REACTOR DESIGN AND COST FOR PRODUCING BIODIESEL FROM

CANOLA OIL FOR lOMILLION GALLONS PER YEAR CONCEPTUAL PLANT

A Thesis

Submitted to the Graduate Faculty of the

University of South Alabama
in partial fulfillment of
the requirements for the degree of

Master of Science
in
Chemical Engineering

by
Shali Vemparala
B.TECH, BRECW (Affiliated with JNT University), 2007
May 2010

UMI Number: 1484491

All rights reserved

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THE UNIVERSITY OF SOUTH ALABAMA

COLLEGE OF ENGINEERING

REACTOR DESIGN AND COST FOR PRODUCING BIODIESEL FROM CANOLA

OIL FOR 10 MILLION GALLONS PER YEAR CONCEPTUAL PLANT
BY
Shali Vemparala
A Thesis
Submitted to the Graduate Faculty of the
University of South Alabama
in partial fulfillment of the
requirements for the degree of
Master of Science
in
Chemical Engineering

May 2010
Approved:
Chair of Thesis Com]

Date:
Q - 2 ) d 4 / 10
Jagdhish C. Dhawan
oijerhj to

Committee Member: Dr. Srinivas Palanki

k
l
H
i ^-.
Committee Member: Dr. Kwang-Ting
K^ang-Tii Hsiao
CCU
._..
Chair of Department: Dr. Srinivas Balanki

Dean of the Graduate School: Dr. B. Keith Harrison

z/y/o

ACKNOWLEDGEMENTS

This work would not have been possible without the support and encouragement of
Dr. Jagdhish C. Dhawan, under whose supervision I chose this topic and began this
thesis. I appreciate the assistance that he has given me throughout my research at
University of South Alabama. I would like to thank Dr. Srinivas Palanki and Dr. KuangTing Hsiao for serving on my committee. I would also like to thank the rest of the
academic staff of Department of Chemical and Biomolecular Engineering for their
cooperation. I cannot end up without thanking my family and friends Mohan, Chaitanya,
Shwetha and Vijyanthi on whose constant encouragement and love, I have relied
throughout my time at the university.

ii

TABLE OF CONTENTS

Page
LIST OF TABLES

vi

LIST OF FIGURES

viii

LIST OF ABBREVIATIONS

NOMENCLATURE

xi

ABSTRACT

xiv

CHAPTER 1: INTRODUCTION

1.1 Energy Consumption in World

1.2 Biodiesel
1.3 Scope and Objectives
1.4 Significance of the Research

1
2
3
4

CHAPTER 2: LITERATURE SURVEY

2.1 History of Biodiesel

2.2 Aliphatic Fatty Acid Chains
2.3 Transesterification of Oils

5
6
8

2.3.1 Base Catalyzed Transesterification Mechanism

2.4 Conceptual Biodiesel Process Block Flow Diagram (BFD)
2.5 Byproduct (Glycerol) Utilization Potential
2.6 Literature Summary - Rate Constants
2.6.1 Reaction Mechanism and Kinetic Rate Data

iii

9
10
12
12
16

CHAPTER 3: BIODIESEL REACTOR DESIGN

3.1 Plug Flow Reactor (PFR) Design
3.2 Performance Equations for a Plug Flow Reactor (PFR)
3.3 MathCAD Solution to PFR Model
3.3.1 Effect of Methanol to Canola Oil Feed Ratio on Conversion
3.4 Aspen Plus Simulation of PFR

20
20
22
25
34
34

3.4.1 Plug Flow Reactor Size for Diameter 0.038m (1.5 inch OD) and 0.051m
(2.0 inch OD) Tubes
36
3.4.2 Effect of Methanol to Canola Oil Molar Feed Ratio on Conversion
43
3.4.3 Plug Flow Reactor Length Required for 1.5 inch OD and 2.0 inch OD Tubes43
3.4.4 Pressure Drop Across Plug Flow Reactor
44
3.4.5 Plug Flow Reactor Cost
46
CHAPTER 4: CONTINUOUS STIRRED TANK REACTOR (CSTR)

48

4.1 Performance Equations Model for a Continuous Stirred Tank Reactor (CSTR)... 48
4.2 MathCAD Solution to CSTR Model
50
4.3 Aspen Plus Simulation of CSTR Model
51
4.3.1 Effect of Residence Time on Conversion
4.3.2 Effect of Reactor Volume on Conversion
4.4 Design Dimensions of the CSTR at Methanol/Oil Molar Feed Ratio of 12
4.5 Continuous Stirred Tank Reactor Cost
4.6 Continuous Stirred Tank Reactor in Series
4.6.1 A System of Three CSTR Biodiesel Reactors in Series
4.6.2 Economic Analysis of Three CSTR in Series
4.6.3 Design of Methanol Recovery Column
4.6.3.1
4.6.3.2
4.6.3.3
4.6.3.4
4.6.3.5

Column Diameter
Tray Hydraulics
Dry Pressure Drop
Check for Down Comer Residence Time
Weeping Check

CHAPTER 5: CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE

RESEARCH
5.1 Conclusions
5.2 Recommendations for Future Research

iv

55
56
56
57
57
57
62
65
65
65
66
69
69

71
71
74

REFERENCES

75

General References

76

APPENDICES

77

Appendix A: MathCAD Program for Solution of PFR for Diameter 0.038m

(1.5 inch OD) and 0.051m (2.0 inch OD) Tubes
Appendix B: PFR Sensitivity Results from Aspen Plus Simulation for Diameter
0.038m (1.5 inch OD) and 0.051m (2.0 inch OD) Tubes
Appendix C: Shell/ Tube Configuration of a PFR
Appendix D: PFR Pressure Drop in 0.038m (1.5 inch OD) and 0.051m
(2.0 inch OD) Tubes
Appendix E: Plug Flow Reactor Cost for Diameter 0.038m (1.5 inch OD) and
0.051m (2.0 inch OD) Tubes
Appendix F: MathCAD Program for a Solution to CSTR
Appendix G: CSTR Sensitivity Results from Aspen Plus Simulation
Appendix H: Sizing of Single CSTR
Appendix I: A Graphical Representation of Purchased Cost of Jacketed and
Stirred Reactors
Appendix J: AspenPlus Input File for Three CSTR in Series with Pump Around
System
Appendix K: Design of Methanol Recovery Column Calculations
BIOGRAPHICAL SKETCH

77
82
92
93
95
99
102
110
111
112
127
139

LIST OF TABLES

Page
Table 1: Fatty acid composition (%wt) in different types of oils

Table 2: Literature summary of biodiesel production from various types of oils

13

Table 3: k values for soybean oil are reported by Noureddini and Zhu, 1997

16

Table 4: k values for vegetable oil are reported by Sharma, 2008

17

Table 5: k values for palm oil are reported by Leevijit, 2004

17

Table 6: k values for soybean oil are reported by Marchetti, 2007

17

Table 7: k values for vegetable oil are reported by Komers, 2002 (based on particular
data regression)

18

Table 8: Reaction kinetics relating rate constants, activation energy and Arrhenius
constant (Noureddini et al., 1997)

19

Table 9: MathCAD results for diameter 0.038m (1.5 inch OD) tube

26

Table 10: MathCAD results for diameter 0.051m (2.0 inch OD) tube

27

Table 11: Summary of ASPEN results of PFR tube OD 0.038m (1.5 inch)

36

Table 12: Summary of ASPEN results of PFR tube OD 0.051m (2.0 inch)

36

Table 13: Cost of plug flow reactor for different diameters

47

Table 14: Summary of MathCAD results for different reactor volume and methanol
to oil molar feed ratio:

51

Table 15: Summary of ASPEN results of CSTR volume 7m3

52

Table 16: Material balance data for three CSTR's in series to produce biodiesel from
canola oil (Plant capacity: 10 million gallons/year of biodiesel product)

60

vi

Table 17: Below summarizes the results of overall conversion as a function of

methanol to canola oil feed ratio

62

Table 18: Total utility cost ($/hr) as a function of methanol to canola oil mole feed
ratio

62

Table 19: Cost of methanol recovery distillation column

63

Appendix
Table 20: Aspen stream results for various methanol to canola oil feed ratios as a the
function of reactor length for diameter 0.038m (1.5 inch OD)

90

Table 21: Aspen stream results for various methanol to canola oil feed ratios as a the
function of reactor length for diameter 0.051m (2.0 inch OD)

91

Table 22: Aspen steam results for various methanol to canola oil molar feed ratio as
function reactor volume of CSTR

109

vii

LIST OF FIGURES

Page
Figure 1: World fuel consumption in year 2008

Figure 2: Schematic diagram of biodiesel production

Figure 3: Schematic diagram of biodiesel production process

11

Figure 4: Canola oil reacts with methanol in PFR to generate biodiesel and glycerol

22

Figure 5: Plug flow reactor length (m) versus conversion of canola oil to biodiesel for
diameter 0.38m (1.5 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)
28
-J

Figure 6: Length (m) of plug flow reactor versus component concentrations (kmol/m )
for diameter 0.038m (1.5 inch OD) at 323K (50C) and 4.053 x 105Pa (4atms)
29
Figure 7: Plug flow reactor length (m) versus conversion of canola oil to biodiesel for
diameter 0.38m (1.5 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)
30
Figure 8: Plug flow reactor length (m) versus conversion of canola oil to biodiesel for
diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)
31
Figure 9: Length of reactor (m) versus component concentrations (kmol/m ) for
diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)

32

Figure 10: Plug flow reactor length (m) versus conversion of canola oil to biodiesel
for diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)

33

Figure 11: ASPEN simulation of PFR diameter-0.038m (1.5 inch) and 0.051m
(2.0 inch) OD

35

Figure 12: Plug flow reactor residence time versus conversion of oil to ester for
diameter 0.038m (1.5 inch OD) at 323K (50C) and 4.053 x 105Pa (4atms)

37

Figure 13: Length of plug flow reactor versus component flow rate for diameter
0.038m( 1.5 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)

38

viii

Figure 14 : Plug flow reactor residence time versus conversion of oil to ester for
diameter 0.38m (1.5 inch OD), 323K (50C) and 4.053 x 105 Pa (4atms)

39

Figure 15: Plug flow reactor residence time versus conversion of canola oil to biodiesel
for diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms)
40
Figure 16: Length of plug flow reactor versus component flow rate for diameter
0.038m (2.0 inch OD) at 323K (50C) and 4.053 x 105Pa (4atms)

41

Figure 17: Plug flow reactor residence time versus conversion of canola oil to biodiesel
for diameter 0.051m (2.0 inch OD), at 323K (50C) and 4.053 x 105 Pa (4atms)
42
Figure 18: 180 degree tube bends of a PFR

44

Figure 19: Canola oil reacts with methanol in a CSTR to produce biodiesel and
glycerol

48

Figure 20: ASPEN Simulation of CSTR volume 7m3

52

Figure 21: Continuous stirred tank reactor residence time versus conversion of canola
oil to biodiesel for methanol to oil ratio 3, 6, 9, 12 varying along the volume of reactor
at 323K (50C) and 4.053 x 105Pa (4tams)
53
Figure 22: Volume of Continuous stirred tank reactor versus component flow rate for
methanol to oil ratio 12 at 323K (50C) and 4.053 x 105Pa (4tams)
54
Figure 23: Continuous stirred tank reactor residence time versus conversion of canola
oil to biodiesel for methanol to oil ratio 12 varying along the volume of reactor at
323K (50C) and 4.053 x 105Pa (4tams)
55
Figure 24: ASPEN simulation of three CSTR's in series

59

Figure 25: Methanol to oil mole ratio versus total cost

64

Figure 26: Schematic diagram of distillation column

65

Appendix
Figure 27: Conversion of canola oil to biodiesel versus length of reactor for diameter
0.038m (1.5 inch OD) tube

79

Figure 28: Conversion of canola oil to biodiesel versus length of reactor for diameter
0.051m (2.0 inch OD) tube

81

Figure 29: Purchased cost of jacketed and stirred reactors (Peters et al., 2003)

ix

111

LIST OF ABBREVIATIONS

FAME

Fatty Acid Methyl Esters

PFR

Plug Flow Reactor

CSTR

Constant Stirred Tank Reactor

LHSV

Liquid Hourly Space Velocity

NOMENCLATURE

English Letters
Symbol

Description

Units

Arrhenius constant

L/mol*min

Ar

Area of the reactor

Area

Area of plug flow reactor

m2

BD

Biodiesel

unitless

concentration

mol/m

CONV

Conversion of canola oil to biodiesel

unitless

Cost

Cost of Plug Flow Reactor (2008)

DG

Diglyceride

unitless

DSheii

Shell inside diameter

Activation Energy

J/mol

Friction factor

unitless

flow rate

mol/s

Fm

Material Factor for a 316 stainless steel pipe

unitless

GY

Glycerol

unitless

ID

Tube inside diameter

Assumed length of a shell

xi

Lreactor

Total length of a PFR

TG, DG, MG, A, BD, GY.

Unitless

Rate constant

m3/mol.min

Kf

Frictional loss in a 180 degree bend

unitless

mins

minutes

minutes

MG

Monoglyceride

unitless

ME

Methanol

unitless

NtUbes

Total number of tubes in a PFR

unitless

OD

Tube out side diametr

APrcactor

Pressure drop in PFR

Pa

APtotal

Pressure drop in all the tubes of a PFR

Pa

Triglyceride of canola oil

unitless

Rate of reaction

min"1

R'

Alcohol group

unitless

TG

Triglyceride

unitless

Volume of reactor

m3

Wj

Conversion of canola oil to biodiesel for a methanol

to oil feed ratio of 3

unitless

Xj

Conversion of canola oil to biodiesel for a methanol

to oil feed ratio of 6

unitless

Yj

Conversion of canola oil to biodiesel for a methanol

to oil feed ratio of 9

unitless

Zj

Conversion of canola oil to biodiesel for a methanol

to oil feed ratio of 12

unitless

xii

Greek Letters
Symbol

Description

Units

Density of liquid in side a tube

kg/ m 3

volumetric flow rate

m /s

velocity in a tube

m/s

residence time

residence time

xiii

ABSTRACT

Vemparala, Shali, M.S., University of South Alabama, May 2010, Reactor Design and
Cost for Producing Biodiesel from Canola Oil for 10 Million Gallons Per Year
Conceptual Plant. Chair of Committee: Dr. Jagdhish C. Dhawan.
Biodiesel can be produced from many natural renewable sources (vegetable oils,
animal fats, algae etc). The present study concentrates on production of biodiesel using
canola oil and methanol as reactants at 298K (25C) and 4.053 x 105 Pa (4atms) in the
presence of sodium methylate acting as catalyst. A plug flow (PFR) and continuous
stirred tank (CSTR) reactors are designed using the rate expressions available from the
literature. Reactor performance was evaluated with respect to conversion versus reactor
volume and the effect of methanol to oil molar feed ratio on conversion at 323K (50C)
and 4.053 x 105 Pa (4atms) was also evaluated. A plug flow reactor of 1.50 inch OD
requires a total length of 2580 meters. The reactor length can be decreased to 1140 meters
when the diameter is 2.0 inch OD. The reactor pressure drop is significantly high and
ranges from 1.317 x 106 Pa (13atms) to 3.445 x 106 Pa (34atms) depending upon the
reactor length. A single CSTR of 7m volume provides 90.3% conversion. However, if
three 5m3 volume CSTR reactors are used in series, an overall conversion of 99.9% can
be achieved. Three CSTR reactors in series with a pump around system for thorough
mixing are recommended. A conversion of 99.9% eliminates the product purification
step to recover the un-reacted material from the product stream.

xiv

CHAPTER 1: INTRODUCTION

1.1 Energy Consumption in World

Energy is an integrated part of human life. Energy can be obtained from two different
sources, renewable and non renewable. The primary source of energy has been from non
renewable sources which are fossil fuels. These fuels include coal, oil and natural gas.
Fuel consumption in the world is shown in the Figure 1 (BP Statistical Review, 2008).

Hydro

^^.Nuclem

6.50%

Figurel: World fuel consumption in year 2008.

The fossil fuel reserves in the world are so unevenly distributed that many countries
have to depend on other countries for their requirements to be fulfilled. The recovery and

processing of fossil fuels is known to damage the environment we live in. When fossil
fuels undergo combustion acids like carbonic, sulfuric and nitric are released, which are
the main cause of acid rains. Small amounts of radioactive materials like uranium and
thorium are also present in fossil fuels; hence these together harm the environment when
released into the atmosphere (Gabbard, 1993). All these factors necessitate continued
search and sustainable development of renewable energy sources such as biofuels that are
environmentally friendly.

1.2 Biodiesel
Energy derived from biological sources is Bio-energy. Bio-energy sources are
biomass (e.g. forest residue), biogas (e.g. methanol), biofuel (biodiesel, bio-ethanol and
bio-methanol). Vegetable oils are used as raw material for biofuels to serve as an
alternative source of transportation fuel.
Biodiesel is a sulfur-free clean burning alternative fuel, which can be produced from
domestic renewable resources. Biodiesel contains no petroleum. It can be blended at any
concentration with petroleum-derived diesel to make a biodiesel blend. It can be used in
diesel engines with little or no modifications. Biodiesel can easily be adapted to reduce
gasoline consumption and is free of sulfur and aromatics.
These biofuels are non toxic, renewable and they are not associated with adverse
effects on the environment because they emit less harmful emissions and green house
gases.

1.3 Scope and Objectives

In this thesis a Plug Flow Reactor (PFR) and a Continous Stirred Tank Reactor
(CSTR) are designed to produce 10 million gallons of biodiesel (Haas et al., 2006 and
Noureddini and Zhu, 1997) from Canola oil.

Figure 2: Schematic diagram of biodiesel production.

The specific objectives are as follows:

1) Design a PFR and a CSTR; make recommendations for reactor choice to produce
biodiesel from Canola oil.
2) Evaluate the impact of methanol to canola oil mole feed ratio on the reactor conversion
3) Conduct Aspen simulations for reactor effluent separation into biodiesel product,
glycerol co-product and recovery and recycle of excess methanol
4) Carry out preliminary equipment sizing of PFR, CSTR and, a sieve tray distillation
column for methanol recovery.
5) Estimate and compare the costs of a PFR and a CSTR.

