane growth is seasonal), it was decided that the plant will only operate 280 days per year.
This was determined because storage tanks for three months worth of ethanol (which would
cover the off-season) would require almost 21.5MM cubic feet of volume, which comes at an
astronomical cost.
Environmental Awareness
One major advantage of this process over hydrocarbon cracking is that ethanol dehydration is
relatively green because it has very low carbon emissions. This in mind, it is reasonable to
expect government support, possibly in the form of subsidies.

55

Section VIII
Location

56

A major factor regarding the profitability of the project is the location of the plant. Based on the
supply of ethanol and demand for ethylene, it was necessary to choose between building in either
the United States or Brazil. Different sites may affect the economics of the plant due to
differences in the site factors, supply of ethanol, price of ethanol, price of ethylene, ability to
transport goods, and environmental regulations. The considerations and explanation of the final
decision to locate in So Paulo, Brazil are discussed here.
Site Factor
Site factors help companies compare the cost of building a plant in various locations based on the
availability of labor, efficiency of the workforce, local rules and customs, and union status
among other considerations. Overall, Brazil has a site factor of 1.0 compared to the United
States Gulf Coast, so these factors do not affect the choice of location. In the past, Brazils site
factor was 0.90 due to lower exchange rates and labor costs. More recently, it has been the
largest and fastest growing economy in South America, so its construction costs have increased.
Also, because the United States has been the center of industry for such a long time, it has grown
more competitive, developing a more low-cost manufacturing economy with decreasing
construction costs despite providing better benefits for laborers.
Ethanol Price
The price of our ethanol feed plays a large factor in the profitability of the project. It is crucial to
find inexpensive ethanol that is near the plant to decrease transportation costs as much as
possible. Corn ethanol, which is largely produced in the United States, is $0.30/L whereas
Brazilian sugar cane ethanol is only $0.22/L. Additionally, since there are many sugar cane
fields near So Paulo, transportation costs will competitive with those in the US, if not lower.
Consequently, locating in Brazil is more economical from an ethanol standpoint.
Ethanol Supply
Differences in the supply of ethanol feed for the plant are enormous. In the United States,
ethanol is largely made from corn while Brazil generally produces ethanol using sugar cane. The
presence of plants to produce the needed quantity of ethanol is essential to the survival of this
project. Corn ethanol is widely available in the Midwest of the United States. Meanwhile,
57

Brazil is a large producer of sugar cane ethanol with the exception of the cold, rainy season
which eliminates the sugar cane supply for ethanol from June-September. To compensate, either
a storage tank of ethanol for those months must be built, or the plant must be operated at higher
capacity for the rest of the year. A storage tank would need to hold 481,000 tonnes of ethanol to
support the plants production. This would consist of many tanks with a total volume of
21.5MM ft
3
, which would cost roughly $87MM. Because the economics of the project are so
tight and space is a big issue, it would be most beneficial to not use a storage tank. Therefore, it
is recommended to operate the plant at a higher capacity for the rest of the year to make up for
the nonproduction during the 3 months. Due to the already incredibly high capacity of this plant,
scaling up is not an issue at all.
Ethylene Price
The price of ethylene gives insight on the market where the product will be introduced. As
discussed in the Economics Section of this report, the price of ethylene worldwide has shown
dramatic fluctuation over the past decade; however, if the price stabilizes around its current value
it is reasonable to estimate a selling price of $0.65/lb in 2014 when the plant is expected to be
complete. This number accounts for the decrease in availability of natural fuels, like
naphthalene, for cracking into ethylene. Since the price for ethylene is the same in both the
Brazilian and American markets, the major concern with the profitability of ethanol becomes the
cost of shipping.
Transportation
A plant is only operable if there is a suitable means of transportation to and from it. This is
necessary because in order for the plant to be built, materials must be shipped to the site.
Additionally, in order for it to run, raw materials, products, and employees must be brought to
and from the site. Good roads, a railway infrastructure, and access to ports and waterways are a
large factor in determining the location of the plant. Locating the plant in Brazil allows for easy
access to both a feed of ethanol from a nearby plant (there are several near So Paulo) and a port
to ship the ethylene product. All of the ethanol plants in the United States are landlocked, so
transportation would have to be by railcar. This limits the shipping quantity of both ethanol and
58

ethylene and also the buyer of ethylene. Access to ports allows for easier access to international
markets than railcars from the central United States.
There are additional benefits to specifically locating in So Paulo. It is a large city with a good
road and rail infrastructure, which means that it can easily supply a sizable workforce. Also, it is
only 220 miles from the major economic center Rio de Janeiro. Sao Paulo also boasts the
availability of freight transportation to Ports Santos and Sepetiba. Finally, it is promising to note
that the Brazilian government is sponsoring projects for improving transportation to and from
Sao Paulo.

59

Section IX
Safety and Other Important
Considerations

60

Safety
Ethanol and ethylene are both very flammable, and as such careful attention must be paid to their
transportation to and from and storage at the facility. Ethanol spontaneously combusts at about
790F. Since the reactors operate near this limit (750F), it is very important to invest in
accurate and careful controllers to ensure that the temperatures in the furnaces and compressor
outlet stream never reach this level. The plant is at no risk of ethylene accidently autoigniting as
ethylenes ignition temperature is 914F and it spends most of the process under cryogenic
conditions. In addition, none of the byproducts are at serious risk.
While spontaneous combustion of ethylene is not a serious concern, it is still a highly volatile
and flammable hydrocarbon. Even while being treated in the cryogenic column at temperatures
as low as -67F, it is still well above its flash point (-218F). Measures should be taken to ensure
that minute leaks in process equipment, particularly the separation units which handle highly
concentrated ethylene, can be quickly detected and isolated. In addition, it is advisable to invest
a greater amount in the piping and transport equipment to lower the risk of leaks. If an ethylene
leak is left undetected, immediate surroundings will rapidly reach the lower flammability limit of
ethylene in air (about 3%) and put the plant, the operators, and the surroundings at serious risk.
Ethanol is not nearly as volatile as ethylene and is thus less likely to cause an explosion.
However, as it is heated to a vapor, ethanol does become quite flammable and a greater risk to
the plant. Similar treatment should be given to the highly concentrated ethanol reactor feed
stream to ensure quick detection of potential leaks.
Another possible concern is the spontaneous free radical polymerization of ethylene. Such
reactions are often used to generate polyethylene on industrial scales. This is not a huge
operational risk in this plant, as free radical polymerization requires astronomically high
pressures (on the order of 1000atm) to occur. However, to prevent runaway in the unlikely event
that a free radical initiator is introduced in the concentrated ethylene streams (particularly stream
S510 and PURGE on Figure 7.5 which carry liquid ethylene), pipes with periodic pinches should
be used. The pinches help prevent the polymerization from spreading throughout the entire plant
and ruining an entire ethylene stock.
61

For feed storage, a floating roof tank is being used. Some pure nitrogen will be available to
ensure that no air contacts the stored ethanol and jeopardizes the feed.
Kinetic Considerations
The reaction kinetic data used in this design was obtained from Fikry Ebeids work. The data
published specifically applies to high-temperature reactions, though there is no mention of the
operating pressure in the paper. As such, it was assumed that the high operating pressures of this
plant would not have a significant impact on the kinetics. It was also necessary to make the
assumption that the rate constant followed the Arrhenius equation with no additional temperature
correction factor. In order to verify that the kinetics are sufficiently independent of pressure, it
would be necessary to conduct a small scale experiment in a laboratory setting.
Additional Considerations
All of the chemicals reacting involved in this plant are well understood. In addition, dehydration
reactions over alumina-based catalysts are also common. Thus there were few additional
assumptions that had to be made.
One assumption was the composition of the byproducts. It was difficult to obtain side-reaction
data, but based on the available material it was assumed that diethyl-ether and acetaldehyde are
the main byproducts formed. Additionally, it was assumed that some quantity of methane would
be formed, potentially posing a problem.
Methane is notoriously difficult to remove. After simulating the cryogenic distillation column
for a host of different operating and inlet conditions, it was determined that using the property
selection model NRTL-RK, it is impossible to purify and ethylene/methane stream to more than
99.92% pure ethylene using distillation. There are two explanations for this behavior. Ethylene
and methane may form an azeotrope at these extremely non-ideal conditions (low temperature,
high pressure). This explanation seems unlikely as both are light hydrocarbons having zero
dipole moments. The second possible explanation is that methane can dissolve in ethylene to
that extent.
62

If the side reactions were adjusted such that more methane was produced, this process may
become infeasible. Since this reaction is so important, the reactor should be modeled to measure
the extent of methane formation before this plant is designed.

