Renewable stabilized naphtha range hydrocarbon feed, thermal cracking process thereof and products thereof

Abstract

The present invention relates to a process involving thermal cracking, a renewable stabilized naphtha range hydrocarbon feed usable in such a process, and a cracked effluent obtained by the use of such a process. The process of the present invention comprises the steps of (a) providing a renewable stabilized naphtha range hydrocarbon feed, (b) thermally cracking the renewable stabilized naphtha range hydrocarbon feed, optionally with co-feeds and / or additives, in a thermal cracking furnace, and (c) subjecting the effluent of the thermal cracking furnace of step (b) to a separation process to provide at least a light olefin fraction.

Description

[Technical field]

[0001] The present invention relates to processes involving thermal cracking, renewable stabilized naphtha range hydrocarbon feeds that can be used in such processes, and products obtained by the use of 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] 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, the light olefins, especially ethylene and propylene, are the most sought after by industry.

[0004] C4 olefins 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.

[0005] 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. Summary of the Invention

[0006] The present invention has been made in view of the above problems, and an object of the present invention is to provide a renewable stabilized naphtha range hydrocarbon feed, a thermal cracking process applying the renewable stabilized naphtha range hydrocarbon feed, and products obtained therefrom, and their use and further processing.

[0007] 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.

[0008] In summary, the present invention relates to one or more of the following items:

[0009] 1. (a) providing a renewable stabilized naphtha range hydrocarbon feed; (b) pyrolyzing the renewable stabilized naphtha range hydrocarbon feed, optionally 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:

[0010] 2. The method according to item 1, wherein the pyrolysis step (b) is carried out at a coil outlet temperature (COT) selected from the range of 780°C to 880°C, preferably 800°C to 86°C, more preferably 820°C to 850°C.

[0011] 3. The process according to item 1 or 2, wherein said 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.

[0012] 4. The method according to any one of the preceding items, wherein the pyrolysis step (b) is a steam cracking step.

[0013] 5. 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 0.85, preferably 0.25 to 0.60, for example 0.35 to 0.55.

[0014] 6. 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.

[0015] 7. 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 a further effluent and / or a fraction thereof to the pyrolysis furnace effluent of step (b) before and / or during the separation process.

[0016] 8. 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.

[0017] 9. The method according to any one of the preceding items, wherein the content of said renewable stabilized naphtha range hydrocarbon feed in the total cracker feed is 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.-% to 100 wt.-%, wherein said total cracker feed means said renewable stabilized naphtha range hydrocarbon feed plus any optional co-feed and any optional additives.

[0018] 10. The method of any one of the preceding items, wherein the co-feed comprises a fossil hydrocarbon co-feed.

[0019] 11. The method of any one of the preceding items, wherein the cofeed comprises a naphtha range feed.

[0020] 12. 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.

[0021] 13. The step (a) of providing a renewable stabilized naphtha range hydrocarbon feed comprises: subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, to at least provide a liquid hydrocarbon stream; and subjecting at least a portion of said liquid hydrocarbon stream to fractionation and recovering at least said renewable stabilized naphtha range hydrocarbon feed. The method according to any one of the preceding items, comprising:

[0022] 14. The hydroprocessing method according to claim 1, wherein the hydroprocessing comprises at least hydrodeoxygenation to provide a hydroprocessed effluent, and the hydroprocessed effluent is subjected to gas-liquid separation to provide a gaseous stream and a first liquid hydrocarbon stream; and 14. The method according to item 13, wherein at least a portion of said first liquid hydrocarbon stream is subjected to further hydroprocessing, including at least hydroisomerization, and then optionally further gas-liquid separation, to provide at least a second liquid hydrocarbon stream, and subjecting at least a portion of said second liquid hydrocarbon stream to fractionation as a liquid hydrocarbon stream, and recovering at least a renewable stabilized naphtha range hydrocarbon feed.

[0023] 15. The process according to item 14, wherein at least a portion of the first liquid hydrocarbon stream and / or the second liquid hydrotreated stream is recycled to hydroprocessing comprising at least hydrodeoxygenation.

[0024] 16. The method according to item 14 or 15, further comprising subjecting said gaseous stream to a propane separation process to provide a propane-rich stream and a propane-depleted stream.

[0025] 17. The process of claim 16, further comprising subjecting at least a portion of the propane from the propane-rich stream to dehydrogenation, preferably catalytic dehydrogenation, to produce propylene.

[0026] 18. The method according to any one of items 13 to 17, wherein the step of subjecting at least a portion of the liquid hydrocarbon stream to fractionation and recovering at least the renewable stabilized naphtha range hydrocarbon feed further comprises recovering a heavy liquid hydrocarbon fraction.

[0027] 19. The process according to item 18, wherein the heavy liquid hydrocarbon fraction is subjected to further fractionation to provide at least an aviation fuel range fraction and a bottoms fraction.

[0028] 20. The method according to any one of items 13 to 17, wherein the step of subjecting at least a portion of the liquid hydrocarbon stream to fractionation and recovering at least the renewable stabilized naphtha range hydrocarbon feed further comprises recovering at least an aviation fuel range fraction and / or a diesel range fraction.

[0029] 21. The method according to any one of items 18 to 20, wherein the diesel range fraction, the aviation fuel range fraction, the heavy liquid hydrocarbon fraction and / or the bottoms fraction has an isoparaffin 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.-%.

[0030] 22. The step of subjecting at least a portion of the liquid hydrocarbon stream to fractionation and recovering at least the renewable stabilized naphtha range hydrocarbon feed comprises at least subjecting at least a portion of said liquid hydrocarbon stream to fractionation to provide a naphtha range fraction; and 22. The method according to any one of items 13 to 21, subjecting the naphtha range fraction to stabilization, said stabilization comprising removing, preferably by distillation techniques, at least a portion of the components boiling below 20° C., preferably at least a portion of the components boiling below 25° C., at least a portion of the components boiling below 30° C., at least a portion of the components boiling below 40° C., or at least a portion of the components boiling below 50° C.

[0031] 23. The method according to any one of items 18 to 20, wherein the heavy liquid hydrocarbon fraction and / or the diesel range fraction has an isoparaffin content of less than 65 wt.-%.

[0032] 24. The step (a) of providing a renewable stabilized naphtha range hydrocarbon feed comprises: subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, to provide a hydroprocessed effluent; subjecting at least a portion of the hydroprocessing effluent to gas-liquid separation to provide a gaseous stream and a first liquid hydrocarbon stream; providing said first liquid hydrocarbon stream as a liquid hydrocarbon stream or subjecting at least a portion of said first liquid hydrocarbon stream to further hydroprocessing, including at least hydroisomerization, followed by optional further gas-liquid separation, to provide at least a second liquid hydrocarbon stream as said liquid hydrocarbon stream; feeding at least a portion of said liquid hydrocarbon stream to a first distillation column, preferably a first stabilization column, to obtain a first overhead fraction and a stabilized heavy liquid hydrocarbon fraction; Optionally, using at least a portion of said stabilized heavy liquid hydrocarbon fraction in diesel fuel and / or recovering at least an aviation fuel range fraction and a bottoms fraction from at least a portion of said stabilized heavy liquid hydrocarbon fraction; separating at least a fuel gas fraction and a naphtha range fraction from said first overhead fraction; refluxing a portion of the naphtha range fraction to said first distillation column, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 85 wt.-%; feeding at least a portion of said naphtha range fraction to a second distillation column, preferably a second stabilization column, to obtain a second overhead fraction, preferably comprising at least a portion of components boiling below 20° C., and a stabilized naphtha range fraction; separating at least a further fuel gas fraction and light liquid hydrocarbons from the second overhead fraction; and refluxing at least a portion of said light liquid hydrocarbons, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 85 wt.-%, to said second distillation column; and recovering at least a portion of said stabilized naphtha range fraction as a renewable stabilized naphtha range fraction hydrocarbon feed. 2. The method according to any one of the preceding items, including

[0033] 25. The method according to any one of items 13 to 24, wherein the hydrotreating comprising at least hydrodeoxygenation further comprises hydroisomerization.

[0034] 26. 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, octene, and sec-butyl alcohol.

[0035] 27. (d) (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 optionally after further purification, to produce a biopolymer composition. The method of any one of the preceding items, further comprising:

[0036] 28. The method according to item 27, wherein the biopolymer composition, optionally together with other ingredients, is further processed to produce a hygiene product, a building material, a packaging material, a coating composition, a paint, a decorative material, e.g. a panel, an interior part of a vehicle, e.g. an interior part of an automobile, a rubber composition, a tire or a tire component, a toner, a personal health care product, a part of a consumer product, a part or housing of an electronic device, a film, a molding, a gasket.

[0037] 29. Renewable stabilized naphtha range hydrocarbon feed for thermal cracking.

[0038] 30. The renewable stabilized naphtha range hydrocarbon feed according to item 29, wherein the renewable stabilized naphtha range hydrocarbon feed has a naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%, based on the total weight of the renewable stabilized naphtha range hydrocarbon feed.

[0039] 31. The renewable stabilized naphtha range hydrocarbon feed according to item 29 or 30, wherein the renewable stabilized naphtha range hydrocarbon feed has 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.-%, 0.8 to 5.8 wt.-%, 1.0 to 5.6 wt.-%, or 1.2 to 5.6 wt.-%.

[0040] 32. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 31, wherein the renewable stabilized naphtha range hydrocarbon feed has an olefin content 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, 0.1.2 wt.-% or less, 0.10 wt.-% or less, 0.07 wt.-% or less, or 0.05 wt.-% or less.

[0041] 33. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 32, wherein the renewable stabilized naphtha range hydrocarbon feed has a combined olefins and naphthenes content in the range of 0.1 wt.-% to 10.0 wt.-%.

[0042] 34. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 33, wherein the renewable stabilized naphtha range hydrocarbon feed has a combined olefins and naphthene content of 0.1 wt.-% to 8.0 wt.-%, for example 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.-%.

[0043] 35. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 34, wherein the renewable stabilized naphtha range hydrocarbon feed has 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.

[0044] 36. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 35, wherein the renewable stabilized naphtha range hydrocarbon feed has a ratio between the naphthene content and the aromatics content that is 1 or more, preferably 10 or more, 50 or more, or 100 or more.

[0045] 37. The renewable stabilized naphtha range hydrocarbon feed is 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 37. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 36 having a combined olefins, aromatics and naphthenes content of 0.0 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.-%.

[0046] 38. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 37, wherein the renewable stabilized naphtha range hydrocarbon feed has 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.

[0047] 39. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 38, wherein the renewable stabilized naphtha range hydrocarbon feed has a content of compounds having a carbon number of C17 or more of 1.0 wt.-% or less, for example 0.0 to 0.9 wt.-%, preferably 0.0 to 0.8 wt.-%, more preferably 0.0 to 0.5 wt.-%, or 0.0 to 0.2 wt.-%.

[0048] 40. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 39, wherein the renewable stabilized naphtha range hydrocarbon feed has a carbon range of 10 or less, preferably 8 or less, 7 or less, 6 or less, or 5 or less, and the carbon range is 1 or more, for example 1 to 10, 2 to 10, 3 to 10, 3 to 8, 3 to 7, or 3 to 6.

[0049] 41. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 40, wherein the renewable stabilized naphtha range hydrocarbon feed has an interventile carbon number range (IVR) of 6.5 or less, preferably 5.0 or less, 4.5 or less, 4.0 or less, or 3.8 or less.