1.4 Significance of the Research

Biodiesel is a liquid transportation fuel that can be produced from renewable raw
material such as Canola oil. Reaction kinetics of transesterification of vegetable oils into
Fatty Acid Methyl Esters (FAME) called Biodiesel, have been experimentally established
and are well documented in the open literature. However, to produce 10 million gallons
of biodiesel per year in a large capacity commercial-size plant, a detailed design and
analysis of biodiesel reactor is required. The main significance of this research is the
design of a suitable PFR or CSTR under most economical conditions.
An important property of biodiesel is that it can be directly blended in any petroleum
based liquid fuels such as diesel. Biodiesel and petroleum diesel blends are designated
with letter ' B \ For example B20 indicates 20% of biodiesel and 80% of petroleum diesel
and B100 indicates pure biodiesel. Biodiesel blends perform better than petroleum
diesel. Biodiesel can also be used in automobiles without any blending with petroleum
derived diesel (National Biodiesel Board, 2001).
Lubricity is an important property of diesel fuel. The National Biodiesel Board found
that one half of samples of petroleum based diesel sold in the Unites States did not meet
the current standard for lubricity (National Biodiesel Board, 2001). Biodiesel has better
lubricity than low sulfur petroleum diesel (500 ppm of sulfur by wt). In 2006 ultra-low
sulfur petroleum (15pp of sulfur by wt) was introduced, which has even less lubricity. A
small percentage (1-2%) of biodiesel in low sulfur petroleum improves lubricity.
In this research we investigate the feasibility of production of biodiesel in a PFR and a
CSTR. The reaction kinetics and rate constants used are those that have been
experimentally determined by Noureddini and Zhu, 1997.

CHAPTER 2: LITERATURE SURVEY

2.1 History of Biodiesel

In 1853 Duffy and Patrick conducted transesterifiction of vegetable oil, before diesel
engine came into existence. Diesel's model, an iron cylinder 1 Oft (3m) long with a
flywheel as its base, was able to run on its own power for the first time in Augsburg,
Germany on Aug 10, 1893. This day is now acknowledged as "International biodiesel
day" (Knothe, 2001).
A diesel engine running on peanut oil built by French Otto Company was
demonstrated by Diesel inl900 at the World Fair in Paris, where it received the Grand
Prix award.
The petroleum industry entered into fuel markets because petroleum oil-based fuel
was much cheaper to produce than biomass-derived fuel. Hence in the 1920s, diesel
engine manufacturers were altering their engines to accommodate a lower viscosity
petroleum fuel rather than vegetable oils. As a result biomass based fuels have been
neglected (Knothe, 2001).
A Beligian Patent granted in 1937 to Chavanne, constitutes the first report on what is
today known as biodiesel (Chavanne, 1938 and Knothe, 2001). It describes the use of
ethyl esters of palm oil as a diesel engine fuel. These esters were obtained by acid
catalyzed transesterification of the oil.

2.2 Aliphatic Fatty Acid Chains

Table 1 shows the typical range of saturated and unsaturated fatty acids concentration
(mass %) of vegetable oils suitable as raw materials to produce biodiesel fuel (McCance
etal., 1991).

Table 1: Fatty acid composition (%wt) in different types of oils.

Saturated

Soybean
oil
Canola oil

Unsaturated
Poly -unsaturated
Mono unsaturated
Capric Laurie Myristi Palmitic Stearic Oleic acid Linoleic Alpha
acid
linoleic
acid
acid
acid c acid
acid
acid
54%
7%
11%
4%
24%

Palm oil
Vegetable
oil

1%
-

4%

2%

62%

22%

45%
15%

4%
5%

40%
25-30%

10%
45-50%

10%
-

2-3%

Chemical structures of typical fatty acids are given below:

1)

Myristic acid (C14H28O2)

O

H3C
2)

H3C

H2C

H2C

H2C

H2C

H2C

H2C

OH

H2C

H2C

Palmitic acid (C,6H3202)

H2C

H2C

H2C

H2C

H2C

C OH

3)

Stearic acid (CibH3602)

0

H3C

4)

H2C

H2C

H2C

H2C

H2C

H2C

H2C

H2C

OH

Oleic acid (Ci 8 H 34 0 2 )

H3C

5)

H2C

H2C

H2C

HC

H2C

H2C

H2C

H2C OH

Linoleic acid (Ci8H 32 0 2 )

0

H3C

6)

H3C

H2C

H2C

HC

HC

H2C

H2C

HC

H2C

H2C

H2C

H2C

OH

Alpha Linoleic acid (Ci8H30O2)

H2C

HC

H2C

H2C

H 2 C OH

2.3 Transesterification of Oils

The transesterification process is the most common chemical approach used for the
production of biodiesel. This process is also called an alcoholysis process. It is a reaction
between an ester and an alcohol in which the -O -R group of the ester and the -O-R'
group of the alcohol trade places, as shown below (Schuchard et al., 1998):

+ H

R
(2.1)

There are several methods for carrying out the transesterification reaction including
the supercritical processes (higher than critical temperature of methanol is considered,
thus eliminating the requirement of catalyst), ultrasonic methods (influence of different
sound frequencies versus traditional stirring) and microwave method (microwave
irradiation than conventional heating for synthesis of FAME from triglycerides).
The most commonly used catalysts for above process are acid catalyst (H2SO4 and
HC1) base catalyst (NaOH and KOH) and enzyme catalyst (lipase). Sodium methylate
(CHsONa) can also be used directly without having to use sodium or potassium
hydroxide crystals. Sodium methylate is soluble in the reacting system at all
compositions.

Transesterfication reaction chemistry:

O

0
CH3 - O - C - Ri
+
0

H 2 - O - C - Ri
O

CH3-O-C-R2
+3CH 3 OH
(KOHorNaOH) +
Q

CH-O-C-R2
0

CH2-OH
+

CH-OH
:H 2 - OH

CH2 - O - - R3

CH3 - O - C - R3

Triglyceride

Methanol

Mixture of fatty esters

Glycerol (2.2)

Transesterification reaction stoichiometry:

3 Biodiesel + Glycerol
(C 19 H 36 0 2 )
(C 3 H 8 0 3 )

Vegetable Oil + 3 MeOH (C57H,O406)

(CH3OH)

(2.3)

2.3.1 Base Catalyzed Transesterification Mechanism

In the first step base reacts with alcohol, producing an alkoxide and the protonated
catalyst. A tetrahedral intermediate is generated when nucleophile of alkoxide attacks the
carbonyl group of triglyceride, from which the alkyl ester and anion of the diglyceride are
produced. "The latter deprotonates acts as a catalyst, thus regenerating the active species,
which is now able to react with a second molecule of the alcohol, which starts another
catalytic cycle". By using the same mechanism, diglycerides and monoglycerides can be
converted to alkyl esters and glycerol (Schuchard et al., 1998).

R-OH

Base

<

RO" + BaseH+

(2.4)

RiCOO - <pH
R" <-

R 2 C O O - C H

OR

(2.5)

H2C - O - c - R 3
O"
R,COO-CH2
-*R2COO - CH + RCOOR3

(2.6)

H2C - O"

RiCOO-CH2

R,COO-CH2
R2COO - CH

R2COO-JH

BH

+ B

(2.7)

H 2 C - OH

H2C - O"

2.4 Conceptual Biodiesel Process Block Flow Diagram (BFD)

A conceptual biodiesel process Block Flow Diagram is shown in Figure 3. Methanol
and sodium methylate solution are mixed and fed to a mixer. This mixture along with
vegetable oil is sent to a reactor R-l with a steam jacket to heat the reacting mixture to
about 333K. Transesterification reaction takes place between oil and methanol to form
FAME and glycerol. FAME and glycerol along with excess methanol are sequentially
separated in two distillation columns D-l and D-2. Recovered methanol is recycled back
to the reactor.

10

j St-1 - Methanol Storage

tank
I St-2 - Catalyst Storage
I tank
j St-3 - Oil Storage tank
M-l - Methanol/Catalyst
Mixer
R-l- Transesterification
Reactor
D-l -Methanol/FAME

Figure 3: Schematic diagram of biodiesel production process.

11

2.5 Byproduct (Glycerol) Utilization Potential

As can be seen from the reaction stoichiometry, glycerol is the only byproduct in the
biodiesel manufacturing process. Approximately 1 kg of glycerol is produced for every 9
kg of biodiesel. Currently, glycerol is used in the making of many products which
include personal care products, food, oral care, tobacco, polymers, cosmetics, soap and
pharmaceuticals. Glycerol is also used in production of monoglycerides, diglycerides
and pyritic acid. Other applications include production of 1, 2-propanediol and 1, 3propanediol by hydrogenation of glycerol replacing the use of petroleum feedstock.
Catalyzed liquid-phase etherification of glycerol to oligomers is another application. The
preparation of the alkyl ethers of glycerol by etherification with isobutylene or other
olefins is one of the possibilities of glycerol utilization. Glycerol pyrolysis followed by
water gas shift reaction may provide a route to generate hydrogen required to operate fuel
cells (Byrd et al., 2008 and Klepacova et al., 2007).

2.6 Literature Summary - Rate Constants

Different oils and catalyst used for transesterification reactions, oil to alcohol molar
ratio, reaction temperature and time as reported in the literature are summarized in the
chronological order in Table 2 (Sharma et al., 2008).

12

Table 2: Literature summary of biodiesel production from various types of oils.

Year Feed stock

Solvent
Used

Molar
ratio
(methanol
:oil)

2004
Sunflower Supercritical
oil
methanol
Supercritical
ethanol
Methanol or
Ethanol

Pongamia
pinnata

Methanol

2005 Madhuca
indica

Methanol

Rubberseed oil

Methanol

40:1

catalyst

Reaction Duration Coversion/

temp(K)
Yeild

473-673
(P= 200
bar)
No catalyst

78-96%
conversion
with increase
in
10-40
mins temperature
23%
coversion
6 hrs
27%
conversion

5:1

Supercritical
C02+lipase
(Novozym4
35) 30% wt
of oil

318

10:1

Different
catalysts

378

1.5 hrs

333

1 hr

318

20-30
mins

318

30 mins

2005

2005

0.30l%v/v
0.35v/v - H2S04, 0.7
0.25 v/v wt% KOH
6:1

9:1

H2S04
0.5% by
volume
NaOH 0.5%
by volume

13

92%
coversion
with KOH,
83% with
ZnO, 59%
withHb
Zeolite, 47%
with
Montmorilno
nite
98% yield

Table 2: continued
Year Feed stock

Solvent
Used

Molar
ratio
(methano
l:oil)

2004
Sunflower Supercritical
oil
methanol
Supercritical
ethanol
Methanol or
Ethanol

Pongamia
pinnata

Methanol

2005 Madhuca
indica

Methanol

Rubberseed oil

Methanol

40:1

catalyst

Reaction Duratio
temp(K)
n

473-673
(P= 200
bar)
No catalyst

78-96%
conversion
with increase
in
10-40
mins temperature
23%
coversion
6 hrs
27%
conversion

5:1

Supercritical
C02+lipase
(Novozym4
35) 30% wt
of oil

318

10:1

Different
catalysts

378

1.5 hrs

333

1 hr

318

20-30
mins

318

30 mins

2005

2005

l%v/v
0.300.35v/v - H2S04, 0.7
0.25 v/v wt% KOH
6:1

9:1

H2S04
0.5% by
volume
NaOH 0.5%
by volume

14

Coversion/
Yeild

92%
coversion
with KOH,
83% with
ZnO, 59%
with Hb
Zeolite, 47%
with
Montmorilno
nite
98% yield

Table 2: continued
Chlorella
2006 protothecoides
Chlorella
protothecoides
Neat
Cannola
oil
2006

Methanol

56:1

Methanol

56:1

Acid catalyst
H2S04
(100%) on
the basis of
oil wt

6:1

NaOH 1.0
%wt

2006

Methanol
Used
Frying oil
2006 Nicotiana
tabacum

7:1

Methanol

18:1

6:1
2006

2006

Pongamia
pinnata
Soybean oil

Methanol
Methanol

6:1
4.5:1

NaOH 1.1
%wt
H2S04(1%
with low
molar ratio)
KOH(l%
based on oil
wt)
KOH(" 1%
by wt)
Tio2/Zr02(
1 lwt% Ti)
A1203/Zr0
2(2.6%wt
Al)
K20/Zr02(
3.3 wt% K)

15

coversion >
80%

303

303

318

333

333

4 hrs

63% yield

Ester content
98wt%
15 mins
Ester content
20 mins 94.6wt%
Yield 91% in
30min
25 mins

39 mins
338
448

2 hrs
2 hrs

Yield 9798%
conver over
95%
coversion
over 100%

2.6.1 Reaction Mechanism and Kinetic Rate Data

K,
C57H104O6 + CH3OH
Canola Oil Methanol <

> C39H72O5 + C19H36O2 AHr =-4752 KJ/Kmole

Diglyceride Biodiesel

(2.7)

> C21H40O4 + C19H36O2 AHr = 91060 KJ/Kmole

Monoglyceride Biodiesel

(2.8)

K2
K3
C39H72O5 + CH3OH
Diglyceride Methanol <
K4
K5
C21H40O4 + CH3OH
> C3H803 + Ci9H3602
AHR = -95340 KJ/Kmole (2.9)
MonoGlyceride Methanol<
Glycerol
Biodiesel
K6
Overall Reaction:
C57Hi04O6 + 3 CH3OH
Canola Oil Methanol <

> 3 C,9H3602 + C 3 H 8 0 3 AHr = -4770 KJ/Kmole

Biodiesel
Glycerol

(2.10)

The second order reversible reaction kinetic data reported by various investigators is
listed in the following tables:

Table 3: k values for soybean oil are reported by Noureddini and Zhu, 1997.
Rate constant

lit/mol*min

kl
k2
k3
k4
k5
k6

0.05
0.11
0.22
1.23
0.24
0.01

m3/mol*hr
0.003
0.0066
0.0129
0.07368
0.01452
0.0042

16

Table 4: k values for vegetable oil are reported by Sharma et al., 2008.
Rate constant

m3/mol*sec

kl

8.33 x 10"5

m3/mol*hr
0.2998

k2

8.217 x 10"5

0.2958

k3

4.945 x 10"

1.7802

k4

5.9 x 10"6

0.0212
5

k5

4.9838 x 10"

0.1794

k6

1.317 x 10"5

0.0474

Table 5: k values for palm oil are reported by Leevijit et al., 2004.

kl

m3/mol*sec m3/mol*hr
1.057 x 10"5 0.0381

k2
k3

0
1.184 x 10"4

0
0.4262

k4

8.187 x 10"5

0.2947

Rate constant

k5

1.31 x 10"

0.4716

k6

2.011 x 10"6

0.0072

Table 6: k values for soybean oil are reported by Marchetti et al., 2007.
Rate constants (L/mol*min)
kl
0.049
k2
0.102
k3
0.218
k4
1.28
k5
0.239
k6
0.007
k7

7.84 x 10"5

k8

1.58 xlO"5

17

In the reference Marchetti et al, 2007, k7 and k8 are rate constants of overall
reversible reaction.

Table 7: k values for vegetable oil are reported by Komers et al., 2002 (based on
particular data regression).
Method

Runge Kutta

Gespi

Averaging mehods

k2

1.297 x 10"4

8.415 x 10"5

8.342 x 10"5

k2r

6.405 x 10"5

4.967 x 10"5

5.908 x 10"5

k4

1.432 x 10"4

1.567 x 10"4

8.215 x 10"5

k4r

4.213 x 10"5

1.219 x 10"4

4.978 x 10"5

k6

3.942 x 10"4

2.53 x 10"4

4.945 x 10"4

k6r

1.172 x 10"5

1.164 x 10"4

1.322 x 10"5

k8

3.9 x 10"7

2.217 x 10"7

2.117 x 10"6

k9

2.27 x 10"6

5.727 x 10"5

3.233 x 10"6

klO

5.84 x 10"6

1.246 x 10"5

5.985 x 10"6

kll

3.208 x 10"6

7.757 x 10"5

1.212 x 10"4

k(m3/mol*sec)

In reference Komers et al., 2002, the first six rate constants are related to the
transesterification reaction (klis k2, k2 is k2r, k3 is k4, k4 is k4r, k5 is k6 and k6 is k6r).
The last four rate constants k8, k9, klO and kl 1 are related to saponification reactions. If
free fatty acids are present in the feed oil, these undergo a saponification reaction.
From these data the forward reaction rates are controlling when compared with
reverse reactions, as the activation energy is high for the forward reactions. Hence the
equilibrium lies in the formation of products.
Reaction rate constants for soybean oil transesterifications have been experimentally
determined by Noureddini and Zhu and are well accepted by other researchers (Sharma,

18

Komers and Marchetti etc). They employed a methanolic solution of NaOH as catalyst
(concentration of catalyst is 0.02% by wt of canola oil) and the reaction temperature was
323K. The results of kinetic parameters were related to Arrhenius equations expressed
in the form of a power law as shown below.

f rp \
k ( T ) = A.

- E
R T

(2.11)

V oy
Numerical values of constants for transesterification of soybean oil are listed in Table 8.

Table 8: Reaction kinetics relating rate constants, activation energy and Arrhenius
constant (Noureddini and Zou., 1997).
Reaction
1
2
3
4
5
6

TG + ME> DG + BD
DG + BD> TG + ME
DG + ME> MG + BD
MG + BD> DG + ME
MG + ME> BD + GY
BD + GY> MG + ME

K
(L/mol*min)
0.05
0.11
0.215
1.228
0.242
0.007

19

E
(J/mol) x 104
5.504
4.158
8.315
6.129
2.688
4.014

A
(L/mol*min)
4.008 x 10'
5.874 x 105
6.093 x 1012
1.012 x 1010
5.41 x 10j
2.186 x 104

CHAPTER 3: BIODIESEL REACTOR DESIGN

Alkali catalyzed transesterification reactions are essentially liquid phase reactions.

The volume change is negligible. Liquid phase reactions are easily carried out either in a
Plug Flow (PFR) or in a Continuous Stirred Tank (CSTR) reactor. As discussed earlier,
there are three series and reversible reactions associated with transesterification of canola
oil. The overall heat of reaction is -4770 KJ/Kmol, which indicates a small increase in
temperature. The temperature rises from 323 K (50C) to 343 K (70C) at about 90%
conversion. This chapter deals with the design of a PFR. The reactants are canola oil
and methanol. The catalyst employed is Sodium methylate (CHsONa), which is highly
soluble in methanol. The reactor products and co-products are biodiesel and glycerol.
Since the reaction chemistry involves three reversible reactions in series, trace amounts
of diglyceride and monoglycerides are also formed as byproducts. The esterification
reaction temperature is around 323 K (50C) to 333 K (60C). Depending upon the
pressure drop, reactor pressure ranges between 2 x 105 Pa (1.97 atms) and 4 x 105 Pa
(3.94 atms). Under these conditions, reactants and products are in liquid phase.

