ISOMERIZATION PROCESS

University of Danang,
University of Science and Honeywell,
Technology, Vietnam UOP, USA
UOP 3122F-01
Outline
• Catalysis Concept
• Industrial Isomerization
▪ Light paraffin isomerization
▪ Light Olefin Isomerization
▪ Aromatic isomerization

2
Catalysis Concepts
• Thermodynamics tells you how much you can convert under a set of
conditions; kinetics tells you how fast you can do it.

• A catalyst is a substance which increases the rate at which a chemical reaction

approaches equilibrium. The catalysts does not change the thermodynamics.
Therefore, a catalyst can only increase the rate of those processes which are
thermodynamically favorable.

• A catalyst operate by providing another mechanism pathway for those reaction.

• The catalyst does not become permanently involved in the reaction.

• Catalysts help to selectively prepare specific products.

Chapter 1: Catalysis
i-Pentane / n-Pentane Equilibrium Plot

100
Mol-% / i-Pentane

80

60

40
100 150 200 250 300

Temperature, oC
4

Chapter 1: Catalysis
Catalysis Concepts

Reaction

Reaction

E Eact

A
B
5
A  B
Chapter 1: Catalysis
Catalysis Concepts

Catalysis: reduce the activation energy

Uncatalyzed
Reaction

Catalyzed
E Eact Reaction

Eact (cat)

A
AX BX B
A + X  AX  BX  B + X 6

Chapter 1: Catalysis
Homogeneous Catalysis
vs.
Heterogeneous Catalysis

• Homogeneous: Reactant and catalyst are present in the

same phase, typically liquid.

• Heterogeneous: Reactant and catalyst are initially in

separate phase, i.e., gas-solid or liquid-solid.

Chapter 1: Catalysis
 Characteristics of
Homogeneous Catalysis

1) Pressure and Temperature

- Relatively low

2) Heat of Reaction
- Reaction are often exothermic: bond-forming reactions of small molecules
that give larger molecules.
- Heat removal from reactor is crucial.

3) Separation
- Catalysts / product separations are significant expense; processing cost is
dominated by the separationห.

Chapter 1: Catalysis
4) Reactant mixing
- Reactant are often gaseous or gaseous-liquid under ambient
conditions. Type and geometry of reactor are crucial in maximizing
the reactants mass transfer.

5) Corrosiveness
- The catalyst solution are corrosive, and the reactors, separation
devices, etc that come in contact with them must be made of
expensive corrosion-resistant materials.

Chapter 1: Catalysis
 Types of Homogeneous Catalysis

1. Acid-Base Catalysis

• H2SO4, HF and KOH are widely applied as catalysts in industrial

organic synthesis.

• The chemistry of acid-base catalysis involves the transfer of H+ (or

hydride H-).

 In acid catalysis, catalyst donates protons to reactant.

 In base catalysis, the reactant donates protons to catalyst.

10

Chapter 1: Catalysis
1. Acid-Base Catalysis

• Donation of H+ to the reactant often forms a carbenium ion (RH+) or an

oxonium ion, which then reacts in the catalytic cycle.

• Example of acid-base catalysis:

 Conversion of phenol and acetone into bisphenol A

 Alkylation of ethylene and i-butane to form C7 or C8 products

11

Chapter 1: Catalysis
Conversion of Phenol and Acetone into Bisphenol A

12

Chapter 1: Catalysis
Catalytic Cycle for the Ehylene and i-Butane Alkylation

13
Carbonium Ion ≠ Carbenium Ion

A. Carbonium Ions have 5 coordinated C atoms

• Genesis: Paraffin + Proton

H H
+
+
CH3 C C2H5 + H [ CH3 C C2H5 ]
H H H

CH4 + [ C3H7 ]+ H2 + [ C4H9 ]+

14

Chapter 1: Catalysis
Carbonium Ion ≠ Carbenium Ion
B. Carbenium Ions have 3 coordinated C atoms

• Genesis: 1. Carbonium Ion Decomposition (see previous slide)

2. Olefin + Proton

CH3 CH3
+
CH3 C CH2 + H CH3 C CH3
+

3) Paraffin minus H- ion

CH3
+
CH3 C CH3 + CH3 CH CH2 CH3
H
CH3
15
CH3 C CH3 + CH3 CH2 CH2 CH3
+
Chapter 1: Catalysis
2. Organometallic Catalysis

• Use organometallic (metal-ligands) as catalysts.

• The chemistry of organotransition metal catalysis is explained by the

bonding and reactivity of ligands bonded to the metals.

• Ligand can be CO, H- (hydride), olefins, etc.

