Kinetic Modeling of Hydrocracking-1 Hemendra Khakhar

Applications of a Mechanistic Hydrocracking Model
A Dissertation
By
Hemendra Khakhar
Submitted to the Office of Graduate Studies of

Texas A&M University
in partial fulfillment of the requirements for the degree of
MASTER OF SCIENCE
December 2004
Major Subject: Chemical Engineering

A Dissertation
By
Hemendra Khakhar
Submitted to Texas A&M University

in partial fulfillment of the requirements
for the degree of
Master of Science
Approved as to style and content by:
Dr. Gilbert F. Froment Dr. Rayford G. Anthony

(Chair of Committee) (Co-Chair of Committee)
Dr. Robert R. Lucchese Dr. K.R.Hall

(Member) (Head of Department)
December 2004
Major Subject: Chemical Engineering
iv
ABSTRACT
Hemendra Khakhar, B.S. (Chemical Engineering), Gujarat University
Chair of Advisory Committee: Dr. G.F.Froment
Hydrocracking is a key refining process in the commercial production of a variety of
transportation fuels. In the overall petroleum refining process, Hydrocracking is one
of the most important processes which upgrade heavier fractions obtained by
distillation of the crude oil or heavier fractions from other refinery units like cokers
and fluidized catalytic cracker units. Kinetic modeling of Hydrocracking is of
paramount importance to simulate/optimize an existing industrial unit or to design a
new unit.
For a model to be effectively predictive, it must be adequately detailed and
extrapolable to different feedstocks and operating conditions. "Single Event
Kinetics Approach” developed by Prof. Froment has been successfully applied to
these kind of zeolite catalyzed oil refining processes. The complete network of
elementary steps is generated with the help of Boolean matrices and
characterization vectors in accordance with well known carbenium ion chemistry
principles. The reaction network describes chemical transformations on the catalyst
surface by means of elementary steps like (de)protonation, isomerization,
(de)hydrogenation, cracking etc. Rate equations are developed based on Hougen
v
Watson kinetics and pseudo steady state approximation. Transition state theory
and thermodynamic constraints keeps the total number of parameters within
tractable range.
Parameter estimation from experimental data is done by Levenberg Marquardt
algorithm. In contrast to present day available kinetic models, single event rate
parameters are independent of feedstock and reactor configuration due to its
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
First, I would like to express my deepest appreciation to my research advisor Dr.
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
advice and financial support.
I am also thankful to Dr. Robert Lucchese for serving on my dissertation
committee. I am grateful to the members of the kinetics, catalysis and reaction
engineering group to their excellent advice and support.
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
emotional support during my study.
viii
TABLE OF CONTENTS
PAGE
ABSTRACT .............................................................................................................V
ACKNOWLEDGMENTS .......................................................................................VIII
TABLE OF CONTENTS .........................................................................................IX
LIST OF FIGURES .................................................................................................IX
LIST OF TABLES ...................................................................................................XI

I. INTRODUCTION ................................................................................................ 1
1. Hydrocracking process description ........................................................... 4
II. LITERATURE REVIEW ........................................................................................ 8

1. Lumped models......................................................................................... 9
2. Fundamental kinetic models ................................................................... 12
III. SINGLE EVENT KINETICS ................................................................................. 16

1. Theory of SEK......................................................................................... 22
2. Rate expressions .................................................................................... 26
IV. NETWORK GENERATION ................................................................................. 35
V. PARAMETER ESTIMATION AND RESULTS ........................................................... 67
REFERENCES...................................................................................................... 79
APPENDIX A......................................................................................................... 81
APPENDIX B......................................................................................................... 93
VITA .................................................................................................................... 113
ix
LIST OF FIGURES
FIGURE
Page
x
LIST OF TABLES
xi
CHAPTER I
INTRODUCTION
Petroleum refining industries is facing several environmental and market
requirements:
1. The demand for more environmentally acceptable products, low in sulfur,
nitrogen and unsaturated compounds, is increasing
2. The demand for gasoline and middle distillates (kerosene and diesel fuels)
is increasing while the value of heavy fuel oils is declining.
3. The middle distillates to gasoline ratio of products is increasing.
4. A high flexibility is required to respond to changing or seasonal market
demands and changing feeds on a weekly basis (Ward, 1993; Quann and
Jaffe, 1996; Minderhound and Van Veen, 1993).
The oil product demand from 2000 to 2005 in the Organization for Economic
Cooperation and Development and developing countries is shown in Table 1.1. It
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
industries require, therefore a process to convert heavy feedstocks, particularly
heavy gas oils, to higher value middle distillate. They can choose from several
processing options such as hydrocracking, fluid catalytic cracking and coking to
convert heavy feedstocks to middle distillate. However, hdyrocracking is the only
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)
and developing countries (Beck, 2001)
Product Demand (1000 b/d) % Change
2000 2001 2002 2003 2004 2005 (2002-2005)
Gasoline 21217 21490 21790 2220 22680 23140 6.2
Middle 24532 24562 24930 25430 25990 26510 6.3
Distillates
Fuel Oil 9958 9852 9990 10200 10390 10570 5.8
Other products 11243 11156 11390 11620 11880 12120 6.4
Total 66950 67060 68100 69470 70940 72340 6.2
2
The history of hydrocracking is found in paper written by Sullivan and Scott
(1983). Thermal hydrocracking is one of the oldest hydrocarbon conversion
processes. An extensive technology for coal conversion was developed in
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
because of thermodynamic equilibrium.
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
refractory cycle stocks produced by catalytic cracking processes, and
introduction of commercial jet aircraft led to increasing demand to convert heavy
fractions into less aromatic liquid fuels.
Once Chevron Research announced a new catalytic hdyrocracking process,
“Isocracking”, in response to this demand in the 1960’s, catalytic hdyrocracking
became a commercial reality and rapidly grew through development of zeolite