3.1 Plug Flow Reactor (PFR) Design

All non reacting molecules have equal residence time in a PFR. Any back mixing is
considered incidental. Natural turbulence provides mixing of reacting material. As a

20

result of chemical reactions, concentration gradients are developed in the axial direction.
PFRs are mostly pipe reactors with pipe diameters ranging from 0.01 to 0.14 m. A single
long tube with several 180 degree return bends can be placed in a shell to make one
reactor unit where the shell side can be used for heating or cooling of the reactor as
shown in Figure 4. The selection of tube diameter depends upon providing a turbulent
flow and a compromise between construction cost, pumping cost and surface area for the
required heat transfer.
Reaction time is the most significant design parameter. Selection of a reaction time
depends upon the reactor volume and volumetric flow rate of reactants. Thus the ratio of
reactor volume to inlet volumetric flow rate defines 'apparent' residence time. The true
residence time (x) is found by integration of reactor volume to volumetric flow rate as
shown below:
r=

rdK=
o

r dn_
J

r*u

(3.1)

In equation (3.1), is volumetric flow rate, r is rate of reaction and n is the local
molal flow rate of canola oil, the key component of the reacting mixture. Often a reactor
design is defined by a related concept of the term called 'space velocity'. Space velocity
in terms of LHSV is defined as the ratio of a flow rate at standard condition (288.7K
(15.7C) and 1.013 x 105 Pa (latm)) to the volume of the reactor. Thus:
LHSV= (Initial liquid volumetric flow rate at 288.7K (15.7C) per hour)/(reactor volume)
A PFR provides higher conversion without external mixing. However, conversion is
directly proportional to the length of the reactor. It should be noted that since conversion

21

increases with length, so does the pressure drop. Thus higher conversion is associated
with higher pressure drop across the reactor.

3.2 Performance Equations for a Plug Flow Reactor (PFR)

The reaction chemistry for the conversion of canola oil into biodiesel involves three
successive liquid phase bimolecular second order reversible reactions in series as
described below:

1=
Canola oil + Methanol-

PFR

Biodiesel + Glycerol

Figure 4: Canola oil reacts with methanol in PFR to generate biodiesel and glycerol.

K,
Triglyceride (TG) + Methanol (ME) ^^Diglyceride (DG) + Biodiesel (BD)
K2

(3.2)

K3
Diglyceride (DG) + Methanol (ME) ^^Monoglyceride (MG) + Biodiesel (BD)
K4

(3.3)

K5
Monoglyceride (MG) + Methanol (ME)

Glycerol (GY) +Biodiesel (BD)

K6

The general material balance for component j in a PFR can be defined as:

22

(3.4)

r
Rate of
Accumulation
< of component j^-

<

r
Rate of
inflow of
component j

>

<

Rate of
outflow of
component j V

Rate of
Generation of
J component j
y
by chemical
reaction

v.

v.

The rate of appearance or disappearance of species 'j' can be expressed in terms of its
molar flow rates Fj (mol/s) and its molar concentration Cj (mol/m3) as follows
(Fogler, 2006):
dF,

r,J

dV

(3.5)

J=CJo

(3.6)

d(CjU0)
r,

dV

(3.7)

The second order reaction rate laws rj for each species of the reactions 3.2 to 3.4 are
related to the rate constant kj and molar concentration Cj as follows:
r

- - k 1C^

- k 1C^

' TG

' DG

' MC,

'ME

TG

TG ^

ME

ME

+T k 2C^ BDC^

- k 2C

DG

DG

BD

(3.8)

- k C
3

DG

ME

+T k"" r4 ^

MG ^

k 3 C DG C ME - k 4 C MG C BD + ^k 5 C
C ME + k 6 ^C GY C
^ MG
^
T

_]r C
v
^

C
TG

+ k C
ME

C
DG

BD

11k C
3

DG

ME

T 4-

(3.9)

BD

BD

(3.10)

k C
C
k C
"" 4 MG ^ BD
5 MG

C
ME

+ n,k6 ^C G r C BD
t

(3.11)
r

BD
k\CTGCME
- k 6C cy C BD

k2 C DG C BD + k3C

OG

C ME

kA C MG C BD +

k5CMGCMr;

(3.12)

23

- rGY - k5CMGCm

k6CGYCBD

(3-13)

Substituting equations 3.8 to 3.13 in equation 3.7 yields six first order differential
equations given below:
d{CTGv())_

+ t r

-o

_k

_ir r

G14)

aK
d(CDGoo)
dV
d{CMGv0)
dv
d(CMUun)
dV

+k C

=0

(3 15)

r
+ K-J^JXJ^ME

-k 4C MG C BD +k 5C MG C ME +k 6C GY C BD = 0

- kxCTGCm

+ k2CDGCHD - k3CDGCMI, + kACMGCBO - k5CMGCm

f3 V-""
16)^

+ k6CGYCBD = 0
(3.17)

BD^O )+ kxCTGC MB k2C DGCBD + k2CDGCMIS k4CMGCBO + k5CMGCME

dV

k6CGYCBD

(3.18)
d{CGYo)
dV

kJ5CMU
MGCMB

ku6CGYCBD - 0

(3.19)

The solution of six ordinary differential equations 3.14 to 3.19 with initial condition
for reactants provides the concentration of all the species as a function of length.
For liquid phase reactions concentrations change can be related to reactor length (L) as
follows:
From the reaction 3.19
ArL = v0d

(3.20)

Differentiating on both sides

AdL = vndO

(3.21)

24

dO = ^-dL
o

(3.22)

dt =

dL

(3.23)

dC,

dC,

dt

A^dL

Where:
j - TG, MG, DG, BD, ME and GY.
Cj- Molar Concentration (mol/m3)
Ar- Area of reactor (m )
no - Intial velocity (m2/s)
L - Length of reactor (m)
k - Rate constant (m /mol.min)
ry - Rate of reaction (min~)
F - Flow rate (mol/s)
-2

V - Volume of reactor (m )
0 - Residence time (s)

3.3 MathCAD Solution to PFR Model

A MathCAD program to solve these differential equations is presented in Appendix A.
For a commercial plant capacity of 10 million gallons per year of biodiesel plant, the
reactor molar flow rates required are 6.575 kmol/hr of canola oil and 19.725 kmol/hr of
MeOH (1 mole oil to 3 moles of methanol). The amount of catalyst added is 116.3 kg

25

(0.02 wt% of canola oil). Using the rate constant values listed in Table 3, the results of
the length versus conversion for different methanol to oil molar feed ratio for 0.038 m
(1.5 inch OD) and 0.051 m (2.0 inch OD) tubes are presented in the Tables 9 and 10
respectively. Graphical representations of these results are shown in Figures 5 through
10.

Table 9: MathCAD results for diameter 0.038m (1.5 inch OD) tube.
Length of reactor MeOH/Oil- 3 MeOH/Oil- 6 MeOH/Oil- 9 MeOH/Oil- 12
Conversion
(m)

(%)

400

21.63

38.02

50.75

60.80

800

35.695

56.95

71.02

80.72

1200

44.57

66.83

80.51

89.05

1600

50.17

72.54

85.77

93.23

2000

53.74

76.21

89.06

95.54

2400

56.06

78.78

91.26

96.87

2580

56.84

79.71

92.02

97.27

26

Table 10: MathCAD results for diameter 0.051m (2.0 inch OD) tube.
Length of reactor MeOH/Oil- 3 MeOH/Oil- 6 MeOH/Oil- 9 MeOH/Oil-12
Conversion
(m)

(%)

200

20.80

36.77

49.29

59.26

400

34.65

55.70

69.78

79.57

600

43.59

65.80

79.54

88.24

800

49.34

71.70

85.01

92.65

1000

53.06

75.50

88.44

95.12

1140

54.89

77.45

90.14

96.21

1200

55.52

78.17

90.75

96.57

27

Figure 5: Plug flow reactor length (m) versus conversion of canola oil to biodiesel
for diameter 0.38m (1.5 inch OD) at 323K (50C) and 4.053 x 10s Pa (4atms).

28

12

10

TGj

DQ

MGj
6

MEj

BDj
4

GY;

0
Li
Figure 6: Length (m) of plug flow reactor versus component concentrations
(kmol/m3) for diameter 0.038m (1.5 inch OD) at 323K (50C) and 4.053 x 105Pa
(4atms).

29

Figure 7: Plug flow reactor length (m) versus conversion of canola oil to biodiesel
for diameter 0.38m (1.5 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms).

30

Figure 8: Plug flow reactor length (m) versus conversion of canola oil to biodiesel
for diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 10s Pa (4atms).

31

Figure 9: Length of reactor (m) versus component concentrations (kmol/m ) for

diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms).

32

Figure 10: Plug flow reactor length (m) versus conversion of canola oil to biodiesel
for diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms).

33

3.3.1 Effect of Methanol to Canola Oil Feed Ratio on Conversion

The reversible transesterification reaction requires high concentration of methanol for
the production of Biodiesel. Desired methanol to oil ratio is 3 but at this concentration
separation is not possible, hence methanol to oil ratio is increased to 6, 9 and 12 but at
higher concentrations separation of methanol from biodiesel is tedious. For the practical
purposes methanol concentration is maintained at optimum levels i.e 12. In the reactor,
the concentration of compounds changes with the length of the reactor as the
transesterification reaction progresses. Reactants (TG, ME, DG and MG) concentrations
decrease along the length of reactor. Products (BD and GY) concentration increase along
the length of reactor. Figures 6 and 9 are the concentration profile for methanol/oil feed
ratio-12. From the Figures 5 and 8, it is observed that as the molar ratio of methanol is
increased from 3 to 12, the conversion of canola oil changes from 54% to 97%.

3.4 Aspen Plus Simulation of PFR

The performance of a PFR was evaluated using, an AspenPlus simulation under the
following operating conditions:
Reactor feed: 298K (25C) and 4.050 x 105Pa (4atms).
Reaction temperature as 323K (50C) and pressure 4.050 x 105Pa (4atms)
Reactor Tube (inside diameter): 0.038m (1.5 inch) OD and 0.051m (2.0 inch) OD.
Reactor length: 2580m and 1140m.
Sensitivity Blockl: vary methanol to canola oil mole ration as 3, 6, 9, 10 and 12.
Sensitivity Block2: vary reactor inside tube diameter as 0.03 and 0.045 meters.

34

A schematic of the process under consideration is shown in Figure 11. The details of
Aspen input file are given in Appendix (B).

Figure 11: ASPEN simulation of PFR diameter-0.038m (1.5 inch) and 0.051m
(2.0 inch) OD.

35

3.4.1 Plug Flow Reactor Size for Diameter 0.038m (1.5 inch OD) and 0.051m
(2.0 inch OD) Tubes
A summary of Aspen simulation results for reactor tube OD of 0.038m (1.5 inch) and
0.05 lm (2.0 inch) is given in Table 11:

Table 11: Summary of ASPEN results of PFR tube OD 0.038m (1.5 inch).
Lengt Ratio CONV
h
(m)
52.12
3
2580
72.87
2580
6
9
2580
84.59
2580
12 90.83

BD

mins
10.85
10.32
9.855
9.343

kg/hr
2053.94
3539.83
4483.67
5012.18

DG
OUT
kg/hr
920.48
650.82
403.25
250.42

MG
OUT
kg/hr
132.82
112.50
84.18
62.56

ME
GY
TG
OUT
OUT
OUT
kg/hr
kg/hr
kg/hr
409.15 144.38 2782.72
879.72 315.17 1576.66
1408.87 430.08 895.85
1982.94 496.12 532.89

Table 12: Summary of ASPEN results of PFR tube OD 0.051m (2.0 inch).
Length Ratio CONV
(m)
1140
1140
1140
1140

3
6
9
12

52.12
72.87
84.58
90.83

BD

mins
10.85
10.32
9.85
9.34

kg/hr
2053.78
3539.59
4483.42
5012.95

DG
OUT
kg/hr
920.49
650.88
403.32
250.48

ME
GY
TG
MG
OUT
OUT
OUT
OUT
kg/hr
kg/hr
kg/hr
kg/hr
132.83 409.36 144.36 2782.87
112.51 879.14 315.14 1576.84
84.19 1408.04 430.04 896.02
62.57 1982.97 496.09 533.04

Graphical representations of results are shown in Figures 12 through 17.

36

Residence time vs Conversion

MeOH/Oil-3
MeOH/Oil-12

MeOH/Oil-6
Length of reactor

MeOH/Oil-9

100
90

'vi
>

80

g>0

so

s feo
o

U 30> 50

e*

mm

o
a40

"3
c

30

61)
C
-J

20
10

0
10

15

20

Residence time (minutes)

Figure 12: Plug flow reactor residence time versus conversion of oil to ester for
diameter 0.038m (1.5 inch OD) at 323K (50C) and 4.053 x 105Pa (4atms).

37

Length of reactor vs Component Flow Rates

BDOUT
-*~GYOUT

MGOUT
TGOUT

-"-DGOUT
MEOUT

80.000
70.000
O

60.000

o o o o o o o o o

-K

X K X X X X X X *

O
O
& 50.000
40.000

cs 30.000
pfj
o 20.000
10.000

-X*-

0.000

500

1500

2500

3500

4500

Length (m)
Figure 13: Length of plug flow reactor versus component flow rate for diameter
0.038m(1.5 inch OD) at 323K (50C) and 4.053 x 105 Pa (4atms).

38

Figure 14 : Plug flow reactor residence time versus conversion of oil to ester for
diameter 0.38m (1.5 inch OD), 323K (50C) and 4.053 x 105 Pa (4atms).

39

Residence time vs Conversion

MeOH/Oil-3
MeOH/Oil-12

MeOH/Oil-6
Length of reactor

MeOH/Oil-9
5000

m 4500
4000
3500
3000

9
-w
w

2500
2000
1500

xi
%

1000 JV

500
10

20

30

40

50

Residence time (minutes)

Figure 15: Plug flow reactor residence time versus conversion of canola oil to
biodiesel for diameter 0.051m (2.0 inch OD) at 323K (50C) and 4.053 x 105 Pa
(4atms).

40

Length of reactor vs Component Flow Rates

BDOUT
* GYOUT

DGOUT
-e-MEOUT

MGOUT
--TGOUT

80.000
70.000
n

Ja 60.000

o&- o

oo

o
o 50.000

a ,40.000
0>
-M
30.000

20.000
E 10.000
0.000

-X

-X
^

500

X X X X X X X *

....
1500

2500

3500

me~e
4500

Length (m)
Figure 16: Length of plug flow reactor versus component flow rate for diameter
0.038m (2.0 inch OD) at 323K (50C) and 4.053 x 105Pa (4atms).

41

Residence time vs Conversion

-MeOH/Oil-12

Length of reactor

100

90

4500

80

4000 J
3500

3000 w
0)
2500 0

70

SO

ia

60

>
e

50

<M
O
JS
1500 W)
G
Ol

U .2 40
-a
o

5000

2000

30
20

1000 J
500

10
0
10

20

30

40

50

Residence time (minutes)

Figure 17: Plug flow reactor residence time versus conversion of canola oil to
biodiesel for diameter 0.051m (2.0 inch OD), at 323K (50C) and 4.053 x 10s Pa
(4atms).

42

3.4.2 Effect of Methanol to Canola Oil Molar Feed Ratio on Conversion

Figures 13 and 16 are the flow rate profiles of TG, DG, MG, ME, BD, GY varying
along the length of the reactor for the two reactors with dimensions of 0.038 m OD, 2580
m long and 0.051 m OD, 1140 m long. In reactor flow rates of compounds vary along the
length of reactor as the transesterification reactions progresses with time. As expected
reactants (TG, ME, DG and MG) flow rates decrease along the length of reactor, whereas
products (BD and GY) flow rates increase along the length of reactor. Residence time
varies with conversion of oil to biodiesel for different methanol to oil molar feed ratios
are shown in Figures 12 and 15. From Figures 12 and 15 it can be concluded that for a
methanol to oil feed ratio of 12, 90.83% overall conversion is achieved under the
residence time of 9.3 minutes.
3.4.3 Plug Flow Reactor Length Required for 1.5 inch OD and 2.0 inch OD Tubes
Two different AspenPlus simulations were carried out. In the first case PFR input
parameters were: 0.38 m (1.5 inch) OD tube diameter, 2580 meters length and methanol
to canola oil molar feed ratio ofl2. In the second case input parameters are: 0.51 m (2.0
inch) OD tube diameter and 1140 meters long and methanol to canola oil feed ratio of 12.
Under these conditions, an overall conversion of canola oil was 90.88% in both the cases.
Then calculations for shell diameter:

Ntuhes=^-

(3.31)

L = 4m
N

t u

t u b

645 for 0.038m (1.5 inch) OD tube

es=

285 for 0.051m (2.0 inch) OD tube

be

43

Dshe = 1.25 * Tubepitch * ^Nluhes

DSheii =3.225 m (10.6ft) for 0.038 m (1.5 inch) OD tube
Dsheii =2.144 m (7.0ft) for 0.051 m (2.0 inch) OD tube
Detailed calculations can be found in Appendix C.
3.4.4 Pressure Drop Across Plug Flow Reactor
For a 90.8% conversion, reactor length was found to be 2580 m for a 0.038 m (1.5
inch OD) tube and at the same value of conversion; a 2.0 inch OD reactor should be 1140
meters long. Assuming a shell-tube configuration, for a shell length of 4-meters, an Stype tube length configuration would require Nbends of 180 degree tube bends as shown
below:

Figure 18: 180 degree tube bends of a PFR.

Pressure drop can be calculated from the following equations (Peters and Timmerhaus,
2003):

44

Pressure drop across straight length tube

2

AP =

a jjj

^SL.)

(3.33)

Pressure drop across 180 degree bend

2

AP = p*^-*(Kf)

(3.34)

Total pressure drop per tube length with one 180 degree bend
2

AP =

jjs

/* jJ>

J-

H22!- + K f )

(3.35)

This pressure drop is for one 4m long one-bend tube

N B e n d s =N l u b e s -l

(3.36)

APlnlal=AP*Nliemh

(3.37)

From the equation 3.37, NreactorCan be assumed and the total reactor pressure drop will
be:
^ a c l n r=^P l l a l *N r e a c , o r

(3.38)

Where:
Lreactor ~ Total length of PFR (m)
p - Density (kg/m )
D - Diameter of tube (m)
/ - Friction factor
ve - Velocity in a tube (m/s)
K f - Frictional loss in a 180 degree bend
AP - Pressure drop (Pa)

45

Neends - Total number of 180 degree bends in a PFR

Ntubes - Total number of tubes in a PFR
Nreactor- Total number of reactors required
APreactor

APtotai

- Pressure drop in a PFR (Pa)

- Pressure drop in all tube of a PFR (Pa)

Detailed pressure drop calculations are summarized in Appendix D. For case 1 (0.038
m (1.5 inch OD) and L = 2580 m) the total pressure drop is found to be 3.55 x 106 Pa (35
atms). In case 2 (0.051 m (2.0 inch OD) and L= 1140), the total pressure reduces to 1.32
x 106 Pa (13 atms). It should be noted that the pressure drop can be further reduced by
increasing the tube diameter. However, tube diameters larger than 0.051 meters (2
inches) may not provide the uniform concentration in axial and radial direction of the
reactor.
3.4.5 Plug Flow Reactor Cost
The cost for the year 2008 of the designed PFR is estimated from the following
correlation (Seider et al., 2004):
Cost = Exp(11.0545 - 0.9228 * In (Area) + 0.0979(ln (Area)2)) * FMh

(3.39)

(3.40)

(3.41)
The results are shown in Table 13

46

Table 13: Cost of Plug flow reactor for different diameters.

