TWI901916B - Renewable stabilized naphtha-range hydrocarbon feed, thermal cracking method and products thereof - Google Patents

Abstract

The present invention relates to a method comprising thermal cracking, a renewable stabilized naphtha-range hydrocarbon feed usable in such a method and a cracking effluent obtainable by use of such a method. The method of the present invention comprises a step (a) of providing a renewable stabilized naphtha-range hydrocarbon feed, a step (b) of thermally cracking the renewable stabilized naphtha-range hydrocarbon feed in a thermal cracking furnace, optionally together with co-feed(s) and/or additive(s), and a step (c) of subjecting the effluent of the thermal cracking furnace of step (b) to a separation treatment to provide at least a light olefin(s) fraction.

Description

Renewable stable petroleum hydrocarbon feedstock, pyrolysis method and its products

This invention relates to a method comprising pyrolysis, a renewable stable petroleum naphtha feedstock for use in this method, and products that can be obtained by using this method.

Thermal pyrolysis, such as steam cracking, is a well-known and established approach for upgrading traditional (mineral oil-based) materials. Recently, thermal pyrolysis of biomaterials has been studied, often attempting to achieve direct pyrolysis of biofeeds (typically with high oxygen content) or to simulate traditional (fossil) feeds.

High-value chemicals produced in pyrolysis processes (such as steam cracking) include ethylene, propylene, butadiene, C4 alkenes, benzene, xylene, and toluene. Among these high-value chemicals, light alkenes, especially ethylene and propylene, are the most sought-after in industry.

C4 alkenes are also valuable products, but may require additional refining steps to extract the chemical and polymer grades of each individual component. Aromatics are less important because they have further manufacturing pathways, such as the recombination of fossil petroleum naphtha. Furthermore, in steam cracking operations, benzene can accumulate in the thermally cracked gasoline fraction of the cracking effluent, which is typically price-stable in fuels. Due to strict limits on permissible benzene levels in such fuel products (due to its carcinogenic effects), it may even become an unwanted byproduct that needs to be removed.

In order to introduce biomolecules into the petrochemical value chain, and in view of the above considerations, it is useful to adopt a method that can maximize the yield of light olefins while suppressing the formation of aromatics (especially benzene).

The present invention was made in view of the above problems, and one object of the present invention is to provide a renewable stable petroleum naphtha range feedstock, a pyrolysis method using the renewable stable petroleum naphtha range feedstock, the products generated from the method, their uses and further processing.

The fundamental problem of this invention can be solved by the objective set forth in the independent claim. Further beneficial developments are proposed in the subsidiary claim.

In short, this invention relates to one or more of the following:

1. A method comprising: (a) providing a feedstock of renewable, stabilized naphtha-range hydrocarbons; (b) thermally cracking the feedstock of renewable, stabilized naphtha-range hydrocarbons in a pyrolysis furnace, optionally together with a co-feed and/or additives; and (c) separating the effluent from the pyrolysis furnace of step (b) to provide at least one light olefin fraction.

2. The method of Item 1, wherein the pyrolysis step (b) is carried out at a solenoid outlet temperature (COT) selected from 780°C to 880°C, preferably 800°C to 860°C, and more preferably 820°C to 850°C.

3. The method of Item 1 or 2, wherein the pyrolysis step (b) is carried out at a coil outlet pressure (COP) selected from 1.3 bar to 6.0 bar, preferably from 1.3 bar to 3.0 bar.

4. The method of any of the preceding items, wherein the pyrolysis step (b) is a steam pyrolysis step.

5. The method of any of the preceding items, wherein the pyrolysis step (b) is carried out in the presence of a pyrolysis diluent at a dilution of 0.10 to 0.85, preferably 0.25 to 0.60, such as 0.35 to 0.55.

6. The method of any of the preceding items, comprising a purification treatment to remove at least one of methylacetylene, _propadiene , CO, _CO2 and _C2H2 , preferably at least one of CO, _CO2 and _C2H2 , as a _purification stage (c') for separating light olefin fractions from the effluent of the thermal cracking furnace in step (b) at least in step (c).

7. The method of any of the foregoing items, comprising performing one or more further pyrolysis operations to provide further pyrolysis effluents, wherein step (c) further comprises adding additional effluents and/or their distillates to the effluents of the thermal pyrolysis furnace of step (b) prior to and/or during the separation treatment.

8. The method of any of the preceding items, wherein the pyrolysis in step (b) is carried out in the presence of a common feed.

9. The method of the aforementioned item, wherein the content of the renewable stabilized petroleum naphtha feed in the total pyrolyzer feed is in the range of 10% to 100% by weight, preferably 20% to 100% by weight, 30% to 100% by weight, 40% to 100% by weight, 50% to 100% by weight, 60% to 100% by weight, 70% to 100% by weight, 80% to 100% by weight, or 90% to 100% by weight, wherein the total pyrolyzer feed refers to the renewable stabilized petroleum naphtha feed plus optional co-feeds and optional additives.

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

11. The method of any of the preceding items, wherein the common feed includes a petroleum brain range feed.

12. The method of any of the preceding items, wherein the total pyrolyzer feed has a sulfur content 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.

13. The method of any of the foregoing items, wherein step (a) of providing the renewable stabilized naphtha range hydrocarbon feed comprises: a stage of hydrogenating the oxygenate bio-renewable feed, the hydrogenation comprising at least hydrogenation deoxygenation to provide at least a liquid hydrocarbon stream, and a stage of fractionating at least a portion of the liquid hydrocarbon stream and recovering at least the renewable stabilized naphtha range hydrocarbon feed.

14. The method of Item 13, wherein the hydrogenation treatment comprises at least hydrogenation deoxygenation to provide a hydrogenation treatment effluent, and gas-liquid separation of the hydrogenation treatment effluent to provide a gas stream and a first liquid hydrocarbon stream, and at least a portion of the first liquid hydrocarbon stream is further hydrogenated, comprising at least hydrogenation isomerization, followed by optionally further gas-liquid separation to provide at least a second liquid hydrocarbon stream, and at least a portion of the second liquid hydrocarbon stream is fractionated as a liquid hydrocarbon stream, and at least the renewable stable petroleum naphtha range hydrocarbon feed is recovered.

15. The method of Item 14, wherein at least a portion of the first liquid hydrocarbon stream and/or the second liquid hydrogenation process stream is recycled back to a hydrogenation process that includes at least hydrogenation deoxygenation.

16. The method of item 14 or 15, further comprising subjecting the gas stream to a propane separation process to provide a propane-rich stream and a depleted propane stream.

17. The method of item 16, further comprising dehydrogenating at least a portion of the propane from the propane-rich stream, preferably by catalytic dehydrogenation, to produce propylene.

18. The method of any one of items 13 to 17, wherein a stage of fractionating at least a portion of the liquid hydrocarbon stream and recovering at least the renewable stable naphtha range hydrocarbon feed further comprises recovering heavy liquid hydrocarbon fractions.

19. The method of item 18, wherein the heavy liquid hydrocarbon fraction is further fractionated to provide at least an aviation fuel range fraction and a bottom fraction.

20. The method of any of items 13 to 17, wherein a stage of fractionating at least a portion of the liquid hydrocarbon stream and recovering at least the renewable stable petroleum naphtha range hydrocarbon feed further includes the recovery of at least aviation fuel range fractions and/or diesel range fractions.

21. The method of any of items 18 to 20, wherein the diesel range fraction, aviation fuel range fraction, heavy liquid hydrocarbon fraction and/or bottom fraction has an isoalkane 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%.

22. The method of any of items 13 to 21, wherein the stage of fractionating at least a portion of the liquid hydrocarbon stream and at least recovering the renewable stabilized naphtha range hydrocarbon feed comprises at least fractionating at least a portion of the liquid hydrocarbon stream to provide a naphtha range fraction, and stabilizing the naphtha range fraction, wherein the stabilization comprises preferably removing at least a portion of components with a boiling point below 20°C by distillation, preferably at least a portion of components with a boiling point below 25°C, at least a portion of components with a boiling point below 30°C, at least a portion of components with a boiling point below 40°C, or at least a portion of components with a boiling point below 50°C.

23. The method of any of items 18 to 20, wherein the heavy liquid hydrocarbon fraction and/or the diesel range fraction has an isoalkane content of less than 65% by weight.

24. The method of any of the foregoing items, wherein step (a) of providing a renewable, stable petroleum naphtha feed comprises: substituting the oxygenated biorenewable feed with hydrogenation treatment, including at least hydrogenation deoxygenation, to provide a hydrogenated effluent; substituting at least a portion of the hydrogenated effluent with gas-liquid separation to provide a gas stream and a first liquid hydrocarbon stream; providing the first liquid hydrocarbon stream as a liquid hydrocarbon stream, or subjecting at least a portion of the first liquid hydrocarbon stream to further hydrogenation treatment, including at least hydrogenation isomerization, and optionally further gas-liquid separation, to provide at least a second liquid hydrocarbon stream as a liquid hydrocarbon stream; and At least a portion of the liquid hydrocarbon stream is fed into a first distillation column, preferably a first stabilizer, to obtain a first column top fraction and a stabilized heavy liquid hydrocarbon fraction. Optionally, at least a portion of the stabilized heavy liquid hydrocarbon fraction is used in diesel fuel, and/or at least an aviation fuel-range fraction and a bottom fraction are recovered from at least a portion of the stabilized heavy liquid hydrocarbon fraction. At least one fuel gas fraction and one petroleum naphtha-range fraction are separated from the first column top fraction. A portion, preferably at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 85% by weight of the petroleum naphtha-range fraction is recycled back to the first distillation column. At least a portion of the naphtha-range fraction is fed into a second distillation column, preferably a second stabilizer, to obtain a second column top fraction, preferably containing at least a portion of components with boiling points below 20°C, and a stabilized naphtha-range fraction. At least another fuel gas fraction and a light liquid hydrocarbon are separated from the second column top fraction. At least a portion, preferably at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 85% by weight of the light liquid hydrocarbon is recycled back to the second distillation column. At least a portion of the stabilized naphtha-range fraction is recovered as feed for the renewable stabilized naphtha-range hydrocarbon.

25. The method of any of items 13 to 24, wherein the hydrogenation treatment comprising at least hydrogenation deoxygenation further comprises hydrogenation isomerization.

26. The method of any of the foregoing items further comprises derivatizing at least a portion of the light olefin to obtain one or more derivatives of the light olefin as a biological monomer, 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), hexamethylene diisocyanate (HDI), (meth)acrylate, ethylidene norcamphene, 1,5,9-cyclododecanetriene, cyclobutane, 1,4-hexadiene, tetrahydrophthalic anhydride, pentanal, 1,2-epoxybutane (1,2-butyloxide), n-butanethiol, terephthalophenol, octene, and dibutanol.

27. The method of any of the foregoing items further comprises step (d), which (co)polymerizes at least one light olefin and/or at least one biopolymer, optionally together with other (co)polymers, isolated in step (c), and/or, after optional further purification, produces a biopolymer composition.

28. The method of item 27, wherein the biopolymer composition is further processed to manufacture hygiene products, building materials, packaging materials, paint compositions, paints, decorative materials such as panels, vehicle interiors such as automobile interiors, rubber compositions, tires or tire components, toners, personal care products, components of consumer products, components or housings of electronic devices, films, moldings, gaskets, and optionally together with other components.

29. A renewable stable petroleum naphtha feedstock for pyrolysis.

30. A renewable stable petroleum naphtha range feed, as in item 29, wherein the renewable stable petroleum naphtha range feed has a cycloalkane content ranging from 0.1 wt% to 10.0 wt% based on the total weight of the renewable stable petroleum naphtha range feed.

31. A renewable stable petroleum naphtha range feedstock, such as that of Item 29 or 30, wherein the renewable stable petroleum naphtha range feedstock has a cycloalkane content of 0.2 to 10.0 wt%, such as 0.5 to 8.0 wt%, 0.5 to 6.0 wt%, 0.6 to 5.8 wt%, 0.8 to 5.8 wt%, 1.0 to 5.6 wt%, or 1.2 to 5.6 wt%.

32. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 31, wherein the renewable stable petroleum naphtha range feedstock has an olefin content of less than 0.50 wt%, preferably less than 0.40 wt%, less than 0.30 wt%, less than 0.25 wt%, less than 0.20 wt%, less than 0.15 wt%, less than 0.12 wt%, less than 0.10 wt%, less than 0.07 wt%, or less than 0.05 wt%.

33. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 32, wherein the renewable stable petroleum naphtha range feedstock has a total content of 0.1% to 10.0% by weight of alkenes and cycloalkanes.

34. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 33, wherein the renewable stable petroleum naphtha range feedstock has a total content of 0.1 wt% to 8.0 wt%, such as 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% of alkenes and cycloalkanes.

35. A renewable stable petroleum naphtha feedstock, as described in any of items 29 to 34, wherein the renewable stable petroleum naphtha feedstock has an aromatic content of less than 0.80 wt%, preferably less than 0.70 wt%, less than 0.60 wt%, less than 0.50 wt%, less than 0.40 wt%, less than 0.35 wt%, less than 0.30 wt%, less than 0.25 wt%, less than 0.20 wt%, or less than 0.15 wt%.

36. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 35, wherein the renewable stable petroleum naphtha range feedstock has a ratio between cycloalkane content and aromatic content of 1 or greater, preferably 10 or greater, 50 or greater, or 100 or greater.

37. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 36, wherein the renewable stable petroleum naphtha range feedstock has a total content 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% of alkenes, aromatics and cycloalkanes.

38. A renewable stabilized petroleum naphtha feedstock of any of items 29 to 37, wherein the renewable stabilized petroleum naphtha feedstock has an oxygen content of less than 1000 ppm by weight, preferably less than 700 ppm by weight, less than 500 ppm by weight, less than 300 ppm by weight, less than 100 ppm by weight, less than 80 ppm by weight, less than 60 ppm by weight, less than 50 ppm by weight, less than 40 ppm by weight, or less than 30 ppm by weight.

39. A renewable stable petroleum naphtha feedstock of any of items 29 to 38, wherein the renewable stable petroleum naphtha feedstock has a content of less than 1.0% by weight, such as 0.0 to 0.9% by weight, preferably 0.0 to 0.8% by weight, more preferably 0.0 to 0.5% by weight, or 0.0 to 0.2% by weight of C17 and higher carbon number compounds.

40. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 39, wherein the renewable stable petroleum naphtha range feedstock has a carbon range of 10 or less, preferably 8 or less, 7 or less, 6 or less, or 5 or less, and the carbon range is 1 or more, such as 1 to 10, 2 to 10, 3 to 10, 3 to 8, 3 to 7, or 3 to 6.

41. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 40, wherein the renewable stable petroleum naphtha range feedstock has an interventile carbon number range (IVR) of less than 6.5, preferably less than 5.0, less than 4.5, less than 4.0, or less than 3.8.

42. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 41, wherein the renewable stable petroleum naphtha range feedstock has an interdecile carbon number range (IDR) of 4.5 or less, preferably 4.0 or less, 3.5 or less, or 3.0 or less.

43. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 42, wherein the renewable stable petroleum naphtha range feedstock has an interquartile carbon number range (IQR) of less than 2.5, preferably less than 2.0, less than 1.8, or less than 1.5.

44. A renewable stabilized petroleum naphtha feedstock, as described in any of items 29 to 43, wherein the renewable stabilized petroleum naphtha feedstock has a C11 and higher carbon content of less than 5.0 wt%, preferably less than 4.5 wt%, less than 4.0 wt%, less than 3.5 wt%, less than 3.0 wt%, less than 2.5 wt%, or less than 2.0 wt%.

45. A renewable stable petroleum naphtha feedstock of any of items 29 to 44, wherein the renewable stable petroleum naphtha feedstock has a T95 temperature of less than 220°C, preferably less than 200°C, less than 180°C, less than 160°C, or less than 140°C.

46. A renewable stable petroleum naphtha feedstock as described in any of items 29 to 45, wherein the renewable stable petroleum naphtha feedstock has a T99 temperature of less than 220°C, preferably less than 200°C, less than 180°C, less than 160°C, or less than 140°C.

47. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 46, wherein the renewable stable petroleum naphtha range feedstock has a final boiling point of less than 220°C, preferably less than 200°C, less than 180°C, or less than 160°C.

48. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 47, wherein the renewable stable petroleum naphtha range feedstock has an initial boiling point of 20°C or higher, preferably 20°C to 60°C, such as 30°C to 50°C, or 30°C to 45°C.

49. A renewable stable petroleum naphtha feedstock, as described in any of items 29 to 48, wherein the renewable stable petroleum naphtha feedstock has a T5 temperature of 40°C or higher, preferably 45°C or higher, 50°C or higher, 55°C or higher, or 60°C or higher.

50. A renewable stable petroleum naphtha feedstock, as described in any of items 29 to 49, wherein the difference between the T10 temperature and the T90 temperature of the renewable stable petroleum naphtha feedstock is less than 100°C, preferably less than 80°C, such as 20°C to 75°C, 30°C to 70°C, or 40°C to 70°C.

51. A renewable stable petroleum naphtha feedstock, as described in any of items 29 to 50, wherein the renewable stable petroleum naphtha feedstock has a total alkane content of 90% by weight or more, preferably 92% by weight or more, 93% by weight or more, 94% by weight or more, or 95% by weight or more.

52. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 51, wherein the renewable stable petroleum naphtha range feedstock has an isoalkane to n-alkane content ratio in the range of less than 1.7, preferably less than 1.5, such as 0.5 to 1.7, or 0.7 to 1.5.

53. The renewable stable petroleum naphtha range feedstock of any of items 29 to 52, wherein the renewable stable petroleum naphtha range feedstock has an isoalkane to n-alkane content ratio of 2.0 or higher, preferably 2.2 or higher.

54. A renewable stable petroleum naphtha range feedstock, as described in any of items 29 to 53, wherein the renewable stable petroleum naphtha range feedstock can be obtained by a hydrogenation process comprising subjecting an oxygenated biorenewable feedstock to at least hydrogenation deoxygenation and optional hydrogenation isomerization.

55. Renewable stable petroleum naphtha range hydrocarbon feedstock, such as in item 54, wherein the method includes hydrogenation isomerization.

56. The renewable stable petroleum naphtha feedstock of any of items 29 to 55 may be obtained by a method comprising: substituting an oxygenated biorenewable feedstock with hydrogenation treatment, including at least hydrogenation deoxygenation, to provide a hydrogenated effluent; substituting at least a portion of the hydrogenated effluent into a gas-liquid stream to provide a gas stream and a first liquid hydrocarbon stream; providing the first liquid hydrocarbon stream as a liquid hydrocarbon stream, or subjecting at least a portion of the first liquid hydrocarbon stream to further hydrogenation treatment, including at least hydrogenation isomerization, followed optionally by further gas-liquid separation, to provide at least a second liquid hydrocarbon stream as a liquid hydrocarbon stream; and At least a portion of the liquid hydrocarbon stream is fed into a first distillation column, preferably a first stabilizer, to obtain a first column top fraction and a stabilized heavy liquid hydrocarbon fraction. At least one fuel gas fraction and one petroleum naphtha-range fraction are separated from the first column top fraction. A portion, preferably at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 85% by weight of the petroleum naphtha-range fraction, is refluxed back into the first distillation column. At least a portion of the petroleum naphtha-range fraction is fed into a second distillation column, preferably a second stabilizer, to obtain a second column top fraction, preferably containing at least a portion of components with boiling points below 20°C, and a stabilized petroleum naphtha-range fraction. At least one other fuel gas fraction and a light liquid hydrocarbon are separated from the top distillation column of the second column, and at least a portion, preferably at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 85% by weight of the light liquid hydrocarbon is recycled back to the second distillation column, and at least a portion of the stable petroleum naphtha range fraction is recovered as feedstock for the renewable stable petroleum naphtha range hydrocarbon.

57. The renewable stable petroleum naphtha range feedstock of Item 56, wherein the hydrogenation process, which includes at least hydrogenation deoxygenation, further includes hydrogenation isomerization.

58. The renewable stable petroleum naphtha feedstock of any of items 29 to 57 has a content of less than 5.0% by weight, preferably less than 2.5% by weight, more preferably less than 2.0% by weight, and even more preferably less than 1.5% by weight of C4 and lower carbon number compounds.

59. The method of any of items 1 to 25, wherein the renewable stable petroleum naphtha range feed is a renewable stable petroleum naphtha range feed as described in any of items 29 to 58.

60. A renewable pyrolysis effluent having a benzene content of less than 6.0% by weight, a total ethylene and propylene content of more than 45.0% by weight, and a carbon monoxide content of less than 0.25% by weight.

61. The benzene content of the renewable pyrolysis effluent of Item 60 is 0.01 wt% to 6.0 wt%, such as 0.1 wt% to 4.0 wt%, 0.1 wt% to 3.6 wt%, 0.1 wt% to 3.4 wt%, 0.1 wt% to 3.2 wt%, 0.1 wt% to 3.0 wt%, 0.1 wt% to 2.8 wt%, 0.1 wt% to 2.6 wt%, 0.2 wt% to 2.4 wt%, 0.3 wt% to 2.2 wt%, or less than 0.5 wt% to 2.0 wt%.

62. The renewable pyrolysis effluent of item 60 or 61, wherein the renewable pyrolysis effluent has a total content of 45% to 65% by weight, preferably 46.0% to 65.0% by weight, 47.0% to 65.0% by weight, 48.0% to 65.0% by weight, 49.0% to 65.0% by weight, 50.0% to 60.0% by weight, or 50.0% to 55.0% by weight of ethylene and propylene.

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

64. A renewable pyrolysis effluent as described in any of items 60 to 63, wherein the renewable pyrolysis effluent is the effluent from the pyrolysis furnace of step (b) of the method as described in any of items 1 to 25.

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

66. The renewable pyrolysis effluent of any one of items 60 to 65, wherein the renewable pyrolysis effluent has a C4 monoolefin content of 6.0% by weight or more, preferably 6.5% by weight or more, 6.8% by weight or more, 7.0% by weight or more, 7.2% by weight or more, or 7.4% by weight or more.

67. A renewable pyrolysis effluent of any one of items 60 to 66, wherein the renewable pyrolysis effluent has a C4 monoolefin content of up to 15.0% by weight or up to 13.0% by weight.

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

69. A renewable pyrolysis effluent of any of items 60 to 68, wherein the renewable pyrolysis effluent has a 1,3-butadiene content of up to 15.0% by weight, up to 13.0% by weight, or up to 11.0% by weight.

70. A renewable pyrolysis effluent of any one of items 60 to 69, wherein the renewable pyrolysis effluent has an isobutylene content of at least 2.0% by weight, preferably at least 2.4% by weight, at least 3.0% by weight, or at least 3.2% by weight.

71. A renewable pyrolysis effluent of any of items 60 to 70, wherein the renewable pyrolysis effluent has an isobutylene content of up to 10.0% by weight, up to 9.0% by weight, or up to 8.0% by weight.

72. The renewable pyrolysis effluent of any one of items 60 to 71, wherein the renewable pyrolysis effluent has a content of 3.0% by weight or more, preferably 3.5% by weight or more, or 4.0% by weight or more of n-C4 monoolefins.

73. A renewable thermal cracking effluent of any of items 60 to 72, wherein the renewable thermal cracking effluent has a content of up to 15.0% by weight, up to 12.0% by weight, or up to 10.0% by weight of C4 monoolefins.

74. The renewable pyrolysis effluent of any one of items 60 to 73, wherein the renewable pyrolysis effluent has a total content of more than 4.0% by weight, preferably more than 4.2% by weight, and more preferably more than 4.3% by weight of C2-C4 alkanes.

75. A renewable thermal cracking effluent of any of items 60 to 74, wherein the renewable thermal cracking effluent has a total content of up to 15.0% by weight, up to 12.0% by weight, or up to 10.0% by weight of C2-C4 alkanes.

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

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

78. The renewable pyrolysis effluent of any of items 60 to 77, wherein the renewable pyrolysis effluent has a total ethylene and propylene content of more than 50.0% by weight, a benzene content of less than 4.0% by weight, and a toluene content in the range of 0.2% to 0.6% by weight.

79. The renewable pyrolysis effluent of any one of items 60 to 78, wherein the renewable pyrolysis effluent has a total content of 45% to 80% by weight, preferably 50% to 75% by weight, 50% to 70% by weight, 50% to 65% by weight, or 55% to 65% by weight of ethylene and propylene and total C4 olefins.

