View
228
Download
0
Category
Preview:
DESCRIPTION
Entry Barriers to Commercial Alpha-Olefin Production Demand for various AO fractions Captive requirements of AO producers Feedstock cost and availability Development of new end uses Product quality requirements Catalyst limitations Sell everything Use what you don’t sell Build it in the right place Work with customers Meet or exceed market requirements Understand the chemistry
Citation preview
New Catalyst Development for the Production of Linear Alpha-Olefins
Acknowledgments• SPE/FlexPack organizers• CPChem • Prof. Mike Carney (U. Wisconsin – Eau Claire), Prof. Jason Halfen, Ben Schmiege, Deidra Gerlach, Tony Buerger• Technicians Ray Rios, Eric Fernandez
29 February 2012
NN
DRn
R'
RFe
ClCl
D = N, S, P
Brooke L. SmallSenior Research ChemistChevron Phillips Chemical Company LPKingwood, TXsmallbl@cpchem.com
Entry Barriers to Commercial Alpha-Olefin Production
• Demand for various AO fractions
• Captive requirements of AO producers
• Feedstock cost and availability
• Development of new end uses
• Product quality requirements
• Catalyst limitations
• Sell everything
• Use what you don’t sell
• Build it in the right place
• Work with customers
• Meet or exceed market requirements
• Understand the chemistry
Projected Growth Rates and Typical Product Distributions
4 6 8 10 12 14 16 18 20 22 240
5
10
15
20
25Typical Distributions for CPChem, Shell, and Ineos
CPChemShellIneos
Carbon Number
Mas
s Pe
rcen
t
• Growth rates for comonomer (C4 - C8) higher than other olefins• Smaller full range producers such as Sabic, Idemitsu• Selective and non-ethylene based processes not shown• Distribution flexibility tied to distillation• CPChem, Shell governed by K value (K = mol Cn+2/mol Cn)• Source: Lappin, Alpha Olefins Applications Handbook, 1989.
Catalyst Limitations
M-H M 1,2
2,1
M1,2
M
M2,1
M
M
-Helim.
-Helim.
-Helim.
M
-Helim.
isom.
isom.
isom.
• Process design must consider specific traits of each catalyst system• Catalyst distribution must be tailored to business need• Intrinsic catalyst limitations must be considered (e.g. Ni isomerization, Zr PE
formation, etc.)
Selective Alpha-Olefin Production – Another Alternative to Supply/Demand Balancing
1-Butene
• Axens (IFP) Alphabutol® processo ~30 plants worldwideo 700 kmt/yr of 1-buteneo Ti catalyst used to dimerize ethyleneo Primarily used in remote locations
• Raffinate distillationo ExxonMobil and Texas Petrochemicalso 450 million lbs/yr
• Much of the growth in the C4 comonomer demand can be met by selective production.
Selective Alpha-Olefin Production – 1-Hexene and 1-Octene
• Cr-pyrrole system for ethylene trimerization – CPChem first to commercialize this system (see, e.g., US 5,198,563; 7,384,886)– Daqing and Mitsui also have announced commercial intentions
• Sasol – 1-hexene and 1-octene via Fischer-Tropsch extraction– 1-octene via hydroformylation/dehydration of 1-heptene– 1/hexene/1-octene plant announced (ethylene tetramerization)
• Dow produces 1-octene from butadiene (Pd catalyst)
Catalysts for 1-Hexene and 1-Octene
P
N
P
RRR
R
H
S
N
SRR
H
R
NPP OMe
MeO
OMe
MeOP
P
P
RRR
R
Ar
NH
CPChem (commercial)
Ineos
ExxonMobilN
X
X= PR2, OR, SR
Rn
R
NPP
Sasol(1-hexene/1-octene)
AmocoBP
N
N
HN
HN
N
Morgan et al, J. Organomet. Chem. (2004) 3641.McGuinness, Chem. Rev. (2011) 2321.Agapie, Coord. Chem. Rev. (2011) 861.