based catalyst and large pore catalysts, which permitted operation at moderate
temperatures (200-400 0C) and lower pressures (3-14 MPa). Seven different
hydrocracking processes were offered by the mid-1970’s. Hydrocracking has
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.
Hydrocracking Process Description
ISOCRACKING hydrocracker designs include single stage once through (SSOT),
single stage recycle (SSREC) and two stage recycle (TSRE) processes. A two
stage hydrocracker with intermediate distillation represents the most common
process configuration for maximizing middle distillates (Fig.1.1).
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
sent to a common fractionation section. To prevent overcracking, lighter products
are removed by distillation. The unconverted oil from the bottom of the
fractionator is routed to the second stage reactor section.
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
second stage operates in a recycle to extinction mode with per-pass-conversions
ranging from 50% to 80%.
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
compressed in stages until it reaches system pressure of reactor sections.
In general, hydrocracking is carried out at 300-450 0C catalyst bed temperature,
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
pressure. Reactions occurring in hydrocracking are hydrogenation –
dehydrogenations and isomerization – cracking, which is accomplished by
catalyst metal function and acid function respectively. As sulfur and nitrogen
compounds contained in the feedstock have a deleterious effect on
hydrocracking catalysts, the feedstock usually requires hydrotreatment prior to
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.
For example, an increase in the operating temperature decreases the extent of
6
aromatics hydrogenation due to thermodynamic limitations (Dufresne et al.,
1987). Also, the presence of ammonia decreases the catalytic activity by
poisoning acid sites (Dufresne et al., 1989).
Hydrocracking can be designed with flexibility in the product slate to meet market
demands (Gosselink and Stork, 1997). The particular products of hydrocracking
are oil, petrochemical feedstocks, feedstocks for FCC and thermal crackers, and
basestock for lubricants. The feedstocks for hydrocracking were generally
conventional straight run heavy gas oils. As the market value of heavy oils is
decreasing, the heavy gas oils produced in residuum-upgrading processes such
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
refractory feedstocks for hydrocracking. Also, the interest in processing
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).
Hydrocracking will continue to play an important role in petroleum industries in
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
be used for catalyst design, preliminary design of new hydrocracker units.
7
CHAPTER II
LITERATURE SURVEY
Modeling hydrocracking process has become necessary since hydrocracking has
become an important secondary process in refineries. Mathematical models are
needed to predict yields of various products for process design, optimization and
control applications. The feedstocks processed in the petroleum industries
consist of a large number of components. A typical feed for an industrial
hydrocracker unit contains paraffins, isoparaffins, naphthenes, aromatics and
naphtheno aromatic components. These components follow very complicated
reaction pathways with carbenium ion intermediates. Modeling such chemical
processes becomes very complex due to extremely large number of reactions
and difficulties in measuring feed and product compositions.
Kinetic models of hydrocracking process can be categorized as Lumped semi
empirical models and fundamental kinetic models. In early seventies, Weekman
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,
extensive experimentation is required for each component if feed is a complex
mixture of hydrocarbons. Therefore rate parameters increase rapidly with number
8
of lumps. Hence, requirement of a fundamental kinetic model arose, which can
reflect actual mechanism keeping number of rate parameters tractable.
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
approach of Krishna (1989), and the Langmuir-Hinshelwood-Hougen-Watson
model by Sundaram et al (1988).
Lumped model of Stangeland (1974)
Stangeland proposed an empirical equation to predict the product distribution of
hydrocracking. One parameter, A, describes the effect of boiling point on the rate
constant, k. Two other parameters, B and C, determine what products will be
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)
Where, T is T b /1000. Experimental data indicate A=0.5. The product distribution
parameter B and butane yield parameter C were also empirically determined to
represent the obtained product distribution.
9
The product distillation curve was predicted with high accuracy using a feedstock
distillation and values of the 3 parameters, A, B and C. However, the parameters
had to be determined experimentally for each feedstock because the information
on boiling point and paraffin content of the feedstock was insufficient to establish
a universal hydrocracking model.
Sundaram Model (1988)
Sundaram et al (1988) analyzed hydrotreating kinetics based on batch reactor
data using a lumped model. The surface reaction was considered as the rate
determining step. Simplified Langmuir-Hinshelwood-Hougen-Watson model were
proposed for the hydroprocessing of quinoline, naphthalene and
dibenzothiophene.
ki ci
ri  n
……….(2.2)
 
1   K j c j 
 
 j 
Where, ki is ith reaction rate constant, ci is concentration of ith species, K j is
adsorption constant for jth species and n is 1 or 2. Then reaction networks for the
hydroprocessing of binary mixtures involving quinoline with naphthalene or
dibenzothiophene were obtained by the superposition of the individual
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
dibenzothiophene, a modification was needed for hydrogenolysis of sulfur
compounds because the sites of hydrogenation and hydrogenolysis of sulfur
compounds are different from each other.
Though the proposed model is still the “ideal hydrocracking” model, their concept
can be applied for the industrial feedstocks with some modifications because the
inhibitors are considered for the hydrocracking of hydrocarbons. Gosselink et al.
(1989) simply used nitrogen for inhibitor content because it was impossible to
determine adsorption constants of all nitrogen-containing compounds in the
industrial feedstocks. The total effect of inhibitors can be written as :
 