16

Chapter 1: Catalysis
2. Organometallic Catalysis

• Examples of organometallic catalysis

 Methanol Carbonylation CH3OH + CO CH3COOH

 Olefin Hydroformylation (The Oxo Process)

CH3CH CH2 + CO + H2 CH3CHCH3 + CH3CH2CH2CHO
CHO

 The Wacker Oxidation of Ethylene to Acetaldehyde

CH2=CH2 + H2O + PdCl2 CH3CHO + Pd + 2 HCl
Pd + 2 CuCl2 PdCl2 + 2 CuCl
2 CuCl + ½ O2 + 2 HCl 2 CuCl2 + H2O

CH2= CH2 + ½ O2 CH3CHO

17

Chapter 1: Catalysis
Catalytic Cycle for Methanol Carbonylation

18
Chapter 1: Catalysis
 Process Diagram for Methanol
Carbonylation to Make Acetic Acid

Reactor

CH3OH + CO CH3COOH
19
Chapter 1: Catalysis
 Process Flow Diagram for the Two-phase
Hydroformylation of Propylene

CHO
CH3CH CH2 + CO + H2 CH3CHCH3 + CH3CH2CH2CHO

20
Chapter 1: Catalysis
 Characteristics of
Heterogeneous Catalysis

1) Pressure and Temperature

- Wide range of T & P are used. However, higher T (~500oC) is commonly
used to increase activity.

2) Heat of Reaction
- Both exothermic and Endothermic reaction are routinely carried out with
solid catalysts.
- Fluidized-bed reactors are preferred for the strongly exothermic reaction.

3) Separation
- Solid catalyst / product (gaseous or liquid) separations are simple and cost
little.

21

Chapter 1: Catalysis
 Properties of Solid Catalysis
1) Support (with binder)
- Porous inorganic material,
zeolites, polymers
- High surface area / pore
volume
- Good strength / attrition
- Stable chemically /
physically
2) Catalytically Active Phase
- Complex
- Active metals (eg. Pt, Pd, Rh,
Cu, Ni, Au)
- Active metal oxides and metal
sulfides
3) Promoters
- Alkalini metals are
used as chemical
promoters
- They are used to
modify or influences
the surface chemistry
22
Chapter 1: Catalysis
 Solid Catalyst
Composition/Preparation

Composition of finished solid catalysts

1. Metal Oxides – Clay (binder), Al2O3, SiO2, Zeolites and / or Super acid

2. Metal –

Noble metal: Pd, Pt, Ag, Au and / or Rh

Base metals: Ni, V and / or Mo
Modifiers: Sn, Ge and / or Re
Promoters: K, Li and / or Na

23

Chapter 1: Catalysis
 Solid Catalyst
Composition/Preparation

Preparation

1. By extrusion – steps are

a) Dough (oxide + binder)
b) extrude
d) Dry, then calcine
e) Metal impregnation, then activation

2. By spray drying – step are

a) Sol (oxide + binder)

b) Sprey
c) Dry, then calcine
e) Metal impregnation, then activation
24

Chapter 1: Catalysis
 Types of Heterogeneous Catalysis

1. Molecular Catalysis on Support

Catalyst – Sulfonated poly (styrene-divinylbenzene)

▪ In the present of excess water, the H in the

SO3H groups.
▪ Are dissociated, and specific acid catalysis
takes place in.
▪ The swelled resin just as it takes place in
an aqueous solution.

Reactions

a) Synthesis of bisphenol A from phenol and acetone

(reaction in homogeneous catalysis)

b) Synthesis of methyl t-butyl ether (MTBE) from methanol and isobutylene

25
CH3OH + C4H8 H+ C4H9OCH3
Chapter 1: Catalysis
2. Catalysis by Metals

1) Atoms at the surface of metals (heterogeneous) have catalytic properties

and reactivities different from those of metals in metal complexes
(homogeneous catalysis).
2) Reaction - example
 CO oxidation catalyzed by Pd: 2 CO + O2 2 CO2
(Automobile exhaust converters)

 Sequence & mechanism are as follows

26

Chapter 1: Catalysis
3. Catalysis by Metal Oxides and Zeolites:

1) Metal oxides are used both as catalyst supports and catalysts such as
-Al2O3 used for ethanol dehydration to give ethylene.

2) Metal oxides supported on metal oxides such as Re2O7/Al2O3 is used for

olefin metathesis.
3) Acid-base chemistry of metal oxide surface is the key in catalysis.

4) The surfaces have both basic and acidic character.

 Base strength of OH and O groups on oxide surfaces increase from

Silica Gel < -AL2O3 < highly dehydroxylated MgO
 Surface OH groups are acidis with proton donor strengths increase
from Al2O3 to SiO2-Al2O3.
 Metal ions exposed at surface are Lewis acids.

27

Chapter 1: Catalysis
Dissociation Energy (Do) of Surface
Hydroxyl Groups with Different
Acid-Base Properties

28

Chapter 1: Catalysis
4. Catalysis by Zeolites

1. Zeolites (Faujasite) are used in catalytic cracking – the FCC (Fluid

Catalytic Cracking) process.

