GB2551118A

GB2551118A - Process

Info

Publication number: GB2551118A
Application number: GB1609546.5A
Authority: GB
Inventors: Zhang Zhaoxi; Xiao Tiancun; P Edwards Peter
Original assignee: Oxford University Innovation Ltd
Current assignee: Oxford University Innovation Ltd
Priority date: 2016-05-31
Filing date: 2016-05-31
Publication date: 2017-12-13
Also published as: GB201609546D0; EP3464518A1; WO2017207976A1

Abstract

The present invention provides a process for producing an upgraded petroleum product which comprises contacting a feedstock with a catalyst composition; wherein the feedstock comprises a petroleum product or at least one component thereof (e.g. FCC gasoline), a pyrolysis oil (e.g. bio-oil) and methanol; and wherein the catalyst composition comprises a solid acid catalyst composition (e.g. H-ZSM-5, or a product obtainable by treating H-ZSM-5 with Na2CO3 and CTAB solution). A catalyst solution comprising the above solid acid catalyst and a sulphur removal catalyst is also claimed.

Description

PROCESS

INTRODUCTION

[001] The present invention is concerned with a new catalytic process for providing upgraded petroleum products from renewable sources. In particular, the present invention provides a process for upgrading a feedstock comprising a petroleum product and/or at least one component thereof, a pyrolysis oil and methanol. The present invention provides a new catalyst composition which is particularly useful in the process of the present invention.

BACKGROUND OF THE INVENTION

[002] Petroleum is a source of a great variety of manmade materials and products that range from gasoline and diesel oil to varied petrochemical and chemical products, including synthetic materials, plastics, and pharmaceuticals. However, this natural resource, formed over the course of eons, is being rapidly depleted and as such will become increasingly costly (G. A. Olah, Angewandte Chemie International Edition 2005, 44, 2636-2639).

[003] In the 1970s, one half of the petroleum consumed worldwide was used to produce transportation fuels. By 2030 it expected that more than two thirds of the petroleum produced will be used for this purpose. Accordingly, there is a need for a renewable source of hydrocarbon-based fuels suitable for use in transportation for example.

[004] Methanol is an alternative source of hydrocarbon-based fuels. Although methanol itself is a potential transport fuel or can be blended with gasoline, it would require large investments to overcome the technical problems connected with the direct use of methanol as a transport fuel (M. Stocker, Microporous and Mesoporous Materials 1999, 29, 3-48, http://dx.doi.Org/10.1016/S1387-1811 (98)00319-9). Therefore, methanol-to-hydrocarbons technology was developed, and this became one of the most investigated reactions in the field of industrial chemistry since it was discovered in 1977 (M. Conte, J. A. Lopez-Sanchez, Q. He, D. J. Morgan, Y. Ryabenkova, J. K. Bartley, A. F. Carley, S. H. Taylor, C. J. Kiely, K. Khalid, Catalysis Science & Technology 2012,2,105-112; A. Corma, Chemical reviews 1997, 97, 2373-2420).

[005] During the methanol-to-hydrocarbon process methanol is converted into an equilibrium mixture of methanol, dimethyl ether and water, which can be processed catalytically to gasoline (methanol-to-gasoline, MTG), olefins (methanol-to-olefin, MTO) or aromatics (methanol-to-aromatics, MTA), depending on the catalyst and/or the process operation conditions (M. Stocker, Microporous and Mesoporous Materials 1999, 29, 3-48, http://dx.doi.Org/10.1016/S1387-1811 (98)00319-9).

[006] The conversion of methanol to hydrocarbons may take place over acidic zeolites. Zeolites are crystalline metallosilicates containing ordered micropores that enable shape-selective transformation (Y. Xin, P. Qi, X. Duan, H. Lin, Y. Yuan, Catalysis letters 2013, 143, 798-806). Given the high thermal stability and strong Bronsted acidity of zeolite catalysts, they are widely used in cracking, disproportionation, isomerization, alkylation, and aromatization (Y. Xin, P. Qi, X. Duan, H. Lin, Y. Yuan, Catalysis letters 2013, 143, 798-806; J. K. Reddy, K. Motokura, T.-r. Koyama, A. Miyaji, T. Baba, Journal of Catalysis 2012, 289, 53-61; Y.-J. Ji, B. Zhang, L. Xu, H. Wu, H. Peng, L. Chen, Y. Liu, P. Wu, Journal of Catalysis 2011,283, 168-177; K. Toch, J. Thybaut, B. Vandegehuchte, C. Narasimhan, L. Domokos, G. Marin, Applied Catalysis A: General 2012, 425, 130-144; T. Odedairo, R. Balasamy, S. Al-Khattaf, Journal of Molecular Catalysis A: Chemical 2011,345, 21-36; Y. H. Kim, K. H. Lee, J. S. Lee, Catalysis Today 2011, 178, 72-78).

[007] Another alternative source of hydrocarbon-based fuel which is presently attracting attention is pyrolysis oil. Pyrolysis oil is often produced by flash pyrolysis of biomass, fossil fuels, rubber and plastic. The process provides high yields of carbon-rich liquids which may provide renewable feedstocks of liquid fuels and chemicals.

[008] However, there are several fundamental challenges inherent in converting pyrolysis oils into transport fuels. Firstly, pyrolysis oils are low quality fuels which may have a high oxygen content of up to 60 wt.% and they are immiscible with conventional hydrocarbon fuels, as such they cannot be used directly in vehicle engines. Secondly, pyrolysis oils are unstable, acidic mixtures that have a water content of around 30%, thus polymerisation and phase separation can take place during storage.

[009] Despite these drawbacks, it is considered feasible to upgrade pyrolysis oils to hydrocarbon fuels. In particular, catalytic processes using zeolite cracking or hydrodeoxygenation (HDO) in order to convert oxygen compounds and higher hydrocarbons present in the pyrolysis oils into lower hydrocarbons by processes such as cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation, and/or hydrogenation have been reported (P.M. Mortensen et al., Applied Catalysis A: General 407 (2011), 1-19).

[0010] Nevertheless, processes for the production of fuels from pyrolysis oil is associated with a number of deficiencies such as low yields of hydrocarbons and poor product stability.

[0011] Another significant problem of known catalytic conversion processes is deactivation of the catalyst due to coke formation, which is a consequence of consecutive reactions between light olefins and Bronsted or Lewis acid sites. Thus, good anti-coke performance of the catalyst during the conversion process is desirable.

[0012] There is a need in the art for the provision of a process for the production of upgraded petroleum products which overcomes at least one of the deficiencies of the prior art and is preferably derived from a renewable source.

SUMMARY OF THE INVENTION

[0013] In a first aspect, the present invention relates to a process for producing an upgraded petroleum product which comprises contacting a feedstock with a catalyst composition; wherein the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol; and wherein the catalyst composition comprises a solid acid catalyst.

[0014] In a second aspect, the present invention relates to an upgraded petroleum product obtainable or obtained according to the process of the first aspect.

[0015] In a third aspect, the present invention relates to a catalyst composition comprising a solid acid catalyst and a sulphur removal catalyst wherein said composition is a heterogeneous mixture of the solid acid catalyst and the sulphur removal catalyst.

