Sustainable pyrolysis methods and their products

Abstract

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

Description

Technical Field

[0001] The present invention relates to a method including pyrolysis, a product obtainable by the use of such a method, and a cracker feed that can be used in such a method.

Background Art

[0002] Pyrolysis, such as steam cracking, is a well-known established route for improving conventional (mineral oil-based) materials. In recent years, pyrolysis of bio-based materials has been studied, but usually attempts have been made to achieve direct decomposition of bio-based feeds (usually high in oxygen content) or to mimic conventional (fossil) feeds.

[0003] The prior art discloses several cracking methods using hydrocarbon feeds, most of which use exclusively fossil raw materials. A cracking method using at least partially renewable hydrocarbon raw materials is disclosed in Patent Document 1. Further, Patent Document 2 discloses a method including pyrolyzing a raw material derived from a renewable raw material and containing at least 60% by weight of isoparaffin. Patent Document 3 discloses a composition containing a paraffin fraction obtained from a biological raw material. Patent Document 4 discloses a method for producing a renewable fuel.

[0004] High-value chemicals produced in pyrolysis processes (such as steam cracking) are ethylene, propylene, butadiene, olefinic C4, benzene, xylene, and toluene, etc. Among these high-value chemicals, propylene and butadiene in particular are interesting as raw materials for specific chemicals and polymers.

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

[0006] To introduce biomolecules into the petrochemical value chain, and from the above perspective, it is useful to adopt a process that maximizes the yield of light olefins while suppressing the production of aromatics, particularly benzene. [Prior art documents] [Patent Documents]

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

[0008] The present invention has been made in view of the above-mentioned problems, and the object of the present invention is to provide an improved method comprising the pyrolysis of renewable cracker feed, and products obtained from the method, and uses and further processing thereof.

[0009] The underlying problem of this invention is solved by the subject matter described in the independent claim. Further beneficial developments are described in the dependent claims.

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

[0011] 1. (a) i-paraffin content of 85.0 wt.-% or more and carbon in the range of 20-32 Sohan A method for providing renewable cracker feed obtained by fractionating an isomer hydrocarbon composition having a boundary into at least a low-boiling point fraction and a high-boiling point fraction, and providing at least a portion of the low-boiling point fraction or at least a portion of the high-boiling point fraction as the renewable cracker feed. (b) a step of pyrolysis the renewable cracker feed in a pyrolysis furnace, optionally together with cofeed and / or additives, and (c) A step of subjecting the effluent from the pyrolysis furnace in step (b) to a separation treatment in order to provide at least a light olefin fraction. A method that includes this.

[0012] 2. The opposite sex body The hydrocarbon composition is 14.0 to 22.0, preferably 14.0 to 20.0, or 15 The method described in item 1, which has a c_50 value in the range of 0 to 20.0.

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

[0014] 4. The method according to any one of the above items, wherein both the low boiling fraction and the high boiling fraction are independently 0.164 or less, preferably 0.160 or less, 0.155 or less, and 0.150 or less, and the ratio of i-paraffin having more than three branches (IP3+) to total i-paraffin (iP) is (iP3+ / iP).

[0015] 5. The method according to any one of the above items, wherein both the low-boiling-point fraction and the high-boiling-point fraction independently contain 10.50 wt.-% or more of i-paraffin (iP3+) having three or more branches relative to the total paraffin, for example, 10.50-16.00, 11.00-15.50, 11.00-15.50, 11.00-15.00, or 1,2.00-15.00.

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

[0017] 7. The method according to any one of the above items, wherein both the low-boiling-point fraction and the high-boiling-point fraction independently contain naphthenes in the range of 0.1 wt.-% to 10.0 wt.-%.

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

[0019] 9. The method according to any one of the above items, having 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, in which case both the low boiling point fraction and the high boiling point fraction are independent of each other.

[0020] 10. The method according to any one of the above items, wherein both the low-boiling fraction and the high-boiling fraction independently contain a total amount of olefins and naphthenes in the range of 0.1 wt.-% to 10.0 wt.-%.

[0021] 11. The method according to any one of the preceding items, wherein both the low-boiling fraction and the high-boiling fraction independently have a total content of olefins and naphthenes 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.-%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0045] 35. The high boiling point fraction is the isomer body The method according to any one of the items, wherein the C50 value is higher than that of the hydrocarbon composition, and the low boiling fraction has a C50 value lower than that of the high boiling fraction.

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

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

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

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

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

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

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

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

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

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

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

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

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

[0059] 49. The method according to any one of the above items, wherein the thermal decomposition step (b) is a steam decomposition step.

[0060] 50. The method according to any one of the above items, wherein the thermal decomposition step (b) is carried out in the presence of a thermal decomposition diluent with a dilution of 0.10 to 0.80, preferably 0.25 to 0.70, for example, 0.35 to 0.50.

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

[0062] 52. This includes performing one or more further disintegration operations in order to provide further disintegration spills, here The method of any one of the items, further comprising step (c) adding further effluent and / or fraction thereof before and / or during the separation process.

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

[0064] 54. The method according to any one of the above items, wherein the content of the renewable cracker 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.-%, where the total cracker feed means the renewable cracker feed with optional cofeed and optional additives added.

[0065] 55. The method according to any one of the above items, wherein the cofeed comprises fossil hydrocarbon cofeed.

[0066] 56. The method according to any one of the above items, wherein the cofeed includes a naphtha range feed, a diesel range feed, an aviation fuel range feed, a marine fuel range feed, or a diesel range feed.

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

[0068] 58. The step (a) of providing the renewable cracker feed, In order to provide at least an isomerized deoxygenated flow, the oxygenated biorenewable feed is subjected to a hydrogenation treatment including at least hydrogenated deoxygenation, and a hydrogen isomerization process. A step of subjecting at least a portion of the isomerized deoxygenated flow to fractionation and recovering at least the isomerized hydrocarbon composition, and A step of subjecting at least a portion of the isomer hydrocarbon composition to further fractionation in order to provide at least the low boiling point fraction and the high boiling point fraction. A method for any one of the above items, including:

[0069] 59. The method according to item 58, wherein the hydrogen isomerization is carried out in the same hydrogenation treatment step as the hydrogenation deoxygenation, and / or the hydrogen isomerization is carried out in a further hydrogenation treatment step after the hydrogenation treatment which includes at least hydrogenation deoxygenation.

