Chapter II

Hydrocracking - Chemistry,
Thermodynamics and Kinetics
 38

CHAPTER II

HYDROCRACKING-CHEMISTRY, THERMODYNAMICS AND KINETICS

CHEMISTRY OF HYDROCRACKING

Hydrocracking is catalytic cracking coupled with catalytic hydrogenation m

an atmosphere of hydrogen in presence of dual-functional catalysts. The chemistry
of hydrocracking is essentially the carbonium ion chemistry of catalytic cracking
coupled with the chemistry of hydrogenation . The carbonium ions form at
the start of the reaction, on the acidic sites of the catalyst, from olefins
obtained by dehydrogenation of saturates on the metallic sites. Skeletal
rearrangement may take place, or the carbonium ion cracks into fragments
of lower carbon number which hydrogenates readily under the high hydrogen
partial pressure. Presence of hydrogen, however, inhibits some of the secondary
reactions particularly readsorption of the olefins from cracking, on to the
catalyst, followed by dehydrogenation leading to coke formation. This results
in longer catalyst life, as compared with catalytic cracking, and simultaneously
allows cracking to proceed at a lower temperature level.

The operating conditions of temperature, pressure, hydrogen partial pressure,

residence time, feed to catalyst ratio and the acidity and hydrogenating -
dehydrogenating activity of the catalyst altogether determine, the nature of
reaction which will predominate and finally the product distribution.

The interesting feature of catalytic hydrocracking is that the hydrocarbons

produced are not in thermodynamic equilibrium, and generally an excess
of branched hydrocarbons result. The isomerisation of hydrocarbons is caused
by the active effect of the acidic sites of the catalysts. Hence, a lower iso-
to-normal ratio may be expected, if a catalyst of much higher hydrogenation
activity (as compared with cracking activity) is used. Branched fragments
are more readily saturated by hydrogen than unbranched ones. This is just
2
what leads to the high ratios of iso-to-normal alkanes in the products .

Another^ characteristics of hydrocracking reaction is the complete absence

of isomers containing quaternary atoms in the products. This can be attributed
to the fact that an intermediate tertiary carbonium ion cracks more readily
 39

than it is converted to a molecule containing quaternary carbon. The conversion

of a tertiary carbonium ion to a molecule containing a quaternary carbon atom
requires passing through a secondary ion intermediate, the energetics for which
are rather unfavourable"^.

To get a clear idea of the reaction chemistry, reactions of the individual

components are to be considered first, which is discussed below.

Alkanes
a
The overall reaction scheme can be presented as

n - Paraffin
i
<h2)

n - Olefin
t

, (A)
Carbonium ions (n "-iso)

(H^) - Hydrogenating - dehydrogenating site of the catalyst.

(A) - Acidic Site of the catalyst.

 40

It starts with the formation of olefins from paraffins at metallic centers and
the formation of carbomum ions from these olefins at the acidic centers.
Next occurs either the skeletal rearrangement of the carbomum ions producing
iso-olefins or the clevage of C-C bond to yield olefins & paraffins. The last
step is the hydrogenation either of the iso-olefins or of the cracked olefins.
Generally, isoparaffins react in the same fashion as n-paraffms with the only
difference in rate which is much more rapid in case of isoparaffins as compared
to n-paraffin of the same carbon number. A characteristics of this family
of hydrocarbons is that the higher molecular weight alkanes are more prone
to hydrocrack. Besides, carbon-carbon bond clevage, hydrogen transfer, hydro­
genation-dehydrogenation and isomerisation, disproportionation and cyclization
can also occur.

The preferential adsorption of other families of hydrocarbons on the catalytic

sites may inhibit the reactions of n-paraffins in a mixture. Hence, shape-selective
zeolite catalysts are favoured for the selective hydrocracking of n-paraffins.
With these catalysts, only those molecules of reactant and product which conform
to a particular size and shape can arrive at "active sites" or depart from these
active sites, resulting in high selectivity.

Cycloalkanes

In hydrocracking, cycloalkanes undergo the processes of decomposition, decycli-

zation, dealkylation particularly 'paring' reactions, ring isomerization and the
hydrogenolysis, depending on the catalyst composition and on the type of
cycloalkane involved.

