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thesis entitled

DESIGN AND ECONOMIC ANALYSIS OF A MALEATED
SOYBEAN OIL AND ESTER PRODUCTION FACILITY

presented by
KENNETH RANDALL SEYBOLD

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6/01 cJCIRC/DatoDuo.pfi5-p.15

 

DESIGN AND ECONOMIC ANALYSIS OF A
MALEATED SOYBEAN OIL AND ESTER PRODUCTION FACILITY

by

Kenneth Randall Seybold

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Chemical Engineering

1997

ABSTRACT

DESIGN AND ECONOMIC ANALYSIS OF A
MALEATED SOYBEAN OIL AND ESTER PRODUCTION FACILITY

By

Kenneth Randall Seybold

Many industrial applications for soybean oil have been developed, such as, drying
oils for paints, epoxidized soybean oil for plastics, and stabilizers for synthetic resins.
Unfortunately, in the past 30 years the market for drying oils has decreased and the use of
epoxidized soybean oil has plateaued in the industry. Concurrently, environmental and
life cycle considerations have excited interest in annually renewable feedstocks. The
significance of the study was to investigate the reaction rate, processability, and
characteristics of maleated soy products. Knowledge gained from laboratory experiments
were applied to the design of a manufacturing process to produce maleated soy products.
A maleated soy ester was produced in the laboratory and was found to be a good
plasticizer for PVC. Two process designs were studied, continuous and batch, as possible
routes to produce maleated soybean oil and the esterification of the oil. The continuous
process was found to be superior to the batch by two methods of analysis, return on initial

investment and internal rate of return.

Cepyright by
Kenneth R. Seybold
l 997

To my parents, sister, brother, and wife.

iv

ACKNOWLEDGMENTS

I wish to thank my advisor, Dr. Ramani Narayan, for providing his uniquely styled
guidance and support. I would also like to express my appreciation to everyone at the
MBI International, BioPlastics Inc., and the Department of Chemical Engineering for

providing an enjoyable working and learning environment.

TABLE OF CONTENTS

Chapter Page
LIST OF TABLES ........................................................................................................... viii
LIST OF FIGURES ........................................................................................................... .x
1. INTRODUCTION ........................................................................................................ 1
1.1 Plasticizers ........................................................................................................... 1
1.2 Coating Materials from Soybean Oil ................................................................... 4
2. LITERATURE BACKGROUND ................................................................................ 6
3. GOALS & OBJECTIVES ............................................................................................ 16
4. EXPERIMENTAL METHODS AND RESULTS ....................................................... 18
4.1 Methods and Material .......................................................................................... 18
4.1.1 Maleation of Soybean Oil ........................................................................... 18
4.1.2 Esterification of Maleated Soybean Oil ...................................................... 20
4.2 Maleation of Soybean Oil Results ........................................................................ 23
4.2.1 Acid Number ............................................................................................... 24
4.2.2 Iodine Value ................................................................................................ 27
4.2.3 Viscosity ..................................................................................................... 31
4.2.4 Fourier Transform Infra Red Spectroscopy Results ................................... 32
4.3 Esterification Results ............................................................................................ 40
4.3.1 Differential Scanning Calorimeter .............................................................. 42
4.4 Experimental Conclusions .................................................................................... 45

vi

5. PRELIMINARY PROCESS DESIGN ......................................................................... 49

5.1 Continuous Process Design ............................................................................. 49
5.2 Batch Process Design ...................................................................................... 6O
6. PRELIMINARY ECONOMIC ANALYSIS ................................................................ 68
6.1 Continuous Process Economics ....................................................................... 68
6.2 Batch Process Economics ................................................................................ 75
6.3 Determination of Internal Rate of Return by a Discounted Cash Flow .......... 79
6.4 Sensitivity and Production Capacity Analysis ................................................ 86
7. CONCLUSIONS AND RECOMMENDATIONS ....................................................... 92
7.1 Conclusions ..................................................................................................... 92
7.2 Recommendations ........................................................................................... 93

7.2.] Task 1: Design, Fabrication and Operation of a

Pilot-Scale Production Line ............................................................................. 94

7.2.2 Task 2: Modification of Soybean Oil ......................................................... 94

7.2.3 Task 3: Esterification of Maleated Soybean Oil ......................................... 95

7.2.4 Task 4: Formulation of Modified Soybean Oil Coating Materials ............. 97

7.2.5 Task 5: The Peroxide Reaction of Soybean Oil .......................................... 97

8. BIBLIOGRAPHY ........................................................................................................ 98

vii

LIST OF TABLES

Table Page

Table 1: US. production of plasticizers from vegetable oil

and petrochemical feedstocks, 1990 .................................................................................... 3
Table 2: Soybean Oil Composition ...................................................................................... 6
Table 3: Reaction Data for Soybean Oil and Maleic Anhydride ...................................... 23
Table 4: Esterification Reactions ...................................................................................... 41

Table 5: Material and Energy Balances for a Maleated Soybean Oil
Esterification Continuous Process ..................................................................................... 57

Table 6: Material and Energy Balances for a Maleated Soybean Oil
Esterification Batch Process .............................................................................................. 65

Table 7: Assumptions for Economic Evaluation .............................................................. 70

Table 8: Equipment List for Maleated Soybean Oil and Maleated
Soybean Oil Ester .............................................................................................................. 71

Table 9: Total Capital Investment for a Maleated Soy Oil and
Ester Production Facility12 ................................................................................................. 73

Table 10: Manufacturing Cost Breakdown of a 2500 ton/yr
MSO Ester and 5000 ton/yr MSO ...................................................................................... 74

Table 11: Estimated Selling Price of Maleated Soy Oil and
Maleated Soy Oil Ester at 15% Return on Investment ...................................................... 75

Table 12: Equipment List for Maleated Soybean Oil and Maleated
Soybean Oil Ester .............................................................................................................. 76

Table 13: Total Capital Investment for a Maleated Soy Oil and
Ester Production Facility12 ................................................................................................. 77

Table 14: Manufacturing Cost Breakdown of a 2500 ton/yr
MSO Ester and 5000 ton/yr MSO ...................................................................................... 78

Table 15: Estimated Selling Price of Maleated Soy Oil and
Maleated Soy Oil Ester at 15% Return on Investment ...................................................... 79

viii

Table Page

Table 16: Discounted Cash Flow Assumptions ................................................................. 83
Table 17: Comparison of M80 and MSO ester Selling Price versus

Production Capacity ........................................................................................................... 90
Table 18: Comparison of Production Capacity versus Total Capital Investment ............. 91
Table 19: Comparison of Production Capacity versus Manufacturing Cost .................... 91

ix

LIST OF FIGURES

Figure Page
Figure 1: Experimental Apparatus for the Maleation of Soybean Oil .............................. 20

Figure 2: Experimental Apparatus for the Esterification of Maleated
Soybean Oil ........................................................................................................................ 22

Figure 3: Comparison of Soybean Oil/Maleic Anhydride Acid Number
and Initial Reaction MA Concentration using Lupersol 101 ............................................. 25

Figure 4: Comparison of Soybean Oil/Maleic Anhydride Acid Number
and Initial Reaction MA Concentration using Tert-Butyl Peroxide .................................. 26

Figure 5: Comparison of Maleated Soybean Oil and Initial Reaction
Concentration using Lupersol 101 ..................................................................................... 26

Figure 6: Comparison of Maleated Soybean Oil and Initial Reaction
Concentration using Tert-Butyl Peroxide .......................................................................... 27

Figure 7: Comparison of Soybean Oil/Maleic Anhydride Iodine Value
and Final Reaction MA Concentration using Lupersol 101 .............................................. 29

Figure 8: Comparison of Soybean Oil/Maleic Anhydride Iodine Value
and Final Reaction MA Concentration using Tert-Butyl Peroxide ................................... 29

Figure 9: Comparison of Soybean Oil/Maleic Anhydride Iodine Value

and Acid Number using Lupersol 101 ............................................................................... 30
Figure 10: Comparison of Soybean Oil/Maleic Anhydride Iodine Value

and Acid Number using Tert-Butyl Peroxide .................................................................... 30
Figure 11: Comparison of Soybean Oil/Maleic Anhydride Viscosity and

Final Reaction MA Concentration using Lupersol 101 at 25 C ......................................... 31
Figure 12: Comparison of Soybean Oil/Maleic Anhydride Viscosity and

Final Reaction MA Concentration using Tert-Butyl Peroxide at 25 C .............................. 32
Figure 13: FTIR spectra of Soybean Oil ........................................................................... 34
Figure 14: FTIR spectra of 0.2 mol MA/mol SO maleated soybean oil ........................... 35

Figure Page

Figure 15: FTIR spectra of 0.5 mol MA/mol SO maleated soybean oil ........................... 36
Figure 16: F TIR Spectra of 1.0 mol MA/mol SO maleated soybean oil .......................... 37
Figure 17: FTIR Spectra of 1.0 mol MA/mol SO maleated soybean oil, hydrolyzed ....... 38
Figure 18: FTIR Spectra of 1.0 mol MA/mol SO maleated soybean oil, esterified .......... 39

Figure 19: Differential Scanning Calorimeter results for PVC/MSO
Ester (Sample 43) ............................................................................................................... 43

Figure 20: Differential Scanning Calorimeter results of PVC/MSO
Ester (sample 44) blends .................................................................................................... 44

Figure 21: Esterification Reaction Rate versus Time for PFR Volume
Determination .................................................................................................................... 52

Figure 22: Continuous Process F low Diagram of a Soybean Oil Maleation

Facility ............................................................................................................................... 54
Figure 23: Continuous Process Flow Diagram of a Maleated Soybean Oil

Esterification Facility ......................................................................................................... 55
Figure 24: Process Flow Diagram of Valve, Meter, and Pump Bypasses ........................ 56
Figure 25: Batch Process Flow Diagram of a Soybean Oil Maleation Facility ................ 63

Figure 26: Batch Process F low Diagram of a Maleated Soybean Oil
Esterification Facility ......................................................................................................... 64

Figure 27: Determination of the Internal Rate of Return by a Discounted
Cash F low for the Proposed Continuous Process .............................................................. 84

Figure 28: Determination of the Internal Rate of Return by a Discounted
Cash Flow for the Proposed Batch Process ....................................................................... 85

Figure 29: Sensitivity Analysis of the Selling Price of Maleated
Soybean Oil at 15 % ROI ................................................................................................... 86

Figure 30: Sensitivity Analysis of the Selling Price of Maleated Soybean
Oil Ester at 15 % ROI ........................................................................................................ 87

xi

Figure Page

Figure 31: Selling Price of Maleated Soybean Oil at 15% R01
(Plant Capacity = 100% M80) .......................................................................................... 88

Figure 32: Selling Price of Maleated Soybean Oil Ester at 15% R01
(Plant Capacity = 100% M30) .......................................................................................... 89

xii

CHAPTER I

 

INTRODUCTION

 

The United States has excess capacity for the production of food and feed crops, so
new industrial uses for agricultural products are being sought. Production of industrial
raw materials from agricultural feedstocks serves to extend our diminishing petroleum
reserves, remedy trade imbalances, protect the environment, and expand market

opportunities for rural economies.

Soybean seed is grown and processed using standard equipment to produce a wide
variety of protein, carbohydrates, and oils. The current production of soybeans in the
world is nearly 100 million metric tons per year with over half of this amount being
raised in the United States‘. With this large amount of soybeans and soy products
coming from this country a large opportunity exists to formulate new value-added
products that can be used in the ever expanding plastic industry, two such potential areas

are plasticizers and coatings.

1.1 Plasticizers
Plasticizers are organic compounds added to plastics to improve workability during
fabrication and to extend or modify the natural properties of the original resin.

Plasticizers are used in molding and shaping plastic resins into consumer end products,

such as bottles and plastic bags, easier. Plasticizers also improve flexibility and other

desired properties in the finished product.

One of the most important uses of plasticizers is molding poly vinyl chloride
(PVC). PVC resin is very brittle and cannot be molded without plasticizers. By the year
2000, PVC will be the leader with an annual volume of 17 x 109 metric tons according to
the Stanford Research Institutez. The widespread use of PVC arises from its high
chemical resistance and a high solubility for additives to give a large number of
reproducible compounds. Thus, with the properly chosen additives, a PVC formulation

can have an enhancement in strength and workability.

For many years, his (2-ethylhexyl) phthalate (DOP) was the accepted industry
standard for a general-purpose plasticizer for PVC and a benchmark for comparisons of
other plasticizers. DOP has an all around performance, eg, compatibility with the resin,
and efficiency in flexibilizing that is so good, that it alone accounts for nearly one-fourth
of all plasticizer production. Although DOP is a “work-horse” plasticizer for PVC, there
are problems with its use. Phthalate plasticizers are moderately toxic (listed on the EPA
section 313 Toxic Release Inventory or as a HAP), volatility can be a concern at higher
temperatures, migration of DOP in the polymer matrix, and extraction under solvent and

soapy water conditions.

