0% found this document useful (1 vote)
250 views119 pages

Complete Report On Formation of Poly Lac PDF

Uploaded by

Madhukar Scribd
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
0% found this document useful (1 vote)
250 views119 pages

Complete Report On Formation of Poly Lac PDF

Uploaded by

Madhukar Scribd
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 119

―(1000 TPD Production Of PLA (Polylactic Acid)‖

(Final Project Report)

Session: 2009-2013

Project Advisor:

Engr. Zia-ul-Haq

Zaheer Abbas 2009-UET-IEFR-CHEM-FD-56

Qamar Abbaas* 2009-UET-IEFR-CHEM-FD-74*

Muazzam Khalil 2009-UET-IEFR-CHEM-FD-94

M Raza Bahadur 2009-UET-IEFR-CHEM-FD-96

Imtiaz Alam 2009-UET-IEFR-CHEM-FD-106

DEPARTMENT OF CHEMICAL ENGINEERING

NFC INSTITUTE OF ENGINEERING & FERTILIZER

RESEARCH, FAISALABAD, PAKISTAN.

2013

i
Acknowledgements

All praises to ALMIGHTY ALLAH, who provided us with the strength to accomplish the final
year project. All respects are for His HOLY PROPHET (PBUH), whose teachings are true
source of knowledge & guidance for whole mankind.

Before anybody else we thank our Parents who have always been a source of moral support and
driving force behind whatever we do. We are indebted to our project advisor Engr. Zia -UL-Haq
for his worthy discussions, encouragement, inspiring guidance, remarkable suggestions, keen
interest, constructive criticism & friendly discussions which enabled us to complete this report.
He spared a lot of his precious time in advising & helping us in writing this report. Without his
painstaking tuition, kind patronization, sincere coaching and continuous consultation, we would
not have been able to complete this arduous task successfully.
We surely want to thanks our parents, who always kept us away from the darks and shades of
life. We simply do not have words to portray our gratitude, respect and honor for their affection,
care and love.
Lastly, we cannot forget our colleagues and friends whose perceptual and magnificent devotion,
courage us to achieve this landmark.

ii
ABSTRACT
Up to now, the industrial synthesis of polylactic acid (PLA) in North America
relies essentially on the production of corn, which is a renewable resource. However, problems
such as overexploitation of fertile soils, the increase of cereal price and the abusive use of
chemical fertilizers, have been raised for this crop production, especially for its non-food
utilization. Agri-food wastes show a promising alternative with their rich carbohydrate content,
relatively stable composition and availability. Therefore, they represent an appealing waste
valorization target for an eventual PLA production. Potato wastewater is one of these. During the
slicing process in potato transformation, water is used to remove the excess of starch. Starch can
be recovered from water after proper centrifugations.
The first chapter provides basic
introduction including different properties and uses of the Lactic Acid, Lactide And poly Lactic
Acid, while the design Process Discription & Flow Sheet are given in chapter 2. Chapter 3
provides Plant Location, while the material balance on the equipments used & energy balance
on every equipment is given in chapter 4 & 5 Respectively. Chapter 6 explains the designing of
each equipment with proper procedure adopted and chapter & 7 describes Instrumentation &
Process Control. The Cost estimation for plant operation is evaluated in the chapter 8 and the
Hazop Study is given in the chapter 9. Appendix Is given In Chapter 10 & References Are
mentioned in Chapter 11.
Authors
Qamar Abbaaas
Zaheer Abbas
Muazzam Khalil
Hafiz Raza Bahadur
Imtiaz Alam

iii
Table of Contents
1. Introduction .......................................................................................................................................... 1
1.1. INTRODUCTION Of PLA ..................................................................................................................... 1
1.2. LACTIC ACID....................................................................................................................................... 2
1.2.1. History of Lactic Acid..................................................................................................................... 2
1.2.2. Physical Properties of Lactic Acid.................................................................................................. 3
1.2.3. Chemistry of Lactic Acid ................................................................................................................ 3
1.3. The Microbes .................................................................................................................................... 4
1.3.1. Stereochemical Purity ................................................................................................................... 4
1.4. Nutrients ........................................................................................................................................... 5
1.5. Starch ................................................................................................................................................ 5
1.6. Batch versus Continuous Fermentation............................................................................................ 5
1.7. Purification Methods for Lactic Acid ................................................................................................. 6
Extraction ...................................................................................................................................................... 6
1.8. Quality/Specifications of Lactic Acid ................................................................................................. 7
1.9. LACTIDE ............................................................................................................................................. 8
1.9.1. Physical Properties of Lactide ....................................................................................................... 8
1.9.2. Temperature ................................................................................................................................. 8
1.9.3. Pressure ........................................................................................................................................ 8
1.9.4. Feed DP ......................................................................................................................................... 8
1.9.5. Catalyst Concentration.................................................................................................................. 9
1.9.6. Racemization ................................................................................................................................. 9
1.10. Impurities ...................................................................................................................................... 9
2. Process Discription .............................................................................................................................. 10
2.1. Lactic Acid From Potato Waste Starch: ........................................................................................... 10
2.2. Concentration of waste starch in potato wastewater to 13% of humidity ................................ 10
2.2.1. Hydro Cyclones: .......................................................................................................................... 10
2.2.2. Vacum Drum ............................................................................................................................... 11
2.3. Fermentor ....................................................................................................................................... 11
2.4. Process Flow Sheet ......................................................................................................................... 12
2.5. Acidification Uuit............................................................................................................................. 13
2.6. Lactic Acid Distillation ..................................................................................................................... 14

iv
2.7. Prepolymerization ........................................................................................................................... 14
2.8. Lactide Reactor ............................................................................................................................... 15
2.9. Lactide Fash Distillation .................................................................................................................. 16
2.10. Polymer Reactor.......................................................................................................................... 16
3. PLANT LOCATION ................................................................................................................................ 17
3.1. Factors Affecting The Selection Of A Plant Site: ............................................................................ 17
3.1.1. Raw Materials Availability:.......................................................................................................... 17
3.1.2. Markets: ...................................................................................................................................... 18
3.1.3. Energy Availability. ...................................................................................................................... 18
3.1.4. Climate: ....................................................................................................................................... 18
3.1.5. Transportation Facilities:. ........................................................................................................... 18
3.1.6. Water Supply:.............................................................................................................................. 19
3.1.7. Waste Disposal:........................................................................................................................... 19
3.1.8. Labor Supply:............................................................................................................................... 19
3.1.9. Taxation And Legal Restrictions .................................................................................................. 19
3.1.10. Site Characteristics:..................................................................................................................... 20
3.1.11. Flood And Fire Protection: .......................................................................................................... 20
3.1.12. Community factors: .................................................................................................................... 20
3.2. Selection of the Plant Site ............................................................................................................... 20
3.3. Potato In Pakistan ........................................................................................................................... 21
3.4. EXISTING INFRASTRUCTURE............................................................................................................ 21
3.5. OPPORTUNITIES IN POTATO PROCESSING FARMING/PROCESSING ............................................... 21
3.6. Business Economics ........................................................................................................................ 22
4. Mass Balance ...................................................................................................................................... 23
4.1. Overall Material Balance ............................................................................................................... 35
5. Energy Balance ................................................................................................................................... 36
5.1. Energy Balance on Dryer ................................................................................................................ 36
5.2. Energy Balance on Fermenter ......................................................................................................... 38
5.3. Energy Balance on Acidification Unit ............................................................................................ 39
5.4. Energy Balance on Triple Effect Evaporator .................................................................................. 40
5.5. Energy Balance On Prepolymer Reactor ........................................................................................ 42
5.6. Energy Balance On Lactide Reactor .............................................................................................. 43

v
5.7. Energy Balance On Lactide Distillation ........................................................................................ 44
5.8. Energy Balance On Polymer Reactor ............................................................................................. 45
5.9. Energy Balance On Devolatilizer ................................................................................................... 45
6. Equipment Design ............................................................................................................................... 46
6.1. Hydrocyclone .................................................................................................................................. 46
6.2. Designing of Hydro cyclones .......................................................................................................... 47
6.3. Designing Of Falling Film Evaporator ........................................................................................... 48
6.4. Design of separator ......................................................................................................................... 52
6.5. Designing of Fermentor .................................................................................................................. 54
6.6. Designing Of Pre polymer Reactor ................................................................................................. 57
6.7. Designing Of Steam Coil ............................................................................................................... 60
6.8. Designing Of Flash Lactide Drum ................................................................................................ 62
6.9. Designing Of Polymer Reactor ....................................................................................................... 64
7. Instrumentation And Process Control ................................................................................................. 69
7.1. Process Variable.............................................................................................................................. 69
7.2. Setpoint ........................................................................................................................................... 70
7.3. Primary Elements/Sensors .............................................................................................................. 70
7.4. Signals ............................................................................................................................................. 70
7.4.1. Pneumatic Signals ....................................................................................................................... 71
7.4.2. Analog Signals ............................................................................................................................ 71
7.4.3. Digital Signals ............................................................................................................................. 71
8. Cost Estimation ................................................................................................................................... 72
9. HAZOP Study ..................................................................................................................................... 75
9.1. Introduction:.................................................................................................................................... 75
9.2. Objective ......................................................................................................................................... 76
9.3. Key Words ...................................................................................................................................... 76
9.3.1. Primary Key Words .................................................................................................................... 76
9.3.2. Secondary Key Words ................................................................................................................ 77
9.4. HAZOP Study Methodology: ......................................................................................................... 77
9.4.1. HAZOP Study Steps[117]........................................................................................................... 78
9.5. Hazop Study On Flash Column ...................................................................................................... 82
9.6. Hazop Sheet OF Flash Column[4] ................................................................................................. 85

vi
9.7. Hazop Study Of Heat Exchanger .................................................................................................... 86
10. Appendix A ................................................................................................................................ 87
10.1. Appendix B ................................................................................................................................. 94
10.2. Appendix C ................................................................................................................................. 99
10.3. Appendix D ............................................................................................................................... 102
11. REFERENCES ............................................................................................................................. 109

vii
Chapter No 1
Introduction
1. Introduction
History
Poly(lactic acid) (PLA) cannot be considered as a new polymer. As early as 1845, PLA
was synthesized by Th_eophile-Jules Pelouze by the condensation of lactic acid [1”]. In 1932,
Wallace Hume Carothers et al. Developed a method to polymerize lactide to produce PLA that
was later patented by dupont in 1954 [2”]. Although PLA existed for several decades, its use was
limited to biomedical applications (e.g., biocompatible sutures, implants, biologically active
controlled release devices) due to its high cost. The lowmolecular weight PLA polymers
obtained also hampered their wide-ranging applications. The breakthrough occurred in the early
1990s when Cargill Inc. Succeeded in polymerizinghigh molecular weight PLA using a
commercially aviable lactide ring opening reaction [3, 4].
Year Vs Number Of Works Appendix A (Fig 1)

1.1. INTRODUCTION Of PLA


Natural polymers, biopolymers, and synthetic polymers based on annually
renewable resources are the basis for the twenty-first-century portfolio of sustainable, eco-
efficient plastics [1]. These biosourced materials will gradually replace The currently existing
family of oil-based polymers as they become cost- and performance-wise competitive.
Polylactide or poly(lactic acid) (PLA) is the front runner in the emerging bioplastics market with
the best availability and the most attractive cost structure. The production of the aliphatic
polyester from lactic acid, a naturally occurring acid and bulk produced food additive, is
relatively straightforward. PLA is a thermoplastic material with rigidity and clarity similar to
Polystyrene (PS) or poly(ethylene terephthalate) (PET). End uses of PLA are in rigid packaging,
flexible film packaging, cold drink cups, cutlery, apparel and staple fiber, bottles, molded
products, extrusion coating, and so on [2]. PLA is bio-based, resorbable, and biodegradable
under industrial composting conditions [1, 3, 4]. PLA can be produced by condensation
polymerization directly from its basic building block lactic acid, which is derived by
fermentation of sugars from carbohydrate sources such as corn, sugarcane, or tapioca, as will be
discussed later in this chapter. Most commercial routes, however, utilize the more efficient
conversion of lactide—the cyclic dimer of lactic acid—to PLA via ring-opening polymerization
(ROP) catalyzed by a Sn(II)-based catalyst rather than polycondensation [2–6]. Both
polymerization concepts rely on highly concentrated polymer-grade lactic acid of excellent

1
Chapter No 1 Introduction

quality for the production of high molecular weight polymers in high yield [2–4, 7]. Purification
of lactic acid produced by industrial bacterial fermentation is therefore of decisive importance
because crude lactic acid contains many impurities such as acids, alcohols, esters, metals, and
traces of sugars and nutrients . The lactide monomer for PLA is obtained from catalytic
depolymerization of short PLA chains under reduced pressure . This prepolymer is produced by
dehydration and polycondensation of lactic acid under vacuum at high temperature. After
purification, lactide is used for the production of PLA and lactide copolymers by ROP, which is
conducted in bulk at temperatures above the melting point of the lactides and below temperatures
that cause degradation of the formed PLA [4]. Processing, crystallization, and degradation
behavior of PLA all depend on the structure and composition of the polymer chains, in particular
the ratio of the L- to the D-isomer of lactic acid [2, 4, 6, 8, 9]. This stereochemical structure of
PLA can be modified by copolymerization of mixtures of L-lactide and meso-, D-, or rac-lactide
resulting in high molecular weight amorphous or semicrystalline polymers with a melting point
in the range from 130 to 1850C [3, 4, 6–10]. Isotactic PLLA homopolymer—comprising L-
lactide only—is a semicrystalline material with the highest melting point, while PLA copolymers
with higher D-isomer content exhibit lower melting points and dramatically slower
crystallization behavior, until they finally become amorphous atd-contents higher than 12–15%
[8–10]. For decades, ROP has been the preferred route to PLA for biomedical applications with
small production volumes. PLLA and copolymers with rac-lactide, glycolide, and ecaprolactone
for resorbable biomedical applications have been produced by, for example, PURAC, previously
known as CCA, since the 1970s [5]. Since the 1990s, the ROP Concept is also used for high-
volume production of PLA grades for other end uses. Large-scale production of PLA,
copolymers of L- and meso-lactide, was started in 2002 by a joint venture of Cargill and Dow
under the name natureworks LLC. Nowadays, July 1, 2009, natureworks LLC is again wholly
owned by Cargill and has a production capacity of 140 ktpa for its Ingeo PLA grades in Blair,
Nebraska [11].

1.2. LACTIC ACID

1.2.1. History of Lactic Acid


Lactic acid was discovered in 1780 by the
experimental Chemist Carl Wilhelm Scheele, who isolated ‗‗acid of milk‘‘ from sour whey [12,
13]. A further description of the history of lactic acid by Holten and Benninga shows that
industrial production of lactic acid started in the United States in the 1880s [14, 15]. Avery
patented and applied a process of fermentation of vegetable sugars [16]. The actual application
was the use of a mixture of calcium lactate and lactic acid as baking powder. Unfortunately, this
application was not a big success, but other applications in food and textile dyeing were
developed.

2
Chapter No 1 Introduction

In 1950, the first commercial production of synthetic lactic acid started in Japan [15].
Lactonitrile was produced from acetaldehyde and hydrogen cyanide and hydrolyzed in the
second stage to lactic acid. For some decades, synthetic lactic acid competed with lactic acid
obtained by fermentation, but currently almost all lactic acid is produced by fermentation.

1.2.2. Physical Properties of Lactic Acid


Lactic acid (2-hydroxypropanoic acid) is the simplest 2-
hydroxycarboxylic acid (or a-hydroxy acid) with a chiral carbon atom and exists in two
enantiomeric forms (Figure 1.1). The chirality of lactic acid often results in confusion regarding
nomenclature. A number of different names are used in the literature. This confusion is the result
of mixing the molecular structure and a physical property (optical rotation). (S)-Lactic acid (or
L-lactic acid) has a slightly positive specific optical rotation and is frequently named L-(þ)-lactic
acid [14]. However, a concentrated solution of (S)-lactic acid at equilibrium contains lactic acid
oligomers, which results in an overall negative optical rotation. Therefore, it is advised to use the
structural R/S notation or the older notation of L and D and avoid the þ and_of the optical
rotation .

1.2.3. Chemistry of Lactic Acid


The lactic acid molecule has a hydroxyl and an acid functional
group, which may result in intermolecular and intramolecular esterification reactions. The first
step is the formation of a linear dimer (lactoyl lactic acid). This condensation Reaction can
proceed to higher oligomers and is promoted by removal of water. Also a cyclic dimer, lactide, is
formed in small amounts. Lactide can be formed by intramolecular esterification of lactoyl lactic
acid or by breakdown of higher oligomers. All reactions are equilibrium reactions (Figure 1.2).
Due to these reactions, a solution of lactic acid at equilibrium consists of monomeric lactic acid,
dimeric lactic acid or lactoyl lactic acid, higher oligomers of lactic acid, and lactide. The ratios
between all substances depend on the amount of water present; for example, a 90.1% lactic acid
solution (total acidity) contains about 59.3% of monomeric lactic acid and 27.3% of lactoyl lactic
acid and higher Oligomers [14].

