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A DISSERTATION
Submitted in partial fulfillment of the
requirements for the award of the degree
of
MASTER OF TECHNOLOGY
in
CHEMICAL ENGINEERING
(W ith S pecialization in C o m pu te r A ided P rocess P lant Design)
By
NAGESHW AR REDDY K
^ R A LU a ,
■ACC No.
-O
Date.
6/
I hereby declare that the work, which is being presented in the dissertation entitled
“M O D E L I N G AND SIMULATION OF CATALYTIC DISTILLATION FOR
ESTERIFICATION O F ACE T I C ACID W I T H M E T H A N O L USING A S P E N PLU S ”,
in the partial fulfillment of the requirements for the award of the degree of Master of
Technology in Chemical Engineering with specialization in “Computer Aided Process Plant
Design”, and submitted to the Department of Chemical Engineering, Indian Institute of
Technology Roorkee, Roorkee, is an authentic record of my own work carried out during the
period from July 2010 fo June 2011 under the guidance of Dr. Surendra kumar, Professor,
Department of Chemical Engineering, Indian Institute ofTechnology Roorkee.
I have not submitted the matter, embodied in this dissertation for the award of any other
degree.
Date:
CERTIFICATE
This is to certify that the above statement made by the candidate is correct to the best of my
knowledge and belief.
Professor
Department of Chemical Engineering
Indian Institute ofTechnology Roorkee
Roorkee-247667 (India)
ACKN O W LED G EM EN T
Thanks are due to Dr. Indra Deo Mall, Professor and Head of the Department, Department
of Chemical Engineering, Indian Institute of Technology Roorkee, Roorkee, for providing
various facilitiesduring this dissertation.
I am greatly indebted to m y friends and all others for their enthusiastic support,
Above all, I want to express m y heartiest gratitude to all m y family members for their love,
faith and support for me, which has always been a constant source of inspiration
( N A G E S H W A R R E D D Y K)
ABSTRACT
By using M E S H equations with the rate kinetic model equation for synthesis of
methyl acetate, mathematical model has been developed. The developed model has been
validated by comparing the composition profile in the liquid phase and variation of methanol
conversion haying the reflux ratio with the experimentaldata of Popken et al (2001).
Comparison shows the deviation of simulation results with the experimental results. Avg.
maximum deviation is found to be 30% in composition profiles, and maximum deviation is
v
found to be 14 % in variation of methanol conversion with reflux ratio.
In the above mentioned design variables, the reflux ratio, feed tray locations, end of
reactive stage and thermodynamic model have most significant effect on the methanol
conversion and methyl acetate composition in the distillate and the remaining column.
CONTENTS
Page No.
C A N D I D A T E ’S D E C L A R A T I O N i
ACKNOWLEDGEMENT ii
ABSTRACT iii
CONTENTS iv
LIST O F FIGURES vi
LIST O F T A B L E S vii
C H A P T E R 1: I N T R O D U C T I O N 1
1.1.W h y RD? 2
1.2.Comparison of Processes in Conventional
Distillation and R D 4
1.3 .Advantages of Reactive Distillation 6
1.4.Some Boundaries and Difficulties in R D „7
1.5. Introduction of Synthesis of Methyl Acetate 7
1.6.Objective of Thesis 8
C H A P T E R 2: L I T E R A T U R E R E V I E W 9
2.5.3. N E Q modeling o f R D 38
Model (homogeneous) 39
C H A P T E R 4: R E S U L T S A N D DISCUSSION 47
C H A P T E R 5: C O N C L U S I O N A N D R E C O M M E N D A T I O N S 60
REFERENCES 62
v
LIST OF FIGURES
Table 2.1 Details ofdifferent catalyst used for synthesis ofmethyl acetate 12
Table 2.2 Parameters and Residual Errors of the Different Kinetic Models 30
Used to Fitthe Experimental Data
Table 2.3 Parameters and Residual Errors of the Different Kinetic Models 31
Used to Fitthe Experimental Data with Amberlystl 5 as the
Catalyst
Table A.3 MeOAc liquid composition Data in distillate for Figure 4.3 68
IN T R O D U C T IO N
Reactive distillation or catalytic distillation process has been installed in many industries
in now-a-days. In this unit two functional works are included one as a reaction and another one is
separation process. By using this unit in industries can reduce the capital cost of equipments by
eliminating the two equipments in (reactor & distillation) industries. The concept of reactive
distillation was applied in the late 1920’s to esterification processes (Keys, 1932). The industrial
application of reactive distillation did not take place before 1980’s. Reactive distillation term
describes both catalytic and non-catalytic distillation. Operation of non-catalytic reactions in R D
is very difficult for separation of compounds. Catalytic distillation is two types one is
heterogeneous and another one is homogeneous reactions. Heterogeneous reactions are operated
easily to compare with the homogeneous reaction in catalytic distillation unit; in homogeneous
catalyst reactions in R D unit separation of catalyst take place is difficult. In this paper we discuss
about simulation and modeling of catalytic distillation for a synthesis of methyl acetate from
methanol and acetic acid. The first patents date back to the 1920s (Backhaus, 1921, 1922,
1923a,b). Early journal articles are by Keyes (1932), Leyes and Othmer (1945a, b), Schniep,
Dunning and Lathrop (1945), Berman, Melnychuk & Othmer (1948b) and Berman et al. (1948a).
The first publications deal mainly with homogeneous self-catalyzed reactions such as
esterifications, trans-esterifications, and hydrolysis. Heterogeneous catalysis in R D is a more
recent development and was firstdescribed by Spes (1966).
Reactive distillation deals with many reactions in now a day. There are many process
examples are available like as esterification, trans-esterification, hydrolysis, etherification,
hydrogenation, dehydrogenation, alkylation, metathesis and disproportionation, hydration and
dehydration, carbonylation, production of polymers, chlorination/amination, synthesis of
carbonates etc.
In this paper, we discuss about esterification of acetic acid and methanol to from methyl
acetate in catalytic distillation. They are many papers were published on esterification process
since 1920’s.RD process effect by many factors like as in conventional distillation are reflux
ratio, distillate flow rates, feed tray location, total number of stages and new factors are start of
reactive section and end of reactive section will studied for different feed configurations(single
feed and double feed).
“The versatility of the fractionating column in the dual role of continuous reactor and
separator as applied to chemical processing iswell established.”
-Berman, Isbenjian, Sedo! and Othmer (1948a).
The quote was more than six decades ago! It provides an interesting historical perspective
because in more recent times we have seen an explosion of interest in the subject of reactive
distillation, and a veritable plethora of papers have appeared in the last 20 years alone. W e start
with why we need R D or catalytic distillation.
1.1 W hy RD? :
Let us begin by considering a reversible reaction scheme: A + B <-> C + D where the
boiling points of the components follow the sequence A, C, D and B. The traditional flow-sheet
for this process consists of a reactor followed by a sequence ofdistillation columns; see Fig. 1(a).
The mixture of A and B is fed to the reactor, where the reaction takes place in the presence of a
catalyst and reaches equilibrium. A distillation train is required to produce pure products C and
D. The un reacted components, A and B, are recycled back to the reactor. In practice the
distillation train could be much more complex than the one portrayed in Fig. 1(a) ifone or more
azeotropes are formed in the mixture. The alternative R D configuration is shown in Fig. 1(b).
The R D column consists of a reactive section in the middle with nonreactive rectifying and
stripping sections at the top and bottom. The task ofthe rectifying section is to recover reactant B
from the product stream C. In the stripping section, the reactant A is stripped from the product
stream D. In the reactive section the products are separated in situ, driving the equilibrium to the
right and preventing any undesired side reactions between the reactants A (or B) with the product
C (or D). For a properly designed R D column, virtually 100% conversion can be achieved.
2
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Ia
A,B— M cc
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3
1.2 Comparison of Processes in Conventional Distillation and RD:
Examples forthe benefits ofR D using in some process:
carried out using the processing scheme shown in Fig. 2(a), which consists of one reactor and a
train of nine distillation columns. In the R D implementation (see Fig. 2(b)) only one column is
required and nearly100% conversion of the reactant is achieved. The capital and operating costs
are significantly reduced (Siirola, 1995).
Reactoi AcO H
MeOH
1 T
i^Pi
h 2o Water
F ig u re 1.2 P rocessin g schem es fo r the e ste rifica tio n rea ctio n M e O H + H O A c <r-> M e O A c + H 20 . (a)
C o n v e n tio n a l p ro ce ssin g schem e co n sistin g o f on e reactor fo llo w e d b y n in e d is tilla tio n co lu m n s, (b) T h e reactive
d is tilla tio n co n fig u ra tio n . T h e re a ctiv e section s are in dica te d b y g rid lin e s. A d a p te d fro m S iir o la (1995).
2. For the acid catalysed reaction between wo-butene and methanol to form methyl te r t -butyl
butcne JWo
PCH
Ca{O H )j
M eOH
rt-ta u te n s
i-buffine J|
L i v e s -le a m
M TEE PG, j
HaO. 4
(d) Ij
F ig u re 1.3 (a) R e a c tiv e d is tilla tio n c o n c e p t fo r syn th e sis o f M T B E fro m the a cid -ca ta ly se d re a ctio n betw een M e O H
and iso-butene. T h e butane feed is a m ix tu re o f re a c tiv e iso -bu tene and n o n -re a ctiv e «-butene. (b ) R e a c tiv e
d is tilla tio n co n ce p t fo r the h y d ra tio n o f e th yle n e o x id e to e th yle n e g ly c o l, (c) R e a c tiv e d is tilla tio n co n c e p t fo r
re a ctio n b etw een ben ze n e and p ro p e n e to fo rm cum ene. (d ) R e a c tiv e d is tilla tio n c o n c e p t fo r re a ctio n p ro d u c tio n o f
p ro p y le n e o x id e fro m p ro p y le n e c h lo ro h y d rin s and lim e . T h e re a ctiv e se ctio n s are in d ica te d b y g rid lin e s
5
4. In several alkylation reactions, aromatic + olefin y * alkyl aromatic are best carried out using
the R D concept not only because of the shift in the reaction equilibrium due to in situ separation
but also due to the fact that the undesirable side reaction, alkyl aromatic+olefin dialkyl
aromatic, is suppressed. The reaction of propene with benzene to form cumene, benzene +
propene cumene (Shoemaker & Jones, 1987; see Fig. 3(c)) is advantageously carried out in a
R D column because not only is the formation of the undesirable di-isopropyl benzene
suppressed, but also the problems posed by high exothermicity of the reaction for operation in a
conventional packed-bed reactor are avoided. Hot spots and runaway problems are alleviated in
the R D concept where liquid vaporisation acts as a thermal flywheel. The alkylation of is o -
butane to wo-octane, wo-butane + n -butene wooctane is another reaction that benefits from a
R D implementation because in situ separation of the product prevents further alkylation: is o -
5. The reaction between propylene chlorohydrin (PCH) and Ca(OH )2 to produce propylene oxide
(PO) is best implemented in an R D column, see Fig. 3(d). Here the desired product PO is
stripped from the liquid-phase by use of live steam, suppressing hydrolysis to propylene glycol
(Bezzo, Bertucco, Forlin & Barolo, 1999)
6
5. Catalytic distillation is particularly advantageous when reactor products, i.e. products and
reactants can form several azeotropes with each other’s,which require additional costs for
separation.
6. Significantlyreduced catalystrequirements forsame degree ofconversion.
7. Reduced formation ofbyproducts.
8. Avoidance ofhotspots and runaways using liquidvaporization asthermal flywheel.
9. Increasedspeed and improved efficiency.
Against the above-mentioned advantages of RD, there are several constraints and
foreseen difficulties(Towler & Frey, 2000):
1. Volatility constraints. The reagents and products must have suitable volatility to maintain
high concentrations ofreactantsand low concentrations ofproducts inthereactionzone.
2. Residence time requirement. Ifthe residence time for the reaction is long, a large column
size and large tray hold-ups will be needed and itmay be more economic to use a reactor-
separatorarrangement.
3. Scale up to large flows. It is difficult to design RD processes for very large flow rates
because ofliquiddistributionproblems inpacked RD columns.
4. Process conditions mismatch. In some processes the optimum conditions oftemperature and
pressurefordistillationmay be farfrom optimal forreaction and viceversa.
5. Understanding of the separation function in reaction zone leads to complex interactions
between vapor-liquid equilibrium, vapor-liquid mass transfer, intra catalyst diffusion (for
heterogeneously catalyzedprocesses) and chemical kinetics.
M e O H + H O A c ^ M e O A c + H 20
The esterification of methanol and acetic acid to form methyl acetate is a reversible
equilibrium controlled reaction. Itis exothermic reaction. W e have different type of rate kinetics
model equations for heterogeneous catalyst reaction, such as adsorption base kinetic model, and
pseudo homogeneous kinetics model. This reaction occurs only in liquid phase in reactive
distillation. There occur two azeotrope mixtures in this reaction. There are different feed set-ups
used for reactive distillation: one feed and two feed set up used for synthesis of methyl acetate.
In two feed set up heavy weight compound to feed at the top of the column and lower weight
compound fed into bottom of the column, in this process acetic acid feed into the column. The
reactive or catalytic distillation unit divided has four zones such as, rectification zone, extractive
zone, reactive zone, and striping zone. W e can simulate the catalytic distillation model as a user
model on aspen plat form.
8
CHAPTER 2
L IT E R A T U R E R E V IE W
Popken et al. (2001): In this paper three different setups were used to perform reactive
distillation experiments for the synthesis and hydrolysis of methyl acetate using the structured
catalytic packing Katapak-S with an acidic ion-exchange resin (Amberlyst-15) as the
heterogeneous catalyst. Those three different setups were as follows: one-feed and two-feed
setups for the methyl acetate synthesis and another two-feed setup for the hydrolysis reaction.
Moreover, studied the influence of several variables, such as reaction kinetics, separation
efficiency, residence time distribution, and heat loss, on the simulation results and most
important was the use of adequate reaction kinetics, that was, an adsorption-based kinetic model
that took into account the selective swelling of the polymeric catalyst. By using tin's model the
synthesis as well as the hydrolysis experiments could be simulated within experimental accuracy.
With pseudo homogeneous kinetics, only the experiments performed for the synthesis of methyl
acetate could be modeled. Also, an equilibrium stage model is capable of describing the
experiments in the packed column when the reaction kinetics, separation efficiency, and heat loss
of the column were taken into account. A large number of experiments for various experimental
setups performed in order to develop a reliable framework for simulating reactive distillationthat
was capable of modeling the methyl acetate synthesis as well as the hydrolysis reaction with the
required accuracy. It was shown that only with an adequate expression for the rate of the
chemical reaction experiments could be described within the experimental accuracy when
compared experimental results with simulation results using the Aspen R A D F R A C model. Also
found that the equilibrium-stage concept was sufficient to model the column behavior. However,
the heat loss of the mini-plant column, which could be measured easily with the required
accuracy, had to be included in the simulation. The residence time distribution had no significant
influence. The difference in the composition profile obtained by assuming ideally mixed
equilibrium stages or a cascade of two or more ideally mixed tank reactors per equilibrium stage
was negligible.
Taylor, R and Krishna, R. (2000): The design and operation issues for reactive distillation
systems are considerably more complex than those involved for either conventional reactors or
conventional distillation columns. In this paper, itwas discussed that the introduction of an in
situ separation function within the reaction zone led to complex interactions between vapor-
liquid equilibrium, vapor-liquid mass transfer, intra-catalyst diffusion (for heterogeneously
catalyzed processes) and chemical kinetics. Such interactions had been shown to lead to the
phenomenon of multiple steady states and complex dynamics, which had been verified in
experimental laboratory and pilotplant units. The development ofmodels that had been used for
design ofreactive distillation columns was traced and suggested future research directions. Also
discussed the complexity of reactive distillation process installing, and explained the neediness
of reactive distillation compare with conventional reactor-distillation process by giving some
process examples. Moreover, developed steady state and dynamic models for equilibrium and
non equilibrium stage reactive distillation and also gave the conceptual design procedure for
estimating reactivezone height, column diameter, and reflux ratio for packed catalystdistillation.
The information of different type of design methods for reactive distillation, such methods was
conceptual method, graphical method, and design via optimization method was given.
Bao et al. (2002): Described the industrial catalytic-distillation process for the production of
methyl tert -butyl ether (MTBE) from methanol and isobutylene was simulated by developing the
process model as a user modular on Aspen plus platform. The model utilized the Aspen plus
system and retained the characteristics of the self-designed model, which had been verified:in
various scale-up processes. The experimentally determined reaction kinetics was applied in the
model. NRTL and Redlick-Kwong-Soave equations were selected for the vapor-liquid
equilibrium calculation. The NRTL binary interaction parameters were estimated from the
experimental data ofthe two-component vapor—liquid equilibrium. Two typical industrial plants
forthe MTBE production, one using the loose-stack-type package technology and the otherusing
the bale-type package technology inthe catalytic-distillation column, were chosen as the sample
i ,t
processes to demonstrate the validity ofthe model. Also, the flow sheet simulations of the two
industrial plants were done on Aspen plus platform, in which the simulation of tlie catalytic-
distillation column used the developed user modular from the advantage ofthe strong database,
flexible simulation functions and optimization tools ofthe Aspen plus system, while retainingthe
10
ch aracteristics o f the p rev io u s v e rifie d m od e l. T h e flo w sheet sim u la tio n s o f the tw o industrial
plants, u sin g the loose-stack-typ e package and the ba le-type package te ch n o lo g ie s in the
ca ta ly tic-d istilla tio n c o lu m n , were sim u lated on the A s p e n p lu s platform . T h e results show ed that
fa ir agreem ents betw een the calculated and operatin g data w ere obtained. T h e y d e ve lop e d the
co n secu tiv e relationship s, and explained the b e h a v io r o f system , its id ea l o r n o n -id e a l and
fo rm a tio n o f azeotrope m ixtures. T h is p ap e r g ave the co n ce p t to rem ove the sid e reactions in
H iw a le et a L (2004): In this paper, the in fo rm atio n about p u b lica tio n and patents in last 30 years
on histogram s. T h is article review s the v e ry recen t app lication s and serves as a su pp lem ent for
in fo rm a tio n o n the o n g o in g research in the e x istin g ap p lica tion s but also elaborated the n e w ly
ch lo ro sila n e d e riv a tiv e s and ch ira l ch em ica ls. M u lt ip le reactions in R D , fa ilu re o f R D in som e
cases and new R D co n fig u ra tio n s to in crease the o v e ra ll y ie ld s are so m e o f the additional aspects
b e in g covered . In this pap er gave the cla rity in fo rm a tio n o f w h ich type o f reactions are operated
dehydrogenation , a lk y la tio n , m etathesis and d isp ro p o rtio n a tio n , h y d ra tio n and d ehydration,
ca rb o n yla tio n , p ro d u ctio n of p o ly m e rs, ch lorin ation /am ination , synthesis o f ' carbonates,
tetram ethyl p ip e rid in e .etc,. In th is paper d iscu sse d flo w sheet o f re a ctive d istilla tio n in p ro cess
in d u stiy g iv e n fo r above process, and gave the co lle cte d in fo rm atio n o f p rocesses co n ve rsio n
w ith d iffe re n t catalyst used b y d iffe ren t authors. A c c o r d in g to o u r re a ctio n m eans esterification
b e lo w table.
11
Table 2.1 Details o f different catalyst used for synthesis of methyl acetate.
and achievements
\
The application domain o f reactive distillation is increasing fast and will continue to
remain on the rising trend. In the last few years, reactive distillation has entered in the well-
established technologies for the manufacture o f carbonates, phenols, and linear alkyl benzenes
etc. It also seemed to be a promising technology in the lucrative business o f chiral chemicals and
to some extent in the production o f organ silicon derivatives. The idea o f coupling more than one
reaction in a single column is taking shape especially for various hydrogenation, reactions.
However, the recent work for some reactions, if not many, has revealed the important limitations
o f RD especially when the side products are formed at high temperatures near reboiler or
because o f the depletion o f one o f the reactants in the reactive zones. Though there is a scope to
overcome this limitation by a prudent choice o f operating parameters, this may be considered as
an important threat to conventional reactive distillation column and modifications like stripped or
Chandakar et al. (2007): This paper dealt with the development o f a mathematical model for
esterification o f acetic acid with methanol by using a packed column with two different feed
setups: a single feed column and a two feed column. The reaction kinetics assumed to be
heterogeneous, also included the solution technique for the solution o f the model. An in-house
code in C++ developed to solve the model equations. Further, the comparison o f the model had
been done with available experimental data. Finally me effect o f design variables namely- reflux
ratio, feed tray location, and start o f reactive section had been studied.
12
M o r e o v e r , stud ied an e ffect o f v a r io u s v a ria b le s fo r e ste rifica tio n o f m etha n ol w ith
a ce tic a cid in ca ta ly tic d is tilla tio n c o lu m n w ith o n e fee d setup c o n ta in in g 10 stages and tw o feed
setup c o n ta in in g 25 stages and also stud ied the e ffe c t o f v a ria b le s w as an attem pt to a ch ie v e the
e q u ilib riu m con straint. The m ath e m a tica l m o d e l .develop ed sh o w n sa tisfa cto ry results in
sim u la tin g a ca ta ly tic d is tilla tio n c o lu m n fo r the e ste rifica tio n o f m e th a n ol w ith a cetic a cid . T h e
results w ere fo u n d in g o o d agreem ent w ith e x p e rim e n tal results o f P o p k e n et al. (2001).
lo ca tio n , start o f rea ctiv e stage o n c o m p o s itio n in d istillate and m ethan ol c o n v e rs io n in ca ta ly tic
d istilla tio n c o lu m n .
d istilla tiv e sep aration are p e rfo rm e d in sin g le e q u ip m e n t. E v e n th o u g h re a ctiv e d is tilla tio n c o u ld
in crease the se le c tiv ity o f the d e sired p ro d u ct b y th e se le ctive re a ctio n this is n o t a lw a ys true as
entrain er and M T B E as in term ed iate p ro d u ct. In the first c o lu m n , isobutene and m ethan ol reacted
m eth a n ol w as p o s sib le o n ly i f n o side reactio ns o c c u r. W h e n the sid e reactio ns w ere taken into
13
the splitting column must be firstly separated rather than being recycled directly to the formation
column. Moreover, an attempt had been made to show how the selectivity of the desired product
isobutene could be critically influenced by the operating parameters such as the reflux ratio. If
the reflux ratio increased, a high quantity of di isobutene and di methyl ether would be obtained
which seriously affects the selectivity of isobutene. The influence o f operating parameters was
investigated by using a continuation method, which shows that bifurcation behavior could appear
This paper concluded the following matter; a system of coupled reactive distillation
columns was studied for the MTBE system, taking the influence o f side reactions into account.
The objective was to obtain high purity products isobutene and n-butene from a feed o f a closely
boiling butenes mixture. If side reactions are not considered, high purity n-butene as one final
product and MTBE as an intermediate product are obtained from the MTBE formation column.
The second final product isobutene and the reactive entrainer methanol leave the top and the
bottom of the MTBE splitting column in high purity, respectively. The bottom product stream of
the splitting column was directly recycled to the formation column. However, the system
behavior changed considerably if side reactions were taken into account. In this case, the
byproducts di isobutene, di methyl ether and water affect the purity o f the products, especially in
the splitting column. The bottom product stream of the splitting column has to be separated in
order to recycle the reactive entrainer methanol. Stein et al. (2000a, 2000b) proposed a coupled
reactive distillation scheme where side reactions were suppressed as far as possible and the in
avoidable byproducts are removed from the system veiy efficiently. Bifurcation analyses show
that multiple steady states exist in the formation as well as the splitting columns. In the formation
column, the multiplicity regions were near to the optimum operating parameters. In the splitting
column, the bifurcation behaviors with reflux ratio propose the operating parameters to obtain
high selectivities of isobutene and methanol. In the future, the dynamic behaviors of the single
columns and the coupled column system would be investigated. Based on these dynamic
Bessling et al. (1998): The production of methyl acetate in a reactive distillation process -prior
art for 15 years - is often used as an example to study the basic phenomena o f reactive
distillation. The present paper dealt with a theoretical and experimental analysis of methyl
14
acetate synthesis in a re a ctive d istilla tio n c o lu m n . A d esign m ethod based o n the interpretation o f
reactive d istilla tio n lin e diagram s was used to id e n tify the m a in process param eters and to
p ro v id e a foun dation fo r ex p e rim e n tal in vestig ation . T h e s ig n ific a n t in flu e n ce o f the re flu x ratio
dem onstrate the ca talytic q u a lity o f th is p a c k in g m aterial. T o sim u late the reactive d istilla tio n
c o lu m n w ith a s im p le stage-to-stage m ethod, the separation e ffic ie n c y o f the ca ta lytic rin g s was
investigated. C o m p a ris o n o f experim ental and sim u la tio n results revealed that a s im p le m o d el
based on the assu m ption o f sim u ltan eou s c h e m ic a l and phase e q u ilib riu m described the
experim ental data q uite w e ll o v e r a w id e range o f re flu x ratios. F u rth erm o re, sim u la tio n results
sh o w ed that the co n v e rsio n depends less o n the n u m b e r o f re a ctive stages than o n the use o f tw o
feed stages.
In this co n trib u tio n the hetero g eneo usly ca ta lyze d p ro d u ctio n o f m e th y l acetate in a
sh ow n b y the expe rim e n tal in vestig ation s and rig o ro u s sim u la tio n s, a sim p le a n a lysis o f reactive
d istilla tio n line d iagram s a c c o rd in g to the design m ethod o f B e s s lin g et al. (1998) p re d icts the
w e ll. B e sid e s, the m ethod sh ow s w h eth er reactive d istilla tio n w ill be e ffic ie n t and h o w a reactive
the ch o ic e o f an o p tim a l re flu x ratio saves capital in vestm e n t and energy co n su m p tio n .
A s im p le m o d e l w h ich is based o n ch e m ica l e q u ilib riu m in the re a ctiv e section and vap o r-
re flu x ratios in co m b in a tio n w ith a d e cre a sin g re sid ence tim e o f the reactants. N ear-to tal
15
c o n v e rsio n req u ires a co n sid e ra b le in crease in the n u m b e r o f re a ctive stages in the reactive
c o n v e rsio n and n e g lig ib le b y -p ro d u c t fo rm a tio n , a ch ie v e d in o u r exp e rim en ts, dem onstrate the
p a c k in g .
tem peratures betw een 3 0 3 .1 5 and 3 43.15 K. at v a rio u s starting c o m p o s itio n s c o v e rin g
co n cen tra tio n ranges fro m the sto ic h io m e tric re g im e to the d ilu te re g io n s. B o th the e ste rifica tio n
w ere used to fit the ad so rp tio n constants to k e e p the n u m b e r o f a djustable p aram e ters the sam e
the k in e tic m o d e l o n ly , w h ile in co rp o ra tin g a d so rp tio n in fo rm a tio n into the k in e tic m o d e l results
T h e d e sig n o f rea ctiv e d is tilla tio n c o lu m n s requires re lia b le k in e tic data b e sid e s oth er
in fo rm a tio n , lik e p hase e q u ilib riu m data, c h e m ic a l e q u ilib riu m data, tra n sp o rt p ro p e rty data, o r
16
the various pure com ponent properties. In this w ork, kinetic expressions for the methyl acetate
system are presented w ith parameters fitted to a fairly large database covering both the
esterification and the hydrolysis reaction. F o r the homogeneous reaction, the kinetic fit is
im proved by using activities instead o f m ole fractions. T h e reaction follow s a rate expression
that suggests catalysis b y m olecular acetic acid instead o f by solvated protons. T h is was
consistent with the results from W illia m so n and H insh elw ood (1934). T h e magnitude o f the
homogeneous reaction rate showed that this reaction could be neglected in reactive distillation
homogeneous m odel im proves the fit only slightly. T a k in g the liquid-phase non-ideality into
account was ob viou sly not sufficient to describe the heterogeneous kinetics. T h e interaction
between the solid catalyst and the reactants had to be considered in the m odel. Despite the fact
that a precise and therm odynam ically consistent treatment o f systems in vo lv in g sw elling ion-
exchange resins was not available, a good fit o f the kinetic experiments could be obtained using
an adsorption-based m odel. F o llo w in g the concept o f Son g et al. (1998) independent adsorption
experiments were used to determine the adsorption equilibrium constants w hich were then
incorporated into the kinetic expression. Including adsorption inform ation led to a m uch better
description o f the kinetic results. B y using an adsorption expression based on adsorbed mass
instead o f adsorbed amount results in further im provem ent o f the fitting result. T h e adsorption
based kinetic m odel could easily be incorporated into com m ercial simulators. A d d itio n a lly, this
m odel provided better agreement between kinetics and therm odynamics (chem ical equilibrium )
G o r a k and H o ffm a n n . (2001): C atalytic D istilla tio n can im prove process design; the design o f
effective catalysis, high separation efficiency, and a w ide loading range simultaneously. In this
w ork the m ain characteristics o f M U L T I P A K -pressure drop, loading range, and separation
efficien cy were determined experim entally. The developed non-equilibrium stage m odel
developed reflects the com plexity o f catalytic distillation processes and com prises correlations
17
conditions. T h e m odel had been im plem ented in the sim ulation environm ent A sp e n C usto m
M o d e le r, and the sim ulation results were com pared w ith experim ental data for the synthesis o f
m ethyl acetate. T h is m odel reflected the process behavior, but differences between simulated
com bined w ith high separation e fficie n cy and catalytic activity had been presented in this article.
T h e m ain p ack in g characteristics pressure drop and separation e ffic ie n c y had been determined
experim entally fo r the w hole lo a d in g range and com pared with data fo r conventional structured
h ydrau lic m odel o f R o c h a et al. (1996), but new m odels considering the special hydrod yn am ic
beh avior o f catalytic packings were necessary to reflect the p ackin g characteristics w ith good
accuracy and to p ro vid e inform ation about the scale-up behavior. A correlation fo r mass transfer
coefficients in both phases was presented that represents the experim ental data w ith good
accuracy.
investigate the beh avior o f a continuous process. A rigorous d ynam ic m odel based on the
M a x w ell-S tefa n approach to describe mass transfer between phases had been m od ified and
im plem ented in the sim ulation environm ent A s p e n C u sto m M o d e le r. Steady-state sim ulations for
the process o f methyl-acetate synthesis had been perform ed and com pared with experim ental
data. It was show n that the m odel is able to reflect the process behavior, but deviation was.
observed between experim ental and theoretical conversion and purity. H o w eve r, by
im plem enting the reaction kinetics and the hydrod yn am ics o f the catalytic packings in the
process sim ulation, their in fluence on design aspects o f reactive distillation colum ns were taken
into account.
i
S c h o e n m a k e rs a n d B e sslin g . (2003): R ea ctive and catalytic distillation has attracted g ro w in g
interest, both in industry and in scientific research. T h is contribution gives an overview w ill o f
the tools that are available today and the m ethods that have now been introduced into the
industrial practice in a large ch em ical com pany. A process synthesis gives good qualitative
reference points. S im u la tio n tools have been developed w h ich are m ain ly equilibrium -based.
18
H o w e v e r, fu rth er steps are nece ssa ry o n the w a y to im p le m e n ta tio n in an in d u stria l plant. T h e
fo r c o n v e n tio n a l d istilla tio n , b u t c o m p lic a te d b y several facts fo r re a ctiv e d is tilla tio n s p e c ific a lly
o p tio n s both fo r h o m o g e n e o u s and h e tero g eneo us c a ta ly sis are p o s sib le and w ill b e d iscu ssed in
the co n trib u tio n . A tte n tio n is d ra w n to the fa ct that a c o m b in a tio n o f rea ctio n and d istilla tio n
In the case o f c o n v e n tio n a l d istilla tio n , a s u ffic ie n t b o d y o f k n o w le d g e has b een acq u ired
O n d r e y ,G .( 1 9 9 6 ) .F o r re a ctiv e d istilla tio n , th e m ethod s o f d e sig n and syn th e sis have been
d on e to ensure that the b e n e fit o f c o m b in in g re a c tio n and d is tilla tio n can b e e n jo ye d to the fu ll
are en clo se d w ith in w ire g au ze e n v e lo p es ("sa n d w ich e s” ), are p ro m is in g reacto r co n fig u ra tio n s
fo r rea ctiv e d istilla tio n and h y d ro co n v e rsio n s. B y a llo w in g p re fere n tia l ch a n n e ls fo r the gas and
ch a n n els. T h e liq u id flo w in the o pen ch a n n e l ca u sed a sharp rise in the p ressure d ro p . A m o d e l
19
rate, the p ressu re d ro p w as fo u n d to in crea se e x p o n e n tia lly w ith the liq u id h o ld u p w ith in the
a g o o d e x ch a n g e o f the liq u id p hase in sid e and o u tsid e the p a c k e d ch a n n e ls. T h e re sid e n ce tim e
o p e ra tin g w in d o w at a m u c h lo w e r p ressure d ro p .
s ig n ific a n t advantages w ith co u n te rcu rre n t o p e ra tio n fo r h y d ro -tre a tin g o p e ra tio n s, w h ic h are
co n c e rn s the h y d r o d y n a m ic s and m ix in g ch a ra cte ristics o f stru ctu red c a ta ly tic a lly p a c k e d bed
reactors, o p e ra tin g in co u n te rcu rre n t flo w o f gas a n d liq u id . T h e p re ssu re d ro p , liq u id h o ld u p and
liq u id p hase re sid e n ce tim e d istrib u tio n o f c a t a ly tic a lly structured p a c k e d c o lu m n s o f 0.1 and
m eth y l acetate b e ca u se o f its c o m m e r c ia l im p o rta n c e , and b eca u se o f the a v a ila b ility o f adequate
p u b lis h e d d ata fo r c o m p a ris o n . In the lim it o f re a c tio n and p h a se e q u ilib riu m , it w as sh o w e d that
ratios that w ill p ro d u ce h ig h c o n v e rs io n s and h ig h p u rity m e th y l acetate, and (3) the e x iste n ce o f
m u ltip le steady states th ro u g h o u t the entire ra n g e o f fe a sib le re flu x ratios. F o r fin ite rates o f
re a ctio n , (4) that the d e sire d p ro d u c t c o m p o s itio n s are fe a sib le o v e r a w id e range o f re a ctio n
rates, up to and in c lu d in g re a ctio n e q u ilib riu m w a s fo u n d , and (5) that m u ltip le steady states d id
o u tsid e the ran ge o f n o rm a l o p e ra tio n . Our ca lc u la tio n s w ere in good a greem en t w ith
20
A h ie r a r c h y o f m e th o d s a n d m o d e ls fo r th e d e s ig n a n d s im u la t io n o f a re a c tiv e d is t illa t io n
c o lu m n f o r th e p r o d u c t io n o f m e t h y l acetate w e re e x p lo r e d . A l s o , fo u n d th at w h e n a s s u m in g
in c r e a s in g p re ss u re .
e q u ilib r iu m lim it . S e n s it iv it y s tu d ie s o n th is k in e t ic m o d e l re v e a le d a re g io n o f m u lt ip le s te a d y
p ro d u c ts w e re fe a s ib le o v e r a w id e ra n g e o f D a m k o h le r n u m b e rs , i.e ., o v e r a w id e ra n g e o f
u s e d to d e v e lo p a c o lu m n d e s ig n w ith re a lis t ic v a lu e s fo r th e se d e s ig n v a r ia b le s .
S e n s it iv it y c a lc u la t io n s f o r v a r io u s D a m k o h le r n u m b e rs s h o w e d th at th e c o n v e r s io n d ro p s
o f f s h a r p ly w h e n o p e r a tio n m o v e s a w a y fr o m t h e o p t im u m r e f lu x ra tio . F u r th e r m o r e , w e fo u n d
th at in c r e a s in g th e D a m k o h le r n u m b e r y ie ld s a n in s ig n if ic a n t in c re a s e in c o n v e r s io n o r o p e r a tin g
ra n g e .
q u ite c lo s e ly .
J
21
2.2. Vapor-liquid equilibrium for multi component distillation:
determine equilibrium -stage requirements. A n a ly tic a l com putation procedures m ust be applied
w ith therm odynam ic properties depending o n temperature, pressure and phase com position,
these equations tend to be com plex. Nevertheless the equations are w id e ly used fo r com puting
phase equilibrium ratios (K-values), enthalpies and densities o f m ixture over a w ide range o f
conditions. V a p o r liqu id equilibrium calculations are usually carried out for separation processes
w ith several versions. T h e prediction o f m ixture vapor-liquid equilib rium is m ore com plicated
than prediction o f pure com ponent. Phase e q uilibrium relation is one o f the fundamental
properties w hich are necessary for the separation processes, and useful equation have been
proposed for expressing relation. E fficie n t design o f distillation equipm ent requires quantitative
understanding o f vapo r-liqu id eq uilibrium in m ulti com ponent m ixture as expressed through
pressure P, the vapor phase fugacity is equal to the liq u id phase fugacity fo r every com ponent
i= l, 2, 3 Nc
T h e vapor phase fugacity can be written in terms o f the vap o r phasefiigacity co efficien t <T>i ;
fi = y f o P '
A ls o the liquid phase fugacity can be written in terms o f liqu id phase activity co efficien t y„
.liquid m ole fraction x,t and liqu id phase properties f as follow s.
fi = XiYifi
22
W h ere,/is calculated using the equation:
y i f p _
ft = o r ^ ' e x p ~^T— -]
A t e q u ilib r iu m ,
Y iP r*xi
yi =
$i K,(P - P f
<I>f“ eXP ^ RT ^
o n ly a fe w parts p e r th o u sa n d . F in a lly , w e g et
n psat
yi = — *i
D a lt o n ’ s la w : P£ = yj P
V
T h e e q u ilib r iu m re la tio n s h ip fo r a n y c o m p o n e n t is d e fin e d as, K, - —
x,
F o r id e a l m ix tu re the K v a lu e c a n b e p re d ic te d fr o m R a o u lt ’ s la w , w h e re .
v. P sa'
*, P
23
2.2.3. Non Ideal V apor-L iquid E quilibrium :
Wheny* = 1, the mixture issaid to be ideal which simplifies the equation to Raoult’s law.
For non-ideal mixture y* =£ 1, exhibits either positive deviation from Raoult’s law (/* > 1), or
negative deviation from Raoult’s law (Yi < !)•
The prediction of liquid phase activity coefficient is most important for design calculation
of non-ideal distillation. Before calculating vapor-liquid equilibrium of non-ideal mixture, the
activity coefficient of each component must be calculated. There are several excess energy (gE)
models to calculate the activity coefficient for multi component systems, the most important
models are of (Wilson, NRTL, UNIFAC, and UNIQUAC). In all these models, the model
parameters are determined by fittingthe experimental data ofbinary mixtures.
Each one of these models has advantages and disadvantages. There is no general model
which has a good representation of all azeotropic mixtures. The selection of appropriate model
for a given mixture is based on three characteristics, which are temperature, pressure and
composition. Ifinappropriate model isselected, the design and simulation ofthe process will not
work well.
24
Wilson and Deal (1962) used the following equation to calculate the liquid phase activity
coefficient.
The Wilson model has the disadvantage that itcannot predict vapor -liquid equilibrium when two
liquids existinthe liquid phase
The NRTL (non-random, two liquid model) was developed by Renon and Prausnitz
(1968). This model uses three binary interaction parameters for each binary pair in multi
component mixture-pairs. For Nc components system, itrequires Nc (Nc -l)/2 molecular binary
pair. This equation is applicable to multi component vapor-liquid, liquid-liquid, and vapor-
liquid-liquid systems.
The main equation used to calculate liquid phase activity coefficient for NRTL model is
(Sim Basis 2003).
\
m j tn mj
In Yi =
*=1
The NRTL group interaction parameters are defined in literature (Gmehling etal. 1977).
Abrams and Prausnitz (1975) developed the UNIQUAC (UNIversal QUAsi Chemical)
25
The combinational part basically accounts for non -ideality of a mixture arising from differences
in size and shape of constituent molecular species; whereas the residual part considers the
difference between inter-molecular and intra molecular interaction energies. The two-parameter
UN IQUAC equation gives a good representation of the vapor-liquid equilibrium of binary and
multi component mixtures (SimBasis 2003).
( NC \
Inr f = - q , In X 6-J p + Nc
/ 7
■=
/=1'
2 .3 .4 . U N IF A C m o d e l, 1975:
The UNIFAC model splits up the activity coefficient for each species in the system into two
components; a combinatorial y c and a residual component y R . For the /thmolecule, the activity
coefficients are broken down as per the following equation:
Iny i = Iny f + In yf
In the UNIFAC model, there are three main parameters required to determine the activity for
each molecule in the system. Firstly there are the group surface area R and volume contributions
Q obtained from the Van der Waals surface area and volumes. These parameters depend purely
upon the individual functional groups on the host molecules. Finally there is the binary
interaction parameter xy, which is related to the interaction energy £/,■ of molecular pairs
26
(equation in "residual" section). These parameters must be obtained either through experiments,
via data fittingor molecular simulation
Combinatorial component:
The combinatorial component of the activity is contributed to by several terms in its equation
(below), and isthe same as forthe UNIQUAC model.
0
Wif z Vi 0£ n
V>iST'
ln y ‘ = ln Ti + 2 q‘ to Wt + L‘ ~ ^ Z XlLl
i
0j and cpiare the molar weighted segment and area fractional components for the i,hmolecule in
the total system and are defined by the following equation; Li is a compound parameter of r, z
and q. z is the coordination number of the system, but the model is found to be relatively
insensitive to itsvalue and isfrequently quoted as a constant having the value of 10.
9i = Z
Ylj71=*l x*j Ha j ; 0 i = ZY i *j =} i' *7 j '7j ) L i = \£- “ 1);Z = 10
ri and qi are calculated from the group surface area and volume contributions R and Q (Usually
obtained via tabulated values) as well as the number of occurrences of the functional group on
each molecule v* such that:
it ii
ri = v k R k ;q t = ^ v k Q k
k=1 k=l
Residual component:
The residual component of the activity y R is due to interactions between groups present in the
system, with the original paper referring to the concept of a "solution-of-groups". The residual
component of the activity for the ilh molecule containing n unique functional groups can be
written as follows:
27
n
Iny/* = ^ \ £ ) P n I ,f t - l n rj-0
k
W here,
4 ° = the activity o f an isolated group in a solution con sistin g only, o f m ole cu le s o f type
.. .. nm
m m
Qm^m
&m ZnQnXn
28
2.4. R ate kinetics in Catalytic distillation:
m ethyl acetate v ia counter current reactive d istillatio n w ith usin g H 2 S O 4 as hom ogeneous
catalyst.
CH3COOH+CH3OH o CHjCOOCH3 + h 2o
C HOAc C MeOH
r = k exp
yR T y K
W h ere
k —k x{ X H iS 0 ^) + k2 ( X H ^s o ^) fo r X HS0 <0.004
Popken et a l (2000) investigated the rate kin e tics fo r synthesis o f m eth y l acetate w ith
h o m o gen eou sly u sin g acetic a cid as s e lf catalyst and heterogeneously b y an a c id ic ion-exchange
® H o m o g e n e o u s R e a c tio n :
T h e kin etic equation fo r the reaction fo r the catalyzed b y acetic acid is expressed as:
1 dx-
r ~ "77 = a H 0Ac (^ 1 a H O Aca MeOH ~ ^-1 a M e O A c ® H zo )
vt at
W h ere at is a ctiv ity o f co m p o n en t i.
i. e. <*i = Y f t
29
Table 2.2 Parameters and Residual Errors of the Different Kinetic Models Used to Fit the
Experimental Data without Catalyst Added:
Mean reative
error (%)
Exponent Activities s"1 Ea,i Ea,-i
1
f * -1 Ideal 3.1 2.54E06 62.5 . ’ 1.00E0T 77.3 .,
|U‘ ,;.4 •• . ’f•' ilf
,, v*3
. 1.406 • Ideal ' 2.2 2.42E06 67.3- ' 9.27E06 1 75.8
|. -■
1 1 dnt u _
r ~ , — K ]a H O A ca M eO H IC - i a M e 0 A c C l H 2 0
Adsorption-based model:
1 1 d rij & H Q Ac a M eO H a M e O A c a H 7Q
mcat Vi d t (a H0Ac + ® M eO H ^ M eO A c + ^ I f 20 )
a\ = - LJ-
M,
30
2.5. Modeling of catalytic distillation column:
feasibility, sim ulation, m od eling , design and experim ental studies in the laboratory and the p ilo t
plant. A co m b in atio n o f a ll o f these m ethods gives rise to the m ost accurate solution to the
problem . O ne v e ry im portant aspect o f pred ictin g the beh avio r in these system s is the m odel used
to design and sim ulate the reactive distillatio n process. A n effective w ay o f d eco m p o sin g the
T h e eq u ilib riu m stage m od e l assumes that the vap or and liq u id stream leaving a given
stage are in therm odynam ic eq u ilibriu m w ith one another (K rish n a and T a y lo r, 1985). A
schem atic diagram o f an e q u ilib riu m stage is show n in V a p o r from the stage b e lo w and liqu id
from the stage above are brought in to contact on stage together with any fresh o r re cycle feeds,
the v a p o r and liq u id streams leaving the stage are assum ed to be in e q u ilib riu m w ith each other.
33
F ig u r e 2.1 E q u ilib r iu m stage m o d e l w ith feed stream and side stream
dtn r c
1 - L M + r M + F j - S ’ - V j - L , - S' + X E V , „ RmJe,
dt n=l /=1
din x r
— ^ L = Lj-lx,J. l + VM y,Jtl + FJzIJ-(.S'j + V ^ j - ( L j + S ‘)X,J + 2> ,
ut m=i
y ,j = Ki j xi j
2 X ,= 1
L - ,
;=1
dE r0
- + = LM hH + Vm H m + Fj H f j - L, h , - S > , +
al m-l/=1
34
high er pressure. T h e term ^
’ J^ v imRmjej is the rate o ft h e disappearance o fth e total m oles due
m=1/=1
to any m reaction o f the stage j. v,-m represents the stoichiom etric co efficien t o f com ponent i in
T h e E equations are phase eq u ilib riu m relations, the com positions o f the stream leaving
stage are in therm odynam ic eq uilibrium . Therefo re, the m ole fractions o f com ponent i in the
liq u id and v ap o r streams leaving stage j b y th e e q u ilib riu m relationship are show n in above
equations
T h e S equation are sum m ation are two equations arise from the necessity that m ole
T h e enthalpy balance is given above, in that the left side represents the accum ulation o f
enthalpy on stage. It represents the total enthalpy o f stage, but fo r the reason given above this
w ill no rm ally be the liqu id phase enthalpy. A t steady state condition, all terms p er time equal to
zero.
So m e authors in clu d e additional equation in their (m ostly unsteady state) m odels, for
A non -equ ilibriu m ( N E Q ) or rate-based m odel em ploys a transport phenom enon approach and
the film m odel description fo r p redictin g the m ass transfer rates. It assum es eq u ilib riu m is
established at the interface between v ap o r and liq u id phases. T h e m odel equation fo r a generic
stage j (T he N E Q stage m ay represent a tray or section o f p ack in g colu m n ) and com ponent i m ay
be represented based on conventional distillation equation that incorporate the ch em ical reaction
term (T a y lo r and K rish n a , 1985). A schem atic representation o f the N E Q stage is show n in
F ig u re 2.2.
35
Figure 2.2 Non-equilibrium stage model with feed stream and side streams.
The component molar balance for the vapor and liquid phases is
Where N/j is the interfacial mass transfer rate, and is the product of the molar flux and the net
interfacial area. The overall molar balances are obtained by summing above equation over the
total number(c) of components in the mixture. The N j , j is obtained from the Maxwell-Stefan
equation modified as follows:
With a similar relation for the vapor phase, the k,J represents the mass transfer coefficient of the
i-k pair in the liquid phase; this coefficient is estimated from information on the corresponding
Maxwell-Stefan diffusivity using the standard procedures discussed in Taylor and Krishna
(1993). ‘a’ is the interfacial area. Only c-1 of above equation are independent .the mole fraction
of the last component is obtained by summation equations for both phases. The enthalpy
balances for both vapor and liquid -phases are:
36
Vj^ - V jH j +FJH I j -E'j - Q ^ 0
L j ^ - L j h j + F ^ - E ’ -Q ^ O
T h e interphase energy transfer rates Ej (equal in both phases) have co n d u ctive and co n ve ctive
contributions
, dTl
E\ = ,a ------ +
—h,a
drj
W ith a sim ila r relation for the v a p o r phase, h‘j \s the heat transfer c o e fficie n t in the liq u id -p h a se .
yu , = V u
W h ere the su bscrip t I denotes the e q u ilib riu m co m po sition s and K i j is the vapor- liq u id
eq u ilib riu m ratio for co m p o sitio n o f the tem perature , pressure and co m p o sitio n o f the interface
In addition to above equations, we have the sum m ation equations fo r the m ole fractions in vap o r
and liq u id phase and equations o f co n tin u ity o f flu x e s o f mass and energy across the interface i s :
K j
= N >,
'J
H e a t flu x ,
Ev.
hj
P y - P y - l- ( A P y - i) = 0
W h ere pj a n d pj.] are the stage pressures and (A p y_,) is the pressure drop p er tray from stage j-1
to stage j. T h e pressure drop o v e r the stage is considered to be a fu nctio n o f t h e stage flo w s, the
37
2.5.3. NEQ modeling of RD:
E Q stage m odel in w h ich we sim p ly (or not so sim p ly ) add a term to account fo r reaction to the
F o r hom ogeneous systems the com ponent m o la r balance for the liquid-phase becom es
Lj XU - LH XKj-l ~ K j ~ K j - X \m R™,jej = 0
m=1
W h ere Rmj is the rate o f reaction m on stage j. v,> represents the stoichiom etric co e fficie n t o f
com ponent i in reaction m and Sj represents the reaction volu m e on stage j . F o r hom ogeneous
reactions this is given b y the total liquid hold-up on stage j and, in an N E Q m od el, is obtained
d irectly from the colum n internals specifications and appropriate hydrod yn am ic correlations.
I f it is su fficie n tly rapid, the reaction w ill also take p lace in the liqu id film adjacent to the phase
interface, and v e iy fast reactions m ay o ccu r o n ly in the film . In either case tlie continuity
equations for the film are required fo r taking into account the effect o f the reaction on the
interphase mass transfer rates. T h e com bined set o f M S and continuity equations u su a lly m ust be
so lved nu m erically.
T h e phase e q u ilib riu m equations for the interface m a y need to be m o d ifie d for the influence o f
F o r a heterogeneous reaction, there are two options for the description o f the reaction term. T h e
sim plest approach is to treat the reaction pseudo-hom ogeneously, w hereby catalyst d iffu sio n and
reaction is lum ped into an overall reaction term. F o r heterogeneous reactions that are m odeled in
this w ay the liquid-phase material balance is as g iven above and £} is given b y the total amount
o f catalyst present on the stage under consideration. In this case, one o n ly needs to specify
catalyst mass and activity. A m ore rigorous approach w o u ld in v o lv e the use o f the dusty flu id
m od el discussed above i f the catalyst is porous, o r reaction at the surface i f not. In this case one
also needs inform ation about the catalyst geom etry (surface area, m ean pore diameter, etc). In
either case it is unnecessary to a llo w fo r reaction in the vapo r-liqu id film and the vapo r-liqu id
38 ,
2.5.4. Dynamic Non-Equilibrium stage model (homogeneous):
B a u r R . a n d K r is h n a R . (2001) developed a d yn a m ic non equilibrium stage m odel fo r reactive
mass and energy in the v ap o r and liqu id phase. B o th the vapor and liqu id phases on the stage are
assumed to be w ell-m ixed. T h e tim e rate o f change o fth e num ber o f m oles o f com ponent i in the
vapor (Miv) and liqu id (Mi1) phase on stage j are given b y the fo llo w in g balance equations:
dM^: v v „
-Vjyj + K j< j-N ljii = 1,2, c
dMf, ,, , ,
- f - ~ Lh xh - L j Xj + F iJ ziJ + N , j + Y t vi * Rk j s j
at jt=i
W here JV,, y is the interfacial mass transfer rate. A total r chem ical reactions take place in the
liq u id phase and Rkj is the rate o f reaction k on stage j, v,> represents stoichiom etric coefficient
o f com ponent i in reaction k and Ej represents the volum etric liqu id hold- up on stage j.
d M y, y * „
^
d L M -LI+F }+t N ^ t t \ A A
Ul k=1 i=l k=\
i ■
T h e m qle fraction o f the vap or and liqu id phases are calculated from the respective phase m olar
hold-ups
Mjt, M j-.
O n ly c-1 o f these m ole fractions is independent because the phase m ole fractions sum to unity.
i = 1
ti = 1
, , ■ .
T h e energy balance for vap or and liquid phases are written in terms o f energy “ hold ups” in
39
jpV cV py
-~ L -V — _l-F v H vf - E v - O v
d: 'm ; 1 > < Uj
dFL Fl Fl
— L = L j ,— ^ - L , — -1r + F j H ' f + E'; - Q'j
dt j 1M ‘ j j j J
The energy hold-ups are related to corresponding molar hold-ups via the stage enthalpies
Ej = H jM '] ;E j = H j M j
Jie Bao et al (2002) developed equilibrium model for a catalytic distillation process for the
MTBE from methanol and isobutylene. The model equations based on equilibrium stage j are as
follows:
Mass balance equation:
djEjXj,)
' ~ Lj_\Xj_t l + Vj+IyJ+Ij LjXjj Vjyjj + FljZIjj + tsRj(
dt
Where FIj and Zlj are feed stock flow rate and composition at stage j respectively. ARj, is
l-e x p
k .+ L (N C 2 - N C I +1).KS.aLkJ_i pj
Where pj is the liquid molar density, k the layer of catalyst package at stage j (1 < k < KS), a is
the contacting efficiency of liquid to catalyst, and 5 is the reaction efficiency in the catalyst
package.
Vapor-liquid equilibrium equation:
y > j= K u xu
Where j is the vapor- liquid equilibrium coefficient for component i at stage j.
40
Component summation equations:
C C
Yj x>j = x and 2 > u =1
i=i
E n th a lp y bala n ce equations:
T h e m ass transfer between liq u id and v a p o r phases are characterized b y the h eig h t o f transfer
un it ( H T U ) .
• M a s s transfer in sid e the catalyst is neglected so that we use quasi-ho m o g eneo us rate
expression.
I f the height o f the co lu m n is sp e cifie d , the n u m b e r o f transfer units ( N T U ) can b e determ ined. In
the fo llo w in g , the m o d e l equations fo r the j th transfer u n it are given, w here the in dex j counts
dow nw ards.
41
Total mass balance of liquid phase:
Lh - li + =0
1=1
T o ta l energy balance:
V L E relationship:
h jfu P u
y<j p
NC NC
Z x , tJ = 1 and £ y UJ = 1
/=! i=1
W here, i= l,2 ,...N C ; j= 0 ,l,..., N T U + 1 , j= 0 means the condenser, j = N T U + l the reboiler ; 1=1, 2,
3..., represents the reaction number; vf/is the stoichiom etric co efficien t o f com ponent i in
R eaction I;
vT , is the m ole change o f reaction I ; Hj, hj, and hfj are enthalpies o f v ap o r and liqu id
phases and the feed, respectively; Ecaij is the am ount o f catalyst at stage j , w h ich is defined b y
42
CH APTER 3
• T h e a ctiv ity o f the com ponents in the liq u id phase is calculated w ith the N R T L m od e l.
43
3.3. M odeling equations:
*ij-i Vjyu
. Ih
J sa
L x V y
j y j« y+i
44
Over all material balance:
L n = Vn +i + Y j Fic-D
<t=1
Component material balance on jth stage:
Rate kinetics:
Rate equation written as
f ij =-kj (xoj X , j - ( X 2J X 3 J / kej)) (i =0 or 1)
nj = kj (x0j xij-(x2jx3j/kej)) (i =2 or 3)
ARi,j —tjLj - in, j
kj and kej ar function of temperature.
Vapor-liquid equilibrium:
y ij~ KijXjj
v frjpi.j
K i, j = -----------
P ‘J
P ij calculated from'Antoine equation and y ij are calculated form NRTL model
Component summation:
(=0 1=0
Enthalpy balance:
The variation of enthalpy with temperature has been incorporated by use of following
correlation.
CHAPTER 4
T h e m athem atical m odel in chapter 3 is used to solve fo r the synthesis o f methyl acetate
by using pseudo hom ogeneous rate kinetics m odel for tw o feed set up. W e sim ulate this m odel
(2001). In the fo llo w in g sections, m odel v a lid ity and effect o f variables nam ely - r e flu x ratio,
feed tray locations, start o f reactive zone and end o f reactive zone, and therm odynam ic m odels
Param eter V a lu e
R e flu x ratio 2 .1
Feed rates(mol/hr)
F HOAc 30.8
F MeOH 32.2
Feed tray
N fl 5
N f2 20
R eactive stage
E n d o f reactive stage(Nre) 19
C o lu m n diameter(m) 0.05
T HOAc 2 1 .1
T MeOH 2 0 .1
47
4.1. Model validation:
m eth yl acetate b y u sin g A S P E N R A D F R A C sim u lator. W e sim u late the reactive zo ne based on
pseudo ho m o gen eou s rate k in etic m o d el. S im u la tio n results g iv e n in A n n e x u re - A and has been
4.1.1. Validation o f liquid phase com position profile for two feed set up:
feed co lu m n and experim ental result o f P o p k e n et al, (2001). T h is d iagram re v e l the variation
betw een experim ental result and sim u la tio n results. T h e average o f m a x im u m d eviatio n w ith the
4.1.2. Variation o f M ethanol conversion with Reflux ratio using two feed set
up:
F ig u re 4.2 show s the variation m ethanol co n ve rsio n w ith re flu x ratio as obtained b y
sim u la tio n o f p seud o hom ogen eou s m odel and experim ental results o f Popken (2001).
O b se rv a tio n o f th is fig u re e x p lain s som e v a ria tio n s is o cc u r betw een experim ental results and
tray lo ca tio n , start o f reactive section and end o f reactive section, and th e rm o d yn a m ic m o d e ls on
the co m p o sitio n o f m e th yl acetate o n trays and distillate, and co n v e rsio n o f m ethan ol b y u sin g
48
Table 4.2 Range of process variables using in two feed stage
Variables Range
Reflux ratio 0.5 to 5.0
Feed tray location
Nfl (Acetic Acid) 2 to 10
Nf2(Methanol) 19 to 23
Start of reactive stage 5 to 15
End of reactive stage 16 to 23
Figure 4.2 shows the effect of reflux ratio on methanol conversion for (D/F=.48 and
Fh o a c ~ F M eO H = 3 2.5 mol/hr) using two feed set up. A close observation of the figure gives
following details about optimum operating conditions.
• Methanol conversion initially increases then decreases with increase in reflux ratio.
• Methanol conversion is high when reflux ratio is 1.6 to 2.1 for two feed set up.
• At low reflux ratio (0.5 to 1.2) insufficient separation of the products from the reactive
zone limits the conversion of methanol.
• At high reflux ratios, the reactants are separated too effectively from each other, thus
limiting conversion is observed.
® For optimum reaction conditions, the concentrations of both the reactants must be high in
reactive zone.
• If a high reflux ratio is used methanol leaves the column with the distillate,
Because of methyl acetate/methanol azeotrope is enriched at top ofthe column.
49
F ig u r e 4.3 show s the e ffe c t o f re flu x ratio o n m e th y l acetate c o m p o s itio n in d istillate u s in g tw o
• M e t h y l acetate c o m p o s itio n in distillate in itia lly increases w ith in crease in re flu x ratio.
1.6.
acetate c o m p o s itio n on each tray o f ca ta lytic d is tilla tio n c o lu m n u s in g tw o feed set up. A c lo s e
• M e t h y l acetate c o m p o s itio n in tray ju s t a b o ve the feed tray N f l increase a b ru p tly that w ith
• M e t h y l acetate c o m p o s itio n o n the d istilla te in itia lly in creases w ith in cre a s in g N f l and
• A t lo w N f l =2 there is n o re ctifica tio n se c tio n and o n ly extractive section in the top and
extractive and re c tifica tio n sectio n the m eth y l acetate c o m p o s itio n in the d istillate
increases.
acetate c o m p o s itio n on each tray o f ca ta lytic d is tilla tio n c o lu m n u sin g tw o feed set up . A c lo s e
• M e th y l acetate c o m p o s itio n in the trays in re c tifica tio n section , in distillate and in? the
• A fte r N£2=21 the m eth yl acetate c o m p o s itio n in trays in re ctifica tio n section and
50
4.2.3. Effect of starting of reactive zone:
F ig u re 4.6 sh ow s the effect o f start o f re a ctive stage (N rs) k e e p in g end o f re a ctiv e stage
(N re ) constant o n m e th yl acetate liq u id p hase c o m p o s itio n o n each tray o f ca ta ly tic d istilla tio n
(N rs) con stan t on m e th y l acetate liq u id phase c o m p o s itio n on each tray o f rea ctive d istilla tio n
c o m p o s itio n in each tray o f ca ta lytic d istilla tio n co lu m n fo r u sin g tw o feed set up . T h is e x p lain s
51
M e O A c c o m p o s it io n
up .
52
F ig u r e 4 .2 C o n v e r s io n v e rsu s R e flu x r a t io fo r s y n t h e s is o f m e th y l a c e ta te u s in g tw o fe e d
c o lu m n
53
Reflux ratio
54
Stage No.
55
F ig u re 4.5 M e O A c C o m p o s itio n o n trays fo r d iffe re n t N C u sin g tw o feed set u p w ith N f l =5.
56
F ig u r e 4 .6 V a r ia t io n o f M e O A c C o m p o s it io n w ith start o f re a c tiv e se ctio n ( N r s ) u s in g tw o feed
se tu p (N re = 1 9 ).
57
F ig u re 4.7 V a ria tio n o f m eth yl acetate co m p o sitio n on trays for d ifferent N re stages w ith N rs= 10
58
MeOAc composition
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
No
Stage
C o n c lu s io n s :
trays to b e h ig h
Recommendations:
F o r a ccu ra te result, the fo llo w in g a ssu m p tio n s and s p e c ific a tio n s s h o u ld be co n sid e re d :
b y ta k in g a n o n - e q u ilib riu m m o d e l.
60
REFERENCES
1400849.
A s p e n p lu s P la tfo rm ” , C h e m . E n g . J. V o l. 90 N o . 3 , 2 5 3 -2 5 9 (2002).
In vestigation s on the synthesis o f m e th y l acetate in a hetero g eneo us rea ctiv e d istilla tio n
62
14. E lle n b e rg e r, J., & K ris h n a , R . (1999). C o u n te r-c u rre n t op e ra tio n o f stru ctu red c a ta ly tic a lly
(2004), R e v ie w R l .
18. K e y e s , D . B . (1932). E s te rific a tio n p ro cesses and eq uip m ent. Industrial and Engineering
Chemistry, 2 4 , 1096-1103.
19. K o lo d z ie j A . , J a ro s z y n s k i M . , H o ffm a n n A . ; a n d G o r a k A . , “ D e te rm in a tio n o f ca ta lytic
p a c k in g ch a ra c te ristics fo r rea ctiv e d is tilla tio n ” , Catal. Today, V o l. 69 , N o . 1-4, 75-85 (2001).
A d v a n c e d sim u la tio n and e x p erim en tal v a lid a tio n . Computers and Chemical Engineering,
2 2 ,3 7 1 -3 7 8 .
k in e tic and d is tilla tio n co n sid e ra tio n s. Transactions of the American Institute of Chemical
Engineers, 41,\S I-196, 481.
23 . L e y e s , C . E ., & O th m e r, D . F . (1 94 5 b). E s te r ific a tio n o f butanol and ace tic acid . Industrial
and Engineering Chemistry, 37, 968-977.
24. L iu , Y . , L o t e r o , E . , G o o d w in Jr. J .M . A c o m p a ris o n o f the e ste rifica tio n o f ace tic a c id w ith
(2 0 0 6 )2 7 8 -2 8 6 .
25 . O n d re y , G ., C h e m . E n g . 6 (1 99 6 ) (N e w sfro n t).
63
2 7 . P o p k e n T . , S te in ig e w e g S ., a n d G m e h lin g J., “ S y n th e s is a n d h y d r o ly s is o f m e th y l acetate b y
re a c tiv e d is t illa t io n stru ctu re d c a ta ly tic packings:'! E x p e rim e n ts and s im u la tio n ” , Ind. Eng.
Chem. Res., V o l . 4 0 , N o .6 , 1 5 6 6 -1 5 7 4 (2 00 1 ).
N o . 2 -3 , 147-163 (2 00 2 ).
P a c k in g s : A C o m p r e h e n s iv e M o d e l fo r T h e i r P e rfo rm a n c e : 2. M a s s - T r a n s fe r M o d e l , ” Ind.
Eng. Chem. Res., 3 5 , 1660 (1 99 6 ).
in “ R e a c t iv e D is t illa t io n ” b y S u n d m a c h e r K . a n d K ie n le A . ( E d s ) , W i le y V C H , G e r m a n y , p p
1-29 (2 00 3 ).
3 6 . S o n g , W .; V e n im a d h a v a n , G .; M a n n in g , J. M . ; M a lo n e , M . F .; D o h e r ty , M . F . M e a s u re m e n t
37 . S p e s, H . (1 96 6 ). K a t a ly t is c h e R e a k tio n e n in Io n e n a u sta u c h e rk o lo n n e n u n te r V e r s c h ie b u n g
A n n u a l M e e t in g , L o s A n g e le s , C A , 2 0 0 0 a .
3 9 . S te in , E ., K ie n le , A , S u n d m a c h e r, K . C h e m . E n g . 107 (2 0 0 0 b ) 6 8 - 7 2 .
64
4 0 . S t ic h lm a ir, J. G ., & F r e y , T . (1 99 9 ). R e a c t iv e d is t illa t io n p ro c e s se s. Chemical Engineering
and Technology, 22, 9 5 -1 0 3 .
5 1 8 3 -5 2 2 9 (2 0 0 0 ).
65
AN NEXU RE-A
T a b le A .1 C o m p o s it io n d a ta f o r F ig u r e 4.1
66
Table A.2: MeOH Conversion Data for Figure 4.2
1 0.761264 0.868
1.2 0.812889
1.4 0.860705
1.5 0.886507
1.6 0.912273
1.7 0.933476
1.8 0.93787
2 0.938493 0.878
2.1 0.938021
2.5 0.934286
3 0.927179
3.5 0.918152
4 0.907545
5 0.882552
67
Table A.3: MeOAc liquid composition Data in distillate for Figure 4.3
R e f l u x ra tio M e O A c in d is t illa t e u s in g tw o fe e d se t u p
0 .5 0 .6 1 4 4 5 7 6 8
1 0 .7 9 2 9 5 5 9 7
1.2 0 .8 4 6 7 4 6 0 3
1.4 0 .8 9 6 5 6 4 4 8
1.5 0 .9 2 3 4 4 2 8 4
1.6 0 .9 5 0 2 8 3 9 3
1.7 0 .9 7 2 3 7 0 2
1.8 0 .9 7 6 9 4 7 9
2 0 .9 7 7 5 9 6 1 8
2.1 0 .9 7 7 1 0 4 1 5
2 .5 0 .9 7 3 2 1 3 3 5
3 0 .9 6 5 8 0 9 7 3
3 .5 0 .9 5 6 4 0 5 7 4
4 0 .9 4 5 3 5 5 6 2
4 .5 0 .9 3 2 8 8 6 1 1
5 0 .9 1 9 3 1 5 5 4
68
Table A.4: MeOAc Composition Data for Figure 4.4
Stage N o . N f l =2 N f l =5 N f l =7 N f l =9 N f l= 1 0
69
Table A.5: MeOAc Composition Data for Figure 4.5
1 0 .9 7 6 1 8 7 0 .9 7 6 18 0 .9 6 7 8 0 9 0 .8 8 8 1 8 3 0 .8 3 6 0 0 3
2 0 .9 8 3 9 9 7 0 .9 8 3 99 3 0 .9 7 9 2 7 9 0 .9 0 0 6 4 0 .6 6 3 2 9 9
3 0.9721 0 .9 7 2 0 9 7 0 .9 6 9 0 2 5 0 .8 9 5 4 5 6 0 .2 3 5 583
4 0 .8 9 7 2 7 2 0 .8 9 7 2 6 9 0 .894301 0 .7 9 5 1 5 2 0 .0 9 3 9 5 7
5 0.611911 0 .6 1 1 9 0 7 0 .6 0 7 2 7 3 0 .4 6 0 6 3 8 0 .0 7 7 0 2 6
6 0 .6 0 6 0 0 2 0 .6 0 5 9 9 6 0 .5 9 8 8 2 2 0 .3 3 2 5 8 4 0 .0 7 6 213
7 0 .5 9 9 9 9 4 0 .5 9 9 9 8 7 0 .5 8 9 8 5 2 0 .2 0 6 6 0 8 0 .0 7 5 9 4 8
8 1 0 .5 9 3 6 8 4 0 .5 9 3 6 7 4 0 .5 7 9 8 1 7 0 .1 3 2 8 3 4 0 .0 7 5 8 5 7
9 0 .5 8 6 8 8 3 0 .5 8 6 87 0 .567961 0 .1 0 1 8 4 7 0 .075821
10 0 .5 7 9 6 0 2 0.579581 0 .5 5 3 2 5 6 0 .0 9 0 5 6 8 0 .0 7 5 7 9 9
11 0 .5 7 0 6 4 6 0 .5 7 0 5 9 8 0 .5 3 1 1 1 6 0 .0 8 6 4 5 9 0 .0 7 5 7 6 5
12 0 .5 5 9 7 7 5 0.559631 0 .4 9 5 4 7 8 0.08501 0 .0 7 5 7 1 6
13 0 .5 4 6 0 1 9 0 .5 4 5 5 5 7 0 .4 3 4 5 9 5 0 .0 8 4 4 3 7 0 .0 7 5 6 2 7
14 0.5 2 8 0 1 3 0 .5 2 6 53 0 .3 4 0 7 6 4 0 .0 8 4 0 7 2 0 .0 7 5 4 4 9
15 0 .5 0 4 1 1 6 0 .4 9 9 5 8 7 0 .2 3 5 8 8 8 0 .0 8 3 5 7 6 0 .0 7 5 075
16 0.4 7 2 6 2 5 0.46 0 .1 5 8 4 3 2 0 .0 8 2 4 8 7 0 .0 7 4 1 9 8
17 0 .4 2 6 2 0 .3 9 6 5 5 0 .1 1 3 5 4 0.0 7 9 38 0 .0 7 1 7 6 5
19 0.1 1 4 5 8 5 0 .0 5 2 5 3 8 0 .0 1 6 6 8 9 0 .0 2 5 0 1 2 0 .0 2 8 3 4 7
20 0 .0 3 1 6 2 8 0 .0 0 8 11 5 0 .0 0 1 30 3 0 .0 0 2 1 7 9 0 .0 0 2 6 7 8
21 0 .0 0 7 3 8 9 0 .0 0 1 8 2 6 0 .0 0 0 1 9 0 .0 0 0 2 5 6 0 .0 0 0 3 0 5
22 0 .0 0 1 5 4 9 0 .0 0 0 3 8 4 .0 3 E -0 5 4 .3 6 E -0 5 4 .2 3 E -0 5
23 0.0 0 0 2 6 3 6 .4 3 E -0 5 7 .0 4 E -0 6 1 .0 1 E -0 5 7 .4 2 E -0 6
24 2 .8 5 E -0 5 6 .9 6 E -0 6 8 .0 4 E -0 7 1.7 8 E -0 6 1 .5 7 E -0 6
25 1 .8 2 E -0 6 4 .4 5 E - 0 7 5 .5 2 E -0 8 2 .1 5 E - 0 7 2 .4 5 E -0 7
70
Table A.6: MeOAc Composition Data for Figure 4.6
23 6 .5 1 E -0 5 6 .4 8 E -0 5 6 .4 3 E -0 5 6 .5 4 E -0 5 6 .8 3 E -0 5
24 7 .1 1 E -0 6 7 .0 6 E -0 6 6 .9 7 E -0 6 7 .0 6 E -0 6 7 .3 7 E -0 6
25 4 .5 6 E -0 7 4 .5 2 E -0 7 4 .4 5 E -0 7 4 .5 2 E -0 7 4 .7 7 E -0 7
71
Table A.7: MeOAc Composition Data for Figure 4.7
Stage
N o. Nre=16 Nre=17 Nre=18 Nre=19 Nre=20 Nre=21 Nre=22 Nre=23
72
Table A.8: MeOAc Composition Data for Figure 4.8
S ta g e N o . W ILS O N N R TL U N IQ U A C U N IFA C
1 0 .9 7 6 1 6 5 0 .9 5 5 7 3 9 0 .9 8 2 4 1 9 0 .9 9 0 0 1
2 0 .9 8 3 9 8 5 0 .9 6 8 0 1 4 0 .9 8 8 8 6 0 .9 8 8 0 8 6
3 0 .9 7 2 0 9 3 0 .9 6 2 6 7 5 0 .9 7 8 4 0 3 0 .9 7 2 2 3 8
4 0 .8 9 7 2 6 5 0 .8 9 2 3 3 1 0 .9 0 0 0 6 4 0 .9 0 1 5 5 2
5 0 .6 1 1 8 9 9 0 .6 1 4 9 7 6 0 .6 2 0 4 4 4 0 .6 1 4 1 6 8
6 0 .6 0 5 9 8 3 0 .6 0 8 3 8 5 0 .6 1 8 2 5 4 0 .6 0 9 3 3 9
7 0 .5 9 9 9 6 8 0 .6 0 2 1 8 4 0 .6 1 5 6 3 4 0 .6 0 3 4 6 1
8 0 .5 9 3 6 4 7 0 .5 9 6 0 2 7 0 .6 1 2 2 0 4 0 .5 9 6 1 6 6
9 0 .5 8 6 8 3 2 0 .5 8 9 6 9 4 0 .6 0 7 6 6 2 0 .5 8 7 0 6 3
10 0 .5 7 9 5 3 1 0 .5 8 3 2 8 6 0 .6 0 2 2 0 7 0 .5 7 6 1 4 3
11 0 .5 7 0 5 2 8 0 .5 7 5 9 0 6 0 .5 9 4 8 4 3 0 .5 6 1 2 9 3
12 0 .5 5 9 5 3 3 0 .5 6 7 3 9 8 0 .5 8 5 8 2 7 0 .5 4 2 1 8
13 0 .5 4 5 4 2 3 0 .5 5 7 0 4 7 0 .5 7 4 2 0 9 0 .5 1 7 1 6 8
14 0 .5 2 6 3 5 5 0 .5 4 3 6 9 5 0 .5 5 8 2 4 6 0 .4 8 4 0 7 9
15 0 .4 9 9 3 8 6 0 .5 2 5 3 7 2 0 .5 3 4 4 6 8 0 .4 4 0 7
16 0 .4 5 9 8 2 1 0 .4 9 8 3 7 8 0 .4 9 5 2 8 6 0 .3 8 6 0 4 4
17 0 .3 9 6 4 4 3 0 .4 5 3 2 0 7 0 .4 2 1 5 4 8 0 .3 1 8 3 9 5
18 0 .2 5 0 4 0 3 0 .3 3 0 7 7 5 0 .2 3 7 0 5 8 0 .1 8 3 1 3
19 0 .0 5 2 5 5 3 0 .0 7 8 8 9 6 0 .0 3 9 4 9 6 0 .0 3 2 6 4 7
20 0 .0 0 8 1 1 8 0 .0 1 2 0 8 7 0 .0 0 5 4 0 7 0 .0 0 4 9 8 1
21 0 .0 0 1 8 2 7 0 .0 0 2 5 9 4 0 .0 0 1 0 9 1 0.001119
22 0 .0 0 0 3 8 0 .0 0 0 5 1 4 0 .0 0 0 2 0 2 0 .0 0 0 2 3
23 6 .4 3 E - 0 5 8 .3 5 E - 0 5 2 .9 1 E - 0 5 . 3 .7 7 E - 0 5
24 6 .9 7 E - 0 6 8 .0 8 E - 0 6 2 .3 2 E - 0 6 3 .5 7 E - 0 6
25 4 .4 5 E - 0 7 3 .8 8 E - 0 7 1.01 E - 0 7 1 .5 5 E - 0 7
73