80. A biopolymer composition which can be obtained by the method of item 27.

In this invention, unless otherwise stated, all contents and content ratios are expressed by weight.

Furthermore, isoalkanes (also known as isochain alkanes) refer to branched noncyclic alkanes, while n-alkanes (also known as n-chain alkanes) refer to straight-chain noncyclic alkanes. Total alkane content refers to the total content of isoalkanes and n-alkanes. Similarly, alkenes refer to straight-chain or branched noncyclic alkenes containing multiple unsaturated groups. Cycloalkanes refer to cyclic non-aromatic branched or unbranched alkanes, alkenes, or alkynes containing multiple unsaturated groups. Aromatic hydrocarbons refer to compounds having at least one aromatic ring.

The contents of n-alkanes, isoalkanes, alkenes, cycloalkanes, and aromatics can be determined using the PIONA method, a GC-GC analytical method, as described by Pyl et al. in the Journal of Chromatography A, 1218 (2011) 3217–3223. Regarding that publication, for samples that have undergone high-rigidity hydrogenation isomerization, the main column and parity column are preferably inverted to improve the separation and identification of isoalkanes from n-alkanes.

In this document, the terms “renewable,” “biobased,” or “bio” refer to materials that are wholly or partially derived from renewable or biological sources. Renewable or bio-derived carbon atoms contain a greater number of unstable radioactive carbon ( ^¹⁴C ) atoms compared to fossil-derived carbon atoms. Therefore, carbon compounds derived from renewable or bio-derived sources or raw materials can be distinguished from those derived from fossil-derived sources or raw materials by analyzing the ratio of ^¹²C and ^¹⁴C isotopes. Thus, this specific ratio of isotopes (producing “biocarbon content”) can be used as a “label” to identify renewable carbon compounds and distinguish them from non-renewable carbon compounds. The isotope ratio does not change during chemical reactions. DIN 51637 (2014), ASTM D6866 (2020), and EN 16640 (2017) are examples of suitable methods for analyzing biocarbon content. Carbon content derived from biological or renewable resources is expressed as biocarbon content, which is the weight percentage of biocarbon in a material relative to the total carbon (TC) in the material. As used herein, biocarbon content is determined according to EN 16640 (2017). In this invention, the terms "renewable,""bio-based," or "bio" preferably refer to materials having a biocarbon content ranging from 1% to 100%.

Specifically, the biocarbon content of renewable stabilized petroleum hydrocarbon feedstock (also known as bio-based pyrolyzer feedstock) is preferably greater than 5% and at most 100%, such as greater than 20%, greater than 40%, greater than 50%, greater than 60%, or greater than 70%, greater than 80%, greater than 90%, or greater than 95%, and even approximately 100%. The biocarbon content of oxygenated biorenewable feedstock is preferably greater than 50% and at most 100%, preferably greater than 60% or greater than 70%, preferably greater than 80%, more preferably greater than 90% or greater than 95%, and even more preferably approximately 100%.

The biocarbon content of the renewable pyrolysis effluent of the present invention may be less than 1%, but preferably at least 1% and at most 100%, such as at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90%, or about 100%.

The biocarbon content of the pyrolysis furnace effluent of step (b) and the products and intermediates downstream of pyrolysis step (b) may be less than 1%, but preferably at least 1% and at most 100%, such as at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90% or about 100%.

In particular, the biocarbon content of the light olefin (distillate) and/or biomonomer and/or biopolymer composition may be less than 1%, but preferably at least 1% and at most 100%, such as at least 2%, at least 5%, at least 10%, at least 20%, at least 40%, at least 50%, at least 75%, at least 90% or about 100%.

The term "optional" or "optional" refers to a feature, characteristic, or step that may exist but is not necessary for the implementation of the invention.

Unless otherwise stated, all test method standards referred to herein are the latest versions available as of December 1, 2021.

Thermolysis

The method of this invention will be described first.

The method of the present invention includes a step (a) of providing a renewable stable naphtha range hydrocarbon feed, a step (b) of thermally cracking the renewable stable naphtha range hydrocarbon feed, optionally together with a co-feed and/or additives, in a pyrolysis furnace, and a step (c) of separating the effluent from the pyrolysis furnace in step (b) to provide at least a light olefin fraction.

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

Step (b) of the thermal pyrolysis process can be referred to as the "thermal pyrolysis process".

The feedstock for renewable stabilized petroleum naphtha preferably has an initial boiling point above 20°C, more preferably between 20°C and 50°C. The initial boiling point is more preferably between 30°C and 45°C. The feedstock for renewable stabilized petroleum naphtha preferably has a T95 temperature (95% volume recovery) below 220°C, more preferably below 200°C, below 180°C, below 160°C, or below 140°C. The renewable stable petroleum naphtha range feedstock can have a T99 temperature (99% volume recovery) below 220°C, preferably below 200°C, 180°C, 160°C, or 140°C, or a final boiling point below 220°C, preferably below 200°C, 180°C, or 160°C.

The difference between the initial boiling point and the T95 temperature (T95-IBP) of the renewable stable petroleum naphtha feedstock is preferably at least 50°C, such as at least 80°C. For example, the difference between the initial boiling point and the T95 temperature can be from 50°C to 155°C, preferably from 60°C to 120°C, 60°C to 100°C, or 65°C to 90°C.

Boiling point and T## temperature (e.g., T95 temperature) are determined according to EN ISO 3405-2019. EN ISO 3405-2019 refers to the determination of distillation characteristics at atmospheric pressure and is applicable to products with boiling points between 0°C and 400°C.

An initial boiling point above 20°C improves the applicability of stable naphtha range hydrocarbon feedstocks for cracking in conventional steam cracking processes. On the other hand, if the initial boiling point exceeds 50°C, a significant amount of usable hydrocarbon may be lost (i.e., price stabilization), which is undesirable.

The term "stable" in the description of "stable petroleum range" means that the content of C4 and lower carbon number compounds is less than 5.0% by weight, preferably less than 2.5% by weight, even more preferably less than 2.0% by weight, and even more preferably less than 1.5% by weight.

In this invention, the " renewable stable petroleum naphtha range hydrocarbon feed " comprises at least 98.5% by weight of hydrocarbon, preferably at least 99.5% by weight. In other words, at least 98.5% by weight of the feed consists of hydrocarbon. Here, hydrocarbon refers to a compound containing only C and H (carbon and hydrogen atoms). This means that up to 1.5% by weight, preferably up to 0.5% by weight of the hydrocarbon feed may consist of non-hydrocarbon substances, such as impurities containing heteroatoms or free water (free water according to ASTM D1364). Non-hydrocarbon substances may specifically be free water and/or substances containing carbon atoms, hydrogen atoms, and heteroatoms, such as at least one of oxygen, nitrogen, sulfur, or phosphorus. Such low concentrations of non-hydrocarbons make renewable, stable petroleum naphtha range hydrocarbon feedstocks particularly suitable for conventional cracking units, thus requiring no special setup.

The pyrolysis step (b) can be a steam pyrolysis step. Steam pyrolysis is resistant to possible impurities commonly found in renewable materials. Furthermore, the method of the present invention has shown to provide particularly good results when steam pyrolysis is employed.

Preferably, the pyrolysis step (b) is carried out at a coil outlet temperature (COT) selected from 780°C to 880°C, more preferably 800°C to 860°C, and even more preferably 820°C to 850°C.

The pyrolysis step (b) can be carried out at a coil outlet pressure (COP) selected from 1.3 bar to 6.0 bar, preferably 1.3 bar to 3.0 bar. In this invention, pressure values or ranges refer to absolute pressures unless otherwise stated.

The pyrolysis step (b) is preferably carried out in the presence of a pyrolysis diluent. Any conventional pyrolysis diluent can be used in the pyrolysis step (b). Examples of such pyrolysis diluents include steam, molecular nitrogen ( _N₂ ), or mixtures thereof. Diluting the pyrolysis feed reduces the hydrocarbon partial pressure in the pyrolysis solenoid and promotes the formation of primary reaction products such as ethylene and propylene. The pyrolysis diluent preferably contains steam.

The pyrolysis step (b) is preferably carried out in the presence of a pyrolysis diluent at a dilution of 0.10 to 0.85, more preferably 0.25 to 0.60, such as 0.35 to 0.55. Dilution refers to the flow rate ratio between the pyrolysis diluent and the total pyrolysis feed (flow rate of pyrolysis diluent [kg/h] / flow rate of total pyrolysis feed [kg/h]). The total pyrolysis feed refers to the feed of renewable stable petroleum naphtha plus optional co-feeds and optional additives, excluding the diluent.

Individual components of the total pyrolysis feed and the diluent can be fed into the pyrolysis furnace as a preformed mixture, as a separate stream, or as a combination of a separate stream and a preformed mixture.

The method may include a purification process to remove at least one of methylacetylene, propadiene, CO, _CO2 and _C2H2 , preferably at least one of CO, _CO2 and _C2H2 , as a purification stage (c') for separating at least the light olefin _fraction from the effluent of _the thermal cracking furnace in step (b) in step (c).

Step (c) may include rapidly cooling and refrigerating the effluent from the pyrolysis furnace of step (b). Typically, at least a portion of CO, _CO2 , _C2H2 , or _combinations thereof is removed from the effluent from the pyrolysis furnace of step (b) during the rapid cooling and refrigeration. In some specific embodiments, step (c) includes fractionating the effluent from the pyrolysis furnace of step (b). Fractionation may include separating fuel oil fractions, PyGas fractions, hydrogen fractions, methane fractions, fuel gas fractions, and light olefin fractions, such as C2 fractions (ethylene fractions), C3 fractions (propylene fractions), and/or C4 fractions, from the pyrolysis effluent. Fractionation can be carried out in a single stage or as a series of fractions, such as first separating the C2/C3 fractions and then recovering the C2 and C3 fractions by a second-stage fractionation. The C2 fraction (ethylene fraction) and C3 fraction (propylene fraction) are particularly suitable for manufacturing polymers, such as biopolymer compositions. Therefore, in some specific embodiments, the method includes, in step (c), separating a C2 fraction, or a C3 fraction, or both C2 and C3 fractions, or a C2/C3 fraction containing C2 and C3 as light olefin fractions from the effluent of the pyrolysis furnace in step (b), and optionally polymerizing at least ethylene derived from the C2 fraction, at least propylene derived from the C3 fraction, or both ethylene and propylene. Ethylene and/or propylene can be derived from the C2 and/or C3 fractions by further purification treatment to obtain polymer-grade materials.

In a preferred embodiment, a C2-rich fraction (C2 fraction) is separated, and then the fraction is further separated into a fraction containing ethylene and a fraction containing ethane. This separation of the C2-rich fraction, for example, a fraction containing 30% to 100% by weight, preferably at least 40% by weight of C2 hydrocarbons, can be fed forward to a C2 separator to provide the ethylene-containing fraction and the ethane-containing fraction. Similarly, a C3-rich fraction can be separated, and then the fraction is further separated into a propylene-containing fraction and a propane-containing fraction. The C3-rich fraction (C3 fraction), for example containing 30% to 100% by weight, preferably at least 40% by weight, of C3 hydrocarbons, can be fed forward to a C3 separator to provide a fraction containing propylene and a fraction containing propane. The C3-rich fraction can be separated after the C2-rich fraction has been separated or can be separated in the same stage. Each of these fractions can be recovered as a product fraction of the method, or can be further purified or post-processed to obtain the product fraction of the method.

The method may include purifying (c') at least a portion of the effluent from the pyrolysis furnace in step (b) within step (c) to remove at least one of CO, _CO2 , or _C2H2 . This is particularly advantageous in specific embodiments where at least a portion of the pyrolysis effluent is subjected to polymerization treatment. CO, _CO2 , and _C2H2 are polymerization catalyst poisons and are therefore undesirable in polymerization processes _. Absorbents, adsorbents, reactants, molecular sieves, and/or purification catalysts may be used in the purification treatment to remove at least one of CO, _CO2 , or _C2H2 and reduce the regeneration frequency of the active _{material .}

The purification treatment that can be performed on at least a portion of the effluent from the pyrolysis furnace in step (b) can be any purification treatment suitable for removing at least one of CO, _CO2 , or _C2H2 . Examples of such purification treatments are described in EP 2679656 A1, WO 2016023973 A1, WO 2003048087 A1 and US 2010331502 _A1 , all of which are incorporated herein by reference in their entirety.

