A method of treating pyrolysis oil

Abstract

A method of treating a pyrolysis oil including feeding pyrolysis oil and an aromatic to a reactor to perform an alkylation reaction in the reactor with a catalyst is provided. The alkylation reaction produces linear alkylbenzenes to be fed to an extractor, where the linear alkylbenzenes and excess aromatic are extracted and fed to a separator. The separator then separates the linear alkylbenzenes from the excess aromatic.

Description

A METHOD OF TREATING PYROLYSIS OIL Inventors Amit A. Gokhale Samantha Au Gee Jinhu Dong Susannah Scott BASF Ref: 240324WO01 LS Ref: 39425-375Attorney Docket No.39425-357 A METHOD OF TREATING PYROLYSIS OIL CROSS REFERENCE TO RELATED APPLICATION(S)

[0001] The present application claims priority to U.S. Provisional Application No. 63 / 692,649 filed on September 9, 2024. The entire contents of which are incorporated in its entirety. FIELD OF THE INVENTION

[0002] Disclosed herein are a method and system of treating pyrolysis oil, including performing an alkylation reaction in the presence of an aromatic compound and catalyst to produce and obtain linear alkylbenzenes. BACKGROUND

[0003] Conversion of plastics-derived pyrolysis oils to olefins via the use of cracker is one of the ways for introducing recycled content into the chemicals or olefins value chain. The intent of such a process is to replace the virgin naphtha feedstocks that are currently used by the petrochemical industry. However, the pyrolysis oils available today often tend to have a heavier grade than is what is acceptable for use as feedstocks for a cracker. Some companies have been able to produce a grade that would be acceptable by distilling away the heavier compounds and either recycling them or disposing of them. This process makes the desirable pyrolysis oil cut considerably more expensive.

[0004] There is a need to generate a lighter cut pyrolysis oil, while also producing higher value linear alkylbenzenes (LABs). LABs are used in detergents and surfactants and have a higher price point compared to naphtha. Thus, producing LABs from this process could help in improving the economic viability of pyrolysis / recycling processes by providing a higher value recycled feedstock for detergents and / or surfactants. SUMMARY

[0005] In some embodiments, a method for treating pyrolysis oil is provided. The method includes feeding pyrolysis oil an aromatic to a first reactor including a catalyst; performing an alkylation reaction in the first reactor to obtain linear alkylbenzenes, byproducts, and unreacted compounds, wherein the unreacted compounds may include excess aromatic, polyaromatics, alkanes and unreacted olefins and dienes; feeding the linear alkylbenzenes, the byproducts and the unreacted compounds to an extractor; extracting the linear alkylbenzenes and the excessAttorney Docket No.39425-357 aromatic and feeding them to a separator; separating the linear alkylbenzenes from the excess aromatic, and an extractant-rich stream and recycling the extractant-rich stream to the extractor. In some embodiments, the pyrolysis oil may include olefins and dienes.

[0006] In some embodiments, the catalyst may include an acid catalyst. In some embodiments, the acid catalyst may include aluminum chloride (AlCl3). In some embodiments, the acid catalyst may include aluminosilicate. In some embodiments, the acid catalyst may include a zeolite. In some embodiments, the zeolite may include beta (BEA), ZSM-5, or ZSM-11.

[0007] In some embodiments of the method, the alkylation reaction may be performed at a temperature of about 20°C to about 280°C. In some embodiments, the linear alkylbenzenes may include compounds with carbon numbers from C12to C20.

[0008] In some embodiments, the method may further include after the separator, recycling the unreacted compounds and byproducts to first reactor.

[0009] In some embodiments of the method, the extracting may include a solvent in the extractor a solvent, wherein the solvent comprises sulfolane.

[0010] In some embodiments of the method, the extractor may extract alkylbenzenes and aromatics into the extractant or the solvent forming the extract phase and leaving behind a phase containing alkanes and unreacted dienes and olefins, i.e., the raffinate phase.

[0011] In some embodiments, the method may further include feeding the raffinate from the extractor to an adsorption bed. In some embodiments, the adsorption bed may remove sulfolane to obtain a purified stream comprising alkanes. In some embodiments, the method may further include feeding the purified stream to a second separator and separating the alkanes into light and heavy fractions. In some embodiments, the light fraction of alkanes may be fed into a naphtha cracker.

[0012] In some embodiments, the heavier fraction of alkanes may be fed to second reactor, wherein cracking, aromatization, or a combination thereof may be performed to obtain alkylbenzenes and short-chain alkanes and alkenes.

[0013] In some embodiments, the second reactor may include a second catalyst. In some embodiments, the second catalyst may include a platinum group metal, and a support. In some embodiments, the platinum group metal and the support may be in a matrix. In some embodiments, herein the platinum group metal may be on the support. In some embodiments, the support may include alumina, fluorinated alumina, chlorinated alumina, or combinations thereof. In some embodiments, the support may include aluminosilicate, silicoaluminophosphate, silica, silica-alumina, or combinations thereof. In some embodiments, the aluminosilicate may include a zeolite. In some embodiments, the catalyst may furtherAttorney Docket No.39425-357 include doping the support with a rare earth metal. In some embodiments, the rare earth metal may include scandium (Sc), lanthanum (La), neodymium (Nd), ytterbium (Yb), gadolinium (Gd), yttrium (Y), cerium (Ce), or a combination thereof. In some embodiments, the platinum group metal may include platinum (Pt), ruthenium (Ru), iridium (Ir), palladium (Pd), rhodium (Rh), or a combination.

[0014] In some embodiments, the catalyst may further include a promoter. In some embodiments, the promoter may include nickel (Ni), cobalt (Co), or a combination thereof.

[0015] In some embodiments, the second reactor may be operated at a temperature of about 200°C to about 350°C.

[0016] In some embodiments, the method may further include performing a removal of extractant such as sulfolane in a second adsorption bed from the linear alkylbenzenes stream in order to purify the same.

[0017] In another embodiment, a system for treating pyrolysis oil is provided. In some embodiments, the system may include a first reactor including a catalyst configured to receive a pyrolysis oil feed and an aromatic; an extractor configured to receive a first reacted stream from the first reactor, wherein the first reacted stream may include linear alkylbenzenes, byproducts, unreacted compounds comprising excess aromatic, polyaromatics, and alkanes; a first separator configured to receive a first portion of an extraction feed from the extractor, wherein the extraction feed may include linear alkylbenzenes, and extractant; and a first adsorption bed configured to perform sulfolane removal to obtain purified linear alkylbenzenes.

[0018] In some embodiments, the first separator may include a distillation column.

[0019] In some embodiments of the system, the extractant may be recovered and recycled back to the extractor. In other embodiments, the extractant may be recovered in a side-draw stream from the first separator. In some embodiments, the extractant may include sulfolane.

[0020] In some embodiments, the system may further include a second adsorption bed to receive the stream comprising of alkane-rich raffinate stream, wherein the second adsorption bed is configured to perform removal of residual extractant. In some embodiments, the system may further include a second separator configured to receive the purified raffinate stream. In some embodiments, the second separator may include a distillation column. In some embodiments, the second separator may separate the stream into a light fraction and a heavy fraction.