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.
This relationship is not rigorous, but as demonstrated by Gosselink et al (1989), it
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
Fundamental kinetic models are based on actual chemistry of the hydrocracking
process. A new methodology has been developed by Froment and co-workers
using carbenium ion chemistry principles (Baltanas et al., 1989; Vynckier and
Froment, 1991). Baltanas and Froment (1985) used a computer algorithm to
generate the complete reaction network for hydrocracking of paraffins, taking in
to account all the reactions involving individual molecules. Vynckier and Froment
(1991) extended the single event approach to complex feedstocks and
introduced the concept of lumping coefficients to formulate rate expressions in a
convenient way. Feng et al. (1993) formalized the single event kinetics for
catalytic cracking and estimated single event rate parameters for catalytic
cracking of paraffins on a RE-Y zeolite catalyst.
Svoboda et al. (1995) estimated single event rate parameters from experiments
carried out on hexadecane and validated single event concept for the
hydrocracking of paraffins in a three phase reactor for the Fischer-Tropsch
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
of C 8 to C 12 paraffins on Pt/US-Y zeolites. Due to the molecular nature of the
12
approach, it was found that a finite and limited number of kinetic parameters
could describe the hydrocracking of heavy feedstocks.
Liguras and Allen (1989) developed an approach based on carbon centers, in
which, the model components are developed using linear programming. This
methodology was used to describe the reactions in catalytic cracking where it
was found that there were no significant differences in the product distribution for
different sets of pseudo components, as long as the number of pseudo
components is large enough. Klein et al. (1991) considered thousands of model
components and generated reaction networks for asphaltene hydroprocessing
using a Monte Carlo simulation approach.
Quann and Jaffe (1992) proposed a novel approach for modeling called Structure
Oriented Lumping (SOL). The lumping strategy is based on the molecular
structure of the feed and product components.
Structure Oriented Lumping (SOL)
Structure Oriented Lumping (SOL) represented individual molecules as vectors.
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
number of alkyl chains of paraffins, bridging between rings, hydrogen deficiency,
13
and heteroatom groups or substitutions in rings and alkyl chains. The vector
representation of molecules is based on the data analyzed by liquid
chromatography coupled with FIMS. As the information on the structure
arrangement of substituent groups or of longer alkyl chain cannot be obtained by
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
development reaction network with a limited set of reaction rules such as a
reactant selection rule and a product generation rule. The algorithm to estimate
the product properties from the conventional characterization of the feedstock,
such as boiling point, sulfur component, specific gravity etc, is as follows:
1. Translate the characterization data into the model feedstock having
molecular composition which was previously analyzed in detail.
2. Predict the product composition from the feedstock composition referring
to the process chemistry.
3. Translate the product composition into the product properties.
To convert mass spectroscopic data into the vector expression, a set of
conventions, which were based on the general knowledge of straight run streams
derived from conventional crude oils, were used and the reaction networks for
the representative structures were proposed. Some conventions cannot be
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
asphaltene, alkylated aromatics, polymerized olefins and so on. Therefore, it will
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
shows the importance of incorporating the actual chemistry in building high
fidelity models for the hydrocracking process. It is strongly believed that the
single event kinetics can contribute to the understanding of the complexities of
the hydrocracking process, provide economic and operational benefits to the
petroleum refineries, and stimulate further research both in academia and
industry.
15
CHAPTER III
SINGLE EVENT KINETICS
Chemical reactions of Hydrocracking Process
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
hydroisomerised and hydrocracked in the second stage.
The hydrocracking of petroleum fractions involves complex chemistry, which
includes hydrogenation-dehydrogenation, isomerization, carbon carbon bond
scission, paring reaction, ring opening, alkylation, disproportionation, and
cyclisaiton reactions. These reactions take place on a bifunctional catalyst
consisting of both cracking (silica /Alumina) and hydrogenation/dehydrogenation
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
accepting electron pairs.
The chemistry of hydrocracking is essentially the carbocation chemistry plus the
chemistry of hydrogenation and dehydrogenation. The carbocations can form by
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
a hydrogen molecule to become a carbenium ion. Hydride abstraction from a
saturated hydrocarbon yields a carbenium ion on a Lewis site. Protonation of
olefinic intermediates (on the Bronsted sites) formed by dehydrogenation of the
metal generates a carbenium ion. The reaction path way of the olefins is still
generally accepted for reforming, hydroisomerization, and hydrocracking.
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
carbenium ion formation increases with an increase in the number of hydrogen
atoms attached to the carbon atom carrying the positive charge. The stability of
the carbenium ion decreases in the order of increasing ionization energies, E + .
The tertiary carbenium ion is by far the most stable species, and it is the easiest
to form and most prevalent whenever it can be formed.
The most common feed to the hydrocracking is VGO. The VGO feed contains
paraffinic, naphthenic, aromatic and naphtheno-aromatic feed components. The
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
degree of branching but it is hypothesized that protonated cyclopropane
branching (PCP) steps alter the number of side chains present in the reactant
molecule. Cracking occurs through scission of the carbon-carbon bond in the β-
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
olefins are hydrogenated to produce highly branched paraffin isomers with
reduced chain lengths.
The hydroisomerization and hydrocracking reactions for the naphthenic feed
components are shown in Fig. 3.2. Dehydrogenation of naphthenes on the metal
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
relative positions of the constituents on the ring.
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
carbon-carbon bond that is part of the ring is known as an endocyclic scission.
Exocyclic β-scission produces an olefinic and a cationic species of reduced
carbon number whereas the endocyclic β-scission produces a single species
containing a double bond and a positively charged carbon atom. The alkene or
cyclo-alkene carbenium ions produced by endocyclic β-scission steps may
further undergo reactions similar to that of alkane and cycloalkane carbenium
ions. Compared to β-scission in an aliphatic chain, endocyclic β-scission is
known to proceed at a much slower rate.
21
Theory of Single Event Kinetics
The theoretical background of the single event kinetics approach is shown in
Figure 3.3. The effect of molecular structure on the rate coefficient of an
elementary step can be described by transition state theory and statistical
thermodynamics (Baltanas et al., 1989). A rate coefficient for the transformation
of a reactant in to a product via the activated complex is given by Erying
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
in terms of the rotational contribution of the third law entropy S 0 . According to
statistical thermodynamics, the S 0 of a species is determined by several
contributions (Willems and Froment, 1988), due to the different motions of the
species such as translation, vibration and rotation and electronic:
S 0  Strans
0
 S vib
0
 S rot
0
 S ele
0
….(3.2)
The rotational contribution, S rot

0
consists of external and internal contributions,
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
geometry of the molecule.
rot  S ext rot  R ln  ext 

0
S ext ˆ0
……….(3.3)
S 0  Sˆ 0  R ln  
int rot int rot int
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
the different enantiomers. For racemic mixtures, this contribution is given by
R ln(2 n ) , where n is the number of the chiral centers in a species, and the term
2 n , is corresponding to the maximum number of stereoisomers that can exist. On
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 
Where, the intrinsic rotational contribution Ŝ rot , is the sum of Ŝ ext ˆ0

rot and S int rot .
0 0
The expression in the parenthesis in equation (3.4) is called global symmetry
number,  gl . The global symmetry number quantifies all symmetry contributions
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 
The last term of equation(3.5) is the difference in standard entropy between
reactant and activated complex due to symmetry changes. In the Eyring
equation, this contribution can be separated from the entropy of activation.
  glr  k T   Sˆ 0   0

 k '     b  exp  exp  H  ……..(3.6)
   h    
 gl   R   RT 
Where, Sˆ 0  S trans

0 0
 S vib 0
 S rot 0
 S ele
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   
Since the effect of a difference in symmetry, i.e., a difference in structure,
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
activation energy ( Eact ) is corresponding to the enthalpy of activation ( H 0 ) or
potential energy difference between the activated complex and the reactant.
Calculation of number of single events
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
Fig. 3.4. Calculation of number of single events for an elementary step
27
proceed at twice the rate of the reverse reaction. The global symmetry numbers
for –methyl-3-heptyl carbenium ion, 3-methyl 2-heptyl carbenium ion and
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
large as the reverse, as expected.
Assumptions concerning single event rate parameters
The number of rate coefficients required to predict the product distribution of
paraffins hydrocracking can be reduced with number of simplifying, but generally
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.
2. The rate coefficient for isomerization of carbenium ions depend only on
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
does depend on the type of the resulting carbenium ion (s=secondary,

~ ~
t=tertiary), introducing two single event rate coefficients, k pr ( s ) and k pr (t ) .
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) .
Reduction in number of parameters by thermodynamic constraints
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
condition leaves an overwhelming number of deprotonation coefficients, which
can only be reduced through a thermodynamic analysis. Baltanas et al (1989)
were able to greatly reduce the number of required deprotonation parameters by
employing the following two thermodynamic constraints:
~ ~ ~
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
same carbon number, and m is either s or t. Or is an isomer with the double
bond preferably in a position that produces both a secondary and a tertiary
carbenium ion on protonation. Equations (3.9) and (3.10) are valid for any carbon
number n. This constraint reduces the number of independent single event

