ChE 462 Chemical Plant Design and Econom

ChE 462
Chemical Plant Design and Economics
PRODUCTION OF PROPIONIC ACID
Final Report
Project No: 5
by
Gökçe AKBALIK
Serhat ARCA
İsmail Can KAZAN
Erbil MİMARLAR
Course Instructor : Assoc. Prof. Ahmet Kerim AVCI

Teaching Assistants : Elif ERDİNÇ
Sinan KOÇ
İrem ŞEN
Date of Submission : 07.06.2013
Group Number : 10
Department of Chemical Engineering

Boğaziçi University
Bebek, Istanbul
ii
DECLARATION OF INDEPENDENT WORK
WE HAVE NEITHER GIVEN NOR RECEIVED ANY

HELP FROM OTHERS ON THIS PROJECT.
Name: Signature:
Name: Signature:
Name: Signature:
Name: Signature:
DATE : 07.06.2013
iii
ABSTRACT
The aim of this project is to estimate the base case design capacity of a propionic acid plant
and to design the plant accordingly. There are several methods for the production of propionic
acid. These methods include the hydrocarboxylation of ethylene and oxidation of
propionaldehyde. The method used in this project is the oxidation of propionaldehyde and it is
mainly chosen because of its lower values for operating temperature and pressure. Rhodium
catalyst will be used in the process. The plant will be constructed in 2013 and it is expected to
operate until 2030. In order to decide on the production capacity, a market search was carried
out. The databases of TUIK and UN were searched for the necessary data and a cross-check
was carried out to compare the results obtained from these two sources. The consumption data
of Italy, France, Austria and Denmark is used in making future consumption prediction for
Turkey. 3 and 5 year moving averages are used to smoothen the data and several trend lines
are added to the data obtained. The R2 values of these fits are compared to decide on the
projection of consumption data. As a result of this procedure, the design capacity is estimated
to be 1020 tonnes per year. In order to produce this amount of propionic acid, 393.13 tonnes
of CO, 28.29 tonnes of H2, 393.74 tonnes of ethylene and 224.56 tonnes of O2 are fed to the
system. The plant is assumed to operate 340 days per year. Different patents are compared for
a number of different properties. As a result, US5410091 was decided to use for the
production of propionaldehyde and US2011/0087038 for production of propionic acid. After
the decision is made on which patent to use, ChemCad is used to simulate the system. The
temperature ranges between 25˚C and 390˚C and the pressure values lie between 1 atm and 15
atm. The product is obtained with a purity of 99.9%.
iv
TABLE OF CONTENTS
DECLARATION OF INDEPENDENT WORK ....................................................................... ii

ABSTRACT .............................................................................................................................. iii
TABLE OF CONTENTS .......................................................................................................... iv
LIST OF TABLES ................................................................................................................... vii
LIST OF FIGURES .................................................................................................................... x
1. INTRODUCTION .................................................................................................................. 1
2. MARKET SURVEY AND CAPACITY DETERMINATION ............................................. 4
2.1. Market Survey ................................................................................................................. 4
2.2. Determination of Consumption In Turkey ...................................................................... 5
2.3. Forecasting....................................................................................................................... 7
3. PROCESS SELECTION AND DESCRIPTION ................................................................. 20
3.1. Propionic Acid Production Methods ............................................................................. 20
3.1.1. Chemical Processes .............................................................................................. 20
3.1.1.1. Reppe Process (Oxo Process) ........................................................................ 20
3.1.1.2. Larson Process ............................................................................................... 21
3.1.1.3. Fischer-Tropsch Process ................................................................................ 21
3.1.2. Fermentation Processes ......................................................................................... 22
3.1.3 Result of Selection .................................................................................................. 22
3.2 Patent Selection .............................................................................................................. 23
3.3 Simple Flow Diagram ..................................................................................................... 25
3.4 Plant Site Location.......................................................................................................... 26
3.5 Process Description ........................................................................................................ 28
3.5.1 Feed Preparation ..................................................................................................... 28
3.5.2 Oxo Process ............................................................................................................ 29
3.5.3 Second Feed Preparation ........................................................................................ 29
3.5.4 Oxidation Process .................................................................................................. 30
3.5.5 Separation .............................................................................................................. 31
4. CALCULATIONS ............................................................................................................... 32
4.1. Assumptions .................................................................................................................. 32
4.2. Physical and Thermochemical Data .............................................................................. 35
4.3. Material Balances .......................................................................................................... 37
4.3.1. Production Capacity .......................................................................................... 37
v
4.3.2. General Mass Balance ......................................................................................... 37

4.3.3. Mass Balances on Reactors ................................................................................. 37
4.3.4. Mass Balances for Separators and Flash Vessels ................................................ 39
4.3.5. Mass Balances for Heat Exchangers ................................................................... 40
4.3.6. Mass Balances for Compressor and Expanders ................................................... 41
4.3.7. Mass Balances for Mixers and Dividers .............................................................. 41
4.4. Energy Balances ............................................................................................................ 43
4.4.1 Energy Balances Around Reactors ....................................................................... 43
4.4.2 Energy Balances Around Heat Exchangers .......................................................... 45
4.4.3 Energy Balances Around Distillation Column and Flash Vessel ......................... 46
4.4.4. Energy Balance Around Compressors and Expanders ........................................ 46
4.4.5 Energy Balances for Mixers and Dividers ............................................................ 48
4.5. Unit Design Calculations ............................................................................................... 49
4.5.1. Unit Design Calculations for Reactors ................................................................ 49
4.5.2. Unit Design Calculations for Distillations........................................................... 53
4.5.3. Unit Design Calculations for Flash Drum ........................................................... 56
4.5.4. Unit Design Calculations for Heat Exchangers ................................................... 60
4.5.5. Unit Designs Calculations for Compressors and Expanders ............................... 67
5. ECONOMIC ANALYSIS .................................................................................................... 69
5.1.Fixed Capital Investment ................................................................................................ 69
5.1.1. Purchased Equipment Cost Estimation................................................................. 69
5.1.1.1. Purchased Equipment Cost of Heat Exchangers .......................................... 70
5.1.1.2. Purchased Equipment Cost of Reactors........................................................ 72
5.1.1.3. Purchased Equipment Cost of Mixers and Dividers ..................................... 74
5.1.1.4. Cost Estimation for Pipes ............................................................................. 76
5.1.1.5. Purchased Equipment Cost of Distillation Columns .................................... 78
5.1.1.6. Cost Estimation for Compressors ................................................................. 81
5.1.1.7. Cost Estimation for Expanders ..................................................................... 83
5.1.1.8. Total Purchased Equipment .......................................................................... 86
5.1.2. Other Costs in FCI ............................................................................................... 86
5.2. Working Capital ............................................................................................................ 88
5.3. Total Capital Investment ............................................................................................... 89
5.4. Land ............................................................................................................................... 89
5.5. Total Product Cost ......................................................................................................... 90
vi
5.5.1. Manufacturing Costs............................................................................................. 90

5.5.1.1. Variable Production Costs ............................................................................. 90
5.5.1.2. Fixed Costs .................................................................................................... 94
5.5.1.3. Plant-overhead Costs ..................................................................................... 96
5.5.1.4. Other Costs .................................................................................................... 96
5.6. Annual Revenue ............................................................................................................ 97
5.7. Cash Flow Analysis ....................................................................................................... 97
5.7.1. Profitability Analysis .......................................................................................... 101
5.7.1.1. Methods that do not consider the Time Value of Money ............................ 101
5.7.1.2. Methods That Consider the Time Value of Money ..................................... 103
6. DISCUSSION .................................................................................................................... 105
6.1 Evaluation of the Capacity ........................................................................................... 105
6.2 Process Selection .......................................................................................................... 106
6.3 Justification of Assumptions ........................................................................................ 107
6.4 Interpretation of Results ............................................................................................... 109
6.5 Discussion of Plant Economy ....................................................................................... 110
6.5.1 Fixed Capital Investment ...................................................................................... 110
6.5.2 Total Product Cost ................................................................................................ 111
6.5.3 Cash Flow ............................................................................................................. 112
6.5.4 Profitability Analysis ............................................................................................ 112
7. CONCLUSION .................................................................................................................. 114
REFERENCES ....................................................................................................................... 115
NOMENCLATURE ............................................................................................................... 119
APPENDIX ............................................................................................................................ 123
A.1 PATENT US 5,410,091 ............................................................................................... 123
A.2 PATENT US 2011/0087038 ........................................................................................ 133
B. ChemCad Summary ....................................................................................................... 144
C.1. MSDS for Ethylene ..................................................................................................... 179
C.2. MSDS for Propionaldehyde ........................................................................................ 181
C.3 MSDS for Propionic Acid ............................................................................................ 183
D. SPECIFICATION SHEETS .......................................................................................... 185
vii
LIST OF TABLES
Table 1.1. Production of Propionic acid in 1000 tones 2
Table 2.1. UN Data for Propionic Acid Consumption. 5
Table 2.2. TUIK and UN Data Cross-Check. 4
Table 2.3. Comparison of Original, 3 YMA and 5 YMA Consumption Values. 8
Table 2.4. Percentage of Propionic Acid Consumption in UN Data. 10
Table 2.5. Growth Rate of Turkey.. 11
Table 2.6. Data for Austria. 11
Table 2.7. Data for Denmark. 12
Table 2.8. Data for France 12
Table 2.9. Data for Italy. 13
Table 2.10. Data for Germany. 13
Table 2.11. N values. 14
Table 2.12. Corresponding Years of Other Countries to Turkey. 15
Table 2.13. Population Projection for Turkey. 15
Table 2.14. Consumption Estimation-Germany. 16
Table 2.15. Consumption Estimation-Austria. 16
Table 2.16. Consumption Estimation-Denmark. 16
Table 2.17. Consumption Estimation-France. 16
Table 2.18. Consumption Estimation-Italy. 17
Table 2.19. Future Production Capacity of Turkey. 19
Table 3.1. Comparison of Selected Patents. 22
Table 4.1. Thermochemical Data. 35
Table 4.2. Coefficients of Liquid Heat Capacity Equation. 35
Table 4.3. Coefficients of Gas Heat Capacity Equation. 35
Table 4.4. Molecular Weights of Compounds. 35
Table 4.5. Standard Heat of Formations 36
Table 4.6. Coefficients for Heat of Vaporization Equation 36
Table 4.7. Coefficients for Liquid Viscosity 36
Table 4.8. Coefficients for Vapor Viscosity 36
Table 4.9. ChemCad Mass Balance Results around Reactors 39
Table 4.10. Mass Balance Results for S 101 40
Table 4.11. Mass Balance Results for F 101 40
viii
Table 4.12. Mass Balance for Heat Exchangers. 40

Table 4.13. Mass Balance for Compressors. 41
Table 4.14. Mass Balance for Expanders. 41
Table 4.15. Mass Balance for Mixers. 42
Table 4.16. Mass Balance for Mixers (Continued). 42
Table 4.17. Mass Balance for Dividers 42
Table 4.18. Energy Balances of Inlet Stream of R 101. 44
Table 4.19. Energy Balances of Outlet Stream of R 101. 44
Table 4.20. Energy Balances of Reactors.. 45
Table 4.21. Energy Balances of Heat Exchangers. 45
Table 4.22. Energy Balances of Distillation Column. 46
Table 4.23. Energy Balances of Flash Vessel 46
Table 4.24. Energy Balances of Compressors 47
Table 4.25. Energy Balances of Expanders 48
Table 4.26. Energy Balances of Mixers and Dividers 48
Table 4.27. Vapor pressure coefficients of components. 53
Table 4.28. Constants for liquid density calculation. 56
Table 4.29. Design Parameters for Distillation Column. 56
Table 4.30. Antoine constants and equilibrium distribution coefficients. 57
Table 4.31. Critical volume and compressibility factors of water. 58
Table 4.32. Critical pressure and temperature values of the components. 58
Table 4.33. Dimensions of F-101. 60
Table 4.34. Constants for thermal conductivity. 61
Table 4.35. Design Parameters for Heat Exchangers. 67
Table 4.36. Unit Design Calculation Result for Compressors. 68
Table 4.37. Unit Design Calculation Result for Expanders. 68
Table 5.1. Chemical Engineering Plant Cost Index for 1987-2012. 69
Table 5.2. Specifications of Heat Exchangers. 70
Table 5.3. Shell Costs of Heat Exchangers. 71
Table 5.4. Total Costs of Heat Exchangers. 72
Table 5.5. Tube Specifications of Reactors. 72
Table 5.6. Pipe Cost of Reactors. 73
Table 5.7. Total Cost of Reactors. 73
Table 5.8. Total Insulation Cost of Reactors. 74
ix
Table 5.9. Mixer and Divider Diameters. 75

Table 5.10. Mixer and Divider Costs. 76
Table 5.11. Purchased Cost of Piping System. 78
Table 5.12. Sizes of Distillation Columns and Flash Separator. 79
Table 5.13. Vertical column and tray costs. 80
Table 5.14. Total Tray Costs. 80
Table 5.15. Cost of distillation columns in 2002. 81
Table 5.16. Cost of distillation columns in 2013. 81
Table 5.17. Power Requirement of the Compressor. 81
Table 5.18. Equipment cost of Compressor. 83
Table 5.19. Cost of Insulation (compressors). 83
Table 5.20. Power Requirement of the Expander. 83
Table 5.21. Equipment Cost of Expanders. 85
Table 5.22. Cost of Insulation (expanders). 85
Table 5.23. Cost of All Units. 86
Table 5.24. Total Capital Investment Calculation. 89
Table 5.25. Annual Cost Estimation for Ethylene. 91
Table 5.26. Annual Cost Estimation for Synthesis Gas. 91
Table 5.27. Annual Cost Estimation for Oxygen. 91
Table 5.28. Determination of Operating Labor with First Method. 92
Table 5.29. Determination of Operating Labor with Second Method. 93
Table 5.30. Determination of Operating Labor. 93
Table 5.31. MACRS Depreciation Rates Percentages. 95
Table 5.32. Depreciation Rates 95
Table 5.33. Other Investments. 96
Table 5.34. Calculation of total product cost in the third year of operation. 96
Table 5.35. Revenue From Sales. 97
Table 5.36. Annual Cash Flow and Cumulative Cash Flow Table. 99
x
LIST OF FIGURES
Figure 2.1. Worldwide Propionic Acid Use Purposes. 4
Figure 2.2. TUIK vs. UN Data. 7
Figure 2.3. Comparison of Original, 3 YMA and 5 YMA Consumption Values. 8
Figure 2.4. 3 YMA Data With Various Trend Lines. 9
Figure 2.5. Future Consumption. 17
Figure 2.6. Future Consumption with Normalized Year. 18
Figure 3.1. Reppe Process for Propionic Acid Formation. 21
Figure 3.2. Simple Flow Diagram. 25
Figure 3.3. Overall Flow Chart of ChemCad. 27
Figure 3.4. Feed Preparation Flow Chart From ChemCad. 28
Figure 3.5. Propionaldehyde Formation. 29
Figure 3.6. Second Preparation Step. 29
Figure 3.7. Second and Third Reactors, R 102 and R 103 30
Figure 3.8. Oxidation Reaction. 30
Figure 3.9. Separation Unit. 31
Figure 4.1. Temperature Correction Factor. 62
Figure 4.2. Shell-bundle Clearence. 63
Figure 4.3. Tube Side Heat Transfer Factors. 64
Figure 4.4. Shell-Side Heat-Transfer Factors, Segmental Baffles. 65
Figure 5.1. CEPCI Plot for Extrapolation. 70
Figure 5.2. Purchased Cost of Welded and Screwed Pipe Per Unit Length. 71
Figure 5.3. Purchased Cost of Horizontal Storage Vessels. 72
Figure 5.4. Thermal conductivity data for fiberglass and mineral wool. 74
Figure 5.5. Cost of Motionless Mixers.. 75
Figure 5.6. Purchased Cost of Welded and Screwed Pipe Per Unit Length. 76
Figure 5.7. Purchased Cost of Pipe Insulation. 77
Figure 5.8. Purchased Cost of Vertical Columns. 79
Figure 5.9. Purchased Cost of Trays in Tray Columns. 80
Figure 5.10. Purchased Cost of Compressors. 82
Figure 5.11. Graph of Purchased Cost of Compressors. 82
Figure 5.12. Purchased Cost of Expanders. 84
Figure 5.13. Operating Labor Determination Chart. 92
Figure 5.14. Annual Cash Flow Chart. 100
Figure 5.15. Cumulative Cash Flow Chart. 100
1
1. INTRODUCTION
Propionic acid is a naturally occurring carboxylic acid. It has the chemical formula
CH3CH2COOH. Propionic acid is used in the production of cellulose esters, plastic dispersions
and herbicides. In addition to these, it is used in pharmaceuticals and in flavors and fragrances to
a limited extent. Propionic acid is starting to become more important for the preservation of
forage cereals and animal feed. The reason for that is that, many putrefying and mold-forming
microorganisms cannot survive in the presence of propionic acid. (Kirk and Othmer, 2001)
Because of its property as an effective mold inhibitor, acetic acid is particularly useful in yeast-
leavened baked products because they do not affect the activity of the yeast. In addition to being
widely used in baked goods, propionic acid is also used as mold inhibitor in cheese foods and
spreads. (J.D. Dziezak, 1986) Propionic acid is a food additive and its INS number is E 280.
(C.Alimentarius, 2011)
Propionic acid can be commercially produced by the reaction of ethylene with CO and water
under Reppe conditions. The reaction takes place at high temperatures and pressures. The
temperature range for this reaction is between 270-320 ˚C and the pressure range lies between
200-240 bar. Nickel propionate is used as a catalyst in this reaction. BASF has used this reaction
since 1952 in an industrial plant whose capacity was increased from 60000 to 80000 tonnes per
year in 1995. (Weissermel and Arpe, 2003)
Propionic acid is also produced by the oxidation of propionaldehyde. With cobalt and manganese
ions, this reaction proceeds at mild temperatures. Propionaldehyde can be produced by the oxo
reaction of ethylene with carbon monoxide and hydrogen. (Riegel 2007). Oxo process requires
temperatures around 100- 150 ˚C and pressures around 20-30 atm.
In addition to all these, propionic acid can be produced biologically. Propionic acid can be
produced as a product of metabolic breakdown of fatty acids containing odd number of carbon
atoms and breakdown of some amino acids. Some bacteria, such as those from genum
Propionibacterium, produce propionic acid as a result of their anaerobic metabolism. (Wood,
1981)
2
The amount of propionic acid produced around the world for different years can be seen in the
following table:
Table 1.1. Production of Propionic acid in 1000 tones (K. Weissermel/H.-J. Arpe)
1996 1997 1999

USA 94 94 105
W.Europe 87 89 96
Japan 3 3 3
Looking at this table, it is possible to say that the importance of propionic acid has increased in
these years which have resulted in an increase in the amount of produced propionic acid.
The production method that is going to be used in this project is oxidation of propionaldehyde.
Propionaldehyde will be obtained by an improved oxo process which requires lower temperature
and pressure values. The lower temperature and pressure values are one of the advantages of the
method used in the project. Lower values of temperature and pressure mean less production cost.
In addition to that, working at a lower temperature and pressure value is a positive in safety
issues. The lower values of operating temperature and pressure mean a lower probability of an
explosion and less losses in case of an accident. In addition to the operating conditions, the
process selected has a fairly high conversion and selectivity value. This is important in producing
the desired product with less amount of money. In addition to that, this is important from the
environmental point of view. Unnecessary energy will not be spent for producing undesired
products in case of high selectivity and conversion. In addition to that, with high values of
selectivity, the amount of undesired product, which will be removed to the environment, will be
smaller.
The aim of this project is to estimate the base case design capacity of a propionic acid plant and
to design the plant accordingly. The design capacity is estimated to be 1020 tonnes/year. In order
to produce propionic acid, oxidation of propionaldehyde method will be used. The report
includes “Market Survey and Capacity Determination”, “Process Selection and Description”,
“Calculations”, “Discussion” and “Conclusions” parts. In “Market Survey and Capacity
Determination” part, the amount to be produces is estimated using the data from previous years.
In “Process Selection and Description”, methods for the production of propionic acid is given in
more detail. The processes and the patents are compared in this part. The ChemCad flow sheet is
also explained. In “Calculations”, material and energy balances are carried out and the
assumptions made in these calculations are stated. The “Discussion” and “Conclusions” parts
3
explain the advantages and disadvantages of the design that is used. The validity of the
assumptions is discussed and the interpretation of the results is given in these parts. The selected
patents, ChemCad summary, MSDS for the materials and material sheets are given in the
Appendix.
4
2. MARKET SURVEY AND CAPACITY DETERMINATION
2.1. Market Survey
In order to make profit by producing Propionic Acid in Turkey, a market survey on the potential
of the product is performed. The survey had two major points to search: Consumption of
Propionic Acid in Turkey and the market in Europe. Through these results consumption forecast
and production capacity are determined.
Propionic acid is majorly used as additive in animal feed and preservative against molding and
fungus in pastry, basically in breads. Its worldwide purpose of use is shown in Figure 2.1.
(O.R.1)
Others
(pharmaceutical
s, packaging,
fungicides)
6% Cellulose
15% Grain
Preservatives
34%
Herbicides
22%
Feed
Preservatives
23%
Figure 2.1. Worldwide Propionic Acid Use Purposes.
Global capacity for propionic acid stood at 349,000 tonnes/year in 2006; 166,800 tonnes of
which was in the US, followed closely by Western Europe with 130,000 tonnes. Asia Pacific,
excluding Japan, was a distant third with 35,180 tonnes/year. Japan and South Africa had
capacities of 10,000 tonnes/year and 7,00 tonnes/year respectively. (O.R. 1)
In Western Europe, propionic acid is supplied by BASF, Germany with the capacity of 110,000
tonnes/year and by Perstorp, Sweden with 50,000 tonnes/year. Both companies increased their
capacities by 30,000 tonnes in years 2009 and 2005 respectively. (O.R. 2 and O.R. 3)
In Turkey, it is used in agriculture and grain product industries; wherein small amount of
propionic acid is efficient for both. Additionally, wide use of esters and salts of propionic acid or
other forms of acids (formic, ascorbic etc.) for the same purposes result in a small market
share.(Gildberg and Raa, 1977)
5
2.2. Determination of Consumption In Turkey
Following formula is applied to determine the consumption of propionic acid.
Consumption= Production + Import-Export (Hortaçsu, 2004)
Similar to many European countries, Turkey is one of the non-producing but importing countries
for propionic acid. In order to determine the trade amounts, Turkish Statistical Institute (TUIK)
data sources is searched with GATT (The General Administration of Tariff and Trade) number
291550000011. Additionally, United Nation’s Data sources are searched to cross-check the
preciseness. Both results are tabulated in Table 2.1. UN Data gives import-export amount for
years between 1989 and 2011 whereas TUIK Data is available for 2000-2011.
Table 2.1. UN Data for Propionic Acid Consumption.
UN DATA
Year Import (kg) Export (kg) Consumption (kg)
1989 182,933 42,250 140,683
1990 301,799 0 301,799
1991 276,560 0 276,560
1992 270,934 0 270,934
1993 316,515 0 316,515
1994 63,762 0 63,762
1995 146,929 0 146,929
1996 104,198 10 104,188
1997 150,144 0 150,144
1998 241,047 0 241,047
1999 433,701 237 433,464
2000 449,906 400 449,506
2001 283,960 20 283,940
2002 151,803 14,040 137,763
2003 99,328 12,050 87,278
2004 175,232 1,750 173,482
2005 304,883 3,800 301,083
2006 231,655 5,550 226,105
2007 367,980 2,110 365,870
2008 411,618 1,001 410,617
2009 444,560 3,077 441,483
2010 505,890 1,493 504,397
2011 652,649 2,659 649,990
6
Table 2.2. TUIK and UN Data Cross-Check.
TUIK DATA UN DATA

Import Export Consumption Import Export Consumption
Year (kg) (kg) (kg) (kg) (kg) (kg)
2000 42,023 0 42,023 449,906 400 449,506
2001 118 0 118 283,960 20 283,940
2002 14,028 0 14,028 151,803 14,040 137,763
2003 22,459 0 22,459 99,328 12,050 87,278
2004 2,886 0 2,886 175,232 1,750 173,482
2005 76,961 0 76,961 304,883 3,800 301,083
2006 42,434 0 42,434 231,655 5,550 226,105
2007 117,864 0 117,864 367,980 2,110 365,870
2008 151,781 1 151,780 411,618 1,001 410,617
2009 116,515 27 116,488 444,560 3,077 441,483
2010 189,658 33 189,625 505,890 1,493 504,397
2011 183,938 32 183,906 652,649 2,659 649,990
As it can be examined in Figure 2.2., UN data is significantly higher than TUIK because UN
data gives propionic acid trade amount under the category of “Propionic Acid, Its Esters and
Salts”. Therefore distributor companies, which are BASF Turkey and Luna Kimya, are contacted
to get information for cross-check. Since they gave the maximum import amount of 200
tones/year, it is more reasonable to take previous years’ data from TUIK source. Sample
consumption amount calculation for Turkey in 2009 through TUIK is as follows:
Consumption = Production + Import - Export
Consumption = 0 + 116,515 - 27 = 116,488 kg/year

7
700,000
600,000
500,000
Consumption (kg/y)
400,000
TUIK
300,000
UNData
200,000
100,000
0
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
Year
Figure 2.2. TUIK vs. UN Data.
Turkey is foreign dependent in propionic acid market. Therefore its trade is affected at the times
when financial crises occur such as 2001 2004 and 2009. One can see that the propionic acid
consumption decreases at those years.
2.3. Forecasting
There are some fluctuations in TUIK data which may result from financial crisis and they can be
eliminated with smoothing via moving average method. The method is applied for 3 and 5 years
and graphed in Figure 2.3. Following formulas are used:
For 3 YMA:
n2000 n2001 n2002

nMA,2001
3
2,023 11 1 ,02
1 , 2 kg/year
3
For 5 YMA:
n2000 n2001 n2002 n2003 n200

nMA, 2002
5
8
2,023 11 1 ,02 22, 59 2,

12,20 kg/year
5
Table 2.3. Comparison of Original, 3 YMA and 5 YMA Consumption Values.
Original 3 YMA 5 YMA

Consumption Consumption Consumption
YEAR (kg) (kg) (kg)
2000 42,023
2001 118 18,723
2002 14,028 12,202 16,303
2003 22,459 13,124 23,290
2004 2,886 34,102 31,754
2005 76,961 40,760 52,521
2006 42,434 79,086 78,385
2007 117,864 104,026 101,105
2008 151,780 128,711 123,638
2009 116,488 152,631 151,933
2010 189,625 163,340
2011 183,906
200,000
180,000
160,000
Consumption (kg/y)
140,000
120,000
100,000 original
80,000 3 YMA
60,000 5 YMA
40,000
20,000
0
1998 2000 2002 2004 2006 2008 2010 2012
Year
Figure 2.3. Comparison of Original, 3 YMA and 5 YMA Consumption Values.