[0050] 42. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 41, wherein the renewable stabilized naphtha range hydrocarbon feed has an adjusted average carbon number range (IDR) of 4.5 or less, preferably 4.0 or less, 3.5 or less, or 3.0 or less.

[0051] 43. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 42, wherein the renewable stabilized naphtha range hydrocarbon feed has an interquartile carbon number range (IQR) of 2.5 or less, preferably 2.0 or less, 1.8 or less, or 1.5 or less.

[0052] 44. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 43, wherein the renewable stabilized naphtha range hydrocarbon feed has a content of C11 or higher carbon number components of less than 5.0 wt.-%, preferably 4.5 wt.-% or less, 4.0 wt.-% or less, 3.5 wt.-% or less, 3.0 wt.-% or less, 2.5 wt.-% or less, or 2.0 wt.-% or less.

[0053] 45. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 44, wherein the renewable stabilized naphtha range hydrocarbon feed has a T95 temperature of 220°C or less, preferably 200°C or less, 180°C or less, 160°C or less, or 140°C or less.

[0054] 46. ​​The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 45, wherein the renewable stabilized naphtha range hydrocarbon feed has a T99 temperature of 220°C or less, preferably 200°C or less, 180°C or less, 160°C or less, or 140°C or less.

[0055] 47. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 46, wherein the renewable stabilized naphtha range hydrocarbon feed has a final boiling point of 220°C or less, preferably 200°C or less, 180°C or less, or 160°C or less.

[0056] 48. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 47, wherein the renewable stabilized naphtha range hydrocarbon feed has an initial boiling point of 20°C or higher, preferably 20°C to 60°C, for example 30°C to 50°C, or 30°C to 45°C.

[0057] 49. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 48, wherein the renewable stabilized naphtha range hydrocarbon feed has a T5 temperature of 40°C or more, preferably 45°C or more, 50°C or more, 55°C or more, or 60°C or more.

[0058] 50. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 49, wherein the difference between the T10 temperature and the T90 temperature of the renewable stabilized naphtha range hydrocarbon feed is less than 100°C, preferably less than 80°C, for example, 20°C to 75°C, 30°C to 70°C, or 40°C to 70°C.

[0059] 51. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 50, wherein the renewable stabilized naphtha range hydrocarbon feed has an aggregate paraffin content of 90 wt.-% or more, preferably 92 wt.-% or more, 93 wt.-% or more, 94 wt.-% or more, or 95 wt.-% or more.

[0060] 52. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 51, wherein the renewable stabilized naphtha range hydrocarbon feed has a content ratio of i-paraffins to n-paraffins of not more than 1.7, preferably not more than 1.5, for example in the range of 0.5 to 1.7, or 0.7 to 1.5.

[0061] 53. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 52, wherein the renewable stabilized naphtha range hydrocarbon feed has a content ratio of i-paraffins to n-paraffins in the range of 2.0 or more, preferably 2.2 or more.

[0062] 54. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 53, wherein the renewable stabilized naphtha range hydrocarbon feed is obtained by a process comprising a step of subjecting an oxygenate bio-renewable feed to hydrotreatment including at least hydrodeoxygenation and optionally to hydroisomerization.

[0063] 55. The renewable stabilized naphtha range hydrocarbon feed according to item 54, wherein the process comprises hydroisomerization.

[0064] 56. Subjecting the oxygenate biorenewable feed to hydroprocessing, including at least hydrodeoxygenation, to provide a hydroprocessed effluent; subjecting at least a portion of the hydroprocessing effluent to gas-liquid separation to provide a gaseous stream and a first liquid hydrocarbon stream; providing said first liquid hydrocarbon stream as a liquid hydrocarbon stream or subjecting at least a portion of said first liquid hydrocarbon stream to further hydroprocessing including at least hydroisomerization followed by optional further gas-liquid separation to provide at least a second liquid hydrocarbon stream as a liquid hydrocarbon stream; feeding at least a portion of said liquid hydrocarbon stream to a first distillation column, preferably a first stabilization column, to obtain a first overhead fraction and a stabilized heavy liquid hydrocarbon fraction; separating at least a fuel gas fraction and a naphtha range fraction from said first overhead fraction; refluxing a portion of said naphtha range fraction, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 85 wt.-%, to said first distillation column; feeding at least a portion of said naphtha range fraction to a second distillation column, preferably a second stabilization column, to obtain a second overhead fraction, preferably comprising at least a portion of components boiling below 20° C., and a stabilized naphtha range fraction; separating at least a further fuel gas fraction and light liquid hydrocarbons from the second overhead fraction; and refluxing at least a portion of said light liquid hydrocarbons, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 85 wt.-%, to said second distillation column; and recovering at least a portion of said stabilized naphtha range fraction as said renewable stabilized naphtha range hydrocarbon feed. 56. A renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 55, obtained by a process comprising the steps of:

[0065] 57. The renewable stabilized naphtha range hydrocarbon feed according to item 56, wherein said hydroprocessing, including at least hydrodeoxygenation, further includes hydroisomerization.

[0066] 58. The renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 57, having a content of C4 or lower carbon number compounds of 5.0 wt.-% or less, preferably 2.5 wt.-% or less, more preferably 2.0 wt.-% or less, even more preferably 1.5 wt.-% or less.

[0067] 59. The method according to any one of items 1 to 25, wherein the renewable stabilized naphtha range hydrocarbon feed is a renewable stabilized naphtha range hydrocarbon feed according to any one of items 29 to 58.

[0068] 60. Renewable pyrolysis effluent having a benzene content not exceeding 6.0 wt.-%, a combined ethylene and propylene content not exceeding 45.0 wt.-%, and a carbon monoxide content not exceeding 0.25 wt.-%.

[0069] 61. A renewable pyrolysis effluent according to item 60 having a benzene content of 0.01 wt.-% to 6.0 wt.-%, for example 0.1 wt.-% to 4.0 wt.-%, 0.1 wt.-% to 3.6 wt.-%, 0.1 wt.-% to 3.4 wt.-%, 0.1 wt.-% to 3.2 wt.-%, 0.1 wt.-% to 3.0 wt.-%, 0.1 wt.-% to 2.8 wt.-%, 0.1 wt.-% to 2.6 wt.-%, 0.2 wt.-% to 2.4 wt.-%, 0.3 wt.-% to 2.2 wt.-%, or 0.5 wt.-% to 2.0 wt.-% or less.

[0070] 62. The renewable pyrolysis effluent according to item 60 or 61, wherein the renewable pyrolysis effluent has a combined content of ethylene and propylene of 45 wt.-% to 65 wt.-%, preferably 46.0 wt.-% to 65.0 wt.-%, 47.0 wt.-% to 65.0 wt.-%, 48.0 wt.-% to 65.0 wt.-%, 49.0 wt.-% to 65.0 wt.-%, 50.0 wt.-% to 60.0 wt.-%, or 50.0 wt.-% to 55.0 wt.-%.

[0071] 63. A renewable pyrolysis effluent according to any one of items 60 to 62, wherein the renewable pyrolysis effluent has a total content of C4 olefins of at least 5.0 wt.-%, for example between 5.0 wt.-% and 20.0 wt.-%, preferably at least 8.0 wt.-%, at least 10.0 wt.-%, at least 11.0 wt.-%, at least 12.0 wt.-%, at least 12.6 wt.-%, at least 13.0 wt.-%, or at least 13.5 wt.-%.

[0072] 64. The renewable pyrolysis effluent according to any one of items 60 to 63, wherein the renewable pyrolysis effluent is the effluent of the pyrolysis furnace of step (b) of the method according to any one of items 1 to 25.

[0073] 65. The regenerable pyrolysis effluent according to any one of items 60 to 64, wherein the regenerable pyrolysis effluent has a carbon monoxide content of 0.23 wt.-% or less, preferably 0.21 wt.-% or less, 0.20 wt.-% or less, 0.19 wt.-% or less, 0.18 wt.-% or less, 0.17 wt.-% or less, 0.16 wt.-% or less, 0.15 wt.-% or less, 0.14 wt.-% or less, 0.13 wt.-% or less, 0.12 wt.-% or less, 0.11 wt.-% or less, 0.10 wt.-% or less, or 0.09 wt.-% or less.

[0074] 66. A renewable pyrolysis effluent according to any one of items 60 to 65, wherein the renewable pyrolysis effluent has a C4 monoolefin content of 6.0 wt.-% or more, preferably 6.5 wt.-% or more, 6.8 wt.-% or more, 7.0 wt.-% or more, 7.2 wt.-% or more, or 7.4 wt.-% or more.

[0075] 67. A renewable pyrolysis effluent according to any one of items 60 to 66, wherein the renewable pyrolysis effluent has a C4 monoolefin content of at most 15.0 wt.-%, or at most 13.0 wt.-%.

[0076] 68. A renewable pyrolysis effluent according to any one of items 60 to 67, wherein the renewable pyrolysis effluent has a 1,3-butadiene content of at least 5.0 wt.-%, preferably at least 5.5 wt.-%, at least 6.0 wt.-%, or at least 6.2 wt.-%.

[0077] 69. The renewable pyrolysis effluent according to any one of items 60 to 68, wherein the renewable pyrolysis effluent has a 1,3-butadiene content of at most 15.0 wt.-%, at most 13.0 wt.-%, or at most 11.0 wt.-%.

[0078] 70. A renewable pyrolysis effluent according to any one of items 60 to 69, wherein the renewable pyrolysis effluent has an isobutene content of at least 2.0 wt.-%, preferably at least 2.4 wt.-%, at least 3.0 wt.-%, or at least 3.2 wt.-%.

[0079] 71. The renewable pyrolysis effluent according to any one of items 60 to 70, wherein the renewable pyrolysis effluent has an isobutene content of at most 10.0 wt.-%, at most 9.0 wt.-%, or at most 8.0 wt.-%.

[0080] 72. A renewable pyrolysis effluent according to any one of items 60 to 71, wherein the renewable pyrolysis effluent has a content of n-C4 monoolefins of 3.0 wt.-% or more, preferably 3.5 wt.-% or more, or 4.0 wt.-% or more.

[0081] 73. The renewable pyrolysis effluent according to any one of items 60 to 72, wherein the renewable pyrolysis effluent has a content of n-C4 monoolefins of at most 15.0 wt.-%, at most 12.0 wt.-%, or at most 10.0 wt.-%.

[0082] 74. The renewable pyrolysis effluent according to any one of items 60 to 73, wherein the renewable pyrolysis effluent has a content of C2 to C4 paraffins in aggregate of 4.0 wt.-% or more, preferably 4.2 wt.-% or more, more preferably 4.3 wt.-% or more.

[0083] 75. The renewable pyrolysis effluent according to any one of items 60 to 74, wherein the renewable pyrolysis effluent has a content of C2 to C4 paraffins in aggregate of at most 15.0 wt.-%, at most 12.0 wt.-%, or at most 10.0 wt.-%.

[0084] 76. The renewable pyrolysis effluent according to any one of items 60 to 75, wherein the renewable pyrolysis effluent has a content of pyrolysis fuel oil (C10 and heavier compounds, abbreviated as "PFO") of less than 1.5 wt.-%, preferably less than 1.2 wt.-%, more preferably less than 1.0 wt.-%.

