Sustainable pyrolysis method and its products

Abstract

The present invention relates to a process comprising the steps of: (a) providing a renewable cracker feed obtained by fractionating an isomeric hydrocarbon composition having an i-paraffin content of 85.0 wt.-% or more and a carbon number range of 20-32 into at least a low boiling fraction and a high boiling fraction, and providing at least a portion of the low boiling fraction or at least a portion of the high boiling fraction as renewable cracker feed, (b) pyrolyzing the renewable cracker feed in a pyrolysis furnace, optionally with co-feeds and / or additives, and (c) subjecting the pyrolysis furnace effluent of step (b) to a separation process to provide at least a light olefin fraction. The present invention further relates to a polymer composition obtained by using the olefins in the light olefin fraction.

Description

[Technical field]

[0001] The present invention relates to processes involving pyrolysis, to products that may be obtained by the use of such processes, and to cracker feed that may be used in such processes. [Background technology]

[0002] Pyrolysis, e.g. steam cracking, is a well-known and established route to upgrading conventional (mineral oil-based) materials. In recent years, pyrolysis of bio-based materials has been investigated, but usually attempts have been made to achieve direct decomposition of a bio-based feed (usually with a high oxygen content) or to mimic a conventional (fossil) feed.

[0003] The prior art discloses several cracking methods using hydrocarbon feeds, most of which use exclusively fossil feedstocks. A cracking method using at least partially renewable hydrocarbon feedstocks is disclosed in US Pat. No. 5,399,663. Furthermore, US Pat. No. 5,499,663 discloses a method comprising pyrolyzing a feedstock derived from a renewable feedstock and containing at least 60% by weight of isoparaffins. US Pat. No. 5,499,663 discloses a composition comprising a paraffin fraction obtained from a biological feedstock. US Pat. No. 5,499,663 discloses a method for producing renewable fuels.

[0004] High-value chemicals produced by pyrolysis processes (such as steam cracking) include ethylene, propylene, butadiene, olefinic C4, benzene, xylene, and toluene. Of these high-value chemicals, propylene and butadiene in particular are of interest as feedstocks for certain chemicals and polymers.

[0005] C4 monoolefins are also valuable products, but additional refining steps may be required to extract chemical and polymer grades of each component. Aromatics are less important because of other production routes, such as reforming of fossil naphtha. Additionally, in the steam cracking process, benzene can be enriched in the pyrolysis gasoline fraction of the cracking effluent, which is usually utilized as a fuel. Since there are strict restrictions on the amount of benzene allowed in such fuel products (due to its carcinogenic effects), it may even become an unwanted by-product that needs to be removed.

[0006] In order to introduce biomolecules into the petrochemical value chain, and in view of the above, it would be useful to employ a process that maximizes the yield of light olefins while limiting the production of aromatics, especially benzene. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2020 / 201614 [Patent Document 2] International Publication No. 2020 / 128156 [Patent Document 3] International Publication No. 2015 / 101837 [Patent Document 4] International Publication No. 2021 / 094655 Summary of the Invention

[0008] The present invention has been made in view of the above problems, and it is an object of the present invention to provide an improved process involving the pyrolysis of renewable cracker feed, and products obtained therefrom, and their use and further processing.

[0009] The problem underlying the present invention is solved by the subject matter set forth in the independent claims. Further advantageous developments are set forth in the dependent claims.

[0010] In summary, the present invention relates to one or more of the following items:

[0011] 1. (a) providing a renewable cracker feed obtained by fractionating an isomeric hydrocarbon composition having an i-paraffin content of 85.0 wt.-% or more and a carbon number range of 20 to 32 into at least a low boiling fraction and a high boiling fraction, and providing at least a portion of the low boiling fraction or at least a portion of the high boiling fraction as the renewable cracker feed; (b) pyrolyzing the renewable cracker feed, optionally together with co-feeds and / or additives, in a pyrolysis furnace; and (c) subjecting the pyrolysis furnace effluent of step (b) to a separation process to provide at least a light olefin fraction. The method includes:

[0012] 2. The method according to item 1, wherein the isomeric hydrocarbon composition has a c_50 value in the range of 14.0 to 22.0, preferably 14.0 to 20.0, or 1.5.0 to 20.0.

[0013] 3. The method according to item 2, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have an i-paraffin content of 92.0 wt.-% or more, preferably 93.0 wt.-% or more, 94.0 wt.-% or more, or 95.0 wt.-% or more.

[0014] 4. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a ratio of i-paraffins with more than three branches (IP3+) to total i-paraffins (iP) (iP3+ / iP) of 0.164 or less, preferably 0.160 or less, 0.155 or less, 0.150 or less.

[0015] 5. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction have, independently of each other, a total content of i-paraffins with more than three branches (iP3+) relative to total paraffins of 10.50 wt.-% or more, for example 10.50 to 16.00, 11.00 to 15.50, 11.00 to 15.50, 11.00 to 15.00, or 1.2.00 to 15.00.

[0016] 6. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a cloud point of -10°C or less, preferably -15°C or less, or -20°C or less.

[0017] 7. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%.

[0018] 8. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a naphthene content of 0.2 to 10.0 wt.-%, for example 0.5 to 8.0 wt.-%, 0.5 to 6.0 wt.-%, 0.6 to 5.8 wt.-%, or 0.8 to 5.6 wt.-%.

[0019] 9. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction have an olefin content which, independently of each other, is 0.50 wt.-% or less, preferably 0.40 wt.-% or less, 0.30 wt.-% or less, 0.25 wt.-% or less, 0.20 wt.-% or less, 0.15 wt.-% or less, 0.1.2 wt.-% or less, 0.10 wt.-% or less, 0.07 wt.-% or less, or 0.05 wt.-% or less.

[0020] 10. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a combined olefin and naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%.

[0021] 11. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction have a combined olefin and naphthene content, independently of each other, of 0.1 wt.-% to 8.0 wt.-%, e.g. 0.1 wt.-% to 6.5 wt.-%, 0.1 wt.-% to 6.0 wt.-%, 0.2 wt.-% to 5.5 wt.-%, 0.5 wt.-% to 5.5 wt.-%, 0.5 wt.-% to 5.0 wt.-%, 0.8 wt.-% to 5.0 wt.-%, 0.9 wt.-% to 5.0 wt.-%, 1.0 wt.-% to 5.0 wt.-%, 1.1 wt.-% to 5.0 wt.-%, or 1.2 wt.-% to 5.0 wt.-%.

[0022] 12. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction have, independently of each other, an aromatics content of 0.80 wt.-% or less, preferably 0.70 wt.-% or less, 0.60 wt.-% or less, 0.50 wt.-% or less, 0.40 wt.-% or less, 0.35 wt.-% or less, 0.30 wt.-% or less, 0.25 wt.-% or less, 0.20 wt.-% or less, or 0.15 wt.-% or less.

[0023] 13. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction have, independently of each other, a combined content of olefins, aromatics and naphthenes of 0.1 wt.-% to 10.0 wt.-%, preferably 0.1 wt.-% to 8.0 wt.-%, 0.1 wt.-% to 6.5 wt.-%, 0.2 wt.-% to 6.0 wt.-%, 0.5 wt.-% to 5.5 wt.-%, 0.5 wt.-% to 5.0 wt.-%, 0.8 wt.-% to 5.0 wt.-%, 0.9 wt.-% to 5.0 wt.-%, 1.0 wt.-% to 5.0 wt.-%, 1.1 wt.-% to 5.0 wt.-%, or 1.2 wt.-% to 5.0 wt.-%.

[0024] 14. The method of any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have an oxygenate content of 1000 wt.-ppm or less, preferably 700 wt.-ppm or less, 500 wt.-ppm or less, 300 wt.-ppm or less, 100 wt.-ppm or less, 80 wt.-ppm or less, 60 wt.-ppm or less, 50 wt.-ppm or less, 40 wt.-ppm or less, or 30 wt.-ppm or less.

[0025] 15. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have modal carbon numbers in the range of from 11 to 21, preferably from 14 to 20, or from 16 to 18.

[0026] 16. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a C14 to C18 i-paraffin content of 70 wt.-% to 95 wt.-%, preferably 75 wt.-% to 91 wt.-%.

[0027] 17. The method according to any one of the preceding items, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have an aggregate paraffin content of 93 wt.-% or more, preferably 94 wt.-% or more, or 95 wt.-% or more.

[0028] 18. The method of any one of the preceding items, wherein at least a portion of the high boiling fraction is provided as the renewable cracker feed.

[0029] 19. The method of any one of the preceding items, wherein the high boiling fraction has an interventile carbon range (IVR) of 5.0 or less, preferably 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, or 2.3 or less.

[0030] 20. The method according to any one of the preceding items, wherein the high boiling fraction has a c_50 value in the range of 16.5 to 20.0, preferably 16.5 to 19.0, or 17.0 to 18.0.

[0031] 21. The method according to any one of the preceding items, wherein the high boiling fraction has a c_50 value of 16.5 or more and an interventile carbon range (IVR) of 5.0 or less.

[0032] 22. The method of any one of the preceding items, wherein at least a portion of the low boiling fraction is provided as the renewable cracker feed.

[0033] 23. The method according to any one of the preceding items, wherein the low boiling fraction has a c_50 value in the range of 11.0 to less than 16.5, preferably 12.0 to 16.0, or 14.0 to 16.0.

[0034] 24. The method according to any one of the preceding items, wherein the low boiling fraction has an interventile carbon number range (IVR) in the range of 5.0 to 12.0, preferably 6.0 to 12.0, or 7.0 to 11.0.

[0035] 25. The method according to any one of the preceding items, wherein the low boiling fraction has a c_50 value of less than 16.5 and an interventile carbon range (IVR) in the range of 5.0 to 12.0.

[0036] 26. The method according to any one of the preceding items, wherein the low-boiling fraction has a content of compounds having a weight fraction in terms of modal carbon number in the range of 20 wt.-% to 40 wt.-%, preferably 22 wt.-% to 37 wt.-%, or 25 wt.-% to 35 wt.-%.

[0037] 27. The method according to any one of the preceding items, wherein the low boiling fraction has a minimum carbon number (C_min) in the range of 5 to 8, preferably 5 to 7, for example 5 to 6.

[0038] 28. The method according to any one of the preceding items, wherein the low boiling fraction has a maximum carbon number (C_max) in the range of 14 to 26, preferably 15 to 23, 16 to 22, or 17 to 21.