[0021] In some embodiments, the system may further include a naphtha cracker configured to receive the light fraction from the second separator.Attorney Docket No.39425-357

[0022] In some embodiments, the system may further include a second reactor including a second catalyst configured to receive the heavy fraction from the purified alkane-rich stream. In some embodiments, the catalyst may include an acid catalyst or a zeolite. In some embodiments, the second catalyst may include a platinum group metal and a support. In some embodiments, the second catalyst may further include a promoter. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] FIG.1 illustrates a system to treat pyrolysis oil according to an embodiment. Definitions:

[0024] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0025] As used herein, “a” or “an” entity refers to one or more of that entity, e.g., “a compound” refers to one or more compounds or at least one compound unless stated otherwise. As such, the terms “a” (or “an”), “one or more”, and “at least one” are used interchangeably herein.

[0026] As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. Additionally, as used herein, “or” means “and / or.” DETAILED DESCRIPTION OF THE PRESENT DISCLOSURE

[0027] The present disclosure relates to an integrated system to produce and separate linear alkylbenzenes (LABs) from plastic pyrolysis oils, such as polyethylene waste. Pyrolysis of waste plastics generates a complex mixture of liquid hydrocarbons with a carbon member distribution. The composition of plastic pyrolysis oils varies depending on the source, but typically includes paraffins, olefins, dienes, cycloalkanes (naphthenes) and aromatics. In certain embodiments, the plastic pyrolysis oil may include about 10 wt% to about 50 wt% n- alkanes, about 10 wt% to about 50 wt% α-olefins, about 5 wt% to about 15 wt% dienes, about 0 wt% to about 20 wt% aromatics including benzene, toluene, and xylene, and about 20 wt%Attorney Docket No.39425-357 to about 40 wt% of other hydrocarbons. In some embodiments, the carbon numbers range from C6to C36, C12to C30, or C18to C24.

[0028] In some embodiments, a method is provided for treating pyrolysis oil. The method includes feeding pyrolysis oil and an aromatic to a first reactor including a catalyst. The method further includes performing an alkylation reaction in the first reactor to obtain linear alkylbenzenes (LABs), byproducts and unreacted compounds. In some embodiments, the unreacted compounds may include excess aromatic, alkanes, and unreacted olefins. The amount of unreacted olefins present depends on the components of the pyrolysis oil in the feed, reaction temperature, amount of catalyst, nature of catalyst, and the residence time in the reactor. In some embodiments, the aromatic may include benzene, toluene, xylene, or a combination thereof.

[0029] The method further includes feeding the LABs, the byproducts and the unreacted compounds to an extractor. The method also includes extracting the LABs and the excess aromatic from the unreacted compounds and feeding them to a separator, then separating the LABs from the excess aromatic and an extractant.

[0030] In some embodiments, the extractant may be sulfolane.

[0031] In some embodiments, the separator may be a distillation column. In some embodiments, the distillation column may have a side-draw, which may be used for removing an extractant-rich phase, with the excess aromatics being removed as distillate product and the linear alkylbenzenes separated out as the bottoms product.

[0032] In some embodiments, the separator may be a distillation column. In some embodiments, the distillation column may have a side-draw, which may be used for removing the linear alkylbenzenes, with the excess aromatics being removed as distillate product and the extractant-rich phase being separated out as the bottoms product.

[0033] In some embodiments, the separator may include 2 or more distillation columns.

[0034] In some embodiments, the method may further include performing a sulfolane removal process on the LABs to purify the LABs using an adsorption bed.

[0035] In some embodiments, the aromatic may be benzene, toluene, xylene, or BTX (a combination of benzene, toluene and xylene) in the method and system of the present disclosure. For ease of explanation, the method or system will be described using benzene, but this is not intended to limit the same.

[0036] In some embodiments, the average molecular weight of the pyrolysis oil may be equivalent to that of n-decane. Thus, in some embodiments, the mass ratio of the pyrolysis oilAttorney Docket No.39425-357 to the catalyst of the first reactor may be about 1:0.10, about 1:0.17, about 1:0.35, about 1:0.54, or about 1:0.70.

[0037] In some embodiments, the alkylation reaction may be performed at a temperature of about 20°C to about 280°C. In some embodiments, the temperature of the alkylation reaction may be about 20°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, or about 280°C. In some embodiments, the alkylation reaction may occur for about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, or about 4 hours, or longer.

[0038] In some embodiments, the method may be operated as a continuous system.

[0039] In some embodiments, the molar ratio of total olefins in the pyrolysis oil to added benzene may be about 1:0 to about 1:15, or about 1:0, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, or about 1:13, about 1:14, about 1:15.

[0040] When the alkylation reaction is performed without excess benzene, the pyrolysis oil is converted to linear alkylbenzenes (LABs). These LABs may be formed in a reaction time of less than about 0.5 hours, where the LABs have carbon numbers from C16to C26. However, due to a combination of residence time in the reactor, side-reactions such as olefin oligomerization, polyalkylation of aromatics, and equilibrium between various compounds, which means all olefins may not get converted to LABs. In fact, the present inventors found that only a fraction of the olefins present in the pyrolysis oil alkylated the aromatic rings already present in the pyrolysis oil.

[0041] Thus, by adding excess benzene / aromatics to the reaction, the present inventors have found that a much larger amount of LABs were produced from the alkylation reaction. That is, the catalyst in combination with excess benzene was able to convert olefins in the pyrolysis oil into the desired LABs while minimizing the side-reactions. It is believed that a majority, if not all, olefins and diolefins in the pyrolysis oil may be converted to LABs. Without being limited to a theory, the excess benzene / aromatic added to the pyrolysis oil serves as both a reactant and solvent, reducing the viscosity of the pyrolysis oil while also promoting alkylation reactions over the side reactions of olefins, such as oligomerization.

[0042] In some embodiments, the catalyst may include an acid catalyst. In some embodiments, the acid catalyst may include aluminum chloride (AlCl3). In some embodiments,Attorney Docket No.39425-357 the acid catalyst may include alumina, chlorinated alumina, fluorinated alumina, sulfated alumina tungstated alumina, or a combination thereof. In some embodiments, the acid catalyst may include an aluminosilicate. The aluminosilicate may be a zeolite. In some embodiments, the acid of the acid catalyst may be a Brønsted acid or a Lewis acid. In some embodiments, the acid catalyst may include a chloroaluminate ionic liquid (AlCl3-IL), where the cation is 1- methyl-3-butylimidazolium, in a ratio of AlCl4- from 1.5 to 2, a chloroaluminate ionic liquid (AlCl3-IL), where the cation is triethylammonium, in a ratio of AlCl4- from 1.5 to 2, or Sc(III) triflate. In some other embodiments, acids such as HF, H2SO4or HCl may also be considered.

[0043] In some embodiments, the zeolite may include a naturally occurring zeolite, a synthetic zeolite, or a combination thereof. In some embodiments, the zeolite may include HY, USY, dealuminated Y, RE-Y, RE-USY, ZSM-5, ZSM-AA, IM-5, MCM-68, ZSM-57, ZSM- 23, CIT-5, ZDM-35, MCM-22, MCM-56, MCM-49, UZM-8, EMM-10, ITQ-2, ITQ-30, TNU- 9, ZSM-22, ZSM-18, EMM-26, Zeolite T, EMC-2, offretite, beta, ITQ-13, Zeolite A, Zeolite L, MCM-35, mordenite, ZSM-12, NU-87, ECR-1, EU-1, ZSM-50, Li-A, Na-Pl, Na-P2, Chabazite, SSZ-13, SAPO-34, zeolite RHO, SSZ-35, SAPO-5, ITQ-12, Stilbite, CIT-7, ITQ- 39, Linde Q, UZM-4, Natrolite, IPC-4, ZSM-48, SSZ-61, ITQ-4, ITQ-51, Mazzite, ZSM-4, SUZ-4, SSZ-48, SSZ—23, SAPO-11, SAPO-31, AIPO-18, SAPO-18, SAPO-18, SAPO-41, ITQ-7, ITQ-3, SSZ-36, MCM-58, ferrierite, Y zeolite, SAPO, or a combination thereof.

