zObjectives:

’ Better balance of gasoline & distillate production

’ Greater gasoline yield.
’ Improved gasoline pool octane quality
’ Supplement FCC to upgrade heavy cracking stocks,
aromatics, cycle oils and cocker oils to gasoline, jet
fuels & light fuel oils.
’ Relative high amount of isobutane production in
butane fraction.

zIndustrial proces:

zFeed:
’ Vacuum gas oil
’ Coker gas oil
’ LCO / HCO

zProducts: Naphtha, jet fuel, diesel, distillates

zOperating conditions: 290-4000C , 80-140 atm

zType of reactor :
’ Fixed bed reactor
’ Single stage / two stage
’ Once through / recycling
zBifunctional Catalyst:

zAcidic function:
’ Amorphous oxide ( SiO2/Al2O3)
’ zeolites

zMetal function:
’ Noble metals ( Pt / Pd)
’ Non Noble metals ( Mo ,Co ,Ni etc.)

zCracking function activity :

Zeolite > Si/Al2O3 > Al2O3 – halogen > Al2O3

zHydrogenation function activity :

Pt ( Pd ) > Ni/W > Ni/Mo > Co / Mo

ELEMENTARY STEPS IN HYDROCRACKING
zKinetic Modeling:

zWhy ??

’ Simulation & Optimization of industrial process

’ Design of fixed bed industrial reactors
’ Extraction of kinetic data

1. Three lump model :

Lumps: Gas Oil

Gasoline
Coke + Light Gases

2.Ten Lump Model:

Lumps :G – Gasoline
C – Coke + C1-C4 Gases
P – Paraffins
N – Naphthenes
AR – Aromatic ring
AS – Aromatic substituent group
l – low boiling fraction
h – heavier fraction

zFeatures:
’ Rate coefficient varies with type of Gas Oil
’ Extensive experimentation required to
characterize gas oil
 Single Event Kinetics

zWhy ??

’ Rate of Hydrocracking increase with chain length

’ Separate experimental work required for different
feeds
’ Model depends on reactor configuration

zFeatures:
’ Rate parameters invariant with respect to chain
length
’ Reduction of # of rate parameters to realistic
amount
’ Independent of type of reactor or type of feed

zHow it works ???

’ Effect of structure on ∆S Single Event Kinetics

’ Effect of structure on ∆H Evans Polanyi Relation
zTransition State Theory:

k T 

 ∆S0 
 
 - ∆H0 
 
k' =

b  exp  exp 

h   R 
 
 RT 
 
 

where, S0 = S0 + S 0 + S 0 + S 0 + S0 sym
trans vib rot ele
0
∴S = S 0 
−Rln σ 



intr  gl 
σ 
0
∴∆S = ∆S 0 
+ Rln σ
 glr 

intr  gla 

 
σ  k T  
∆S 0 
 - ∆H0 
 

∴k' =  σ glr 
b 
 exp intr
 
 exp
  

 h  R  RT 
 gla   


  
    
σ 
σ
where, σ = n & ne =  σ

 glr 

gl 2  gla 

 
∴k' = nek
HOW TO DETERMINE NO. OF SINGLE EVENTS

*
+

* CH3+

*
ne = 12 ne = 6

*
CHARACTERIZATION OF SPECIES
(BOOLEAN MATRICES AND AUXILIARY VECTORS)
NETWORK GENERATION ALGORITHM

Storage of feed paraffins

and naphthenes

Dehyrogenation of paraffins
and naphthenes

Protonation of olefin

Isomerisation, cracking and

deprotonation of carbenium ion

Next
carbenium ion

Hydrogenation of diolefin

Hydrogenation of olefin
Next diolefin

Next olefin
Network generation completedNext parafffin or napthene
 NETWORK GENERATION FOR n-OCTANE

zMechanism:
Reaction network generation for Hydrocracking:

’ Feed: n – Octane
Species: 14 Octanes
5 Paraffinic products
9 olefinic products
49 Octenes
42 Octyl Carbenium ions
6 Carbenium ions with small Carbon no.