Of the 1.6 billion pounds of plasticizers produced in the United States in 1990, only
230 million pounds, or 15 percent, were derived from plant matter. Most of these plant-
based materials are from vegetable oil feedstocks (Table 1). Epoxidized soybean oil
(ESO) accounted for 100 million pounds, while acrylic esters, which are derived from a
variety of plant sources (including wood extractives and coconut oil), accounted for 74
million pounds. Over a dozen companies produce E80. E80 is used as a secondary
plasticizer to DOP as the primary plasticizer, only 2.5% ESO usage as opposed to 31%
DOP usage.

Table 1: US production of plasticizers from vegetable oil and petrochemical
feedstocks, 1990

Category Production Million Pounds
Epoxidized soybean oil 100
Epoxidized linseed oil 6
Other epoxidized esters 14
Oleic acid esters 12
Stearic acid esters 8
Palmitic acid esters 6
Sebacic acid esters 6
Isopropylmyristate 4
Other acrylic acid esters 74
Total 230
Petrochemical-based plasticizers 1,324

Total Plasticizers 1,554

Epoxidized soybean oil has many strong qualities but also many problems. As a
plasticizer, ESO tends to lose compatibility due to photo-oxidation, high viscosity at

ambient temperatures, and a relatively high cost. ESO is also difficult to produce because

of the use of preformed-peracetic acid techniques which employs an explosive hazard,
acids, bases and solvents. These chemicals and techniques tend to increase both
manufacturing and equipment costs. The high costs of the ESO process can be seen from
the current market price of 1.1-1.3 dollars per pound. Therefore, an opportunity exists to
increase plasticizer marketshare given DOP’s problems if the properties of ESO or a new

derivative can meet the requirements.

1.2 Coating materials from Soybean oil

In the US, thermoset coatings represent an 8 billion pound per year market.
Alkyds, amino resins, epoxies, acrylics, and polyurethane systems are the most widely
used coating materials. Thermoset coatings are almost entirely produced from petroleum

feedstocks.

Drying oils, from plant matter, are the basis for corrosion resistant coatings, traffic
paints, wire enamels, can linings, marine finishes, container and tube coatings, metal
decorating, and aluminum paints. The drying oils provide: superior impact resistance;

flexibility; gloss; chemical resistance; adhesion; flow and leveling.

The use of soybean oil in oil-based paints has steadily been declining in the past 30

years due to the rise of latex and other water-based systems. Since 1960 the use of paints

and varnishes have increased from 200 to 300 million pounds per year while the percent

of oil based products have fallen from 50 to 15 percent of the market.

With the loss of oil based applications, there is a need to investigate the

functionalized soybean oil applications with emphasis on the large market of plastics.

CHAPTER 2

 

LITERATURE BACKGROUND

 

Soybean oil is a triglyceride of fatty acids. Soybean oil has the following

composition and structures:

Table 2: Soybean Oil Composition

Carboxylic acida Chemical Acronm“ Wt% Soybean Oil“I
Fatty Acid
Saturated fatty acid
Palmitic acid 16:0 10.7
Stearic acid 18:0 3.87
Unsaturated fatty acid
Oleic acid 18:1 22.8
Linoleic acid 18:2 50.8
Linolenic acid 18:3 6.76
a -- Ref 1

‘Chain length, number of double bonds, and functional groups, if any

 

WCOOH—R
— 3

PALMITIC (16:0)-- 11%

 

 

WOOD-q

 

 

—3

STEARIC ACID (18:O)--4%

 

r —

OLEIC (18:1.9c)--23%

 

 

 

WCOOm—R

LINOLEIC (18:2;9c.12c)--51%

 

 

 

 

We <7ch

i — a

LINOLENIC (18:3;96.12c,15c)--7%

 

 

COMPOSITION OF SOYBEAN OIL

6

Unfortunately, soybean oil contains mostly non-conjugated double bonds. Due to the
prevalence of non-conjugated double bonds, a catalyst will be needed to facilitate the
reaction. There is a great deal of literature discussing the addition of maleic anhydride to
soybean oil using a peroxide catalyst. Root3 describes the use of benzoyl peroxide
catalyst in a maleation reaction. Under these conditions the reaction takes place at a
much lower temperature of 110 C as compared to 160-190 C without catalyst. Root
postulates that soybean oil in the presence of a catalyst, like a peroxide, results in the
conjugation of the non-conjugated double bonds. The conjugated double bonds can then
undergo a 1-4 Diels-Alder type of reaction.

13 1211 10 9
CH3(CH2)4CH=CHCH20H=CH(CH2)7COOR

l peroxide

CH3(CH2)4CHZCH=CHCH=CH(C H2)-,COOR
+

fix
1

CH=CH
CH3(CH2)4CHZCH H(CH2)-,COOR

(Root et. Al.) 0 O O

The resultant product is more viscous than that prepared at higher temperatures. The
experimental work in this thesis was based on the peroxide catalyzed reactions discussed

by Root3.

There is considerable study on the nature of the maleic anhydride addition reaction.
Conjugated oil systems were the focus of Morrel and Samuels4 who showed that it was a
diene addition. The study was of conjugated oil fatty acids from china wood and oiticica
oils. The reaction product is a typical Diels-Alder 1-4 adduct:

(1)

CH3(CH2)2 HCH=CH HCH=CH(CH2)7000R

  

In the case of non-conjugated oils, the determination of the structure of the adduct
has been more difficult. Structural information was indefinite for a long time, but this did
not forestall the preparation and use of maleated oils. Thus, the patents of Bevan and
Tervet5 admittedly make no attempt to define the nature of the reaction. Clocker‘5

postulated a cyclobutane structure for the oleic acid adduct:

(2)
CH3(CH2)-, H H(CH2)7COOH

In the case of polyunsaturated acids, a 1-4 diene addition similar to 1 for the
conjugated oil has been suggested. This assumes that the reaction is proceeds by a shift
from the non-conjugated to conjugated forms. If maleic anhydride is present it can react

to form a Diels-Alder adduct which in the case of linoleic esters occurs as follows:

(3)
13 1211 10 9

CH3(CH2)4CH=CHCHZCH=CH(C H2)-,COOR

l

C H3(C H2)4C H20 H=C HC H=C H(C H2)7C 00R
+

o/Q.
l

CH=CH
CH3(C H2)4CH2CH H(C H2)7COOR

High temperatures favor the conjugated structure.

The formation of a substituted succinic type adduct is also possible for maleated

oils. It is this structure that is the preference to the DieIs-Alder adduct, although the

presence of a small amount of the latter has not been excluded. Bickford et al.7, Teeter et
31.8 and Kappelmeier, and Van der Neut9 support the succinic type structure. Their work
includes reactions of maleic anhydride with pure methyl oleate, methyl linoleate and
methyl linolenate. From this work it appears that a hydrogen on a carbon atom a to a
double bond become activated to form a compound of the succinic type with maleic

anhydride.

The structures presented in the succeeding formula are suggestions of the above
groups of investigators. Addition to oleic acid may occur at the eighth carbon atom.

The adduct of oleic acid may be as follows:
(4A)

CH3(CH2)70H=CHCH(CH2)6COOR

0

0'0

or at the eleventh carbon atom,
(43)

C

e ' o

The majority of unsaturated acids in soybean oil is linoleic acid. The postulated reaction

of linolate with maleic anhydride, in the presence of a catalyst, will result in three simple

10

succinic-type adducts with the reaction occurring at the 8, ll, 14 carbon atoms. Of these
types the methylene at the 11 position is probably the majority (SB).

Lenoleic ester and maleic anhydride:
13 12 11 10 9

CH3(CH2)4CH=CHCHZCH=CH(CH2)7COOR
+

A,

Reaction products:

(5A)
1413121110 9 8
CH3(CH2)3CHZCH=CHCHZCH=CHCH(CH2)BCOOR

o'o

(SB)
CH3(CH2)3CHZCH=CHCHCH=CH(CH2)7COOR

O

o ' 0
(5C)

0'0

11

Kappelmeier and Van Den Neut9 suggest that conjugation may occur
simultaneously with attack at a methylene carbon, or that the initial adduct such as 5A

and 5C may rearrange to the conjugated structure as follows:

(6)
1211 10 9 a

0'0

Diels-Alder addition of a second mole of maleic anhydride to the conjugated

structure would give:
(7)
1 1 1O
H= H
13/C C\9 8
o ' o '

O 0

Alternatively the unconjugated structures 5A, B, and C may add a second mole of

maleic anhydride at a methylene carbon to give a structure such as:

12

(8)

12 11
CH3(CH2)41CH=CHCH—CH=CH—CH(CH2)6COOR

A A

With linolenic acid, the first adduct posses a structure analogous to those of 4 or 5.
A second addition probably gives structures analogous to 8, or if conjugation takes place,

to 7. Introduction of a third mole of maleic anhydride is possible, for which is following

structure:
(9)
H= H
CH3CH2CHCH CH—CH20H=CH—CH(CH2)6COOR
o ' o

In addition to the structures shown by 5, 6, 7, 8, and 9, Plimmer10 believes that the
second maleic anhydride can add to the opposite side of the hexene ring. The Diels-Alder

type adduct, shown in structure 1 or 1 A, may form the following:

13

(10)

/CHCK

RCHZCH CCHZR

o ' 0
Considering differences in acid and saponification values, Plimmer10 also postulates

a second type of structure, in which the maleic residue acts as a bridge between two acid

chains. The Diels-Alder adduct (structure 1) reacts further as shown in 11 and 12 as

follows:
(11)
H=CH
CH3(C H2)4C{_l/DH(C H2)BCOOC H3R
O=C C=O
OH

 

RCH=C HC HC H=C HR

This ketone, 11, enolizes and forms a lactone, thus:

14

(12)

/°”‘°\”

RCH CHR

0

RC H=C HCCH=C HR

According to Flett et a1.l 1, the succinic type adduct such as 4, 5, and 8 predominates

over types represented by 6, 7, and 9.

The work to establish the identity of the various adducts described above were made
from higher percentages of maleic anhydride than are used in the maleated oils of
commerce. Most maleic additives do not exceed about 8 percent. This means that for 1
mole of drying oil (mol. wt. ca. 870) about 70 grams of anhydride would be required for
an 8 percent modification. This is equivalent to about 0.72 mole of maleic anhydride for

each mole of oil, or, for 3 moles of fatty acid in triglyceride form.
Though much work has been done to investigate the reaction of drying oils with

maleic anhydride, no work has been done to design and engineer maleated soyproducts

for their use as plasticizers, coatings, and composite matrix materials.

15

CHAPTER 3

 

GOALS AND OBJECTIVES

 

The goal of this thesis was to develop a new value-added product from soybean oil

feedstock and to design an economical route for its production.

The reaction that was investigated was the addition of maleic anhydride to soybean
oil via the use of a peroxide. Previous work outlines that non-conjugated double bonds in
the presence of a peroxide allows for the conjugation of the bonds and thus addition via a
Diels-Alder type reaction. Characterization of the maleated soybean oil (MSO) was

performed by acid number, iodine values, viscosity, and F TIR spectroscopy.

The maleated soybean product was then modified to an ester for possible
application as a plasticizer. Characterization of the ester product (MSOE) was performed
by acid number and plasticization capability with poly vinyl chloride by the use of a

differential scanning calorimeter.

A preliminary engineering and economical analysis was performed from the
experimental data to determine the most effective and economical route. Two alternative
process scenarios were investigated, continuous and batch. These two alternatives were

then analyzed by a return on initial investment and internal rate of return determined by a

16

discounted cash flow. The best scenario for the production of maleated soybean oil ester

was determined to be a continuous method.

17

CHAPTER 4

 

EXPERIMENTAL METHODS AND RESULTS

 

4.1 Methods and Material
4.1.1 Maleation of Soybean Oil

The experimental procedure to determine maleation of soybean oil is as follows.
The reaction includes refined soybean oil of approximately 872 gram molecular weight
purchased from Cargill as a vegetable oil. The maleic anhydride was 99% pure reagent
grade. The two catalysts used were Lupersol 101 (2,5-Dimethyl-2,5-di-tert-butylperoxy-
hexane, Di-tert-butyl peroxide, 3,3,6,6—tetramethyl-1,2-dioxacyclohexane, 2,2,5,5-
tetramethyl tetrahydrofuran) and tert-butyl peroxide (98% purity, reagent grade).

Proposed reaction chemistry:

18

13 12 11 1O 9
CH3(CH2)4CH=CHCHZCH=CH(CH2)7COOR

l peroxide

CH3(CH2)4CH2CH=CHCH=CH(CH2)7COOR
+

.M
l

CH3(C H2),c HZC H=C H5130 H(C H2)7C 00R

 

CH=CH

CH3(CH2)4CHZCH H(CH2)7COOR

0

Measured quantities of the reactants were added to a 50 ml glass bottle with a magnetic

stir bar. The bottle was sealed with a rubber septum and placed into an oil bath. To

reduce oxidation, nitrogen was introduced to the reaction via a slow rate over the reaction

contents by using needles (MA sublimes and some of it is lost by the Nitrogen flow).

The bottle was placed in an oil bath (at various temperatures) on a stir plate. After the

desired time, a vacuum was applied to the bottle to remove excess anhydride and catalyst.