63

Section X
Equipment List and Unit Descriptions

64

Equipment ID Type
P101 A/B Multistage Centrifugal Pump
P102 A/B Multistage Centrifugal Pump
P301 A/B Centrifugal Pump
Equipment ID Type
HX101 Shell and Tube Heat Exchanger
HX301
Shell and Tube Partial
Condenser
HX302 U Tube Kettle Reboiler
HX502
Shell and Tube Partial
Condenser
HX503 U Tube Kettle Reboiler
F101 Furnace
F102 Furnace
F103 Furnace
Equipment ID Type
FEED TANK Floating Cylinder Tank
PRODUCT TANK Spherical Tank
PRODUCT TANK Spherical Tank
AC301 Reflux Accumulator
AC501 Reflux Accumulator
TANKS
PUMPS
HEAT EXCHANGERS
Equipment ID Type
R101 A/B Fixed Bed Catalytic Reactor
FL201 Flash Vessel
FL202 Flash Vessel
Equipment ID Type
D301 Distillation Tower
D501 Distillation Tower
AD401 A/B Packed Tower
Equipment ID Type
C301 Multistage Compressor
C401 Multistage Compressor
PRESSURE VESSELS
TOWERS
COMPRESSORS
Table 7.1

65

Unit Descriptions
100_Reactors Section
Reaction Vessels
R101 is a horizontal adiabatic reactor, made of carbon steel, with a length of 8.46 feet and a
diameter of 5.81 feet. The wall thickness is 1.84 inches, with a total reactor volume for 224
cubic feet. 36,111lb of one cm -Alumina diameter pellets are used as catalyst to convert
ethanol to ethylene. The 578,839 lb/hr inlet flow enters at 752F and 618psi and leaves at 590F
and 616psi.
R102 is a horizontal adiabatic reactor, made of carbon steel, with a length of 8.07 meters and a
cubic feet. It requires 41,227lb of catalyst. The 578,839 lb/hr inlet flow enters at 752F and
608psi and leaves at 590F and 600psi.
R103 is a horizontal adiabatic reactor, made of carbon steel, with a length of 7.78 feet and a
cubic feet. It requires 49,872lb of catalyst. The 578,839 lb/hr inlet flow enters at 752F and
600psi and leaves at 590C and 597psi.
Each reactor has an identical spare available in case of repair and catalyst regeneration. The
catalyst is replaced every 90 days.
The choice of using three reactors is to ensure a proper conversion of ethanol to ethylene,
achieving a required conversion of 98%. Due to the endothermic nature of the ethanol
dehydration reaction, temperature is a clear factor in the reaction kinetics. The ability to reheat
the reactants before running the catalyzed reactants ensures a high rate of reaction before an
equilibrium state is reached. Additionally, the recycle stream is fed before the final reactor in
order to reduce the heat duty of the furnaces for the two previous reactors. Finally, the choice of
using three adiabatic reactors instead of using isothermal reactors is due to the tremendous
amount of energy necessary to run an isothermal reactor at the necessary temperature. Due to
66

the endothermic nature of the reaction, sustaining an isothermal reactor is incredibly
cumbersome; adiabatic reactors coupled with re-heating furnaces are more efficient.
Heat Exchanger
HX101 is a shell and tube heat exchanger is used to simultaneously cool S110 (reactor effluent)
while heating S102 (reactor inlet). The heat exchanger is made of carbon steel with a heat
transfer area of 30,000 ft
2
. The total heat duty used is 361MM BTU/h.
Furnaces
F101 is a fired heater used to heat stream S103 from an inlet temperature of 572F to the desired
temperature of 752F before entering R101. Due to the fact that the feed is essentially at room
temperature, a relatively large amount of heat must be used in order to reach the aforementioned
reactor feed temperature. The heater supplies 63MM BTU/hr of heat, while utilizing 60,000
SCF/h of natural gas as fuel. Chromium-Molybdenum Steel is used as a construction material in
order to withstand the high heating temperatures. A total mass of 580,000 lb/hr enters and exits
the heater, consisting mainly of ethanol and water.
temperature of 752F before entering R102. The heater supplies 55.5MM BTU/hr of heat, while
utilizing 53,000 SCF/h of natural gas as fuel. Chromium-Molybdenum Steel is used as a
construction material in order to withstand the high heating temperatures. A total mass of
580,000 lb/hr enters and exits the heater.
temperature of 752F before entering R103. The heater supplies 56.4MM BTU/hr of heat, while
utilizing 53,000 SCF/h of natural gas as fuel. Chromium-Molybdenum Steel is used as a
construction material in order to withstand the high heating temperatures. A total mass of
580,000 lb/hr enters and exits the heater.
F101, F102, and F103 all emit flue streams that are released to the atmosphere.

67

Pumps
P101 and P102 are identical cast iron three stage pumps. Each pump provides a pressure
increase of 588 psi. Because of the considerable mass of the feed, it was necessary to use two
pumps in parallel to raise its pressure; just one large pump would have had to be unreasonably
large.
200_Flash Distillation Section
Flash Distillation
FL201 is a flash distiller used to remove water and ethanol from the product stream. Stream
S203, the product of the reactor section at a temperature and pressure of 122
o
F and 574 psi, is fed
into the distiller. This stream is about 55.6% ethylene, with significant amounts of water and
ethanol, as well as trace amounts of ether, ethane, acetaldehyde, methane, and acetic acid. After
separation, the top product, stream S205, consists of 98.2% ethylene by weight along with trace
amounts of the other components. The bottoms, stream S204, contains 3.8% ethanol and 95.2%
water along with other impurities.
FL202 also serves to remove more water and ethanol from the product stream coming from the
top of the previous flash distiller (FL201). Stream S207, the cooled and throttled top product of
FL201, is fed into this distiller to achieve a more thorough separation of water and ethanol. The
stream is at 569 psi and 57.2
o
F, and the resulting top stream is 98.6% ethylene by weight. The
bottoms product contains 346 lb/hr ethanol (24.3% by weight). This stream will be recycled
later.
Heat Exchangers
HX201 is used to cool the reactor product using cooling water introduced in stream CW201. The
reactor product, stream S110, was cooled to 180
o
F from a previous exchanger, and is now further
cooled to 122
o
F before entering the flash distiller. This temperature is required to achieve an
effective separation of ethanol and water from the ethylene product. The 182 tubes with 2 shell
and 2 tube passes has a total transfer area is 7,630 ft
2
with an overall transfer coefficient of 80
BTU/hr*ft
2
*R and a heat duty of -27,014,000 BTU/hr.
68

HX202 is used to cool the ethylene rich stream from the 1
st
flash vessel using the product stream
which exits the top of the cryogenic distiller, stream CRYO-OUT. This cold ethylene product
stream at -35.4
o
F cools the flash feed stream from 122
o
F to 57.2
o
F so that the water and ethanol
can be further separated from other impurities. HX202 also warms the cold product to 52.4
o
F,
bringing it somewhat closer to the environmental temperature so that there is less expansion as
the ethylene warms during shipment. The 250 tubes with 1 shell and 2 tube passes has a total
transfer area is 2,629 ft
2
with an overall transfer coefficient of 60 BTU/hr*ft
2
*R and a heat duty
of 12,630,433 BTU/hr.
Valves
V201 is a throttle which decreases the pressure of the reactor product to 569 psi. This allows the
stream to be at a pressure suitable for feeding into the flash distiller to achieve an efficient
separation. This throttle also conveniently lowers the temperature to 122
o
F.
V202 brings the stream exiting FL201 from 569 to 441 psi for the 2
nd
, more thorough ethanol
and water separation which takes place in FL202. The lowered pressure also helps to decrease
the temperature of the stream to 36.6
o
F from the 57.2
o
F stream which was heat exchanged with
the cryogenic distiller overhead.
300_Distillation Column Section
Distillation Column
D301 is the distillation column responsible for the recycle stream. Its purpose is to take the
bottoms products from both flash distillers, stream S302, and separate the ethanol from the water
and other components. The tower is made of carbon steel and stands 64 feet tall with 26 trays
spaced 2 feet apart and a diameter of 6 feet. It is operated at 122
o
F and 30.9 psi, resulting in an
ethanol-rich stream as the top product. The distillate, S303, passes through a partial condenser
which operates at 29.4 psi and 206
o
F while the bottoms, S309, pass through a reboiler operating
at 31.2 psi and 252
o
F. The towers reflux ratio given by the reflux accumulator, AC301, is 0.85.
The distillate, a 10,044 lb/hr ethanol stream, is later recycled into the 3
rd
reactor. The distiller is
very efficient with only 2 lb/hr of ethanol being lost to the bottoms stream.
69

Heat Exchanger
HX301 is a carbon steel shell and tube heat exchanger that makes up the partial condenser
section of the distillation tower. Using cooling water, it partially condenses the vapor stream
exiting the top of the column so that it can enter the reflux accumulator (AC301). The condenser
contains 122 tubes with one shell pass and one tube pass. The total transfer area is 642 ft
2
with an
overall transfer coefficient of 180 BTU/hr*ft
2
*R. This condenser has a heat duty of 9,063,300
BTU/hr.
HX302 is carbon steel U-tube kettle reboiler which uses steam at 50 psi to vaporize the bottoms
product (S309) which is then put back into the column. The kettle reboilers total transfer area is
5,684 ft
2
and the overall transfer coefficient is 80 BTU/hr*ft
2
*R with a heat duty of 49,469,600
BTU/hr.
Reflux Accumulator
AC301 accumulates the partially condensed reflux from D301 to send back to the column. It is 5
ft high with a 3 ft diameter and a storage volume of 264 gallons and is made of carbon steel. The
accumulator operates at 206.4
o
F and 28 psi.
Multistage Compressor
C301 is responsible for compressing the distillation columns distillate stream (S305) by 570 psi.
The resulting stream is at 600 psi, which is the appropriate pressure for combining with the 3
rd

reactor feed, S107. Without the compressor, there cannot be a stream to recycle the 10,044 lb/hr
ethanol.
Centrifugal Pumps
P301 A/B is a centrifugal pump responsible for pumping the reflux from the accumulator back
into the top of the column after it is condensed. It operates on electricity, is made of cast iron,
and pumps 44 gallons per minute of the condensed vapor from stream S307 back into the
column. The pump efficiency is 0.7 and consumes 1,356 BTU/hr. The discharge pressure will be
29.4 psi with a pressure head of 76 feet.
70

P302 A/B is the centrifugal pump which forces the bottoms product, S311, of the distillation
tower away from the process to undergo waste treatment for disposal. The pump is also made of
cast iron and consumes 16,426 BTU/hr of electricity to pump 597 gallons per minute of the
purge (S311) which consists mainly of water and a little bit of ethanol and acetic acid.
Valve
V301 is the valve which decreases the pressure of the feed into the distillation tower. The
combined flash distiller bottoms (S209) is at 455.6 psi and must be reduced to 30.9 psi to achieve
a good separation of ethanol from water. The valve is the piece of equipment which allows us to
achieve this pressure drop.
400_Adsorption Tower Section
Adsorption Towers
AD401 is an adsorption column which is fed with the ethylene-rich top product stream of the
series of flash distillators (S210). It contains a 13X, 3mm spherical zeolite filling whose purpose
is to absorb the rest of the water and ethanol as well as all other condensables that would clog the
cryogenic distiller. The column is made of carbon steel and requires 772 ft
3
of zeolite filling. The
eluent is 4,800 lb/hr of 350
o
F nitrogen. The ethylene stream feed enters at 335,339 lb/hr with
residence time of 22 sec and a breakthrough time of 24 hr. It experiences a pressure drop of 15
psi and the columns heat of adsorption is 113,400 BTU/hr. The exit, stream S404 is now an
ethylene stream along with various light key impurities that will not freeze at cryogenic
temperatures.
AD402 is an identical adsorption tower to AD401 but alternates in productivity so that the plant
can continue to run while one adsorption tower is being maintained. Maintenance of the tower
occurs after one day of productivity and consists of cleaning the zeolite filling using a
compressed nitrogen purge stream. The zeolite also needs to be replaced every 3 years.