[0085] 77. The renewable pyrolysis effluent according to any one of items 60 to 76, wherein the renewable pyrolysis effluent has a toluene content in the range of 0.2 wt.-% to 1.8 wt.-%, preferably 0.2 wt.-% to 1.6 wt.-%, 0.2 wt.-% to 1.4 wt.-%, 0.2 wt.-% to 1.2 wt.-%, 0.2 wt.-% to 1.0 wt.-%, 0.2 wt.-% to 0.9 wt.-%, 0.2 wt.-% to 0.8 wt.-%, 0.2 wt.-% to 0.7 wt.-%, or 0.3 wt.-% to 0.6 wt.-%.

[0086] 78. The renewable pyrolysis effluent according to any one of items 60 to 77, wherein the renewable pyrolysis effluent has a combined ethylene and propylene content of not less than 50.0 wt.-%, a benzene content of not more than 4.0 wt.-%, and a toluene content in the range of 0.2 wt.-% to 0.6 wt.-%.

[0087] 79. A renewable pyrolysis effluent according to any one of items 60 to 78, wherein the renewable pyrolysis effluent has a content of ethylene and propylene and total C4 olefins of 45 wt.-% to 80 wt.-%, preferably 50 wt.-% to 75 wt.-%, 50 wt.-% to 70 wt.-%, 50 wt.-% to 65 wt.-%, or 55 wt.-% to 65 wt.-%.

[0088] 80. A biopolymer composition obtainable by the method according to item 27. [Brief description of the drawings]

[0089] [Figure 1] FIG. 1 is a diagram showing linear interpolation to obtain the c_50 value. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0090] In the present invention, contents and content ratios are provided on a weight basis unless otherwise specified.

[0091] 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.

[0092] 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.

[0093] 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 and 14By 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%.

[0094] In particular, the biogenic carbon content of the renewable stabilized naphtha range hydrocarbon 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%.

[0095] 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%.

[0096] 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%.

[0097] 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%.

[0098] 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.

[0099] Unless otherwise noted, all test method standards referred to in the text are current as of December 1, 2021.

[0100] Pyrolysis method First, the method of the present invention will be described.

[0101] The process of the present invention comprises the steps of (a) providing a renewable stabilized naphtha range hydrocarbon feed, (b) pyrolyzing the renewable stabilized naphtha range hydrocarbon feed in a pyrolysis furnace, optionally with a co-feed 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.

[0102] 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.

[0103] The pyrolysis step (b) is sometimes called the "thermal cracking step."

[0104] The renewable stabilized naphtha range hydrocarbon feed preferably has an initial boiling point of 20°C or more, preferably between 20°C and 50°C. The initial boiling point is more preferably within the range of 30°C to 45°C. The renewable stabilized naphtha range hydrocarbon feed preferably has a T95 temperature (95 vol% recovery) of 220°C or less, preferably 200°C or less, 180°C or less, 160°C or less, or 140°C or less. The renewable stabilized naphtha range hydrocarbon feed may have a T99 temperature (99 vol% recovery) of 220°C or less, preferably 200°C or less, 180°C or less, 160°C or less, or 140°C or less, or a final boiling point of 220°C or less, preferably 200°C or less, 180°C or less, or 160°C or less.

[0105] The difference between the initial boiling point and the T95 temperature (T95-IBP) of the renewable stabilized naphtha range hydrocarbon feed is preferably at least 50° C., for example at least 80° C. For example, the difference between the initial boiling point and the T95 temperature may be 50° C. to 155° C., preferably 60° C. to 120° C., 60° C. to 100° C., or 65° C. to 90° C.

[0106] Boiling points and T## temperatures (e.g. T95 temperature) were determined in accordance with EN ISO 3405-2019, which refers to the measurement of distillation characteristics at atmospheric pressure appropriate for products boiling between 0°C and 400°C.

[0107] An initial boiling point above 20° C. improves the suitability of the stabilized naphtha range hydrocarbon feed for cracking in conventional steam cracking procedures, whereas an initial boiling point above 50° C. can result in significant loss of usable hydrocarbons (i.e., not being valued), which is undesirable.

[0108] The term "stabilized" in the expression "stabilized naphtha-range" means that the content of carbon number compounds having carbon numbers of C4 or less is 5.0 wt.-% or less, preferably 2.5 wt.-% or less, more preferably 2.0 wt.-% or less, and even more preferably 1.5 wt.-% or less.

[0109] In the present invention, a "renewable stabilized naphtha-range hydrocarbon feed" comprises at least 98.5 wt.-% of hydrocarbons, preferably at least 99.5 wt.-% of hydrocarbons. In other words, at least 98.5 wt.-% of the feed is composed of hydrocarbons. By hydrocarbons we mean compounds containing only C and H (carbon and hydrogen atoms). This means that up to 1.5 wt.-%, preferably up to 0.5 wt.-%, of the hydrocarbon feed may be composed of non-hydrocarbon species, such as heteroatom-containing impurities or free water (free water according to ASTM D1364). The non-hydrocarbon species may in particular be free water and / or species containing carbon atoms, hydrogen atoms and at least one heteroatom, such as oxygen, nitrogen, sulfur or phosphorus. Such low levels of non-hydrocarbon species make the renewable stabilized naphtha-range hydrocarbon feed particularly suitable for conventional cracking units, which do not require special configurations.

[0110] 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.

[0111] Preferably, the pyrolysis step (b) is carried out at a coil outlet temperature (COT) selected in the range of 780°C to 880°C, preferably 800°C to 860°C, more preferably 820°C to 850°C.

[0112] 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.

[0113] 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.

[0114] 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 0.85, preferably 0.25 to 0.60, for example 0.35 to 0.55. 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.

[0115] 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 preformed mixtures.

[0116] The process may comprise, as purification stage (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.

[0117] Step (c) may include quenching and cooling the pyrolysis furnace effluent of step (b). Typically, at least one of CO, CO2, C2H2 or a combination thereof is removed from the pyrolysis furnace effluent of step (b) during quenching and cooling. In an embodiment, step (c) may include fractionating the pyrolysis furnace effluent of step (b). Fractionation may include separating a fuel oil fraction, a PyGas fraction, a hydrogen fraction, a methane fraction, a fuel gas fraction, and a light olefin fraction, such as a C2 fraction (ethylene fraction), a C3 fraction (propylene fraction), and / or a C4 fraction, from the cracked effluent. Fractionation may be performed in a single stage or as a series of fractionations, such as first separating the C2 / C3 fraction and then recovering the C2 and C3 fractions by a second stage fractionation. The C2 fraction (ethylene fraction) and the C3 fraction (propylene fraction) are particularly suitable for use in producing polymers such as biopolymer compositions. Thus, in an embodiment, the method includes, in step (c), separating the C2 fraction, or the C3 fraction, or both the C2 fraction and the C3 fraction, or the C2 / C3 fraction containing C2 and C3 as light olefin fractions from the pyrolysis furnace effluent of step (b), and optionally subjecting at least ethylene from the C2 fraction, at least propylene from the C3 fraction, or both ethylene and propylene to a polymerization process. Ethylene and / or propylene may be derived from the C2 and / or C3 fraction by further purification processes to obtain polymer grade materials.

[0118] In a preferred embodiment, a fraction rich in C2 hydrocarbons (C2 fraction) is separated, which is then further separated into a fraction consisting of at least ethene and a fraction consisting of ethane. Such a separation of a fraction rich in C2 hydrocarbons, for example a fraction containing 30 wt.-% to 100 wt.-%, preferably at least 40 wt.-%, of C2 hydrocarbons, can be sent to a C2 splitter to provide a fraction containing ethene and a fraction containing ethane. Similarly, a fraction rich in C3 hydrocarbons can be separated, which is then further separated into a fraction containing at least propene and a fraction containing propane. Such a separated fraction rich in C3 hydrocarbons (C3 fraction), for example a fraction containing 30 wt.-% to 100 wt.-%, preferably at least 40 wt.-%, of C3 hydrocarbons, can be sent to a C3 splitter to provide a fraction containing propene and a fraction containing propane. The fraction enriched in C3 hydrocarbons may be separated after the fraction enriched in C2 hydrocarbons has been separated or may be separated at the same stage, each of which may be recovered as a product fraction of the process and may be further purified or worked up to provide a product fraction of the process.

[0119] The method may include subjecting at least a portion of the pyrolysis furnace effluent of step (b) to a purification process (c') in step (c) to remove at least one of CO, CO2, or C2H2. This is particularly advantageous in embodiments in which at least a portion of the cracking effluent is subjected to a polymerization process. CO, CO2, and C2H2 are polymerization catalyst poisons and therefore undesirable in the polymerization process. Absorbents, adsorbents, reactants, molecular sieves, and / or purification catalysts can be used in the purification process to remove at least one of CO, CO2, or C2H2 and reduce the frequency of active material regeneration.

[0120] The purification process to which at least a portion of the pyrolysis furnace effluent of step (b) is subjected can be any purification process suitable for removing at least one of CO, CO2, or C2H2. Examples of such purification processes are described in EP 2679656, WO 2016 / 023973, WO 2003 / 048087, and EP 2010331502, all of which are incorporated herein by reference in their entirety.

[0121] In certain embodiments, the purification process includes contacting at least a portion of the decomposition effluent with an active material, such as an absorbent, adsorbent, purification catalyst, reactant, molecular sieve, or combinations thereof, to remove at least one of CO, CO2, or C2H2.

[0122] The active material may include, for example, copper oxide or copper oxide catalysts, oxides of Pt, Pd, Ag, V, Cr, Mn, Fe, Co, or Ni, optionally supported on alumina, Au / CeC, optionally supported on alumina, alumina-based absorbents or catalysts, such as Selexsorb™ COS or Selexord™ CD, molecular sieves made of alumina, aluminosilicates, aluminophosphates, or mixtures thereof, or any combination thereof.

[0123] The active material may include an adsorbent or adsorbents as described in WO 03 / 048087, p. 11, line 11 to p. 12, line 11, line 3; p. 12, line 11, line 18 to p. 15, line 11, line 29, and / or p. 17, line 11, line 21 to p. 21, line 11, line 2, and / or a molecular sieve or molecular sieve as described in WO 03 / 048087, p. 21, line 11, line 3 to p. 22, line 11, line 26. The active material may be composed of a purification catalyst or catalyst as described in U.S. Patent No. 2010 / 0331502, paragraphs

[0105] to

[0116] , or a molecular sieve or molecular sieve as described in U.S. Patent No. 2010 / 0331502, paragraphs

[0117] to

[0119] . The active material may include a refinery catalyst or catalyst as described in WO 2016 / 023973, paragraphs

[0061] ,

[0062] ,

[0063] , and / or

[0064] .

[0124] The purification process may be as described in EP 2679656, paragraphs

[0043] to

[0082] . The purification process may be as described in US 2010 / 0331502, paragraphs

[0092] to

[0119] , and / or paragraph

[0126] , and / or Example 2. The purification process may be as described in WO 2016 / 023973, paragraphs

[0056] to

[0067] . The purification process may be as described in WO 03 / 048087, pages 11, 11.12 to 15, 11.29, and / or pages 16, 11.1 to 21, 11.2, and / or pages 23, 11.14 to 24, 11.13, and / or Example 1 and / or Example 2.

[0125] Typically, impurities inactivate or contaminate the active material during the purification process, so the active material can be regenerated until its purified activity is at least partially restored.

