PENEX PROCESS

TECHNOLOGY
OVERVIEW

PENEX Process Objectives

Why PENEX???
Conversion of normal paraffins to iso-paraffins
Principal application of isomerization is the
conversion of normal C5 and C6 material
Pentane (C5) Hexane (C6) Isomerization
provides higher octane (82-91 RONC)
components to the gasoline pool.
Benzene saturation reaction helps meet aromatic
concentration standards

Component Blended Octane Values

Process Benefits
100% benzene saturation
High Yields
Low severity reactor operations
Operating pressure (31.5 kg/cm2(g))
Low Temperatures (< 204C)

Excellent catalyst stability

Up to 10-12 year catalyst lives

Capable of processing wide range of feedstocks

Chemistry

Isomerization
Benzene Saturation
Ring Opening
Hydrocracking
Heavies Formation
Reactions take place over a dual function catalyst
- Metal function (platinum)
- Acid function (chloride)

Isomerization Reactions

C-C-C-C-C

C
C-C-C-C

n-Pentane (nC5)

Isopentane (iC5)

61.8 RON
6RON

93 RON
93.5 RON

C
Cyclohexane (CH)

Methylcyclopentane (MCP)

84 RON
84.0 RON

89.3 RON
96.0 RON

Isomerization Reactions
C
C-C-C-C-C

C
C-C-C-C-C

2-Methylpentane (2MP)
73.4 RONN

3-Methylpentane (3MP)
74.5 RON

C-C-C-C-C-C
C
C-C-C-C
C

n-hexane (nC6)
24.8 RON
31.0 RON

2,2-Dimethylbutane (2,2DMB)
91.8 RON

C
C-C-C-C
C

2,3-Dimethlybutane (2,3DMB)
104.3 RON

Isomerization Reactions

Requires metal and acid functions

Equilibrium limited
Slightly exothermic
No hydrogen consumed
Increases octane

Benzene Saturation
Benzene saturates to cyclohexane
Cyclohexane (CH) in equilibrium with
methylcyclopentane (MCP)
Requires only metal function
100%

3H2 +
Benzene
120.0 RON

40-60%

Pt

Cyclohexane
84.0 RON

MCPentane
96.0 RON

Benzene Saturation

Immediate with platinum sites and presence of hydrogen

No acid sites required
100% complete
Highly exothermic (25x isomerization, 5x hydrocracking)
Consumes 3 moles H2 per mole of benzene
Reduces octane (120 Bz 84 CH & 96 MCP)
Limit Bz in feed to ~5 vol%
~11C Rx bed deltaT / 1 vol% Bz
~55C total deltaT / reactor

Ring Opening Reactions

CH and MCP open to C6 paraffins
Cyclohexane (CH) in equilibrium with
methylcyclopentane (MCP)
C-C-C-C-CC

30%
100%

3H2 +
Benzene
120.0 RON

30%

40-60%

Pt

Cyclohexane
84.0 RON

MCPentane
96.0 RON

Ring Opening Reactions

Competes for the platinum sites

Moderately exothermic
20-40 wt% opening
Consumes 1 moles H2 per mole of ring opened
Reduces octane
Increases with lead reactor temperature increase
Higher temperatures favor MCP

Hydrocracking
Longer chain molecules break to smaller ones

Hydrocracking
Triggered by high reactor temperatures and catalyst
acid sites
Exothermic
Consumes 1 moles H2 per mole of cracked material
C5 and C6 paraffin hydrocracking is minimal
About 50% of C7+ paraffins hydrocrack to C4 and C3
paraffins
C5+ yield loss
Caused by:
Higher C7+ in feed
Higher rx temperatures pushing equilibrium
Temperature excursion

Heavies Formation
C7+ Formed in PENEX reactors due to Alkylation
Formation of C7+ &Hydrocracking are simultaneous.

Isomerization Catalyst
Dual function catalyst (metal/acid)
Metal is platinum
Acid is chloride

Metal impregnated on a high surface area alumina-oxide

Active sites are bound alumina-chloride
Gray extrudate or gray trilobe extrudate

Dual function balance is maintained by:

Perchloroethylene injection

Sensitive to contaminants and non-regenerable

Catalyst Promotor - Chloride

Continuous chloride injection required to maintain activity.
C2Cl4 + 5H2 --------> 4HCl + C2H6 , T>105OC
Hydrogen and hydrocarbon can strip bound chlorides from the
catalyst if the partial pressure of chloride surrounding the catalyst
is too low.
Low or loss of chloride injection will permanently deactivate the
catalyst.