’ Total Reactions: 383

♦ Protonation - 75
♦ Deprotonation - 85
♦ Hydride Shift - 88
♦ Methyl Shift - 24
♦ PCP Branching - 96
♦ B – Scission - 15

’ Characterization of Molecules / Carbenium Ions :

♦ Boolean Matrices ( Aij )

♦ Auxiliary Vectors:
♦ Three Rows :
1: Charged / Uncharged
2: Nature of carbon atom ( p/s/t/)
3: Type of carbon atom
zAssumptions:
1. Methyl and primary carbenium ions are so
unstable that they can be disregarded in the
construction of reaction networks.
2. For Isomerisation single events, only the type of
carbenium ion ( s or t ) not the identity ( # of
carbon atoms ) determines its activity.
3. The rate coefficient of protonation is independent
of the olefin.
4. Rate coefficient of deprotonation is independent of
the no. of carbon atoms from C5 onwards.
5. The rate coefficient of cracking is independept of
olefin.
6. Rate determining Step occurs on acid sites .
7. Hydrogenation and dehydrogenation steps are in
equillibrium.

zReduction of # of Single Event Rate Coefficients:

1.Thermodynamic Constraint
Deprotonation :
k (m; O ) = k (m; Or ) k (O ⇔ O )
De ij De isom r j
Isomerisation :
k (t; s) k (t; s) k (t; s) k (s) k De (t; O j )
HS = MS = PCP = Pr
k (s; t) k (s; t) k (s; t) k (t) k (s; O )
HS MS PCP Pr De j

2.Evans Polanyi Relation :

Ea = E - α ∆Hr .......Exothermic Reaction
0
Ea = E + (1 - α) ∆Hr .......Endothermic Reaction
0
Parameters : E = Intrinsic Activation Energy
0
α = Transfer Coefficient
Rate Equations :

P ⇔ O +H
i ij 2
R = ∑ [ k (ji) C P -k (ij) C ] ....(1)
Pi j H Oij H2 DH Pi

R +ij,m 
O + H+ ⇔
 1 R+ +
ij  
R +ij,m 
; v → Oij + R w
 2
R =k (ij)C - k (ji)C p
Oij DH Pi H Oij H2
+ k (m ,O )C + + k (m ,O )C +
De 1 ij R De 2 ij R
ij,m ij,m
1 2
- [k (m ) + k (m ) ] C C + + k (v; w,O )CR = 0 .....(2)
Pr 1 Pr 2 Oij H Cr ij +
v

At Pseudo Steady State : R =0

Oij

If RDS is on acid sites,

R = ∑ { k (m ,O )C + + k (m ,O )C +
Pi j De 1 ij R De 2 ij R
ij,m ij,m
1 2
- [k (m ) + k (m ) ] C C + + k (v; w,Oij)C + } ......(3)
Pr 1 Pr 2 Oij H Cr Rv
R + = { ∑ k (m)C C + + ∑ k (q; m)C + + ∑ k (r;m)C + + ∑ k (u; m) C + + ∑ k
R Pr O H HS R MS R u PCP R
m O q q r r u v
− { ∑k (m; O) + ∑ k (m; q) + ∑ k (m; r) + ∑ k (m; u) + ∑ k (m; z, O' )}C +
O De q HS r MS u PCP z Cr R
m

At Pseudo Steady State : R + =0

R
m

Site Balance : C = C + + ∑ C +
t H m Rm

C K
Pi DHij
Dehydrogenation : CO =
ij p
H2
C K p
s,sat L,i i
Langmuir Adsorption : C =
Pi 1+ ∑ K p
m L,m m

C K K p
s,sat L,i DHij i
∴ CO =
ij p (1+ ∑ K p )
H2 m L,m m
zFinal Rate Coefficients:

Elementary Rate Coefficients #

Step
KPr (Oj;s), (Oj;t) 2
KDe (s;Oj), (t;Oj) 2
KHS (s;s),(s;t),(t;s),(t;t) 3
KMS (s;s),(s;t),(t;s),(t;t) 3
KPCP (s;s),(s;t),(t;s),(t;t) 3
KCr (s; s,Oj), (s; t,Oj) 4

zEquillibrium Constants:
Benson group contribution method
z# Of single Events & ∆Hr :
Quantum Chemical Packages
( MOPAC, GAMESS, GAUSSIAN)