[0044] In some embodiments, the zeolite may be a large-pore zeolite, for example framework types FAU, MOR and the like. In some embodiments, the zeolite may be a small- pore zeolite, for example framework types ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CHA, CDO, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, TH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON, MFI, LTA, BEA and the like. Specific examples may be ZSM-11, MFI zeolite and MCM.

[0045] In some embodiments, the zeolite may include beta (BEA), ZSM-5, or ZSM-11.

[0046] In some embodiments, the linear alkylbenzenes may include molecules with carbon numbers from C12 to C20. In some embodiments, the LAB may be C12, C13, C14, C15, C16, C17, C18, C19, C20, or a combination thereof.

[0047] In some embodiments, the method may further include recycling the unreacted compounds and the byproducts to the first reactor after the separator, and the extractant may be recycled back to the extractor unit.

[0048] In some embodiments, the method may further include feeding the stream rich in linear alkylbenzenes from the separator to an adsorption bed. In some embodiments, theAttorney Docket No.39425-357 adsorption bed may remove sulfolane from the linear alkylbenzenes to obtain a purified stream of linear alkylbenzenes. In some embodiments, the purified stream may have low-sulfur content. As understood herein, “low-sulfur” refers to a stream including sulfur in an amount of less than about 100 ppm, less than about 50 ppm, less than about 25 ppm, or less than about 10 ppm.

[0049] In some embodiments, the method may further include a raffinate stream from the extractor. In some embodiments, the raffinate stream may be alkane-rich. In some embodiments, the method may further include feeding the alkane-rich raffinate stream containing some unreacted compounds and byproducts from the extractor to an adsorption bed. In some embodiments, the adsorption bed may remove sulfolane from the alkane-rich stream to obtain a low-sulfur stream. As understood herein, the extraction process produces an extract stream comprising a solvent and extractants, and a raffinate stream comprising other residual compounds, such as unreacted compounds and byproducts.

[0050] In some embodiments, the method may further include feeding the purified stream having low-sulfur content to a second separator and separating it into a heavy fraction and a light fraction. In some embodiments the heavy fraction may include compounds including more than 16 carbon atoms, and / or may be a distillation cut with normal boiling range above about 400°F to at most about 500°F. In some embodiments the light fraction may include compounds having less than 16 carbon atoms, and / or may have normal boiling range below about 400°F. In some embodiments, the second separator may be a distillation column as described herein. In some embodiments, the method may further include feeding the light fraction alkane-rich stream to a naphtha or diesel cracker. In some embodiments, the light fraction alkane-rich stream may include low boiling alkanes and byproducts. As used herein, the low boiling alkanes refer to having less than 16 carbon atoms or less than 24 carbon atoms.

[0051] In some embodiments, the heavy fraction stream may be fed to a second reactor, wherein cracking, aromatization, or a combination thereof may be performed to obtain alkylbenzenes, alkanes and alkenes with average chain length shorter than the average chain length in the feed. In some embodiments, the heavy fraction stream may include linear alkylbenzenes and high boilings including alkanes and other compounds. As used herein, the high boilings refer to a mixture of compounds which gives a normal boiling range largely above about 400°F or about 500°F. In some embodiments, the product stream containing alkylbenzenes, alkanes and alkenes may be fed to the extractor after the first reactor.Attorney Docket No.39425-357

[0052] In some embodiments, the second reactor may include an inert gas, or moderate pressure of H2. In some embodiments, the pressure of H2may be about 1 bar, about 2 bar, about 3 bar, about 4 bar, or about 5 bar.

[0053] In some embodiments, the second reactor may include a second catalyst. In some embodiments, the second catalyst may include a platinum group metal and a support. In some embodiments, the platinum group metal and the support may be in a matrix.

[0054] In some embodiments, the platinum group metal may include platinum (Pt), ruthenium (Ru), iridium (Ir), palladium (Pd), rhodium (Rh), or a combination thereof. In some embodiments, the platinum group metal may be included in an amount of about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, or about 1 wt% to about 3 wt%.

[0055] In some embodiments, the support may include alumina, chlorinated alumina, fluorinated alumina, sulfated alumina, tungstated alumina, or a combination thereof. In some embodiments, the support may include aluminosilicate, silicoaluminophosphate, silica, silica- alumina, a zeolite, or combinations thereof. In some embodiments, the support may include aluminosilicate. In some embodiments, the aluminosilicate may be a zeolite.

[0056] In some embodiments, the zeolite may include a naturally occurring zeolite, a synthetic zeolite, or a combination thereof. In some embodiments, the zeolite may include HY, USY, dealuminated Y, RE-Y, RE-USY, ZSM-5, ZSM-AA, IM-5, MCM-68, ZSM-57, ZSM- 23, CIT-5, ZDM-35, MCM-22, MCM-56, MCM-49, UZM-8, EMM-10, ITQ-2, ITQ-30, TNU- 9, ZSM-22, ZSM-18, EMM-26, Zeolite T, EMC-2, offretite, beta, ITQ-13, Zeolite A, Zeolite L, MCM-35, mordenite, ZSM-12, NU-87, ECR-1, EU-1, ZSM-50, Li-A, Na-Pl, Na-P2, SAPO- 34, zeolite RHO, SSZ-35, SAPO-5, ITQ-12, Stilbite, CIT-7, ITQ-39, Linde Q, UZM-4, Natrolite, IPC-4, ZSM-48, SSZ-61, ITQ-4, ITQ-51, Mazzite, ZSM-4, SUZ-4, SSZ-48, SSZ— 23, SAPO-11, SAPO-31, AIPO-18, SAPO-18, SAPO-18, SAPO-41, ITQ-7, ITQ-3, SSZ-36, MCM-58, ferrierite, Y zeolite, SAPO, or a combination thereof.

[0057] In some embodiments, the zeolite may be a large pore zeolite, for example framework types FAU, MOR and the like. In some embodiments, the zeolite may be a small pore zeolite, for example framework types ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CHA, CDO, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, TH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON, MFI, LTA, BEA and the like. Specific examples may be ZSM-11, MFI zeolite and MCM.

[0058] In some embodiments, the second catalyst may further include doping the support with a rare earth metal. In some embodiments, the rare earth metal may include scandium (Sc),Attorney Docket No.39425-357 lanthanum (La), neodymium (Nd), ytterbium (Yb), gadolinium (Gd), yttrium (Y), cerium (Ce), or a combination thereof.

[0059] In some embodiments, the second catalyst may further include a promoter. In some embodiments, the promoter may include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), vanadium (V), manganese (Mn), molybdenum (Mo), chromium (Cr), tin (Sn), tungsten (W), indium (In), silver (Ag), zirconium (Zr), or a combination thereof.