2. Zeolites are ion exchangers. The cations may be catalytically active.

When the cation are H+, the zeolites are acidic.

3. The OH groups located near AlO4 tetrahedral are strong Bronsted acids
and responsible for the catalytic activity.

29

Chapter 1: Catalysis
 Classical Mechanism of n-Alkane
isomerization with Change in Branching

30
Chapter 1: Catalysis
Reforming – Bifunctional Catalysis

1. It is a catalytic process to convert nephtha to high octane number gasoline.

2. It is a bifunctional surface catalysis. The catalysts consist of:

 Metal: Re and/or Pt
 Metal Oxides: transition alumina functions as “Acidic” catalyst
31
Reforming – Bifunctional Catalysis

3. The metal oxide support must not be too strongly or too weakly acidic:
chlorinated Al2O3 is optimal.

4. Dehydrocyclization reaction requires both metal and the acid.

 Metal alones does not catalyze the branching reaction; they require
an acidic function to generate carbenium ions, which undergo the
desired isomerization.

 The acidic function alone is not sufficient to generate the carbenium

ions because it is too weakly acidic to protonate paraffins; metal
catalyzes dehydrogenation of paraffins to give olefins, which are
easily protonated and thereby converted by carbenium ion routes.

32
Reforming – Bifunctional Catalysis
5. The presence of excess hydrogen is required
 minimize catalyst deactivation

6. Catalytic reforming is first developed by UOP in mid-1940 (World War II)

 The UOP Platforming Process

33
5. Catalysis by Metal Sulfides

1. Metal sulfides such as MoS2, WS2, and others are typically several order of
magnitude less active than metals.

2. They are stable (not being poisoned) to sulfur-containing and nitrogen-

containing feed.
3. Applications
 Hydrodesulfurization
✓ Reaction of organosulfur compounds with hydrogen to give
hydrocarbons and H2S.
✓ Removal of sulfur from naphtha feed.
 Hydrodenitrogenation
✓ Reaction of organonitrogen compounds with hydrogen to give
hydrocarbons and ammonia.
✓ Removal of nitrogen from hydrocracking feed.

34
 Barrel of Oil Utilization – Transport Fuels

120
Increased need for
light clean fuels
100 Internal combustion
engine developed –
% Transport Fuels/Barrel

gasoline in demand
Fuel oil replaces coal in World War II
naval ships
80 High octane aviation
gasoline required to Bottoms
support Allied war effort Conversion
Advent of high UniflexTM
compression
60 engines requires CCR PlatformingTM
higher octane
Hydrocracking
Platforming
40 Poly Gasoline
FCC + Alkylation

Kerosene
20 replaces whale
oil in lamps
Dubbs
Cracking
0
1870 1890 1910 1930 1950 1970 1990 2010 2020

Primary Focus Was on Utilization

Going Forward, Efficiency and Value Add 35
35 UOP 6521B-35
36
 Industrial Isomerization

Chapter 14 of Zeolites in Industrial

Separation and Catalysis
John Bauer, Feng Xu, Paula Bogdan, Greg Gajda

37
 Isomerization Outline

I. Light Paraffin Isomerization to enhance octane

gasoline

II. Light Olefin Isomerization

III. Aromatic Isomerization

38
I. Light Paraffin Isomerization
to Enhance Octane Gasoline

39
 Equilibrium vs. Temperature for n-Hexane
Isomerization (Vapor phase)

60% 90

RONC (full n-hexane conversion)

50% 85

MPs/C6s
40% 80
RONC @ equilibrium
mole%

RONC
30% 75
22DMP/C6s

20% 70
n-hexane/C6s

10% 65
23DMP/C6s

0% 60
100 150 200 250 300
Temperature, °C 40
 Paraffin Isomerization

• Conversion of normal paraffins to iso-paraffins

is one type of isomerization
• Principal application of isomerization is the
conversion of normal C4, C5 and C6 material
• Butane (C4) Isomerization provides iso-butane
feed to an alkylation process or MTBE Complex
• Pentane (C5) – Hexane (C6) Isomerization
provides higher octane (82-91 RONC)
components to the gasoline pool

Section 15-41 UOP - CONFIDENTIAL Isomerization

 Paraffin Isomerization Background

• WWII requirement for iso-butane for alkylation

• 1941 – 1st unit based on Friedel-Craft chemistry
- Used corrosive aluminum chloride catalyst
- High costly maintenance
- 38 units fulfilled needs of the time
• 1950s – Development of high temperature dual
function, reforming-like catalyst systems
• 1959 – 1st C4 unit based on low temperature
dual function catalyst systems
• 1969 – 1st C5/C6 unit; now >235 units worldwide

Section 15-42 UOP - CONFIDENTIAL Isomerization

 Chemistry

• Isomerization
• Benzene Saturation
• Ring Opening
• Hydrocracking

Reactions take place over a dual function catalyst

- Metal function (platinum)
- Acid function (chloride)