[0039] 29. The method according to any one of the preceding items, wherein the low boiling fraction has a modal carbon number in the range of 12 to 17, for example 13 to 17, 14 to 16, or 15 to 16.

[0040] 30. The method according to any one of the preceding items, wherein the low boiling fraction has an interquartile carbon number range (IQR) in the range of 1.5 to 4.0, preferably 2.0 to 3.5, or 2.0 to 3.0.

[0041] 31. The method according to any one of the preceding items, wherein the low boiling fraction has an adjusted average carbon number range (IDR) in the range of 4.0 to 14.0, 6.0 to 10.0, or 7.0 to 9.0.

[0042] 32. The method according to any one of the preceding items, wherein the low boiling point fraction has an interventile carbon number range (IVR) in the range of 6.0 to 11.0, 7.0 to 11.0, or 8.0 to 10.5.

[0043] 33. The method according to any one of the preceding items, wherein the low boiling fraction has an 80% carbon span (CS_80) in the range of 3.0 to 9.0, preferably 4.0 to 8.0, or 4.5 to 7.0.

[0044] 34. The method according to any one of the preceding items, wherein the low boiling fraction has a cloud point of -20°C or less, preferably -30°C or less, -40°C or less, -45°C or less, and most preferably -50°C or less.

[0045] 35. The method of any one of the preceding items, wherein the high boiling fraction has a higher c_50 value than the isomeric hydrocarbon composition, and the low boiling fraction has a lower c_50 value than the high boiling fraction.

[0046] 36. The method according to any one of the preceding items, wherein the high boiling fraction has a c_50 value that is at least 0.5 higher, preferably at least 1.0 higher, or at least 15 higher than the c_50 value of the isomeric hydrocarbon composition.

[0047] 37. The method according to any one of the preceding items, wherein the low boiling fraction has a c_50 value that is at least 0.5 lower, preferably at least 1.0 lower, or at least 1.5 lower than the c_50 value of the high boiling fraction.

[0048] 38. The method according to any one of the preceding items, wherein the high-boiling fraction has a content of compounds having a weight fraction in terms of modal carbon number in the range of 40 to 95 wt.-%, 50 to 92 wt.-%, 60 to 90 wt.-%, 65 to 89 wt.-%, 70 to 88 wt.-%, 75 to 87 wt.-%, 76 to 86 wt.-%, or 77 to 85 wt.-%.

[0049] 39. The method according to any one of the preceding items, wherein the high-boiling fraction has a minimum carbon number (C_min) in the range of 8 to 20, preferably 10 to 18, 11 to 17, 12 to 16, or 13 to 16.

[0050] 40. The method according to any one of the preceding items, wherein the high boiling fraction has a maximum carbon number (C_max) in the range of 22 to 40, preferably 24 to 38, 26 to 36, 26 to 35, or 27 to 34.

[0051] 41. The method according to any one of the preceding items, wherein the high-boiling fraction has a modal carbon number in the range of 17 to 22, preferably 18 to 21, 18 to 20, or 18 to 19.

[0052] 42. The method according to any one of the preceding items, wherein the high boiling point fraction has an interquartile carbon number range (IQR) in the ranges of 0.1 to 3.0, 0.2 to 2.0, 0.3 to 1.0, or 0.4 to 0.8.

[0053] 43. The method according to any one of the preceding items, wherein the high boiling fraction has an adjusted average carbon number range (IDR) in the range of 0.5 to 4.0, 0.6 to 3.0, 0.7 to 2.0, or 0.8 to 1.6.

[0054] 44. The method according to any one of the preceding items, wherein the high boiling point fraction has an interventile carbon number range (IVR) in the range of 1.1 to 5.0, 1.3 to 4.0, 1.4 to 3.5, 1.6 to 3.2, 1.8 to 3.0, or 1.8 to 2.8.

[0055] 45. The method of any one of the preceding items, wherein the high boiling fraction has an 80% carbon span (CS_80) in the range of 0.1 to 3.0, preferably 0.2 to 2.5, 0.3 to 2.0, 0.4 to 1.6, or 0.5 to 1.4.

[0056] 46. ​​The method according to any one of the preceding items, wherein the high boiling fraction has a cloud point of -10°C or less, preferably -15°C or less, -20°C or less, -25°C or less, or -27°C or less.

[0057] 47. The method according to any one of the preceding items, wherein the pyrolysis step (b) is carried out at a coil outlet temperature (COT) selected from the range of 780°C to 900°C, preferably 805°C to 865°C, more preferably 815°C to 850°C.

[0058] 48. A method according to any one of the preceding items, wherein the pyrolysis step (b) is carried out at a coil outlet pressure (COP) selected from the range of 1.3 bar to 6.0 bar, preferably 1.3 bar to 3.0 bar.

[0059] 49. The method according to any one of the preceding items, wherein the pyrolysis step (b) is a steam cracking step.

[0060] 50. A method according to any one of the preceding items, wherein the pyrolysis step (b) is carried out in the presence of a pyrolysis diluent at a dilution factor in the range of 0.10 to 0.80, preferably 0.25 to 0.70, for example 0.35 to 0.50.

[0061] 51. A method according to any one of the preceding items, comprising, as purification step (C') in step (c) of separating at least a light olefin fraction from the effluent of the pyrolysis furnace of step (b), a purification treatment for removing at least one of methylacetylene, propadiene, CO, CO2 and C2H2, preferably at least one of CO, CO2 and C2H2.

[0062] 52. performing one or more further cracking operations to provide a further cracked effluent, wherein 2. The method of any one of the preceding items, wherein step (c) further comprises adding further effluent and / or fractions thereof before and / or during the separation process.

[0063] 53. The method according to any one of the preceding items, wherein the pyrolysis in step (b) is carried out in the presence of a cofeed.

[0064] 54. The method according to any one of the preceding items, wherein the content of the renewable cracker feed in the total cracker feed is between 10 wt.-% and 100 wt.-%, preferably between 20 wt.-% and 100 wt.-%, 30 wt.-% and 100 wt.-%, 40 wt.-% and 100 wt.-%, 50 wt.-% and 100 wt.-%, 60 wt.-% and 100 wt.-%, 70 wt.-% and 100 wt.-%, 80 wt.-% and 100 wt.-%, or 90 wt.-% and 100 wt.-%, wherein the total cracker feed means the renewable cracker feed plus any optional co-feed and any optional additives.

[0065] 55. The method of any one of the preceding items, wherein the co-feed comprises a fossil hydrocarbon co-feed.

[0066] 56. The method of any one of the preceding items, wherein the cofeed comprises a naphtha range feed, a diesel range feed, an aviation fuel range feed, a marine fuel range feed, or a gas oil range feed.

[0067] 57. The method according to any one of the preceding items, wherein the total cracker feed has a sulfur content in the range of 20 to 300 ppm by weight, preferably 20 to 250 ppm by weight, more preferably 20 to 100 ppm by weight, and even more preferably 50 to 65 ppm by weight.

[0068] 58. The step (a) of providing the renewable cracker feed comprises: subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, and to hydroisomerization, to at least provide an isomerized deoxygenated stream; subjecting at least a portion of said isomerized deoxygenated stream to fractionation and recovering at least said isomeric hydrocarbon composition; and subjecting at least a portion of said isomeric hydrocarbon composition to further fractionation to provide at least said low boiling fraction and said high boiling fraction. 2. The method according to any one of the preceding items, comprising:

[0069] 59. The process according to item 58, wherein the hydroisomerization is carried out in the same hydroprocessing stage as the hydrodeoxygenation and / or the hydroisomerization is carried out in a further hydroprocessing stage after the hydroprocessing, which comprises at least hydrodeoxygenation.

[0070] 60. The process according to item 58 or 59, comprising gas-liquid separation after said hydrotreating, which includes at least hydrodeoxygenation, and / or after said further hydrotreating, and recovering at least one gaseous stream and said isomerized deoxygenated stream.

[0071] 61. The method of claim 60, further comprising subjecting the gaseous stream to a propane separation process to provide a propane-rich stream and a propane-depleted stream.

[0072] 62. The process of claim 61, further comprising subjecting at least a portion of the propane from the propane-rich stream to dehydrogenation, preferably catalytic dehydrogenation, to produce propylene.

[0073] 63. The renewable cracker feed is selected from the group consisting of: subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, to hydroisomerization, and to gas-liquid separation to provide said isomerized deoxygenated stream; feeding the isomerized deoxygenated stream to a first distillation column, preferably a stabilization column, to obtain at least a naphtha range fraction and a stabilized heavy liquid fraction; feeding at least a portion of said stabilized heavy liquid fraction as said isomeric hydrocarbon composition to a second distillation column, and recovering at least said low boiling fraction and said high boiling fraction. 3. The method according to any one of the preceding items, obtained by

[0074] 64. The method according to any one of items 58 to 63, wherein the isomerized deoxygenated stream has an i-paraffin content of at least 65 wt.-%, preferably at least 70 wt.-%, at least 75 wt.-%, at least 80 wt.-%, at least 85 wt.-%, or at least 90 wt.-%.

[0075] 65. The method of any one of the preceding items, further comprising derivatizing at least a portion of the light olefin to obtain one or more derivatives of the light olefin as a biomonomer, such as, for example, acrylic acid, acrylonitrile, acrolein, propylene oxide, ethylene oxide, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, adiponitrile, hexamethylenediamine (HMDA), hexamethylene diisocyanate (HDI), (methyl)methacrylate, ethylidenenorborene, 1,5,9-cyclododecatriene, sulfolane, 1,4-hexadiene, tetrahydrophthalic anhydride, valeraldehyde, 1,2-butyl oxide, n-butyl mercaptan, o-sec-butylphenol, propylene, octene, sec-butyl alcohol, and the like.

[0076] 66. The method according to any one of the preceding items, wherein the renewable cracker feed is obtained by a process comprising a step of subjecting an oxygenate bio-renewable feed to hydroprocessing, including at least hydrodeoxygenation, and to hydroisomerization.

[0077] 67. The method according to any one of the preceding items, wherein at least a portion of the low boiling fraction is subjected to the pyrolysis step (c) in a first pyrolysis furnace and at least a portion of the high boiling fraction is subjected to the pyrolysis step (c) in a second pyrolysis furnace.

[0078] 68. The process according to any one of the preceding items, wherein at least a portion of the low boiling fraction and at least a portion of the high boiling fraction are alternately subjected to the pyrolysis step (c).

[0079] 69. The method according to any one of the preceding items, wherein at least a portion of the low boiling fraction and at least a portion of the high boiling fraction are subjected to the pyrolysis step (c) alternately in the same pyrolysis furnace.