Case

Tube OD

Reactor
Length

Gear Pump
cost

Reactor
cost

Total
cost

0.038 m (1.5 inch)

2580 meters

$22000

$97,000

$166,700

0.051 m (2.0 inch)

1140 meters

$9,400

$169,000

$250,000

As the diameter is increased from 0.038 m (1.5 inch) OD to 0.051 m (2.0 inch) OD the
cost of a PFR is increased by 66.7%. Details of plug flow reactor cost calculations are
summarized in Appendix E.

47

CHAPTER 4: CONTINUOUS STIRRED TANK REACTOR (CSTR)

The continuous stirred tank reactor (CSTR) is also known as an ideal reactor or an
agitated tank reactor. This reactor can be used for liquids and slurries as reactants.

4.1 Performance Equations Model for a Continuous Stirred Tank Reactor (CSTR)
A general material balance relationship for liquid phase chemical reactions a CSTR is
presented in Figure 19:

Canola oil + Methanol-

CSTR

-Biodiesel + Glycerol

Figure 19: Canola oil reacts with methanol in a CSTR to produce biodiesel and
glycerol.

r
Rate of
Accumulation
< of component j/"

v.

r
Rate of
inflow of
component j >

v.

48

Rate of
outflow of
+
< component j r

Rate of
J Generation of
a Component j
by chemical
reaction
v.

>

The rate of appearance or disappearance of species 'j' can be expressed in terms of its
molar flow rates Fj (mol/s), molar concentration Cj (mol/m3) as follows (Fogler, 2006):
F
(4- 1 )
F]=CJv0

(4.2)

(C

-C,)*o0

V
9 =

(4.4)

The second order reaction rate laws

for each specie can be related to the rate

constant kj and the molar concentration C7 are described below.

Substituting equations 3.8 to 3.13 for r, in equation 4.3 yield:
Cm -CTGa + {-kxC1GC
Cdg

~ Cdg

Cmg

~ CMg

ME

+ k2CBDCDG) * 0 = 0

(4.5)

(kiCTGCME k2CDGCBD k3C/x;CME + kACMGCBD) * 6 = 0

(4.6)

(k3CDGCME k4CMGCljn + k5CMGCME + k6CGrC

(4.7)

Cmi^m/:,

k]CTGCME + k2CDGCBD

+ k6CGyCBD)*0

BD)

k3CDGCME + k4CMGCBD

* (9 = 0
k5CMGCME

+(kiCTGCME ~k2CDGCME + k2CDGCME k4CMGCBD + k5CMGCME

- k6CGyCBD)* 0 = 0
Cbd

Q,y

b d

(4.8)

=0

+ (k5CMG CME - k6CGY CBD )* 0 = 0

A solution of these six equations (Equations 4.5-4.10) with initial condition for
reactants provides the concentration of each compound as a function of time (0).

49

(4.9)

(4.10)

Where:
j - TG, MG, DG, BD, ME and GY.
Cj- Molar Conentration (mol/m3)
Ar- Area of reactor (m )
Do - Intial velocity (m /s)
L - Length of reactor (m)
k - Rate constant (m /mol.min)
Xj - Rate of reaction (min 1 )
F - Flow rate (mol/s)
V - Volume of reactor (m )
0 - Residence time (s)

4.2 MathCAD Solution to CSTR Model

A MathCAD program to solve these differential equations 4.5 to 4.10 is presented in
Appendix F. The reactor feed conditions and flow rates are same as described earlier for
the design of PFR.

50

Table 14: Summary of MathCAD results for different reactor volume and methanol
to oil molar feed ratio.
Reactor
Volume
(m J )
6
7
7
8
8
8
9
9
9
10
10
10
10

Methanol to
Oil Ratio

Conversion

12
11
12
10
11
12
10
11
12
9
10
11
12

88.08
88.46
89.48
87.8
89.59
90.56
89.39
90.42
91.41
88.34
90.07
91.21
92.11

(%)

Residence
time
(minutes)
34.01
40.93
40.00
47.90
47.08
46.00
55.01
53.00
52.02
62.03
61.01
60.03
58.03

Biodiesel
Production rate
(kg/hr)
4888.21
4910.84
4991.20
5038.54
4992.37
5071.00
4969.66
5050.63
5131.80
4896.52
5021.54
5194.21
5187.00

4.3 Aspen Plus Simulation of CSTR Model

The performance of a CSTR was also evaluated using an AspenPlus simulation under
the following operating conditions:
The details of Aspen input file are given in Appendix (G).
Reactor feed: 298K (25C) and 4.053 x 105 Pa (4atms).
Reaction temperature: 323K (50C)
Pressure: 4.053 x 105 Pa (4atms)
Reactor volume: 7m3.
Sensitivity Blockl: vary methanol to canola oil mole ration as 3, 6, 9 and 12.
Sensitivity Block2: vary reactor volume 1 to 10 m .

51

The details of Aspen input file are given in Appendix (G). Figure 20 shows a
schematic diagram of the process under consideration. A summary of Aspen simulation
results for a CSTR volume of 7m3 is given in the Table 15.

Table 15: Summary of ASPEN results of CSTR volume 7m3.

X
Lengt Ratio CONV
h
mins
(m)
45.34
7
3 54.737
7
6 76.489 45.06
7
9 86.257 43.28
12 90.318 40.62
7

BD
Product
kg/hr
2492.67
3992.66
4728.02
5054.03

DG
OUT
kg/hr
671.76
437.39
391.78
269.81

52

MG
OUT
kg/hr
74.30
66.87
55.07
46.41

ME
GY
OUT
OUT
kg/hr
kg/hr
361.72 212.22
830.76 380.49
1382.46 466.76
1978.41 506.26

TG
OUT
kg/hr
2630.82
1366.52
798.81
562.75

Graphical representations of results are shown in Figures 21 to 23 and analysis of

these results is presented below in 4.3.1 and 4.3.2.
Details of all simulation results are given in Appendix G.

Figure 21: Continuous stirred tank reactor residence time versus conversion of
canola oil to biodiesel for methanol to oil ratio 3, 6, 9,12 varying along the volume of
reactor at 323K (50C) and 4.053 x 105Pa (4tams).

53

Volume vs Component Flow rates

BDOUT
-m-MGOUT

-~TGOUT
--AOUT

DGOUT
-GYOUT

Volume (m3)

Figure 22: Volume of Continuous stirred tank reactor versus component flow rate
for methanol to oil ratio 12 at 323K (50C) and 4.053 x 105Pa (4tams).

54

Figure 23: Continuous stirred tank reactor residence time versus conversion of
canola oil to biodiesel for methanol to oil ratio 12 varying along the volume of
reactor at 323K (50C) and 4.053 x 10sPa (4tams).

4.3.1 Effect of Residence Time on Conversion

These results show that if the reactions are carried out in a single reactor, conversion
depends upon the methanol to canola oil molar feed ratio under the same residence time
in the range of 40 to 45 minutes. As it can be seen from Figure 21, at a given reactant
feed ratio, increasing residence time beyond 40 minutes, there is no significant increase
in the overall conversion. Over 90% conversion can be achieved under 40 minutes of
residence time, if the methanol to oil feed ratio is increased to 12.

55

4.3.2 Effect of Reactor Volume on Conversion

At reactant feed ratio of 12, a single reactor with 7 m3 volume would be required for
90% conversion. Increasing the reactor volume from 4 to 10 m3, there is no significant
increase the production of bio diesel as shown in Figure 22. The reactor performance
with respect to residence time, volume and conversion is shown in Figure 23.

4.4 Design Dimensions of the CSTR at Methanol/Oil Molar Feed Ratio of 12

Input= Fresh feed
Volumetric flow rate = (Fresh feed)/ (pavg)
Assuming
Design Residence time =1.5* Reactor residence time
Design Volume of reactor = Volumetric flow rate* Residence time
Area of reactor = 3.14* (diameter)2 / 4
Height of reactor = Design Volume of reactor / Area
Actual feed volume = Volumetric flow rate*Reactor residence time
Reactor Design Volume = Area of reactor * Height of reactor
Percent over design = Reactor Design Volume/ Actual feed volume
Percent over reactor volume (based on rules of thumb). Calculations of CSTR sizing
can be found in Appendix design for CSTR of volume 7 m 3 is 1.5. The author
recommends a 50% over design in H.

56

4.5 Continuous Stirred Tank Reactor Cost

Using M and S index (Chemical Engineering Magazine, 2009) and Figure H, cost of
single CSTR with material of construction as stainless steel is $77,880.
Details of utility cost of CSTR can be found in Appendix I. This represents over
324% lower reactor cost when compared with the PFR cost of $250,000.

4.6 Continuous Stirred Tank Reactor in Series

In a CSTR reactor design, it is important that reactor contents are thoroughly mixed
since perfect mixing is the fundamental basis of reactor performance for desired
conversion. Therefore reactor residence time should be greater than the mechanical
mixing time. Typically, the reactor residence time should be at least 5 times the
mechanical mixing time. It is economically beneficial to operate several CSTR units in
series. The multiple reactors in series require a smaller reactor volume and offer higher
overall conversion. In the production of biodiesel, reactants, catalyst and products are all
in liquid phase, a simple pump around configuration ensures vigorous mixing. This
approach for mixing offers better economics since pumping energy required is much less
than the energy requirements for impeller type mechanical mixing.

4.6.1 A System of Three CSTR Biodiesel Reactors in Series

Figure 24 shows an Aspen simulation diagram of three reactors in series. The material
balance results are presented in Table 16. Each reactor volume is 3 m3. The feed to the
first reactor consists of canola oil, methanol at 323 K (50 C) and 4 x 105 Pa (4atms) (abs)
pressure. The effluent stream from each reactor is subjected to a pump around system

57

where 90 % of the reactor effluent stream is recycled back to the reactor. The recycle
stream is cooled to 313 K (40 C) before entering the first reactor. As a result of inter
cooling; feed to the second reactor is at 322 K (49 C). Under adiabatic conditions, the
temperature in the second reactor increases from 322 K to 343 K (49 C to 70 C). In the
third reactor, temperature rises from 343 K to 382 K (70 C to 79 C). It should be
pointed out that the reaction rate constants used in this study were determined
experimentally at 333 K (60 C). If these rate constants are assumed to be valid up to
353 K (80 C), then no inter cooling for the second and the third reactor will is required.
The Aspen simulation of methanol recovery from reactor effluent stream using direct
distillation reveals that sodium methoxide catalyst will boil-off with methanol in the
overhead stream to be recycled. This is mainly due to lack of liquid phase dissociation of
methanol- sodium methylate system. Thus reactor effluent may be cooled and separated
into two liquid phases. The recovery of various compounds for each liquid phase can be
accomplished by approaches similar to those found in literature (Apostolakou et al., 2009
and Haas et al., 2006).

58

Figure 24: ASPEN simulation of three CSTR's in series.

59

Table 16: Material balance data for three CSTR's in series to produce biodiesel
from canola oil (Plant capacity: 10 million gallons/year of biodiesel product).
Rl-OUT Rl-RCY

Stream Name

TG

Methanol

Rl-IN

Phase
Mass Flow
(kg/hr)
TG
BD
Methanol
GY
DG
MG
Mass fraction

Liquid

Liquid

Liquid

Liquid

6144
0
0
0
0
0

0
0
3336
0
0
0

6144
0
3336
0
0
0

TG
BD
Methanol
GY
DG
MG
Total Flow
(kmol/hr)

1
0
0
0
0
0
7

0
0
1
0
0
0
104.3

Total Flow
(kg/hr)

6144

Temperature
(C)
Pressure (bar)
Density
(kg/cum)
Average
(MW)

R2-IN

R2-OUT

Liquid

Liquid

Liquid

10115
48396
28126
4757
2653
734

9103
43556
25313
4282
2388
661

1012
4840
2813
476
265
73

1974
58538
27030
5965
976
305

0.648
0
0.352
0
0
0
111.2

0.107
0.511
0.297
0.05
0.028
0.008
1111.9

0.107
0.511
0.297
0.05
0.028
0.008
1000.7

0.107
0.511
0.297
0.05
0.028
0.008
111.2

0.021
0.681
0.285
0.063
0.01
0.003
1111.9

3336

9480

9478.2

85302

9478

94789

15

15

50

50

50

50

50

909.4

803.6

588

778.8

778.7

778.7

826.4

884

32

85.3

85.2

85.2

85.2

85.2

60

Table 16: continued

Stream Name

R3-IN

R3-OUT

RAW1

M-RCY

RAW2

RAW3

GY

Phase
Mass Flow
(kg/hr)
TG
BD
Methanol
GY
DG
MG
Mass fraction

Liquid

Liquid

Liquid

Liquid

Liquid

Liquid

Liquid

197
5854
2703
597
98
31

611
60418
26824
6201
529
198

61
6042
2682
620
53
20

0
0
2682
0
0
0

61
6042
1
620
53
20

61
6042
0
1
53
20

0
0
1
620
0
0

TG
BD
Methanol
GY
DG
MG
Total Flow
(kmol/hr)

0.021
0.618
0.285
0.063
0.01
0.003
111.2

0.006
0.637
0.283
0.065
0.006
0.002
1111.9

0.006
0.637
0.283
0.065
0.006
0.002
111.2

0
0
1
0
0
0
83.8

0.009
0.889
0
0.091
0.008
0.003
27.4

0.01
0.978
0
0
0.009
0.003
20.6

0
0
0.001
0.999
0
0
6.8

Total Flow
(kg/hr)

9479

94782

9478

2682

6797

6176

620

Temperature

50

50

50

224

25

25

(C)
Pressure (bar)

1.1

1.1

826.2

835.2

835

740.3

723.6

863.6

1271

85.2

85.2

85.2

32

248.2

299.3

91.9

Density
(kg/cum)
Average
(MW)

67

61

Table 17: Below summarizes the results of overall conversion as a function of

methanol to canola oil feed ratio.
Methanol to Canola
Oil mole ratio
3
6
9
12
15

%Conversion
CSTR -1
48.1
67.4
77.1
80.8
83.5

%Conversion
CSTR-2
21.5
45.6
65.2
75.2
80.5

%Conversion
CSTR-3
7.8
24.7
44.1
59.6
69.1

%Conversion
Over all
62.4
86.7
95.5
98.1
99.0

4.6.2 Economic Analysis of Three CSTR in Series

The utility requirements for heat exchangers, methanol recycle distillation column and
transfer pumps are summarized in Table 18. The size (diameter and height) and cost of
methanol recycle distillation column at various methanol to canola oil ratios is given in
Table 18. The utility prices used in Table 18 are: $0.59/1000 kg steam; $0,045/1000 kg
cooling water; $0.085/kWh electricity.

Table 18: Total utility cost ($/hr) as a function of methanol to canola oil mole feed
ratio.
Methanol/Canola Oil

Ratio

Ratio

Ratio

Distillation

3
cost($/hr)

6
cost($/hr)

9
cost($/hr)

Reboiler steam cost

$2.16

$5.40

$9.72

Condenser water cost

$6.12

$10.08

$16.20

$23.04

$29.88

Power cost for Pump -1

Power cost for Pump -1
Power cost for Pump -1

$1.44
$1.44
$1.44

$1.44
$1.44
$1.44

$1.44
$1.44
$1.44

$1.44
$1.44
$1.44

$1.80
$1.80
$1.80

Total Utility Cost ($/hr)

Overall Conversion

$12.60
62.40%

$19.80
86.70%

$30.30
95.50%

$41.90
98.10%

$53.80
99.00%

62

Ratio
Ratio
12
15
cost($/sec) cost($/sec)
$14.40
$19.08

For each value of methanol to canola oil mole feed ratio, the amortized cost of
methanol distillation column is shown in Table 19

Table 19: Cost of methanol recovery distillation column.

Methanol/Canola
3
6
Oil ratio
Column diameter
0.5
0.7
(m)*
$331,200
Methanol Column
$252,000
Cost**
Amortized Cost
$32,508.0 $42,724.8
($/yr)***
Column Cost $/hr
$4.5
$5.9
* Column height 11 meters,
**Cost includes installation and auxiliaries
*** Amortization factor (A/P, 10, 5) = 0.129

12

15

0.8

1.2

1.4

$388,800

$504,000

$684,000

$50,155.2

$65,016.0

$88,236

$7.0

$9.0

$12.3

In order to carryout an economic analysis of incremental change in methanol feed

ratio to incremental increase in canola oil conversion, the equipment cost of reactors,
pumps and heat exchanger will not have any impact on the outcome of results since these
costs will be the same for all cases. Therefore the total cost can be expressed as the sum
of the Methanol distillation column cost (Fixed cost) plus the utility cost (variable cost).
The results of total cost form the data given in Table 18 and 19 are presented in Figure 25
as shown below:

63

Cost ($/hr) v's Biodiesel Product Purity as a function of

Methanol to Oil mole Ratio
Utility

-Conversion A eqpcost

Total-Cost

$86.3
$69.0

t" $51.8

U)

$37.2
- Jr$30.3

o $34.5

$17.3

$17.1

$19.8

$T2.6

12.3

nA-7.0

-A-5t9
$0.0

* 62.4%,

86.7%r

95.5%r

98.1%,

12

Methanol to Oil mole Ratio

Figure 25: Methanol to oil mole ratio versus total cost.

64

99.0%
15

4.6.3 Design of Methanol Recovery Column

Methanol recovery column was designed using following rigorous correlations
(Wankat, 2007):

Figure 26: Schematic diagram of distillation column.

4.6.3.1 Column Diameter: Fair Flow parameter (Csb) is used determine column
diameter at top and bottom column conditions. The calculated results are
Djop = 1.361 m
DBottom= 1.614 m
Use 1.614 m diameter column
4.6.3.2 Tray Hydraulics: To carry out tray hydraulic calculations, the following tray
layout was assumed:
Tray Thickness = T t r a y = 0.0019 m (0.078 inch)
Hole diameter = 0.0047 m (3/16 inch)
Column Area = AT

65

Down comer Area = Ad = 12% of AT

Net Area = An = 88% of AT (Vapor Flow Area)
Active Area = A a = (AT - 2Ad)
Hole Area = Ah = 10% AT
Weir Length = lw = 77% of Diameter (Top or Bottom)
Using the above tray specifications, the following results are obtained:
i) Bottom column area = 2.055 m ,
ii) Net tray area = 1.808 m2,
iii) Down comer flow area = 0.247 m2,
iv) Active tray area = 1.561 m2,
v) Tray hole area = 0.156 m2,
vi)Weir Length = 1.243 m
Pressure drop across the tray consists of pressure drop caused by the various
hydrodynamic heads which include dry pressure drop (hdC) plus static head by the weir
(hweir)

plus head caused by the liquid crest (hcrest) plus static head of the liquid under the

down comer (hdU).

hdc

W Dry + Kveir+ ^crest + hdu

Calculation results of each of these terms are presented below. Detailed calculations are
presented in Appendix K.
4.6.3.3 Dry Pressure Drop: It should be noted that all pressure drop results in inches (m)
of water.