9
3 YMA and 5 YMA results are quite similar but using 5 YMA method would lead to loss of 4
data points. 3 YMA is preferred since it is better to have more data for coming calculations. For
estimation of future consumption, 3 YMA data is expanded by adding polynomial, logarithmic,
linear and power trend lines.
700,000
y = 770.07x2 + 7731.2x - 16136
R² = 0.9606
600,000
y = 2720.7x1.6696
500,000 R² = 0.8596
400,000 y = 18512x - 46168

Consumption (kg/y)
R² = 0.9478
300,000 y = 100063ln(x) - 98400
R² = 0.8201
200,000 3 YMA
Polynomial
Polinom. (3
100,000
YMA)
Logarithmic
Log. (3 YMA)
0
2003
2020
2000
2001
2002
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015
2016
2017
2018
2019
2021
2022
Doğrusal
Linear (3
-100,000 YMA)
Year ÜsExponential
(3 YMA)
-200,000
Figure 2.4. 3 YMA Data With Various Trend Lines.
All trend lines give precise results for about 5 more years; R2 values range is between 0.8201 and
0.9606. But this figure is not enough to make precise forecasting. The use of industrialized
countries’ data for the estimation of future consumption is common practice. (Hortaçsu, 2004) For
this purpose, consumption trends of Germany, France, Italy, Denmark and Austria are
investigated.
It is known that in Western Europe, production is present only in Germany and Sweden. (O.R. 1)
BASF Company in produces is examined to see the trend of a country with high capacity
production. The plant in Ludwigshafen is known to operate at full capacity of 80,000 tonnes/year
and it is expanded to 110,000 tonnes/year with an investment in 2007.(O.R. 4) Neglecting the
increase period up to 2009, production data is listed in Table 2.4.
Import and export data of countries are obtained from UN data but they are listed under
“propionic acid, its salts & esters” category. To obtain pure propionic acid amount, percentage of
TUIK data in UN data for Turkey is calculated for every year. For the countries with no
10
production, each year’s consumption is decreased with same percentage. Sharp fluctuations are
eliminated during construction of consumption graph (Figure 2.6.)
TUIKTurkey,2010 1 9, 25
100 100 3 .59
UN DataTurkey,2010 50 ,39
Table 2.4. Percentage of Propionic Acid Consumption in UN Data.
TUIK Data
YEAR UN Data (kg) %
(kg)
2000 42,023 449,506 9.35
2001 118 283,940 0.04
2002 14,028 137,763 10.18
2003 22,459 87,278 25.73
2004 2,886 173,482 1.66
2005 76,961 301,083 25.56
2006 42,434 226,105 18.77
2007 117,864 365,870 32.21
2008 151,780 410,617 36.96
2009 116,488 441,483 26.39
2010 189,625 504,397 37.59
2011 183,906 649,990 28.29
According to the model proposed by Hortaçsu, consumption per capita in one country is assumed
to be proportional to the purchasing power of capita. Also, present consumption of industrialized
countries can be the potential future consumption of Turkey. In order to calculate the time that
Turkey will reach that consumption value following formula is proposed:
GDP i
log GDP
Turkey
N
log(1
Where N is the number of years between countries, GDPppp is the Gross Domestic Products per
capita in Purchasing Power Parity and is the average growth rate of Turkey. GDP per capita in PPP
and growth rate data are extracted from World Bank.
11
Table 2.5. Growth Rate of Turkey.
GDP per capita, PPP

GDP growth
Year Population (current international
(annual %)
$)
2000 63,627,862 9,262.02 6.77
2001 64,544,914 8,693.54 -5.70
2002 65,446,165 8,741.44 6.16
2003 66,339,433 8,864.74 5.27
2004 67,235,927 10,237.60 9.36
2005 68,143,186 11,464.73 8.40
2006 69,063,538 12,944.40 6.89
2007 69,992,754 13,939.23 4.67
2008 70,923,730 15,057.64 0.66
2009 71,846,212 14,455.49 -4.83
2010 72,752,325 15,829.77 9.16
2011 73,639,596 17,110.12 8.50
average α % 4.15
. .1 5.2 9.3 . . 9 . 0. 9.1 .50

.15
10
Table 2.6. Data for Austria.
P.Acid GDP per

Consumption
Import Export Consumption Amount in capita, PPP
Year Population per capita
(kg) (kg) (kg) Consumption (current int.
(kg/person)
(kg) $)
2000 270,700 54,529 216,171 45,531 8,011,566 0.0056832 28,905
2001 365,217 71,356 293,861 122 8,042,293 0.0000152 29,035
2002 449,456 89,836 359,620 36,619 8,081,957 0.0045310 30,464
2003 403,238 74,940 328,298 84,480 8,121,423 0.0104021 31,318
2004 361,949 353,277 8,672 144 8,171,966 0.0000177 32,845
2005 435,700 265,006 170,694 43,632 8,227,829 0.0053029 33,626
2007 396,700 84,412 312,288 100,603 8,300,788 0.0121197 38,053
2008 367,578 12,957 354,621 131,082 8,336,926 0.0157230 39,783
2009 312,290 11,571 300,719 79,347 8,365,275 0.0094852 38,888
2010 458,720 54,265 404,455 152,052 8,389,771 0.0181235 40,401
2011 326,208 13,656 312,552 88,432 8,419,000 0.0105039 42,196
12
Table 2.7. Data for Denmark.
P. Acid GDP per

Consumption
(kg) (kg) (kg) Consumption (current int.
(kg/person)
(kg) $)
2000 541,749 9,575 532,174 49,751 5,339,616 0.00932 28,818
2001 675,683 12,369 663,314 276 5,358,783 0.00005 29,433
2002 987,724 3,886 983,838 100,181 5,375,931 0.01864 30,757
2003 570,425 33,101 537,324 138,268 5,390,574 0.02565 30,438
2004 484,420 127,843 356,577 5,932 5,404,523 0.00110 32,280
2005 728,085 92,029 636,056 162,585 5,419,432 0.03000 33,193
2006 936,081 55,933 880,148 165,181 5,437,272 0.03038 35,999
2007 758,314 114,881 643,433 207,280 5,461,438 0.03795 37,693
2008 664,462 141,712 522,750 193,229 5,493,621 0.03517 39,830
2009 651,357 140,506 510,851 134,791 5,523,095 0.02441 38,268
2010 774,183 46,118 728,065 273,712 5,547,683 0.04934 40,588
2011 807,291 74,832 732,459 207,240 5,574,000 0.03718 40,908
Table 2.8. Data for France.
P. Acid GDP per

Consumption
(kg) (kg) (kg) Consumption (current
(kg/person)
(kg) int. $)
2000 2,786,600 181,373 2,605,227 243,555 60,910,922 0.00400 25,168
2001 3,169,300 272,431 2,896,869 1,204 61,355,563 0.00002 26,537
2002 2,494,600 259,600 2,235,000 227,583 62,242,266 0.00366 27,204
2003 2,403,900 187,300 2,216,600 570,391 61,803,045 0.00923 27,587
2004 3,144,400 117,000 3,027,400 50,363 62,701,871 0.00080 28,090
2005 3,175,901 140,100 3,035,801 775,993 63,175,934 0.01228 29,453
2006 2,745,700 110,817 2,634,883 494,499 63,617,567 0.00777 31,274
2007 3,597,823 440,900 3,156,923 1,016,994 64,012,051 0.01589 33,007
2008 3,749,702 867,059 2,882,643 1,065,537 64,720,232 0.01646 33,657
2009 3,610,574 1,319,700 2,290,874 604,461 64,370,515 0.00939 34,041
2010 3,133,200 1,117,533 2,015,667 757,778 65,075,569 0.01164 34,262
2011 3,139,900 826,786 2,313,114 654,465 65,436,552 0.01000 35,246
13
Table 2.9. Data for Italy.
Year Import Export Consumption P. Acid Consumption GDP per

(kg) (kg) (kg) Amount in Population per capita capita, PPP
Consumption (kg/person) (current int.
(kg) $)
2000 5,037,016 11,478 5,025,538 469,823 56,942,108 0.00825 9,262
2001 5,564,941 21,341 5,543,600 2,304 56,977,217 0.00004 8,694
2002 5,401,682 85,401 5,316,281 541,341 57,157,406 0.00947 8,741
2003 7,245,986 66,050 7,179,936 1,847,593 57,604,658 0.03207 8,865
2004 6,139,024 190,545 5,948,479 98,957 58,175,310 0.00170 10,238
2005 5,665,986 121,361 5,544,625 1,417,283 58,607,043 0.02418 11,465
2006 6,299,871 318,685 5,981,186 1,122,512 58,941,499 0.01904 12,944
2007 4,654,801 837,305 3,817,496 1,229,796 59,375,289 0.02071 13,939
2008 4,752,873 878,415 3,874,458 1,432,150 59,832,179 0.02394 15,058
2009 5,388,339 1,056,976 4,331,363 1,142,857 60,192,698 0.01899 14,455
2010 6,320,427 1,734,340 4,586,087 1,724,112 60,483,385 0.02851 15,830
2011 6,807,583 3,061,213 3,746,370 1,059,985 60,770,000 0.01744 17,110
Table 2.10. Data for Germany.

GDP
P. Acid per
Consumption
Import Export Production Consumption Amount in capita,
(kg) (kg) (kg) (kg) Consumption PPP
(kg/person)
(kg) (cur
int. $)
2000 8,219,830 50,876,900 80,000,000 37,342,930 3,491,081 82,211,508 0.04246 25,757
2001 11,083,685 43,989,500 80,000,000 47,094,185 19,571 82,349,925 0.00024 26,714
2002 9,594,040 47,301,000 80,000,000 42,293,040 4,306,576 82,488,495 0.05221 27,444
2003 11,696,914 52,207,500 80,000,000 39,489,414 10,161,699 82,534,176 0.12312 28,360
2004 12,592,507 40,071,000 80,000,000 52,521,507 873,734 82,516,260 0.01059 29,679
2005 8,765,670 48,052,800 80,000,000 40,712,870 10,406,776 82,469,422 0.12619 31,115
2006 13,593,276 36,837,300 80,000,000 56,755,976 10,651,614 82,376,451 0.12930 33,503
2007 8,820,763 29,353,200 80,000,000 59,467,563 19,157,310 82,266,372 0.23287 35,538
2008 9,315,167 28,204,200 80,000,000 61,110,967 22,588,988 82,110,097 0.27511 37,119
2009 11,971,917 26,474,321 80,000,000 65,497,596 17,281,943 81,902,307 0.21101 35,631
2010 14,157,848 21,383,400 110,000,000 102,774,448 38,637,432 81,776,930 0.47247 37,652
2011 11,934,164 25,753,346 110,000,000 96,180,818 27,213,079 81,726,000 0.33298 39,491

14
N values are calculated and tabulated for each country. Sample calculation for Austria & Turkey
in 2005;
GDPppp,Austria = 33,672 $
GDPppp,Turkey = 11,465 $
GDPppp,i 33, 2
log log 11, 5
GDPppp,Turkey
N 2 .5 years
log(1 log(1 0.0 15
Therefore GDP per capita of Turkey in 2031 will be equal to the GDP per capita of Austria in
2005.
Table 2.11 N values.
N values
Turkey Austria Denmark France Germany Italy
0 28 28 25 25 25
0 30 30 27 28 28
0 31 31 29 28 28
0 31 30 27 29 28
0 29 28 25 26 24
0 26 26 23 25 22
0 26 25 22 23 21
0 25 24 21 23 20
0 24 24 21 22 20
0 24 24 20 22 20
0 23 23 19 21 17
0 22 21 18 21 16
15
Table 2.12. Corresponding Years of Other Countries to Turkey.
Year Austria Denmark France Germany Italy

2000 2028 2028 2025 2025 2025
2001 2031 2031 2028 2029 2029
2002 2033 2033 2031 2030 2030
2003 2034 2033 2030 2032 2031
2004 2033 2032 2029 2030 2028
2005 2031 2031 2028 2030 2027
2006 2032 2031 2028 2029 2027
2007 2032 2031 2028 2030 2027
2008 2032 2032 2029 2030 2028
2009 2033 2033 2029 2031 2029
2010 2033 2033 2029 2031 2027
2011 2033 2032 2029 2032 2027
Next step is the calculation of consumption values for above future years. For each original year,
consumption per capita amount of relevant country is multiplied with the estimated population of
Turkey in corresponding future year. Population projection data up to 2075 is taken from TUIK.
Original year = 2000

Estimated year for Turkey = 2028
Consumption per capita for Austria = 0.00568 kg/person,year
Population of Turkey in 2028 = 87,349,415
Consumption of Turkey in 2028 = 87,349,415 0.00568 = 496,421 kg/year
Table 2.13. Population Projection for Turkey.
Year Population Year Population

2013 76 481 847 2024 84 936 010
2014 77 323 892 2025 85 569 125
2015 78 151 750 2026 86 182 900
2016 78 965 645 2027 86 776 550
2017 79 766 012 2028 87 349 415
2018 80 551 266 2029 87 900 467
2019 81 321 569 2030 88 427 604
2020 82 076 788 2031 88 929 672
2021 82 816 250 2032 89 406 656
2022 83 540 076 2033 89 857 527
2023 84 247 088 2034 90 282 341
16
Table 2.14. Consumption Estimation- Germany.
Consumption
Year per capita Corresponding Consumption in
(kg/person) Year Turkey (kg)
2000 0.04246 2025 3,633,661
2007 0.23287 2029 11,365,892
2006 0.12930 2030 11,158,636
2010 0.47247 2031 18,764,765
2011 0.33298 2032 29,770,580
Table 2.15. Consumption Estimation-Austria.
Consumption
2000 0.00568 2028 496,421
2007 0.01212 2032 1,083,578
2008 0.01572 2032 1,405,743
2009 0.00949 2033 852,319
2010 0.01812 2033 1,628,537
2011 0.01050 2033 943,855
Table 2.16. Consumption Estimation- Denmark
Consumption
2000 0.00932 2028 808,533
2005 0.03000 2031 2,667,920
2006 0.03038 2031 2,701,625
2008 0.03517 2032 3,144,726
2011 0.03718 2032 3,324,110
Table 2.17. Consumption Estimation-France.
Consumption
2000 0.00400 2025 342,152
2002 0.00366 2030 811,249
2005 0.01228 2028 1,072,917
2008 0.01646 2029 1,023,564
2011 0.01000 2029 879,138
17
Table 2.18. Consumption Estimation- Italy.
Consumption
2000 0.00825 2025 706,021
2006 0.01904 2027 1,693,623
2007 0.02071 2027 1,851,813
2008 0.02394 2028 2,090,806
2011 0.01744 2027 1,513,607
Since consumption forecasting based on different countries is determined, these values are added
to Figure 2.4. and years are expanded to 2035. However, as in Figure 2.5. , Germany data points
are so distant from others that graph became unclear. Because of this, Germany data points are
eliminated. Also graph is normalized to obtain more accurate trend line equations.
3 YMA
Germany
35,000,000 Austria
France
30,000,000
Denmark
25,000,000 Italy
Polynomial
Polinom.
Consumption (kg/year)
(3 YMA)
20,000,000 Log. (3
Logarithmic
YMA)
Doğrusal
Linear
15,000,000 (3 YMA)
Üs (3
Exponential
YMA)
10,000,000 y = 770.07x2 + 7731.2x - 16136
R² = 0.9606
y = 2720.7x1.6696
5,000,000 R² = 0.8596
y = 18852x - 47868
0
R² = 0.935
0
16
10
12
14
18
20
22
24
26
28
30
32
34
-5,000,000 y = 100063ln(x) - 98400

R² = 0.8201
Year
Figure 2.5. Future Consumption.

18
3 YMA
Austria
3500000 France
Denmark
Italy
3000000
Polynomial
Polinom.
(3 YMA)
Log. (3
Logarithmic
2500000 YMA)
Doğrusal
Linear
(3 YMA)
Üs (3
Exponential
YMA)
2000000
y = 770.07x2 + 7731.2x - 16136
Consumption(kg/y)
R² = 0.9606
1500000
y = 2720.7x1.6696
R² = 0.8596
1000000
y = 18852x - 47868
R² = 0.935
500000
y = 100063ln(x) - 98400
R² = 0.8201
0
4
28
0
10
12
14
16
18
20
22
24
26
30
32
34
-500000
Year
Figure 2.6. Future Consumption with Normalized Year.

19
When figure 2.6 is examined, the R2 values are 0.8201 for logarithmic, 0.8596 for power, 0.935
for linear and 0.9606 for second order polynomial trend line. The best fits are achieved for linear
and second order polynomial trend lines but it is clearly seen that 2nd order polynomial trend line
is below Italy and Denmark but above France and Austria values. Therefore it is more
convenient to choose that trend line with equation:
y = 770.07x2 + 7731.2x - 16136
Since there is no production present in Turkey, it is planned to supply 100% need of the market.
As a result, production capacity of the plant for 2030 is estimated as 1,020 tonnes.
Table 2.19. Production Capacity.
Year Production Year Production

2015 337,845 2025 753,987
2016 372,528 2026 804,072
2017 408,752 2027 855,698
2018 446,516 2028 908,863
2019 485,820 2029 963,568
2020 526,664 2030 1,019,814
2021 569,049 2031 1,077,600
2022 612,973 2032 1,136,926
2023 658,438 2033 1,197,792
2024 705,443 2034 1,260,198
20
3. PROCESS SELECTION AND DESCRIPTION
3.1. Propionic Acid Production Methods
3.1.1. Chemical Processes
Several processes exist for the production of propionic acid. These include the Reppe process
from ethylene, carbon monoxide and steam, and the Larson process from ethanol and carbon
monoxide using boron trifluoride as a catalyst. The acid is also obtained by oxidation of
propionaldehyde, as a by-product in the Fischer-Tropsch process for the synthesis of fuel and in
wood distillation as a by-product of the pyrolysis. Very pure propionic acid can be obtained from
propionitrile.
Fewer supplies and the higher cost of oil, the opportunity to use by-products of the food industry
as inexpensive media, the increasing consumer demand for organic natural products and the
emergence of more efficient fermentation processes have led to a new opportunity for microbial
production to be economically attractive.
3.1.1.1. Reppe Process (Oxo Process)
A branch of industrial chemistry that is based on reactions of acetylene under high pressure and
also of the products so obtained and that includes vinylation, ethynylation, polymerization to
cyclic compounds, and carbonylation.(Ullmann's, 2011)
Hydroformylation of olefins is an important and largest scale application of homogeneous

catalysis in industry, used for the manufacture of aldehydes and alcohols. Hydroformylation of
ethylene is one such example leading to propionaldehyde and n-propanol as major products
having applications such as solvent, intermediates in the manufacture of pharmaceuticals,
pesticides, and perfumery products. (Bigelow, 1947)
Propionaldehyde is mainly produced through Reppe Process, by combining synthesis gas

(carbon monoxide and hydrogen) with ethylene using a metal catalyst. (Figure 3.1) In general,
this reaction is catalyzed by Rh (Rhodium) catalyst. The reaction takes place at around 100
and 15 atm. (Deshpande, 1998)
21
Figure 3.1. Reppe Process for Propionic acid formation.
After formation of propionaldehyde, it is processed by oxygen to form propionic acid. This

oxidation process occurs between temperatures 60 and 90 and pressure at 2 atm. (US
2011/0087038)
3.1.1.2. Larson Process
Larson Process is the preparation of propionic acid and esters but particularly the preparation of
propionic acid by the interaction of ethanol and carbon monoxide in the presence of boron
fluoric as the catalyst. (Ullmann's, 2011) This mechanism provides the preparation of propionic
acid exceedingly high yields from ethanol and carbon monoxide. This process can be carried out
at temperature between 125 and 1800 , and at pressure between 16 atm and 25 atm.
3.1.1.3. Fischer-Tropsch Process
The Fischer–Tropsch process (or Fischer–Tropsch Synthesis) is a set of chemical reactions that
convert a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. (Ullmann's,
2011) The process, a key component of gas to liquids technology, produces a petroleum
substitute, typically from coal, natural gas or biomass for use as synthetic lubrication oil and as
synthetic fuel.
The Fischer–Tropsch process involves a series of chemical reactions that lead to a variety of
hydrocarbons. Useful reactions give alkanes:
(2n+1) H2 n CO → CnH(2n+2)+ n H2O
where 'n' is a positive integer. The formation of methane (n = 1) is generally unwanted. Most of
the alkanes produced tend to be straight-chain alkanes, although some branched alkanes are also
formed. In addition to alkane formation, competing reactions result in the formation of alkenes,
22
as well as alcohols and other oxygenated hydrocarbons. Usually, only relatively small quantities
of these non-alkane products are formed, although catalysts favoring some of these products
have been developed. (Rofer-DePoorter, 1981)
Generally, the Fischer–Tropsch process is operated in the temperature range of 150–300 °C (302
– 5 2 °F . Higher temperatures lead to faster reactions and higher conversion rates but also tend
to favor methane production. (Ullmann's, 2011) As a result, the temperature is usually
maintained at the low to middle part of the range. Increasing the pressure leads to higher
conversion rates and also favors formation of long-chained alkanes both of which are desirable.
Typical pressures range from one to several tens of atmospheres. Even higher pressures would be
favorable, but the benefits may not justify the additional costs of high-pressure equipment.
3.1.2. Fermentation Processes
The first works on propionic acid fermentation resulted in the formulation of the Fitz equation:
3 Lactic Acid → 2 Propionic Acid 1 Acetic Acid 1 CO2 + 1 H20
or
1.5 Glucose → 2 Propionic Acid 1 Acetic Acid 1 CO2 + 1 H20
Theoretical maximum yields are 54.8% (w/w) as propionic acid and 77% as total acids.
Formation of propionic acid is accompanied by the formation of acetate for stoichiometric
reasons and to maintain hydrogen and redox balances. The dicarboxylic acid pathway is the most
common pathway for the formation of propionic acid. The acrylic pathway, restricted to a few
species of bacteria (Clostridium propionicum, Megasphaera elsdenii, Bacteroides ruminicola),
also leads to propionic acid formation.
3.1.3 Result of Selection
Oxidation of propionaldehyde is chosen for carrying out this project. This project aims to
produce propionic acid catalytically so biological methods are not taken into account in making
the decision. Oxidation of propionaldehyde gives a high yield with high selectivity of propionic
acid. A high selectivity means less undesired product which are easily manageable. In addition to
that, this process requires significantly lower temperature and pressure values. Lower operating
conditions mean less energy requirement and therefore less cost. Lower temperature and pressure
values are good in a safety point of view. Working with lower operating conditions decreases the
risk of an explosion and also decreases the losses in case of one. When these reasons are taken
23
into consideration, it was concluded that the oxidation of propionaldehyde route is more
preferable.
3.2 Patent Selection
Table 3.1. Comparison of Selected Patents.
Data Raw Catalyst Conversion- Operating Product Total

PATENTS Pollution
Availability Material Requirement selectivity Conditions Purity
Rating 8 4 5 7 9 6 7
US 3989747 6 7 5 5 5 7 6 265
US 5410091 9 8 8 8 7 7 9 368
US
9 8 7 8 9 8 9 387
2011/0087038
US 4008270 4 8 5 4 6 5 6 243
US 3989675 6 7 4 6 5 7 4 253
US
3 7 4 3 4 6 6 213
2007/0299280
US 3944603 6 8 7 3 6 4 5 249
US 4732855 7 6 7 6 3 3 6 244
US 7629491
3 6 4 5 4 6 5 210
B2
The aim of this project is to produce propionic acid in Turkey. The design capacity for the
production is found to be 1020 tons per year. This capacity is defined after brief researching
through both domestic and international market.
The corresponding processes for the production are selected after eliminating several patents.
These patents were searched through internet and libraries and analyzed in details. In order to
figure out the most appropriate path to propionic acid formation from ethylene, syngas and
oxygen; patent analysis is conducted through qualitative and quantitative assessment. Different
ratings are given to chosen parameters according to their relative importance in decisions making
24
process. Then the patents are given points out of 10 for each of these parameters. A weighted
sum is calculated for each of the patents and the ones with the highest sums are chosen to be
used in this project.
The highest rating is given to the operating conditions because it is considered to be one of the
most important parameters in decision making process. Operating conditions is directly related
with cost. High temperature and pressure values costs more money and it also increases the risk
of hazardous conditions to emerge. Patents with lower operating conditions are given higher
points for this parameter.
One of the most crucial aspects of the selection is the availability of data. Lack of data may cause
some problems in operation. Sufficient information is one of the key elements in certain
assessment. It is also important to gather all the information from the same source because
different sources might give information that do not match with each other well.
High reactor conversion is recommended for an efficient manufacturing procedure. High

conversion is not enough alone for choosing one patent over the other. Selectivity of the process
should also be high. High selectivity along with high conversion means a high fraction of the raw
materials is converted to the desired product. Because of this, conversion and selectivity is given
a high rating.
Another criterion in making the decision about the patent is the price of the raw materials. The
price of the raw materials is important because it directly affects the cost of the product. The
points given to the patents for this criterion are more or less the same since all the patents use
almost the same raw materials.
Catalyst specification and cost is essential during the process selection due to price and servicing
stability. Costly catalysis can make up its adverse impact on price by extending the life-time of
the procedure therefore the catalysts requirement costs and switch lifetime specifications are
examined throughout the patents simultaneously.
Purity is also taken into consideration in decision making process. The product should be at
certain purity so that it can be sold in the market. In addition to that, if the purity of product is
low, further separation will be necessary which means additional cost. Because of that, purity is
given a high rating.
Two patents got higher total score than the others so this project is composed with the
combination of these. US patent 2011/0087038 has gained the highest score due its moderate
25
operating conditions, thus low operating costs and also high selectivity and conversion in the
reactions. This patent is used in the second part of the process where propionaldehyde is
oxidized to produce propionic acid. US 5410091 got the second highest point and it is used for
the first part of the process where syngas and ethylene react to produce propionaldehyde.
3.3 Simple Flow Diagram
Figure 3.2. Simple Flow Diagram.

26
The syngas and ethylene are fed to the system and are brought to the operating conditions for the
first reactor, which are 15 atm and 100 ˚C. Syngas and ethylene react in the first reactor to
produce propionaldehyde. Oxygen is also fed to the system and is mixed with the feed leaving
the first reactor. The mixture is brought to the operating conditions of the second reactor which
are 2 atm and 5 ˚C. In this reactor, oxidation of propionaldehyde takes place to produce
propionic acid. The feed leaving the second reactor is sent to a separator where propionic acid is
obtained with a high purity.
3.4 Plant Site Location
The location of the plant is chosen to Kütahya, Tavsanlı. There are several reasons for this
choice. Firstly, this plant location is close to the raw materials. Syngas is bought from Turkish
Petroleum Company, which is located in Tavsanlı. The plant will be built in an industrial zone
where waste disposal facilities will be high. In addition to that, there will be plenty of labor
because of its location in an industrial zone. The climax is moderate and it will not have a
negative effect on the production.
The size of the plant site is decided to be 12000 m2. In order to estimate the cost of land,
information about the cost of various lands in Tavsanlı is collected and the average cost per m2 is
determined to be 93$. This gives a total cost of 1,120,000$ for land.
27
CHEMCAD
28
3.5 Process Description
3.5.1 Feed Preparation
In the feed preparation step, ethylene and syngas which are Stream 1 and 2, are taken at ambient
conditions and carried to the reaction conditions, namely 100 C and 15 atm. Compressors are
used to increase the temperature of the feed to the reactor conditions. These two adiabatic
compressors C 101 and C 102 increases the pressure from 1 to 3.87 and from 3.87 to 15
respectively. The compressors are operating at an efficiency of 0.75 (Sinnott and Towler, 2009).
A heat exchanger is used to balance the temperature change caused by the compressors. The feed
temperature is set to 100 C by the heat exchanger to match the reactor conditions. Here is the
detailed flow sheet of the feed preparation step:
Figure 3.4. Feed Preparation Flow Chart From ChemCad.

29
3.5.2 Oxo Process
The oxo process is carried out in the reactor R 101. The reactor operates isothermally under
100 and 15 atm pressure. The reaction between syngas and ethylene occurs under these
circumstances. The reaction can be called hydroformylation. (Figure 3.5.)
Figure 3.5. Propionaldehyde formation.
The conversion of ethylene to propionaldehyde is 0.99 in the reactor. Rhodium is used as a

catalyst. Rhodium catalyst increases the effectiveness of the process compared to cobalt catalyst
which is the predecessor. The reaction catalyzed by rhodium, also, requires lower temperature
values compared to cobalt catalyst.
3.5.3 Second Feed Preparation
After unit R 101 the exit stream is subjected to expansion. Two

expanders, E 101 and E 102, are used for decreasing the pressure
from 15 atm to, firstly, 5 atm and then 2 atm respectively. The
expander efficiencies are set as 0.8. (Sinnott and Towler, 2009)
As a result of adiabatic expansion the temperature must be
adjusted before any further progression. A heat exchanger is used
to increase the temperature of the stream to 75 which is the
required reactor temperature for the second process.
Oxygen is required for the second part of the process. An oxygen

feed at ambient conditions is projected to the system. Its
temperature is increased to match the conditions before mixing
with the exit stream of the first reactor. Oxygen is mixed with the
feed leaving the first reactor, Stream 42. The mixture is then fed
to the reactor. The process diagram for this step is as follows:
.
Figure 3.6. Second Preparation Step.
30
3.5.4 Oxidation Process
The exit stream from M 102 is fed to the reactor. The operating conditions for the reactors are
75 and 2 atm and they work isothermally. The oxidation reaction (Figure 3.8.) is performed
two times to maintain maximum oxygen usage. The conversion values of propionaldehyde to
propionic acid in the reactors are 0.937 and 0.985 respectively. The reactors, R 102 and R 103, in
this step are connected in series to achieve high conversion values. Recycle stream, Stream 12, is
sent to M 102 to mix with the feed before entering R 102. A process flow diagram for the step is
as follows:
Figure 3.7. Second and Third Reactors.
Excess amount of oxygen is used for the process to ensure the process is carried out at its
optimum conversion value.
Figure 3.8. Oxidation Reaction.

31
3.5.5 Separation
The exit stream after last recycle is fed into a separator, S 101. (Figure 3.9.) This unit separates
propionic acid from other products including some extent of unused propionaldehyde. For this
purpose, a distillation column with 12 trays is used.
Figure 3.9. Separation Unit.

32
4. CALCULATIONS
4.1. Assumptions
- The operating time is assumed to be 24 hours a day and 340 days per year. The remaining
days are reserved for the maintenance of the plant and the holidays.
- Propionic acid consumption in Turkey is assumed to be equal to TUIK
- 3-years-moving-average method is applied to consumption data to eliminate sharp
increases and decreases
- Economic growth of one country is same with the chemical’s industrial growth.
(Hortaçsu, 2004)
- Population growth of Turkey up to 2035 is taken from TUIK
- In order to calculate import & export amount of other countries, a relationship between
TUIK and UN Data of Turkey is determined and TUIK Data is preferred.
- In economical aspects, economical growth rate (alpha values) is taken as the average of
the alpha values of the related years when calculations are being conducted.
- Decreases in the import of prop acid due to economic crisis are eliminated with 3-years-
moving-average method
- European countries such as Germany, France, Italy, Denmark and Austria are assumed to
have the similar consumption trend with Turkey so their consumption amounts are
considered to make future projection.
- The production data of the European countries are obtained by taking their production
capacities into consideration. It is assumed that these countries are operating with their
full capacities between 2000-2011.
- The construction period of the plant is assumed to be 2 years and plant is assumed to
reach its full capacity in 3 years (including start-up) after construction.
- Both the salvage value and start-up costs are taken as zero.
- The tax rate is taken to be 35%. [O.R. 5]
- Location of plant is built at Tavsanli, Kütahya district to be able to provide syngas easily.
[O.R.6]
- The total area of the plant is decided to be 11,000 m2 and the cost of land is found a total
of $ 1,120,000.
- It is assumed that the plant reaches full capacity on the 3rd year of production
- Depreciation is calculated using the method of 10 years straight line method.
- Fixed capital investment is made on 2013 and working capital investment is made on
2014.
33
- Minimum acceptable rate of return is assumed to be 20% (Peters, et. al. 2004)
- Continuous operation is assumed.
- There are three reactors in the process and they operate isothermally.(U.S. Patent
5,490,011 and U.S. Patent 2011/0087038)
- First reactor is assumed to operate at 100oC and 15 atm according to the given ranges in
the chosen patent.
- Total conversion of Ethylene to Propionaldehyde in oxo process is taken from data given
in U.S. Patent 5,490,011.
- Conversion of the reactor is assumed to be 0.99 although in the patent it is given as full
conversion.
- Second and third reactors are assumed to operate at 75oC and 2 atm according to the
given ranges in the chosen patent.
- Total conversion of Propionaldehyde to Propionic Acid in oxidation reaction is taken
from data given in the U.S. Patent 2011/0087038.
- Conversion of second reactor is assumed to be 0.937 and the latter one is 0.985 although
in the patent it is given as full conversion in order to increase the total yield.(U.S. Patent
2011/0087038)
- Unreacted ethylene is inert with respect to the R-101.
- Unreacted propionaldehyde is inert with respect to the R-102 and R-103.
- The side reactions for the reactors are neglected.
- Mixers are operating with full efficiency and the enthalpy of mixing is neglected.
- For heat capacity calculations reference condition is taken as 25oC at 1 atm.
- For the gases, ideal gas heat capacity is utilized.
- All reactors have continuous flow of reactants and products and operate isothermally.
- Plug flow reactors are used.
- The reactors are assumed to be stoichiometric reactions therefore the stoichiometric ratios
are entered instead of kinetic data.
- Rhodium based catalyst was used in all reactors. (Brown, 1994)
- Compressors in the process is assumed to work adiabatically as their compression ratio is
less than 4. (Sinnott and Towler, 2009)
- The efficiencies of compressors and expanders are taken as 0.75 and 0.8 respectively.
(Sinnott and Towler, 2009)
- The compressor in the process is of reciprocating-motor type and made of carbon steel.
- Adiabatic units have very good thermal insulation.
34
- The oxygen which is introduced into the reaction mixture is generally pure oxygen.
[O.R.7]
- Heat exchangers are designed to have 1 shell and 1 tube pass.
- In S-101 column, %99.9 of propionic acid is separated from the bottom stream as well as
trace amounts of propionaldehyde, ethylene.
- Reflux ratio in the distillation column is assumed 1.2.
- L/D ratio for S-101 is 3.67.
- Distillation columns are bubble cap tray columns made of carbon steel trays for the
purpose of increasing mass transfer and S-101 has 12 trays.
- Pipe diameters are assumed as 0.3 m and the pipe lengths are taken between 3-10 m.
(ASME,2010)
- All reactors, pipes and heat exchangers are insulated with fiberglass to conduct feasible
operation.
35
4.2. Physical and Thermochemical Data
The required data which are taken from ChemCad component database are listed in the following
tables.
Table 4.1. Thermochemical Data
Component Tc (K) Pc (atm) ω Tboiling (K)