71

C401 is a multistage compressor that sends the nitrogen into the adsorption column that is not in
operation as a purge used to clean that tower. The nitrogen needs to be condensed to raise the
temperature for optimal cleaning. Therefore, this carbon steel, one-stage compressor consumes
295,482 BTU/hr of electricity to condense the nitrogen stream by 26 psi, causing a temperature
rise of 247
o
F. The compressor condenses 67,506 ft
3
/hr of nitrogen to 36,171ft
3
/hr for cleaning
purposes.
Valves
V401 and V404 decide which adsorption tower to send the future product stream (S210) to. This
depends on which one is cleaned and ready for use while the other one is undergoing
maintenance.
V403 and V406 open the pipe that contains the ethylene-rich stream exit (S404 or S407) from
whichever adsorption tower is used. It is then sent to be further treated before being fed into the
cryogenic distiller.
V407 and V408 determine the route of the nitrogen purge stream (S408), sending it to the unused
adsorption tower that is to be cleaned.
V402 and V405 release the cleaning nitrogen purge stream. This condensed nitrogen is later sent
through a heat exchanger to warm the cold cryogenic ethylene product stream.
500_Cryogenic Distillation Section
Cryogenic Distiller
D501 is a cryogenic distiller which operates at the cold temperature of about -35
o
F to effectively
separate ethylene from other light impurities such as ether, ethane, and methane. The impurities
exit out the bottom as stream S511 which is burned and purged. The tower distillate (S507)
contains 330,473 kg/hr of the final 99.96% pure ethylene product at -68
o
F. The cryogenic
distiller is made of stainless steel because carbon steel is brittle at such low temperatures. The
feed stream, S503, enters on the 3
rd
of 8 stages with 2 foot spacing. The tower is 24 feet with a
72

diameter of 10.5 feet. The tray efficiency is 0.75. With the cryogenic distiller, enough impurities
are removed to achieve the 99.96% ethylene purity required to qualify as polymer grade.
Heat Exchangers
HX501 cools the stream entering the cryogenic column by running it through this stainless steel
shell and tube heat exchanger against the cold product stream exiting the cryogenic distiller. The
exchanger consists of 144 tubes with a total transfer area of 2,951 ft
3
with an overall heat transfer
coefficient of 30 BTU/hr*ft
2
*R and a heat duty of 6,591,610 BTU/hr. The -68
o
F ethylene
product is warmed to -35
o
F while the cryogenic feed is cooled from 40
o
F to 7
o
F to reduce the
necessary refrigeration in the cryogenic distillation column.
HX502 is a floating head shell and tube partial condenser which uses 420,000 lb/hr propylene
introduced in stream R501 at -90
o
F to condense the 420,000 lb/hr vapor overhead of the
cryogenic distiller so that it can be accumulated and reintroduced into the column for a more
thorough separation. The condensed exit stream is partially sent to the HX501 exchanger and the
other part is sent to the reflux accumulator. It is made of stainless steel and has 1,122 tubes with
8 tube and 2 shell passes, having a total transfer area of 188,500 ft
2
with an overall transfer
coefficient of 50 BTU/hr*ft
2
*R and a heat duty of 56,357,300 BTU/hr. Exiting HX502 is the
cold but purified product stream of 99.96% ethylene.
HX503 is a U-tube kettle reboiler for vaporizing the bottoms product (S510) using steam to
reintroduce into the column again. 199,282 lb/hr of steam is used to partially vaporize 49,342
lb/hr of the eventual purge. It is made of stainless steel and has a total transfer area of 2,105 ft
2

with an overall transfer coefficient of 45 BTU/hr*ft
2
*R and a heat duty of 49,039,968 BTU/hr.
Valve
V501 decreases the pressure of the feed into the cryogenic distillation tower from 452.5 psi to
279.2 psi. The decrease in pressure also causes a convenient temperature decrease from 6.8
o
F to -
35.1
o
F which improves the separation in the cryogenic distiller. Without the valve, S503 would
not be at an optimal temperature and pressure for removing the light keys from the ethylene
product.
73

Reflux Accumulator
AC501 accumulates the partially condensed reflux from D501 to send back to the column. It is
20 ft high with a 7 ft diameter and a storage volume of 4,965 gallons. The accumulator operates
at -68
o
F and 238 psi. Reflux accumulators for cryogenic distillers are made of stainless steel to
withstand cold temperatures.
Pumps
P501 A/B is the centrifugal pump which works to send the reflux of condensed overhead (S508)
back into the cryogenic distiller. This pump is made of stainless steel to withstand the low
temperatures. It pumps 791 gallons per minute back into the column and causes a pressure rise of
41 psi and a pressure head of 107 feet. It consists of one stage with an efficiency of 0.70 and
uses 36,566 BTU/hr of electricity. The result is stream S509 which is sent back into the column.

74

75

Section XI
Specification Sheets

76

Reactor Section

Block Type: Floating Roof Storage Tank
Function: Stores 1 month supply of feed
Materials:
Mass Fraction:
Ethanol
Water
Operating Conditions:
Pressure (psi)
Temperature (F)
Design Data:
Construction Material
Volume (gal)
Diameter (ft)
Height (ft)
Purchase Cost:
Bare Module Cost:
Annual Operating Cost:
Feed Storage Tank
$0
$1,819,580
$574,000
270
350.000
1,110,000
Carbon Steel
80
14.7
0.05
0.95
77

Block Type: Multistage Centrifugal Pump
Function:
Materials: Inlet Outlet
Stream FEED S102
Pressure Increase (psi)
Pressure Head (ft)
Flow Rate (GPM)
Design Data:
Number of Stages
Pump Efficiency
Consumed Power (BTU/h)
Power Source
Purchase Cost:
Bare Module Cost:
$103,913
$129,367
P101 A/B
3
1
Raise the FEED pressure
$32,780
587.8
1680
788
Cast Iron
Electricity
839,261
78

Block Type: Multistage Centrifugal Pump
Function:
Stream FEED S102
Pressure Head (ft)
Flow Rate (GPM)
Design Data:
Number of Stages
Pump Efficiency
Power Source
Purchase Cost:
Bare Module Cost:
$32,780
$103,913
$129,367
Cast Iron
3
1
839,261
Electricity
788
P102 A/B
Raise the FEED pressure
587.8
1680
79

Block Type:
Function: Heat FEED ethanol and cool S110
Tube: Inlet Outlet
Stream S102 S103
Shell:
Stream S110 SEP
Tube Flow Rate (lb/h)
Shell Flow Rate (lb/h)
Design Data:
Flow Direction
Number of Tubes
Number of Tube Passes
Number of Shell Passes
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
Annual Utilities Cost:
$271,316
$860,073
$0
4
2
U-Tube Shell and Tube Heat Exchanger
360,714,029
HX101
Carbon Steel
Countercurrent
367
30,084
578,839
594,547
Overall Heat Transfer Coefficient
(BTU/h*ft
2
*R)
70
80

Block Type: Fixed Bed Catalytic Reactor
Function: Convert hot ethanol from S104 into ethylene
Materials: Inlet
Stream S104
Mass Flow (lb/h) 578,839
Volumetric Flow (ft
3
/h) 265,590
Breakdown (lb/h):
Ethanol 549,897
Water 28,942
Ethylene 0
Diethyl-Ether 0
Methane 0
Acetaldehyde 0
Ethane 0
Acetic Acid 0
Hydrogen 0
Operating Conditions: Inlet
Temperature (F) 752
Pressure (psi) 618.0
Design Data:
Construction Material Cr-Mo Steel SA-387B Catalyst -Alumina
Vessel Weight (lb) 17,759 Residence Time (s) 3.14
Volume (ft
3
) 224 Catalyst Volume (ft
3
) 157.00
Diameter (ft) 5.81 Catalyst Weight (lb) 36,111
Length (ft) 8.46 Catalyst Cost $180,555
Wall Thickness (in) 1.84 Catalyst Life (days) 90
Purchase Cost: $63,104
Bare Module Cost: $192,467
Annual Catalyst Cost: $15,885
Outlet
590
616.0
161,532
179,995
234,402
2,212
38
421
36
179
24
R101
Outlet
S105
578,839
435,582
81

Function: Convert ethanol in S106 to ethylene
Materials: Inlet
Stream S106
Volumetric Flow (ft
3
/h) 271,109
Breakdown (lb/h):
Ethanol 161,532
Water 179,995
Ethylene 234,402
Diethyl-Ether 2,212
Methane 38
Acetaldehyde 421
Ethane 36
Acetic Acid 179
Hydrogen 24
Temperature (F) 752
Design Data:
Volume (ft
3
3
) 179.46
Annual Operating Cost: $573,286
R102
Outlet
S107
578,839
435,582
Outlet
590
606.0
43,816
225,728
305,225
3,187
72
529
46
211
26
82