Section 15-43 UOP - CONFIDENTIAL Isomerization

Classical Mechanism of n-Alkane Isomerization
with Change in Branching

x +

44

Chapter 1: Catalysis
 Isomerization Reactions

C
C-C-C-C C-C-C
n-Butane (nC4) C Isobutane (iC4)
C
C-C-C-C-C C-C-C-C
n-Pentane (nC5) Isopentane (iC5)
61.7 RON 93.5 RON

Cyclohexane (CH) Methylcyclopentane (MCP)

84.0 RON 96.0 RON

Section 15-45 UOP - CONFIDENTIAL Isomerization

 Isomerization Reactions

C C
C-C-C-C-C C-C-C-C-C
2-Methylpentane (2MP) 3-Methylpentane (3MP)
74.4 RON 75.5 RON

C-C-C-C-C-C
n-hexane (nC6)
31.0 RON
C C
C-C-C-C C-C-C-C
C C
2,2-Dimethylbutane (2,2DMB) 2,3-Dimethlybutane (2,3DMB)
93.5 RON 105.0 RON
Section 15-46 UOP - CONFIDENTIAL Isomerization
 Benzene Saturation

• Benzene saturates to cyclohexane

• Cyclohexane (CH) in equilibrium with
methylcyclopentane (MCP)

100% 40-60% C
3H2 +
Pt
Benzene Cyclohexane MCPentane
120.0 RON 84.0 RON 96.0 RON

Section 15-47 UOP - CONFIDENTIAL Isomerization

 Ring Opening Reactions

• CH and MCP open to C6 paraffins

• Cyclohexane (CH) in equilibrium with
methylcyclopentane (MCP)

C-C-C-C-C-C

30% 30%

100% 40-60% C
3H2 +
Pt
Benzene Cyclohexane MCPentane
120.0 RON 84.0 RON 96.0 RON

Section 15-48 UOP - CONFIDENTIAL Isomerization

 Isomerization Reactions

• Requires metal and acid functions

• Equilibrium limited
• Slightly exothermic
• No hydrogen consumed
• Increases octane

Section 15-49 UOP - CONFIDENTIAL Isomerization

 Isomerization Catalyst

• Dual function catalyst (metal/acid)

- Metal is always platinum
- Acid is always chloride
• Metal impregnated on a high surface area alumina-oxide
• Active sites are bound alumina-chloride
• Gray extrudate or gray trilobe extrudate
Pt
Pt

Cl Cl
• Dual function balance is maintained by:
- Perchloroethylene injection
• Sensitive to contaminants and non-regenerable

Section 15-50 UOP - CONFIDENTIAL Isomerization

 Butane Isomerization Process
(UOP Hydrogen Once Through Butamer)

MU Gas
Driers

Make-up
Hydrogen Gas to Scrubbing
and Fuel
Steam Condenser
Reactors

Receiver

C2Cl4

Stabilizer

Liquid
Driers Reboiler

Isomerate
Treated Butanes

Section 15-51 UOP - CONFIDENTIAL Isomerization

 52
Butamer Unit Location in Refinery

Propane
Mixed
Butanes -n-Butane

Alkylation Alkylate
Unit Product

C3/C4 Olefin
Rich Stream

FCC Feed FCC Butamer

FCC Products
(Gasoline, etc.)
 Paraffin isomerization enhance gasoline octane number

n-Pentane i-Pentane
61.7 93.5

OR

n-Hexane 2-MP 3-MP

31.0 74 76

OR

n-Hexane 2,2-DMB 2,3-DMB

31.0 94 105

53
Classical Mechanism of n-Alkane Isomerization
with Change in Branching

54

Chapter 1: Catalysis
A Bi-Functional Pt/Zeolite for n-Hexane Isomerization

Pt
Zeolite- OH

Zeolite - O-

55
Olefins and carbenium ions as key intermediates

II
+

I transport

+
+
Pt H2
Zeolite- OH

Zeolite - O-
branched
olefins

56
A Bi-Functional Mechanism of Pt/Zeolite
Catalyzed n-Hexane Isomerization
+
III
dialkyl PCP
II + proton jump
+

I transport

+
+
Pt H2
hydrogen Zeolite- OH
transfer

IV Zeolite - O-
V branched
olefins

+ +
+

trialkyl PCP III-B

+ proton jump

57
 Butane Isomerization

1. To make isobutane for alkylation or isobutane as feed to dehydro

units
2. Isobutane to dehydro decreasing due to MTBE environmental
problems
3. Pt/AlCl3/Al2O3 commercial catalyst
4. But, zeolite-metal obtained more study