66

Calculate orifice coefficient (C0) for a tray hole using the following Kesseler and
Wankat correlation:
dhole N

C 0 := 0 . 8 5 0 3 2 - 0 . 0 4 2 3 1 -

rd

hole V

0.0017954-

V ^tray )

vW

C 0 = 0.759
P VBottom

hAP_Dry := 0.003'ftV

jb

P water
v

PLBottom .

ft3

IV ^APDry = 0.025 m

C r A "13
Ijrr
hcrest := 0.092-Fwear

gal
V min J

in

w Bottom

Merest = 0.022 m

Assume negligible gradient pressure drop,

hgrad

:= 0

hdu := 0.56-

gal
V min
449

in

Adu
ft2

hdu = 7.641 x 10

-3

67

"

in

hweir = 0.051 m
hdc : = hAP Dry + hweir + hcrest + Hju
hdc = 0.106m

\ic_aerated

hdc
<Pdc

hdc_aerated = 0.211m
This value is less than 0.61 m (24 inch) tray spacing. There should be no problem for
vapor to flow to the above tray.
Where:
Lg = Liquid Flow Rate (L/min)
Fweir = Factor accounting for a curvature of the column wall in the down comer
hgrad= The liquid gradient across the tray (m)
hdc = Total Head of clear liquid in the down comer (m)
hdc_areated = Head of clear liquid in the down comer due to aeration (m)
hdu = Frictional loss due to flow in the down comer and under the down comer onto the
tray (m)
hweir static head by the weir (m)
hcrest= static head by the liquid crest (m)
(3 = Area of hole to active area (unit less)
Adu = Flow area under the down comer (m2)

68

4.6.3.4 Check for Down Comer Residence Time: According to the rule of thumbs, a
minimum down comer residence time should be at least 3 seconds. Based on foaming
tendency of the liquid, this residence time ranges from 3 seconds (low foaming) to 7
seconds (very high foaming) liquids (Kister, 1992).

(Ad
tdc

Bottom "PL Bottom hdc)

=
^Bottom +

e e

t<ic = 3.695 s
Where
ee = entrainment
tdc = Down comer residence time
This value is greater than the minimum residence time of 3 seconds, there should be
no problem to maintain the proper liquid flow.
4.6.3.5 Weeping Check: Weeping relates to the direct flow of the liquid through sieves
without maintaining a proper vapor liquid contact. Excessive weeping is estimated using
Fair's (Wankat, 2007) correlation for a surface tension head(ha).
f

dyne

V cm

ho := 0.04in-

PLBottom

dhole

lb

V in ;

ha = 1.299 X 10

-3

69

Excessive weeping is defined by equality that the term (h^p )ry+h a) should be
greater than the value of the term (.10392+0.25119x-0.021675x 2 )h A P Q r y+h a > 0.10392+0.25119x-0.021675x

where x is deined as: h W eir + hcrest + hgrad t * ien

h

AP_Dry+ha= i-047

0.10392+0.25119x-0.021675x

= 0.645

These calculations show that the inequality is satisfied. Therefore, Weeping should
not be a problem. All of the design calculations are presented in Appendix K.

70

CHAPTER 5: CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE

RESEARCH

5.1 Conclusions
In this study, reactions of canola oil with methanol to produce biodiesel were
examined in a PFR as well as in a CSTR reactors. Based on kinetic rate expression
available from the literature, a Plug Flow Reactor (PFR) was designed to determine the
reactor length as a function of conversion of canola oil. Two different reactor tube
diameters were investigated in the plug flow reactor system.
For a Plug Flow Reactor with 0.038m (1.5 inch) OD tube, nearly 91% conversion was
achieved in a 2580m long reactor at methanol to oil molar feed ratio of 12 ( as compared
to the stoichiometric ratio of 3) with 9.3 minutes of reactor residence. The total pressure
drop for this reactor was found to be around 35.463 x 105 Pa(35atms). The requirement
of a long tubular reactor is mainly due to the desired conversion of canola oil beyond
90%.Gear pumps must be used to provide the pressure of the feed system to overcome
the prevailing pressure drop.
According to the information on gear pumps from reference (Seider et al., 2004),
"Although gear pumps can be designed to operate over a wide range of flow rates and
discharge pressure, typical ranges are 10 - 1500 gpm, and up to 200 psi for high viscosity
fluids.", for a 0.038 m (1.5 inch) OD diameter PFR, the pressure drop requirements can

71

not be met with a single off-the-shelf gear pump. If two plug flow reactors of 0.038 m
(1.5 inch) OD tube are used, the developed pressure drop of 17.97 x 105 Pa (17.732atms)
per reactor would still be higher and exceeds the pressure developed by the standard size
gear pump, hence more than one gear pumps will be needed. The total estimated cost for
this PFR (diameter of 0.038 m (1.5 inch) OD tube and 2580 m length) using two gear
pumps will be $166,700 (2008). For a PFR with 0.051m (2.0 inch) OD tube, the reactor
tube length decreases to 1140 meters under the same conditions as in for PFR of diameter
0.038 m (1.5 inch) OD tube. The resulting pressure of 13.17 x 10 5 Pa (13atms) can be
attained with a single gear pump unit. The total estimated cost of 1140m long and 2.0
inch OD PFR will be $250,000 (2008). Therefore it is concluded to use a 0.051 m (2
inch) OD tube.
In the case of a CSTR, reactor volume was determined as a function of conversion.
Under each type of reactor design study, methanol to canola oil molar feed ratio was used
as an independent parameter. The reactant flow rates were based on producing 10
million gallons of biodiesel per year. For a 7m3 volume CSTR and methanol to oil molar
feed ratio of 12 yields 90.3% conversion with 41 minutes of reactor residence time.
The estimated cost of a 316-s.s CSTR with 50% capacity over design is found to be
$77,880. The capacity over design provides 30 minutes of hold up volume to
accommodate startup and process upsets.
The CSTR reactor design also included the evaluation of three CSTR reactors in series
with a pump around loop to provide vigorous mixing.

The reactor effluents were

separated by distilling the un-reacted methanol for recycle.

When the value of 'R'

(defined as mole feed ratio of methanol to canola oil) is between 3 (stoichiometric feed

72

ratio) and 15, an additional distillation column will be required for product purification in
order to meet ASTM- D6751 (biodiesel product standard) which requires > 99 wt% of
biodiesel product purity. The boiling point of biodiesel is approximately 598K (325 C).
Biodiesel is thermally decomposed when temperature exceeds 523K (250 C). The
thermal decomposition temperature for glycerol is about 423K (150 C). In order to keep
low distillation temperature, purification column must be operated under vacuum. Based
on Aspen simulation, 10 milli-bar of vacuum would be required to operate the distillation
column below the decomposition temperatures of these products. If the value of 'R' is
>15, product will meet the biodiesel quality as set forth under the ASTM-D6751 standard
without additional purification. The purification cost via vacuum distillation would be
$40.40/hr. To increase product purity from 87 wt% to 99 wt%, the methanol recovery
and recycle cost increases by $40/hr which comes out to be nearly the same when
compared with vacuum distillation of biodiesel product. However, the vacuum
distillation process step will be eliminated.
Because of a very large difference in the boiling points of methanol (33 8K or 65C)
and biodiesel (598K or 325C), separation of excess methanol can be easily accomplished
by simple distillation with nearly 100% methanol recovery for recycle.
A detailed design of a sieve tray distillation column using rigorous correlations
suggests a single column of 1.6 meters diameter and a total height of 10 m (33 ft) would
be required. This column will have 12 stages with 24 inches of tray spacing. The feed
will enter at stage 6. The column is designed to operate at 75% flooding. The column
operation for weeping and entrainment was checked, using tray hydraulic correlations.

73

5.2 Recommendations for Future Research

The results of this thesis provide the necessary guidelines for the production of 10
million gallons per year of biodiesel from canola oil. The following recommendations
for future research are made:
A reactor consisting of a reactive distillation column should be investigated as it will
serve as a reactor as well as a separator for the recycle of methanol.
It is recommended that total cost of a 'Reactive Distillation' column should be compared
with the CSTR reactor system.
If commercial scale biodiesel plants are built, there will a glut of glycerol co-product
(1 kg of glycerol is produced for every 10 kg of biodiesel manufacture). It is
recommended that some new process chemistry to convert glycerol into more useful and
economically attractive products be explored. For example, pyrolysis of glycerol may
yield synthesis gas as envisioned by the following reaction (C3H8O3 ->3CO + 4H2).

74

REFERENCES

REFERENCES

Apostolakou, A.A., Kookos, I.K., Marazoiti, C., and Angelopoulos, K.C. (2009). Technoeconomic analysis of a biodiesel production process from vegetable oils. Fuel
Processing Technology, 90, 1023-1031.
Byrd, A.J., Pant, K.K., and Gupta, R.B. (2008). Hydrogen production from glycerol by
reforming in supercritical water over Ru/A1203 catalyst. American Chemical Society,
Fuel 87, 2956-2960.
BP Statistical Review of world energy 2008. Available from BP statistical review 2008
internet pages <http://www.investis.com/bp_acc_ia/stat_review_2008/htdocs
/reports/reportl 9.html>.
Chavanne, C.G. (1938). Belgian Patent 422, 8 77, Aug. 31, 1937; Chem. Abs.52:4313.
Chemical Engineering Magazine. (2009). M & S index, Pg 64, September edition.
Fogler, H.S. (2006). Elements of Chemical Reaction Engineering. 4th ed. Prentice Hall,
NJ.
Gabbard, A. (1993). Coal Combustion Nuclear Resource or Danger. Oakridge National
Laboratory Review (ORNL), 26, 25-33.
Haas, M.J., McAloon, A.J., Yee, W.C. and Foglia, T.A. (2006). A process model to
estimate biodiesel production costs. Biosource Technology, 97, 671-678.
Kister, H.Z. (1992). Distillation Design. McGraw Hill, NY.
Klepacova, K., Mravec, D., Kaszonyi, A. and Bajus, M. (2007). Etherification of glycerol
and ethylene glycol by isobutylene. Applied catalysis, 328, 1-13.
Knothe, G. (2001). Historical Perspectives on Vegetable Oil- Based Diesel Fuel. Inform
12(11), 1103-1107, Retrieved 2009-06-24.
Komers, K., Skopal, F., Stloukal, R., and Machek, J. (2002). Kinetics and mechanism of
the KOH - catalyzed methanolysis of rapeseed oil for biodiesel production. European
Journal of Lipid Science and Technology, 104(11), 728-737

75

Leevijit, T., Wistmethangoon, W., Prateepchaikul, G., Tongurai, G., and Allen, M.
(2004). A second order kinetics of palm oil transesterification. Joint International
Conference on Sustainable Energy and Environment (SEE), 3, 277-281.
Marchetti, J.M., Miguel, V.U., and Errazu, A.F. (2007). Possible methods for biodiesel
Production. Renewable and Sustainable Energy Reviews, 11, 1300-1311.
McCance, R. A., Widdowson, E.M., Holland, B., and Paul, A. A. (1991). The
Composition Of Food. 5th ed. Ministry of Agriculture, Fisheries and Food., Royal Society
of Chemistry, Cambridge.
National Biodiesel Board, cited in Pearl, G.G. (2001, August). Biodiesel Production in
the U.S. Render Magazine.
Noureddini, H., and Zhu, D. (1997). Kinetics of Transesterification of Soybean oil.
JAOCS, 74, 1457-1463.
Peters, M.S., and Timmerhaus, K.D. (2003). Plant Design and Economics for Chemical
Engineers. 5th ed. McGraw-Hill Companies, Inc., NY.
Schuchard, U., Sercheli, R., and Vargas, R.M. (1998). Transesterification of Vegetable
Oils: A Review. J. Braz. Chem. Soc., 9, 199-210.
Seider, W.D., Sieder, J.D., and Lewin, D.R. (2004). Product and Process Design
Principles:Synthesis, Analysis and Evaluation. 2nd Ed. John Wiley and Sons, Inc.
Sharma, Y.C., Singh, B., and Upadhyay, S.N. (2008). Advancements in development and
characterization of biodiesel: A review, fuel, 87, 2355-2373.
Wankat, P.C. (2007). Separation Process Engineerin. 2nd Ed. Prentice Hall, NJ.

General References
Krik - Othmer. (1991). Encyclopedia of Chemical Technology. 4th ed. Wiley Inter
Science, Inc.
Turner, T.L. (2005). MS thesis. Modeling and Simulation of Reaction Kinetics for
Biodiesel Production. North Carolina State University

76

Appendix A
MathCAD Program for Solution of PFR for Diameter 0.038m (1.5
inch OD) and 0.051m (2.0 inch OD) Tubes

MathCAD program for solution of PFR for diameter 1.5 inch OD tube:
kl := 0.05

k2 := 0.11

k3 := 0.215

k4 := 1.228

k5 := 0.242

k6 := 0.007

A := 0.0009

v 0 := 0.1582

kl,k2,k3,k4,k5 and k6 are rate constants in Lit/mol*min Units

TG(t) = (-kl TG(t) ME(t) + k2 DG(t) BD(t))

dL
v0
DG(t) = (kl TG(t)ME(t) - k2 DG(t) BD(t) - k3 DG(t) ME(t) + k4 MG(t) BD(t))
dL
v0

MG(t) = (k3DG(t)ME(t) - k4MG(t)BD(t) - k5MG(t)ME(t) + k6GY(t)BD(t))

dL
v0

ME(t) = / - k l TG(t) ME(t) + k2DG(t)BD(t) - k3 DG(t) ME(t) ...

dL
v0 ^+k4-MG(t)-BD(t) - k5 MG(t)-ME(t) + k6 GY(t) BD(t)

BD(t) = / k l TG(t) ME(t) - k2 DG(t) BD(t) + k3 DG(t) ME(t) - k4 MG(t) BD(t)

v
dL
o ^+k5 MG(t)-ME(t)-k6 GY(t)-BD(t)

GY(t) = (k5 MG(t) ME(t) - k6 GY(t) BD(t))

dL
vc

77

Here:
A- Flow Area of tube 1.5 inch OD tube (m )
v0- volumetric flow rate of the feed (m /s)

TG=Q0, DG=Q1, MG=Q2, ME=Q3, BD=Q4 and GY=Q5

- ( - k l Q 0 - Q 3 + k2-Q1-Q4)
v0
<kl Q0 Q3 - k2-Qi -Q4 - Id-Q, Q 3 + k4 Q 2 -Q 4 )
v0
(k3Q 1 Q 3 - k4 Q 2 Q 4 - k 5 Q 2 Q 3 + k 6 Q 5 Q 4 )
D(L,Q) :=
- ( - k l -Qo-Qs + k2-Qi Q 4 - k3-Q1 Q 3
v, U k 4 - Q Q - k 5 - Q - Q + k6-Q Q
2
4
2
3
5
4
A

kl Q0 Q3 - k2 Q1 Q 4 + k3 Q1 Q 3 - k4-Q2 Q 4 ...
+ k5 Q 2 Q 3 - k6 -Q5 Q 4
-(k5-Q2Q3-k6Q5Q4)

Note: Subscripts are vectors. Must start from 0 to n.

f ! \

ic :=

0
0
12

0
V0 J

LI := 3000

Npts := 3000

L0 := 0

i := 1.. 2600

1 - TGi_
i~1 100
Wj :=

Yj :=

1 - TGj_-i
1

Xj :=

100

Zj :=

1 - TGm
1

1 - TGj-!
100

100

S := rkfixed(IC ,L0 ,L1 ,Npts ,D)

L :=

TG := S^

DG := S<2>

MG := S<3>

i := 0.. Npts

78

ME :=

BD :=

GY := S ^

Figure 27: Conversion of canola oil to biodiesel versus length of reactor for diameter
0.038m (1.5 inch OD) tube.

Where:

W 40 0= 50.75

Y 4 0 0 = 50.75

X400= 50.75

W 800 = 71.03
W 1200 = 80.51

W20oo= 89.07
W2400 = 91.27
W 258 o= 92.02

71.03

Y 1 2 0 0 = 80.51

X 1200 = 80.51
x

W16oo= 85.78

8 0 0

X8oo= 71.03

Y16OO= 85.78

1600= 85.78

Z400 = 6 0 . 8

Zgoo= 80.72

Zl200 = 89.06

Z 1 6 0 0 = 93.24

Y2OOO= 89.07

Z 2 ooo= 95.54

X 24 00 = 91.27

Y 2 4 0 o = 91.27

Z24oo= 96.87

X2580 92.02

Y 25 80 = 92.02

Z2580 = 97.27

X 2 0 0 0 = 89.07

79

MathCAD program for solution of PFR for diameter 2.0 inch OD tube:
A := 0.002

v 0 := 0.16

Here
A- Flow Area of tube 2.0 inch tube (m2)
Using same MathCAD program used for diameter 0.038m OD, then the results are:

' 1^
0

Npts := 3000

1C :=

12

Wj :=

L0 := 0

LI := 2000

1 - TGn
1 - TGj_i
1 !
100 Xj :=
:
r- - --100
1
1

Y; :=

1 - TGj_j
-100
1

0
V

o;

Zj :=

1 - TGj_i

100

S := rkfixec^IC ,L0,L1 ,Npts,D)

L:=S (0>
i

TG:=S 0 >

DG := S<2)

MG := S ^

0.. Npts

80

ME := S ^ BD :=

GY := S<6>

L,
Figure 28: Conversion of canola oil to biodiesel versus length of reactor for diameter
0.051m (2.0 inch OD) tube.

Where:

W200 = 49.29

200 = 49.29

200 = 49.29

^400 = 69.78

400 = 69.78

2400 = 79.58

600 = 79.55

Z600 = 88.25

800 = 85.01

Z800 = 92.66

1000= = 88.44

1140= = 90.15

1200= = 90.75

4 0 0 = 69.78

6 0 0 = 79.55

^600 = 79.55

Wgoo= 85.01

^800 = 85.01
X

1000= = 88.44

1140= = 90.15

1140= = 90.15

1200= : 90.75

1200= = 90.75

1000= = 88.44

81

200 = 59.27

1000= =95.13

Zll40= = 96.22

1200= = 96.58

Appendix B
PFR Sensitivity Results from Aspen Plus Simulation for Diameter
0.038m (1.5 inch OD) and 0.051m (2.0 inch OD) Tubes

Aspen input data for PFR simulation:

7
8
10

DYNAMICS
DYNAMICS RESULTS=ON
TITLE 'SIMULATRION OF PFR REACTOR FOR BIODIESEL FROM

CANOLA OIL'
12

IN-UNITS SI ENTHALPY-J/kg' FLOW='kg/hr' MASS-FLOW='kg/hr* &

13

MOLE-FLO W='kmol/hr' VOLUME-FLO W='cum/hr' PRESSURE=psia

14

TEMPERATURES DELTA-T=C PDROP='N/sqm' HEAT-

&

FLUX='kJ/hr-m'
16

DEF-STREAMS CONVEN ALL

18

SIM-OPTIONS

19

IN-UNITS ENG

20

SIM-OPTIONS OLD-DATABANK=NO

22

DESCRIPTION"

23

Chemical Simulation with English Units :

24

F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.