In some specific embodiments, the purification process includes contacting at least a portion of the pyrolysis effluent with an active material, such as an absorbent, adsorbent, purification catalyst, reactant, molecular sieve, or combination thereof, to remove at least one of CO, _{CO2 ,} or _C2H2 .

The active material may include, for example, copper oxide or copper oxide catalyst, oxides of Pt, Pd, Ag, V, Cr, Mn, Fe, Co or Ni optionally supported on alumina, Au/CeC optionally supported on alumina, zeolites, especially type A and/or type X zeolites, alumina-based absorbents or catalysts such as Selexsorb™ COS or Selexord™ CD, molecular sieves comprising alumina, aluminosilicates, aluminum phosphates or mixtures thereof, or any combination thereof.

The active material may contain one or more adsorbents as described in WO 03/048087 A1, pages 11, lines 12-3, 12, 18-29, 17, and 21-26, and/or one or more molecular sieves as described in WO 03/048087 A1, pages 21, 3-22. The active material may contain one or more purification catalysts as described in US 2010/0331502 A1, paragraphs [0105] to [0116], or one or more molecular sieves as described in US 2010/0331502 A1, paragraphs [0117] to [0119]. The active material may contain one or more purification catalysts as described in paragraphs [0061], [0062], [0063] and/or [0064] of WO 2016/023973 A1.

Purification treatment may be the purification treatment described in paragraphs [0043] to [0082] of EP 2679656 A1. Purification treatment may be the purification treatment described in paragraphs [0092] to [0119] and/or paragraph [0126] and/or Embodiment 2 of US 2010/0331502 A1. Purification treatment may be the purification treatment described in paragraphs [0056] to [0067] of WO 2016/023973 A1. Purification treatment may be as described in WO 03/048087 A1, page 11, line 12 to page 15, line 29, and/or page 16, line 1 to page 21, line 2, and/or page 23, line 14 to page 24, line 13, and/or Embodiment 1, and/or Embodiment 2.

Typically, impurities can deactivate or contaminate active materials during purification. Therefore, active materials can be regenerated to at least partially restore their purified activity.

In certain specific embodiments, the purification treatment includes at least one of the following steps: i) contacting at least a portion of the pyrolysis effluent with a CuO catalyst to remove oxygen; ii) contacting at least a portion of the pyrolysis effluent with _H₂ to remove _C₂H₂ by _{hydrogenation} ; iii) contacting at least a portion of the pyrolysis effluent with a _CuO₂ catalyst to remove CO by oxidation; or iv) contacting at least a portion of the pyrolysis effluent with a zeolite molecular sieve to remove _CO₂ . Alternatively, the purification treatment may include removing secondary impurities, such as at least one of COS, _H₂S , or _CS₂ , by contacting at least a portion of the pyrolysis effluent with an activated alumina catalyst such as Selexorb ^™ .

The method may include performing one or more further pyrolysis operations to provide further pyrolysis effluents, wherein step (c) further includes adding additional effluents and/or their distillates before and/or during the separation process.

Specifically, the pyrolysis effluent obtained in step (b) may be combined with other effluents, such as effluents from further pyrolysis processes produced in other thermal pyrolysis furnaces, i.e., the further pyrolysis effluents and/or their distillates in step (c). The further pyrolysis effluents and/or their distillates may be referred to simply as the co-feed of step (c). In this case, the amount of effluent from the pyrolysis furnace in step (b) is preferably 10% to 100% by weight, more preferably 20% to 100% by weight, 30% to 100% by weight, 40% to 100% by weight, 50% to 100% by weight, 60% to 100% by weight, 70% to 100% by weight, 80% to 100% by weight, or 90% to 100% by weight, relative to the total amount of the effluent from the pyrolysis furnace in step (b) and the common feed in step (c). For example, a minimum of 10% by weight ensures a certain proportion of bio-derived material is maintained, thus contributing to sustainability. However, even the minimum amount of bio-derived material in step (c) contributes to sustainability.

One or more further cracking operations are preferably carried out in one or more additional cracking furnaces. One or more further cracking operations can be thermal cracking operations and/or cracking operations other than thermal cracking, such as FCC (fluidized catalytic cracking).

Further pyrolysis can be carried out with any suitable feedstock, including fossil feedstocks (crude oil-based feedstocks), renewable feedstocks, or combinations thereof. Further pyrolysis is preferably carried out under conditions different from step (b), with at least one of the total pyrolyzer feed composition and pyrolysis conditions, such as COT, COP, or dilution.

The further pyrolysis effluent can be purified, gas-liquid separated, and/or fractionated before being added to step (c), or it can be added as is, i.e., as a coarse effluent. Addition can be performed before the separation treatment in step (c). In this case, the further pyrolysis effluent undergoes separation treatment. This option is particularly suitable if coarse effluent is added as a further effluent. Addition can be performed during or after the separation treatment in step (c). In this case, it is advantageous that the further pyrolysis effluent is at least partially purified, gas-liquid separated, and/or fractionated before being added to step (c).

The thermal pyrolysis in step (b) is preferably carried out in the presence of a co-feed.

Preferably, the content of renewable stable petroleum naphtha feed in the total cracker feed ranges from 10 wt% to 100 wt%, more 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%. The upper limit can also be 90 wt% or 80 wt%, meaning the content can be, for example, in the range of 10 wt% to 90 wt% or 10 wt% to 80 wt%.

The invention is highly effective by using at least 10% by weight of renewable stable petroleum naphtha range hydrocarbon feed. The total cracker feed may consist of renewable stable petroleum naphtha range hydrocarbon feed, i.e., its content may be 100% by weight.

Co-feeds can include fossil hydrocarbon co-feeds. Fossil co-feeds, especially fossil naphtha, are readily available and well-suited for pyrolysis.

In this invention, the "fossil hydrocarbon co-feed" comprises at least 98.5% by weight of hydrocarbons, preferably at least 99.5% by weight. In other words, at least 98.5% by weight of the co-feed consists of hydrocarbons. This means that up to 1.5% by weight, preferably up to 0.5% by weight of the hydrocarbon co-feed can be composed of non-hydrocarbon substances, such as impurities containing heteroatoms, especially sulfur-containing impurities.

Preferably, the co-feed includes naphtha-range feed, as this provides high compatibility with renewable stabilized naphtha-range hydrocarbon feed. Furthermore, since renewable stabilized naphtha-range hydrocarbon feed is a well-defined (narrow-range) feed, it is preferable to use a narrow-range co-feed, such as fossil naphtha, to fully utilize the advantages of the invention. A particularly preferred co-feed is light naphtha, specifically fossil light naphtha. The light naphtha is preferably boiling within the range of 20°C (IBP) to 120°C (FBP), such as 30°C (IBP) to 90°C (FBP).

The sulfur content of the total cracker feed is preferably 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.

The inventors of this case were surprised to find that a (total) cracker feed containing renewable stable petroleum naphtha range hydrocarbons (and optional co-feeds and/or additives) and having sulfur content within the above limits resulted in a significantly reduced coking trend during pyrolysis.

Since renewable stabilized naphtha range hydrocarbon feedstocks typically have inherently low or no sulfur content, sulfur can be incorporated into the overall cracker feedstock by using sulfur-containing co-feeds such as fossil hydrocarbon feedstocks. The sulfur can further be derived, partially or entirely, from sulfur-containing additives, which include conventional cracking additives. Specifically, any conventional pyrolysis additive can be added to the renewable stabilized naphtha range hydrocarbon feedstock disclosed herein, to an optional co-feed, or to the pre-formed overall cracker feedstock or co-feed to the pyrolysis furnace, or can be added to a pyrolysis diluent and thus fed into the pyrolysis furnace. Examples of such conventional pyrolysis additives include sulfur-containing substances (sulfur additives), such as dimethyl disulfide (DMDS) or carbon disulfide ( _CS₂ ). DMDS is particularly preferred as a sulfur additive. Before being fed into the pyrolysis furnace, the sulfur additive can be mixed with a renewable stable petroleum naphtha range feed, an optional co-feed, or a pre-formed total pyrolysis furnace feed. Alternatively, the sulfur additive can be added by injecting a pyrolysis diluent, preferably steam, containing the sulfur additive into the pyrolysis furnace.

Step (a) of providing a stable naphtha range hydrocarbon feedstock may, for example, include hydrogenating the oxygenated biorenewable feedstock, which includes at least hydrogenation deoxygenation, and optionally further hydrogenation, which includes at least hydrogenation isomerization, and gas-liquid separation after hydrogenation to provide a liquid hydrocarbon stream and a gas stream. In a subsequent stage, the optionally isomerized liquid hydrocarbon stream may be fractionated to recover at least the renewable stable naphtha range hydrocarbon feedstock. Furthermore, other fractions may be recovered from the fractionation, including but not limited to gas fractions, diesel range fractions, aviation fuel range fractions, marine fuel fractions, and electrical fluid fractions. In addition, propane distillates can be recovered at least from the gas stream separated from the liquid hydrocarbon stream.

Exemplary aviation fuel fractions boil in the range of 100°C to 300°C, for example, in the range of 150°C to 300°C. Exemplary gasoline fuel fractions boil in the range of 25°C to 220°C. Exemplary diesel fuel fractions boil in the range of 160°C to 380°C. Exemplary marine fuel fractions boil in the range of 180°C to 600°C.

Generally, as disclosed herein, a petroleum naphtha range fraction refers to a fraction having an initial boiling point greater than 0°C, preferably greater than 20°C or greater than 30°C, and a T95 temperature below 220°C, preferably below 200°C, 180°C, 160°C, or 140°C. A petroleum naphtha range fraction has a T99 temperature below 220°C, preferably below 200°C, 180°C, 160°C, or 140°C, or a final boiling point below 220°C, preferably below 200°C or 180°C.

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

Step (a) in the above specific embodiment is preferably included as a further hydrogenation process including at least hydrogenation isomerization following a hydrogenation process including at least hydrogenation deoxygenation (HDO), and/or may include hydrogenation isomerization as part of a hydrogenation process including at least HDO.

In other words, hydrogenation isomerization can be carried out in a separate further hydrogenation process following a hydrogenation process that at least includes HDO. Alternatively or additionally, hydrogenation isomerization can be carried out as part of a hydrogenation process that at least includes HDO, for example, by means of a catalyst or catalyst system to complete hydrogenation deoxygenation and hydrogenation isomerization in a single step.

An effluent from a hydrogenation process containing at least HDO, referred to as a hydrogenation process effluent, can undergo gas-liquid separation to provide a gas stream and a first liquid hydrocarbon stream. At least a portion of the first liquid hydrocarbon stream can be provided as the aforementioned liquid hydrocarbon stream. Alternatively or additionally, at least a portion of the liquid hydrogenation process effluent can be further hydrogenated in a subsequent stage, comprising at least hydrogenation isomerization, preferably to provide a second liquid hydrocarbon stream after gas-liquid separation, which can be provided as the aforementioned liquid hydrocarbon stream.

The gas stream obtained in the second gas-liquid separation can be combined with and processed together with the gas stream obtained in the first gas-liquid separation. Condensable hydrocarbons, if available, can be separated from the gas stream and combined with the liquid hydrocarbon stream.

At least a portion of the first liquid hydrocarbon stream and/or the second liquid hydrocarbon stream can be recycled back to a hydrogenation process that includes at least hydrogenation deoxygenation. This recycling is suitable for achieving temperature control.

The aforementioned gas stream can be subjected to a propane separation process to provide a propane-rich stream and a depleted propane stream. The propane, at least partially contained in the propane-rich stream, can be dehydrogenated, preferably by catalytic dehydrogenation, to produce propylene.

Propane (or propane-rich stream) can also be recovered from the stabilization phase and subjected to this dehydrogenation. The propane (or propane-rich stream) recovered from the stabilization phase can be dehydrogenated in a separate reactor or combined with propane (or propane-rich stream) separated after hydrogenation to improve the gross yield of light olefins per unit of oxygenated biorenewable feedstock treated with hydrogenation.

Alternatively or additionally, this C3-rich stream (i.e., a propane-rich stream recovered after hydrogenation, a stream recovered from stabilization, or a combined stream) can be thermally cracked, such as by steam cracking, in a separate furnace.