[0016] In a fourth aspect, the present invention relates to a process for preparing a catalyst composition according to the third aspect comprising mechanically mixing a solid acid catalyst and a sulphur removal catalyst.

[0017] In a fifth aspect, the present invention relates to use of a catalyst composition according to the third aspect for upgrading a feedstock wherein the feedstock comprises one or more of (i) a petroleum product or at least one component thereof, (ii) a pyrolysis oil and (iii) methanol.

BRIEF DESCRIPTION OF THE DRA WINGS

[0018] Figure 1 shows an example of a fixed bed reactor on which the process of the invention may be performed.

[0019] Figure 2 shows an example of the phase separation between the upper raffinate phase and the extract phase (LPM) comprising an FCC extract, methanol and bio-oil.

[0020] Figure 3 shows a comparison of the levels of hydrogen and carbon monoxide generated on catalytic upgrading of a feedstock consisting of a bio-oil and methanol mixture and a feedstock consisting of LPM.

[0021] Figure 4 shows a comparison of the levels of paraffins and olefins generated on catalytic upgrading of a feedstock consisting of a bio-oil and methanol mixture and a feedstock consisting of LPM. The arrows indicate the condition providing the largest peak.

[0022] Figure 5 shows a comparison of the oil phase yield after the catalytic upgrading process performed on a feedstock consisting of a bio-oil and methanol mixture and a feedstock consisting of LPM.

[0023] Figure 6a shows an overlaid comparison of the oil phase aromatic hydrocarbon profile by GCMS after the catalytic upgrading process performed on a feedstock consisting of a biooil and methanol mixture and a feedstock consisting of LPM. Figure 6b shows an exploded-view comparison.

[0024] Figure 7 shows a comparison of the levels of hydrogen and carbon monoxide generated on catalytic upgrading of a feedstock consisting of LPM at different pressures.

[0025] Figure 8 shows a comparison of the levels of paraffins and olefins generated on catalytic upgrading of a feedstock consisting of LPM at different pressures. The arrows indicate the condition providing the largest peak.

[0026] Figure 9 shows a comparison of the oil phase yield after the catalytic upgrading process performed on a feedstock consisting of LPM at different pressures.

[0027] Figure 10a shows an overlaid comparison of the oil phase aromatic hydrocarbon profile by GCMS after the catalytic upgrading process performed on a feedstock consisting of LPM is done at different pressures. Figure 10b shows an exploded-view comparison.

[0028] Figure 11 shows a comparison of the levels of hydrogen and carbon monoxide generated on catalytic upgrading of a feedstock consisting of LPM using different catalysts.

[0029] Figure 12 shows a comparison of the levels of paraffins and olefins generated on catalytic upgrading of a feedstock consisting of LPM using different catalysts. The arrows indicate the condition providing the largest peak.

[0030] Figure 13 shows a comparison of the oil phase yield after the catalytic upgrading process is performed on a feedstock consisting of LPM using different catalysts.

[0031] Figure 14a shows an overlaid comparison of the oil phase aromatic hydrocarbon profile by GCMS after the catalytic upgrading process is performed on a feedstock consisting of LPM using different catalysts. Figure 14b shows an exploded-view comparison.

[0032] Figure 15 shows the visual appearance of (a) the oil phase generated after the catalytic upgrading process was performed on a feedstock consisting of bio-oil/methanol and (b) after the same oil phase was stored for one month. Figure 15c shows a comparison by GCMS.

[0033] Figure 16 shows the appearance of (a) the oil phase generated after the catalytic upgrading process was performed on a feedstock consisting of LPM at atmospheric pressure and (b) after the same oil phase was stored for one month. Figure 16c shows a comparison by GCMS.

[0034] Figure 17 shows the appearance of (a) the oil phase generated after the catalytic upgrading process was performed on a feedstock consisting of LPM at 301 KPa and (b) after the same oil phase was stored for one month. Figure 17c shows a comparison by GCMS.

[0035] Figure 18 shows the appearance of (a) the oil phase generated after the catalytic upgrading process was performed on a feedstock consisting of LPM with a modified catalyst and (b) after the same oil phase was stored for two months.

[0036] Figure 19 shows a boiling point analysis of the oil phase product generated after the catalytic upgrading process was performed on a feedstock consisting of LPM with a modified catalyst.

[0037] Figure 20 shows a comparison of the 0.10C60 catalyst and unmodified catalyst HZSM-5 by XRD.

[0038] Figure 21 shows a comparison of XRD patterns of three batches of 0.10C60 catalyst.

[0039] Figure 22 shows a comparison of the FTIR spectra of the 0.10C60 catalyst and unmodified HZSM-5 catalyst.

[0040] Figure 23 shows an analysis of post-reaction HZSM-5 and post-reaction 0.10C60+HDS mixed catalyst by Laser Raman.

[0041] Figure 24 shows an analysis of post-reaction HZSM-5 by TGA.

[0042] Figure 25 shows an analysis of post-reaction 0.10C60+HDS mixed catalyst by TGA.

[0043] Figure 26 shows a comparison of post-reaction HZSM-5 and pre-reaction HZSM-5 by XRD.

[0044] Figure 27 shows a comparison of post-reaction 0.10C60+FIDS mixed catalyst and prereaction 0.10C60+FIDS mixed catalyst by XRD.

DETAILED DESCRIPTION OF THE INVENTION

Process [0045] In a first aspect, the present invention relates to a process for producing an upgraded petroleum product which comprises contacting a feedstock with a catalyst composition; wherein the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol; and wherein the catalyst composition comprises a solid acid catalyst.

[0046] The process of contacting the feedstock with the catalyst composition is typically performed at an elevated temperature. Thus the process typically comprises contacting the feedstock with the catalyst composition at a temperature above ambient temperature. For instance, the temperature is typically above 25 SC.

[0047] In one embodiment, the feedstock is contacted with the catalyst composition at a temperature equal to or above about 100‘O, for example equal to or above 250 eC, for example equal to or above about 300 eC, for example equal to or above about 350 eC, for example equal to or above about 400^0.

[0048] In a one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of from about 100 eC to about 800 SC, for example from about 100 eC to about 700 SC, for example from about 100 SC to about 600 SC, for example from about 100 eC to 500 SC.

[0049] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of from about 200 eC to about 800 °C, for example from about 200 eC to about 700 eC, for example from about 200 eC to about 600 SC, for example from about 200 SC to about 500 SC.

[0050] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of from about 300 eC to about 800 SC, for example from about 300 eC to about 700 eC, for example from about 300 eC to about 600 SC, for example from about 300 SC to about 500 SC.

[0051] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of from about 400 eC to about 800 eC, for example from about 400 eC to about 700 eC, for example from about 400 eC to about 600 eC, for example from about 400 eC to about 500 eC.

[0052] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of about 450 SC.

[0053] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at ambient pressure or above ambient pressure. For instance, the process may comprise contacting the feedstock with the catalyst composition at a pressure of about 1 atmosphere (atm) or about 101 KPa. In another embodiment, the process may comprise contacting the feedstock with the catalyst composition at a pressure of greater than about 1 atmosphere (atm) or about 101 KPa.