[0126] In certain embodiments, the purification process includes at least one of the following steps: i) contacting at least a portion of the cracked effluent with a CuO catalyst to remove oxygen, ii) contacting at least a portion of the cracked effluent with H to remove C2H2 by hydrogenation, iii) contacting at least a portion of the cracked effluent with a CuO2 catalyst to remove CO by oxidation, or iv) contacting at least a portion of the cracked effluent with a zeolite molecular sieve to remove CO2. Optionally, the purification process includes contacting at least a portion of the cracked effluent with an activated alumina catalyst, such as Selexorb™, to remove secondary impurities, such as at least one of COS, H2S, and CS2.

[0127] 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.

[0128] In particular, the cracking effluent obtained in step (b) may be combined in step (c) with other streams, e.g. effluents from further cracking steps produced in other pyrolysis furnaces, i.e. further cracking effluents and / or fractions thereof, which may simply be referred to as co-feeds of step (c). In this case, the pyrolysis furnace effluent of step (b) is preferably in an amount 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.-% to 100 wt.-% relative to the total amount of the pyrolysis furnace discharge of step (b) and the cofeed of step (c). A minimum value of, for example, 10 wt.-% ensures the presence of a certain proportion of biologically derived material and thus contributes to sustainability. Nevertheless, even a minimal amount of biological raw materials in step (c) contributes to sustainability.

[0129] The one or more further cracking operations are preferably carried out in one or more further cracking furnaces. The one or more further cracking operations may be thermal cracking operations and / or cracking operations other than thermal cracking, such as FCC (fluid catalytic cracking).

[0130] The further cracking operation can be carried out using any suitable feed, including a fossil feed (crude oil based feed), a renewable feed, or a combination thereof. The further cracking operation is preferably carried out under conditions different from step (b) in at least one of the total cracker feed composition and cracking conditions, such as COT, COP, or dilute.

[0131] The further cracked effluent may be subjected to purification, gas-liquid separation and / or fractionation before being added in step (c) or may be added as it is, i.e. as a crude effluent. The addition may be carried out before the separation treatment in step (c). In this case, the further cracked effluent is subjected to a separation treatment. This option is particularly preferred when the crude effluent is added as the further effluent. The addition may be carried out during or after the separation treatment in step (c). In this case, it is preferred that the further cracked effluent is at least partially subjected to purification, gas-liquid separation and / or fractionation before being added in step (c).

[0132] The pyrolysis in step (b) is preferably carried out in the presence of a cofeed.

[0133] Preferably, the content of renewable stabilized naphtha range hydrocarbon feed in the total cracker feed is in the range of 10wt.-% to 100wt.-%, preferably 20wt.-% to 100wt.-%, 30wt.-% to 100wt.-%, 40wt.-% to 100wt.-%, 50wt.-% to 100wt.-%, 60wt.-% to 100wt.-%, 70wt.-% to 100wt.-%, 80wt.-% to 100wt.-%, or 90wt.-% to 100wt.-%. The upper limit may also be 90wt.-% or 80wt.-%, i.e. the content may be in the range of, for example, 10wt.-% to 90wt.-%, or 10wt.-% to 80wt.-%.

[0134] The use of at least 10 wt.-% of the renewable stabilized naphtha range hydrocarbon feed ensures that the effects of the present invention are significant. The total cracker feed may be composed of renewable stabilized naphtha range hydrocarbon feed, i.e., its content may be 100 wt.-%.

[0135] The co-feed may include a co-feed of fossil hydrocarbons. Fossil co-feeds, especially fossil naphtha, are readily available and highly suitable for pyrolysis.

[0136] In the present invention, a "fossil hydrocarbon co-feed" comprises at least 98.5 wt.-% hydrocarbons, preferably at least 99.5 wt.-% hydrocarbons. In other words, at least 98.5 wt.-% of the co-feed is made up of hydrocarbons. This means that up to 1.5 wt.-%, preferably up to 0.5 wt.-%, of the hydrocarbon co-feed may be made up of non-hydrocarbon species such as heteroatom-containing impurities, especially sulfur-containing impurities.

[0137] Preferably, the co-feed(s) comprises a naphtha range feed, since it provides high compatibility with the renewable stabilized naphtha range hydrocarbon feed. Moreover, since the renewable stabilized naphtha range hydrocarbon feed is a well-defined (narrow range) feed, in order to fully utilize the advantages of the present invention, it is preferred to employ a narrow range co-feed, such as fossil naphtha. A particularly preferred co-feed is light naphtha, in particular fossil light naphtha. The light naphtha preferably boils in the range of 20°C (IBP) to 120°C (FBP), for example in the range of 30°C (IBP) to 90°C (FBP).

[0138] 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.

[0139] 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.

[0140] Since renewable stabilized naphtha range hydrocarbon feeds typically have inherently low to no 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 stabilized naphtha range hydrocarbon 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 stabilized naphtha range hydrocarbon 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.

[0141] The step (a) of providing a stabilized naphtha range hydrocarbon feed may, for example, comprise subjecting the oxyacid salt biorenewable feed to hydrotreatment consisting of at least hydrodeoxygenation, optionally followed by further hydrotreatment consisting of at least hydroisomerization, followed by gas-liquid separation to provide a liquid hydrocarbon stream and a gaseous stream. In a subsequent step, the optionally isomerized liquid hydrocarbon stream may be subjected to fractionation from which at least a renewable stabilized naphtha-hydrocarbon feed is recovered. Furthermore, other fractions may be recovered from the fractionation, including, but not limited to, a fuel gas fraction, a diesel fraction, an aviation fuel fraction, a marine fuel fraction, and an electrical technology fluid fraction. Furthermore, at least propane may be recovered from the gas stream separated from the liquid hydrocarbon stream.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] Step (a) in the above embodiment may preferably include hydrotreating comprising at least hydrodeoxygenation (HDO) followed by further hydrotreating comprising at least hydroisomerization and / or may include hydroisomerization as part of the hydrotreating comprising at least HDO.

[0146] In other words, hydroisomerization can be carried out in a separate, further hydroprocessing step after hydroprocessing that includes at least HDO. Alternatively, or in addition, hydroisomerization can be carried out as part of hydroprocessing that includes at least HDO, for example, using a catalyst or catalyst system that achieves both hydrodeoxygenation and hydroisomerization in a single step.

[0147] The effluent from hydroprocessing, which includes at least HDO, referred to as hydroprocessing effluent, may be subjected to gas-liquid separation to provide a gaseous stream and a first liquid hydrocarbon stream. At least a portion of the first liquid hydrocarbon stream may be provided as the liquid hydrocarbon stream described above. Alternatively or additionally, at least a portion of the liquid hydroprocessing effluent may be subjected to further hydroprocessing, including at least hydroisomerization, at a subsequent stage, preferably after gas-liquid separation, to provide a second liquid hydrocarbon stream, which may be provided as the liquid hydrocarbon stream described above.

[0148] The gaseous stream from the second gas-liquid separation may be combined with the gaseous stream from the first gas-liquid separation for processing, and any condensable hydrocarbons may be separated from the gaseous stream and combined with the liquid hydrocarbon stream.

[0149] At least a portion of the first liquid hydrocarbon stream and / or at least a portion of the second liquid hydrocarbon stream may be recycled to hydroprocessing, including at least hydrodeoxygenation. Such recycling may be suitable for achieving temperature control.

[0150] 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 contained in the propane-rich stream may be subjected to dehydrogenation, preferably catalytic dehydrogenation, to produce propylene.

[0151] Propane (or a propane-rich stream) may be recovered from the stabilization step and subjected to such dehydrogenation. The propane (or propane-rich stream) recovered from the stabilization step may be subjected to dehydrogenation in a separate reactor or may be combined with the propane (or propane-rich stream) separated after hydroprocessing to improve the overall yield of light olefins per oxygenate biorenewable feed to hydroprocessing.

[0152] Alternatively or in addition, such a C3-rich stream (i.e., the propane-rich stream recovered after hydroprocessing, the stream recovered from the stabilization process, or a combined stream) may be subjected to thermal cracking, such as steam cracking, in a separate furnace.

[0153] If a heavy liquid hydrocarbon fraction is recovered from the above separation, the method may further comprise subjecting the heavy liquid hydrocarbon fraction to further fractionation to provide at least an aviation fuel range fraction and a bottoms fraction. Suitable methods for fractionation, as well as usable fraction cut-offs, resulting fractions and their uses, are described in WO 2021 / 094656, the contents of which are incorporated herein in their entirety. In WO 2021 / 094656, the bottoms fraction is referred to as an electrotechnical fluid.

[0154] Each of the diesel range fraction, the aviation fuel range fraction, the heavy liquid hydrocarbon fraction, the aviation fuel range fraction and the bottoms fraction may individually have an isoparaffin 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.-%. The isoparaffin content is calculated relative to the total diesel range fraction or to each of the other fractions. A high degree of isomerization of a fraction, in particular the diesel fuel fraction or the aviation fuel fraction, indicates that the production process was carried out in a highly isomerizing mode, for example under severe isomerization conditions. In such cases, the yield of naphtha range hydrocarbons tends to be higher, and the naphtha range fraction also tends to have a higher isoparaffin content. This improves the overall yield of the process of the invention.

[0155] The above-mentioned step of subjecting at least a portion of the liquid hydrocarbon stream to fractionation to recover at least a renewable stabilized naphtha range hydrocarbon feed preferably includes the steps of subjecting at least a portion of the liquid hydrocarbon stream to fractionation to provide a naphtha range fraction, and subjecting the naphtha range fraction to stabilization. In this regard, stabilization includes removing at least a portion of the components boiling below 20° C., preferably removing at least a portion of the components boiling below 25° C., removing at least a portion of the components boiling below 30° C., removing at least a portion of the components boiling below 40° C., or removing at least a portion of the components boiling below 50° C., preferably by distillation techniques. If desired, optional additional treatments such as stripping with N2, H2, or steam may be performed on the liquid stream(s) during the fractionation step to separate gases and impurities into the gas phase.

[0156] The stabilization step can form part of the fractionation from which the naphtha range fraction is recovered. Alternatively, or in addition, the stabilization step can be carried out as a separate step after fractionation, i.e., a step for removing components from the recovered naphtha range fraction.

[0157] The stabilization step is preferably carried out by distillation techniques.

[0158] As used herein, distillation (or fractionation) may refer to any type of distillation, i.e., stripping, flashing, and other similar separation operations based on differences in the vapor pressures of the components. Selection of appropriate feed rates, operating temperatures, pressures, equipment types and designs, and other engineering details for the present fractionation disclosure will be within the ability of one of ordinary skill in the art.

[0159] The heavy liquid hydrocarbon fraction and / or the diesel range fraction may alternatively have an isoparaffin content of less than 65 wt.-%.

[0160] The bottom fraction may be subjected to further pyrolysis, preferably steam cracking. This further cracking step is preferably carried out separately from the pyrolysis step (b), i.e. in a different furnace and / or at a different time. The cracking conditions may be different from those employed in step (b), but the same conditions may be employed as those usable in step (b).

[0161] Step (a) may involve the hydrotreatment of an oxyacid salt biorenewable feed, such as oils and / or fats of vegetable, animal or other biological origin, i.e., as already pointed out above, the renewable stabilized naphtha range hydrocarbon feed may be based on a hydrotreated oxyacid salt feed.

[0162] Step (a) may include a step (a') of pre-treating the bio-renewable oils and / or fats to reduce contaminants in the oils and fats to produce an oxyacid salt bio-renewable feed. Alternatively, the oils and fats can be used as the oxygen-containing bio-renewable feed without pre-treatment.

