1. DIMERIZATION & OILGOMERIZATION

2. Homogeneous Catalysis- Major Industrial Processes
Processes/Products
Terephthalic acid & Poly(Ethylene Terephthalate)
Acetic acid & acetyl chemicals
Aldehydes and alcohols- Hydroformylation
Adiponitrile- Hydrocyanation
Detergent-range alkenes- SHOP- Oligomerization
Alpha Olefins (C4- C20)- Dimerization & Oligomerization
Total fine chemicals manufacture
Olefins Polymerization (60% uses Ziegler-Natta) 9 7 6 1 4
< 1 60
Production, MTA
Oligomerization & Dimerization – Key homogeneous processes

3. Dimerization & Oligomerization Processes
Dimerization of ethylene to Butene-1- Co-monomer in LLDPE- IFP & SABIC processes
Dimerization of propylene- Methyl pentenes & Hexenes- Gasoline additives- DIMERSOL- IFP Sumitomo & BP processes
Dimerization of Butadiene- 1,5 Cyclo-octadiene-Cyclooctene- (ROP)- Vestenamer-Hulls process
Trimerization of Butadiene-Cyclododecatriene- (ROP)-
Vestamid-Hulls process
Butadiene+ Ethylene co-polymerization-EPDM rubber-
DuPont-Process
Oligomerization of ethylene to Linear Alpha Olefins- LAO
- Chevron-Phillips,(Gulf Oil)-GULFTENE, Ineos (Ethyl), Idemitsu, Conaco, Shell (SHOP), SABIC (-SABLIN)
Basis for the production of wide range of useful olefins & monomers

4. Alpha Olefins-Applications
C4 to C6        Co-monomers in polyethylene (4-12%)
C8 to C10      Plasticizer alcohols C10 to C12    Synthetic lubricants
C12 to C16    Detergents - Linear Alkyl Benzene (LAB)
Alpha Olefin Sulphonates (LAO)
C16 to C18     Lube oils, Surfactants C20 to C30+  Oil field Chemicals, Wax replacements

6. Alpha Olefins via Ziegler Process
100 C, 10MPa
300 C, 1MPa
Gulf Oil (1966) / Chevron (1983) Process
One step process with simultaneous chain growth & elimination
At 200 C & 25 Mpa ethylene pressure, with heptane as solvent
0.4 wt% AlET3 w.r.t ethylene
Ethyl’s process is an improved version of Gulf’s

7. Processes for  - Olefins - Comparison of product quality
Processes → Products↓
Wax Cracking
Chevron
Ethyl
SHOP
-Olefins
83-89
91-97
63-98
96-98
Branched olefins
3-12
2-8
2-29
1-3
Paraffins
1-2
1.4
0.1
Dienes
3-6 -
Mono olefins
92-95 99
>99
99.9

8. Shell Higher Olefins Process (SHOP)
Involves four processes
Oligomerization of ethylene to C4-C20+ α- olefins 80 to 120 °C and 70 to 140 bar (7 to 14 MPa) with a nickel phsophine complex (C6H5)2P(CH2)2COONi- Homogeneous
Isomerization of α-olefins to internal olefins- Heterogeneous
Metathesis of C20+olefins with C4-C8 olefins- Heterogeneous
Isomerization, hydroformylation & hydrogenation to α-alcohols- Homogeneous

9. Shell’s SHOP Process-Stepwise conversions
Step. 1- Oligomerization
H2C=CH → H (CH2-CH2)n-CH=CH2 n= 1 to 19
Ni complex
Step.2- Fractionation of alpha-olefins
C10-C14 - Olefins
C4-C10 - Olefins
C16-C40 - Olefins
Step.3 – Hydroformylation of C10-C14 Olefins
C10-C14 Olefins →C11-C15 alcohols
H2+CO
CH3(CH2)7-CH=CH →CH3(CH2)7-CH2- CH2 –CHO
Co(Co) ↓ H2
CH3(CH2)7-CH2- CH2 –CH2- OH

10. Shell’s SHOP Process-Stepwise Conversions
Step.4 – Isomerization
Catalyst Na/K on Al2O3 or Mgo
C4-C10 - Olefins → C4-C10 Internal olefins
C16 –C40 - Olefins → C16 –C40 Internal olefins
CH3-CH2-CH=CH → CH3-CH=CH-CH3
CH3 (CH2)17 -CH=CH → CH3-(CH2)8-CH=CH-(CH2)8-CH3
Step.5- Metathesis of C4-C10and C16-C40 internal olefins
Catalyst Mo/W/Re on Al2O3
CH3-CH=CH-CH3 + CH3-(CH2)8-CH=CH-(CH2)8-CH3
(i-C4) ↓ (iC20)
2 CH3-CH=CH –(CH2)8-CH3
Step.6 – Fractionation of internal olefins
C10-C14 Internal Olefins
C4-C10 Internal Olefins
C16-C40 Internal Olefins
Separation of C10-C14 olefins & Hydroformylation to alcohols

11. Shell’s SHOP Process- Stepwise conversions
Step.7 – Hydroformylation of C10-C14 Olefins
C10-C14 Olefins →C11-C15 alcohols
H2+CO
CH3(CH2)7-CH=CH →CH3(CH2)7-CH2- CH2 –CHO
Co(Co) ↓ H2
CH3(CH2)7-CH2- CH2 –CH2- OH
Step.8 – Repeat of steps 5,6 & 7 to exhaustion

13. Shell’s SHOP Process- Block flow diagram

14. Flow scheme of Shell’s SHOP Process

15. Ethylene Oligomerization- Ni Complex catalyst

16. Oligomerization-Addition of ethylene

18. Dimerization of Propylene & Butadiene, Trimerization of Butadiene &
Co-polymerization of Butadiene & ethylene to yield EPDM rubber

19. Conversions with butadiene

20. Olefin metathesis-Process steps
Formation of metal alkylidene complexes
Step.2
Formation of metallocyclobutanes
Step.3
Opening of metallocyclobutane to form products
Majority of metathesis reactions involve heterogeneous
catalysis, Mo/W/Re supported on alumina
Homogeneous systems are also known

21. Olefin Metathesis- Mechanism

22. Alkene Metathesis-General cycle

23. Different types of Olefin metathesis reactions