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WO-2026093317-A1 - CO-PRODUCTION OF RENEWABLE-BASED LINEAR ALKYLBENZENE AND HYDROCARBON COMPOSITIONS

WO2026093317A1WO 2026093317 A1WO2026093317 A1WO 2026093317A1WO-2026093317-A1

Abstract

The present invention relates to a production method and apparatus for alkylbenzenes from natural oils and kerosene and the co-production of a renewable content hydrocarbon composition, e.g. a renewable content hydrocarbon fluid composition and/or a renewable content fuel composition, without a hydrocracking or isomerization step. The invention also relates to a hydrocarbon fluid composition, to the use of said composition as hydrocarbon fluid and to an apparatus for the manufacture of linear alkylbenzene and a hydrocarbon composition.

Inventors

  • LAZARO MUÑOZ, Jesús Javier
  • FRONTELA DELGADO, Juana María
  • PEDRAZA VALIENTE, Manuel Jesús
  • MATEOS CAMACHO, María
  • ROMERO VÁZQUEZ, María Ángeles

Assignees

  • MOEVE CHEMICALS, S.A.U.

Dates

Publication Date
20260507
Application Date
20251028
Priority Date
20241029

Claims (16)

  1. 1. A process for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition comprising: combining a stream of fossil kerosene comprising hydrocarbons C9-C16 with a stream of natural oil comprising fatty acid chains of C10, C12 and C14 to obtain a mixture (200); hydrotreating and hydrodeoxygenating the mixture (200) to form a hydrotreated and hydrodeoxygenated stream (202); separating said hydrotreated and hydrodeoxygenated stream (202) to obtain a stream enriched in normal paraffins (203) and a stream depleted in normal paraffins (204); fractionating said stream enriched in normal paraffins (203) to obtain a first fraction of normal paraffins (206) comprising normal paraffins in the range between C9-C14 and a second fraction of normal paraffins (209) comprising normal paraffins in the range between C14-C18; producing linear alkylbenzene (243) from said first fraction of normal paraffins (206); and combining at least a part of the second fraction of normal paraffins (209), without being subjected to a hydrocracking or hydroisomerization reaction, with: either at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins; and/or a product of hydrodearomatization of at least a part of the stream depleted in normal paraffins or a product of hydrodearomatization of a fraction of said stream depleted in normal paraffins; and/or at least a part of the stream depleted in normal paraffins or a fraction of said stream depleted in normal paraffins to form a combined stream, and hydrodearomatizing said combined stream; to form at least a hydrocarbon composition.
  2. 2. The process according to claim 1 , wherein the natural oil is a lauric oil, preferably selected from the group consisting of coconut oil, palm kernel oil, babassu oil, macauba kernel oil, animal derived lauric oils and mixtures thereof.
  3. 3. The process according to claim 2, wherein the natural oil is selected from the group consisting of coconut oil, palm kernel oil and mixtures thereof. 39
  4. 4. The process according to any one of claims 1 to 3, wherein at least a part of the second fraction of normal paraffins (209) is combined with at least a part of the stream depleted in normal paraffins (204) to form a hydrocarbon composition (211) suitable as fuel, preferably a jet fuel that has a boiling range between 140 °C and 270 °C, a cloud point below -47 °C and a content of normal paraffins in the range C14- C18 of up to 10%.
  5. 5. The process according to any one of claims 1 to 4, wherein at least part of the stream depleted in normal paraffins (204) is subjected to fractionation to obtain at least a first fraction (215) comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics, and said fraction (215) is subjected to hydrodearomatization prior to combination with at least part of the second fraction of normal paraffins (209) so as to form a hydrocarbon composition (220) suitable as fluid that preferably has a flash point between 90-130 °C and a boiling range between 220-320 °C.