TiR2
Hessen
R'''
P
N
NR
R' R''
R'''
CPChem (1-hexene/1-octene) P
N P
HNSABIC/Linde
Full Range Commercial Catalysts
• 1966 – Gulf Chevron CPChem alpha-olefin process• 1970 – Ethyl Albemarle Amoco BP Ineos AO process
– Both processes based on triethylaluminum, TEA– CPChem distribution is Schulz-Flory; Ineos distribution is stoichiometric (i.e. no chain
termination)
• 1983 –Shell Higher Olefins Process (SHOP)
• 1989 – Idemitsu – ZrCl4 based system with Al-alkyl cocatalyst– SABIC also uses Zr
ONi
P
O
R
Pendant Donor Modified a-Diimine Complexes
• Develop a hybrid between the A and B• Create a favorable steric environment• Develop a fairly rigid backbone• Create new IP for alpha-olefin production• Product distribution flexibility• Lower pressure process than triethylaluminum (TEA)
N N
XX
RRNi
Br
NNN Fe
ClCl RRBr
NN
D Rn
R'
RFe
Cl Cl
D = N, S, PA B
Structural “Knobs”
Y Y
O N
NH2L
MCl2
Y Y
N NM
LCl
Cl
Rn Rn
Four “handles” on the pre-catalyst complexes offer remarkable diversity of structures.
O OO O Rn
NH2 numerous options for steric tuningFe most active
NNH2 P
NH2S
NH2
Rn
Rn
Rn
Structural Diversification
SCl NH2 S NH2 S NH2
SO NH2 S NH2
P NH2P NH2P NH2P NH2
O N FeCl2
Rn
N N
Fe Rn+
- H2O PCl Cl
PHR'n
P NH2
R'n
n-BuOH
R'n
R'n
P NH2
R'n
R'nR'n
R'n
O N SFeCl2
Rn
N N
Fe Rn
+- H2O
SCl Cl
NH2
R'n
R'n
SHR'n
+ ClNH2
.HClK2CO3 S NH2
R'nCH2Cl2
CyH
NONO NO NO NO Br NO
Catalyst Studies
• Steric changes on N-aryl affect distribution• Steric changes on P affect distribution and activity• NNS complexes tend toward higher K values• Modular approach provides significant “K-tunability”• Extraordinary product quality (> 99% 1-octene in C8 fraction)
NN
P FeCl
Cl
NN
P FeCl
Cl
NN
P FeCl
Cl
NN
P FeCl
Cl
NN
P FeCl
Cl
NN
P FeCl
Cl
NN
P FeCl
Cl
NNFe
ClCl
S
NNFe
ClCl
S
NN
P FeCl
Cl
NN
P FeCl
Cl
K = mol (Cn+2)/mol (Cn)
0.4 0.5 0.6butene 0.7 0.8 0.9
A Practical Consideration of K Tunability
4 6 8 10 12 14 16 18 200
5
10
15
20
25
30
35
40
45
Catalyst Blending Effects
K = 0.4
Blend of 0.4 and 0.7 (K varies)
K = 0.55
K = 0.7
Carbon Number
Mas
s %
Conclusions
• Commercialization of alpha-olefin technology presents significant entry barriers
• NNP and NNS Fe systems provide an attractive full range catalyst opportunity:– K tunability– Outstanding product purity – Easily accessible portfolio of complexes
• Our publications– B. L. Small,* R. Rios, E. R. Fernandez, M. J. Carney Organometallics 2007, 26, 1744.– B. L. Small,* R. Rios, E. R. Fernandez, D. L. Gerlach, J. A. Halfen, M. J. Carney Organometallics
2010, 29, 6723.– B. M. Schmiege, M. J. Carney,* B. L. Small, D. L. Gerlach, J. A. Halfen, Dalton Trans. 2007, 2547. – US Patents 7,977,269; 7,728,161; 7,728,160; 7,727,926; 7,271,121; 7,268,096; 7,129,304
Recommended