[0054] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a pressure of equal to or greater than about 125 KPa, for example greater than about 150 KPa, for example greater than about 175 KPa, for example greater than about 200 KPa, for example greater than about 225 KPa, for example greater than about 250 KPa, for example greater than about 275 KPa.

[0055] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 101 KPa to about 1000 KPa. For example, a pressure of from about 101 KPa to about 500 KPa. For example, a pressure of from about 101 KPa to about 475 KPa. For example, a pressure of from about 101 KPa to about 450 KPa. For example, a pressure of from about 101 KPa to about 425 KPa. For example, a pressure of from about 101 KPa to about 400 KPa. For example, a pressure of from about 101 KPa to about 375 KPa. For example, a pressure of from about 101 KPa to about 350 KPa.

[0056] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 150 KPa to about 1000 KPa. For example, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 150 KPa to about 500 KPa. For example, a pressure of from about 150 KPa to about 475 KPa. For example, a pressure of from about 150 KPa to about 450 KPa. For example, a pressure of from about 150 KPa to about 425 KPa. For example, a pressure of from about 150 KPa to about 400 KPa. For example, a pressure of from about 150 KPa to about 375 KPa. For example, a pressure of from about 150 KPa to about 350 KPa.

[0057] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 200 KPa to about 1000 KPa. For example, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 200 KPa to about 500 KPa. For example, a pressure of from about 200 KPa to about 475 KPa. For example, a pressure of from about 200 KPa to about 450 KPa. For example, a pressure of from about 200 KPa to about 425 KPa. For example, a pressure of from about 200 KPa to about 400 KPa. For example, a pressure of from about 200 KPa to about 375 KPa. For example, a pressure of from about 200 KPa to about 350 KPa.

[0058] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 250 KPa to about 1000 KPa. For example, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 250 KPa to about 500 KPa. For example, a pressure of from about 250 KPa to about 475 KPa. For example, a pressure of from about 250 KPa to about 450 KPa. For example, a pressure of from about 250 KPa to about 425 KPa. For example, a pressure of from about 250 KPa to about 400 KPa. For example, a pressure of from about 250 KPa to about 375 KPa. For example, a pressure of from about 250 KPa to about 350 KPa.

[0059] In another embodiment, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 300 KPa to about 1000 KPa. For example, the process comprises contacting the feedstock with the catalyst composition at a pressure of from about 300 KPa to about 500 KPa. For example, a pressure of from about 300 KPa to about 475 KPa. For example, a pressure of from about 300 KPa to about 450 KPa. For example, a pressure of from about 250 KPa to about 425 KPa. For example, a pressure of from about 300 KPa to about 400 KPa. For example, a pressure of from about 300 KPa to about 375 KPa. For example, a pressure of from about 300 KPa to about 350 KPa. For example, a pressure of from about 300 KPa to about 340 KPa. For example, a pressure of from about 300 KPa to about 330 KPa. For example, a pressure of from about 300 KPa to about 320 KPa. For example, a pressure of from about 300 KPa to about 310 KPa.

[0060] Although the process may be performed batch-wise, a continuous mode may be employed. Thus, the process typically comprises continuously feeding said feedstock over the catalyst composition. In one embodiment, the process is performed using a micro-reactor. A suitable micro-reactor is a fixed bed micro-reactor.

[0061] Any suitable space velocity may be employed for feeding the feedstock over the catalyst composition. For instance, the feedstock may be fed over the catalyst composition at a weight hour space velocity (WHSV) of equal to or greater than about 0.1 hr1. For instance, the feedstock may be fed over the catalyst composition at a weight hour space velocity (WHSV) of equal to or greater than about 0.5 hr1. Suitably, the weight hour space velocity is equal to or greater than about 1.0 hr1, for instance equal to or greater than about 1.5 hr1, or for example equal to or greater than about 2.0 hr1.

[0062] In one embodiment WHSV is from about 0.1 hr1 to about 5 hr1. For example, a WHSV of from about 0.1 hr1 to about 4.5 hr1. For example, a WHSV of from about 0.1 hr1 to about 4.0 hr1. For example, a WHSV of from about 0.1 hr1 to about 3.5 hr1. For example, a WHSV of from about 0.1 hr1 to about 3.0 hr1. For example, a WHSV of from about 0.1 hr1 to about 2.5 hr1.

[0063] In one embodiment WHSV is from about 0.5 hr1 to about 5 hr1. For example, a WHSV of from about 0.5 hr1 to about 4.5 hr1. For example, a WHSV of from about 0.5 hr1 to about 4.0 hr1. For example, a WHSV of from about 0.5 hr1 to about 3.5 hr1. For example, a WHSV of from about 0.5 hr1 to about 3.0 hr1. For example, a WHSV of from about 0.5 hr1 to about 2.5 hr1.

[0064] In another embodiment, the WHSV is from about 1.0 hr1 to about 5 hr1. For example, a WHSV of from about 1.0 hr1 to about 4.5 hr1. For example, a WHSV of from about 1.0 hr1 to about 4.0 hr1. For example, a WHSV of from about 1.0 hr1 to about 3.5 hr1. For example, a WHSV of from about 1.0 hr1 to about 3.0 hr1. For example, a WHSV of from about 1.0 hr1 to about 2.5 hr1.

[0065] In another embodiment, the WHSV is from about 1.5 hr1 to about 2.5 hr1, for instance, about 2.0 hr1.

[0066] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of greater than about 100°C and a pressure of greater than about 125 KPa.

[0067] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 200 eC to about 600 eC and a pressure of from about 200 KPa to about 500 KPa.

[0068] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 300 eC to about 600 eC and a pressure of from about 250 KPa to about 500 KPa.

[0069] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 300 eC to about 500 eC and a pressure of from about 250 KPa to about 450 KPa.

[0070] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 350 eC to about 500 SC and a pressure of from about 250 KPa to about 400 KPa.

[0071] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 400 eC to about 500 SC and a pressure of from about 250 KPa to about 350 KPa.

[0072] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 425^0 to about 475°C and a pressure of from about 275 KPa to about 325 KPa.

[0073] In another embodiment, the process comprises contacting the feedstock with a catalyst composition at a temperature of from about 425^0 to about 475°C and a pressure of from about 275 KPa to about 325 KPa.

[0074] In another embodiment, the process comprises contacting the feedstock with a catalyst at a temperature of about 450°C and a pressure of about 300 KPa.

[0075] In another embodiment, the process comprises contacting the feedstock with a catalyst at a temperature of about 450^ and a pressure of about 300 KPa and a WHSV of about 2.0 hr1.

Feedstock [0076] In one embodiment, the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol. In another embodiment, the feedstock essentially consists of a petroleum product or at least one component thereof, a pyrolysis oil and methanol. In another embodiment, the feedstock consists of a petroleum product or at least one component thereof, a pyrolysis oil and methanol.

[0077] As used herein the term “petroleum product” refers to materials derived from crude oil, plastics or rubber compounds. For instance, petroleum products include fuel oil, diesel, kerosene (e.g. jet fuel) and gasoline (which may be interchangeably referred to as petrol), hydrocarbon products derived from cracking plastic and rubber compounds (e.g. vehicle tyres). In one embodiment, the petroleum products are selected from fuel oil, diesel, kerosene (e.g. jet fuel) and gasoline. In another embodiment, the petroleum product is selected from hydrocarbon products derived from cracking plastic and rubber compounds (e.g. vehicle tyres).