[0080] 70. At least a part of the low-boiling fraction is subjected to the pyrolysis step (c), and at least a part of the high-boiling fraction is recovered as a specific fluid or its component such as, for example, an electro-technical fluid, a lubricating oil, a coolant or its component, and / or as a fuel component such as, for example, a marine fuel component, according to any one of the items described above.

[0081] 71. At least a part of the high-boiling fraction is subjected to the pyrolysis step (c), and at least a part of the low-boiling fraction is recovered as a fuel component, preferably as an aviation fuel component, according to any one of the items described above.

[0082] 72. A part of the low-boiling fraction is subjected to the pyrolysis step (c), and another part of the low-boiling fraction is recovered as a fuel component, preferably as an aviation fuel component, according to any one of the items described above.

[0083] 73. A part of the high-boiling fraction is subjected to the pyrolysis step (c), and another part of the high-boiling fraction is recovered as a specific fluid or its component such as, for example, an electro-technical fluid, a lubricating oil, a coolant or its component, and / or as a fuel component such as, for example, a marine fuel component, according to any one of the items described above.

[0084] 74. The low-boiling fraction has a content of hydrocarbons having less than 18 carbon atoms (<C18) of 55 wt.% or more, preferably 60 wt.% or more, 65 wt.% or more, 70 wt.% or more, 75 wt.% or more, or 80 wt.% or more, according to any one of the items described above.

[0085] 75. The low-boiling fraction has a ratio (≧C18 / <C18) of the content of hydrocarbons having 18 or more carbon atoms (≧C18) to the content of hydrocarbons having less than 18 carbon atoms (<C18) of 0.90 or less, preferably 0.85 or less, 0.80 or less, 0.70 or less, 0.60 or less, 0.50 or less, 0.40 or less, or 0.30 or less, according to any one of the items described above.

[0086] 76. The method according to any one of the preceding items, wherein the high-boiling fraction has a content of hydrocarbons having 18 or more carbon atoms (≧C18) of 50 wt.% or more, preferably 55 wt.% or more, 60 wt.% or more, 65 wt.% or more, 70 wt.% or more, 75 wt.% or more, or 80 wt.% or more.

[0087] 77. The method according to any one of the preceding items, wherein the high-boiling fraction has a ratio (≧C18 / <C18) of the content of hydrocarbons having 18 or more carbon atoms (≧C18) to the content of hydrocarbons having less than 18 carbon atoms (<C18) of 1.0 or more, preferably 1.5 or more, 2.0 or more, 3.0 or more, 4.0 or more, 5.0 or more, or 6.0 or more.

[0088] 78. A step of (co)polymerizing (e) at least one of the light olefins separated in the step (c) and / or at least one of the biobased monomers, optionally together with other (co)monomers and / or after optional further purification, for producing the biopolymer composition. The method according to any one of the preceding items, further comprising the step.

[0089] 79. The method according to item 78, wherein the biopolymer composition is further processed, optionally together with other components, for producing sanitary products, building materials, packaging materials, coating compositions, paints, decorative materials such as panels, interior parts of vehicles such as interior parts of automobiles, rubber compositions, tires or tire components, toners, personal health care products, parts of consumer goods, parts or housings of electronic devices, films, molded articles, gaskets.

[0090] 80. A biopolymer composition obtained by the method according to item 78 or 79.

Brief Description of the Drawings

[0091] [Figure 1]FIG. 1 shows linear interpolation to obtain the c_50 value (graph A) and the carbon span at 80% (graph B). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0092] In the present invention, contents and content ratios are provided on a weight basis unless otherwise specified.

[0093] Furthermore, i-paraffins (also called isoparaffins) refer to branched acyclic alkanes, and n-paraffins (also called normal paraffins) refer to straight-chained acyclic alkanes. Total paraffin content refers to the combined content of i-paraffins and n-paraffins. Similarly, olefins refer to straight-chained or branched acyclic alkenes containing multiple unsaturations. Naphthenes refer to cyclic non-aromatic branched or unbranched alkanes, alkenes or alkynes containing multiple unsaturations. Aromatics refer to compounds with at least one aromatic ring.

[0094] The n-paraffin, i-paraffin, olefin, naphthene and aromatics content can be measured using the PIONA method, which is a GC×GC analytical method as described in the GC×GC description by Pyl et al., Journal of Chromatography A, 1218 (2011) 3217-3223, which states that in samples that have been subjected to high severity hydroisomerization, it is desirable to reverse the primary and secondary columns to enhance the separation and identification of isoparaffins from n-paraffins.

[0095] In the context of the present invention, the terms "renewable" or "bio-based" or "bio-" refer to materials that are derived wholly or partially from renewable or biological sources. Renewable or biologically derived carbon atoms contain a greater number of unstable radiocarbons ( 14 C) contains atoms. Therefore, 12 C and14 By analyzing the isotope ratio with C, it is possible to distinguish carbon compounds from renewable or biological sources or raw materials from those from fossil sources or raw materials. Thus, the specific ratio of the isotopes (resulting in the "biogenic carbon content") can be used as a "tag" to identify renewable carbon compounds and to distinguish them from non-renewable carbon compounds. The isotope ratio does not change during the course of chemical reactions. Examples of methods suitable for analyzing biogenic carbon content include DIN 51637 (2014), ASTM D6866 (2020), and EN 16640 (2017). The content of carbon from biological or renewable sources is expressed as biogenic carbon content, which means the amount of biogenic carbon in a material as a weight percentage of the total carbon (TC) in the material. As used herein, biogenic carbon content is determined according to EN 16640 (2017). In the present invention, the terms "renewable" or "bio-based" or "bio-" preferably refer to materials having a biogenic carbon content ranging from 1% to 100%.

[0096] In particular, the biogenic carbon content of the isomeric hydrocarbon composition and / or of the renewable cracker feed, which may also be referred to as bio-based cracker feed, is preferably greater than 5% and up to 100%, for example, greater than 20%, greater than 40%, greater than 50%, greater than 60%, or greater than 70%, greater than 80%, greater than 90%, or greater than 95%, and may be about 100%. The biogenic carbon content of the oxygenate bio-renewable feed is preferably greater than 50% and up to 100%, preferably greater than 60%, or greater than 70%, preferably greater than 80%, more preferably greater than 90%, or greater than 95%, and even more preferably about 100%.

[0097] The biogenic carbon content of the renewable pyrolysis effluent of the present invention may be less than 1%, but is preferably at least 1% and up to 100%, such as at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90%, or about 100%.

[0098] The biogenic carbon content of the pyrolysis furnace effluent of step (b) and of the downstream products and intermediates of the decomposition step (b) may be less than 1%, but is preferably at least 1% and up to 100%, such as at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90%, or about 100%.

[0099] In particular, the biogenic carbon content of the light olefin (fraction) and / or biomonomer and / or biopolymer composition may be less than 1%, but is preferably at least 1% and up to 100%, such as at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90%, or about 100%.

[0100] The term "optionally" or "optional" refers to a feature, characteristic or step that may be present, but is not necessary for the practice of the invention.

[0101] Unless otherwise noted, all test method standards referred to in the text are current as of December 1, 2021.

[0102] Pyrolysis method First, the method of the present invention will be described.

[0103] The present invention relates to a sustainable pyrolysis process. In particular, the present invention relates to a process using a feed that has not been used in pyrolysis before and shows surprisingly good results in pyrolysis. The process of the present invention comprises the steps of: providing a renewable cracker feed obtained by fractionating an isomeric hydrocarbon composition having an i-paraffin content of 85.0 wt% or more and a carbon range ranging from 20 to 32 into at least a low boiling fraction and a high boiling fraction; and providing at least a part of the low boiling fraction or at least a part of the high boiling fraction as renewable cracker feed; (b) pyrolyzing the renewable cracker feed in a pyrolysis furnace, optionally with cofeeds and / or additives; and (c) subjecting the pyrolysis furnace effluent of step (b) to a separation process to provide at least a light olefin fraction.

[0104] The process of the present invention provides a light olefin fraction, which may include further purification of the light olefin fraction to provide one or more light olefins, preferably of industrial grade, or even polymer grade.

[0105] In the present invention, the low-boiling fraction and the high-boiling fraction can be obtained by fractionating the isomeric hydrocarbon composition. Thus, depending on the sharpness of the fractionation (distillation), the respective fractions can have overlapping boiling ranges. As a result of fractionation, the high-boiling fraction will usually contain a greater amount of heavy (high-boiling) components, and the low-boiling fraction will contain a greater amount of light (low-boiling) components.

[0106] The isomeric hydrocarbon composition preferably has a c_50 value in the range of 14.0-22.0, preferably 14.0-20.0, or 15.0-20.0. In the present invention, the c_50 value is the fractional carbon number representing a 50 wt.-% sample. Details of how to calculate the c_50 value and other fractional carbon numbers are described below. The carbon range is the difference between C_max and C_min (carbon range = C_max - C_min), where C_max (the highest carbon number) and C_min (the lowest carbon number) are determined by PIONA (the GC x GC method described herein), and for the measurement of C_min and C_max, it is assumed that there are no carbon numbers with a measured abundance of 0.10 wt.-% or less. In other words, when determining C_min and C_max, and therefore when determining the carbon range, carbon numbers with a measured abundance of 0.10 wt.-% or less are not taken into account.

[0107] The inventors have surprisingly found that in the fractionation of an isomeric hydrocarbon composition having a high i-paraffin content of 85% or more into at least two fractions, each resulting fraction exhibits superior thermal cracking properties than the isomeric hydrocarbon composition. Conventionally, such separated fractions have been used as fuel or as a specific fluid. While a portion of the low boiling fraction and / or the high boiling fraction can still be used for such purposes, at least a portion of the low boiling fraction or at least a portion of the high boiling fraction is used as renewable cracker feed in the process of the invention. Because these fractions are based on renewable feedstocks, the process of the invention achieves improved sustainability. In addition, because it may be difficult (or costly) to produce an isomeric hydrocarbon composition in such a way that the relative amounts of low boiling fraction and high boiling fraction actually needed or required (exactly) to be used for fuel or a specific fluid purpose are produced, the invention further allows for the renewal of surplus material that would otherwise be stored or even burned. Using only a portion of the low or high boiling fraction can be achieved, for example, by simply splitting the low or high boiling fraction stream into two streams or aliquots / aliquots for further processing or by batchwise directing streams or batches of these fractions to different processing routes.