[0070] 60. The method according to item 58 or 59, comprising gas-liquid separation after the hydrogenation treatment, and / or the further hydrogenation treatment, and recovery of at least one gaseous stream and the isomerized deoxygenated stream.

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

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

[0073] 63. The aforementioned renewable cracker feed is as follows: In order to provide the isomerized deoxygenated flow, the oxygenated biorenewable feed is subjected to a hydrogenation treatment including at least hydrogenation deoxygenation, hydrogen isomerization, and gas-liquid separation. A step of supplying the isomerized deoxygenated stream to a first distillation column, preferably a stabilization column, in order to obtain at least a naphtha range fraction and a stabilized heavy liquid fraction, and The process involves supplying at least a portion of the stabilized heavy liquid fraction as the isomerized hydrocarbon composition to a second distillation column, and recovering at least the low-boiling fraction and the high-boiling fraction. A method for any one of the above items obtained by

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

[0075] 65. The method according to any one of the above items, further comprising the derivatization of at least a portion of a light olefin to obtain one or more derivatives of a light olefin as a biomonomer, such as acrylic acid, acrylonitrile, acrolein, propylene oxide, ethylene oxide, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, adiponitrile, hexamethylenediamine (HMDA), hexamethylenediisocyanate (HDI), (methyl) methacrylate, ethylidene norvorine, 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, etc.

[0076] 66. The method according to any one of the above items, wherein the renewable cracker feed is obtained by a method comprising a step of applying an oxygenated biorenewable feed to a hydrogenation treatment including at least hydrogenated deoxygenation and hydrogen isomerization.

[0077] 67. At least a portion of the low boiling point fraction is used in the first pyrolysis furnace for the pyrolysis process ( b ) is subjected to the above, and at least a portion of the high boiling point fraction is subjected to the above pyrolysis step in the second pyrolysis furnace ( b The method described in any one of the above items attached to ).

[0078] 68. At least a portion of the low boiling point fraction and at least a portion of the high boiling point fraction alternately in the thermal decomposition step ( b The method described in any one of the above items attached to ).

[0079] 69. At least a portion of the low boiling point fraction and at least a portion of the high boiling point fraction alternately in the same pyrolysis furnace during the pyrolysis process. b The method described in any one of the above items attached to ).

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

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

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

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

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

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

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

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

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

[0089] [[ID=​​

[0090] 80. A biopolymer composition obtained by the method described in item 78 or 79. [Brief explanation of the drawing]

[0091] [Figure 1] Figure 1 shows the linear interpolation used to obtain the c_50 value (Graph A) and the carbon span at 80% (Graph B). [Modes for carrying out the invention]

[0092] In this invention, unless otherwise specified, the content and content ratio are given on a weight basis.

[0093] Furthermore, i-paraffins (also called isoparaffins) refer to branched acyclic alkanes, and n-paraffins (also called normal paraffins) refer to linear acyclic alkanes. Total paraffin content means the total content of i-paraffins and n-paraffins. Similarly, olefins refer to linear or branched acyclic alkenes containing multiple unsaturated rings. Naphthenes refer to cyclic non-aromatic branched or unbranched alkanes, alkenes, or alkynes containing multiple unsaturated rings. Aromatic refers to compounds that have at least one aromatic ring.

[0094] The content of n-paraffins, i-paraffins, olefins, naphthenes, and aromatics can be measured using the PIONA method, which is a GC×GC analytical method as described by Pyl et al. in the Journal of Chromatography A, 1218 (2011) 3217-3223. According to this literature, in samples subjected to high hydrogen isomerization, it is desirable to invert the primary and secondary columns to improve the separation and identification of isoparaffins from n-paraffins.

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

[0096] In particular, the bio-based carbon content of isomerized hydrocarbon compositions and / or renewable cracker feeds, also known as bio-based cracker feeds, is preferably more than 5% and up to 100%, for example, more than 20%, more than 40%, more than 50%, more than 60%, or more than 70%, more than 80%, more than 90%, or more than 95%, and about 100%. The bio-based carbon content of oxygenated bio-renewable feeds is preferably more than 50% and up to 100%, preferably more than 60% or more than 70%, preferably more than 80%, more preferably more than 90%, or more than 95%, and even more preferably about 100%.

[0097] The biocarbon 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%, for example, 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 biocarbon content of the pyrolysis furnace effluent of step (b), as well as the products and intermediates downstream of decomposition step (b), may be less than 1%, but preferably at least 1% and up to 100%, for example, at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90%, or about 100%.

[0099] In particular, the bio-derived 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%, for example, at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90%, or about 100%.

[0100] The terms "optionally" or "optional" mean any characteristic, feature, or process that may exist but is not necessarily required for carrying out the present invention.

[0101] Unless otherwise noted, all test method standards mentioned in this document are the latest versions as of December 1, 2021.

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

[0103] The present invention relates to a sustainable pyrolysis method. More particularly, the present invention relates to a method using feed that has not been previously used for pyrolysis and that shows surprisingly good results in pyrolysis. The method of the present invention provides a renewable cracker feed obtained by fractionating an isomeric hydrocarbon composition having an i-paraffin content of 85.0% by weight or more and a carbon range in the range of 20 to 32 into at least a low-boiling fraction and a high-boiling fraction, and provides at least a portion of the low-boiling fraction or at least a portion of the high-boiling fraction as renewable cracker feed (a); pyrolyzes the renewable cracker feed in a pyrolysis furnace, optionally together with cofeed and / or additives (b); and subject the effluent from the pyrolysis furnace in step (b) to a separation treatment in order to provide at least a light olefin fraction (c).