For substituted cycloalkanes, 'paring' reaction is the most common one. This
reaction is believed to occur by successive isomerizations of feed molecule
adsorbed on the catalyst until a four carbon atom side chain is formed which
can then readily be cracked off at the prevailing hydrocracking conditions,
without severely affecting the ring itself. Regardless of the nature of the
starting substituents (tetra-, penta-, hexa-methyl, n-butyl, sec-butyl, isobutyl,
tert-butyl), this reaction gives one acyclic (mainly isobutane) and one cyclic
product containing four carbons less than the parent cycloparaffm . Here also,
a high ratio of iso-to-normal paraffins (as the acyclic product is concerned),
which is far greater than the thermodynamic ratio, results. Decrease in temper­
ature results in higher selectivity for the paring reaction of polymethyl
 41
cyclohexanes. Paring reaction can be represented 5 as below

A. Olefin formation
5 i 3
Cl ewK_
OH,
Metal eJsz
Cl;^V

CH, B. Carbonium ion formation and isomerization

CH, CHrj®yM3
Acid
CH.
V V
C. Cracking and isomerization Cn,
OH. QBj cfe>C®
c
OH-C -CHa
GHipV c H3 Acid GH, -0U, 9i °H3
V

■OH,
CH3
Isobukme+ l®
0H-o®ev CH,

D. Hydrogenation
^3 Metal •CH,

Multinng naphthenes, on the other hand, hydrocrarks yielding light paraffins

of higher iso-to-normal ratio and a large amount of single-ring naphthenes.
The latter are resistant to further hydrocracking at normal process conditions
and contain a higher than equilibrium ratio of methylcyclopentane to cyclo­
hexane. In general, multming cycloparaffins hydrocrack more readily than
the corresponding normal paraffin. The breaking of naphthenic rings with the
retention of a single ring is characteristic of hydrocracking reactions. The
2
following scheme of reaction can be envisaged for perhydroacenaphthene :

+ ACA
 42

In addition, hydragenolysis of a number of polymethylcyclo-pentanes over

Pt-on-alumina catalyst and that of alkylcyclohexanes over a Ni-on-alumina
catalyst have been reported by several researchers. In case of alkyl cyclopentanes,
ring clevage to produce paraffins is the main reaction while for alkyl cyclo­
hexanes, successive removal of methyl groups without ring clevage is the
1
predominant one . For example, for methylclopentane at 300°C over a platinum
2
catalyst, the reaction proceeds as follows :

(12%)

(66%)

(22%)

Besides, a substantial dehydrogenation of cyclohexanes to arenes occurs over

an alumina-cobalt-molybdenum catalyst, m contrast to a platinum one.

Alkenes

Alkenes, either present initially, as m feedstocks from secondary processes,

or formed as an intermediate product, are the most important one as hydrocra­
cking reactions are concerned. From the thermodynamic viewpoint, alkenes
can be hydrogenated, polymerized or form rings. High hydrogen pressure favors
the hydrogenation reaction, which is also supported by the reaction kinetics,
because the rate of hydrogenation is higher as compared with the other processes.
For high molecular weight hydrocarbons at high temperatures, m addition to
hydrogenation, further decomposition at C-C bonds is possible, followed by
saturation of the resultant fragments (destructive hydrogenation). Preferential
hydrogenation of alkenes over polymerization and condensation reactions allows
hydrocracking to be conducted without any substantial deposition of coke on
the catalyst surface - which is one of the mam advantages of hydrocracking.

Arenes

Hydrocracking of aromatics are more dependent on the structure of the reactants

as compared with cycloparaffins.
 43

For alkylaromatics, isomerization, dealkylation, paring and cyclization are

the reactions that take place. The larger the alkyl side chains, the more complex
is the product distribution particularly due to cyclization reactions. Ring clevage
is almost absent and hydrogenolysis to form methane is at a minimum. Aromatic
products from hydrocracking generally form mixtures approximating thermo­
dynamic equilibrium.

In case of polycyclic aromatics, the principal reaction is the partial hydrogena­

tion of polycyclic aromatic rings, followed by rapid splitting of the saturated
rings to form substituted monocyclic aromatics. Hydrogenation makes such
type of aromatics (polycyclic ones) which are refractory stocks in catalytic
cracking, to readily crackable naphthenes. However, this hydrogenation is
effective only at higher severity of the reaction, and proceeds stepwise. First,
the extreme rings are hydrogenated, and then the central ones. However, some
of the large multinng aromatics, such as, Coronene and Ovalene, once hydro­
genated, dehydrogenate rather than crack^.