[0108] In the present invention, either the high boiling fraction or the low boiling fraction is employed as renewable cracker feed. It is also possible to employ both fractions or a part of them as renewable cracker feed in the present invention. However, in this case, the high boiling fraction and the low boiling fraction must be pyrolyzed separately, i.e., not mixed. For example, the high boiling fraction and the low boiling fraction must not be used as renewable cracker feed at the same time in the same furnace.

[0109] Preferably, both the low boiling fraction and the high boiling fraction have an i-paraffin content of 92.0 wt.-% or more, independently of each other. This means that both fractions each have an i-paraffin content of 92.0 wt.-% or more (i.e., in the range of 92.0 wt.-% to 100 wt.-%), but do not necessarily have to have the same i-paraffin content, as long as both fractions have an i-paraffin content within that range. The i-paraffin content may more preferably be 93.0 wt.-% or more, 94.0 wt.-% or more, or 95.0 wt.-% or more, independently of each other. The high i-paraffin content of the renewable cracker feed results in a lower viscosity and, therefore, easier handling. Furthermore, this high i-paraffin content has been found to result in favorable cracking properties, in particular an improved yield of valuable light olefins (VLO).

[0110] In the present invention, when a content is mentioned, this content is based on the whole material. For example, a low boiling fraction having an i-paraffin content of 92.0 wt.-% or more means that the i-paraffin content is 92.0 wt.-% or more based on the weight of the total low boiling fraction.

[0111] Preferably, both the low boiling fraction and the high boiling fraction have, independently of each other, a ratio of i-paraffins with more than three branches (IP3+) to total i-paraffins (iP) (iP3+ / iP) that is 0.164 or less, more preferably 0.160 or less, 0.155 or less, 0.150 or less. The relatively low amount of IP3+ components results in reduced aromatics, especially benzene, yields, thus improving the value of the cracking effluent for use in polymer chemistry and other areas where aromatics should be removed before further use.

[0112] The content of i-paraffins (IP3+) having more than three branches can be determined by the methods disclosed in WO 2020 / 201614, the entirety of which is incorporated herein by reference. Specifically, the content of i-paraffins (IP3+) having more than three branches can be determined by the following method:

[0113] The N-paraffin and i-paraffin content in the samples is analyzed by gas chromatography (GC). The samples are analyzed as is without any pretreatment. The method is suitable for C2-C36 hydrocarbons. The N-paraffin and i-paraffin groups (C1-, C2-, C3-substituted and ≧C3-substituted) are identified using mass spectrometry and a mixture of known n-paraffins in the range C2-C36. The chromatogram is separated into three groups of paraffins (C1-, C2- / C3-, and ≧C3-substituted i-paraffins / n-paraffins) or two groups of paraffins (C1- / C2- / C3-, and ≧C3-substituted i-paraffins / n-paraffins) by integrating the groups against the baseline of the chromatogram immediately after the n-paraffin peak. N-Paraffins are separated from ≧C3-substituted i-paraffins (iP3+) by tangentially integrating the n-paraffin peaks from valley to valley. Compounds or compound groups are quantified by normalizing with a relative response factor of 1.0 for all hydrocarbons. The limits of quantification for individual compounds are typically 0.01 wt.-%. Appropriate settings for the GC are given below:

[0114] TIFF2025502786000002.tif79143

[0115] Preferably, both the low-boiling fraction and the high-boiling fraction have, independently of each other, a total content of i-paraffins with more than three branches (iP3+) relative to the total paraffins of 10.50 wt.-% or more, for example 10.50-16.00, 11.00-15.50, 11.00-15.50, 11.00-15.00, or 1.2.00-15.00. By total paraffins is meant the total amount of n-paraffins and i-paraffins. In the context of the present invention, the branches of i-paraffins are typically methyl branches.

[0116] Preferably, both the low boiling fraction and the high boiling fraction have, independently of each other, a cloud point below -10°C, preferably below -15°C or below -20°C, for example in the range of -70°C to -10°C.

[0117] In the present invention, the cloud point can be determined according to ASTM D7689.

[0118] Preferably, both the low boiling fraction and the high boiling fraction have a naphthene content, independently of each other, in the range of 0.1 wt.-% to 10.0 wt.-% based on the weight of the total renewable cracker feed. In high polymerization degree isomerization, some cyclization (formation of naphthenes) may occur. According to the present invention, the content of naphthenes in the low boiling fraction and the high boiling fraction, and thus in the renewable cracker feed, is desirably low, but does not have to be 0 wt.-%. That is, naphthenes may be present to some extent and do not have to be removed. Naphthenes are easily converted to aromatics, which are compounds that may react to coke but not to the desired products. Therefore, a low content of naphthenes is preferred.

[0119] For example, the naphthene content may be, independently of one another, between 0.2 wt.-% and 10.0 wt.-%, e.g., between 0.5 wt.-% and 8.0 wt.-%, between 0.5 wt.-% and 6.0 wt.-%, between 0.6 wt.-% and 5.8 wt.-%, or between 0.8 wt.-% and 5.6 wt.-%.

[0120] Preferably, the low boiling fraction and the high boiling fraction have an olefin content, independently of each other, of 0.50 wt.-% or less, preferably 0.40 wt.-% or less, 0.30 wt.-% or less, 0.25 wt.-% or less, 0.20 wt.-% or less, 0.15 wt.-% or less, 0.12 wt.-% or less, 0.10 wt.-% or less, 0.07 wt.-% or less, or 0.05 wt.-% or less. Olefins are undesirable components in the low boiling fraction and in the high boiling fraction in the renewable cracker feed of the present invention. That is, the inventors have found that olefins have a strong coking tendency, even higher than aromatics, and therefore the content of olefins should be kept low. The content of olefins, independently of each other, can be 0%, i.e., no detectable amount of olefins is included.

[0121] Preferably, both the low boiling fraction and the high boiling fraction have, independently of each other, a combined olefin and naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%. Combined olefin and naphthene content means the combined content of olefins and naphthenes. More preferably, the total content of olefins and naphthenes is, independently of one another, between 0.1 wt.-% and 8.0 wt.-%, for example between 0.1 wt.-% and 6.5 wt.-%, between 0.1 wt.-% and 6.0 wt.-%, between 0.2 wt.-% and 5.5 wt.-%, between 0.5 wt.-% and 5.5 wt.-%, between 0.5 wt.-% and 5.0 wt.-%, between 0.8 wt.-% and 5.0 wt.-%, between 0.9 wt.-% and 5.0 wt.-%, between 1.0 wt.-% and 5.0 wt.-%, between 1.1 wt.-% and 5.0 wt.-%, or between 1.2 wt.-% and 5.0 wt.-%.

[0122] Preferably, the low boiling fraction and the high boiling fraction have an aromatics content that is, independently of each other, 0.80 wt.-% or less, preferably 0.70 wt.-% or less, 0.60 wt.-% or less, 0.50 wt.-% or less, 0.40 wt.-% or less, 0.35 wt.-% or less, 0.30 wt.-% or less, 0.25 wt.-% or less, 0.20 wt.-% or less, or 0.15 wt.-% or less. Aromatics, such as benzene, do not react with the desired products. Rather, they tend to react with coke (i.e., are coke precursors). Thus, their content should be low, since their presence in pyrolysis reduces the yield of the desired products. In the present invention, the aromatics content is preferably low and may be 0.00%. The aromatics content may be determined by PIONA analysis.

[0123] Preferably, the low boiling fraction and the high boiling fraction have, independently of one another, a combined content of olefins, aromatics and naphthenes of between 0.1 wt.-% and 10.0 wt.-%, preferably between 0.1 wt.-% and 8.0 wt.-%, between 0.1 wt.-% and 6.5 wt.-%, between 0.2 wt.-% and 6.0 wt.-%, between 0.5 wt.-% and 5.5 wt.-%, between 0.5 wt.-% and 5.0 wt.-%, between 0.8 wt.-% and 5.0 wt.-%, between 0.9 wt.-% and 5.0 wt.-%, between 1.0 wt.-% and 5.0 wt.-%, between 1.1 wt.-% and 5.0 wt.-%, or between 1.2 wt.-% and 5.0 wt.-%. Naphthenes, aromatics, and olefins are coke precursors and their contents should be low. However, since strongly reducing the contents of these components can be laborious, some of their contents can be tolerated. However, their total contents can be reduced to and including 0%, independently of each other.

[0124] Preferably, both the low-boiling fraction and the high-boiling fraction have an oxygenate content, independently of each other, of 1000 wt.-ppm or less, preferably 700 wt.-ppm or less, 500 wt.-ppm or less, 300 wt.-ppm or less, 100 wt.-ppm or less, 80 wt.-ppm or less, 60 wt.-ppm or less, 50 wt.-ppm or less, 40 wt.-ppm or less, or 30 wt.-ppm or less. Here, oxygenate means a molecule that contains carbon and hydrogen and further contains covalently bonded oxygen in its structure (molecule). In the present invention, a low oxygenate content is preferred, including no oxygenate. On the other hand, higher values, such as 100 wt.-ppm to 1000 wt.-ppm, may be used, especially when applying low oxygenate co-feeds (e.g. fossil hydrocarbon co-feeds) of, for example, 10 wt.-% or more, independently of one another, in which case the effort to minimize the oxygenate content is minimized, which increases the overall efficiency of the process.

[0125] Preferably, both the low boiling fraction and the high boiling fraction have, independently of each other, a modal carbon number in the range of from 11 to 21, preferably from 14 to 20, or from 16 to 18.

[0126] Preferably, both the low boiling fraction and the high boiling fraction, independently of each other, have a content of C14-C18 i-paraffins of 70 wt.-% to 95 wt.-%, preferably 75 wt.-% to 91 wt.-%. In the present invention, the content of C14-C18 i-paraffins can be determined by the same measurement method as that adopted for measuring the iP3+ content.

[0127] Preferably, both the low boiling fraction and the high boiling fraction, independently of each other, have an aggregate paraffin content of 93 wt.-% or more, preferably 94 wt.-% or more, or 95 wt.-% or more.

[0128] If both the high boiling fraction and the low boiling fraction have similar properties, such as cloud point, modal carbon number and / or i-paraffin content, it is possible to easily switch from providing only (a portion of) the low boiling fraction as renewable cracker feed to providing only (a portion of) the high boiling fraction as renewable cracker feed, i.e., in such a case, these fractions provide, at least at a general level, approximately the same desired product slate and pyrolysis benefits. In such a case, the other fraction can be flexibly used for another high value-added purpose depending on demand.