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

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

[0106] The isomerized hydrocarbon composition preferably has a c_50 value in the range of 14.0 to 22.0, more preferably 14.0 to 20.0, or 15.0 to 20.0. In this invention, the c_50 value is the fractional carbon number representing a 50 wt.-% sample. Details of the calculation methods for the c_50 value and other fractional carbon numbers will be described later. The carbon range is the difference between C_max and C_min (carbon range = C_max - C_min), where C_max (the largest carbon number) and C_min (the smallest carbon number) are determined by PIONA (the GC × GC method described herein), and for the measurement of C_min and C_max, it is assumed that there are no carbon numbers with a measured abundance of 0.10 wt.-% or less. In other words, when determining C_min and C_max, and consequently the carbon range, carbon numbers with a measured abundance of 0.10 wt.-% or less are not considered.

[0107] The inventors have surprisingly found that in the fractionation of an isomeric hydrocarbon composition having a high i-paraffin content of 85% or more into at least two fractions, each resulting fraction exhibits superior pyrolysis properties compared to the isomeric hydrocarbon composition. Conventionally, such separated fractions have been used as fuel or for specific fluids. While portions of the low-boiling and / or high-boiling fractions can still be used for such purposes, at least portions of the low-boiling or high-boiling fractions are used as renewable cracker feed in the method of the present invention. Since these fractions are based on renewable raw materials, the method of the present invention achieves improved sustainability. In addition, because it can be difficult (or costly) to produce isomeric hydrocarbon compositions in a manner that produces the relative amounts of low-boiling and high-boiling fractions that are (precisely) needed or required for use as fuel or for specific fluid purposes, the present invention can further update surplus materials that would otherwise be stored or even burned. Using only a portion of the low-boiling point fraction or the high-boiling point fraction can be achieved, for example, by simply splitting the stream of the low-boiling point fraction or the high-boiling point fraction into two streams or aliquots / aliquots for further processing, or by guiding the streams or batches of these fractions to different processing routes in a batch manner.

[0108] In this invention, either a high-boiling-point fraction or a low-boiling-point fraction is used as the renewable cracker feed. It is also possible to use both fractions, or parts thereof, as the renewable cracker feed of this invention. However, in this case, the high-boiling-point fraction and the low-boiling-point fraction must be pyrolyzed separately, i.e., not mixed. For example, the high-boiling-point fraction and the low-boiling-point fraction should not be used simultaneously as renewable cracker feed in the same furnace.

[0109] Preferably, both the low-boiling and high-boiling fractions independently have an i-paraffin content of 92.0 wt.-% or more. This means that both fractions independently have an i-paraffin content of 92.0 wt.-% or more (i.e., in the range of 92.0 wt.-% to 100 wt.-%), but they do not necessarily have the same i-paraffin content as long as both fractions have an i-paraffin content within that range. More preferably, the i-paraffin content may be 93.0 wt.-% or more, 94.0 wt.-% or more, or 95.0 wt.-% or more, independently of each other. A higher i-paraffin content in the renewable cracker feed results in lower viscosity, which in turn makes it easier to handle. Furthermore, this high i-paraffin content has been found to result in desirable decomposition characteristics, particularly improved yields of high-value light olefins (VLOs).

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

[0111] Preferably, both the low-boiling and high-boiling fractions have a ratio (iP3+ / iP) of i-paraffins (IP3+) with more than three branches to total i-paraffins (iP) of 0.164 or less, more preferably 0.160 or less, 0.155 or less, and 0.150 or less, independently of each other. Relatively small amounts of IP3+ component result in a reduced yield of aromatics, particularly benzene, and thus improve the value of the decomposition effluent for use in polymer chemistry and other fields where aromatics should be removed before further use.

[0112] The content of i-paraffins with more than three branches (IP3+) may be determined by the method disclosed in International Publication No. 2020 / 201614, which is incorporated herein by reference in its entirety. Specifically, the content of i-paraffins with more than three branches (IP3+) may be determined by the following method:

[0113] The N-paraffin and i-paraffin content in a sample is analyzed by gas chromatography (GC). The sample is analyzed without pretreatment. This method is suitable for C2-C36 hydrocarbons. The groups of N-paraffins and i-paraffins (C1-, C2-, C3-substituted, and ≥C3-substituted) are identified using mass spectrometry and mixtures of known n-paraffins in the C2-C36 range. The chromatogram is divided into three groups of paraffins (C1-, C2- / C3-, and ≥C3-substituted i-paraffins / n-paraffins) or two groups of paraffins (C1- / C2- / C3-, and ≥C3-substituted i-paraffins / n-paraffins) by integrating the groups against the baseline of the chromatogram immediately following the n-paraffin peak. N-paraffins are separated from ≥C3-substituted i-paraffins (iP3+) by integrating the n-paraffin peaks tangentially from valley to valley. Compounds or groups of compounds are quantified by normalization using a relative response coefficient of 1.0 for all hydrocarbons. The limit of quantification for individual compounds is typically 0.01 wt.-%. Appropriate GC settings are shown below:

[0114] TIFF0007894936000001.tif79143

[0115] Preferably, both the low-boiling-point fraction and the high-boiling-point fraction independently contain 10.50 wt.-% or more of i-paraffins (iP3+) having more than three branches relative to the total paraffins, for example, 10.50-16.00, 11.00-15.50, 11.00-15.50, 11.00-15.00, or 1,2.00-15.00. Total paraffins refer to the total amount of n-paraffins and i-paraffins. In the context of the present invention, the i-paraffin branching is typically methyl branching.

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

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

[0118] Preferably, both the low-boiling and high-boiling fractions independently have a naphthene content in the range of 0.1 wt.-% to 10.0 wt.-% based on the total weight of the renewable cracker feed. In high-degree-of-polymerization isomerization, some degree of cyclization (naphthene formation) may occur. According to the present invention, it is desirable that the naphthene content in the low-boiling and high-boiling fractions, and therefore in the renewable cracker feed, be low, but it does not need to be 0 wt.-%. That is, some naphthenes may be present and do not need to be removed. Naphthenes are readily converted to aromatics, which are compounds that may react with coke but do not react to the desired product. Therefore, a low naphthene content is preferable.