[0163] The pretreatment step (a') may be a step to reduce contaminants containing S, N and / or P in the oils and / or fats to produce an oxyacid salt biorenewable feed. Alternatively or additionally, the pretreatment step (a') may be a step to reduce metal-containing contaminants in the oils and / or fats to produce an oxyacid salt biorenewable feed. Preferably, the pretreatment step reduces the content of one or more of S, N, P, alkali metals, alkaline earth metals, Si, Al, Fe, Zn, Cu, Mn, Cd, Pb, As, Cr, Ni, V, Sn.

[0164] Suitable methods for carrying out the pretreatment step (a') include one or more selected from washing, degumming, bleaching, distillation, fractionation, rendering, heat treatment, evaporation, filtration, adsorption, hydrotreating such as hydrodeoxygenation, centrifugation or precipitation. These pretreatment methods are simple and effective ways to remove metal contaminants (metals and / or metal compounds), including S, N and P contaminants, which may be catalyst poisons, as well as metalloid contaminants such as Si-containing impurities. Pretreatment step (a') may alternatively or additionally comprise at least one of partial hydrogenation, partial deoxygenation, hydrolysis and transesterification.

[0165] The oxygen-containing bio-renewable feed may include fatty acid esters of glycerol.

[0166] The effluents of hydrotreating and optional isomerization, preferably after gas-liquid separation, are subjected to fractionation which can be further processed, such as stabilization, to obtain either a renewable stabilized naphtha range hydrocarbon feed directly or to provide a renewable stabilized naphtha range hydrocarbon feed.

[0167] The total feed that can be subjected to hydrotreating in step (a) preferably comprises, in addition to the oxygenate bio-renewable feed, a hydrotreating diluent consisting of paraffinic hydrocarbons. The hydrotreating diluent is particularly suitable for temperature control during hydrotreating, especially during hydrodeoxygenation. The hydrotreating diluent may comprise at least one of recycled paraffinic hydrocarbons from hydrotreating effluent and / or isomerization effluent, renewable hydrocarbons obtained by Fischer-Tropsch synthesis using biosyngas, and fossil hydrocarbons. Preferably, the hydrotreating diluent comprises recycled paraffinic hydrocarbons from hydrotreating effluent and / or isomerization effluent. When a hydrotreating diluent is used, the hydrotreating feed preferably comprises at least 2 wt.-%, for example between 2 wt.-% and 100 wt.-%, preferably 3 wt.-%, at least 4 wt.-%, at least 5 wt.-%, at least 6 wt.-%, at least 7 wt.-%, at least 8 wt.-%, at least 9 wt.-%, at least 10 wt.-%, at least 11 wt.-%, at least 12 wt.-%, at least 15 wt.-%, at least 20 wt.-%, at least 25 wt.-%, at least 50 wt.-%, at least 75 wt.-%, at least 90 wt.-% or at least 95 wt.-%, or at least 99 wt.-% of the oxygenate bio-renewable feed. The feed subjected to hydrotreating in step (a) may comprise an oxygen-containing bio-renewable feed of 99 wt.-% or less, for example 2 wt.-% to 99 wt.-%, preferably 90 wt.-%, preferably 75 wt.-%, 50 wt.-% or less, 40 wt.-% or less, 35 wt.-% or less, 30 wt.-% or less, 25 wt.-% or less, 20 wt.-% or less, 15 wt.-% or less, or 10 wt.-% or less.

[0168] When the hydrotreating diluent consists of recycled paraffinic hydrocarbons from the hydrotreating step, the hydrotreating feed preferably comprises between 10 wt.-% and 98 wt.-%, preferably at least 25 wt.-%, at least 40 wt.-%, at least 50 wt.-%, at least 60 wt.-%, at least 70 wt.-%, at least 75 wt.-%, at least 80 wt.-%, at least 85 wt.-%, at least 90 wt.-%, or at least 92 wt.-% recycled paraffinic hydrocarbons from the hydrotreating step. The hydrotreating feed may likewise comprise up to 98 wt.-%, up to 95 wt.-%, up to 92 wt.-%, up to 90 wt.-%, up to 85 wt.-%, up to 80 wt.-%, up to 70 wt.-%, up to 60 wt.-%, up to 40 wt.-% or up to 25 wt.-% of regenerated paraffinic hydrocarbons from the hydrotreating step, for example 10 wt.-% to 25 wt.-%. The recycle product from the hydrotreating step is preferably a hydrocarbon, but may also be material that has been partially deoxygenated and then recycled to the hydrotreating step for further deoxygenation.

[0169] In the present invention, hydrotreating can include hydrodeoxygenation (HDO) as well as decarbonylation and / or decarboxylation, which reactions yield carbon monoxide or carbon dioxide and a hydrocarbon chain with one less carbon than the original chain.

[0170] Hydroprocessing, preferably HDO, can be carried out, for example, by feeding hydrogen and the natural fat or its derivatives (co-currently or counter-currently) through a catalyst bed. Suitable processes and apparatus are described in EP 1741767, see FIG. 1 and items

[0061] to

[0064] .

[0171] Hydrogenation, preferably HDO, is carried out at a temperature of preferably 100° C. to 500° C., more preferably 250° C. to 350° C., more preferably 280° C. to 345° C., and most preferably 280° C. to 310° C. The preferred pressure is 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa, and most preferably 4 MPa to 8 MPa.

[0172] Hydrotreating, preferably HDO, can be carried out in the presence of a hydrotreating catalyst comprising one or more metals from groups 6 to 10 of the periodic table (IUPAC 1990), preferably a supported catalyst, more preferably one or more of the above metals supported on alumina and / or silica. Preferred hydrotreating catalysts are Pd, Pt, Ni, NiMo or CoMo supported on alumina and / or silica. Most preferred catalysts are NiMo / Al2O3 and CoMo / Al2O3 in sulfided form.

[0173] In the present invention, the term "hydrotreating" is meant to include the removal of oxygen from organic oxygen compounds as water, i.e. hydrodeoxygenation (HDO), the removal of sulfur from organic sulfur compounds as dihydrogen sulfide (HS), i.e. hydrodesulfurization (HDS), the removal of nitrogen from organic nitrogen compounds as ammonia (NH), i.e. hydrodenitrogenation (HDN), the removal of halogens, e.g. chlorine, from organic chlorine compounds as hydrochloric acid (HCl), i.e. hydrodechlorination (HDCl), the removal of metals by hydrodemetallization, and the hydrogenation of unsaturated bonds (if present). When isomerization is performed simultaneously with hydrotreating, this can be achieved, for example, by combining HDO with hydrocracking, or by combining HDO with hydroisomerization. In particular, hydrocracking may be performed to increase the yield of naphtha range hydrocarbons, which is beneficial to the overall process.

[0174] Optional isomerization, carried out separately as part of hydrotreating or after hydrotreating, including at least hydrodeoxygenation, results in a high yield of naphtha range hydrocarbons and thus improves the overall yield of the process. If isomerization is omitted, the process can be tailored towards the production of other fractions, in particular at least a diesel fraction, while utilizing the naphtha range fraction as a by-product. In this case, it is preferred to recover the diesel fraction in addition to the naphtha range fraction.

[0175] The optional isomerization, if included as a separate stage, can be carried out at a temperature selected from the range of 200°C to 500°C, preferably 280°C to 400°C, and at a pressure selected from the range of 20 to 150 bar (absolute), preferably 30 to 100 bar. The isomerization (isomerization process) can be carried out in the presence of known isomerization catalysts, for example catalysts containing molecular sieves and / or metals selected from group VIII of the periodic table and a support. Preferably, the isomerization catalyst is a catalyst containing SAPO-11 or SAPO-41 or ZSM-22 or ZSM-23 or ferrierite, Pt, Pd or Ni, and Al2O3 or SiO2. Typical isomerization catalysts are, for example, Pt / SAPO-11 / Al2O3, Pt / ZSM-22 / Al2O3, Pt / ZSM-23 / Al2O3 and / or Pt / SAPO-11 / SiO2. Catalyst deactivation may be mitigated by the presence of molecular hydrogen in the isomerization process. Therefore, it is preferred to add hydrogen to the isomerization process. If any isomerization is included as a separate stage, the hydrotreating catalyst and the isomerization catalyst may not be contacted simultaneously with the reaction feed (oxygenate biorenewable feed and / or the deoxygenated stream derived therefrom). For example, hydrotreating and isomerization are carried out in separate reactors.

[0176] The isomerization may be advanced isomerization. Advanced isomerization in the present invention refers to techniques that achieve a high isoparaffin content in the naphtha range fraction, typically 50-60 wt.-% or 55-60 wt.-%. A high i-paraffin content (and a high ratio between i-paraffins and n-paraffins) can be achieved especially for paraffins with longer chains, i.e. with carbon numbers near the upper carbon number limit of the naphtha range.

[0177] If hydrotreating and subsequent high degree of polymerization isomerization are performed, the following procedure may be carried out, as exemplified for triglyceride-based biomass as oxygenate biorenewable feed. In the first stage, triglyceride-based biomass is deoxygenated under hydrogen pressure over a hydrotreating catalyst, such as NiMo catalyst supported on Al2O3. To keep the catalyst in a sulfided state, it is preferable to add a sulfur component to the inlet stream. In the first stage, triglyceride oils and fatty acids are converted to n-alkanes with small amounts of branched alkanes (usually in the range of 1 wt.-%). Oxygen is removed in the form of water (hydrodeoxygenation), carbon monoxide (decarboxylation) and carbon dioxide (decarboxylation). Oxygen removal by decarbonylation and decarboxylation consumes less hydrogen than hydrodeoxygenation, but the resulting alkanes have one less carbon atom than the original fatty acid chain. In the second stage, isomerization is carried out over platinum-impregnated molecular sieves, for example Pt / ZSM-22.

[0178] The method of the present invention may further comprise derivatizing at least a portion of the light olefin(s) to obtain one or more derivative(s) of the light olefin(s) as biomonomer(s), 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.

[0179] The process of the present invention may further comprise a step (d) of (co)polymerizing the light olefins separated in step (c) and / or at least one of said biomonomers, optionally together with other (co)monomers and / or optionally after further purification, to produce a biopolymer composition.

[0180] In this context, acrylic is meant to include any type of acrylic monomer, such as those based on (meth)acrylic acid, (meth)acrylic acid esters, and / or (meth)acrylates, and acrylic polymer is meant to include any type of acrylic polymer, such as those that include structural units derived from (meth)acrylic acid, (meth)acrylic acid esters, and / or (meth)acrylates.

[0181] Light olefins and / or biomonomers can be (co)polymerized to obtain biopolymer compositions including, for example, polybutadiene, styrene butadiene rubber, nitrile rubber, polychloroprene, acrylonitrile butadiene styrene resin (ABS), styrene butadiene latex, TPE, nylons, such as nylon 6,6, polyurethane methyl methacrylate-butadiene-styrene (MBS), nitrile barrier resins, butyl rubber, polyisobutylene, methyl methacrylate (MMA), MTBE / ETBE, polyolefin (co)polymers, polybutene-1, polypropylene (PP), ethylene-propylene-copolymer (EPM), polyethers, polyether polyols, polyesters, polymeric or oligomeric surfactants, or ethylene-propylene-diene-copolymer (EPDM).

[0182] Derivatization includes, for example, oxidation and / or ammoxidation. Oxidation is preferably carried out by gas phase oxidation.

[0183] The polymerization can be carried out in the presence of a polymerization catalyst. The polymerization may be initiated by a polymerization initiator.