3
Chapter No 1 Introduction

Physical Properties at Appendix B (Table 1)


The condensation reactions are also the reason that it is quite difficult to obtain pure, solid, and
enantiopure lactic acid. This can only be achieved by crystallization [27, 28]. The kinetics of the
condensation reactions determine the stability of a solution of monomeric lactic acid and have a
large influence on the stability of solid lactic acid.

1.3. The Microbes


There are several important features a microorganism used for the production
of lactic acid must have in order to be industrially attractive:
 High productivity to reduce fermentation time.
 High conversion yield to reduce carbohydrate costs.
 Ability to use cheap sources of nutrients to reduce nutrient costs.
 High end concentration to reduce evaporation costs.
 Low amount of by-products to increase purification yield, and, of course.
 The organisms must be robust with regard to contamination and infections.
Every microorganism has its own benefits and drawbacks, but lactobacilli (present in many food
fermentations) and Rhizopus (a fungus) are the most reported [40]. Besides lactobacilli and
Rhizopus, Streptococcus, Pediococcus, Sporolactobacillus inulinus, Bacillus coagulans, and
several yeasts are mentioned in the excellent overview by Vaidya Et al. [41]. Lactobacilli
generally have high productivity, but special and often expensive nutrient requirements.
Rhizopus needs much less nutrients, but has a lower yield, needs oxygen, and
Its morphology is sometimes difficult to handle. Of course, via genetic manipulation, researchers
have tried to make an ideal lactic acid producing microorganism.

1.3.1. Stereochemical Purity


In order to make semicrystalline, high-melting PLA, stereochemically pure
lactic acid is needed. Not all microorganisms yield such stereochemically pure lactic acid and
some even produce a racemic mixture [29]. Therefore, a strain must be chosen that meets the
quality demands. Finding such a strain that produces L-lactic acid in an economically feasible
manner is relatively easy. Producing D-lactic acid by bacterial fermentation on an industrial scale
is far more difficult. Several natural D-lactic acid producing bacterial species exist;
Sporolactobacillus inulinus, Sporolactobacillus laevolacticus (previously Bacillus laevolacticus),
and Lactobacillus delbrueckii are among these bacteria [29, 42, 43]. Also, patents have been filed
claiming the production of D-lactic acid by a genetically modified microorganism. Several
different species such as Kluyveromyces and Escherichia coli have been claimed so far [44, 45].

4
Chapter No 1 Introduction

1.4. Nutrients
The most well-known lactic acid producing organisms, such as Lactobacillus and
Lactococcus species, are members of the taxonomic order of Lactobacillales, also commonly
referred to as lactic acid bacteria. These lactic acid bacteria have their really complex nutrient
need in common [29]. Vitamins and peptides need to be added to the medium to enable growth.
This can be done by adding peptones, yeast extract, or corn steep liquor, but this is expensive.
Nutrients for lactic acid production can also be derived from nutrient-rich waste streams such as
rice bran, fish waste, or vinification lees [46–48].

1.5. Starch
Starch occurs in discrete granules and is usually a mixture of two homopolymers of
glucose, amylopectin and amylose. Starch can be derived from corn, wheat, potato, or tapioca
[54]. Although some microorganisms are able to degrade and ferment starch directly to lactic
acid, most lactic acid producing microorganisms cannot hydrolyze starch themselves. A solution
is to hydrolyze the starch to glucose prior to fermentation with the commercially available
enzymes, a-amylase and glucoamylase. This can be done in a separate process, so no
incompatibilities are present between the optimal ph and temperatures of the enzymes on one
hand and the optimal ph and temperature of the microbes on the other. However, if the right
combination of enzymes, microorganisms, ph, and temperature is carefully chosen, the
hydrolysis and fermentation can be carried out in one reactor. This process is generally called
SSF (simultaneous saccharification and fermentation) [55]. Prior to SSF, the starch granules
usually must be gelatinized at high temperature by cooking. However, even a cooker is optional
nowadays as commercial enzymes are becoming available that are able to attack and hydrolyze
the granules efficiently and fast enough at relatively low temperatures.

1.6. Batch versus Continuous Fermentation


A process can be run in batch or continuous
mode. In continuous mode, there is a constant flow of fermented sugar out of the reactor that is
equal to a continuous flow of fermentation medium into the reactor. During batch fermentation,
there can be an inflow of medium, but there is no outflow [58]. Batch fermentation needs to be
inoculated with a starter culture every time, whereas this is not needed in a continuous
fermentation setup. However, in case of problems, the continuous fermentation needs to be
restarted, so an infrastructure for starter cultures is needed anyway. A high volumetric
production rate can be achieved when combining continuous fermentation with biomass
retention, leading to smaller fermenter size [59]. It must be stated that the lactic acid Is lower
compared to batch culture [58]. The concentration of lactic acid influences the water balance in
the production plant. In all scenarios, microorganisms produce an aqueous lactic acid solution,
comprising mainly lactate and counterions from the base, impurities from raw materials or
fermentation by-products, residual sugars and polysaccharides, and the microorganism itself.

5
Chapter No 1 Introduction

1.7. Purification Methods for Lactic Acid


Crude lactic acid, which may be upgraded by
simple active carbon treatment and/or ion exchange to remove impurities and salts, can be
directly used in a large number of food applications. Traditionally, taste, smell, and heat stability
for color formation have been used to express lactic acid quality. The presence of acids (e.g.,
acetic acid and pyruvic acid), alcohols (e.g., methanol and ethanol), and esters can directly
influence taste and smell [4]. The presence of residual sugar and nitrogen compounds greatly
influences heated color, that is, browning of the liquid upon heating. The formation of color upon
heating prohibits the use of crude acid in foods that need to undergo pasteurization/sterilization.
Over the decades, the demand for purer lactic acid with improved color stability upon heating
has increased, as exemplified by the need for ultrapure lactic acid as a sodium lactate base in
pharmaceutical infusion products. At present, a chemical engineer can choose from a number of
mature industrial methods to purify lactic acid. Table 1.2 lists their relative advantages and
disadvantages. Choices in an overall process are governed by raw material costs, utility costs,
and, last but not least, outlets for by-products. The purification methods described above each
involve considerable technological know-how:
Esterification/Saponification
Esterification of lactic acid with methanol/ethanol yields systems
with good separation characteristics to separate many impurities with different boiling points
[60]. However, the energy demand of a full reaction/distillation route from crude acid to pure
acid is high.
Crystallization
Crystallization can yield an excellent lactic acid grade, but the yield is low.
Lactic Acid Distillation
Industrial equipment is available to distill lactic acid at low vacuum.
Higher molecular weight components such as sugar and protein will leave the system as a
residue. Heat-stable lactic acid is obtained as the top product. In the stages of dewatering the
crude lactic acid prior to distillation, the formation of oligomers will limit an overall high
distillation yield.

Extraction
An extraction/back-extraction process, for example, with the well-described tertiary
amine systems, is a suitable way to purify lactic acid [61, 62]. The possible combination of
extraction with low-ph fermentation yields an elegant concept to arrive at a gypsum-free process.
For future large-scale, low-cost lactide/PLA production, lactic acid DSP will need to meet new
challenges:
Use of Low-Cost and Nonedible Substrates
Whereas production of lactic acid from sucrose or
glucose syrup is well established, crude sources (starches, sugars, or future lignocellulose

6
Chapter No 1 Introduction

hydrolysates) will form the next hurdle as they contain much more impurities and possible
fermentation inhibitors.
Gypsum-Free Processing
For large-scale, sustainable PLA production, a fermentation process
that does not coproduce a mineral salt is a must.
Gypsum-Free Lactic Acid Production
Gypsum-free lactic acid production can be briefly
categorized as follows:
Low-pH
Fermentations Coupled to In Situ Product Removal. As discussed in Section 1.2.4,
fermentations can be carried out without neutralization at ph 2–3 with genetically modified yeast
or at ph 4 with LAB with partial neutralization [50]. When a separation method to recover the
undissociated acid is integrated with fermentation, a process route can be designed in which no
gypsum is produced. In the literature, a number of separation methods are described with an
emphasis on extraction [63]. Cost efficiency in the fermentation (e.g., nutrients, yield) and the
practical processing of large dilute streams need breakthroughs for economical processing.

1.8. Quality/Specifications of Lactic Acid


The dehydration of lactic acid to make the
prepolymer should start with an _OH to _COOH ratio of 1:1. All other components with _OH
and _COOH functionality disrupt the stoichiometric balance and may be incorporated as
comonomers during prepolymerization, which limits the final lactide production yield from lactic
acid. Little public information is available on the technical and economic relationship between
lactic acid quality and lactide synthesis. Only a few patents mention the effect of metal
impurities on racemization [68, 69]. Stereochemical purity is one of the key parameters
determining lactic acid purity. Lactic acid purified by crystallization may be taken as the
benchmark in lactide manufacture, but the expected unfavorable economics of making crystalline
acidin relation to mother liquor processing may prevent its commercial use for lactide/ PLA. The
next level of quality with the right commercial relevance is heat-stable lactic acid. Heat stability
puts constraints on the content of sugar, and thus on the DSP method used in the process. It is
unlikely that suitable acid for making lactide will contain sugar because of the high temperatures
involved (see the next section) and the well-known practical decompositionproblemswhensugars
are cracked. In practice, his means that color, or actually heated color (color after heating of the
acid), is an important indicator for the suitability of the acid for lactide/PLA production [6, 70].
The appeal for lactic acid with little or no sugar and the DSP method mentioned in practice lead
to demands for separation methods that are similar for sugar and other heavy components such as
proteins, amino acids, and polysaccharides. It is expected that the desired quality of lactic acid
for making lactide/PLA will evolve, with overall process yields and economics as the criteria.

7
Chapter No 1 Introduction

1.9. LACTIDE

1.9.1. Physical Properties of Lactide


The dehydrated, cyclic dimer of lactic acid is commonly called
lactide (3,6-dimethyl-1,4-dioxane-2,5-dione).

Due to the two asymmetric carbon atoms in the molecule, lactide exists in three different forms
(Figure 1.6). In addition to the three diastereomeric structures mentioned above, also a racemate
of D-lactide and L-lactide exists: rac-lactide or DL-lactide .
Physical Properties Of Lactide at Appendix B (Table 2)

1.9.2. Temperature
Intrinsic reaction rates increase with temperature. At higher temperature also, the
vapor pressure of lactide above the reaction mixtures increases. The reaction rate of racemization
will also increase with temperature. In Witzke‘s Ph.D. Study, information on activation energies
can be found [6].

1.9.3. Pressure
Pressures of 10 mbar or less are used. At higher pressures, the driving force for
lactide evaporation will be lower, and the overall reaction rate will be lower. Low pressures will
require detailed considerations of equipment size, vacuum systems, condensers, and so on.

1.9.4. Feed DP
The feed DP has two effects. First, a low DP feed will contain more monomer lactic
acid that boils at a lower temperature than lactide, and this will contaminate the crude lactide
distilled off from the reactor. Also, monomer lactic acid can be released from DP 3 with the
catalyst, leading to more acidity in the crude lactide. Second, it is to be expected that at a higher
feed DP .The residue in the reactor will have a higher DP and viscosity with consequences for

8
Chapter No 1 Introduction

equipment design. The influence of prepolymer DP on the meso-lactide level formed during
lactide synthesis was discussed by Gruber et al. [69]. Increasing feed DP clearly resulted in a
decrease in the lactic acid concentration in the crude lactide. A drawback is that the meso-lactide
concentration also increased significantly.

1.9.5. Catalyst Concentration


More catalyst will increase the overall reaction rate. In practice, this
effect may not be linear, since next to kinetics mass transfer in the equipment will play a role.

1.9.6. Racemization
In the production of stereochemically pure lactide, formation of the other lactic
acid enantiomerandmeso- lactide is unwanted. Higher temperatures, longer reaction times, and
increased catalyst levels result in increased rates of racemization [4, 6, 69]. Since temperature
and catalyst influence the rate of lactide formation as well, controlling the racemization rate can
become quite complex.

1.10. Impurities
Data in the literature on the role and fate of impurities from the feed in the synthesis
are scarce. Some metal cations such as sodium and potassiumin the feed increase racemization
risk, while other metals (Al, Fe) are catalytically active in transesterification, resulting in
competitive polylactide formation [68, 69]. Through corrosion, metals may be released in the
residue and will build up there [6, 75]. Some patents discuss the presence of acid impurities in
the process [6, 7, 67, 78]. Mono- and dicarboxylic fermentation acids are responsible for
stoichiometric imbalance in the lactic acid polycondensation reaction. Consequently, the
composition of the obtained lactic acid oligomer chains can differ from pure PLA, resulting in
impeded and incomplete catalytic depolymerization of the oligomers into lactide. In PLA
manufacture, degradation reactions play a role, mainly via intramolecular chain scission, and this
may also affect lactide synthesis. On the one hand, it can be concluded that the lactide synthesis
is straightforward in the sense of making a prepolymer and releasing lactide by thermal catalytic
depolymerization at low pressure. On the other hand, it can be concluded that the scale-up from a
lab-scale process to an economical, large-scale process with high yield and no compromises on
stereochemical purity is a complex multifaceted task.

9
Chapter No 2
Process Discription
2. Process Discription

2.1. Lactic Acid From Potato Waste Starch:


The major steps in the process of lactic acid production
from potato waste starch are presented
Below:
1. Concentration of starch in potato wastewater to 13% of humidity;
2. Fermentation of potato waste starch media with L. Amylophilus;
3. Lactic acid purification.

2.2. Concentration of waste starch in potato wastewater to 13%


of humidity
First, starch waste water and grinded rejected potatoes pass
through a vibrating screen for the recuperation of bigger solid residues. Those residues may be
pieces of peel or potato flesh and are given to farmers for animal alimentation. The starch
solution ends up in a residence tank (―Tank 1‖ in Flow Sheet) after which it is centrifuged
through hydro cyclones.

2.2.1. Hydro Cyclones:


― A hydro cyclone is a static device that applies centrifugal force to a liquid
mixture so as to promote the separation of heavy and light components‖.
A hydro cyclone often referred to in the shortened form cyclone is a device to classify, separate
or sort particles in a liquid suspension based on the ratio of their centripetal force to fluid
resistance

10
Chapter No2 process Discription

2.2.2. Vacum Drum


The solid phase, the starch residue, is conducted to a vacuum drum, while the
liquid is redirected to another residence tank (see ―Tank 2‖ in Flow Sheet). To optimize starch
recovery efficiency, this liquid is centrifuged a second time. The centrifuged liquid will end up in
a drain, to be treated by the Waste water treatment facility. A vacuum drum will lower the water
content of starch residue around 40%. To reach a lower moisture content, starch is transferred to
an Fallimg Film Evaporator from which the moisture content is reduced to at least 13%, the
aimed set value. This level of humidity enables a sufficient conservation of the product.

2.3. Fermentor
The fermentation of starch media The medium (water, starch residue and nutrients) is initially
fed to the fermentor. As mentioned before, due to its compact form and its insolubility at ambient
temperature, starch has to be gelatinized to improve its hydrolysis rate. This step is realized
directly in the fermentor, with a proper agitation to maintain starch dispersion. Steam and water
are respectively fed to the jacket/coil of the fermentor for heating to 90ºC, and then to cool the
media to 37ºC, the set fermentation temperature. Fermentations are realized in a batch mode and
are inoculated with a preculture of L. amylophilus (inoculum). The culture medium is maintained
at 37°C with the help of water through the jacket/coils of the fermentor. The pH is maintained at
6 with calcium hydroxide. Starch is saccharified into dextrose, and dextrose is assimilated by
bacteria to produce biomass and lactic acid. At pH 6, lactic acid is essentially all under its
dissociated form (Carlson, et al., 2002). For the sake of simplification, it will be considered that
100% of lactic acid was under the calcium lactate form.