[0119] For example, the naphthene content can be independently between 0.2 wt.-% and 10.0 wt.-%, such as 0.5 wt.-% to 8.0 wt.-%, 0.5 wt.-% to 6.0 wt.-%, 0.6 wt.-% to 5.8 wt.-%, or 0.8 wt.-% to 5.6 wt.-%.

[0120] Preferably, the low-boiling-point fraction and the high-boiling-point fraction have 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, independently of each other. Olefins are undesirable components in the renewable cracker feed of the present invention, in the low-boiling-point fraction and the high-boiling-point fraction. That is, the inventors have found that olefins have a strong coking tendency, even higher than aromatics, and therefore the olefin content should be kept low. The olefin content can be 0%, independently of each other, i.e., no detectable amount of olefin is present.

[0121] Preferably, both the low-boiling-point fraction and the high-boiling-point fraction independently have a total olefin and naphthene content in the range of 0.1 wt.-% to 10.0 wt.-%. The total olefin and naphthene content refers to the total content of olefins and naphthenes. More preferably, the total content of olefins and naphthenes is independently between 0.1 wt.-% and 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.-%.

[0122] Preferably, the low-boiling-point fraction and the high-boiling-point fraction have an aromatic 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, independently of each other. Aromatics such as benzene do not react with the desired product. Rather, they tend to react with coke (i.e., they are coke precursors). Therefore, their presence in thermal decomposition reduces the yield of the desired product, so their content should be low. In the present invention, the aromatic content is preferably low, and may be 0.00%. The aromatic content can be determined by PIONA analysis.

[0123] Preferably, the low-boiling-point fraction and the high-boiling-point fraction independently have a total content of olefins, aromatics, and naphthenes of 0.1 wt.-% to 10.0 wt.-%, preferably 0.1 wt.-% to 8.0 wt.-%, 0.1 wt.-% to 6.5 wt.-%, 0.2 wt.-% to 6.0 wt.-%, 0.5 wt.-% to 5.5 wt.-%, 0.5 wt.-% to 5.0 wt.-%, 0.8 wt.-% to 5.0 wt.-%, 0.9 wt.-% to 5.0 wt.-%, 1.0 wt.-% to 5.0 wt.-%, 1.1 wt.-% to 5.0 wt.-%, or 1.2 wt.-% to 5.0 wt.-%. Naphthenes, aromatics, and olefins are coke precursors, and their content should be low. However, since drastically reducing the content of these components can be laborious, some level of their content may be acceptable. Nevertheless, their total content can be reduced to 0%, independently of each other, which includes 0%.

[0124] Preferably, both the low-boiling-point fraction and the high-boiling-point fraction have an oxygenated 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, independently of each other. Here, an oxygenated substance means a molecule that contains carbon and hydrogen, and further contains covalently bonded oxygen in its structure (molecule). In the present invention, it is preferable to have a low oxygenated content, including the absence of oxygenated substances. On the other hand, especially when applying low-oxygenated cofeeds (e.g., fossil hydrocarbon cofeeds) of 10 wt.-% or higher, higher values, such as 100 wt.-ppm to 1000 wt.-ppm, can be used independently of each other. In such cases, the effort required to minimize the oxygenated content is minimized, which improves the overall efficiency of the process.

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

[0126] Preferably, both the low-boiling-point fraction and the high-boiling-point fraction independently contain 70 wt.-% to 95 wt.-% of C14-C18 i-paraffin, preferably 75 wt.-% to 91 wt.-%. In the present invention, the C14-C18 i-paraffin content can be determined by the same measurement method used for measuring the iP3+ content.

[0127] Preferably, both the low-boiling-point fraction and the high-boiling-point fraction independently have a total paraffin content of 93 wt.-% or more, preferably 94 wt.-% or more, or 95 wt.-% or more.

[0128] If both the high-boiling-point and low-boiling-point fractions have similar properties, such as cloud point, modal carbon number, and / or i-paraffin content, it is possible to easily switch from providing only the low-boiling-point fraction (or portion thereof) as renewable cracker feed to providing only the high-boiling-point fraction (or portion thereof) as renewable cracker feed. In other words, in such cases, these fractions provide, at least at a general level, substantially the same desired product slate and advantages in pyrolysis. In such cases, the other fraction can be flexibly used for other high-value-adding purposes as needed.

[0129] Traditionally, isomerization treatments that yield high i-paraffin content have also yielded high content of highly branched i-paraffins, particularly those with more than three branches. Various methods can be used to achieve a high share of i-paraffin, but nevertheless, only low amounts of IP3+ components are produced. For example, it is possible to reduce the degree of isomerization (e.g., lower the temperature). However, in some cases, lowering the isomerization temperature requires a much longer residence time, which can also increase the yield of IP3+ components. In this case, it may be preferable to increase the isomerization temperature while simultaneously shortening the residence time. Alternatively or additionally, a suitable catalyst for isomerization can be selected. For example, a catalyst with a specific pore structure can be used, in which case the catalytically active component for isomerization is supplied into small pores so that linear paraffins, or only linear paraffins, can reach the active site. Such shape-selective catalysts are commercially available.