~ ~
deprotonation coefficients to two k De ( s; Or ,n ) and k De (t ; Or ,n ) , for each carbon
number.
Equation (3.10), which applies for all the isomerization steps, leads to two more
reductions in the number of parameters. First, concerning isomerization, equation
(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
and protonation parameters are assumed independent of the carbon number:

~
k De (t ; Or )
~  f ( n) …………..(3.11)
k De ( s; Or )
The final number of independent deprotonation parameters is arrived at through
judicious selection of a homologous series of reference olefins (Froment,1991).
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
number of independent single event deprotonation coefficients to two,

~ ~
k De ( s; Or ) and k De (t ; Or ) , where Or is a reference olefin in the homologous series.
From C 5 onward the deprotonation coefficients for the 2-methyl-2-alkenes are
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
is assumed to be independent of the chain length. For C 5 , two references can be
chosen (2-methyl-2-butene and 1-pentene). They are connected through
equation (3.9).
Rate equations for Paraffin Hydrocracking
The kinetic rate equations for observables and surface intermediates can be
formulated in terms of the elementary steps (Baltanas et al.,1989)
First, a paraffin Pi physically adsorbed into the pore of zeolite catalyst.
Pi ( gas )  Pi (ads ) ………(3.12)
Hereafter, the (ads) indication is dropped for ease of notation. The
concentrations of the physisorbed paraffins are determined by a Langmuir
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
The adsorbed paraffin is dehydrogenated on the metal phase of the bifunctional
catalyst.
Pi  Oij  H 2 ………(3.14)
The olefin Oij is given a second index j because more than one olefin can be
formed from a single paraffin Pi . The (de)hydrogenation step is assumed to be in
quasi equilibrium; therefore the concentration of the olefin is calculated from
thermodynamic equilibrium.
K DH ,ij C Pi
COij  …………..(3.15)
pH 2
Protonation of olefins on Bronsted sites results in carbenium ions :
Oij  H   Rik ………(3.16)
32
Which in turn undergo isomerization and cracking steps:
Rik  Rlo ………(3.17)
Rlo  Rqr  Ouv ………(3.18)
After deprotonation of the carbenium ions and hydrogenation of the produced
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
olefins on the acid sites:
RPi   ROij ………(3.19)

j
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
of carbenium ion concentrations as follows.

~ ~ ~
ROij   ne k De (mik ; Oij )C R    ne k pr (mik )CO C H    ne k cr (mlo ; mqr , Oij )C R 
ik ij lo
k k i o
…….(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
steady state approximation for the carbenium ions.
~ ~ ~
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)
and a balance on the Bronsted sites :
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
those above can be developed for naphthenes and aromatics too.
34
CHAPTER IV
NETWORK GENERATION
The reaction network for the hydrocracking is practically impossible to be
constructed manually because of the overwhelming number of elementary steps
linked in an extremely complicated manner. For this reason, Clymans and
Froment (1984) developed a computer algorithm for the radical reactions
occurring in the thermal cracking of hydrocarbons. This algorithm has been
continuously updated by Prof. Froment’s research group depending on the type
of the catalytic processes.
Numerical representation of species
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
relation matrices, in combination with a characterization vector further
characterizing the chemical species. Implementing a computer algorithm for the
network generation requires a numerical representation of the species involved n
the elementary steps. Species involved in the elementary steps are represented
by a Boolean relation matrix based on binary representation (0 or 1). The bond
between carbon atoms in a molecule can be readily described by the binary
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
corresponding carbon skeleton.
As a first step for the representation of the olefins or carbenium ions, the carbon
atoms of the species are numbered in an arbitrary sequence. Then the
dimension of the binary relation matrix is given by C N X C N , where C N is the
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.
if there is a carbon-carbon bon, a value of “1” is assigned. Otherwise, the
elements are set to “0”.
The constructed matrices based upon this rule are always symmetrical. The
Boolean relation matrix provides general characteristics of the molecule, as well
as the required information to reconstruct the hydrocarbon skeleton of molecule.
The dimension of the matrix provides the number of carbon atoms, while the
number of non-zero elements in a row or column indicates the type of each
carbon atom, i.e., whether it is a primary, secondary, tertiary and quaternary. The
Boolean relation matrices for 2-methyl-3-hexyl and 3-methyl-2-hexyl carbenium
ions is shown in figure 4.1 as an example.
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
and characterization vectors
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.
In order to solve former problem, Vynckier and Froment(1991) introduced a
characterization (auxiliary) vector which represents the component
unequivocally. It consists of 3 rows. The position of positively charge atom is
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
nature of carbon atom (1: bridge-head aromatic, 2: bridge-head cyclo olefinic, 3:
bridge-head naphthenic, 4: aromatic, 5: cyclo-olefinic, 6: naphthenic, 7: acyclic
olefinic, 8: acyclic paraffinic). Figure 1 also shows the characterization vectors for
2-methyl-3-hexyl and 3-methyl-2-hexyl carbenium ions. The first row of H 1 and
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.
The non-uniqueness of the matrix representation can be overcome by
introducing following rules which specify the priority for numbering the various
carbon atoms.
1. The numbering should start at a primary carbon atom.
38
2. The starting atom is chosen so as to obtain the longest possible backbone
with the smallest possible side chain.
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
code describing its nature.
5. The carbon atom of the main chain connected to the highest degree of
substitution is attributed the lowest possible number.
6. The carbon atom with the longest side chain is assigned by the lowest
possible number. These rules make it possible to number the carbon
atoms in the main chain unequivocally. Starting at the tertiary of
quaternary carbon atom with the lowest number, the carbon atoms in the
remaining branched chain are numbered from the main chain towards the
most remote primary carbon atom.
Based upon the definition of the characterization vector and the standardization
rules for numbering the carbon atom, a unique representation of species with
unequivocally defined carbon atoms becomes available for the network
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
characterization vector with the standardization rules provides a remarkable
reduction of the computer memory for the storage of the species of the reaction
network. To generate the elementary steps, however, the matrix representation is
required to obtain the necessary information, as will be discussed next.
Generation of the elementary steps
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
means of elementary matrix operations, additional information can also be found.
Implementing reactions in the network generation program is based upon these
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)
Elimination of a C-C bond in M n , representing β-scission results into two
separate matrices representing the two products of scission.
As shown in Fig.4.1 the isomer 3-methyl-2-hexyl carbenium ion is obtained from
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
to one. The position of the positive charge is adapted in the characterization
vectors from H 1 to H 2 . The location of the tertiary carbon atom is changed also
and stored in the characterization vectors.
The network generation involves all the species, molecules and ions, and their
elementary steps yielding intermediates and products. The number of species in
the network tremendously increases with the number of C-atoms of the
components in the feed. The detailed reaction network results for Paraffins and
naphthenes are shown in the following plots.
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
Fig. 4.2. Number of Paraffins generated with respect to different Carbon

number of n-Paraffin in the feed
42
700
600
500
Number of Olefins
400
300
200
100
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.3. Number of Olefins generated with respect to different Carbon

number of n-Paraffin in the feed
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
Fig. 4.4. Number of Carbenium ions generated with respect to different