Microfiltration is used to remove Biomass Produced in the Fermentor

11
Chapter No2 process Discription

2.4. Process Flow Sheet

12
Chapter No2 process Discription

The purification of lactic acid

2.5. Acidification Uuit


The purification steps are based on Vink et al. (2007). Lactic acid is
purified by the dissociation of calcium lactate with sulfuric acid, which leads to the formation of
gypsum (calcium sulphate; CaSO4), following the reaction shown in the equation below:

Even if some new methods are being developed to reduce the production of waste like gypsum,
this purification method is presented in NatureWorks and Purac last published flowsheet (Purac,
2009; Vink, et al., 2007). For this reason, the basic purification process with sulfuric acid, which
might has been improved in the industry by solvent addition (Joglekar, et al., 2006), was chosen.
The four major steps of the purification process are:
 Removal of biomass through microfiltration;(After Fermentor)
 Precipitation of gypsum to dissociate lactic acid from calcium, with the help of sulfuric
acid; (After Acidification Unit)
 Removal of gypsum with a rotary filter;
 Removal of water by a multi-effect evaporator, to lead to a 88 wt% lactic acid solution,
neglecting final impurities. The final concentration of lactic acid is based on USP/FCC
grade (United States Pharmacopeial/Food Chemical Codex) (González, et al., 2007).
The purification steps follow well-known heuristics (“rules of thumb”) in bioseparation
processes, taken from Bioseparations Science and Engineering (2003), chapter 11:
 Remove the most plentiful impurities first;
 Remove the easiest-to-remove impurities first;
 Make the most difficult and expensive separations last;
 Select processes that make use of the greatest differences in the properties of the product
and its impurities.
In accordance with the first two heuristics presented and to limit fouling of units, it has been
decided that biomass would be removed by microfiltration, prior to acidification. The
microfiltration is preferred to centrifugation in the industry, due to its low operational cost
(Arcand, 2010). Following the acidification step, gypsum is removed by rotary filtration, as
suggested by NatureWorks (Vink, et al., 2007). Other insoluble parts may be removed by the
filtration units. Concentration of lactic acid follows. Since high quantity of water has to be
removed, it is expected that multi-effect evaporators are used in the industry (Bohlmann, 2004).
The evaporator will be assumed as having 3 effects. Final purification, to remove trace of water
and soluble contaminants, such as proteins and sugars, follows.
Summary Of Polymerization

13
Chapter No2 process Discription

Inthe first step, water is removed in a continuous condensation reaction of aqueous lactic acid to
produce low molecular- weight prepolymer. Next, the prepolymer is catalytically converted into
the cyclic dimer, lactide. The molten lactide mixture is then purified by distillation. Finally,
highmolecular- weight PLA polymer is produced using a ring-opening lactide polymerization.
NatureWorks process does not use solvents. After the polymerization is complete, any remaining
lactide monomer is removed and recycled within the process.

2.6. Lactic Acid Distillation


Industrial equipment is available to distill lactic acid at low vacuum.
Higher molecular weight components such as sugar and protein will leave the system as a
residue. Heat-stable lactic acid is obtained as the top product. In the stages of dewatering the
crude lactic acid prior to distillation, the formation of oligomers will limit an overall high
distillation yield.

2.7. Prepolymerization
It is known that lactic acid undergoes a condensation reaction to
form polylactic acid when water is removed by evaporation or other means. The overall
polymerization reaction is represented by:

While step n of said polymerization reaction is represented by:

14
Chapter No2 process Discription

2.8. Lactide Reactor


As Dorough (U.S. Patent No. 1,995,970) recognized and disclosed, the
resulting polylactic acid is limited to a low molecular weight polymer of limited value, based on
physical properties, due to a competing depolymerization reaction in which the cyclic dimer of
lactic acid, lactide, is generated. As the polylactic acid chain lengthens, the polymerization
reaction rate decelerates until it reaches the rate of the depolymerization reaction, which
effectively, limits the molecular weight of the resulting polymers. An example of this
equilibrium reaction is represented below.

Given this understanding, Dorough was convinced that high molecular weight polymers could
not be generated directly from lactic acid. He was, however, successful in generating high
molecular weight polymers from lactide, through the lactic acid dimer generated from the low
molecular weight polymers of lactic acid. Because these polymers are generated from lactide,
they are known as polylactides. It is well known that lactic acid exists in two forms which are
optical enantiomers, designated as D-lactic acid and L-lactic acid. Either D-lactic acid, L-lactic
acid or mixtures thereof may be polymerized to form an intermediate molecular weight
polylactic acid which, upon further polymerization, generates lactide as earlier disclosed. The
lactide, or the cyclic dimer of lactic acid, may have one of three types of optical activity
depending on whether it consists of two L-lactic acid molecules, two D-lactic acid molecules or
an L-lactic acid molecule and a D-lactic acid molecule combined to form the dimer. These three
dimers are designated L-lactide, D-lactide and meso-lactide, respectively. In addition, a 50/50

15
Chapter No2 process Discription

mixture of L-lactide and D-lactide with a melting point of about 126°C is often referred to in the
literature as D,L-lactide.

2.9. Lactide Fash Distillation


After Lactide Formatin 6 % water is evaporated from the lactide
because 98.2 % Lactide Is requires For The Ring opening Polymerization.

2.10. Polymer Reactor


Polymerization The theoretical description of the Sn(Oct)2-catalyzed ROP of
cyclic esters has been studied by many authors, but there does not appear to be a theory that
consistently explains all experimental results of the coordination–Insertion polymerization [3, 4,
82–84]. Different polymerization mechanisms may dominate, depending on polymerization
conditions, catalyst and initiator concentration, and the presence of a solvent. Here it is assumed
that lactide is polymerized in bulk with Sn(Oct)2—a Lewis acid—and that the mechanism
follows the model proposed by Kowalski et al. [84]. Since lactide is a cyclic ester, its ring can be
opened by nucleophilic attack on the ester bond to start polymerization. Suitable initiators
(nucleophiles) are water and alcohols, including the hydroxyl group of lactic acid. One ester
linkage of a lactide ring is cleaved by reaction of the OH group of the initiator R-OH, creating a
new R-O-C(O)- ester end group and an OH end group (Figure 1.8).
Every initiating molecule is covalently bonded as an end group to each polymer chain [84]. Via
transesterification

Devolatilizer Condenses unreacted Prepolymer And they Are Recycled Back Into The Lactide
reactor.It Is superheated and crystals of PLA are added which causes crystal formation and By
Drying 98.2 % PLA Pallets Are Obtained.

16
Chapter No 3
Plant Location
3. PLANT LOCATION
The geographical location of the final plant can have
strong influence on the success of an industrial venture. Considerable care must be exercised in
selecting the plant site, and many different factors must be considered. Primarily, the plant
should be located where the minimum cost of production and distribution can be obtained, but
other factors, such as room for expansion and safe living conditions for plant operation as well as
the surrounding community, are also important.

3.1. Factors Affecting The Selection Of A Plant Site:


1) Raw materials availability
2) Markets
3) Energy availability
4) Climate
5) Transportation facilities
6) Water supply
7) Waste disposal
8) Labor supply
9) Taxation and legal restrictions
10) Site characteristics
11) Flood and fire protection .
12) Community factors
The factors that must be evaluated in a plant-location study indicate the need for a vast amount
of information, both quantitative (statistical) and qualitative.

3.1.1. Raw Materials Availability:


The source of raw materials is one of the most important factors
influencing the selection of a plant site. This is particularly true if large volumes of raw materials
are consumed, because location near the raw-materials source permits considerable reduction in
transportation and storage charges. Attention should be given to the purchased price of the raw
materials, distance from the source of supply, freight or transportation expenses, availability and
reliability of supply, purity of the raw materials, and storage requirements.

17
Chapter No 3 Plant Location

3.1.2. Markets:
The location of markets or intermediate distribution centers affects the cost of product
distribution and the time required for shipping. Proximity to the major markets is an important
consideration in the selection of a plant site, because the buyer usually finds it advantageous to
purchase from nearby sources. It should be noted that markets are needed for by-products as well
as for major final products.

3.1.3. Energy Availability.


Power and steam requirements are high in most industrial plants, and fuel
is ordinarily required to supply these utilities. Consequently, power and fuel can be combined as
one major factor in the choice of a plant site. Electrolytic processes require a cheap source of
electricity, and plants using electrolytic processes are often located near large hydroelectric
installations. If the plant requires large quantities of coal or oil, location near a source of fuel
supply may be essential for economic operation. The local cost of power can help determine
whether power should be purchased or self-generated.

3.1.4. Climate:
If the plant is located in a cold climate, costs may be increased by the necessity for
construction of protective shelters around the process equipment, and special cooling towers or
air-conditioning equipment may be required if the prevailing temperatures are high. Excessive
humidity or extremes of hot or cold weather can have a serious effect on the economic operation
of a plant, and these factors should be examined when selecting a plant site.

3.1.5. Transportation Facilities:.


Water, railroads, and highways are the common means of transportation
used by major industrial concerns. The kind and amount of products and raw materials determine
the most suitable type of transportation facilities. In any case, careful attention should be given to
local freight rates and existing railroad lines. The proximity to railroad centers and the possibility
of canal, river, lake, or ocean transport must be considered: Motor trucking facilities are widely
used and can serve as a useful supplement to rail and water facilities. If possible, the plant site
should have access to all three types of transportation, and, certainly, at least two types should be
available. There is usually need for convenient air and rail transportation facilities between the
plant and the main company headquarters, and effective transportation facilities for the plant
personnel are necessary.

18
Chapter No 3 Plant Location

3.1.6. Water Supply:


The process industries use large quantities of water for cooling, washing, steam
generation, and as a raw material. The plant, therefore, must be located where a dependable
supply of water is available. A large river or lake is preferable, although deep wells or artesian
wells may be satisfactory if the amount of water required is not too great. The level of the
existing water table can be checked by consulting the state geological survey, and information on
the constancy of the water table and the year-round capacity of local rivers or lakes should be
obtained. If the water supply shows seasonal fluctuations, it may be desirable to construct a
reservoir or to drill several standby wells. The temperature, mineral content, silt or sand content,
bacteriological content, and cost for supply and purification treatment must also be considered
when choosing a water supply.

3.1.7. Waste Disposal:


In recent years, many legal restrictions have been placed on the methods for
disposing of waste materials from the process industries. The site selected for a plant should have
adequate capacity and facilities for correct waste disposal. Even though a given area has minimal
restrictions on pollution, it should not be assumed that this condition will continue to exist. In
choosing a plant site, the permissible tolerance levels for various methods of waste disposal
should be considered carefully, and attention should be given to potential requirements for
additional waste-treatment facilities.

3.1.8. Labor Supply:


The type and supply of labor available in the vicinity of a proposed plant site must
be examined. Consideration should be given to prevailing pay scales, restrictions on number of
hours worked per week, competing industries that can cause dissatisfaction or high turnover rates
among the workers, and variations in the skill and productivity of the workers.

3.1.9. Taxation And Legal Restrictions


State and local tax rates on property income, unemployment
insurance, and similar items vary from one location to another. Similarly, local regulations on
zoning, building codes, nuisance aspects, and transportation facilities can have a major influence
on the final choice of a plant site. In fact, zoning difficulties and obtaining the many required
permits can often be much more important in terms of cost and time delays than many of the
factors discussed in the preceding sections.

19
Chapter No 3 Plant Location

3.1.10. Site Characteristics:


The characteristics of the land at a proposed plant site should be examined
carefully. The topography of the tract of land and‘ the soil structure must be considered, since
either or both may have a pronounced effect on construction costs. The cost of the land is
important, as well as local building costs and living conditions. Future changes may make it
desirable or necessary to expand the plant facilities. Therefore, even though no immediate
expansion is planned, a new plant should be constructed at a location where additional space is
available.

3.1.11. Flood And Fire Protection:


Many industrial plants are located along rivers or near large bodies
of water, and there are risks of flood or hurricane damage. Before selecting a plant site, the
regional history of natural events of this type should be examined and the consequences of such
occurrences considered. Protection from losses by fire is another important factor in selecting a
plant location. In case of a major fire, assistance from outside fire departments should be
available. Fire hazards in the immediate area surrounding the plant site must not be overlooked.

3.1.12. Community factors:


The character and facilities of a community can have quite an effect on
the location of the plant. If a certain minimum number of facilities for satisfactory living of plant
personnel do not exist, it often becomes a burden for the plant to subsidize such facilities.
Cultural facilities of the community are important to sound growth. Churches, libraries, schools,
civic theaters, concert associations, and other similar groups, if active and dynamic, do much to
make a community progressive. The problem of recreation deserves special consideration. The
efficiency, character, and history of both state and local government should be evaluated. The
existence of low taxes is not in itself a favorable situation unless the community is already well
developed and relatively free of debt.

3.2. Selection of the Plant Site


The major factors in the selection of most plant sites are
(1) Raw materials,
(2) Markets,
(3) Energy supply,
(4) Climate,
(5) Transportation facilities, and
(6) Water supply.

20
Chapter No 3 Plant Location

For a preliminary survey, the first four factors should be considered. Thus, on the basis of raw
materials, markets, energy supply, and climate, acceptable locations can usually be reduced to
one or two general geographical regions.

3.3. Potato In Pakistan


Production of potatoes varies from district to district in a province. The
main potato producing districts are as follows:
Punjab: Okara, Sahiwal, Pakpattan, Sialkot, Kasur, Jhang & Lahore.
NWFP: Nowshera, Mardan, Swat, Dir & Mansehra.
Balochistan: Killa Saifullah, Kalat & Pishin.
Sindh: Khairpur & Shikarpur.
Major Elogical Zones Of Pakistan in Appendix B (Table 3)

3.4. EXISTING INFRASTRUCTURE


The irrigated area of Pakistan is served by more than 40 major
canal commands. Main canals start from a barrage or dam or weir on a river. There are three
major groups of canal system:
1. Canals on upper-Indus tributaries
2. System on the Indus
3. System west of the Indus
The irrigation system in Punjab region is based on canal water and tube-
wells. The irrigation in Balochistan area is based on Karazes (rain and spring water channels) &
tube-wells. The irrigation in NWFP is being done through canals, rain/spring water channels and
Tube-wells. On average the potato crop requires about 36-acre inch of water. There is very
limited infrastructure available as in terms of storage facilities. It is due to this that a substantial
amount of potato cultivation is wasted after harvest. Following is some information on the
storage facilities currently available for different uses.

3.5. OPPORTUNITIES IN POTATO PROCESSING


FARMING/PROCESSING
Government Incentives
1) No sanction is required for setting up such a project. No "No Objection Certificate
(NOC)" required from the provincial government
2) There is no minimum foreign investment limit. Foreign investors are permitted 100%
ownership of projects
3) Corporate agriculture has been declared an industry. and remittance of capital, profits,
and dividends will be allowed

21
Chapter No 3 Plant Location

4) There is no ceiling on maximum land holding. State land is available on lease for 50
years, which is extendable for another 49 years
5) No customs duty on agriculture machinery if it is not manufactured locally
6) Investment Tax Credit (ITC) to the tune of 75% allowed

3.6. Business Economics


Cost of potato production in Pakistan
The cost of production is high in the first year of
operations, which decreases substantially afterwards. The reason for this is because in the first
year of operations the potato seed has to be purchased from the market while in the second year
potato seed comes from the previous year's harvest. The cost break-up for the first year and the
subsequent years is illustrated in the table below.
Potato Production Cost In Pakistan Appendix B (Table 4)
Pakistan Is Producing 3.5 millions ton of Potatoes Per Year And Exporting 50,000 tons per year,
We neeed 646617 Tons Per Year ,2803383 tons per year remaining
Million=10 lakh
Punjab is the best location for our plant

22
Chapter No 4
Mass Balance
4. Mass Balance
Basis:1 day operation

Input =2199289.207 Kg Output = 2199289.207 Kg

23
Chapter No 4 Mass Balance

Input = 2693750.575 Kg Output = 2693750.575 Kg

Input = 438517.7035 Kg Output = 438517.7035 Kg

24
Chapter No 4 Mass Balance

Input = 3132268 Kg Output = 3132268 Kg

Input = 12180520.15 Kg Output = 12180520.15 Kg

25
Chapter No 4 Mass Balance

Input = 11641770 Kg Output =11641770Kg

26
Chapter No 4 Mass Balance

Input = 35030926.03 Kg Output = 35030926.03 Kg

27
Chapter No 4 Mass Balance

Waste 10968.84 Kg

Input = 35030926.03 Kg Output = 35030926.03 Kg

28
Chapter No 4 Mass Balance

Input = 34349875 Kg Output = 34349875Kg

29
Chapter No 4 Mass Balance

Input = 34349875 KgOutput = 34349875 Kg

30
Chapter No 4 Mass Balance

Input = 33259521 Kg Output = 33259521 Kg

31
Chapter No 4 Mass Balance

Input = 1159596 Kg Output = 1159596 Kg

Input = 1442626 Kg Output = 1442626 Kg

32
Chapter No 4 Mass Balance

Input = 1412371 Kg Output = 1412371 Kg

Input =1355877Kg Output = 1355877Kg

33
Chapter No 4 Mass Balance

Input =1355877 Kg Output = 1355877Kg

34
Chapter No 4 Mass Balance

4.1. Overall Material Balance

35
Chapter No 5
Energy Balance
5. Energy Balance

5.1. Energy Balance on Dryer


CpOf Air=1 KJ/Kg.K

Cp Of Water Vapour(WV)=2.01 KJ/Kg.K

Cpw=4.18889KJ/Kg.K

Flow rate of dry gas

Qin = mairCp(Tair - T0) + mWVCp (Tair – T0)

Qin = [mairCp (air) + mWVCp (WV (Tair – T0)

Qin = [(G)(1) + (0.006G)(2.01)](385-273)