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

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

[0132] The Intervital Radical Range (IVR) is the range of carbon atoms that contains 90% of the mass (i.e., 5 wt.-% to 95 wt.-%). Similarly, the Interquartile Range (IQR) is the range of carbon atoms that contains 50% of the mass between 25 wt.-% and 75 wt.-%., and the Adjusted Mean Carbon Range (IDR) is the range of carbon atoms that contains 80% of the mass between 10 wt.-% and 90 wt.-%. Linear interpolation means that it is assumed that the content range between two carbon atoms is linear. For example, a sample containing 0% C1, 0% C2, 0% C3, 5% C4, 5% C5, and 8% C6 would have a C_2.5 value of 3.5 (carbon atoms) (i.e., a fraction of carbon atoms corresponding to 2.5 wt.% of the sample), even if C4 was actually the lowest carbon atom present. Since the cumulative amount of C1+C2+C3+C4+C5 is exactly 10 wt.-%, the C_5 (C_05) value (the fractional number of carbon atoms corresponding to a 5 wt.-% sample) is 4 (C4), and the C_10 value (the fractional number of carbon atoms corresponding to a 10 wt.-% sample) is 5 (C5). The C_15 value (15 wt.-%) is between 5 and 6 (C5 is 10 wt.-%), and C6 is 18 wt.-%). Linear interpolation is easily calculated, and for example, the number of carbon atoms in a 15 wt.-% content (C_15 value) can be calculated as follows. 5{Highest number of carbon atoms not yet contributing to 15wt.-%}+ [{15%{Target content}-10%{Cumulative content of C5}} / (18% {cumulative C6 content} - 10% {cumulative C5 content}) =5 + [5% / 8%] = 5 + 0.625, that is, the number of carbon atoms is 5.625.

[0133] In other words, the following formula is used to determine the C_XX value: {XXwt.-% has the highest number of carbon atoms that has not yet contributed}+ [({Target content: XXwt.-%}-{Cumulative content of the highest number of carbon atoms that has not yet contributed to XXwt.-%}) / ({Cumulative content of the lowest number of carbon atoms that exceeds XXwt.-%} - {Cumulative content of the highest number of carbon atoms that has not yet contributed to XXwt.-%}).

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

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

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

[0137] In one embodiment, the high-boiling-point fraction has a c_50 value of 16.5 or higher and an interventional carbon number range (IVR) of 5.0 or lower. In other words, it is particularly preferable that the high-boiling-point fraction is a heavy (high-boiling-point) fraction having a narrow carbon number distribution and a high c_50 value.

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

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

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

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

[0142] Preferably, the high-boiling fraction has a ratio (≧C18 / <C18) of the content of hydrocarbons having 18 or more carbon atoms (≧C18) to the content of hydrocarbons having less than 18 carbon atoms (<C18) of 1.0 or more, preferably 1.5 or more, 2.0 or more, 3.0 or more, 4.0 or more, 5.0 or more, or 6.0 or more. The ratio can be, for example, 200.0 or less (i.e., the ratio can be in the range of, for example, 1.0 to 200.0), but preferably it is 150.0 or less, for example 100.0 or less, 50.0 or less, 30.0 or less, 2-0.0 or less, 15.0 or less, 12.0 or less, or 10.0 or less.

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

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

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

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

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

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

[0149] The low-boiling fraction preferably has an interquartile carbon number range (IQR) in the range of 1.5 to 4.0, more preferably 2.0 to 3.5, or 2.0 to 3.0. In other words, the low-boiling fraction may have a broader carbon number distribution than the high-boiling fraction, but even in such cases, it is preferable that this fraction has a certain degree of sharpness, as indicated by IQ and R. That is, such a clearly defined fraction allows the decomposition process to be specifically tailored to the feed characteristics, thereby further improving the yield of high-value products and minimizing side reactions.

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

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

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

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

[0154] Preferably, the high-boiling fraction has a higher c50 value than the isomeric hydrocarbon composition, and the low-boiling fraction has a lower c50 value than the high-boiling fraction. In particular, it is preferable that the high-boiling fraction is a fraction mainly comprising the heavy portion of the isomeric hydrocarbon composition. For example, the high-boiling fraction may be the bottom fraction, and the low-boiling fraction may be one or only non-bottom fractions.

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

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

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

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

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

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

[0161] The thermal decomposition step (b) may also be a steam decomposition step. Steam decomposition is tolerant of impurities that may be present in renewable materials. In addition, the method of the present invention has been shown to yield particularly good results when steam decomposition is employed.

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

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

[0164] The pyrolysis step (b) is preferably carried out in the presence of a pyrolysis diluent. Any conventional pyrolysis diluent may be used in pyrolysis step (b). Examples of such pyrolysis diluents include water vapor, 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 water vapor.

[0165] The pyrolysis step (b) is preferably carried out in the presence of a pyrolysis diluent at a dilution of 0.10 to 0.80, preferably 0.25 to 0.70, for example, 0.35 to 0.50. The dilution refers to the flow rate of the pyrolysis diluent to the total cracker feed (flow rate of pyrolysis diluent [kg / h] / flow rate of total cracker feed [kg / h]). The total cracker feed refers to renewable cracker feed with optional cofeed and optional additives, and does not include the diluent.

[0166] The individual components and diluents of the total cracker feed can be supplied to the pyrolysis furnace as a pre-formed mixture, as separate streams, or as a combination of separate streams and the pre-formed mixture.

[0167] The method may include one or more further decomposition operations to provide further decomposition effluent, wherein step (c) further includes adding further effluent and / or fractions thereof before and / or during the separation process.

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

[0169] Preferably, the content of renewable cracker feed in the total cracker feed is in the range of 10 wt.-% to 100 wt.-%, preferably 20 wt.-% to 100 wt.-%, 30 wt.-% to 100 wt.-%, 40 wt.-% to 100 wt.-%, 50 wt.-% to 100 wt.-%, 60 wt.-% to 100 wt.-%, 70 wt.-% to 100 wt.-%, 80 wt.-% to 100 wt.-%, or 90 wt.-%, where total cracker feed means renewable cracker feed with optional cofeed and optional additives added. The upper limit may also be 90 wt.-% or 80 wt.-%; that is, the content may be in the range of, for example, 10 wt.-% to 90 wt.-% or 10 wt.-% to 80 wt.-%.