Carbon number of n-Paraffin in the feed
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
Fig. 4.5. Number of Protolytic Scission reactions with respect to different

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
Fig. 4.6. Number of Hydride transfer reactions with respect to different

46
Reactions ofOlefins
1200
1000
800
Protonations
600
400
200
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.7. Number of Protonation reactions with respect to different

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
Fig. 4.8. Number of Hydride shift reactions with respect to different

48
400
350
300
250
Methyl Shift
200
150
100
50
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.9. Number of Methyl shift reactions with respect to different

49
2500
2000
PCP Branchings
1500
1000
500
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.10. Number of PCP branching reactions with respect to different

50
800
700
600
Hydride Transfer
500
400
300
200
100
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.11. Number of Hydride transfer reactions with respect to different

51
300
250
200
β-scission
150
100
50
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.12. Number of β-Scission reactions with respect to different

52
1400
1200
1000
Deprotonations
800
600
400
200
0
3 4 5 6 7 8 9 10 11
Carbon number
Fig. 4.13. Number of Deprotonation reactions with respect to different

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
Fig. 4.14. Number of Paraffins generated with respect to different Carbon

number of naphthenes in the feed
Here,
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
Fig. 4.15. Number of olefins generated with respect to different Carbon

number of naphthenes in the feed
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
Fig. 4.16. Number of Naphthenes and aromatics generated with respect

to different Carbon number of naphthenes in the feed
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
Fig. 4.17. Number of carbenium ions generated with respect to different

Carbon number of naphthenes in the feed
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
Fig. 4.18. Number of Naphthene reactions with respect to different

58
Reactions of cyclic olefins
1400
1200
1000
Protonations
800
600
400
200
0
6 7 8 9 10
Carbon Number
Fig. 4.19. Number of cyclic olefin reactions with respect to different

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
Fig. 4.20. Number of cyclic carbenium ion reactions with respect to

different Carbon number of naphthenes in the feed
60
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
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
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
160
140
120
Aromatizations
100
80
60
40
20
0
6 7 8 9 10
Carbon Number
Fig. 4.24. Number of Aromatization reactions for cyclic carbenium ions

64
1400
1200
1000
Deprotonations
800
600
400
200
0
6 7 8 9 10
Carbon Number
Fig. 4.25. Number of Deprotonation reactions for cyclic carbenium ions

65
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
66
CHAPTER V
PARAMETER ESTIMATION AND RESULTS
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
higher temperatures and lower pressures, the product distribution is no longer a
unique function of conversion. The isomerization conversion decreases with
increasing temperature and decreasing pressure. The longer the chain length,
the more important this phenomenon. In such conditions, hydrocracking is
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.
This happens because of a relative decrease in the rate of hydrogenation on
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
rates of hydrogenation reactions on metal sites have to be explicitly considered.
Consider a molecular scheme of hdyrocracking (Fig.5.1), in which paraffin A is
hydroisomerized and hydrocracked in to isoparaffin B. The rate expressions
based on Langmuir-Henshelwood-Hougen-Watson kinetics can be derived as
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
 
cR1
O1  H  R K5 
po1 cH
1
 
cR2
R1  R K6 
cR1
2

R2  R3  O2
 
po2 cH
R  O2  H K8 
cR3
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
Case – I: RDS is on acid sites (Cracking step)
r  kCR2
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
Case – II: RDS is on metal sites (Dehydrogenation step)
 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
mathematically complex and shown in appendix B.
69
Experimental evidence for hydrocracking of n-Hexadecane
The experiments at severe operating conditions (high temperature and lower
pressure) can be modeled if the hydrogenation-dehydrogenation reactions on
metal sites are explicitly considered. The change in isomerization conversion with
total conversion for hydrocracking of n-hexadecane is shown in figure 5.2. and
5.3. As we can see from these plots that at higher temperatures and lower
pressures, the isomerization conversion is significant and it is unique function of
total conversion. This is the case where RDS is on the acid sites. At higher
temperatures and lower pressures, isomerization conversion is rather low. Such
a behavior would be observed when the rate of the carbenium ion reactions on
the acid sites is no longer rate determining.
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
more reactions. (Debrabandere et al., 1997)
The isomer distribution of C 16 isomers in C 16 hydrocracking is shown in fig. 5.4.
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
from n-hexadecane through hydrogenolysis.
70
n-Hexadecane Hydrocracking
Catalyst-2
30
25
20
Xiso
15
10
5
0
0 20 40 60 80 100
X
220 0C, 20 bar 200 0C, 10 bar 220 0C, 10 bar

200 0C, 20 bar Poly. (220 0C, 20 bar) Poly. (200 0C, 10 bar)
Poly. (220 0C, 10 bar) Poly. (200 0C, 20 bar)
Fig.5.2 Change in isomerization conversion with respect to change in total

conversion for n-hexadecane hydrocracking for catalyst-2
71
n-Hexadecane Hydrocracking
Catalyst-3
30
25
20
Xiso
15
10
0
0 20 40 60 80 100
X
240 0C, 10 bar 240 0C, 10 bar

Poly. (240 0C, 10 bar) Poly. (240 0C, 10 bar)
Fig.5.3 Change in isomerization conversion with respect to change in total

conversion for n-hexadecane hydrocracking for catalyst-2
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%)
nC16 MBC16 DBC16
Fig.5.4 Distribution of C16 isomers in n-hexadecane hydrocracking
73
Kinetic modeling of hydrocracking of n-hexadecane (Molecular Scheme)
As discussed earlier, the ‘non ideal’ conditions can be modeled by explicitly
accounting for rates of hydrogenations on metal sites. The reaction scheme for
the hydrocracking of C 16 is shown in fig. 5.5. The monobranched and
multibranched isomers are lumped, since they are in thermodynamic equilibrium
(Froment, 1985).
Derivation of rate expressions
Paraffins are physisorbed in zeolite pores and that can be described by Langmuir
isotherm as shown in chapter 3.
cs K Li pi
cPi  ………..(5.3)
1   K Li pi
i
Where, K Li is the physisorption coefficient for component i.
The rate of dehydrogenation on the metal sites can be expressed , according to
Dumez and Froment (1981) as :
 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 
The protonation of olefins is so fast compared to other reactions on acid sites
that it can be considered to be in pseudo equilibrium.
Oi  H   Ci
cCi
K Ci  ………..(5.6)
pOi cH
Here, is the chemisorption constant for the component i.
Now, A site balance on acid sites gives ,
 