When recovering heavy liquid hydrocarbon fractions from the above fractionation, the method may further include further fractionation of the heavy liquid hydrocarbon fractions to provide at least an aviation fuel range fraction and a bottom fraction. A suitable fractionation method, along with available fractionation cut-offs, the resulting fractions, and their uses, are described in WO 2021/094656 A1 and are incorporated herein by reference. In WO 2021/094656 A1, the bottom fraction is referred to as an electrotechnical fluid.

Each of the diesel range fraction, aviation fuel range fraction, heavy liquid hydrocarbon fraction, aviation fuel range fraction, and bottom fraction may individually have an isoalkane content of at least 65% by weight, preferably at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, or at least 90% by weight. The isoalkane content is calculated relative to the total diesel range fraction or relative to other fractions. A high degree of isomerization in the fraction, particularly in the diesel or aviation fuel range fraction, indicates that the manufacturing process is carried out in a highly isomerized manner, for example, under stringent isomerization conditions. In this case, the yield of naphtha range hydrocarbons tends to be higher, and the naphtha range fraction also tends to have a higher isoalkane content. This improves the overall yield of the method of the present invention.

The aforementioned stage of fractionating at least a portion of the liquid hydrocarbon stream and at least recovering the renewable stabilized naphtha range hydrocarbon feed preferably includes a stage of fractionating at least a portion of the liquid hydrocarbon stream to provide naphtha range fractions and a stage of stabilizing the naphtha range fractions. In this regard, stabilization may include, preferably, removing at least a portion of components with boiling points below 20°C by distillation technology, more preferably removing at least a portion of components with boiling points below 25°C, removing at least a portion of components with boiling points below 30°C, removing at least a portion of components with boiling points below 40°C, or removing at least a portion of components with boiling points below 50°C. If desired, the liquid stream can be subjected to optional additional treatments during the fractionation stage, such as stripping with _N2 , _H2, or steam, to separate the gas and impurities into a gaseous phase.

The stabilization stage can be part of the fractionation process, from which the naphtha range fraction is recovered. Alternatively or additionally, the stabilization stage can be carried out as a separation stage after fractionation, i.e., removing individual components from the recovered naphtha range fraction.

The stabilization phase is best carried out using distillation technology.

As used herein, distillation (or fractionation) can refer to any type of distillation, including stripping, flash distillation, and any other similar separation operation based on component vapor pressure differences. The selection of appropriate feed rates, operating temperatures, pressures, equipment types and designs, and other engineering details disclosed herein will be within the capabilities of those skilled in the art.

The aforementioned heavy liquid hydrocarbon fractions and/or diesel-range fractions may alternatively have an isoalkane content of less than 65% by weight.

The bottom fraction described above can undergo further thermal cracking, preferably steam cracking. This further cracking stage is preferably carried out separately from the thermal cracking step (b), i.e., in a different furnace and/or at a different time. The cracking conditions may differ from those used in step (b), but the same conditions available in step (b) may also be used.

Step (a) may involve hydrogenating an oxygenated biorenewable feedstock, such as plant-, animal-, or other biologically derived oils and/or fats. That is, as noted above, renewable stable petroleum naphtha range hydrocarbon feedstocks may be based on hydrogenated oxygenated feedstocks.

Step (a) may include pretreating the biorenewable oils and/or fats to reduce contaminants in the oils and/or fats in order to produce an oxygenated biorenewable feedstock (a'). Alternatively, the oils and/or fats may be used as an oxygenated biorenewable feedstock without pretreatment.

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

Suitable methods for performing pretreatment step (a') include one or more of the following: washing, degumming, bleaching, distillation, fractionation, rendering, heat treatment, evaporation, filtration, adsorption, hydrogenation treatment such as hydrogen deoxygenation, centrifugation, or precipitation. These pretreatment methods are simple and effective for removing S, N, and P contaminants, as well as metallic contaminants (metals and/or metal compounds), including metalloid contaminants such as Si-containing impurities, that may poison the catalyst. Pretreatment step (a') may alternatively or additionally include at least one of partial hydrogenation, partial deoxygenation, hydrolysis, and transesterification.

Oxygen-containing biorenewable feedstocks may contain fatty acid esters of glycerol.

The hydrogenated and optionally isomerized effluent is fractionated, preferably after gas-liquid separation. Fractionation can directly produce a renewable stable naphtha range feed or can be further processed, such as stabilized, to provide a renewable stable naphtha range feed.

In addition to the oxygenated biorenewable feedstock, the total feedstock for hydrogenation in step (a) preferably contains a hydrogenation treatment diluent comprising alkanes. The hydrogenation treatment diluent is particularly suitable for temperature control during hydrogenation, especially during hydrogenation deoxygenation. The hydrogenation treatment diluent may contain at least one of the following: recycled cycloalkanes from hydrogenation effluents and/or isomerization effluents; renewable hydrocarbons obtained using biosynthetic gas via Fischer-Tropsch synthesis; and fossil-based hydrocarbons. Preferably, the hydrogenation treatment diluent comprises recycled cycloalkanes derived from hydrogenation treatment effluents and/or isomerized effluents. When using the hydrogenation treatment diluent, the hydrogenation treatment feed preferably contains at least 2% by weight of oxygenated biorenewable feed, such as 2% to 100% by weight, preferably 3% by weight, at least 4% by weight, at least 5% by weight, at least 6% by weight, at least 7% by weight, at least 8% by weight, at least 9% by weight, at least 10% by weight, at least 11% by weight, at least 12% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 50% by weight, at least 75% by weight, at least 90% by weight, or at least 95% by weight, or at least 99% by weight. The feed subjected to hydrogenation in step (a) may contain less than 99% by weight of oxygenated biorenewable feed, for example, from 2% to 99% by weight, preferably less than 90% by weight, less than 75% by weight, less than 50% by weight, less than 40% by weight, less than 35% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight, or less than 10% by weight.

When the hydrogenation treatment diluent contains recycled cycloalkane from the hydrogenation treatment step, the hydrogenation treatment feed preferably contains 10% to 98% by weight of recycled cycloalkane from the hydrogenation treatment step, preferably at least 25% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 92% by weight. The hydrogenation feed may similarly contain up to 98 wt%, 95 wt%, 92 wt%, 90 wt%, 85 wt%, 80 wt%, 70 wt%, 60 wt%, 40 wt%, or 25 wt% of recycled cycloalkane from the hydrogenation step, for example, 10 wt% to 25 wt%. The recycled product from the hydrogenation step is preferably a hydrocarbon, but may also be a partially deoxidized material recycled to the hydrogenation step for further deoxidation.

In this invention, in addition to hydrogen deoxygenation (HDO), hydrogenation treatment can involve decarbonylation and/or decarboxylation. These reactions produce carbon monoxide or carbon dioxide and a hydrocarbon chain with one less carbon atom than the original chain.

Hydrogenation, preferably HDO, can be carried out, for example, by feeding hydrogen and natural fats or their derivatives (co-current or counter-current) through a catalyst bed. A suitable method and apparatus are described in EP1741767 A1, see Figure 1 and items [0061] to [0064], which are incorporated herein by reference.

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

Hydrogenation treatment, preferably with HDO, can be carried out in the presence of a hydrogenation catalyst containing one or more metals from Groups 6 to 10 of the periodic table (IUPAC 1990), preferably a supported catalyst, and more preferably one or more of the aforementioned metals supported on alumina and/or _silica . Preferred hydrogenation catalysts are Pd, Pt, Ni, NiMo, or CoMo supported on alumina and/or silica. The most preferred catalysts are NiMo/ _Al₂O₃ and _CoMo / _Al₂O₃ in sulfide form.

In this invention, the term "hydrogenation treatment" is intended to encompass the removal of oxygen from organic oxygen-containing compounds in the form of water, i.e., hydrogenation deoxygenation (HDO); the removal of sulfur from organic sulfur compounds in the form of dihydrogen sulfide ( _H₂S ), i.e., hydrogenation desulfurization (HDS); the removal of nitrogen from organic nitrogen compounds in the form of ammonia ( _NH₃ ), i.e., hydrogenation denitrification (HDN); the removal of halogens, for example, the removal of chlorine from organic chlorides in the form of hydrochloric acid (HCl), i.e., hydrogenation dechlorination (HDCl); the removal of metals by hydrogenation demetallization; and, if unsaturated bonds are present, hydrogenation of unsaturated bonds. When isomerization is performed in conjunction with hydrogenation treatment, this can be accomplished, for example, by combining HDO with hydrogenation cracking or by combining HDO with hydrogenation isomerization. Specifically, hydrogenation cracking can be performed to increase the yield of hydrocarbons in the petroleum naphtha range, which is beneficial to the entire process.

Optional isomerization, whether performed as part of a hydrogenation process or separately after a hydrogenation process that at least includes hydrogenation deoxygenation, results in higher yields of naphtha-range hydrocarbons, thus improving the overall yield of the process. By omitting isomerization, the process can be adapted to produce other fractions, particularly at least diesel-range fractions, while using naphtha-range fractions as a byproduct. In this case, it is preferable to recover the diesel-range fraction in addition to the naphtha-range fraction.

The optional isomerization, if included as a separate stage, can be carried out at a temperature selected from 200°C to 500°C, preferably 280°C to 400°C, and at a pressure selected from 20 to 150 bar (absolute value), preferably 30 to 100 bar. The isomerization (isomerization treatment) can be carried out in the presence of a known isomerization catalyst, for example, a catalyst comprising a molecular sieve and/or a metal and support selected from Group VIII of the periodic table. Preferably, the isomerization catalyst is a catalyst comprising SAPO-11 or SAPO-41 or ZSM-22 or ZSM-23 or magnesium alkali zeolite and Pt, Pd or Ni and _{Al₂O₃ or SiO₂} . Typical isomerization catalysts include _, for example, Pt/SAPO-11/ _Al₂O₃ , Pt/ZSM-22/ _Al₂O₃ , Pt/ZSM-23/ _{Al₂O₃ ,} and/or Pt/SAPO-11/ _SiO₂ . The presence of molecular hydrogen in the isomerization process can reduce catalyst deactivation. Therefore, it is preferable to have added hydrogen in the isomerization process. In _the case where optional isomerization is included as a separate stage, the hydrogenation catalyst and the isomerization catalyst may not be in simultaneous contact with the reaction feed (oxygenated biorenewable feed and/or the deoxygenation stream derived therefrom). For example, the hydrogenation process and the isomerization process are carried out in separate reactors.

Isomerization can be high-rigidity isomerization. High-rigidity isomerization in this invention refers to any technique for achieving a high isoalkane content in naphtha fractions, typically 50–60% by weight or 55–60% by weight. For alkanes with longer chains, i.e., those with carbon numbers close to the upper limit of the naphtha range, a particularly high isoalkane content (and a high ratio between isoalkanes and n-alkanes) can be achieved.

With hydrogenation and subsequent high-strict isomerization, the following procedures can be performed, as illustrated by using triglyceride-based biomass as an oxygenated biorenewable feedstock. In the first step, the triglyceride-based biomass is deoxygenated on a hydrogenation catalyst, such as _a NiMo catalyst supported on _Al₂O₃ under hydrogen pressure. Preferably, a sulfur component is added to the inlet stream to keep the catalyst in a sulfidated state. During the first step, the triglyceride oil and fatty acids are converted into n-alkanes and small amounts of branched alkanes (typically within the range of 1% by weight). It should be noted that oxygen content can be removed in the form of water (hydrogenation deoxygenation), carbon monoxide (decarbonylation), and carbon dioxide (decarboxylation). Compared to hydrogenation deoxygenation, removing oxygen via decarbonylation and decarboxylation consumes less hydrogen, but results in an alkane with one less carbon atom than the original fatty acid chain. In the second step, isomerization is carried out on a platinum-impregnated molecular sieve, such as Pt/ZSM-22.

The method of the present invention may further include derivatizing at least a portion of the light olefins to obtain one or more derivatives of the light olefins as biomonomers, 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), hexamethylene diisocyanate (HDI), methyl methacrylate, ethylidene norboreen, 1,5,9-cyclododecanetriene, cyclobutane, 1,4-hexadiene, tetrahydrophthalic anhydride, pentanal, 1,2-epoxybutane (1,2-butyloxide), n-butanethiol, terephthalophenol, propylene, octene, and terephthalool.

The method of the present invention may further include step (d), which polymerizes at least one light olefin and/or at least one of the above-mentioned biopolymers isolated in step (c), optionally together with other (co)polymers, and/or after optional further purification, to produce a biopolymer composition.