[0184] The biopolymer composition can be further processed to produce hygiene products, building materials, packaging materials, coating compositions, paints, decorative materials such as panels, vehicle interior parts such as automobile interior parts, rubber compositions, tires or tire parts, toners, personal health care products, consumer goods parts, electronic device parts or housings, films, moldings, gaskets, optionally with other ingredients. In particular, the acrylic polymer can be a water-absorbing polymer that is further processed to produce hygiene products such as diapers, sanitary napkins, incontinence sheets.

[0185] The present invention further relates to biopolymer compositions obtainable by embodiments of the process of the present invention comprising the polymerization of light olefins and / or their derivatives.

[0186] Renewable stabilized naphtha range hydrocarbon feed The present invention further relates to a renewable, stabilized naphtha range hydrocarbon feed for thermal cracking.

[0187] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a naphthene content in the range of 0.1 wt.-% to 10.0 wt.-% based on the weight of the total renewable stabilized naphtha range hydrocarbon feed. More preferably, the renewable stabilized naphtha range hydrocarbon feed has 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.-%, 0.8 to 5.8 wt.-%, 1.0 to 5.6 wt.-% or 1.2 to 5.6 wt.-%. Naphthenes are easily converted to aromatics, which are compounds that may react to coke but not to desired products. Therefore, it is preferred that the naphthenes content in the renewable stabilized naphtha range hydrocarbon feed is low.

[0188] Preferably, the renewable stabilized naphtha range hydrocarbon feed has an olefin content 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 renewable stabilized naphtha range hydrocarbon 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.

[0189] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a combined olefin and naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%, where combined olefin and naphthene content refers to the combined olefin and naphthene content based on the combined weight of the renewable stabilized naphtha range hydrocarbon feed. More preferably, the renewable stabilized naphtha range hydrocarbon feed has a combined olefin and naphthene content of from 0.1 wt.-% to 8.0 wt.-%, e.g., from 0.1 wt.-% to 6.5 wt.-%, from 0.1 wt.-% to 6.0 wt.-%, from 0.2 wt.-% to 5.5 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.-%.

[0190] Preferably, the renewable stabilized naphtha range hydrocarbon feed has 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. Aromatics, such as benzene, do not react with the desired products. Rather, they tend to react with coke (i.e., are coke precursors). Therefore, their content in the feed should be low, since their presence in the feed reduces the yield of the desired products. In the present invention, the content of aromatics is preferably low and may be 0.00%. The content of aromatics may be determined by PIONA analysis.

[0191] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a ratio of aromatics content to naphthene content (weight content of naphthenes divided by weight content of aromatics) of 1 or more, preferably 10 or more, 50 or more, or 100 or more. Both naphthenes and aromatics tend to increase the yield of cyclic compounds in thermal cracking. Therefore, it is preferable that the contents of both are low. However, when both are contained, naphthenes are preferred over aromatics. There is no particular upper limit to this ratio, and it may be infinite when no aromatics are contained.

[0192] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a combined olefin, aromatic and naphthene content of from 0.1 wt.-% to 10.0 wt.-%, preferably from 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.-%. 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.

[0193] Preferably, the renewable stabilized naphtha range hydrocarbon feed has 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. 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, including no oxygenate, is preferred. On the other hand, higher values, such as 100 wt.-ppm to 1000 wt.-ppm, may be used, independently of each other, especially when applying low oxygenate cofeeds (e.g. fossil hydrocarbon cofeeds) of, for example, 10 wt.-% or more. In such cases, the effort to minimize oxygenate content is minimized, which increases the overall efficiency of the process. Because the renewable stabilized naphtha range hydrocarbon feed of the present invention is a naphtha range feed, the number of possible oxyacid salts is limited. In accordance with the present invention, the oxyacid salt content is determined based on ASTM D7 423 (i.e., determination of C2-C5 oxyacid salts by gc-FIDq, i.e., gas chromatography-flame ionization detection), modified to capture a longer list of oxyacid salts in the spectrum. Specifically, the following oxygen acid salts may be present in the renewable stabilized naphtha-hydrocarbon feed of the present invention: ETBE (ethyl t-butyl ether), MTBE (methyl t-butyl ether), TAME (t-amyl methyl ether), DIPE (diisopropyl ether), propyl ether, isobutyraldehyde, butyraldehyde, isobutanol, n-butanol, sec-butanol, tert-butanol, methanol, acetone, vinyl acetate, ethyl acetate, MEK (methyl ethyl ketone), isobutaldehyde, valeraldehyde, ethanol, isopropanol, n-propanol, allyl alcohol, diethyl ether, acetaldehyde, and the like.The total content of all oxyacid esters identified by GC-FID is assumed to correspond to the total content of oxyacid esters in the sample, i.e., in the renewable stabilized naphtha range hydrocarbon feed.

[0194] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a content of C17 and higher carbon number compounds of 1.0 wt.-% or less, for example 0.0 to 0.9 wt.-%, preferably 0.0 to 0.8 wt.-%, more preferably 0.0 to 0.5 wt.-%, or 0.0 to 0.2 wt.-%.

[0195] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a carbon range of 10 or less, preferably 8 or less, 7 or less, 6 or less, or 5 or less. The carbon range is preferably 1 or more, 2 or more, or 3 or more. Thus, the carbon range is preferably in the range of 1 to 10, for example, 2 to 10, 3 to 10, 3 to 8, 3 to 7, 2 to 6, 3 to 6, 2 to 5, or 3 to 5. In the present invention, the carbon range is the difference between C_max and C_min (carbon range=C_max-C_min), where C_max (highest carbon number) and C_min (lowest carbon number) are determined by PIONA (GC×GC method described herein), and for the purpose of measuring C_min and C_max, it is assumed that there are no carbon numbers with a measured abundance of 0.10 wt.-% or less. It is assumed that there are no carbon numbers with wt.-% or less. In other words, carbon numbers with a measured abundance below 0.10 wt.-% are not taken into account when determining C_min and C_max, and therefore when determining the carbon range. Carbon range is more sensitive to low amount outliers in the carbon number distribution and therefore more accurate than analytical techniques based on distillation characteristics as determined according to EN ISO 3405-2019. In other words, carbon range gives a good impression of the quality of the feed in terms of homogeneity.

[0196] Preferably, the renewable stabilized naphtha-range hydrocarbon feed has an interventile carbon number range (IVR) of 6.5 or less, preferably 5.0 or less, 4.5 or less, 4.0 or less, or 3.8 or less. 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 (and other c_xx values) are also determined from linear interpolation of the data (cumulative content vs. carbon number) obtained from the PIONA carbon number analysis.

[0197] The IVR is the carbon number range that contains 90% of the mass (i.e., 5 wt.-% to 95 wt.-%). Similarly, the IQR (interquartile carbon number 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.-%. Similarly, the IQR (interquartile carbon number 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 the two carbon numbers is assumed to be linear. For example, a sample containing 0% C1 (0% components with one carbon atom), 0% C2, 0% C3, 5% C4, 5% C5, and 8% C6 would have a C_2.5 value (i.e., fractional carbon number equivalent to 2.5 wt.-% of the sample) of 3.5 (number of carbons), even though 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 equivalent to 5 wt.-% of the sample) is 4 (C4) and the C_10 value (fractional carbon number equivalent to 10 wt.-% of the sample) is 5 (C5). The C_15 value (15 wt.-%) is between 5 and 6 (C5 is 10 wt.-%, C6 is 18 wt.-%). Linear interpolation is easily performed, for example the number of carbon atoms present at 15 wt.-% (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.

[0198] 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.-%})].

[0199] 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.

[0200] The IVR, IDR and IQR ranges are less susceptible to tail effects and therefore provide more stable results than the carbon ranges.

[0201] Preferably, the renewable stabilized naphtha range hydrocarbon feed has an adjusted average carbon number range (IDR) of 4.5 or less, preferably 4.0 or less, 3.5 or less, or 3.0 or less. Preferably, the renewable stabilized naphtha range hydrocarbon feed has an interquartile carbon number range (IQR) of 2.5 or less, preferably 2.0 or less, 1.8 or less, or 1.5 or less.

[0202] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a C11 or higher carbon number content of 5.0 wt.-% or less, preferably 4.5 wt.-% or less, 4.0 wt.-% or less, 3.5 wt.-% or less, 3.0 wt.-% or less, 2.5 wt.-% or less, or 2.0 wt.-% or less. For example, the C11 or higher carbon number content can be 0.0 to 5.0 wt.-%, or 0.1 to 5.0 wt.-%.

[0203] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a T95 temperature of 220°C or less, preferably 200°C or less, 180°C or less, 160°C or less, or 140°C or less.

[0204] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a T99 temperature of 220°C or less, preferably 200°C or less, 180°C or less, 160°C or less, or 140°C or less.

[0205] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a final boiling point of 220°C or less, preferably 200°C or less, 180°C or less, or 160°C or less.

[0206] Preferably, the renewable stabilized naphtha range hydrocarbon feed has an initial boiling point of 20°C or above, preferably from 20°C to 60°C, for example from 30°C to 50°C or from 30°C to 45°C.

[0207] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a T5 temperature of 40°C or greater, preferably 45°C or greater, 50°C or greater, 55°C or greater, or 60°C or greater.

[0208] In the present invention, the renewable stabilized naphtha range hydrocarbon feed has a low content of light and extra light components.

[0209] An initial boiling point and / or T5 temperature within the above ranges improves the yield of more valuable products, particularly propylene and ethylene, than the C3 and C4 products in the pyrolysis furnace effluent of step (b).

[0210] Preferably, the difference between the T10 temperature and the T90 temperature (T90-T10) of the renewable stabilized naphtha range hydrocarbon feed is less than 100°C, preferably less than 80°C, for example, 20°C to 75°C, 30°C to 70°C, or 40°C to 70°C.

[0211] The difference between the T10 and T90 values ​​is a stable and very reliable measure for describing the uniformity of the composition since it largely ignores the outliers (tails) of the boiling point distribution.Within the above limits, renewable stabilized naphtha range hydrocarbon feeds have been found to produce favorable product distributions while utilizing significant amounts of material, thus contributing to high overall yield improvements.

[0212] Preferably, the renewable stabilized naphtha range hydrocarbon feed has an aggregate paraffin content of 90 wt.-% or more, preferably 92 wt.-% or more, 93 wt.-% or more, 94 wt.-% or more or 95 wt.-% or more.

[0213] The total paraffin content in the renewable stabilized naphtha range hydrocarbon feed of the present invention means the combined amount of n-paraffins and i-paraffins relative to the total weight of the renewable stabilized naphtha range hydrocarbon feed. The inventors have found that a higher total paraffin amount further improves the yield of valuables and reduces the tendency to coke.

[0214] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a content ratio of i-paraffins to n-paraffins of not more than 1.7, preferably not more than 1.5, such as in the range of from 0.5 to 1.7, or from 0.7 to 1.5.

[0215] Particularly high ethylene yields are obtained if the ratio of i-paraffins to n-paraffins is within the above ranges, which ratio is defined in the present invention on a weight basis, i.e. as the weight content of i-paraffins divided by the weight content of n-paraffins.

[0216] Preferably, the renewable stabilized naphtha range hydrocarbon feed has an i-paraffin to n-paraffin content ratio in the range of 2.0 or more, preferably 2.2 or more.