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
acid sites as follows:
 cMBC  
r21  k 21  cnC   16  ………..(5.8)
 16 K 
 21 
76
 cmultiC  
r22  k 22  cMBC   16  ………..(5.9)
 K 22 
 
16
ri  ki cmultiC  ; i  23,24,25,26,27,28 ………..(5.10)

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
olefins can be written as:
 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
assumed for all olefins.
ROi  0 ………..(5.15)
From equations (15), the partial pressures of the paraffins can be expressed as a
function of the partial pressures of the olefins.
Rearranging equation (14), the expression for partial pressure of n-hexadecane
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
parameter estimation of n-hexadecane hydrocracking in a Berty reactor, which is
a gas phase reactor with complete internal mixing.
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
5  8  16  8 A
 
P  k' D '
 H2   15 M 
Pn  PnC    P
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
 
Fig. 5.6 Rate equations for n-C 16 hydrocracking
79
The optimal values of the model parameters (Fig.5.6) in a model are determined
by minimizing an objective function with respect to the parameters.
 
 
 

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
values cited by Debrabandere et al. (1997).
80
APPENDIX A
LEVENBERG MARQUARDT OPTIMISATION ALGORITHM
function [f,p,kvg,iter,corp,covp,covr,stdresid,Z,r2]= ...
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;
% x=vec or mat of indep variables, 1 row/observation: x=[x0 x1....xm]
% y=vec of obs values, same no. of rows as x.
% wt=vec(dim=length(x)) of statistical weights. These should be set
% to be proportional to (sqrt of var(y))^-1; (That is, the covariance
% matrix of the data is assumed to be proportional to diagonal with diagonal
81
% equal to (wt.^2)^-1. The constant of proportionality will be estimated.),
% default=ones(length(y),1).
% pin=vector of initial parameters to be adjusted by leasqr.
% dp=fractional incr of p for numerical partials,default= .001*ones(size(pin))
% dp(j)>0 means central differences.
% dp(j)<0 means one-sided differences.
% Note: dp(j)=0 holds p(j) fixed i.e. leasqr wont change initial guess: pin(j)
% F=name of function in quotes,of the form y=f(x,p)
% dFdp=name of partials M-file in quotes default is prt=dfdp(x,f,p,dp,F)
% stol=scalar tolerances on fractional improvement in ss,default stol=.0001
% niter=scalar max no. of iterations, default = 20
% options=matrix of n rows (same number of rows as pin) containing
% column 1: desired fractional precision in parameter estimates.
% Iterations are terminated if change in parameter vector (chg) on two
% consecutive iterations is less than their corresponding elements
% in options(:,1). [ie. all(abs(chg*current parm est) < options(:,1))
% on two consecutive iterations.], default = zeros().
% column 2: maximum fractional step change in parameter vector.
% Fractional change in elements of parameter vector is constrained to be
% at most options(:,2) between sucessive iterations.
% [ie. abs(chg(i))=abs(min([chg(i) options(i,2)*current param estimate])).],
% default = Inf*ones().
82
% OUTPUT VARIABLES
% f=vec function values computed in function func.
% p=vec trial or final parameters. i.e, the solution.
% kvg=scalar: =1 if convergence, =0 otherwise.
% iter=scalar no. of interations used.
% corp= correlation matrix for parameters
% covp= covariance matrix of the parameters
% covr = diag(covariance matrix of the residuals)
% stdresid= standardized residuals
% Z= matrix that defines confidence region
% r2= coefficient of multiple determination
if(exist('verbose')~=1), %If verbose undefined, print nothing
verbose=0; %This will not tell them the results
end;
if (nargin <= 8), dFdp='dfdp'; end;
if (nargin <= 7), dp=.001*(pin*0+1); end; %DT
if (nargin <= 6), wt=ones(length(y),1); end; % SMB modification
if (nargin <= 5), niter=20; end;
if (nargin == 4), stol=.0001; end;
83
y=y(:); wt=wt(:); pin=pin(:); dp=dp(:); %change all vectors to columns
% check data vectors- same length?
m=length(y); n=length(pin); p=pin;[m1,m2]=size(x);
if m1~=m ,error('input(x)/output(y) data must have same number of rows ') ,end;
if (nargin <= 9),
options=[zeros(n,1), Inf*ones(n,1)];
nor = n; noc = 2;
else
[nor, noc]=size(options);
if (nor ~= n),
error('options and parameter matrices must have same number of rows'),
end;
if (noc ~= 2),
options=[options(noc,1), Inf*ones(noc,1)];
end;
end;
pprec=options(:,1);
maxstep=options(:,2);
% set up for iterations
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;
epstab=[.1, 1, 1e2, 1e4, 1e6];
% 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;
% above loop could ? be replaced by:
% 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);
% check the change constraints and apply as necessary
ochg=chg;
for iii=1:n,
if (maxstep(iii)==Inf), break; end;
chg(iii)=max(chg(iii),-abs(maxstep(iii)*pprev(iii)));
86
chg(iii)=min(chg(iii),abs(maxstep(iii)*pprev(iii)));
end;
if (verbose & any(ochg ~= chg)),
disp(['Change in parameter(s): ', ...
sprintf('%d ',find(ochg ~= chg)), 'were constrained']);
end;
aprec=abs(pprec.*pbest); %---
% ss=scalar sum of squares=sum((wt.*(y-f))^2).
if (any(abs(chg) > 0.1*aprec)),%--- % only worth evaluating function if
p=chg+pprev; % there is some non-miniscule change
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);
% [aprec, chg, chgprev]
if (all(abs(chg) < aprec) & all(abs(chgprev) < aprec)),
kvg=1;
if (verbose),
fprintf('Parameter changes converged to specified precision\n');
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);
if kvg ~= 1 , disp(' CONVERGENCE NOT ACHIEVED! '), end;
% CALC VARIANCE COV MATRIX AND CORRELATION MATRIX OF
PARAMETERS
% re-evaluate the Jacobian at optimal values
jac=feval(dFdp,x,f,p,dp,F);
msk = dp ~= 0;
n = sum(msk); % reduce n to equal number of estimated parameters
jac = jac(:, msk); % use only fitted parameters
if vernum(1) >= 4,
Q=sparse(1:m,1:m,(0*wt+1)./(wt.^2)); % save memory
Qinv=inv(Q);
else
Q=diag((0*wt+1)./(wt.^2));
Qinv=diag(wt.*wt);
89
end;
resid=y-f; %un-weighted residuals
covr=resid'*Qinv*resid*Q/(m-n); %covariance of residuals
Vy=1/(1-n/m)*covr; % Eq. 7-13-22, Bard %covariance of the data
jtgjinv=inv(jac'*Qinv*jac); %argument of inv may be singular
covp=jtgjinv*jac'*Qinv*Vy*Qinv*jac*jtgjinv; % Eq. 7-5-13, Bard %cov of parm est
d=sqrt(abs(diag(covp)));
corp=covp./(d*d');
covr=diag(covr); % convert returned values to compact storage
stdresid=resid./sqrt(diag(Vy)); % compute then convert for compact storage
Z=((m-n)*jac'*Qinv*jac)/(n*resid'*Qinv*resid);
%%% alt. est. of cov. mat. of parm.:(Delforge, Circulation, 82:1494-1504, 1990
%%disp('Alternate estimate of cov. of param. est.')
%%acovp=resid'*Qinv*resid/(m-n)*jtgjinv
%Calculate R^2 (Ref Draper & Smith p.46)
r=corrcoef(y,f);
if (exist('OCTAVE_VERSION'))
r2=r^2;
90
else
r2=r(1,2).^2;
end
if (verbose),
eval(plotcmd);
disp(' Least Squares Estimates of Parameters')
disp(p')
disp(' Correlation matrix of parameters estimated')
disp(corp)
disp(' Covariance matrix of Residuals' )
disp(covr)
disp(' Correlation Coefficient R^2')
disp(r2)
sprintf(' 95%% conf region: F(0.05)(%.0f,%.0f)>=
delta_pvec''*Z*delta_pvec',n,m-n)
% runs test according to Bard. p 201.
91
n1 = sum((f-y) < 0);
n2 = sum((f-y) > 0);
nrun=sum(abs(diff((f-y)<0)))+1;
if ((n1>10)&(n2>10)), % sufficent data for test?
zed=(nrun-(2*n1*n2/(n1+n2)+1)+0.5)/(2*n1*n2*(2*n1*n2-n1-n2)...
/((n1+n2)^2*(n1+n2-1)));
if (zed < 0),
prob = erfc(-zed/sqrt(2))/2*100;
disp([num2str(prob),'% chance of fewer than ',num2str(nrun),' runs.']);
else,
prob = erfc(zed/sqrt(2))/2*100;
disp([num2str(prob),'% chance of greater than ',num2str(nrun),' runs.']);
end;
end;
end;
92
APPENDIX B
RATE EXPRESSION FOR MOST GENERAL CASE
 2
  k1  k3  k4  k11  k8  ( k13 k1 paph pm k13 )
  
