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EP-4399263-B1 - HEAVY OLIGOMER COMPOSITIONS OF A SELECTIVE 1-HEXENE AND 1-OCTENE CATALYST

EP4399263B1EP 4399263 B1EP4399263 B1EP 4399263B1EP-4399263-B1

Inventors

  • SYDORA, ORSON, L.

Dates

Publication Date
20260506
Application Date
20220901

Claims (15)

  1. A composition comprising at least 55 wt. % C 10 mono-olefins, the C 10 mono-olefins comprising: i) from 11 to 45 wt. % 1-decene; ii) at least 0.5 wt. % 2-butyl-1-hexene; iii) at least 1 wt. % 3-propyl-1-heptene; iv) from 0.5 to 12 wt. % 4-ethyl-1-octene; v) at least 4 wt. % 4-penten-1-yl-cyclopentane; and vi) from 2 to 40 wt. % 5-methyl-1-nonene.
  2. The composition of claim 1, wherein the C 10 mono-olefins comprise from 12 to 42 wt. %, from 12 to 30 wt. %, from 15 to 38 wt. %, from 17 to 35 wt. %, or from 20 to 30 wt. % 1-decene; and/or wherein the C 10 mono-olefins comprise from 0.5 to 10 wt. %, from 0.75 to 7 wt. %, from 0.75 to 5 wt. %, from 1 to 5 wt. %, or from 1 to 4 wt. % 4-ethyl-1-octene; and/or wherein the C 10 mono-olefins comprise a weight ratio of 4-penten-1-yl-cyclopentane to 1-decene from 0:1:1 to 3:1, from 0.2:1 to 2:1, from 0.2:1 to 1.2:1, from 0.3:1 to 1.5:1, from 0.3:1 to 1:1, or from 0.4:1 to 0.9:1.
  3. The composition of claim 1 or 2, wherein the composition comprises: (a) from 55 to 98 wt. %, from 70 to 95 wt. %, from 85 to 95 wt. %, from 55 to 85 wt. %, from 60 to 92 wt. %, or from 65 to 85 wt. % C 10 mono-olefins; and from 1 to 20 wt. %, from 2 to 18 wt. %, from 3 to 15 wt. %, from 5 to 13 wt. %, or from 7 to 13 wt. % pentylcyclopentane; and/or (b) at least 90 wt. %, at least 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt. % C 10 hydrocarbons.
  4. The composition of any one of claims 1-3, wherein the C 10 mono-olefins comprise: from 0.5 to 12 wt. %, from 0.75 to 12 wt. %, from 1 to 8 wt. %, or from 2 to 6 wt. % 2-butyl-1-hexene; from 1 to 27 wt. %, from 3 to 25 wt. %, from 5 to 22 wt. %, or from 7 to 17 wt. % 3-propyl-1-heptene; from 4 to 40 wt. %, from 4 to 37 wt. %, from 5 to 34 wt. %, from 7 to 30 wt. %, or from 10 to 25 wt. % 4-penten-1-yl-cyclopentane; and from 2 to 38 wt. %, from 4 to 40 wt. %, from 4 to 33 wt. %, from 6 to 33 wt. %, or from 10 to 28 wt. % 5-methyl-1-nonene.
  5. A C 10-14 composition comprising: (a) from 25 to 47 wt. %, from 30 to 42 wt. %, or from 33 to 39 wt. % of the composition comprising at least 55 wt. % C 10 mono-olefins of any one of claims 1-4; (b) from 30 to 55 wt. %, from 35 to 47 wt. %, or from 38 to 44 wt. % of a composition comprising at least 60 wt. % C 12 mono-olefins, the C 12 mono-olefins comprising: i) at least 8 wt. % 1-dodecene; and ii) at least 0.5 wt. % 6-hepten-1-yl-cyclopentane; wherein the composition comprises heptylcyclopentane and n-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from 0:3:1 to 8:1; and (c) from 12 to 35 wt. %, from 15 to 27 wt. %, or from 18 to 24 wt. % of a composition comprising at least 60 wt. % C 14 mono-olefins, the C 14 mono-olefins comprising: i) at least 12 wt. % 1-tetradecene; and ii) at least 0.5 wt. % 8-nonen-1-yl-cyclopentane; wherein the composition comprises a total of from 3 to 30 wt. % of n-tetradecane and nonylcyclopentane.