[0217] If the ratio of i-paraffin (iP) to n-paraffin (nP) is within the above range, the propylene yield is particularly high. In other words, by appropriately adjusting the ratio of i-paraffin to n-paraffin, it is possible to adjust the product distribution toward the desired product, and the degree of freedom in the product range is increased.

[0218] Intermediate values ​​within 1.7 to 2.0 may also be applied, but are not preferred since they are neither optimal for ethylene production nor optimal for propylene production.

[0219] In addition, such high iP / nP ratios reduce viscosity and improve mixing and blending properties, which is particularly beneficial (but not limited to) when a cofeed is used in the cracking process.

[0220] Preferably, the renewable stabilized naphtha range hydrocarbon feed is obtainable by a process as disclosed for step (a) above which provides a renewable stabilized naphtha range hydrocarbon feed in the process of the present invention.

[0221] In particular, the renewable stabilized naphtha range hydrocarbon feed is preferably obtainable by a process comprising hydrotreating and optionally isomerizing an oxygenate bio-renewable feed. Preferably, the process comprises isomerization.

[0222] It should be noted that the renewable stabilized naphtha range hydrocarbon feed employed in the present process is preferably a renewable stabilized naphtha range hydrocarbon feed as disclosed herein, i.e., having the properties described herein.

[0223] In one embodiment, the renewable stabilized naphtha range hydrocarbon feed is prepared by subjecting an oxygenate bio-renewable feed to hydroprocessing, including at least hydrodeoxygenation, to provide a hydroprocessed effluent; subjecting at least a portion of the hydroprocessed effluent to gas-liquid separation to provide a gaseous stream and a first liquid hydrocarbon stream; providing the first liquid hydrocarbon stream as a liquid hydrocarbon stream, or subjecting at least a portion of the first liquid hydrocarbon stream to further hydroprocessing, including at least hydroisomerization, and then optionally further gas-liquid separation, to provide at least a second liquid hydrocarbon stream as a liquid hydrocarbon stream; and feeding at least a portion of the liquid hydrocarbon stream to a first distillation column, preferably a first stabilization column, optionally using at least a portion of the stabilized heavy liquid hydrocarbon fraction in diesel fuel, to obtain a first overhead fraction and a stabilized heavy liquid hydrocarbon fraction; and / or recovering at least an aviation fuel range fraction and a bottoms fraction from at least a portion of the stabilized heavy liquid hydrocarbon fraction. recovering the first overhead fraction from the first distillation column; separating at least a fuel gas fraction and a naphtha range fraction from the first overhead fraction; refluxing a portion of the naphtha range fraction, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 85 wt.-%, to the first distillation column; refluxing at least a portion of the naphtha range fraction to a second distillation column, preferably a second stabilization column, to obtain a second overhead fraction, preferably comprising at least a portion of the components boiling below 20° C., and a stabilized naphtha range fraction. separating at least a further fuel gas fraction and light liquid hydrocarbons from the second overhead fraction; refluxing at least a portion of the light liquid hydrocarbons, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, even more preferably at least 85 wt.-%, to the second distillation column; and recovering at least a portion of the stabilized naphtha range fraction as a renewable stabilized naphtha range hydrocarbon feed.

[0224] Cracking Effluent The invention further relates to a renewable pyrolysis effluent having a benzene content of 6.0 wt.-% or less, a combined ethylene and propylene content of 45.0 wt.-% or more, and a carbon monoxide content of 0.25 wt.-% or less. The benzene content is 0.01 wt.-% to 6.0 wt.-%, for example 0.1 wt.-% to 4.0 wt.-%, 0.1 wt.-% to 3.6 wt.-%, 0.1 wt.-% to 3.4 wt.-%, 0.1 wt.-% to 3.2 wt.-%, 0.1 wt.-% to 3.0 wt.-%, 0.1 wt.-% to 2.8 wt.-%, 0.1 wt.-% to 2.6 wt.-%, 0.2 wt.-% to 2.4 wt.-%, 0.3 wt.-% to 2.2 wt.-%, or 0.5 wt.-% to 2.0 wt.-% or less.

[0225] Preferably, the renewable pyrolysis effluent has a combined ethylene and propylene content of 45 wt.-% to 65 wt.-%, preferably 46.0 wt.-% to 65.0 wt.-%, 47.0 wt.-% to 65.0 wt.-%, 48.0 wt.-% to 65.0 wt.-%, 49.0 wt.-% to 65.0 wt.-%, 50.0 wt.-% to 60.0 wt.-%, or 50.0 wt.-% to 55.0 wt.-%.

[0226] Preferably, the renewable pyrolysis effluent has a total C4 olefin content of at least 5.0 wt.-%, for example 5.0 wt.-% to 20.0 wt.-%, preferably at least 8.0 wt.-%, at least 10.0 wt.-%, at least 11.0 wt.-%, at least 12.0 wt.-%, at least 12.6 wt.-%, at least 13.0 wt.-%, or at least 13.5 wt.-%.

[0227] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a total C4 olefin content of at least 5.0 wt.-%, for example from 5.0 wt.-% to 20.0 wt.-%, preferably at least 8.0 wt.-% to 20.0 wt.-%, 10.0 wt.-% to 20.0 wt.-%, 12.0 wt.-% to 20.0 wt.-%, 12.6 wt.-% to 20.0 wt.-%, 13.0 wt.-% to 20.0 wt.-%, or 13.5 wt.-% to 20.0 wt.-%.

[0228] The total C4 olefins refers to 1-butene, 2-butene (including cis-2-butene and trans-2-butene), 1,3-butadiene, and isobutene. The total ethylene and propylene content and the total C4 olefins content can also be referred to as the total high-value light olefins content.

[0229] The regenerable pyrolysis effluent is preferably the pyrolysis furnace effluent of step (b) of the method of the present invention. Similarly, step (b) of the method preferably provides a pyrolysis furnace effluent having the regenerable pyrolysis effluent characteristics described herein.

[0230] Preferably, the renewable pyrolysis effluent has a carbon monoxide content of 0.23 wt.-% or less, preferably 0.21 wt.-% or less, 0.20 wt.-% or less, 0.19 wt.-% or less, 0.18 wt.-% or less, 0.17 wt.-% or less, 0.16 wt.-% or less, 0.15 wt.-% or less, 0.14 wt.-% or less, 0.13 wt.-% or less, 0.12 wt.-% or less, 0.11 wt.-% or less, 0.10 wt.-% or less, or 0.09 wt.-% or less.

[0231] Carbon monoxide acts as a catalyst poison for polymerization catalysts. Therefore, it is preferable to minimize the carbon monoxide content at an early stage to reduce the effort required for removal. The present invention provides a means to achieve very low CO content even without the need for CO removal.

[0232] Preferably, the renewable pyrolysis effluent has a C4 monoolefin content of 6.0 wt.-% or more, preferably 6.5 wt.-% or more, 6.8 wt.-% or more, 7.0 wt.-% or more, 7.2 wt.-% or more, or 7.4 wt.-% or more. The upper limit can be, for example, 15.0 wt.-%, for example 13.0 wt.-%. In other words, the renewable pyrolysis effluent can have a C4 monoolefin content in the range of, for example, 6.0 wt.-% to 15.0 wt.-%, for example 6.5 wt.-% to 13.0 wt.-%.

[0233] Preferably, the renewable pyrolysis effluent has an isobutene content of at least 2.0 wt.-%, preferably at least 2.4 wt.-%, more preferably at least 3.0 wt.-%, even more preferably at least 3.2 wt.-%. The upper limit can be, for example, 10.0 wt.-%, for example 9.0 wt.-%, or 8.0 wt.-%. In other words, the renewable pyrolysis effluent can have an isobutene content in the range of, for example, 2.0 wt.-% to 10.0 wt.-%, for example 2.5 wt.-% to 9.0 wt.-% or 3.0 wt.-% to 8.0 wt.-%.

[0234] Among the C4 olefins, isobutene is a very attractive molecule because it can be easily converted and transported by reaction with methanol or ethanol to obtain methyl tert-butyl ether (MTBE) or ethyl tert-butyl ether (ETBE), respectively, and then MTBE / ETBE can be converted back in a similar manner to isobutene and the corresponding alcohols. MTBE and ETBE are also very valuable gasoline components. Furthermore, derivatives of isobutene are more valuable than derivatives of linear C4 olefins, such as butyl rubber, polyisobutene, methyl methacrylate, and gasoline alkylates.

[0235] In addition, it is relatively easy to separate isobutene from other C4 olefins, for example by reacting methanol or ethanol with the C4 olefin fraction containing isobutene to obtain MTBE or ETBE, respectively, and the resulting ethers are then separated from the remaining C4 olefin mixture.

[0236] Preferably, the renewable pyrolysis effluent has a total content of n-C4 monoolefins of at least 3.0 wt.-%, preferably at least 3.5 wt.-%, for example at least 4.0 wt.-%, with an upper limit of, for example, 15.0 wt.-%, for example 12.0 wt.-%, or even 10.0 wt.-%.

[0237] Preferably, the renewable pyrolysis effluent has a 1,3-butadiene content of at least 5.0 wt.-%, preferably at least 5.5 wt.-%, more preferably at least 6.0 wt.-%, or at least 6.2 wt.-%. The upper limit can be, for example, 15.0 wt.-%, such as 13.0 wt.-% or 11.0 wt.-%. In other words, the renewable pyrolysis effluent can have a 1,3 butadiene content in the range of, for example, 5.0 wt.-% to 15.0 wt.-%, such as 5.5 wt.-% to 13.0 wt.-% or 5.5 wt.-% to 11.0 wt.-%.

[0238] Specifically, the renewable stabilized naphtha range hydrocarbon feed of the present invention is particularly suitable for achieving high butadiene content, in other words, it is as suitable as fossil naphtha and can be co-fed with fossil naphtha in a wide range of blend ratios without reducing the butadiene content.

[0239] Preferably, the renewable stabilized naphtha range hydrocarbon feed has a toluene content in the range of 0.2 wt.-% to 1.8 wt.-%, preferably 0.2 wt.-% to 1.6 wt.-%, 0.2 wt.-% to 1.4 wt.-%, 0.2 wt.-% to 1.2 wt.-%, 0.2 wt.-% to 1.0 wt.-%, 0.2 wt.-% to 0.9 wt.-%, 0.2 wt.-% to 0.8 wt.-%, 0.2 wt.-% to 0.7 wt.-%, or 0.3 wt.-% to 0.6 wt.-%.

[0240] The pyrolysis effluent of the present invention is particularly suitable for further upgrading to monomers for polymerization. EXAMPLES

[0241] The present invention will now be further illustrated by the following examples, which should not be construed as limiting the invention in any way.

[0242] The pyrolysis of five feed compositions (C1, C2, C3, E1, E2) was evaluated. Fossil fuel (C1) corresponds to conventional fossil light naphtha. The remaining four feeds correspond to hydrotreated and isomerized bio-renewable oils and fats with different degrees of isomerization and boiling ranges. Of these, feed composition C2 is a broad cut naphtha composition, feed composition C3 is a highly isomerized diesel range composition, feed composition E1 is a stabilized naphtha range composition, and feed composition E2 is a stabilized highly isomerized naphtha range composition.

[0243] The PIONA data and oxygen content of these compositions are shown in Table 1 below.

[0244] [Table 1]

[0245] Table 2 below shows the boiling properties (according to EN ISO 3405-2019) and the carbon number analysis based on PIONA data related to carbon number (assumed to be a floating number by linear interpolation) versus the content range (weight ratio) of the aggregate composition, as well as the calculated IQR, IDR and IVR values.