Function: Convert remaining ethanol in S109 to ethylene
Materials: Inlet
Stream S109
Volumetric Flow (ft
3
/h) 535,522
Breakdown (lb/h):
Ethanol 53,834
Water 228,889
Ethylene 306,083
Diethyl-Ether 3,627
Methane 72
Acetaldehyde 1,701
Ethane 104
Acetic Acid 211
Hydrogen 26
Temperature (F) 752
Design Data:
Volume (ft
3
3
) 216.83
Annual Catalyst Cost: $775,784
R103
Outlet
S110
594,547
521,378
Outlet
590
597.0
10,266
245,822
332,309
93
3,952
1,747
111
221
26
83

Block Type:
Function: Heat stream S103
Material Stream S103 S104
Mass Flow (lb/h) 578,839 578,839
Fuel Stream FUEL-1 FLUE-1
Operating Conditions: Inlet Outlet
Design Data:
Heat Duty (BTU/h)
Fuel Type
Fuel Flow (SCF/h)
Purchase Cost:
Bare Module Cost:
F101
Fired Heater
$2,176,170
Cr-Mo Steel SA-387B
$1,836,640
$4,022,242
63,111,000
Natural Gas
60,106
84

Block Type:
Mass Flow (lb/h) 578,839 578,839
Design Data:
Heat Duty (BTU/h)
Fuel Type
Fuel Flow (SCF/h)
Purchase Cost:
Bare Module Cost:
$1,665,130
$3,646,634
$1,915,565
F102
Fired Heater
Cr-Mo Steel SA-387B
55,553,211
Natural Gas
52,908
85

Block Type:
Mass Flow (lb/h) 578,839 578,839
Design Data:
Heat Duty (BTU/h)
Fuel Type
Fuel Flow (SCF/h)
Purchase Cost:
Bare Module Cost:
$1,685,002
$4,690,155
$1,945,465
F103
Fired Heater
Cr-Mo Steel SA-387B
56,420,329
Natural Gas
53,734
86

Flash Separation Section

Block Type: Floating Head Shell and Tube Heat Exchanger
Function:
Shell: Inlet Outlet
Stream CW201 CW202
Tube:
Stream SEP S202
Design Data:
Flow Direction
Number of Tubes
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
-27,014,000
$79,870
$253,186
$55,068
903,320
594,547
Overall Heat Transfer
Coefficient (BTU/h*ft
2
*R)
Cool SEP for flash separation using cooling water
HX201
Carbon Steel
Countercurrent
7,630
80
182
2
2
87

Block Type:
Function: Heat stream S205 for flash separation
Shell: Inlet Outlet
Stream CRYO-OUT PRODUCT
Temperature (F) -34 52
Pressure (psi) 276 276
Tube:
Stream S205 S206
Design Data:
Flow Direction
Number of Tubes
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
12,630,433
$46,879
$148,607
$0
HX202
Shell and Tube Heat Exchanger
Carbon Steel
Countercurrent
2,629
(BTU/h*ft
2
*R)
60
330,473
667,938
250
2
1
88

Block Type: Flash Drum
Function:
Materials: Inlet Overhead Bottoms
Stream S203 S205 S204
Phase MIX VAP LIQ
Mass Flow (kg/h) 594,547 337,465 257,082
Volumetric Flow (L/h) 4,391 100,528 24
Breakdown (kg/h):
Ethanol 10,266 592 9,674
Water 245,822 1,046 244,776
Ethylene 332,309 331,472 837
Ether 3,952 3,542 410
Methane 93 93 0
Acetaldehyde 1,747 640 1,107
Ethane 111 54 57
Acetic Acid 221 1 220
Hydrogen 26 26 0
Pressure (psi)
Temperature (F)
Equilibrium
Design Data:
Construction Material Carbon Steel Diameter (ft) 6.5
Weight (lb) 31,000 Height (ft) 19.5
Volume (gal) 4,841
Purchase Cost:
Bare Module Cost:
$251,680
$0
565.0
FL201
122
Vapor-Liquid Equilibrium
$60,500
Remove most of the water and ethanol
from S203
89

Block Type: Flash Drum
Function:
Materials: Inlet Overhead Bottoms
Phase MIX VAP LIQ
Mass Flow (kg/h) 337,465 336,043 1,422
Breakdown (kg/h):
Ethanol 592 246 346
Water 1,046 88 958
Ethylene 331,472 331,451 21
Ether 3,542 3,511 31
Methane 93 93 0
Acetaldehyde 640 575 65
Ethane 54 53 0
Acetic Acid 1 0 1
Hydrogen 26 26 0
Pressure (psi)
Temperature (F)
Equilibrium
Design Data:
Construction Material Carbon Steel Diameter (ft) 6
Weight (lb) 18,300 Height (ft) 12
Volume (gal) 2,538
Purchase Cost:
Bare Module Cost:
Annual Operating Cost:$0
FL202
455.6
39
Vapor-Liquid Equilibrium
$43,100
$179,296
Remove further amounts of ethanol
and
90

Distillation Section

Block Type:
Function:
Materials: Inlet Distillate Bottoms
Phase LIQ VAP LIQ
Mass Flow (kg/h) 258,504 15,708 242,796
Volumetric Flow (L/h) 10,794 109,081 4,351
Temperature (F) 122 206 253
Breakdown (lb/h):
Ethanol 10,020 10,019 1
Water 245,735 3,161 242,573
Ethylene 858 858 0
Ether 440 440 0
Methane 0 0 0
Acetaldehyde 1,172 1,172 0
Ethane 57 57 0
Acetic Acid 221 0 221
Hydrogen 0 0 0
Condenser Pressure (psi)
Condenser Temperature (F)
Reboiler Pressure (psi)
Reboiler Temperature (F)
Reflux Ratio
Design Data:
Construction Material Carbon Steel Tray Efficiency 0.69
Weight (lb) 57,900 Number Trays 26
Diameter (ft) 6 Feed Stage 7
Height (ft) 64 Tray Spacing (ft) 2
Exterior Components:
Condenser
Reflux Accumulator
Pump
Reboiler
Annual Operating Cost: $0
HX302
0.85
D301
29.4
Seive Tray Distillation Tower
HX301
AC301
P301
Remove water and from S302 and enrich
stream S305 in ethanol
31.18
206
252
91

Block Type:
Function:
Shell: Inlet Outlet
Stream S312 TO-REBOIL
Tube:
Stream S303 S304
Pressure (psig) 31.2 30.0
Design Data:
Flow Direction
Number of Tubes
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
$17,900
$84,000
$24,100
642
2
*R)
9,063,300
180
122
1
Countercurrent
1
HX301
Fixed Head Shell and Tube
Partial Condenser
Carbon Steel
Condense vapor product from D301
using cooling water
258,504
18,480
92

Block Type:
Function:
Tube: Inlet Outlet
Stream STEAM301 STEAM302
Shell:
Stream S309 S310
Design Data:
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
$379,766
$1,091,736
258,504
54,267
$119,800
HX302
U Tube Kettle Reboiler
Vaporize liquid product from D301
using 50psi steam
5,684
49,469,600
2
*R)
80
Carbon Steel
93

Block Type: Reflux Accumulator - Horizontal Vessel
Function: Accumulate reflux from D301
Stream S306 S307
Pressure (psi)
Temperature (F)
Design Data:
Storage Volume (gal)
Diameter (ft)
Height (ft)
Purchase Cost:
Bare Module Cost:
AC301
Carbon Steel
$10,500
$32,025
$0
28.0
206.383
264
3
5
94

Block Type:
Function: Return reflux to D301
Stream S307 S308
Discharge Pressure (psi)
Pressure Head (ft)
Flow Rate (gpm)
Design Data:
Number of Stages
Pump Efficiency
Power Source
Purchase Cost:
Bare Module Cost:
$16,170
$160
29.4
76
44
Cast Iron
$4,900
1
0.7
P301 A/B
Centrifugal Pump
1,356
Electricity
95

Block Type:
Function: Pump purge water
Stream S311 TREAT
Pressure Head (ft)
Flow Rate (gpm)
Design Data:
Number of Stages
Pump Efficiency
Power Source
Purchase Cost:
Bare Module Cost:
Annual Operating Cost: $1,941
P302 A/B
Centrifugal Pump
14.7
38
597
Cast Iron
16,426
Electricity
$8,300
$27,390
1
0.711
96

Block Type:
Function:
Stream S305 RECYCLE
Pressure Change (psi)
Temperature Rise (F)
Inlet Flow Rate (ft
3
/h)
Outlet Flow Rate (ft3/h)
Design Data:
Number of Stages
Interstage Cooling
Power Source
Purchase Cost:
Bare Module Cost:
Compress S305 so it can be
recycled to the reactor section
$452,562
C301
570.0
109,081
Carbon Steel
2,936,625
Electricity
$1,403,400
$4,631,220
8,027
428
3
N/A
97

Block Type: Spherical Storage Tank
Number of Units: 2
Function: Stores one hour of ethylene product
Materials:
Mass Fraction:
Ethylene
Hydrogen
Methane
Pressure (psi)
Temperature (F)
Design Data:
Volume (gal)
Diameter (ft)
Purchase Cost:
Bare Module Cost:
Product Storage Tank
$0
0.00008
0.00003
0.99960
14.7
80
Carbon Steel
1,000,000
63.439
$1,343,000
$4,257,310
98