  6. The composition of claim 5, wherein the C 10-14 composition comprises from 60 to 99 wt. %, from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. % C 10-14 mono-olefins; and/or wherein the C 10-14 composition comprises at least 90 wt. %, at least 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt. % C 10-14 hydrocarbons.
  7. A C 10-18 composition comprising: (a) from 15 to 40 wt. %, from 19 to 35 wt. %, or from 22 to 30 wt. % of the composition comprising at least 55 wt. % C 10 mono-olefins of any one of claims 1-4; (b) from 19 to 40 wt. %, from 23 to 36 wt. %, or from 27 to 33 wt. % of a composition comprising at least 60 wt. % C 12 mono-olefins, the C 12 mono-olefins comprising: i) at least 8 wt. % 1-dodecene; and ii) at least 0.5 wt. % 6-hepten-1-yl-cyclopentane; wherein the composition comprises heptylcyclopentane and n-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from 0:3:1 to 8:1; (c) from 7 to 25 wt. %, from 10 to 22 wt. %, or from 13 to 19 wt. % of a composition comprising at least 60 wt. % C 14 mono-olefins, the C 14 mono-olefins comprising: i) at least 12 wt. % 1-tetradecene; and ii) at least 0.5 wt. % 8-nonen-1-yl-cyclopentane; wherein the composition comprises a total of from 3 to 30 wt. % of n-tetradecane and nonylcyclopentane; and (d) at least 18 wt. %, at least 22 wt. %, at least 25 wt. %, from 18 to 40 wt. %, from 22 to 36 wt. %, or from 25 to 33 wt. % C 16-18 hydrocarbons.
  8. The composition of claim 7, wherein the C 10-18 composition comprises from 60 to 99 wt. %, from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. % C 10-18 mono-olefins; and/or wherein the C 10-18 composition comprises at least 90 wt. %, at least 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt. % C 10-18 hydrocarbons.
  9. A C 10-12 composition comprising: (a) from 30 to 60 wt. %, from 35 to 55 wt. %, or from 40 to 50 wt. % of the composition comprising at least 55 wt. % C 10 mono-olefins of any one of claims 1-4; and (b) from 38 to 68 wt. %, from 43 to 63 wt. %, or from 48 to 58 wt. % of a composition comprising at least 60 wt. % C 12 mono-olefins, the C 12 mono-olefins comprising: i) at least 8 wt. % 1-dodecene; and ii) at least 0.5 wt. % 6-hepten-1-yl-cyclopentane; wherein the composition comprises heptylcyclopentane and n-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from 0:3:1 to 8:1.
  10. The composition of claim 9, wherein the C 10-12 composition comprises from 60 to 99 wt. %, from 70 to 98 wt. %, from 75 to 95 wt. %, or from 80 to 95 wt. % C 10-12 mono-olefins, and/or wherein the C 10-12 composition comprises at least 90 wt. %, at least 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt. % C 10-12 hydrocarbons.