26

Property Method: NRTL

28

Flow basis for input: Mole

30

Stream report composition: Mole flow

31
33

DATABANKS 'APV71 PURE20' / 'APV71 SOLIDS' / 'APV71 INORGANIC'

&
34
36

/ NOASPENPCD
PROP-SOURCES 'APV71 PURE20' / 'APV71 SOLIDS' / 'APV71

INORGANIC'
38

COMPONENTS

39

TGCANOLA C57H10406 /

40

BDIESEL C19H3602 /

41

METHANOL CH40 /

42

GLYCEROL C3H803 /

43

DG C39H7205 /

44

MG C21H4004 /

45

WATER H20

47

FLOWSHEET

48

BLOCK R-PLUG IN=PFR-IN OUT=PFR-OUT

49

BLOCK B3 IN=CANOLA MEOH OUT=PFR-IN

51
52
54
55

PROPERTIES UNIFAC TRUE-COMPS=YES

PROPERTIES ELECNRTL / IDEAL / NRTL / NRTL-RK
STRUCTURES
STRUCTURES BDIESEL CI C2 S / C2 0 4 D / C2 0 3 S / 0 3 &

56

C5 S / C5 C6 S / C6 C7 S / C7 C8 S / C8 C9 &

57

S/C9C10S/C10C11 S / C l l C12S/C12C13 &

58

D/C13C14S/C14C15S/C15C16S/C16 &

59

C 1 7 S / C 1 7 C 1 8 S / C 1 8 C 1 9 S / C 1 9 C20 S / &

60

C20 C21 S

62

PROP-DATA

63

PROP-LIST ATOMNO / NO ATOM

64

PVAL BDIESEL 6 1 8 / 1 9 . 36. 2.

84

66
67

STRUCTURES
STRUCTURES DG CI C2 S / C2 0 3 S / 0 3 C4 S / C4 0 5 &

68

D / C4 C6 S / C6 C7 S / C7 C8 S / C8 C9 S / &

69

C 9 C 1 0 S / C 1 0 C 1 1 S / C l l C12 S / C 1 2 C 1 3 S / &

70

C13C14S/C14C15D/C15C16S/C16C17S / &

71

C17 C18 S / C18 C19 S / C19 C20 S / C20 C21 S / &

72

C21 C22 S / C22 C23 S / CI 024 S / 024 C25 S / &

73

C25 026 D / C25 C27 S / C27 C28 S / C28 C29 S / &

74

C 2 9 C 3 0 S / C 3 0 C 3 1 S / C 3 1 C32 S / C32 C33 S / &

75

C33 C34 S / C34 C35 D / C35 C36 S / C36 C37 S / &

76

C37 C38 S / C38 C39 S / C39 C40 S / C40 C41 S / &

77

C41 C42 S / C42 C43 S / CI 044 S

79

PROP-DATA

80

PROP-LIST ATOMNO / NO ATOM

81

PVAL DG 6 1 8 / 39. 72. 5.

83
84

STRUCTURES

STRUCTURES GLYCEROL CI C2 S / C2 C3 S / CI 0 4 S / &

85

85
87

C2 0 5 S / C3 0 6 S
PROP-DATA

88

PROP-LIST ATOMNO / NO ATOM

89

PVAL GLYCEROL 6 1 8 / 3. 8. 3.

91
92
94

STRUCTURES
STRUCTURES METHANOL CI 0 2 S
PROP-DATA

95

PROP-LIST ATOMNO / NO ATOM

96

PVAL METHANOL 6 8 1 / 1 . 1 . 4 .

98
99

STRUCTURES
STRUCTURES MG CI 0 2 S / CI C3 S / C3 0 4 S / C3 C5 &

100

S / C5 0 6 S / 0 6 C7 S / C7 0 8 D / C7 C9 S / &

101

C9C10S/C10C11 S / C l l C12S/C12C13 S/ &

102

C13 C 1 4 S / C 1 4 C 1 5 D / C 1 5 C 1 6 S / C 1 6 C 1 7 S / &

103

C 1 7 C 1 8 S / C 1 8 C 1 9 S / C 1 9 C20 S / C20 C21 D / &

104

C21 C22 S / C22 C23 S / C23 C24 S / C24 C25 S / &

105

C25 C26S

86

107

PROP-DATA

108

PROP-LIST ATOMNO / NO ATOM

109

PVALMG6 1 8 / 2 1 . 4 0 . 4.

111

112

STRUCTURES
STRUCTURES TGCANOLA CI C2 S / CI C3 S / CI 0 4 S / &

113

0 4 C5 S / C5 0 6 D / C5 C7 S / C7 C8 S / C8 &

114

C9 S / C9 CIO S / C 1 0 C 1 1 S / C l l C 1 2 S / C 1 2 &

115

C13 S / C 1 3 C 1 4 S / C 1 4 C 1 5 D / C 1 5 C 1 6 S / &

116

C16C17S/C17C18 S / C 1 8 C 1 9 S / C 1 9 C 2 0 S / &

117

C20 C21 D / C21 C22 S / C22 C23 S / C2 024 S / &

118

024 C25 S / C25 026 D / C25 C27 S / C27 C28 S / &

119

C28 C29 S / C29 C30 S / C30 C31 S / C31 C32 S / &

120

C32 C33 S / C33 C34 S / C34 C35 D / C35 C36 S / &

121

C36 C37 S / C37 C38 D / C38 C39 S / C39 C40 S / &

122

C40 C41 S / C41 C42 S / C42 C43 S / C3 044 S / &

123

044 C45 S / C45 046 D / C45 C47 S / C47 C48 S / &

124

C48 C49 S / C49 C50 S / C50 C51 S / C51 C52 S / &

87

125

C52 C53 S / C53 C54 S / C54 C55 D / C55 C56 S / &

126

C56 C57 S / C57 C58 S / C58 C59 S / C59 C60 S / &

127

C60C61 S / C 6 1 C 6 2 S / C 6 2 C 6 3 S

129

PROP-DATA

130

PROP-LIST ATOMNO / NO ATOM

131

PVAL TGCANOLA 6 1 8 / 57. 104. 6.

133

ESTIMATE ALL

134

IN-UNITS ENG

225

STREAM CANOLA

226

SUBSTREAM MIXED TEMP=25. PRES=4. <atm>

227

MOLE-FLOW TGCANOLA 6.575

229

STREAM MEOH

230

SUBSTREAM MIXED TEMP=25. PRES=4. <atm>

231

MOLE-FLOW METHANOL 78.9

233
234

STREAM PFR-IN
SUBSTREAM MIXED TEMP=15. PRES=15. FREE-WATER=NO

NPHASE=1 &

88

235
236
238
239
241
242

PHASE=L
MOLE-FLOW TGCANOLA 6.575 / METHANOL 45.4
BLOCK B3 MIXER
PARAM T-EST=15
BLOCK R-PLUG RPLUG
PARAM TYPE-T-SPEC LENGTH= 1140. DIAM= 1.76 <in> NPHASE= 1

&
243

PHASE=L PRES=20. PDROP=5. <psi> FLASH=NO

244

T-SPEC 0.0 50.

245

COOLANT TOLO.OOl

246

BLOCK-OPTION RESTART=YES FREE-WATER=NO ENERGY-

BAL=YES &
247
248

FLASH-METHOD=INSIDE-OUT
REACTIONS RXN-IDS=R-1

250

EO-CONV-OPTI

301

STREAM-REPOR MOLEFLOW MASSFLOW

Table 20: Aspen stream results for various methanol to canola oil feed ratios as a
the function of reactor length for diameter 0.038m (1.5 inch OD).
MEOH Reactoi
Mole
Ratio Length RATIO CONV

BD
kmol/
hr
6.32
6.49
6.66
6.82
6.94

DG
OUT
kmol/
hr
1.47
1.48
1.48
1.48
1.48

MG
OUT
kmol/
hr
0.41
0.40
0.39
0.38
0.37

GY
OUT
kmol/
hr
13.41
13.23
13.07
12.91
12.79

TG
ME
OUT OUT
kmol/ kmol/
hr
hr
1.34 3.35
1.40 3.29
1.47 3.24
1.52 3.19
1.57 3.15

1
2
3
4
5

kmol/hr
19.725
19.725
19.725
19.725
19.725

meters
2200
2300
2400
2500
2580

3
3
3
3
3

%
mins
49.03 9.2
49.94 9.6
50.78 10.0
51.55 10.5
52.12 10.9

6
7
8
9
10

39.45
39.45
39.45
39.45
39.45

2200
2300
2400
2500
2580

6
6
6
6
6

69.25
70.32
71.29
72.20
72.87

8.7
9.1
9.5
10.0
10.3

11.00
11.28
11.53
11.78
11.96

1.14
1.12
1.09
1.07
1.05

0.37
0.36
0.34
0.33
0.32

28.45
28.17
27.92
27.67
27.49

3.04
3.15
3.25
3.35
3.43

2.02
1.95
1.89
1.83
1.78

11
12
13
14
15

59.175
59.175
59.175
59.175
59.175

2200
2300
2400
2500
2580

9
9
9
9
9

80.92
82.00
82.99
83.91
84.59

8.3
8.7
9.1
9.5
9.9

14.13
14.42
14.70
14.96
15.15

0.77
0.74
0.70
0.67
0.65

0.29
0.28
0.26
0.25
0.24

45.05
44.75
44.48
44.22
44.03

4.26
4.38
4.49
4.60
4.67

1.25
1.18
1.12
1.06
1.01

16
17
18
19
20

78.9
78.9
78.9
78.9
78.9

2200
2300
2400
2500
2580

12
12
12
12
12

87.53
88.52
89.42
90.23
90.83

7.8
8.2
8.6
9.0
9.3

16.00
16.28
16.53
16.76
16.93

0.52
0.49
0.45
0.43
0.40

0.23
0.21
0.20
0.19
0.18

62.90
62.62
62.37
62.14
61.97

5.01
5.12
5.23
5.32
5.39

0.82
0.75
0.70
0.64
0.60

90

Table 20: Aspen stream results for various methanol to canola oil feed ratios as a
the function of reactor length for diameter 0.038m (1.5 inch OD).
MEOH Reactoi
Mole
Ratio Length RATIO CONV

MG
OUT
kmol/
hr
0.44
0.42
0.40
0.37
0.37
0.35

GY
OUT
kmol/
hr
1.12
1.28
1.43
1.57
1.57
1.69

ME
TG
OUT OUT
kmol/ kmol/
hr
hr
14.06 3.58
13.58 3.41
13.16 3.27
12.79 3.15
12.79 3.15
12.46 3.05

kmol/hr
m
1
19.73
800
2
19.73
900
3
19.73 1000
4
19.73 1100
5
19.73 1140
6
19.73 1200

3
3
3
3
3
3

DG
OUT
BD
kmol/ kmol/
hr
%
mins hr
45.50 7.5 5.67 1.43
48.12 8.5 6.14 1.47
50.30 9.5 6.56 1.48
52.09 10.5 6.93 1.48
52.121 10.9 6.87 1.48
53.58 11.5 7.26 1.48

7
8
9
10
11
12

39.45
39.45
39.45
39.45
39.45
39.45

800
900
1000
1100
1140
1200

6
6
6
6
6
6

65.09 7.0 9.98

68.19 8.0 10.73
70.73 9.0 11.38
72.84 10.0 11.95
72.871 10.3 11.84
74.61 11.0 12.44

1.22
1.17
1.11
1.05
1.05
0.99

0.43
0.39
0.35
0.32
0.32
0.29

2.63
2.93
3.19
3.42
3.43
3.62

29.47
28.72
28.07
27.50
27.47
27.01

2.30
2.09
1.92
1.79
1.78
1.67

13
14
15
16
17
18

59.18
59.18
59.18
59.18
59.18
59.18

800
900
1000
1100
1140
1200

9
9
9
9
9
9

76.64 6.7 12.98

79.83 7.6 13.83
82.42 8.5 14.54
84.55 9.5 15.14
84.584 9.85 14.99
86.32 10.5 15.64

0.89
0.80
0.72
0.65
0.65
0.59

0.36
0.31
0.27
0.24
0.24
0.21

3.79
4.14
4.43
4.67
4.67
4.88

46.20
45.35
44.63
44.04
44.00
43.54

1.54
1.33
1.16
1.02
1.01
0.90

19
20
21
22
23
24

78.90
78.90
78.90
78.90
78.90
78.90

800
900
1000
1100
1140
1200

12
12
12
12
12
12

83.49 6.3 14.88

86.52 7.2 15.72
88.90 8.1 16.39
90.80 9.0 16.92
90.829 9.34 16.77
92.32 9.9 17.36

0.65
0.55
0.47
0.41
0.40
0.35

0.29
0.25
0.21
0.18
0.18
0.15

4.55
4.89
5.17
5.39
5.39
5.57

64.02
63.18
62.51
61.98
61.97
61.54

1.09
0.89
0.73
0.60
0.59
0.51

91

Appendix C
Shell/ Tube Configuration of a PFR

Shell/ Tube configuration for a PFR of diameter 0.038m (1.5 inch OD):
Total_Length:= 2580m
:=

LReactor

4m

TubeoD := 0.038m
Tubqo : = 0.03m

TotalLength
N r u b e s :=

LReactor

= 13.123 f t

LReactor
Nlubes = 645

Tube_Pitch:= 0.10169m
Shell_Dia:= 1.25 Tube_PitchA/

NTubes

Shell Dia= 10.591ft

Shell Dia= 3.228m
Shell/Tube configuration for a PFR of diameter 0.051m (2.0 inch OD):
Total_Length:= 1140m
LReactor

N Tubes

4m
:

TubeoD := 0.051m
Tubq D := 0.045m

TotalLength
=

LReactor

= 13.123ft

LReactor
N-rubes = 2 8 5

Tube Pitch.- 0.10169m

Shell_Dia:= 1.25-Tube_Pitch^N Tubes
Shell Dia= 7.04 ft
Shell Dia= 2.146 m

92

Appendix D
PFR Pressure Drop in 0.038m (1.5 inch OD) and 0.051m
(2.0 inch OD) Tubes

Pressure Drop caluclations for PFR of diameter 0.038m (1.5 inch OD) Tu
m
vel:= 1
s
p := 800

D id := 0.03m

L := 4m
kg

f := 0.01

K f := 1.5

m
AP := 4.f.

+ Kf

(vel)2-p

AP = 0.027 atm

ThisAP is for one 4m long one bend tube

Nbends := 6 4 6

Total_L:= 4m-N ben ds

Total_L= 2.5 84 x 103m

APtotal : = AP-Nbends

APtotal

= 17.426atm

^reactors

Pall Reactor : = N reaC [ 0rs AP tota |

Pall_Reactor

= 34.853 atm

93

Pressure Drop caluclations for PFR of diameter 0.051m (2.0 inch) OD Tube
m
vel := 1 . 5 1 5 - L := 4m
s
p := 800

kg

D id := 0.045m

f := 0.01

Kf

:= 1.5

m
4-f-f

A P :=
.

(vel)2-p
+

VidJ

AP = 0.046 atm

ThisDP is for one 4m long one bend tube

N b e n d s := 2 8 6

Total_L := 4m-Nb en ds

TotalL = 1.144 x 10 3 m
AP

total : =

AP-Nbends

AP tota] = 13.101 atm

Nreactors

P a l l Reactor
P a l l Reactor

reactors APtotal

= 13.101 atm

94

Appendix E
Plug Flow Reactor Cost for Diameter 0.038m (1.5 inch OD) and 0.051m (2.0 inch
OD) Tubes

Reactor Cost for diameter 0.038m (1.5 inch OD) Tube

D = 0.03 m

12

L := 8465ft

LL := 2580m

dollars := 1

A := 7tD-L

A = 240.886 m
A = 2.593 x 10 3 ft 2
Area := 2593
F m := 1.75 + 0.13

^ Area ^
V 100 j

F m = 5.121
Cost := _(exp( 11.0545 - 0.9228 -ln(Area) + 0.0979 -ln(Area)2)) -F M dollars
Cost = 9.707 x 10 dollars
Gear Pump Cost
QQ := 65

gal

no_of_gear_pumps := 2

min

QQ = 4.101 x 10

-3 m
s

Q := 65
Fm := 2

For 316 Stainless Steel

CostQearpump : 2[exp[ 7.2744 + 0.19868 ln(Q) + 0.029-(ln(Q) 2 ) ]-Fm] dollars

CostcearPump

= 2.193

10 dollars

95

MS Factor :=

1538
1097.7

Total_Reactor_Plus_Gear_Pump_Cost_2008=

MSFactor

Cost...
v CostQearpump

Total_Reactor_Plus_Gear_Pump_Cost_2008= 166727 dollars

Approx Total Reactor Plus Gear Pump Cost 2008= 166700dollars

96

Reactor Cost for diameter 0.051m (2.0 inch OD) Tube

D := f t

D = 0.045 m

dollars := 1

12

L := 8465ft

LL := 2580m

A := 7iD-L
A = 362.358m2
A = 3.9 x 10 3 ft 2
Area := 3900
F m := 1.75 + 0.13

^ Area^
V 100 j

F m = 6.82
Cost := _(exp( 11.0545 - 0.9228-ln( Area) + 0.0979-ln( Area)2) )-F M dollars
Cost = 1.69 x 105 dollars
Gear Pump Cost
QQ := 4 6 - ^
min
3

QQ = 2.902 x 10" 3
s
Q := 46
Fm := 2

For 316 Stainless Steel

CostQearpump: [exp[ 7.2744 + 0.19868 ln(Q) + 0.029-(ln(Q) 2 )]-Fm]dollars

3
CostQearPump

= 9.446 x 10 dollars

MS Factor :=

1538
1097.7

97

Total_Reactor_Plus_Gear_Pump_Cost_2008=

MS Factor- Cost...
+ CostG ear p um p
Total_Reactor_Plus_Gear_Pump_Cost_2008= 250006 dollars
Approx_Total_Reactor_Plus_Gear_Pump_Cost_2008= 250000dollars

98

Appendix F
MathCAD Program for a Solution to CSTR

v := 0.175-

Vr := 7-m

min

6 :=

9 = 40 min

kmol := lOOOmol

kl := 0.05-

mol-min

k4 := 1.228mol-min

CTGO

: =

kmol
0.626

k2 := 0.11

mol-min

k5 := 0.242
mol-min

Cdgo

kmol

kmol
= 0

kmol

kmol
CGYO :

CMGO : = 0

mol-min

k6 := 0.007
mol-min

kmol

CMEO : = 7 . 5 1 2

m
CBDO

k3 := 0.215

Guess Values
C t g := 2

kmol

kmol

Cdg := 1

kmol

CME : = 1

kmol
Cmg := 1
m

CBD : = 1

kmol
Cqy := 2

kmol

Given
CMEO - CME +

- k l -Ctg-Cme+ k2-C DG -CBD- k3-CDG'C]viE

+ K 4 -CMG'CBD - K 5 -C M G-CME + K 6 - C Q Y CBD

CTGO - C T G +

( - k l -CTG-CME + k2-CDG-CBD)-9 = 0

99

0 = 0

CDGO-CDG+ ( kl-C TG'CME-k2-CDG-CBD-k3-CDG-CME+ ^-CMG'CBD)'0 = 0

MGO~ CMG + k3-CDG'CME- k4-CjviG-CBD- k5-CMG'CME

+ k6CGY-CBD

0 = 0

CGYO~CGY+ (k5-CMG-CME~ k6-CGY'CBD) -0 = 0

kl -Ctg-Cme- k2-CDG"CBD+ k3-CDG'CME- k4-CMG'cBD + k5 -CmG'Cme - k6-CoY-CBD

Cbdo-Cbd-

CME^

'CmE

Ctg

Ctg

Cdg

:= Find

Cmg

Cmg

CGy

Cgy

Cbd j

v Cbd

Cme^

5.906^

Ctg

0.066

Cdg

0.031

kmol

Cmg

0.013

Cgy

0.516
v

Cbd,

C TG 0

Cdg

TG = Triglyceride
ME= Methanol
DG= Diglyceride
MG= Monoglyceride
GY= Glycerol
BD= BioDiesel

T G + ME = DG + BD
DG + ME = MG + BD
MG + ME = GY + BD

1.606 ;

kmol
0.626-

m
Conv :=

CtG0-CTG

100

CtGO

Conv = 89.485

M a s s I N :=

MW=884
MW=32
MW=620
MW=356
MW=92
MW=296

CMEO-32- + CTGO-884-
mol
moly

100

0 = 0

Mass OUT := 3 2 - & C M E + 8 8 4 - & C T G + 6 2 0 - ^ C d g + 3 5 6 - ^ - C m g

mol
mol
mol
mol
+ 9 2 - ^ ] C g y + 296-^i-Cbd
mol
mol

MassIN = 2.315
s
BDProduct := C B D v 2 9 6

kg
MassOUT = 2.315
s
kg
kmol

BD Product = 4991.2
hr

101

Appendix G
CSTR Sensitivity Results from Aspen Plus Simulation

Aspen input data for CSTR simulation:

7
8
12

DYNAMICS
DYNAMICS RESULTS=ON
IN-UNITS SI ENTHALPY-J/kg' FLOW='kg/hr' MASS-FLOW='kg/hr' &

13

MOLE-FLOW='kmol/hr' VOLUME-FLOW='cum/hr' PRESSURE=psia

14

TEMPERATURE=C DELTA-T=C PDROP='N/sqm' HEAT-

&

FLUX-kJ/hr-m'
15
16

DEF-STREAMS CONVEN ALL

18

SIM-OPTIONS

19

IN-UNITS ENG

20

SIM-OPTIONS OLD-DATABANK=NO

22

DESCRIPTION"

23

Chemical Simulation with English Units :

24

F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.