In this document, acrylic acid is intended to include any type of acrylic-based monomer, such as those based on (meth)acrylic acid, (meth)acrylates, and/or (meth)acrylate salts. Acrylic polymers are intended to include any type of acrylic-based polymers, such as those containing structural units derived from (meth)acrylic acid, (meth)acrylates, and/or (meth)acrylate salts.

Light olefins and/or biopolymers can be (co)polymerized to produce biopolymer compositions, including, for example, polybutadiene, styrene-butadiene rubber, nitrile rubber, polychloroprene, acrylonitrile-butadiene-styrene resin (ABS), styrene-butadiene latex, TPE, nylon such as nylon 6,6, polyurethane, methyl methacrylate-butadiene-styrene (MBS), nitrile barrier resins, butyl rubber, polyisobutylene, methyl methacrylate (MMA), MTBE/ETBE, polyolefin (co)polymers, polybutene-1, polypropylene (PP), ethylene-propylene copolymer (EPM), polyether, polyether polyol, polyester, polymer or oligomer surfactants, or ethylene-propylene-diene copolymer (EPDM).

Derivatization may include, for example, at least one of oxidation and ammoxidation. Oxidation is preferably carried out by gas-phase oxidation.

Polymerization can be carried out in the presence of a polymerization catalyst. Polymerization can be initiated by a polymerization initiator.

Biopolymer compositions can be further processed to manufacture hygiene products, building materials, packaging materials, coating compositions, paints, decorative materials such as panels, vehicle interiors such as automotive interiors, rubber compositions, tires or tire components, toners, personal care products, components of consumer products, components or housings of electronic devices, films, moldings, gaskets, optionally together with other components. In particular, acrylic polymers can be absorbent polymers, which can be further processed to manufacture hygiene products such as diapers, sanitary napkins, and incontinence draw sheets.

The present invention further relates to biopolymer compositions obtainable by specific embodiments of the method of the present invention, the method comprising the polymerization of light olefins and/or their derivatives.

Renewable stable petroleum naphtha feedstock

This invention further relates to a renewable, stable petroleum naphtha feedstock for pyrolysis.

Preferably, the renewable stabilized naphtha feedstock has a cycloalkane content ranging from 0.1 wt% to 10.0 wt% based on the total weight of the renewable stabilized naphtha feedstock. More preferably, the renewable stabilized naphtha feedstock has a cycloalkane content of 0.2 to 10.0 wt%, such as 0.5 to 8.0 wt%, 0.5 to 6.0 wt%, 0.6 to 5.8 wt%, 0.8 to 5.8 wt%, 1.0 to 5.6 wt%, or 1.2 to 5.6 wt%. Cycloalkanes readily convert to aromatics, which are compounds that may react to form coke but not the desired product. Therefore, a low cycloalkane content in the renewable stabilized naphtha feedstock is preferred.

Preferably, the renewable stabilized naphtha feedstock has an olefin content of less than 0.50 wt%, more preferably less than 0.40 wt%, less than 0.30 wt%, less than 0.25 wt%, less than 0.20 wt%, less than 0.15 wt%, less than 0.12 wt%, less than 0.10 wt%, less than 0.07 wt%, or less than 0.05 wt%. Olefins are an undesirable component in the renewable stabilized naphtha feedstock of this invention. That is, the inventors have found that olefins have a strong coking tendency, even higher than that of aromatics, therefore the olefin content should be kept low. The olefin content can be 0%, i.e., no detectable amount of olefins.

Preferably, the renewable stabilized naphtha range hydrocarbon feedstock has a total content of alkenes and cycloalkanes ranging from 0.1% by weight to 10.0% by weight. The total content of alkenes and cycloalkanes refers to the total content of alkenes and cycloalkanes based on the total weight of the renewable stabilized naphtha range hydrocarbon feedstock. More preferably, the renewable stable petroleum naphtha range hydrocarbon feedstock has a total content of 0.1 wt% to 8.0 wt%, such as 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% of alkenes and cycloalkanes.

Preferably, the renewable stable petroleum naphtha feedstock has an aromatic content of less than 0.80 wt%, more preferably less than 0.70 wt%, less than 0.60 wt%, less than 0.50 wt%, less than 0.40 wt%, less than 0.35 wt%, less than 0.30 wt%, less than 0.25 wt%, less than 0.20 wt%, or less than 0.15 wt%. Aromatics such as those in benzene do not react to form the desired product. Instead, they tend to react to form coke (i.e., they are coke precursors). Therefore, their presence in the feedstock reduces the yield of the desired product, and thus their content in the feedstock should be low. In this invention, the aromatic content is preferably low, and can be 0.00%. The aromatic content can be determined by PIONA analysis.

Preferably, the renewable stable petroleum naphtha feedstock has an aromatics-to-cycloalkanes ratio (weight of cycloalkanes divided by weight of aromatics) of 1 or more, more preferably 10 or more, 50 or more, or 100 or more. Both cycloalkanes and aromatics tend to increase the yield of cyclic compounds during pyrolysis. Therefore, it is preferable that both are present in low amounts. However, if both are included, cycloalkanes are preferred over aromatics. There is no specific upper limit to this ratio, and it can even be infinitely large in the absence of aromatics.

Preferably, the renewable stable petroleum naphtha feedstock has a total content of 0.1 wt% to 10.0 wt%, more 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% of alkenes, aromatics, and cycloalkanes. Cycloalkanes, aromatics, and alkenes are coke precursors, and their content should be low. However, since drastically reducing the content of all these components can be difficult, some of their content is tolerable. Nevertheless, their total content can be reduced to 0%, which contains 0%.

Preferably, the renewable stable petroleum hydrocarbon feedstock has an oxygen content of less than 1000 wt ppm, more preferably less than 700 wt ppm, less than 500 wt ppm, less than 300 wt ppm, less than 100 wt ppm, less than 80 wt ppm, less than 60 wt ppm, less than 50 wt ppm, less than 40 wt ppm, or less than 30 wt ppm. Oxygen content herein refers to molecules containing carbon and hydrogen and further comprising covalently bonded oxygen in their structure (molecule). In this invention, a low oxygen content is preferred, and it may be oxygen-free. On the other hand, particularly when using a low oxygen content co-feedstock (e.g., fossil hydrocarbon co-feedstock) of, for example, 10 wt% or more, higher values can be used, such as from 100 wt ppm to 1000 wt ppm. In this case, the effort to minimize the oxygen content is minimized, which increases the overall efficiency of the process. Since the renewable stable petroleum naphtha range feed of this invention is a petroleum naphtha range feed, the possible amount of oxygen-containing compounds is limited. According to this invention, the oxygen-containing compound content is based on ASTM D7423 (determining C2-C5 oxygen-containing compounds by GC-FID, i.e., gas chromatography-flame ionization detection), which has been modified to obtain a longer list of oxygen-containing compounds in the spectrum. Specifically, the following oxygen-containing compounds may be present in the renewable stable petroleum naphtha range hydrocarbon feedstock of this invention: ETBE (ethyl tetrabutyl ether), MTBE (methyl tetrabutyl ether), TAME (tetrapentyl methyl ether), DIPE (diisopropyl ether), propyl ether, isobutyraldehyde, butyraldehyde, isobutanol, n-butanol, dibutanol, tertiary butanol, methanol, acetone, vinyl acetate, ethyl acetate, MEK (methyl ethyl ketone), isopentanal, pentanal, ethanol, isopropanol, n-propanol, allyl alcohol, diethyl ether, acetaldehyde, etc. It is assumed that the total content of all oxygen-containing compounds identified by GC-FID corresponds to the total content of oxygen-containing compounds in the sample (i.e., in the renewable stable petroleum naphtha range hydrocarbon feedstock).

Preferably, the renewable stable petroleum naphtha feedstock has a content of less than 1.0% by weight, such as 0.0 to 0.9% by weight, more preferably 0.0 to 0.8% by weight, even more preferably 0.0 to 0.5% by weight, or 0.0 to 0.2% by weight of C17 and higher carbon number compounds.

Preferably, the renewable stable petroleum naphtha feedstock has a carbon range of 10 or less, more preferably 8, 7, 6, or 5 or less. A carbon range of 1 or more, 2 or more, or 3 or more is also preferred. Therefore, the carbon range is preferably in the range of 1 to 10, such as 2 to 10, 3 to 10, 3 to 8, 3 to 7, 2 to 6, 3 to 6, 2 to 5, or 3 to 5. In this invention, the carbon range refers to the difference between C_max and C_min (carbon range = C_max - C_min), where C_max (highest number of carbons) and C_min (lowest number of carbons) are determined by PIONA (GCxGC method), and for the purpose of determining the C_min and C_max carbon numbers, carbons with an abundance of 0.10% by weight or less are assumed to be non-existent. In other words, when determining C_min and C_max, and therefore when determining the carbon range, carbon numbers with a content of less than 0.10 wt% are not considered. The carbon range is more sensitive to small outliers in the carbon number distribution and is therefore more accurate than analytical techniques based on distillation characteristics (such as those measured according to EN ISO 3405-2019). In other words, the carbon range provides a good indicator of feed quality in terms of uniformity.

Preferably, the renewable stable petroleum naphtha feedstock has an interventile carbon number range (IVR) of 6.5 or less, more preferably 5.0 or less, 4.5 or less, 4.0 or less, or 3.8 or less. The IVR is a calculated carbon number range determined by linear interpolation of data (cumulative content relative to carbon number) obtained from PIONA carbon number analysis. Similarly, the IDR, IQR, and c_50 (and other c_xx values) are determined by linear interpolation of data (cumulative content relative to carbon number) obtained from PIONA carbon number analysis.

IVR (Interquartile Range) represents the range of carbons containing 90% of the mass (i.e., from 5 wt% to 95 wt%). Similarly, IQR (Interquartile Range) represents the range of carbons containing 50% of the mass, from 25 wt% to 75 wt%, and IDR (Decidecile Range) represents the range of carbons containing 80% of the mass, from 10 wt% to 90 wt%. Linear interpolation assumes that the range between two carbon numbers is linear. For example, a sample containing 0% C1 (0% of the component has 1 carbon atom), 0% C2, 0% C3, 5% C4, 5% C5, and 8% C6 will have a c_2.5 value (representing the fractional carbon number of 2.5% of the sample) of 3.5 (carbon number), even though C4 is the lowest actual carbon number. The c_5 value (representing the fractional carbon number of 5% of the sample) is 4 (C4), and the c_10 value (10% by weight) is 5 (C5) because the cumulative amount of C1+C2+C3+C4+C5 is exactly 10% by weight. The c_15 value (15% by weight) is between 5 and 6 (C5 is 10% by weight, C6 is 18% by weight). Linear interpolation is easy to calculate. For example, the carbon number (c_15 value) for a 15% weight content is: 5 {the highest carbon number not yet contributing 15% weight} + [(15% {content to be estimated} - 10% {cumulative C5 content}) / (18% {cumulative C6 content} - 10% {cumulative C5 content})] =5 + [5%/8%] = 5 + 0.625, i.e., carbon number 5.625. In other words, to determine the value of c_XX, use the following equation: {Highest carbon number not yet contributing XX wt%} + [({To be estimated content: XX wt%} - {Cumulative content of the highest carbon number not yet contributing XX wt%}) / ({Cumulative content of the lowest carbon number exceeding XX wt%} - {Cumulative content of the highest carbon number not yet contributing XX wt%})]

The linear interpolation method can be easily understood from the illustration in Figure 1. In Figure 1, the y-axis represents the cumulative content of compounds, while the carbon numbers are arranged sequentially on the x-axis. The bars represent the individual content of compounds with their respective carbon numbers. The dots represent the cumulative content (cumulative mass fraction) of their respective carbon numbers, and the lines represent linear interpolation values (i.e., drawing a straight line between adjacent points). The carbon number at the intersection of the line and the 50% cumulative mass fraction (horizontal line) is the c_50 value, which is slightly greater than 16 in Figure 1, as shown by the dashed line.

The IVR, IDR, and IQR ranges are less sensitive to tail effects, thus providing more stable results than the carbon range.

Preferably, the renewable stabilized naphtha range hydrocarbon feedstock has an interdecimal carbon number range (IDR) of 4.5 or less, more preferably 4.0 or less, 3.5 or less, or 3.0 or less. More preferably, the renewable stabilized naphtha range hydrocarbon feedstock has an interquartile range (IQR) of 2.5 or less, more preferably 2.0 or less, 1.8 or less, or 1.5 or less.