Carbon Monoxide 132.95 34.53 0.093 81.7
Ethylene 282.41 49.66 0.087 169.47
Hydrogen 33.27 12.79 -0.22 20.39
Oxygen 154.58 50.10 0.019 90.17
Propionaldehyde 504.40 48.56 0.256 321.15
Propionic Acid 600.81 45.57 0.575 414.32
Water 373.15
Table 4.2. Coefficients of liquid heat capacity equation (J/kmol.K)
Component A B C D E
Carbon Monoxide 55140 70.40 - - -
Ethylene 247390 -4428.00 40.94 -0.1697 0.00026
Hydrogen 22560 -1985.9 115.47 -1.2598 -
Oxygen 68337 -613.54 7.93 -0.0317 -
Propionaldehyde 99306 115.73 - - -
Propionic Acid 213660 -702.70 1.66 - -
Water 276000 -2090 8.13 -0.01 0
Table 4.3. Coefficients of gas heat capacity equation (J/kmol.K)
Component A B C D E
Carbon Monoxide 29108 8773 3085.1 8455 1538.2
Ethylene 33380 94790 1596.0 55100 740.8
Hydrogen 27617 9560 2466.0 3760 567.6
Oxygen 29103 10040 2526.5 9356 1153.8
Propionaldehyde 71740 191400 2014.4 117080 930.6
Propionic Acid 69590 177780 1709.8 126540 -763.8
Water 33400 26800 2610 8890 1170
Table 4.4. Molecular weights of compounds
Component Molecular Weight

Carbon Monoxide 28.010
Ethylene 28.054
Hydrogen 2.016
Oxygen 31.999
Propionaldehyde 58.080
Propionic Acid 74.079
Water 18.020
36
Table 4.5. Standard heat of formations
Component Ho (kJ\mol)
Carbon Monoxide -110.53
Ethylene 52.28
Propionaldehyde -186.30
Propionic Acid -453.50
Water -241.82
Table 4.6. Coefficients for heat of vaporization equation (J/kmol)
Component A B C D
Carbon Monoxide 8003000 0.318
Ethylene 19570000 0.686 -0.727 0.439
Hydrogen 1219900 1.429 -2.982 1.937
Propionaldehyde 41492000 0.368
Propionic Acid 40000000 1.394 -2.947 1.794
Oxygen 8040000 -0.098 0.599 -0.189
Water 52053000 0.319 -0.212 0.258
Table 4.7. Coefficients for liquid viscosity (Pa.s)
Component A B C D E
Carbon Monoxide -4.974 97.67 -1.1088 -7E-26 10
Ethylene -2.402 194.50 -1.4576
Hydrogen -11.986 26.26 -0.1774 4.4E-16 10
Propionaldehyde -9.918 839.53 -0.1674
Propionic Acid -23.931 1834.60 1.9124
Oxygen -17.27 287.5 1.2290 -1.04E22 10
Water 51.96 3671 5.73 -5.35E-29 10
Table 4.8. Coefficients for vapor viscosity (Pa.s)
Component A B C D
Carbon Monoxide 1.113E-6 0.5338 94.70
Ethylene 2.078E-6 0.4163 352.70
Hydrogen 1.560 E-7 0.7060 -5.87 210
Propionaldehyde 1.753E-7 0.7269 119.93
Propionic Acid 1.610E-7 0.7457 159.30 1.794
Oxygen 8.038E-7 0.6048 70.30
Water 2.699E-6 0.4980 1257.70 -19570
37
4.3. Material Balances
4.3.1. Production Capacity
The plant was designed to produce 100,000 tons of Propionic Acid per year. For 340 working
days hourly production would be:
tons kg 1 year 1 day kg

1020 1000
year ton 3 0 day 2 hour hour
On molar basis:
k 1 kmol kmol
125 1.
hour .0 kg hour
In order to produce 1.687 kmol/h Propionic Acid, 1.72 kmol/h Ethylene, Hydrogen and Carbon
Monoxide and 0.86 kmol/hr Oxygen should be fed to the system.
4.3.2. General Mass Balance
General mass balance equation is
Rate of mass Rate of mass Rate of mass Rate of mass

Accumulated in out generated
where F is mass flow rate.
Since steady state condition is assumed, the equation (4.1) becomes
All mass balance equation around units will be based on this equation.
4.3.2. Mass Balances on Reactors
For reactors, the sign of the generation term depends on whether it is reactant or product. Then,
the mass balance equation becomes (Fogler, 2010):
min mout (Fkey M Si 0 i component

i
i
38
Where X is the stoichiometric coefficient that is related to the conversion, S is the selectivity,
MWi is the molecular weight of the component and Fkey is the molar flow rate of the compound.
Selectivity and conversion data are obtained from the selected patents.
Reaction equations for R 101:
Ethylene + Hydrogen Carbon Monoxide → Propionaldehyde
Key component in R 101 is Ethylene and from Patent US 5,410,091 conversion of the ethylene is
0.99 with 1.0 Propionaldehyde selectivity. Stoichiometries are calculated by dividing kmol of
reacting compound to reacting kmol of key component.
1. 2 1. 2
C2 H 1 H2 1
1. 2 1. 2
1. 2 1. 2
1 C3 H O 1
1. 2 1. 2
Material balances:
min mout (Fkey M Si 0 i component

i
i
Reaction equations for R 102 and 103:
Propionaldehyde + Oxygen → Propionic Acid
Key component in R 102 and 103 is Propionaldehyde and from Patent US 2011/00870338
conversion of the ethylene is 0.937 with 1.0 Propionic Acid selectivity. Stoichiometries are
calculated by dividing kmol of reacting compound to reacting kmol of key component.
39
Table 4.9. ChemCad Mass Balance Results around Reactors.
R 101 R 102 R 103

In (kg/h) Out(kg/h) In (kg/h) Out(kg/h) In (kg/h) Out(kg/h)
Stream No 4 5 14 24 44 45
Carbon Monoxide 48.177 0.483 0.537 0.537 0.537 0.537
Ethylene 48.253 0.483 0.538 0.538 0.538 0.538
Hydrogen 3.467 0.035 0.039 0.039 0.039 0.039
Propionic Acid 0.000 0.000 14.003 132.180 132.180 140.030
Propionaldehyde 0.000 98.896 98.905 6.251 6.251 0.096
Oxygen 0.000 0.000 27.552 2.028 2.028 0.333
Total 99.897 98.897 141.574 141.573 141.573 141.573
4.3.3. Mass Balances for Separators and Flash Vessels

The general mass balance equation for the separators (4.1);
i=the component flowing into the system
j= the inflow stream
k=outflow stream from the system
When the equation (4.1) is rearranged for one inlet & two outlet case, mass balance of i th
component on the top outlet stream is determined as:
out,i in,i SF (4.3)
Where, SF is the fraction of separation and is determined for every separator. Bottom outlet
stream equation is:
out,i in,i 1-SF (4.4)
The conservation equation for any species is expressed as in the below.(Geankoplis, 2003)
out,i,top out,i,bottom in,i (4.5)

out,i,bottom in,i (4.6)
out,i,top
ChemCad results of the material balance around the separators are tabulated in the following
table.
40
Table 4.10. Mass Balance Results for S 101.
S-101 Feed (kg/h) Top (kg/h) Bottom (kg/h)

Stream No 51 17 52
Carbon Monoxide 0.483 0.478 0.005
Ethylene 0.484 0.460 0.024
Hydrogen 0.035 0.035 0.000
Propionic Acid 126.028 2.823 123.205
Propionaldehyde 0.087 0.040 0.047
Oxygen 0.299 0.297 0.002
TOTAL 127.416 4.133 123.283
Table 4.11. Mass Balance Results for F 101.
S-101 Feed (kg/h) Vapor (kg/h) Liquid (kg/h)

Stream No 34 11 27
Water 174.746 0.046 174.700
TOTAL 174.746 0.046 174.700
4.3.4. Mass Balances for Heat Exchangers

Since there are no Accumulation and generation in exchangers,
mout,i = min,i i=component
Table 4.12. Mass Balance for Heat Exchangers.
H 101 H 102
Components In (kg/h) Out(kg/h) In (kg/h) Out(kg/h)
Stream 33 7 50 48
Carbon Monoxide 48.177 48.177 0.483 0.483
Ethylene 48.253 48.253 0.484 0.484
Hydrogen 3.467 3.467 0.035 0.035
Propionic Acid 0.000 0.000 0.000 0.000
Oxygen 0.000 0.000 27.519 27.519
Total 99.897 99.897 127.417 127.417
Stream
Water 174.746 174.746 174.746 174.746
Total 174.746 174.746 174.746 174.746
41
4.3.5. Mass Balances for Compressor and Expanders

Since there are no accumulation and generation in the compressor and expanders,
mout,i = min,i i=component
Table 4.13. Mass Balance for Compressors.
C101 C 102 C 103

Components In (kg/h) Out(kg/h) In (kg/h) Out(kg/h) In (kg/h) Out(kg/h)
Stream 19 31 32 6 35 8
Carbon Monoxide 48.177 48.177 48.177 48.177 0.000 0.000
Ethylene 48.253 48.253 48.253 48.253 0.000 0.000
Hydrogen 3.467 3.467 3.467 3.467 0.000 0.000
Propionic Acid 0.000 0.000 0.000 0.000 0.000 0.000
Oxygen 0.000 0.000 0.000 0.000 27.519 27.519
Total 99.897 99.897 99.897 99.897 27.519 27.519
Table 4.14. Mass Balance for Expanders.
E 101 E 102
Components In (kg/h) Out(kg/h) In (kg/h) Out(kg/h)
Stream 40 22 41 23
Carbon Monoxide 0.483 0.483 0.483 0.483
Ethylene 0.483 0.483 0.483 0.483
Hydrogen 0.035 0.035 0.035 0.035
Propionic Acid 0.000 0.000 0.000 0.000
Oxygen 0.000 0.000 0.000 0.000
Total 98.897 98.897 98.897 98.897
4.3.6. Mass Balances for Mixers and Dividers

Mass balance equation around the mixer is:
j = inflow stream to the mixer. Mixers have two inlet streams and one outlet stream; however,
dividers have one inlet stream and two outlet streams.
42
Table 4.15. Mass Balance for Mixers.
M 101 M 102
Components In (kg/h) Out (kg/h) In (kg/h) Out (kg/h)
Stream 29 30 3 42 43 49
Carbon Monoxide 0.000 48.177 48.177 0.483 0.000 0.483
Ethylene 48.253 0.000 48.253 0.484 0.000 0.484
Hydrogen 0.000 3.467 3.467 0.035 0.000 0.035
Propionic Acid 0.000 0.000 0.000 0.000 0.000 0.000
Oxygen 0.000 0.000 0.000 0.000 27.519 27.519
Total 48.253 51.644 99.897 98.897 27.519 127.416
Table 4.16. Mass Balance for Mixers (Continued)

M 103
Components In (kg/h) Out (kg/h)
Stream 47 12 13
Ethylene 0.484 0.054 0.538
Hydrogen 0.035 0.004 0.039
Propionic Acid 0.000 14.003 14.003
Oxygen 27.519 0.033 27.552
Total 127.417 14.157 141.574
Table 4.17. Mass Balance for Dividers
D 101
Components In (kg/h) Out (kg/h)
Stream 46 9 16
Ethylene 0.538 0.054 0.484
Hydrogen 0.039 0.004 0.035
Propionic Acid 140.030 14.002 126.028
Oxygen 0.333 0.034 0.299
Total 141.573 14.157 127.416
43
4.4. Energy Balances
A general equation can be stated for the conservation of energy:
Since the system is at steady state, is equal to 0. For heat duty,
(4.8)
4.4.1 Energy Balances Around Reactors
For the energy calculations residual enthalpy is taken into account due to the non-ideality of the
conditions. Lee-Kesler Correlation which uses a modified form of the Benedict/Webb/Rubin
equation is used for the following calculations. (Smith et. al, 2005)
The values of and are gained from Lee-Kesler by using the

reduced temperature and pressure data.
(4.10)
(4.11)
The values of residual enthalpy HR are obtained from the following equation.
44
From Equations 4. (9-16)., Following tables 4.16 and 4.17 are calculated.
Table 4.18. Energy Balances of Inlet Stream of R 101.
Carbon
0.434 -0.713 0.002 0.046 0.137 0.003 -55.49
Monoxide
Ethylene 0.302 10.799 -0.187 0.327 0.086 0.169 -447.7
Hydrogen 1.173 -0.417 0.074 0.001 0.139 2.51E-06 9.57
Propionaldehyde 0.309 0.432 -0.600 1.478 -0.471 3.459 -3198.63
Table 4.19. Energy Balances of Outlet Stream of R 101.
Carbon
0.434 -0.713 0.002 0.046 0.137 0.003 -55.50
Monoxide
Ethylene 0.302 10.799 -0.187 0.327 0.086 0.170 -447.84
Hydrogen 1.173 -0.417 0.0742 0.001 0.139 2.51E-06 9.57
Propionaldehyde 0.309 0.432 -0.601 1.478 -0.471 3.461 -3199.28
Ideal enthalpy is calculated by:
(4.17)
Heat of formation values are taken from ChemCad as in Table 4.5.
The mean heat capacity formulas for vapors can be calculated following equation :
(4.18)
where A,B,C,D and E are tabulated in Table 4.3.
Finally, Hact can be calculated as the equation (4.19) :
(4.19)
45
Observing the difference between inlet and outlet streams of the reactor, the value of heat duty is
found:
(4.20)
Table 4.20. Energy Balances of Reactors.
R-101 R-102 R-103

Inlet Outlet Inlet Outlet Inlet Outlet
Stream
4 5 14 24 44 45
No
Enthalpy
-91.457 -350.989 -404.320 -873.204 -873.204 -901.909
(MJ/h)
Heat Duty
-259.532 -468.884 -28.705
(MJ/h)
4.4.2 Energy Balances Around Heat Exchangers

In order to calculate the energy requirement of a heat exchanger, the heat load has to be
calculated by simply utilizing the same formula (4.20);
Again the enthalpies of the streams can be calculated by the given procedure above. The phase of
the streams has to be taken into account and proper calculation way has to be used. Since there is
no reaction taking place in the heat exchanger the composition of the feed and the exit streams
remains the same.
For the heat exchanger H 101, the inlet stream is Stream 33 and exit stream is Stream 7. Water
is coming from stream 28, and exiting stream 21. So the energy balance for this unit is;
Table 4.21. Energy Balances of Heat Exchangers.
H-101 H-102
Inlet Outlet Inlet Outlet
Stream No 33 28 7 21 50 26 48 25
Temperatur
386.45 25.00 96.38 100.12 39.53 95.00 55.36 46.45
e (°C
Enthalpy
-30.262 -2771.244 -91.457 -2710.049 -349.678 -2720.032 -314.131 -2755.579
(MJ/h)
Heat Duty
-259.532 35.547
(MJ/h)
46
4.4.3 Energy Balances Around Distillation Column and Flash Vessel

In distillation columns, the inlet feed, top and bottom products can be in different phases. Liquid and
gas heat capacity are calculated from different equations according to the data given in Table 4.2 and
4.3. The overall enthalpy is the difference between the feed stream and sum of enthalpy of top and
bottom products.
(4.21)
Table 4.22. Energy Balances of Distillation Column.
S-101
Feed Top Bottom
Stream No 51 17 52
Temperature
75.00 132.60 153.49
(°C
Enthalpy
-811.717 -17.399 -767.538
(MJ/h)
Heat Duty
31.195
(MJ/h)
Table 4.23. Energy Balances of Flash Vessel.
F-101
Feed Top Bottom
Stream No 34 11 27
Temperature
100.07 95.00 95.00
(°C
Enthalpy
-2716.299 -7.329 -2720.032
(MJ/h)
Heat Duty
-11,062
(MJ/h)
4.4.4. Energy Balance Around Compressors and Expanders

Since the compressors and expanders operate as the similar principles but reverse action, the
energy balance of these units are shown together.
The work required (or produced) for adiabatic compressors and expanders are found from the
given formula below, (Sinnott and Towler, 2009)
where,
47
Ta: Inlet temperature , °R

γ: Cp/Cv
P: Power of compressor , hp.
: efficiency
: the volume of gas compressed, ft3/min
There are two compressor in the process in order to pump the gaseous mixtures into the system.
For this compressor C-101 whose inlet stream is Stream 19 and outlet stream is Stream 31, the
general energy balance is;
W is the work done by the compressor. Also it has to be stated that the compressor works
adiabatically.
For expander E-101, the inlet stream is Stream 40 and the outlet stream is Stream 22. The energy
balance is;
W is the work done by the expander.
Table 4.24. Energy Balances of Compressors.
C-101 C-102 C-103

Inlet Outlet Inlet Outlet Inlet Outlet
Stream
19 31 32 6 35 8
No
Pressure
1 3.87 3.87 15 1 2
(atm)
Enthalpy
-100.183 -71.018 -71.018 -29.544 -2.09E-7 2.193
(MJ/h)
Heat Duty
29.164 41.474 2.193
(MJ/h)
48
Table 4.25. Energy Balances of Expanders.
E-101 E-102
Stream
40 22 41 23
No
Pressure
15 5 5 2
(atm)
Enthalpy
-350.989 -351.333 -351.333 -351.861
(MJ/h)
Heat Duty
-0.344 -0.528
(MJ/h)
4.4.5 Energy Balances for Mixers and Dividers

The inlet and outlet conditions for a mixer and divider is almost the same and in such a case the
enthalpy of vapor (or liquid) does not changed due to the mixing. In other words, the enthalpy of
mixing vanishes. No heat duty is present.
Table 4.26. Energy Balances of Mixers and Dividers.
M-101 M-102
Stream No 29 30 3 43 42 49
Enthalpy
89.929 -190.112 -100.183 2.193 -351.861 -349.668
(MJ/h)
Heat Duty
0 0
(MJ/h)
M-103 D-101
Stream No 47 12 13 46 9 16
Enthalpy
-314.098 -90.191 -404.289 -901.909 -90.191 -811.718
(MJ/h)
Heat Duty
0 0
(MJ/h)
49
4.5. Unit Design Calculations
4.5.1. Unit Design Calculations for Reactors
R 101
First reactor of the process is an isothermal PFR where reaction between Ethylene and syngas
occurs to form propionaldehyde. The reactor works at 100 and 15 atm. The reaction that takes
place is shown below. Key component is Ethylene and from Patent US 5410091conversion of
the ethylene is 0.99.
H2 + CO + CH2 = CH2 → CH3CH2CHO
Relevant rate expressions found from literature [Eley, 1998] is as follows,
r1 k1 CEthylene C
is rate constant which is calculated as follows,
Ea
ki Ai exp
R T
12.
k1 320 exp
R T
Where R is taken as 8.3144 J/mol K , T as K and, the units of and are m3 / kmol s and kJ
respectively.
The reaction is assumed as vapor reaction, mixed phase and the total volumetric flow is constant,
CHEMCAD result gave volume as 0.971367 m3.
Design parameters:
The length of the tubes and inner diameter of the tubes are selected as 1.8 m and 0.022 m
respectively. The length of the reactor is selected as 2m.This selection depends on real life
industrial applications. [ASME Tanks & CNC]
The diameter of the reactor is calculated by assuming it as a cylinder and a bottom surface area
of 0.5 m2. The necessary number of tubes is 1358.
50
The cooling water amount can be calculated by using the heat duty value from CHEMCAD
results which is -259.636MJ/h. The water amount can be estimated from,
Rhodium catalyst is used for this process. The catalyst amount is given in the patent as a
proportional amount to the feed of the reactor. It is found as 433 kg annually.
R 102
Propionic acid production occurs in an isothermal PFR. The reactor works at 75 and 2 atm.
Relevant reaction is given below. Key component in the reactor is propionaldehyde and from
Patent US20110087038 conversion is 0.937.
CH3CH2COH ½ O2 → CH3CH2COOH
Relevant rate expressions found from literature [NIST, 2013] is as follows,
r1 k1 CPropionaldehyde C
, is rate constant which is calculated as follows,
Ea
ki Ai exp
R T
1 33
k1 exp
R T
Where R is taken as 6.132 ft lb K-1 g-mol-1 , T as K and, the units of and are ft3 / kmol s
and btu respectively.
51
Design parameters:
respectively. The length of the reactor is selected as 1.5m.This selection depends on real life
R 103
Propionic acid production occurs in an isothermal PFR. Relevant reaction is given below. The
reactor works at 75 and 2 atm. Key component in the reactor is propionaldehyde and from
Patent US20110087038 conversion is 0.985.
CH3CH2COH ½ O2 → CH3CH2COOH
Relevant rate expressions found from literature [NIST, 2013] is as follows,
r1 k1 CPropionaldehyde C
, is rate constant which is calculated as follows,

52
Ea
ki Ai exp
R T
1 33
k1 exp
R T
Where R is taken as 6.132 ft lb K-1 g-mol-1 , T as K and, the units of and are ft3 / kmol s
and btu respectively.
Design parameters:
respectively. The length of the reactor is selected as 2.8m.This selection depends on real life
53
4.5.2. Unit Design Calculations for Distillations
As the first step of distillation column design, the top and bottom temperatures are to be found. A
trial and error procedure is necessary to estimate the bottom temperature.
where K is the vapor-liquid equilibrium coefficient and xi is the liquid mole fraction of
component i. From Raoult’s Law
Pi is the vapor pressure of the component i at a given temperature and P is the total pressure. The
relative volatilities of the components are calculated by the division of K values of each
component to the K value of the heavy key.
The vapor pressures are calculated using the following equation from ChemCad. The equation
gives the pressure values in Pa.
The coefficients for the calculation of vapor pressures are given in Table 4.27
Table 4.27 Vapor pressure coefficients of components.
Substance A B C D E
Carbon monoxide 124.200 -1815.0 -22.734 0.11795 1
Ethylene 48.173 -2301.7 -4.579 1.563 10-5 2
Hydrogen 12.752 -95.133 1.095 0.00034 2
Propionic acid 54.552 -7149.4 -4.277 1.18 10-18 6
Propionaldehyde 80.581 -5896.1 -8.930 8.22 10-6 2
Oxygen 52.486 -1213.4 -6.706 0.029764 1
Water 72.550 -7206.7 -7.139 4.046 10-6 2
At the assumed temperature, the vapor pressure is calculated. By using the vapor pressure the
vapor-liquid equilibrium coefficients are calculated. This procedure is done until = 1. The
temperature at which the summation becomes 1 is the bottom temperature.
54
The same procedure is followed for the calculation of the top temperature. However, there is one
difference. For calculation of the top temperature, the following equation should be satisfied
After finding the top and bottom temperatures, the minimum number of stages is calculated from
the Fenske Equation.
where LK/HK is the geometric average of the relative volatility of the light key at the top and
bottom temperatures and it is given by
As the first step for the calculation of Rm the following equation is used. (Sinnott et al, 2009):
ith a trial and error procedure the value of θ is found. After finding the value of θ, the
minimum reflux ratio is calculated by the use of following equation (Sinnott et al, 2009):
The reflux ratio is chosen between 1.2-1.5 Rmin as a rule of thumb.
After calculating R and Rmin the following values are calculated. They are used in determining
the ideal number of stages by Erbar-Maddox Correlation
55
After finding these values, the Figure from Sinnott and Towler is used to find the value of Nm/N.
Nm was calculated previously so it is easy to determine the number of ideal stages.
Kirkbride correlation can be used to find the feed location to the column (Sinnott et al,2009)
In this equation Ne and Ns are the number of stages above and below the feed location. Knowing
the number of trays, the exact location of feed point can be estimated.
Knowing the ideal number of trays, the actual number of trays can be calculated as
In order to find actual number of trays, column efficiency is needed. O’Connell correlation gives
reasonable results with an error around %10. The analytical formula derived by Eduljee is used
to calculate the column efficiency (Sinnott et al, 2009) :
E0 = 51 – 32.5 log (µa a)
where µa is viscosity of the mixture. The viscosity values are calculated by the equation given in
ChemCad.
The constants used in this calculation from Table 4.8:
For the calculation of the diameter of the column, the following equation is used (Sinnott et al,
2009)
where Ṽw is the maximum vapor rate and ûv is the maximum allowable vapor velocity. In order
to find the maximum allowable vapor velocity, the equation by Souders and Brown can be used
(Sinnott et al,2009)
56
where is the plate spacing.
For these calculations, the densities of liquid and vapor are necessary. The vapor density is
calculated by making use of the ideal gas equation. For the calculation of the liquid density, the
following formula from ChemCad is used:
The constants used in this equation are given in the following table:
Table 4.28. Constants for liquid density calculation.
Substance A B C D
Carbon monoxide 2.944 0.27655 132.92 0.29053
Ethylene 2.1433 0.28061 282.36 0.28571
Hydrogen 5.384 0.3473 33.18 0.2756
Propionic acid 1.1041 0.25659 600.81 0.26874
Oxygen 3.9143 0.28772 154.48 0.2924
Water 5.459 0.30542 647.13 0.081
The plate spacing can have a value between 0.15 and 1.0 m. The height of the column can be
calculated by
= Nact ɭt
The specifications for the distillation column is given in the following table:
Table 4.29. Design Parameters for Distillation Column
Real Stage 12
Height 6.6 m
Diameter 1.84 m
4.5.3. Unit Design Calculations for Flash Drum

In flash drum, F-101, liquid and gas water is separated. The operating temperature and pressure
are 95 0C and 1 atm respectively. For designing the flash drum, first L/V ratio is calculated.
57
Here, yi/xi is the equilibrium distribution coefficient, Ki. If the validity of Raoult’s law is
assumed, Ki becomes;
Saturation vapor pressure of components are obtained from Antoine’s equation.
The Antoine constants for water is taken (Sinnott and Towler, 2009) and tabulated below with
the equilibrium distribution coefficients for the operating condition of distillation column.
Table 4.30. Antoine constants and equilibrium distribution coefficients
A B C
H2O 18.3036 3816.44 -46.13
After inserting equilibrium coefficient, Antoine equation takes the following form;
First, K values of all components are calculated. Then, an L/V ratio is assumed. Using teabove
equation V is found and using the proper new value for L is obtained. Hence, a new value is
obtained for L/V ratio. This procedure goes on until the two L/V ratios hold. After iterations,
L/V ratio is found to be 0.2. This procedure is the same done in the distillation column part.
The total flow rate and the liquid vapor mass ratio are used to calculate the mass flow rates of
both liquid and vapor in the feed stream. Mass flow rates are converted to molar flow rates by
dividing mass flow rate to molecular weight of streams.
Determination of Liquid Volume
The specific volume of liquid is found by using the Rackett equation. (Smith, et al., 2005)
58
Table 4.31. Critical volume and compressibility factors of water (Sinnott and Towler, 2009)
Vc
Zc
[m3/mol]
H2O 0.056 0.229
For the mixture, the linear combination of the critical properties are calculated by using their
fractions.
The total liquid volume of flash drum can be found by multiplying the specific volume of liquid
with molar flow rate of liquid and the residence time.
Determination of Vapor volume
Specific volume of vapor is calculated by using Redlich/Kwong equation. (Smith, et al., 2005)
Table 4.32. Critical pressure and temperature values of the components (Sinnott and Towler,
2009)
Pc [bar] Tc [K]
H2O 220.5 647.3
59
For the mixture, the linear combination of the critical properties are calculated by using their
fractions.
A trial and error procedure to the Redlich/Kwong equation is applied for finding the specific
volume of vapor. The total volume of vapor is calculated by taking residence time into
consideration.
Determination of the size of the Flash Drum
A cylindrical drum with L/D ratio of 3.16 is used. The drum consists of cylindrical shell and two
hemispherical heads.
From the above equation, L and D are found.
Thickness for the cylindrical part of drum can be estimated using the following formula (Sinnott
and Towler, 2009):
where E and S are found from Table 13.2 (Sinnott and Towler, 2009) for carbon steel.
For the hemispherical parts, the following equation estimates the wall thickness:
60
Table 4.33. Dimensions of F-101
V [m3] 14.09
L/D 2.88
L [m] 5.3
D [m] 1.84
t [mm] 2.4
4.5.4. Unit Design Calculations for Heat Exchangers
There are two heat exchangers in the system. Both heat exchangers are one shell one tube pass
heat exchangers. In order to carry out the design, the density, heat capacity, thermal conductivity
and viscosity values of stream components are calculated.
The density is calculated by the rearrangement of the ideal gas equation.
The heat capacities of the components are calculated by the following equation
In this equation the units of Cp is J/kmol-K and that of T is K. The values of the coefficients are
given in Table 4.3.
Obtained heat capacity values are multiplied by the molecular weight to get them in units of .
Heat capacity of the tube side is found by multiplying the heat capacity of each component with
their mass fraction and then adding them.
The thermal conductivity of the vapor components is calculated by
the coefficients to be used in this calculation are given in Table 4.34