102

26

Property Method: NRTL

28

Flow basis for input: Mole

30

Stream report composition: Mole flow

31
33

DATABANKS 'APV71 PURE20' / 'APV71 SOLIDS' / 'APV71 INORGANIC

&
34
36

/ NOASPENPCD
PROP-SOURCES 'APV71 PURE20' / 'APV71 SOLIDS' / 'APV71

INORGANIC'
38

COMPONENTS

39

TGCANOLA C57H10406/

40

BDIESEL C19H3602/

41

METHANOL CH40 /

42

GLYCEROL C3H803 /

43

DG C39H7205 /

44

MG C21H4004 /

45

WATER H20

47

FLOWSHEET

48

BLOCK MIX-1 IN=CANOLA MEOH OUT=CSTRIN

49

BLOCK CSTR-1 IN=CSTRIN OUT=CSTROUT

51
52
54
55

PROPERTIES UNIFAC TRUE-COMPS=YES

PROPERTIES ELECNRTL / IDEAL / NRTL / NRTL-RK
STRUCTURES
STRUCTURES BDIESEL CI C2 S / C2 0 4 D / C2 0 3 S / 0 3 &

56

C5 S / C5 C6 S / C6 C7 S / C7 C8 S / C8 C9 &

57

S / C 9 C 1 0 S / C10C11 S / C l l C 1 2 S / C 1 2 C 1 3 &

58

D/C13C14S/C14C15S/C15C16S/C16 &

59

C 1 7 S / C 1 7 C 1 8 S / C 1 8 C 1 9 S / C 1 9 C20 S / &

60

C20 C21 S

62

PROP-DATA

63

PROP-LIST ATOMNO / NO ATOM

64

PVAL BDIESEL 6 1 8 /19. 36. 2.

66
67

STRUCTURES
STRUCTURES DG CI C2 S / C2 0 3 S / 0 3 C4 S / C4 0 5 &

104

68

D / C4 C6 S / C6 C7 S / C7 C8 S / C8 C9 S / &

69

C9C10S/C10C11 S / C l l C12S/C12C13 S/ &

70

C13 C 1 4 S / C 1 4 C 1 5 D / C 1 5 C 1 6 S / C 1 6 C 1 7 S / &

71

C17 C18 S / C18 C19 S / C19 C20 S / C20 C21 S / &

72

C21 C22 S / C22 C23 S / CI 024 S / 024 C25 S / &

73

C25 026 D / C25 C27 S / C27 C28 S / C28 C29 S / &

74

C29 C30 S / C30 C31 S / C31 C32 S / C32 C33 S / &

75

C33 C34 S / C34 C35 D / C35 C36 S / C36 C37 S / &

76

C37 C38 S / C38 C39 S / C39 C40 S / C40 C41 S / &

77

C41 C42 S / C42 C43 S / CI 044 S

79

PROP-DATA

80

PROP-LIST ATOMNO / NO ATOM

81

PVAL DG 6 1 8 / 3 9 . 72. 5.

83
84
85
87

STRUCTURES

STRUCTURES GLYCEROL CI C2 S / C2 C3 S / CI 0 4 S / &

C2 0 5 S / C3 0 6 S
PROP-DATA

105

88

PROP-LIST ATOMNO / NO ATOM

89

PVAL GLYCEROL 6 1 8 / 3. 8. 3.

91
92
94

STRUCTURES
STRUCTURES METHANOL CI 0 2 S
PROP-DATA

95

PROP-LIST ATOMNO / NO ATOM

96

PVAL METHANOL 6 8 1 / 1 . 1 . 4 .

98
99

STRUCTURES
STRUCTURES MG CI 0 2 S / CI C3 S / C3 0 4 S / C3 C5 &

100

S / C5 0 6 S / 0 6 C7 S / C7 0 8 D / C7 C9 S / &

101

C9C10S/C10C11 S / C l l C12S/C12C13 S/ &

102

C13 C14 S / C14 C15 D / C15 C16 S / C16 C17 S / &

103

C17 C18 S / C18 C19 S / C19 C20 S / C20 C21 D / &

104

C21 C22 S / C22 C23 S / C23 C24 S / C24 C25 S / &

105

C25 C26 S

107
108

PROP-DATA
PROP-LIST ATOMNO / NO ATOM

106

109
111
112

PVALMG6 1 8 / 2 1 . 4 0 . 4
STRUCTURES
STRUCTURES TGCANOLA CI C2 S / CI C3 S / CI 0 4 S / &

113

0 4 C5 S / C5 0 6 D / C5 C7 S / C7 C8 S / C8 &

114

C9S/C9C10S/C10C11 S / C l l C12S/C12 &

115

C13S/C13C14S/C14C15D/C15C16S / &

116

C16C17S/C17C18 S / C 1 8 C 1 9 S / C 1 9 C 2 0 S / &

117

C20 C21 D / C21 C22 S / C22 C23 S / C2 024 S / &

118

024 C25 S / C25 026 D / C25 C27 S / C27 C28 S / &

119

C28 C29 S / C29 C30 S / C30 C31 S / C31 C32 S / &

120

C32 C33 S / C33 C34 S / C34 C35 D / C35 C36 S / &

121

C36 C37 S / C37 C38 D / C38 C39 S / C39 C40 S / &

122

C40 C41 S / C41 C42 S / C42 C43 S / C3 044 S / &

123

044 C45 S / C45 046 D / C45 C47 S / C47 C48 S / &

124

C48 C49 S / C49 C50 S / C50 C51 S / C51 C52 S / &

125

C52 C53 S / C53 C54 S / C54 C55 D / C55 C56 S / &

126

C56 C57 S / C57 C58 S / C58 C59 S / C59 C60 S / &

107

127
129

C60 C61 S / C61 C62 S / C62 C63 S

PROP-DATA

130

PROP-LIST ATOMNO / NO ATOM

131

PVAL TGCANOLA 6 1 8 / 57. 104. 6.

133

ESTIMATE ALL

134

IN-UNITS ENG

225

STREAM CANOLA

226

SUBSTREAM MIXED TEMP=15. PRES=15.

227

MOLE-FLOW TGCANOLA 6.57

229

STREAM MEOH

230

SUBSTREAM MIXED TEMP=15. PRES=15.

231

MOLE-FLOW METHANOL 78.

233

BLOCK MIX-1 MIXER

234

PARAM T-EST=15

236

BLOCK CSTR-1 RCSTR

237

PARAM VOL=7. TEMP=50. PRES=15. NPHASE=1 PHASE=L

238

BLOCK-OPTION FREE-WATER=NO

108

239

REACTIONS RXN-IDS=R-1

241
285

EO-CONV-OPT
PROPERTY-REP PCES NOPARAM-PLUS

Table 22: Aspen steam results for various methanol to canola oil molar feed ratio as
function reactor volume of CSTR.
Mole
Ratio Volume RATIO CONV

TG
OUT
kmol/
hr
3.49
3.29
3.15
3.05
2.98

DG
OUT
kmol/
hr
1.13
1.13
1.11
1.10
1.08

MG
OUT
kmol/
hr
0.27
0.25
0.23
0.22
0.21

ME
OUT
kmol/
hr
13.00
12.37
11.92
11.57
11.30

GY
OUT
kmol/
hr
1.68
1.91
2.08
2.20
2.31

kmol/hr
1 19.725
2 19.725
3 19.725
4 19.725
5 19.725

m
3
4
5
6
7

3
3
3
3
3

%
46.94
50.00
52.07
53.58
54.74

mins
18.9
25.5
32.1
38.7
45.3

BD
kmol/
hr
6.72
7.36
7.81
8.15
8.42

6
7
8
9
10

39.45
39.45
39.45
39.45
39.45

3
4
5
6
7

6
6
6
6
6

66.04
70.11
72.89
74.92
76.49

18.4
25.0
31.7
38.3
45.1

11.03 2.23
11.97 1.97
12.63 1.78
13.11 1.65
13.49 1.55

0.86
0.81
0.77
0.73
0.71

0.26
0.23
0.21
0.20
0.19

28.42
27.48
26.82
26.34
25.96

3.21
3.56
3.81
3.99
4.14

11
12
13
14
15

59.175
59.175
59.175
59.175
59.175

3
4
5
6
7

9
9
9
9
9

76.06
80.14
82.86
84.80
86.26

17.7
24.0
30.4
36.8
43.3

13.51 1.57
14.48 1.31
15.14 1.13
15.61 1.00
15.97 0.90

0.63
0.56
0.51
0.47
0.44

0.23
0.20
0.18
0.17
0.15

45.67
44.69
44.04
43.56
43.20

4.14
4.51
4.76
4.94
5.07

16
17
18
19
20

78.9
78.9
78.9
78.9
78.9

3
4
5
6
7

12
12
12
12
12

81.14
84.91
87.34
89.05
90.32

16.7
22.6
28.6
34.6
40.6

14.82
15.74
16.34
16.76
17.07

1.24
0.99
0.83
0.72
0.64

0.49
0.42
0.37
0.33
0.31

0.21
0.18
0.16
0.14
0.13

64.08
63.16
62.56
62.14
61.83

4.64
4.99
5.22
5.38
5.50

109

Appendix H
Sizing of Single CSTR

Reactor Sizing of Single CSTR

Feed

kg
:= 8342
hr

V Flow Rate

p := 771.9
Feed

:=

kg
3
mm3
= 0.18
min

V Flow Rate

Reactorresidencetime

:= 40.6 min

Assume design Residence time=1.5*Reactor residence time

DesignResidenceTime

:= 1.5 -Reactorresidencetime

DesignResidenceTime

= 60.9 min

Volume r := V F l o w R a t e

Design Residence Time

Volume r = 10.969 m3
Assume Diameter

Dia := 5.5

ft

Area

Volume r
H

:=

HR

Area

:= n

(Dia)2
4

Area

= 2.207 mz

= 4.97 m

HR

Dia

= 2.965

ActualFeedVolume

:= V F l o w R a t e

ActualFeedVolume

= 7.313 m3

-Reactorresidencetime

/ T~V \ 2

Reactor Design Volume

:= n -HR

Reactor Design Volume

= 10.969 m3

PercentOverDesign
PercentOverDesign

ReactorDesignVolume
Actual_Feed_Volume
= 1.5

110

Appendix I
A Graphical Representation of Purchased Cost of Jacketed and Stirred Reactors

Capacity, geu

Capacity, m 3

Figure 29: Purchased cost of jacketed and stirred reactors (Peters et al., 2003).

Ill

Appendix J

AspenPlus Input File for Three CSTR in Series with Pump Around System

10

TITLE '3 Reactors in Series with Pumparound'

12

IN-UNITS SI MASS-FLOW='kg/hr' MOLE-FLO W='kmol/hr' ENTHALPY-

FLO=kW &
13

PRESSURE=bar TEMPERATURE=C HEAT=kW-hr PDROP='N/sqm'

15

DEF-STREAMS CONVEN ALL

17

SIM-OPTIONS

18

IN-UNITS ENG

19

SIM-OPTIONS OLD-DATABANK=NO

21

DESCRIPTION"

22

Chemical Simulation with English Units :

23

F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.

25

Property Method: NRTL

27

Flow basis for input: Mole

29
30

Stream report composition: Mole flow

32

DATABANKS 'APV71 PURE20' / 'APV71 SOLIDS' / 'APV71 INORGANIC

&
33
35

/ NOASPENPCD
PROP-SOURCES 'APV71 PURE20' / 'APV71 SOLIDS' / 'APV71

INORGANIC'
37

COMPONENTS

38

TGCANOLA C57H10406/

39

BDIESEL C19H3602/

40

METHANOL CH40 /

41

GLYCEROL C3H803 /

42

DG C39H7205 /

43

MG C21H4004 /

44

WATER H20

46

FLOWSHEET

47

BLOCK MIX-1 INCANOLA MEOH OUT=R-IN

48

BLOCK STR-1 IN=R1-RCY Rl-IN OUT=Rl-OUT

49

BLOCK PI IN=Rl-OUT OUT=Pl-OUT

50

BLOCK SPT1 IN=P1-0UT 0UT=R1-RCY R2-IN

51

BLOCK STR-2 IN=R2-IN R2-RCY OUT=R2-OUT

52

BLOCK STR-3 IN=R3-IN R3-RCY OUT=R3-OUT

53

BLOCK P2 IN=R2-OUT OUT=P2-OUT

54

BLOCK P3 IN=R3-OUT OUT=P3-OUT

55

BLOCK SPT2 IN=P2-OUT OUT=R2-RCY R3-IN

56

BLOCK SPT3 IN=P3-OUT OUT=R3-RCY RAW1

57

BLOCK HX1 IN=R-IN OUT=Rl-IN

58

BLOCK COL1 IN=RAW1 OUT=M-RCY RAW2

59

BLOCK SEP1 IN=5 OUT=RAW3 GLY

60

BLOCK HX2 IN=RAW2 OUT=5

62
63
65
66

PROPERTIES UNIFAC TRUE-COMPS=YES

PROPERTIES ELECNRTL / IDEAL / NRTL / NRTL-RK
STRUCTURES
STRUCTURES BDIESEL CI C2 S / C2 0 4 D / C2 0 3 S / 0 3 &

67

C5 S / C5 C6 S / C6 C7 S / C7 C8 S / C8 C9 &

68

S/C9C10S/C10C11 S / C l l C12S/C12C13 &

114

69

D / C 1 3 C14 S / C 1 4 C15 S / C 1 5 C16 S /C16 &

70

C 1 7 S / C 1 7 C 1 8 S / C 1 8 C 1 9 S / C 1 9 C20 S / &

71

C20 C21 S

73

PROP-DATA

74

PROP-LIST ATOMNO / NO ATOM

75

PVAL BDIESEL 6 1 8 / 19. 36. 2.

77
78

STRUCTURES
STRUCTURES DG CI C2 S / C2 0 3 S / 0 3 C4 S / C4 0 5 &

79

D / C4 C6 S / C6 C7 S / C7 C8 S / C8 C9 S / &

80

C9C10S/C10C11 S / C l l C12S/C12C13S/ &

81

C13 C14 S / C14 C15 D / C15 C16 S / C16 C17 S / &

82

C 1 7 C 1 8 S / C 1 8 C 1 9 S / C19 C20 S / C20 C21 S / &

83

C21 C22 S / C22 C23 S / CI 024 S / 024 C25 S / &

84

C25 026 D / C25 C27 S / C27 C28 S / C28 C29 S / &

85

C29 C30 S / C30 C31 S / C31 C32 S / C32 C33 S / &

86

C33 C34 S / C34 C35 D / C35 C36 S / C36 C37 S / &

87

C37 C38 S / C38 C39 S / C39 C40 S / C40 C41 S / &

115

88
90

C41 C42 S / C42 C43 S / CI 044 S

PROP-DATA

91

PROP-LIST ATOMNO / NO ATOM

92

PYAL DG 6 1 8 / 39. 72. 5.

94
95
96
98

STRUCTURES
STRUCTURES GLYCEROL CI C2 S / C2 C3 S / CI 0 4 S / &
C2 0 5 S / C3 0 6 S
PROP-DATA

99

PROP-LIST ATOMNO / NOATOM

100

PVAL GLYCEROL 6 1 8 / 3. 8. 3.

102

103
105

STRUCTURES
STRUCTURES METHANOL CI 0 2 S
PROP-DATA

106

PROP-LIST ATOMNO / NOATOM

107

PVAL METHANOL 6 8 1 / 1 . 1 . 4 .

109
110

STRUCTURES
STRUCTURES MG CI 0 2 S / CI C3 S / C3 0 4 S / C3 C5 &

116

Ill

S / C5 0 6 S / 0 6 C7 S / C7 0 8 D / C7 C9 S / &

112

C9C10S/C10C11 S / C l l C12S/C12C13 S/ &

113

C13C14S/C14C15D/C15C16S/C16C17S / &

114

C17 C18 S / C18 C19 S / C19 C20 S / C20 C21 D / &

115

C21 C22 S / C22 C23 S / C23 C24 S / C24 C25 S / &

116

C25 C26S

118

PROP-DATA

119

PROP-LIST ATOMNO / NOATOM

120

PVAL MG 6 1 8 / 2 1 . 4 0 . 4.