Adsorption Section

Block Type:
Function:
Stream NITROGEN S408
Pressure Change (psi)
Temperature Rise (F)
Inlet Flow Rate (ft
3
/h)
Outlet Flow Rate (ft3/h)
Design Data:
Number of Stages
Interstage Cooling
Power Source
Purchase Cost:
Bare Module Cost:
Annual Nitrogen Cost
Carbon Steel
295,482
Electricity
$87,800
1
N/A
C401
Compress the nitrogen to both
raise the temperature and
26.0
67,506
36,171
$289,740
$45,547
247
$91,800
99

Block Type: Adsorption Column
Function:
Materials: Inlet
Stream ADSORB
Volumetric Flow (GPM) 12,533
Temperature (F) 39.00
Breakdown (lb/h):
Ethylene 331,451
Ethanol 246
Water 67.7
Diethylether 3,511.3
Methane 42.0
Acetaldehyde 260.9
Hydrogen 11.8
Acetic Acid 0.035
Breakthrough Time (h) 24 Pressure Drop (psi) 15
Maximum Capacity (lb) 7,320 Residence Time (s) 22
Heat of Adsorption (BTU/hr) 113,400
Regeneration:
Eluent NITROGEN Temperature (F) 350
Mass Flow (lb/h) 4,800 Regeneration Time (h) 24
Design Data:
Construction Material Carbon Steel Volume (ft
3
) 839
Vessel Weight (lb) 75,890 Diameter (ft) 7.50
Adsorbant:
Adsorbant Type Zeolite 13X Adsorbant Weight (lb) 13,550
Spherical Diameter (mm) 3 Adsorbant Cost $15,000
Adsorbant Volume (ft
3
) 772 Adsorbant Life (yrs) 3
Bare Module Cost:
Annual Adsorbant Cost:
42.0
260.9
$10,000
Overhead
Remove trace water and ethanol from ADSORB so it
cannot damage D501
AD401 A/B
CRYO
$729,300
335,005
12,574
39.6
441.0
331,451
11.8
0.035
0
0
3,511.3
100

Cryogenic Distillation Section

Block Type:
Function: Purify ethylene product
Materials: Inlet Distillate Bottoms
Phase MIX VAP LIQ
Mass Flow (kg/h) 335,710 330,473 5,237
Temperature (F) -35 -68 -21
Breakdown (kg/h):
Ethanol 0 0 0
Water 0 0 0
Ethylene 331,451 330,327 1,124
Ether 3,511 0 3,511
Methane 93 93 0
Acetaldehyde 575 0 575
Ethane 53 28 26
Acetic Acid 0 0 0
Hydrogen 26 26 0
Condenser Pressure (psi)
Condenser Temperature (F)
Reboiler Pressure (psi)
Reboiler Temperature (F)
Reflux Ratio
Design Data:
Construction Material Stainless Steel Tray Efficiency 0.75
Weight (lb) 76,800 Number Trays 8
Diameter (ft) 10.5 Feed Stage 3
Height (ft) 24 Tray Spacing (ft) 2
Exterior Components:
Condenser
Reflux Accumulator
Pump
Reboiler
Annual Operating Cost: $0
AC501
P501
HX503
D501
Seive Tray Distillation Tower
279.2
0.75
279.8
-21.15
-67.5
HX502
101

Block Type:
Function: Heat CRYO-IN and cool S507
Shell: Inlet Outlet
Stream S507 CRYO-OUT
Temperature (F) -68 -35
Tube:
Stream CRYO-IN S502
Design Data:
Flow Direction
Number of Tubes
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
$157,463
$0
HX501
Stainless Steel
Countercurrent
2,951
6,591,610
2
*R)
30
$49,673
330,473
144
1
1
335,710
Shell and Tube Heat Exchanger
102

Block Type:
Function:
Shell: Inlet Outlet
Stream R501 R502
Tube:
Stream S504 S505
Design Data:
Number of Tubes
Transfer Area (ft
2
)
(BTU/h*ft2*R)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
Annual Utilities Cost: $5,368,643
HX502
Floating Head Shell and
Tube Partial Condenser
Condense vapor product from D501
using propylene refrigerant
420,000
Stainless Steel
56,357,300
$2,985,500
$9,464,035
188,500
50
1,122
8
2
2818
103

Block Type:
Function:
Tube: Inlet Outlet
Stream S512 REBOIL-OUT
Shell:
Stream S510 S511
Temperature (F) -21.2 -21.2
Design Data:
Transfer Area (ft
2
)
Heat Duty (BTU/h)
Purchase Cost:
Bare Module Cost:
Stainless Steel
(BTU/h*ft
2
*R)
45
HX503
U Tube Kettle Reboiler
Vaporizes the bottoms to return as
boilup
49,342
199,282
$59,500
$224,700
-$3,930
2,105
49,039,968
104

Block Type:
Function: Accumulate reflux from D501
Stream S506 S508
Pressure (psi)
Temperature (F)
Design Data:
Storage Volume (gal)
Diameter (ft)
Height (ft)
Purchase Cost:
Bare Module Cost:
AC501
Reflux Accumulator
Stainless Steel
$0
$43,900
$267,790
238.0
-68
4,965
7
20
105

Block Type:
Function:
Stream S508 S509
Pressure Rise (psi)
Pressure Head (ft)
Flow Rate (gpm)
Design Data:
Number of Stages
Pump Efficiency
Power Source
Purchase Cost:
Bare Module Cost:
P501 A/B
Centrifugal Pump
36,566
Electricity
Pumps the reflux
back
into the column
$32,670
$4,321
41.0
107
791
Stainless Steel
$9,900
1
0.70
106

107

Section XII
Conclusions and Recommendations

108

The profitability of this plant is highly dependent on the prices of ethylene and ethanol, both of
which fluctuate often. At currently available market prices, it is not likely to be profitable. The
economic analysis conducted in this report shows that ethylene prices must rise significantly and
ethanol prices must fall significantly before the plant will return a positive Net Present Value or
Internal Rate of Return. While this is not entirely unreasonable, intense market research will be
necessary to determine if the risk associated with building a plant at the present time is
worthwhile.
There is a strong incentive to find ways to lower the operating cost of this process. Ethanol
dehydration is preferable to the currently prevalent ethylene-yielding process of hydrocarbon
cracking. For one, ethanol is renewable; it can be derived from sugar cane or corn, two major
crops grown in South and North America. Additionally, ethanol dehydration produces far less
waste and carbon emissions than cracking does. Governments worldwide are currently
incentivizing the preference of green industry.
The two factors that make operating this plant expensive are heating the feed to extreme
temperatures, and running cryogenic distillation to separate the final product. If more effective
systems for heating or refrigeration were developed, this plant could potentially operate closer to
profitability. In the future, it is recommended to research these areas to help improve the
potential of this plant to succeed.

109

Section XIII
Acknowledgements

110

We would like to take this opportunity to thank the following faculty, consultants, and fellow
colleagues for their guidance in the successful completion of this report:
Dr. Raymond Gorte, our faculty advisor, for his weekly guidance throughout the project in
dealing with the AspenPLUS simulation and chemical engineering calculations.
Professor Leonard Fabiano for sharing his extensive industrial expertise and his considerable
help with AspenPLUS.
Industrial consultants Bruce Vrana, Steven Tieri, John Wismer, and Gary Sawyer for providing
advice, information, and design experience to our project.
In addition, we would also like to thank two of our fellow classmates. Peter Terpeluk for
knowing how to answer every question we asked and his incredible willingness to help even at
his own expense. Also, we would like to thank Steve Lantz for sharing his extensive knowledge
of Excel with us, making some of our analysis much easier (and prettier).

111

Section XIV
Bibliography

112

Agncia Nacional do Petrleo (ANP). 2012. Web. 22 Mar 2012 <http://www.anp.gov.br/>.
Braskem Ethanol-to-Ethylene Plant, Brazil. Chemicals Technology. Net Resources
International, 2011. Web. 16 Jan. 2012. <http://www.chemicals-
technology.com/projects/braskem-ethanol/>.
"Brazil Freight Transport Report." Business Monitor. Business Monitor International, Ltd., 2012.
Web. 27 Feb. 2012. <http://www.slideshare.net/john_pellizzetti/brazil-freight-transport-
report>.
Code of Federal Regulations. National Archives and Records Administration.e-CFR, 26 Mar.
2012. Web. 28 Mar. 2012. <http://ecfr.gpoaccess.gov/cgi/t/text/text-
idx?c=ecfr&sid=081cc5c5cd4e7c46ceebea27be14e038&rgn=div5&view=text&node=49:
2.1.1.3.9&idno=49>.
Ebeid, Fikry M. "Mechanism of Dehydratio of Ethanol Over Gamma-Alumina." Qatar
University Science Journal. 1.1 (1981): 117-127. Print.
The Economist, March 3-9, 2007 Fuel for Friendship p. 44
"Ethanol/Ethyl Alcohol." Ethanol Material Safety Data Sheet. The Online Distillery Network for
Distilleries & Fuel Ethanol Plants Worldwide, 2001. Web. 27 Mar. 2012.
<http://www.distill.com/materialsafety/msds-eu.html>.
Ethanol Facts. Renewable Fuels Association. RFA, 2012. Web. 9 Jan. 2012.
<http://ethanolrfa.org/pages/ethanol-facts>.
"Ethylene: Prices, Markets, and Analysis." ICIS. Reed Business Information Limited, 2012.
Web. 20 Jan. 2012. <http://www.icis.com/chemicals/ethylene/>.
"Ethylene Product Stewardship Guidance Manual." LyondellBasell. American Chemistry
Council and Chemstar, Dec. 2004. Web. 27 Mar. 2012.
<http://www.lyondellbasell.com/techlit/techlit/Handbooks%20and%20Manuals/ACC_Et
hylene_Manual%203096.pdf>.
113