 k3 k4 k13 k12 k14 k15 k22 k19 

r2   
 k2 k14 k15 ( 1k1 pak3 phk4 pmk11 pbk8 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

1k1 pak3 phk4 pmk11 pbk8 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 paph pm k13 ) 
 k12 k14 k15 k22 k19  
 
( 1k1 pak3 phk4 pmk11 pbk8 pn ) 2 

ct2 ( k13 k1 paph pm k13 )
 0
( 1k1 pak3 phk4 pmk11 pbk8 pn ) 2
Solution of Rate equation : ( r )
1
( ( k14 k15 k22 k19 k13 k2 k1 pasqrt( 2 k142 k152 k222 k192 k132 k22 k1 pa k11 pb
2
2 k152 k222 k192 k132 k22 k142 k8 pnk152 k222 k192 k132 k22 k142 k112 pb2
2 k152 k222 k192 k132 k22 k142 k11 pb2 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 pm22 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 k1222 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 pn22 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 pb2 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 pn2 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 pa2k152 k222 k192 k132 k22 k142
2 k152 k222 k192 k13 k22 k142 k124 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 pak152 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 k12k152 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 pa22 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 pak15 k22 k19 k3 k42 k13 pm2 k12
k15 k22 k19 k3 k4 k13 pm k12 k8 pn2 k15 k13 k2 k22 k19 k3 k12 ph pm
k15 k22 k19 k3 k4 k13 pm k12k15 k22 k19 k32 k4 k13 pm k12 ph
k15 k14 k22 k19 k12 k2 k11 pbk15 k14 k22 k19 k12 k2 k4 pm
2 k15 k14 k22 k8 k12 k13 k2 k1 pa2 k15 k14 k13 k2 k22 k8 k12 ph pm
k15 k12 k22 k19 k3 k4 k13 pm k1 pak14 k22 k19 k3 k4 k13 ph k12 k11 pb
k14 k22 k19 k3 k4 k13 ph k12k15 k22 k19 k13 k2 k14 k4 pm
k14 k22 k19 k32 k4 k13 ph2 k12k14 k22 k19 k3 k4 k13 ph k12 k8 pn
2 k14 k22 k19 k4 k12 k13 k2 k1 pak14 k22 k19 k3 k42 k13 ph k12 pm
k15 k22 k19 k13 k2 k14 k11 pbk15 k22 k19 k13 k2 k14
k14 k12 k22 k19 k3 k4 k13 ph k1 pak15 k22 k19 k13 k2 k14 k8 pn
k15 k14 k22 k19 k12 k2 k8 pnk15 k14 k12 k22 k19 k2
2 k15 k14 k13 k2 k19 k11 k12 ph pmk15 k14 k22 k19 k13 k2 k3 ph
k15 k22 k19 k3 k4 k13 pm k12 k11 pb2 k15 k14 k19 k11 k12 k13 k2 k1 pa
2 k15 k14 k22 k19 k12 k13 k2 pa2 k15 k14 k22 k19 k13 k2 k1 ph pm
k15 k14 k22 k19 k12 k2 k3 phk15 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 pbk13 k2 k13 k142 k152 k222 k192 pa
k222 k192 k4 k122 k142 k2 k15k222 k19 k8 k122 k142 k152 k2 k4 pm
k3 k42 k13 k14 k15 k122 k222 k192 pmk222 k192 k1 k142 k152 k13 k2
k222 k192 k12 k142 k152 k13 k2 pak222 k192 k3 k12 k152 k13 k2 k14
100
k22 k192 k11 k122 k142 k152 k2k22 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 pak222 k19 k8 k12 k142 k152 k13 k2
k32 k4 k13 k14 k15 k122 k222 k192 phk3 k4 k13 k14 k15 k122 k222 k192
k22 k192 k11 k122 k142 k152 k2 k1 pak222 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 pbk222 k192 k32 k122 k152 k2 k14 ph
k222 k19 k82 k122 k142 k152 k2 pn2 k13 k2 k3 k122 k15 k222 k192 k4 k14 ph pm
k222 k192 k3 k122 k152 k2 k14k22 k192 k11 k12 k142 k152 k13 k2
k222 k192 k1 k142 k152 k12 k2k222 k192 k42 k122 k142 k3 k13 ph
k222 k192 k4 k12 k142 k13 k2 k15k222 k192 k42 k122 k142 k32 k13 ph2
k22 k192 k11 k12 k142 k152 k13 k2 k1 pak22 k192 k112 k12 k142 k152 k13 k2 pb
k3 k4 k13 k14 k15 k122 k222 k192 k82 pn2k222 k19 k8 k122 k142 k152 k2
k222 k19 k8 k122 k142 k152 k2 k11 pbk222 k19 k82 k12 k142 k152 k13 k2 pn
k222 k192 k32 k122 k152 k42 k13 pm2k222 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 pbk222 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 pnk32 k4 k13 k14 k15 k122 k222 k192 k1 pa ph
k22 k192 k11 k122 k142 k152 k2 k4 pmk22 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 pnk222 k192 k12 k142 k152 k12 k2 pa
k222 k192 k42 k122 k142 k2 k15 pmk3 k42 k13 k14 k15 k122 k222 k192 pm k8 pn
k13 k2 k12 k142 k152 k222 k192 ph pmk13 k2 k32 k122 k152 k222 k192 ph pm
k13 k2 k32 k122 k152 k222 k192 k1 pak22 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 pnk222 k192 k4 k122 k142 k2 k15 k11 pb
k222 k192 k1 k142 k152 k13 k2 k8 pnk222 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 pbk222 k192 k1 k142 k152 k13 k2 k4 pm
k22 k192 k11 k122 k142 k15 k3 k42 k13 ph pmk222 k192 k1 k142 k152 k13 k2 k3 ph
101
k222 k192 k4 k122 k142 k2 k15 k1 pak222 k192 k3 k122 k152 k2 k14 k1 pa
k222 k192 k33 k122 k152 k4 k13 pm phk222 k192 k42 k122 k142 k3 k13 ph k8 pn
k222 k19 k8 k122 k14 k152 k3 k42 k13 pm2k222 k192 k1 k142 k152 k12 k2 k8 pn
k22 k192 k11 k122 k14 k152 k3 k42 k13 pm2k222 k192 k1 k142 k152 k12 k2 k11 pb
k222 k192 k1 k142 k152 k12 k2 k4 pmk222 k192 k1 k142 k152 k12 k2 k3 ph
k222 k192 k32 k12 k152 k13 k2 k14 phk22 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 pnk222 k192 k3 k122 k152 k2 k14 k11 pb
k222 k192 k3 k122 k152 k2 k14 k4 pmk13 k2 k112 k122 k142 k152 k192 ph pm
k13 k2 k112 k122 k142 k152 k192 k1 pak22 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 pak13 k2 k82 k122 k142 k152 k222 ph pm
k13 k2 k82 k122 k142 k152 k222 k1 pak13 k2 k42 k122 k142 k222 k192 ph pm
k13 k2 k42 k122 k142 k222 k192 k1 pak222 k19 k82 k122 k14 k152 k3 k4 k13 pm pn
k222 k192 k4 k122 k142 k2 k15 k3 phk22 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 pbk222 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 phk222 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 k12k222 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 phk222 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 pbk222 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