[0078] In one embodiment, the petroleum product is selected from diesel and gasoline. In another embodiment, the petroleum product is gasoline.

[0079] In one embodiment, the petroleum product is gasoline obtained/obtainable from fluid catalytic cracking (FCC), thermal cracking or delayed coking of hydrocarbons. Suitably, the petroleum product is gasoline obtained/obtainable from fluid catalytic cracking (FCC).

[0080] FCC is a process whereby high molecular weight hydrocarbons are converted to lower molecular weight hydrocarbons. The process is well known in the art.

[0081] Typically, FCC is a process whereby hydrocarbons having a boiling point of greater than about 340 °C are converted to hydrocarbons with a lower boiling point (less than or equal to about 340°C, or typically less than or equal to about 200^) by a catalytic process. A variety of catalysts may be used in an FCC process.

[0082] Typically, a solid acid catalyst such as a zeolite catalyst is used. An FCC process may convert long chain alkanes (for instance, C11-20 alkanes) to shorter chain hydrocarbons including alkanes, cycloalkanes and alkenes (for instance C3-10 alkanes, C3-10 alkenes, C4-10 cycloalkanes). Gasoline produced by an FCC process typically has a greater alkene content than gasoline obtained by fractional distillation of crude oil. Furthermore, gasoline obtainable by an FCC process may comprise organosulfur compounds in an amount of greater than or equal to 0.01 wt %, typically greater than or equal to 0.05 wt %. Gasoline obtained via an FCC process is commonly known as FCC gasoline.

[0083] In one embodiment, the feedstock comprises a petroleum product which is FCC gasoline.

[0084] In one embodiment, the petroleum product is FCC gasoline comprising 0.1 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.095 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.09 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.085 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.08 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.05 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.03 wt% or greater organosulphur compounds. In another embodiment, the petroleum product is FCC gasoline comprising 0.01 wt% or greater organosulphur compounds.

[0085] In another embodiment, the petroleum product is FCC gasoline comprising 30 wt.% or greater of olefins. In another embodiment, the petroleum product is FCC gasoline comprising 28 wt. % or greater of olefins. In another embodiment, the petroleum product is FCC gasoline comprising 26 wt. % or greater of olefins. In another embodiment, the petroleum product is FCC gasoline comprising 20 wt. % or greater of olefins. In another embodiment, the petroleum product is FCC gasoline comprising 18 wt. % or greater of olefins. In another embodiment, the petroleum product is FCC gasoline comprising 16 wt. % or greater of olefins.

[0086] The feedstock may comprise at least one component of a petroleum product. In one embodiment, the feedstock comprises at least one component of FCC gasoline.

[0087] In one embodiment, the at least one component of a petroleum product, for instance FCC gasoline, is selected from paraffins (interchangeably also referred to as alkanes), aromatics, olefins (interchangeably also referred to as alkenes) and organic sulphur compounds. In another embodiment, the at least one component of a petroleum product is selected from paraffins, olefins and organic sulphur compounds. In another embodiment, the at least one component of a petroleum product is selected from olefins and organic sulphur compounds.

[0088] Suitable olefins may be selected from one or more of C2-18 alkenes and C4-10 cycloalkenes. More typically, one or more C4-14 alkenes and C4-10 cycloalkenes, for instance from C4-12 alkenes and C4-10 cycloalkenes.

[0089] Suitable cycloalkenes are C5-8 cycloalkenes. Thus, the olefins in the feedstock may be selected from one or more of C4-12 alkenes and C5-8 cycloalkenes, or C4-10 alkenes and C5-8 cycloalkenes.

[0090] In one embodiment, the olefin is selected from a C5-6 alkene or a C5-6 cycloalkene, suitably a C6 alkene or a C6 cycloalkene, suitably 1-pentene or 1-hexene.

[0091] In one embodiment, the feedstock comprises at least one olefin in an amount of at least about 0.01 % by weight (wt %). The feedstock may for instance comprise the at least one alkene in an amount of at least about 0.1 wt %, or, for instance, in an amount of at least about 1.0 wt %, for instance an amount of at least about 2.0 wt %, or for example an amount of at least about 4.5 wt %. It may for instance comprise the at least one alkene in an amount of at least about 5.0 wt %, or for instance in an amount of at least about 7.0 wt %, or in an amount of at least about 10.0 wt %. The feedstock, for instance, may comprise at least one alkene in an amount of at least about 11.0 wt %, or for instance in an amount of at least about 13.0 wt %, or an amount of at least about 15.0 wt %.

[0092] In one embodiment, the feedstock comprises at least one olefin in an amount of from about 0.01 wt % to about 30 wt %, for instance in an amount of from about 0.01 wt % to about 20 wt %.

[0093] In another embodiment, the feedstock comprises at least one olefin in an amount of from about 0.1 wt % to about 30 wt %, for instance in an amount of from about 0.1 wt % to about 20 wt %. In another embodiment, the feedstock comprises at least one olefin in an amount of from about 4.5 wt % to about 30 wt %, for instance in an amount of from about 5.0 wt % to about 30 wt %, or from about 8.0 wt % to about 30 wt %, or from about 10.0 wt % to about 25 wt %, or from about 11.0 wt % to about 20 wt %.

[0094] In one embodiment, the feedstock comprises at least one component of a petroleum product which is an organosulphur compounds. The organosulfur compound in the feedstock may be one or more organosulfur compounds selected from substituted or unsubstituted C4-18 organosulfur compounds, more typically from substituted or unsubstituted C4-12 organosulfur compounds.

[0095] In another embodiment, the organosulfur compound may be one or more organosulfur compounds comprising a thiophene ring, a benzothiophene ring or a dibenzothiophene ring.

[0096] For instance, the organosulfur compound be one or more compounds selected from substituted or unsubstituted thiophene, substituted or unsubstituted benzothiophene, and substituted or unsubstituted dibenzothiophene.

[0097] Typically, if the organosulfur compound is substituted, it is substituted with one or more, for instance from one to four, or for example, one, two or three, C1 -6 alkyl groups.

[0098] In another embodiment, the organosulfur compound is at least one unsubstituted or substituted thiophene. When thiophene is substituted, it is typically substituted with one or more C1 -6 alkyl groups, for instance from one to four, or for example, one, two or three, C1 -6 alkyl groups.

[0099] In one embodiment, the at least one organosulfur compound is (i.e. it consists of) thiophene, i.e. unsubstituted thiophene, and no other organosulfur compounds are present in the feedstock. In another embodiment, however, the at least one organosulfur compound in the feedstock comprises unsubstituted thiophene and at least one further organosulfur compound which is other than unsubstituted thiophene.

[00100] In one embodiment, the feedstock comprises an organosulfur compound in an amount of at least about 10 ppm (i.e. 0.001 %) by weight. In another embodiment, the feedstock comprises an organosulfur compound in an amount of at least about 50 ppm by weight, or, for instance, in an amount of at least about 100 ppm by weight, for instance an amount of at least about 200 ppm by weight, or for instance, an amount of at least about 400 ppm by weight. It may for instance comprise the at least one organosulfur compound in an amount of at least about 500 ppm by weight, or for instance in an amount of at least about 700 ppm by weight, or in an amount of at least about 900 ppm by weight.