"Handling and Transportation Guide for Ethylene, Refrigerated Liquid (Cryogenic Ethylene)."
LyondellBasell. American Chemistry Council, Apr. 2004. Web. 27 Mar. 2012.
<http://www.lyondellbasell.com/techlit/techlit/Handbooks%20and%20Manuals/3424%2
0ethylene%20cryo%20guide.pdf >.
http://wpage.unina.it/avitabil/testi/PE.pdf
Melby, Kory. Infrastructure: Railroads. Ag Consulting Services and Investment Tours. Brazil
International. Web. 20 Feb. 2012.
< http://www.brazilintl.com/agsectors/infrastructure/railroads/menu_railroads.htm>.
Piel, Christian. Polymerization of Ethene and Ethene-co--Olefin: Investigations on Short- and
Long- Chain Branching and Structure-Property Relationships, Dissertation, University of
Hamburg. Hamburg: 2005
Seider, Warren D. Product and Process Design Principles: Synthesis, Analysis, and Evaluation.
Hoboken, NJ: John Wiley & Sons, 2010. Print.
Schill, Susanne Retka. Braskem Starts Off Ethanol-to-Ethylene Plant. Ethanol Producer
Magazine | EthanolProducer.com. BBL International, 23 Sept. 2010. Web. 16 Jan. 2012.
<http://ethanolproducer.com/articles/7022/braskem-starts-up-ethanol-to-ethylene-plant/>.
Valladares Barrocas, Helcio V. Process for Preparing Ethene. Petroleo Brasileiro S.A.-Petrobras,
assignee. Patent 4232179. 4 Nov. 1980. Print.
Valladares Barrocas, Helcio V. Process for Dehydration of a Low Molecular Weight Alcohol.
Petroleo Brasileiro S.A.-Petrobras, assignee. Patent 4396789. 2 Aug. 1983. Print.

114

115

Section XV
Appendix



Appendix Table of Contents
Section
A. Sample Calculations
B. ASPEN Printouts
C. Problem Statement
D. Relevant Documents
E. MSDS Reports



Appendix A
Sample Calculations


CALCULATIONS FOR DISTILLATION COLUMN SIZING (D301)
Weighted liquid density (
L
)
( )( )
L i i
p p MassFrac = (0.1)
Where
i
= density of each component in the stream
MassFrac
i
= mass fraction of that component within the stream

L
= (1000 kg/m
3
H
2
O)(~1.0)= 1000 kg/m
3

Weighted gas density (
g
)
( )( )
i i
MW MW MassFrac = (0.2)
Where MW= weighted molecular weight of gas stream
MassFrac
i
= mass fraction of that component within the stream

*
*
g
MW P
p
R T
= (0.3)
Where P= pressure at the top tray
R= ideal gas constant
T= absolute temperature at that tray

MW= (0.0461 kg/mol ethanol)(0.515)+(0.016 kg/mol H
2
O)(0.318)+(0.0461kg/mol
ether)(0.049)+(0.026 kg/mol acetylene)(0.080)= 0.034 kg/mol

3 3
5
(0.034 )(20.4 )
18.5
(8.314 10 )(449 )
g
kg
bar
kg
mol
p
m bar m
x K
K mol
= =

Flooding Correlation (F
LG
)

0.5
( )
G
LG
L
p L
F
G p
= (0.4)
Where L= liquid rate
G= gas rate

3
0.5
3
88500 18.5
( )( ) 0.250
48200 1000
LG
kg kg
hr m
F
kg kg
hr m
= =

Parameter C
SB

(Use table in Seider et al pg.505)
For 18 inch spacing, C
SB
= 0.2ft/s

Surface Tension Factor (F
ST
)

0.20
( )
20
ST
F
o
= (0.5)
= surface tension (dyne/cm)~20
0.20
20
( ) 1
20
ST
dyne
cm
F = ~
Foaming Factor (F
F
)
For non-foaming systems, F
F
=1

Hole-Area Factor (F
HA
)
1 for

0.1
h
T
A
A
> (0.6)
Where A
h=
total hole area on tray
A
a
= is the active area of the tray
Capacity Parameter (C)

SB ST F HA
C C F F F = (0.7)

C=(0.2ft/s)(1)(1)(1)= 0.2ft/s

Flooding Velocity (U
f
)

(1.8)

Ratio A
d
/A
T
(for 0.1F
LG
1.0)

(1.9)

Fraction of Inside Cross-sectional Area to Vapor Flooding Velocity (f)


Assume f=0.85

Tower Inside Diameter (D
T
)

(1.10)

Tower Height (H)
( 1) *( ) 4 10
trays
H N spacing ft ft = + + (1.11)

H=(26-1)*2.0ft+4ft+10ft=64 feet

REACTOR COSTING CALCULATIONS (R101)



APPENDIX B
ASPEN Reports


The following are ASPEN block results for the blocks representing R101, HX101, FL101, D501,
and F101.
BLOCK: R1 MODEL: RSTOIC
------------------------------
INLET STREAM: REACTIN
OUTLET STREAM: 20
PROPERTY OPTION SET: NRTL-RK RENON (NRTL) / REDLICH-KWONG
HENRY-COMPS ID: HC-1

*** MASS AND ENERGY BALANCE ***
IN OUT GENERATION RELATIVE
DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 6142.95 9938.61 3795.66
0.00000
MASS(KG/HR ) 262557. 262557.
0.00000
ENTHALPY(GCAL/HR ) -301.338 -272.172 -
0.967891E-01

*** CO2 EQUIVALENT SUMMARY ***
FEED STREAMS CO2E 0.00000 KG/HR
PRODUCT STREAMS CO2E 434.297 KG/HR
NET STREAMS CO2E PRODUCTION 434.297 KG/HR
UTILITIES CO2E PRODUCTION 0.00000 KG/HR
TOTAL CO2E PRODUCTION 434.297 KG/HR

*** INPUT DATA ***
STOICHIOMETRY MATRIX:

REACTION # 1:
SUBSTREAM MIXED :
ETHANOL -1.00 WATER 1.00 ETHYLENE 1.00

REACTION # 2:
SUBSTREAM MIXED :
ETHANOL -2.00 WATER 1.00 ETHER 1.00

REACTION # 3:
SUBSTREAM MIXED :
ETHANOL -1.00 WATER -1.00 AACID 1.00 HYDROGEN
2.00

REACTION # 4:
SUBSTREAM MIXED :
ETHANOL -1.00 ACETALD 1.00 HYDROGEN 1.00

REACTION # 5:
SUBSTREAM MIXED :
ETHANOL -1.00 WATER 1.00 METHANE 2.00 HYDROGEN -
2.00

REACTION # 6:
SUBSTREAM MIXED :
ETHANOL -1.00 WATER 1.00 ETHANE 1.00 HYDROGEN -
1.00

REACTION CONVERSION SPECS: NUMBER= 6
REACTION # 1:
SUBSTREAM:MIXED KEY COMP:ETHANOL CONV FRAC: 0.7000
REACTION # 2:
SUBSTREAM:MIXED KEY COMP:ETHANOL CONV FRAC: 0.5000E-02
REACTION # 3:
REACTION # 4:
REACTION # 5:
REACTION # 6:

ONE PHASE TP FLASH SPECIFIED PHASE IS VAPOR
SPECIFIED TEMPERATURE C 310.000
SPECIFIED PRESSURE BAR 40.2767
MAXIMUM NO. ITERATIONS 30
CONVERGENCE TOLERANCE 0.000100000
SIMULTANEOUS REACTIONS
GENERATE COMBUSTION REACTIONS FOR FEED SPECIES NO

*** RESULTS ***
OUTLET TEMPERATURE C 310.00
OUTLET PRESSURE BAR 40.277
HEAT DUTY GCAL/HR 29.166

REACTION EXTENTS:

REACTION REACTION
NUMBER EXTENT
KMOL/HR
1 3790.0
2 13.536
3 1.3536
4 4.3314
5 0.54142
6 0.54142

BLOCK: FURN1 MODEL: HEATER
------------------------------
INLET STREAM: FROMRHX

OUTLET STREAM: REACTIN

IN OUT RELATIVE
DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 6142.95 6142.95 0.00000
MASS(KG/HR ) 262557. 262557. 0.00000
ENTHALPY(GCAL/HR ) -317.242 -301.338 -0.501316E-
01


*** INPUT DATA ***
TWO PHASE TP FLASH
SPECIFIED TEMPERATURE C 400.000
CONVERGENCE TOLERANCE
0.000100000

*** RESULTS ***
HEAT DUTY GCAL/HR 15.904
OUTLET VAPOR FRACTION 1.0000
PRESSURE-DROP CORRELATION PARAMETER -1165.8

V-L PHASE EQUILIBRIUM :

COMP F(I) X(I) Y(I) K(I)
ETHANOL 0.88138 0.96486 0.88138
1.8458
WATER 0.11862 0.35136E-01 0.11862
6.8219

BLOCK: FLASH1 MODEL: FLASH3
------------------------------
INLET STREAM: SEPFEEDC
OUTLET VAPOR STREAM: FTOP
FIRST LIQUID OUTLET: FMIDDLE
SECOND LIQUID OUTLET: FBOTTOM


IN OUT RELATIVE
DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 11717.4 11717.4 -0.155238E-
15
MASS(KG/HR ) 269682. 269682. -0.431676E-
15
ENTHALPY(GCAL/HR ) -361.947 -361.947 0.743684E-
09


*** INPUT DATA ***
THREE PHASE PQ FLASH
SPECIFIED HEAT DUTY GCAL/HR 0.0
NO KEY COMPONENT IS SPECIFIED
KEY LIQUID STREAM: FBOTTOM

*** RESULTS ***
VAPOR FRACTION 0.46334
1ST LIQUID/TOTAL LIQUID 1.0000

V-L1-L2 PHASE EQUILIBRIUM :