When the maleic anhydride and catalyst were fully removed, by visual inspection to

confirm no bubble formation in the reaction, the bottle was removed from the oil, cooled

l9

to room temperature, and refn'gerated. The following figure shows the experimental

apparatus.

Nitrogen in

   

Nitrogen out
/ reaction mixture

 

stir bars

 

 

 

 

hot plate

 

 

 

Figure 1: Experimental Apparatus for the Maleation of Soybean 011

Table 3 shows the results of the maleation of soybean oil experiments. Included in the
table are reaction conditions, acid numbers, iodine values, viscosity measurements, and
yields of each experiment.
4.1.2 Esterification of Maleated Soybean Oil

The experimental procedure to produce the maleated soy product ester is as
follows. The reaction includes a sufficiently high maleated soy product of approximately
1 mole of maleic anhydride per mole of soybean oil prepared in a manner outlined in
section 4.1.1. A measured quantity of maleated soy product was added to a high pressure
Parr reactor (refer to Figure 2) with a small amount of deionized water and a alcohol.
The alcohol that was studied was 1-octanol of 99% pure reagent grade purchased fi'om

Aldrich Chemical. The reactor was sealed and placed into the heater mantle and the

20

thermocouple, water seal, and mixer were connected. The controller was set to 300 C and
the contents of the reactor allowed to mix at temperature for various time. Proposed

reaction chemistry:

R'OOCH2
CH=CH TOOTH
CH3(CH2)4CH2 H CH(CH2)7COOCH2 + 2 H20
0
R'oocle2
R"OOCH

CH=CH l

CH3(CH2)4CH2 H CH(CH2)-,COOCH2

O
OH H

21

R'OOCH2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

CH=CH R 00TH
CH3(CH2)4CH2 H cmcmmoocr-r2 '1'? 2 R0”
0 O
OH H l
R'OOCH2
CH=CH R 00TH
/ .1. 2 H20
CH3(CH2)4CH2 H CH(CH2)7COOCH2
O '1‘ Various By-Products
OR R
Temperature
. Probe Motor
1. —— — —— —| M l
I _
I [J
I ' I
—- — —] OD
Temp. Motor Heating 05"
c RPM MonUe
C
Process Controller
Heating
Mantle
Process
_ _ _. — — Electrical

Control

 

 

Figure 2: Experimental Apparatus for the Esterification of Maleated Soybean Oil

22

4.2 Maleation of Soybean Oil Results

Table 3: Reaction Data for Soybean Oil and Maleic Anhydride

Sample Soyoil

Soyoil

OOVOMwa-I

gm

40:35
40.14

40.35
40.71
40.49
40.93
40.78
40.32
40.55
40.49

40.56
40.36
40.59
40.61

40.37
40.45
40.49

MA
gm

Cat.
gm

Cat.
type

0.5 Lup 101
0.5 Lup 101
0.4 Lup 101
0.2 Lup 101
0.2 Lup 101
0.2 Lup 101
0 Lup 101
0.54 Lup 101
0.53 Lup 101
0.57 Lup 101
1.04 Lup 101
0 Lup 101
0.55 Lup 101
0.56 Lup 101
0 Lup 101

0 Lup 101
0.58 Lup 101
0.56 Lup 101
0.55 Lup 101
0.56 Lup 101
0.52 Lup 101
0.59 Lup 101
0.56 Lup 101
0.51 Lup 101
0.53 Tort-but.
0.55 Tort-but.
0.52 Tort-but.
0.56 Tart-but.
0.52 Tort-but.
0.52 Tort-but
0.52 Teri—but.
0.51 Tort-but.
0.53 Tort-but.
0.22 Tort-but.
0.21 Teri-but.

0.22 Tort-but.
1.06 Tort-but.

0.5 Tort-but.
0.51 Tort-but.
0.51 Tort-but.
0.51 Tort-but.

0.5 Tort-but.
0.52 Tertobut.

Rxn time Temp.
min C

60 150
60 150
60 150
60 150
60 150
60 150
60 150
60 120
60 120
60 120
60 150
720 amb.
120 150
240 150
60 150
60 150
120 150
30 150
30 150
30 150
120 150
60 100
60 100
60 100
60 150
60 150
60 150
30 150
30 150
30 150
120 150
120 150
120 150
60 150
60 150
60 150
60 150
60 120
60 120
60 120
240 150
45 150

5 150

23

 

 

Acid Number Iodine V Viscosity

Mean mol MAI % Yield llodine V Viscosity

Acid # mol SO cps
13.51 0.17 78.63 144.20 80
42.89 0.57 89.46 118.62 190
79.62 1.12 89.63 98.70 3580
13.96 0.18 81.13 139.59 80
32.59 0.43 66.61 126.90 110
81.24 1.15 95.02 106.71 650
17.45 0.22 38.82 136.30 70
15.80 0.20 91.60 134.83 55
42.54 0.57 88.41 120.86 215
81.18 1.15 91.14 96.44 32000
42.68 0.57 89.00 106.60 310

7.21 0.09 14.53 140.26 50
45.00 0.60 92.55 114.21 330
43.28 0.58 89.34 113.98 400
18.36 0.24 102.50 130.80 50
40.98 0.55 43.55 128.17 60
82.20 1.17 91.56 86.19 100000
16.62 0.21 93.99 123.52 65
74.09 1.04 82.42 86.88 67000
35.28 0.47 74.18 107.87 355
15.65 0.20 87.80 122.02 90
15.21 0.20 81.81 131.98 110
37.41 0.50 76.84 120.89 260
61 .89 0.85 67.47 102.79 3230
14.81 0.19 80.27 131.78 90
37.60 0.50 76.03 118.97 85
66.64 0.92 72.82 108.69 29000
14.52 0.19 78.52 133.58 60
36.13 0.48 73.67 107.56 210
68.10 0.94 74.82 102.58 900
16.72 0.21 93.39 130.60 65
38.35 0.51 79.78 110.51 350
71.98 1.00 79.42 107.59 500
14.89 0.19 82.99 129.95 75
37.74 0.50 77.79 130.19 65
73.08 1.02 81.98 103.64 1000
38.95 0.52 80.52 114.21 195
16.08 0.21 86.97 117.94 55
37.17 0.49 76.31 128.63 355
74.16 1.04 82.64 93.36 25600
14.26 0.18 82.60 127.75 80
17.17 0.22 93.47 130.07 50
22.39 0.22 95.10 133.25
0.00 0.00 139.31 50

4.2.1 Acid Number (Figure 3-6):

ASTM ntunber 1045-86 was the basis for the experimental acid numbers. The

data present three general conclusions.

1. All the acid numbers increased with initial maleic anhydride concentration and
constant peroxide concentration. The reaction rate appeared to be first order in maleic
anhydride and zero order in the peroxide catalyst. The reaction rates at these
temperatures were very fast and experimental data at various points during the reaction

were unattainable.

2. Peroxide concentration did not affect the acid number, experiments 1-3 (~0.5
grams Lupersol 101) and 4-6 (~0.2 grams Lupersol 101). The experiments in which no
peroxide was present resulted in lower acid numbers, experiments 7, 14, and 15. Some
residual maleic anhydride was apparent in these samples due to visual crystal formation
which would have resulted in false high acid numbers. Experiment 11B was a reaction at
ambient temperatures with no catalyst for 720 minutes which resulted in a very low acid

number (AN1 13 = 7..2)

The use of tert-butyl peroxide as the reaction catalyst gave similar results when

compared with the Lupersol 101. At high initial maleic anhydride concentrations tert-

butyl peroxide resulted in lower acid numbers then Lupersol 101.

24

3. Temperature had a slight affect on the acid number, as seen from experiments 21-
23 (T=100 C) and 1-3 (T=150 C). The lower temperature reaction resulted in lower acid
numbers at higher maleation. The reaction approaches completion within the first 30
minutes, experiments 17-19.

Figures 5 and 6 show that the maleation reaction was nearly complete for both
catalysts. The final titrated amount of maleic acid (determined from a calibration curve
of the KOH titration) was close to the initial amount of maleic anhydride added to the
reaction, as seen from the diagonal line. The corresponding yields of the experiments

were 80 to 100 percent.

 

i
l r
,‘

 

 

90.00 i
.. 80.00 i
a i
3 70.00 a
O a
E 60.00 .

‘ : 50.00

l g 40.00 i

l a '

i 2 30.00 _._ w.

l 2 ,+T-150C.t-80mn.-02munenol101

I 0 2000 {+1-120cheom.-0.5gnumoi101.

i ( ' 1+1-150c1-eom,1.04wnumol101‘

i 10.00 i+r-1oo c r-oo «111.. ~05 mhp101

0.00 g
0.00 020 0.40 0.60 0.80 1.00 120 1.40 l

1 Initial Concentration of MA (gmoi MAIgmoI 80) i

 

Figure 3: Comparison of Soybean Oil/Maleic Anhydride Acid Number and Initial
Reaction MA Concentration using Lupersol 101

25

801D

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

70.0) ,/
‘ 60m
‘ E ‘3 /
. E 50.00
I go //
‘2! 40.00 ,
1' a a 1+T31mcF1mM'O5WTII-BM:
g '5 E 3000 .+r-1mcumm-azgnm-am.
l < V ' ,_._'r-150<:.1-<nn‘n-<Ie'lgurcn.taujiI
E 2000 ;_._r-1:oc1-alm. 059nm ‘
é ' l+r=1mcnmm,-asmru1-myl
l 10.00
g 0.00
4 0.00 0.20 0.40 0.60 0.8) 1.0) 1 .20
i

Inlflal Concentration of MA (gmol MNgmol 80)

1.40

 

Figure 4: Comparison of Soybean Oil/Maleic Anhydride Acid Number and Initial
Reaction MA Concentration using Tert-Butyl Peroxide

 

-__._.__.__._.L.__ 4“.“ - ---.__.

 

Maleated Soy Oll
(gmol MAIgmol 30)

0.00

0.20 0.40 0.60

+

l
+msocmm 412mm 101

+1h120c1-eom-asgnuuu1mi
+1: met-110m 1.04mum101
+1-100cr-eom. '0.5’l|LID101
l+mmmm

 

0.80 1.00 120 1.40

Initial Concentration of MA (gmol MAIgmol SO)

.. ._.._._.._.....__..._ .__._._.... -..__..J

 

Figure 5: Comparison of Maleated Soybean Oil and Initial Reaction Concentration

using Lupersol 101

26

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1. 1‘1
00 g
. = 6 /
O (D /
_ 0.80
a g /
m a
‘ j
g g i 060
g 2 g 1+181506F120nhn059nTen-alyl‘
l i a 0.40 '+r=150c:1-eom-0.2ngm-anyl
l v / ._.._T=150c1:eom cumin-army
i+T=150c.1-00m.-0.5ng-1-auyl l
o 20 +T=120C tr=60 m. ‘0.5fi‘flT.‘I-MI‘ ‘ r
‘ ' L+MWAWW i z
. 0.00 3
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1

Initial Concentration of MA (gmol MAlgmol 80)

Figure 6: Comparison of Maleated Soybean Oil and Initial Reaction Concentration
using Tert-Butyl Peroxide

4.2.2 Iodine Values (Figges 7-10):
A.O.C.S. methods Cd 1-25, Tg 1-64, Tg 2a-64 were the basis for the experimental

iodine values. The data present three general conclusions.

1. All the iodine values decreased with increasing maleic anhydride content. The
decrease in the iodine value is an indication of double bond saturation by the addition of
maleic anhydride via a 1-4 Diels-Alder type reaction. Soybean oil contains
approximately 4.3 double bonds per mole of soybean oil. The addition of 1 mole of
maleic anhydride (using the proposed chemistry of Section 4.1.1) will reduce the total

double bonds to ~33 bonds per mole of soybean oil.

27

2. Peroxide concentration only affected the iodine value in reactions that contained
maleic anhydride. The experiments with no peroxide, only a small reduction in iodine
values are apparent, experiments 7, 14, and 15. Experiment 11B was a reaction at
ambient temperatures, with no catalyst, a reaction time of 720 minutes, with no apparent
decrease in iodine value (IVHB = 140.3 and IVsoyoi. = 140). The reaction approaches

completion within the first 30 minutes, experiments 17-19.

The use of tert-butyl peroxide as the reaction catalyst gave similar results when
compared with the Lupersol 101. At high initial maleic anhydride concentrations tert-
butyl peroxide resulted in higher iodine values then Lupersol 101. A higher iodine value

would mean that fewer double bonds were attacked by the tert-butyl peroxide

3. Temperature did not significantly affect the iodine value as seen from experiments

21-23 (T=100 C) and 1-3 (T=150 C). Catalyst concentration did not affect the iodine

value, experiments 1-3 (~0.5 grams Lupersol 101) and 4-6 (~O.2 grams Lupersol 101).

28

 

 

 

 

 

 

 

 

 

 

140.00 “x
:1
\
12000 \
\
s 2 ‘H
g 3 80.00
2 8000 +r-150C1-mm-osgnuumi101

(4.1-1500. man-029nm 101 .

