The document discusses the alkylation process in refining, focusing on the use of zeolite-based solid acid catalysts for alkylation of isobutane and butenes to produce high-octane gasoline. It covers various catalyst technologies, environmental benefits, and optimal reaction conditions, highlighting the efficiency and advantages of solid acid catalysis in this process. Additionally, it details available solid catalyst technologies, including different zeolites and their specific applications and performance metrics.

1. The Use of zeolite base SOLID ACID
CATALYST FOR ALKYLATION OF
ISOBUTANE/BUTENE
INDIAN INSTITUTE OF PETROLEUM
DEHRADUN

2. Table of Contents

Introduction

Importance of Alkylation solid acid catalyst
process

Use of Catalysts in Alkylation process

Available solid technology

Future of solid acid catalyzed alkylation

3. Table of Contents

Introduction

Importance of Alkylation solid acid catalyst
process

Use of Catalysts in Alkylation process

Available solid technology

Future of solid acid catalyzed alkylation

4. Introduction
What is Alkylation
Alkylation in refining is the chemical reaction of a low
molecular weight olefin with an isoparaffin to form a liquid
product alkylate, that has a high octane number and is used
to improve the anti knocking properties of the gasoline.
iso-C4 + n-C4= iso-C8 iso-C9+
iso-C5-7
iso-butane n-butene iso-octane
Alkylation Multiple Alkylation
Cracking
Reaction mechanism

7. Introduction
Gasoline alkylation chemistry
Reaction of C3-C5 olefin with isobutane to product primarily
gasoline boiling range C7-C9 iso-paraffins.
Primary reaction
C
C
C
C
C
C
C
C
C
C
C
C C
C
C
C
+
=
-
-
-
-
-
-
- -
-
-
-
-
Temp. 75-140o
C
Pre. 20-40 Bar
TMP
Secondary reaction yield
DMHs
C3- C5s
C9+

8. Introduction
Role of Alkylates
Alkylates are ideal gasoline blending compounds with
following advantages
No olefins
No Aromatics compounds
No Sulphur
Low reid vapor pressure
High octane number (both motor & research)

9. Table of Contents

Introduction

Importance of Alkylation solid acid catalyst
process

Use of Catalysts in Alkylation process

Available solid technology

Future of solid acid catalyzed alkylation

10. Importance of Alkylation solid
acid catalyst process
Environmental friendly process
High octane number of obtain product
Feed easily obtain
Low catalyst consumption

11. Reactors used in Alkylation
process
Continuous flow stirred tank reactor
Up flow fixed reactor with controlled pressure,
Temperature &WHSV
Multiple fixed bad reactor
High pressure fixed bad reactor
Supercritical fluid reactor
Low & High pressure reactor
Slurry reactor

12. Conclusion of solid acid catalyst
alkylation reaction
Conversion of olefin 80-100%
High percentage of TMP in alkylates
Alkylates yield obtain 35-57%
High octane number

13. catalyst characteristics
Si/Al Ratio 1.0-14.0
Acidity
pore size
Shape selectivity
Condition of solid acid
catalyst alkylation reaction
Temperature 75-140o
C
Pressure 20-40 Bar
OWHSV 0.1-.08 h-1
Paraffin/ olefin Ratio 5-30

14. Table of Contents

Introduction

Importance of Alkylation solid acid catalyst
process

Use of Catalysts in Alkylation process

Available solid technology

Future of solid acid catalyzed alkylation

15. Use of Catalysts in Alkylation
process
Liquid Acid Catalysts
Solid Acid Catalyst
HCl - Alcl3
H2SO4
HF
Zeolite
X Zeolite
Y Zeolite
Beta Zeolite
ZSM 5
Sulfated Zirconia and related materials

16. Table of Contents

Introduction

Importance of Alkylation solid acid catalyst
process

Use of Catalysts in Alkylation process

Available solid technology

Future of solid acid catalyzed alkylation

17. Available solid technology
UOP Alkylene process-HF catalyst
Lummus Alkyclean process-zeolite USY
Exelus (ExSact) process-zeolite
Haldor Topsoe (FBA) process
Lurgi (Eurofuel) process-zeolite

18. Available solid technology
Lummus Alkyclean process-zeolite USY
Feed=Isoparaffins/
olefin ( 8-15/1 )
Temp=50-90 0
C
Pres.=
RON of alkylates=95-
96 %
Yields=
Catalyst life= 10 hr.

19. Available solid technology
UOP Alkylene process-HF catalyst

20. Alkylation of isobutane with alkenes

23. S.no catalyst Si/Al Condition Conversion in (in %) Alk.yeald
(in %)
Reactor
Temp (o
C) P (Bar) WSHV/OSV P/O
1. .4Pt. LaY Zeo. 2.82 75o
C 20 .5h-1 9 80-85 continuous flow stirred tank reactor
2. H Beta Zeo.
H LaY Zeo.
HB13.9
HY 4.1
140o
C 8.0 MPa 0.33 h-1 107 HB 95
HY 97.3
53.3
48.3
Up flow fixed reac. with controlled
P,T & WHSV
3. LaX Zeo.
LaX
Lax 1.2
LaY 2.5
40-130oC
75o
C
32 Osv .17-.80
18 h-1
6.7
6.7 100% (11h) 60%(selc.)
Stirred tank reactor
4. LaX Zeo. 1.2 75o
C 20 .2 h-1 10 99% (12.9h) CSTR
5. Y Zeo. 80-100o
C 20atm .75 h-1 12
6. Zeolite 50-80o
C 21 Other condition are similar to those of HF & H2SO4 alkylation process Multiple fixed bad reactor
7. NaX Zeo.
NaY Zeo.
1.1
2.4
75o
C 20 .2 h-1 10
8. Usy Zeo. 2.5-30
USY-2.5
USY-6
USY-15
USY-30
80o
C
“
“
“
“
300psig
“
“
“
“
.5 h-1
“
“
“
“
20
“
“
“
“
90-92.4
91.5
91.6
92.4
90.8
(5min.)
49.5
47.7
45.0
42.0
High pressure fixed bad reactor
9. LaX Zeo.
LaY Zeo.
1.1
2.4
75o
C 20 .2 h-1 10 100% for 7hY Zeo. 13h X Zeo. Stirred tank reactor
10 .25Pt/USY Zeo. 59.7%Si
39.5%Al
90o
C
60o
C
“
“
“
42
“
“
“
“
.1 h-1
0.09 h-1
“
0.21 h-1
“
25.4
25.1
25.1
24.7 24.7
100 %
100 %
100 %
100%
88 (1.7h)
89 (2.4h)
109( 1.7h) 102
(2.4h)
Supercritical fluid reactor
11. Beta Zeo.
Y Zeo.
13
3
75o
C
75o
C
40
40
11 h-1
11 h-1
20,5
20,5
100%
100%
90
81 Slurry reactor
12. USY Zeo. Y-2.5
Y-6
Y-30
Y-40
80oC 300psig .1 h-1 98 100%
100%
99.44%
98.51%
54.66
48.32
43.64
39.98
Low T & high P reactor
Compression in catalysts (Zeolite), conditions, and results of alkylation (isobutene/butene)