Escolar Documentos
Profissional Documentos
Cultura Documentos
A Dissertation
By
Hemendra Khakhar
MASTER OF SCIENCE
December 2004
By
Hemendra Khakhar
Master of Science
December 2004
iv
ABSTRACT
distillation of the crude oil or heavier fractions from other refinery units like cokers
new unit.
these kind of zeolite catalyzed oil refining processes. The complete network of
v
Watson kinetics and pseudo steady state approximation. Transition state theory
tractable range.
algorithm. In contrast to present day available kinetic models, single event rate
fundamental nature. These rate equations can be plugged into 1-D heterogeneous
model for simulation and optimization of industrial fixed bed reactors. Obtained
kinetic model can also be used for catalyst design, preliminary design of new
hydrocracker units.
vi
To My Parents
vii
ACKNOWLEDGMENTS
Gilbert F. Froment for all his sincere support and guidance throughout the course
of this research. I would like to thank Co-chairman Dr. R.G.Anthony for his valuable
I also feel the deepest amount of gratitude to my all friends here at Texas A&M for
their moral support and enjoyable time. Finally, I cannot adequately expression my
appreciation for my parents and Madhvi for their love, encouragements and
viii
TABLE OF CONTENTS
PAGE
ABSTRACT .............................................................................................................V
ACKNOWLEDGMENTS .......................................................................................VIII
REFERENCES...................................................................................................... 79
APPENDIX A......................................................................................................... 81
APPENDIX B......................................................................................................... 93
ix
LIST OF FIGURES
FIGURE
Page
x
LIST OF TABLES
xi
CHAPTER I
INTRODUCTION
requirements:
2. The demand for gasoline and middle distillates (kerosene and diesel fuels)
demands and changing feeds on a weekly basis (Ward, 1993; Quann and
The oil product demand from 2000 to 2005 in the Organization for Economic
has been reported that one of the fastest increases in 3 years from 2002 to 2005
will be in demand for middle distillates (Beck et al, 2001). The petroleum
heavy gas oils, to higher value middle distillate. They can choose from several
option to produce high quality middle distillate with high hydrogen content.
1
Table 1.1 Outlook for Petroleum demand for Organization for Economic Cooperation and Development (OECD)
Distillates
2
The history of hydrocracking is found in paper written by Sullivan and Scott
Germany between 1915 and 1945. Germany needed a secure supply of liquid
fuels derived form coal. The quantity of liquid fuels was important but their quality
was not considered at that time. Therefore, typical reaction conditions were quite
severe: 21-69 MPa and 375-525 0C, giving liquid fuels that were highly aromatic
There was a parallel development in the United States, which was directed
toward the upgrading heavier petroleum fractions. The reaction conditions were
somewhat milder but still severe: 21-31 MPa and >375 0C. After the end of World
War II, thermal hydrocracking became less popular because of the availability of
middle Eastern crude oils and development of new catalytic cracking processes.
During 1950’s, the trend toward automobile engines with high compression
ratios, the shift by the railroads from steam to diesel locomotives, an excess of
temperatures (200-400 0C) and lower pressures (3-14 MPa). Seven different
grown at a slow pace in the United States since the late 1970’s; however,
worldwide hydrocracker capacity will grow to 3.9 MM barrels per day in 2006.
single stage recycle (SSREC) and two stage recycle (TSRE) processes. A two
The vacuum gas oil is sent to the first stage of the hydrocracker and is severely
hydrotreated. Most of the sulfur and nitrogen compounds are removed from the
oil and many of the aromatics are saturated. In addition, significant conversion to
light products occurs in the first stage. The liquid product from the first stage is
are removed by distillation. The unconverted oil from the bottom of the
The second reaction stage saturates almost all of the aromatics and cracks the
oil feed to light products. Due to the aromatics saturation, the second stage
4
Fig. 1.1. Process flow diagram for “Isocracking” Process
5
produces excellent quality products. The liquid product from the second stage is
then sent to the common fractionator where light products are distilled. The
The overhead liquid and vapor from the hydrocracker fractionator is further
processed in a light ends recovery unit where fuel gas and liquefied petroleum
gas (LPG) and naphtha are separated. The hydrogen supplied to the reactor
sections of the hydrocracker comes from the steam reformers. The hydrogen is
8.5-20 MPa pressure, 0.5-2.5 hr-1 liquid hourly space velocity, 505-1685 normal
m3/m3 hydrogen to oil ratio and 200-590 normal m3/m3 hydrogen consumption.
The major drawback of hydrocracking is its high price due to the use of high
catalyst metal function and acid function respectively. As sulfur and nitrogen
contact with the hydrocracking catalyst. The operating conditions and properties
of the feedstock have a significant impact on the yield and quality of the products.
6
aromatics hydrogenation due to thermodynamic limitations (Dufresne et al.,
Hydrocracking can be designed with flexibility in the product slate to meet market
are oil, petrochemical feedstocks, feedstocks for FCC and thermal crackers, and
conventional straight run heavy gas oils. As the market value of heavy oils is
as coker gas oils are becoming important feedstocks for hydrocracking (Sullivan
et al., 1989). As these heavy gas oils have much more nitrogen and sulfur
compounds and aromatics than conventional straight run heavy gas oils, they are
feedstocks from different origins, such as tar sands and coal, is growing because
world reserves of conventional crude oil are dwindling (Kim et al., 1997).
the future. Our goal is to develop a kinetic hydrocracking model for simulation
and optimization of industrial fixed bed reactors. Obtained kinetic model can also
7
CHAPTER II
LITERATURE SURVEY
needed to predict yields of various products for process design, optimization and
and Nace from Mobil proposed a simple model containing three pseudo
components: Gasoline, Gas oil and light gases with 3 reactions for the catalytic
cracking of gas oil fractions. Jacob et al. (1976) revised this three lump model to
a ten lump model with 17 reactions. The limitation of these lump models is that
rate parameters vary with the type of feed and configuration of reactor. So,
8
of lumps. Hence, requirement of a fundamental kinetic model arose, which can
Various types of lump models have been proposed: a model based on a series of
fixed boiling range cuts by Stangeland (1974), the compound type distribution
hydrocracking. One parameter, A, describes the effect of boiling point on the rate
generated as each cut cracks. The boiling point distributions of the feedstock and
product are segregated into fixed boiling ranges of 50oF each and the apparent
1st order rate constant k for each component was expressed by a function of the
true boiling point T b (oF) and one cracking rate parameter A as follows:
k (T ) T A(T 3 T ) ……….(2.1)
9
The product distillation curve was predicted with high accuracy using a feedstock
on boiling point and paraffin content of the feedstock was insufficient to establish
data using a lumped model. The surface reaction was considered as the rate
dibenzothiophene.
ki ci
ri n
……….(2.2)
1 K j c j
j
adsorption constant for jth species and n is 1 or 2. Then reaction networks for the
components based on the competitive adsorption mechanism. The model for the
mixture of quinoline and naphthalene was obtained without any modification for
10
each component. In the case of the model for the mixture of quinoline and
Though the proposed model is still the “ideal hydrocracking” model, their concept
can be applied for the industrial feedstocks with some modifications because the
(1989) simply used nitrogen for inhibitor content because it was impossible to
n
K l N K l , j N j ………..(2.3)
j 1
Where, N and N j are total nitrogen and individual nitrogen species respectively.
has empirical value for real feedstocks, where the number of components is very
large.
As the reviewed models are adjusted for some particular conventional straight
run heavy gas oil or set of model compounds, it will be impossible to apply them
for the various feedstocks from different origins with significant adjustments and
accuracy.
11
Fundamental kinetic models
using carbenium ion chemistry principles (Baltanas et al., 1989; Vynckier and
to account all the reactions involving individual molecules. Vynckier and Froment
convenient way. Feng et al. (1993) formalized the single event kinetics for
catalytic cracking and estimated single event rate parameters for catalytic
Svoboda et al. (1995) estimated single event rate parameters from experiments
carried out on hexadecane and validated single event concept for the
process. Dewachtere et al. (1999) applied a single event kinetic model in the
simulation of an industrial riser reactor for the catalytic cracking of vacuum oil.
Martens et al. (2000) applied a single event kinetic model for the hydrocracking
12
approach, it was found that a finite and limited number of kinetic parameters
which, the model components are developed using linear programming. This
was found that there were no significant differences in the product distribution for
Quann and Jaffe (1992) proposed a novel approach for modeling called Structure
The vector elements are referred to as structural increments, which are three
aromatic and six naphthenic ring structures, a –CH 2 - group to specify the carbon
13
and heteroatom groups or substitutions in rings and alkyl chains. The vector
these analyses, all isomers at a specific carbon number were lumped. For
example, three isomers of xylene, which are o-xylene, m-xylene and p-xylene,
are in a group. It was assumed that the isomers of a molecular class at a given
carbon number would exhibit similar properties. The SOL method enabled the
reactant selection rule and a product generation rule. The algorithm to estimate
conventions, which were based on the general knowledge of straight run streams
derived from conventional crude oils, were used and the reaction networks for
14
applied for the streams from residuum upgrading processes such as coker gas
oil. For example, the alkyl groups on ring compounds are assumed to be a long
alkyl chain and an average of one methyl group per ring. However, the alkyl
groups of a coker gas oils are random because they are thermal cracked
be impossible to represent each group by one structure in the case of coker gas
oils.
The recent shift in research towards the fundamental kinetic models clearly
fidelity models for the hydrocracking process. It is strongly believed that the
industry.
15
CHAPTER III
Hydrocracking in the petroleum industry is often carried out in two stages. In the
first stage, sulfur and nitrogen containing compounds are decomposed and
aromatics are hydrogenated. The liquid fraction coming form the first stage is
metal components. The cracking catalysts such as SiO 2 -Al 2 O 3 and the zeolites
have been found to have both bronsted and Lewis acid sites (Gates et al., 1979).