122
123

STRUCTURES
STRUCTURES TGCANOLA CI C2 S / CI C3 S / CI 0 4 S / &

124

0 4 C5 S / C5 0 6 D / C5 C7 S / C7 C8 S / C8 &

125

C9S/C9C10S/C10C11 S / C l l C12S/C12 &

126

C13 S / C13 C14 S / C14 C15 D / C15 C16 S / &

127

C 1 6 C 1 7 S / C 1 7 C 1 8 S / C 1 8 C 1 9 S / C 1 9 C20 S / &

128

C20 C21 D / C21 C22 S / C22 C23 S / C2 024 S / &

129

024 C25 S / C25 026 D / C25 C27 S / C27 C28 S / &

117

130

C28 C29 S / C29 C30 S / C30 C31 S / C31 C32 S / &

131

C32 C33 S / C33 C34 S / C34 C35 D / C35 C36 S / &

132

C36 C37 S / C37 C38 D / C38 C39 S / C39 C40 S / &

133

C40 C41 S / C41 C42 S / C42 C43 S / C3 044 S / &

134

044 C45 S / C45 046 D / C45 C47 S / C47 C48 S / &

135

C48 C49 S / C49 C50 S / C50 C51 S / C51 C52 S / &

136

C52 C53 S / C53 C54 S / C54 C55 D / C55 C56 S / &

137

C56 C57 S / C57 C58 S / C58 C59 S / C59 C60 S / &

138

C60 C61 S / C61 C62 S / C62 C63 S

140

PROP-DATA

141

PROP-LIST ATOMNO / NO ATOM

142

PVAL TGCANOLA 6 1 8 / 57. 104. 6.

144

ESTIMATE ALL

145

IN-UNITS ENG

232

STREAM CANOLA

233

IN-UNITS ENG

234

SUBSTREAM MIXED TEMP=59.00000 PRES=15.

118

235
237

MOLE-FLOW TGCANOLA 6.95 <kmol/hr>

STREAM MEOH

238

IN-UNITS ENG

239

SUBSTREAM MIXED TEMP=59.00000 PRES=15.

240

MOLE-FLOW METHANOL 104.25 <kmol/hr

242

BLOCK MIX-1 MIXER

243

IN-UNITS ENG

244

PARAM PRES=1. <bar> NPHASE=1 PHASE=L T-EST=59.

245

BLOCK-OPTION FREE-WATER=NO

247

BLOCK SPT1 FSPLIT

248

IN-UNITS ENG

249

FRAC Rl-RCY 0.9

251
252

BLOCK SPT2 FSPLIT

FRAC R2-RCY 0.9

254

BLOCK SPT3 FSPLIT

255

FRAC R3-RCY 0.9

257

BLOCK HX1 HEATER

119

258
260
261

263
264

PARAM TEMP=50. PRES=4.

BLOCK HX2 HEATER
PARAM TEMP=25. PRES=4.
BLOCK SEP1 DECANTER
PARAM TEMP=25. PRES=2. L2-COMPS=GLYCEROL

266

BLOCK COL1 RADFRAC

267

PARAM NSTAGE=6

268

COL-CONFIG CONDENSER=TOTAL

269

FEEDS RAW1 4

270

PRODUCTS M-RCY 1 L / RAW2 6 L

271

P-SPEC 1 1.1

272

COL-SPECS DP-COL=0. MOLE-D=83.8 MOLE-RR=2.

273

TRAY-SIZE 1 2 5 SIEVE

274

TRAY-RATE 1 2 5 SIEVE DIAM= 1.40946 P-UPDATE=NO

276

BLOCK STR-1 RCSTR

277

IN-UNITS ENG

278

PARAM VOL=3. <cum> TEMP=50. <C> PRES=1. <bar> NPHASE=1 &

120

279

PHASE=L

280

BLOCK-OPTION FREE-WATER=NO

281

REACTIONS RXN-IDS=R-1

283

BLOCK STR-2 RCSTR

284

PARAM VOL=3. TEMP=50. PRES=1. NPHASE=1 PHASE=L

285

BLOCK-OPTION FREE-WATER=NO

286

REACTIONS RXN-IDS=R-1

288

BLOCK STR-3 RCSTR

289

PARAM VOL=3. TEMP=50. PRES=1. NPHASE=1 PHASE=L

290

BLOCK-OPTION FREE-WATER=NO

291

REACTIONS RXN-IDS=R-1

293

BLOCK PI PUMP

294

IN-UNITS ENG

295

PARAM PRES=5. <bar>

297
298
300

BLOCK P2 PUMP
PARAM PRES=5.
BLOCK P3 PUMP

121

301

PARAM PRES=5

303

EO-CONV-OPTI

305

SENSITIVITY S-l

306

IN-UNITS ENG

307

DEFINE OILOUT MOLE-FLOW STREAM=RAW 1

SUBSTREAM=MIXED &
308
309

COMPONENT=TGCANOLA
DEFINE OILIN MOLE-FLOW STREAM=R-IN SUBSTREAM=MIXED

&
310
311

COMPONENT=TGCANOLA
DEFINE TIME 1 BLOCK-VAR BLOCK=STR-1 VARIABLE=RT-C ALC

&
312
313

SENTENCE=RESULTS
DEFINE TIME2 BLOCK-VAR BLOCK=STR-2 VARIABLE=RT-CALC

&
314
315

SENTENCE=RESULTS
DEFINE TIME3 BLOCK-VAR BLOCK=STR-3 VARIABLE=RT-C ALC

&

122

316

SENTENCE=RESULTS

317

CONV=(OILIN-OILOUT)* lOO/OILIN

318

MIN=TIME*60

319

TABULATE 1 "CONV"

320

TABULATE 2 "TIME1"

321

TABULATE 3 "TIME2"

322

TABULATE 4 "TIME3"

323

VARY MOLE-FLOW STREAM=MEOH SUBSTREAM=MIXED &

324
325
327

COMPONENT=METHANOL
RANGE LOWER="20.85" UPPER="41.7" INCR="20.85"
BLOCK-REPORT INCL-BLOCKS=COLl HX1 HX2 MIX-1 PI P2 P3 SEP1

&
328
330

SPT1 SPT2 SPT3 STR-1 STR-2 STR-3

STREAM-REPOR MOLEFLOW MASSFLOW MASSFRAC INCL-

STREAMS=5 CANOLA &

331

GLY M-RCY MEOH PI-OUT P2-OUT P3-OUT R-IN Rl-IN Rl-OUT

332

Rl-RCY R2-IN R2-OUT R2-RCY R3-IN R3-OUT R3-RCY RAW1 &

&

123

333

RAW2 RAW3

335

PROPERTY-REP NOCOMPS NOPARAM-PLUS

337

REACTIONS R-l POWERLAW

338

IN-UNITS ENG

339

REAC-DATA1

340

REAC-DATA 2

341

REAC-DATA 3

342

REAC-DATA 4

343

REAC-DATA 5

344

REAC-DATA 6

345

RATE-CON 1 PRE-EXP=0.0008333 ACT-ENERGY=0.0 TEMP-

EXPONENT. &
346

T-REF=59.00000

347

RATE-CON 2 PRE-EXP=0.003583 ACT-ENERGY=0.0 TEMP-

EXPONEN=l. &
348

T-REF=59.00000
f

349

RATE-CON 3 PRE-EXP=0.004033 ACT-ENERGY=0.0 TEMP-

EXPONENT. &

124

350
351

T-REF=59.00000
RATE-CON 4 PRE-EXP=0.001833 ACT-ENERGY=0.0 TEMP-

EXPONEN=l. &
352
353

T-REF=59.00000
RATE-CON 5 PRE-EXP=0.02047 ACT-ENERGY=0.0 TEMP-

EXPONEN=l. &
354
355

T-REF=59.00000
RATE-CON 6 PRE-EXP=0.0001167 ACT-ENERGY=0.0 TEMP-

EXPONEN=l. &
356
357
358
359
360
361
362
363
364

T-REF=59.00000
STOIC 1 MIXED TGCANOLA -1. / METHANOL -1. / BDIESEL 1. / &
DG 1.
STOIC 2 MIXED DG -1. / METHANOL -1. / BDIESEL 1. / MG &
1.
STOIC 3 MIXED MG -1. / METHANOL -1. / BDIESEL 1. / &
GLYCEROL 1.
STOIC 4 MIXED DG -1. / BDIESEL -1. / TGCANOLA 1. / &
METHANOL 1.

125

365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380

STOIC 5 MIXED MG -1. / BDIESEL -1. / DG 1. / METHANOL &

1.
STOIC 6 MIXED GLYCEROL -1. / BDIESEL -1. / MG 1. / &
METHANOL 1.
POWLAW-EXP 1 MIXED TGCANOLA 1. / MIXED METHANOL 1. / &
MIXED BDIESEL 0. / MIXED DG 0.
POWLAW-EXP 2 MIXED DG 1. / MIXED METHANOL 1. / MIXED &
BDIESEL 0. / MIXED MG 0.
POWLAW-EXP 3 MIXED MG 1. / MIXED METHANOL 1. / MIXED &
BDIESEL 0. / MIXED GLYCEROL 0.
POWLAW-EXP 4 MIXED DG 1. / MIXED BDIESEL 1. / MIXED &
TGCANOLA 0. / MIXED METHANOL 0.
POWLAW-EXP 5 MIXED MG 1. / MIXED BDIESEL 1. / MIXED DG &
0. / MIXED METHANOL 0.
POWLAW-EXP 6 MIXED GLYCEROL 1. / MIXED BDIESEL 1. / &
MIXED MG 0. / MIXED METHANOL 0.

Appendix K
Design of Methanol Recovery Column Calculations

Top and Bottom Property Data from AspenPlus Simulation

kg

P L_Top := 7 3 9 . 8 2 ^ 3

p L _Bottom

:= 8 8 4 . 1 3

:= 1 - 2 6 3 9 k g
m

aTop

:= 0 . 0 3 7 7 9 3

VTop

:= 8045.8

pv_Bottom

:=

2.6121 ^

m
~

LTop

:= 5 3 6 4 . 2

^
hr

kg
Vsottom

m
:= 0 . 0 5 9

:= 1 4 6 4 9

c s b Bottom

^
hr

:= 0 . 0 5 6

Column Diameter

LV_Top :

f TLt,op

P V Top

V VTop J

P LTop

0.5

^Top

vTop

F L V_Top

0.667

= 0.028

v0.5

LV_Bottom

LBottom

P VBottom

VBottom

V P L Bottom

'=

^Bottom
=

1.464

^Bottom

L V Bottom

Bottom

== 0 - 0 1 8 6 9 9

hr
C sb Top

p is density o f the material

m
PV_Top

kg

= 0.08

127

is surface t e n s i o n

bottom

:= 2 1 4 4 5

^
hr

C s b = Fair's F l o o d Factor

^nf Top := Csb_Top

\0.2

Top

,PL_Top ~ P V Top j

dyne
20
V
cm y

0.5

PVTop

ft

VnfTop = 5.314
v

nf_Top = 1.62
s

V f Bottom

\0.2

CT

Bottom

Csb Bottom
20

, P L Bottom ~ PVBottom)

dyne

PV Bottom

cm y

Vnf Bottom = 3.33

s

nfBottom = 1.015
S

Assuming Flooding = 75%

Assume downcomer occupies 15% of cross-sectional area
v

n_Top

0.75-Vnf

Top

Vn_Top = 3.986s
Vn Top = 1.215s

Vn Bottom : = 0.75-Vnf Bottom

VnBottom = 0.761
S

V_dotTop :=

VT,op
PVTop
ft

V_dotTop = 62.447

V_dotTop = 1.768
s

128

0.5

^Bottom

V_dot Bottom :=

P V Bottom

ft3

V_dot Bot tom = 55.014

V_dot B ottom = 1-558

V_dot Top
Area Top :=
VnTop

Area Top = 15.667 ft2

2

Areaxop = 1.456 m
DTop:=/4-

Areaxop
71

D T o p = 1.361 m
Area Bottom : -

V_dotBottom
' n Bottom

2
AreaBott0m

= 22.027 ft

AreaBott0m

= 2.046 m2
Area B o t tom

B o t t o m :=

71

^Bottom

= 5.296 ft

DBottom =

1.614 m

Tray Hydraulics
Rules of thumb for Tray specidicatic

Tray t h i c k n e s s = t

= 14 g a u g e ( 0 . 0 7 8 i n c h / 0 . 0 0 1 9 m )

tray

H o l e diameter = 0 . 0 0 4 7 m (3/16 inch)

Column Area = A

D o w n c o m e r Area =

Net Area = A

Active Area= A

Hole Area = A

Weir Length = 1

=12% of A

= 88% of A

h=

= (A

10% A

(Vapour Flow Area)

-2Ad)

= 7 7 % o f D i a m e t e r ( T o p or B o t t o m )

2
ATBottom

:= 2 2 . 1 1 5 f t
2

AT_Bottom

= 2.055 m

A n Bottom

AnBottom

= 19.461

A n Bottom

= 1 - 8 0 8 m2

AdBottom

:= 0 . 1 2 - A x Bottom

A d Bottom
A d Bottom

= 2 . 6 5 4 ft2
= 0-247 m 2

A a _Bottom

= 0 . 8 8 - A x Bottom
ft2

= ( A T _ B o t t o m " 2-A(j_Bottom )
2

A a _Bottom

= 1 6 . 8 0 7 ft

A a _Bottom

= 1.561 m

A h Bottom

'= 0-1 A a _Bottom

AhBottom = L681 ft

2
AhBottom

= 0.156 m

130

IwBottom
IwBottom

0.77-Deottom
= 4.078 ft

lw Bottom = 1 . 2 4 3 m

^Bottom

Vr, :=

P v Bottom' A h Bottom

ft
v0 = 32.732s
v0 =

9.977-

Dry Pressure Drop

dhole := i n

16

-3
dhole = 4 . 7 6 2 x 10

ttray := 0.078in
t t r a y = 1 . 9 8 1 x 10

Ahole :=

(dhole2)

Ahole = 1 - 7 8 1 X 1 0

m2

C 0 := 0.85032-0.04231-

dhole ^
+ 0.0017954-

VW

dhole V

^ ttray j

131

C 0 = 0.759
lb
Pwater :=

6 1 . 0 3 -ft?

Pwater =

977.607

kg
m
A h Bottom
A a Bottom
|3 = 0.1

v0 = 32.732
v0 = 9 . 9 7 7 lb
PL_Bottom= 55.194
ft

PL_Bottom= 8 8 4 . 1 3 ^
m
lb
Pv_Bottom =0.163
ft

hAP_Dty

:= 0.003-

'ftV

hiP_Dry

PV_Bottom f P water 1
lb

^PL_Bottom J

= 0.996 in

132

in

hAP Dry = 0.025 m

For 75% flooding

Flv = 0.05, y = 0.045(relative entrainment)
v|/ := 0.045
4 lb

L Bottom

= 4.728 X 10
hr

LBottom = 5.957

ee := u/

kg

L Bottom

3 lb
ee = 2.228 x 10
hr
ee = 0.281
s
Entrainment := LBottom +

ee

4 lb
Entrainment = 4.951 x 10
hr
Entrainment = 6.238
s
F w =Weir Correction Factor due to wall curvature.
For large Diameter Column F w approaches 1.0
otherwise use figure by Bolles
Lg = Liquid Flow rate including entrainmen (L+ee)
in the units of gallons/min
(ee + LBottom)
L g :=
Pl

Bottom

133

L = 111.826

gal
min

LP = 7.055 x 10

= 4.078 ft

Bottom

l w Bottom = 1 . 2 4 3 m

Abscissa :=
V

\ 2 -5

Bottom

ft

Abscissa = 3.33

Parameter

w Bottom
^Bottom

Parameter = 0.77

F\vear

1-035

(fromgraph)

La ^
gal

hcrest := 0.092-Fv

V min y

in

'w_Bottom
ft

hcrest =

0.866 in

hcrest = 0.022 m

134

Assume negligible h

g r a dient.

See

P Figure

h grad := Oin

Assume Downcomer gap= 1 inch

Gap := lin
Gap = 0.025 m

:= Iw Bottom

Adu

-Gap

A d u = 0.34 ft 2
A d u = 0.032 m 2

gal
V min

hdu := 0.56

449

Adu

in

ft2

h du = 0.301 in
hdu = 7.641 x 10" 3 m
h dc = total Head of clear liquid in the Downcomer
Assume Weir Height = 2.0 inches
hweir := 2in
hweir = 0 . 0 5 1

hdc

= hAP_Dry + h w e i r

+ h crest + h du

h dc = 4.163 in

135

hdc = 0.106m
Note : In the operating column, the liquid in the Downcomer is Aerated. The densi
aerate liquid will be less than that of clear liquid. Thus the height of liquid in
Downcomer will be greater thar\j|a
For normal operatiorfdc=0.5
(j)dc := 0.5
hdc
hdcaerated
<Pdc

hdcaerated

= 8.325 in

hdcaerated =

0.211m

This value is less than 24 inch tray spacing.

There should be no problem for vapour flow to the tray above.

Check for Downcomer time t d c

hdc

4.163 in

- 0.106m
hdc
( A d . Bottom "PL Bottom "hdc
^Bottom +

e e

tdc :

tdc = 3.695 s
The value is greater the minimum residence time of 3 seconds.
There should be no problem.

136

Weeping Check
Caluclate surface tension head h a
Excessive weeping based on Fair correlation
if X

= IVEIR+HCREST+HGRAD

then

hAP_Dry+h CT >0.10392+0.25119x-0.021675x2

a := 13.2

dhole

dyne
cm

:= 0.187in
-3

dhole = 4 . 7 5 x 1 0

< a

dyne
V

ho := 0.04in-

cm

\
f

PLBottom
jb

dhole ^

V in J

ft3

ho = 0.051 in
-3
dhole = 4 . 7 5 x 1 0

'

dyne

ho := 0.04in-

cm

J
\

PLBottom
lb

^ dhole ^

V in J

ft

ho = 0.051 in

137

ha =

1.299 X 10

hweir = 2 i n

hweir = 0 . 0 5 1

hgrad = 0 i n

hcrest

= 0.866 in

hcrest

= 0.022 m

x := (2 + 0.865 + 0)
x = 2.865
H

AP_DRY+ha

>0.10392+0.25119x-0.021675x

RHS := 0.10392 + 0.2511 - x - 0.021675 -x2

RHS = 0.645
hAP Dry - 0.996 in
hAP Dry

0.025 m

ha = 0.051 in
ha = 1.299 x 10~ 3 m
hAP Dry + ha = 0.027 m
hAP Dry + h a

= 1.047 in

LHS := 1.047
LHS (1.047) > RHS (0.645)
The inequality is satisfied.
Therefore, Weeping should not be a problem.

138

BIOGRAPHICAL SKETCH

BIOGRAPHICAL SKETCH

Name of the Author:

Shali Vemparala

Place of Birth:

Hyderabad, India

Date of Birth:

July 14, 1985

Graduate and Undergraduate Schools Attended:

University of South Alabama, Mobile, Alabama
Bhoj Reddy Engineering College for Women, Hyderabad, India
Degrees Awarded:
Masters of Science in Chemical Engineering, 2010, Mobile, Alabama
Bachelors of Science in Chemical Engineering, 2007, Hyderabad, India

139