Mechanism is dehydro / isom / hydro

58
 Butane Isomerization by zeolite-metal
Zeolite SiO2/Al2O3 Metal Feed H2/HC WHSV Temp Pressure Conversion Product Notes Reference
ratio (wt%)
AFI Pt (2.0) n-C4 4 1.5 450C 1 atm 15% 42% to iC4 SAPO-5 1
Beta 22 Pt (2.0) n-C4 1 1.6 350C 1 atm 28% 85% to iC4 2
MFI 70 Pt (2.0) n-C4 1 1.6 350C 1 atm 12% 66% to iC4 2
MFI 15 Pd (0.82) n-C4 8.3 1 350- 1 atm 25% 73.3% to iC4 3
430
MOR 10 Pd (0.82) n-C4 8.3 1 350- 1 atm 25% 65.2% to iC4 3
430
MOR 45 Pd (0.82) n-C4 8.3 1 350- 1 atm 25% 71.3% to iC4 3
430
MOR 45 Pd (0.82) n-C4 8.3 1 350- 1 atm 25% 78.2% to iC4 Bound 35/65 3
430 zeolite/bentonite
MOR 19 Pt (0.47) n-C4 5 90 550C 45% 10% iC4, 13% iC4=, 25% 4
1-C4=, 29% t-2-C4=; 18%
c-2-C4=
MOR 10 - n-C4 - 250C 1 atm 5% yield iC4 2% in He 5
MOR 15 - n-C4 - 250C 1 atm 13% yield iC4 2% in He 5
MOR 20 - n-C4 - 250C 1 atm 7% yield iC4 2% in He 5
MOR 20 Pt (2.0) n-C4 4 1.5 350C 1 atm 32% 53% to iC4 1

1
Kumar, N., Villegas, J.I., Salmi, T., Murzin, D.Y., Heikkila, T. Isomerization of n-butane to isobutane over Pt-SAPO-5, SAPO-5, Pt-H-mordenite and H-
mordenite catalysts Catal. Today 2005; 100, 355-61.
2
Villegas, J.I., Kumar, N., Heikkila, T., Lehto, V.-P., Salmi, T., Murzin, D.Y. Isomerization of n-butane to isobutane over Pt-modified beta and ZSM-5 zeolite
catalyst: catalyst deactivation and regeneration Chem. Eng. J. 2006; 120, 83-9.
3
Cañizares, P., Dorado, F., Sanchez, P., Romero, R. Hydroisomerization of n-butane over Pd/HZSM-5 and Pd/Hmordenite with and without binder Stud. Surf.
Sci. Catal. 2002; 142, 707-15.
4
de Agudelo, M.M., Romero, T., Guaregua, J., Gonzalez, M. Catalyst for use in the dehydrogenation and isomerization of paraffins and method US Patent
5880324 (1999).
5
Asuquo, R.A., Eder-Mirth, G., Lercher, J.A. n-butane isomerization over acidic mordenite J. Catal. 1995; 155, 376-82.

Metal loading helps with dehydro step, thereby increasing yield

59
 Light Naphtha Isomerization
1. To isomerize straight run naphtha into high octane gasoline blend
stock
2. Typically Pt/AlCl3/Al2O3 catalyzed, but many zeolites have been
studied

Mechanism is dehydro / isom / hydro

60
 Isomerization of C5/C7 to Increase Octane Number
Compound RON MON (R + M) / 2
n-pentane 62 63 62
i-pentane (2-methylbutane) 92 90 91
neopentane (2,2-dimethylpropane) 85 80 83
n-hexane 25 26 25
methylcyclopentane (MCP) 91 80 86
2-methylpentane (2MC5) 73 73 73
3-methylpentane (3MC5) 74 74 74
2,2-dimethylbutane (22DMC4) 92 93 93
2,3-dimethylbutane (23DMC4) 101 94 98
n-heptane 0 0 0
2-methylhexane (2MC6) 42.4 46.4 44
2,3-dimethylpentane 91.1 88.5 90