Preferably, the renewable stabilized petroleum hydrocarbon feedstock has a C11 and higher carbon content of less than 5.0 wt%, more preferably less than 4.5 wt%, less than 4.0 wt%, less than 3.5 wt%, less than 3.0 wt%, less than 2.5 wt%, or less than 2.0 wt%. For example, the C11 and higher carbon content can be from 0.0 to 5.0 wt%, or from 0.1 to 5.0 wt%.

Preferably, the renewable stable petroleum naphtha feedstock has a T95 temperature below 220°C, more preferably below 200°C, below 180°C, below 160°C, or below 140°C.

Preferably, the renewable stable petroleum naphtha feedstock has a T99 temperature below 220°C, more preferably below 200°C, below 180°C, below 160°C, or below 140°C.

Preferably, the renewable stable petroleum naphtha feedstock has a final boiling point below 220°C, more preferably below 200°C, below 180°C, or below 160°C.

Preferably, the renewable stable petroleum naphtha feedstock has an initial boiling point of 20°C or higher, more preferably 20°C to 60°C, such as 30°C to 50°C, or 30°C to 45°C.

Preferably, the renewable stable petroleum naphtha feedstock has a T5 temperature of 40°C or higher, more preferably 45°C or higher, 50°C or higher, 55°C or higher, or 60°C or higher.

In this invention, the renewable stable petroleum naphtha range hydrocarbon feedstock has a low content of light components and extremely light components.

Having an initial boiling point and/or T5 temperature within the above range improves the yield of valuable products, particularly propylene and ethylene, and C3 and C4 products in the effluent of the pyrolysis furnace beyond step (b).

Preferably, the difference between the T10 temperature and the T90 temperature of the renewable stable petroleum naphtha feed (T90-T10) is less than 100°C, more preferably less than 80°C, such as 20°C to 75°C, 30°C to 70°C, or 40°C to 70°C.

The difference between T10 and T90 values largely ignores outliers (tails) in the boiling distribution, making it a stable and highly reliable measure of compositional homogeneity. Within the aforementioned limits, feedstocks of renewable, stable petroleum naphtha have been found to produce favorable product distributions while still utilizing a substantial amount of material, thus contributing to improved overall yields.

Preferably, the total alkane content of the renewable stable petroleum naphtha feedstock is 90% by weight or more, more preferably 92% by weight or more, 93% by weight or more, 94% by weight or more, or 95% by weight or more.

The total alkane content in the renewable stabilized petroleum naphtha feed of this invention refers to the total amount of n-alkanes and isoalkanes relative to the total weight of the renewable stabilized petroleum naphtha feed. The inventors have found that a high amount of total alkane further increases the yield of valuable products and reduces coking tendency.

Preferably, the renewable stable petroleum naphtha range hydrocarbon feedstock has an isoalkane to n-alkane content ratio of less than 1.7, more preferably less than 1.5, such as 0.5 to 1.7, or 0.7 to 1.5.

The ratio of isoalkane to n-alkane provides particularly high ethylene yields within the aforementioned range. In this invention, this ratio is defined on a weight basis, that is, the weight content of isoalkane divided by the weight content of n-alkane.

Preferably, the renewable stable petroleum naphtha feedstock has an isoalkane to n-alkane content ratio in the range of 2.0 or higher, more preferably 2.2 or higher.

The isoalkane (iP) to n-alkane (nP) ratio within the aforementioned range provides particularly high propylene yields. In other words, by appropriately adjusting the isoalkane to n-alkane ratio, the product distribution can be adjusted to achieve the desired product, thus providing greater flexibility in the product range.

A range of 1.7 to 2.0 can also be used, although it is not the best, as it is not optimal for either ethylene or propylene production.

Furthermore, such a high iP/nP ratio reduces viscosity and improves mixing properties and composability, which is particularly (but not exclusively) advantageous when co-feeding is used in the pyrolysis step.

Preferably, the renewable stable petroleum naphtha range hydrocarbon feedstock can be obtained by the method disclosed in step (a) above, as in the method of the present invention, for providing the renewable stable petroleum naphtha range hydrocarbon feedstock.

Specifically, renewable stable petroleum naphtha feedstock is preferably obtained by a method comprising hydrogenation treatment of an oxygen-containing biorenewable feedstock and optional isomerization. This method preferably includes isomerization.

It should be noted that the renewable stable naphtha range hydrocarbon feed used in this method is preferably the renewable stable naphtha range hydrocarbon feed disclosed herein, i.e., it has the characteristics mentioned herein.

In one specific embodiment, a renewable stable naphtha range feedstock can be obtained or acquired by a method comprising hydrogenating an oxygenated biorenewable feedstock, the hydrogenation process including at least hydrogenation deoxygenation to provide a hydrogenated effluent, and subjecting at least a portion of the hydrogenated effluent to gas-liquid separation to provide a gas stream and a first liquid hydrocarbon stream, providing the first liquid hydrocarbon stream as a liquid hydrocarbon stream or subjecting at least a portion of the first liquid hydrocarbon stream to... The further hydrogenation process includes at least hydrogenation isomerization, followed optionally further gas-liquid separation to provide at least a second liquid hydrocarbon stream as a liquid hydrocarbon stream, and at least a portion of the liquid hydrocarbon stream is fed to a first distillation column, preferably a first stabilizer, to obtain a first column top fraction and a stabilized heavy liquid hydrocarbon fraction, optionally used in diesel fuel. At least a portion of the stabilized heavy liquid hydrocarbon fraction and/or from at least a portion of the stabilized heavy liquid hydrocarbon fraction are also used. The process involves recovering at least an aviation fuel-range fraction and a bottom fraction from a liquid hydrocarbon fraction, separating at least a fuel gas fraction and a naphtha-range fraction from the top fraction of a first distillation column, recirculating a portion, preferably at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 85% by weight, of the naphtha-range fraction back to the first distillation column, and feeding at least a portion of the naphtha-range fraction to a second distillation column, preferably a second stabilization column, to obtain the top fraction of the second column. Preferably, the distillation process includes at least a portion of components with boiling points below 20°C and a stable petroleum naphtha range fraction. At least additional fuel gas fractions and light liquid hydrocarbons are separated from the top distillation of the second column, and at least a portion, preferably at least 50% by weight, more preferably at least 70% by weight, and even more preferably at least 85% by weight, of the light liquid hydrocarbons is returned to the second distillation column. At least a portion of the stable petroleum naphtha range fraction is recovered as a feedstock for renewable stable petroleum naphtha range hydrocarbons.

pyrolysis effluent

This invention further relates to a renewable pyrolysis effluent having a benzene content of less than 6.0 wt%, a total ethylene and propylene content of more than 45.0 wt%, and a carbon monoxide content of less than 0.25 wt%. The benzene content can be from 0.01 wt% to 6.0 wt%, such as 0.1 wt% to 4.0 wt%, 0.1 wt% to 3.6 wt%, 0.1 wt% to 3.4 wt%, 0.1 wt% to 3.2 wt%, 0.1 wt% to 3.0 wt%, 0.1 wt% to 2.8 wt%, 0.1 wt% to 2.6 wt%, 0.2 wt% to 2.4 wt%, 0.3 wt% to 2.2 wt%, or less than 0.5 wt% to 2.0 wt%.

Preferably, the renewable pyrolysis effluent has a total ethylene and propylene content of 45% to 65% by weight, more preferably 46.0% to 65.0% by weight, 47.0% to 65.0% by weight, 48.0% to 65.0% by weight, 49.0% to 65.0% by weight, 50.0% to 65.0% by weight, 50.0% to 60.0% by weight, or 50.0% to 55.0% by weight.

Preferably, the renewable pyrolysis effluent has a total content of 45% to 80% by weight, more preferably 50% to 75% by weight, 50% to 70% by weight, 50% to 65% by weight, or 55% to 65% by weight of ethylene and propylene and total C4 olefins.

Preferably, the renewable pyrolysis effluent has a total C4 olefin content of at least 5.0 wt%, such as 5.0 wt% to 20.0 wt%, more preferably 8.0 wt% to 20.0 wt%, 10.0 wt% to 20.0 wt%, 12.0 wt% to 20.0 wt%, 12.6 wt% to 20.0 wt%, 13.0 wt% to 20.0 wt%, or 13.5 wt% to 20.0 wt%.

Total C4 olefins refer to 1-butene, 2-butene (including cis-2-butene and trans-2-butene), 1,3-butadiene, and isobutene. The total content of ethylene, propylene, and total C4 olefins can also refer to the total content of valuable light olefins.

The renewable pyrolysis effluent is preferably the effluent from the pyrolysis furnace of step (b) of the method of the present invention. Similarly, step (b) of the method is preferably to provide a pyrolysis furnace effluent having the properties of the renewable pyrolysis effluent mentioned herein.

Preferably, the renewable pyrolysis effluent has a carbon monoxide content of less than 0.23% by weight, more preferably less than 0.21% by weight, less than 0.20% by weight, less than 0.19% by weight, less than 0.18% by weight, less than 0.17% by weight, less than 0.16% by weight, less than 0.15% by weight, less than 0.14% by weight, less than 0.13% by weight, less than 0.12% by weight, less than 0.11% by weight, less than 0.10% by weight, or less than 0.09% by weight.

Carbon monoxide acts as a catalyst poison for polymerization catalysts. Therefore, it is best to minimize its concentration in the early stages, thereby reducing the amount of work required to remove it. This invention provides a means to achieve very low CO concentrations, or even eliminate the need for CO removal.

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

Preferably, the renewable pyrolysis effluent has an isobutylene content of at least 2.0% by weight, more preferably at least 2.4% by weight, more preferably at least 3.0% by weight, and even more preferably at least 3.2% by weight. Its upper limit may be, for example, 10.0% by weight, such as 9.0% by weight, or 8.0% by weight. In other words, the renewable pyrolysis effluent may have an isobutylene content, for example, ranging from 2.0% by weight to 10.0% by weight, such as 2.5% by weight to 9.0% by weight, or 3.0% by weight to 8.0% by weight.

Among C4 alkenes, isobutylene is a highly attractive molecule because it can be readily converted by reacting with methanol or ethanol to yield methyl tetrabutyl ether (MTBE) or ethyl tetrabutyl ether (ETBE), respectively, which is then transported. MTBE/ETBE can then be reverse-converted in a manner similar to that of isobutylene and its corresponding alcohol. MTBE and ETBE are also high-value gasoline components. Furthermore, isobutylene derivatives are more valuable than those of linear C4 alkenes, including butyl rubber, polyisobutylene, methyl methacrylate, alkylated gasoline, and a few other examples. Furthermore, isobutylene is relatively easy to separate from other C4 olefins, for example, by reacting methanol or ethanol with the isobutylene-containing C4 olefins to obtain MTBE or ETBE respectively, and then separating the resulting ether from the remaining C4 olefin mixture.

Preferably, the renewable pyrolysis effluent may have a total content of 3.0% by weight or more, more preferably 3.5% by weight or more, such as 4.0% by weight or more of n-C4 monoolefins. Its upper limit may be, for example, 15.0% by weight, such as 12.0% by weight or 10.0% by weight.

Preferably, the renewable pyrolysis effluent has a 1,3-butadiene content of at least 5.0 wt%, more preferably at least 5.5 wt%, and even more preferably at least 6.0 wt%, or at least 6.2 wt%. Its upper limit may be, for example, 15.0 wt%, such as 13.0 wt%, or 11.0 wt%. In other words, the renewable pyrolysis effluent may have a 1,3-butadiene content of, for example, from 5.0 wt% to 15.0 wt%, such as from 5.5 wt% to 13.0 wt%, or from 5.5 wt% to 11.0 wt%.

Specifically, the renewable stable naphtha range of hydrocarbons of this invention is particularly suitable for achieving high butadiene content. In other words, this feed is also suitable as fossil naphtha, and therefore can be co-fed with fossil naphtha at a wide blending ratio without reducing the butadiene content.

Preferably, the renewable pyrolysis effluent has a toluene content in the range of 0.2 wt% to 1.8 wt%, more preferably 0.2 wt% to 1.6 wt%, 0.2 wt% to 1.4 wt%, 0.2 wt% to 1.2 wt%, 0.2 wt% to 1.0 wt%, 0.2 wt% to 0.9 wt%, 0.2 wt% to 0.8 wt%, 0.2 wt% to 0.7 wt%, or 0.3 wt% to 0.6 wt%.