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

[0171] Cofeed may include cofeed of fossil hydrocarbons. Fossil cofeed, particularly fossil naphtha, is readily available and very suitable for pyrolysis. To fully enjoy the effects of the present invention, it is preferable that the cofeed has a composition, particularly a carbon number distribution, similar to that of the renewable cracker feed. Specifically, the cofeed may include naphtha range feed, diesel range feed, aviation fuel range feed, marine fuel range feed, or diesel range feed. In particular, when a high-boiling point fraction (or a portion thereof) is used as renewable cracker feed, the cofeed may include a heavy fossil fraction, such as a diesel fraction.

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

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

[0174] Since renewable cracker feed typically has an inherently low or no sulfur content, sulfur can be incorporated into the total cracker feed by using a sulfur-containing cofeed, such as fossil hydrocarbon feed. Sulfur can also be derived, partially or total, from sulfur-containing additives, including conventional cracking additives. Specifically, any conventional pyrolysis additive may be added to the renewable cracker feed of this disclosure, to an optional cofeed, or to a pre-formed total cracker feed, or co-feeded to a pyrolysis furnace, or added to a 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) and carbon disulfide (CS2). DMDS is a particularly preferred sulfur additive. The sulfur additive may be mixed with the renewable cracker feed, the optional cofeed, or the pre-formed total cracker feed before being fed to the pyrolysis furnace. Optionally, sulfur additives may be added to a pyrolysis diluent, preferably steam, containing sulfur additives by injecting it into the pyrolysis furnace.

[0175] Step (a) of providing a renewable cracker feed may include, for example, a step of subjecting an oxygenated biorenewable feed to a hydrogenation treatment including at least hydrogenated deoxygenation and hydrogenated isomerization in order to provide at least an isomerized deoxygenated flow; a step of subjecting at least a portion of the isomerized deoxygenated flow to fractionation and recovering at least an isomerized hydrocarbon composition; a step of subjecting at least a portion of the isomerized deoxygenated flow to fractionation and recovering at least an isomerized hydrocarbon composition; and a step of subjecting at least a portion of the isomerized hydrocarbon composition to further fractionation in order to provide at least a low boiling point fraction and a high boiling point fraction. The isomerized deoxygenated flow is preferably a liquid isomerized deoxygenated flow.

[0176] In addition to the isomer hydrocarbon composition, other fractions may be recovered, for example, but not limited to, at least one of the following: fuel gas fraction, marine fuel fraction, naphtha range fraction, diesel range fraction, aviation fuel fraction, or electrical fluid fraction. The propane fraction may be recovered from gas-liquid separation after hydrotreatment. Preferably, one or more fractions that can be used as liquid transport fuels such as diesel fuel, gasoline fuel, aviation fuel, or marine fuel are recovered.

[0177] The exemplary aviation fuel range fraction may boil in the range of 100°C to 300°C, for example, in the range of 150°C to 300°C. The exemplary gasoline fuel fraction may boil in the range of 25°C to 220°C. The exemplary diesel fuel fraction may boil in the range of 160°C to 380°C. The exemplary marine fuel may boil in the range of 180°C to 600°C.

[0178] Generally, the naphtha range fraction disclosed herein may mean a fraction having an initial boiling point higher than 0°C, preferably higher than 20°C, or higher than 30°C, and a T95 temperature of 220°C or lower, preferably 200°C or lower, 180°C or lower, 160°C or lower, or 140°C or lower. The naphtha range fraction may have a T99 temperature of 220°C or lower, preferably 200°C or lower, 180°C or lower, 160°C or lower, or 140°C or lower, or a final boiling point of 220°C or lower, preferably 200°C or lower, or 180°C or lower.

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

[0180] In the present invention, hydrogen isomerization may be carried out in the same hydrogenation treatment as hydrogenation deoxygenation. In other words, hydrogen isomerization may be part of a hydrogenation treatment that includes at least hydrogenation deoxygenation. Alternatively, or in addition, hydrogen isomerization may be carried out in a further hydrogenation treatment following a hydrogenation treatment that includes at least hydrogenation deoxygenation.

[0181] Hydrogenation treatments, including hydrogenation deoxygenation and hydrogen isomerization, can be carried out, for example, using a catalyst or catalytic system that achieves both hydrogenation deoxygenation and hydrogen isomerization in a single step.

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

[0183] In one embodiment, the renewable cracker feed may be obtained by a method comprising the steps of: subjecting an oxygenated biorenewable feed to a hydrogenation treatment including at least hydrogenated deoxygenation, hydrogen isomerization, and gas-liquid separation in order to provide at least an isomerized deoxygenated stream; feeding the isomerized deoxygenated stream to a first distillation column, preferably a stabilization column, in order to obtain at least a naphtha range fraction and a stabilized heavy liquid fraction; and feeding at least a portion of the stabilized heavy liquid fraction as an isomerized hydrocarbon composition to a second distillation column and recovering at least a low-boiling point fraction and a high-boiling point fraction.

[0184] The step of obtaining the liquid paraffinic hydrocarbon intermediate is disclosed in International Publication No. 2021 / 094655, which is incorporated herein by reference in its entirety. In particular, this step is disclosed in International Publication No. 2021 / 094655 with reference to Figures 1 and 2 and the accompanying text, which are incorporated herein by reference in detail. In this respect, the liquid paraffinic hydrocarbon intermediate corresponds to the stabilized heavy liquid fraction described above.

[0185] Generally, the following steps can be taken: The isomerized deoxygenated flow is introduced into a stabilization column, preferably at a lower pressure than the isomerization pressure, to stabilize, where a top fraction is formed in addition to the stabilized heavy liquid fraction. The top fraction contains hydrocarbons in the naphtha range (e.g., C4-C8). This top fraction from stabilization can be recovered and used as a gasoline component, or, preferably, it can be returned to stabilization, preferably into the stabilization column, for reflux. Thus, preferably according to the present invention, the oxygenated biorenewable is subjected to hydrogenation and isomerization, and its liquid product is sent to stabilization at a pressure lower than the isomerization pressure. The amount of naphtha-range hydrocarbons recycled for reflux may be 80 wt.-% or more, preferably 90 wt.-% or more, for example 90-95 wt.-%, of the naphtha-range hydrocarbons formed at the top of the stabilization column. High recycling rates facilitate the subsequent separation of light and heavy fractions and improve the yield of the resulting low-boiling and high-boiling fractions. Typically, higher reflux requires adjustment of the apparatus for larger flows. Therefore, preferably in the present invention, a top fraction containing hydrocarbons in the naphtha range (C4-C8) is formed during stabilization, and 60 wt.-% or more, e.g., 90 wt.-% or more, e.g., 90-95 wt.-% of the naphtha range hydrocarbons formed at the top of the stabilization column is returned to stabilization.

