1. Selective Oligomerization of Ethylene by Homogenous Catalysts
PETROTECH, 2010
New Delhi
Selective Oligomerization of Ethylene by Homogenous Catalysts
Reliance Technology Group, Reliance Industries Limited
Vadodara Manufacturing Division
Vadodara

2. Linear Alpha Olefins

3. Applications of Alpha Olefins
* Data Ref.2005

4. Major producers of C4-C18 range LAO Shell Oligomerization / Metathesis, SHOP BP-Phillips Cr /TEAL/donor catalyst IFP α-Select , Ziegler chain growth SABIC- Linde α-SABLIN UOP/Union Carbide Linear Sasol produces α-olefins from coal-based synthesis gas using F-T process
1 –C Wt %
1 –C Wt %
1 –C Wt %
1 –C Wt %
C12+
Desired
C4-C10
K = C n+2 / C n
(~ ) 

5. Typical -Olefin Distribution
Desired Maxima
( ) Albemarle () Chevron (_ _ _) Idemitsu and Shell ( )

6. Product distribution of full range LAO producers - mass (%)

7. Processes for Alpha Olefins
LAO Trimerization Tetramerization
1 –C %
1–C %
1–C %
1 –C %
Poly < %
1–C < %
1–C %
1–C %
1–C < %
Poly %
1–C %
1–C %
1–C %
1 –C %
Poly < %
Proven Technology Commercialized Not yet commercialized
Early 2005
The process is commercially viable
when the overall C6 + C8 yields = 90 %

8. Comparison of Product Distribution (Wt%)
Process †
Gulf/Chevron Amoco
Shell
Sablin
RIL *
α-Olefin
Heavy
Light
Typical
Medium C4
13.9
22.9 12 24
40.2 30 C6
14.6
20.6 13
27.1
28.1
33.5 C8
13.7
16.2
13.2 14
18.5
C10
12.3
11.2
8.4
9.1
C12 10
8.9
8.3 5
8.6
C14
8.2
6.2 8
5.8
2.3
C16
4.3 7
4.8
1.4
C18
5.2
2.9 6
0.5
C20
14.9
5.3 20
2.8
0.1
Co-monomers
for PE
Heavy AO
* Lab Process (Zr-Cat.)
US (2005)

9. Typical LAO process & reactor
LAO Reactor

10. Examples of Oligomerization Catalyst Systems
SHOP, Shell LAO
PPh3
Phillips Hexene-1
BP Hexene-1 +
Sasol - Hexene-1 +
Octene-1
Sasol - Hexene-1 +

11. Examples of Oligomerization Catalysts
Alpha Olefins
HDPE
VERSIPOL® (DuPont)
M = Fe, Co
L = N,N,N tridentate
Alpha Olefins
Idemitsu , Sabic-Linde
Zr(OR)4 / ZrCl4
TiCl4 +
Mitsui - Hexene-1

12. Phillips Trimerization catalyst & process (CPC)
+ DEAC, 1150C, 100 bar C2 , toluene
+ decenes
Knudsen et.al US , (1999)

13. SASOL Tetramerization Catalyst & Process
[Cr] activator productivity PE C C MAO (g/g Cr) (%) (%) (%) _______________________________________________________ eq
Sel
1-C4 = 0.2; C10 + = ~ 13.1
Internal Hexenes ~ %
By products : Methyl / Methyelene cyclopentane

14. Metallacyclic Mechanism for ethylene oligomerization
Butene-1
Dimerization
Trimerization

15. Metal Hydride Mechanism of Oligomerization
M-H + C2H4
M-C2H5
M-H + 1-C8H16
M-C8H17
M-H + 1-C10H20
M-C10H21
M-H + 1-C6H12
M-C6H13
M-H + 1-C4H8
M-C4H9
C2H4
Cossee-Arlman

16. Present Work
 Synthesis of Novel Ligands  Complexation with Cr(III) salts (in-situ)  Evaluation of catalysts for selective ethylene oligomerization

17. Synthesis of Schiff Base Ligands

18. Tridentate [OSN], [PNO] ligands
L L L3
L L L6

19. High Pressure Ethylene Oligomerization System
4 x 100 mL High Pressure Parallel Parr reactors (4593) with gas pipette dosing arrangement connected to 4871 process controllers.

20. Ethylene Oligomerization with Schiff Base ligands
Run
Ligand
Oligomer % PE
Productivity
(g/moleCr)
Distribution of α-olefins, wt%
1-C C C C C12+ 1 L1 93 7
7140
21.0
48.0
20.6
6.5
4.0 2 L2 70 30
4620
24.8
38.4
18.1
9.2
9.5 3 L3 87 13
3360
13.8
29.9
19.5
12.3
24.4 4 L4 42 58
1680 -
19.2
15.3
65.5 5 L5 48 52
1974
12.1
23.8
18.8
13.3
31.8 6 L6 80 20
2016
0.48
7.1
34.4
56.9
1.1 8* 91 9
8960
12.8
23.3
19.1
31.6
Reaction conditions :
Cr(acac)3-Lig-MAO (Cr/Al=500); 70 0C, PC2H4 =300 psi , toluene, 1hr, 600 RPM

21. Synthesis of Imidazolyl Ligands
Characterization : Micro analysis, IR, NMR, Mass

22. Multidentate Imidazolyl Ligands

23. Ethylene Oligomerization with Cr-Imidazolyl Ligand
Run
Ligand
% C2H4 conversion
Productivi ty, gm/g.Cr
Distribution of α-olefins, wt%
1-C C C C C12 + PE % 1 L7
92.6
7987
11.2
27.4 22
14.6
24.7
11.5 2 L8
93.1
8097
18.5
30.7
21.5
12.6
16.7
12.3 3 L9
78.1
7636
21.4
29.7
19.4
11.4
18.1 4
L10
78.6
7099
14.8
28.6
24.8
13.9
17.8
Reaction conditions :
Cr(acac)3-Lig-MAO (Cr/Al = 250 ) ; 45 0C, PC2H4 =400 psi , toluene, 1hr, 600 RPM

24. SUMMARY
 New Ligands based on S, N ,O, P synthesized and characterized
 Complexation with Cr-salt leads to active catalyst system for
ethylene oligomerization
 Optimization of process can offer a unique catalyst for tailoring
the desired range of -olefin for end use