2,2,3-trimethylbutane 112 101.3 106

61
 C5/C7 Isom
Zeolite SiO2/Al2O3 Metal Feed H2/HC WHSV Temp Pressure Conversion Product Notes Reference
ratio (wt%)
AEL Pt(0.4) nC6 5 1 300C 1 atm 65 82.5% isom, 17.5% 1
cracking
ATO Pt(0.4) nC6 5 1 325C 1 atm 63 85% isom, 15% cracking 1
BEA 25 Pt (0.5) nC6 4-8 3.7 275C 1 atm 69 25.5mol% 2MC5, 11% cracking 2
16.5%3MC5, 8% products
22DMC4; 8% 23DMC4
FAU/ 10 Pt(0.18 nC5 350C 1 atm 45 35% yield isopentane 2:1 H2/N2 3
EMT saturated in
Pentane @ -3C
FAU 9.5 Pt(0.11) nC5 350C 1 atm 28 25% yield isopentane 2:1 H2/N2 3
saturated in
Pentane @ -3C
FAU 3.4 Pt (1.0) nC7 autoclave 260C 500 psig 77 71% isom, 6% cracking X zeolite 4
nC7/cat=10
FAU 5.8 Pt (0.5) nC7 autoclave 270C 500 psig 84 70% isom, 14% cracking Y zeolite 4
nC7/cat=10
FAU 60 Pt (0.5) nC6 4-8 3.7 275C 1 atm 14.5 7mol% 2MC5, 5%3MC5, 0.3% cracking 2
0.5% 22DMC4; 1% products
23DMC4
FER 55 Pt (0.5) nC6 4-8 3.7 275C 1 atm 4 3mol% 2MC5, 1%3MC5 2
MFI 80 Pt (0.5) nC6 4-8 3.7 275C 1 atm 51 31.5mol% 2MC5, 1.1% cracking 2
16%3MC5, 0.5% products
22DMC4; 1% 23DMC4
MOR 20 Pt (0.5) nC6 4-8 3.7 275C 1 atm 60.5 23.5mol% 2MC5, 8.5% cracking 2
14.5%3MC5, 7.5% products
22DMC4; 7% 23DMC4
MOR 90 Pt (0.5) nC6 4-8 3.7 275C 1 atm 45 22mol% 2MC5, 2% cracking 2
14%3MC5, 1.5% products
22DMC4; 5.5% 23DMC4

1
Sinha, A.K., Sivasanker, S. Hydroisomerization of n-hexane over Pt-SAPO-11 and Pt-SAPO-31 molecular sieves Catal. Today 1999; 49, 293-302. 62
2
Roldan, R., Romero, F.J., Jimenez-Sanchidrian, C., Marinas, J.M., Gomez, J.P. Influence of acidity and pore geometry on the product distribution in the
hydroisomerization of light paraffins on zeolites Appl. Catal. A. 2005; 288, 104-15.
 C10+ Isomerization
▪ Isomerize long chain alkanes to give mono-methylalkanes for
pour point / cloud point reduction
▪ Sometimes called dewaxing
▪ Desire to have shape selective catalysis

Steric repulsion with 10MR rings In 12MR rings dimethyl product

limits dimethyl product not hindered

63
Zeolite Mordenite (MOR)

1-D 12MR

8MR
side pocket

For C10+ Isomerization

64
 C10+ isomerization
Zeolite SiO2/Al2O3 Metal Feed H2/HC LHSV Temp Pressure Yield Product Notes Refere
ratio (wt%) nce
BEA 23 Pt (1.0) n-C10 20 220C 30 bar 57% 39% monobranch, 1
15% multibranch,
3% cracking
FAU 2.8 Pt (0.5) n-C10 100 0.3 250C 0.35MPa 45% Branched C10 2
FAU / 2.8 / 45 Pt (0.5) n-C10 100 0.3 230C 0.35MPa 78% Branched C10 2
TON
MCM-22 34 Pt (1.0) n-C10 20 220C 30 bar 51% 24% monobranch, 1
(MWW) 18% multibranch,
9% cracking
MFI 50 Pt (1.0) n-C10 20 220C 30 bar 52% 30% monobranch, 1
3% multibranch,
19% cracking
MRE 200 Pt(0.6) n-C10 240C 1 atm 81% Iso-C10 ZSM-48 3
MRE 90 Pt(0.6) n-C10 240C 1 atm 84% Iso-C10 ZSM-48 3
MRE 200 Pt(0.6) 600N slack 2500 1 315C 1000psig 370C+ pour point ZSM-48 3
wax a) sccf/bbl
MTT Pt 500N 4000a 1 2300psig 97% Viscosity index SSZ-32X 4
(0.325) hydrocrackate; difference =2 a) sccf/bbl
PP=51C
SFH 110 Pt (0.27) n-C10 100 0.35 220C 1 atm 10% 10% cracking, SSZ-53 5
WH 10% isom
~75% of isom is
2-Me C9
SSZ-25 30 Pt(1.0) Hydrocracked 343C 2150psig Pour point 10ºF, 6
(MWW) North Slope Lube yield 69%
VGO, pour
point 100ºF
TON 45 Pt (0.5) n-C10 100 0.3 220C 0.35MPa 68% Branched C10 2

1
Soualah, A., Lemberton, J.L., Pinard, L., Chater, M., Magnoux, P., Moljord, K. Hydroisomerization of long-chain n-alkanes on bifunctional Pt/zeolite catalysts:
Effect of the zeolite structure on the product selectivity and on the reaction mechanism Appl. Catal. A. 2008; 336, 23-8.
2
Parton, R., Uytterhoeven, L., Martens, J.A., Jacobs, P.A., Froment, G.F. Synergism of ZSM-22 and Y zeolites in the bifunctional conversion of n-alkanes Appl.
Catal. 1991; 76, 131-42.
3
4
Mazzone, D.N., Lai, F.W., Helton, T.E. High activity ZSM-48 and methods for dewaxing World Patent Application 2007/070521. 65
Zones, S.I., Krishna, K. Isomerization process using metal-modified small crystallite MTT molecular sieve US Patent Application 20080083657.
5
Tontisirin, S., and Ernst, S. Zeolite SSZ-53: An extra-large-pore zeolite with interesting catalytic properties Angew. Chem. Int. Ed. 2007; 46, 7304-6.
UOP’s SafeCatTM Process Scheme