[00101 ] In another embodiment, the feedstock comprises an organosulfur compound in an amount of at least about 1,000 ppm by weight, or for instance in an amount of at least about 1,500 ppm by weight, or an amount of at least about 3,000 ppm by weight.

[00102] In one embodiment, the feedstock comprises an organosulfur compound in an amount of from about 10 ppm (i.e. 0.001 %) by weight to about 50,000 ppm (i.e. 5 %) by weight, for instance in an amount of from about 100 ppm (i.e. 0.01 %) to about 10,000 ppm (i.e. 1 %) by weight, or for instance in an amount of from about 200 ppm (i.e. 0.02%) to about 5.000 ppm (i.e. 0.5%) by weight.

[00103] In another embodiment, the feedstock comprises an organosulfur compound in an amount of from about 50 ppm to about 50,000 ppm by weight, for instance in an amount of from about 100 ppm to about 50,000 ppm by weight. Thus, for instance, the feedstock comprises an organosulfur compound in an amount of from about 200 ppm to about 10,000 ppm by weight, for instance in an amount of from about 400 ppm to about 10,000 ppm by weight. In another embodiment, the feedstock comprises an organosulfur compound in an amount of from about 500 ppm to about 10,000 ppm by weight, for instance in an amount of from about 700 ppm to about 5,000 ppm by weight, or for example in an amount of from about 1.000 ppm to about 4,000 ppm by weight, for instance from about 1,500 ppm to about 5,000 ppm by weight, or from about 3,000 ppm to about 10,000 ppm by weight.

[00104] In one embodiment, the feedstock comprises at least one component of a petroleum product which is an aromatic hydrocarbon.

[00105] In one embodiment, the aromatic hydrocarbon compound comprises one or more aromatic hydrocarbon compounds selected from C6-14 aromatic compounds. More typically, the at least one aromatic hydrocarbon compound comprises one or more aromatic hydrocarbon compounds selected from C6-12 aromatic compounds, for instance from C6-10 aromatic compounds. The at least one aromatic hydrocarbon compound may for instance comprise one or more aromatic hydrocarbon compounds selected from benzene, toluene, xylene, ethylbenzene, methylethylbenzene, trimethylbenzene, diethylbenzene, naphthalene, methylnaphthalene and ethylnaphthalene, all of which are examples of C6-12 aromatic compounds.

[00106] In one embodiment, the feedstock comprises one or more aromatic hydrocarbons selected from benzene substituted with one, two, three or four methyl or ethyl groups.

[00107] In another embodiment, the feedstock comprises one or more aromatic hydrocarbons selected from toluene, o-xylene, m-xylene, p-xylene, and 1,2,3-trimethylbenzene.

[00108] In one embodiment, the feedstock comprises an aromatic hydrocarbon in an amount of at least about 0.01 % by weight (wt %). For instance, in one embodiment, the feedstock comprises the at least one aromatic hydrocarbon compound in an amount of at least about 0.05 wt %, or, for instance, in an amount of at least about 0.1 wt %, for instance an amount of at least about 0.2 wt %, or for example an amount of at least about 0.4 wt %. It may for instance comprise at least one aromatic hydrocarbon compound in an amount of at least about 0.5 wt %, or for instance in an amount of at least about 1.0 wt %, or in an amount of at least about 1.2 wt %. The feedstock may comprise at least one aromatic hydrocarbon compound in an amount of at least about 5 wt %, or for instance in an amount of at least about 8 wt %, or an amount of at least about 15 wt %.

[00109] In one embodiment, the feedstock comprises at least one aromatic hydrocarbon compound in an amount of from about 0.01 wt % to about 30 wt %, for instance in an amount of from about 0.01 wt % to about 20 wt %.

[00110] In another embodiment, the feedstock comprises at least one aromatic hydrocarbon compound in an amount of from about 0.05 wt % to about 30 wt %, for instance in an amount of from about 0.05 wt % to about 25 wt %. Thus, for instance, the feedstock comprises at least one aromatic hydrocarbon compound in an amount of from about 0.1 wt % to about 20 wt %, for instance in an amount of from about 0.2 wt % to about 15 wt %. For example, the feedstock comprises at least one aromatic hydrocarbon in an amount of from about 0.4 wt % to about 10 wt %, for instance in an amount of from about 0.5 wt % to about 8 wt %, or for example in an amount of from about 1.0 wt % to about 5 wt %, for instance from about 1.2 wt % to about 10 wt %, or from about 5 wt % to about 20 wt % or from about 8 wt % to about 25 wt %.

[00111] In one embodiment, the feedstock comprises at least one component of a petroleum product which is an alkane or cycloalkane.

[00112] The alkane or cycloalkane may be selected from one or more C1 -18 alkanes. For instance, one or more C4-18 alkanes. Thus, the one or more alkanes, when present, may comprise one or more C4-14 alkanes, or more typically, for example, one or more C4-12 alkanes, or for instance one or more C6-10 alkanes. Often, the one or more alkanes, when present, include a C8 alkane. Often, they include octane, for instance n-octane.

[00113] In another embodiment, the feedstock comprises one or more C3-10 cycloalkanes. For instance one or more C4-8 cycloalkanes or one or more C5-8 cycloalkanes.

[00114] In one embodiment, the feedstock comprises at least one alkane or cycloalkane in an amount of at least about 0.01 % by weight (wt %). For instance, the feedstock may comprise the at least one alkane or cycloalkane in an amount of at least about 0.1 wt %, or, for instance, in an amount of at least about 0.5 wt %, for instance an amount of at least about 1.0 wt %, or for example an amount of at least about 1.5 wt %. It may for instance comprise the at least one alkane or cycloalkane in an amount of at least about 2.0 wt %, or for instance in an amount of at least about 3.5 wt %, or in an amount of at least about 4.0 wt %. In another embodiment, the feedstock comprises at least one alkane or cycloalkane in an amount of at least about 5.0 wt %, or for instance in an amount of at least about 7.0 wt %, or an amount of at least about 12.0 wt %.

[00115] In one embodiment, the feedstock comprises at least one alkane or cycloalkane in an amount of from about 0.01 wt % to about 30 wt %, for instance in an amount of from about 0.01 wt % to about 20 wt %, or, for instance in an amount of from about 0.01 wt % to about 15 wt %. The feedstock may for instance comprise the at least one alkane or cycloalkane in an amount of from about 0.01 wt % to about 10 wt %, for instance from about 0.01 wt % to about 8 wt %.

[00116] In another embodiment, the feedstock comprises the at least one alkane or cycloalkane in an amount of from about 0.1 wt % to about 30 wt %, for instance in an amount of from about 0.1 wt % to about 20 wt %. Thus, for instance, the feedstock comprises at least one alkane or cycloalkane in an amount of from about 0.5 wt % to about 30 wt %, for instance in an amount of from about 1.0 wt % to about 20 wt %. In another embodiment, the feedstock comprises one alkane or cycloalkane in an amount of from about 1.5 wt % to about 20 wt %, for instance in an amount of from about 2.0 wt % to about 20 wt %, or for example in an amount of from about 3.5 wt % to about 18 wt %, for instance from about 4.0 wt % to about 15 wt %, or from about 5.0 wt % to about 15 wt %.