The bronsted sites are responsible for proton donation and the Lewis sites for
16
several different paths. The protonation of a saturated hydrocarbon in the
presence of a superacid with very high proton donor strength generates a non
classical carbonium ion intermediate. The penta co-ordinated carbon atom loses
metal generates a carbenium ion. The reaction path way of the olefins is still
In the primary carbenium ions, the positively charged carbon is connected to two
hydrogen atoms and one alkyl group. The methyl carbenium ion is a primary
cation with three hydrogen atoms connected to the charged carbon. In secondary
carbenium ions, the carbon atom with the positive charge is connected to two
methyl groups and a hydrogen atom. Similarly, in tertiary ions, the charged
carbon atom is connected to three alkyl groups. The energy required for
atoms attached to the carbon atom carrying the positive charge. The stability of
The tertiary carbenium ion is by far the most stable species, and it is the easiest
The most common feed to the hydrocracking is VGO. The VGO feed contains
reactions for paraffins are given in fig 3.1. After physisorption in the zeolite
17
Fig.3.1. Typical Elementary steps for hydrocracking of Paraffins
18
Fig.3.2. Typical Elementary steps for hydrocracking of naphthenes
19
cages of a hydrocracking catalyst, the paraffins are dehydrogenated on the metal
component of the catalyst. The resulting olefins are protonated in the Bronsted
acid sites, yielding the alkane carbenium ions. These cations isomerize through
hydride shifts and methyl shifts. Hydride shifts and methyl shifts preserve the
branching (PCP) steps alter the number of side chains present in the reactant
position with respect to the carbon atom carrying the positive charge. Cracking
requires that the β-carbon with respect to the positively charged carbon be a
tertiary carbon atom. This ensures that the hydrocracking reactions avoid
producing or produce very little amount of methane and ethane in the cracked
products. After deprotonation of the alkane carbenium ions the resulting acyclic
sites of the catalyst leads to the formation of cyclic mono-olefins, which are
protonated to cyclic carbenium ions. The cyclic carbenium ions isomerize through
hydride shift, methyl shift and PCP branching. Hydride and methyl shifts do not
alter the branching degree in naphthenes. However, methyl shifts alter the
20
Three different kinds of PCP steps are possible in naphthenes. The first one,
known as acyclic PCP branching, which is similar to the PCP step in paraffins,
changes the branching degree in the alkyl side chain attached to the ring. The
second type is known as the intra-ring alkyl shift, which leads to ring contraction
or ring expansion without altering the branching degree of the naphthenic ring.
The third type is known as the cyclic PCP step, which causes the ring contraction
or ring expansion while altering the degree of branching of the naphthenic ring.
There are two kinds of β-scissions possible with the naphthenic carbenium ions.
If the β-scission occurs on the alkyl side chain or if the alkyl side chain is severed
from the ring, then it is known as the exocyclic β-scission. The cleavage of a
containing a double bond and a positively charged carbon atom. The alkene or
21
Theory of Single Event Kinetics
equation:
k T S 0 H 0
k ' b exp exp ……. (3.1)
h R RT
The influence of the molecular structure on the rate coefficient can be described
contributions (Willems and Froment, 1988), due to the different motions of the
S 0 Strans
0
S vib
0
S rot
0
S ele
0
….(3.2)
i.e., S rot
0
S ext
0
rot S int rot . The S ext rot and S int rot are composed of two terms: the
0 0 0
22
Fig. 3.3. Theoretical Concept behind Single Event Kinetics (adapted from
Park,1998)
23
‘intrinsic’ value, Ŝ 0 and a term due to symmetry, , which depends on the
When optically active species are involved, the symmetry contribution to the
standard entropy has to be augmented with the contribution due to the mixing of
R ln(2 n ) , where n is the number of the chiral centers in a species, and the term
the basis of equation (3.3) with the effect of racemic mixtures, the rotational
contribution, S rot
0
is given by
0
S rot Sˆrot
0
R ln ext n int ………(3.4)
2
of a species.
24
Inserting equation(3.4) in to equation(3.2), the standard entropy of activation
S 0 , which is the S 0 difference between the reactant and the activated complex
is given by
glr
S 0 Strans
0 0
S vib 0
S rot 0
S ele R ln ……..(3.5)
gl
glr k T Sˆ 0 0
k ' b exp exp H ……..(3.6)
h
gl R RT
The rate coefficient of the elementary step k ' , can now be written as a multiple of
~
the single event rate coefficient, k (Vynckier and Froment,1991)
~
k ' ne k ………(3.7)
~
Where, the number of single events ne , and the single event rate coefficient k ,
are defined as
25
glr
ne
gl
………….(3.8)
~ kbT Sˆ 0 H 0
&k
exp
h exp RT
R
between the reactant and the activated complex has been factored out by
introducing the number of single events, ne , the single event rate coefficient now
truly characterizes the reaction itself at the fundamental level. Comparing this
expression for k ' with the rate coefficient in Arrhenius form indicates that the
potential energy difference between the activated complex and the reactant.
A simple example can be used to illustrate the need for distinguishing between
elementary steps and single events. Consider the 1,2-methyl shift between 2 –
methyl-3-heptyl carbenium ion and 3-methyl 2-heptyl carbenium ion shown in the
figure 3.2. The activated complex for a methyl shift is commonly regarded as an
alkyl bridged cation where the shifting methyl group is bound to two carbon
atoms via two electrons, three center bond. Both reactants are secondary
carbenium ions, but two methyl groups can shift in the forward reaction, while
only one in the reverse reaction. One might suspect the forward reaction to
26
*
+
* CH 3
*
ne = 4 ne = 2
27
proceed at twice the rate of the reverse reaction. The global symmetry numbers
transition state are 33, 33/2 and 33/22 respectively. These global symmetry
numbers correspond to four single events in the forward reaction and two single
events in the reverse reaction. The forward reaction rate constant is twice as
accepted assumptions.
1. Primary carbenium ions and the methyl ions are far less stable than
secondary and tertiary ions and are not retained in the network of
elementary steps.
the type of the reactant and the product requiring four single event rate
~ ~ ~ ~
coefficients, kisom ( s; s ), kisom ( s; t ), kisom (t ; s ), kisom (t ; t ) , for each type of
isomerization.
28
3. The rate coefficient of protonation is independent of the olefin involved but
4. The cracking rate coefficients depend only on the type of carbenium ions
involved, not on the olefin produced, leading to four single event rate
~ ~ ~ ~
coefficients, k cr ( s; s, O ), k cr ( s; t , O ), kcr (t ; s, O), kcr (t ; t , O) .
While simple assumptions maintain the number of single event rate coefficients
within tractable range for the protonation, isomerization and cracking reactions,
the same cannot be accomplished for the deprotonation rate coefficients. The
~ ~
single event rate coefficients of deprotonation, k De ( s; Oij ) and k De (t ; Oij ) , depend
both on the type of carbenium ion and the character of the olefin Oij . This
~ ~ ~
k De (m; Oij ) k De (m; Or ) K isom (Or ; Oij ) ……..(3.9)
29
~ ~ ~
kisom (t ; s ) k De (t ; Or ) k pr ( s )
~ ~ ~ ……..(3.10)
kisom ( s; t ) k pr (t ) k De ( s; Or )
In the equation (3.9), Oij is any olefin, Or is a selected reference olefin of the
carbenium ion on protonation. Equations (3.9) and (3.10) are valid for any carbon
number.
Equation (3.10), which applies for all the isomerization steps, leads to two more
(3.10) reveals that the rate coefficient for (t ; s ) isomerization is not independent.
This constraint leaves only three parameters for each type of isomerization.
~ ~
Second, concerning deprotonation, the ratio of k De (t ; Or ) to k De ( s; Or ) in equation
(3.10) must be independent of the carbon number n since both the isomerization
30
The rates of deprotonation of the carbenium ions in the homologous series are
assumed equal. This assumption coupled with equation (3.10), reduces the
assumed to be equal, since they have the same structure. For the olefins up to
C 5 , the 1-alkenes are taken as reference olefins and the deprotonation coefficient
equation (3.9).
The kinetic rate equations for observables and surface intermediates can be
31
isotherm, as was concluded in previous lumped kinetic studies (Steijns and
Froment, 1981)
Csat K Li pi
C Pi ………(3.13)
1 K Li pi
i
catalyst.
Pi Oij H 2 ………(3.14)
The olefin Oij is given a second index j because more than one olefin can be
thermodynamic equilibrium.
K DH ,ij C Pi
COij …………..(3.15)
pH 2
32
Which in turn undergo isomerization and cracking steps:
olefins the resulting isoparaffins and cracked paraffins can desorb from the
zeolite.
The acid catalyzed steps are assumed to be rate determining, making the
reaction rates of the paraffins identical to the reaction rates of the corresponding
This can be derived from the pseudo steady state approximation for the olefins.
The rates of formation of the olefins on the acid sites can be expressed in terms
…….(3.20)
33
Where mik is the type of (s or t) of carbenium ion Rik .The concentrations of the
carbenium ions are not directly accessible but can be calculated from the pseudo
~ ~ ~
RR ne k pr (mik )CO C H ne k De (mik ; Oij )C R ne kisom (mik ; mlo )C R
ik ij ik ik
k k i o
~ ~ ~
ne kisom (mlo ; mik )C R ne kcr (mik ; mlo , Ouv )C R ne kcr (mlo ; mik , Ouv )C R 0
lo ik lo
i o i o i o
……..(3.21)
Ct C H C R ………(3.22)
ik
i k
The last two equations form a linear system which can be solved to yield the
unknown C R ‘s and C H , which in turn can be used to calculated the net rates of
ik
formation of the paraffins from equations (3.19) and (3.20). Similar equations to
34
CHAPTER IV
NETWORK GENERATION
It is clear that such a large reaction network can only be generated by computer.