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

[0187] The method further comprises the derivatization of at least a portion of a light olefin to obtain one or more derivatives of a light olefin as a biomonomer, such as acrylic acid, acrylonitrile, acrolein, propylene oxide, ethylene oxide, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, adiponitrile, hexamethylenediamine (HMDA), hexamethylenediisocyanate (HDI), (methyl) methacrylate, ethylidene norvorine, 1,5,9-cyclododecatriene, sulfolane, 1,4-hexadiene, tetrahydrophthalic anhydride, valeraldehyde, 1,2-butyl oxide, n-butyl mercaptan, o-sec-butylphenol, propylene, octene, and sec-butyl alcohol.

[0188] In the present invention, it is preferable that the renewable cracker feed can be obtained by a method comprising hydrogenation and isomerization of oxygenated biorenewable feed.

[0189] Specific embodiments of the present invention relate to an integrated method and at least a biorefinery adapted to perform such an integrated method. For example, at least a portion of the low boiling fraction is subjected to a pyrolysis process in a first pyrolysis furnace ( b ) is subjected to a thermal decomposition process in a second thermal decomposition furnace, and at least a portion of the high-boiling-point fraction is subjected to a thermal decomposition process in a second thermal decomposition furnace. b ) are subjected to the same process. Similarly, at least a portion of the low-boiling point fraction and at least a portion of the high-boiling point fraction are alternately subjected to the pyrolysis process in the same pyrolysis furnace. b It is possible to attach it to ).

[0190] Therefore, by utilizing both components, the advantages of the present invention, namely superior decomposition properties compared to isomer hydrocarbon compositions, can be achieved.

[0191] Furthermore, at least a portion of the low boiling point fraction is used in the thermal decomposition process. b) is subjected to a pyrolysis process, and at least a portion of the high-boiling-point fraction can be recovered as a specific fluid or component, such as an electrical fluid, lubricating oil, coolant or a component thereof, and / or as a fuel component, such as a component of marine fuel. Furthermore, at least a portion of the high-boiling-point fraction can be subjected to a pyrolysis process ( b The low-boiling-point fraction is then subjected to a special treatment, and at least a portion of it can be recovered as a fuel component, preferably as an aviation fuel component.

[0192] Furthermore, a portion of the low boiling point fraction is used in the thermal decomposition process. b ) is subjected to a pyrolysis process, and another portion of the low boiling point fraction can be recovered as a fuel component, preferably as an aviation fuel component. Similarly, a portion of the high boiling point fraction is subjected to a pyrolysis process ( b ) and another portion of the high-boiling-point fraction may be recovered as a specific fluid or component thereof, such as electrical fluids, lubricating oils, coolants or components thereof, and / or as a fuel component, such as marine fuel components.

[0193] All of the above options for integrated methods share the advantage of providing flexibility to the integrated method, namely, the ability to adjust the method according to the demand for various components. For example, in order to maximize the value of various product flows, each product may be recovered in varying quantities from time to time, depending on market needs, price, desired composition and / or quality, or based on the availability of raw materials, such as oxygenated biorenewable feed.

[0194] The method of the present invention may further include a step (e) for producing a biopolymer composition, in which at least one light olefin and / or at least one biomonomer separated in step (c), optionally together with other (co)monomers and / or after optional further purification.

[0195] Polymers may be further processed, optionally with other components, for the manufacture of sanitary products, building materials, packaging materials, coating compositions, paints, decorative materials such as panels, vehicle interior parts such as automotive interior components, rubber compositions, tires or tire components, toners, personal healthcare products, consumer goods components, electronic device components or housings, films, molded articles, and gaskets.

[0196] The present invention further relates to biopolymer compositions that can be obtained by the method of the present invention. [Examples]

[0197] The present invention will be further explained by examples. Please understand that the examples are not intended to limit the present invention.

[0198] The pyrolysis of five feed compositions (C1-C3, E1, E2) was evaluated. Composition C1 corresponds to a renewable composition obtained by hydrogenation and fractionation, including hydrogenation deoxygenation and moderate to severe hydrogen isomerization of an oxygenated biorenewable feed, for providing materials mainly in the range of diesel fuels. Composition C2 corresponds to a renewable composition obtained by hydrogenation and fractionation, including hydrogenation deoxygenation and moderate to severe hydrogen isomerization of an oxygenated biorenewable feed, for providing materials mainly in the range of diesel fuels. Composition C3 corresponds to a renewable composition obtained by hydrogenation and fractionation, including hydrogenation deoxygenation and severe hydrogen isomerization of an oxygenated biorenewable feed, for providing materials mainly in the range of diesel fuels. Composition C3 corresponds to the isomerized hydrocarbon composition described herein.

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

[0200] [Table 1]

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

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

[0203] [Table 2]

[0204] [Table 3]

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

[0206] In embodiments of the present invention, where the iP content is kept high but the amount of iP3+ substitution is minimized by combining it with a more uniform carbon number range, such as a low IQR and / or a low carbon span, such as CS@80%(CS_80), the formation of benzene may be suppressed in preference to the formation of expensive olefins, and the formation of lighter contaminants such as acetylene, methylacetylene, and propadiene may be reduced.

[0207] Table 3 shows that the material performs well over a wide temperature range, which could allow for further optimization of product yield. Of particular interest is the conversion at lower temperatures, which can promote propylene formation with reduced benzene formation, saving valuable heating work and enabling lower carbon emissions in manufacturing.