[00117] In one embodiment, the at least one components of a petroleum product are obtainable by extracting a petroleum product (e.g. FCC gasoline) with an extraction solution. Suitable extraction solutions are disclosed in WO 2015/177531 the teachings of which are incorporated herein by reference. For instance, components of a petroleum products are obtainable by extracting a petroleum product (e.g. FCC gasoline) with an extraction solution which comprises/essentially consists of/consists of a polar organic solvent. In one embodiment, the polar organic solvent is an alcohol, for example, methanol or ethanol.

[00118] In one embodiment, the feedstock comprises a pyrolysis oil. Pyrolysis oil is a substance known to the skilled person. Pyrolysis oil may be obtained from a number of sources including fossil fuels, plastic, rubber and biomass. In one embodiment, the pyrolysis oil is obtainable or obtained by pyrolysis of biomass.

[00119] Suitable categories of biomass include virgin wood (i.e. from forestry or wood processing), crops (e.g. food crops, such as wheat straw and rice straw), agricultural residues (e.g. animal waste), domestic and industrial waste (e.g. food waste).

[00120] Typically, pyrolysis is carried out at high temperature (greater than 400¾) and with very high heating rates in the absence of oxygen.

[00121] In one embodiment, the pyrolysis oil is a pyrolysis bio-oil.

[00122] In one embodiment, the feedstock comprises a further solvent. For instance, a solvent selected from ethanol, propanol, isopropanol, butanol, sec-butanol, iso-butanol, water, ethyleneglycol, propylene glycol, and propane-1,3-diol.

[00123] In one embodiment, in addition to a petroleum product or at least one component thereof, a pyrolysis oil and methanol, the feedstock comprises water.

[00124] In one embodiment, the feedstock comprises pyrolysis oil in an amount of greater than or equal to about 1 wt.%. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 90 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 60 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 50 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 40 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 30 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 20 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 1 wt. % to about 10 wt. %.

[00125] In one embodiment, the feedstock comprises pyrolysis oil in an amount of greater than or equal to about 2 wt.%. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 90 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 60 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 50 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 40 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 30 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 20 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 2 wt. % to about 10 wt. %.

[00126] In one embodiment, the feedstock comprises pyrolysis oil in an amount of greater than or equal to about 5 wt.%. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 90 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 60 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 50 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 40 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 30 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 20 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 5 wt. % to about 10 wt. %.

[00127] In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. % to about 90 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. % to about 60 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. % to about 50 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. % to about 40 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. % to about 30 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. % to about 20 wt. %. In another embodiment, the feedstock comprises pyrolysis oil in an amount of about 10 wt. %.

[00128] In one embodiment, the feedstock comprises methanol in an amount of greater than or equal to about 40 wt.%. In another embodiment, the feedstock comprises methanol in an amount of about 40 wt. % to about 95 wt. %. In another embodiment, the feedstock comprises methanol in an amount of about 50 wt. % to about 95 wt. %. In another embodiment, the feedstock comprises methanol in an amount of about 60 wt. % to about 95 wt. %. In another embodiment, the feedstock comprises methanol in an amount of about 70 wt. % to about 95 wt. %. In another embodiment, the feedstock comprises methanol in an amount of about 80 wt. % to about 95 wt. %. In another embodiment, the feedstock comprises methanol in an amount of about 80 wt. %.

[00129] In another embodiment, the feedstock comprises a pyrolysis oil in an amount of about 1 to about 50 wt. %, and methanol in an amount of about 99 to about 50 wt. %.

[00130] In another embodiment, the feedstock comprises a pyrolysis oil in an amount of about 5 to about 50 wt. %, and methanol in an amount of about 95 to about 50 wt. %.

[00131] In another embodiment, the feedstock comprises a pyrolysis oil in an amount of about 5 to about 50 wt. %, and methanol in an amount of about 90 to about 50 wt. %, and water in an amount of 0 to about 10 wt.%.

[00132] In one embodiment, the feedstock comprises the petroleum product or at least one component thereof in an amount of less than or equal to 50 wt. %, for example less than 40 wt. %, for example less than 30 wt. %, for example less than about 20 wt. %, for example less than about 10 wt. %, for example less than about 5 wt. %, for example less than about 2.5 wt. %, for example less than about 1 wt. %.

[00133] In one embodiment, the feedstock comprises the petroleum product or at least one component thereof in an amount of less than or equal to 5 wt. %, for example less than 4 wt. %, for example less than 3 wt. %, for example less than about 2 wt. %, for example less than about 1 wt. %, for example less than about 0.5 wt. %, for example less than about 0.25 wt. %, for example less than about 0.1 wt. %.

[00134] In one embodiment, the feedstock is a feedstock obtainable/obtained by extracting FCC gasoline with an extraction solution wherein said extraction solution comprises/essentially consists of/consists of a pyrolysis oil and methanol. In another embodiment, the feedstock is a feedstock obtainable/obtained by extracting FCC gasoline with an extraction solution wherein said extraction solution comprises/essentially consists of/consists of a pyrolysis bio-oil and methanol.

[00135] The FCC gasoline can be extracted with the extraction solution by means known in the art.

[00136] Typically, the FCC gasoline and the extraction solution are firstly mixed by any means known in the art. Typically, the FCC gasoline and the extraction solution will be intimately mixed. For instance, the FCC gasoline and the extraction solution may be added to vessels, reactors or mixers commonly used in the art and the two components may be intimately mixed. Intimate mixing may comprise vigorous agitation of the two components by a mixing means. For instance, the two components may be mixed together by stirring or by shaking.

[00137] The mixing of the two components may occur more than once. For instance, after mixing the FCC gasoline and the extraction solution for the first time, the resulting two phases may be mixed again, possible numerous times. The steps of contacting and formation of two phases may be continuous. Thus, the two components may pass through a mixing means before entering a separating chamber in which the first and second phases are formed. The contacting of the two components may be performed using a propeller, counter-current flow means, an agitation means, a Scheibel® column, a KARR® column or a centrifugal extractor.

[00138] The FCC gasoline may be repeatedly mixed multiple times with fresh batches of extraction solution to yield multiple batches of feedstock.

[00139] In one embodiment, the mixing is carried out at ambient temperature and pressure. Typically, a temperature of between about 10 to 40^. For instance, a temperature of between about 10 to 25 °C, more typically between about 21 and 25°C, and a pressure of about 101 kPa. Accordingly, expense and other problems associated with high temperature or pressure conditions are avoided.

[00140] Typically, the ratio of FCC gasoline to extraction solution is from about 20:1 to about 1:20. In one embodiment, the ratio of FCC gasoline to extraction solution is from about 10:1 to about 1:10. In one embodiment, the ratio of FCC gasoline to extraction solution is about 10:1 to about 1:5. In one embodiment the ratio of FCC gasoline to extraction solution is about 5:1 to about 1:5. In one embodiment the ratio of FCC gasoline to extraction solution is about 5:1 to about 1:1. In one embodiment the ratio of FCC gasoline to extraction solution is about 5:1 to about 2:1. In one embodiment the ratio of FCC gasoline to extraction solution is about 5:1.