Baltanas and Froment first generated the elementary steps by means of Boolean
the elementary steps. Species involved in the elementary steps are represented
relation matrix. Note that hydrogen atoms in hydrocarbon are not necessarily to
35
be accounted for in this representation because they can be determined by the
As a first step for the representation of the olefins or carbenium ions, the carbon
number of carbon atoms of the given species. The element of the matrix (I,j) is
determined by the existence of a bond between carbon atom I and carbon atom j.
The constructed matrices based upon this rule are always symmetrical. The
The dimension of the matrix provides the number of carbon atoms, while the
carbon atom, i.e., whether it is a primary, secondary, tertiary and quaternary. The
The Boolean relation matrix does not provide all the information on the
hydrocarbon species, however. The two binary relation matrices for the olefin
and equivalent carbenium ion would be identical. This is because the information
on the position of double bond and the positively charged carbon atom can not
36
Fig.4.1 Representation of a methyl shift by means of Boolean relation matrices
37
be stored in the binary relation matrix. In addition, several binary relation
matrices can represent the same species because the carbon atoms are
numbered arbitrary.
specified in the first row. The type of carbon atom is given by the second row (1:
primary, 2: secondary, 3: tertiary, 4:quarternary), while the third row indicates the
olefinic, 8: acyclic paraffinic). Figure 1 also shows the characterization vectors for
H 2 is 3 and 2 because the positively charged carbon atoms in both ions are 3rd
and 2nd respectively. The type and nature of the carbon atoms are shown in
second and third row of the characterization vectors for both carbenium ions.
introducing following rules which specify the priority for numbering the various
carbon atoms.
38
2. The starting atom is chosen so as to obtain the longest possible backbone
3. The lowest possible number is selected for the electron deficient atom.
4. The lowest possible number is given to the carbon atom with the lowest
5. The carbon atom of the main chain connected to the highest degree of
6. The carbon atom with the longest side chain is assigned by the lowest
quaternary carbon atom with the lowest number, the carbon atoms in the
remaining branched chain are numbered from the main chain towards the
Based upon the definition of the characterization vector and the standardization
rules for numbering the carbon atom, a unique representation of species with
generation program.
39
For species with a large number of carbon atoms the Boolean relation matrices
become very sparse, but they occupy considerable computer memory. The
reduction of the computer memory for the storage of the species of the reaction
The total number of carbon atoms, the type of each carbon atom, and the
neighboring carbon atoms can be obtained from the Boolean relation matrix. By
operations.
The β-neighbors of each carbon atom can be obtained by squaring the Boolean
relation matrices B.
Bn B1 B1 I ……….(4.1)
The diagonal elements are irrelevant, since these amounts to double counting
the α-bond, so they are all set to zero. Higher order relations ( -positions, etc.)
can be obtained by
40
Bn B Bn 1 Bn 2 , n 3,4..... ….(4.2)
the first by a methyl-shift. The methyl shift changes the structure of the
hydrocarbon chain, and hence the Boolean matrix. The first step is to generate
this type of elementary step is to locate a neighbor of the charge bearing carbon
atom with a methyl substitute. Then, a new bond is created between the methyl
group and the charge bearing carbon atom, and the previous bond of the methyl
group is broken. The positive charge is shifted to the carbon atom which
originally carried the methyl group. In the Boolean relation matrix B 1 , the element
(2,7) and (7,2) are set to zero, whereas in B 2 the element (3,7) and (7,3) are set
vectors from H 1 to H 2 . The location of the tertiary carbon atom is changed also
The network generation involves all the species, molecules and ions, and their
components in the feed. The detailed reaction network results for Paraffins and
41
Reaction Network for Paraffins
160
140
120
Number of Paraffins
100
80
60
40
20
0
3 4 5 6 7 8 9 10 11
Carbon number
42
700
600
500
Number of Olefins
400
300
200
100
0
3 4 5 6 7 8 9 10 11
Carbon number
43
800
700
600
Number of Carbenium ions
500
400
300
200
100
0
3 4 5 6 7 8 9 10 11
Carbon number
44
Reactions of Paraffins
1600
1400
1200
Protolytic Scissions
1000
800
600
400
200
0
3 4 5 6 7 8 9 10 11
Carbon number
45
Reactions of Paraffins
700
600
500
Hydride Transfer
400
300
200
100
0
3 4 5 6 7 8 9 10 11
Carbon number
46
Reactions ofOlefins
1200
1000
800
Protonations
600
400
200
0
3 4 5 6 7 8 9 10 11
Carbon number
47
Reactions of Carbenium ions
1200
1000
800
Hydride Shift
600
400
200
0
3 4 5 6 7 8 9 10 11
Carbon number
48
Reactions of Carbenium ions
400
350
300
250
Methyl Shift
200
150
100
50
0
3 4 5 6 7 8 9 10 11
Carbon number
49
Reactions of Carbenium ions
2500
2000
PCP Branchings
1500
1000
500
0
3 4 5 6 7 8 9 10 11
Carbon number
50
Reactions of Carbenium ions
800
700
600
Hydride Transfer
500
400
300
200
100
0
3 4 5 6 7 8 9 10 11
Carbon number
51
Reactions of Carbenium ions
300
250
200
β-scission
150
100
50
0
3 4 5 6 7 8 9 10 11
Carbon number
52
Reactions of Carbenium ions
1400
1200
1000
Deprotonations
800
600
400
200
0
3 4 5 6 7 8 9 10 11
Carbon number
53
Reaction Network for Naphthenes
Network of Paraffins
100
90
80
70
Number of Paraffins
60
50
40
30
20
10
0
6 7 8 9 10
Carbon Number
C 6 – n- Cyclohexane
C 7 – n- methyl Cyclohexane
C 8 – n- ethyl Cyclohexane
C 9 – n- propyl Cyclohexane
C 10 – n- butyl Cyclohexane
54
Network of Olefins
800
700
600
Number of Olefins
500
400
300
200
100
0
6 7 8 9 10
Carbon Number
Olefins Cyclic Olefins
55
Network of Cyclic compounds
160
140
Number of Cyclic compounds
120
100
80
60
40
20
0
6 7 8 9 10
Carbon Number
Naphthenes Aromatics
56
Network of Carbenium ions
900
800
700
Number of Carbenium ions
600
500
400
300
200
100
0
6 7 8 9 10
Carbon Number
n-Carbenium ions Cyclic carbenium ions Olefinic carbenium ions
57
Reaction of Naphthenes
900
800
700
600
Reactions
500
400
300
200
100
0
6 7 8 9 10
Carbon Number
Exocyclic Protolytic Scissions Endocyclic Protolytic Scissions Hydride Astractions
58
Reactions of cyclic olefins
1400
1200
1000
Protonations
800
600
400
200
0
6 7 8 9 10
Carbon Number
59
Reactions of cyclic carbenium ions
1400
1200
1000
Reactions
800
600
400
200
0
6 7 8 9 10
Carbon Number
Hydride shifts Methyl Shifts
60
Reactions of cyclic carbenium ions
300
250
200
Alkyl shifts
150
100
50
0
6 7 8 9 10
Carbon Number
Alkyl shifts Intra ring alkyl shifts
Fig. 4.21. Number of Alkyl shift reactions for cyclic carbenium ions with
respect to different Carbon number of naphthenes in the feed
61
Reactions of cyclic carbenium ions
3500
3000
2500
PCP Branchings
2000
1500
1000
500
0
6 7 8 9 10
Carbon Number
Fig. 4.22. Number of PCP branching reactions for cyclic carbenium ions
with respect to different Carbon number of naphthenes in the feed
62
Reactions of cyclic carbenium ions
400
350
300
250
β scissions
200
150
100
50
0
6 7 8 9 10
Carbon Number
Exocyclic β scissions Endocyclic β scissions
Fig. 4.23. Number of β-Scission reactions for cyclic carbenium ions with
respect to different Carbon number of naphthenes in the feed
63
Reactions of cyclic carbenium ions
160
140
120
Aromatizations
100
80
60
40
20
0
6 7 8 9 10
Carbon Number
64
Reactions of cyclic carbenium ions
1400
1200
1000
Deprotonations
800
600
400
200
0
6 7 8 9 10
Carbon Number
65
Reactions of cyclic carbenium ions
900
800
700
Hydride donations
600
500
400
300
200
100
0
6 7 8 9 10
Carbon Number
Fig. 4.26. Number of Hydride donation reactions for cyclic carbenium ions
with respect to different Carbon number of naphthenes in the feed
66
CHAPTER V
In the kinetic modeling of Hydrocracking, it had been generally accepted that the
rates of carbenium ion reactions on the acid sites are rate determining. But, that
is not true for whole range of operating conditions. At severe operating conditions
increasing temperature and decreasing pressure. The longer the chain length,
termed as “non ideal” cracking. The term ‘non ideal” has frequently been
associated with skewed curves for the product distributions but these are also
observed when secondary cracking occurs, which is always the case for longer
chain lengths, in particular at higher conversions. In this work “Non ideal” is only
used to express that the rate determining step is not only on the acid sites.
metal sites, compared to the rate of carbenium ion reactions on acid sites. In
other words, the reactions on acid sites are no longer rate determining and to
follows.