Di-and polycyclic aromatics joined by only one bond rather than by two common
carbon atoms are readily cleaved by hydrogen and converted into single ring
aromatics.

The reaction scheme of alkylaromatics can be postulated5 as below :

A. Carbonium ion formation

V
03H7.GU
o + o3vqh.
©

Aside from the hydrocarbon type structures discussed above, feedstocks may
<WCH<

also contain considerable quantities of sulfur, nitrogen and oxygen compounds.

Such materials, under normal hydrocracking conditions, are converted to hydro­
carbons with essentially complete removal of the heteroatoms.
 44

The above discussion reveals that the presence of hydrogen as well as the
presence of hydrogenating-dehydrogenating active sites, in hydrocracking,
make possible the transformation of all types of hydrocarbons to a varying
extent. This leads to complete conversion (100%) of feedstock m hydrocracking
operations.

THERMODYNAN1CS OF HYDROCRACKING

Thermodynamic study of a chemical process make it possible to determine

the direction m which the process may proceed and also the thermal effect
of the reaction. In this connection, the change of free energy (4F°) of the
chemical process is very important to ascertain the feasibility as well as extent
of reaction under certain conditions of temperature, pressure and the other
reaction parameters.

Little has been published on the thermodynamics of hydrocracking of hydro­

carbons. As discussed by Meyers , hydrocracking reactions can be classified
as below, for consideration of the thermochemistry of the reaction :

i) Hydrogenation of olefins, aromatic rings, sulfur compounds, nitrogen

compounds and oxygen compounds,

u) Cracking reaction of C-C bonds.

The net effect of cracking reactions is a slightly endothermic heat of reaction

whereas hydrogenation reactions are highly exothermic; when their contribution
are added, the net heat of hydrocracking reaction is exothermic - resulting
m a large adiabatic temperature rise.

Hence, as temperature of the hydrocracking reaction is concerned, low temperature

( ~400°C) favour hydrogenation reactions while high temperature favours cracking.
Increase in temperature, however, enhance the rates of both hydrogenation
and cracking reactions, but the extent to which hydrogenation can proceed
decreases'. So a compromise must be made in selecting the temperature for
hydrocracking m order to maintain a proper balance between the hydrogenation
and cracking reactions required for the particular product distribution.
 45

The Law of Mass action states that the rate of any reaction involving hydrogen
will be increased by an increase of the pressure and therefore the concentration
of hydrogen. Hence, the general effect of increase of pressure is a greater
absorption of hydrogen, leading towards those reactions involving reduction
in volume. A profound effect of using high pressure m hydrocracking reactions
is achieved in hydrogenation of olefins and aromatics which are the most
g
important reactions in hydrocracking. As per literature , hydrogenation of
the olefinic and aromatic compounds, are thermodynamically unfavourable
(AF°>0) at the normal temperature range used for hydrocracking. This effect
is, however, compensated by the use of hydrogen under pressure which makes
AF° negative at the prevailing temperature range, according to the equation
AF° = -3RT lognat P.

KINETICS OF HYDROCRACKING

Kinetic study of a particular process is important in the sense that it makes

possible to evaluate the rate - constant of a reaction and its dependance on
temperature. The rate constant, again, gives an idea about the fastness of
the reaction.

Kinetic study of the hydrocracking reaction was done by several authors, among
which the works of Scott and Bridge”*1, Filimonov et. al.1^, Qader & Hill1"5,
IS 1A
Eqbal and Sarkar , Bennet and Bourne , Krishna , and few others were
9 10
worth mentioning. Mcketta and Hobson & Pohl also discussed on this topic
in their book. Krishna interpreted the result obtained by Bennet and Bourne
in hydrocracking Kuwait vacuum gas oil, and succeeded to determine pseudo-first
order rate constants for the various compound types. The result is presented
in Fig. 2.1 from which the hydrocarbons can be arranged in the following
sequence of decreasing reactivity :

SC > MCA > PCP > PC A :> MCP > P '

SC -- Sulfur compounds
MCA — Monocycloaromatics
 ‘ FIG. 2,1 ; RATE CONSTANTS IN HYDROCRACKING
______________ P l lo t D qta From B n tis h P etroleum

m
I

M/l
5
Compound Types
FIRST ORDER RATE CONSTANTS. ( K /L H S V ) h"1,FOR VARIOUS COMPOUND TYPES
 46
PCP -- Polycycloparaffins
PCA -- Polycyclo aroma tics
MCP -- Monocycloparaffins
P — Paraffins

Krishna also presented a usable kinetic model for hydrocracking with a view
to selection of optimum conditions for design and operation.