Kinetic Modeling of Hydrocracking-1 Hemendra Khakhar

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Kinetic Modeling of Hydrocracking-1 Hemendra Khakhar

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Applications of a Mechanistic Hydrocracking Model

Submitted to the Office of Graduate Studies of

Major Subject: Chemical Engineering

Submitted to Texas A&M University

Approved as to style and content by:

Dr. Gilbert F. Froment Dr. Rayford G. Anthony

Dr. Robert R. Lucchese Dr. K.R.Hall

Major Subject: Chemical Engineering

Applications of a Mechanistic Hydrocracking Model

Hemendra Khakhar, B.S. (Chemical Engineering), Gujarat University

Chair of Advisory Committee: Dr. G.F.Froment

Hydrocracking is a key refining process in the commercial production of a variety of

transportation fuels. In the overall petroleum refining process, Hydrocracking is one

of the most important processes which upgrade heavier fractions obtained by

and fluidized catalytic cracker units. Kinetic modeling of Hydrocracking is of

paramount importance to simulate/optimize an existing industrial unit or to design a

For a model to be effectively predictive, it must be adequately detailed and

extrapolable to different feedstocks and operating conditions. "Single Event

Kinetics Approach” developed by Prof. Froment has been successfully applied to

elementary steps is generated with the help of Boolean matrices and

characterization vectors in accordance with well known carbenium ion chemistry

principles. The reaction network describes chemical transformations on the catalyst

surface by means of elementary steps like (de)protonation, isomerization,

(de)hydrogenation, cracking etc. Rate equations are developed based on Hougen

and thermodynamic constraints keeps the total number of parameters within

Parameter estimation from experimental data is done by Levenberg Marquardt

parameters are independent of feedstock and reactor configuration due to its

First, I would like to express my deepest appreciation to my research advisor Dr.

advice and financial support.

I am also thankful to Dr. Robert Lucchese for serving on my dissertation

committee. I am grateful to the members of the kinetics, catalysis and reaction

engineering group to their excellent advice and support.

emotional support during my study.

TABLE OF CONTENTS .........................................................................................IX

LIST OF FIGURES .................................................................................................IX

LIST OF TABLES ...................................................................................................XI

II. LITERATURE REVIEW ........................................................................................ 8

III. SINGLE EVENT KINETICS ................................................................................. 16

IV. NETWORK GENERATION ................................................................................. 35

V. PARAMETER ESTIMATION AND RESULTS ........................................................... 67

VITA .................................................................................................................... 113

Petroleum refining industries is facing several environmental and market

1. The demand for more environmentally acceptable products, low in sulfur,

nitrogen and unsaturated compounds, is increasing

is increasing while the value of heavy fuel oils is declining.

3. The middle distillates to gasoline ratio of products is increasing.

4. A high flexibility is required to respond to changing or seasonal market

Jaffe, 1996; Minderhound and Van Veen, 1993).

Cooperation and Development and developing countries is shown in Table 1.1. It

industries require, therefore a process to convert heavy feedstocks, particularly

processing options such as hydrocracking, fluid catalytic cracking and coking to

convert heavy feedstocks to middle distillate. However, hdyrocracking is the only

and developing countries (Beck, 2001)

Product Demand (1000 b/d) % Change

2000 2001 2002 2003 2004 2005 (2002-2005)

Gasoline 21217 21490 21790 2220 22680 23140 6.2

Middle 24532 24562 24930 25430 25990 26510 6.3

Fuel Oil 9958 9852 9990 10200 10390 10570 5.8

Other products 11243 11156 11390 11620 11880 12120 6.4

Total 66950 67060 68100 69470 70940 72340 6.2

(1983). Thermal hydrocracking is one of the oldest hydrocarbon conversion

processes. An extensive technology for coal conversion was developed in

because of thermodynamic equilibrium.

refractory cycle stocks produced by catalytic cracking processes, and