Qin = 113.35G KJ/sec

Heat Of Slurry in

36
Chapter No 5 Energy Balance

Qin = [msCp(s) (Ts – T0)] + [mH2OCp(H2O)(Ts –T0)]

Qin = [(6985062)(1.22) + (4656708)(4.18889)](295 – 273)

Qin = [(8521775.64) + 19506484.14)](22)

Qin = 616621715.2 kJ

Heat out with Air

Qout (air) = mairCp (air) (Tair – T0) + mWVCpWV (Tair – T0)

Qout (air) = [(G) (1) + (0.006G)(2.01)](310 – 273)

Qout (air) = 37.45G KJ/sec

Heat out PWS

Qout = mpwsCpws (Tpws – T0) + mwCp (w) (Tw – T0)

Qout = mpwsCpws (305– 273) + mwCp (w) (305 – 273)

Qout = [(1274445.6) (1.22) + (190434.47) (4.1889)](32)

Qout = 75281097.29 KJ

Heat out Water vapors

Qwv = mWvλ at 37oC

Q wv = (10177290) (2466.1)

Qwv = 25098214869 KJ

Qin = Qout

113.35G + 7136.83 = 37.45G + 871.31 + 290488.598

G = 3744.704585 Kg/sec

Qin =Qout

113.35(3744.704585) + 7136.83 = 37.45(3744.704585)

431599.0947 KJ/sec = 431599.0947 KJ/sec

37290157660.8KJ=37290157660.8KJ

37
Chapter No 5 Energy Balance

5.2. Energy Balance on Fermenter


Reaction and Heat of Formation

C6H12O6 +Ca(OH)2 C3H5O-CaO3H5C3 +2H2O +Biomass

ΔHr = ∑ Product - ∑ Reactant

ΔHr = [ (-1386.1) + 2(-285.84)] - [(-1262.4) – (986.09)]

ΔHr = -9.29 KJ/mole

In terms of mass

ΔHr = -19.1735 KJ/Kg

ΔHr298= -19.1735 KJ/Kg * 1387156 Kg/day

ΔHr298= -26596635.57 KJ

Heat balance around fermentation Unit

ΔH298 + m<Cp>H (T - 37) = 0

m<Cp>H (T – 37) = -ΔH298

T – 37 = - ΔH298/m<Cp>H

T = 37 - ΔH298/m<Cp>H

ΔH298 = -19.1735 KJ/day * 1387156 Kg/day

ΔH298 = -26596635.57 KJ/ day

T = 37 + (26596635.57)/ [(35030926.03) (13.98634)]

T = 37 + (26596635.57)/ [(35030926.03) (13.98634)]

T = 37 +0.054 K

T = 37.054 K0
Heat Consumption = Heat of reaction + ( Heat of reactants) + (Heat of products)
Heat of consumption = ΔH298 + ∫ +∫

38
Chapter No 5 Energy Balance

Heat Consumption = (-26596635.57) + (35030926.03) (4.0879) (25 – 37) + [(35030926.02)


(14.24194) (37.05 – 25)
Heat of Consumption = -1246123359.1 KJ

5.3. Energy Balance on Acidification Unit


Reaction and Heat of Formation

C3H5O3-Ca+O3-H5C3 + H2SO4 CaSO4 + 2C3H6O3

ΔHr = ∑ Product - ∑ Reactant

ΔHr = (-1434.5 + 2(-686.30) – (-1686.1 – 907.51)

ΔHr = -214.49 KJ/mole

In terms of mass

ΔHr = -8.7947 KJ/Kg

ΔHr298 = -8.7967 KJ/kg *1375760 Kg/day

ΔHr298 =-12102147.99 KJ

ΔH298 + m<Cp>H (T - 37) = 0

m<Cp>H (T – 37) = -ΔH298

T – 37 = - ΔH298/m<Cp>H

T = 37 - ΔH298/m<Cp>H

T = 37.05 + [(12102147.99/ ((34349873) (7.94551))]

T = 37.09 K0

Heat balance around Acidification Unit


Heat Consumption=ΔHr(298 )+Heat Of Reactants +Heat Of Products
Heat Consumption = ΔHr(298 )+∫ +∫

39
Chapter No 5 Energy Balance

Acidification Unit Avg Cp


Product Reactants Avg Cp
Potato Sta ch 1.22 Potato Starc (s) 1.22
( )
Water (l) 4.18889 Water (l) 4.18889
L ctic acid (l) 1.38349 Calcium lactate (aq) 263.835
Gypsum (s) 0.54313 Sulfuric acid (aq) 50.1618
CSL 0.61 CSL 0.61
7.94551 320.01569
Heat Consumption = (-12102147.99)+(34349873)(320.0157)(25- 37.05)+
[(34349873)(7.94551)(37.09-25)

Heat Consumption = -1.32461E+11KJ

5.4. Energy Balance on Triple Effect Evaporator

Effect 1

D0λ0 = GFCp(T1 – Tf) +D1λ1

2139.1D0 = (33259521) (3.9049) (89 – 37) + 2222.5D1

2139.1D0 = 6753562285 + 2222.5D1………………….. (1)

Effect 2

40
Chapter No 5 Energy Balance

D1λ1+(Gf – D1) Cp (T1 – T2) = D2λ2

2222.5D1 + (33259521 –D1) (3.9049329) (89 – 25) = 2254.6D2

2171.74D1 + 1688390571 = 2254.6D2…………………. (2)

Effect 3

D2λ2 + Cp (Gf – D1 – D2) (T2 – T3) = D3λ3

2254.6D2 + (33259521 – D1 – D2) (3.9049329)(76 – 25) = (30531870-D1-D2)2302.1

67689900000+2224D1=4478.6D2 ……………………… (3)

Multiply Eq2With 4478.6 and Eq3 With 2254.6

9726354.764D1=7.56163E+12+10097452D2 …………..(2)”

5014230.4D1=1.52614E+14+10097452D2……………………….(3)”

Subtract (2)” and (3)”

14740585.16D1-1.45052E+14=0

D1=9840316.4 Kg

Put in equation 1

2139.1D0=6753562285+21870103289

D0=13381172.26Kg

Put d1 in equation 2

D2=10227534.55
D3=30531870-D1-D2
D3=30531870-9840316.4 -10227534.55
D3=10463528 Kg
Heat in

D0λ0 = (133871173) (2139.1)

D0 λ0 = 28623667079 KJ

Q = msCp(s) ΔT

Q = (33259521) (3.9049329)(12)

Q = 1558514373 KJ

41
Chapter No 5 Energy Balance

Total Heat in = 30182181452 KJ……………………… (A)

Heat Out

Steam Condensate(mc)

Q = mscCp (sc) ΔT

Q = (13381173) (4.18889)(121 – 25)

Q = 5381017114 KJ

D3λ3 = (104635280(2302.1)

Q = 24088087256 KJ

Q = mLACp ΔT + mimpCp (imp) ΔT

Q = [(1129340) (1.62345744) (56 -25)] + [(1444304) (1.62345744) (56 – 25)]

Q = (1129340 + 1444304) (1.62345744) (31)

Q = 129524246.5 KJ
Q = 0.6mCp ΔT + 0.4mCp ΔT
Q = (0.6) (154006) (4018889) (89 – 25) + (0.4)9154006) (4.1885) (76 – 25)
Q = 37931489.3 KJ

Total Qout = 29636560106 KJ………………………. (B)

A – B = 545621346.5 KJ

Heat losses = (545621346.5/30182181452)*100


Heat losses = 1.807759811%

5.5. Energy Balance On Prepolymer Reactor


Operating conditions

195 (C) Operating Temp

4-5 mbar mbar Pressure

Stannus 2- ethylexanate Catalyst (.05-.2%)by weight

Conversion 93.72%

42
Chapter No 5 Energy Balance

Heat Consumption = ΔH (298 )+ +


r

Qin (Lactic Acid)


0
Mass Cp(LA)56 C ΔT Qin
Units Kg KJ/Kg.K K KJ
1159596 1.5035 25-56 -54047030
QOu t (Water Vapours)
Mass Λ T Qout
0
Units Kg KJ/Kg.K C KJ
72845.8 2368.4 195 172527993
Qout (Pre Polymer L A)

0
Mass Cp(LA) 195 C ΔT Qout (lactic acid)
Units Kg Kj/Kg.K K KJ
1086750 1.89777 195-25 10728656
0
Heat of Reaction At 25 C =41349020 KJ
Heat consumption =4277402060KJ

5.6. Energy Balance On Lactide Reactor


Operating conditions
213(C) Operating Temp
4-5 mbar Pressure
Tin 2- Octate Catalyst (.05%)by weight ,Conversion 97.9%

43
Chapter No 5 Energy Balance

Heat Consumption = ΔHr(298 ) + +

Qin (Monomers of lactides)


Ma s Cp(LA)195 0C ΔT Qin
Units Kg KJ/Kg.K K KJ
1442626 1.89777 25-195 -4.658*108
QOu t (Lactide)
Mass Cp ΔT Qout
Units Kg KJ/Kg.K K KJ
1412371 2.06341 213-25 547888484
Qout (Lactic acid) Recycle stream
Mass Cp(LA) 2130C ΔT Qout (lactic acid)
Units Kg Kj/Kg.K K KJ
30255.02 1.88621 213-25 10728656
Heat of Reaction =34290136.33382 KJAt 250C
Heat consumption 127485978 KJ

5.7. Energy Balance On Lactide Distillation


Crude Lactide m Cp ΔT Qin
At (213)C
Units Kg KJ/Kg.K K KJ
1412371 2.06341 213 - 25 547888484
Water Vapour m Λ Q out
0
Units Kg KJ/Kg 238 k(213 C)
56494.86 1886 106549306
Purified Lactide m Cp ΔT QOut
Units Kg KJ/Kg K KJ
1355877 2.20486487 172.6285 - 25 441339178
(Total Heat Out put) 547888484 KJ
Diff B/W Heat In and out 2.7977376KJ

44
Chapter No 5 Energy Balance

5.8. Energy Balance On Polymer Reactor


Heat Of Reaction = -7062492.1176 KJ
Qin (Purified Lactides)
Mass Cp ΔT Qin
Units Kg KJ/Kg.K K KJ
1355877 2.204865 25-172.6285 -4.41*10^8
Qout (Lactide Polymer)
Mass Cp ΔT Qout
Units Kg KJ/Kg.K K KJ
1355877 1.88914 210-25 473866673
Heat of consumption 908143381.8KJ

5.9. Energy Balance On Devolatilizer


Mass at output Mass Fraction Specific heat Avg. Cp
Units Kg ………………… (KJ/Kg.K) KJ/Kg.K
355876.5 0.26247 2.009411 0.927409
1000000 0.73753 0.779906 0.575204
Total 1355877 1 2.789317 1.102614

Formula
Qin = mCp ΔT
Qout = mCp ΔT
Mass Cp ΔT Qin
Units Kg KJ/Kg.K K KJ
1355877 2.789317 150 -25 346019810
Mass Avg. Cp ΔT Qout
Units Kg KJ/Kg.K K KJ
1355877 1.102614 23.496612 346019811
Difference b/w Qin &Qout -0.264147 KJ

45
Chapter No 6
Design Of Equipment
6. Equipment Design

6.1. Hydrocyclone
Definition
― A hydro cyclone is a static device that applies centrifugal force to a liquid mixture
so as to promote the separation of heavy and light components‖.
A hydro cyclone often referred to in the shortened form cyclone is a device to classify, separate
or sort particles in a liquid suspension based on the ratio of their centripetal force to fluid
resistance.
Difference Between Hydro cyclone & Centrifuge
Hydro cyclones are also related to centrifuges in that both are intended
to separate heavies and lights by application of centrifugal force to liquids. The key difference is
that hydro cyclones are passive separators capable of applying modest amounts of centrifugal
force, whereas centrifuges are dynamic separators that are generally able to apply much more
centrifugal force than hydro cyclones
Another key difference between hydro clones and centrifuges is cost. Centrifuges are expensive
precision rotating machines that often need sophisticated control, whereas hydro cyclones have
no moving parts and usually no controls at all so they are lower cost devices.
Hydro cyclones, also known as liquid cyclones, are an important device for the separation of
solid-liquid suspensions. The principle employed is centrifugal sedimentation, i.e., the particles
in the suspension are subjected to centrifugal forces, which causes their separation from the fluid.
Like centrifuges, which make use of the same principle.
Applications
In the potato, cassava, wheat and corn starch industry for both concentration and
washing of the crude starch milk. Hydro cyclones replace separators as a more price efficient
separation technique.
 In pulp and paper mills to remove sand, plastic particles and other contaminants.
 In industry to separate oil from water or vice versa.
 In metal working to separate metal particles from cooling liquid.
 To remove sand and silt particles from irrigation water for drip irrigation purposes.
 These devices are widely utilized in mineral, chemical, petrochemical, textile and
metallurgical industries.

46
Chapter No 6 Design Of Equipments


 Clarification of slurry (removing solids) and thickening (removing liquids)
 Sorting of solids
 Washing of solids
 Removing gases from liquid
 Removing immiscible liquid from liquid
Advantages
 They are very versatile.
 They are simple and cheap to buy, install and operate.
 They need only a little space.
 Do not have moving parts
 Require a low installation and maintenance investment and are simple to operate.
 Low capital cost (few parts, easy to assemble)
 Ability to operate at high temperatures (all metal parts)
 Low maintenance requirements (no moving parts).
Disadvantages
 They are not flexible.
 The power of separation is quite poor.
 Great flow rate may cause weariness.
 Low collection efficiencies (especially for very small particles)
 High operating costs

6.2. Designing of Hydro cyclones


Diagram of a Hydrocyclone at Appendix C (Fig 1, Fig 2)
Design procedure
 Inside diameter of hydro cyclones
 Diameter of vortex
 Length of inner vortex
 Efficiency of hydro cyclones
 Inside diameter of hydro cyclone
 Feed flow rate = 3132268 kg/day
 Volumetric flow rate = Mass Flow Rate/Density
 Feed flow rate = 3132268 kg/day
 Volumetric flow rate = Mass Flow Rate/Density
 Density of solid particle =1.55 g/cm3
 Density of liquid = 1g/cm3
 Density difference = 0.55g/cm3
o Particle diamete = 44 microns

47
Chapter No 6 Design Of Equipments

 Diameter for separation


 Diameter = 40cm
 =(40cm)(1inch)/2.54 cm
 =15.74″
 Inside diameter of Hydro cyclone = 15.74″
 Many cyclones are used with same diameter. Each cyclone is feed with same amount of
solids having same particle size distribution.
 In this case we are using eleven hydro cy clones
Diameter
Diameter of inner vortex is 35% of hydro cyclone chamber
(The sizing and selection of hydrocyclones
By Richard A. Arterburn)
Dv = (15.74) (0.25)
Dv=5.509″
Length of inner vortex
Length of inner vortex is 55 % of hydro cyclone is
Lv=(15.74)(0.55)
Lv=8.657″
Efficiency of Hydro cyclone
Efficiency of Hydro cyclone is 94 % at 44 microns particle diameter from
(Figure 10.22. Page#422, Coulson & Richardson Chemical Engineering Volume 6)

Efficiency= 100[1-e-- (d/d50-0.115)3]


Efficiency =94%
For Diameter Graph Appendic A (Fig 2 & Fig 3)
Specification Sheet At Appendix D (SS1)

6.3. Designing Of Falling Film Evaporator


What is Evaporation?
It is the passage of a solvent in a solution from liquid form to vapour
form by the application of heat
Evaporator selection
The selection of the most suitable evaporator type for a particular
application will depend on the following factors:
 The throughput required.
 The viscosity of the feed and the increase in viscosity during evaporation.
 The nature of the product required; solid, slurry, or concentrated solution.
 Whether the materials are fouling or non-fouling..

