Download SHOP Shell Higher Olefins Process

SHOP
hell Higher
igher Olefins
lefins Process
rocess
Shell
By Kamila Stefańska, 2009.
Basic info on the SHOP:
•Based on the homogenous catalysis
•Comprises 3 steps:
- oligomerization
- isomerization
- methathesis
•Used for production of linear a – olefins
and internal olefins
•Designed by the Royal Dutch Shell
• Oligomerization – The process of
converting a monomer or a mixture of
monomers into an oligomer (consists of
limitted nb of monomers)
•Isomerization – rearrangement reaction
that occurs when compounds with the
same formula exhibit different structures
(e.g. 1 – butene and 2 – butene)
•Metathesis – catalytic reaction in
which alkenes are converted into new
products by breaking - up and
reformation of C-C double bonds.
Linear a – olefins (LAO)
•Olefins = Alekenes
CnH2n
• Linear Alpha Olefins (LAO) or
Normal Alpha Olefins (NAO)
• Internal olefins
Overview of SHOP
Oligomerization of ethylene
• Catalyst : Ni complex
(usually includes a phosphorous – oxygen chelate
and organic part)
Examples:
• catalyst is dissolved in 1,4 - butanediol (polar)
Catalytic cycle for the SHOP
oligomerization step
Products of oligomerization:
Linear even numbered a – olefins
ranging from C4 to C40
They are separated by the means of
distillation :
• C10 – C14
a – olefins
• C4 – C8
a – olefins
• C16+
a – olefins
Linear hydroformylation of
C10 – C14 a - olefins
C10 – C14 a – olefins  C11 – C15 alcohols
Isomerization of C4 – C8 and
C16 – C40 a - olefins
•heterogenous catalyst:
Na/K on Al2O3 or a MgO in the liquid phase
C4 – C8 a – olefins  C4 – C8 internal olefins
C16 – C40 a – olefins  C16 – C40 internal
olefins
Metathesis of C4 – C8 and
C16 – C40 internal olefins
• Short and long chain internal olefins
disproportionate
CH3CH=CHCH3 + CH3(CH2)8CH=CH(CH2)8CH3
C4 Internal olefin
C20 internal olefin
2 CH3CH=CH(CH2)8CH3
C12 internal olefin
* Noble Prize 2005 for Development of the
Olefin Metathesis Method in Organic Synthesis
Catalytic cycle of
alkene metathesis
Fractionation of internal olefins
• C10 – C14 internal olefins
• C4
– C8 internal olefins
• C16 –
C40 internal olefins
C4 – C8 and C16 – C40
are again subjected to metathesis
Linear hydroformylation of
C10 – C14 internal olefins
CH3(CH2)8CH=CH-CH3 
C12 internal olefin
CH3(CH2)8CH2CH2CH2CHO 
CH3(CH2)11CH2CH2OH
C14 alcohol
Flexibility of SHOP process
•At each step we can decide to stop further „processing” of
olefins, adjusting production to present needs.
Example Applications of linear olefins
• Drilling liquid – C14 – C18 a - olefins
Suitable physical
properties:
High purity
 Viscosity
Pour point
Flash point
•Drilling muds – C15 – C18 internal olefins
• Monomers – C4 – C10 a – olefins
For the production of polymers
•Plasticizers – C6 – C10 a – olefins
for plastics, cement, concrete, wallboard and clay
bodies.
•Biodegradable detergents – C12 – C20 a – olefins
And many others...
Other ways for
a – olefins production
THE OLDEST:
- Thermal cracking of waxes (1970’)
- Chlorination
PROCESSES THAT USE
OLIGOMERIZATION:
1. Giving wide range of alpha olefin:
-
ethyl corporation, Ineos, Gulf, SHOP
2. Giving only kind of olefin:
- Pilips, IFP
References:
1. D. D. Eley, Bruce C. Gates, Werner O. Haag, Helmut Knözinger; Advances in Catalysis
2. Harold A. Wittcoff, Bryan G. Reuben, Jeffrey S. Plotkin; Industrial organic chemicals
3. Handzlik J. ; Metateza olefin
4. G. Rothenberg; Catalysis: concepts and green applications
5. Catalysis from A to Z; red.: Cornils
6. http://scienzechimiche.unipr.it/didattica/att/bfe8.9521.file.pdf
J.C. Mol „Industrial application of olefin metathesis”
7.http://chem.ncue.edu.tw/leehm/teaching/92.1/92.1.PG1%20organometallic%20chemistry/C
h7.doc
8. http:// www.shell.com