[0246] [Table 2]

[0247] Comparative Examples 1, 2, and 3 and Examples 1 and 2 The five compositions were subjected to steam cracking at a dilution (water / oil ratio) of 0.5, a coil outlet pressure (COP) of 1.7 bar (absolute) and two coil outlet temperatures (COT) of 820°C and 850°C.

[0248] The yields obtained for each product are shown in Table 3 below.

[0249] [Table 3]

[0250] As can be seen from the above data, the steam cracker feed compositions E1 and E2 according to the invention provide low aromatic and high light olefin yields, especially at relatively low COT. In particular, a low COT can be employed while achieving high yields, as compared to conventional (fossil) naphtha. Furthermore, low coke formation was observed for the compositions according to the invention and the fossil naphtha composition C1. Furthermore, a high benzene content was observed in the cracking effluent produced from the fossil naphtha. This is presumably due to the relatively high content of benzene in the fossil naphtha cracking feedstock (which is not converted during the cracking process) and the high content of naphthenes in the fossil naphtha, which are also converted to aromatics, such as benzene.

[0251] The low to moderately isomerized composition E1 provides especially improved yields of ethylene and butadiene, and the highly isomerized composition E2 provides especially good yields of propylene and C4 monoolefins.

[0252] The above data show that by using the regenerable stabilized naphtha range hydrocarbon compositions of the present invention, such as compositions E1 and E2, as steam cracker feed, it is possible to obtain very high combined yields of ethylene and propylene, and high yields of total C4 olefins, especially 1,3-butadiene. At the same time, even at elevated COT:s, almost no coke is generated, aromatics, especially benzene, are minimal, and heavies are also minimally formed. Advantageously, these advantages are already observed at low COT:s, where the production of C4 monoolefins is favored.

[0253] According to the present invention, by separating and recycling the formed C2-C4 paraffins, the total yield of ethylene and propylene can be further increased. Moreover, the product slate can be easily adjusted in the desired direction, for example, depending on market demand, product prices, further refining or post-processing capabilities, etc. For example, by selecting a renewable stabilized naphtha range hydrocarbon feed with a lower content ratio of i-paraffins to n-paraffins and / or by using a higher COT in the thermal cracking, it is possible to increase the weight ratio of ethylene to propylene and the weight ratio of 1,3-butadiene to C4 monoolefins in the cracking effluent.

Claims

1. (a) providing a renewable stabilized naphtha range hydrocarbon feed; (b) pyrolyzing the renewable stabilized naphtha range hydrocarbon feed, optionally 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 method of claim 1, wherein the pyrolyzing step (b) is a steam cracking step.

3. 3. The process according to claim 1 or 2, wherein the pyrolysis step (b) is carried out at a coil exit temperature (COT) selected from the range of 780°C to 880°C, preferably 800°C to 86°C, more preferably 820°C to 850°C.

4. The content of said renewable stabilized naphtha range hydrocarbon feed in the total cracker feed is from 10 wt.-% to 100 wt.-%, preferably from 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.-% to 100 wt.

4. The process according to any one of claims 1 to 3, wherein the thermal cracking step (b) is preferably carried out in the presence of a co-feed, wherein the total cracker feed means the renewable stabilized naphtha range hydrocarbon feed plus any optional co-feed and any optional additives.

5. the separation process in step (c) further provides a fraction comprising one or more C2-C4 paraffins; and 5. The process according to any one of claims 1 to 4, wherein the process comprises recycling at least a portion of said fraction as a co-feed to step (b) and / or recovering at least a portion of said fraction as an NGL (natural gas liquids) composition.

6. an optional step further comprising derivatizing at least a portion of said light olefins to obtain one or more derivatives of said light olefins as biomonomers; and (d) (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 5, further comprising:

7. A biopolymer composition obtainable by the method of claim 6.

8. Renewable stabilized naphtha range hydrocarbon feed for thermal cracking.

9. The renewable stabilized naphtha range hydrocarbon feed according to claim 8, wherein the renewable stabilized naphtha range hydrocarbon feed has a content of C4 or lower carbon number compounds of 5.0 wt.-% or less, preferably 2.5 wt.-% or less, more preferably 2.0 wt.-% or less, even more preferably 1.5 wt.-% or less.

10. said renewable stabilized naphtha range hydrocarbon feed having a naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%, preferably 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.-%, 0.8 to 5.8 wt.-%, 1.0 to 5.6 wt.-%, or 1.2 to 5.6 wt.-%, based on the total weight of said renewable stabilized naphtha range hydrocarbon feed; and / or The renewable stabilized naphtha range hydrocarbon feed according to claim 8 or 9, wherein the renewable stabilized naphtha range hydrocarbon feed has an olefin content 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, 0.1.2 wt.-% or less, 0.10 wt.-% or less, 0.07 wt.-% or less, or 0.05 wt.-% or less.

11. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 10, wherein the renewable stabilized naphtha range hydrocarbon feed has 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.

12. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 11, wherein the renewable stabilized naphtha range hydrocarbon feed has a carbon range of 10 or less, preferably 8 or less, 7 or less, 6 or less, or 5 or less.

13. the renewable stabilized naphtha range hydrocarbon feed has an interquartile carbon range (IQR) of 2.5 or less, preferably 2.0 or less, 1.8 or less, or 1.5 or less; and / or the renewable stabilized naphtha range hydrocarbon feed has an interventile carbon number range (IVR) of 6.5 or less, preferably 5.0 or less, 4.5 or less, 4.0 or less, or 3.8 or less; and / or The renewable stabilized naphtha range hydrocarbon feed has an adjusted average carbon number range (IDR) of 4.5 or less, preferably 4.0 or less, 3.5 or less, or 3.0 or less. A renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 12.

14. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 13, wherein the renewable stabilized naphtha range hydrocarbon feed has a content of C11 or higher carbon number components less than 5.0 wt.-%, preferably 4.5 wt.-% or less, 4.0 wt.-% or less, 3.5 wt.-% or less, 3.0 wt.-% or less, 2.5 wt.-% or less, or 2.0 wt.-% or less.

15. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 14, wherein the renewable stabilized naphtha range hydrocarbon feed has a content of compounds with carbon numbers of C17 and above of 1.0 wt.-% or less, for example 0.0 to 0.9 wt.-%, preferably 0.0 to 0.8 wt.-%, more preferably 0.0 to 0.5 wt.-%, or 0.0 to 0.2 wt.-%.

16. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 15, wherein the renewable stabilized naphtha range hydrocarbon feed has an aggregate paraffin content of 90 wt.-% or more, preferably 92 wt.-% or more, 93 wt.-% or more, 94 wt.-% or more, or 95 wt.-% or more.

17. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 16, wherein the renewable stabilized naphtha range hydrocarbon feed has a content ratio of i-paraffins to n-paraffins of not more than 1.7, preferably not more than 1.5, for example in the range of 0.5 to 1.7, or 0.7 to 1.

5.

18. The renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 16, wherein the renewable stabilized naphtha range hydrocarbon feed has a content ratio of i-paraffins to n-paraffins in the range of 2.0 or more, preferably 2.2 or more.

19. The process according to any one of claims 1 to 6, wherein the renewable stabilized naphtha range hydrocarbon feed is a renewable stabilized naphtha range hydrocarbon feed according to any one of claims 8 to 18.

20. A renewable pyrolysis effluent having a benzene content of 6.0 wt.-% or less, a combined ethylene and propylene content of 45.0 wt.-% or more, and a carbon monoxide content of 0.25 wt.-% or less.

21. 21. The renewable pyrolysis effluent of claim 20, having a benzene content of 0.01 wt.-% to 6.0 wt.-%, for example 0.1 wt.-% to 4.0 wt.-%, 0.1 wt.-% to 3.6 wt.-%, 0.1 wt.-% to 3.4 wt.-%, 0.1 wt.-% to 3.2 wt.-%, 0.1 wt.-% to 3.0 wt.-%, 0.1 wt.-% to 2.8 wt.-%, 0.1 wt.-% to 2.6 wt.-%, 0.2 wt.-% to 2.4 wt.-%, 0.3 wt.-% to 2.2 wt.-%, or 0.5 wt.-% to 2.0 wt.-% or less.

22. 22. Renewable pyrolysis effluent according to claim 20 or 21, wherein the regenerable pyrolysis effluent has a combined ethylene and propylene content of 45 wt.-% to 65 wt.-%, preferably 46.0 wt.-% to 65.0 wt.-%, 47.0 wt.-% to 65.0 wt.-%, 48.0 wt.-% to 65.0 wt.-%, 49.0 wt.-% to 65.0 wt.-%, 50.0 wt.-% to 60.0 wt.-%, or 50.0 wt.-% to 55.0 wt.-%.

23. Renewable pyrolysis effluent according to any one of claims 20 to 22, obtainable by the process according to any one of claims 1 to 6 and 19.

24. 24. Renewable pyrolysis effluent according to any one of claims 20 to 23, wherein the regenerable pyrolysis effluent has a carbon monoxide content of 0.23 wt.-% or less, preferably 0.21 wt.-% or less, 0.20 wt.-% or less, 0.19 wt.-% or less, 0.18 wt.-% or less, 0.17 wt.-% or less, 0.16 wt.-% or less, 0.15 wt.-% or less, 0.14 wt.-% or less, 0.13 wt.-% or less, 0.12 wt.-% or less, 0.11 wt.-% or less, 0.10 wt.-% or less, or 0.09 wt.-% or less.

25. The regenerable pyrolysis effluent comprises: a total content of C4 olefins of at least 8.0 wt.-%, at least 10.0 wt.-%, at least 11.0 wt.-%, at least 12.0 wt.-%; and / or a 1,3-butadiene content of at least 5.0 wt.-%, at least 5.5 wt.-%, or at least 6.0 wt.-%, and / or at most 15.0 wt.-%, at most 13.0 wt.-%, or at most 11.0 wt.-%; and / or a content of C4 monoolefins of 6.0 wt.-% or more, preferably 6.5 wt.-% or more, 6.8 wt.-% or more, 7.0 wt.-% or more, 7.2 wt.-% or more, or 7.4 wt.-% or more, and / or up to 15.0 wt.-% or up to 13.0 wt.-%; and / or an isobutene content of at least 2.0 wt.-%, at least 2.4 wt.-%, or at least 3.0 wt.-%, and / or at most 10.0 wt.-%, at most 9.0 wt.-%, or at most 8.0 wt.-%; and / or A content of n-C4 monoolefins of 3.0 wt.-% or more, preferably 3.5 wt.-% or more, or 4.0 wt.-% or more, and / or up to 15.0 wt.-%, up to 12.0 wt.-%, or up to 10.0 wt.-%. The renewable pyrolysis effluent of any one of claims 20 to 24, having a

26. The regenerable pyrolysis effluent comprises: a content of C2-C4 paraffins in total equal to or greater than 4.0 wt.-%, preferably equal to or greater than 4.2 wt.-%, more preferably equal to or greater than 4.3 wt.-%, and / or equal to or less than 15.0 wt.-%, equal to or less than 12.0 wt.-%, or equal to or less than 10.0 wt.-%; and / or Pyrolysis fuel oil (C10 and heavier compounds) content of less than 1.5 wt.-%, preferably less than 1.2 wt.-%, more preferably less than 1.0 wt.-% The renewable pyrolysis effluent of any one of claims 20 to 25, having a molecular weight of 0.01 to 0.01.

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