COMP F(I) X1(I) X2(I) Y(I) K1(I)
K2(I)
ETHANOL 0.863E-02 0.151E-01 0.151E-01 0.107E-02 0.709E-01
0.709E-01
WATER 0.528 0.980 0.980 0.485E-02 0.495E-02
0.495E-02
ETHYLENE 0.459 0.215E-02 0.215E-02 0.987 458.
458.
ETHER 0.206E-02 0.399E-03 0.399E-03 0.399E-02 10.0
10.0
METHANE 0.224E-03 0.389E-06 0.389E-06 0.483E-03 0.124E+04
0.124E+04
ACETALD 0.154E-02 0.181E-02 0.181E-02 0.121E-02 0.670
0.670
ETHANE 0.143E-03 0.136E-03 0.136E-03 0.150E-03 1.10
1.10

AACID 0.143E-03 0.265E-03 0.265E-03 0.129E-05 0.485E-02
0.485E-02
HYDROGEN 0.499E-03 0.819E-06 0.819E-06 0.108E-02 0.131E+04
0.131E+04

BLOCK: CRYO MODEL: RADFRAC
-------------------------------
INLETS - INCRYO STAGE 3
OUTLETS - CRYOVER STAGE 1
CPURGE STAGE 6

IN OUT RELATIVE
DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 5395.80 5395.80 -0.384217E-
09
MASS(KG/HR ) 152275. 152275. -0.322460E-
09
ENTHALPY(GCAL/HR ) 60.3259 58.4819 0.305663E-
01

NET STREAMS CO2E PRODUCTION 0.879258E-04 KG/HR
TOTAL CO2E PRODUCTION 0.879258E-04 KG/HR

**********************
**** INPUT DATA ****
**********************

**** INPUT PARAMETERS ****

NUMBER OF STAGES 6
ALGORITHM OPTION STANDARD
ABSORBER OPTION NO
INITIALIZATION OPTION STANDARD
HYDRAULIC PARAMETER CALCULATIONS NO
INSIDE LOOP CONVERGENCE METHOD BROYDEN
DESIGN SPECIFICATION METHOD NESTED
MAXIMUM NO. OF OUTSIDE LOOP ITERATIONS 150
MAXIMUM NO. OF INSIDE LOOP ITERATIONS 10
MAXIMUM NUMBER OF FLASH ITERATIONS 30
FLASH TOLERANCE 0.000100000
OUTSIDE LOOP CONVERGENCE TOLERANCE 0.000100000

**** COL-SPECS ****


MOLAR VAPOR DIST / TOTAL DIST 1.00000
MASS REFLUX RATIO 0.75000
MASS DISTILLATE RATE KG/HR 149,900.

**** PROFILES ****

P-SPEC STAGE 1 PRES, BAR 19.2518

*******************
**** RESULTS ****
*******************

*** COMPONENT SPLIT FRACTIONS ***

OUTLET STREAMS
--------------
CRYOVER CPURGE
COMPONENT:
ETHANOL 1.0000 0.0000
WATER .33271E-07 1.0000
ETHYLENE .99661 .33920E-02
ETHER .11471E-04 .99999
METHANE 1.0000 .46106E-06
ACETALD .28257E-04 .99997
ETHANE .51445 .48555
AACID .31932E-10 1.0000
HYDROGEN 1.0000 .80519E-12

*** SUMMARY OF KEY RESULTS ***

TOP STAGE TEMPERATURE C -55.2971
BOTTOM STAGE TEMPERATURE C -29.5271
TOP STAGE LIQUID FLOW KMOL/HR 4,007.41
BOTTOM STAGE LIQUID FLOW KMOL/HR 45.9789
TOP STAGE VAPOR FLOW KMOL/HR 5,349.82
BOILUP VAPOR FLOW KMOL/HR 3,115.93
MOLAR REFLUX RATIO 0.74907
MOLAR BOILUP RATIO 67.7686
CONDENSER DUTY (W/O SUBCOOL) GCAL/HR -14.2018
REBOILER DUTY GCAL/HR 12.3579

**** MAXIMUM FINAL RELATIVE ERRORS ****

DEW POINT 0.24631E-05 STAGE= 6
BUBBLE POINT 0.18015E-07 STAGE= 6
COMPONENT MASS BALANCE 0.75536E-06 STAGE= 5 COMP=ETHER
ENERGY BALANCE 0.25259E-06 STAGE= 6

**** PROFILES ****

**NOTE** REPORTED VALUES FOR STAGE LIQUID AND VAPOR RATES ARE THE FLOWS

FROM THE STAGE INCLUDING ANY SIDE PRODUCT.

ENTHALPY
STAGE TEMPERATURE PRESSURE KCAL/MOL HEAT DUTY
C BAR LIQUID VAPOR GCAL/HR

1 -55.297 19.252 7.7196 11.238 -14.2018
2 -55.083 19.260 7.2006 11.249
3 -55.029 19.268 7.1344 11.258
4 -55.000 19.277 7.0945 11.245
5 -54.772 19.285 6.5640 11.210
6 -29.527 19.293 -35.601 11.152 12.3578

STAGE FLOW RATE FEED RATE PRODUCT RATE
KMOL/HR KMOL/HR KMOL/HR
LIQUID VAPOR LIQUID VAPOR MIXED LIQUID
VAPOR
1 4007. 5350.
5349.8226
2 3528. 9357. 5392.8552
3 3530. 3485. 2.9462
4 3526. 3484.
5 3162. 3480.
6 45.98 3116. 45.9789

**** MASS FLOW PROFILES ****

STAGE FLOW RATE FEED RATE PRODUCT RATE
KG/HR KG/HR KG/HR
LIQUID VAPOR LIQUID VAPOR MIXED LIQUID
VAPOR
1 0.1124E+06 0.1499E+06
.14990+06
2 0.9997E+05 0.2623E+06 .15209+06
3 0.1001E+06 0.9778E+05 190.2472
4 0.1000E+06 0.9775E+05
5 0.9039E+05 0.9765E+05
6 2375. 0.8802E+05 2375.3259

**** MOLE-X-PROFILE ****
STAGE ETHANOL WATER ETHYLENE ETHER
METHANE
1 0.13347E-30 0.45921E-14 0.99965 0.24372E-04
0.78486E-04
2 0.76656E-31 0.12748E-10 0.99247 0.54650E-02
0.50126E-04
3 0.17813E-30 0.62459E-10 0.99140 0.60986E-02
0.81251E-05
4 0.53303E-51 0.62530E-10 0.99019 0.61132E-02
0.13170E-05
5 0.16056E-71 0.71148E-10 0.98083 0.10081E-01
0.21267E-06
6 0.10881E-69 0.47946E-08 0.39536 0.46733
0.26274E-07

**** MOLE-X-PROFILE ****
STAGE ACETALD ETHANE AACID HYDROGEN
1 0.10906E-04 0.22100E-03 0.28876E-12 0.11853E-04
2 0.16098E-02 0.39387E-03 0.10782E-07 0.68311E-05
3 0.16824E-02 0.81084E-03 0.16649E-06 0.75451E-07
4 0.16902E-02 0.20048E-02 0.16668E-06 0.83378E-09
5 0.36909E-02 0.53937E-02 0.18670E-06 0.91971E-11
6 0.12879 0.85168E-02 0.12782E-04 0.10224E-12

**** MOLE-Y-PROFILE ****
METHANE
1 0.45270E-10 0.13710E-17 0.99834 0.46074E-07
0.48977E-03
2 0.25883E-10 0.19674E-14 0.99890 0.10464E-04
0.31363E-03
3 0.60285E-10 0.95588E-14 0.99964 0.11760E-04
0.50798E-04
4 0.18048E-30 0.95147E-14 0.99927 0.11818E-04
0.82320E-05
5 0.54007E-51 0.97801E-14 0.99805 0.19714E-04
0.13340E-05
6 0.23695E-73 0.14484E-11 0.98947 0.33336E-02
0.21542E-06

**** MOLE-Y-PROFILE ****
1 0.31277E-07 0.77554E-04 0.35079E-17 0.10913E-02
2 0.46888E-05 0.13899E-03 0.12367E-12 0.62902E-03
3 0.49305E-05 0.28662E-03 0.19245E-11 0.69253E-05
4 0.49646E-05 0.70915E-03 0.19332E-11 0.76447E-07
5 0.10992E-04 0.19188E-02 0.21971E-11 0.84479E-09
6 0.18450E-02 0.53477E-02 0.84414E-09 0.93313E-11

**** K-VALUES ****
METHANE
1 0.10000E+21 0.29856E-03 0.99869 0.18905E-02 6.2402
2 0.10000E+21 0.15433E-03 1.0065 0.19147E-02 6.2568
3 0.10000E+21 0.15304E-03 1.0083 0.19283E-02 6.2520
4 0.10000E+21 0.15216E-03 1.0092 0.19332E-02 6.2508
5 0.10000E+21 0.13746E-03 1.0176 0.19557E-02 6.2728
6 0.21777E-03 0.30210E-03 2.5027 0.71333E-02 8.1988

**** K-VALUES ****
1 0.28678E-02 0.35092 0.12148E-04 92.069
2 0.29127E-02 0.35288 0.11470E-04 92.082
3 0.29307E-02 0.35348 0.11559E-04 91.785
4 0.29373E-02 0.35372 0.11598E-04 91.687
5 0.29782E-02 0.35574 0.11768E-04 91.854
6 0.14326E-01 0.62789 0.66041E-04 91.266


**** MASS-X-PROFILE ****
METHANE
1 0.21918E-30 0.29489E-14 0.99964 0.64393E-04
0.44882E-04
2 0.12465E-30 0.81065E-11 0.98275 0.14298E-01
0.28384E-04
3 0.28933E-30 0.39672E-10 0.98058 0.15938E-01
0.45957E-05
4 0.86568E-51 0.39712E-10 0.97927 0.15974E-01
0.74481E-06
5 0.25874E-71 0.44835E-10 0.96250 0.26137E-01
0.11934E-06
6 0.97032E-70 0.16720E-08 0.21469 0.67051
0.81590E-08