61
Table 4.34. Constants for thermal conductivity.
Substance A B C
Carbon monoxide 0.000839 0.6409 86.05
Ethylene -0.012748 0.5155 -3768.1
Hydrogen 0.002547 0.7444 9
Propionic acid -9.2642 -0.8741 -1065.5
Propionaldehyde 1165.1 0.90419 5.47*109
Oxygen 0.0004943 0.734 70
Water 6.977*105 1.1243 844.9
The tube side and the shell side thermal conductivities are obtained by multiplying the thermal
conductivity value of each component with its mass fraction and then adding them all up.
For viscosity calculations, the equation given in ChemCad library is used
where the constants are given in Table 4.8. After the calculation of these parameters, amount of
heat transferred to the cooling fluid is calculated by duty of heat exchangers is calculated by:
(Sinnott, 2009)
mshell CP T
The log-mean temperature is then calculated by
(T1 t2 (T2 t1
Tlm
T t
ln 1 2
T2 t1
where
T1:tube-side inlet temperature t1: shell-side inlet temperature
T2:tube-side inlet temperature t2:shell-side inlet temperature
Ft is the temperature correction factor. In order to find this value, R and S values need to be
calculated
T1 T2
R
t2 t1
t2 t1
S
T1 t1
After calculation of R and S values, Ft is read from Figure 4.1
62
Figure 4.1. Temperature Correction Factor, Ft (Perry et al., 2008)
Temperature correction factor is necessary to find the delta mean temperature Tm. It is calculated
by the following formula
Tm Tlm Ft
In order to calculate heat transfer area an of overall heat transfer coefficient, U is assumed.
A
U Tm
After calculating the heat transfer area, the length, inner and outer diameters of the tubes are
specified. The area of one tube is calculated as
At do L
where do is the outer diameter and L is the length of the tube. After calculating the area of a tube,
the number of tubes is found by
A
Nt
At
After choosing the pitch, the bundle diameter Db, is calculated where K1 and n1 are constants for
chosen pitch pattern:
1
Nt n1
Db do
K1
63
A clearance length (Dc) is needed between the tubes and shell inner diameter which can be
obtained from Figure 4.2.
Figure 4.2. Shell-bundle clearence (Sinnott and Towler, 2009)
Shell diameter Ds is the bundle diameter and shell-bundle clearance
Ds Db Dc
Total cross-sectional flow area is calculated by:
NT
AT AC
pass per tube
Tube side heat transfer coefficient is found from the following equation.
0.1
kf kf
hi Nu i h
RePr0.33
di di w
64
ut di
Re
CP
Pr
kf
where
: Density of the tube side fluid
di: Internal diameter
µ: Viscosity of the inside fluid
L/di ratio and Reynolds numbers are calculated and the tube side heat transfer factor jh is read
from Figure 4.3.
Figure 4.3. Tube Side Heat Transfer Factors (jh) (Sinnott and Towler, 2009)
Therefore, tube side heat transfer coefficient is :
Nu h
RePr0.33
kf
ht Nu
di
65
After finding the tube side heat transfer coefficient, the shell-side heat transfer coefficient is
calculated. In order to do that, baffle spacing Ib is and tube pitch pt is chosen. Cross-flow area is
calculated by
pt do Ds lB
As
pt
Shell side equivalent diameter is calculated according to chosen pitch arrangement:
1.1 2
de (p 0.91 do 2
do t
Reynolds and Prandtl numbers for shell side are found from below equations:
us de
Re
CP
Pr
kf
Heat transfer factor jh which is required for further calculations is read from following chart
according to baffle cut value chosen
Figure 4.4 Shell-side heat-transfer factors, segmental baffles (jh) (Sinnott and Towler, 2009)
66
Shell side heat transfer coefficient:
kf
hs RePr0.33
de h
Overall heat transfer coefficient is determined from the following equation:
do
1 do 1 do 1 do ln di 1 1
Uo di hi di hid 2kw ho hod
where
Uo: overall heat transfer coefficient
ho: outside fluid heat transfer coefficient
hi: inside fluid heat transfer coefficient
hod: outside dirt coefficient
hid: inside dirt coefficient
kw: thermal conductivity of tube wall material
di: inside tube diameter
do: outside tube diameter
An iterative procedure is carried out until the percent error value is smaller than the allowable
error percentage.
The tube side pressure drop is calculated by
L ut 2
Pt Np f
2.5
di 2
The shell side pressure drop is calculated from the following equation
1 Ds L us 2
Ps ( f
2 de lB 2
67
The specifications for the distillation column are given in the following table
Table 4.35. Design Parameters for Heat Exchangers.
H 101 H 102
2
U (W/m .K) 90.59 241.33
Area per shell (m2) 1.19 2.41
Tube diameter (m) 0.0191 0.0191
Tube length (m) 1 1.1
Number of tubes 22 40
Shell diameter (m) 0.17 0.19
4.5.5. Unit Designs Calculations for Compressors and Expanders
For compressor power, the value of is necessary. Calculation of requires an iterative

procedure since the outlet temperature is not known. Since the compressor is operating
adiabatically, the following equation can be written
and the value of is found from
The below equation is made use of to calculate the ideal gas heat capacity
In this equation the units of Cp is J/kmol-K and that of T is K. The values of the coefficients are
given in Table 4.8.
Mean heat capacity is found by using the following equation
First a Tout is assumed and the value of Cp,mean is estimated at this temperature. is calculated
with the calculated Cp,mean and the new outlet temperature is found from . This procedure is
repeated until convergence is achieved. After calculating the outlet temperature, the power is
calculated from
68
Where
is the volume of gas compressed
is the efficiency of the compressor
Tin is the inlet temperature
The results obtained for the compressors are given in the table below
Table 4.36. Unit Design Calculation Result for Compressors.
C 101 C 102 C 103

1.33 1.27 1.40
Power (kW) 8.06 11.56 0.61
Outlet T (˚C 188.8 389.5 113.8
The expanders are also assumed to be working adiabatically. Expander design is carried out in a
similar manner to the compressor design. The results obtained for the expenders are in the table
below.
Table 4.37. Unit Design Calculation Result for Expanders.
E 101 E 102
1.27 1.24
Power (kW) -0.05 0.19
Outlet T (˚C 96 64.3
69
5. ECONOMIC ANALYSIS
The purpose of performing this project is to investigate whether one can make profit from the
industrial production of propionic acid. Up to now, market is analyzed and required amount is
calculated. The process that will produce it is designed. What needed now is to make an economic
feasibility analysis that the production is related with. Land, construction, utilities, services, labor etc.
are examples of sources of costs and revenue coming from sales is the income. In order to pay all
costs, a Total Capital Investment is needed at the beginning. The capital needed to supply the
required manufacturing and plant facilities is called the Fixed Capital Investment (FCI), while that
necessary for the operation of the plant is termed the Working Capital (WC). (Peters et. al,2004)
5.1.Fixed Capital Investment
5.1.1. Purchased Equipment Cost Estimation

The cost of purchased equipment is the basis of several predesign methods for estimating capital
investment.(Peters et al., 2004) For this purpose, cost of each plant unit according to their
specifications are calculated from reference tables and figures. Since the charts used are giving
the result of base years, costs are updated to 2013 in accordance with Chemical Engineering Cost
Index (CEPCI).
Table 5.1. Chemical Engineering Plant Cost Index for 1987-2012 [O.R.8]
Year CEPCI Year CEPCI

1987 324 2000 394.1
1988 343 2001 394.3
1989 355 2002 390.4
1990 357.6 2003 402
1991 361.3 2004 444.2
1992 358.2 2005 468.2
1993 359.2 2006 499.6
1994 368.1 2007 525.4
1995 381.1 2008 575.4
1996 381.7 2009 521.9
1997 386.5 2010 550.8
1998 389.5 2011 585.7
1999 390.6 2012 584.6
Obtained data is plotted as in Figure 5.1, and extrapolated to 2013 with the equations of 2nd
order, 3rd order and 4th order polynomial trend line. CEPCI of 2013 is determined as 588.9.
70
CEPCI
800
y = -0.0052x4 + 41.242x3 - 123734x2 + 2E+08x -
8E+10
R² 0.9 9
600
y = 0.4443x2 - 1766.9x + 2E+06
R² 0.9
CEPCI
400 CEPCI
Polinom. (CEPCI)
Polinom. (CEPCI)
200
0
1985 1990 1995 2000 2005 2010 2015
YEAR
Figure 5.1. CEPCI Plot for Extrapolation
5.1.1.1. Purchased Equipment Cost of Heat Exchangers

There two heat exchangers in the process; first one cools down the raw material mixture stream
and second one heat up the feed the stream for second and third reactors. Both heat exchangers
are one shell-one pass tube type. The cost is determined by the chart in Figure 5.2 where heat
surface area is the key determiner. However, surface area of H 101 is 1.19 m2 and 2.41 m2 for
H102; much smaller than the values given in the chart. Therefore another calculation model is
needed. Heat exchangers consist of long thin pipes and a shell covering the pipes. For each
exchanger, tube cost charts and vessel cost charts are taken as models.
Table 5.2. Specifications of Heat Exchangers.

Tube Tube Shell Shell
Unit Tubes
Diameter(m) Length(m) Diameter(m) Length(m)
H101 22 0.019 1 0.17 2
H102 40 0.019 1.1 0.19 2
For each tube, cost is determined according to their diameter, and multiplied with length.
71
Figure 5.2. Purchased Cost of Welded and Screwed Pipe Per Unit Length. (Peters et al.2004)
Table 5.3. Shell Costs of Heat Exchangers.
Unit Shell Cost Total Pipe Cost($)

H 101 48 1,056
H 102 52.8 2,112
Pipes in H101 have 0.019 m diameter, from the chart purchased cost of Schedule 40 carbon steel
pipe is read as 48 $/m. There are 22 pipes that are 1 m long. Total pipe cost of H101 is:
22 1m m 1 05
For shell calculation, pressure vessel cost chart is taken as basis. Assuming 2 m length for each
vessel, cost is determined from the chart as 1,300$ for H101 and H102. Also, pressure of H101 is
15 atm (1,520 kPa) so value is multiplied with 1.6 adjustment factor which is 1 for H102.
1 300 1. 2,0 0
72
Figure 5.3. Purchased Cost of Horizontal Storage Vessels. (Peters et al.2004)
Costs determined from the chart are for 2002; therefore each heat exchanger cost is updated to
2013 by CEPCI.
5 .9
313 , 30.5
390.
Table 5.4. Total Costs of Heat Exchangers.
Total Pipe
Unit Shell Cost($) Total Cost ($) Updated Cost($)
Cost($)
H101 1,056 2,080 3,136 4,730.5
H102 2,112 1,300 3,412 5,146.8
TOTAL 9,877.3
5.1.1.2. Purchased Equipment Cost of Reactors

The process includes 3 plug flow reactors; material of the reactors is selected as carbon steel.
Since the reactor is tubular; the cost estimation is assumed to be the same with shell-and-tube
heat exchanger. Volumes of the reactors are 0.97 m3, 1.13 m3, 2.25 m3. For each reactor tube
diameter, tube length, vessel diameter and length are tabulated:
Table 5.5. Tube Specifications of Reactors.
Tube Outer Tube Shell Shell

Unit Tubes
Diameter(m) Length(m) Diameter(m) Length(m)
R101 1358 0.022 1.8 0.8 2.0
R102 2066 0.022 1.4 1.0 1.5
R103 2066 0.022 2.4 1.0 2.8
73
By charts in Purchased Equipment Cost of Heat Exchanger section, cost for 0.022 m diameter
Schedule 40 carbon steel pipe is 45$/m. For R101 ,there are 1358 pipes that are 1.8 m long. Total
pipe cost of R101 is:
135 1. m 5 m 109,99
Table 5.6. Pipe Cost of Reactors.
Unit Tubes Total Pipe Cost($)
R101 1358 109,998

R102 2066 130,158
R103 2066 223,128
For vessel calculation, vessel cost chart Figure 5.3 is taken as basis. According to their outer
shell diameters , costs are determined from the chart and tabulated. Also, pressure of R101 is 15
atm (1,520 kPa) so value of R101 is multiplied with 1.6 adjustment factor.
2,200 1. 3,520
R101 gives total purchased cost as 113,518$ in 2002. By indexing the value to 2013:
5 .9
113,51 1 0,2
390.
Table 5.7. Total Cost of Reactors.
Pipe Total Updated Total

Unit Shell Cost($)
Cost($) Cost($) Cost ($)
R101 109,998 3,520 113,518 170,277
R102 130,158 2,000 132,158 198,237
R103 223,128 2,600 225,728 338,592
TOTAL 707,106
Adding to the cost reactors, insulation is needed.

For choosing insulation material, 2 well-known and used materials are compared. These are
fiberglass and mineral wool. The following figure shows thermal conductivity data for the
insulation materials chosen.
74
Figure 5.4. Thermal conductivity data for fiberglass and mineral wool. (Figure at left is for
fiberglass, and the one at right is for mineral wool) [O.R.9]
For better insulation low thermal conductivity is needed, so fiberglass is selected as the
insulation material.
For insulation purposes thermal acoustic blankets are used. [O.R.10] Blankets are selected as
2.5″ thick. This type of blankets can decrease temperature loss by 100 to 00 C. Also, noise
reduction is estimated as 10-13 DBA. The surface areas of the reactors are 5.53 m3, 5.96 m3 and
9.11 m3 for R101, R102 and R102 respectively. The commercial cost of this kind of insulation is
300 $/m2. [O.R.10] Estimated cost for usage is as follows.
Table 5.8. Total Insulation Cost of Reactors.
Equip. Cost Updated

Name cost ($)
No. ($)
12 R101 1,659 2,488
13 R102 1,788 2,682
17 R103 2,733 4,100
Total 6,180 9,270
Therefore total cost of reactors 716,376 $.
5.1.1.3. Purchased Equipment Cost of Mixers and Dividers

The plant design has 4 mixers and two dividers within. Mixers combine several input streams
and perform an adiabatic flash calculation at the output pressure of the mixer. The divider splits
an input stream into several output streams of the same composition and intensive properties.
Assuming all the mixers and dividers are motionless, Figure 5.4 helps to predict their cost by
means of diameter.
75
Figure 5.5. Cost of Motionless Mixers. (Peters et al.2004)
Table 5.9. Mixer and Divider Diameters.
Unit Name Diameter (m)

M101 0.03
M102 0.03
M103 0.03
D101 0.03
The material for all the mixers and dividers are selected as carbon steel; giving the material
adjustment factors as 1.0. Sample calculation for M101 is as follows:
0.03m diameter shows purchased cost as 600$ in 2002. By indexing the value to 2013:
5 .9
00
390.
Costs of all mixers and dividers is tabulated:
76
Table 5.10. Mixer and Divider Costs.

Unit Name Cost($)
M101 905.07
M102 905.07
M103 905.07
D101 905.07
TOTAL 3,620.28
5.1.1.4. Cost Estimation for Pipes

In order to estimate the cost for piping of the plant; the length and diameter of the pipes and
isolation methods must be determined. For the cost estimation, a step by step sample calculation
for the pipe with the unit number 19 is performed.
Throughout the process, Schedule 40 carbon steel welded pipes are used. Schedule 40 is used
because:
1. It works for most applications and is readily available.
2. In small quantities, it is only slightly more expensive than the thinner wall Schedule 120.
3. The wall is thick enough so that it will not distort when walked on.
. From 1/2" to 2", it is rated at no less than 1 0 psi at 3°F. The highest pressure typically found
at any facility is 65 psi, which is the average city water supply.
According to the diameter of the pipe, the cost of pipe in $/m is obtained from the figure (Peters
et. al, 2004):
Figure 5.6. Purchased Cost of Welded and Screwed Pipe Per Unit Length. (Peters et al,2004)
77
The diameter of the pipe is 0.03 m, so the purchased cost becomes 62 $/m. Pipe length is 10 m.
The purchased cost of the pipe itself is calculated:
10 m 2 m 20
Adding to the cost of pipe, insulation is needed. Figure shown below is used as a reference for
insulation cost estimation.
Figure 5.7. Purchased Cost of Pipe Insulation. (Peters et al., 2004)
The type of insulation is selected as 0.5 in. Fiberglass and the purchased cost of insulation is
obtained from the figure above. (Peters et. al, 2004):
From the graph, it is determined that the purchased cost of insulation is about 5.5 $/m. So the
insulation cost for the pipe becomes:
10 m 5.5 m 55
Finally, overall cost for the pipe is calculated simply by summing the costs.
620 $ + 55 $ = 675 $
With the same approach, cost estimations for all pipes are summarized in the table below:
78
Table 5.11. Purchased Cost of Piping System.

Pipe Pipe
Equip. Pipe Cost Insulation Total
Diameter Length
No. ($/m) Cost ($) Cost ($)
(m) (m)
19 0.03 10 620 55 675
20 0.03 10 620 55 675
21 0.03 3 186 16.5 202.5
22 0.03 1 62 5.5 67.5
23 0.03 5 310 27.5 337.5
24 0.03 9 558 49.5 607.5
25 0.03 10 620 55 675
26 0.03 7 434 38.5 472.5
30 0.03 7 434 38.5 472.5
31 0.03 1 62 5.5 67.5
32 0.03 2 124 11 135
33 0.03 2 124 11 135
34 0.03 5 310 27.5 337.5
35 0.03 8 496 44 540
36 0.03 11 682 60.5 742.5
37 0.03 5 310 27.5 337.5
38 0.03 6 372 33 405
39 0.03 5 310 27.5 337.5
40 0.03 7 434 38.5 472.5
41 0.03 10 620 55 675
42 0.03 10 620 55 675
43 0.03 10 620 55 675
Total 9,720
The overall cost for piping system in Jan, 2002 is calculated as 9720 $.
Using CEPCI, the present (2013) cost of piping is calculated:
5 .9
9 20 1 , 3
390.
5.1.1.5. Purchased Equipment Cost of Distillation Columns

There is one distillation column in the Propionic Acid production plant, S-101. In addition there
is also a flash separator F 101. For cost estimation first the cost of the towers are estimated from
Figure 7.3, the flash separator is also treated as a column with no trays. For the purpose the
characteristics of the columns are listed as:
79
Table 5.12. Sizes of Distillation Columns and Flash Separator.
Equipment Vertical Height Diameter

ID (m) (m)
S 101 6.6 1.84
F 101 5.3 1.84
The separation of propionic acid from liquid mixture takes place in S-101 at 2 atm. The
distillation column is designed as sieve tray columns. The purchased equipment cost of the
columns are calculated from Figure 7.4. and 7.5. as the summation of cost of vertical column and
cost of trays. The costs of the shells are read from the graph (Peters et. al. 2004):
Figure 5.8. Purchased Cost of Vertical Columns (Peters et al., 2004)
The cost of the tower can directly be read from figure 7.4. using the diameter and height of the
column. For the cost of trays, the type and material of tray are required. As the operating
pressure is much lower than 1035 kPa (150 kPa) the pressure adjustment factor is taken as 1. On
the other hand, the material used is carbon steel since there aren’t corrosive fluids, therefore the
material adjustment factor is also taken to be 1. According to the dimensions of distillation
columns S-101 and F-101, the column and tray costs are;
Cost of Vertical Column Cost Paf Maf 20,000 1 1 20,000
80
Table 5.13. Vertical column and tray costs
Equipment No Column Cost [$] Tray Cost [$/tray]

S-101 20,000 690
F-101 17,000 690
Figure 5.9. Purchased Cost of Trays in Tray Columns (Peters et al., 2004)
Since the costs of trays are given as $/tray, they must be multiplied with the number of trays.
Also, the quantity effect must be taken into consideration as multiplication. There are 12 trays in
S-101 with a quantity factor of 1.40. Since cost tray calculation of flash drum is not taken into
consideration. So, the total tray costs are;
Cost of trays Unit Cost Number of Tray uantity Factor 90 12 1. 0 11,592
Table 5.14. Total tray costs.
Equipment No Tray Cost [$]

S-101 11,592
The costs of distillation columns are the summation of total tray cost and vertical column cost.
81
Table 5.15. Cost of distillation columns in 2002.
Equipment No Cost [$]

S-101 31,592
F-101 17,000
However these costs are based on 2002 values, in order to get costs based on 2013 values, the
following step has performed.
Chemical Engineering Plant Cost Index:
2002 (January) : 390.4
2013 : 588.9
Purchased equipment cost of T-101 in 2013 is
5 .9
31,592 , 55
390.
Purchased equipment cost of F-101 in 2013 is
5 .9
1 ,000 25,
390.
Table 5.16. Cost of distillation columns in 2013.
Equipment No Cost [$]

S-101 47,655
F-101 25,644
5.1.1.6. Cost Estimation for Compressors
The capacity and the operating pressure of the compressors in our process are found to be in the
range of reciprocating compressors. (Sinnott and Towler, 2009) The power requirement of the
compressors is given below:
Table 5.17. Power Requirement of the Compressor.

Actual
Equip. Pressure Theoretical Actual
Name Efficiency power
No. out (atm) power (MJ/h) power (kW)
(MJ/h)
12 C 101 4 0.75 22.48 29.97 8.32
13 C 102 15 0.75 30.50 40.66 11.30
17 C 103 2 0.75 1.64 2.19 0.61
The compressors in the process is of reciprocating-motor type and made of carbon steel. For the
cost estimation of the compressors, figure below is used.
82
Figure 5.10. Purchased Cost of Compressors. (Peters et al., 2004)
To read the purchased equipment cost of the compressors, extrapolation is required. The figure
below shows the extrapolation according to the data given by figure above using reciprocating
motor compressor fit.
2400000
y = 671.86x + 18457
2100000
R² = 0.9906
1800000
Purchased cost, $
1500000
1200000
900000
600000
300000
0
0 500 1000 1500 2000 2500 3000 3500
Power required, kW
Figure 5.11. Graph of Purchased Cost of Compressors.
The purchased cost read from the figure above is as follows,

83
Table 5.18. Equipment cost of Compressor

Equip.
Name Cost ($)
No.
12 C 101 24,050
13 C 102 26,046
17 C 103 18,866
Total 68,962
Furthermore, material adjustment factor which is 1.0 should also be taken into consideration. But
it does not change the values so the determined cost are let unchanged.
For insulation purposes thermal acoustic blankets are used. [O.R.10]) Blankets are selected as
reduction is estimated as 10-13 DBA. The surface areas of the compressors are 1.22, 1.36, and
1.11 m2 for C101, C102, C103 respectively. The commercial cost of this kind of insulation is
300 $/m2. [O.R.10] Estimated cost for usage is as follows.
Table 5.19. Cost of insulation (compressors)

Equip.No. Name Cost ($)
12 C 101 366
13 C 102 408
17 C 103 333
Total 1,107
The total cost is calculated as follows.

9 2 110 00 9
As the purchased-cost graphs are based on year 2002, a cost index should be transformed.
Using CEPCI, the present (2013) cost of compressors is calculated:
5 .9
00 9 105, 9
390.
5.1.1.7. Cost Estimation for Expanders

The expanders being used in the process is radial type and made of carbon steel. The power
requirement of the expanders are given below:
Table 5.20. Power Requirement of the Expander
Equip. Pressure Theoretical power Actual power Actual power

Name Efficiency
No. out (atm) (MJ/h) (MJ/h) (kW)
15 E 101 8 0.8 -0.23 -0.18 -0.05
16 E 102 2 0.8 -0.86 -0.69 -0.19
84
For the cost estimation of the expanders, the figure below is used.
Figure 5.12. Purchased Cost of Expanders. (Peters et al., 2004)
To read the purchased equipment cost of the expanders, extrapolation is required. The figure
below shows the extrapolation according to the data given by figure above using radial type
expander line.
120000
100000 y = 164.58x + 13196

R² = 0.9959
Purchased cost, $
80000
60000
40000
20000
0
0 100 200 300 400 500 600
Power required, kW
Figure 5.13. Graph of Purchased Cost of Expanders.

85
The purchased costs are tabulated below.
Table 5.21. Equipment Cost of Expanders
Equip.
Name Cost ($)
No.
15 E 101 13,204
16 E 102 13,227
Total 26,431
Furthermore, material adjustment factor which is 1.0 should also be taken into consideration. But
it does not change the values so the determined cost are let unchanged.
For insulation purposes thermal acoustic blankets are used. [O.R.10] Blankets are selected as
reduction is estimated as 10-13 DBA. The surface area of the expanders are 1.45, and 1.46 m2 for
E 101, and E 102 respectively. The commercial cost of this kind of insulation is 300 $/m 2.
[O.R.10] Estimated cost for usage is as follows.
Table 5.22. Cost of insulation (expanders).

Equip.
Name Cost ($)
No.
15 E 101 435
16 E 102 438
Total 873
The total cost is calculated as follows.
2 31 3 2 30
As the purchased-cost graphs are based on year 2002, a cost index should be transformed.
Using CEPCI, the present (2013) cost of expanders is calculated:
5 .9
2 30 1,1
390.
86
5.1.1.8. Total Purchased Equipment

Finally all the purchased equipment costs per equipment are added and tabulated to give the total
purchased equipment cost:
Table 5.23. Cost of All Units.
Unit Cost ($)
Compressors 105,696
Distillation Column 47,655
Flash Drum 25,644
Heat Exchangers 9,878
Mixers & Dividers 3,620
Reactors 716,376
Pipes 9,720
Expander 41,187
Total 959,776
5.1.2. Other Costs in FCI
Purchased equipment cost is one of the elements of manufacturing part of Fixed Capital
Investment. There are another manufacturing costs such as installation of equipments,
instrumentation and controls, piping, electrical systems, buildings, yard improvements, service
facilities and land. Non-manufacturing FCI includes cost of engineering and supervision,
construction expenses, legal expenses, contractor’s fee and contingency.
Various methods can be employed for estimating capital investment. In this project, percentage
delivered equipment method is preferred where all other costs are assumed to be a percentage of
PE. Depending on the ratio factors given by Peters et al, costs are determined.
Purchased Equipment Installation: The installation of the process equipments consists of the
labor foundations, supports, platforms, construction expenses and the other factors directly
related to the erection of purchased equipment.(Peters et al,2004) In the chemical plant of
propionic acid production, the purchased-equipment installation is taken as 47 %.
Instrumentation and Controls: Instrument costs, installation labor costs and expenses for
equipments like controllers, field and control room terminal panels, alarms, indicating
instruments, control computers and local data-processing units; and control room display
graphics. The control that is required for the plant affects the amount of the cost. The percentage
of instrumentation is chosen as 25 in the propionic acid production plant.
Piping: The piping cost includes labor, valves, fittings, pipe, supports and other items involved
in the complete erection of all piping used directly in the process. (Peters et al, 2004) Since the
87
transportation of fluids is highly crucial, piping has a very high ratio, which is 72% for the
propionic acid production plant.
Electrical Systems: Power wiring, lighting, transformation and service, instrument and control
wiring are main components of electrical system. It is determined as 11%.
Buildings: The cost of buildings, including service, consists of expenses for labor, materials, and
supplies involved in the erection of all buildings connected with the plant. (Peters et al, 2004) .
Production are will be newly built, therefore it is logical to take percentage of building cost
should be taken as 45%.
Yard Improvement: Yard improvement cost involves fencing, grading, roads, sidewalks,
sidings, landscaping and similar items. (Peters et al, 2004) It is usually 10 to 20 percent of the
delivered purchased-equipment cost and for propionic acid production plant it is chosen as 10.
Service Facilities: Utilities for supplying steam, water, power, compressed air, and fuel, waste
disposal, fire protection, and miscellaneous service item such as shop, first aid, and cafeteria
equipment and facilities require capital investment that are included under the general heading of
service facilities cost. (Peters et al, 2004) The total cost for service facilities in chemical plants
generally ranges from 30 to 80 percent of the delivered purchased equipment cost. The ratio
factor is selected as 65 percent for propionic acid chemical plant since it consumes a significant
amount of utilities.
Engineering and Supervision: The costs for construction design and engineering, including
internal or licensed software, computer-based drawings, purchasing, accounting, construction
and cost engineering, travel, communications, and home office expense plus overhead, constitute
the capital investment for engineering and supervision. (Peters et al, 2004) This cost is an
indirect cost in fixed-capital investment and is approximately 30 percent of the delivered
equipment cost.
Legal Expenses: Legal costs result largely from land purchases, equipment purchase, and
construction constructs. (Peters et al, 2004) It usually varies from 1 to 4 percent of fixed capital
investment. In the propionic acid production plant, 4 percent is chosen.
Construction Expenses: Construction or field costs include the temporary construction and
operation, construction tools and rentals, home office personnel located at the construction site,
construction payroll, travel and living, taxes and insurance, and other construction overhead.
88
(Peters et al, 2004) In the propionic acid production plant the construction costs are taken as 41
percent of the delivered purchased equipment cost.
Contractor’s Fee: The contractor’s fee is taken as 22 percent of delivered equipment cost for
this process.
Contingencies: A contingency amount is included in all but the smallest estimates of capital
investment in recognition; however, there will be unexpected events and changes that inevitably
increase the cost of the project. (Peters et al, 2004) In this process, this cost is 44 percent of the
delivered equipment cost.
5.2. Working Capital
As mentioned before total capital investment is the sum of FCI and working capital which is the
capital investment for a chemical plant consists of the total amount of money invested in raw
materials and supplies carried in stock; finished products in stock and semi-finished products in
the process of being manufactured; accounts receivable; cash kept on hand for monthly payment
of operating expenses (salaries, wages) and raw material purchases; accounts payable and taxes
payable. (Peters et al,2004)
Generally, chemical plants use an initial working capital amount to 10 to 20 percent of the total
capital investment. In our case, 15 percent of delivered purchased-equipment is taken as working
capital investment.
CI 0.15/0. 5 5. M 9 0, 3
89
Table 5.24. Total Capital Investment Calculation.
Fluid Processing Propionic Acid Calculated

Plant Plant values
Direct costs
Purchase equipment delivered 100 100 1,055,754
Purchase equipment installation 47 47 496,204
Instrumentation and controls 36 25 263,938
Piping 68 72 760,142
Electrical systems 11 11 116,132
Buildings 18 45 475,089
Yard improvements 10 10 105,575
Service facilities 70 65 686,240
Total direct plant cost 360 375 3,959,078
Indirect costs
Engineering and supervision 33 30 316,726
Construction expenses 41 41 432,859
Legal expenses 4 4 42,230
Contractor’s fee 22 22 232,265
Contingency 44 44 464,531
Total indirect plant cost 144 141 1,488,613
Fixed capital investment 504 516 5,447,691
Working capital 89 111 1,117,887
Land 114 114 1,120,000
Total capital investment 707 741 7,823,137
5.3. Total Capital Investment
The total capital investment is the sum of fixed capital investment and working capital investment.
FCI+WCI = TCI,w/o land
5,447,691+1,117,887 = 6,565,578 $
5.4. Land
It has decided to locate the propionic acid chemical plant in Tavsanli, Kutahya due to lowering
transportation cost of syn-gas. Since, the plant will be constructed in an area of 12,000 m2, the
cost of land is found as 1.12 M $. [O.R.11]
90
Fixed capital investment is calculated as 5,447,691 which can be seen in the table above, adding
up the value of working capital to FCI plus land cost, total capital investment with land can be
found;
TCI FCI CI Land Cost
TCI 5, , 91 1,11 , 1,120,000 , 23,13
5.5. Total Product Cost
Total product cost is one of the essential components of an economic analysis in the plant. The
sum of operating the plant, selling the products, recovering the capital investment, contributing
to corporate functions gives the value of total product cost. It is divided into two categories:
manufacturing costs and general expenses. Manufacturing costs are also named as operating or
production cost. (Peters et al, 2004)
5.5.1. Manufacturing Costs
Manufacturing costs also known as operating costs, are connected with the manufacturing
operations or the physical equipment of a process plant itself are included in the manufacturing
costs. It is divided into three categories:
1-Variable Production Costs

2-Fixed Charges
3-Plant Overhead Costs
5.5.1.1. Variable Production Costs
All the expenses associated with the manufacturing operation are the components of variable
costs. These types of costs are expenditures of the raw materials, operating labor, operating
supervision maintenance and repair costs, operating supplies. The raw materials, labor cost and
catalyst are estimated separately.
Raw Material
In order to start the production, some chemical materials should be bought. The materials that are
directly consumed in making the final products are named as raw materials. Raw materials
involving in this process are ethylene, syn-gas and oxygen. In the heat exchangers, water is used
for heating/cooling. Operation in the plant is assumed to be 340 days/year.
91
Cost for ethylene = 0.94 $/kg [O.R.12]
Cost for syngas 3$/GJ and syngas fuel as heating value for 27.8 MJ/kg [O.R.13 & 14]
Cost for oxygen 0.7789 $/year [O.R.7]
Cost for water 0.00079 $/kg [O.R.15]
Table 5.25. Annual Cost Estimation for Ethylene.

Year of Capacity Annual required amount Annual raw material
production Utilization Ratio of raw material [tons/year] cost [$/year]
1 0.4 157.488 148,038
2 0.8 314.976 296,077
3 1 393.720 370,097
Table 5.26. Annual Cost Estimation for Synthesis Gas.

1 0.4 20.6576 5,662
2 0.8 41.3152 22,649
3 1 51.644 35,389
Table 5.27. Annual Cost Estimation for Oxygen.