[0060] In some embodiments, the second reactor may be operated at a temperature of about 200°C to about 350°C. In some embodiments, the second reactor may be operated at a temperature of about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, or about 350°C.

[0061] In some embodiments, the method may further include performing a sulfolane removal process in a second adsorption bed on the linear alkylbenzenes to purify the linear alkylbenzenes. In some embodiments, linear alkylbenzenes may be purified before using them for any suitable applications, such as sulfonation for making surfactants and detergents.

[0062] In some embodiments, the LABs present after the alkylation reaction may be separated by liquid-liquid extraction. In some embodiments, the liquid-liquid extraction may include sulfolane to selectively dissolve aromatics. In some embodiments, the LAB and aromatic-rich phase may be separated and distilled to recycle the excess benzene and recover the LAB products. The LAB products may be separated as bottoms product, and an extractant- rich phase may be obtained via a side-draw, and recycled back to the extractor. In some embodiments, the LAB products may be obtained as a side-draw product from a distillation column while the extractant may be obtained as the bottoms product. In some embodiments, the LABs may be further purified by passing them over an adsorbent to remove additional sulfolane extractant so that the product has low sulfur content, such as low sulfolane, and can subsequently be sulfonated to form linear alkylbenzene sulfonates.

[0063] In some embodiments, the mixture that is rich in alkanes and not extracted into the solvent in the extractor may be collected. In some embodiments, if the normal boiling point range for vaporizing > 95% by weight is less than about 400°F, or about 500°F, or about 600°F, this stream may be passed over an adsorbent to produce a low-sulfur product that may be fed to a naphtha cracker for further processing to chemical feedstocks such as olefins and aromatics.

[0064] In another embodiment, a system for treating pyrolysis oil is provided. The system includes a first reactor including a catalyst. The first reactor may be configured to receive aAttorney Docket No.39425-357 pyrolysis oil feed and an aromatic. An alkylation reaction as described above may be performed in the first reactor. The system further includes an extractor that is configured to receive a first reacted stream from the first reactor. The first reacted stream may include linear alkylbenzenes, alkanes, byproducts, and unreacted compounds including excess aromatic, alkanes and unreacted olefins. The system further includes a first separator that is configured to receive a first portion of an extraction feed from the extractor. The extraction feed may include linear alkylbenzenes and excess aromatic. The system may further include a first adsorption bed configured to perform sulfolane removal to obtain purified linear alkylbenzenes.

[0065] In some embodiments, the first separator may include a distillation column.

[0066] In some embodiments, the first separator may be a distillation column or may including a plurality of distillation columns. In some embodiments, the first separator may include a plurality of distillation equipment including at least two distillation columns. In some embodiments, the first separator may be configured to effectively separate into at least 3 streams, a light aromatic stream including a majority of molecules containing less than 10 carbon atoms, an extractant-rich stream, and a LAB-rich stream including a majority of compounds having more than 10 carbon atoms.

[0067] In some embodiments, the system may further include a second adsorption bed to receive a raffinate stream from the extractor. The second adsorption bed may be configured to perform sulfolane removal to obtain a purified stream.

[0068] In some embodiments, the system may further include a second separator configured to receive the purified stream. The second separator may include a distillation column. In some embodiments, the second separator may separate the purified stream into a lighter fraction and a heavier fraction. The lighter fraction refers to a stream such that at least about 95 wt% of the product boils at temperatures of up to about 400°F, or up to about 500°F, while the heavier fraction may include the remainder of the alkane stream.

[0069] In some embodiments, the system may include a naphtha cracker configured to receive the light fraction the second separator. In some embodiments, the system may further include a second reactor configured to receive the heavier fraction from the second separator. The second reactor may include a second catalyst.

[0070] In some embodiments, the catalyst of the first reactor may include an acid catalyst. In some embodiments, the acid catalyst may be aluminum chloride (AlCl3). In some embodiments, the acid catalyst may be an aluminosilicate. In some embodiments, the aluminosilicate may be a zeolite. In some embodiments, the acid catalyst may includeAttorney Docket No.39425-357 anhydrous AlCl3, imidazolium-based chloroaluminate ionic liquids (AlCl3-IL), trialkylammonium chloroaluminate ionic liquid (AlCl3-IL), or Sc(III) triflate.

[0071] In some embodiments, the second catalyst of the second reactor may include a platinum group metal and a support. In some embodiments, the platinum group metal and the support may be in a matrix.

[0072] In some embodiments, the platinum group metal may include platinum (Pt), ruthenium (Ru), iridium (Ir), palladium (Pd), rhodium (Rh), or a combination thereof. In some embodiments, the platinum group metal may be included in an amount of about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%, or about 1 wt% to about 3 wt%.

[0073] In some embodiments, the support may include alumina, or chlorinated alumina, fluorinated alumina, sulfated alumina, tungstated alumina, or a combination thereof. In some embodiments, the support may include aluminosilicate, silicoaluminophosphate, silica, silica- alumina, a zeolite, or combinations thereof. In some embodiments, the support may include aluminosilicate. In some embodiments, the aluminosilicate may be a zeolite.

[0074] In some embodiments, the zeolite may include a naturally occurring zeolite, a synthetic zeolite, or a combination thereof. In some embodiments, the zeolite may include HY, USY, dealuminated Y, RE-Y, RE-USY, ZSM-5, ZSM-AA, IM-5, MCM-68, ZSM-57, ZSM- 23, CIT-5, ZDM-35, MCM-22, MCM-56, MCM-49, UZM-8, EMM-10, ITQ-2, ITQ-30, TNU- 9, ZSM-22, ZSM-18, EMM-26, Zeolite T, EMC-2, offretite, beta, ITQ-13, Zeolite A, Zeolite L, MCM-35, mordenite, ZSM-12, NU-87, ECR-1, EU-1, ZSM-50, Li-A, Na-Pl, Na-P2, SAPO- 34, zeolite RHO, SSZ-35, SAPO-5, ITQ-12, Stilbite, CIT-7, ITQ-39, Linde Q, UZM-4, Natrolite, IPC-4, ZSM-48, SSZ-61, ITQ-4, ITQ-51, Mazzite, ZSM-4, SUZ-4, SSZ-48, SSZ— 23, SAPO-11, SAPO-31, AIPO-18, SAPO-18, SAPO-18, SAPO-41, ITQ-7, ITQ-3, SSZ-36, MCM-58, ferrierite, Y zeolite, SAPO, or a combination thereof.

[0075] In some embodiments, the zeolite may be a large-pore zeolite, for example framework types - FAU, MOR and the like. In some embodiments, the zeolite may be a small pore zeolite, for example 8-10 membered rings include framework types ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, CDO, DDR, DFT, EAB, EDI, EPI, ERI, GIS, GOO, IHW, ITE, ITW, LEV, KFI, MER, MON, NSI, OWE, PAU, PHI, RHO, TH, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG, ZON, MFI, LTA, BEA and the like. Specific examples may be ZSM-11, MFI zeolite and MCM.

[0076] In some embodiments, the second catalyst may further include doping the support with a rare earth metal. In some embodiments, the rare earth metal may include scandium (Sc),Attorney Docket No.39425-357 lanthanum (La), neodymium (Nd), ytterbium (Yb), gadolinium (Gd), yttrium (Y), cerium (Ce), or a combination thereof.