66
II. Zeolite-Metal Catalyzed
Light Olefin Isomerization

67
 To understand

1. Olefin isomerization has three possible reactions

- Cis/Trans
- Double Bond
- Skeletal
2. Byproduct reactions include dimerization and cracking
3. Different reactions require different acid strengths
4. Need to select right catalysts with right acid strengths

68
Olefin Reaction Types

-HR > -0.82

cis-trans

-HR > 4.04

positional

-HR > 6.63

skeletal
69
 Byproduct Reactions

Dimerization

Cracking

70
 Equilibrium Composition of Butenes
0.8

0.7

0.6

0.5
Mole fraction

0.4

0.3

0.2

0.1

0
200 300 400 500 600 700 800 900 1000 1100

Temperature, K
1-Butene cis-2-butene trans-2-butene isobutene

71
 Light olefin isomerization

1. Used to convert butenes to isobutene for MTBE application

2. Decreasing in importance due to MTBE issues
3. Isobutene to n-butene for metathesis increasing

72
 Light olefin isom
Zeolite SiO2/Al2O3 Feed SV Temp Pressure Conversion Product Notes Reference
ratio
AEL 2-butenes 75 WHSV 530 15 psia 29.4% 98.3% to 1-butene 1
ATN 1-pentene 1 LHSV 400F 12psig 65.5 67% to t-2-C5=; N2/HC=2.6 2
27% to c-2-C5=; SAPO-39
2% to MC4=
CHA 1-pentene 1 LHSV 450F 12psig 66 58% to t-2-C5=; N2/HC=2.6 2
38% to c-2-C5=; SAPO-34
4% to MC4=
CHA 0.32 2-butenes 60 WH 480 40 psia 27% 96.7% to 1-butene SAPO-34 1
CLI 11.5 1-butene 30,000 GH 400C 1 atm 20 20% to iC4= 10.1kPa butene in He 3
FER 17.5 1-butene 30,000 GH 400C 1 atm 42 83% to iC4= 10.1kPa butene in He 3
FER 2-butenes 1500 WHSV 480 40 psia 34.5% 94.6% to 1-butene commercial catalyst 1
partially Ca exchanged
FER 27 1-butene 20.6 350C 1atm 14.6 19.4% C3H6, 61.2% iC4=, 4
4.5% n-C4H10, 10.7% C5=
FER 17 1-butene 400C 1atm 42 81% to iC4= 10.1kPa butene Error!
Bookmark
not
defined.a
MFI 27 1-butene 30,000 GH 400C 1 atm 88 12% to iC4= 10.1kPa butene in He 3

MFS 49 1-butene 30,000 GH 400C 1 atm 80 20% to iC4= 10.1kPa butene in He 3

MTT 120 1-butene 5.34 WH 420C 1 atm 80.7 21.4% to iC4= 50% butene, 50% N2 5

MTT 120 1-butene 21.4 WH 420C 1 atm 65.7 46.1% to iC4= 50% butene, 50% N2 5

MTT 120 1-butene 85.4 WH 420C 1 atm 45.2 64.6% to iC4= 50% butene, 50% N2 5

STI
[i Brown,14S.H., Vaughn, S.N.,1-butene 400C 1 atm 50 39% to iC4= 10.1kPa butene Error!
] Santiesteban, J.G., Strohmaier, K.G. Method for isomerizing a mixed olefin feedstock to 1-olefin US Patent Application 20030233018. Bookmark
[ii] Miller, S.J. Process for olefin isomerization US Patent 6281404 (2001).
not
[iii] Lee, S.-H., Shin, C.-H., Hong, S.B. Investigations into the origin of the remarkable catalytic performance of aged H-ferrierite for the skeletal isomerization of 1-butene J. Catal. 2004; 223, 200.
defined.a
[iv] Guisnet, M., Andy, P., Gnep, N.S., Benazzi, E., Travers, C. Skeletal isomerization of n-butenes J. Catal. 1996; 158, 551-60.
TON 67 1-butene 30,000 GH 400C 1 atm 58 40% to iC4= 10.1kPa butene in He;
[v] Xu, W.-Q., Yin, Y.-G., Suib, S.L., O’Young, C.-L. Selective conversion of n-butene to isobutylene at extremely high space velocities on ZSM-23 zeolites J. Catal. 1994; 150, 34-45.
ZSM-22
3
73
[vi] Byggningsbacka, R., Kumar, N., Lindfors, L.-E. Kinetic model for skeletal isomerization of n-butene over ZSM-22 Ind. Eng. Chem. Res. 1999; 38, 2896-901.
TON 16
[vii] Byggningsbacka, 1-butene
R., Lindfors, L.-E.,Kumar,30,000 GH activity
N. Catalytic 400C
of ZSM-221 atm 32 skeletal isomerization
zeolites in the 67% toreaction
iC4= of 1-butene Ind. Eng. 10.1kPa
Chem. Res.butene in2990-5.
1997; 36, He; 3
SUZ-4
 Butesom Process Flowscheme