[0129] Traditionally, isomerization processes that result in high i-paraffin contents have at the same time resulted in high contents of hyperbranched i-paraffins, especially i-paraffins with more than three branches. Various methods can be used to achieve a high share of i-paraffins, but nevertheless only low amounts of IP3+ components are produced. For example, it is possible to reduce the extent of the isomerization process (e.g., reduce the temperature). However, in some cases, reducing the isomerization temperature requires a much longer residence time, which may also increase the yield of IP3+ components. In this case, it may be preferable to increase the isomerization temperature and at the same time reduce the residence time. Alternatively or additionally, the catalyst for isomerization can be appropriately selected. For example, it is possible to use catalysts with a specific pore structure, in which the components catalytically active for isomerization are provided in small pores so that mainly or only linear paraffins can reach the active sites. Such shape-selective catalysts are commercially available.

[0130] Preferably, the high boiling fraction has an interventile carbon number range (IVR) of 5.0 or less, preferably 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, or 2 or 3. An IVR within this range indicates that the high boiling fraction is relatively narrow.

[0131] The IVR is a calculated carbon number range determined from linear interpolation of the data (cumulative content vs. carbon number) obtained from the PIONA carbon number analysis. Similarly, the IDR, IQR, and c_50 are also determined from linear interpolation of the data (cumulative content vs. carbon number) obtained from the PIONA carbon number analysis.

[0132] The IVR is the carbon number range that contains 90% of the mass (i.e., 5 wt.-% to 95 wt.-%). Similarly, the IQR (interquartile range) is the carbon number range that contains 50% of the mass from 25 wt.-% to 75 wt.-%, and the IDR (adjusted mean carbon number range) is the carbon number range that contains 80% of the mass from 10 wt.-% to 90 wt.-%. Linear interpolation means that the content range between two carbon numbers is assumed to be linear. For example, a sample containing 0% C1, 0% C2, 0% C3, 5% C4, 5% C5, and 8% C6 would have a C_2.5 value of 3.5 (carbon numbers) (i.e., the fractional carbon number that corresponds to 2.5 wt.% of the sample), even if C4 was the lowest carbon number actually present. The cumulative amount of C1+C2+C3+C4+C5 is exactly 10 wt.-%, so the C_5 (C_05) value (fractional carbon number corresponding to 5 wt.-% of the sample) is 4 (C4), and the C_10 value (fractional carbon number corresponding to 10 wt.-% of the sample) is 5 (C5). The C_15 value (15 wt.-%) is between 5 and 6 (C5 is 10 wt.-% and C6 is 18 wt.-%). Linear interpolation is easily done, for example the 15 wt.-% carbon content (C_15 value) may be calculated as follows: 5 {the highest carbon number not yet contributing to 15 wt.-%}+ [{15%{content of target}-10%{cumulative content of C5}} / (18% {cumulative content of C6} - 10% {cumulative content of C5})] =5+[5% / 8%]=5+0.625, i.e., the number of carbon atoms is 5.625.

[0133] In other words, to determine the C_XX value, the following formula is used: {the highest carbon number not already contributing to XX wt.-%}+ [({content of target: XX wt.-%}-{cumulative content of highest carbon number that has not yet contributed to XX wt.-%}) / ({cumulative content of the lowest carbon number that has a cumulative content exceeding XX wt.-%} - {cumulative content of the highest carbon number that has not yet contributed to XX wt.-%})].

[0134] Linear interpolation can be easily understood from the description of the graph in Figure 1. In Figure 1 (Graph A), the Y-axis represents the cumulative content of compounds, and the carbon numbers are arranged in numerical order on the X-axis. The bars represent the individual contents of compounds of each carbon number. The dots represent the cumulative content (cumulative mass fraction) of each carbon number, and the line graph represents linear interpolation (drawing a straight line between adjacent dots). The carbon number at which the line graph intersects with the 50% cumulative mass fraction (horizontal line) is the c_50 value, which is slightly above 16 as shown by the dotted line in Figure 1.

[0135] The IVR, IDR and IQR ranges are less susceptible to tail effects and therefore provide more stable results than the carbon ranges.

[0136] Preferably, the high boiling fraction has a c_50 value in the range of 16.5 to 20.0, preferably 16.5 to 19.0, or 17.0 to 18.0, which indicates that the fraction is a relatively high boiling fraction, such as a bottom fraction, obtained from fractionation.

[0137] In one embodiment, the high boiling fraction has a c_50 value of 16.5 or more and an interventile carbon number range (IVR) of 5.0 or less. In other words, it is particularly preferred that the high boiling fraction is a fraction that has a narrow carbon number distribution and is a heavy (high boiling) fraction with a high c_50 value.

[0138] Preferably, the low-boiling fraction has a c_50 value in the range of 11.0 to less than 16.5, preferably 12.0 to 16.0, or 14.0 to 16.0. Since conventional renewable isomer hydrocarbon compositions contain a high share of C18 hydrocarbons, the above range indicates that a significant amount of high-boiling components, particularly those with a boiling point of C18 or higher, are contained in fractions other than the low-boiling fraction. Specifically, the low-boiling fraction may be the top fraction.

[0139] Preferably, the low-boiling fraction has a content of hydrocarbons having less than 18 carbon atoms (<C18) of 55 wt.-% or more, more preferably 60 wt.-% or more, 65 wt.-% or more, 70 wt.-% or more, 75 wt.-% or more, or 80 wt.-% or more. The upper limit can be 100 wt.-% (i.e., the content can be, for example, in the range of 55 wt.-% to 100 wt.-%), but is preferably 99 wt.-% or less, more preferably 98 wt.-% or less, such as 95 wt.-% or less, 92 wt.-% or less, or 90 wt.-% or less.

[0140] Preferably, the low-boiling fraction has a ratio (≧C18 / <C18) of the content of hydrocarbons having 18 or more carbon atoms (≧C18) to the content of hydrocarbons having less than 18 carbon atoms (<C18) of 0.90 or less, preferably 0.85 or less, 0.80 or less, 0.70 or less, 0.60 or less, 0.50 or less, 0.40 or less, or 0.30 or less. The ratio may be 0 when low, but is preferably at least 0.02 (i.e., the ratio can be, for example, in the range of 0.02 to 0.90), more preferably at least 0.05, such as at least 0.08, at least 0.10, at least 0.12, or at least 0.15.

[0141] Preferably, the high-boiling fraction has a content of hydrocarbons having 18 or more carbon atoms (≧C18) of 50 wt.% or more, preferably 55 wt.% or more, 60 wt.% or more, 65 wt.% or more, 70 wt.% or more, 75 wt.% or more, or 80 wt.% or more. The upper limit can be 100 wt.-% (i.e., the content can be in the range of, for example, 50 wt.-% to 100 wt.-%), but is preferably 99 wt.-% or less, more preferably 98 wt.-% or less, for example 95 wt.-% or less, 93 wt.-% or less, 91 wt.-% or less, or 90 wt.-% or less.

[0142] Preferably, the high-boiling fraction has a ratio (≧C18 / <C18) of the content of hydrocarbons having 18 or more carbon atoms (≧C18) to the content of hydrocarbons having less than 18 carbon atoms (<C18) of 1.0 or more, preferably 1.5 or more, 2.0 or more, 3.0 or more, 4.0 or more, 5.0 or more, or 6.0 or more. The ratio can be, for example, 200.0 or less (i.e., the ratio can be in the range of, for example, 1.0 to 200.0), but is preferably 150.0 or less, for example 100.0 or less, 50.0 or less, 30.0 or less, 20.0 or less, 15.0 or less, 12.0 or less, or 10.0 or less.

[0143] Preferably, the low-boiling fraction has an interventile carbon number range (IVR) in the range of 5.0 to 12.0, preferably 6.0 to 12.0, or 7.0 to 11.0. The low-boiling fraction can have a relatively wide carbon number distribution while achieving preferable cracking characteristics. That is, in the low-boiling fraction, it is possible for the carbon number distribution to be narrow, but it is not absolutely necessary. In fact, considering the yield, it can even be said that it is preferable to allow a certain extent of the carbon number distribution so that a high share of the isomeric hydrocarbon composition can reach the method of the present invention. In particular, it is a preferable option that the isomeric hydrocarbon composition is fractionated into two fractions such that the total amount of the low-boiling fraction and the high-boiling fraction corresponds to 90 wt.% to 100 wt.%, preferably at least 95 wt.%, or at least 97 wt.% of the isomeric hydrocarbon composition to which the fractionation is applied.

[0144] Preferably, the low boiling fraction has a c_50 value of less than 16.5 and an interventile carbon range (IVR) in the range of 5.0 to 12.0.

[0145] Step (a) of the present invention may include fractionating the isomeric hydrocarbon composition to provide at least a low boiling fraction and a high boiling fraction. Alternatively, renewable cracker feed may be provided by a parallel process or may be purchased.

[0146] The low boiling fraction may have a content of compounds having a weight fraction in the range of 20 wt.-% to 40 wt.-%, preferably 22 wt.-% to 37 wt.-%, or 25 wt.-% to 35 wt.-% at the modal carbon number. This means that the low boiling fraction may have a reasonably broad carbon number distribution, i.e., a significant weight fraction at and usually near the modal carbon number. The modal carbon number is the carbon number with the greatest abundance in the PIONA analysis.

[0147] The low boiling fraction preferably has a minimum carbon number (C_min) in the range of 5 to 8, preferably 5 to 7, for example 5 to 6. The low boiling fraction preferably has a maximum carbon number (C_max) in the range of 14 to 26, preferably 15 to 23, 16 to 22, or 17 to 21. Within these ranges, the effects of the present invention are particularly pronounced. In addition, especially the above C_max ranges result in easy evaporation of the renewable cracker feed and a low coking tendency in the conversion section of the thermal cracker.

[0148] The low boiling fraction preferably has a modal carbon number in the range of 12-17, for example 13-17, 14-16, or 15-16.

[0149] The low boiling fraction preferably has an interquartile carbon number range (IQR) ranging from 1.5 to 4.0, preferably from 2.0 to 3.5, or from 2.0 to 3.0. In other words, the low boiling fraction may have a broader carbon number distribution than the high boiling fraction, but even in such a case, this fraction preferably has a certain sharpness, as indicated by the IQ R. That is, such well-defined fractions allow the cracking process to be specifically tailored to the feed characteristics, thus further improving the yield of valuable products and minimizing side reactions.