**** MASS-X-PROFILE ****
1 0.17126E-04 0.23688E-03 0.61812E-12 0.85173E-06
2 0.25031E-02 0.41803E-03 0.22855E-07 0.48606E-06
3 0.26130E-02 0.85963E-03 0.35250E-06 0.53626E-08
4 0.26249E-02 0.21252E-02 0.35286E-06 0.59253E-10
5 0.56876E-02 0.56733E-02 0.39219E-06 0.64853E-12
6 0.10982 0.49573E-02 0.14858E-04 0.39896E-14

**** MASS-Y-PROFILE ****
METHANE
1 0.74432E-10 0.88150E-18 0.99956 0.12188E-06
0.28042E-03
2 0.42533E-10 0.12643E-14 0.99959 0.27667E-04
0.17947E-03
3 0.98997E-10 0.61383E-14 0.99962 0.31071E-04
0.29049E-04
4 0.29636E-30 0.61096E-14 0.99920 0.31224E-04
0.47072E-05
5 0.88674E-51 0.62794E-14 0.99787 0.52080E-04
0.76273E-06
6 0.38644E-73 0.92372E-12 0.98268 0.87474E-02
0.12234E-06

**** MASS-Y-PROFILE ****
1 0.49175E-07 0.83228E-04 0.75183E-17 0.78515E-04
2 0.73679E-05 0.14908E-03 0.26491E-12 0.45231E-04
3 0.77423E-05 0.30721E-03 0.41196E-11 0.49763E-06
4 0.77954E-05 0.76005E-03 0.41379E-11 0.54929E-08
5 0.17258E-04 0.20563E-02 0.47024E-11 0.60694E-10
6 0.28773E-02 0.56926E-02 0.17946E-08 0.66593E-12

*** ASSOCIATED UTILITIES ***

UTILITY USAGE: HW (WATER)
------------------------------

REBOILER 2.2428+04 0.4486
------------- -------------
TOTAL: 2.2428+04 KG/HR 0.4486 $/HR
=============

BLOCK: REACTHX MODEL: HEATX
-----------------------------
HOT SIDE:
---------
INLET STREAM: REACTOUT
OUTLET STREAM: SEPFEED
COLD SIDE:
----------
INLET STREAM: TORHX
OUTLET STREAM: FROMRHX

IN OUT RELATIVE
DIFF.
TOTAL BALANCE
MOLE(KMOL/HR ) 17860.4 17860.4 0.00000
MASS(KG/HR ) 532239. 532239. 0.00000
ENTHALPY(GCAL/HR ) -672.382 -672.382 -0.169081E-
15


*** INPUT DATA ***

FLASH SPECS FOR HOT SIDE:
TWO PHASE FLASH

FLASH SPECS FOR COLD SIDE:
TWO PHASE FLASH

FLOW DIRECTION AND SPECIFICATION:
COUNTERCURRENT HEAT EXCHANGER
SPECIFIED COLD OUTLET TEMP
SPECIFIED VALUE C 300.0000
LMTD CORRECTION FACTOR 1.00000


PRESSURE SPECIFICATION:
HOT SIDE OUTLET PRESSURE BAR 39.8000
COLD SIDE OUTLET PRESSURE BAR 41.0500

HEAT TRANSFER COEFFICIENT SPECIFICATION:
OVERALL COEFFICIENT KCAL/HR-SQM-K 1220.6069

*** OVERALL RESULTS ***

STREAMS:
--------------------------------------
| |
REACTOUT ----->| HOT |-----> SEPFEED
T= 3.1000D+02 | | T=
8.1840D+01
P= 4.0074D+01 | | P=
3.9800D+01
V= 1.0000D+00 | | V=
4.7123D-01
| |
FROMRHX <-----| COLD |<----- TORHX
T= 3.0000D+02 | | T=
2.6026D+01
P= 4.1050D+01 | | P=
4.1543D+01
V= 1.0000D+00 | | V=
0.0000D+00
--------------------------------------

DUTY AND AREA:
CALCULATED HEAT DUTY GCAL/HR 90.8984
CALCULATED (REQUIRED) AREA SQM 2794.9152
ACTUAL EXCHANGER AREA SQM 2794.9152
PER CENT OVER-DESIGN 0.0000

HEAT TRANSFER COEFFICIENT:
AVERAGE COEFFICIENT (DIRTY) KCAL/HR-SQM-K 1220.6069
UA (DIRTY) CAL/SEC-K 947636.8860

LOG-MEAN TEMPERATURE DIFFERENCE:
LMTD CORRECTION FACTOR 1.0000
LMTD (CORRECTED) C 26.6448
NUMBER OF SHELLS IN SERIES 1

PRESSURE DROP:
HOTSIDE, TOTAL BAR 0.2740
COLDSIDE, TOTAL BAR 0.4932

PRESSURE DROP PARAMETER:
HOT SIDE: 154.74
COLD SIDE: 779.31


APPENDIX C
Problem Statement


Ethylene from Ethanol
(Recommended by Bruce M. Vrana, DuPont)
Ethylene is conventionally produced from fossil-fuel feedstocks such as ethane or naphtha in
huge, expensive ethylene crackers. Typical crackers produce 1 million tonnes of ethylene per
year and cost over a billion dollars to build. The ethylene market is large and growing
worldwide. The industry needs about 5 million tonnes per year of new capacity by 2030 in the
U.S. alone. Ethylene is one of the basic building blocks of the chemical industry, going into a
wide variety of products, including polyethylene, polystyrene, ethylene glycol, and PVC. To
reduce your companys dependence on fossil fuels, your team has been assembled to design a
plant to make 1MM tonnes of ethylene per year from ethanol, made by fermentation of
renewable resources. The goal is to be cost competitive with fossil ethylene while reducing
greenhouse gas emissions.
Ethanol dehydration to ethylene was practiced commercially in the first half of the 20
th
century
in the U.S. and Europe, and in the second half of the century in Brazil and elsewhere, but was
abandoned largely with the global expansion of the petrochemical industry. However, with the
increase in the cost of, and limited supply of, fossil fuels, and the growing production of ethanol,
companies are beginning to consider this technology again.
Ethanol dehydration to ethylene is an endothermic reaction, usually carried out at 300 to 400C
at moderate pressure over an activated alumina or silica catalyst. Ethanol conversion is 98%, and
selectivity to ethylene is about 98%. Ethylene must be 99.96% pure to meet polymer grade specs.
There are two different reactor technologies. An isothermal fixed bed reactor can be run at 350C
with a liquid hourly space velocity of 0.2/hr. Catalyst is typically packed in tubes of a heat
exchanger, with heating on the outside to maintain isothermal operation. The catalyst must be
regenerated to remove coke approximately every 1 to 2 months, so your design should consider
this fact. Regeneration takes about 3 days. Most plants built in the 20th century used isothermal
technology. (If you cannot find selectivity data, you may assume the same product distribution as
in the Petrobras patent for adiabatic reactors without steam co-feed at whatever pressure you
wish to operate).

Alternatively, an adiabatic fixed bed reactor can be used, with an inlet temperature of 450C.
Petrobras technology used steam in the feed to solve the coking problem, and catalyst life was
about 1 year. The Petrobras patent gives more details. You may use either isothermal or adiabatic
reactor technology, and if adiabatic, you may add steam to the feed or not. You should justify
your choice based on economic estimates as well as technical feasibility. The United States and
Brazil produce most of the worlds ethanol by fermentation of local agricultural feedstocks. The
U.S. industry is almost entirely based on corn, while Brazil uses sugar cane. Process efficiencies
in both countries have improved dramatically in recent years, with increasing ethanol production
for use in transportation fuels; thus, do not use process or cost data that is more than 2-3 years
old. You may locate your plant in either the U.S. or Brazil, using appropriate construction costs
for your location, and local ethanol costs and specs.
If you decide to locate in Brazil, one important factor to consider in your economics is that
ethanol price increases dramatically during the inter-harvest period, typically 3-4 months of the
year when sugar cane cannot be harvested and local ethanol plants shut down. In recent years,
Brazil has imported ethanol from the U.S. during this part of the year. Corn ethanol in the U.S.
has no such restriction, as corn can be stored year-round. Be sure to include freight to your plant
site in the cost of the ethanol.
You will need to make many assumptions to complete your design, since the data you have is far
from complete. State them explicitly in your report, so that management may understand the
uncertainty in your design and economic projections before considering the next step toward
commercialization designing and running a pilot plant. Test your economics to reasonable
ranges of your assumptions. If there are any possible showstoppers (i.e., possible fatal flaws, if
one assumption is incorrect that would make the design either technically infeasible or
uneconomical), these need to be clearly communicated and understood before proceeding.
The plant design should be as environmentally friendly as possible, at a minimum meeting
Federal and state emissions regulations. Recover and recycle process materials to the maximum
economic extent. Also, energy consumption should be minimized, to the extent economically
justified. The plant design must also be controllable and safe to operate. Remember that you will

be there for the plant start-up and will have to live with whatever design decisions you have
made.
References
U.S. Patent 4,232,179, November 4, 1980, assigned to Petrobras.
The Renewable Fuels Association web site has a good description of the fuel ethanol process and
industry. http://www.ethanolrfa.org


APPENDIX D
MSDS Reports


APPENDIX E
Relevant Documents


*************************************************************************
* *
* Calculations were completed normally *
* *
* All Unit Operation blocks were completed normally *
* *
* All streams were flashed normally *
* *
* All Utility blocks were completed normally *
* *
* All Convergence blocks were completed normally *
* *
*************************************************************************

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