1 0.4 89.82 27,984
2 0.8 179.64 111,936
3 1 224.55 174,900
Operating Labor
In general, operating labor may be divided into skilled and unskilled labor. By the help of the a
table introduced in Table 5.28, number of workers can be determined. The number of workers in
the plant is determined by considering number of units and shifts. Propionic Acid production
plant consists of 3 reactors, 2 heat exchangers, 1 distillation column, 1 flash drum, 3
compressor, 3 mixer and 1 divider.
92
Table 5.28. Determination of operating labor.
Type of Equipment Workers/unit/shift Number of Units Worker/shift

Compressor 0.2 3 0.6
Distillation Column 0.5 1 0.5
Flash Drum 0.3 1 0.3
Heat Exchanger 0.1 2 0.2
Reactor (PFR) 0.5 3 1.5
Mixer 0.3 3 0.9
Divider 0.2 1 0.2
From the table, it can be obtained that there 4.2 worker/shift is required for propionic acid plant.
If one shift is 8 hours that means there are 3 shifts in a day, the number of unskilled worker can
be calculated as following,
worker shift worker

.2 3 12.
shift day day
worker employee hours employee hours

12. 100.
day worker day
By using another method;
Figure 5.13. Operating Labor Determination Chart. (Peters et al,2004)

The process is assumed to be on average conditions(B) with 5 principal processing steps which are
feed preparation, heat exchanging step, oxo process step, oxidation step and distillation step
respectively. The labor requirements for the years are read from the table as:
93
Table 5.29. Determination of Operating Labor with Second Method.
Year Capacity Capacity Labor Labor

Utilization (kg/day) hours/day/step hours/day
2014 0.4 1223.14 8.8 44
2015 0.8 2446.27 17.6 88
2016 1 3057.84 22 110
It can be seen that two methods are giving close results, so their arithmetic average can be taken
into consideration.
110 100.
105. work hr /day
2
work hr number of worker

105. 13.1 1 worker
day work hr
The wage for unskilled worker is determined as 1.140,07 TL [O.R.16] TL/$ = 1.85 [O.R.17];
hence, the total amount of cost of unskilled workers is simply,
11 0.0 TL 1 12months
1 workers 103,531/year
month 1. 5 TL 1 year
Whereas for skilled labor, the wage is taken as 2,000 TL per month, and it is determined that
propionic acid plant requires three skilled workers. Therefore the total cost of skilled labor can
be found as;
2,000 TL 1 12months
3 workers 3 ,919/year
month 1. 5 TL 1 year
Total annual operating labor cost is calculated by;
103,531 3 ,919
1 2, 50/year
year year
Table 5.30. Determination of Operating Labor with First Method
Year Capacity Labor Cost $/ year

Utilization
2014 0.4 56.980
2015 0.8 113.960
2016 1 142.450
94
Utilities
The cost for utilities depends on the plant location and source. For propionic acid chemical plant,
utilities that have been used are electricity.
Electricity consumed in the plant during a year 974.52 MJ/h and the unit cost of electricity has
found as 18.04 KR/kwh [O.R.18] and with an exchange rate of 1.6, KR is converted to US
dollars [O.R.17] The total amount of cost for electricity is calculated as;
Hours of operation = 2 3 0 920 h yr
Power Requir ment 9 .52 M /h
Electric Requirement:
M kwh h
9 .52 0.2 920 2,1 ,115 kwh/yr
h M /h yr
kwh KR 1 TL 1 USD
2,1 ,115 1 .0 209,0 0/year
yr kwh 100 KR 1. 5 TL
5.5.1.2. Fixed Costs
Fixed costs are not affected from the amount of the production. It includes the depreciation, local
taxes, insurance, loan and interests. The financing arrangements and capital investments determine
the fixed costs.
Depreciation
Depreciation is the process that a company gradually records the loss in value of a fixed asset.
Each time a company prepares its financial statements, it records a depreciation expense to
allocate the loss in value of equipments, physical facilities, shipping, construction etc. Working
capital, land and start-up costs are not depreciable. Briefly, Fixed capital investment without land
is the depreciable amount; therefore FCI value of this project is depreciated as follows.
Depreciation results in a reduction in income tax payable in the years in which it is charged. (Peters
et al., 2004) From various depreciation methods, Straight-Line Method (SL) and Modified
Accelerated Cost Recovery System (MACRS) for 5, 7 and 10 years are examined. For SL
method, recovery period is selected as 10 years which is the determined value for chemical
production plants by Ministry of Finance. Salvage values are taken as zero.
95
Fixed Capital Investment of the project is 5,447,691 $. In straight line method, each year is
calculated as follows:
FCI 5, , 91
3 3,1 9
N 15
In MACRS method, FCI is multiplied with each year’s corresponding percentage that is given in
Table 5.31.
Table 5.31. MACRS Depreciation Rates Percentages.
MACRS Depreciation Rate %

5-year 7-year 10-year
20 14.29 10
32 24.49 18
19.2 17.49 14.4
11.52 12.49 11.52
11.52 8.93 9.22
5.76 8.92 7.37
8.93 6.55
4.46 6.55
6.56
6.55
3.28
Table 5.32 Shows the results for different depreciation rates for different methods. Turkish
Ministry of Finance allows 10 year straight line depreciation for chemical production plants.
[O.R.19]. Therefore, although MACRS 5-year method depreciates the depreciable amount in a
shorter period, SL method is selected for depreciation.
Table 5.32. Depreciation rates.
MACRS
Year SL method
5-year 7-year 10-year
1 544,769 1,089,538 778,475 544,769
2 544,769 1,743,261 1,334,139 980,584
3 544,769 1,045,957 952,802 784,468
4 544,769 627,574 680,417 627,574
5 544,769 627,574 486,479 502,277
6 544,769 313,787 485,934 401,495
7 544,769 - 486,479 356,824
8 544,769 - 242,967 356,824
9 544,769 - - 357,369
10 544,769 - - 356,824
11 - - 178,684
96
5.5.1.3. Plant-overhead Costs
The medical services or hospital costs, plant maintenance and overhead, safety services, payroll
overhead including pensions, vacation allowances, social security, and life insurance; packaging,
restaurant and recreation facilities, salvage services, control laboratories, property protection,
plant
5.5.1.4. Other Costs
The catalyst costs and the cooling water costs are calculated. It is assumed that, the catalyst,
cooling water will be changed once throughout the lifetime, in the 3rd year of operation. The
costs of changing the catalyst and cooling liquids are calculated [O.R.20] and [O.R.15]
Table 5.33. Other Investments.
Catalyst Amount Catalyst Price Total ($)

(kg) ($/kg)
Reactor 1 433 30.00 12,990
Reactor 2 260 30.00 7,800
Reactor 3 260 30.00 7,800
Changed Amount Unit Price ($/kg) Total ($)
(kg)
Water 1,425,923 0.0078 11,122
Gross Total 39,712
Table 5.34. Calculation of total product cost in the third year of operation
Item Factor Basis Cost, $/year

Raw materials Calculated separately 580,386
Operating labor Calculated separately 142,450
Operating supervision 0.15 operating labor 213,075
Utilities Calculated separately 209,080
Maintenance and repairs 0.07 FCI 381,338
Operating supplies 0.15 maintenance & repairs 57,200
Laboratory charges 0.15 operating labor 8,580
Patents and Royalties 0.01 TPC without depreciation 25,716
Fixed Charges
Depreciation Calculated separately 544,769
Local Taxes 0.02 FCI 108,954
Insurance 0.01 FCI 54,475
Rent 0 TCI 0,000
Financing 0 TCI 0,000
labor, supervision and
Plant Overhead Costs 0.65 478,961
maintenance
General Expenses
97
Administration 0.20 labor 28,490

Distribution & marketing 0.05 TPC without depreciation 128,579
Research & development 0.06 TPC without depreciation 154,295
0.88 of TPC without depreciation 2,262,989
TPC without Depreciation 2,571,578
5.6. Annual Revenue
The selling price of propionic acid is 8.00 $/kg [O.R.21] The annual total revenue is then
calculated for the year 2016:
propionic acid
Revenue201 1,005,353 kg .00 ,0 2, 2
year kg p.acid
The values for all years are tabulated:
Table 5.35. Revenue From Sales.
Year Sales Revenue $/year

2014 1 3,217,130
2015 2 6,434,259
2016 3 8,042,824
2017 4 8,042,824
2018 5 8,042,824
2019 6 8,042,824
2020 7 8,042,824
2021 8 8,042,824
2022 9 8,042,824
2023 10 8,042,824
2024 11 8,042,824
2025 12 8,042,824
2026 13 8,042,824
2027 14 8,042,824
2028 15 8,042,824
2029 16 8,042,824
2030 17 8,042,824
5.7. Cash Flow Analysis
Cash flow of a company over a period is equal to the change in cash balance over this period.
Briefly, for a production plant sales revenue (s) is the inflow and operating costs (c) is the
outflow of the balance. In order to calculate net cash flow, firstly, depreciation (d) is subtracted
from gross profit which is the difference of sales and operating costs. Then, income taxes are
subtracted and net profit is obtained. Lastly, depreciation is added to net profit and net cash flow
is determined.
98
Gross profit with depreciation s co d
Income Taxes (s co d
Net profit (s co d (s co d (s co d (1
Net cash flow (s co d (1 d
Sales revenue that is going to be obtained from propionic acid, depreciation and costs are already
calculated. First two years are considered as the start-up period operation. Fixed capital
investment and land cost are organized to be paid at the end of first year whereas working capital
investment will be paid at the end of second year. Also, plant is assumed to achieve full capacity
production at the fifth year, which is the third year of production. Income tax rate is determined
as 35% [O.R.5]
99
Table 5.36. Annual Cash Flow And Cumulative Cash Flow Table
Total
End
Year Sales Product Other Gross
of Investment Depr. Net profit Cash Flow CCF DCF DCCF
(Norm.) Revenue Cost (ex. cost profit
Year
depr.)
2013 1 -6,567,691 - - - - - - -6,567,691 -6,567,691 -6,567,691 -6,567,691
2014 2 -1,117,887 - - - - - - -1,117,887 -7,685,578 -1,016,261 -7,583,952
2015 3 - 3,217,130 1,028,631 15,885 554,769 1,617,845 1,051,599 1,606,368 -6,079,210 1,327,577 -6,256,375
2016 4 - 6,434,259 2,057,262 31,770 544,769 3,800,458 2,470,298 3,015,067 -3,064,143 2,265,264 -3,991,111
2017 5 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 657,023 2,541,607 -1,449,504
2018 6 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 4,378,190 2,310,551 861,048
2019 7 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 8,099,356 2,100,501 2,961,549
2020 8 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 11,820,522 1,909,547 4,871,096
2021 9 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 15,541,688 1,735,952 6,607,047
2022 10 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 19,262,855 1,578,138 8,185,185
2023 11 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 22,984,021 1,434,671 9,619,856
2024 12 - 8,042,824 2,571,578 39,712 544,769 4,886,765 3,176,397 3,721,166 26,705,187 1,304,246 10,924,102
2025 13 - 8,042,824 2,571,578 39,712 - 5,431,534 3,530,497 3,530,497 30,235,684 1,124,925 12,049,027
2026 14 - 8,042,824 2,571,578 39,712 - 5,431,534 3,530,497 3,530,497 33,766,181 1,022,659 13,071,686
2027 15 - 8,042,824 2,571,578 39,712 - 5,431,534 3,530,497 3,530,497 37,296,679 929,690 14,001,376
2028 16 - 8,042,824 2,571,578 39,712 - 5,431,534 3,530,497 3,530,497 40,827,176 845,173 14,846,549
2029 17 - 8,042,824 2,571,578 39,712 - 5,431,534 3,530,497 3,530,497 44,357,673 768,339 15,614,888
2030 18 2,237,887 8,042,824 2,571,578 39,712 - 5,431,534 3,530,497 3,530,497 47,888,170 698,490 16,313,378
100
5,000,000
4,000,000
3,000,000
2,000,000
Cash flow ($/year)
1,000,000
0
-1,000,000 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
-2,000,000
-3,000,000
-4,000,000
-5,000,000
-6,000,000
-7,000,000
-8,000,000
Year (normalized)
Figure 5.14. Annual Cash Flow Chart.
60,000,000
50,000,000
40,000,000
Cash flow ($/year)
30,000,000
20,000,000
10,000,000
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
-10,000,000
-20,000,000
Year (normalized)
Figure 5.15. Cumulative Cash Flow Chart.

101
5.7.1. Profitability Analysis
The main objective of design this project is to examine whether it can make profit or not under
economic perspective. This part includes the calculations on the purpose of analyzing the
profitability of the project with various profitability methods; three of them do not consider the
time value of money whereas two other methods considers.
5.7.1.1. Methods that do not consider the Time Value of Money
Return on Investment (ROI) Method :
ROI is a performance measure used to evaluate the efficiency of an investment or to compare the
efficiency of a number of different investments. To calculate ROI, annual net profit is divided by
total cost of the investment; the result is expressed as a percentage or a ratio. The return on
investment formula:
N
(1/N 1 Np, Np,ave
ROI
TCI TCI
ROI is usually used to compare different investment choices for the same project to determine
the better option. In this analysis, ROI value is compared with minimum acceptable return which
is the rate of earning that must be achieved by an investment in order for it to be acceptable to
the investor. For this project, minimum acceptable rate of return is determined as 20% from the
Table 8-1 in PTW. Propionic acid production is not present in Turkey; so it will newly enter into
the established market.
As it can be seen in the Cash Flow Analysis table, total net profit in 16 years is $. By dividing
the value to the years, average net profit is calculated as 3,132,254 $/year. Since total capital
investment is 7,611,986 $.
ROI 100 0
, 23,13
Since ROI exceeds the minimum acceptable return which is 20% it can be said that project is
worthwhile and the project is feasible for the investment.
102
Payback Period Method :
Payback period is the length of time necessary for the total return to equal the capital investment.
It is calculated with the following formula, where V is manufacturing fixed-capital investment,
Ax is the nonmanufacturing fixed-capital investment, V+Ax is the fixed capital investment, and
Aj the annual cash flow.
V Ax
PBP
A
Aj is the summation of average net profit ( Np,ave ) and average depreciation dj,ave.
V Ax V Ax
PBP
(1/N N 1 A Np,ave d ,ave
V Ax 5, , 91
PBP 1. year
Np,ave d ,ave 3,132,25 5 , 9
In order to investigate the economic feasibility of the project, PBP calculated is compared with a
reference payback period obtained from the minimum acceptable rate of return (mar) . which is
equal to 0.20. An approximated value for reference can be obtained by; (Peters et al., 2004)
0. 5 0.
PBPref 3. 0 years
mar 0. 5/N 0.2 0. 5/1
So, the payback period for the proposed project is lower than the reference payback period;
which means the proposed project is worthwhile to make investment.
Net Return Method :
The net return method calculates the amount of cash flow over and above that required to meet
the minimum acceptable rate of return and recover the total capital investment. The net return is
calculated by:
N N N
Rn Np, d rec TCI mar N TCI

1 b b
Where Rn is the net return in dollars and recj the dollars recovered from the working capital and
the sale of physical assets (equipment, buildings, land, etc.) in year j. Where Rn is the net return
in dollars and recj the dollars recovered from the working capital and the sale of physical assets
103
(equipment, buildings, land, etc.) in year j. (Peters et al., 2004) By simplifying the equation
becomes:
Rn Np,ave mar TCI
Rn 3,132,25 0.2 , 23,13 1,5 , 2
Since the value obtained is greater than zero; it means that the cash flow to project is greater than
the amount necessary to repay the investment and obtain a return that meets the minimum
acceptable rate. As a result, project is investible.
5.7.1.2. Methods That Consider the Time Value of Money
Net Present Value :
Net present value (NPV) is the present value of an investment's expected cash inflows minus the
costs of acquiring the investment.
N N
NPV P Fcf,i s c0 d 1 d – P Fv TCI

1 b
Where NPW is the net present worth, PWFcf,i the selected present worth factor for the cash
flows in year j, sj the value of sales in year j, coj the total product cost not including depreciation
in year j, PWFv,j the appropriate present worth factor for investments occurring in year j, and
TCIj the total investment in year j. An earning rate is incorporated into the present worth factors
by the discount rate used. (Peters et al.,2004)
Another way of calculating net present value is to tabulate each year’s cash flow value and
discount it to the investment years. This method is already applied in Table5.35. and discounted
cumulative cash flow value in the last year is the net present worth of the project.
NPV= 47,888,170 $
The net present worth is positive, then the project provides a return at a rate greater than the
discount rate 10% used in the calculations. Therefore the project is profitable.
104
Discounted Cash Flow Rate of Return :
The discounted cash flow rate of return is the return obtained from an investment in which all
investments and cash flows are discounted. It is determined by setting the NPW equal to zero
and solving for the discount rate that satisfies the resulting equation. (Peters et al., 2004)
N N
0 P Fcf, s c0 d 1 d – P Fv TCI
1 b
Since NPV that is calculated does not equals zero, the discounted cash flow rate of return of the
project must be re-calculated from the equation above, which requires an iterative procedure. By
using Excel solver, discount rate that makes NPV zero is determined as 31.16 %.
105
6. DISCUSSION
to design the plant accordingly. In order to estimate the consumption trend, a comprehensive
market search is carried out. The consumption trend is important because it will be used in
determining the production capacity of the plant.
6.1 Evaluation of the Capacity
The capacity of the plant is determined to be 1019.8 tonnes per year. This is the estimated
production value in 2030. Consumption data is needed to estimate the total market volume. In
order to estimate the consumption values, production, import and export data are needed. There
is no production of propionic acid in Turkey. The import and export data is taken from the
database of TUIK and is cross checked with UN data. The data taken from TUIK and UN data
for import and export values are tabulated in Table 2.1.
After cross checking of the data, 3 year and 5 year moving averages are done to eliminate sharp
increases and decreases. By applying moving averages, a smoother data is obtained. This can be
seen in Figure 2.3. After plotting the data, linear, logarithmic, second order polynomial and
power trend lines are fitted. The R2 values obtained from these ranged between 0.8201 and
0.9606.
For predicting the future value of consumption, the current consumption values of Germany,
France, Italy, Denmark and Austria are taken. In deciding which countries to choose, the
similarity of the economic structure was the criteria. Countries such as USA or China are not
taken into consideration because they are highly industrialized. Choosing these countries would
not result in realistic future guesses. In addition to that, chemical consumption per capita and the
economic profiles of the countries were taken into consideration in deciding which countries to
use as a model.
As a result of all these steps, the trend that propionic acid consumption of Turkey is going to
follow is determined as the 2nd order polynomial trend line. The plant is expected to operate until
2030. It is desired to produce %100 of the market share. This can be possible since there are no
propionic acid producers in Turkey. The base design capacity is estimated to be 1019.8 tonnes
per year.
106
6.2 Process Selection
The process selected involves the reaction of ethylene with carbon monoxide and hydrogen to
produce propionaldehyde, which is then oxidized to produce propionic acid. The reaction
conditions for both steps are reasonable. The highest operating temperature for the reactions is
around 100 ˚C which is not very high. The highest pressure value is 15 atm. Especially the patent
used for the production of propionaldehyde gives lower operating conditions for the reactions
when it is compared to other patents for the same process. The patents used for both steps give a
high conversion and selectivity value.
The main advantage of the process used is that it requires lower operating conditions compared
to other production methods. Lower temperature and pressure values mean that less energy will
be spent and it will result in a lower production cost. In addition to this, the method chosen gives
high conversion and selectivity values. A high selectivity value means that less money will be
spent on the production of the undesired products. The reactions that are taking place are all
exothermic. This means that, cooling water will be necessary to maintain isothermal operation in
the reactors. The cooling water will be heated for this purpose. This heated water can be used in
the heat exchangers for heating purposes. This could decrease the energy consumption.
In addition to these economic advantages, the process also has some environmental advantages.
One of these advantages is related with the high selectivity values for these processes. A high
selectivity value means that, there will be less amount of undesired product that is going to be
separated and removed to the environment.
The plant site selection is also reasonable. The plant is to be constructed at a site close to the raw
materials of the process. In addition to that, the plant is to be constructed in an organized
industrial site, where the potential number of labors and waste treatment facilities are high.
Because of these reasons, it is possible to say that the chosen plant site has many advantages and
it is a successful choice.
The process has the advantages listed above. However, there are some risks involved in the
process. The reactions that are taking place are all exothermic reactions. Cooling water is needed
to obtain isothermal operation in the reactors. In case of an interruption of cooling water to the
reactors, the reactor temperature might increase significantly. This might result in an explosion.
In addition to that, some flammable materials, such as ethylene and carbon monoxide, are used
in this process. Even a spark can result in a fire.
107
Considering the advantages and possible risks of the design, it is possible to conclude that the
design is advantageous and satisfactory. This process is the process that is used by Dow
Chemicals. This fact supports the claim about the success of the design and process.
6.3 Justification of Assumptions
In deciding for the base case capacity of the plant, it was assumed that no investment will be
made on propionic acid. Currently, there are no propionic acid producers in Turkey and it was
assumed that no investment other than this one would be made. Capacity is chosen to supply for
the %100 of the Turkey. This assumption might not hold because propionic acid is gaining
importance because it is used in a wide range of industries. Because of that, there may be other
investments in Turkey to produce propionic acid.
It is also assumed that the economic growth of a country is the same with the chemical’s
industrial growth. This assumption is reasonable since the economic growth of a country is
highly related with the industrial growth. Industry is an important part of the economy and this
assumption should be valid.
For deciding on the future consumption data, European countries were taken as models. This
assumption is valid because Turkey is getting industrialized quite fast and it is very possible that
it will catch up with the European countries taken into consideration in the next years.
The operating period of the plant was assumed to be 340 days per year. The remaining days are
reserved for maintenance. Since the number of the units is not high, 25 days should be enough
for maintenance and this assumption should be valid.
It was assumed that the start-up period of the plant is 2 years. When a literature search is made, it
is seen that the startup period for most chemical industries is between 2 and 5 years. Because of
this, the assumption is valid.
In addition to these, formation of undesired products was neglected because of the high
selectivity values of the reactions. This assumption is valid and can be supported by the patents
selected.
Isothermal operation was assumed for the reactors. Since the reactions are exothermic, an
adiabatic reactor could not be used because of the dramatic temperature rises. Isothermal
operation assumption is valid and it can be obtained by the use of a water jacket.
108
The compressors are assumed to be working adiabatically. This assumption is hard to achieve in
real life situations. In order to obtain adiabatic operation, equipment should be very well
insulated. Perfect insulation prevents energy losses and under perfect insulation conditions
adiabatic operation assumption can be made.
The fluids are assumed to be compressible and Lee-Kesler correlations are made use of in energy
balance calculations. Lee-Kesler correlations can be used for a wide range of temperature and
pressure and therefore this assumption is valid.
For the depreciation calculations, straight line depreciation with 10 years is used. Straight line
depreciation does not allow fast recovery of capital in early years. A method such as MACRS is
good for fast recovery of capital in the early years. MACRS is composed of double-declining
method and straight-line method. The depreciated amounts are calculated for each year by the
two methods and the higher value of depreciation is used in MACRS. Looking at this
information, it is obvious that the use of MACRS method would be more beneficial. However,
straight line method is used instead because MACRS type of depreciation is not allowed in
Turkey. In addition to this, the salvage value is assumed to be zero. The depreciable amount is
therefore the difference between the fixed capital investment and the value of the land. The
assumption about the salvage value is a reasonable one since the machines are not thrown away
when they are still useful.
The plant is assumed to reach %40 of the total capacity in the first year, which means a capacity
utilization ratio of 0.4. The capacity utilization ration for the second and the following years are
assumed to be 0.8 and 1.0 respectively. This is a reasonable assumption since the plants work at
a lower capacity to avoid loss of money. There might be specification and product problems in
the first years of plant operation. Because of that, the capacity is kept at a lower level to avoid
production of out-of-spec products and to allow for tuning of the operation units.
Minimum rate of return is assumed to be 0.20 from (Peters et. al, 2004). This is a reasonable rate
of return value since this will be the first propionic acid producing plant in Turkey. The discount
rate is taken as 0.10 which is a widely used value and which is acceptable.
The pipes are assumed to be made of carbon steel. Since the materials in the system are not
corrosive and carbon steel has a relatively low price, this assumption is reasonable.
As a result it is possible to say that the assumptions will not contradict with the expected results
and they are valid.
109
6.4 Interpretation of Results
The market volume estimation resulted in a value of 1020 tonnes per year. This capacity is quite
low for a continuous operation. A batch operation could be more suitable for production of
propionic acid. In addition to that, the calculated capacity is consistent with the regime seen in
the European countries. In this sense, the capacity estimation is considered to be successful.
There are both negative and positive values for energy requirements of heat exchangers. A
negative value for energy requirement means that the exchanger is used for cooling purposes
whereas a positive value of energy requirement is for heating purposes. The energy requirement
values are quite low since the flow rates are low.
The highest value of heat duty is in the reactors is around -470 MJ/h. The reactions taking place
in the reactors are all exothermic. The negative value of the heat duty is a result of the
exothermic nature of the reactions. The heat duty value is quite low since the amounts of
reactants entering the reactors are also low. The exothermic nature of the reactions is the main
reason for using an isothermal reactor. If an adiabatic reactor was used instead a very high
temperature rise would be obtained. This could result in an explosion.
The height and diameter of the distillation column are estimated to be 1.84 and 6.6 m. If the L/D
ratio is calculated using these values, it is seen that this ratio is smaller than 20, which means that
the design is reasonable. The number of stages in the distillation column is found to be 12. This
is a low value because the products do not have close boiling points. 12 stages is a reasonable
value for the number of stages of a distillation column.
The highest value of power requirement for the compressors is around 11 kW. The compressors
are operating adiabatically. The power requirements of compressors are quite low which means
that the adiabatic compression ratio is tolerable. The highest value of heat output for the
expanders is around 0.2 kW. This value is very small and it is a result of the low flow rates and
low expansion ratios.
The pipes are designed to minimize the pressure drop. The pressure drop in the pipe is around
10-3 atm which is an acceptable value.
As a result it is possible to say that the obtained values are reasonable and consistent with the
design made. Because of this, the design can be described as successful.
110
6.5 Discussion of Plant Economy
6.5.1 Fixed Capital Investment
Accurate fixed capital investment estimation is very important because it is one of the major
components to get an accurate profitability analysis.
One of the first things to do was to estimate the value of CEPCI index in 2013. The value in this
year is not available. Because of that, the existing values are plotted to get an estimate for 2013.
Polynomial regression gives an R2 value of 0.97. Since the R2 value is quite high, it can be
concluded that the CEPCI estimation is a good one. CEPCI index is used in transforming the
purchased equipment cost to today’s price and therefore it is very important.
The highest purchased equipment cost comes from the reactors which are 716,376 $. The reactor
volumes range between 0.97 m3 and 2.25 m3. These are not very high reactor volumes when
compared to other commercial plants. However, these volumes are large when compared to other
units of this design. The reactors are one of the most important parts of the design. Because of
these reasons high reactor costs are reasonable and affordable.
The cost for the distillation column came out to be 47,655 $ which is not a very high value. The
main reason for such a low value of cost is that the number of trays is not a high value. Because
of this reason, the height of the column is estimated to be quite small. In addition to that, the
flow rate to the distillation column is quite low which results in a small diameter. When these are
combined, the cost for the distillation column is reasonable.
The compressors are usually the highest priced purchased equipment. However, this is not the
case in this design. The highest power requirement for the compressors was found to be around
11 kW which is a low value. The reason for such a low value is mainly the low flow rates. A low
power requirement means a low cost. The cost for compressors is estimated to be 105,696 $.
This is a low amount and it is reasonable because of the low power requirements. Expanders are
cheaper equipment due to their design (Peter et. al, 2004) The cost for expanders came out to be
lower, as expected, and the amount is estimated to be 41,187 $.
There are quite a number of pipes in the system. However, the cost of the pipelines is quite low,
namely 9,720 $. This value is obtained after the addition of pipe fittings and insulations.
Insulation is necessary since the system is working at quite high temperatures. The cost of the
pipeline is not a very big part of the fixed capital investment and the obtained value of price is
reasonable.
111
The total cost of heat exchangers is 9,878 $ which is not a large fraction of the total purchased
equipment cost. The main reason for having such low values for heat exchangers is that the flow
rates are quite small. In addition to that, the system works at moderate temperatures. A relatively
small temperature change is to be observed across the entrance and exit of the heat exchanger.
Because of this, a small heat transfer area is needed and the cost of the heat exchangers is low.
When all these values are used in the necessary calculations, the fixed capital investment and the
total capital investment come out to be 5,447,691 $ and 7,823,137 $ respectively.
As a result, it is possible to conclude that even though this is a preliminary design, the fixed
capital investment is reasonable.
6.5.2 Total Product Cost
The total product cost is calculated for 0.4, 0.8 and 1.0 utilization ratios and the values for these
different ratios came out to be 148000$, 296,000$ and 370,000$ respectively. These costs are
calculated separately since the production cost does not linearly depend on production cost.
The raw material cost came out to be 580386$. This is a quite high fraction of total product cost.
However, this was expected because ethylene and oxygen are expensive raw materials. Pure
oxygen is fed to the system instead of air. Because of this, it is expected that oxygen would have
a high cost. The main reason for using pure oxygen instead of air is that using pure oxygen
results in smaller feeds and smaller equipment.
The utility cost is estimated to be 209,080 $, which is not a very high value for a commercial
plant. The plant operates at a low capacity. Because of that, the electric cost was not expected to
be very high. As a result, it is possible to say that the estimated electricity cost is reasonable.
Maintenance cost is directly related with the purchased equipment cost. The reason for that is
that more equipment will require more maintenance cost. The maintenance cost is estimated to
be 381,338 $ which is a quite high value when compared to total product cost. This value is
reasonable because of relatively high purchased equipment cost.
The labor costs came out to be a relatively small value. This is mainly because the plant is highly
automatized. Another reason for that might be the low production capacity. The value estimated
for labor cost is 142,450 $ which is a reasonable value.
The cost for the catalyst is estimated to be 28,590 $. However, this amount will not be paid on a
yearly basis. The catalyst has a certain lifetime and it will be necessary to pay for the catalyst
112
only at the end of its lifetime. Therefore, this amount will be paid only twice or three times
during the operation of the plant.
For the depreciation calculation, straight line method with 10 years is used even though MACRS
method is better for fast recovery of money. The reason for using straight line method is that
MACRS method is not allowed in Turkey. A depreciation amount of 544,769 $ is charged for 10
years and is used in profitability analysis.
As a result it is seen that the fixed capital investment makes up a high fraction of the total capital
investment. This is reasonable for a highly automated plant with low production capacity, which
is the case in this project.
6.5.3 Cash Flow
Table 5.36 shows that the cash flow is negative for the investment period. It is positive in the
production periods. The sales revenue at full capacity is estimated to be 8,042,824 $ and it is
assumed to stay the same since the chemical prices tend to stay the same. The annual cash flow
more or less stays the same after the full capacity is reached. In the last year, a big increase in
cash flow is observed. The reason for that is that the working capital and the land are recovered
at the final year of operation. When the cumulative cash flow is checked, it is seen that the
cumulative cash flow becomes positive in the 5th year. This means that the investment is fully
recovered in 5 year. In the final year of operation, the cumulative cash flow is estimated as
47,888,170 $. In this calculation, the time value of money is not taken into account.
A more realistic approach involves the time value of money in cash flow analysis. The time
value of money is important because money today is worth more than money tomorrow. When
Table 5.36 is investigated, it is seen that the discounted cash flow is positive for all the operation
years. It can also be seen that, it takes more time for discounted cash flow to reach positive
values. The surplus at the end of operation time is found to be 16,313,378 $ which is
significantly lower than the value calculated without taking discount rate into account.
6.5.4 Profitability Analysis
For carrying out profitability analysis by methods that do not consider the time value of money,
three different tests are done. The average return on investment is found to be 40% which is
much higher than the minimum acceptable rate of 20%. This means that the investment will
bring a large profit and the capital will be recovered in a short period of time.
113
Secondly, the payback period method gives a value of 1.48 for the value of payback period. This
value is significantly lower than the reference value of 3.4 years. This result means that this
design is worth to invest.
Lastly, the net return method is used. The net return is found by subtracting the minimum
acceptable rate of return from the cumulative cash flow. The net return is estimated to be
1,5 , 2 $ which is higher than zero. This means that the plant will yield a profit and the design
is worth to invest.
Looking at the results above, it is seen that all methods that do not consider the time value of
money are on the same line which is the expected result. All of these methods give a result that
the project is worth to invest.
When the time value of money is taken into account, it is expected that the profitability will
decrease. The reason for that is that the investments are made in early years and therefore they
are not discounted or discounted slightly. On the other hand, the revenue is obtained in later
years and is discounted more. The discounted cumulative cash flow is found to be 16,313,378 $
at the end of operation time which is higher than zero. This means that the project will yield a
profit. Since this value came out to be positive, a larger return will be obtained compared to m ar.
This amount of return is found by DCFR method. After carrying out the necessary calculations, a
net discounted return of 31.16 % is obtained. This means that the project is profitable when the
time value of money is taken into account.
As a result, it is possible to say that this project is worth to invest whether the time value of
money is taken into account or not. Both methods result in profit. However, this is a preliminary
calculation and there might be deviations as large as 20%. Therefore, the investment should be
made with care.
114
7. CONCLUSION
to design the plant accordingly. Two of the biggest producers of propionic acid are BASF and
Dow Chemicals. In order to estimate the future consumption data, and thus the design capacity,
consumption data of Italy, France, Austria and Denmark is used. The necessary data in carrying
out this calculation is taken from the databases of TUIK and UN Data. The base design capacity
is determined to be 1019.8 tonnes per year. For the production, the route using the oxidation of
propionaldehyde is chosen. US5410091 is used for obtaining propionaldehyde from ethylene,
carbon monoxide and hydrogen. US2011/0087038 is used for the oxidation of propionaldehyde.
For carrying out the production, the feeds to the system are ethylene, carbon monoxide,
hydrogen and oxygen. ChemCad is used for the simulation of the system. The temperature range
is between 25˚C and 390˚C. The pressure range is between 1 atm and 15 atm.
Assuming an operation period of 340 days per year, the amount of ethylene, carbon monoxide,
hydrogen and oxygen feeds to the system are 393.74, 393.13, 28.29 and 224.56 tonnes per year
respectively. The purity of the obtained product is 99.9%.
The fixed capital investment is estimated to be 5.5 million $ and the total capital investment is
7.6 million $. Straight line method with 10 year period is used in calculating depreciation. When
a profitability analysis is made by taking the time value of money into account, the project is
found to be profitable. The plant is determined to have 1,5 , 2 net return. When the time
value of money is not taken into account, the project again came out to be profitable. A return on
investment value of 40 percent was found which shows that the project will yield a profit.
As a result, the obtained production capacity is reasonable. In addition to that, equipment designs
were carried out and the results for these are also reasonable. A profitability analysis is made by
both taking and not taking the time value of money into account. Both methods said that the
investment is profitable. Therefore, it can be concluded that the project is worth to invest.
115
REFERENCES
Bigelow, M. H., 1947, "Reppe's Acetylene Chemistry." Chemical & Engineering News vol. 25
pp. 1038-042.
Brown, A.P, 1994, "Studies of the role of Tin(II) in the rhodium(I) chloride catalysed
hydrocarbonylation of alkenes". Doctoral thesis, Durham University
ChemCAD library.
Codex Alimentarius, 2011, "Class Names and the International Numbering System for Food
Additives CAC/GL, vol.36.
Custom Steel Fabrication & ASME Tanks, Steel Fabrication, ASME Tanks, & CNC Machining.
N.p., n.d. Web. 09 Jan. 2013.
Deshpande, Raj Madhukar, Bhalchandra Mahadeo Bhanage, Sunil Sadashiv Divekar,