[0150] For the same reason, the low boiling fraction has an adjusted average carbon range (IDR) in the range of 4.0 to 14.0, 6.0 to 10.0, or 7.0 to 9.0. Preferably, the low boiling fraction has an interventile carbon range (IVR) in the range of 6.0 to 11.0, 7.0 to 11.0, or 8.0 to 10.5.

[0151] The low boiling fraction preferably has an 80% carbon span (CS_80) in the range of 3.0 to 9.0, preferably 4.0 to 8.0, or 4.5 to 7.0.

[0152] In the present invention, the 80% carbon span (CS_80) and other carbon spans are determined similarly to the C_80 value by linear interpolation. However, whereas the C_80 value is obtained by sorting the carbon numbers in numerical order (i.e., C1, C2, C3, etc.), the carbon spans (such as CS_80) are determined based on data in which the carbon numbers are sorted in order of abundance, as obtained by PIONA analysis, and the most abundant carbon number is given index 1, the next most abundant carbon number is given index 2, and so on. The CS_80 is then calculated based on linear interpolation by determining the index that corresponds to 80% of the sample. Figure 1 shows the CS_80 values ​​in graph B, based on the same samples as shown in graph A, where the X-axis shows the indexed carbon numbers. The graph further shows the actual carbon numbers (for reference only) above the bar graph. In the case of Figure 1, the CS_80 is very close to, but slightly below, 3, as shown by the dotted line (index 3 corresponds to C17).

[0153] The low boiling fraction preferably has a cloud point of −20° C. or less, more preferably −30° C. or less, −40° C. or less, −45° C. or less, and most preferably −50° C. or less. The cloud point may be, for example, in the range of −70° C. to −20° C., or in the range of −65° C. to −40° C. A low cloud point provides favorable cracking properties and facilitates handling of renewable cracker feed.

[0154] Preferably, the high boiling fraction has a higher c_50 value than the isomeric hydrocarbon composition, and the low boiling fraction has a lower c_50 value than the high boiling fraction. In particular, it is preferred that the high boiling fraction is a fraction that mainly contains the heavy part of the isomeric hydrocarbon composition. For example, the high boiling fraction can be the bottom fraction, and the low boiling fraction can be one of the non-bottom fractions or the only non-bottom fraction.

[0155] Preferably, the high-boiling fraction has a c_50 value that is at least 0.5 higher than the c_50 value of the isomeric hydrocarbon composition, preferably at least 1.0 higher or at least 15 higher, meaning that the fractional carbon number representing 50 wt.-% of the high-boiling fraction is increased by at least 0.5 relative to the fractional carbon number representing 50 wt.-% of the isomeric hydrocarbon composition.

[0156] Preferably, the low boiling fraction has a c_50 value that is at least 0.5 lower, preferably at least 1.0 lower, or at least 15 lower than the c_50 value of the high boiling fraction.

[0157] The high boiling point fraction preferably has a content of compounds having a weight fraction in the range of 40 to 95 wt.-%, 50 to 92 wt.-%, 60 to 90 wt.-%, 65 to 89 wt.-%, 70 to 88 wt.-%, 75 to 87 wt.-%, 76 to 86 wt.-%, or 77 to 85 wt.-% in terms of modal carbon number.

[0158] Preferably, the high boiling fraction has a minimum carbon number (C_min) in the range of 8 to 20, preferably 10 to 18, 11 to 17, 12 to 16, or 13 to 16. Preferably, the high boiling fraction has a maximum carbon number (C_max) in the range of 22 to 40, preferably 24 to 38, 26 to 36, 26 to 35, or 27 to 34. Preferably, the high boiling fraction has a modal carbon number in the range of 17 to 22, preferably 18 to 21, 18 to 20, or 18 to 19. It has been shown that the effects of the present invention are particularly remarkable within these ranges.

[0159] Preferably, the high boiling fraction has an interquartile carbon number range (IQR) in the range of 0.1 to 3.0, 0.2 to 2.0, 0.3 to 1.0, or 0.4 to 0.8. Preferably, the high boiling fraction has an adjusted mean carbon number range (IDR) in the range of 0.5 to 4.0, 0.6 to 3.0, 0.7 to 2.0, or 0.8 to 1.6. Preferably, the high boiling fraction has an interventile carbon number range (IVR) in the range of 1.1 to 5.0, 1.3 to 4.0, 1.4 to 3.5, 1.6 to 3.2, 1.8 to 3.0, or 1.8 to 2.8. Preferably, the high boiling fraction has an 80% carbon span (CS_80) in the range of 0.1 to 3.0, for example 0.2 to 2.5, 0.3 to 2.0, 0.4 to 1.6, or 0.5 to 1.4. As described above for the low boiling fraction, it is preferable for the process of the present invention to have a narrow carbon number distribution. In particular, in the case of the high boiling fraction, it is preferable to have a very narrow carbon number distribution, which leads to a particularly pronounced effect of the present invention.

[0160] The high boiling fraction preferably has a cloud point of -10°C or less, preferably -15°C or less, -20°C or less, -25°C or less, or -27°C or less. Because it is a high boiling fraction, the cloud point is not necessarily as low as the low boiling fraction. The cloud point may be, for example, in the range of -60°C to -10°C, or in the range of -40°C to -15°C.

[0161] The pyrolysis step (b) may be a steam cracking step. Steam cracking is tolerant of possible impurities common to renewable materials. In addition, the method of the present invention has been shown to produce particularly good results when steam cracking is employed.

[0162] Preferably, the pyrolysis step (b) is carried out at a coil outlet temperature (COT) selected in the range of 780°C to 900°C, preferably 805°C to 865°C, more preferably 815°C to 850°C.

[0163] The pyrolysis step (b) may be carried out at a coil outlet pressure (COP) selected from the range of 1.3 bar to 6.0 bar, preferably 1.3 bar to 3.0 bar. In the present invention, pressure values ​​or pressure ranges refer to absolute pressures, unless otherwise specified.

[0164] The pyrolysis step (b) is preferably carried out in the presence of a pyrolysis diluent. Any conventional pyrolysis diluent can be used in the pyrolysis stage (b). Examples of such pyrolysis diluents include steam, molecular nitrogen (N2), or mixtures thereof. Dilution of the pyrolysis feed reduces the hydrocarbon partial pressure in the pyrolysis coil and promotes the formation of primary reaction products, such as ethylene and propylene. The pyrolysis diluent preferably includes steam.

[0165] The pyrolysis step (b) is preferably carried out in the presence of a pyrolysis diluent with a dilution factor in the range of 0.10 to 0.80, preferably 0.25 to 0.70, for example 0.35 to 0.50. By dilution factor is meant the flow rate of pyrolysis diluent and total cracker feed (flow rate of pyrolysis diluent [kg / h] / flow rate of total cracker feed [kg / h]). By total cracker feed is meant renewable cracker feed plus any optional co-feeds and any optional additives, excluding the diluent.

[0166] The individual components of the total cracker feed and the diluent may be fed to the pyrolysis furnace as a preformed mixture, as separate streams, or as a combination of separate streams and a preformed mixture.

[0167] The method may include carrying out one or more further cracking operations to provide a further cracked effluent, where step (c) further comprises adding the further effluent and / or a fraction thereof before and / or during the separation process.

[0168] The pyrolysis in step (b) is preferably carried out in the presence of a cofeed.

[0169] Preferably, the content of renewable cracker feed in the total cracker feed is in the range of 10 wt.-% to 100 wt.-%, preferably 20 wt.-% to 100 wt.-%, 30 wt.-% to 100 wt.-%, 40 wt.-% to 100 wt.-%, 50 wt.-% to 100 wt.-%, 60 wt.-% to 100 wt.-%, 70 wt.-% to 100 wt.-%, 80 wt.-% to 100 wt.-%, or 90 wt.-%, where total cracker feed means renewable cracker feed plus any optional co-feeds and any optional additives. The upper limit may also be 90 wt.-% or 80 wt.-%, i.e. the content may be within the range of, for example, 10 wt.-% to 90 wt.-%, or 10 wt.-% to 80 wt.-%.

[0170] The use of at least 10 wt.-% renewable cracker feed ensures that the effects of the present invention are significant. The total cracker feed may be composed of renewable cracker feed, i.e. its content may be 100 wt.-%.

[0171] The co-feed may include a co-feed of fossil hydrocarbons. Fossil co-feeds, especially fossil naphtha, are readily available and very suitable for pyrolysis. To fully enjoy the benefits of the present invention, it is preferred that the co-feed has a composition, especially a carbon number distribution, similar to that of the renewable cracker feed. In particular, the co-feed may include a naphtha range feed, a diesel range feed, an aviation fuel range feed, a marine fuel range feed, or a gas oil range feed. In particular, when the high boiling fraction (or a portion thereof) is used as the renewable cracker feed, the co-feed may include a heavy fossil fraction, such as a gas oil fraction.

[0172] The total cracker feed preferably has a sulfur content in the range of 20 to 300 ppm by weight, more preferably 20 to 250 ppm by weight, more preferably 20 to 100 ppm by weight, and even more preferably 50 to 65 ppm by weight.

[0173] The inventors have surprisingly found that a (total) cracker feed containing renewable cracker feed (and optionally co-feeds and / or additives) and having a sulfur content within the above ranges results in significantly reduced coking tendency during pyrolysis.

[0174] Since renewable cracker feeds typically have low to no inherent sulfur content, sulfur can be incorporated into the total cracker feed by using a sulfur-containing co-feed, such as a fossil hydrocarbon feed. Sulfur can also come from sulfur-containing additives, including conventional cracking additives, in part or in total. Specifically, any conventional pyrolysis additive can be added to the renewable cracker feed of the present disclosure, to the optional co-feed, or to the preformed total cracker feed, or co-fed to the pyrolysis furnace, or added to the pyrolysis diluent and thus fed to the pyrolysis furnace. Examples of such conventional pyrolysis additives include sulfur-containing species (sulfur additives), such as dimethyl disulfide (DMDS), carbon disulfide (CS2), and the like. DMDS is a particularly preferred sulfur additive. The sulfur additive can be mixed with the renewable cracker feed, the optional co-feed, or the preformed total cracker feed before being fed to the pyrolysis furnace. Optionally, the sulfur additive may be added to the pyrolysis diluent, preferably steam, which contains the sulfur additive, by injection into the pyrolysis furnace.