48
Chapter No 6 Design Of Equipments

 Whether direct or indirect heating can be used

Falling Film Evaporator


Main features
 Low pressure drops
 Short residence time on the heated tube surface
 Suitable for operation under deep vacuum
 Low susceptibility for fouling
 Process vapors and liquid flow co-currently or counter-currently
 Can be used for liquids containing small amount of solids
 Most economical
Falling Film Evaporator
Is mainly a heat exchanger with vertical tubes.
The Product flows from top to bottom FALLING
The Product is fed so that it forms a thin FILM inside the tube
Viscosity Graph at Appendix A (Fig 4)
Falling Film Evaporator at Appendix C (Fig 5)
Designing Steps For Evaporator
• Design Of Calendria
• Design Of Separator
Designing steps of calendria
1) Define the duty: heat-transfer rate, fluid flow-rates, temperatures.
2) Collect together the fluid physical properties required: density, thermal conductivity.
3) Decide on the type of exchanger to be used.
4) Select a trial value for the overall coefficient, U.
5) Calculate the mean temperature difference.
6) Calculate the area required from equation 12.1.RC vol 6
7) Decide the exchanger layout.
8) Calculate the individual coefficients.
9) Calculate the overall coefficient and compare with the trial value. If the calculated value
differs significantly from the estimated value.
10) Calculate the exchanger pressure drop
Properties Data
Shell side(air flue gases)
T1=Inlet temp. of flue gases(air)=112oC
T2=outlet temp of air and moist= 37oC
Cp of air=1 KJ/Kg . K
k: 0.039 W/m . K

49
Chapter No 6 Design Of Equipments

flow rate, m = 3744 kg/hr


Calculations
Heat duty:
Q=m Cp ∆T
= 3744*1*75
= 280852.5KJ/hr
LMTD

Tlm =

Tlm =48.8 0C
Where t2=(1120C-320C)=80 0C
T1 =( 370C -2200C )=150C
R = 1.2
S = 0.4
Ft = 1 (Fig 12.21, Vol. 6, Richard and Coulson page 658)
Heat Transfer area
∆T = Tlm x Ft = 48.8* 1 = 48.8 oC
Ud = 60 W/m2.oC (Table 12.1from RC vol.6 page 635)
A= Q/Ud ∆T= 280852.5/(60*48.8)= 27m2
Tube selection
16BWG
do=0.019 m, di = 0.0157 m, length of one tube = 4.88m (RC VOL.6 page no 645)
Area of one tube =πd0L= 0.291 m
Number of tubes, Nt = 27/0.291 = 92
Tube side Co-efficient
Mean temperature = (22+32)/2 = 270C
Tube cross-sectional area = π/4 * ID2
= 193*10-6 mm2
As 2 passes are used so number of tubes per pass = 92/2 = 46
Total flow area = 46*193*10-6 mm2
= 0.0088 m2
Mass velocity G = mt/at
= 799 kg/s.m2
Re = GD/ 
=1.0*104
Jh = 4*10-2 (RC vol.6 fig 12.23 page 665)
hi = k/di* ( Pr ).33 * Re * Jh* ( /w ).14

50
Chapter No 6 Design Of Equipments

= 280 W/m2.oC
hio = hi * ID/OD
= 226 W/m2.oC
Shell side Co-efficient
Pitch
Square pitch selected
Pt = 1.25*do (Table 12.4 vol. 6 page 649)
= 0.02375 m
K1 = 0.156, n1 = 2.291 (Table 12.4, Vol.6)

Bundle diameter

(eq 12.3 &648 RC 6)


= 0.306 m
(From Figure 12.10 , volume 6 page 646)
BDC = 0.055m
Shell Diameter, Ds = Db+BDC
= 0.306+0.055= 0.361 m
Baffle spacing, lb = DS/5
= 0.5166/5= 0.103m

(Eq no 12.21 RC vol 6 page 674)


As = 0.0052 m
Mass velocity G = m/a
= 200 kg/m2sec
Equivalent dia equation: ( 12.25 page 672 RC vol 6 )

Re = GDe/ 

51
Chapter No 6 Design Of Equipments

Re = 1.47*103

JH = 1.2*10-1 ( fig.12.29 page 672 RC vol.6 )

hs=h0 = 129 W/m2.oC


Uc = hio*ho/hio+ho
= 82 W/m2.oC
Ud = Uc /1+Rd Uc Rd= 0.002
= 75 W/m2.oC
Shell side Pressure Drop

(Eq 12.26 page 675 RC vol 6)


Re = 1.47*103, for square pitch
jf = 5*10-1 (Fig. 12.30, Vol. 6 page 673)
us = 0.004 m/s
∆Ps = 24.7 kPa
Tube side Pressure Drop

(Eq 12.19 page 666 RC vol 6)

Re = 1.01*104
jf = 5*10-2 (Fig. 12.24, Vol. 6 page 667)
Us = 0.002 m/s
∆Ps = 13.2 kPa
Specification Sheet At Appendix D (SS2)

6.4. Design of separator


Separator
Droplets of liquid must be separated from the vapours: Vapour discharge at top
Droplets, liquid, downwards

52
Chapter No 6 Design Of Equipments

Data used for designing

Mass flow rate of liquid = ml = 61020 Kg/h


Mass flow rate of air & vapour = mav = 424053.7 Kg/h
Residence time = ts = 500 sec
Constant = kv = 0.2m/s
Liquid density = dl = 1200Kg/m³
Vapor density = dav = 190 Kg/m³
(From chemical engg progress by Wayne D .Monneray nd William University Calgary, table
1,2,6,7,9 pages from 30-40)
(Potato science and technoloy by G Lisinska page 548)
CALCULATIONS FOR THE DIAMETER OF SEPARATOR
Volumetric Flow Rate of air & vapour =Vav´= mav/dav
Vav´= 0.61996m³/s
Air & vapour Velocity = vv = kv((dl-dv)/dv)1/2
Vv = 0.25 m/s
Area = A = Vav´/ vv
A = 2.48 m²
Diameter of Separator = D = (4*A/3.14)1/2
D = 1.78 m
Calculations for the length of separator

Volumetric Flow Rate of Liquid = VL = ml/dl VL = 0.014 m3/s


Liquid Level in the Separator = LL = VL*ts/A
LL = 2.8 m
Length of Separator = L= LL + 1.5*D +0.457
L = 5.97 m
Since The Ratio ‗ L/D ‘ =3.35
Thus the design is satisfactory for a vertical Vapor Liquid Separator.
Material of construction for Evaporator
Identification:
Item name: Evaporator
Item no.: V-410
No. Required: 1
For the construction of vertical long tube falling film evaporator 304 & 316 type stainless steel
are used.
Separator Figure Appendix C (Fig 6)
Specification Sheet At Appendix D (SS3)

53
Chapter No 6 Design Of Equipments

6.5. Designing of Fermentor


Process Description
Bacteria is Lactobacillus Amylophilus
There are four phase
 Lag phase
 Exponential growth phase
 Antibiotics produced during the stationary phase
 Death phase

Given Data
From patent
Fermentor Temperature = 370C
Fermentor Pressure = 1.8 atm
Start-up time = 60 hr
Conversion = 90%
Lag time = 12 hr
Growth rate
Formula: cx = cx0exp(µ(t – t0))
( from elements of chemical engineering, 4th ed, eq.#7-77)
T = startup time
T0 = lag time
Cx = cell concentration at t
Cx0 = concentration at lag time t0 when exponential growth start
From the graph in patent
Cx = 36 g/l
Cx0 = 0.9 g/l
µ = 0.0768 hr-1
Concentration of Substrate

54
Chapter No 6 Design Of Equipments

Formula: µ = (µmaxcx)/(CM + CS)


( from elements of Chemical Engineering, 4th ed, eq.#7-52)
µmax = kcx
µmax = 2.764 g/(l*hr)
CM = Monod constant for glucose = 1.68 g/l
Putting Values
0.0768 = (2.764*36)/(1.68 + Cs)
Cs = 1294.64 g/l
Rate Equation
Formula: -rs =- rx(Cs/Cx)…………(A)
-rx = µcscx /(Cs + CM)
(from elements of Chemical Engineering, 4th ed, eq.#7.55, 7-53)
-Rx = (0.0768*36*1294.64)/(1294.64+ 1.68)
-rx = 3.45 g/(l*hr)
Putting values in a
-rs = 3.45*(1294.64/36)
-rs = 124.2645 g/(l*hr)
Volume of cstr
Using performance equation of CSTR
V/Fs0 = ΔX/-rs
(From CRE, 3rd ed, octave levenspiel, chap#5, eq#11)
V = 35030925.9*(0.9/124.2645)
V = 12685.82 m3
For one reactor
V1 = 12685.82/18
V1 = 704.767 m3
Residence time
Vo=33920.127m3/day
V= 12685.82m3
Formula

Residence time = 0.373hr = 22.439min


Space velocity = 2.68hr-1
Mechanical Designing
Diameter
Formula V = hπd2/4
704.767 = (3.14*1.5D3)/3.14
H = 1.5D

55
Chapter No 6 Design Of Equipments

D = 8.427m
Radius
R = 4.213m
Height
H = 1.5D
H = 12.641m
Formula: thickness = Pi Di/(2jf – Pi)
(Volume 6, page 812, Ch # 13 ,Equation 13.39a)
Pi = design pressure = 1.8atm*1.1 = 1.98atm = 0.198N/mm2
F = design stress of Carbon steel = 135N/mm2
(RC VOL 6 by RK Sinot,Ch # 13, Table # 13.2 Page # 809)
J = joint efficiency = 1
Putting vaues
E = (0.198*8.427)/(2*1*135 – 0.198)
E = 6.184mm
After adding corroision allowance = 0.1mm/year for 20years we have corroision allowance
2mm
E = 6.184 + 2
E = 8.184mm
Ellipsoidal Head
Formula: e = (pidi)/(2jf – 0.2Pi)
(RC Vol 6 ,Ch # 13,Page # 816, eq # 13.43)
Putting values
• E = (0.198*8.427)/(2*1*135 – 0.2*0.198)
• E = 6.180mm
Fermentor Figure Appendix C (Fig 3)
Impeller Figure On Appendix C (Fig 4)
Impeller Designing
Da = di/3
Da = 8.427/3
Da = 2.809m
H/di = 1
H/8.427 = 1
H =8.427m
J = di/12
J = 8.427/12
J = 0.70225m
E = di/3
E = 8.427/3

56
Chapter No 6 Design Of Equipments

E = 2.809m
W = da/5
W = 2.809/5
W = 0.5618m
L = da/4
L = 2.809/4
L = 0.70225m
Power
Formula: p = kt n3da5⍴
Re = da2n⍴/ µ
N = 100rpm = 1.67rev/sec
⍴mix= 1150kg/m3
µ = 1260.142*10-3 g/(cm*sec)
Putting values
Re = 2.8092*1.67*1047/ 1260.142*10-3
Re = 109483.114788
Kt = Reynold number is more than 10^4 so,
Kt = 5.75 (unit operation of Chemical Engineering, Mocabe &Smith Harriott,table #9.2)
Putting values
P = Kt n3Da5⍴
P = 5.75*1.673*2.8095*1047
P = 4903.685 K watt
Specification Sheet At Appendix D (SS4)

6.6. Designing Of Pre polymer Reactor


Pre polymer Reactor Figure At Appendix D (Fig 7)

Chemical reaction
c3h6o3 c3h5o3-[c3h4o2]n-2-c3h5o3+(n-2)h20
lactic acid prepolymer lactic acid + water

a b+c

Reversible 1st order reaction.


Constant density system.
-ra=k1CA-k2CBCC
-ra=k1CA0(1-XA)-k2CB0(1+XB)CC0(1+XC)
-ra=k1CA0(1-XA)-k2 (CB0+ CB0XA) (CC0+ CC0XA)
-ra=k1CA0(1-XA)-k2 (CB0+ CA0XA) (CC0+ CA0XA)

57
Chapter No 6 Design Of Equipments

Because intital concentrations of CB0 & CC0 is zero


CB0X0=CA0XA & CC0XC=CA0XA
-ra= k1CA0(1-XA)-k2 ( CA0XA) (CA0XA)
-ra== k1CA0(1-XA)-k2 ( CA02) (XA2)
=keq CA0(1-XA)- ( CA02) (XA2)
-ra=keqk2 CA0(1-XA)- k2( CA02) (XA2)
*k1=1.51*10-4 /sec
k2=(1.51*10-4*3600*24)=13.0464/day
*k2=1.07*10-4 /sec
K2=(1.07*10-4*3600*24)=9.2448/day
*keq=1.4112
*journel of molecular modeling may 2008, volume 14, issue5, pp367-374
Mass flow rate=1141251 kg/day
Molar flow rate=1141251/90.08=12669 (kgmole/day)
Mass flow rate=1141251 kg/day
Volumetric flow rte=(1141251/1224)=932 m3/day
CA0=molar flow rate/volumetric flow rate
CA0=(12669/932) kgmole/m3
CA0=(13.59) kgmole/m3
-ra=(1.4112)(9.2448)(13.59)( 1-XA)-9.2448(13.59)2 ( 1-XA)2
-ra=2409.5( 1-XA)-1707.4( 1-XA)2
………………………………….(1)
t =ca0∫
Table is Given At Appendix B (Table 5)
Graph At Appendix A (Fig 5)
Using symson’s rule
=1(f(xa))+ 4(f(xa))+ 2(f(xa))+4(f(xa))+ 1(f(xa))
=1(.0005)+4(.00075)+2(.0012)+4(.006)+1(.0083)
=.0382
Putt values in 1
T=(13.59)*(.0382)*(24)
T=12.4593 hrs
12.4593=volume/volumetric flow rate
Volume=(12.4593*932)/24
Volume =483.830 m3
Allowance =20%
Total volume=1.2*483.830
V=580.60 m3
Using rule of thumb

58
Chapter No 6 Design Of Equipments

L=1.5d
V=(3.14)(d2)(l)/4…………………..(2)
V= v=(3.14)(d2)(d)/4
580.60=(3.14*d3*1.5)/4
D=7.9m
580.60 =(3.14*3.4382*l)/4
L=11.85 m
Mechanical design
Operating pressure
Operating pressure =4.5mbar
Operating pressure =((4.5*10-3*105)/106)
Operating pressure =4.5*10-4n/mm2
Atmospheric pressure
Atmospheric pressure=(101325/106)n/mm2
Atmospheric pressure=.101325 n/mm2
Hrdrostatic pressure
Hrdrostatic pressure=𝝆gh
Hrdrostatic pressure =(1240*9.8*5.157)/(106)
Hrdrostatic pressure =.0626n/mm2
Total pressure= operating pressure + atmospheric pressure+ hrdrostatic pressure
Total pressure =4.510-4n/mm2+.101325 n/mm2+.0626n/mm2
Total pressure=.164435 n/mm2
Design pressure
Design pressure=1.1*operating pressure
Design pressure=(1.1*4.510-4)n/mm2
Design pressure=(4.95510-4)n/mm2
Design stress
For100-20 0 0c design stress (f)=105 n/mm2 for carbon steel Volum 6, page 218, ch # 13
E=(pidi/2f-pi)
E=((4.95*10-4)*(3.438*103))/(2(105)-4.95*10-4)
E=.0081mm
Corrision allowance
E=4mm maximum
So total wall thickness=4+.0081=4.0081mm
Joint efficenccy=.9
Thickness of ellipsoidal head
ellipsoidal head is allowed upto 15 bar pressure and our operating pressure is 4.5 mbar.
E=(pidi/2jf-.2pi)
E=((4.95*1-4)*(3.438-103))/((2*.9*105)-(.2*4.95*10-4))
E=.09mm

59
Chapter No 6 Design Of Equipments

Corrosion allowance
E=4mm (maximim )
Total corrosion allowance for ellipsoidal head=4+.09=4.09mm
Specification Sheet At Appendix D (SS5)

6.7. Designing Of Steam Coil


Tavg=(220+220)/2
Tavg=2200C or 428 0F
Tavg=(56+195)/2
Tavg=125.50C or 257.59 0C
For feed
Q=mcp(195-25)
Q=117527993kj/day
Q=(117527993)/(1055*24)
Q=4641706 btu/hr
For steam
Q=m0λ
4641706btu/hr= m0(965.2kj/kg)

m0 =

M0=10248.59 lb/hr

LMTD=

LMTD=

LMTD=172.93 0F
Dia Of Vessel=7.9 m
Outer Dia Of pipe Of Coil=DV / 30
RC Volume (6) , Ch#12, Page #775
Outer Dia Of pipe Of Coil=7.9/30=.263m
Outer Dia Of pipe Of Coil=.263*3.2808*12
Outer Dia Of pipe Of Coil =10.367 Inch=.864 ft
Schedule # 40
A(t)=Flow Area Per Pipe inch2=78.8 inch2
A(t)=Flow Area Per Pipe=78.8/144

60
Chapter No 6 Design Of Equipments

A(t)=Flow Area Per Pipe=.547 ft2


Mass Velocity=Gt=m0/a(t)
Mass Velocity=18736
At 2200C & 17.186 Psi
Μ= =.03751
Re No=gtdi/ μ
Re No=
Re No=431562
Jh Factor=800
hi=jh*[k(Cp μ/k)1/3] /DI
hi=800*[.02175(.46*.03751/.02175) 1/3] / .864

hi=18.64

hio=hi*

hio=18.64*

hio =17.68633

UC=(hohio)/ (ho + hio)

UC=

UC =15.82091

Rd=.01(hr.ft2 .0F/ Btu) & hd=100


Ud=(Uc * hd)/ (Uc + hd)
Ud=(15.82091*100)/( 15.82091+100)
Ud= 13.6598
Q=UdA/Δt
A=Q/ (UdΔt)
A=(4641706)/( 13.6598*110)
A=3089.161ft2
Δt
Assume h0=50 (Btu/hr.ft2 0F)
tw=tAVG +( hio/hio+h0)(TAVG -tAvg)
tw=257.9+((17.68633)/(17.68633+50))(428-257.9)
tw =376.875 oF

61
Chapter No 6 Design Of Equipments

tf=1/2(tw + tAvg)
tf=1/2(376.875 + 257.9)
tf=317.38 0F
Δt =tw - tavg
Δt=(tw-tAvg)
Δt=(375.8409-257.9)
Δt=110 0F
Δt/d0=110/10.367
Δt/d0= 10.61
Q=UdA Δt
A=Q/U Δt

A=

A=3089 ft2
Πd=3.14*10.367/12
Πd=2.814 ft
length of one coil =3089/2.814
Length of one coil =1098
Number of turns=1098/2.814
Number of turns=390
Specification Sheet At Appendix D (SS6)

6.8. Designing Of Flash Lactide Drum


For Dew Point =115 Appendix B (Table 6)
Bubble Point =125 Appendix B (Table 7)
Flash point=[(dew point)+(bubble point)]/2
Flash point=[(115)+(125)]/2
Flash point=120 0c
√𝝆 𝝆
U(t)= 𝝆

Ut = settling velocity, nvs,


s — slurry density, kg/m3,
v — vapour density, kg/m3.