H+Cl- C5
H2
C6
Cl- ClClCl
ClClC5, C6, H2, HCl

METHANATOR
Sensitivity of isomerisation catalyst to oxygenates
(CO/CO2)
CO + 3H2 --------> CH4 +
CO2 + 4H2 --------> CH4 +

H2O + Heat , T= 204OC

2H2O + Heat , T= 316OC

Side reactions: Olefin hydrogenation, C2+ cracking

Operating temperature : 204OC 250 OC
CO2 & moisture removed by Makeup Gas Driers.

18

C5 - C6 Isomerization Terms
Product Ratios, wt% or mol%

iC5/C5P = iC5/(iC5+nC5) x 100%

2,2DMB/C6P = 2,2DMB/C6 Paraffins x 100%
2,3DMB/C6P = 2,3 DMB/C6 Paraffins x 100%
C6 Paraffins = 2,2DMB + 2,3DMB + MP + MCP + CH + nC6

PIN (Paraffin Isomerization Number), wt%

(iC5/C5P + 2,2DMB/C6P + 2,3DMB/C6P)

Feed X-factor, wt%

(MCP + CH + BZ + C7+)

Lead Rx

Lag Rx

iC5/C5P
iC4/C4P

(2MP+3MP)/C6P
2-2 DMB/C
6P

2-3 DMB/C6P

121 C

149 C

177 C

204 C

RON

Lead Rx

90
88
86
84
82
80
78
76
74
72
70
100

Lag Rx

Octanes of Equilibrium Mixtures

C5 Para
ffins
Total C
5 -C6

C6 Pa
r a f f in
s

302F
150

392F
200
250
Temperature, C

300

IC5/C5 PARAFFINS PRODUCT RATIO, Wt%

Lead and Lag Rx IC5 Product

Ratio
IC5
Pro
duc
77
t Ra
tio
SOR
Equ
ilibr
ium
72
EOR
SOR

EOR

45

Feed (Minimum)
116 C
240
Reactor Outlet Temperature, F

167 C
204 C
330350 400

PENEX PROCESS
FLOW &
EQUIPMENTS

PENEX Process Objectives

Basic flow diagram

Feed Section
Reactor & Exchanger section.
Stabilizer
Net Gas Scrubber
DIH

Basic Flow Diagram

MU Gas
Driers
Steam
Heater

Make-up
Hydrogen
Reactors

H.O.T. Penex

Deisohexanizer (DIH)
Overhead

Receiver

C5p, DMB

Scrubber
Gas
to Fuel

C2Cl4
HCFE

CCFE

Product
Side Draw

Stabilizer

MPs, n-C6

Reboiler
Surge
Drum

Liquid
Driers

Fresh/Spent
Caustic

Isomerate
Light
Naphtha

Bottoms
C7+, min n-C6

FEED SECTION: FEED & MAKEUP GAS

DRIERS

26

FEED DRIERS

27

MAKEUP GAS DRIERS

28

REACTOR & EXCHANGER SECTION

Steam
Heater

Reactors
LEAD

LAG

C2Cl4
To Stabilizer
HCFE

CCFE

NAPHTHA FROM FEED SURGE

DRUM

HYDROGEN FROM MAKEUP

GAS DRIERS
29

Stabilizer & Net Gas Scrubber

Chiller

To Fuel Gas
Coalescer

To Fuel Gas
Header

Receiver

Stabilizer

LPG Stripper

Scrubber

Caustic

To DIH
30

De-Isohexanizer
DIH
Receiver
Overhead

From
Stabiliser

C5p, DMB

DIH

Side-draw to Feed
Driers

Side Draw
MPs, n-C6

Bottoms
C7+, min n-C6

MP
Steam

Total Isomerate

31

Isomerization Reactions
Step 1: Formation of Olefin Intermediate
Step 2: Formation of Carbonium Ion
Step 3: Carbonium Ion Rearrangement

Step 4: Formation of Iso-olefin intermediary

Step 5:

???????

INDIAN GASOLINE SPECIFICATIONS

Characteristics

Unit

BS-II

BS-III

Sulphur, Total,
Max

PPM

500

150

Lead Content(as
Pb), Max

g/l

0.013

0.005

Benzene, Content

% Volume

88

91

Research Octane
Number

34