Claims

1. (a) A step of providing renewable cracker feed by fractionating an isomer hydrocarbon composition having an i-paraffin content of 85.0 wt. -% or more and a carbon range in the range of 20 to 32 into at least a low boiling point fraction and a high boiling point fraction, and providing at least a portion of the low boiling point fraction or at least a portion of the high boiling point fraction as the renewable cracker feed, wherein the low boiling point fraction has a modal carbon number in the range of 12 to 17. (b) A step of pyrolysis the renewable cracker feed, optionally together with cofeed and / or additives, in a pyrolysis furnace, and (c) A step of subjecting the effluent from the pyrolysis furnace in step (b) to a separation treatment in order to provide at least a light olefin fraction. A method that includes this.

2. The method according to claim 1, wherein the isomerized hydrocarbon composition has a c_50 value in the range of 14.0 to 22.0, or 14.0 to 20.0, or 15.0 to 20.

0.

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

4. The method according to claim 1, wherein both the low-boiling fraction and the high-boiling fraction have a ratio of i-paraffin (IP3+) having more than three branches to the total i-paraffin (iP) (iP3+ / iP), where each fraction is independently 0.164 or less, or 0.160 or less, 0.155 or less, and 0.150 or less.

5. The method according to claim 1, wherein both the low-boiling-point fraction and the high-boiling-point fraction independently contain 10.50 wt. -% or more of the total i-paraffin (iP3+) having three or more branches relative to the total paraffin, or 10.50 to 16.00, 11.00 to 15.50, 11.00 to 15.50, 11.00 to 15.00, or 12.00 to 15.

00.

6. Both the low-boiling-point fraction and the high-boiling-point fraction independently have a cloud point of -10°C or lower, or -15°C or lower, or -20°C or lower; and / or Both the low-boiling-point fraction and the high-boiling-point fraction are independent of each other in the range of 0.1 wt. -% to 10.0 wt. -%, or 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. Having a total content of olefins, aromatics and naphthenes of -%; and / or Both the low-boiling-point fraction and the high-boiling-point fraction independently have modal carbon numbers in the range of 11 to 21, 14 to 20, or 16 to 18. The method according to claim 1.

7. The method according to claim 1, wherein the high boiling point fraction has a c_50 value in the range of 16.5 to 20.0, or 16.5 to 19.0, or 17.0 to 18.

0.

8. The method according to claim 1, wherein the high-boiling-point fraction has a modal carbon number in the range of 17 to 22, or 18 to 21, 18 to 20, or 18 to 19.

9. The method according to claim 1, wherein the high boiling point fraction has an adjusted average carbon number range (IDR) in the range of 0.5 to 4.0, 0.6 to 3.0, 0.7 to 2.0, or 0.8 to 1.

6.

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

4.

11. The method according to claim 1, wherein the high boiling point fraction has an interventile carbon number range (IVR) of 5.0 or less, or 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, or 2.3 or less.

12. The method according to claim 1, wherein the low boiling point fraction has a c_50 value in the range of 11.0 to less than 16.5, or 12.0 to 16.0, or 14.0 to 16.

0.

13. The method according to claim 1, wherein the low boiling point fraction has a modal carbon number in the range of 13 to 17, 14 to 16, or 15 to 16.

14. The method according to claim 1, wherein the low boiling point fraction has an adjusted average carbon number range (IDR) in the range of 4.0 to 14.0, 6.0 to 10.0, or 7.0 to 9.

0.

15. The method according to claim 1, wherein the low boiling point fraction has an 80% carbon span (CS_80) in the range of 3.0 to 9.0, or 4.0 to 8.0, or 4.5 to 7.

0.

16. The method according to claim 1, wherein the low boiling point fraction has an interventile carbon number range (IVR) of 5.0 to 12.0, or 6.0 to 12.0, or 7.0 to 11.

0.

17. (A) At least a portion of the low boiling point fraction is subjected to the pyrolysis step (b) in a first pyrolysis furnace, and at least a portion of the high boiling point fraction is subjected to the pyrolysis step (b) in a second pyrolysis furnace, and / or (B) At least a portion of the low boiling point fraction and at least a portion of the high boiling point fraction are alternately subjected to the pyrolysis step (b) in the same pyrolysis furnace, and / or (C) At least a portion of the low boiling point fraction is subjected to the pyrolysis step (b), and at least a portion of the high boiling point fraction is recovered as a specific fluid or component thereof, or as an electrical fluid, lubricant, coolant or component thereof, and / or as a fuel component, or as a marine fuel component, and / or (D) At least a portion of the high boiling point fraction is subjected to the pyrolysis step (b), and at least a portion of the low boiling point fraction is recovered as a fuel component or as an aviation fuel component, and / or (E) A portion of the low boiling point fraction is subjected to the pyrolysis step (b), and another portion of the low boiling point fraction is recovered as a fuel component or as an aviation fuel component, and / or (F) A portion of the high-boiling fraction is subjected to the pyrolysis step (b), and another portion of the high-boiling fraction is recovered as a specific fluid or component thereof, or as an electrical fluid, lubricant, coolant or component thereof, and / or as a fuel component, or as a marine fuel component. The method according to claim 1.

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

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

20. The thermal decomposition step (b) is a steam decomposition step; and / or The thermal decomposition in step (b) is carried out in the presence of cofeed. The method according to claim 1.

21. The aforementioned renewable cracker feed is as follows: In order to provide an isomerized deoxygenated flow, an oxygenated biorenewable feed is subjected to a hydrogenation treatment including at least hydrogenated deoxygenation, hydrogen isomerization, and gas-liquid separation. A step of supplying the isomerized deoxygenated stream to a first distillation column or stabilization column in order to obtain at least a naphtha range fraction and a stabilized heavy liquid fraction, The process involves supplying at least a portion of the stabilized heavy liquid fraction as the isomerized hydrocarbon composition to a second distillation column, and recovering at least the low-boiling fraction and the high-boiling fraction. The method according to claim 1 obtained by...

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

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