 

 

 

 

 

 

 

 

 

 

 

 

 

mm +7-1Zicmm-Q5WUW101

,+T-1§)C. mm 1.01qu 101

20.11) 1+T-100c1-801m. 415000-9101 ‘
0.00 i
0m 0.2) 0.40 OH) 0m 1.“) 120 i

mmamwmmsq 1

Figure 7: Comparison of Soybean Oil/Maleic Anhydride Iodine Value and Final
Reaction MA Concentration using Lupersol 101

 

 

141(1)

121(1)
0 10000 i
, 2 A .
1 § g 80.00 j
. o
1 . e
l 0- " mm + ‘05” I,
E '8 1+T31$Cmmfl29nmw
- l+T=15)C.t-<!)m-059nTC1-&1yl . i
41m ._._r=1mcemm.-asanrm-am ‘ i
:+rnmcr-mm.-osgnTu-aryl l
2000 i

0.00

. l
020 040 080 0.80 1.00 1.20}
FinalConeentrationofMAwnolMNgrmlSO) l

l

,0
8

 

Figure 8: Comparison of Soybean Oil/Maleic Anhydride Iodine Value and Final
Reaction MA Concentration using Tert-Butyl Peroxide

29

100.1!)

801!)

(39 "9)

V I iodine Value

60m --0— (IN-W
+r=1socueomczgnuuw101 '
+r-120c1-eom-asgnum101

“'00 +rs1soc1-eom 1.04metad101
1+r-100cr-80m ~0.59'nup.!d101

l 20.00 M—

 

0.00

0.00 10.00 20.00 30.00 40.00 50.00 60.1!) 70.1!) 80!!) $.00 ;

Acid Mmrbeflmg KOI-llg solution)

 

Figure 9: Comparison of Soybean Oil/Maleic Anhydride Iodine Value and Acid
Number using Lupersol 101

 

140.00
I 120.00
I g 100.00
. 2 A
i; g 8000
I g 3 l+ m
I g " 60m +rx180c1-eom-02gnr-1-eryi’

4am +12150c1=eom,-0.59nru1-aryi '
+rs1mcu=80m.-05gnre1.my1;

 

I 0.00 10.00 20.1!) 301!) 40.00 50.00 60.00 70.00 80.00
{ Acid Minibar (mg KOI-Ug solution)

Figure 10: Comparison of Soybean Oil/Maleic Anhydride Iodine Value and Acid
Number using Tert-Butyl Peroxide

30

4.2.3 Vigzositv (Figures 11 and 12):
The equipment used for this experiment was a Brookfield, model EX100,

viscometer, with a constant temperature bath.

The viscosity of the maleated soybean oil increases with the final maleic
anhydride concentration. Viscosity of maleated soybean oil does not appear to be a

function of reaction temperature, initial catalyst concentration, or duration of reaction.

 

 

I 1000 i
l 900 I
l 800 I
700 I
I E. 5
‘8 a“ a
o i
.9 3 50° :
i > 41'!) i
I _+T=1$Canh-059nuwad101 _ I
I 300 I+T=15)Ct=mnh~029nuwad101 I
an I+T=1mce80m~csm101 ’
I+T=1EJGt=mnh1049nuwad101
1‘” I+T=1mCt=mnh,-059nuwad101I
0 . .

l
0.00 020 040 06) 0&1 1.00 120;

mmamwmmsq r

 

Figure 11: Comparison of Soybean Oil/Maleic Anhydride Viscosity and Final
Reaction MA Concentration using Lupersol 101 at 25 C

31

—0— 1:12—01"! FTKW
+r=1500 1=80 m ~02 mien-am
+r=150 c mom ‘059‘I'ITU1—alyl
+rz15001=80m.-0.5gnrm-myi '
+T=120C.tt=60n'n. 059111311-thle

"7:33"
.sessssssss

 

I
0.00 0.20 0.40 0.60 0.80 1.00 1.20
Final Concentration of MA (gmol MAIgmol SO) I

I
I
I
l
L

Figure 12: Comparison of Soybean Oil/Maleic Anhydride Viscosity and Final
Reaction MA Concentration using Tert-Butyl Peroxide at 25 C

4.2.4 Fourier Transform Infra Red Spectrometer Results (FTIR)

The equipment used for this experiment was a Perkin-Elmer, model 1600, F TIR,
with the horizontal ATR accessory. Sample fluid was applied to the ATR’s sample

crystal and measured by FTIR.

A strong correlation exists between the increase in maleated soybean oil and the
area of two FTIR peaks at approximately 1775 and 1850 cm]. In the case of soybean oil
(Figure 13) both the peaks at 1775 cm"1 and 1850 cm'1 are not apparent; only the peak at
1740 cm'1 is apparent, most-likely the ester linkages from the triglyceride. An increase in
maleic anhydride increases the peaks at 1775 and 1850 cm'1 as apparent on inspection of

Figures 14-16. Apparently the peaks at 1775 and 1850 cm'1 are ester anhydride peaks

32

because hydrolysis of the sample will result in a broad peak above 3000 cm'l, refer to

Figure 17.

The maleated soybean oil was hydrolyzed (Figure 17) by the addition of excess
water and mixed at temperatures of 150-160 C for 90 minutes. It can be noted that a
reduction in both the anhydride groups and triglyceride are apparent due to the reduction

in the ester peaks at 1740, 1775, and 1850 cm".

The esterified, maleated soybean oil (Figure 18) was prepared with a maleated oil
of 1.0 mole maleic anhydride per mol soybean oil, as in Figure 16, according to the
procedure outlined in section 4.1.2. Figure 18 shows that the anhydride groups had been
hydrolyzed, no apparent peaks at 1775 and 1850 cm", with only a small amount
converted to acid, small group of peaks above 3000 cm’l. If the maleic anhydride was
completely converted to acid the spectra would look similarto Figure 17. Though in the
esterified samples the peak at 1740-1750 cm'1 became larger in size due to the ester

linkages to the maleic acid groups and the triglyceride esters.

The conclusions from the FTIR data are similar to the previous analytical results.
The extent of reaction does not appear to be a function of catalyst concentration, reaction
temperatures (in the region of 100-150 C), or the type of peroxide (tert-butyl or Lupersol
101). The F TIR data also prove that the reaction of maleated soybean oil and l-octanol

result in a esterified, maleated product in the triglyceride form.

33

iaZIaaIWI-wifrmr W'MWW‘I

 

 

 

 

 

 

 

 

 

 

 

0.80 . 1 ‘ . .

100.004.

‘ m i

 

 

0.08 .l I l
1% _ 1880 1701 ctrl

Figure 13: FTIR spectra of Soybean Oil

34

”WWW“

T e
. , I

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

0.00 . . .
3808 2m in or'
lwmi
'/.T
8% . . r
1900 180 Im 01"

Figure 14: FTIR spectra of 0.2 mol MA/mol SO maleated soybean oil

35

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

0M . .' . . . .
1m 2m . me 81"

180.094
7.1

I

I
.08” - r l T ‘ '

1988 18m 17% 08"

Figure 15: FTIR spectra of 0.5 mol MA/mol SO maleated soybean oil

36

"190. 884'

 

 

 

 

 

 

 

 

 

 

38m 2888 1m 00"

 

 

8' m‘ r 1 . m I
1900 1999 . 1701 on

Figure 16: FTIR Spectra of 1.0 mol MA/mol SO maleated soybean oil

37

160.881 [It
I

‘ I" ”I I

 

 

 

 

 

 

 

 

0.80 - r l 1
3m 2088 . 18% 0| I
188%-
'41

 

 

8.88 T r r
1900 1890 I769 884

 

Figure 17: FTIR Spectra of 1.0 mol MA/mol SO maleated soybean oil, hydrolyzed

38

180.80
7.1

 

 

 

 

 

 

 

 

 

 

 

 

0.88 . . . .
am am 1% 01"
108.084
7.1
8.86 y r ‘r -I I
1900 1850 1838 1750 lm crl

Figure 18: FTIR Spectra of 1.0 mol MA/mol SO maleated soybean oil, esterified

39

4.3 Esterification Results

The experimental results outlined in Table 4 were obtained by the procedure
outlined in section 4.1.2. The results show some very interesting trends in the
esterification data. Sample 44 represents a maleated soybean oil of approximately 1 mole
maleic anhydride per mole of soybean oil. Esterification of sample 44 for 120 minutes
resulted in a substantial decrease in acid number which can be attributed to the hydrolysis
then esterification of the anhydride group. Sample 45 is also a maleated soybean oil of
approximately 1 mole maleic anhydride per mole of soybean oil. Reactions of 60 and
180 minutes resulted in a substantial decrease in the acid number by esterification.
Sample 46a show that if near stoichiometric quantities of alcohol are used in the
experiment; the esterification of the anhydride groups are greatly reduced. Sample 54a
was run with a stoichiometric amount of octanol without water and resulted in a
significant reduction in initial acid number (AV54 = 68.3 mg KOH/g). Sample 54c was
run with 50% excess alcohol and nearly all anhydride was esterified as seen in the low
acid number of 3.03 mg KOH/g. Sample 54b was run with 50% excess octanol and water
but at a low temperature of 150 C instead of the normal temperature of 300 C. The lower
reaction temperature resulted in a much lower amount of esterification. Sample 54b can
be compared with sample 44d which had similar concentrations of reactants but was run
at 300 C. Sample 44d had a much higher level of esterification than 54b as seen from the

much lower acid number.

40

Samples 47 through 51 were obtained with soybean oil to verify the reactions of
the triglyceride with various reactants under the given conditions. Sample 47 was
conducted with only soybean oil and resulted in a near zero acid number showing that the
triglyceride will not split apart in the absence of water. Comparison of sample 48 and 50
shows that soybean oil in the presence of octanol will result in a moderate amount of
esterification of the glyceride over a sample in absence of octanol. Sample 51 was run
with octanol but no water and resulted in a very low acid number thereby confirming a

very low amount of triglyceride hydrolysis and thus esterification.

Table 4: Esterification Reactions

Sample Rxn Time Rxn Temp. M80 80 1-octanoi DI H20 Mean Stand.
min C am am gm 9m Acid 8 Deviation
44 na na na na na na 85.57 0.74
44d 120 300 220.00 0.00 102.10 12.90 9.33 0.04
45 na na na na na as 62.06 0.24
450 60 300 70.70 0.00 40.90 5.00 18.43 0.28
45c 180 300 80.40 0.00 45.60 5.00 10.01 0.12
46 na na na na na na 62.99 0.54
488 120 300 70.00 0.00 21.10 5.00 33.74 0.07
47 150 300 0.00 40.16 0.00 0.00 0.09 0.01
48 60 300 0.00 70.40 20.20 5.20 16.25 0.64
49 60 300 0.00 80.40 0.00 0.00 2.86 0.21
50 300 0.00 81.10 0.00 5.40 34.78 0.07
51 60 300 0.00 71.20 21.20 0.00 1.72 0.22
54 na na na na na na 68.26 0.79
548 120 300 71.10 0.00 21.40 0.00 25.17 1.04
548 120 150 59.90 0.00 31.20 5.00 53.47 0.66
54c 120 300 52.50 0.00 27.00 0.00 3.03 4.29

Further tests of the ester products with the use of a differential scanning
calorimeter revealed plasticization characteristics of the maleated soybean ester product

as outlined in the following section.

41

4.3.1 Differential Scanning Calorimeter (DSC)

The differential scanning calorimeter used was a Perkin-Elmer DSC 7 connected
to a DECstation Personal Workstation via a TAC 7/DX Thermal Analysis Instrument
Controller. The personal workstation utilizes the Perkin-Elmer 7 series/UNIX Thermal
Analysis System software. ASTM D3418-82 titled “Standard Test Method for Transition
Temperatures of Polymers By Thermal Analysis” was the basis for the experimental

procedure.

Several samples of maleated soybean oil (MSO) were tested with the DSC to
determine any plasticization qualities. The MSO resulted in no measurable reduction in

the glass transition temperature, thus MSO offers no advantage as a plasticizer

Figure 19 shows the results of DSC experiments with PVC resin and maleated
soybean oil ester (section 4.3). The maleated oil, deionized water, and l-octanol reacted
at 300 C in a pressurized reactor for 60 minutes. Vacuum removal of excess water and

alcohol. Refiigerate the sample until the DSC test.

The DSC results include four samples, pure PVC, 12% MSOE in PVC,
33% MSOE in PVC, 52% MSOE in PVC. Figure 20 is the inversion of glass transition
temperature as the dependent variable and ester concentration as the independent
variable. The resulting graph revealed a regressed line of R2=0.97, which would mean

MSO ester is a plasticizer for PVC.

42

3.6

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

.
3.5 1’
3.4 F? = 0.9709 ’/
A
:1- 3.3 //
a 32 .
~ a: 31 /
P o 3 /
8 I . WMBOesbr(smple43)
1- 2.9 e I_Lhear(WONSOesw(sarple43))‘———
I 2.8
2.7
0.“) 10.“) 20.0) 30.00 40.00 50.00 60%

I

Concentration (wt% MSOE) I

Figure 19: Differential Scanning Calorimeter results for PVC/MSO Ester (Sample
43)

Figure 20 shows the results of DSC experiments with PVC resin and maleated
soybean oil ester, prepared in a manner outlined in section 4.1.1. The soybean oil, diethyl
maleate, and Lupersol 101 reacted at 150 C in a pressurized reactor for 60 minutes.