[0175] The step (a) of providing a renewable cracker feed may, for example, include the steps of subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, and to hydroisomerization to provide at least an isomerized deoxygenated stream, subjecting at least a portion of the isomerized deoxygenated stream to fractionation and recovering at least an isomerized hydrocarbon composition, subjecting at least a portion of the isomerized deoxygenated stream to fractionation and recovering at least an isomerized hydrocarbon composition, and subjecting at least a portion of the isomerized deoxygenated stream to further fractionation to provide at least a low boiling fraction and a high boiling fraction. The isomerized deoxygenated stream is preferably a liquid isomerized deoxygenated stream.

[0176] In addition to the isomeric hydrocarbon composition, other fractions may be recovered, such as, but not limited to, at least one of a fuel gas fraction, a marine fuel fraction, a naphtha range fraction, a diesel range fraction, an aviation fuel fraction, or an electrical technology fluid fraction. A propane fraction may be recovered from gas-liquid separation after hydroprocessing. Preferably, one or more fractions usable as liquid transportation fuels, such as, for example, diesel fuel, gasoline fuel, aviation fuel, or marine fuel, are recovered.

[0177] An exemplary aviation fuel range fraction may boil within the range of 100°C to 300°C, such as within the range of 150°C to 300°C. An exemplary gasoline fuel fraction may boil within the range of 25°C to 220°C. An exemplary diesel fuel fraction may boil within the range of 160°C to 380°C. An exemplary marine fuel may boil within the range of 180°C to 600°C.

[0178] Generally, naphtha range fractions disclosed herein may refer to fractions having an initial boiling point above 0° C., preferably above 20° C. or above 30° C., and a T95 temperature of 220° C. or less, preferably 200° C. or less, 180° C. or less, 160° C. or less, 140° C. or less. Naphtha range fractions may have a T99 temperature of 220° C. or less, preferably 200° C. or less, 180° C. or less, 160° C. or less, 140° C. or less, or a final boiling point of 220° C. or less, preferably 200° C. or less, or 180° C. or less.

[0179] Unless otherwise specified, the boiling properties in the present invention, such as T95 temperature (95 vol-% recovery), T99 temperature (99 vol-% recovery), final boiling point, initial boiling point, T5 temperature (5 vol-% recovery), and T10 temperature (10 vol-% recovery), are measured according to EN ISO 3405-2019.

[0180] In the present invention, hydroisomerization may be carried out in the same hydrotreatment as hydrodeoxygenation. In other words, hydroisomerization may be part of hydrotreatment that includes at least hydrodeoxygenation. Alternatively, or in addition, hydroisomerization may be carried out in a further hydrotreatment after hydrotreatment that includes at least hydrodeoxygenation.

[0181] Hydroprocessing, including hydrodeoxygenation and hydroisomerization, may be carried out, for example, using a catalyst or catalyst system that accomplishes both hydrodeoxygenation and hydroisomerization in a single step.

[0182] Step (a) may further comprise a gas-liquid separation stage after hydrotreating and / or after further hydrotreating, and recovering at least one gaseous stream and an isomerized deoxygenated stream. The gaseous stream may be subjected to a propane separation process to provide a propane-rich stream and a propane-depleted stream. At least a portion of the propane from the propane-rich stream may be subjected to dehydrogenation, preferably catalytic dehydrogenation, to produce propylene. The gaseous streams from the gas-liquid separation may be combined or may be processed separately. The gas-liquid separation further provides a liquid stream. At least a portion of the liquid stream recovered after hydrotreating and / or after further hydrotreating may be used as an isomerized deoxygenated stream.

[0183] In one embodiment, the renewable cracker feed can be obtained or is obtained by a process comprising the steps of subjecting an oxygenate bio-renewable feed to hydroprocessing, including at least hydrodeoxygenation, to hydroisomerization, and to gas-liquid separation to at least provide an isomerized deoxygenated stream, feeding the isomerized deoxygenated stream to a first distillation column, preferably a stabilization column, to obtain at least a naphtha range fraction and a stabilized heavy liquid fraction, and feeding at least a portion of the stabilized heavy liquid fraction, as an isomeric hydrocarbon composition, to a second distillation column and recovering at least a low boiling fraction and a high boiling fraction.

[0184] The step of obtaining a liquid paraffinic hydrocarbon intermediate is disclosed in WO 2021 / 094655, which is incorporated herein by reference in its entirety. In particular, this step is disclosed in WO 2021 / 094655 with reference to Figures 1 and 2 and the accompanying text, which are specifically incorporated herein by reference. In this respect, the liquid paraffinic hydrocarbon intermediate corresponds to the stabilized heavy liquid fraction described above.

[0185] In general, the following steps can be adopted: The isomerized deoxygenated stream is introduced to stabilization in a stabilization tower, preferably at a pressure lower than the isomerization, where an overhead fraction is formed in addition to the stabilized heavy liquid fraction. The overhead fraction comprises hydrocarbons in the naphtha range (for example C4-C8). This overhead fraction from the stabilization can be recovered and used as a gasoline component or, preferably, it can be returned to the stabilization for reflux, preferably in the stabilization tower. Thus, preferably according to the invention, the oxygenate biorenewable is subjected to hydrotreating and isomerization, and the liquid product is sent to the stabilization at a pressure lower than the pressure of the isomerization. The recycle amount of naphtha range hydrocarbons used for reflux can be 80 wt.-% or more, preferably 90 wt.-% or more, for example 90-95 wt.-%, of the formed hydrocarbons in the naphtha range at the top of the stabilization tower. A high recycle amount helps the subsequent separation of light and heavy fractions, as well as improves the yield of the resulting low and high boiling fractions. Usually, more reflux requires the adjustment of the equipment for a larger flow. Therefore, preferably, in the present invention, during stabilization, an overhead fraction containing naphtha range (C4-C8) hydrocarbons is formed, and an amount of 60 wt.-% or more, for example 90 wt.-% or more, for example 90-95 wt.-%, of the naphtha range hydrocarbons formed at the stabilization tower overhead is returned to the stabilization.

[0186] The isomerized deoxygenated stream may have an i-paraffin content of at least 65 wt.-%, preferably at least 70 wt.-%, at least 75 wt.-%, at least 80 wt.-%, at least 85 wt.-%, or at least 90 wt.-%.

[0187] The method further includes derivatizing at least a portion of the light olefins to obtain one or more derivatives of the light olefins as biomonomers, such as, for example, acrylic acid, acrylonitrile, acrolein, propylene oxide, ethylene oxide, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, adiponitrile, hexamethylenediamine (HMDA), hexamethylene diisocyanate (HDI), (methyl)methacrylate, ethylidenenorborene, 1,5,9-cyclododecatriene, sulfolane, 1,4-hexadiene, tetrahydrophthalic anhydride, valeraldehyde, 1,2-butyl oxide, n-butyl mercaptan, o-sec-butylphenol, propylene, octene, sec-butyl alcohol, and the like.

[0188] In the present invention, it is preferred that the renewable cracker feed may be obtained by a process comprising hydrotreating and isomerization of an oxygenate bio-renewable feed.

[0189] Certain embodiments of the present invention relate to an integrated process and at least to a biorefinery adapted for carrying out such an integrated process. For example, at least a portion of the low boiling fraction is subjected to pyrolysis step (c) in a first pyrolysis furnace, and at least a portion of the high boiling fraction is subjected to pyrolysis step (c) in a second pyrolysis furnace. Similarly, at least a portion of the low boiling fraction and at least a portion of the high boiling fraction can be subjected to pyrolysis step (c) alternately in the same pyrolysis furnace.

[0190] Thus, both components can be utilized while still achieving the advantages of the present invention, namely, superior cracking properties over isomeric hydrocarbon compositions.

[0191] It is also possible that at least a portion of the low boiling fraction is subjected to a thermal cracking step (c) and at least a portion of the high boiling fraction is recovered as a specific fluid or component thereof, such as, for example, an electrical technical fluid, a lubricant, a coolant or component thereof, and / or as a fuel component, such as, for example, a marine fuel component. It is also possible that at least a portion of the high boiling fraction is subjected to a thermal cracking step (c) and at least a portion of the low boiling fraction is recovered as a fuel component, preferably as an aviation fuel component.

[0192] It is further possible that a part of the low boiling fraction is subjected to a thermal cracking step (c) and another part of the low boiling fraction is recovered as a fuel component, preferably as an aviation fuel component. Similarly, it is also possible that a part of the high boiling fraction is subjected to a thermal cracking step (c) and another part of the high boiling fraction is recovered as a specific fluid or component thereof, such as for example an electrical technical fluid, a lubricant, a coolant or component thereof, and / or as a fuel component, such as for example a marine fuel component.

[0193] All the above options for the integrated process have in common the advantage that they provide flexibility to the integrated process, i.e. the process can be adjusted depending on the demand for the various components. For example, to maximize the value of the various product streams, each product can be recovered from time to time in different amounts depending on market needs, prices, desired composition and / or quality, or based on the availability of raw materials, e.g. oxygenate bio-renewable feeds.

[0194] The method of the present invention may further comprise a step (e) of (co)polymerizing at least one of the light olefins separated in step (c) and / or at least one of the biomonomers, optionally together with other (co)monomers and / or after optional further purification, to produce a biopolymer composition.

[0195] The polymers can be further processed, optionally with other ingredients, to produce hygiene products, building materials, packaging materials, coating compositions, paints, decorative materials such as panels, interior parts of vehicles such as automobile interior parts, rubber compositions, tires or tire components, toners, personal health care products, parts of consumer goods, parts or housings of electronic devices, films, moldings, gaskets.

[0196] The present invention further relates to a biopolymer composition obtainable by the method of the present invention. EXAMPLES

[0197] The present invention will now be further illustrated by the following examples, which should not be construed as limiting the invention in any way.

[0198] Pyrolysis of five feed compositions (C1-C3, E1, E2) was evaluated. Composition C1 corresponds to a renewable composition obtained by hydrotreating and fractionating an oxygenate biorenewable feed, including hydrodeoxygenation and medium to high hydroisomerization, to provide a material that is mainly in the diesel fuel range. Composition C2 corresponds to a renewable composition obtained by hydrotreating and fractionating an oxygenate biorenewable feed, including hydrodeoxygenation and medium to high hydroisomerization, to provide a material that is mainly in the diesel fuel range. Composition C3 corresponds to a renewable composition obtained by hydrotreating and fractionating an oxygenate biorenewable feed, including hydrodeoxygenation and high hydroisomerization, to provide a material that is mainly in the diesel fuel range. Composition C3 corresponds to an isomeric hydrocarbon composition as described herein.