[00141] Once suitably mixed, the mixture of FCC gasoline and extraction solution are allowed to separate into two phases consisting of an extracted FCC gasoline phase and an extract of FCC gasoline phase, wherein said extract of FCC gasoline is comprised of at least one component extracted from FCC gasoline, pyrolysis oil and methanol.

[00142] The extract of FCC gasoline phase tends to be a higher density than the extracted FCC gasoline phase and thus will typically be the lower phase. This lower phase mixture (LPM) in one embodiment is used as the feedstock in the process of the present invention.

[00143] The LPM may be separated from the extracted FCC gasoline by any means used in the art, and is typically separated by a physical process. For instance, the LPM may be isolated by draining at least part of the LPM from the container comprising the LPM and the extracted FCC gasoline.

[00144] In one embodiment, the extraction solution referred to above comprises further solvents such as water, an alcohol, an aldehyde, a ketone, an ether, a carboxylic acid, an ester, a carbonate, an acid anhydride, an amide, an amine, a heterocyclic compound, an imine, an imide, a nitrile, a nitro compound, a sulfoxide, and a haloalkane. For instance, the extraction solution may further comprise water or an alcohol.

[00145] In one embodiment, the extraction solution comprises pyrolysis bio-oil, methanol and a further solvent selected from ethanol, propanol, isopropanol, water, ethylene glycol, and propylene glycol.

[00146] In one embodiment, the extraction solution comprises (i) a pyrolysis oil, (ii) methanol, (iii) at least one further alcohol solvent selected from ethylene glycol, propylene glycol, and propane-1,3-diol; and (iv) water.

[00147] In one embodiment, the extraction solution essentially consists of (i) a pyrolysis oil, (ii) methanol, (iii) at least one further alcohol solvent selected from ethylene glycol, propylene glycol, and propane-1,3-diol; and (iv) water.

[00148] In one embodiment, the extraction solution consists of (i) a pyrolysis oil, (ii) methanol (iii) at least one further alcohol solvent selected from ethylene glycol, propylene glycol, and propane-1,3-diol; and (iv) water.

[00149] In one embodiment, the extraction solution comprises (i) a pyrolysis oil, (ii) methanol (iii) ethylene glycol; and (iv) water.

[00150] In one embodiment, the extraction solution essentially consists of (i) a pyrolysis oil, (ii) methanol (iii) ethylene glycol; and (iv) water.

[00151] In one embodiment, the extraction solution consists of (i) a pyrolysis oil, (ii) a methanol (iii) ethylene glycol; and (iv) water.

[00152] In one embodiment, the extraction solution comprises (i) a pyrolysis oil, (ii) a methanol, and (iii) water.

[00153] In one embodiment, the extraction solution essentially consists of (i) a pyrolysis oil, (ii) methanol, and (iii) water.

[00154] In one embodiment, the extraction solution consists of (i) a pyrolysis oil, (ii) a methanol, and (iii) water.

[00155] In one embodiment, the extraction solution comprises (i) a pyrolysis bio-oil, (ii) methanol (iii) at least one further alcohol solvent selected from ethylene glycol, propylene glycol, and propane-1,3-diol; and (iv) water.

[00156] In one embodiment, the extraction solution essentially consists of (i) a pyrolysis bio-oil, (ii) methanol (iii) at least one further alcohol solvent selected from ethylene glycol, propylene glycol, and propane-1,3-diol; and (iv) water.

[00157] In one embodiment, the extraction solution consists of (i) a pyrolysis bio-oil, (ii) methanol (iii) at least one further alcohol solvent selected from ethylene glycol, propylene glycol, and propane-1,3-diol; and (iv) water.

[00158] In one embodiment, the extraction solution comprises (i) a pyrolysis bio-oil, (ii) methanol (iii) ethylene glycol; and (iv) water.

[00159] In one embodiment, the extraction solution essentially consists of (i) a pyrolysis bio-oil, (ii) methanol (iii) ethylene glycol; and (iv) water.

[00160] In one embodiment, the extraction solution consists of (i) a pyrolysis bio-oil, (ii) methanol (iii) ethylene glycol; and (iv) water.

[00161] In one embodiment, the extraction solution comprises (i) a pyrolysis bio-oil, (ii) methanol and (iii) water.

[00162] In one embodiment, the extraction solution essentially consists of (i) a pyrolysis bio-oil, (ii) methanol and (iii) water.

[00163] In one embodiment, the extraction solution consists of (i) a pyrolysis bio-oil, (ii) methanol and (iii) water.

[00164] In another embodiment, the extraction solution comprises a pyrolysis oil in an amount of between about 1 to about 50 wt. %, and methanol in an amount of about 99 to about 50 wt. %.

[00165] In another embodiment, the extraction solution comprises a pyrolysis oil in an amount of between about 1 to about 50 wt. %, and methanol in an amount of about 90 to about 50 wt. %, and water in an amount of 0 to about 10 wt.%.

[00166] In another embodiment, the extraction solution comprises a pyrolysis oil in an amount of between about 10 to about 50 wt. %, and methanol in an amount of about 90 to about 50 wt. %.

[00167] In another embodiment, the extraction solution comprises a pyrolysis oil in an amount of between about 10 to about 50 wt. %, and methanol in an amount of about 90 to about 50 wt. %, and water in an amount of 0 to about 10 wt.%.

[00168] In one embodiment, the extraction solution comprises pyrolysis oil, methanol and optionally water in following proportions:

[00169] In one embodiment, the extraction solution comprises pyrolysis oil in an amount of about 10 wt. %.

[00170] In one embodiment, the extraction solution comprises pyrolysis oil in an amount of about 10 wt. % and methanol in an amount of about 80%.

[00171 ] In one embodiment, the extraction solution comprises pyrolysis oil in an amount of about 10 wt. %, methanol in an amount of about 80% and water in amount of about 10 wt. %.

Catalytic Composition [00172] The process of the invention comprises contacting the feedstock with a catalyst composition, wherein the catalyst composition comprises a solid acid catalyst.

[00173] In one embodiment, the catalyst composition essentially consists of/consists of a solid acid catalyst.

[00174] Solid acid catalysts are well known to the skilled person. Well known examples include zeolites and alumina silicates.

[00175] In one embodiment, the solid acid catalyst may be an acidic zeolite. As the skilled person will appreciate, aluminosilicate zeolites comprise Si04 and AI04 tetrahedra, and each AI04 tetrahedron, with its trivalent aluminium, bears an extra negative charge, which is balanced by mono-, bi- or tri- valent cations. Such zeolites are often prepared in their sodium form. However, surface acidity can be generated (to produce an acidic zeolite) by replacing Na+ by H+. Protons can be introduced into the structure through ion-exchanged forms, hydrolysis of water, or hydration of cations or reduction of cations to a lower valency state. In the case of hydrogen zeolites, protons associated with the negatively charged framework aluminium are the source of Bronsted acid activity and a linear relationship between catalytic activity and the concentration of protonic sites associated with framework aluminium has been demonstrated (W. O. Haag et al., Nature, 309, 589, 1984).

