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WO 2013/089962 Al 20 June 2013 (20.06.2013) W P O P C T

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WO 2013/089962 Al 20 June 2013 (20.06.2013) W P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2013/089962 Al 20 June 2013 (20.06.2013) W P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every B01J 31/04 (2006.01) B01J 31/18 (2006.01) kind of national protection available): AE, AG, AL, AM, B01J 31/14 (2006.01) B01J 31/22 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (21) Number: International Application DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, PCT/US20 12/065285 HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, (22) International Filing Date: KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, 15 November 2012 (15.1 1.2012) ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, (25) Filing Language: English RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, (26) Publication Language: English TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 13/323,328 12 December 201 1 (12. 12.201 1) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): CHEV¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, RON PHILLIPS CHEMICAL COMPANY LP UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, [US/US]; 10001 Six Pines Drive, The Woodlands, Texas TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, 77380 (US). EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, (72) Inventors; and TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, (71) Applicants (for US only): SYDORA, Orson [CA/US]; ML, MR, NE, SN, TD, TG). 25 18 Oakdale Street, Houston, Texas 77004 (US). KNUD- SEN, Ronald [US/US]; 1412 Meadow Lane, Bartlesville, Published: Oklahoma 74006 (US). BARALT, Eduardo [US/US]; — with international search report (Art. 21(3)) 3615 Spruce Park Circle, Kingwood, Texas 77345 (US). (74) Agent: CONLEY ROSE, P.C.; 5601 Granite Parkway, Suite 750, Piano, TX 75024-6608 (US). 00 o (54) Title: PREPARATION OF AN OLEFIN OLIGOMERIZATION CATALYST ¾ (57) 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 an- hydrous metathesis. In another aspect, the catalyst system comprise a chromium carboxylate that is prepared by anhydrous metathes- is and a metal pyrrolide compound. The catalyst systems imparts improved performance and/or reduced catalyst system cost to an ol- efin trimerization process. PREPARATION OF AN OLEFIN OLIGOMERIZ ATION CATALYST TECHNICAL FIELD OF THE INVENTION [0001] This disclosure relates to a catalyst system, methods for preparing the catalyst system, and methods for using the catalyst system for preparing a trimerization product. BACKGROUND OF THE INVENTION [0002] The trimerization of ethylene to produce l-hexene constitutes a commercially significant process for the selective preparation of this alpha olefin, which in turn is useful for preparing a range of polyolefms, usually as a comonomer with ethylene. One widely employed ethylene trimerization catalyst system comprises a chromium carboxylate, a pyrrole compound, and a metal aikyl. For example, one ethylene trimerization catalyst system comprises a tris(2-ethylhexanoate) chromium(rn), 2,5-dimethylpyrrole, triethylaluminum, and d ethy a u inum chloride. [ 003] Typically, any method of preparing an active catalyst system can present challenges with respect to the chromium carboxylate utilized in the ethylene trimerization catalyst system. Batch-to- batch variations in the quality of commercial el romium( ) 2-ethylhexanoate, and the attendant inconsistency in catalytic system performance, have can have significant impacts upon the ethylene trimerization catalyst system productivity and selectivity. Therefore, it would be useful to discover and develop ne catalyst systems, ne methods for preparing the catalyst systems, and new methods for using the catalyst systems for preparing a trimerization product that might provide greater efficiency and cost effectiveness. In one aspect, new catalyst systems and methods for preparing the catalyst systems are needed that might reduce the amount of expensive activators in a catalyst system , or that might lower the cost or increase the efficiency of preparing chromium compounds used in the catalyst system. SUMMARY OF THE INVENTION [0004] This disclosure provides for a composition, a . process for producing a catalyst system, and/or processes for trimerizing olefins utilizing a catalyst system. [0005] n an aspect, the composition can comprise a cl romium T ) C3-C25 carboxylate composition that can be characterized as having a Br pellet infrared spectrum with a ym (C0 2) infrared absorbance peak within 1 cm of the ym (C0 2) infrared peak and having an infrared absorbance peak height ratio of a sym (C0 2) infrared absorbance peak