[0077] In some embodiments, the second catalyst may further include a promoter. In some embodiments, the promoter may include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), vanadium (V), manganese (Mn), molybdenum (Mo), chromium (Cr), tin (Sn), tungsten (W), indium (In), silver (Ag), zirconium (Zr), or a combination thereof.

[0078] Referring now to the Figure, the system 100 according to an embodiment of the present disclosure is provided. Not all the streams in the process are shown on the process flow diagram. For e.g., in some embodiments, catalytic reactions produce some components that are difficult to condense in condensers of distillation columns and may be vented or recovered using additional refrigeration loops. Some such gaseous streams are not shown. Similarly, the process may include heat exchangers, pumps, compressors, storage vessels, and other ancillary equipment but these are not shown in the Figure. Excluding such streams and process equipment, the system includes a first reactor 105. The first reactor 105 includes a catalyst. In some embodiments, the first reactor 105 may be a fixed bed reactor. In some embodiments, the catalyst in the first reactor 105 may be an acid catalyst, as described above. The system includes feeding a pyrolysis oil and excess aromatic to the first reactor 105. The first reactor 105 performs an alkylation reaction, which may occur at a temperature of about 20°C to about 280°C. In some embodiments, the temperature of the alkylation reaction may be about 20°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, about 150°C, about 160°C, about 170°C, about 180°C, about 190°C, about 200°C, about 210°C, about 220°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, or about 280°C.

[0079] The alkylation reaction produces linear alkylbenzenes, byproducts and unreacted compounds including excess aromatic, alkanes and unreacted olefins, which are fed to an extractor 110. The extractor 110 is configured to extract the linear alkylbenzenes and the excess aromatic from the stream. The extracted linear alkylbenzenes and the unwanted compounds including the excess aromatics are then fed to a separator 115. The separator 115 may be a distillation column. In the separator 115, the linear alkylbenzenes are separated to the bottom of the distillation column and then flow to a first adsorption bed 120. In the first adsorption bed 120, the linear alkylbenzenes are flowed through to remove traces of sulfolane and produce a purified stream. In the separator 115, the excess aromatics and other unreacted compounds are separated to the top of the column and are recycled to the first separator 105.Attorney Docket No.39425-357 The separator 115 may also have a side draw, where an extractant-rich stream may be obtained and sent back to the extractor110 (material stream shown with dashed line).

[0080] As can be seen in the Figure, a stream from the extractor is fed to a second adsorption bed 125. This stream is a mixture of components that are not extracted by the extractant and is referred to as the raffinate. This raffinate stream may be lean (for example, less than 10%) in aromatics and is alkane-rich. The second adsorption bed 125 is configured to remove any sulfolane from the alkane-rich stream and to produce a purified stream. The purified stream is then fed to a second separator 130. The second separator 130 may be a distillation column. In some embodiments, the light fractions as described herein may be separated through the top of the distillation column 130 and may be fed to a naphtha cracker (not pictured). The second separator 130 may also produce a heavy alkane-rich stream which may also contain unwanted products as a bottom product. This is fed to a second reactor 135. The second reactor may include a second catalyst as described herein. The second catalyst may include a platinum group metal and a support as described herein. In some embodiments, the platinum group metal and the support may be in a matrix.

[0081] In some embodiments, the reaction of the second reactor 135 may include cracking, aromatization, or a combination thereof to obtain alkylbenzenes, short-chain alkanes, and alkenes. The obtained stream of alkylbenzenes, short-chain alkanes, and alkenes may then be formed to the extractor 110.

[0082] Claims or descriptions that include “or” or “and / or” between at least one members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The disclosure includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The disclosure includes embodiments in which more than one, or all the group members are present in, employed in, or otherwise relevant to a given product or process.

[0083] Furthermore, the disclosure encompasses all variations, combinations, and permutations in which at least one limitation, element, clause, and descriptive term from at least one of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include at least one limitation found in any other claim that is dependent on the same base claim. Where elements are presented as lists, such as, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should be understood that, in general, whereAttorney Docket No.39425-357 the disclosure, or aspects of the disclosure, is / are referred to as comprising particular elements and / or features, embodiments of the disclosure or aspects of the disclosure consist, or consist essentially of, such elements and / or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. Where ranges are given (such as, e.g., from [X] to [Y]), endpoints (such as, e.g., [X] and [Y] in the phrase “from [X] to [Y]”) are included unless otherwise indicated. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the disclosure, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0084] Those of ordinary skill in the art will recognize or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein. Such equivalents are intended to be encompassed by the following claims. EXAMPLES

[0085] The following examples are intended to be illustrative and are not meant in any way to limit the scope of the disclosure.

[0086] Tests were conducted to analyze pyrolysis oil feeds, catalytic alkylation (Example 1-7). Catalytic cracking-aromatization (Example 8-15) of the pyrolysis oils was conducted separately. Pyrolysis Oil Feed

[0087] Three pyrolysis oils were used in the present tests, each having a varying number of components.

[0088] Pyrolysis oil No.1 included approximately 15 wt% n-alkanes, 37 wt% α-olefins, 8 wt% dienes, 13 wt% aromatics (mostly benzene, toluene, xylenes and ethylbenzene), and 28 wt% of other hydrocarbons (iso-alkanes, cycloalkanes, etc.). The carbon numbers ranged from C5 to C35, with most components being in the range of C6 to C20.

[0089] Pyrolysis oil No.2 included approximately 21 wt% n-alkanes, 41 wt% α-olefins, 9 wt% dienes, 0.2 wt% aromatics, and 28 wt% of other hydrocarbons (iso-alkanes, cycloalkanes, etc.). The carbon numbers ranged from C5to C30, with most components being in the range of C6 to C20.

[0090] Pyrolysis oil No.3 included approximately 34 wt% n-alkanes, 16 wt% α-olefins, 5 wt% dienes, 0.4 wt% aromatics, and 44 wt% of other hydrocarbons (iso-alkanes, cycloalkanes,Attorney Docket No.39425-357 etc.). The carbon numbers ranged from C5 to C32, with most components being in the range of C11to C30. Example 1

[0091] Catalytic alkylation of pyrolysis oil No.1 was tested with anhydrous AlCl3as catalyst at 25 °C, in a batch reactor under N2 atmosphere.

[0092] A test was conducted in which the pyrolysis oil was mixed with excess benzene. The molar ratio of benzene to the olefins in the pyrolysis oil was approximately 5, and the molar ratio of AlCl3 to the olefins in the pyrolysis oil was approximately 0.65.

[0093] After allowing the reaction to proceed for 2 hours, LABs were confirmed to be present. Compositional analysis was performed which showed that the products contained 28 wt% LABs, 30 wt% n-alkanes, 16% aromatics (toluene, xylenes, ethylbenzene), and 26 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil were converted to LABs.

[0094] Structure analysis indicated that the LABs were a mixture of 2-phenylalkanes, 3- phenylalkanes, 4-phenylalkanes, 5-phenylalkanes, etc., with a range of chain lengths. The carbon numbers of the LABs range from C11 to C30.

[0095] Specifically, LAB isomers accounted for approximately 71 wt%, 67 wt%, and 66 wt% of the C16, C17, and C18 products. Among them, the molar ratio of 2-phenylalkanes : 3- phenylalkanes : 4-phenylalkanes : 5-phenylalkanes was approximately 100 : 57 : 47 : 39.