  6. 6. The process according to any one of claims 1 to 5, wherein at least part of the stream depleted in normal paraffins (204) is subjected to fractionation to obtain at least a first fraction (215) comprising C13-C16 iso-paraffins, cyclic paraffins and aromatics prior to combination with at least part of the second fraction of normal paraffins (209), and the combined stream (221) is subjected to hydrodearomatization so as to form a hydrocarbon composition (222) suitable as fluid that preferably has a flash point between 90-130 °C and a boiling range between 220-320 °C.
  7. 7. The process according to claim any of claims 1 to 6, wherein at least part of the second fraction of normal paraffins (209) is combined with at least part of the stream of hydrocarbons depleted in normal paraffins (204) and the combined stream is subjected to fractionation and hydrodearomatization so as to form a hydrocarbon composition (230) suitable as fluid that preferably has a flash point between 90-130 °C and a boiling range between 220-320 °C.
  8. 8. The process according to any one of claims 1 to 7, wherein the separation to form the stream enriched in normal paraffins (203) and the stream of hydrocarbons depleted in normal paraffins (204) is carried out using molecular sieves. 40
  9. 9. The process according to any one of claims 1 to 8, wherein in the fractionation of the stream enriched in normal paraffins (203) at least three further fractions are separated, said fractions being a light fraction comprising normal paraffins of C9 (205) and two intermediate normal paraffin fractions comprising normal paraffins of C14 (207) and C14+C15 (208) respectively.
  10. 10. The process according to any one of claims 1 to 9, further comprising the steps for the manufacture of linear alkylbenzene of: dehydrogenating the first fraction of normal paraffins (206) to obtain a dehydrogenated stream (231) comprising mono-olefins, di-olefins, and aromatics; selectively hydrogenating said dehydrogenated stream (231) to obtain a stream enriched in mono-olefins (234); alkylating said stream enriched in mono-olefins (234) with benzene under alkylation conditions to obtain a stream comprising linear alkylbenzene (237); and isolating a linear alkylbenzene product (243) from the linear alkylbenzene stream (237).
  11. 11 . The process according to any one of claims 9 to 10, wherein the linear alkylbenzene product (243) is further sulfonated to form linear alkylbenzene sulfonic acid.
  12. 12. The process according to claim 11 wherein the linear alkylbenzene sulfonic acid is neutralized to form linear alkylbenzene sulfonate.
  13. 13. The process according to claim 12, wherein the linear alkylbenzene sulfonate is added to a detergent formulation.
  14. 14. A hydrocarbon composition consisting of: from 75 wt.% to 99 wt.% of a mix of n-paraffins, iso-paraffins and cyclic paraffins in the C12-C16 range; from 1 wt.% to 20 wt.% of n-paraffins in the C17-C18 range; from 0-5 wt.% of other paraffins, and less than 1000 ppm by weight of aromatics; wherein the hydrocarbon composition has a flash point between 90-130 °C and the boiling range is between 220-320 °C.
  15. 15. Use of a hydrocarbon composition as defined in claim 14 as a hydrocarbon fluid, preferably as a hydrocarbon solvent and/or base oil.
  16. 16. An apparatus for the manufacture of linear alkylbenzene (243) and a hydrocarbon composition according to the process of any one of claims 1 to 13, said apparatus comprising a hydrodeoxygenation I hydrotreating unit (HDO-HT) (101), a separator unit (N/l SEP) (102), a fractionation unit (FRAC) (103), and alkylbenzene production unit (104), and optionally a hydrodearomatization unit (HDA) (106”’).