Vacuum removal of excess water and ester, refiigerate the sample until the DSC test.

The purpose of the experiment was to investigate the reaction of soybean oil and
an alkyl maleate. The alkyl maleate reaction could offer a cost saving over the maleic
anhydride reaction with soybean oil. The savings could be attributed to material and
reduced labor costs. The reduction in manufacturing cost and capital equipment cost

could reduce the selling price of the maleated soybean oil ester.

43

Three samples were prepared for the DSC test, pure PVC, 30% MSOE in PVC,
50% MSOE in PVC. The glass transition temperature of each sample was inverted and
graphed using concentration as the independent variable. The resulting graph revealed a
regressed line of R2=0.93, which would mean the M80 ester is a plasticizer for PVC.
This MSO ethyl ester did not plasticize the PVC to the degree of the M80 octyl ester
reduced the glass transition temperature. This may be due to the interpenetrations of the

octyl chains into the PVC matrix.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

I 3.3
I A . // fl
: :I- 3.1 // .
I g / Fri-08288 I
I 3 / _ ' I
I g I
I 8 29 / I
' O // I . WONBOesbrtsarpie43) I
I ‘— .__1m' woweo ter 43 I
28 I r as (same i).

2.7
I 0.00 5.00 10.00 1500 20.00 25.00 30.00 35.00 40.00 45.00 50.00
» Concentration (wt% MSOE)

 

Figure 20: Differential Scanning Calorimeter results of PVC/MSO Ester (sample 44)
blends

4.4 Experimental Conclusions

Maleated soybean oil (MSO) was produced relatively quickly and easily in the
laboratory. Results of acid number, iodine number, viscosity, and FTIR show that the
maleic anhydride was bonded to the soybean oil. The maleic anhydride was bonded to
the soybean oil by the use of a peroxide catalyst which allowed the conjugation of double

bonds and in turn allowed for a 1-4 Diels-Alder type reaction3.

13 1211 10 9
CH3(CH2)4CH=CHCHZCH=CH(CH2)7COOR

l peroxide

CH3(CH2)4CHZCH=CHCH=CH(CH2)7COOR

 

CH=CH

CH3(CH2)4CHZCH H(CH2)-,COOR

45

Any of the afore mentioned analytical techniques can be used to determine the degree of

maleation with good accuracy.

The maleated soybean oil can then be reacted with alcohols to produce an ester

(MSOE), that in turn can be used as a resin plasticizer.

  

R'OOCH2
/CH=C< R"oocI:H
CH3(CH2)4CH2 H CH(CH2)7COOCH2 + 2 H20
0 l
R'OOCH2
R"OOCH

CH=CH I

\

(mam-1940112 H CH(CH2)-,COOCH2

O
OH H

46

R'OOCH2

CH=CH R 00TH
CH3(CH2)4CH2 H CH(CH2)7COOCH2 + 2 R0”
0
OH H I
R'oooH2
CH=CH R 00TH
41- 2 H20
CH3(CH2)4CH2 H CH(CH2)-,COOCH2
O + Various By-Products

OR R

The various products that are produced during the esterification reaction appear to be
“splintered” triglycerides that had been hydrolyzed during the reaction. These
“splintered” glycerides may be in the mono-, di-, or linoleic ester state.

Hoc:H2

CH=CH “OT”?

CH3(CH2)4CH2 H CH(CH2)7000CH2 + R-ooH + R"OOH

. /

OR R
R'OOR + H20 R"OOR + H20

 

 

47

HOCH2

CH=CH R OOCIH

\

CH3(C H2)4C H2 H CH(C H2)7COOC H2 + R'OOH

 

 

O RCH
R
OR R'OOR + H20
HOCH2

CH=CH ‘ I
CH3(CH2)4CH2 H CH(CH2)-,COOR + H20 + ”OCHz

o HOCH2

0R R + R'OOR + R"OOR

By-products from the mono- and diglyceride reactions may further react into light weight
esters. The differential scanning calorimeter experiments showed that these “splintered”
triglycerides show no real limitation in the plasticization characteristics of the overall
product and perhaps may increase plasticization.

Thin layer chromatography seems to support the conclusion that a certain amount

of the triglyceride is reduced to the mono- and di-glyceride state.

48

CHAPTER 5

 

PRELIMINARY PROCESS DESIGN

 

5.1 Continuous Process Design

A flow diagram and material and energy balances (refer to figure 22, 23, and
Table 5) of a soybean maleation and a esterification process was determined from
experimental data. The basis for the design was:
0 5000 ton per year of maleated soybean oil (M80).
0 2500 ton per year of MSOE will be produced which translates into a raw material
requirement of 2005 ton per year of maleated soybean oil.

0 operation of 8000 hours per year.

Due to the relatively fast reaction rate of the soybean oil and maleic anhydride, a
continuous stirred tank reactor could be used in the process. A reaction rate was
determined from the experimental data to be rMA = (N Mm) - NMA) /(t "' V) = -l .9
mol/hr*L. From the design basis the maleic anhydride feed rate was determined to be
729 gmol/hr and the conversion was determined from experiment to be approximately
90%. The volume of the continuous stirred tank reactor for the design basis would be

V = FMA(o) X/-rMA = 345.3 L or 92 gallons.

49

Reactants will be added to the reactor from storage tanks. The soybean oil tank
will be 25,000 gallons in size and constructed out of stainless steel, with an internal
nitrogen atmosphere to prevent oxidation of the oil. The soybean oil will be added to the
continuous reactor by a centrifugal pump, a pneumatic control valve, and flowmeter that
will allow real-time process control. The catalyst tank will operate with a similar control
configuration as the soybean oil tank. The maleic anhydride vessel will be placed on
electronic load cells to record the loss of material gravimetrically. The maleic anhydride
will be added to the reactor by a auger. The continuous reactor will be 100 gallons,
constructed of stainless steel, internal baffles, external steam jacket, and mounted with a
10 horsepower motor and agitator. The temperature control will consist of a remote
temperature device (RTD) that will be inserted into the reactor by the use of a stainless
steel thermal well. The thermal well will allow for access to the RTD without
contamination of the reactor contents. The RTD will monitor temperature and relay the
information to the control computer which will adjust steam to compensate any deviation

from temperature setpoint.

The maleated soybean oil will be removed from the reactor by an overflow well
which will be connected to the devolitilizer. The difference in pressure from the reactor
(0-5 psig) and the devolitilizer (vacuum, 0.1 atmosphere) will be the driving force for the
transfer. The MSO will be depressurized through a pneumatic control valve with the
flow monitored into the devolitilizer. Any residual maleic anhydride will sublime and the

catalyst will evaporate and removed via a compressor. At 150 C the maleic anhydride

50

and catalyst will be compressed to 10 psig, a 10% purge stream removed and sewared,
and the remaining reinjected into the reactor. The devolitilizer will also consist of a
stainless steel mixing vessel with a steam jacket, RTD with thermal well, and a 5
horsepower agitator and assembly. The maleated soybean oil will be removed by
centrifugal pump, flowmeter and control valve. The MSO will be cooled in a stainless
steel, tube and shell heat exchanger to 25 C and pumped into a 25,000 gallon, stainless

steel storage tank.

All control valves and meters will be piped with a bypass in the event of failure
(refer to Figure 24). The bypass valves will allow for quick removal and replacement

with a minimal disturbance of the overall process.

The esterification reactor volume was determined using a similar procedure as
used in the maleated soybean oil reactor. The experimental alcohol reaction rate for
esterification of the maleated soybean oil was determined to be 6.15, 1.88, and 0.87
mol/hr/L at 5, 30, 90 minutes, respectively. The reaction rates were graphed over time

and integrated to determine the plug flow reactor volume.

51

1.2

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

3 /
g /
0.8
3 0.3 /
2 /
C
§ 0.4 / '
‘ fl
? 3
? F /
I 0.2 l
0
0 10 20 30 4o 50 50 70 so 90
Time (minutes)

 

Figure 21: Esterification Reaction Rate versus Time for PFR Volume

Determination

The alcohol for the esterification reaction will be set at a 20% excess to assure good
esterification. The feed rate of the alcohol will be 510 gmth and the conversion of
alcohol will be 80%. Integration of the area beneath the curve in Figure 21 and the molar
flow of the reactant will result in the PF R volume, V = FMMOJdM-rm = 458 L or 122.1
gallons. This volume will equal a PFR of 6 inch diameter pipe of 83 ft in length which

would be fabricated according to the given plant lay out.

A market determined amount of maleated soybean oil ester (MSOE) will be
produced in an operation next to the MSO process. MSO, deionized water, and alcohol

are added to a 50 gallon, stainless steel, agitated reactor. The reactor will heat the

52

contents to 250-300 C. The contents are then metered into a continuous stainless steel
loop that will represent a plug flow reactor. The PF R will be of sufficient volume to
represent a 90 minute residence time and will be well insulated to maintain a 250-300 C
temperature. The MSOE and excess alcohol and water will be metered into a
devolitilizer that will remove the excess alcohol and water. The alcohol and water are
then condensed in a heat exchanger and sewared. The MSOE is then pumped through a

heat exchanger and cooled to 20 C for storage in a 15,000 gallon stainless steel tank.

Control of the system will originate from a computer interface to the process.
F lowmeters and RTDs will operate at a 4-20 mA signal which will then be interrupted by
the computer into the corresponding process variables. The computer will operate a
control program such as "Paragon" manufactured by Intel Inc., which can emulate a
proportional, integral, derivative controller. The program will evaluate the incoming
signal, evaluate, and send out the response based on PID parameters set by the plant
engineers. The response signal will be transmitted to a VP transducer which will convert
the electronic signal of 4-20 mA to a pneumatic signal of 3-15 psig. The pneumatic
signal will control the corresponding control valve. A pneumatic signal is desired over a
electronic signal to an electric actuator because of the fire hazard associated with an
electric actuator failure. The description of the control system sounds complex but offers
many advantages over a manual control system. Advantages include process data
collection/management, a very consistent product quality, and a minimization of operator

input.

53

Figure 22: Continuous Process Flow Diagram of a Soybean Oil Maleation Facility

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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5.2 Batch Process Design
Flow diagrams and material and energy balances of a batch process to produce
maleated soybean oil and ester are shown in Figure 25, 26, and Table 6, respectively. The
basis for the design was:
0 5000 ton per year of maleated soybean oil.
0 2500 ton per year of MSOE will be produced which translates into a raw material
requirement of 2005 ton per year of maleated soybean oil.

0 operation of 8000 hours per year.

Reactants will be added to the reactor from storage tanks. The soybean oil tank
will be 25,000 gallons, constructed out of stainless steel, and blanketed with nitrogen to
prevent oxidation of the oil. The soybean oil will be added to the batch reactor by a
centrifugal pump and a manual on/ofl‘ valve. The catalyst tank will operate with a similar
pump and valve as the soybean oil tank. The maleic anhydride will be added to the
reactor by a auger. The batch reactor will be 500 gallons, constructed of stainless steel,
internal baffles, external steam jacket, and mounted with a 10 horsepower motor and
agitator. The volume of the reactor allows for batches to be completed in 3 hour cycles
which would include charging, reaction, and cleaning of the reactor. A temperature
indicator will be inserted into the reactor by the use of a stainless steel thermal well. The
thermal well will allow for access to the temperature indicator without contamination of
the reactor contents. The reactor will be mounted on load cells so that the mass can be

measured.

60

The maleated soybean oil will be removed from the reactor by a valve and pump.
The MSO will be removed at the end of a run to the devolitilizer. Any residual maleic
anhydride will sublime and the catalyst will evaporate and removed via a compressor. At
150 C the maleic anhydride and catalyst will be compressed to 10 psig, a 10% purge
stream removed and sewared, and the remaining reinj ected to the next batch run. The
devolitilizer will also consist of a steam jacket and a temperature indicator for operator
assisted temperature control The maleated soybean oil will be removed by centrifugal
pump. The MSO will be cooled in a stainless steel, tube and shell heat exchanger to 25 C

and pumped into a 25,000 gallon, stainless steel storage tank.

A market determined amount of maleated soybean oil ester (MSOE) will be
produced in an operation next to the M80 process. MSO, deionized water, and alcohol
are added to a 500 gallon, stainless steel, agitated reactor. The reactor will heat the
contents to 250-300 C for 60-120 minutes. The excess alcohol and water will be removed
by vacuum, condensed in a heat exchanger, and sewared. The MSOE is then pumped
through a heat exchanger and cooled to 20 C for storage in a 15,000 gallon stainless steel

tank.

