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