  11. The composition of claims 5, 7 or 9, wherein the C 12 mono-olefins comprise: (a) from 8 to 40 wt. %, from 9 to 35 wt. %, from 10 to 33 wt. %, from 12 to 29 wt. %, or from 13 to 23 wt. % 1-dodecene; and from 0.5 to 40 wt. %, from 1 to 35 wt. %, from 2 to 40 wt. %, from 2 to 32 wt. %, from 3 to 20 wt. %, or from 4 to 15 wt. % 6-hepten-1-yl-cyclopentane; and/or (b) from 22 to 90 wt. %, from 29 to 88 wt. %, from 60 to 86 wt. %, from 60 to 80 wt. %, from 35 to 85 wt. %, from 33 to 50 wt. %, or from 33 to 40 wt. % non-cyclic branched C 12 mono-olefins; and the non-cyclic branched C 12 mono-olefins comprise 5-methyl-1-undecene, 7-methyl-1-undecene, 4-ethyl-1-decene, 6-ethyl-1-decene, 3-propyl-1-nonene, 5-propyl-1-nonene, 2-butyl-1-octene, 3-butyl-1-octene, 4-butyl-1-octene, or any combination thereof; and/or (c) a weight ratio of 1-dodecene to 6-hepten-1-yl-cyclopentane from 0:4:1 to 12:1, from 0.6 to 10:1, from 0.9:1 to 6:1, or from 1.5:1 to 4:1.
  12. The composition of claims 5, 7 or 9, wherein the composition comprising at least 60 wt. % C 12 mono-olefins comprises: (a) from 60 to 99 wt. %, from 62 to 97 wt. %, from 70 to 98 wt. %, or from 75 to 95 wt. % C 12 mono-olefins; and the weight ratio of heptylcyclopentane to n-dodecane is from 0:3:1 to 6:1, from 0.3:1 to 3:1, from 0.5:1 to 5:1, from 0.5:1 to 2:1, from 0.8:1 to 8:1, from 0.8:1 to 4:1, or from 0.8:1 to 1.8:1; and/or (b) from 0.25 to 25 wt. %, from 0.5 to 23 wt. %, from 1 to 23 wt. %, from 3 to 20 wt. %, from 1 to 18 wt. %, or from 3 to 10 wt. % heptylcyclopentane; and from 0.25 to 18 wt. %, from 0.5 to 16 wt. %, from 0.5 to 10 wt. %, from 0.75 to 8 wt. %, from 1 to 12 wt. %, from 8 to 14 wt. %, or from 0.75 to 10 wt. % n-dodecane; and/or (c) at least 90 wt. %, at least 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt. % C 12 hydrocarbons.
  13. The composition of claim 5 or 7, wherein the composition comprising at least 60 wt. % C 14 mono-olefins comprises a total of from 3 to 28 wt. %, from 3 to 26 wt. %, from 4 to 28 wt. %, from 5 to 25 wt. %, or from 6 to 20 wt. % n-tetradecane and nonylcyclopentane.
  14. The composition of claim 5 or 7, wherein the C 14 mono-olefins comprise: (a) from 12 to 50 wt. %, from 14 to 45 wt. %, from 15 to 40 wt. %, from 16 to 38 wt. %, from 18 to 36 wt. %, or from 20 to 35 wt. % 1-tetradecene; and from 0.5 to 30 wt. %, from 0.75 to 28 wt. %, from 1.5 to 26 wt. %, from 2 to 24 wt. %, or from 5 to 15 wt. % 8-nonen-1-yl-cyclopentane; and/or (b) from 25 to 85 wt. %, from 30 to 80 wt. %, from 45 to 80 wt. %, from 55 to 70 wt. %, from 36 to 78 wt. %, or from 50 to 75 wt. % non-cyclic branched C 14 mono-olefins; and the non-cyclic branched C 14 mono-olefins comprise 7-methyl-1-tridecene, 6-ethyl-1-dodecene, 5-propyl-1-undecene, 4-butyl-1-decene, 3-pentyl-1-nonene, or any combination thereof.
  15. The composition of claim 5 or 7, wherein the composition comprising at least 60 wt. % C 14 mono-olefins comprises: (a) from 60 to 99 wt. %, from 68 to 96 wt. %, from 75 to 98 wt. %, or from 75 to 95 wt. % C 14 mono-olefins; and a weight ratio of 1-tetradecene to 8-nonen-1-yl-cyclopentane is from 0:5:1 to 15:1, from 0.75:1 to 12:1, from 1:1 to 10:1, from 1.5:1 to 9:1, or from 2:1 to 8:1; and/or (b) wherein the composition comprises at least 90 wt. %, at least 95 wt. %, at least 96 wt. %, at least 97 wt. %, or at least 98 wt. % C 14 hydrocarbons.