(i-butene)

(N-butenes)

74
 Notice

1. Demand for MTBE (Methyl t-butyl ether) was so large, available

olefin supply from FCC and steam crackers was insufficient.
2. Primary supply of isobutene came from on-purpose production
using isomerization of n-butane to i-butane (Butamer ®) followed by
dehydrogenation to isobutene (C4 Oleflex ®).
3. Consequently, no olefin isomerization units were constructed
because demand of MTBE is decreasing and replaced by alcohol.

75
III. Zeolite-Metal Catalyzed
C8 Aromatics Isomerization

76
Major aromatic petrochemical demand

Million tons/year (2005-2008)

Benzene 40
p-Xylene 26
o-Xylene 5
m-Xylene 0.4

77

77
 p-Xylene Demand Issues
Contributors to Polyester Resin Growth

Average Annual Growth Rates, % 2003-2013

35

30 • Largest consumers of PET are soft

drinks (CSD) and water
25
• Demand Drivers
20 – Substitution for aluminum & glass
– New Applications: milk, sport
15 drinks, beer, food
– Lifestyle changes: mobility,
10
convenience, sanitation
5

0
CSD Water Food Beer Sheet

78
Source: PCI PET Packaging, Resin & Recycling Ltd
 C8-Aromatic Isomerization Process

Goal: maximize production of p-Xylene from a C8

Aromatics feedstock.

- Example C8A Feed ($850/MT (mixed xylenes))

$1000/MT
Para Xylene Meta Xylene Ortho Xylene Ethyl Benzene

22% 48% 22% 8% Bz

79
Contaminants in C8-Aromatic Isom Process

1. Feed to Isomerization systems typically very clean

Removed upstream by hydrotreating, fractionation, etc.
Especially in adsorptive separation systems, which are often
more sensitive to contaminants, especially polar compounds.

2. Basic contaminants may adsorb on acid sites

3. Olefins alkylate with aromatics, forming heavies

4. Olefins polymerize on catalyst surface

80
 Xylene Isomerization

Acid Catalyzed Xylene Isomerization

H+ H+

• Bronsted acid sites in zeolitic catalysts

• 1,2 methyl shift route

• kinetic studies indicate some direct OX => PX

81
Bimolecular Xylene Isomerization

82
Ethylbenzene Isomerization

83
 C8 Naphthene Interconversion

1M1ECP

o-X
trimethyl
EB cyclo-
pentanes

m-X
n-,iPr-CPs
p-X

84
Side Reactions: Transalkylation

H+

H+

85
Side Reactions: Dealk and cracking

H+

C2

M H+

86
 C8Aromatic Isomerization catalyst history

1. Earliest catalysts used amorphous supports (alumina) with

halogen - favored cracking.

2. Due to water sensitivity and corrosion, replaced with large-

pore zeolites - favored bimolecular transalkylation.

3. In both cases, net xylene gains were small.

4. Newer catalysts have smaller pores, optimized acidity - reduce

cracking, transalkylation and larger xylene gain.

87
C8Aromatic Isomerization Zeolites structures

Mordenite

MOR
smaller pore,

MFI, ZSM-5, Silicalite

MFI
88
Optimizing C8Aromatic Isomerization Catalysts

1. Crystallite size
2. Small pore zeolites
3. Control acidity with cations
4. Modify metal amount
5. Combinations of zeolites

89
 Acid & metal Catalyzed Isomerization

H+ H+

Acid Catalyzed Xylene Isomerization

H+ and metal functions

(cyclic olefin intermediates)

Bi-functional Naphthenic Ethylbenzene Isomerization

90
Increasing p-X yields: Isomar

91
 Isomar Process

Metal • Main demand is for pX to

+ H2
EB make polyester resin
mX
• EB, mX oX and pX can be
oX
Acid
brought back to equilibrium
over a suitable catalyst

• EB is harder to isomerize so
Metal
two types of Isomar

+ paraffins due to cracking

– EB dealkylation (to Bz)
pX
– EB isom (to C8 mix)
~24 mol% pX eqbm yield
92
 Isomar Flowscheme

Reactor Light Ends

Net Gas

Product
Separator Net Liquid
Charge
Heater
Deheptanizer

Combined Feed
Exchanger Clay
Treate
Product r
Condenser
To Aromatic
Compressor Fractionation Unit

Feed from Makeup H2

Parex Unit

93