67
c Al
A( g ) l Al K1
p Acl
co1l cH 2l
Al l O1l H 2l K2
c Al cl
p H 2 cl
H 2l H 2 ( g ) l K3
c H 2l
po1 cl
O1l O1 l K4
co1l
cR1
O1 H R K5
po1 cH
1
cR2
R1 R K6
cR1
2
R2 R3 O2
po2 cH
R O2 H K8
cR3
3
co2l
O2 l O2l K9
po2 cl
c H 2l
H 2( g ) l H 2l K10
pH 2 cl
cBl cl
O2l H 2l Bl l K11
co2l cH 2l
p B cl
Bl B( g ) l K12
cBl
68
Fig.5.1. Hydrocracking reaction scheme of paraffin A to isoparaffin B
r kCR2
k ' C s A K L A p A Ct
………..(5.1)
k k (1 k6 )Cs A K LA C s B K LB
p H DH 5
2
1 K Li pi
K H 1 K Li pi
Where,
k DH k1k 2 k3 k 4
k H k9 k10 k11k12
k ' kk5 k6 k DH
po pH
ki' p pi i 2
K DH i
r
2 ………..(5.2)
1 K i' M pi
K H 2 pH 2 1 K Li pi
M
1 Li i
K p
Case – III: Most general case (No RDS, neither on acid catalyzed reactions, nor
on metal catalyzed reactions)
In this case, rate expressions are written for all the elementary steps according to
LHHW model and equated rates of all steps. The generalized solution is
69
Experimental evidence for hydrocracking of n-Hexadecane
metal sites are explicitly considered. The change in isomerization conversion with
5.3. As we can see from these plots that at higher temperatures and lower
total conversion. This is the case where RDS is on the acid sites. At higher
a behavior would be observed when the rate of the carbenium ion reactions on
The reason that ‘non-ideal’ effects are more pronounced for heavier feed, is that
longer chain paraffins are more active on the acid sites, because they undergo
For ‘ideal’ hdyrocracking conditions, monobranched isomers are the only primary
products and dibranched isomers are secondary products. While, for the ‘non-
ideal’ conditions, dibranched isomers and cracked products are produced directly
70
n-Hexadecane Hydrocracking
Catalyst-2
30
25
20
Xiso
15
10
5
0
0 20 40 60 80 100
X
71
n-Hexadecane Hydrocracking
Catalyst-3
30
25
20
Xiso
15
10
0
0 20 40 60 80 100
X
72
Isomer distribution for C16 feed
100
80
Mole Fraction of C16
60
40
20
0
0 20 40 60 80 100
Total Conversion (X%)
73
Kinetic modeling of hydrocracking of n-hexadecane (Molecular Scheme)
accounting for rates of hydrogenations on metal sites. The reaction scheme for
(Froment, 1985).
Paraffins are physisorbed in zeolite pores and that can be described by Langmuir
cs K Li pi
cPi ………..(5.3)
1 K Li pi
i
pO pH
ki' p pi i 2
K DH i
rDH i '
………..(5.4)
DM
74
nC16 MB C16 mul C16
nC16 MB C16 mul C16
nC16 MB C16 mul C16 C3
21 22 23 4
C3 C3
C13
5
C13 C13
C4
6
C4 C4
C12
7
C 12 C12
C5
8
C5 C5
C11
9
C11 C11
C6
10
C6 C6
C10
11
C10 C10
C7
12
C7 C7
C9
13
C9 C9
C8
14
C8 C8
75
Here, ki' k DH i kiM cM2 ,i cs K Li
2
pi
DM 1 K i
' 'M
K H 2 pH 2 1 K Li pi
M
………..(5.5)
i 1 K Li pi i
i
Oi H Ci
cCi
K Ci ………..(5.6)
pOi cH
ct cH cCi cH 1 cOi K Ci ………..(5.7)
i i
Now, we can write the rate expressions for all the carbenium ion reactions on the
cMBC
r21 k 21 cnC 16 ………..(5.8)
16 K
21
76
cmultiC
r22 k 22 cMBC 16 ………..(5.9)
K 22
16
Combining equation (8) with equations (3),(6) and (7) that rate of monobranched
carbenium ions is :
pMBC
' 16
k 21 pnC
16
K 21
'
r21 ………..(5.11)
1 K Li pi pOi K Ci
i i
Where,
'
k 21 k 21 K c ct cs K L
nC16 nC16
K11 K cnC16 K L
K
'
11
nC16
………..(5.12)
Kc KL
MBC16 MBC16
DA 1 K Li pi pOi K Ci
i i
Rate equations for the net rate of formation of n-hexadecane paraffins and
pnC pH 2
k1 pnC16 16
K 21'
RnC16 ………..(5.13)
DM'
77
pnC p H 2 pMBC
k1 pnC16 16 k 21
'
pnC 16
K 21' 16 '
K 21
RnC ………..(5.14)
16
DM' DM'
Since the concentrations of the olefins are very low, pseudo steady state can be
ROi 0 ………..(5.15)
From equations (15), the partial pressures of the paraffins can be expressed as a
is derived as:
p k'
H 2 k '11 DM '
D ' ………..(5.16)
pn P p 11 M
C nC K1 k D MBC k K ' D
16 16 1 A 16 1 11 A
Similarly expressions for partial pressure of all the normal paraffins are derived
as shown in fig. 5.6. It leads to set of 12 non linear equations. These non linear
equations is combined with non linear continuity equations (for CSTR) to perform
78
P k'
H 2 k '11 DM '
D '
Pn PnC P
11 M
C 16 K k D MBC ' D
16 1 1 A kK
16 1 11 A
P k' D '
H2 13 M
Pn PnC P
C 3 K mulC k4 DA
3 4
16
P k' D '
H2 13 M
Pn PnC P
C 13 5 mulC k5 DA
K
13 16
P k' D '
H2
Pn PnC P 14 M
C
4 4 6 mulC k6 DA
K
16
P k' D '
H
Pn PnC 2 P 14 M
C 12 K mul C k D
12 7 16 7 A
P k' D '
H2 15 M
Pn PnC P
C 5 K mul C k D
5 8 16 8 A
P k' D '
H2 15 M
Pn PnC P
C 11 K mul C k D
11 9 16 9 A
P k' D '
H2 16 M
Pn PnC P
C
6 6 K
10 mulC k10 DA
16
P k' D '
H2 16 M
Pn PnC P
C 10 11 mulC k11 DA
K
10 16
P k' D '
H2 17 M
Pn PnC P
C 7 12 mulC k12 DA
K
7 16
P
H k' D '
Pn PnC 2 P 17 M
C 9 K mul C k D
9 13 16 13 A
P k'
H2 D '
Pn PnC P 18 M
C 8 K mul C k D
8 14 16 14 A
79
The optimal values of the model parameters (Fig.5.6) in a model are determined
n
f jk F j (i ) F j (i ) Fk (i ) Fk (i )
k 1 j 1 i 1
Here, F j (i ) is the observed and F j (i ) is the predicted value of the response
variable for the ith experiment, is the number of dependent variables. The
weights jk consist of the elements of the inverse of the error covariance matrix.
A MATLAB code was developed for the Levenberg Marquardt (LM) optimization
algorithm (Appendix A). The LM algorithm is used for minimization because of its
ability to change the distance and direction of every optimization step. The initial
guess for the parameters is made from the n-dodecane hydrocracking parameter
80
APPENDIX A
leasqr(x,y,pin,F,stol,niter,wt,dp,dFdp,options)
vernum= sscanf(version,'%f');
if vernum(1) >= 4,
global verbose
plotcmd='plot(x(:,1),y,''+'',x(:,1),f); figure(gcf)';
else
plotcmd='plot(x(:,1),y,''+'',x(:,1),f); shg';
end;
if (exist('OCTAVE_VERSION'))
global verbose
plotcmd='plot(x(:,1),y,"+;data;",x(:,1),f,";fit;");';
end;
81
% equal to (wt.^2)^-1. The constant of proportionality will be estimated.),
% default=ones(length(y),1).
% Note: dp(j)=0 holds p(j) fixed i.e. leasqr wont change initial guess: pin(j)
% default = Inf*ones().