Description

CO-PRODUCTION OF RENEWABLE-BASED LINEAR ALKYLBENZENE AND HYDROCARBON COMPOSITIONS DESCRIPTION TECHNICAL FIELD OF THE INVENTION The present invention relates to a process and an apparatus for the production of linear alkylbenzenes (LAB) from natural oils and kerosene and the co-production of a renewable content hydrocarbon composition, e.g. a renewable content hydrocarbon fluid composition and/or a renewable content hydrocarbon fuel composition. Advantageously, the linear alkylbenzene can be produced in a conventional industrial alkylbenzene production plant without substantial modification. Another benefit is that the heavy normal paraffin fraction (C14-C18) which results from the hydrodeoxygenation of the natural oils is upgraded into the renewable content hydrocarbon composition without any hydrocracking and/or isomerization step. The invention also relates to a hydrocarbon fluid composition, to the use of said composition as hydrocarbon fluid and to an apparatus for the manufacture of linear alkylbenzene and a hydrocarbon composition. Linear alkylbenzenes (LAB) are extensively used as a chemical intermediate to form linear alkylbenzene sulfonates (LAS), substances widely employed in detergents and cleaning products as well as in a variety of other applications, whereas hydrocarbon fluids may be used as solvents and base oils in a variety of applications including lubricants, agricultural chemical applications (e.g. spray oil applications), etc. and hydrocarbon fuels (e.g. diesel or jet fuel) are mainly used as energy source for propulsion in transport. BACKGROUND OF THE INVENTION Linear alkylbenzenes are organic compounds with the formula CeHsCnHhn+i. While n can have any practical value, current commercial use of alkylbenzenes requires that n lies in the range of 10 to 16, or in the range of 8 to 15, or in the range of 10 to 13, or in the range of 12 to 15, or in the range of 9 to 14. These specific ranges are often required when the alkylbenzenes are used as intermediates in the production of surfactants for detergents. Because the surfactants created from alkylbenzenes are biodegradable, the production of alkylbenzenes has grown rapidly since their initial uses in detergent production in the 1960s. The linearity of the paraffin chain in the alkylbenzenes is key to the material's biodegradability and effectiveness as a detergent. A major factor in the final linearity of the alkylbenzenes is the linearity of the paraffin component. While detergents made utilizing alkylbenzene-based surfactants are biodegradable, processes for creating alkylbenzenes are not based on renewable sources. Specifically, alkylbenzenes are currently produced from kerosene extracted from the earth. Due to the growing environmental concerns over fossil fuel extraction and economic concerns over exhausting fossil fuel deposits, there may be support for using an alternate source for biodegradable surfactants in detergents and in other industries. To date industrial processes for the manufacture of detergent range alkylbenzenes are entirely based on fossil resources extracted from gaseous or liquid resources extracted from the ground from fossil deposits. Current process units to produce linear alkylbenzene do not usually intrinsically comprise a unit that performs hydrocracking or hydroisomerization reactions of paraffinic intermediates. In EP1857525 the hydrotreatment (HDT) of combined streams of fossil kerosene and natural oils to obtain N-paraffins suitable for detergent production is described. In particular, short chain lauric natural oils are described to be able to be hydrotreated in the invention, among which palm kernel oil, obtained from oleaginous palm trees (Elaeis guineensis, Jacq.), babassu oil (Orbignya speciosa, Mart.) Barb. Rodr., and ouricuri oil or licuri oil also obtained from a palm tree (Syagrus Coronata (Martius) Beccari) are preferred. The proposed hydrotreatment process is described as involving hydrocracking reactions to reduce the number of carbon atoms in the chains of the vegetable oils used, followed by hydrotreatment to remove the oxygenated compounds, and followed by hydrogenation of olefins to remove double bonds. Suitable catalysts for the process are described as commercial sulfided NiMo catalysts and sulfided CoMo catalysts supported in gamma alumina. In US2014364355 a method for the production of linear alkylbenzenes from natural oils is described. In the preferred embodiments, the natural oils include one or more of coconut oil, babassu oil, castor oil, cooking oil, and other vegetable, nut or seed oils. The natural oils typically comprise triglycerides, free fatty acids, or a combination of triglycerides and free fatty acid. Hydrodeoxygenation of the natural oil is effected in a hydrodeoxygenation unit. Catalysts may include those containing one or more of Ni, Mo, Co, P, such as Ni — Mo, Ni — Mo — P, Ni — Co — Mo, or Co — Mo, on aluminas, silica, titania, zirconia, and mixtures thereof. Th