[0096] When the molar ratio of benzene to olefins in the pyrolysis oil was approximately 2.5, the products contained 22 wt% LABs, 33 wt% n-alkanes, 14% aromatics (toluene, xylenes, ethylbenzene), and 30 wt% other hydrocarbons, not including benzene.

[0097] When the molar ratio of benzene to the olefins in the pyrolysis oil was approximately 10, the products contained 30 wt% LABs, 32 wt% n-alkanes, 13% aromatics (toluene, xylenes, ethylbenzene), and 26 wt% other hydrocarbons, not including benzene.

[0098] When the molar ratio of benzene to the olefins in the pyrolysis oil was approximately 15, the products contained 35 wt% LABs, 28 wt% n-alkanes, 13% aromatics (toluene, xylenes, ethylbenzene), and 23 wt% other hydrocarbons, not including benzene.

[0099] The similar yield of LABs was achieved when anhydrous AlCl3 was replaced by a chloroaluminate ionic liquid (AlCl3-IL), where the cation was 1-methyl-3-butylimidazolium or triethylammonium.Attorney Docket No.39425-357 Comparative Example 2 [000100] Catalytic alkylation of pyrolysis oil No.1 was tested with anhydrous AlCl3as catalyst at 25 °C, where the reaction took place in a batch reactor under N2 atmosphere under the same conditions as Example 1. [000101] The test was conducted without added benzene, with a molar ratio of AlCl3 to olefins in the pyrolysis oil of approximately 0.65. The molar ratio of aromatics to olefins in the pyrolysis oil No.1 was estimated to be roughly 0.3 : 1. [000102] LABs were formed due to alkylation of aromatics present in the pyrolysis oil by olefins also present in the pyrolysis oil, but side-reactions like olefin oligomerization, polyalkylation of aromatics, etc. occurred simultaneously, as evidenced by a shift in the molecular weight distribution to higher values. This observation confirms the value of using excess aromatic in the feed. Example 3 [000103] Catalytic alkylation of pyrolysis oil No.2 was tested with anhydrous AlCl3 as catalyst at 25 °C, where the reaction took place in a batch reactor under N2 atmosphere and the same reaction conditions as Example 1. [000104] The test was conducted in which the pyrolysis oil was mixed with excess benzene, the molar ratio of benzene to the olefins in the feeding pyrolysis oils was approximately 10, the molar ratio of AlCl3 to the olefins in the feeding pyrolysis oils was approximately 0.65. [000105] After performing the reaction, a large number of LABs were produced. Composition analysis showed that the products contained 42 wt% LABs, 42 wt% n-alkanes, and 16 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil had been converted to LABs. [000106] Structure analysis indicated that LABs are isomers mixture of 2-phenylalkanes, 3- phenylalkanes, 4-phenylalkanes, 5-phenylalkanes, etc. with a range of chain lengths.. The total carbon numbers of LABs are from C12 to C30. [000107] Specifically, LAB isomers accounted for approximately 65 wt%, 59 wt%, and 63 wt% of the C16, C17, and C18 products. Among them, the molar ratio of 2-phenylalkanes : 3- phenylalkanes : 4-phenylalkanes : 5-phenylalkanes is approximately 100 : 61 : 49 : 42. [000108] If the molar ratio of benzene to the olefins in the feeding pyrolysis oils was be approximately 2.5, the products contained 28 wt% LABs, 53% wt% n-alkanes, and 19 wt% other hydrocarbons, not including benzene.Attorney Docket No.39425-357 [000109] If the molar ratio of benzene to the olefins in the feeding pyrolysis oils was be approximately 5, the products contained 36 wt% LABs, 47 wt% n-alkanes, and 17 wt% other hydrocarbons, not including benzene. [000110] If the molar ratio of benzene to the olefins in the feeding pyrolysis oils was be approximately 15, the products contained 42 wt% LABs, 40 wt% n-alkanes, and 18 wt% other hydrocarbons, not including benzene. Example 4 [000111] Catalytic alkylation of pyrolysis oil No.2 was tested with anhydrous AlCl3 as catalyst at 25 °C, where the reaction took place in a batch reactor under N2atmosphere. [000112] The test was conducted in which the pyrolysis oil was mixed with excess benzene, the molar ratio of benzene to the olefins in the feeding pyrolysis oils was approximately 10, the molar ratio of AlCl3 to the olefins in the feeding pyrolysis oils was approximately 0.65. [000113] After reaction of 0.5 h, composition analysis shows that the products contain 34 wt% LABs, 47 wt% n-alkanes, and 19 wt% other hydrocarbons, not including benzene. [000114] After reaction of 1 h, composition analysis shows that the products contain 37 wt% LABs, 45 wt% n-alkanes, and 19 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil had been converted to LABs. [000115] After reaction of 4 h, composition analysis showed that the products contain 39 wt% LABs, 45 wt% n-alkanes, and 17 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil had been converted to LABs. [000116] Structure analysis supported that LABs are isomers mixture of 2-phenylalkanes, 3- phenylalkanes, 4-phenylalkanes, 5-phenylalkanes, etc. with a range of chain lengths. The total carbon numbers of LABs are from C12 to C30. Example 5 [000117] Catalytic alkylation of pyrolysis oil No.2 was tested with anhydrous AlCl3as catalyst at 25 °C, where the reaction took place in a batch reactor under N2 atmosphere. [000118] The test was conducted in which the pyrolysis oil was mixed with excess benzene, the molar ratio of benzene to the olefins in the feeding pyrolysis oils was approximately 10. The reaction time were 2 h.Attorney Docket No.39425-357 [000119] When the molar ratio of AlCl3 to the olefins in the feeding pyrolysis oils was approximately 0.33, composition analysis shows that the products contain 37 wt% LABs, 45 wt% n-alkanes, and 18 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil had been converted to LABs. [000120] When the molar ratio of AlCl3to the olefins in the feeding pyrolysis oils was approximately 0.65, composition analysis shows that the products contain 42 wt% LABs, 42 wt% n-alkanes, and 16 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil had been converted to LABs. [000121] When the molar ratio of AlCl3 to the olefins in the feeding pyrolysis oils was approximately 1.3, composition analysis shows that the products contain 37 wt% LABs, 44 wt% n-alkanes, and 20 wt% other hydrocarbons, not including benzene. Olefins and diolefins were undetectable, indicating that all olefins and diolefins in the pyrolysis oil had been converted to LABs. [000122] Structure analysis indicated that LABs are isomers mixture of 2-phenylalkanes, 3- phenylalkanes, 4-phenylalkanes, 5-phenylalkanes, etc. with a range of chain lengths. The total carbon numbers of LABs are from C12 to C30. Example 6 [000123] Catalytic alkylation of pyrolysis oil No.2 was tested with anhydrous AlCl3as catalyst at 25 °C, where the reaction was run in a batch reactor under N2 atmosphere. [000124] The test was conducted in which the pyrolysis oil was mixed with excess aromatic, the molar ratio of aromatic to the olefins in the feeding pyrolysis oils was approximately 10. The reaction time were 2 h. The molar ratio of AlCl3to the olefins in the feeding pyrolysis oils was approximately 0.65. [000125] When the added aromatic was toluene, composition analysis showed that the products contain 55 wt% LABs, 35 wt% n-alkanes, and 10 wt% other hydrocarbons, not including toluene. The total carbon numbers of LABs are from C13to C31. [000126] When the added aromatic was xylenes, composition analysis shows that the products contain 65 wt% LABs, 24 wt% n-alkanes, and 11 wt% other hydrocarbons, not including xylenes. The total carbon numbers of LABs are from C14 to C32. Example 7Attorney Docket No.39425-357 [000127] Catalytic alkylation of pyrolysis oil No.2 was tested with chlorinated Al2O3 as catalyst at 150 °C for 1 hour, in a 10 mL autoclave reactor under N2atmosphere. The chlorine content of the catalyst was approx.5 wt%. [000128] In the test, the pyrolysis oil No.2 was mixed with excess benzene, for a molar ratio of benzene to the olefins in the pyrolysis oil of approximately 5. The molar ratio of Al2O3 to olefins in the pyrolysis oil was approximately 1.3. [000129] Product analysis showed that approximately 10 wt% of the olefins were converted into LABs, and significant isomerization of the α-olefins occurred, leading to various internal olefin isomers. [000130] The present example supports that the chlorinated Al2O3as catalyst was successful in an alkylation reaction. Example 8 [000131] Catalytic cracking-aromatization of pyrolysis oil No.1 was tested with a Pt / γ-Al2O3catalyst, in a 10 mL autoclave reactor under 1 bar Ar. Pt loading on γ-Al2O3 is 1.5wt% and Pt dispersion is about 80%. The mass ratio of Pt metal to pyrolysis oil No.1 was approximately 1 : 40.120 mg pyrolysis oil No.1 was loaded. [000132] At 280 °C, after reaction times of 1 h, 6 h, and 12 h, the reactor contained H2 at pressures of 4, 53 and 83 mbar, respectively. The products showed a carbon number distribution ranging from C1 to C36, centered at C8. α-Olefins and dienes were completely hydrogenated after 6 h, with liquid n-alkanes and iso-alkanes representing ~50 wt% and ~30 wt%, respectively, of the products. Compared to the original pyrolysis oil, the amount of aromatic compounds with carbon numbers less than C10in the liquid products did not change significantly, remaining at approximately 13 wt%. However, GC-MS revealed the formation of long-chain alkylaromatics (with total carbon numbers up to C24). [000133] At 572 °F, after reaction times of 1 h and 6 h, the measured H2 pressures were 5 mbar and 233 mbar, respectively. Similar to the reaction at 536 °F, the hydrocarbon products showed a broad carbon number distribution ranging from C1 to C30: α-olefins and dienes were hydrogenated in less than 1 h, giving n-alkanes and iso-alkanes at approximately 50 wt% and 30 wt% of the products, respectively. After a reaction time of 6 h, the content of light aromatics (Cn<10), 17 wt%, in the liquid products was higher at 300 °C than at 280 °C (13 wt%), but GC- MS analysis showed that long chain alkylbenzenes (up to C24) were formed at both temperatures.Attorney Docket No.39425-357 Example 9 [000134] Catalytic cracking-aromatization of pyrolysis oil No.1 was tested with a Pt / SiO2- Al2O3catalyst, with a Si / Al molar ratio of of 5.1. Pt loading is 1.5wt% and Pt dispersion is about 65%. The reaction was conducted in a 10 mL autoclave reactor under 1 bar Ar. The mass ratio of Pt metal to pyrolysis oil No. 1 was approximately 1 : 40. 120 mg pyrolysis oil No. 1 was loaded. [000135] The Pt / SiO2-Al2O3catalyst exhibited higher overall activity than the Pt / γ-Al2O3catalyst. At 280 °C, more gaseous hydrocarbon products (<C7) were generated, and H2 pressures were 595, 872 and 902 mbar after reaction times of 1 h, 6 h, and 12 h, respectively. α-olefins and dienes were completely hydrogenated after 1 h, while liquid n-alkanes and iso- alkanes accounted for ~30 wt% and ~45 wt% of , respectively. The increased yield of iso- alkanes is attributed to the stronger acidity of SiO2-Al2O3, compared to γ-Al2O3. Additionally, GC-MS analysis revealed the presence of alkylaromatics (total carbon numbers up to C13). [000136] At 300 °C, the final H2 pressures were 730 and 1100 mbar after reaction times of 1 h and 6 h, respectively. n-alkanes accounted for ~30 wt% and iso-alkanes accounted for ~50 wt% in liquid products. Again, GC-MS analysis revealed the presence of alkylbenzenes (up to C13). Example 10 [000137] Catalytic cracking-aromatization of pyrolysis oil No.2 was tested with Pt / γ-Al2O3catalyst, where the reaction was run in a 10 ml autoclave reactor under 1 bar Ar. Pt loading on γ-Al2O3is 1.5wt% and Pt dispersion is about 80%. The mass ratio of Pt metal to pyrolysis oil No.2 was approximately 1 : 40.120 mg pyrolysis oil No.2 was loaded. [000138] At 280 °C, the H2 pressures that developed in the reactor were 0.6 and 57 mbar after 1 and 6 h, respectively. The products showed a distribution from C1to C30. α-olefins and dienes were gradually converted, leaving residual total amounts (α-olefins + dienes) of 77 wt% (after 1 h) and 0 wt% (after 6 h). In the liquid phase, n-alkanes and iso-alkanes accounted for 70 and 25 wt%, respectively, after 6 h. The molar selectivity to alkylaromatics in the liquid products was estimated to be ~10 mol%, the long-chain alkylbenzenes own total carbon numbers up to C24. [000139] At 300 °C, the H2 pressures that developed in the reactor were 5.0 mbar after 1 h, the liquid products consisted of 61 wt% n-alkanes and 38 wt% iso-alkanes / other hydrocarbonAttorney Docket No.39425-357 species. 78 wt% of total products are liquid, the C8-C14 range species accounted for 50 wt% and alkylbenzene yield was 14 wt%. Example 11 [000140] Catalytic cracking-aromatization of pyrolysis oil No.2 was tested with Pt / SiO2- Al2O3catalyst, with molar ratio of Si / Al to be 5.1, where the reaction was run in a 10 ml autoclave reactor under 1 bar Ar. Pt loading on SiO2-Al2O3 is 1.5wt% and Pt dispersion is about 65%. The mass ratio of Pt metal to pyrolysis oil No. 2 was approximately 1 : 40. 120 mg pyrolysis oil No.2 was loaded. [000141] At 280 °C, the H2pressures that developed in the reactor were 870 mbar (after 1 h) and 1100 mbar (after 6 h). The average carbon number of the products decreased to C7. No α- olefins and dienes were detected in each case, while n-alkanes accounted for ~38 wt% of the liquid products after 6 h. The molar selectivity to alkylaromatics in the liquid products was estimated to be ~10 mol%. [000142] At 300 °C, the H2 pressures that developed in the reactor were 870 mbar after 1 h, the yield of liquid products was 79 wt%, which consisted of 38 wt% n-alkanes and 62 wt% iso- alkanes / other hydrocarbon species. Among them, species in the C8-C14 range accounted for 53 wt% and alkylbenzene yield was 13 wt%. Example 12 [000143] Catalytic cracking-aromatization of pyrolysis oil No.2 was tested with Pt / SiO2- Al2O3 catalyst, with molar ratio of Si / Al to be 6.7, where the reaction was run in a 10 ml autoclave reactor under 1 bar Ar. Pt loading on SiO2-Al2O3is 1.5wt% and Pt dispersion is about 65%. The mass ratio of Pt metal to pyrolysis oil No. 2 was approximately 1 : 160. 240 mg pyrolysis oil No.2 was loaded. [000144] At 300 °C, the H2 pressures that developed in the reactor were 237 mbar after 1 h, the average weight of the products decreased to C10. 80 wt% of total products were liquid, of which species in the C8-C14 range accounted for 59 wt% and alkylbenzene yield was 15 wt% by mass. Example 13 [000145] Catalytic cracking-aromatization of pyrolysis oil No.3 was tested with Pt / γ-Al2O3 catalyst, where the reaction was run in a 10 ml autoclave reactor under 1 bar Ar. Pt loading on