Subbareddiar Kanagasabapathy, and Raghunath Vitthal Chaudhari., 1998, "Kinetics of
Hydroformylation of Ethylene in a Homogeneous Medium: Comparison in Organic and
Aqueous Systems." Industrial & Engineering Chemistry Research vol. 37.6 pp. 2391-396.
Eley, D. D.,1998, Advances in Catalysis. San Diego, CA: Academic
Engineering Standards News and Resources for Engineers - ASME." Engineering Standards
News and Resources for Engineers - ASME. N.p., n.d. Web. 06 June 2013.
Fogler H. S., Elements of Chemical Reaction Engineering, Prentice Hall, 2005
Geankoplis, C. J., Transport Processes and Separation Process Principles, Prentice Hall, 2003
GiIdberg. A. and I. Raa, 1977. Properties of a propionic acid/formic acid preserved silage of cod
viscera. 1. Sci. Food Agric. vol.28 pp. 647-653
Hortaçsu, Ö., Kimya Sanayi'inde Ekonomik Değerlendirmeler, Boğaziçi University, 200
J.D. Dziezak, 1986, Food Technol., vol. 40(9), pp.105
Kirk, Raymond and Othmer, Donald, 2001, Concise Encyclopedia of Chemical Technology,
Wiley, New York.
116
NIST Chemical Kinetics Database." NIST Chemical Kinetics Database. N.p., n.d. Web. 06 June
2013..
Perry, R.H., Green, D.V., 2008, Perry’s Chemical Engineers Handbook, 8th Edition, McGraw-
Hill,
Riegel, Emil Raymond, 2007, Kent and Riegel's handbook of industrial chemistry and
biotechnology: Vol. 1, Springer.
Rofer-DePoorter and Cheryl K., 1981, "A Comprehensive Mechanism for the Fischer-Tropsch
Synthesis." Chemical Reviews vol. 81.5 pp. 447-74..
Sinnott R. and Towler G., Chemical Engineering Design, 5th Edition, 2009
Smith . M., Van Ness, M. M. Abbott, ”Introduction to Chemical Engineering

Thermodynamics”, Mcgraw Hill, 2005.
Ullmann's Encyclopedia of Industrial Chemistry. Weinheim, 2011, Wiley-VCH-Verl., Print.
Weissermel, Klaus and Arpe H.-J., 2003, Industrial Organic Chemistry, John Wiley & Sons,
New York
Wilkes J. O., 2009, Fluid Mechanics for Chemical Engineers, Prentice Hall.
Wood, H. G., 1981, "Metabolic cycles in the fermentation by propionic acid bacteria." Curr.
Top Cell Regul. vol. 18, pp.255–287
Online References
1. Worldwide usage of propionic acid:

http://www.vivid-host.com/rbi/icis/trainingcd/pdfs/Propionic_acid.pdf
2. BASF Propionic acid production :

http://www.afera.com/files_content/P510-e-
Two%20million%20tons%20of%20propionic%20acid%20made%20by%20BASF.pdf
3. Perstrop Propionic Acid production:

http://www.accessmylibrary.com/coms2/summary_0286-19471385_ITM
4. BASF's future plans for propionic acid:

http://www.chemeurope.com/en/news/66890/basf-to-increase-propionic-acid-capacity-in-
ludwigshafen-and-nanjing.html
117
5. Tax Rate for Turkey:

http://www.gib.gov.tr/fileadmin/beyannamerehberi/2013menkulsermaye.pdf
6. Syngas Production in Turkey:

http://www.hurriyetdailynews.com/turkey-holds-its-breath-for-shale-gas-and-
syngas.aspx?pageID=238&nid=41568
7.Oxygen production and price:

http://www.chemicool.com/elements/oxygen.html
8.CEPCI Values:
http://www.marshallandswift.com
9. Thermal Conductivity :
http://www.engineeringtoolbox.com/thermal-conductivity-d_429.html
10. Insulation sizes and prices :

http://www.blanket-insulation.com/HTML/energy-savings.html
11. Land in Tavsanli district:

http://www.emlak.net/19214075-Satilik-Sanayi-Arsasi-Kutahya-Eskisehir-Karayolu-5-
Kmde-Yola-Cepheli
12. Ethylene Price:

http://www.kippreport.com/fcs/gloom-over-saudi-petchem-sector-may-be-overdone/
13. Syngas Price:

http://www.ucg-gtl.com/current-issues.html
14. Syngas Heating Value

http://www.hindawi.com/journals/ame/2010/342357/
15. Water Price:

http://www.iski.gov.tr/web/statik.aspx?KID=1000484
16. Unskilled wage in Turkey:

http://www.csgb.gov.tr/csgbPortal/cgm.portal?page=asgari
17. Turkish Lira for US Dollar Parity :

http://www.bloomberg.com/quote/XU100:IND
18. Electricity Wages for Industries in Turkey:

http://www.tedas.gov.tr/BilgiBankasi/Sayfalar/ElektrikTarifeleri.aspx
19. Depreciation laws in Turkey:

http://www.alomaliye.com/vuk_tebligleri/vuk_55_ek1.htm
20. Rhodium catalyst Price:

http://www.alibaba.com/product-gs/751675289/Rhodium_catalyst.html
21. Propionic Acid Price:

http://www.alibaba.com/product-gs/651181663/Propionic_acid.html
118
119
NOMENCLATURE
A Annual Cash Flow, $
A Heat transfer area, m2
c Cost
Cp Specific Heat Capacity, J/kgmol.K
d Diameter, m
Ea Activation energy, kJ/mol
F Molar flow rate, kmol/h
g Gravitational acceleration, m/s2
GDP Gross Domestic Product
H Enthalpy, MJ/h
h Heat transfer coefficient
h Height, m
HK Heavy Key
K Vapor liquid equilibrium coefficient
k0 Pre-exponential factor
L Length, m
LK Light Key
lt Plate spacing, m
lb Baffle spacing, mm
Mass flow rate, kg/h
MA Moving Averages
120
MW Molecular weight, kg/kmol
n Number of moles
Molar flow rate, kgmol/h
NPSH Net Positive Suction Head
P Power, kW
P Pressure, atm
Pt Tube pitch, mm
q Volumetric flow rate, ft3/min
Heat duty rate, kW
R Ideal Gas Constant
R Represent the deviation of fitted line to data point
R Reflux Ratio
S Selectivity
T Temperature, K
TUIK Turkish Statistical Institute
u Linear velocity, m/s
U Overall heat transfer coefficient, W/(m2.K)
V Molar volume, m3/h
W Weight, kg
W Work, J/kg
W Bottom stream
X Conversion
x Liquid Mol fraction

121
y Vapor Mol Fraction
z Elevation, m
Greek Letters
Growth rate
Relative volatility
Difference
η Efficiency
Viscosity, Pa.s
υ Stoichiometric coefficient
Heat capacity ratio
Density, kg/ m3
Accentric Factor
Subscripts
av Average
b Bundle
bot Bottom
c Critical
e Equivalent
f Feed Stream
f Formation
i Component number “i”
i Inner
122
in Material/energy coming into the system boundaries
j Component number “ ”
key Key component
lm Logarithmic Mean
m Mean
min Minimum
mix Mixture
out Material/energy going out of the system boundaries
r Reduced
ref Reference
s Shell side
t Tube side
v Vapor
Superscripts
act Actual
ig Ideal gas
in Inlet
out Outlet
R Residual
vap Vaporization
123
APPENDIX
A.1 PATENT US 5,410,091

124
125
126
127
128
129
130
131
132
133
A.2 PATENT US 2011/0087038

134
135
136
137
138
139
140
141
142
143
144
B. ChemCad Summary
CHEMCAD 6.4.0 Page 1
Simulation: ChE_462_Group10_Final Date: 06/07/2013 Time: 10:09:17

FLOW SUMMARIES:
Stream No. 1 2 3 4
Stream Name Ethylene SynGas
Temp C 25.0000* 25.0000* 31.4451 96.9279
Pres atm 1.0000* 1.0000* 0.9700 14.9889
Enth MJ/h 89.929 -190.11 -100.18 -91.353
Vapor mass frac. 1.0000 1.0000 1.0000 1.0000
Total kmol/h 1.72 3.44 5.16 5.16
Total kg/h 48.25 51.64 99.90 99.90
Total std L m3/h 0.14 0.11 0.25 0.25
Total std V m3/h 38.55 77.10 115.65 115.65
Flow rates in kg/h
Carbon Monoxide 0.00 48.18 48.18 48.18
Ethylene 48.25 0.00 48.25 48.25
Hydrogen 0.00 3.47 3.47 3.47
Propionic Acid 0.00 0.00 0.00 0.00
Oxygen 0.00 0.00 0.00 0.00
Water 0.00 0.00 0.00 0.00
Stream No. 5 6 7 8
Stream Name
Temp C 100.0000 389.5265 96.9322 113.8274
Pres atm 15.0000 15.0000 14.9935 2.0000
Enth MJ/h -350.99 -29.544 -91.353 2.1931
Vapor mass frac. 0.010337 1.0000 1.0000 1.0000
Total kmol/h 1.75 5.16 5.16 0.86
Total kg/h 99.90 99.90 99.90 27.52
Total std L m3/h 0.12 0.25 0.25 0.02
Total std V m3/h 39.32 115.65 115.65 19.28
Flow rates in kg/h
Carbon Monoxide 0.48 48.18 48.18 0.00
Ethylene 0.48 48.25 48.25 0.00
Hydrogen 0.03 3.47 3.47 0.00
Propionic Acid 0.00 0.00 0.00 0.00
Oxygen 0.00 0.00 0.00 27.52
Water 0.00 0.00 0.00 0.00

FLOW SUMMARIES:
Stream No. 9 10 11 12
Stream Name Oxygen
Temp C 75.0000 25.0000* 95.0000 74.9995
Pres atm 1.9994 1.0000* 1.0000 1.9994
Enth MJ/h -90.191 -2.0909E-007 0.00000 -90.191
Vapor mass frac. 0.010406 1.0000 1.0000 0.010406
Total kmol/h 0.20 0.86 0.00 0.20
Total kg/h 14.16 27.52 0.00 14.16
145
Total std L m3/h 0.01 0.02 0.00 0.01

Total std V m3/h 4.39 19.28 0.00 4.39
Flow rates in kg/h
Carbon Monoxide 0.05 0.00 0.00 0.05
Ethylene 0.05 0.00 0.00 0.05
Hydrogen 0.00 0.00 0.00 0.00
Propionic Acid 14.00 0.00 0.00 14.00
Oxygen 0.03 27.52 0.00 0.03
Water 0.00 0.00 0.00 0.00
Stream No. 13 14 16 17
Stream Name
Temp C 71.8441 71.4888 75.0000 132.6081
Pres atm 1.9659 1.9348 1.9994 1.9984
Enth MJ/h -404.29 -404.29 -811.72 -17.423
Vapor mass frac. 0.84887 0.84989 0.010406 1.0000
Total kmol/h 2.81 2.81 1.76 0.10
Total kg/h 141.57 141.57 127.42 4.14
Total std L m3/h 0.16 0.16 0.13 0.01
Total std V m3/h 62.99 62.99 39.53 2.21
Flow rates in kg/h
Ethylene 0.54 0.54 0.48 0.46
Hydrogen 0.04 0.04 0.03 0.03
Propionic Acid 14.00 14.00 126.03 2.83
Oxygen 27.55 27.55 0.30 0.30
Water 0.00 0.00 0.00 0.00

FLOW SUMMARIES:
Stream No. 18 19 21 22
Stream Name
Temp C 132.6089 31.4097 100.1232 88.7295
Pres atm 1.9984 0.9446 0.9833 5.0000
Enth MJ/h -17.423 -100.18 -2709.4 -351.33
Vapor mass frac. 1.0000 1.0000 0.017235 0.069950
Total kmol/h 0.10 5.16 9.70 1.75
Total kg/h 4.14 99.90 174.75 99.90
Total std L m3/h 0.01 0.25 0.17 0.12
Total std V m3/h 2.21 115.65 217.41 39.32
Flow rates in kg/h
Carbon Monoxide 0.48 48.18 0.00 0.48
Ethylene 0.46 48.25 0.00 0.48
Hydrogen 0.03 3.47 0.00 0.03
Propionic Acid 2.83 0.00 0.00 0.00
Oxygen 0.30 0.00 0.00 0.00
Water 0.00 0.00 174.75 0.00
Stream No. 23 24 25 26
Stream Name
Temp C 64.3039 75.0000 46.4216 95.0000
Pres atm 2.0000 2.0000 0.9632 0.9998
Enth MJ/h -351.86 -873.20 -2755.6 -2720.0
Vapor mass frac. 0.17966 0.027460 0.00000 0.00000
146
Total kmol/h 1.75 2.01 9.70 9.70

Total kg/h 99.90 141.57 174.75 174.75
Total std L m3/h 0.12 0.14 0.17 0.17
Total std V m3/h 39.32 45.12 217.41 217.41
Flow rates in kg/h
Ethylene 0.48 0.54 0.00 0.00
Hydrogen 0.03 0.04 0.00 0.00
Propionic Acid 0.00 132.18 0.00 0.00
Oxygen 0.00 2.03 0.00 0.00
Water 0.00 0.00 174.75 174.75

FLOW SUMMARIES:
Stream No. 27 28 29 30
Stream Name
Temp C 95.0000 25.0000* 24.9692 36.3067
Pres atm 1.0000 1.0000* 0.9869 0.9700
Enth MJ/h -2720.0 -2771.2 89.929 -190.11
Vapor mass frac. 0.00000 0.00000 1.0000 1.0000
Total kmol/h 9.70 9.70 1.72 3.44
Total kg/h 174.75 174.75 48.25 51.64
Total std L m3/h 0.17 0.17 0.14 0.11
Total std V m3/h 217.41 217.41 38.55 77.10
Flow rates in kg/h
Carbon Monoxide 0.00 0.00 0.00 48.18
Ethylene 0.00 0.00 48.25 0.00
Hydrogen 0.00 0.00 0.00 3.47
Propionic Acid 0.00 0.00 0.00 0.00
Oxygen 0.00 0.00 0.00 0.00
Water 174.75 174.75 0.00 0.00
Stream No. 31 32 33 34
Stream Name
Temp C 189.4059 189.4023 389.5219 99.9590
Pres atm 3.8700 3.8668 14.9938 0.9775
Enth MJ/h -71.018 -71.018 -29.544 -2709.4
Vapor mass frac. 1.0000 1.0000 1.0000 0.017538
Total kmol/h 5.16 5.16 5.16 9.70
Total kg/h 99.90 99.90 99.90 174.75
Total std L m3/h 0.25 0.25 0.25 0.17
Total std V m3/h 115.65 115.65 115.65 217.41
Flow rates in kg/h
Carbon Monoxide 48.18 48.18 48.18 0.00
Ethylene 48.25 48.25 48.25 0.00
Hydrogen 3.47 3.47 3.47 0.00
Propionic Acid 0.00 0.00 0.00 0.00
Oxygen 0.00 0.00 0.00 0.00
Water 0.00 0.00 0.00 174.75

FLOW SUMMARIES:
147
Stream No. 35 40 41 42
Stream Name
Temp C 25.0000 99.9998 88.7292 64.2947
Pres atm 0.9955 14.9999 4.9999 1.9994
Enth MJ/h -2.0909E-007 -350.99 -351.33 -351.86
Vapor mass frac. 1.0000 0.010337 0.069951 0.17971
Total kmol/h 0.86 1.75 1.75 1.75
Total kg/h 27.52 99.90 99.90 99.90
Total std L m3/h 0.02 0.12 0.12 0.12
Total std V m3/h 19.28 39.32 39.32 39.32
Flow rates in kg/h
Ethylene 0.00 0.48 0.48 0.48
Hydrogen 0.00 0.03 0.03 0.03
Propionic Acid 0.00 0.00 0.00 0.00
Oxygen 27.52 0.00 0.00 0.00
Water 0.00 0.00 0.00 0.00
Stream No. 43 44 45 46
Stream Name
Temp C 113.8259 74.9990 75.0000 75.0000
Pres atm 1.9994 1.9988 2.0000 1.9994
Enth MJ/h 2.1931 -873.20 -901.91 -901.91
Vapor mass frac. 1.0000 0.027464 0.010405 0.010406
Total kmol/h 0.86 2.01 1.96 1.96
Total kg/h 27.52 141.57 141.57 141.57
Total std L m3/h 0.02 0.14 0.14 0.14
Total std V m3/h 19.28 45.12 43.93 43.93
Flow rates in kg/h
Ethylene 0.00 0.54 0.54 0.54
Hydrogen 0.00 0.04 0.04 0.04
Propionic Acid 0.00 132.18 140.03 140.03
Oxygen 27.52 2.03 0.33 0.33
Water 0.00 0.00 0.00 0.00

FLOW SUMMARIES:
Stream No. 47 48 49 50
Stream Name
Temp C 54.9748 55.3172 39.5968 39.5001
Pres atm 1.9659 1.9893 1.9994 1.9904
Enth MJ/h -314.10 -314.10 -349.67 -349.67
Vapor mass frac. 0.99225 0.99146 0.47215 0.47248
Total kmol/h 2.61 2.61 2.61 2.61
Total kg/h 127.42 127.42 127.42 127.42
Total std L m3/h 0.15 0.15 0.15 0.15
Total std V m3/h 58.60 58.60 58.60 58.60
Flow rates in kg/h
Ethylene 0.48 0.48 0.48 0.48
Hydrogen 0.03 0.03 0.03 0.03
Propionic Acid 0.00 0.00 0.00 0.00
148
Oxygen 27.52 27.52 27.52 27.52

Water 0.00 0.00 0.00 0.00
Stream No. 51 52 53
Stream Name
Temp C 74.9997 153.4754 153.4755
Pres atm 1.9984 1.9984 1.9982
Enth MJ/h -811.72 -767.52 -767.52
Vapor mass frac. 0.010407 0.00000 0.00000
Total kmol/h 1.76 1.67 1.67
Total kg/h 127.42 123.28 123.28
Total std L m3/h 0.13 0.12 0.12
Total std V m3/h 39.53 37.32 37.32
Flow rates in kg/h
Ethylene 0.48 0.02 0.02
Hydrogen 0.03 0.00 0.00
Propionic Acid 126.03 123.20 123.20
Oxygen 0.30 0.00 0.00
Water 0.00 0.00 0.00

STREAM PROPERTIES
Stream No. 1 2 3
4
Name Ethylene SynGas
- - Overall - -
Molar flow kmol/h 1.72 3.44 5.16
5.16
Mass flow kg/h 48.25 51.64 99.90
99.90
Temp C 25.00 25.00 31.45
96.93
Pres atm 1.00 1.00 0.97
14.99
Vapor mole fraction 1.000 1.000 1.000
1.000
Enth MJ/h 89.929 -190.11 -100.18 -
91.353
Tc C 9.26 -181.18 -95.59 -
95.59
Pc atm 49.66 37.52 67.11
67.11
Std. sp gr. wtr = 1 0.350 0.471 0.404
0.404
Std. sp gr. air = 1 0.969 0.518 0.668
0.668
Degree API 272.79 169.05 219.15
219.15
Average mol wt 28.05 15.01 19.36
19.36
Actual dens kg/m3 1.15 0.61 0.75
9.57
Actual vol m3/h 41.83 84.18 132.85
10.44
Std liq m3/h 0.14 0.11 0.25
0.25
149
Std vap 0 C m3/h 38.55 77.10 115.65

115.65
- - Vapor only - -
5.16
Mass flow kg/h 48.25 51.64 99.90
99.90
Average mol wt 28.05 15.01 19.36
19.36
9.57
Actual vol m3/h 41.83 84.18 132.85
10.44
Std liq m3/h 0.14 0.11 0.25
0.25
Std vap 0 C m3/h 38.55 77.10 115.65
115.65
Cp kJ/kg-K 1.53 1.93 1.75
1.87
Z factor 0.9942 1.0003 0.9993
0.9986
Visc N-s/m2 1.021e-005 1.691e-005 1.370e-005 1.612e-
005
Th cond W/m-K 0.0207 0.0743 0.0508
0.0620

STREAM PROPERTIES
Stream No. 5 6 7
8
Name
- - Overall - -
0.86
Mass flow kg/h 99.90 99.90 99.90
27.52
Temp C 100.00 389.53 96.93
113.83
Pres atm 15.00 15.00 14.99
2.00
1.000
Enth MJ/h -350.99 -29.544 -91.353
2.1931
Tc C 226.65 -95.59 -95.59 -
118.57
Pc atm 52.10 67.11 67.11
50.10
Std. sp gr. wtr = 1 0.802 0.404 0.404
1.128
Std. sp gr. air = 1 1.966 0.668 0.668
1.105
Degree API 44.96 219.15 219.15 -
6.00
Average mol wt 56.94 19.36 19.36
32.00
Actual dens kg/m3 473.01 5.31 9.57
2.01
150
Actual vol m3/h 0.21 18.83 10.44

13.66
Std liq m3/h 0.12 0.25 0.25
0.02
Std vap 0 C m3/h 39.32 115.65 115.65
19.28
- - Vapor only - -
0.86
Mass flow kg/h 1.03 99.90 99.90
27.52
Average mol wt 30.19 19.36 19.36
32.00
Actual dens kg/m3 15.39 5.31 9.57
2.01
Actual vol m3/h 0.07 18.83 10.44
13.66
Std liq m3/h 0.00 0.25 0.25
0.02
Std vap 0 C m3/h 0.77 115.65 115.65
19.28
Cp kJ/kg-K 1.73 2.34 1.87
0.94
Z factor 0.9610 1.0066 0.9986
1.0008
Visc N-s/m2 1.338e-005 2.511e-005 1.612e-005 2.498e-
005
Th cond W/m-K 0.0471 0.1093 0.0620
0.0333
- - Liquid only - -
Molar flow kmol/h 1.72
Mass flow kg/h 98.86
Average mol wt 57.47
Actual dens kg/m3 686.08
Actual vol m3/h 0.14
Std liq m3/h 0.12
Std vap 0 C m3/h 38.56
Cp kJ/kg-K 2.47
Z factor 0.0502
Visc N-s/m2 0.0001703
Th cond W/m-K 0.1355
Surf. tens. N/m 0.01

STREAM PROPERTIES
Stream No. 9 10 11
12
Name Oxygen
- - Overall - -
0.20
Mass flow kg/h 14.16 27.52 0.00
14.16
Temp C 75.00 25.00 0.00
75.00
Pres atm 2.00 1.00 0.00
2.00
151

0.03294
Enth MJ/h -90.191 -2.0909E-007 0.00000 -
90.191
Tc C 321.61 -118.57 0.00
321.61
Pc atm 51.57 50.10 0.00
51.57
Std. sp gr. wtr = 1 0.989 1.128 0.000
0.989
Std. sp gr. air = 1 2.494 1.105 0.000
2.494
Degree API 11.63 -6.00 0.00
11.63
Average mol wt 72.24 32.00 0.00
72.24
Actual dens kg/m3 133.51 1.31 0.00
133.51
Actual vol m3/h 0.11 21.03 0.00
0.11
Std liq m3/h 0.01 0.02 0.00
0.01
Std vap 0 C m3/h 4.39 19.28 0.00
4.39
- - Vapor only - -
Molar flow kmol/h 0.01 0.86
0.01
Mass flow kg/h 0.15 27.52
0.15
Average mol wt 22.82 32.00
22.82
Actual dens kg/m3 1.62 1.31
1.62
Actual vol m3/h 0.09 21.03
0.09
Std liq m3/h 0.00 0.02
0.00
Std vap 0 C m3/h 0.14 19.28
0.14
Cp kJ/kg-K 1.59 0.92
1.59
Z factor 0.9990 0.9997
0.9990
Visc N-s/m2 1.626e-005 2.040e-005 1.626e-
005
Th cond W/m-K 0.0538 0.0262
0.0538
- - Liquid only - -
0.19
14.01
73.92
933.05
0.02
Std liq m3/h 0.01
0.01
152

4.25
Cp kJ/kg-K 2.30
2.30
Z factor 0.0077
0.0077
Visc N-s/m2 0.0005663
0.0005663
0.1379
0.02

STREAM PROPERTIES
Stream No. 13 14 16
17
Name
- - Overall - -
0.10
Mass flow kg/h 141.57 141.57 127.42
4.14
Temp C 71.84 71.49 75.00
132.61
Pres atm 1.97 1.93 2.00
2.00
1.000
Enth MJ/h -404.29 -404.29 -811.72 -
17.423
Tc C 188.52 188.52 321.61
164.77
Pc atm 102.67 102.67 51.57
131.57
Std. sp gr. wtr = 1 0.867 0.867 0.989
0.746
Std. sp gr. air = 1 1.739 1.739 2.494
1.447
Degree API 31.72 31.72 11.63
58.13
Average mol wt 50.37 50.37 72.24
41.90
Actual dens kg/m3 4.06 3.99 133.51
2.85
Actual vol m3/h 34.89 35.46 0.95
1.45
Std liq m3/h 0.16 0.16 0.13
0.01
Std vap 0 C m3/h 62.99 62.99 39.53
2.21
- - Vapor only - -
0.10
Mass flow kg/h 120.18 120.32 1.33
4.14
Average mol wt 48.40 48.41 22.82
41.90
153

2.85
Actual vol m3/h 34.87 35.43 0.82
1.45
Std liq m3/h 0.14 0.14 0.00
0.01
Std vap 0 C m3/h 55.65 55.71 1.30
2.21
Cp kJ/kg-K 1.37 1.37 1.59
1.57
Z factor 0.9797 0.9800 0.9990
0.9887
Visc N-s/m2 1.158e-005 1.157e-005 1.626e-005 1.326e-
005
Th cond W/m-K 0.0189 0.0188 0.0538
0.0434
- - Liquid only - -
Mass flow kg/h 21.40 21.25 126.09
Average mol wt 65.32 65.37 73.92
Actual dens kg/m3 827.15 828.19 933.05
Actual vol m3/h 0.03 0.03 0.14
Std liq m3/h 0.02 0.02 0.13
Std vap 0 C m3/h 7.34 7.29 38.23
Cp kJ/kg-K 2.34 2.33 2.30
Z factor 0.0071 0.0070 0.0077
Visc N-s/m2 0.0003362 0.0003382 0.0005663
Th cond W/m-K 0.1426 0.1427 0.1379
Surf. tens. N/m 0.02 0.02 0.02