[0199] Compositions E1 and E2 correspond to the low-boiling and high-boiling fractions described herein, respectively, obtained by fractionation of a composition produced in a manner similar to that applied to composition C3, but under conditions suppressing the generation of iP3+ species. The PIONA data, carbon number analysis based on the PIONA data, cloud point, and iP3+ analysis of these compositions are shown in Table 1 below:

[0200] [Table 1]

[0201] Comparative Examples 1 to 3 and Examples 1 to 4 The composition was subjected to steam cracking at a coil outlet temperature (COT) of 820° C., a dilution (water / oil ratio) of 0.5, and a coil outlet pressure (COP) of 1.7 bar (absolute).

[0202] The yields of related products obtained are shown in Table 2 below. In addition, compositions E1 and E2 were subjected to decomposition at 880° C., with the remaining conditions kept the same. The results are shown in Table 3 below, in comparison with Examples 1 and 2 (820° C.).

[0203] [Table 2]

[0204] [Table 3]

[0205] Increasing the degree of isomerization lowers the cloud point, which allows for easier handling and storage of the feed material. In addition, in the comparative example, the yield of valuable propylene, combined with unwanted benzene, increases with increasing degree of isomerization.

[0206] In embodiments of the present invention where the iP content is kept high but the amount of iP3+ substitution is minimized in combination with a more uniform carbon number range, e.g., a low IQR and / or a low carbon span, e.g., CS@80% (CS_80), the production of benzene can be suppressed in favor of valuable olefin formation, and additionally the production of light pollutants, e.g., acetylene, methylacetylene, and propadiene, can be reduced.

[0207] Table 3 shows that the materials perform over a wide temperature range, which may allow further optimization of product yields, and of particular interest is the conversion at lower temperatures, which may promote propylene formation with reduced benzene formation, saving valuable heating operations and allowing for lower carbon emissions in production.

Claims

1. (a) providing a renewable cracker feed obtained by fractionating an isomeric hydrocarbon composition having an i-paraffin content of 85.0 wt.-% or more and a carbon number range ranging from 20 to 32 into at least a low boiling fraction and a high boiling fraction, and providing at least a portion of the low boiling fraction or at least a portion of the high boiling fraction as the renewable cracker feed; (b) pyrolyzing the renewable cracker feed, optionally together with co-feeds and / or additives, in a pyrolysis furnace; and (c) subjecting the pyrolysis furnace effluent of step (b) to a separation process to provide at least a light olefin fraction. The method includes:

2. 2. The process of claim 1, wherein the isomeric hydrocarbon composition has a c_50 value in the range of from 14.0 to 22.0, preferably from 14.0 to 20.0, or from 1.5.0 to 20.

0.

3. 3. The process according to claim 1 or 2, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have an i-paraffin content of 92.0 wt.-% or more, preferably 93.0 wt.-% or more, 94.0 wt.-% or more, or 95.0 wt.-% or more.

4. 4. The method according to any one of claims 1 to 3, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a ratio of i-paraffins with more than three branches (IP3+) to total i-paraffins (iP) (iP3+ / iP) of 0.164 or less, preferably 0.160 or less, 0.155 or less, 0.150 or less.

5. 5. The method according to any one of claims 1 to 4, wherein both the low boiling fraction and the high boiling fraction, independently of each other, have a total content of i-paraffins with more than three branches (iP3+) relative to total paraffins of 10.50 wt.-% or more, for example 10.50 to 16.00, 11.00 to 15.50, 11.00 to 15.50, 11.00 to 15.00, or 1.2.00 to 15.

00.

6. Both the low boiling fraction and the high boiling fraction, independently of each other, have a cloud point of −10° C. or less, preferably −15° C. or less, or −20° C. or less; and / or Both the low boiling fraction and the high boiling fraction, independently of each other, have a mercury content of from 0.1 wt.-% to 10.0 wt.-%, preferably from 0.1 wt.-% to 8.0 wt.-%, from 0.1 wt.-% to 6.5 wt.-%, from 0.2 wt.-% to 6.0 wt.-%, from 0.5 wt.-% to 5.5 wt.-%, from 0.5 wt.-% to 5.0 wt.-%, from 0.8 wt.-% to 5.0 wt.-%, from 0.9 wt.-% to 5.0 wt.-%, from 1.0 wt.-% to 5.0 wt.-%, from 1.1 wt.-% to 5.0 wt.-%, or from 1.2 wt.-% to 5.0 wt.-%. -% combined olefins, aromatics and naphthenes; and / or Both the low boiling fraction and the high boiling fraction, independently of each other, have modal carbon numbers ranging from 11 to 21, preferably from 14 to 20, or from 16 to 18. The method according to any one of claims 1 to 5.

7. 7. The process according to any one of claims 1 to 6, wherein the high boiling fraction has a c_50 value in the range of 16.5 to 20.0, preferably 16.5 to 19.0, or 17.0 to 18.

0.

8. The process according to any one of claims 1 to 7, wherein the high boiling fraction has a modal carbon number in the range of from 17 to 22, preferably from 18 to 21, from 18 to 20, or from 18 to 19.

9. 9. The process of any one of claims 1 to 8, wherein the high boiling fraction has an adjusted average carbon number range (IDR) in the range of 0.5 to 4.0, 0.6 to 3.0, 0.7 to 2.0, 0.8 to 1.

6.

10. 10. The method of any one of claims 1 to 9, wherein the high boiling fraction has an 80% carbon span (CS_80) in the range of 0.1 to 3.0, preferably 0.2 to 2.5, 0.3 to 2.0, 0.4 to 1.6, or 0.5 to 1.

4.

11. 11. The method of any one of claims 1 to 10, wherein the high boiling fraction has an interventile carbon range (IVR) of 5.0 or less, preferably 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, or 2.3 or less.

12. 12. The process according to any one of claims 1 to 11, wherein the low boiling fraction has a c_50 value in the range of from 11.0 to less than 16.5, preferably from 12.0 to 16.0, or from 14.0 to 16.

0.

13. The process according to any one of claims 1 to 12, wherein the low boiling fraction has a modal carbon number in the range of from 12 to 17, such as from 13 to 17, such as from 14 to 16, or from 15 to 16.

14. 14. The process of any one of claims 1 to 13, wherein the low boiling fraction has an adjusted average carbon number range (IDR) in the range of 4.0 to 14.0, 6.0 to 10.0, 7.0 to 9.

0.

15. 15. The method according to any one of claims 1 to 14, wherein the low boiling fraction has a carbon span at 80% (CS_80) in the range of 3.0 to 9.0, preferably 4.0 to 8.0, or 4.5 to 7.

0.

16. 16. The method according to any one of claims 1 to 15, wherein the low boiling fraction has an interventile carbon range (IVR) in the range of 5.0 to 12.0, preferably 6.0 to 12.0, or 7.0 to 11.

0.

17. (A) at least a portion of the low boiling fraction is subjected to the pyrolysis step (c) in a first pyrolysis furnace and at least a portion of the high boiling fraction is subjected to the pyrolysis step (c) in a second pyrolysis furnace; and / or (B) at least a portion of the low boiling fraction and at least a portion of the high boiling fraction are subjected to the pyrolysis step (c) alternately in the same pyrolysis furnace; and / or (C) at least a portion of the low boiling fraction is subjected to the thermal cracking step (c) and at least a portion of the high boiling fraction is recovered as a specific fluid or component thereof, such as, for example, an electrical technical fluid, a lubricant, a coolant or component thereof, and / or as a fuel component, such as, for example, a marine fuel component; and / or (D) at least a portion of the high boiling fraction is subjected to the thermal cracking step (c) and at least a portion of the low boiling fraction is recovered as a fuel component, preferably as an aviation fuel component; and / or (E) a part of the low boiling fraction is subjected to the thermal cracking step (c) and another part of the low boiling fraction is recovered as a fuel component, preferably as an aviation fuel component; and / or (F) a part of the high boiling fraction is subjected to the thermal cracking step (c) and another part of the high boiling fraction is recovered as a specific fluid or component thereof, such as, for example, an electrical technical fluid, a lubricant, a coolant or component thereof, and / or as a fuel component, such as, for example, a marine fuel component. The method according to any one of claims 1 to 16.

18. 18. The process according to any one of claims 1 to 17, wherein the low boiling point fraction has a minimum carbon number (C_min) in the range of 5 to 8 and a maximum carbon number (C_max) in the range of 14 to 26, preferably a minimum carbon number (C_min) in the range of 5 to 7 and a maximum carbon number (C_max) in the range of 15 to 23, a minimum carbon number (C_min) that is 5 or 6 and a maximum carbon number (C_max) in the range of 16 to 22, or a minimum carbon number (C_min) that is 5 or 6 and a maximum carbon number (C_max) in the range of 17 to 21.

19. 19. The process according to any one of claims 1 to 18, wherein the high boiling point fraction has a minimum carbon number (C_min) in the range of 8 to 20 and a maximum carbon number (C_max) in the range of 22 to 40, preferably a minimum carbon number (C_min) in the range of 10 to 18 and a maximum carbon number (C_max) in the range of 24 to 38, a minimum carbon number (C_min) in the range of 11 to 17 and a maximum carbon number (C_max) in the range of 26 to 36, a minimum carbon number (C_min) in the range of 12 to 16 and a maximum carbon number (C_max) in the range of 26 to 35, or a minimum carbon number (C_min) in the range of 13 to 16 and a maximum carbon number (C_max) in the range of 27 to 34.

20. the pyrolysis step (b) is a steam cracking step; and / or The pyrolysis in step (b) is carried out in the presence of a cofeed.

20. The method according to any one of claims 1 to 19.

21. The renewable cracker feed comprises: subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, to hydroisomerization, and to gas-liquid separation to provide said isomerized deoxygenated stream; feeding the isomerized deoxygenated stream to a first distillation column, preferably a stabilization column, to obtain at least a naphtha range fraction and a stabilized heavy liquid fraction; feeding at least a portion of said stabilized heavy liquid fraction as said isomeric hydrocarbon composition to a second distillation column, and recovering at least said low boiling fraction and said high boiling fraction. The method according to any one of claims 1 to 20, obtained by

22. an optional step further comprising derivatizing at least a portion of the light olefins to obtain one or more derivatives of the light olefins as biomonomers; and (e) (co)polymerizing at least one of the light olefins and / or at least one of the biomonomers separated in step (c), optionally together with other (co)monomers and / or after optional further purification, to produce a biopolymer composition. The method of any one of claims 1 to 21, further comprising:

23. A biopolymer composition obtainable by the method of claim 22.

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