Claims

Attorney Docket No.39425-357 [000153] By Pt / SiO2-Al2O3 catalyst with Pt loading of 1.5 wt% and dispersion of 65%, with molar ratio of Si / Al to be 6.7, the H2partial pressures was 1941 mbar, the mass content of C8- C14 hydrocarbons was 43.0 wt%, the yield of alkylbenzenes in the liquid products was 7.3 wt%, the selectivity of alkylbenzenes in total alkylaromatics was 49 mol%.Attorney Docket No.39425-357 What is claimed is:

1. A method for treating pyrolysis oil comprising: feeding pyrolysis oil and an aromatic to a first reactor comprising a catalyst, wherein the pyrolysis oil comprises olefins and dienes; performing an alkylation reaction in the first reactor to obtain linear alkylbenzenes, byproducts, and unreacted compounds, wherein the unreacted compounds comprise excess aromatic, polyaromatics, alkanes and unreacted olefins and dienes; feeding the linear alkylbenzenes, the byproducts and the unreacted compounds to an extractor; extracting the linear alkylbenzenes and the excess aromatic and feeding them to a separator; separating the linear alkylbenzenes from the excess aromatic, and an extractant- rich stream; and recycling the extractant-rich stream to the extractor.

2. The method of claim 1, wherein the catalyst comprises an acid catalyst.

3. The method of claim 2, wherein the acid catalyst comprises aluminum chloride (AlCl3).

4. The method of claim 2, wherein the acid catalyst comprises aluminosilicate.

5. The method of claim 2, wherein the acid catalyst comprises a zeolite.

6. The method of claim 5, wherein the zeolite comprises beta (BEA), ZSM-5, or ZSM-11.

7. The method of any of the preceding claims, wherein the alkylation reaction is performed at a temperature of about 20°C to about 280°C.

8. The method of any one of the preceding claims, wherein the linear alkylbenzenes comprise carbon numbers from C12 to C30.Attorney Docket No.39425-357 9. The method of claim 1, further comprising after the separator, recycling the unreacted compounds and byproducts to the first reactor.

10. The method of claim 1, wherein the extracting comprises an extractor comprising a solvent, wherein the solvent comprises sulfolane.

11. The method of claim 10, wherein the extractor extracts alkylbenzenes and aromatics from alkanes and unreacted dienes and olefins.

12. The method of claim 1, further comprising feeding the linear alkylbenzenes, unreacted compounds, and byproducts from the extractor to an adsorption bed.

13. The method of claim 12, wherein the adsorption bed removes sulfolane to obtain a purified stream comprising linear alkylbenzenes and alkanes.

14. The method of claim 13, further comprising feeding the purified stream to a second separator and separating the alkanes into light and heavy fractions.

15. The method of claim 14, wherein the light alkanes are fed into a naphtha cracker.

16. The method of claim 14, wherein the heavy fraction of alkanes is fed to second reactor, wherein cracking, aromatization, or a combination thereof is performed to obtain alkylbenzenes and short-chain alkanes and alkenes.

17. The method of claim 16, wherein the second reactor comprises a second catalyst.

18. The method of claim 17, wherein the second catalyst comprises a platinum group metal, and a support.

19. The method of claim 18, wherein the platinum group metal and the support are in a matrix.

20. The method of claim 18, wherein the support comprises alumina, fluorinated alumina, chlorinated alumina, sulfated zirconia, tungstated alumina or combinations thereof.Attorney Docket No.39425-357 21. The method of claim 18, wherein the support comprises aluminosilicate, silicoaluminophosphate, silica, silica-alumina, or combinations thereof.

22. The method of claim 21, wherein the aluminosilicate comprises a zeolite.

23. The method of claim 17, wherein the catalyst further comprises doping the support with a rare earth metal.

24. The method of claim 23, wherein the rare earth metal comprises scandium (Sc), lanthanum (La), neodymium (Nd), ytterbium (Yb), gadolinium (Gd), yttrium (Y), cerium (Ce), or a combination thereof.

25. The method of claim 18, wherein the platinum group metal comprises platinum (Pt), ruthenium (Ru), iridium (Ir), palladium (Pd), rhodium (Rh), or a combination.

26. The method of claim 18, wherein the catalyst further comprises a promoter.

27. The method of claim 26, wherein the promoter comprises nickel (Ni), cobalt (Co), or a combination thereof.

28. The method of claim 16, wherein the second reactor is operated at a temperature of about 200°C to about 350°C.

29. The method of claim 1, further comprising performing a sulfolane removal process in a second adsorption bed on the linear alkylbenzenes to purify the linear alkylbenzenes.

30. A system for treating pyrolysis oil comprising: a first reactor comprising a catalyst configured to receive a pyrolysis oil feed and an aromatic; an extractor configured to receive a first reacted stream from the first reactor, wherein the first reacted stream comprises linear alkylbenzenes, byproducts, unreacted compounds comprising excess aromatic, polyaromatics and alkanes; a first separator configured to receive the extract from the extractor, wherein the extract comprises linear alkylbenzenes, and extractant, ; andAttorney Docket No.39425-357 a first adsorption bed configured to perform extractant removal to obtain purified linear alkylbenzenes.

31. The system of claim 30, wherein the first separator comprises a distillation column.

32. The system of claim 30, wherein the extractant is recovered and recycled back to the extractor.

33. The system of claim 30, wherein the extractant is recovered in a side-draw stream from the first separator.

34. The system of claim 30, wherein the extractant comprises sulfolane.

35. The system of claim 30, further comprising a second adsorption bed to receive a raffinate from the extractor, wherein the second adsorption bed is configured to perform removal of traces of the extractant to obtain a purified raffinate stream that is alkane- rich.

36. The system of claim 35, further comprising a second separator configured to receive the purified raffinate stream.

37. The system of claim 36, wherein the second separator comprises a distillation column.

38. The system of claim 36, wherein the second separator separates the stream into light fraction and heavy fraction.

39. The system of claim 38, further comprising a naphtha cracker configured to receive the light fraction from the second separator.

40. The system of claim 38, further comprising a second reactor comprising a second catalyst configured to receive the heavy fraction from the purified stream.

41. The system of claim 30, wherein the catalyst comprises an acid catalyst or a zeolite.Attorney Docket No.39425-357 42. The system of claim 40, wherein the second catalyst comprises a platinum group metal and a support.

43. The system of claim 42, wherein the second catalyst further comprises a promoter.

44. The system of any one of claims 30-43, wherein the pyrolysis oil feed and aromatic is recycled back to the first reactor.

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