STREAM PROPERTIES
Stream No. 18 19 21
22
Name
- - Overall - -
1.75
Mass flow kg/h 4.14 99.90 174.75
99.90
Temp C 132.61 31.41 100.12
88.73
Pres atm 2.00 0.94 0.98
5.00
0.08606
Enth MJ/h -17.423 -100.18 -2709.4 -
351.33
Tc C 164.77 -95.59 374.20
226.65
Pc atm 131.57 67.11 218.29
52.10
Std. sp gr. wtr = 1 0.746 0.404 1.000
0.802
Std. sp gr. air = 1 1.447 0.668 0.622
1.966
Degree API 58.13 219.15 10.00
44.96
154
Average mol wt 41.90 19.36 18.01

56.94
Actual dens kg/m3 2.85 0.73 32.70
102.24
Actual vol m3/h 1.45 136.41 5.34
0.98
Std liq m3/h 0.01 0.25 0.17
0.12
Std vap 0 C m3/h 2.21 115.65 217.41
39.32
- - Vapor only - -
0.15
Mass flow kg/h 4.14 99.90 3.01
6.99
Average mol wt 41.90 19.36 18.01
46.28
8.26
Actual vol m3/h 1.45 136.41 5.16
0.85
Std liq m3/h 0.01 0.25 0.00
0.01
Std vap 0 C m3/h 2.21 115.65 3.75
3.38
Cp kJ/kg-K 1.57 1.75 1.89
1.59
Z factor 0.9887 0.9993 0.9918
0.9436
Visc N-s/m2 1.326e-005 1.370e-005 1.218e-005 1.065e-
005
Th cond W/m-K 0.0434 0.0508 0.0248
0.0244
- - Liquid only - -
1.60
92.91
57.94
708.90
0.13
Std liq m3/h 0.17
0.11
Std vap 0 C m3/h 213.67
35.94
Cp kJ/kg-K 4.22
2.44
Z factor 0.0008
0.0169
Visc N-s/m2 0.0002802
0.0001862
0.1404
0.01
155

STREAM PROPERTIES
Stream No. 23 24 25
26
Name
- - Overall - -
9.70
Mass flow kg/h 99.90 141.57 174.75
174.75
Temp C 64.30 75.00 46.42
95.00
Pres atm 2.00 2.00 0.96
1.00
0.0000
Enth MJ/h -351.86 -873.20 -2755.6 -
2720.0
Tc C 226.65 313.10 374.20
374.20
Pc atm 52.10 57.26 218.29
218.29
Std. sp gr. wtr = 1 0.802 0.980 1.000
1.000
Std. sp gr. air = 1 1.966 2.428 0.622
0.622
Degree API 44.96 12.88 10.00
10.00
Average mol wt 56.94 70.34 18.01
18.01
Actual dens kg/m3 21.37 71.33 989.37
961.38
Actual vol m3/h 4.67 1.98 0.18
0.18
Std liq m3/h 0.12 0.14 0.17
0.17
Std vap 0 C m3/h 39.32 45.12 217.41
217.41
- - Vapor only - -
Std liq m3/h 0.02 0.01
Std vap 0 C m3/h 7.68 2.92
Cp kJ/kg-K 1.50 1.28
Z factor 0.9621 0.9982
Visc N-s/m2 9.369e-006 1.726e-005
Th cond W/m-K 0.0174 0.0390
- - Liquid only - -
9.70
Mass flow kg/h 81.95 137.69 174.75
174.75
Average mol wt 58.05 73.14 18.01
18.01
Actual dens kg/m3 742.92 923.56 989.37
961.38
156
Actual vol m3/h 0.11 0.15 0.18

0.18
Std liq m3/h 0.10 0.14 0.17
0.17
Std vap 0 C m3/h 31.64 42.20 217.41
217.41
Cp kJ/kg-K 2.38 2.30 4.18
4.21
Z factor 0.0069 0.0076 0.0009
0.0008
Visc N-s/m2 0.0002236 0.0005385 0.0006016
0.0002969
Th cond W/m-K 0.1481 0.1384 0.6332
0.6735
Surf. tens. N/m 0.02 0.02 0.07
0.06

STREAM PROPERTIES
Stream No. 27 28 29
30
Name
- - Overall - -
3.44
Mass flow kg/h 174.75 174.75 48.25
51.64
Temp C 95.00 25.00 24.97
36.31
Pres atm 1.00 1.00 0.99
0.97
1.000
Enth MJ/h -2720.0 -2771.2 89.929 -
190.11
Tc C 374.20 374.20 9.26 -
181.18
Pc atm 218.29 218.29 49.66
37.52
Std. sp gr. wtr = 1 1.000 1.000 0.350
0.471
Std. sp gr. air = 1 0.622 0.622 0.969
0.518
Degree API 10.00 10.00 272.79
169.05
Average mol wt 18.01 18.01 28.05
15.01
Actual dens kg/m3 961.38 996.71 1.14
0.57
Actual vol m3/h 0.18 0.18 42.38
90.08
Std liq m3/h 0.17 0.17 0.14
0.11
Std vap 0 C m3/h 217.41 217.41 38.55
77.10
- - Vapor only - -
3.44
157

51.64
15.01
0.57
90.08
Std liq m3/h 0.14
0.11
77.10
Cp kJ/kg-K 1.53
1.93
Z factor 0.9943
1.0004
Visc N-s/m2 1.021e-005 1.739e-
005
0.0765
- - Liquid only - -
Mass flow kg/h 174.75 174.75
Std liq m3/h 0.17 0.17
Std vap 0 C m3/h 217.41 217.41
Cp kJ/kg-K 4.21 4.19
Z factor 0.0008 0.0010
Visc N-s/m2 0.0002969 0.0009227
Th cond W/m-K 0.6735 0.6062
Surf. tens. N/m 0.06 0.07

STREAM PROPERTIES
Stream No. 31 32 33
34
Name
- - Overall - -
9.70
Mass flow kg/h 99.90 99.90 99.90
174.75
Temp C 189.41 189.40 389.52
99.96
Pres atm 3.87 3.87 14.99
0.98
0.01754
Enth MJ/h -71.018 -71.018 -29.544 -
2709.4
Tc C -95.59 -95.59 -95.59
374.20
Pc atm 67.11 67.11 67.11
218.29
Std. sp gr. wtr = 1 0.404 0.404 0.404
1.000
158
Std. sp gr. air = 1 0.668 0.668 0.668

0.622
Degree API 219.15 219.15 219.15
10.00
Average mol wt 19.36 19.36 19.36
18.01
31.99
Actual vol m3/h 50.65 50.69 18.83
5.46
Std liq m3/h 0.25 0.25 0.25
0.17
Std vap 0 C m3/h 115.65 115.65 115.65
217.41
- - Vapor only - -
0.17
Mass flow kg/h 99.90 99.90 99.90
3.06
Average mol wt 19.36 19.36 19.36
18.01
0.58
Actual vol m3/h 50.65 50.69 18.83
5.28
Std liq m3/h 0.25 0.25 0.25
0.00
Std vap 0 C m3/h 115.65 115.65 115.65
3.81
Cp kJ/kg-K 2.03 2.03 2.34
1.89
Z factor 1.0010 1.0010 1.0066
0.9918
Visc N-s/m2 1.923e-005 1.923e-005 2.511e-005 1.218e-
005
Th cond W/m-K 0.0762 0.0762 0.1093
0.0248
- - Liquid only - -
Molar flow kmol/h
9.53
Mass flow kg/h
171.68
Average mol wt
18.01
Actual dens kg/m3
957.84
Actual vol m3/h
0.18
Std liq m3/h
0.17
Std vap 0 C m3/h
213.60
Cp kJ/kg-K
4.22
Z factor
0.0008
Visc N-s/m2
0.0002807
Th cond W/m-K
0.6760
159
Surf. tens. N/m

0.06

STREAM PROPERTIES
Stream No. 35 40 41
42
Name
- - Overall - -
1.75
Mass flow kg/h 27.52 99.90 99.90
99.90
Temp C 25.00 100.00 88.73
64.29
Pres atm 1.00 15.00 5.00
2.00
0.1954
Enth MJ/h -2.0909E-007 -350.99 -351.33 -
351.86
Tc C -118.57 226.65 226.65
226.65
Pc atm 50.10 52.10 52.10
52.10
Std. sp gr. wtr = 1 1.128 0.802 0.802
0.802
Std. sp gr. air = 1 1.105 1.966 1.966
1.966
Degree API -6.00 44.96 44.96
44.96
Average mol wt 32.00 56.94 56.94
56.94
Actual dens kg/m3 1.30 473.00 102.24
21.36
Actual vol m3/h 21.13 0.21 0.98
4.68
Std liq m3/h 0.02 0.12 0.12
0.12
Std vap 0 C m3/h 19.28 39.32 39.32
39.32
- - Vapor only - -
0.34
Mass flow kg/h 27.52 1.03 6.99
17.95
Average mol wt 32.00 30.19 46.28
52.37
Actual dens kg/m3 1.30 15.39 8.26
3.93
Actual vol m3/h 21.13 0.07 0.85
4.57
Std liq m3/h 0.02 0.00 0.01
0.02
Std vap 0 C m3/h 19.28 0.77 3.38
7.68
Cp kJ/kg-K 0.92 1.73 1.59
1.50
160
Z factor 0.9997 0.9610 0.9436

0.9621
Visc N-s/m2 2.040e-005 1.338e-005 1.065e-005 9.368e-
006
Th cond W/m-K 0.0262 0.0471 0.0244
0.0174
- - Liquid only - -
1.41
81.95
58.05
742.93
0.11
Std liq m3/h 0.12 0.11
0.10
Std vap 0 C m3/h 38.56 35.94
31.64
Cp kJ/kg-K 2.47 2.44
2.38
Z factor 0.0502 0.0169
0.0069
Visc N-s/m2 0.0001703 0.0001862
0.0002236
Th cond W/m-K 0.1355 0.1404
0.1481
0.02

STREAM PROPERTIES
Stream No. 43 44 45
46
Name
- - Overall - -
1.96
Mass flow kg/h 27.52 141.57 141.57
141.57
Temp C 113.83 75.00 75.00
75.00
Pres atm 2.00 2.00 2.00
2.00
0.03294
Enth MJ/h 2.1931 -873.20 -901.91 -
901.91
Tc C -118.57 313.10 321.61
321.61
Pc atm 50.10 57.26 51.57
51.57
Std. sp gr. wtr = 1 1.128 0.980 0.989
0.989
Std. sp gr. air = 1 1.105 2.428 2.494
2.494
161
Degree API -6.00 12.88 11.63

11.63
Average mol wt 32.00 70.34 72.24
72.24
Actual dens kg/m3 2.01 71.28 133.55
133.51
Actual vol m3/h 13.67 1.99 1.06
1.06
Std liq m3/h 0.02 0.14 0.14
0.14
Std vap 0 C m3/h 19.28 45.12 43.93
43.93
- - Vapor only - -
0.06
Mass flow kg/h 27.52 3.89 1.47
1.47
Average mol wt 32.00 29.84 22.82
22.82
1.62
Actual vol m3/h 13.67 1.84 0.91
0.91
Std liq m3/h 0.02 0.01 0.00
0.00
Std vap 0 C m3/h 19.28 2.92 1.45
1.45
Cp kJ/kg-K 0.94 1.28 1.59
1.59
Z factor 1.0008 0.9982 0.9990
0.9990
Visc N-s/m2 2.498e-005 1.726e-005 1.626e-005 1.626e-
005
Th cond W/m-K 0.0333 0.0390 0.0538
0.0538
- - Liquid only - -
1.90
Mass flow kg/h 137.69 140.10
140.10
73.92
933.05
0.15
Std liq m3/h 0.14 0.14
0.14
Std vap 0 C m3/h 42.20 42.48
42.48
Cp kJ/kg-K 2.30 2.30
2.30
Z factor 0.0076 0.0077
0.0077
Visc N-s/m2 0.0005385 0.0005663
0.0005663
Th cond W/m-K 0.1384 0.1379
0.1379
0.02
162

STREAM PROPERTIES
Stream No. 47 48 49
50
Name
- - Overall - -
2.61
Mass flow kg/h 127.42 127.42 127.42
127.42
Temp C 54.97 55.32 39.60
39.50
Pres atm 1.97 1.99 2.00
1.99
0.5570
Enth MJ/h -314.10 -314.10 -349.67 -
349.67
Tc C 174.20 174.20 174.20
174.20
Pc atm 103.96 103.96 103.96
103.96
Std. sp gr. wtr = 1 0.855 0.855 0.855
0.855
Std. sp gr. air = 1 1.683 1.683 1.683
1.683
Degree API 33.95 33.95 33.95
33.95
Average mol wt 48.73 48.73 48.73
48.73
6.84
Actual vol m3/h 34.70 34.30 18.54
18.63
Std liq m3/h 0.15 0.15 0.15
0.15
Std vap 0 C m3/h 58.60 58.60 58.60
58.60
- - Vapor only - -
1.46
Mass flow kg/h 126.43 126.33 60.16
60.20
Average mol wt 48.67 48.67 41.33
41.34
3.25
Actual vol m3/h 34.70 34.30 18.45
18.54
Std liq m3/h 0.15 0.15 0.07
0.07
Std vap 0 C m3/h 58.22 58.18 32.62
32.64
Cp kJ/kg-K 1.35 1.35 1.20
1.20
Z factor 0.9756 0.9754 0.9880
0.9880
163
Visc N-s/m2 1.092e-005 1.093e-005 1.321e-005 1.320e-

005
Th cond W/m-K 0.0170 0.0170 0.0198
0.0198
- - Liquid only - -
1.16
Mass flow kg/h 0.99 1.09 67.26
67.21
Average mol wt 58.05 58.05 58.03
58.03
Actual dens kg/m3 755.05 754.63 773.24
773.36
Actual vol m3/h 0.00 0.00 0.09
0.09
Std liq m3/h 0.00 0.00 0.08
0.08
Std vap 0 C m3/h 0.38 0.42 25.98
25.96
Cp kJ/kg-K 2.36 2.36 2.33
2.33
Z factor 0.0069 0.0070 0.0072
0.0072
Visc N-s/m2 0.0002412 0.0002405 0.0002753
0.0002756
Th cond W/m-K 0.1510 0.1509 0.1554
0.1555
Surf. tens. N/m 0.02 0.02 0.02
0.02

STREAM PROPERTIES
Stream No. 51 52 53
Name
- - Overall - -
Mass flow kg/h 127.42 123.28 123.28
Temp C 75.00 153.48 153.48
Pres atm 2.00 2.00 2.00
Enth MJ/h -811.72 -767.52 -767.52
Tc C 321.61 327.49 327.49
Pc atm 51.57 45.67 45.67
Std. sp gr. wtr = 1 0.989 1.000 1.000
Std. sp gr. air = 1 2.494 2.556 2.556
Degree API 11.63 10.07 10.07
Average mol wt 72.24 74.04 74.04
Actual dens kg/m3 133.45 844.57 844.57
Actual vol m3/h 0.95 0.15 0.15
Std liq m3/h 0.13 0.12 0.12
Std vap 0 C m3/h 39.53 37.32 37.32
- - Vapor only - -
Mass flow kg/h 1.33
Std liq m3/h 0.00
164

Cp kJ/kg-K 1.59
Z factor 0.9990
Visc N-s/m2 1.625e-005
- - Liquid only - -
Mass flow kg/h 126.09 123.28 123.28
Average mol wt 73.92 74.04 74.04
Actual dens kg/m3 933.06 844.57 844.57
Actual vol m3/h 0.14 0.15 0.15
Std liq m3/h 0.13 0.12 0.12
Std vap 0 C m3/h 38.23 37.32 37.32
Cp kJ/kg-K 2.30 2.92 2.91
Z factor 0.0077 0.0069 0.0069
Visc N-s/m2 0.0005663 0.0003188 0.0003188
Th cond W/m-K 0.1379 0.1254 0.1254
Surf. tens. N/m 0.02 0.01 0.01
COMPONENTS
ID # Name Formula
1 48 Carbon Monoxide CO
2 22 Ethylene C2H4
3 1 Hydrogen H2
4 143 Propionic Acid C3H6O2
5 261 Propionaldehyde C3H6O
6 47 Oxygen O2
7 62 Water H2O
THERMODYNAMICS
K-value model : TSRK

Vapor Phase Association
Enthalpy model : Latent Heat
Liquid density : Library
Std vapor rate reference temperature is 0 C.

Atmospheric pressure is 1.0000 atm.

EQUIPMENT SUMMARIES
Kinetic Reactor Summary
Equip. No. 1 2 3
Name R 103
Reactor type 2 2 2
Reaction phase 3 3 3
Thermal mode 1 1 1
Pressure In atm 2.0000 2.0000 15.0000
Tout C 75.0000 75.0000 100.0000
Q MJ/h -468.9148 -28.7052 -259.6358
Reactor volume m3 1.1353 2.2542 0.9714
165
Specify calc. mode 1 1 1

Conversion 0.9370 0.9850 0.9900
Key 5 5 2
No. of Reactions 1 1 1
Molar Flow Unit 0 0 1
Activ. E/H of Rxn Unit 0 0 4
Time Unit 0 0 2
Overall IG Ht of Rxn -426.2610 -28.3143 -218.0434
(MJ/h)
Mass unit 0 0 1
Partial P unit 1 0 2
Reaction Stoichiometrics and Parameters for unit no. 1
Reaction 1
RateConst = 1.4330e+003 Act.E = 7.2300e+000 Hrxn = 0.0000e+000
Comp Stoich. Exp.factor AdsorbFac. AdsorbE AdsorbExp.
5 -1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
6 -5.00e-001 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
4 1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
Reaction 1
5 -1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
6 -5.00e-001 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
4 1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
Reaction 1

EQUIPMENT SUMMARIES
2 -1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000

1 -1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
3 -1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
5 1.00e+000 0.0000e+000 0.0000e+000 0.0000e+000 0.0000e+000
Plug Flow Profile for unit no. 1
Vol Temp Press Total Mole frac Mole frac

m3 C atm kmol/h Carbon Monoxide Ethylene
0.00 75.00 2.00 2.81 6.820E-003 6.820E-003
0.06 75.00 2.00 2.74 6.992E-003 6.992E-003
0.11 75.00 2.00 2.67 7.169E-003 7.169E-003
0.17 75.00 2.00 2.61 7.351E-003 7.351E-003
0.23 75.00 2.00 2.54 7.536E-003 7.536E-003
0.28 75.00 2.00 2.48 7.724E-003 7.724E-003
0.34 75.00 2.00 2.42 7.911E-003 7.911E-003
0.40 75.00 2.00 2.37 8.095E-003 8.095E-003
0.45 75.00 2.00 2.32 8.274E-003 8.274E-003
166
0.51 75.00 2.00 2.27 8.446E-003 8.446E-003

0.57 75.00 2.00 2.23 8.607E-003 8.607E-003
0.62 75.00 2.00 2.19 8.757E-003 8.757E-003
0.68 75.00 2.00 2.16 8.893E-003 8.893E-003
0.74 75.00 2.00 2.13 9.016E-003 9.016E-003
0.79 75.00 2.00 2.10 9.124E-003 9.124E-003
0.85 75.00 2.00 2.08 9.218E-003 9.218E-003
0.91 75.00 2.00 2.06 9.300E-003 9.300E-003
0.96 75.00 2.00 2.05 9.370E-003 9.370E-003
1.02 75.00 2.00 2.03 9.429E-003 9.429E-003
1.08 75.00 2.00 2.02 9.480E-003 9.480E-003
1.14 75.00 2.00 2.01 9.523E-003 9.523E-003

m3 C atm kmol/h Hydrogen Propionic Acid
0.00 75.00 2.00 2.81 6.820E-003 6.726E-002
0.06 75.00 2.00 2.74 6.992E-003 1.193E-001
0.11 75.00 2.00 2.67 7.169E-003 1.730E-001
0.17 75.00 2.00 2.61 7.351E-003 2.282E-001
0.23 75.00 2.00 2.54 7.537E-003 2.844E-001
0.28 75.00 2.00 2.48 7.724E-003 3.412E-001
0.34 75.00 2.00 2.42 7.911E-003 3.979E-001
0.40 75.00 2.00 2.37 8.095E-003 4.538E-001
0.45 75.00 2.00 2.32 8.275E-003 5.081E-001
0.51 75.00 2.00 2.27 8.446E-003 5.601E-001
0.57 75.00 2.00 2.23 8.608E-003 6.091E-001
0.62 75.00 2.00 2.19 8.757E-003 6.544E-001
0.68 75.00 2.00 2.16 8.894E-003 6.957E-001
0.74 75.00 2.00 2.13 9.016E-003 7.328E-001

EQUIPMENT SUMMARIES
0.79 75.00 2.00 2.10 9.124E-003 7.656E-001

0.85 75.00 2.00 2.08 9.218E-003 7.943E-001
0.91 75.00 2.00 2.06 9.300E-003 8.190E-001
0.96 75.00 2.00 2.05 9.370E-003 8.402E-001
1.02 75.00 2.00 2.03 9.430E-003 8.583E-001
1.08 75.00 2.00 2.02 9.480E-003 8.735E-001
1.14 75.00 2.00 2.01 9.523E-003 8.865E-001

m3 C atm kmol/h Propionaldehyde Oxygen
0.00 75.00 2.00 2.81 6.059E-001 3.064E-001
0.06 75.00 2.00 2.74 5.708E-001 2.889E-001
0.11 75.00 2.00 2.67 5.346E-001 2.709E-001
0.17 75.00 2.00 2.61 4.974E-001 2.524E-001
0.23 75.00 2.00 2.54 4.595E-001 2.335E-001
0.28 75.00 2.00 2.48 4.212E-001 2.144E-001
0.34 75.00 2.00 2.42 3.829E-001 1.954E-001
0.40 75.00 2.00 2.37 3.453E-001 1.767E-001
0.45 75.00 2.00 2.32 3.086E-001 1.585E-001
0.51 75.00 2.00 2.27 2.736E-001 1.410E-001
0.57 75.00 2.00 2.23 2.405E-001 1.246E-001
0.62 75.00 2.00 2.19 2.100E-001 1.094E-001
0.68 75.00 2.00 2.16 1.821E-001 9.549E-002
0.74 75.00 2.00 2.13 1.571E-001 8.305E-002
0.79 75.00 2.00 2.10 1.350E-001 7.204E-002
0.85 75.00 2.00 2.08 1.156E-001 6.243E-002
167
0.91 75.00 2.00 2.06 9.896E-002 5.413E-002

0.96 75.00 2.00 2.05 8.466E-002 4.702E-002
1.02 75.00 2.00 2.03 7.249E-002 4.096E-002
1.08 75.00 2.00 2.02 6.218E-002 3.583E-002
1.14 75.00 2.00 2.01 5.347E-002 3.150E-002

m3 C atm kmol/h Water
0.00 75.00 2.00 2.81 0.000E+000
0.06 75.00 2.00 2.74 0.000E+000
0.11 75.00 2.00 2.67 0.000E+000
0.17 75.00 2.00 2.61 0.000E+000
0.23 75.00 2.00 2.54 0.000E+000
0.28 75.00 2.00 2.48 0.000E+000
0.34 75.00 2.00 2.42 0.000E+000
0.40 75.00 2.00 2.37 0.000E+000
0.45 75.00 2.00 2.32 0.000E+000
0.51 75.00 2.00 2.27 0.000E+000
0.57 75.00 2.00 2.23 0.000E+000
0.62 75.00 2.00 2.19 0.000E+000
0.68 75.00 2.00 2.16 0.000E+000
0.74 75.00 2.00 2.13 0.000E+000

EQUIPMENT SUMMARIES
0.79 75.00 2.00 2.10 0.000E+000

0.85 75.00 2.00 2.08 0.000E+000
0.91 75.00 2.00 2.06 0.000E+000
0.96 75.00 2.00 2.05 0.000E+000
1.02 75.00 2.00 2.03 0.000E+000
1.08 75.00 2.00 2.02 0.000E+000
1.14 75.00 2.00 2.01 0.000E+000

0.00 75.00 2.00 2.01 9.523E-003 9.523E-003
0.11 75.00 2.00 2.00 9.588E-003 9.588E-003
0.23 75.00 2.00 1.99 9.636E-003 9.636E-003
0.34 75.00 2.00 1.98 9.670E-003 9.670E-003
0.45 75.00 2.00 1.98 9.695E-003 9.695E-003
0.56 75.00 2.00 1.97 9.714E-003 9.714E-003
0.68 75.00 2.00 1.97 9.728E-003 9.728E-003
0.79 75.00 2.00 1.97 9.739E-003 9.739E-003
0.90 75.00 2.00 1.97 9.747E-003 9.748E-003
1.01 75.00 2.00 1.97 9.754E-003 9.754E-003
1.13 75.00 2.00 1.96 9.759E-003 9.759E-003
1.24 75.00 2.00 1.96 9.764E-003 9.764E-003
1.35 75.00 2.00 1.96 9.767E-003 9.767E-003
1.47 75.00 2.00 1.96 9.770E-003 9.770E-003
1.58 75.00 2.00 1.96 9.772E-003 9.772E-003
1.69 75.00 2.00 1.96 9.774E-003 9.774E-003
1.80 75.00 2.00 1.96 9.776E-003 9.776E-003
1.92 75.00 2.00 1.96 9.777E-003 9.777E-003
2.03 75.00 2.00 1.96 9.778E-003 9.778E-003
2.14 75.00 2.00 1.96 9.779E-003 9.779E-003
168
2.25 75.00 2.00 1.96 9.780E-003 9.780E-003

0.00 75.00 2.00 2.01 9.523E-003 8.865E-001
0.11 75.00 2.00 2.00 9.589E-003 9.065E-001
0.23 75.00 2.00 1.99 9.636E-003 9.208E-001
0.34 75.00 2.00 1.98 9.670E-003 9.312E-001
0.45 75.00 2.00 1.98 9.695E-003 9.388E-001
0.56 75.00 2.00 1.97 9.714E-003 9.445E-001
0.68 75.00 2.00 1.97 9.728E-003 9.488E-001
0.79 75.00 2.00 1.97 9.739E-003 9.521E-001
0.90 75.00 2.00 1.97 9.748E-003 9.547E-001
1.01 75.00 2.00 1.97 9.754E-003 9.567E-001
1.13 75.00 2.00 1.96 9.760E-003 9.583E-001

EQUIPMENT SUMMARIES
1.24 75.00 2.00 1.96 9.764E-003 9.596E-001

1.35 75.00 2.00 1.96 9.767E-003 9.607E-001
1.47 75.00 2.00 1.96 9.770E-003 9.615E-001
1.58 75.00 2.00 1.96 9.773E-003 9.622E-001
1.69 75.00 2.00 1.96 9.774E-003 9.628E-001
1.80 75.00 2.00 1.96 9.776E-003 9.633E-001
1.92 75.00 2.00 1.96 9.777E-003 9.637E-001
2.03 75.00 2.00 1.96 9.778E-003 9.640E-001
2.14 75.00 2.00 1.96 9.779E-003 9.643E-001
2.25 75.00 2.00 1.96 9.780E-003 9.645E-001

0.00 75.00 2.00 2.01 5.347E-002 3.150E-002
0.11 75.00 2.00 2.00 3.998E-002 2.478E-002
0.23 75.00 2.00 1.99 3.030E-002 1.997E-002
0.34 75.00 2.00 1.98 2.330E-002 1.648E-002
0.45 75.00 2.00 1.98 1.815E-002 1.392E-002
0.56 75.00 2.00 1.97 1.432E-002 1.202E-002
0.68 75.00 2.00 1.97 1.142E-002 1.057E-002
0.79 75.00 2.00 1.97 9.189E-003 9.464E-003
0.90 75.00 2.00 1.97 7.457E-003 8.602E-003
1.01 75.00 2.00 1.97 6.093E-003 7.924E-003
1.13 75.00 2.00 1.96 5.008E-003 7.384E-003
1.24 75.00 2.00 1.96 4.137E-003 6.950E-003
1.35 75.00 2.00 1.96 3.432E-003 6.600E-003
1.47 75.00 2.00 1.96 2.858E-003 6.314E-003
1.58 75.00 2.00 1.96 2.386E-003 6.079E-003
1.69 75.00 2.00 1.96 1.998E-003 5.886E-003
1.80 75.00 2.00 1.96 1.677E-003 5.726E-003
1.92 75.00 2.00 1.96 1.410E-003 5.593E-003
2.03 75.00 2.00 1.96 1.187E-003 5.483E-003
2.14 75.00 2.00 1.96 1.001E-003 5.390E-003
2.25 75.00 2.00 1.96 8.447E-004 5.312E-003

0.00 75.00 2.00 2.01 0.000E+000
0.11 75.00 2.00 2.00 0.000E+000
0.23 75.00 2.00 1.99 0.000E+000
169
0.34 75.00 2.00 1.98 0.000E+000

0.45 75.00 2.00 1.98 0.000E+000
0.56 75.00 2.00 1.97 0.000E+000
0.68 75.00 2.00 1.97 0.000E+000
0.79 75.00 2.00 1.97 0.000E+000
0.90 75.00 2.00 1.97 0.000E+000
1.01 75.00 2.00 1.97 0.000E+000
1.13 75.00 2.00 1.96 0.000E+000

EQUIPMENT SUMMARIES
1.24 75.00 2.00 1.96 0.000E+000

1.35 75.00 2.00 1.96 0.000E+000
1.47 75.00 2.00 1.96 0.000E+000
1.58 75.00 2.00 1.96 0.000E+000
1.69 75.00 2.00 1.96 0.000E+000
1.80 75.00 2.00 1.96 0.000E+000
1.92 75.00 2.00 1.96 0.000E+000
2.03 75.00 2.00 1.96 0.000E+000
2.14 75.00 2.00 1.96 0.000E+000
2.25 75.00 2.00 1.96 0.000E+000

0.00 100.00 15.00 5.16 3.333E-001 3.333E-001
0.05 100.00 15.00 4.79 3.204E-001 3.204E-001
0.10 100.00 15.00 4.46 3.071E-001 3.071E-001
0.15 100.00 15.00 4.16 2.934E-001 2.934E-001
0.19 100.00 15.00 3.90 2.797E-001 2.797E-001
0.24 100.00 15.00 3.68 2.660E-001 2.660E-001
0.29 100.00 15.00 3.48 2.525E-001 2.525E-001
0.34 100.00 15.00 3.30 2.394E-001 2.394E-001
0.39 100.00 15.00 3.15 2.269E-001 2.269E-001
0.44 100.00 15.00 3.01 2.147E-001 2.147E-001
0.49 100.00 15.00 2.88 2.018E-001 2.018E-001
0.53 100.00 15.00 2.75 1.877E-001 1.877E-001
0.58 100.00 15.00 2.62 1.724E-001 1.724E-001
0.63 100.00 15.00 2.50 1.555E-001 1.555E-001
0.68 100.00 15.00 2.37 1.370E-001 1.370E-001
0.73 100.00 15.00 2.24 1.166E-001 1.166E-001
0.78 100.00 15.00 2.12 9.431E-002 9.431E-002
0.83 100.00 15.00 2.00 7.017E-002 7.017E-002
0.87 100.00 15.00 1.89 4.509E-002 4.509E-002
0.92 100.00 15.00 1.80 2.257E-002 2.257E-002
0.97 100.00 15.00 1.75 9.832E-003 9.832E-003