at 516 ± 15 cm to infrared absorbance peak located at 700 ± 50 cm 1 greater t an or equal to 3:1 . In another aspect, the composition can comprise a chromium(IIl) C3-C25 carboxylate composition that can be characterized as having a goodness of fit test value, R2, of at least 0.6 when comparing high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition to calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(llI) acetate over an r range from 1.3 Angstroms to 4 Angstroms. In yet another aspect, the composition can comprise a chromium(lll) C3- C 2 carboxylate composition that can be produced by a process comprising contacting under substantially anhydrous and substantially acid-free conditions 1) a chromium(III) precursor having a formula C L where each X independently is a halide, each L independently is a C2-C10 ether, a C2 Cio thioether, a C2-C5 nitrile, a . C - amine, or a C3-C30 phosphine, or any combination thereof, and ranges from 0 to 7, 2) a Group 1 or Group 2 metal C3-C25 carboxylate, and 3) a first solvent to form a chromium(TIl) carboxylate. The catalyst system can further comprise a pyrrole compound, a metal hydrocarbyl compound, and optionally, a halogen containing compound. [Θ 6] In an aspect, the composition can be utilized as a catalyst system. In an aspect, a process to prepare the catalyst system can comprise contacting a chromium(III) C3-C25 carboxylate composition, a pyrrole compound, a metal hydrocarbyl compound, and optionally, a halogen containing compound. In some embodiments, the process to prepare the catalyst system can further comprise contacting two or more of the chromium(III) C3-C25 carboxylate composition, the pyrrole compound, the metal hydrocarbyl compound, and the optional halogen containing compound in the presence of an unsaturated organic compound. n embodiment, the unsaturated organic compound can comprise a C to C2 aliphatic hydrocarbon olefin, a C to C2oarene, or any combination thereof. In some embodiments, the process to prepare the catalyst system can comprise contacting the chromiurn(III) carboxylate composition, the pyrrole compound, and the metal hydrocarbyl compound simultaneously n other embodiments, the process to prepare the catalyst system can comprise contacting the pyrrole compound and the metal hydrocarbyl compound (all or a portion thereof) to form a pyrrole/metal hydrocarbyl compound mixture prior to contacting the pyrrole compound with the chromium ) carboxylate composition. [0007] In an embodiment wherein the catalyst system comprises a halogen containing compound, the halogen containing compound can be, comprise, or consist essentially of, inorganic metal halide, a . hydrocarbyl metal halide, a halogenated hydrocarbon, or any combination thereof. In some embodiments, wherein the catalyst system comprises a halogen containing compound, a composition containing the halogen containing compound can comprise, or consist essentially of, (i) an inorganic metal halide, (ii) a hydrocarbyl metal halide, (iii) a mixture of an inorganic metal halide and a . non- halide metal hydrocarbyl compound, or (iv) a mixture of a hydrocarbyl metal halide and a non-haiide metal hydrocarbyl compound. In an embodiment where the catalyst system comprises a metal halide, the process to prepare a catalyst system can comprise contacting the chromium(IIT) carboxylate composition with at least one of the pyrrole compound or the metal halide prior to contacting the chromium(lll) carboxylate composition with the metal hydrocarbyl compound; alternatively, the method can comprise contacting the metal hydrocarbyl compound with at least one of the pyrrole compound or the metal halide prior to contacting the chromium(lii) carboxylate composition with the metal hydrocarbyl compound; or alternatively, the method can comprise contacting the chromium(III) carboxylate composition, the pyrrole compound, or a composition comprising the chromium(III) carboxylate composition and the pyrrole compound with a non-halide metal hydrocarbyl compound prior to contacting the composition containing the metal halide. In another embodiment where the catalyst system comprises a halogen containing compound, the chromium(IH) C3-C25 carboxylate composition, the pyrrole compound, or a composition comprising the chromiuni(III) C3-C25 carboxylate composition and the pyrrole compound can be contacted with a non-halide metal hydrocarbyl compound prior to contacting a composition containing the halogen containing compound; or alternatively, the chromium(ITl) C3-C25 carboxylate composition and the pyrrole compound are contacted prior to contacting the pyrrole compound or the chromium(III) C3-C25 carboxylate composition with the composition containing the halogen containing compound.
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