Control of the system will be by operator only. All materials will be weighed by

addition to the reactor and recording the load cell measurement. Agitation will be started

61

 

and steam applied manually to the reactor jacket to bring the reactor to 150 C. The
reaction will proceed for 30 to 60 minutes at 150 C. Operators will remove the reaction
product from the reactor by a pump to the devolitilizer and prepare the reactor for another
cycle. The reactor will then be cleaned and prepared for the next reaction. Soybean oil,
maleic anhydride, and catalyst will then be heated to reaction temperature and the recycle
from the devolitilizer will be added back to the reaction. The maleic anhydride and
catalyst recycle pipe will be well insulated to prevent any crystallization of maleic
anhydride. A check valve on the recycle line will prevent any of the reactor contents to
fill the recycle pipe. A ten percent purge will be used to minimize any undesirable
contaminants. The devolitilizer will be constructed of stainless steel, well insulated, a
exterior steam jacket, and a agitator with motor and assembly. When the M80 has been
devolitilized of the catalyst and maleic anhydride, the vessel will be adjusted to ambient
pressure, and the contents removed by a pump. The MSO will be cooled to 25 C in a heat

exchanger before being pumped into a storage tank.

62

 

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66.6 66.6 8.6 86 86 8.6 86 8.6 86 86 8.6 8.6 ..0 6666666
05:62

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.6. 66. 3. 66. 66. .6. 6. 6. 6. 6. 6. 6. .62 6.6666
”866.66 .666......

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u .636 62.83 .0 .3662

.9866 6666 668660 8.66

.33 0000000. 6.68

625. .260

6.8666 666. .66 66.666...

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=0 563.66 0866.62 6 .06 660:6.6m >060cm 0:6 26.3.6.2 no 036...

66

 

 

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.. > 322.

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”82.6.8 5.655

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86 86 86 86 86 86 86 86 .282
86 86 86 86 86 86 86 86 .28 02...
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86 86 86 86 86 86 86 86 06.2
86 86 86 86 86 86 86 86 22.28
86 86 86 86 86 86 86 86 68622.52 0.6.6....
86 86 86 86 86 86 86 86 ..o 58.28
8.32

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=0 :ucnaom 2623.65. 6 .8 32.6.3 33cm .25 3:82.. 6 63¢...

67

CHAPTER 6

 

PRELIMINARY ECONOMIC ANALYSIS

 

6.1 Continuous Process Economics

Table 7 lists the assumptions that were used in the economic evaluation of the
preposed plant. Many of the assumptions made for non-manufacturing labor and utilities
came from Peters and Timmerhaus12 . Material costs for given chemicals were
determined from the current addition of Chemical Marketing Reporterl3 . The plant will
produce 5000 tons per year of maleated soybean oil. Approximately 2005 ton per year of
maleated soybean oil will be converted to an ester for use a resin plasticizer. The plant
will operate 8000 hours per year. The total capital investment will return a rate of 15 %
afier taxes. The plant will operate for 10 years at which time the salvage value will be
considered ten percent of the initial fixed capital investment. The depreciation will be
straight-line over the 10 year period for 90% of the fixed capital investment. Labor will
be paid $15 per hour. Two operators will be required per shift for the continuous plant
and six operators for the batch plant. Supervision, maintenance, and local taxes and
insurance will be 8%, 7%, and 2% of fixed capital investment, respectively. Future R &
D, marketing, and general, sales, administration expenses will be 5%, 5%, and 4% of total

manufacturing costs, respectively.

68

Utility costs will be purchased at $0.07 per Kilowatt hour for electrical power,
$2.5 per 1000 pounds of 90 psig steam, and deionized water will cost $0.001 per pound.
Cooling water will be purchased at $0.15 per 1000 gallons, chilled water at $0.25 per

1000 gallons and sewer will cost $0.015 per gallon.

Purchased chemicals will cost $0.3 per pound for soybean oil, $0.51 per pound

maleic anhydride, $2.5 per pound for the peroxide catalyst, and $0.925 per pound alcohol.

69

Table 7: Assumptions for Economic Evaluation

Built plant next to an existing bean elevator with the desired utilities

8000 hours per year
5000 ton/year
2500 ton/year

15 percent after taxes

9 percent. straight-line

Plant capacity factor

Maleated Soybean Oil Production
Maleated Oil Ester

Long-term return on investment:
Depreciation:

Total Federal taxes:

Working capital:

Plant lifetime

Base rate operating labor:

Supervision:
Maintenance
Local Taxes and

Insurance:
R & D:

Marketing:
General. Sales. Admin. Expense:

Utilities Costs:

Purchased electric power.

Steam: 90

psig:

DI Water.

Tower Cooling Water Q 60

F.
Chilled Water @ 10 C
Sewer.

Purchased Chemicals:

Soybean Oil
Maleic Anhydride
Catalyst

DI Water

Alcohol

34 percent

15 % Total Capital

10 years

$15per
hour

8 percent fixed capital investment
7 percent fixed capital investment

2 percent fixed capital investment

5 percent total manufacturing costs
5 percent total manufacturing costs
4 percent total manufacturing costs

0.070
2.500

0.0004
0.150

0.25
0.015

per Kwhr
per 1000 pounds

3 per pound
3 per 1000 gallons

3 per 1000 gallons
5 per gallon

0.3 5 per pound

0.51 5 per pound

2.5 3 per pound

0.001 3 per pound
0.925 5 per pound

Table 8 shows the equipment description and cost adjusted to 1995 for the proposed

process in Figures 22, 23 and 22, 23. Equipment costs (1990) were taken from Peters and

Timmerhaus12 and adjusted to 1995 using a Marshall and Swift Index”.

70

Table 8: Equipment List for Maleated Soybean Oil and Maleated Soybean Oil
Ester

 

FLOW-
SHEET EQUIPMENT DESCRIPTION Total Cost
NUMBER 1995 5

 

 
  
   
 
 
 
 
 
 
 
 
 
  
 
 
 
    
  
  
  
 
 
  
 

Reactor. 100 gal.. 316-88. WI 10 Hp motor and mixing $44,810I
shaft

1 itator kettle. 50 gal.. 316-88 WI 5 Hp and mixing $11,202
shaft
Soybean Oil Storage. 25000 gal.. 304-88 $56,012

Maleated Soybean Oil Storage. 25000 gal.. 304-88
Catalyst Storage Tank. 250 gal.. 304-88

M80 Heat Exchanger, 10 ft‘2. 316-88

Gravirnetric Feeder. 100 gal. 316-88

Soybean Oil Feed Pump, 10 gpm. 50 ft head. 316-88
Maleated Soybean Oil Feed Pump, 10 gpm. 50 ft head.
316-88

Catalyst Pump, 1 gpm. 50 ft head. 316-88

acuum Compressor. 150 CFM

Flow Meter

Pneumatic control valve

IIP Transducer

mputer wl control program

itator kettle. 50 gal.. 316—88 w/ 5 Hp and mixing

hafi

PFR. 316-88. 90 minute residence time

Flow Meter

hol Feed Pump, 10 gpm. 50 ft head. 316-88

DI Water Feed Pump. 10 gpm. 50 ft head. 316-88
Maleated Soybean Oil Feed Pump. 10 gpm. 50 1t head.
316-88

hol/water condenser Heat Exchanger, 10 M2. 316-

 

did-bun.“

 
  
  

SS
80E Heat Exchanger. 10 «*2. 316-88

hol Storage. 1000 gal.. 304-88

Maleated Soybean Oil Ester Storage, 15000 gal.. 304-

NNN N NNNNN N-fi-l-A-b-t-d

 

 

 

 

71

Table 9 shows the total capital investment that would be needed to construct a facility
capable of producing 2500 tons of maleated soybean ester and 5000 ton per year of
maleated soybean oil (2995 tons per year to be sold for east film production). All costs
are industrial averages for new plant fabrication based on work by Peters and

. 12
Timmerhaus .

The total capital investment is calculated using the equipment cost as a basis and
industrial averages for needed accessories. The equipment installation is 39% of
equipment cost, instrumentation and controls installation will be 13% of the equipment
cost, piping will be 31% of the equipment cost. Electrical, buildings, and yard
improvements will be considered 10%, 29%, and 10% of equipment costs, respectively.
Installed service facilities and land will be considered 55% and 6% of equipment costs,
respectively. Indirect costs such as engineering and supervision, and construction
expenses will be 32% and 34% of equipment costs. Contractor’s fees and contingency
will be 5% and 10% of direct and indirect costs. The above mentioned expenses will be
defined as fixed capital investment. The working capital will be 15% of the total capital
investment. The total capital investment will be the fixed capital investment and working

capital.

72

Table 9: Total Capital Investment for a Maleated Soy Oil and Ester Production

e e ‘2
Facility
Production Plant Capacity (M80) 10,000,000 #lyr
(MSOE) 5,000,000 #Iyr
Direct Estimated 8
Costs:
Purchased Equipment: 410,417
Purchased Equipment installation 160,063
Instrumentation and controls (installed) 53.354
Piping 127,229
(installed)
Electrical (installed) 41,042
Buildings (including services) 1 19,021
Yard Improvements 41,042
Service facilities (installed) 225,730
Land (if purchase is required) 24,625
Total direct plant cost 1,202,523
Indirect Costs:
Engineering and supervision 131,334
Construction expenses 139,542
Total direct and indirect plant costs 270,876
Contractor's fee (5% of direct and indirect plant costs) 73,875
Contingency (10 % of direct and indirect plant costs) 147,750
Fixed Capital investment 1,695,024
Working
Capital
Working Capital (~15% of TCI)
Total Working Capital 299,122
Total Capital Investment 1,994,146

Table 10 shows a manufacturing cost breakdown of the proposed production facility.
Included in Table 10 are the variable and material for the facility, determined from mass
and energy balances of Table 5. The fixed costs include process operators at 2 per shift
for the required 8000 hour year. Supervision, maintenance, depreciation, and local taxes

and insurance will be 8%, 7%, 10%, and 2% of the fixed capital investment. R & D,

73

Marketing, and GS & A are 5%, 5%, and 4% of total manufacturing costs, respectively.
It should be noted that the manufacturing cost is most sensitive to the cost of the raw

materials. Energy and labor costs are fair less then the cost of raw materials.

Table 10: Manufacturing Cost Breakdown of a 2500 ton/yr MSO Ester and 5000
ton/yr MSO

 

 

 

Quantity Cost
Slunit year Slyear
Variable Cost (excluding material cost)
Utilities (unit)
Steam: 90 psig (1000 lb) 2.5 1725281 4,313
Industrial Water (1000 gal) 0.75 1000000 750
Chilled Water (1000 gal) 0.25 30068898 7,517
Sewer (gal) 0.015 2000000 30.000
Electricity (Kwhr) 0.07 50557 5.308
Total Variable Costs 47,889
Material Cost
Soybean Oil 0.3 8750000 2,625,000
Maleic Anhydride 0.51 1259129 642,156
Catalyst 2.5 57566 143.914
DI Water 0.001 88257 88
Alcohol 0.925 1 168588 1,080,944
Total Material Cost 4.492.103
Fixed Costs
Labor, 2 person/shift 2 15 8000 240,000
Supervision (8% FCI) 135,602
Maintenance (7% FCI) 118.652
Depreciation (10% Salvage, 9% FCI) 152.552
Local Taxes and Insurance (2% F01) 33,900
Total Fixed Coats 680,706
Total manufacturing cost 5,220,698
R 8 D (5% TMC) 261,035
Marketing (5% TMC) 261.035
General, Sales. Administration Expense (4% TMC) 208,828
Total operating cost 6,961,696

Table 11 shows the selling price of the maleated soy oil and the ester at 15 percent return
on investment. The selling prices were determined from the total operating cost plus the

required return and principal divided by the annual production of maleated soy oil and

74

ester. Using this approach the selling price of the maleated soybean oil consists of a

portion of the alcohol costs associated in producing the ester.

Table 11: Estimated Selling Price of Maleated Soy Oil and Maleated Soy Oil Ester
at 15% Return on Investment

Minimum Selling Price MSO = 8 0.5989
(ROI = 15%)
Minimum Selling Price MSOE = 8 0.7174
(ROI = 15%)

Note the cost of the maleated soybean oil ester at 15 % return on investment is $0.717 $/#
compared to DOP at 0.52 $/# and epoxidized soybean oil of $1.1-1.3/#. The large
difference in maleated versus epoxidized soybean oil is due to the reduction in process

difficulty.

6.2 Batch Process Economics

The assumptions for the batch process are identical to the continuous process with
one exception. The reactor size will allow for 3750 pounds of MSO to be produced in
one reaction. The reactor capacity will allow for a three hour cycle time for the MSO
reactor with 2,667 reactions per year to produce the desired ten million pound per year

production.

75

Table 12 shows the equipment description and 1995 cost estimate the proposed
batch process in Figures 25, 26, and Table 6. Equipment costs (1990) were taken from

Peters and Timmerhaus12 and adjusted using a Marshall and Swift Index”.