Blackwell (1984) fit Watkins Correlation to the Equation Given Below


Kdrum=exp[(A + B(lnFSV) + C(lnFSV)2 + D(lnFSV)3 + E(lnFSV)4]
A= -1.877478097
B= -.8145804597
C= -.1870744085

62
Chapter No 6 Design Of Equipments

D= -.0145228667
E= -.0010148518
FSV=(WS/Wv)*SQRT(𝝆v/𝝆s)
Fsv=(1355977/59694.86)*SQRT(2.16/1296)
FSV=1.0611
Kdrum=exp[(-1.877478097)+( -.8145804597 )(ln(1.0611)) + (-.1870744085)(ln(1.0611)2 )
+(-.0145228667) (ln(1.0611)3) + (-.0010148518)(ln(1.0611)4)]
Kdrum=.144152
The diameter of the vessel must be large enough to slow the gas down to below the
velocity at which the particles will settle out. So the minimum allowable diameter will

√ or DV=SQRT(4*VV)/πUs)

where
Dv = minimum vessel diameter, m,
Vv = gas, or vapour volumetric flow-rate, m3/s,
No Dimester Pad Is Used So U(t)=0.15 ut
Water Contents In Slurry=81917.518 Kg/day
Lactide Contents In Slurry=1330453.482 Kg/day

Or 𝝆m=100/[((Cw/𝝆s)+((100-CW)/𝝆l)]
3
m= Density Of Slurry = 1105 Kg/m
Cw=Concentration Of Solids by Weight In Slurry =94.2%
3
s=Density Of Solids (Lactide)=1320 Kg/m
3
l=Density Of Liquid Without Solids =1000 Kg/m
𝝆 𝝆
U(t) =KDrum√ or U(t)=Kdrum*SQRT((𝝆s-𝝆v)/ (𝝆v))
𝝆

U(t) =.144152√ or U(t)=.144152*SQRT((1105-2.16)/2.16)

U(t) =3.257242 m/Sec

Because No Dimester Pad


U(s) =3.257242 m/Sec *.15
U (s)=.488586 m/Sec
Mass Flow Rate Of Vapours =56494.86 Kg/Day
Mass Flow Rate Of Lactide = 1355877 Kg/Day
Hold Up =10 minute Holdup
Volumetric Flow Rate Of vapours= (Mass Flow rate Of Vapours/ Density Of vapours)
Volumetric Flow Rate Of vapours=(56494.861)/(2.16*24*3600)

63
Chapter No 6 Design Of Equipments

Volumetric Flow Rate Of vapours=VV= .302720229 m3/Sec


Volumetric Flow Rate Of Lactide= (Mass Flow rate OfLactides/ Density Of vapours)
Volumetric Flow Rate Of Lactide=(1355877)/(1105*24*3600)
Volumetric Flow Rate Of Lactide=.014201829 (m3/Sec)
Hold Up =10 minute Holdup
Volume Of column=(.014201829*10*60)
Volume Of column =8.521097 m3
10 % Allowance
Volume Of column=9.3732067 m3
Diameter Calculation

Dv (minimum Vessel Diameter)=√ DV=SQRT(4*VV)/πUs)

Dv=√ or Dv=SQRT((4*.302720229/π*.488586))
Dv=.888414m
Length Calculation
Accordind To Rule Of Thumb
L=3+.5D+D
L=3 + 1.5D
L=3 + 1.5(.888414m)
L=4.332621 m
L/D=(4.332621/.888414)=4.876808 Because if L/D ratio is inbetween 3-5 Design Is acceptable
for Vertical Flash Drum

6.9. Designing Of Polymer Reactor


Design procedure for reactor
Molar flow rate from given mass flow rates
Volumetric flow rate from molar flow rate
Initial concentration from volumetric flow rate
Concentration for given conversion
Rate of reaction by the given kinetic equation
Residence time
Reactor volume
Actual volume of reactor
Dimension of reactor
Power
Parameters of mechanical design
Data
Flow rate Of lactide = 1355877 Kg/day
Density of lactide =1340 Kg/m3

64
Chapter No 6 Design Of Equipments

M.W of of lactide = 144.12 Kg/Kgmol


Flow rate Of Catalyst =101.185Kg/day
Density of catalyst(Tin Octoate) =1250 Kg/m3
M.W of catalyst=405.1 Kg/Kgmol
Temperature of reactor =195 oc
Conversion =73.76 %
CALCULATION OF PARAMETERS
Mass Flow Rate = 1355877 Kg/day
Molecular Wt. of Lactide = 144.12 Kg/Kgmol
Molar flow rate:
Molar Flow rate = Mass Flow rate / Mol.wt
Molar flow rate of Lactide = 9407.97 Kgmol / day
Volumetric Flow Rate:
Volumetric Flow Rate = Mass Flow Rate/Density
Density of Lactide = 1340 Kg/m3
Volumetric Flow Rate of lactide = 1011.85 m3/day
Initial Concentration
Mo=molar flow rate/Vol. Flow rate
Initial Conc. Of Lactide=9.29 Kgmol/m3
Initial Conc. Of Catalyst=0.0002497 Kgmol/m3
I = catalyst concentration in mole %=2.6%
Rate of reaction
A reversible kinetic model for the polymerization of lactide, catalyzed by tin octoate in bulk.
Rate Equation
Mo = Initial Concentration of Lactide Monomer=9.29 Kgmol/m3
I = catalyst concentration in mole % (2.6mol%)
Kp = propagation rate constant in [1/cat. mole%-hr]
Ref :MODELING AND SIMULATION OF POLYMERIZATION OF LACTIDE TO
POLYLACTIC ACID, Boyd T. Safrit, LIST USA, Inc., Charlotte, NC George E. Schlager, LIST
USA, Inc., Charlotte, NC Ziang Li, University of Texas at Austin, Austin, TX
Rate constant
Kp = 86 e(ea/rt )
Ea= energy of activation 69900 j/mol
R = gas constant 8.314 j/mol.k
T=temp. (1146 k)
So,
Kp = 0.059 mol%-1hr-1

65
Chapter No 6 Design Of Equipments

Rate of reaction

-rp = dM(t)/dt = 1.118Kgmole/m3.hr


Residence Time:
As for CSTR (Conversion 73.74 %)
Conversion Graph Appendix A (Fig 6)

So,
=5.78 hr
Reactor Volume
Vr= *VFR
So,
V=243.79 m3
There are two reactors in series and the ratio of their residence time is given in literature. 1
So,
Reactor Volume of the 1st reactor=121.89m3
Reactor Volume of the 2nd reactor=121.89m3
By giving 20% allowance
Volume of the 1st reactor=146.268 m3
Volume of the 2nd reactor=146.268m3
Time & coversion model
Conversion Graph Appendix C1
Design of impeller Reactor 01
Dimensions of the reactor:
Height of the reactor=H=1.5*D
Diameter of the reactor=D

So,

66
Chapter No 6 Design Of Equipments

D = 4.91 m & H = 7.36 m


Shape Factors of impeller:
Diameter of impeller=Da=4.91*0.33=1.6m
Height of impeller =E=0.33*4.91=1.6m
Length of Blade =L=0.25*1.6=0.4m
Width of Blade =W=0.20*1.6=0.32m

Design of impeller
Reactor 02
Dimensions of the reactor:
Height of the reactor=H=1.5*D
Diameter of the reactor=D

So,
D = 4.91 m & H = 7.36 m
Shape Factors of impeller:
Diameter of impeller=Da=4.91*0.33=1.6m
Height of impeller =E=0.33*4.91=1.6m
Length of Blade =L=0.25*1.6=0.4m
Width of Blade =W=0.20*1.6=0.32m
Liquid Height=H=4.91m
Six Blade Disk Turbine Selected
Power Calculation
Power(P)
P = Kln2Da3µ
Reynolds number
Re = Da2n⍴/ µ
N = 0.5 rev/sec ⍴= 1340kg/m3
µmix =300 pa.sec
By Putting values
Re =5.7
Kl=65 (from table 9.2 Mccabe Smith,page 256)
So, power will be;
P=19968W
P=19.968 kw
Mechanical Design
Operating Pressure =1333Pa
Atmospheric Pressure=101325Pa
Hrdrostatic Pressure=density*gh

67
Chapter No 6 Design Of Equipments

Hrdrostatic Pressure =1340*9.8*4.91


Hrdrostatic Pressure =64478.12Pa
Total Pressure= (Operating Pressure + Atmospheric Pressure+ Hydrostatic Pressure)
Total Pressure=167136.12Pa
Design Pressure
Design Pressure=1.1*Operating pressure
Design Pressure=(1.1*167136.12)
Design Pressure=183.84973kpa
Design Stress
For100-200 0C Design Stress (f)=105 N/mm2 for carbon Steel
Wall Thickness
E=(pidi/2jf-Pi)
E=Thickness of Wall
Pi =Internal pressure=183.8497kpa
Ft=Design stress=105*106 pa
J=Joint efficiency=0.85
C=Corrosion allowance=4mm
So,
E = .0051m or e = 5.06mm
Corrision Allowance = 4mm
E = 9.06mm
Specification Sheet At Appendix D (SS7)

68
Chapter No 7
Instrumentation & Process Control
7. Instrumentation And Process Control
Process control refers to the methods that are used to control process
variables when manufacturing a product. For example, factors such as the proportion of one
ingredient to another, the temperature of the materials, how well the ingredients are mixed, and
the pressure under which the materials are held can significantly impact the quality of an end
product. Manufacturers control the production process for three reasons:
1) Reduce variability
2) Increase efficiency
3) Ensure safety
The three tasks associated with any control loop are
1) Measurement,
2) Comparison
3) Adjustment.

7.1. Process Variable


A process variable is a condition of the process fluid (a liquid or gas) that can
change the manufacturing process in some way. In the example of you sitting by the fire, the
process variable was temperature. While Controlling the Level , the process variable is level
Common process variables include:
a) Pressure
b) Flow
c) Level
d) Temperature
e) Density
f) Ph (acidity or alkalinity)
g) Liquid interface (the relative amounts of different liquids that are combined in a vessel)
h) Mass
i) Conductivity

69
Chapter No 7 Instrumentation And Process Control

7.2. Setpoint
The setpoint is a value for a process variable that is desired to be maintained. For
example, if a process temperature needs to kept within 5 °C of 100 °C, then the setpoint is 100
°C. A temperature sensor can be used to help maintain the temperature at setpoint. The sensor is
inserted into the process, and a contoller compares the temperature reading from the sensor to the
setpoint. If the temperature reading is 110 °C, then the controller determines that the process is
above setpoint and signals the fuel valve of the burner to close slightly until the process cools to
100 °C. Set points can also be maximum or minimum values. For example, level in tank cannot
exceed 20 feet.

7.3. Primary Elements/Sensors


In all cases, some kind of instrument is measuring changes in the
process and reporting a process variable measurement. Some of the greatest ingenuity in the
process control field is apparent in sensing devices. Because sensing devices are the first element
in the control loop to measure the process variable, they are also called primary elements.
Examples of primary elements include:
1. Pressure sensing diaphragms, strain gauges, capacitance cells
2. Resistance temperature detectors (RTDs)
3. Thermocouples
4. Orifice plates
5. Pitot tubes
6. Venturi tubes
7. Magnetic flow tubes
8. Radar emitters and receivers
9. Ultrasonic emitters and receivers
Primary elements are devices that cause some change in their property with changes in process fluid
conditions that can then be measured. For example, when a conductive fluid passes through the magnetic
field in a magnetic flow tube, the fluid generates a voltage that is directly proportional to the velocity of
the process fluid. The primary element (magnetic flow tube) outputs a voltage that can be measured and
used to calculate the fluid‘s flow rate. With an RTD, as the temperature of a process fluid surrounding the
RTD rises or falls, the electrical resistance of the RTD increases or decreases a proportional amount. The
resistance is measured, and from this measurement, temperature is determined.

7.4. Signals
There are three kinds of signals that exist for the process industry to transmit the process
variable measurement from the instrument to a centralized control system.

70
Chapter No 7 Instrumentation And Process Control

1. Pneumatic signal
2. Analog signal
3. Digital signal

7.4.1. Pneumatic Signals


Pneumatic signals are signals produced by changing the air pressure in a
signal pipe in proportion to the measured change in a process variable. The common industry
standard pneumatic signal range is 3–15 psig. The 3 corresponds to the lower range value (LRV)
and the 15 corresponds to the upper range value (URV). Pneumatic signaling is still common.
However, since the advent of electronic instruments in the 1960s, the lower costs involved in
running electrical signal wire through a plant as opposed to running pressurized air tubes has
made pneumatic signal technology less attractive.

7.4.2. Analog Signals


The most common standard electrical signal is the 4–20 mA current signal. With
this signal, a transmitter sends a small current through a set of wires. The current signal is a kind
of gauge in which 4 mA represents the lowest possible measurement, or zero, and 20 mA
represents the highest possible measurement.

7.4.3. Digital Signals


Digital signals are the most recent addition to process control signal technology.
Digital signals are discrete levels or values that are combined in specific ways to represent
process variables and also carry other information, such as diagnostic information. The
methodology used to combine the digital signals is referred to as protocol.
Manufacturers may
use either an open or a proprietary digital protocol. Open protocols are those that anyone who is
developing a control device can use. Proprietary protocols are owned by specific companies and
may be used only with their permission. Open digital protocols include the HART® (highway
addressable remote transducer) protocol,

71
Chapter No 8
Cost Estimation
8. Cost Estimation
Equipments Cost Year Cost Index 2007 2013
Fermentor 2007 525.4 55800 63721.18
11 Hydro Cyclones 2013 655.5 138600 158275.2
Prepolymer Rector N 0.6 799900 913451
Lactide Reactor 986200 1126198
Calendria 56300 64292.15
Polymer Reactor 622600 710982.1
Crystalizer 435000 496751.1
Micro Filter 621200 709383.4
Rotary Filter 185100 211376.2
Vibrating Screen 18700 21354.59
2 Tank Cost 73400 83819.61
2 Flash Column Cost 23000 26265
Triple Effect Evaporator 132600 151423.4
Vacume Drum 621600 709840.2
Vessel 46700 53329.37
Acidification Unit 70500 80507.94
Grinder 64700 73884.59
Devolatilizer 91800 104831.6
Dryer 80900 92384.28
Total Equipment Cost in 2007 5124600
Total Equipment Cost in 2013 5851535

)^.6 1.141852

Cost Index Table Appendix B (Table 8)


Cost Index Graph At Appendix A (Fig 7)

72
Chapter No 8 Cost Esrimation

Cost in 2013=cost in 2007*((cost index in 2013)/( *(cost index in 2007))n


Cost in 2013=5124600*(655.5/525.4).6
Cost in 2013= 5851535 $
Normalized %
Components Selected %age Of FCI Estimated Cost
age of FCI
Direct Cost (Dollar)

Purchased Equipment 26 5851535 18.05556

Purchased equipment 2025531 6.25


9
installation
Instrumentation 1350354 4.166667
6
Installed

9 2025531 6.25
Piping (installed)

5 1125295 3.472222
Electrical (Installed)

Building (Including 2025531 6.25


9
Services)

Yard Improvements 3 675177.1 2.083333

Service Facilities 4051063 12.5


18
(Installed)

Land 1 225059 0.694444

19355077
Total direct Plant cost

Indirect Cost (Rs)


Engineering & 2475649 7.638889
11
Supervision

10 2250590 6.944444
Construction Expense

1 225059 0.694444
Legal Expense

3 675177.1 2.083333
Contractor's fee

9 2025531 6.25
Contrigency

7652007
Total indirect Plant cost

WCI (20 % of TCI)


5401417 16.66667

32408502 100
TCI

73
Chapter No 8 Cost Esrimation

Plant Capacity Vs Labour Graph Appendix A (Fig 8)


Life Period Vs Asset Graph Appendix A (Fig 9)
SurfaceArea Vs Relative Cost Graph Appendix A ( Fig 10)

74
Chapter No 9
Hazop Study
9. HAZOP Study

9.1. Introduction:
The technique of hazard operability studies or in more common terms HAZOP, has
been used and develop approximately decades for identifying potential hazard and operability
problems caused by deviation from the design intent of both and new and existing process plants.
Before processing further, it might be as well to clarify some aspects of these statements.
[113]
HAZOP can be defined as
“In it we look at the hazard associated with the process when the process departs from normal
Operation‖
Industries in Which the Technique Is Applied
HAZOP were initially invented by ICI in the
United Kingdom but the technique only started to be more widely used within the chemical
industries after the Fix borough disaster in which a chemical plant explosion kill 28 people,
many if were ordinary house holders living nearby. Through the general exchange of ideas and
personnel, the system was adopted by the petroleum industries, which has a similar potential of
major disasters. This was then followed by the food and water industry, where the hazard
potential is as great, but of a different nature, the concern being more to do with contamination
rather than explosions or chemical release.
Basic Concept:
Essentially the HAZOP procedure involves taking a full description of process
and systematically questioning every part of it establishes how deviation from the design intent
and their consequences can have a negative effect upon the safe end and efficient operation of
plant. If consider necessary action is then taken to remedy the situation. The critical analysis is
applied in a structured way by a HAZOP team and it relies upon them releasing their imagination
in an effort to discover credible causes of deviations. In practice, many causes will br fairly,
obvious such as pump failure causing of circulation loss in a cooling water facility mentioned
above. However, than a mechanistic checklist type of review. The result is that there good chance
that potential failures and problems will be identified, which had not previously been
[113,114]
experienced in the type of plant being studied.

