Preparation of an olefin oligomerization catalyst

Patent metadata

Field	Value
Publication number	US-9956548-B2
Application number	US-201113323328-A
Country	US
Kind code	B2
Filing date	Dec 12, 2011
Priority date	Dec 12, 2011
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

This disclosure provides for new catalyst systems and new methods for preparing and using the catalyst systems for generating a trimerization product. In an aspect, the new catalyst systems comprise a chromium carboxylate that is prepared by anhydrous metathesis. In another aspect, the catalyst system comprise a chromium carboxylate that is prepared by anhydrous metathesis and a metal pyrrolide compound. The catalyst systems imparts improved performance and/or reduced catalyst system cost to an olefin trimerization process.

First claim

We claim:

1. A composition comprising:
a) a chromium(III) C 3 -C 25 carboxylate composition
i) having a KBr pellet infrared spectrum with a υ asym (CO 2 ) infrared absorbance peak within 110 cm −1 of the υ sym (CO 2 ) infrared peak and having an infrared absorbance peak height ratio of a υ asym (CO 2 ) infrared absorbance peak at 1516±15 cm −1 to infrared absorbance peak located at 700±50 cm −1 greater than or equal to 3:1,
ii) having a goodness of fit test value, R 2 , of at least 0.6 when comparing high-energy X-ray diffraction g(r) data points of the chromium(III) C 3 -C 25 carboxylate composition to calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate over an r range from 1.3 Angstroms to 4 Angstroms, wherein atomic coordinates of the theoretical model of mononuclear chromium(III) acetate have been optimized to the following values

Atom
X
Y
Z

Cr
0
0
0

C1
1.843475
−0.40852
−1.43058

O1
0.738585
−1.038$81
−1.567619

O2
1.90289
0.461636
−0.494039

C2
3.026757
−0.697968
−2.303537

H1
3.586188
0.221029
−2.49448

H2
2.70492
−1.158746
−3.239287

H3
3.689716
−1.395002
−1.777323

O3
−0.772555
1.631901
−0.909192

O4
0.481341
1.511899
1.249048

C4.
−1.400219
3.584765
0.389991

C3
−0.872192
2.190556
0.236797

H4
−1.932477
3.891686
−0.511821

H5
−2.054935
3.640368
1.263653

H6
0.55862
4.266381
0.559197

O5
0.288007
−1.521043
1.29563

O6
−1.664703
−1.059059
0.43961

C5
−0.959016
−1.79628
1.210803

C6
−1.568434
−2.912588
2.003767

H7
−2.492313
−3.252317
1.531746

H8
−1.803373
−2.543365
3.009177

H9
−0.856348
−3.735188
2.102561

and wherein R 2 =1−(SS err /SS tot ) where S err is a calculated high energy X-ray diffraction g(r) data points for a theoretical model of the mononuclear chromium carboxylate and S tot is a summation of the squares of the differences between a high energy X-ray diffraction g(r) data points of the chromium carboxylate composition and a mean of the high energy X-ray diffraction g(r) data points of the chromium carboxylate composition, or
iii) produced by a process comprising
contacting under substantially anhydrous and substantially acid-free conditions
1) a chromium(III) precursor having a formula CrX 3 L l where each X independently is a halide, each L independently is a C 2 -C 10 ether, a C 2 -C 10 thioether, a C 2 -C 5 nitrile, a C 1 -C 30 amine, or a C 3 -C 30 phosphine, or any combination thereof, and l ranges from 0 to 7,
2) a Group 1 or Group 2 metal C 3 -C 25 carboxylate, and
3) a first solvent,
wherein the chromium(III) C 3 -C 25 carboxylate composition produced by the process has a KBr pellet infrared spectrum having a υ asym (CO 2 ) infrared absorbance peak at 1516±15 cm −1 and the υ asym (CO 2 ) infrared absorbance peak is within 110 cm −1 of the υ sym (CO 2 ) infrared peak;

b) a pyrrole compound; and
c) a metal hydrocarbyl compound.

2. The composition of claim 1 , wherein the C 3 -C 25 carboxylate has a formula ( − O 2 C) r R 1c where r is an integer from 1 to 4 and R 1c is a hydrocarbon group or a substituted hydrocarbon group.

3. The composition of claim 1 , wherein the C 3 -C 25 carboxylate has a formula − O 2 CR 2c where R 2c is a hydrocarbyl group or a substituted hydrocarbyl group.

4. The composition of claim 1 , wherein the C 3 -C 25 carboxylate comprises a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, a dodecanoate, a tridecanoate, a tetradecanoate, a pentadecanoate, a hexadecanoate, a heptadecanoate, an octadecanoate, or any combination thereof.

5. The composition of claim 1 , wherein the C 3 -C 25 carboxylate comprises 2-ethylhexanoate.

6. The composition of claim 1 , wherein the pyrrole compound has formula P1

where R 2p , R 3p , R 4p , and R 5p independently are hydrogen atoms or C 1 -C 30 organyl groups.

7. The composition of claim 1 ,

Assignees

• Sydora Orson L
• Knudsen Ronald D
• Baralt Eduardo J
• Chevron Phillips Chemical Co Lp

Inventors

• Sydora Orson L
• Knudsen Ronald D
• Baralt Eduardo J

Classifications

• B01J2531/62

  Chromium · CPC title

• B01J31/2239

  Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands · CPC title

• B01J31/04 Primary

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• B01J31/2226

  Anionic ligands, i.e. the overall ligand carries at least one formal negative charge · CPC title