Table 12: Equipment List for Maleated Soybean Oil and Maleated Soybean Oil
Ester

 

 

 
  
   
   
 
   
    
   
  
    

 

 
  
 
 
  

FLOW-
HEET EQUIPMENT DESCRIPTION Total Cost
NUMBER 1995 8
1 eactor, 500 gal.. 316-SS, w/ 10 Hp motor and mixing shaft $112,025
1 itator kettle. 500 gal.. 316-88 1»! 5 Hp and mixing shaft $89,620
1 oybean Oil Storage. 25000 gal.. 304-88 $56,012
1 aleated Soybean Oil Storage. 25000 gal.. 304-88 $56,012
1 atalyst Storage Tank. 250 gal.. 304-88 $5,601
1 80 Heat Exchanger. 10 ft‘2, 316-88 $5,044
1 aleic Feeder. 100 gal, 316-88 $50,436
1 oybean Oil Feed Pump. 10 gpm. 50 1t head. 316-88 82.240
1 aleated Soybean Oil Feed Pump, 10 gpm. 50 It head, 316-88 82,2
1 talyst Pump. 1 gpm. 50 ft head, 3116-88 81.12
1 acuum Compressor. 150 CFM $16,804
2 Reactor, 500 gal.. 316—SS. w/ 10 Hp motor and mixing shaft $112.02
2 itator kettle. 500 gal.. 316-88 wl 5 Hp and mixing shaft $89,620
2 cohol Feed Pump. 10 gpm. 50 It head. 316-88 82,2
2 DI Water Feed Pump, 10 gpm. 50 It head. 316-88 32.2
2 aleated Soybean Oil Feed Pump. 10 gpm. 50 It head, 316-88 $2,240
2 cohol/water condenser Heat Exchanger. 10 It“2, 316-88 $5,044
2 SOE Heat Exchanger. 10 ft"2. 316-88 $5,044
2 lcohol Storage, 1000 gal.. 304-88 85.601
2 aleated Soybean Oil Ester Storage, 15000 gal.. 304-88 $39.2
otal Purchased Cost $660,418
Delivery $33,021
otal Cost $693,439

 

 

 

76

Table 13 shows the total capital investment that would be needed to construct a facility
capable of producing 2500 tons of maleated soybean ester and 2995 tons of maleated
soybean oil for cast film production. All costs are industrial averages for new plant

fabrication based on work by Peters and Timmerhaus12 .

Table 13: Total Capital Investment for a Maleated Soy Oil and Ester Production
Facility12

Production Plant Capacity ("80) 10,000,000 #iyr
(MSOE) 5,000,000 9/yr

Direct Coats: Estimated 8
Purchased Equipment: 693,439
Purchased Equipment installation 270,441
lnstrurnentation and controls (installed) 90.147
Piping (installed) 214,966
Electrical (installed) 69.344
Buildings (including services) 201.097
Yard Improvements 69,344
Service facilities (installed) 381.391
Land (if purchase is required) 41,606

Total direct plant coat 2,031 .776
Indirect Costs:
Engineering and supervision 221,900
Construction expenses 235,769

Total direct and Indirect plant coats 467,670
Contractor's fee (5% of direct and indirect plant costs) 124.819
Contingency (10 % of direct and indirect plant costs) 249.638

Fixed Capital Investment 2,883,902
Working Capital

Working Capital (~15% of TCI)

Total Working Capital 605,394

Total Capital Investment 3,369,296

77

Table 14 shows a manufacturing cost breakdown of the proposed production facility.
Included in Table 14 are the variable, material, and fixed costs for the facility determined
from mass and energy balances of Table 25, 26, and Table 6. Additional labor was
included in the batch process, 6 persons per shift, compared to the continuous process
which used just 2 operators per shift. The manufacturing cost of the batch process is still
most sensitive to the cost of the raw materials. Energy and labor costs are fair less then

the cost of raw materials.

Table 14: Manufacturing Cost Breakdown of a 2500 ton/yr MSO Ester and 5000
ton/yr MSO

 

 

 

Quantity Cost
Slunit year Slyear
Variable Cost (excluding material cost)
Wises (unit)
Steam: 90 psig (1000 lb) 2.5 2417040 6.043
Industrial Water (1000 gal) 0.75 1000000 750
Chilled Water (1000 gal) 0.25 30068898 7,517
Sewer (gal) 0.015 2000000 30,000
Electricity (Kwhr) 0.07 50557 5.308
Tobl Variable Costs 49,618
Material Cost
Soybean Oil 0.3 8750000 2,625,000
Maleic Anhydride 0.51 1259129 642,156
Catalyst 2.5 57566 143.914
DI Water 0.001 88257 88
Alcohol 0.925 1 168588 1,080,944
Tobi Material Cost 4.492.103
Fixed Costs
Labor. 2 person/shift 6 15 8000 720.000
Supervision (8% FCI) 229,112
Maintenance (7% FCI) 200.473
Depreciation (10% Salvage. 9% FCI) 257.751
Local Taxes and Insurance (2% FCI) 57,278
Tobi Fixed Costs 1,464,614
TobI manufacturing cost 6,006,336
R 8 D (5% TMC) 300.317
Marketing (5% TMC) 300,317
General. Sales, Administration Expense (4% TMC) 240,253
Tobi operating cost 6,847,222

78

Table 15 shows the selling price of the maleated soy oil and the ester at 15 percent return
on investment. The selling prices were determined from the total operating cost plus the
required return and principal divided by the annual production of maleated soy oil and

CSICI’.

Table 15: Estimated Selling Price of Maleated Soy Oil and Maleated Soy Oil Ester
at 15% Return on Investment

Minimum Selling Price M80 8 8 0.7441
(ROI = 15%)
Minimum Selling Price MSOE = 5 0.8912
(ROI = 15%)

Note the cost of the maleated soybean oil ester produced by the batch process at 15 %
return on investment is $0.891 $/# compared to the continuous process MSO ester at
0.717 $/#. The large difference in the batch versus continuous process maleated ester is
due to increased labor force and total capital investment. The selling price depends a
great deal on the purchase price of the proposed equipment. Therefore, the purchase of
used equipment rather then new could greatly reduce the equipment costs and thus reduce

the required selling price of the products.

6.3 Determination of the Internal Rate of Return by a Discounted Cash Flow

In industrial operations, it is often possible to produce equivalent products in
different ways. The method for a profitability evaluation by discounted cash flow takes
into account the time value of money and is based on the amount of the investment that is

unretumed at the end of each year during the estimated life of the project. A trial-and-

79

error procedure is used to determine a rate of return which can be applied to annual cash
flow so that the original investment is reduced to zero or to salvage and land value plus
working capital. Thus, the rate of return by this method is equivalent to the maximum
interest rate (normally after taxes) at which money could be borrowed to finance the
project under conditions where the net cash flow to the project over its life would be just
sufficient to pay all principal and interest accumulated on the outstanding principal. The
specific discount method used in this thesis is a net present worth or a venture worth

method. All discount factors used are continuous.

As a basis for this method the selling price of the maleated soybean oil and the
ester were set at $ 0.6/# and $ 0.8/#, respectively. The capacity was held constant at 2995
ton/year of maleated soybean oil and 2500 ton/year maleated soybean oil ester. The cash
flow was then determined using the given capacity and selling price of each product. The
land, fixed capital cost minus the land, working capital, salvage, and cash flow were then

used to determine a discounted cash flow.

Determination of cash position at zero time must be calculated in terms of the

unknown profitability index r.

The land will be purchased one year before the zero reference point of plant start-
up. Therefore, the land value at zero time is the future worth after one year with

continuous compounding, e'.

80

The total construction cost in this case is the fixed capital investment minus the
land purchase and will occur one year before plant start-up in a uniform series over that
year. The compounded construction cost at zero time, therefore, is the future worth after

one year flowing uniformly throughout the year with continuous compounding, (er - l)/r.

The working capital investment must be supplied at the time of plant start-up or at
the reference point of zero time.

The resulting cash position at the reference point will be:

CP 2,... ...... = Land ( e') + Construction (er - 1)/r + working capital

After plant start-up, the annual cash flow to the project (net profit plus
depreciation) will flow continuously and uniformly at a constant annual level through the
life of the project. At the end of each year, the compounded cash flow to the project, with
continuous flow and continuous compounding will be:

S cash flow, mm... = Cash Flow (er - 1)/r
At the end of 10 years, the total future worth (S) of the cash flows to the project becomes

(A) s = Cash Flow (6 -1)/r(e9' + e8r + e7r + + 6 +1)

The future worth of the total flow to the project after 10 years must be equal to the
future worth of the total cash position at zero time (CP mo time) compounded continuously

for 10 years minus the salvage value, land value, and working capital investment.

(B) S = (CP m t...,..,)(e'°') - Salvage - Land - Working Capital

8]

Equating equation (A) and (B) gives the following result with r as the only
unknown, and a trial-and-error solution will give the profitability index r.

Cash Flow (6 - 1)/r (6"r + e8r + e7r + + e' + 1) - (CP m, ti......)(e‘o') + Salvage +
Land + Working Capital = 0

This equation can be simplified by dividing by elor and substituting the expression
for CP we ...... to give the present value or discounted cash flow equation as follows:

Cash Flow (er - 1)/r (e9r + e“r + e7r + + e' + 1)(1/ e'°' ) - (Land ( e') +
Construction (er - 1)/r + Working Capital) + (Salvage + Land + Working Capital)
(1/ 6“ ) = o

For the case of continuous cash flow and interest compounding:

(er -1)/r(e9' + e8r + e7' + + er + l) = (em - l)/rem
The resulting discounted equation:

(C) Cash Flow (em - 1)/re"' (1/ 6‘” ) - (Land ( e') + Construction (6 - 1)/r +
Working Capital) + (Salvage + Land + Working Capital) (1/ cm ) = 0
Equation (C) is then used to determine the profitability or internal rate of return of the

proposed process’.

The assumed values that were used for this calculation are given below.

82

 

Table 16: Discounted Cash Flow Assumptions

Item Continuous Batch
Project Life. n. years 10 10
M80 Capacity. #lyr 5,990,000 5,990,000
MSOE Capacity, #lyr 5.000.000 5.000.000

Selling Price M80. 8”! 0.6 0.6
Selling Price MSOE. $/# 0.8 0.8
Land. 5 24.625 41.606
Construction of FCI- 1,670,399 2,822,295
land. $
Working Capital, 8 299.122 505.394
Salvage, $ 167.040 282.230

Cash Flow,$/yr 1,031,012 403,693

Equation (C) was then used by trial and error with the above assumptions to produce the

diagrams of the net present value. The internal rate of return is the point at which the net

present value is equal to zero. This rate of return is equivalent to the maximum interest

rate (normally after taxes) at which money could be borrowed to finance the project under

conditions where the net cash flow to the project over its life would be just sufficient to

pay all principal and interest accumulated on the outstanding principal.

Figure 27 shows several different discounted rates and the net present value as

determined from equation (C) for the proposed continuous process. The internal rate of

return for the proposed continuous process with the assumptions of Table 16 is

approximately 53 percent.

83

2000

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

o 1500 a
o
6 \
,.
‘3 1000
6‘ \
2 \ IRR = 53%
g 500
an \
c
o
I” o
o
E (1 1b 2f ab 4b so so 70 so
“
O \
- oo
2 5 \\
-1ooo

 

Discount Rate, percent interest

 

Figure 27 : Determination of the Internal Rate of Return by a Discounted Cash
Flow for the Proposed Continuous Process

Figure 28 shows several different discounted rates and the net present value as
determined from equation (C) for the proposed batch process. The internal rate of return
for the proposed batch process, with the assumptions of Table 16, is approximately 6.7

percent.

84

 

1500

1000 .\\

= o
500 \ IRR 5.7 A

 

 

 

 

 

 

-500

 

-1000

-1500 \\

-2000 ‘52.

 

 

Net Present Value, x31000

 

 

 

 

 

 

 

 

-2500 7

 

Discount Rate, percent interest

 

Figure 28: Determination of the Internal Rate of Return by a Discounted Cash Flow
for the Proposed Batch Process

The resulting internal rates of return of the two proposed process’ show that a
continuous process would generate a higher return then the batch process given the
selling price of the products. Therefore, the best alternative process is the continuous and
not a batch production facility. The reason that the batch process is far less profitable is
the high cost of the land, construction, working capital and the low annual cash flow

compared to the continuous process.

85

6.4 Sensitivity and Production Capacity Analysis

The assumptions made for the sensitivity analysis were:

0 Production capacity of 5 million pounds per year maleated soy ester and 5.9 million

pounds per year maleated soybean oil.

0 Condition of zero reflects the proposed economical analysis of 6.1, the proposed

continuous process.

0 Return on Investment of 15%.

A sensitivity analysis of the maleated soybean oil’s selling price to variations in

key manufacturing cost variables is shown in Figure 29.