82
% OUTPUT VARIABLES
end;
83
y=y(:); wt=wt(:); pin=pin(:); dp=dp(:); %change all vectors to columns
if m1~=m ,error('input(x)/output(y) data must have same number of rows ') ,end;
options=[zeros(n,1), Inf*ones(n,1)];
nor = n; noc = 2;
else
[nor, noc]=size(options);
if (nor ~= n),
end;
if (noc ~= 2),
options=[options(noc,1), Inf*ones(noc,1)];
end;
end;
pprec=options(:,1);
maxstep=options(:,2);
84
f=feval(F,x,p); fbest=f; pbest=p;
r=wt.*(y-f);
sbest=r'*r;
nrm=zeros(n,1);
chgprev=Inf*ones(n,1);
kvg=0;
epsLlast=1;
% do iterations
for iter=1:niter,
pprev=pbest;
prt=feval(dFdp,x,fbest,pprev,dp,F);
r=wt.*(y-fbest);
sprev=sbest;
sgoal=(1-stol)*sprev;
for j=1:n,
if dp(j)==0,
nrm(j)=0;
else
prt(:,j)=wt.*prt(:,j);
nrm(j)=prt(:,j)'*prt(:,j);
85
if nrm(j)>0,
nrm(j)=1/sqrt(nrm(j));
end;
end
prt(:,j)=nrm(j)*prt(:,j);
end;
% prt=prt.*wt(:,ones(1,n));
% nrm=dp./sqrt(diag(prt'*prt));
% prt=prt.*nrm(:,ones(1,m))';
[prt,s,v]=svd(prt,0);
s=diag(s);
g=prt'*r;
for jjj=1:length(epstab),
epsL = max(epsLlast*epstab(jjj),1e-7);
se=sqrt((s.*s)+epsL);
gse=g./se;
chg=((v*gse).*nrm);
ochg=chg;
for iii=1:n,
chg(iii)=max(chg(iii),-abs(maxstep(iii)*pprev(iii)));
86
chg(iii)=min(chg(iii),abs(maxstep(iii)*pprev(iii)));
end;
end;
aprec=abs(pprec.*pbest); %---
f=feval(F,x,p);
r=wt.*(y-f);
ss=r'*r;
if ss<sbest,
pbest=p;
fbest=f;
sbest=ss;
end;
if ss<=sgoal,
break;
end;
end; %---
end;
87
epsLlast = epsL;
if (verbose),
eval(plotcmd);
end;
if ss<eps,
break;
end
aprec=abs(pprec.*pbest);
kvg=1;
if (verbose),
end;
break;
else
chgprev=chg;
end;
if ss>sgoal,
break;
end;
end;
88
% set return values
p=pbest;
f=fbest;
ss=sbest;
kvg=((sbest>sgoal)|(sbest<=eps)|kvg);
PARAMETERS
jac=feval(dFdp,x,f,p,dp,F);
msk = dp ~= 0;
if vernum(1) >= 4,
Qinv=inv(Q);
else
Q=diag((0*wt+1)./(wt.^2));
Qinv=diag(wt.*wt);
89
end;
d=sqrt(abs(diag(covp)));
corp=covp./(d*d');
Z=((m-n)*jac'*Qinv*jac)/(n*resid'*Qinv*resid);
%%acovp=resid'*Qinv*resid/(m-n)*jtgjinv
r=corrcoef(y,f);
if (exist('OCTAVE_VERSION'))
r2=r^2;
90
else
r2=r(1,2).^2;
end
if (verbose),
eval(plotcmd);
disp(p')
disp(corp)
disp(covr)
disp(r2)
delta_pvec''*Z*delta_pvec',n,m-n)
91
n1 = sum((f-y) < 0);
nrun=sum(abs(diff((f-y)<0)))+1;
zed=(nrun-(2*n1*n2/(n1+n2)+1)+0.5)/(2*n1*n2*(2*n1*n2-n1-n2)...
/((n1+n2)^2*(n1+n2-1)));
prob = erfc(-zed/sqrt(2))/2*100;
else,
prob = erfc(zed/sqrt(2))/2*100;
end;
end;
end;
92
APPENDIX B
2
k1 k3 k4 k11 k8 ( k13 k1 paph pm k13 )
k3 k4 k13 k12 k14 k15 k22 k19
r2
k2 k14 k15 ( 1k1 pak3 phk4 pmk11 pbk8 pn ) 2
k1 k3 k4 k11 k8 1 k13 k3 k4 k13 pm k3 k4 k13 ph
k12 k14 k15 k22 k19 k2 k15
k12 k2 k14
1k1 pak3 phk4 pmk11 pbk8 pn
k13 k3 k4 k13 pm k3 k4 k13 ph
ct 1
k12 k2 k14 k2 k15
r
1 k1 pa k3 ph k4 pm k11 pb k8 pn
2 ct
k1 k3 k4 k11 k8
( k13 k1 paph pm k13 )
k12 k14 k15 k22 k19
( 1k1 pak3 phk4 pmk11 pbk8 pn ) 2
ct2 ( k13 k1 paph pm k13 )
0
( 1k1 pak3 phk4 pmk11 pbk8 pn ) 2
1
( ( k14 k15 k22 k19 k13 k2 k1 pasqrt( 2 k142 k152 k222 k192 k132 k22 k1 pa k11 pb
2
2 k152 k222 k192 k132 k22 k142 k8 pnk152 k222 k192 k132 k22 k142 k112 pb2
2 k152 k222 k192 k132 k22 k142 k11 pb2 k152 k222 k192 k132 k22 k142 k3 ph
2 k142 k152 k222 k192 k132 k22 k1 pa
k152 k222 k192 k32 k42 k132 pm2 k122 k82 pn2
2 k152 k222 k192 k32 k42 k132 pm2 k122 k8 pn
2 k152 k222 k192 k3 k43 k132 pm3 k12 k2 k14
4 k15 k222 k192 k33 k43 k132 pm2 k122 k14 ph2
4 k15 k222 k192 k32 k43 k132 pm2 k122 k14 ph k8 pn
4 k15 k222 k192 k32 k43 k132 pm2 k122 k14 ph
2 k152 k222 k192 k32 k43 k132 pm3 k122 k1 pa
93
4 k15 k222 k192 k32 k43 k132 pm2 k122 k14 ph k11 pb
4 k152 k222 k192 k3 k42 k13 pm2 k122 k14 k2 k11 pb
2 k152 k222 k192 k32 k43 k132 pm3 k122 k8 pn
8 k15 k222 k192 k32 k122 k132 k2 k1 pa k14 k4 ph k8 pn
2 k152 k222 k192 k33 k43 k132 pm3 k122 ph
2 k152 k222 k192 k3 k43 k13 pm3 k122 k14 k2
4 k15 k222 k192 k33 k122 k132 k2 k1 pa k14 k4 ph2
8 k15 k222 k192 k32 k122 k132 k2 k1 pa k14 k4 ph
8 k15 k222 k192 k32 k122 k132 k2 k1 pa k14 k4 ph k11 pb
k152 k222 k192 k32 k44 k132 pm4 k122
4 k142 k15 k222 k192 k132 k2 k1 pa k3 k4 ph k12 k8 pn
2 k142 k152 k222 k192 k132 k22 k1 pa k4 pm
2 k152 k222 k192 k32 k43 k132 pm3 k122
4 k142 k15 k222 k192 k132 k2 k1 pa k3 k4 ph k12 k11 pb
4 k142 k15 k222 k192 k132 k2 k1 pa k32 k4 ph2 k12
4 k142 k152 k222 k192 k13 k22 k1 pa k12 k4 pm
4 k14 k152 k222 k192 k132 k2 k1 pa k3 k4 pm k12
4 k142 k152 k222 k192 k13 k22 k1 pa k12 k11 pb
4 k14 k152 k222 k192 k132 k2 k1 pa k32 k4 pm k12 ph
2 k14 k152 k222 k192 k132 k2 k12 pa2 k12 k3 k4 pm
4 k142 k15 k222 k192 k132 k2 k1 pa k3 k4 ph k12
k142 k152 k222 k192 k132 k22 k12 pa2
4 k14 k152 k222 k192 k132 k2 k1 pa k3 k42 pm2 k12
4 k14 k152 k222 k192 k132 k2 k1 pa k3 k4 pm k12 k8 pn
2 k142 k222 k192 k33 k42 k132 ph3 k122
4 k15 k142 k222 k192 k122 k2 k42 pm k32 k13 ph2
4 k15 k142 k222 k192 k122 k2 k42 pm k3 k13 ph k8 pn
4 k15 k142 k222 k192 k122 k2 k42 pm k3 k13 ph k11 pb
4 k15 k142 k222 k192 k122 k2 k42 pm k3 k13 ph
4 k152 k14 k222 k192 k122 k2 k42 pm2 k3 k13 k1 pa
k152 k142 k222 k192 k122 k22 k42 pm22 k152 k142 k222 k192 k12 k22 k42 pm2 k13
k152 k222 k192 k132 k22 k142 k42 pm2
4 k15 k142 k222 k192 k122 k2 k11 pb k3 k4 k13 ph k8 pn
4 k152 k142 k222 k192 k12 k22 k11 pb k13 k4 pm
4 k15 k142 k222 k192 k122 k2 k11 pb k32 k4 k13 ph2
4 k152 k14 k222 k192 k122 k2 k11 pb k3 k4 k13 pm k1 pa
94
2 k15 k142 k222 k192 k122 k2 k112 pb2 k3 k4 k13 ph
4 k15 k142 k222 k192 k122 k2 k11 pb k3 k4 k13 ph
2 k152 k142 k222 k192 k122 k22 k11 pb k4 pm
4 k152 k222 k192 k32 k42 k132 pm2 k12 ph k2 k14
2 k15 k222 k192 k34 k42 k132 pm k122 ph3 k14
2 k152 k222 k192 k33 k42 k132 pm2 k122 ph k1 pa
4 k15 k222 k192 k33 k42 k132 pm k122 ph2 k14 k11 pb
k152 k142 k222 k192 k122 k22 k112 pb2
4 k152 k222 k192 k32 k4 k13 pm k122 ph k14 k2 k11 pb