75
Chapter No 9 Hazop Study

9.2. Objective
The objectives of a HAZOP study can be summarized as follows:
1) To identify (areas of the design that may possess a significant hazard potential.
2)To identify and study features of the design that influence the probability of a hazardous
incident occurring.
3) To familiarize the study team with the design information available.
4) To ensure that a systematic study is made of the areas of significant hazard potential.
5) To identify pertinent design information not currently available to the team.
6) To provide a mechanism for feedback to the client of the study team's detailed comments.

9.3. Key Words


As essential feature in this questioning and systematic analysis is the use of Key
words to focus the attention of the team upon deviations and their possible causes. The key
words are divided into two subsets.Primary key words: which focus upon a particular aspect of
the design intent or a n associated process condition or parameter. Secondary key words: which
[115]
when combined with a primary key word, suggest possible deviations.
The entire technique of HAZOP revolves around the effective use of key words, so their meaning
and use must be clearly understood by the team. Example often used key words are listed below.

9.3.1. Primary Key Words


These reflect both the process design intent and operational aspects of the
plant being studied. Typical process oriented words might be as follows. The list below is purely
illustrative, as the words employed in a review will depend upon the plant being studied.
Remembering that the technique is called Hazard and Operability studies, added to the above
[113]
might be relevant operational words such as mentioned below:

Flow Pressure
Isolate Drain
Temperature Level
Vent Purge
Separate (settle, Composition
filter, centrifuge) Inspect Maintain
React Corrode
Start up Shut down

76
Chapter No 9 Hazop Study

9.3.2. Secondary Key Words


As mentioned above, when applied in a conjunction with a primary key word, these suggest
the potential deviations or problems.
They tend to be a standard set as listed below:

Word Meaning
No The design intent does not occur (e.g. flow), or the optional aspect is not
achieved (Isolate/No)
Less A quantitative decrease in the design intent occur (e.g. Pressure/Less)
More A quantitative increase in the design intent occur (e.g.
Temperature/More)
Reverse The opposite of the design intent occurs (e.g. Flow/Reverse)
Other The activity occurs, but not in the way intended (e.g. Flow/Other) could indicate
a leak or product flowing where it should not, or composition/other might
suggest unexpected proportions in a feedstock
As well as A quantitative increase
Part of A quantitative decrease

–Early: something happens earlier in time than intended


–Late: something happens later in time than intended
–Before: something happens earlier in a sequence than intended
[117]
–After: something happens later in a sequence than intended

9.4. HAZOP Study Methodology:


In simple terms the HAZOP study process involves applying in a
systematic way all relevant keywords combining to the plant in question in an effort to uncover
potential problems. The results are recorded in a columnar format under the headings,

Deviation Cause Consequences Safeguard Action

In considering the information to be recorded in each of these columns is given below.


Deviation:
The key words combination being applied (e.g. Flow/No)
Cause:

77
Chapter No 9 Hazop Study

Potential cause which would result in the deviation occurring (e.g. ―strainer blockage due
to impurities in Dosing tank‖ might be a cause of Flow/No).
Consequences:
The consequences which would arise, both from the effect of the deviation (e.g.
―Loss of dosing results in complete separation‖) and, if appropriate from the cause itself (e.g.
―cavitation‖ in pumps, with possible damage if prolonged‖).
Safeguards:
Any existing protective devices, which either prevent the cause or safeguards against
the adverse consequences, would be recorded in this column. For example you may consider
recording ―Local pressure gauge in discharge from pump might indicate problem was arising‖.
Note that safeguard need not to be restricted hardware where appropriate credit can be taken for
procedural aspects such as regular plants inspections (if you sure that they will actually be
carried out).
Action:
Where a credible cause results in a negative consequence, it must be decided whether
some action should be taken. It is at this stage that consequences and associated safeguards are
considered. If it is deemed that the protective measures are adequate, then no action need to take,
and words to that effects are recorded in the action column. Action falls in two groups:
1. Action that remove the cause
2. Action that mitigate or eliminate the consequences

Whereas former is to be preferred, it is not always possible especially when dealing with
equipments malfunction. However, always investigate removing the cause first and only where
necessary mitigate the consequences. Finally always take into account the label of training
experience especially of personnel who will operate the plant. Actions, which call for elaborate
and sophisticated protective systems, are wasted, as well as being inherently dangerous, if
operators do not and never will, understand how they function. It is not unknown for devices to
be disabled, either deliberately or in error, because no one knows how to maintain and calibrate
them. Having gone through the operations involve in recording a single deviation, these can now
be put into the context of the actual study meeting procedure. From the flow diagram below it
can be seen that it is very much an iterative process, applying in a structured and systematic way
the relevant keyword combinations in order to identify potential problems.

9.4.1. HAZOP Study Steps[117]


A HAZOP study is conducted in the following steps:

78
Chapter No 9 Hazop Study

1) Specify the purpose, objective, and scope of the study. The purpose may be the
analysis of a yet to be built plant or a review of the risk of an existing unit.
Given the purpose and the circumstances of the study, the objectives listed above
can he made more specific. The scope of the study is the boundaries of the
physical unit, and also the range of events and variables considered. For
example, at one time HAZOP's were mainly focused on fire and explosion
endpoints, while now the scope usually includes toxic release, offensive odor,
and environmental endpoints. The initial establishment of purpose, objectives,
and scope is very important and should be precisely set down so that it will be
clear, now and in the future, what was and was not included in the study. These
decisions need to be made by an appropriate level of responsible management.

2) Select the HAZOP study team. The team leader should be skilled in HAZOP and
in interpersonal techniques to facilitate successful group interaction. As many
other experts should be included in the team to cover all aspects of design,
operation, process chemistry, and safety. The team leader should instruct the
team in the HAZOP procedure and should emphasize that the end objective of a
HAZOP survey is hazard identification; solutions to problems are a separate
effort.

Guide Meaning
Words
No Negation of design
intent
Less
Quantitative decrease
More
Quantitative increase
Part of
Qualitative decrease
As well as
Qualitative Increase
Reverse
Logical opposite of the
Other than intent

Complete substitution

79
Chapter No 9 Hazop Study

3) Conduct the study. Using the information collected, the unit is divided into
study "nodes" and the sequence diagrammed in Figure, is followed for each
node. Nodes are points in the process where process parameters (pressure,
temperature, composition, etc.) have known and intended values. These values
change between nodes as a result of the operation of various pieces of
equipment' such as distillation columns, heat exchanges, or pumps. Various
forms and work sheets have been developed to help organize the node process
parameters and control logic information.

When the nodes are identified and the parameters are identified, each node is studied by applying
the specialized guide words to each parameter. These guide words and their meanings are key
elements of the HAZOP procedure.
Repeated cycling through this process, which considers how and why each parameter might vary
from the intended and the consequence, is the substance of the HAZOP study.
4) Write the report. As much detail about events and their consequence as is
uncovered by the study should be recorded. Obviously, if the HAZOP identifies
a not improbable sequence of events that would result in a disaster, appropriate
follow-up action is needed. Thus, although risk reduction action is not a part of
the HAZOP, the HAZOP may trigger the need for such action.
The HAZOP studies are time consuming and expensive. Just getting the P & ID's up to date
on an older plant may be a major engineering effort. Still, for processes with significant
risk, they are cost effective when balanced against the potential loss of life, property,
business, and even the future of the enterprise that may result from a major release.

80
Chapter No 9 Hazop Study

Sequence For Conducting Hazop Study

81
Chapter No 9 Hazop Study

9.5. Hazop Study On Flash Column

82
Chapter No 9 Hazop Study

[114,117]
More CAUSES can be identified for one DEVIATION.
Causes for LESS LEVEL in V-40
•FCV8 stuck open
•LESS inlet Flow
•MORE Flow in line 8
Consequences
1) The results of the DEVIATION, in case it occurs. CONSEQUENCES may both comprise
process hazards and operability problems, like plant shutdown.
2) More CONSEQUENCES can follow from one cause and, in turn, one CONSEQUENCE
can have several CAUSES
3) Consequence for LESS LEVEL in V40
–V-40 empty, leading to pump P8 running dry
–No separation
Protection
1) These are facilities that help to reduce the occurrence frequency of the DEVIATION or to
mitigate its CONSEQUENCES.
2) There Are In Principle Five Types Of Safe Guards
i. Facilities that identify the DEVIATION. eg. alarm instrumentation and human
operator detection.
ii. Facilities that compensate the DEVIATION, e.g., an automatic control system
iii. Facilities that prevent the DEVIATION to occur. e.g. an inert blanket gas in
storages of flammable substances.

83
Chapter No 9 Hazop Study

iv. Facilities that prevent a further escalation of the DEVIATION, e.g., by (total)
trip of the activity (SIS facility)
v. Facilities that relieve the process from the hazardous DEVIATION. These
comprise for instance: pressure safety valves (PSV) and vent systems.
–Protection against LESS LEVEL in V40
LIC8 controlling the liquid level
Action/Recommendation
1) Where a credible cause results in a negative consequence, it must be decided whether
some action should be taken.
2) It is at this stage that consequences and associated safeguards are considered. If it is
deemed that the protective measures are adequate, then no action need be taken, and
words to that effect are recorded in the Action column.
3) Actions fall into two groups:
i. Actions that remove the cause.
ii. Actions that mitigate or eliminate the consequences.

Action
1) Existing Protection for LESS LEVEL is considered not adequate.
2) Actions Proposed
i. Add Low level Alarm (LAL and LALL)
ii. Add SIS to stop pump P8 when LALL triggered.

84
Chapter No 9 Hazop Study

9.6. Hazop Sheet OF Flash Column[4]

85
Chapter No 9 Hazop Study

9.7. Hazop Study Of Heat Exchanger

Deviation Cause of Consequenc Additional Indication Notes and


Deviation es of Element
Consequences Questions
Deviation
Decrease in Fouling Acquired Downstream Temperatu Fluid in the
Heat transfer temperature Equipment will re indicator Exchanger
conditions get disturbed should be
not achieved analyzed
frequently.

Erosion of Disturbance The rate of The fluid in Pressure Preventive and


tubes. in PH of heat tubes might indicator schedule
cooling transfer leak into the Analyzer Maintenances
water. and shell or vice should must be
integrity of versa. This performed.
Erosion due
the heat could cause a
to sulphur
exchanger serious
Abnormal with problem for the
pressure respect to plant.
and strength
temperature will
conditions. decrease.

86
Chapter No 10
Appendix
10. Appendix A

87
Chapter No 10 Appendixes

Figure 4

88
Chapter No 10 Appendixes

Figure 5

0.009

0.008

0.007

0.006

0.005
-1/rA

0.004

0.003

0.002

0.001

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
XA ( Conversion)

Figure 6

89
Chapter No 10 Appendixes

Figure 7

Cost Index
800

700

600

500
Cost($)

400

300 Cost Index

200

100

0
1985 1990 1995 2000 2005 2010 2015 2020
Year

90
Chapter No 10 Appendixes

91
Chapter No 10 Appendixes

92
Chapter No 10 Appendixes

93
Chapter No 10 Appendixes

10.1. Appendix B

94
Chapter No 10 Appendixes

Table 3

95
Chapter No 10 Appendixes

Table 4
Potato Production Costs in Pakistan per Acre
Potato yield / acre for Norland / Atlantic
11 Year 1 Year 2
variety (MT)
Unit Quantity Rate Amount Quantity Rate Amount
Seed
Norland or Atlantic Varieties from USA
No. 25 1,450 36,250 25 nil -
(25kg Crate)
Fertilizer
DAP (50 kg Bag) No. 3.00 750 2,250 3 750 2,250
Urea (50 kg Bag) No. 4.00 395 1,580 4 395 1,580
SOP (50 kg Bag) No. 3.00 797 2,391 3 797 2,391
Pesticide
Alpha Cyper (1 Spray of 500 ml) Litre 0.50 300 150 0.50 300 150
Monitor (1 Spray of 500 ml) Litre 0.50 205 103 0.50 205 103
Imedacleparid (1 Spray of 200 grams) Kg 0.20 1,380 276 0.20 1,380 276
Fungicide
Dithane-M Kg 1.00 325 325 1.00 325 325
Intracol Kg 1.00 340 340 1.00 340 340
Ridonal (250 Grams) Kg 0.25 912 228 0.25 912 228
Weedicide
1 Spray of 250 Grams Kg 0.25 1,565 391 0.25 1,565 391
Preparation of Land
Tillage (on basis of renting tractor
390 390
services) per Acre
Seed Bed Preparation
Making of Ridges for Plantation (Fuel
390 390
Consumption + Tractor) per Acre
Sowing of Seeds/Tubers
5 persons sow 4 Acres in 8 hours shift (4
unskilled laborers + 1 Seed Planter Man hrs 10 20 195 10 20 195
Operator) Average Sowing Cost per Acre
Irrigation
12 waterings per Acre per Crop by
Turbine operated tubewell (cost per hour Hrs 12 95 1,145 12 95 1,145
for running trubine)
Harvesting
Harvesting Charges per Acre 490 490
Other Costs
Land Revnue (Malia) per Acre per acre 50 50
Land Lease for 3 months crop season per acre 2,000 2,000
Casual Labour for the Crop Season of 90
Man hrs 720 8 5,998 720 8 5,998
Days
Cost of Storage Potatoes for Seeds (flat
6 150 900
rate 6 months)
Cost of Production per Acre (in Rs) 54,936 19,586
Cost (Rs) / Metric Ton 4,994 1,781
Cost (US $) / Metric Ton (Rs/US $ = 62) 80.55 28.72
Cost (US $) / Kg (Rs/US $ = 62) 0.08 0.03

96
Chapter No 10 Appendixes

Table 5

XA 1-XA XA2 -rA -1/rA

0.16 0.84 0.256 1980.271 0.000505

0.32 0.68 0.1024 1463.622 0.000683

0.48 0.52 0.2304 859.55 0.001163

0.64 0.36 0.4096 168.069 0.00595

0.8 0.2 0.64 120.863 0.008274

Dew Point (Table 6)

Xi ( Weight
VP K Value weight
Components Fraction) Xi*K
(Bar) ( Pi/P) (Kg)
Water 6.85 2.28333333 81917.52 0.058 0.132433
Lactide 2.776 0.92533333 1330453 0.942 0.871664
1412371 1 1.001097

Bubble Point (Table 7)

yi ( Weight
VP K Value weight
Components Fraction) Yi/K
(Bar) ( Pi/P) (Kg)
Water 7.8 3.01 81917.52 0.058 0.019269
Lactide 3.2 0.96 1330453 0.942 0.98125
1412371 1 1.000519

97
Chapter No 10 Appendixes

Table 8

Year Cost Index


1987 324
1988 343
1989 355
1990 357.6
1991 361.3
1992 358.2
1993 359.2
1994 368.1
1995 381.1
1996 381.7
1997 386.5
1998 389.5
1999 390.6
2000 394.1
2001 394.3
2002 390.4
2003 402
2004 444.2
2005 468.2
2006 499.6
2007 525.4
2008 575.4
2009 521.9
2010 550.8
2011 585.7
2012 620.6
2013 655.5
2014 690.4
2015 725.3

98
Chapter No 10 Appendixes

10.2. Appendix C
Figure 1

Figure 2

Figure 3

99
Chapter No 10 Appendixes

Figure 4

Figure 5

100
Chapter No 10 Appendixes

Figure 6

Figure 7

101
Chapter No 10 Appendixes

10.3. Appendix D
Specification Sheet (SS1)

Inside diameter 15.74″


Diameter of inner vortex 5.509″
Length of inner vortex 8.657″
Efficiency of hydro cyclones 94%