The pyrolysis effluent of this invention is particularly suitable for further upgrading into monomers for polymerization. Examples

The invention is further illustrated by the embodiments. It should be understood that the embodiments should not limit the invention in any way.

The pyrolysis of five feed compositions (C1, C2, C3, E1, and E2) was evaluated. The fossil feed composition (C1) corresponds to conventional fossil light naphtha. The other four feeds correspond to hydrogenated and isomerized biorenewable fats/oils with different degrees of isomerization and boiling point ranges. Among them, feed composition C2 is a wide-fraction naphtha composition, feed composition C3 is a highly isomerized diesel-range composition, feed composition E1 is a stable naphtha-range composition, and feed composition E2 is a stable and highly isomerized naphtha-range composition.

The PIONA data and oxygen content of these components are shown in Table 1 below.

Table 1: Components C1 C2 C3 E1 E2 n-Alkanes (nP) 34.0% 33.1% 8.4% 41.4% <40% Isoalkylene(iP) 39.9% 59.5% 91.5% 53.9% >60% Alkenes (O) 0% 0.3% 0% 0% 0% Cycloalkanes (N) 25.4% 6.3% 0% 4.3% 1.9% Aromatic compounds (A) 0.7% 0.8% 0.1% 0.4% 0% oxygen na na <3 ppm 10 ppm 4 ppm *na indicates that the result could not be obtained or was not measured.

Table 2 below shows the boiling characteristics (according to EN ISO 3405-2019) and carbon number analysis (assuming floating-point numbers with linear interpolation) based on PIONA data co-correlated with carbon number relative to the total composition content range (by weight), and the calculated IQR, IDR and IVR values.

Table 2: C1 C2 C3 E1 E2 IBP (0 volume %) na na 187°C 47°C 46°C 5. Temperature per unit volume (T5) na na 246°C 61°C 62°C 95% volumetric temperature (T95) na na 295°C 137°C 122°C FBP na na 309°C 170°C 137°C C_min (measured) 4 3 5 5 5 C_max (measured) 7 18 20 13 10 c_05 4.1 4.3 12.2 4.4 4.4 c_10 4.4 4.8 14.2 4.7 4.9 c_25 5.0 5.7 15.2 5.4 5.5 c_50 5.3 6.9 16.1 6.2 6.3 c_75 5.7 8.4 17.2 7.0 7.0 c_90 5.9 9.6 17.7 7.9 7.7 c_95 5.9 10.7 17.9 8.5 8.0 IQR 0.7 2.6 2.0 1.6 1.5 IDR 1.5 4.8 3.5 3.1 2.9 IVR 1.8 6.5 5.6 4.2 3.5 carbon range 3 15 15 8 5 *IBP = Initial boiling point, FBP = Final boiling point, c_05 = Carbon fraction corresponding to 5% of mass when sorted in ascending order of carbon number (c_10 and others are similar, as explained above).

Comparative example 1 , 2 , 3 and implementation examples 1 , 2

The five components were subjected to steam cracking at two different solenoid outlet temperatures (COT) of 820°C and 850°C, a dilution of 0.5 (water/oil ratio), and a solenoid outlet pressure (COP) of 1.7 bar (absolute).

The yields of the related products are shown in Table 3 below.

Table 3: CEx.1 CEx.2 CEx.3 Ex1 Ex2 C1 C2 C3 E1 E2 COT 820°C ethylene 21.3 27.3 29.6 29.2 27.9 propylene 16.0 19.5 18.7 20.1 21.9 Ethylene + Propylene 37.3 46.8 48.3 49.3 49.8 butadiene 4.4 5.8 6.7 6.6 5.9 C4 monoene 3.9 4.6 4.3 5.1 6.1 Isobutylene 2.8 3.9 3.0 4.0 4.9 C4 monoene 6.7 8.5 7.3 9.1 11.0 C2-C4 alkyl hydrocarbons 4.0 -* 4.4 5.5 4.7 benzene 4.5 3.2 6.7 1.4 1.1 Toluene 0.6 1.6 2.7 0.6 0.4 PFO (C10 and higher carbon numbers) 0.3 -** 1.2 0.2 0.2 carbon monoxide 0.00 0.32 0.05 0.04 0.08 COT 850°C ethylene 29.0 30.9 na 32.5 30.8 propylene 17.5 17.6 17.8 19.1 Ethylene + Propylene 46.5 48.5 50.3 49.9 butadiene 5.0 5.4 6.6 6.3 C4 monoene 3.1 2.8 3.6 3.7 Isobutylene 2.7 3.1 2.4 3.5 C4 monoene 5.8 5.9 6.0 7.2 C2-C4 alkyl hydrocarbons 4.4 - 5.2 4.4 benzene 5.8 5.6 3.8 3.2 Toluene 1.1 2.1 1.3 1.1 PFO (C10 and higher carbon numbers) 3.1 - 0.8 0.7 carbon monoxide 0.04 0.23 0.08 0.16 *Free of propane/butane; **Free of heavy components

The data above show that the steam cracker feed compositions E1 and E2 of this invention provide low aromatic and high light olefin yields, especially at relatively low COT. In particular, compared to conventional (fossil) petroleum naphtha, a low COT can be achieved while still maintaining high yields. Furthermore, low coke formation was observed for both the composition of this invention and the fossil petroleum naphtha composition C1. Additionally, the cracking effluent from fossil petroleum naphtha exhibits a high benzene content. It is speculated that this is because if the amount of fossil petroleum naphtha cracker feed is relatively high (and not converted during the cracking process), it contains benzene, and because fossil petroleum naphtha contains a large amount of cycloalkanes, these cycloalkanes are also converted into aromatics, such as benzene.

The low- to moderately isomerized composition E1 offers particularly improved ethylene and butadiene yields, while the highly isomerized composition E2 offers exceptionally good propylene and C4 monoolefin yields.

The data above show that by using the renewable, stable petroleum-based hydrocarbon compositions of this invention, such as compositions E1 and E2, as steam cracker feed, very high combined yields of ethylene and propylene, as well as high total C4 olefin yields, especially 1,3-butadiene, can be obtained. Simultaneously, even at elevated COT:s, very little coke, very little aromatics, especially benzene, and very little heavy compounds are formed. Conveniently, these benefits have already been observed at low COT:s, which also favor the formation of C4 monoolefins.

According to the present invention, the combined yield of ethylene and propylene can be further increased by separating and recycling the C2-C4 alkanes. Furthermore, the product list can be easily adjusted to the desired direction, depending on market demand, product price, further purification, or post-processing capacity. For example, by selecting a renewable stable petroleum naphtha feedstock with a lower isoalkane to n-alkane ratio and/or using a higher COT in thermal cracking, the weight ratio of ethylene to propylene and 1,3-butadiene to C4 monoolefins in the cracking effluent can be increased.

without.

Figure 1 illustrates the linear interpolation method used to obtain the c_50 value.

without.

Claims (23)

A method for producing a light olefin fraction includes: (a) providing a renewable stabilized naphtha range hydrocarbon feedstock, wherein the renewable stabilized naphtha range hydrocarbon feedstock has a content of less than 5.0 wt% of C4 and lower carbon number compounds, a content of less than 1.0 wt% of C17 and higher carbon number compounds, and a content of less than 2.0 wt% of C11 and higher carbon number components, and an interquartile carbon number range (IQR) of less than 2.0; (b) thermally cracking the renewable stabilized naphtha range hydrocarbon feedstock in a thermal cracking furnace, wherein the feedstock and/or additives are thermally cracked together if present; and (c) separating the effluent from the thermal cracking furnace in step (b) to provide at least a light olefin fraction. The method of claim 1, wherein the pyrolysis step (b) is a steam pyrolysis step. The method of claim 1 or 2, wherein the pyrolysis step (b) is performed at a coil outlet temperature (COT) selected from the range of 780°C to 880°C. The method of claim 1 or 2, wherein the content of the renewable stabilized petroleum naphtha feed in the total pyrolyzer feed is in the range of 10% by weight to 100% by weight, and the pyrolysis in step (b) is carried out in the presence of a co-feed, wherein the total pyrolyzer feed refers to the renewable stabilized petroleum naphtha feed plus, if present, the co-feed and, if present, additives. The method of claim 1 or 2, wherein the separation process in step (c) further provides a fraction comprising one or more C2 to C4 alkanes, and the method includes recycling at least a portion of the fraction as a co-feed to step (b), and/or recovering at least a portion of the fraction as an NGL (natural gas liquids) composition. The method of claim 1 or 2 further comprises: (d) co-polymerizing at least one light olefin and/or at least one biopolymer isolated in step (c), wherein, if other copolymers are present, they are co-polymerized together to produce a biopolymer composition. The method of claim 1 or 2 further comprises: (d) a step of derivatizing at least a portion of the light olefin to obtain one or more derivatives of the light olefin as biopolymers; and (c) a step of (co)polymerizing the at least one light olefin and/or at least one biopolymer isolated in step (c), wherein, if other (co)polymers are present, they are co-polymerized together to produce a biopolymer composition. The method described in Request 6 further includes a purification step following the (co)aggregation step. The method described in claim 7 further includes a purification step following the (co)aggregation step. A renewable stabilized naphtha range hydrocarbon feedstock for pyrolysis, wherein the renewable stabilized naphtha range hydrocarbon feedstock has a content of less than 5.0 wt% of C4 and lower carbon number compounds, a content of less than 1.0 wt% of C17 and higher carbon number compounds, and a content of less than 2.0 wt% of C11 and higher carbon number components, and the interquartile range of carbon number is less than 2.0. Such as the renewable stabilized petroleum naphtha feedstock of claim 10, wherein the renewable stabilized petroleum naphtha feedstock has an aromatics content of less than 0.80% by weight. Such as the renewable stabilized petroleum naphtha range hydrocarbon feedstock of claim 10, wherein the renewable stabilized petroleum naphtha range hydrocarbon feedstock has a carbon range of less than 10. For example, the renewable stabilized naphtha range feedstock of claim 10, wherein the renewable stabilized naphtha range feedstock has an interventile carbon number range (IVR) of 6.5 or less, and/or the renewable stabilized naphtha range feedstock has an interdecile carbon number range (IDR) of 4.5 or less. Such as the renewable stabilized petroleum naphtha feedstock of claim 10, wherein the renewable stabilized petroleum naphtha feedstock has a total alkane content of 90% by weight or more. The renewable stabilized naphtha range feed, as claimed in claim 10, wherein the renewable stabilized naphtha range feed has an isoalkane content ratio of less than 1.7 to n-alkane. The renewable stabilized naphtha range feed, as claimed in claim 10, wherein the renewable stabilized naphtha range feed has an isoalkane content ratio to n-alkane in the range of 2.0 or higher. A renewable pyrolysis effluent having a benzene content of less than 6.0% by weight, a total ethylene and propylene content of more than 45.0% by weight, and a carbon monoxide content of less than 0.25% by weight. The renewable pyrolysis effluent, as described in claim 17, has a benzene content of 0.01% to 6.0% by weight. Such as the renewable pyrolysis effluent of claim 17 or 18, wherein the renewable pyrolysis effluent has a total ethylene and propylene content of 45% to 65% by weight. The renewable pyrolysis effluent, such as that in claims 17 or 18, can be obtained by the method described in claim 1. The renewable pyrolysis effluent, as described in claims 17 or 18, has a carbon monoxide content of less than 0.23% by weight. The renewable pyrolysis effluent of claim 17 or 18, wherein the renewable pyrolysis effluent has: a total C4 olefin content of at least 8.0 wt%; and/or a 1,3-butadiene content of at least 5.0 wt% and/or at most 15.0 wt%; a C4 monoolefin content of at least 6.0 wt% and/or at most 15.0 wt%; an isobutene content of at least 2.0 wt% and/or at most 10.0 wt%; and/or a n-C4 monoolefin content of at least 3.0 wt% and/or at most 15.0 wt%. The renewable pyrolysis effluent, as claimed in claims 17 or 18, comprises: a total C2-C4 alkane content of more than 4.0% by weight and/or up to 15.0% by weight; and/or less than 1.5% by weight of pyrolysis fuel oil, which is a C10 or heavier compound.