4 k152 k222 k192 k32 k42 k13 pm2 k122 ph k14 k2
k152 k222 k192 k34 k42 k132 pm2 k122 ph2
4 k15 k222 k192 k33 k42 k132 pm k122 k14 ph2
2 k152 k222 k192 k32 k42 k132 pm2 k122 k1 pa
4 k15 k222 k192 k32 k42 k132 pm k122 k14 ph k11 pb
2 k15 k222 k192 k32 k42 k132 pm k122 k14 ph
4 k152 k222 k192 k3 k42 k132 pm2 k12 k2 k14
4 k152 k222 k192 k3 k4 k13 pm k122 k14 k2 k11 pb
4 k152 k222 k192 k3 k42 k13 pm2 k122 k14 k2
k152 k222 k192 k32 k42 k132 pm2 k1222 k152 k222 k192 k33 k42 k132 pm2 k122 ph
4 k15 k132 k2 k222 k192 k33 k122 ph3 pm k14 k4
8 k15 k132 k2 k222 k192 k32 k122 ph2 pm k14 k4
8 k15 k132 k2 k222 k192 k32 k122 ph2 pm k14 k4 k8 pn
8 k15 k132 k2 k222 k192 k32 k122 ph2 pm k14 k4 k11 pb
2 k15 k222 k192 k32 k42 k132 pm k122 k82 pn2 k14 ph
4 k15 k222 k192 k33 k42 k132 pm k122 k8 pn k14 ph2
4 k15 k222 k192 k32 k42 k132 pm k122 k8 pn k14 ph k11 pb
4 k15 k222 k192 k32 k42 k132 pm k122 k8 pn k14 ph
4 k152 k222 k192 k3 k42 k132 pm2 k12 k8 pn k2 k14
2 k152 k222 k192 k32 k42 k132 pm2 k122 k8 pn k1 pa
4 k152 k222 k192 k3 k42 k13 pm2 k122 k8 pn k14 k2
2 k152 k222 k192 k33 k42 k132 pm2 k122 k8 pn ph
4 k152 k222 k192 k3 k4 k13 pm k122 k8 pn k14 k2 k11 pb
8 k15 k222 k192 k32 k122 k132 k2 k12 pa2 k14 k4 ph
8 k15 k222 k192 k32 k122 k132 k2 k1 pa k14 k42 ph pm
4 k142 k152 k222 k192 k13 k22 k1 pa k12 k3 ph
2 k142 k152 k222 k192 k132 k22 k1 pa k3 ph
95
4 k142 k152 k222 k192 k13 k22 k1 pa k12 k8 pn
4 k14 k152 k222 k192 k132 k2 k1 pa k3 k4 pm k12 k11 pb
2 k142 k15 k222 k192 k132 k2 k12 pa2 k12 k3 k4 ph
2 k142 k152 k222 k192 k132 k22 k1 pa k8 pn
4 k142 k15 k222 k192 k132 k2 k1 pa k3 k42 ph k12 pm
k142 k222 k192 k32 k42 k132 ph2 k122 k82 pn2
k152 k222 k192 k132 k22 k142 k82 pn22 k152 k142 k122 k222 k192 k22 k3 ph
4 k142 k152 k222 k192 k13 k22 k1 pa k12
2 k142 k222 k192 k33 k42 k132 ph3 k122 k8 pn
4 k15 k222 k192 k132 k2 k142 k42 pm k3 ph k12 k8 pn
4 k15 k222 k192 k132 k2 k142 k42 pm k32 ph2 k12
2 k142 k222 k192 k32 k42 k132 ph2 k122 k8 pn
4 k142 k222 k192 k3 k42 k132 ph k12 k15 k2 pm
k142 k222 k192 k32 k42 k132 ph2 k122
2 k142 k222 k192 k33 k42 k132 ph3 k122 k11 pb
2 k142 k222 k192 k32 k42 k132 ph2 k122 k11 pb k8 pn
2 k142 k222 k192 k32 k42 k132 ph2 k122 k11 pb
4 k142 k222 k192 k3 k42 k132 ph k12 k11 pb k15 k2 pm
k142 k222 k192 k34 k42 k132 ph4 k122
k142 k222 k192 k32 k42 k132 ph2 k122 k112 pb2
4 k15 k122 k222 k192 k32 k42 k132 pm k1 pa k14 ph
4 k15 k122 k222 k192 k33 k42 k132 pm k1 pa k14 ph2
4 k15 k122 k222 k192 k32 k42 k132 pm k1 pa k14 ph k8 pn
4 k15 k122 k222 k192 k32 k42 k132 pm k1 pa k14 ph k11 pb
2 k142 k152 k222 k192 k13 k22 k12 pa2 k12
4 k152 k222 k192 k13 k22 k142 k12 k3 ph
k152 k122 k222 k192 k32 k42 k132 pm2 k12 pa2
4 k152 k222 k192 k32 k4 k13 pm k122 ph k14 k2 k1 pa
2 k152 k142 k222 k192 k12 k22 k112 pb2 k13
2 k152 k222 k192 k33 k42 k132 pm2 k122 ph k11 pb
2 k152 k222 k192 k33 k4 k132 pm k12 ph2 k14 k2
2 k152 k222 k192 k33 k4 k13 pm k122 ph2 k14 k2
4 k152 k142 k222 k192 k12 k22 k11 pb k13
4 k152 k222 k192 k32 k4 k132 pm k12 ph k2 k14 k11 pb
4 k152 k222 k192 k32 k4 k13 pm k122 k14 k2 ph
4 k152 k222 k192 k3 k4 k13 pm k122 k14 k2 k1 pa
96
8 k15 k222 k192 k3 k42 k132 pm2 k122 k14 k2 ph
2 k152 k222 k192 k32 k42 k132 pm2 k122 k11 pb
4 k152 k222 k192 k32 k4 k132 pm k12 k14 k2 ph
2 k152 k142 k222 k192 k122 k22 k11 pb2 k152 k222 k192 k3 k4 k13 pm k122 k14 k2
4 k152 k222 k192 k3 k4 k132 pm k12 k2 k14 k11 pb
2 k152 k222 k192 k3 k4 k132 pm k12 k2 k14
8 k15 k222 k192 k3 k42 k132 pm k122 k14 k2 k1 pa
8 k15 k132 k2 k222 k192 k32 k122 ph2 pm k14 k4 k1 pa
8 k15 k222 k192 k3 k42 k132 pm2 k122 k8 pn k14 k2 ph
2 k152 k142 k222 k192 k122 k22 k4 pm
8 k15 k132 k2 k222 k192 k32 k122 ph2 pm2 k14 k42
2 k152 k222 k192 k32 k42 k132 pm2 k122 k8 pn k11 pb
4 k152 k222 k192 k32 k4 k13 pm k122 k8 pn k14 k2 ph
4 k152 k222 k192 k3 k4 k13 pm k122 k8 pn k14 k2
4 k152 k222 k192 k3 k4 k13 pm k122 k8 pn k14 k2 k1 pa
4 k152 k142 k222 k192 k12 k22 k4 pm k13
2 k152 k222 k192 k3 k4 k132 pm k12 k82 pn2 k2 k14
2 k152 k222 k192 k3 k4 k13 pm k122 k82 pn2 k14 k2
4 k152 k222 k192 k3 k4 k132 pm k12 k8 pn k2 k14 k11 pb
4 k152 k222 k192 k3 k4 k132 pm k12 k8 pn k2 k14
8 k15 k222 k192 k3 k42 k132 pm k122 k8 pn k14 k2 k1 pa
4 k15 k222 k192 k3 k43 k132 pm3 k122 k14 k2 ph
4 k152 k222 k192 k32 k4 k132 pm k12 k8 pn k14 k2 ph
2 k15 k222 k192 k32 k44 k132 pm3 k122 k14 ph
4 k152 k222 k192 k3 k42 k132 pm2 k12 k2 k14 k11 pb
4 k15 k222 k192 k3 k43 k132 pm2 k122 k14 k2 k1 pa
4 k15 k222 k192 k32 k43 k132 pm2 k122 k14 ph k1 pa
2 k152 k222 k192 k32 k43 k132 pm3 k122 k11 pb
4 k142 k222 k192 k32 k4 k13 ph2 k122 k15 k2
2 k142 k222 k192 k3 k4 k13 ph k122 k15 k2
4 k142 k222 k192 k32 k4 k132 ph2 k12 k15 k2
4 k142 k222 k192 k3 k4 k132 ph k12 k15 k2 k8 pn
4 k142 k222 k192 k3 k4 k13 ph k122 k15 k2 k8 pn
4 k152 k222 k192 k13 k22 k142 k12 k8 pn
2 k14 k222 k192 k32 k42 k132 ph k122 k112 pb2 k15 pm
4 k142 k222 k192 k32 k4 k132 ph2 k12 k11 pb k15 k2
97
2 k142 k222 k192 k32 k43 k132 ph2 k122 pm
4 k142 k222 k192 k3 k4 k132 ph k12 k11 pb k15 k2 k8 pn
2 k142 k222 k192 k3 k4 k132 ph k12 k112 pb2 k15 k2
4 k142 k222 k192 k3 k4 k132 ph k12 k11 pb k15 k2
2 k142 k222 k192 k32 k42 k132 ph2 k122 k11 pb k1 pa
2 k152 k222 k192 k132 k22 k142 k4 pm
8 k15 k122 k222 k192 k3 k42 k132 pm2 k1 pa k14 k2 ph
2 k142 k222 k192 k3 k4 k132 ph k12 k15 k2
2 k152 k122 k222 k192 k3 k4 k13 pm k12 pa2 k14 k2
2 k142 k222 k192 k32 k43 k132 ph2 k122 k11 pb pm
2 k152 k122 k222 k192 k32 k42 k132 pm2 k1 pa k11 pb
2 k15 k122 k222 k192 k32 k42 k132 pm k12 pa2 k14 ph
8 k15 k122 k222 k192 k3 k42 k132 pm k12 pa2 k14 k2
2 k142 k222 k192 k32 k42 k132 ph2 k122 k1 pa
2 k152 k142 k222 k192 k122 k22 k8 pn2 k152 k142 k222 k192 k122 k22 k4 pm k1 pa
2 k152 k142 k222 k192 k122 k22 k4 pm k3 ph
4 k152 k142 k222 k192 k12 k22 k4 pm k13 k3 ph
4 k15 k142 k222 k192 k122 k2 k42 pm k3 k13 ph k1 pa
4 k152 k142 k222 k192 k12 k22 k4 pm k13 k8 pn
2 k15 k142 k222 k192 k122 k2 k43 pm2 k3 k13 ph
2 k152 k142 k222 k192 k122 k22 k4 pm k8 pn
2 k152 k14 k222 k192 k122 k2 k112 pb2 k3 k4 k13 pm
2 k152 k142 k222 k192 k122 k22 k11 pb k3 ph
2 k152 k142 k222 k192 k122 k22 k11 pb k1 pa
2 k152 k142 k222 k192 k122 k22 k11 pb k8 pn
4 k15 k142 k222 k192 k122 k2 k11 pb k3 k4 k13 ph k1 pa
4 k152 k142 k222 k192 k12 k22 k11 pb k13 k8 pn
4 k152 k142 k222 k192 k12 k22 k11 pb k13 k3 ph
8 k14 k222 k192 k42 k122 k132 k2 k1 pa k15 k3 pm k11 pb
4 k142 k222 k192 k3 k4 k13 ph k122 k8 pn k15 k2 k1 pa
2 k142 k222 k192 k3 k4 k132 ph k12 k82 pn2 k15 k2
2 k142 k222 k192 k3 k4 k13 ph k122 k82 pn2 k15 k2
k142 k222 k192 k32 k44 k132 ph2 k122 pm2
2 k142 k222 k192 k32 k42 k132 ph2 k122 k8 pn k1 pa
4 k142 k222 k192 k32 k4 k13 ph2 k122 k15 k2 k1 pa
2 k142 k222 k192 k33 k4 k13 ph3 k122 k15 k2
98
4 k142 k222 k192 k32 k4 k13 ph2 k122 k15 k2 k8 pn
k152 k142 k222 k192 k122 k22 k82 pn2
4 k142 k222 k192 k32 k4 k132 ph2 k12 k15 k2 k8 pn
2 k142 k222 k192 k33 k4 k132 ph3 k12 k15 k2
2 k142 k222 k192 k32 k43 k132 ph2 k122 k8 pn pm
2 k142 k222 k192 k33 k42 k132 ph3 k122 k1 pa
2 k142 k222 k192 k33 k43 k132 ph3 k122 pm
2 k152 k222 k192 k132 k22 k142 k4 pm k3 ph
2 k152 k222 k192 k132 k22 k142 k4 pm k11 pb
2 k15 k222 k192 k132 k2 k142 k43 pm2 k3 ph k12
2 k152 k222 k192 k132 k22 k142 k4 pm k8 pn
4 k142 k222 k192 k3 k4 k13 ph k122 k15 k2 k1 pa
2 k152 k222 k192 k132 k22 k142 k11 pb k3 ph
2 k152 k222 k192 k132 k2 k14 k112 pb2 k3 k4 pm k12
2 k152 k222 k192 k132 k22 k142 k11 pb k8 pn
2 k142 k222 k192 k32 k43 k132 ph2 k122 pm k1 pa
k142 k122 k222 k192 k32 k42 k132 ph2 k12 pa2k152 k222 k192 k132 k22 k142
2 k152 k222 k192 k13 k22 k142 k124 k152 k222 k192 k13 k22 k142 k8 pn k12 k3 ph
2 k152 k222 k192 k132 k22 k142 k8 pn k3 ph
2 k152 k222 k192 k13 k22 k142 k82 pn2 k12
2 k142 k122 k222 k192 k3 k4 k13 ph k12 pa2 k15 k2
2 k152 k142 k122 k222 k192 k22 k1 pak152 k142 k122 k222 k192 k22
2 k152 k142 k222 k192 k122 k22 k8 pn k1 pa
2 k152 k142 k222 k192 k122 k22 k8 pn k3 ph
8 k15 k222 k192 k3 k42 k132 pm2 k122 k11 pb k14 k2 ph
k152 k222 k192 k32 k42 k132 pm2 k122 k112 pb2
2 k152 k142 k222 k192 k13 k22 k32 ph2 k12k152 k142 k222 k192 k132 k22 k32 ph2
4 k3 k4 k132 k14 k15 k122 k222 k192 k2 ph pm
8 k3 k4 k132 k14 k15 k122 k222 k192 k1 pa k2 ph pm
8 k3 k4 k132 k14 k15 k122 k222 k192 k12 pa2 k2
4 k3 k4 k132 k14 k15 k122 k222 k192 k12 pa2 k2 ph pm
4 k3 k4 k132 k14 k15 k122 k222 k192 k112 pb2 k2 k1 pa
4 k3 k4 k132 k14 k15 k122 k222 k192 k112 pb2 k2 ph pm
4 k3 k4 k132 k14 k15 k122 k222 k192 k13 pa3 k2
k152 k142 k122 k222 k192 k22 k12 pa22 k152 k142 k222 k192 k122 k22 k3 ph k1 pa
k152 k142 k222 k192 k122 k22 k32 ph2
99
8 k3 k4 k132 k14 k15 k122 k222 k192 k12 pa2 k8 pn k2
8 k3 k4 k132 k14 k15 k122 k222 k192 k1 pa k8 pn k2 ph pm
8 k3 k4 k132 k14 k15 k122 k222 k192 k8 pn k2 ph pm
8 k3 k4 k132 k14 k15 k122 k222 k192 k8 pn k2 k1 pa
8 k3 k4 k132 k14 k15 k122 k222 k192 k11 pb k8 pn k2 ph pm
8 k3 k4 k132 k14 k15 k122 k222 k192 k11 pb k8 pn k2 k1 pa
4 k3 k4 k132 k14 k15 k122 k222 k192 k82 pn2 k2 ph pm
4 k3 k4 k132 k14 k15 k122 k222 k192 k82 pn2 k2 k1 pa
8 k3 k4 k132 k14 k15 k122 k222 k192 k11 pb k2 k1 pa
8 k3 k4 k132 k14 k15 k122 k222 k192 k11 pb k2 ph pm
4 k3 k4 k132 k14 k15 k122 k222 k192 k2 k1 pa
8 k3 k4 k132 k14 k15 k122 k222 k192 k1 pa k11 pb k2 ph pm
8 k3 k4 k132 k14 k15 k122 k222 k192 k12 pa2 k11 pb k2 )
2 k15 k22 k19 k3 k12 k13 k2 k1 pak15 k22 k19 k3 k42 k13 pm2 k12
k15 k22 k19 k3 k4 k13 pm k12 k8 pn2 k15 k13 k2 k22 k19 k3 k12 ph pm
k15 k22 k19 k3 k4 k13 pm k12k15 k22 k19 k32 k4 k13 pm k12 ph
k15 k14 k22 k19 k12 k2 k11 pbk15 k14 k22 k19 k12 k2 k4 pm
2 k15 k14 k22 k8 k12 k13 k2 k1 pa2 k15 k14 k13 k2 k22 k8 k12 ph pm
k15 k12 k22 k19 k3 k4 k13 pm k1 pak14 k22 k19 k3 k4 k13 ph k12 k11 pb
k14 k22 k19 k3 k4 k13 ph k12k15 k22 k19 k13 k2 k14 k4 pm
k14 k22 k19 k32 k4 k13 ph2 k12k14 k22 k19 k3 k4 k13 ph k12 k8 pn
2 k14 k22 k19 k4 k12 k13 k2 k1 pak14 k22 k19 k3 k42 k13 ph k12 pm
k15 k22 k19 k13 k2 k14 k11 pbk15 k22 k19 k13 k2 k14
k14 k12 k22 k19 k3 k4 k13 ph k1 pak15 k22 k19 k13 k2 k14 k8 pn
k15 k14 k22 k19 k12 k2 k8 pnk15 k14 k12 k22 k19 k2
2 k15 k14 k13 k2 k19 k11 k12 ph pmk15 k14 k22 k19 k13 k2 k3 ph
k15 k22 k19 k3 k4 k13 pm k12 k11 pb2 k15 k14 k19 k11 k12 k13 k2 k1 pa
2 k15 k14 k22 k19 k12 k13 k2 pa2 k15 k14 k22 k19 k13 k2 k1 ph pm
k15 k14 k22 k19 k12 k2 k3 phk15 k14 k12 k22 k19 k2 k1 pa
2 k14 k13 k2 k22 k19 k4 k12 ph pm ) k19 k22 k15 k14 k12 ct ) (
k3 k42 k13 k14 k15 k122 k222 k192 pm k11 pbk13 k2 k13 k142 k152 k222 k192 pa
k222 k192 k4 k122 k142 k2 k15k222 k19 k8 k122 k142 k152 k2 k4 pm
k3 k42 k13 k14 k15 k122 k222 k192 pmk222 k192 k1 k142 k152 k13 k2
k222 k192 k12 k142 k152 k13 k2 pak222 k192 k3 k12 k152 k13 k2 k14
100
k22 k192 k11 k122 k142 k152 k2k22 k192 k112 k122 k142 k152 k2 pb
k3 k4 k13 k14 k15 k122 k222 k192 k112 pb2
k3 k4 k13 k14 k15 k122 k222 k192 k12 pa2
2 k13 k2 k11 k122 k142 k152 k19 k8 k22 k1 pa
2 k3 k4 k13 k14 k15 k122 k222 k192 k1 pak222 k19 k8 k12 k142 k152 k13 k2
k32 k4 k13 k14 k15 k122 k222 k192 phk3 k4 k13 k14 k15 k122 k222 k192
k22 k192 k11 k122 k142 k152 k2 k1 pak222 k192 k32 k122 k152 k4 k13 pm
2 k13 k2 k4 k122 k142 k22 k192 k11 k15 k1 pa
k32 k4 k13 k14 k15 k122 k222 k192 ph k8 pn
2 k3 k4 k13 k14 k15 k122 k222 k192 k11 pbk222 k192 k32 k122 k152 k2 k14 ph
k222 k19 k82 k122 k142 k152 k2 pn2 k13 k2 k3 k122 k15 k222 k192 k4 k14 ph pm
k222 k192 k3 k122 k152 k2 k14k22 k192 k11 k12 k142 k152 k13 k2
k222 k192 k1 k142 k152 k12 k2k222 k192 k42 k122 k142 k3 k13 ph
k222 k192 k4 k12 k142 k13 k2 k15k222 k192 k42 k122 k142 k32 k13 ph2
k22 k192 k11 k12 k142 k152 k13 k2 k1 pak22 k192 k112 k12 k142 k152 k13 k2 pb
k3 k4 k13 k14 k15 k122 k222 k192 k82 pn2k222 k19 k8 k122 k142 k152 k2
k222 k19 k8 k122 k142 k152 k2 k11 pbk222 k19 k82 k12 k142 k152 k13 k2 pn
k222 k192 k32 k122 k152 k42 k13 pm2k222 k19 k8 k122 k142 k152 k2 k1 pa
k222 k192 k43 k122 k142 k3 k13 ph pm
k32 k4 k13 k14 k15 k122 k222 k192 ph k11 pbk222 k19 k8 k122 k142 k152 k2 k3 ph
2 k3 k4 k13 k14 k15 k122 k222 k192 k11 pb k8 pn
k22 k192 k11 k122 k142 k152 k2 k8 pnk32 k4 k13 k14 k15 k122 k222 k192 k1 pa ph
k22 k192 k11 k122 k142 k152 k2 k4 pmk22 k192 k11 k122 k142 k152 k2 k3 ph
k3 k42 k13 k14 k15 k122 k222 k192 k1 pa pm
2 k3 k4 k13 k14 k15 k122 k222 k192 k8 pnk222 k192 k12 k142 k152 k12 k2 pa
k222 k192 k42 k122 k142 k2 k15 pmk3 k42 k13 k14 k15 k122 k222 k192 pm k8 pn
k13 k2 k12 k142 k152 k222 k192 ph pmk13 k2 k32 k122 k152 k222 k192 ph pm
k13 k2 k32 k122 k152 k222 k192 k1 pak22 k192 k11 k12 k142 k152 k13 k2 k3 ph
k22 k192 k112 k122 k14 k152 k3 k4 k13 pm pb
k222 k192 k42 k12 k142 k13 k2 k15 pm
2 k3 k4 k13 k14 k15 k122 k222 k192 k1 pa k8 pn
k222 k192 k4 k122 k142 k2 k15 k8 pnk222 k192 k4 k122 k142 k2 k15 k11 pb
k222 k192 k1 k142 k152 k13 k2 k8 pnk222 k192 k1 k142 k152 k13 k2 k11 pb
k22 k192 k11 k122 k14 k152 k32 k4 k13 pm ph
k22 k192 k112 k122 k142 k15 k3 k4 k13 ph pbk222 k192 k1 k142 k152 k13 k2 k4 pm
k22 k192 k11 k122 k142 k15 k3 k42 k13 ph pmk222 k192 k1 k142 k152 k13 k2 k3 ph
101
k222 k192 k4 k122 k142 k2 k15 k1 pak222 k192 k3 k122 k152 k2 k14 k1 pa
k222 k192 k33 k122 k152 k4 k13 pm phk222 k192 k42 k122 k142 k3 k13 ph k8 pn
k222 k19 k8 k122 k14 k152 k3 k42 k13 pm2k222 k192 k1 k142 k152 k12 k2 k8 pn
k22 k192 k11 k122 k14 k152 k3 k42 k13 pm2k222 k192 k1 k142 k152 k12 k2 k11 pb
k222 k192 k1 k142 k152 k12 k2 k4 pmk222 k192 k1 k142 k152 k12 k2 k3 ph
k222 k192 k32 k12 k152 k13 k2 k14 phk22 k192 k11 k12 k142 k152 k13 k2 k8 pn
2 k3 k4 k13 k14 k15 k122 k222 k192 k1 pa k11 pb
k222 k192 k3 k122 k152 k2 k14 k8 pnk222 k192 k3 k122 k152 k2 k14 k11 pb
k222 k192 k3 k122 k152 k2 k14 k4 pmk13 k2 k112 k122 k142 k152 k192 ph pm
k13 k2 k112 k122 k142 k152 k192 k1 pak22 k192 k11 k12 k142 k152 k13 k2 k4 pm
k222 k19 k8 k122 k14 k152 k32 k4 k13 pm ph
k222 k192 k12 k142 k15 k3 k4 k13 ph k12 pa
k22 k192 k11 k122 k142 k15 k3 k4 k13 ph k8 pn
k222 k192 k1 k14 k152 k3 k42 k13 pm2 k12
k22 k192 k11 k122 k142 k15 k32 k4 k13 ph2
k222 k192 k1 k142 k15 k3 k42 k13 ph k12 pm
k222 k192 k42 k122 k142 k3 k13 ph k1 pak13 k2 k82 k122 k142 k152 k222 ph pm
k13 k2 k82 k122 k142 k152 k222 k1 pak13 k2 k42 k122 k142 k222 k192 ph pm
k13 k2 k42 k122 k142 k222 k192 k1 pak222 k19 k82 k122 k14 k152 k3 k4 k13 pm pn
k222 k192 k4 k122 k142 k2 k15 k3 phk22 k192 k11 k122 k142 k15 k3 k4 k13 ph
k222 k192 k1 k142 k15 k3 k4 k13 ph k12
k222 k19 k8 k122 k14 k152 k3 k4 k13 pm k11 pb
k22 k192 k11 k122 k14 k152 k3 k4 k13 pm
k222 k19 k8 k12 k142 k152 k13 k2 k11 pbk222 k19 k8 k12 k142 k152 k13 k2 k4 pm
k22 k192 k11 k122 k14 k152 k3 k4 k13 pm k1 pa
k222 k19 k8 k12 k142 k152 k13 k2 k3 phk222 k192 k32 k122 k152 k4 k13 pm k8 pn
k222 k192 k1 k142 k15 k3 k4 k13 ph k12 k11 pb
k222 k192 k42 k122 k142 k3 k13 ph k11 pb
k222 k19 k8 k122 k142 k15 k3 k4 k13 ph k1 pa
k222 k192 k1 k142 k15 k32 k4 k13 ph2 k12k222 k192 k3 k12 k152 k13 k2 k14 k8 pn
k222 k192 k4 k12 k142 k13 k2 k15 k8 pn
k222 k192 k1 k142 k15 k3 k4 k13 ph k12 k8 pn
k222 k192 k4 k12 k142 k13 k2 k15 k11 pb
k222 k19 k8 k122 k14 k152 k3 k4 k13 pm k1 pa
k222 k192 k1 k14 k152 k3 k4 k13 pm k12 k8 pn
k222 k192 k4 k12 k142 k13 k2 k15 k3 phk222 k192 k4 k12 k142 k13 k2 k15 k1 pa
102
2 k13 k2 k1 k14 k152 k222 k192 k3 k12 ph pm
k222 k192 k1 k14 k152 k3 k4 k13 pm k12 k11 pb
k222 k192 k12 k14 k152 k3 k4 k13 pm k12 pa
k222 k192 k1 k14 k152 k3 k4 k13 pm k12
k222 k192 k32 k122 k152 k4 k13 pm k11 pbk222 k19 k8 k122 k142 k15 k3 k4 k13 ph
k222 k19 k8 k122 k14 k152 k3 k4 k13 pm
k222 k192 k1 k14 k152 k32 k4 k13 pm k12 ph
k222 k192 k3 k12 k152 k13 k2 k14 k1 pa
2 k13 k2 k3 k122 k152 k222 k19 k8 k14 ph pm
k222 k192 k3 k12 k152 k13 k2 k14 k11 pb
2 k13 k2 k4 k122 k142 k222 k19 k8 k15 k1 pa
2 k13 k2 k3 k122 k152 k222 k19 k8 k14 k1 pa
k222 k192 k3 k12 k152 k13 k2 k14 k4 pm
2 k13 k2 k3 k122 k152 k22 k192 k11 k14 ph pm
2 k13 k2 k3 k122 k152 k22 k192 k11 k14 k1 pa
2 k13 k2 k4 k122 k142 k222 k19 k8 k15 ph pm
2 k13 k2 k3 k122 k15 k222 k192 k4 k14 k1 pa
2 k13 k2 k12 k142 k15 k222 k192 k4 k12 pa
2 k13 k2 k12 k14 k152 k222 k192 k3 k12 pa
2 k13 k2 k1 k142 k152 k222 k19 k8 k12 ph pm
k222 k19 k8 k12 k142 k152 k13 k2 k1 pa
k22 k192 k11 k122 k142 k15 k3 k4 k13 ph k1 pa
2 k13 k2 k12 k142 k152 k222 k19 k8 k12 pa
2 k13 k2 k4 k122 k142 k22 k192 k11 k15 ph pm
k22 k192 k11 k122 k14 k152 k3 k4 k13 pm k8 pn
k222 k19 k82 k122 k142 k15 k3 k4 k13 ph pn
k222 k19 k8 k122 k142 k15 k32 k4 k13 ph2
k222 k19 k8 k122 k142 k15 k3 k42 k13 ph pm
2 k13 k2 k1 k142 k15 k222 k192 k4 k12 ph pm
2 k13 k2 k1 k142 k152 k22 k192 k11 k12 ph pm
k222 k192 k32 k122 k152 k4 k13 pm k1 pa
2 k13 k2 k11 k122 k142 k152 k19 k8 k22 ph pm
2 k13 k2 k12 k142 k152 k22 k192 k11 k12 pa
k222 k19 k8 k122 k142 k15 k3 k4 k13 ph k11 pb )
103
VITAE
Mr. Hemendra Khakhar received his B.S. in Chemical Engineering with summa
cum laude from Gujarat University, India in 1999. Then, he worked for two years
as a process engineer with Indian Petrochemicals Corporation Limited (IPCL) ,
India. He has been a graduate student in the Department of Chemical
Engineering at Texas A&M University since January 2002. He has been working
with Prof. G.F.Froment and Prof. R.G.Anthony in the area of reaction
engineering. His contact details are :
Hemendra Khakhar
413 Nagle St. # 7
College Station,TX-77840
Tel:979-571-2353
E-mail:hmkhakhar@yahoo.com
104