102
Chapter No 10 Appendixes

Specification Sheet (SS2)

103
Chapter No 10 Appendixes

Specification Sheer (SS3)

104
Chapter No 10 Appendixes

Specification Sheet (SS4)

Specification Sheet Values

Growth rate or rate constt, µ or k 0.0768hr-1

Residence time 0.49 hr or 29.4 min

Space velocity, s 2.04hr-1

Monod Constant, CM 1.68g/l

Order of reaction, n 1

Temperature 37oc or 310k

Operating pressure 1.8atm

Design pressure, Pi 1.98atm

Number or reactor 18

Volume, V 12685.82m3

Volume of each reactor, v1= 704.767m3


v2=…..v18

Height of vessel, h 12.641m

Diameter, Di 8.427m

Wall thickness, e 6.184mm

Domed head 8mm

Ellipsoidal head 6.180mm

Impeller diameter, Da 2.809m

Speed of impeller, n 100RPM or 1.67rev/s

Power, P 4903.68 KW

105
Chapter No 10 Appendixes

Specification Sheet (SS5)

For Prepolymer Reactor

Residence Time 12.4593 hr

Volume 580.60 m3

Diameter Of Reactor 7.9m

Length Of Reactor 11.85 m

Operating Pressure .455N/mm2

Design Stress 105 N/mm2

Design Pressure .4955 N/mm2

Hydrostatic Pressure .0626N/mm2

Atmospheric Pressure .101325 N/mm2

Total Pressure .164435 N/mm2

Total Wall Thickness 13.028mm

Thickness Of Ellipsoidal Head 13.009mm

106
Chapter No 10 Appendixes

Specification Sheet (SS6)

Heat Rate 4641706 Btu/hr

LMTD 172.93 0F

Outer Dia Of pipe Of Coil 10.367 Inch or =.864 ft

Flow Area Per Pipe .547 ft2

Mass Velocity 18736 lb/hr.ft2

Re No. 431562

Jh 800

UC 15.82091 Btu/hr.ft2 0F

Ud 13.6598 Btu/hr.ft2 0F

Area Of Coil A=3089.161ft2

Circumference Of coil Πd 2.814 ft

Length Of One Coil 1098 ft

Number Of Turns 390

107
Chapter No 10 Appendixes

Specification (SS7)
Parameter Value

Reactor Type CSTR

Temperature 195

Operating pressure 1333Pa

Design pressure, Pi 183.84kpa

Number or reactor 2 reactor

Residence time 5.78 hr

Space Velocity 0.17 hr-1

Volume, Vr 243.79m3
Volume of each reactor, V1=V2 146.268m3

Height of vessel, h 7.36m

Diameter, Di 4.91m

Power 19.968 KW

Wall thickness, e 9.06 mm

108
Chapter No 11
References
11. REFERENCES
[1”] H. Benninga, A History of Lactic Acid Making, Springer, New York, 1990.
[2”] W. H. Carothers, G. L. Dorough, F. J. Van Natta. J. Am. Chem. Soc.1932, 54, 761–772.
[3”] P. R. Gruber, E. S. Hall, J. J. Kolstad, M. L. Iwen, R. D. Benson, R. L. Borchardt, U.S.
Patent 6,326,458, 2001.
[1]. R. Narayan, Drivers & rationale for use of biobased materials based on life cycle assessment
(LCA), GPC 2004 Paper Abstract #18, Michigan State University, 2004.
[2]. D. Garlotta, J. Polym. Environ. 2001, 9(2), 63–84.
[3]. A. P. Gupta, V. Kumar, Eur. Polym. J. 2007, 43, 4053–4074.
[4]. M. H. Hartmann, High molecular weight polylactic acid polymer, in: D. L. Kaplan (Ed.),
Biopolymers from Renewable Resources, Springer, Berlin, 1998, Chapter 15, pp. 367–411.
[5]. J. Nieuwenhuis, Clin. Mater. 1992, 10, 59–67.
[6]. D. R. Witzke, Introduction to properties, engineering, and prospects of polylactide polymers,
Ph.D. thesis, Department of Chemical Engineering, Michigan State University, East Lansing,
MI, 1997.
[7]. D. E. Henton, P. Gruber, J. Lunt, J. Randall, Polylactic acid technology, in: A. K. Mohanty,
M. Misra, L. T. Drzal (Eds.), Natural Fibers, Biopolymers, and Biocomposites, CRC Press, 2005,
Chapter 16, pp. 527–577.
[8]. D. W. Grijpma, A. J. Pennings, Macromol. Chem. Phys. 1994, 196, 1649–1663.
[9]. J. J. Kolstad, J. Appl. Polym. Sci. 1996, 62, 1079–1091.
[10]. R. G. Sinclair, E. S. Lipinsky, U.S. Patent PATN 5,502,158, 1996 (to Ecopol LLC).
[11]. Cargill/NatureWorks LLC Press Release, July 1, 2009, available at
http://www.natureworksllc.com (accessed date: July 24, 2009).

109
Chapter No 11 References

[12]. C. W. Scheele, Kgl. Vetenskaps-Academiens nya Handlingar (Stockholm) 1780, 1, 116–


124.
[13]. L. Dobbin, The Collected Papers of Carl Wilhelm Scheele, G. Bell & Sons Ltd, London,
1931.
[14]. C. H. Holten, A. M€uller, D. Rehbinder, Lactic Acid, Verlag Chemie, Weinheim, 1971.
[15]. H. Benninga, A History of Lactic Acid Making, Kluwer Academic Publishers, Dordrecht,
1990.
[16]. C. Avery, U.S. Patent 243,827, 1881 (to Avery Lactate Company).
[17]. F. Kraft, W. A. Dyes, Ber. Dtsch. Chem. Ges. 1895, 28, 2589–2597.
[18]. H. Borsook, H. M. Huffman,Y. P. Liu, J. Biol. Chem. 1993, 102, 449–460.
[19]. A. Schouten, J. A. Kanters, J. van Krieken, J. Mol. Struct. 1994, 323, 165–168.
[20.] PURAC internal data.
[21]. G. Saville, H. A. Gundry, Trans. Faraday Soc. 1959, 55, 2036–2038.
[22]. A. S ˇ epitka, Pru_ mysl Potravin 1961, 13, 661–665.
[23]. R. A. Troupe,W. L. Aspy, P. R. Schrodt, Ind. Eng. Chem. 1951, 43, 1143–1146.
[24]. W. Ostwald, Z. Phys. Chem. 1889, 3, 170–197, 241–288, 369–22.
[25]. H. M. Huffman, E. L. Ellis, H. Borsook, J. A. Chem. Soc. 1940, 62, 297–299.
[26]. G. S. Parks, S. B. Thomas, D.W. Light, J. Chem. Phys. 1936, 4, 64–69.
[27]. J. van Breugel, J. van Krieken, A. Cerda Baro, J. M. Vidal Lancis, M. Camprubi Vila, WO
00/56693, 2000 (to PURAC).
[28]. J. van Krieken, WO 02/022546, 2002 (to PURAC).
[29]. W. P. Hammes, C. Hertel, The genera Lactobaccilus and Carnobacterium, in: M. Dworkin,
S. Falkow, E. Rosenberg, K.-H. Schleifer, E. Stackebrandt (Eds.), The Prokaryotes, 3rd edition,
Springer, New York, 2006, pp. IV/320 ff. 30. M. T. Madigan, J. M. Martinko, J. Parker, Brock
Biology of Microorganisms, 9th edition, Prentice Hall, New Jersey, 2000, pp. 118–121.
[31]. O. Kandler, Antonie van Leeuwenhoek 1983, 49, 209–224.
[32]. C. Plumed-Ferrer, K. M. Koistinen, et al., Appl. Environ. Microbiol. 2008, 74, 5349–5358.
[33]. M. H. Saier, J. J. Ye, et al., J. Bacteriol. 1996, 178, 314–316.
[34]. A. M. Rodas, et al., Int. J. Syst. Evol. Microbiol. 2006, 56, 513–517.
[35]. M. Cocaign-Bousquet, C. Garrigues, P. Loubiere, N. D. Lindley, Antonie van
Leeuwenhoek 1996, 70, 253–267.
[36]. A. P. Oliveira, J. Nielsen, J. F€orster,BMCMicrobiol. 2005, 5, 39.
[37]. B. Teusink, et al., J. Biol. Chem. 2006, 281, 40041–40048.
[38]. N. V. Narendranath, et al., Appl. Environ. Microbiol. 1997, 63, 4158–4163.
[39]. W. F. Kemper, et al., Proc. Natl. Acad. Sci. USA 2001, 98, 723–728.
[40]. Z. Ying Zhang, B. Jin, J. M. Kelly, Biochem. Eng. J. 2007, 35, 251–263.
[41]. A. Vaidya, R. Pandey, S. Mudliar, M. Kumar, T. Chakrabarti, S. Devotta, Crit. Rev.
Environ. Sci. Technol. 2005, 35, 429–467.
[42]. O. Michio, K. Kimitoshi, Jpn. Patent 61293388, 1986 (to Daicel Chemical Industries).
[43]. J. P. de Boer, et al., Appl. Environ. Microbiol. 1993, 59, 2474–2478.
[44]. V. Rajgarhia, et al., WO 03/102201, 2003 (to Cargill Dow LCC).
[45]. M. Wada, et al., WO 05/033324, 2005 (to Mitsui Chemicals).

110
Chapter No 11 References

[46]. G. Bustos, A. B. Moldes, J. M. Cruz, J. M. Dominquez, J. Agric. Food Chem. 2004, 52,
801 808.
[47]. M.-T. Gao, et al., Bioresour. Technol. 2008, 99, 3659–3664.
[48]. M.-T. Gao, M. Hirata, E. Toorisaka, T. Hano, Bioresour. Technol. 2007, 97, 2414–2420.
[49]. T. J. Carlson, E. M. Peters, U.S. Patent 6,475,759, 2002 (to Cargill Inc.).
[50]. S. Saitoh, et al., Appl. Environ. Microbiol. 2005, 71, 2789–2792.
[51]. A. J. A. van Maris, et al., Appl. Environ. Microbiol. 2004, 70, 2898–2905.
[52]. W. N. Konings, et al., Antonie van Leeuwenhoek Int. J. Gen. Mol. Microbiol. 1997, 71(1–
2), 117–128.
[53]. D. Visser, J. van Breugel, J. M. de Bruijn, P. A‘Campo, WO 08/000699, 2008 (to PURAC
Biochem BV).
[54]. R. L. Whistler, J. N. BeMiller, Carbohydrate Chemistry for Food Scientists, 1st edition,
American Association of Cereal Chemist Inc., St. Paul, 1997, 117 pp.
[55]. R. Anuradha, A. K. Suresh, K. V. Venkatesh, Process Biochem. 1999, 35, 367–375.
[56]. E. Y. Park, P. Ngoc Anh, N. Okuda, Bioresour. Technol. 2004, 93, 77–83.
[57]. S. I. Abe, M. Tagaki, Biotechnol. Bioeng. 1991, 37, 93–96.
[58]. S. Ding, T. Tan, Process Biochem. 2006, 41, 1451–1454.
[59]. E. Ohleyer, H. W. Blanch, C. R. Wilke, Appl. Biochem. Biotechnol. 1985, 11, 317–332.
[60]. A. A. Dietz, E. F. Degering, H. H. Shopmeyer, Ind. Eng. Chem. 1947, 39, 82–85.
[61]. B. I. Veldhuis-Stribos, et al., WO 0127064 A1, 2000 (to PURAC).
[62]. J. van Krieken, et al., WO 05123647A1, 2005 (to PURAC).
[63]. A. M. Eyal, et al., WO 9919290, 1999 (to Cargill Inc.)
[64]. M. Bailly, Desalination 2002, 144, 157–162.
[65]. A. M. Baniel, et al., U.S. Patent 5,510,526, 1994 (to Cargill Inc.).
[66]. A. Kumagai, et al., EP 0614983A3, 1996 (to Musashino).
[67]. J. Martak, S. Schlosser, Sep. Purif. Technol. 2007, 57, 483–494.
[68]. P. Gruber, J. Kolstad, et al., U.S. Patent 5,338,822, 1992 (to Cargill Inc.); U.S. Patent
5,258,488, 1993 (to Cargill Inc.).
[69]. P. Gruber, J. Kolstad, et al., U.S. Patent 6277951B1, 1999 (to Cargill Inc.).
[70]. P. Coszach, J. C. Bogaert, F. van Gansberghe, U.S. Patent 0014975A1, 2006 (to Galactic).
[71]. J. Pelouze, J. Chem. Pharm. 1845, 53, 112–124.
[72]. H. Pohl, U.S. Patent 1,095,205, 1914 (to Gruter).
[73]. R. G. Sinclair, R. A. Markle, R. K. Smith, U.S. Patent 9,205,167, 1992 (to Battelle).
[74]. M. Noda, H. Okuyama, Chem. Pharm. Bull. 1999, 47, 467–471.
[75]. W. O‘Brien, L. A. Cariello, T. F. Wells, WO 9606092, 1995 (to Ecological Chemical
Products Company).
[76]. T. Matsuo, et al., U.S. Patent 25222379A1, 2005 (to Hitachi/ Toyota).
[77]. M. Kamikawa, et al., EP 1873185A1, 2006 (to Hitachi).
[78]. Th. M. Ford, U.S. Patent 5,310,599, 1993 (to Du Pont de Nemours & Co.).
[79]. J. Meerdink, A. S€odergard,WO05056509A1, 2003 (to Hycail).
[80]. I. D. Fridman, J. Kwok, U.S. Patent 5,264,592, 1993 (to Camelot Industries).
[81]. R. U. Scholz, R. P. M. van der Steen, (2007), WO/2007/148975, Purification of Lactide
Streams.

111
Chapter No 11 References

[82]. H. R. Kricheldorf, et al., Macromolecules 2000, 33, 702–709.


[83]. X. Zhang, et al., J. Polym. Sci. Part A 1994, 32, 2965–2970.
[84]. A. Kowalski, et al., Macromolecules 2000, 33, 7359–7370.
[85]. W. G. O‘Brien, et al., DE 44044838A1, 1993 (to Du Pont de Nemours & Co.).
[86]. W. G. O‘Brien, et al., U.S. Patent 5,521,278, 1994 (to Ecological Chemical Products).
[87]. P. Kruger, J. Hall, J. J. Kolstad, et al., U.S. Patent 6,005,067, 1998 (to Cargill Inc.).
[88]. P. Gruber, J. Hall, J. J. Kolstad, et al., WO 9509879A1, 1993 (to Cargill Inc.).
[89]. H. Tsuji, Macromol. Biosci. 2005, 5, 569–597.
[100]"Chemical Engineering Design, 4th Ed", By R. K. Sinnott, Elsevier Butterworth-
Hienemann, NY, 2005, ISBN 0-7506-6538-6
[101]"Chemical Engineering Economics", By D. E. Garrett, Van Nostrand Reinhold, NY, 1989,
ISBN 0-442-31801-4
[102]"Chemical Process Equipment - Selection and Design" by S. M. Walas, Butterworth-
Heinemann, Boston, 1990, ISBN 0-409-90131-8
[103]"Conceptual Cost Estimating Manual", by John S. Page, Gulf Publishing, Houston, 1996,
ISBN 0-88415-267-7
[104]"Costs for Hazardous Waste Incineration" by R. J. McCormick, etal., Noyes Pub, Park
Ridge, NJ, 1985, ISBN 0-8155-1047-0
[105]"Estimating Costs of Air Pollution Control", by W. M. Vatavuk, Lewis Publishing,
Chelsea, MI, 1990, ISBN 0-87371-142-4
[106]"Mine and Mill Equipment Costs" by Western Mine Engineering Inc, 1995,
www.westernmine.com
[107]"Mining and Mineral Process Equipment Cost and Preliminary Capital Cost Estimations"
by A. L. Mular, CIMM, 1982, ISBN 0-919086-02-0
[108] "Perry's Chemical Engineers' Handbook, 6th Ed.", by R. H. Perry & D. Green, McGraw-
Hill, NY, 1984, ISBN 0-07-049479-7
[109] "Plant Design and Economics for Chemical Engineers" by M. S. Peters & K. D.
Timmerhaus, McGraw-Hill, NY, 1991, ISBN 0-07-049613-7
[110]"Preliminary Chemical Engineering Plant Design, 2nd Ed", by W. D. Baasel, Van
Norstrand Reinhold, NY, 1990, ISBN 0-442-23440-6
[111]"Process Plant Construction Estimating Standards", by Richardson Engineering Service,
Mesa, AZ, 1995, (602) 497-2062
[112]"Shedding New Light on Titanium in CPI Construction" by J. S. Grauman & B. Willey,
Chem. Eng. Aug 1998, p 106 1998 Granger Catalog

112

You might also like

pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy