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The SHELL Olefin Higher Process

SHOP

SHOP
The Oligomerization of ethylene to terminal olefins.

C4 - C8
Ni catalyst

40%
(ready market)

C2H4

C10 - C16 40% C18 + 20%

The 3 fractions are separated by distillation. The lower and higher olefins are recycled to give more C10-C16 products.

The C10-C16 fraction is used to make other useful products e.g.


CH3(CH2)7-11-CH=CH2
1) Isomerization 2) Hydroformylation 3) Hydrogenation

CH3(CH2)8-13-CH2OH
Detergent alcohols

SHOP

Catalyst

C4 - C8

40%
(ready market)

SHOP
Ph Ni Ph3P O HPh2 P CH CPh
Initiation Labile

Ni catalyst

C2H4

C10 - C16 40% C18 + 20%

From alkene, exchanges with Ph from complex

H Ni Ph3P

HPh2 P CH O CPh +

Ph

Side product

Catalyst Precursor

Active catalyst

Can be represented as:

H Ni

Vacant site

SHOP
Vacant site Alkene occupies here

Active catalyst

H Ni

O
H H C H C H Ni O
Vacant site regenerated and another alkene molecule binds, then Inserts between Ni-C bond

H Ni

Insertion of alkene between Ni-H bond

SHOP

Ni(longer chain)

The SHELL HIGHER OLEFIN PROCESS (SHOP) CHEM3162 Learning Objectives


Draw a catalytic cycle for the oligomerization of ethylene to terminal olefins and apply skills for describing a catalytic cycle to this cycle. Demonstrate by means of exemplified equations, how the various processes of oligomerization, isomerization, metathesis, hydroformylation* and hydrogenation are utilized by the SHOP process to produce detergent alcohols. (R)

SHOP - Optimization
C4 - C8
Ni catalyst

40%
(ready market)

C2H4

C10 - C16 40% C18 + 20%

CH3(CH2)1-5 CH=CH2
CH3(CH2)13-17 CH=CH2

Isomerization & Methathesis

CH3(CH2)7-11-CH=CH2

Class Activity
Show how H3C(CH2)16-CH2-CH=CH2 may be converted to H3C(CH2)8-CH2=CH2

Hydroformylation

Hydroformylation
The reaction between an alkene, carbon monoxide and hydrogen, to form an aldehyde containing one more carbon atoms than the original alkene.

Hydroformylation

Aldehydes produced are usually reduced to alcohols which are used as solvents, plasticizers and in the synthesis of detergents. Co and Rh catalysts are usually employed.

Rh/phosphine catalyst is more active e.g. with RhH(CO)(PPh3)3, hydroformylation occurs at moderate temperatures and pressures (100oC, 1 atm). c.f. Co catalyst at 150oC, 250 atm.

Hydroformylation - Catalyst
Dicobaltoctacarbonyl combines with H2 at high pressure to yield the known tetracarbonylcobalthydride:

Co2(CO)8 + H2

2 [HCo(CO)4]

It is proposed that this complex loses CO to produce the coordinatively unsaturated [HCo(CO)3]:

[HCo(CO)4]

[HCo(CO)3] + CO

O HCCH2CH2CH3

HCo(CO)4 a

- CO + CO

HCo(CO)3 b H2CCHCH3

H2

Coordination of alkene gives c.

Attack by H2 on e Co(CO)4 (or acidic [HCo(CO)4]) gives aldehyde and O C regenerates [HCo(CO)3].

HCo(CO)3 c e H2C CHCH3

CH2CH2CH3 d
- CO

CO insertion gives e.
CO

Co(CO)4 CH2CH2CH3

+ CO

Hydride migration gives d.

Electron counts: a = 18; b= 16: c= 18; d= 18; e= 18.

Discussion Question
Kinetic studies indicate that the hydroformylation reaction rate is enhanced by an increase in H2 pressure and inhibited by an increase in CO pressure. How is the mechanism in the cycle consistent with these observations? Model Response
Co2(CO)8 + H2
O HCCH2CH2CH3 HCo(CO)4 a

2 [HCo(CO)4]
- CO + CO

HCo(CO)3 b H2CCHCH3

H2

From these two equations, H2 pressure leads to the conversion of Co2(CO)8 to the more active catalyst, HCo(CO)4, which is necessary to begin the proposed cycle. However, CO is required for the reaction stoichiometry.

Co(CO)4 O C e

HCo(CO)3 c H2C CHCH3

CH2CH2CH3 d
- CO

CO pressure leads to conversion of the 16e tricarbonyl species to the stable tetracarbonyl species, thus preventing the cycle from going forward.

Co(CO)4
CO

+ CO

CH2CH2CH3

However, CO is required for the reaction stoichiometry.

Hydroformylation:
A significant portion of branched aldehydes are also formed:

The linear aldehydes are preferred e.g. to make linear alcohols for biodegradable detergents. Addition of an alkyl phosphine (e.g. PBu3) gives higher selectivity for the linear product. It is proposed that bulky phosphines disfavors formation of sterically crowded, 2o alkyl groups.

The End