Description

REFERENCE TO RELATED APPLICATION This application is being filed as a PCT International Patent Application and claims the benefit of U.S. Provisional Patent Application No. 63/241,121, filed on September 7, 2021. FIELD OF THE INVENTION The present disclosure relates generally to C10+ olefins, and more particularly, relates to linear, branched, and cyclic C10-C14 olefins produced from ethylene oligomerization processes. BACKGROUND OF THE INVENTION Many hydrocarbons heavier than 1-octene are produced in ethylene oligomerization processes. However, isolation and identification of various mono-olefins and hydrocarbons in the C10-C14 range are difficult. It would be beneficial to determine the compositional breakdown of C10-C14 mono-olefins and hydrocarbons in the oligomer product resulting from ethylene oligomerization processes. Accordingly, it is to these ends that the present invention is generally directed. WO 2017/011127 A1 describes a composition comprising at least 76 mol% C10 mono-olefins. SUMMARY OF THE INVENTION The present invention provides a composition comprising at least 55 wt. % C10 mono-olefins as set out in claim 1. This summary is provided to introduce a selection of concepts in a simplified form that are further described herein. This summary is not intended to identify required or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter. Olefin compositions are described herein. A first composition consistent with this disclosure comprises at least 55 wt. % C10 mono-olefins. In the first composition, the C10 mono-olefins comprise from 11 to 45 wt. % 1-decene, at least 0.5 wt. % 2-butyl-1-hexene, at least 1 wt. % 3-propyl-1-heptene, from 0.5 to 12 wt. % 4-ethyl-1-octene, at least 4 wt. % 4-penten-1-yl-cyclopentane, and from 2 to 40 wt. % 5-methyl-1-nonene. As one of skill in the art would readily recognize, the total of these and other components does not exceed 100 wt. %. Also described herein is a second composition which can comprise at least 60 wt. % C12 mono-olefins. In the second composition, the C12 mono-olefins can comprise at least 8 wt. % 1-dodecene and at least 0.5 wt. % 6-hepten-1-yl-cyclopentane, and the composition can comprise heptylcyclopentane and n-dodecane at a weight ratio of heptylcyclopentane to n-dodecane from 0:3:1 to 8: 1. Also described herein is a third composition which can comprise at least 60 wt. % C14 mono-olefins. In the third composition, the C14 mono-olefins can comprise at least 12 wt. % 1-tetradecene and at least 0.5 wt. % 8-nonen-1-yl-cyclopentane, and the composition can comprise a total of from 3 to 30 wt. % of n-tetradecane and nonylcyclopentane. Also described herein are C10-C12 compositions, which can comprise generally from 30 to 60 wt. % of the first composition and from 38 to 68 wt. % of the second composition, and C12-C14 compositions, which can comprise generally from 45 to 85 wt. % of the second composition and from 20 to 50 wt. % of the third composition. Similarly, a C10-C14 composition consistent with this disclosure often can contain from 25 to 47 wt. % of the first composition, from 30 to 55 wt. % of the second composition, and from 12 to 35 wt. % of the third composition. In like manner, a C10-C18 composition provided herein can comprise from 15 to 40 wt. % of the first composition, from 19 to 40 wt. % of the second composition, from 7 to 25 wt. % of the third composition, and from 18 to 40 wt. % of C16-C18 hydrocarbons. Both the foregoing summary and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations can be provided in addition to those set forth herein. For example, certain aspects can be directed to various feature combinations and subcombinations described in the detailed description. DEFINITIONS To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997), can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document mentioned herein conflicts with the definition or usage provided herein, the definition or usage provided herein controls. Herein, features of the subject matter can be described such that, within particular aspects, a combination of different features can be envisioned. For each and every aspect and/or feature disclosed herein, all combinations that do not detrimentally affect the designs, composit