Hobson & Pohl mentioned the sequence of hydrogenation and cracking reactions
of light catalytic cycle oil and determined the rate constants of the various
reactions. The results are presented below (Fig. 2.2) from which it can be
concluded that:

a) Polycyclic aromacits are partially hydrogenated rapidly,

b) Naphthene rings in polycyclic compounds are readily removed by
ring opening followed by cracking,
c) Single-ring naphthenes and paraffins are more resistant to cracking,
d) Single-ring aromatics are difficult to hydrogenate.

RING OPENING (FOLLOWD BY DE-ALKYL AT ION)

H Y D R O G E N A T IO N

Fig. 2.2 :- Relative rate constants in isothermal hydrocracking of light cycle

oil at 103 bars.
 47

Eqbal and Sarkar, on the basis of the assumption that the overall hydrocracking
reaction follows first-order kinetics, derived the following equation for the
reaction rate constant

K = 3.311 x 109 exp (-33400/RT) h“1 * * *

for hydrocracking the reduced crude sample m high-pressure autoclaves. Their

result is comparable with those reported by others and thus upholds the validity
of the theoretical treatment. Qader and Hill reported that gas oil hydrocracking5
desulfurisatian and denitrogenation were all first-order and the rate constants
could be represented by :

1 x 107 exp (-21,100/RT) h“1

0.6814 x 105 * exp (-16,800/RT) h'1
0.8253 x 105 exp (-1 7,400/RT) h"1

They studied the hydrocracking process using gas oil (300-430°C) in a fixed
bed tubular-flow reactor.

17
Hisamitsu and Ozaki in their report stated that the hydrocracking and hydro-
denitrogenation of vacuum gas oils had 1st order kinetics. The reaction order
of hydrodesulfurisation, however, decreased with increasing temperature. As
temperature increased, the effect of pressure on the hydrocracking and hydro-
desulfunsation rates decreased, but remained constant for the hydrodeni trogena-
tion rate.
 48

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1. Chouo.-iury, N. and Saraf, D.N.t lnd. Eng. Chem.

Prod- Res. Dev., 1 4(2), 1975, p. 77

2. Erikh, V.N.? Rasina, M.G.; Rudin, M.G., 'The Chemistry and Technology
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3. Clough, H, lnd. Eng. Chem. 49, 195 7, p. 6 73

4. Le Page, J.F., "Applied Heteroqeneons Catalysis11,

Editions Technip, Paris, 1987, p. 450

5. Meyers, R.A., "Handbook of petroleum refining processes",

McGraw-Hill Book Company.

6. Ward, J.W., "Preparation of Catalysts HI", Elsevier,

Amsterdam, 1983, p. 589

7. King, J G., "Science of Petroleum", 111,

Oxford University Press, 1938, P. 2156

8. Sachanen, A.N., "Conversion of Petroleum",

Reinhold Publishing Corporation, New York, 1948

9. Kenneth, A. Kobe and Mcketta, J., "Advances in Petroleum Chemistry

and Refining", Interscience, 196 4

10. Hobson, G.D. and Pohl.W. (Ed.), "Modern Petroleum Technology",

Vol. 1, John Wiley & Sons, 1986, p. 436

11. Scott, J.W.j Bridge, A.G., Advan. Chem. Ser. No. 103, 19 71, p. 113

12. Filimonov, V.A.; Popov, A.A.', Khavkin, V.A.*, Perezhigina, I.Y.; Osipov,
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p. 21
 49

13. Qader, S.A. and Hill, G.R. Ind. Eng. Chem. Proc Des. Dev., 8_, 1969,
p. 98

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1 7. Hisamitsu, T.; Ozaki,H, Sekiyu Gakkaishi, 29(4j, 1986, p. 295,

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