 

0.04

0.79

0.74

0.60

0.64

Selling Price (sis use) I

0.59

0.54

0.49

0.44

 

 

 

4*: .—-—MSO Utility Costs ,
....MSO Material Costs 71

\ l+MSO Fixed Costs i
2.2MSO TCI .2

 

i+MSO Soybean OII s

.—.—MSO MA

 

(...—M80 Catalyst
:—.—MSO AICOIIOI

l

.—

 

 

 

 

 

\E

 

 

 

 

 

 

 

 

 

50

0
% Change in Variable

 

Figure 29: Sensitivity Analysis of the Selling Price of Maleated Soybean Oil at 15 %

ROI

86

 

 

:_ NIISOE Utility Costs
2.. MSOE Maerial Costs
... MSOE Fixed Costs
.... MSOE TCI

\\ : x 3.2m“
5

 

 

.0
‘1
o

...—MSOECatdyst -—* '
l+MSOEAlcohoI

 

 

 

 

v

N

V

 

1

.0
a:
to

 

SeIIInEPrIce ($188180 ester) 7
o
3

0.49

 

/ //l

 

 

 

 

 

0.39

 

i 50 o -50
: %Change inVarlabIe ?
l I

Figure 30: Sensitivity Analysis of the Selling Price of Maleated Soybean Oil Ester at
15 % ROI

Both the maleated soybean oil and ester exhibit a high sensitivity in selling price
to variations in material cost, in particular to soybean oil. Variation in other quantities

such as utility and fixed costs, exhibit little effect on the selling price of the two products

because of the low energy and labor costs associated with the proposed process.
Figure 31 shows similar results for the process that only produces maleated

soybean oil. Note the reduction in selling price for maleated soybean oil from a process

that only produces maleated soy oil ($ 0.59/# M80) to a process that also produces the

87

soy ester ($0.60/# MSO). This reduction in selling price can mainly be attributed to no

cost associated with the alcohol needed for esterification.

 

 

0.79

4 J i
\ .... MSO Utility Costs i i

0-74 2.2 M80 Material Costs __ ‘.
\ ;_._ Mso Fixed Costs 1 '

i .... MSO rcr i E

0.69 3

 

 

 

 

 

 

 

 

 

 

 

 

 

8 >\\\ i... M80 MA .
In 0.64 :\ \ ._._MSO Catdyst 3__ g
‘ g ‘ \\ 1... M80 Alcohol r' z
1 8 0.59 _
'C
l n- \
l 8

§\ N .
.... \ 1
\

0.39
,‘ 50 0 -50
l % Change in Variable l

 

 

 

 

 

 

 

 

 

Figure 31: Selling Price of Maleated Soybean Oil at 15% R01 (Plant Capacity =
100% M80)

Figure 32 shows a sensitivity analysis of a process that produces only maleated
soybean oil ester. In the case of a process producing only maleated soy oil ester there
will be an increase in selling price ($0.721/# MSO ester) over a process that can sell both
products ($0.7143/# MSO ester). The process that can sell two products can distribute

the extra material cost over two products instead of just the one.

88

 

1.09

 

 

... MSOE Utility Costs

 

 

0.99 “2 ... MSOE Material Costs~
... MSOE Fixed Costs
2.2. MSOE TCI 1

0.89 2.. MSOE Soybean Oil _

I\ \ ._._ MSOE Catalyst
0.79 2.2 MSOE Alcohol

Selling Price (8M M80 ester)

 

 

 

 

 

 

 

 

0.49 \ f

5 0.39 I
l 50 o -50
. % Change In Variable '

 

 

 

 

 

 

 

Figure 32: Selling Price of Maleated Soybean Oil Ester at 15% ROI (Plant Capacity
= 100% M80)

The most important conclusion that can be drawn from this type of analysis is the
high sensitivity of the selling price to the price of soybean oil. Therefore, profit margins
for the selling price of the products should be set high enough, so that an increase in

soybean oil price does not adversely effect the profitability of the proposed process.

Production capacity is also an important variable to determine the optimum size

of plant. This analysis will investigate the selling price that can be achieved for the

incremental increase in manufacturing cost and capital investment.

89

 

Table 17 shows the change in product selling price (at 15% R01) versus the

production capacity.

Table 17: Comparison of MSO and M80 ester Selling Price versus Production
Capacity

Capacity (x Mil M80) M80 MSOE
1 1.03 1.23
10 0.6 0.72
100 0.492 0.59
1000 0.456 0.55

The change in selling price of the products are due to the slower increase in equipment
cost versus the faster increase in production from such equipment. Equipment cost will

roughly follow the 0.6 rule of scaling, shown below.

Cost of Equipment B = Cost of Equipment A * (Capacity B/Capacity A)°'6

This equation was used to determine the various equipment costs and then the total

capital investments shown in Table 18.

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Table 18: Comparison of Production Capacity versus Total Capital Investment

Capacity (xM# M80) Total Capital lnv.

1 0.506
10 1.99
100 7.87

1000 31.11

Table 19 shows the change in manufacturing cost versus the production capacity.

Table 19: Comparison of Production Capacity versus Manufacturing Cost

Capacity (xM# MSO) Mani. Cost

1 2.17
10 5.24
100 48.8
1000 462.7

From tables 17-19 the comparisons show that at a capacity of ten million pounds
per year, a sizable reduction in the selling price of the products can be achieved with a
moderate increase in both the total capital investment and manufacturing cost. From the
ten million pounds per year capacity, significant increases in total capital investment and
manufacturing costs would only result in a small decrease in the product selling price.
Therefore, ten million pounds per year production facility would be the optimum size
given the limited knowledge of market share displacement and availability of capital

investment.

91

CHAPTER 7

 

CONCLUSIONS AND RECOMMENDATIONS

 

7.1 Conclusions

The proposed continuous process offers a more economical route for maleated
soybean oil and ester products over the alternative batch process. The continuous process
was found to have a selling price (15% ROI) of maleated soybean oil and ester of $0.61
and $0.71 per pound compared to $0.75 and $0.89 for the batch process, respectively. A
discounted cash flow of the continuous and batch process designs (at a selling price of
maleated soy oil of $ 0.6 per pound and $ 0.8 per pound for the ester) revealed an internal

rate of return of 53% and 7%, respectively.

The continuous process offers a number of important advantages for soybean oil.

0 The process will add value to soybean oil, thus improving the soybean market for
American farmers.

- The addition of maleic anhydride to soybean oil is a low temperature reaction thus
reducing oil oxidation problems and the need for exotic equipment design in a large
scale process.

0 The maleation process is less hazardous and energy intensive then the current process
for the production of epoxidized soybean oil.

0 The process is continuous, thereby minimizing processing time while maximizing

process reliability.

92

o The proposed process automation will require a minimum of operator control and
judgment.

0 The new low-cost process can be retrofitted in an existing production facility.

The maleated soybean oil ester was found to have a good plasticization capability
for poly vinyl chloride. The attractive selling price coupled with its non-toxic and low
ability to leach will make maleated soybean oil ester very competitive with dioctyl
phthalate. Though the price of dioctyl phthalate is lower than maleated soybean oil ester,
dioctyl phthalate is considered toxic and can leach under various conditions. The selling
price of maleated soybean oil ester could be further reduced if used equipment rather then
new equipment could be purchased. Therefore, a small displacement of dioctyl
phthalate’s market (estimated at 1.0 x 109 metric tons per year) could generate a terrific

opportunity for maleated soybean oil esters.

7.2 Recommendations

Further research should incorporate three thrusts of optimizing the soybean
oil/maleic anhydride reaction, developing coating formulations suitable for industrial
applications, and suitability of maleated soy oil ester as a resin plasticizer. Closely
integrating these thrusts will facilitate more rapid progress and a better overall
understanding of the commercialization potential of modified soybean oil. The specific

objectives of further research:

93

 

(1) Design, fabricate, and operate a pilot scale plant to produce maleated

soybean oil and ester at optimum conversion for extended periods of time.

(2) Develop in detail the continuous modification of soybean oil by maleic

anhydride and ester maleate.

(3) Esterify maleated soybean oil with an alcohol to produce a novel
plasticizer

(4) Formulate modified soybean oil coating materials.

(5) Characterize reaction with maleic anhydride, soybean oil, and
peroxide.

Details of the research to be conducted in pursuit of the above objectives follow in the

next section.

7.2.1 Task 1: Design, Fabrication, and Omration of a Pilot-Scale Production Line

The objectives of this task are to design, fabricate, and operate a pilot-scale
process to produce maleated soybean oil and ester. The maleated soybean oil and ester
pilot-process will be similar to Figures 22 and 23 for the plant design. The information
gathered from the pilot plant will allow for the optimization of unit operations and the
elimination of any process flow bottle necks. The data from the pilot plant would be vital

for process scale-up.

94

7.2.2 Task 2: Modification of soybean oil

The addition of maleic anhydride to soybean oil should be a continuous process.
Also to be tested would be the use of an ester maleate and catalyst to produce the
maleated ester directly. The optimization of reaction temperature, duration, and ratio of
maleic anhydride to soybean oil should be within the following ranges:

- Reaction temperature: 100°C ---150°C.

0 Reaction duration : 10 minutes to 1 hours.

0 Ratio of maleic anhydride/ soybean oil: 0.1/1.0 to 2.0/1.0.

Additional comparisons of vacuum operation, nitrogen purge, and addition of
oxidation inhibitors should be performed. The goal would be to produce high
functionality and low bulk viscosity, and reduce or eliminate oxidation of double bonds
in soybean oil during the modification. Results in thisthesis indicated that by increasing
the extent of maleation, the bulk viscosity of modified soybean oil increases. It is
possible that oxidative crosslinking of double bonds in soybean oil occurs during the

modification. Suitable inhibitors should be added to prevent oxidation of double bonds.

Characterization of the modified soybean oil should include the determination of
acid value (carboxyl group content), acid anhydride content, bulk viscosity, iodine value,
percent unreacted maleic anhydride, molecular weight and molecular weight distribution

of modified and unmodified soybean, and FTIR and NMR spectroscopy.

95

7.2.3 Task 3: Esterification of maleated soybean oil

The maleated soybean oil should be modified using an alcohol that would produce
the best plasticization capability of the resulting ester. Plasticization should be
determined using a differential scanning calorimeter (ASTM # D3418-82) to scan
various concentrations of the ester in poly vinyl chloride. Reaction temperature, duration,
and ratio of alcohol and water to maleated soybean oil should be optimized within the
following ranges:

0 reaction temperature: 200°C ---300°C.

0 reaction duration : 1 minutes to 3 hours.

0 ratio of alcohol and water/maleic content in the maleated soybean oil: 0.5/1.0

to 2.5/1.0.

Additional comparisons of vacuum operation, nitrogen purge, and addition of
oxidation inhibitors should be performed. The goal would be to produce high
esterification at high alcohol conversion and reduce or eliminate oxidation of double

bonds in soybean oil during the modification.
Characterization of the modified soybean oil should include the determination of

acid value (carboxyl group content), acid anhydride content, bulk viscosity, iodine value,

percent unreacted alcohol, and FTIR and NMR spectroscopy.

96

The production of maleated soybean oil ester should allow for the evaluation of

the product in end-user trials as a resin plasticizer.

7.2.4 Task 4: Formulation of modified Soybean oil coating materials

In order to demonstrate the commercial applicability of modified soybean oil,
some preliminary coating formulations should be created. Various curing agents,
catalysts, and polymers containing reactive groups, such as epoxy, amino, amide, thiol,
hydroxyl, and chlorosulfonic, could be used to form multi-component, multi-phase,
interpenetrating polymer networks (IPN's). Optimization of formulation and curing

profile must be determined.

When formulations are determined, extrusion and calendering experiments would

need to be conducted to determine processing conditions for commercial development.

7.2.5 Task 5: The Peroxide Reaction of Soybean Oil

Experiments should be conducted to fully characterize the reaction of soybean oil
and maleic anhydride with the use of a peroxide. The complex chemistry of this system
was not fully investigated due to the goals and objectives of this work. The proposed
method was chosen on the merit of the chemisdy and the good fit of the data.

The reaction should be investigated with electron spin resonance (ESR) and the

products fully analyzed by high pressure liquid chromotography (HPLC).

97

CHAPTER 8

 

BIBLIOGRAPHY

 

[1] Kirk - 0thmer, “Soybeans and Other Oilseeds”, Encyclopgdia of Chemical
Technology, p. 422, (1983)

[2] Kirk - Othmer, “Vinyl Polymers (PVC)”, Encyclopedia of Chemical Technology, p.
886, (1983)

[3] Root, F.B., 1945, US. Patent # 2374381.
[4] Morrel RS. and Samuels H. (1932), J. Chem. Soc. 2251
[5] Bevan EA. and Tervet J .R. (1939) Brit. Pat. 500348-51

[6] Clocker, 13.1., (1940) US. Patent # 2188882

[7] Bickford W.G., Fisher G.S., Kyame L. and Swift CE. (1948) J. Amer. Oil Chem.
Soc. 25, 254.

[8] Teeter H.M., Geerts M.J., and Cowan J .C. (1948) J. Amer. Oil Chem. Soc. 25, 158.

[9] Kappelmeier CPA. and Van Der Neut J .A. (1950) Paint Oil Chem. Rev. 113 (81),
11.

[10] Plimmer H. and Robinson EB. (1944) Brit. Pat. 565432.

[11] Flett L.H., Gardner W.H. and Terrill KL (1953) Paint and Varnish Production, 43,
40.

[12] Peters, MS. and Tirnmerhaus, K.D., Plant Desigg and Economics for Chemical
Engineers, Fourth Edition, McGraw-Hill, Inc., 1991.

[13] Chemical Marketing Reporter, Schnell Publishing Comp., January 20, 1997, pg 25
Volume 251, Number 3.

[14] Chemical Engineering, McGraw-Hill, “Marshall and Swift Index”, pg 162, January
1997.

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