0.00 100.00 15.00 5.16 3.333E-001 0.000E+000
0.05 100.00 15.00 4.79 3.204E-001 0.000E+000
0.10 100.00 15.00 4.46 3.071E-001 0.000E+000
0.15 100.00 15.00 4.16 2.934E-001 0.000E+000
0.19 100.00 15.00 3.90 2.797E-001 0.000E+000
0.24 100.00 15.00 3.68 2.660E-001 0.000E+000
0.29 100.00 15.00 3.48 2.525E-001 0.000E+000
170
0.34 100.00 15.00 3.30 2.394E-001 0.000E+000


EQUIPMENT SUMMARIES
0.39 100.00 15.00 3.15 2.269E-001 0.000E+000

0.44 100.00 15.00 3.01 2.147E-001 0.000E+000
0.49 100.00 15.00 2.88 2.018E-001 0.000E+000
0.53 100.00 15.00 2.75 1.877E-001 0.000E+000
0.58 100.00 15.00 2.62 1.724E-001 0.000E+000
0.63 100.00 15.00 2.50 1.555E-001 0.000E+000
0.68 100.00 15.00 2.37 1.370E-001 0.000E+000
0.73 100.00 15.00 2.24 1.166E-001 0.000E+000
0.78 100.00 15.00 2.12 9.431E-002 0.000E+000
0.83 100.00 15.00 2.00 7.017E-002 0.000E+000
0.87 100.00 15.00 1.89 4.509E-002 0.000E+000
0.92 100.00 15.00 1.80 2.257E-002 0.000E+000
0.97 100.00 15.00 1.75 9.832E-003 0.000E+000

0.00 100.00 15.00 5.16 0.000E+000 0.000E+000
0.05 100.00 15.00 4.79 3.868E-002 0.000E+000
0.10 100.00 15.00 4.46 7.872E-002 0.000E+000
0.15 100.00 15.00 4.16 1.196E-001 0.000E+000
0.19 100.00 15.00 3.90 1.609E-001 0.000E+000
0.24 100.00 15.00 3.68 2.020E-001 0.000E+000
0.29 100.00 15.00 3.48 2.424E-001 0.000E+000
0.34 100.00 15.00 3.30 2.817E-001 0.000E+000
0.39 100.00 15.00 3.15 3.194E-001 0.000E+000
0.44 100.00 15.00 3.01 3.559E-001 0.000E+000
0.49 100.00 15.00 2.88 3.946E-001 0.000E+000
0.53 100.00 15.00 2.75 4.367E-001 0.000E+000
0.58 100.00 15.00 2.62 4.829E-001 0.000E+000
0.63 100.00 15.00 2.50 5.335E-001 0.000E+000
0.68 100.00 15.00 2.37 5.891E-001 0.000E+000
0.73 100.00 15.00 2.24 6.502E-001 0.000E+000
0.78 100.00 15.00 2.12 7.171E-001 0.000E+000
0.83 100.00 15.00 2.00 7.895E-001 0.000E+000
0.87 100.00 15.00 1.89 8.647E-001 0.000E+000
0.92 100.00 15.00 1.80 9.323E-001 0.000E+000
0.97 100.00 15.00 1.75 9.705E-001 0.000E+000

0.00 100.00 15.00 5.16 0.000E+000
0.05 100.00 15.00 4.79 0.000E+000
0.10 100.00 15.00 4.46 0.000E+000
0.15 100.00 15.00 4.16 0.000E+000
0.19 100.00 15.00 3.90 0.000E+000
0.24 100.00 15.00 3.68 0.000E+000
0.29 100.00 15.00 3.48 0.000E+000
0.34 100.00 15.00 3.30 0.000E+000

EQUIPMENT SUMMARIES
0.39 100.00 15.00 3.15 0.000E+000

171
0.44 100.00 15.00 3.01 0.000E+000

0.49 100.00 15.00 2.88 0.000E+000
0.53 100.00 15.00 2.75 0.000E+000
0.58 100.00 15.00 2.62 0.000E+000
0.63 100.00 15.00 2.50 0.000E+000
0.68 100.00 15.00 2.37 0.000E+000
0.73 100.00 15.00 2.24 0.000E+000
0.78 100.00 15.00 2.12 0.000E+000
0.83 100.00 15.00 2.00 0.000E+000
0.87 100.00 15.00 1.89 0.000E+000
0.92 100.00 15.00 1.80 0.000E+000
0.97 100.00 15.00 1.75 0.000E+000
Mixer Summary
Equip. No. 4 7 9
Name M 101 M 102 M 103
Heat Exchanger Summary
Equip. No. 8 14
Name H 101
1st Stream dp atm 0.0011 0.0003
2nd Stream dp atm 0.0366 0.0166
Input heat duty MJ/h 35.5693 61.8091
U W/m2-K 241.3231 90.5884
Area/shell m2 2.4126 1.1952
Shells in Series 1 1
No. of SS Passes 1 1
No. of TS Passes 1 1
Calc Ht Duty MJ/h 35.5693 61.8091
LMTD (End points) C 18.7606 156.2168
LMTD Corr Factor 1.0000 1.0000
Calc U W/m2-K 241.3231 90.5884
Calc Area m2 2.4126 1.1952
1st Stream Pout atm 1.9893 14.9935
2nd Stream Pout atm 0.9632 0.9833
Install factor 2.0000
Material factor 1.0000
Pressure factor 0.9043
Type factor 0.4131
Basic cost $ 0 4803
Total purchase cost $ 0 3032
Total installed cost 0 6064

EQUIPMENT SUMMARIES
($)
Simulation Mode 1 1
Tube fouling m2-K/W 0.0002 0.0002
Shell fouling m2-K/W 0.0002 0.0002
Syphon Recir. Tout C 95.0000 100.1232
172

EQUIPMENT SUMMARIES
Divider Summary
Equip. No. 10
Name D 101
Output stream #1 0.1000
SCDS Rigorous Distillation Summary
Equip. No. 11
Name
No. of stages 12
1st feed stage 12
Condenser type 1
Condenser mode 1
Condenser spec 1.2000
Reboiler mode 2
Reboiler spec. 31.1951
Est. dist. rate 0.4817
(kmol/h)
Est. reflux rate 0.5779
(kmol/h)
Est. T top C 159.2840
Est. T bottom C 164.4430
Calc cond duty MJ/h -4.4172
Calc rebr duty MJ/h 31.1951
Initial flag 6
Calc Reflux mole 0.1185
(kmol/h)
Calc Reflux ratio 1.2000
Calc Reflux mass kg/h 8.7645
Optimization flag 1
Calc. tolerance 1.2711e-008

EQUIPMENT SUMMARIES
Compressor Summary
Equip. No. 12 13 17
Name C 101 C 102 C 103
Pressure out atm 3.8700 15.0000 2.0000
Type of Compressor 1 1 1
Efficiency 0.7500 0.7500 0.7500
Actual power MJ/h 29.1644 41.4739 2.1931
Cp/Cv 1.3272 1.2699 1.3971
Theoretical power 21.8733 31.1055 1.6448
(MJ/h)
Ideal Cp/Cv 1.3258 1.2681 1.3956
Calc Pout atm 3.8700 15.0000 2.0000
173
Calc. mass flowrate 99 99 27

(kg/h)
Expander Summary
Equip. No. 15 16
Name E 101 E 102
Pressure out atm 5.0000 2.0000
Type of Expander 1 1
Efficiency 0.8000 0.8000
Actual power MJ/h -0.3435 -0.5281
Cp/Cv 1.2675 1.1758
Theoretical power -0.4294 -0.6602
(MJ/h)
Ideal Cp/Cv 1.1016 1.1039
Calc Pout atm 5.0000 2.0000
Three Phase Flash Summary
Equip. No. 18
Name
Flash Mode 1
Param1 95.0000
Param2 1.0000
Heat duty MJ/h -10.5967
Single phase flag 1

EQUIPMENT SUMMARIES
Pipe / Line Sizing Summary
Equip. No. 19 20 21
Name
Method 6 6 3
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 10.0000 10.0000 3.0000
Roughness factor m 4.5720e-005 4.5720e-005 4.5720e-005
Pressure drop atm 0.0131 0.0300 0.0254
Reynolds # vap 55732.9102 36000.6992 85933.0078
Fric factr vap 0.0253 0.0266 0.0243
Avg density kg/m3 1.1536 0.6135 0.7520
Calc. Velocity m/sec 16.4285 33.0603 52.1756
DP friction atm 0.0131 0.0300 0.0254
Output press. atm 0.9869 0.9700 0.9446
DP/100ft, psi 0.5857 1.3458 3.7918
Gas Flow kg/h 48.2529 51.6444 99.8973
Gas Density kg/m3 1.1536 0.6135 0.7520
Gas Viscosity N-s/m2 1.0207e-005 1.6912e-005 1.3705e-005
Total ELength m 10.0000 10.0000 3.0000
Iteration mass rate 48.2529 51.6444 99.8973
(kg/h)
174
Friction fac. model 1 1 1

Incl. expansion fac. 1 1 1
Pipe wall cond W/m-K 51.2818 51.2818 51.2818
Equip. No. 22 23 24
Name
Method 6 6 6
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 1.0000 5.0000 9.0000
Reynolds # vap 61232.7891 46899.5352
Fric factr vap 0.0250 0.0258
Avg density kg/m3 1.9723 5.3062 32.7019
DP friction atm 0.0032 0.0062 0.0057
Flow regime 3.0000
Output press. atm 3.8668 14.9938 0.9775
DP/100ft, psi 1.4428 0.5517 0.2857
Gas Flow kg/h 99.8973 99.8973 3.0118
Liquid Flow kg/h 171.7337
Gas Density kg/m3 1.9723 5.3062 0.5832
Liquid Density kg/m3 957.7244
Liq Viscosity N-s/m2 0.0003

EQUIPMENT SUMMARIES
Surface Tension N/m 0.0586

Total ELength m 1.0000 5.0000 9.0000
DP acceleration atm 3.1097e-005
(kg/h)
Equip. No. 25 26 30
Name
Method 3 6 6
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 10.0000 7.0000 7.0000
Reynolds # vap 15901.0244 73075.3672
Fric factr vap 0.0304 0.0246
Avg density kg/m3 1.3085 9.5732 473.0051
DP friction atm 0.0045 0.0046 0.0002
Flow regime 2.0000
Output press. atm 0.9955 14.9889 14.9998
DP/100ft, psi 0.2007 0.2921 0.0098
Gas Flow kg/h 27.5191 99.8973 1.0326
Gas Density kg/m3 1.3085 9.5732 15.3902
175

Total ELength m 10.0000 7.0000 7.0000
(kg/h)
Equip. No. 31 32 33
Name
Method 6 6 3
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 1.0000 2.0000 2.0000
Pressure drop atm 6.8591e-005 0.0006 0.0006
Reynolds # vap 12986.2471
Fric factr vap 0.0316

EQUIPMENT SUMMARIES
Avg density kg/m3 102.2437 21.3704 2.0141

DP friction atm 6.8586e-005 0.0006 0.0006
Flow regime 2.0000 2.0000
Output press. atm 4.9999 1.9994 1.9994
DP/100ft, psi 0.0307 0.1443 0.1354
Gas Flow kg/h 6.9878 17.9479 27.5191
Liquid Flow kg/h 92.9098 81.9497
Gas Density kg/m3 8.2599 3.9322 2.0141
Liquid Density kg/m3 708.9027 742.9166
Liq Viscosity N-s/m2 0.0002 0.0002
Surface Tension N/m 0.0134 0.0167
Total ELength m 1.0000 2.0000 2.0000
DP acceleration atm 4.6354e-009 1.0200e-006
(kg/h)
Equip. No. 34 35 36
Name
Method 6 6 6
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 5.0000 8.0000 11.0000
Pressure drop atm 0.0012 0.0311 2.7452e-005
Avg density kg/m3 71.3296 4.0575 133.5129
DP friction atm 0.0012 0.0308 2.7452e-005
Flow regime 2.0000 4.0000 1.0000
Output press. atm 1.9988 1.9348 1.9994
DP/100ft, psi 0.1083 1.7222 0.0011
Gas Flow kg/h 3.8876 120.1776 0.1473
Liquid Flow kg/h 137.6857 21.3965 14.0100
Gas Density kg/m3 2.1178 3.4468 1.6185
176
Liquid Density kg/m3 923.5594 827.1500 933.0534

Liq Viscosity N-s/m2 0.0005 0.0003 0.0006
Surface Tension N/m 0.0206 0.0182 0.0208
Total ELength m 5.0000 8.0000 11.0000
DP acceleration atm 7.5134e-007 0.0004 1.1187e-010
(kg/h)

EQUIPMENT SUMMARIES
Equip. No. 37 38 39
Name
Method 6 6 6
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 5.0000 6.0000 5.0000
Avg density kg/m3 133.5483 3.7149 6.8719
DP friction atm 0.0006 0.0233 0.0089
Flow regime 2.0000 4.0000 4.0000
Output press. atm 1.9994 1.9659 1.9904
DP/100ft, psi 0.0497 1.7410 0.7947
Gas Flow kg/h 1.4731 126.3288 60.1603
Liquid Flow kg/h 140.1002 1.0880 67.2565
Gas Density kg/m3 1.6189 3.6833 3.2599
Liquid Density kg/m3 933.0527 754.6280 773.2392
Liq Viscosity N-s/m2 0.0006 0.0002 0.0003
Surface Tension N/m 0.0208 0.0179 0.0198
Total ELength m 5.0000 6.0000 5.0000
DP acceleration atm 1.4074e-007 0.0001 6.8905e-005
(kg/h)
Equip. No. 40 41 42
Name
Method 6 6 6
Pipe diameter m 0.0300 0.0300 0.0300
Pipe Length m 7.0000 10.0000 10.0000
Pressure drop atm 0.0002 0.0010 6.5543e-005
Reynolds # vap 3677.9370
Reynolds # liq 6938.5264
Fric factr vap 0.0433
Fric factr liq 0.0365
Avg density kg/m3 961.3817 133.5129 2.8502
DP friction atm 0.0002 0.0010 6.5543e-005
Flow regime 2.0000
177
Output press. atm 0.9998 1.9984 1.9984

DP/100ft, psi 0.0132 0.0460 0.0029
Gas Flow kg/h 1.3259 4.1376
Liquid Flow kg/h 174.7455 126.0901

EQUIPMENT SUMMARIES
Gas Density kg/m3 1.6185 2.8502

Liquid Density kg/m3 961.3817 933.0536
Gas Viscosity N-s/m2 1.6255e-005 1.3262e-005
Liq Viscosity N-s/m2 0.0003 0.0006
Surface Tension N/m 0.0596 0.0208
Total ELength m 7.0000 10.0000 10.0000
(kg/h)
Equip. No. 43
Name
Method 6
Pipe diameter m 0.0300
Pipe Length m 10.0000
Roughness factor m 4.5720e-005
Pressure drop atm 0.0002
Reynolds # liq 4558.7134
Fric factr liq 0.0407
Avg density kg/m3 844.5745
Calc. Velocity m/sec 0.0573
DP friction atm 0.0002
Output press. atm 1.9982
DP/100ft, psi 0.0083
Total ELength m 10.0000
Iteration mass rate 123.2784
(kg/h)
Friction fac. model 1
Incl. expansion fac. 1
Pipe wall cond W/m-K 51.2818
* Pipe flow regime ( Baker)

0 = Single phase, 1 = Dispersed flow, 2 = Annular flow ,
3 = Bubble flow , 4 = Stratified , 5 = Wave flow ,
6 = Slug flow , 7 = Plug flow , 8 = Vertical flow
* Pipe flow regime ( Beggs and Brill )
0 = Single phase, 1 = Segregated , 2 = Transition ,
3 = Intermittent, 4 = Distributed

178
Overall Mass Balance kmol/h kg/h

Input Output Input Output
Carbon Monoxide 1.720 0.017 48.177 0.483
Ethylene 1.720 0.017 48.253 0.484
Hydrogen 1.720 0.017 3.467 0.035
Propionic Acid 0.000 1.701 0.000 126.028
Oxygen 0.860 0.009 27.519 0.300
Water 9.700 9.700 174.745 174.745
Total 15.720 11.464 302.162 302.161
Overall Energy Balance MJ/h

Input Output
Feed Streams -2871.43
Product Streams -3540.54
Total Heating 31.1951
Total Cooling -772.27
Power Added 72.8315
Power Generated -0.871687
Total -3540.54 -3540.54

179
C.1. MSDS for Ethylene

180
181
C.2. MSDS for Propionaldehyde

182
183
C.3 MSDS for Propionic Acid

184
185
D. SPECIFICATION SHEETS
Equipment
C 101
No.
COMPRESSOR DATA SHEET Description Compressor
Sheet No 1
Function : Increase the pressure of inlet gaseous stream
Operation : Continuous
Materials handled : Carbon Monoxide, Ethylene , Hydrogen
Operation Conditions
In Out
Temperature
Pressure 0.9446 atm 3.87 atm
Material of Construction Carbon Steel
Flowrate 99.8973 kg/h
Design Data
Type Centrifigual (Adiabatic)
Cp/Cv 1.325578
Power Required 29.1644 MJ/h
Efficiency 0.75
186
Equipment
C 102
No.
Sheet No 2
Materials handled : Carbon Monoxide, Ethylene , Hydrogen
In Out
Temperature
Pressure 3.86 atm 15 atm
Design Data
Cp/Cv 1.26807
Efficiency 0.75
187
Equipment
C 103
No.
Sheet No 3
Materials handled : Oxygen
In Out
Temperature
Design Data
Cp/Cv 1.39561
Efficiency 0.75
188
Equipment
D 101
No.
Distillation
DISTILLATION COLUMN DATA SHEET Description
Column
Sheet No 4
Function : Separates mixture as gaseous and liquid stream
Carbon Monoxide, Ethylene, Oxygen, Hydrogen, Propionaldehyde,

Materials handled :
Propionic Acid
Design Data
Vertical Height 6.6 m
Diameter 1.8 m
Column Type Tray Column
Column Material Carbon Steel
Condenser Type Total
Number of Stages 12
Feed Stages 12
Reflux Ratio 1.2
Condenser Duty -4.41721 MJ/h
Reboiler Duty 31.1951 MJ/h
Top Temperature 159.284
Bottom Temperature 164.443
Light Key- Heavy Key Propionaldehyde - Propionic Acid

189
Equipment
D 101
No.
DIVIDER DATA SHEET Description Divider
Sheet No 5
Function : Divides the streams with different compositions
Carbon Monoxide, Ethylene, Oxygen, Hydrogen, Propionaldehyde,

Materials handled :
Propionic Acid
In Out
14.1573 kg/h
127.4160 kg/h
Temperature 75
Pressure 1.9994 atm
Design Data
Split Ratio 0.9/0.1

190
Equipment
HEX 101
No.
Heat
HEAT EXCHANGER DATA SHEET Description
Exchanger
Sheet No 6
Function : Cool the feed from 389.5219 to 96.9322
Materials handled : Carbon Monoxide, Ethylene, Oxygen, Hydrogen
Size 1.19524 m2 Type Shell and Tube
Shell per unit 1 Tube Per Pass Unit 1
Performance of One Unit
Tube Side Shell Side
Carbon Monoxide, Ethylene,

Material Water
Oxygen, Hydrogen
Total Flow Entering 99.8973 kg/h 174.7455 kg/h
In Out In Out
Temperature 389.5219 96.9322
Pressure 14.9938 atm 14.9935 atm 1 atm 0.9833 atm
Overall Heat Transfer

90.5884 W/m2.K
Coefficient
Heat Duty 61.8091 MJ/h
Utility Water
191
Equipment
HEX 102
No.
Heat
HEAT EXCHANGER DATA SHEET Description
Exchanger
Sheet No 7
Function : Heat the feed from 39.5001 to 55.3172
Materials handled : Carbon Monoxide, Ethylene, Oxygen, Hydrogen, Propionaldehyde
Size 2.41256 m2 Type Shell and Tube
Shell per unit 1 Tube Per Pass Unit 1
Performance of One Unit
Tube Side Shell Side
Carbon Monoxide, Ethylene,

Material Oxygen, Hydrogen, Water
Propionaldehyde
Total Flow Entering 127.4167 kg/h 174.7455 kg/h
In Out In Out
Temperature 39.5001 96.9322
Pressure 1.9904 atm 1.9893 atm 0.9998 atm 0.9632 atm
Overall Heat Transfer

241.323 W/m2.K
Coefficient
Heat Duty 35.5693 MJ/h
Utility Water
192
Equipment
MIX 101
No.
MIXER DATA SHEET Description Mixer
Sheet No 8
Materials handled : Carbon Monoxide, Ethylene, Hydrogen,
In Out
51.6444 kg/h
Flowrate 99.89.73 kg/h
48.2529 kg/h
Temperature 31.4451
Design Data
Outlet Pressure 0.97 atm

193
Equipment
MIX 102
No.
Sheet No 9
Materials handled : Carbon Monoxide, Ethylene, Hydrogen, Oxygen
In Out
99.8976 kg/h
27.5191 kg/h
Temperature 39.5968
Design Data

194
Equipment
MIX 103
No.
Sheet No 10
Materials handled : Carbon Monoxide, Ethylene, Hydrogen, Oxygen
In Out
127.4167 kg/h
14.1573 kg/h
Temperature 71.8441
Design Data

195
ID No. 19
PIPE DATA SHEET Description Pipe Simulator
Sheet No 11
Materials handled : Ethylene
Temperature 25
Pressure 1 atm
Design Data
Thermal Mode Adiabatic
Pipe Length 10 m
Pipe Diameter 0.03 m
Roughness Factor 4.572*10-5 m
Pressure Drop 0.0131 atm
Fitting -
Equivalent Length 10 m

196
ID No. 20
Sheet No 12
Materials handled : Carbon Monoxide, Hydrogen
Temperature 25
Pressure 1 atm
Design Data
Pipe Length 10 m
Fitting -

197
ID No. 21
Sheet No 13
Materials handled : Ethylene, Carbon Monoxide, Hydrogen
Temperature
Pressure 0.97 atm
Design Data
Pipe Length 3m
Fitting -
Equivalent Length 3m

198
ID No. 22
Sheet No 14
Temperature
Pressure 3.87 atm
Design Data
Pipe Length 1m
Fitting -

199
ID No. 23
Sheet No 15
Temperature
Pressure 15 atm
Design Data
Pipe Length 5m
Fitting -

200
ID No. 24
Sheet No 16
Materials handled : Water
Temperature
Pressure 0.9833 atm
Design Data
Pipe Length 9m
Fitting -

201
ID No. 25
Sheet No 17
Temperature
Pressure 1 atm
Design Data
Pipe Length 10 m
Fitting -

202
ID No. 26
Sheet No 18
Temperature
Pressure 14.9935 atm
Design Data
Pipe Length 7m
Fitting -

203
ID No. 30
Sheet No 19
Materials handled : Ethylene, Carbon Monoxide, Hydrogen, Propionaldehyde
Temperature
Pressure 15 atm
Design Data
Pipe Length 7m
Fitting -

204
ID No. 31
Sheet No 20
Temperature
Pressure 5 atm
Design Data
Pipe Length 1m
Fitting -

205
ID No. 32
Sheet No 21
Temperature
Pressure 5 atm
Design Data
Pipe Length 2m
Fitting -

206
ID No. 33
Sheet No 22
Temperature
Pressure 2 atm
Design Data
Pipe Length 2m
Fitting -

207
ID No. 39
Sheet No 23
Materials handled : Ethylene, Carbon Monoxide, Hydrogen, Propionaldehyde, Oxygen
Temperature
Pressure 1.9994 atm
Design Data
Pipe Length 5m
Fitting -

208
ID No. 40
Sheet No 24
Temperature
Pressure 1 atm
Design Data
Pipe Length 7m
Fitting -

209
ID No. 38
Sheet No 25
Materials handled : Ethylene, Carbon Monoxide, Hydrogen, Propionaldehyde, Oxygen
Temperature
Pressure 1.9893 atm
Design Data
Pipe Length 6m
Fitting -

210
ID No. 35
Sheet No 26
Ethylene, Carbon Monoxide, Hydrogen, Propionaldehyde, Oxygen,

Materials handled :
Propionic Acid
Temperature
Pressure 1.9659 atm
Design Data
Pipe Length 8m
Fitting -

211
ID No. 34
Sheet No 27

Materials handled :
Propionic Acid
Temperature
Pressure 2 atm
Design Data
Pipe Length 5m
Fitting -

212
ID No. 37
Sheet No 28

Materials handled :
Propionic Acid
Temperature
Pressure 2 atm
Design Data
Pipe Length 5m
Fitting -

213
ID No. 36
Sheet No 29

Materials handled :
Propionic Acid
Temperature
Pressure 1.9994 atm
Design Data
Pipe Length 11 m
Fitting -

214
ID No. 41
Sheet No 30

Materials handled :
Propionic Acid
Temperature
Pressure 1.9994 atm
Design Data
Pipe Length 10 m
Fitting -

215
ID No. 42
Sheet No 31

Materials handled :
Propionic Acid
Temperature
Pressure 1.9984 atm
Design Data
Pipe Length 10 m
Fitting -

216
ID No. 43
Sheet No 32

Materials handled :
Propionic Acid
Temperature
Pressure 1.9984 atm
Design Data
Pipe Length 10 m
Fitting -

217
Equipment
R 101
No.
REACTOR DATA SHEET Description Reactor
Sheet No 33
Function : Production of Propionaldehyde
Operation : Isothermal
Design Data
Type of Reactor Plug Flow
Number of Reactions 1
Conversion 0.99
Reactor Volume 0.971367 m3
Amount Feed 99.8973 kg/h
Diameter of Tubes 0.022 m
Number of Tubes 1358
Material Construction Carbon Steel
Catalyst Rhodium
Catalyst Weight 433 kg
Operating Conditions
In Out
Temperature 100 100
Pressure 15 atm 15 atm

218
Equipment
R 102
No.
Sheet No 34
Function : Production of Propionic Acid

Materials handled :
Propionic Acid
Design Data
Conversion 0.937
Catalyst Rhodium
In Out
Temperature 75 75

219
Equipment
R 103
No.
Sheet No 35
Function : Production of Propionic Acid

Materials handled :
Propionic Acid
Design Data
Conversion 0.985
Catalyst Rhodium
In Out
Temperature 75 75

220
Equipment
F 101
No.
FLASH DRUM DATA SHEET Description Reactor
Sheet No 36
Function : Separate vapor from liquid
Design Data
Volume 14.09 m3
Lenght 5.3 m
Diameter 1.84 m
In Out
Temperature 99.959 95

ChE 462 Chemical Plant Design and Econom

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ChE 462 Chemical Plant Design and Econom

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ChE 462

Chemical Plant Design and Economics

PRODUCTION OF PROPIONIC ACID

Course Instructor : Assoc. Prof. Ahmet Kerim AVCI

Department of Chemical Engineering

DECLARATION OF INDEPENDENT WORK

WE HAVE NEITHER GIVEN NOR RECEIVED ANY

DECLARATION OF INDEPENDENT WORK ....................................................................... ii

4.3.2. General Mass Balance ......................................................................................... 37

5.5.1. Manufacturing Costs............................................................................................. 90

Table 4.12. Mass Balance for Heat Exchangers. 40

Table 5.9. Mixer and Divider Diameters. 75

1996 1997 1999

2. MARKET SURVEY AND CAPACITY DETERMINATION

2.1. Market Survey

Figure 2.1. Worldwide Propionic Acid Use Purposes.

2.2. Determination of Consumption In Turkey

Following formula is applied to determine the consumption of propionic acid.

Consumption= Production + Import-Export (Hortaçsu, 2004)

Table 2.1. UN Data for Propionic Acid Consumption.

Table 2.2. TUIK and UN Data Cross-Check.

TUIK DATA UN DATA

Consumption = Production + Import - Export

Consumption = 0 + 116,515 - 27 = 116,488 kg/year

Figure 2.2. TUIK vs. UN Data.

n2000 n2001 n2002

n2000 n2001 n2002 n2003 n200

2,023 11 1 ,02 22, 59 2,

Table 2.3. Comparison of Original, 3 YMA and 5 YMA Consumption Values.

Original 3 YMA 5 YMA

Figure 2.3. Comparison of Original, 3 YMA and 5 YMA Consumption Values.

400,000 y = 18512x - 46168

Figure 2.4. 3 YMA Data With Various Trend Lines.

Table 2.4. Percentage of Propionic Acid Consumption in UN Data.

Table 2.5. Growth Rate of Turkey.

GDP per capita, PPP

. .1 5.2 9.3 . . 9 . 0. 9.1 .50

Table 2.6. Data for Austria.

P.Acid GDP per

Table 2.7. Data for Denmark.

P. Acid GDP per

Table 2.8. Data for France.

P. Acid GDP per

Table 2.9. Data for Italy.

Year Import Export Consumption P. Acid Consumption GDP per

Table 2.10. Data for Germany.

2001 11,083,685 43,989,500 80,000,000 47,094,185 19,571 82,349,925 0.00024 26,714

2002 9,594,040 47,301,000 80,000,000 42,293,040 4,306,576 82,488,495 0.05221 27,444

2003 11,696,914 52,207,500 80,000,000 39,489,414 10,161,699 82,534,176 0.12312 28,360

2004 12,592,507 40,071,000 80,000,000 52,521,507 873,734 82,516,260 0.01059 29,679

2005 8,765,670 48,052,800 80,000,000 40,712,870 10,406,776 82,469,422 0.12619 31,115

2006 13,593,276 36,837,300 80,000,000 56,755,976 10,651,614 82,376,451 0.12930 33,503

2007 8,820,763 29,353,200 80,000,000 59,467,563 19,157,310 82,266,372 0.23287 35,538

2008 9,315,167 28,204,200 80,000,000 61,110,967 22,588,988 82,110,097 0.27511 37,119

2009 11,971,917 26,474,321 80,000,000 65,497,596 17,281,943 81,902,307 0.21101 35,631

2010 14,157,848 21,383,400 110,000,000 102,774,448 38,637,432 81,776,930 0.47247 37,652

2011 11,934,164 25,753,346 110,000,000 96,180,818 27,213,079 81,726,000 0.33298 39,491

Table 2.11 N values.

Table 2.12. Corresponding Years of Other Countries to Turkey.

Year Austria Denmark France Germany Italy

Original year = 2000

Table 2.13. Population Projection for Turkey.

Year Population Year Population

Table 2.14. Consumption Estimation- Germany.