[00176] In one embodiment, the solid acid catalyst is a hydrogen zeolite (an H-zeolite). For instance, H-ZSM-5, Η-Beta, H-Y or H-Mordenite.

[00177] In another embodiment, acidic silicon aluminium phosphate (SAPO) zeolites may also be employed, for instance SAPO-34. SBA is also a suitable zeolite catalyst that may be employed.

[00178] In another embodiment, the solid acid catalyst may be used in combination with a mixed metal oxide. Examples of metal oxides and acidic mixed metal oxides that may be suitably employed are ZnO, V0P04 (e.g. V0P04.2H20), Zr02/W032', Zr02/S042-, Al203/P043' , Al203/Ti02/Zn0, Al203/Zr02/W03 and Ti02/S042\ [00179] In another embodiment, the solid acid catalysts may be a solid heteropolyacids. Suitable solid heteropolyacids include, for example, CsxHx-3PWi204o, H3PWi2O40.6H2O, H3PWi204o/K-10 clay, Ago.5H2.5PWi204o, Zro.7Ho.2PWi204o and H3PWi204o/Zr02.

[00180] In one embodiment, the solid acid catalyst is selected from an acidic aluminosilicate zeolite or an acidic silicon aluminium phosphate (SAPO) zeolite.

[00181] In another embodiment, the solid acid catalyst is an acidic aluminosilicate zeolite having the general formula (I):

(I) wherein M is H+ or M is two or more different cations, one of which is H+; and the Si/AI ratio y/x is from 1 to 300.

[00182] In one embodiment, the Si/AI ratio y/x may for instance be from about 20 to about 90, for instance be from about 30 to about 90, for instance from about 40 to about 80, or for example from about 50 to about 70, or from about 55 to about 65. In one embodiment, the Si/AI ratio y/x is about 60.

[00183] When M is two or more different cations, one of which is H+, the charge ratio of H+ to the other cations M is typically equal to or greater than 1. In other words at least half of the positive charges arising from all the Mn+ cations are typically due to protons.

[00184] In one embodiment, the solid acid catalyst is H-ZSM-5.

[00185] Typically, the solid acid catalyst is H-ZSM-5 with an Si/AI ratio of from 20 to 90, for instance from 30 to 90, for instance from 40 to 80, or for example from 50 to 70, or from 55 to 65. In one embodiment, the solid acid catalyst is H-ZSM-5 with an Si/AI ratio of about 60. Such H-ZSM-5 catalysts are commercially available from ZEOLYST international Company.

[00186] In one embodiment, the catalyst composition comprises a mesopororus solid acid catalyst. The meaning of the term “mesoporous” in the context of catalysis is well known in the art. For instance, the IUPAC Goldbook defines mesoporous as meaning pores of intermediate size between microporous and macroporous, in particular with widths between 2 nm and 0.05 pm.

[00187] In one embodiment, the catalyst composition comprises/essentially consists of/consists of a crystalline, mesoporous solid acid catalyst.

[00188] In one embodiment, the catalyst composition comprises an ordered mesoporous solid acid catalyst. In another embodiment, the catalyst composition comprises a non-ordered mesoporous solid acid catalyst.

[00189] In one embodiment, the catalyst composition essentially consists of/consists of a mesoporous solid acid catalyst. In another embodiment, the catalyst composition essentially consists of/consists of a non-ordered mesoporous solid acid catalyst. In another embodiment, the catalyst composition essentially consists of/consists of an ordered mesoporous solid acid catalyst.

[00190] In one embodiment, the mesoporous catalyst may be any of the solid acid catalysts referred to above in mesoporous form. In one embodiment, the catalyst composition comprises a mesoporous zeolite catalyst, suitably a mesoporous H-zeolite catalyst.

[00191] In one embodiment, the catalyst composition comprises a mesoporous solid acid catalyst selected from a mesoporous acidic aluminosilicate zeolite or a mesoporous acidic silicon aluminium phosphate (SAPO) zeolite.

[00192] In another embodiment, the catalyst composition comprises a mesoporous catalyst which is mesoporous H-ZSM-5.

[00193] The mesoporous solid acid catalyst may be prepared by adding a zeolite to a solution of base and optionally a surfactant. Accordingly, in one aspect the present invention relates to a mesoporous solid acid catalyst obtainable/obtained by treating a solid acid catalyst with a base and optionally a surfactant. In one embodiment, the solid acid catalyst is as defined above. For instance, the solid acid catalyst is an acidic zeolite, for example H-ZSM- 5.

[00194] In one embodiment, the base may be selected from carbonate and hydroxide-based bases. For instance, the base may be selected from Na2C03, NaHC03, NaOH, KOH, Ba(OH)2, CaC03 and Ca(OH)2. In one embodiment, the base is Na2C03.

[00195] In one embodiment, the solid acid catalyst is treated with base at a concentration of about 0.01 to 1 M, suitably about 0.05 to 0.2 M, suitably about 0.1 M.

[00196] In one embodiment, the surfactant may be any polar surfactant. Suitable surfactants include cationic, nonionic, and anionic surfactants. In various embodiments, cationic surfactants or nonionic surfactants are used. Non-limiting examples of cationic surfactants include cetyl trimethyl ammonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride and dioctadecyldimethylammonium bromide (DODAB).

[00197] Non-limiting example of non-ionic surfactants are polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, polyoxyethylene glycol octylphenol ethers, polyoxyethylene glycol alkylphenol ethers, polyoxyethylene glycol sorbitan alkyl esters, and block copolymers of polyethylene glycol and polypropylene glycol.

[00198] In one embodiment, the surfactant is cetyltrimethylammonium bromide (CTAB) [00199] In one embodiment, the solid acid catalyst is treated with surfactant at a concentration of about 0.01 to 1g of surfactant per 1g of catalyst, suitably about 0.05g to 0.2g per 1 g of catalyst, suitably about 0.1g of surfactant per 1g of catalyst.

[00200] In one embodiment, the catalyst composition comprises/essentially consists of/consists of a solid acid catalyst and a sulphur removal catalyst.

[00201] As used herein the term “sulphur removal catalyst” refers to a catalyst commonly employed in hydrodesulfurization reactions. Sulphur removal catalysts may also be referred to as HDS catalysts. Examples of sulphur removal catalysts are well known to the skilled person. For example, a sulphur removal catalyst is typically based on metals from groups VIB and VIII of the Periodic Classification of the Elements. For instance, sulphur removal catalyst typically comprises a transition metal capable of forming bonds to sulphur or oxygen, for example, Ni, Mo, Co, Cu, Zn, W, Fe, W, Pd, Pt, Rh, Ru.

[00202] Accordingly, the sulphur removal catalyst may be a sulphur removal catalyst comprising oxides and/or sulphides of transition metals, e.g. Ni, Mo, Co, Cu, Zn, W, Fe, W,

Pd, Pt, Rh, Ru as catalytic components. The transition metal catalyst may be supported on materials with high surface areas, e.g. alumina, TiO?, zeolites etc.

[00203] In one embodiment the sulphur removal catalyst is a bimetallic sulphur removal catalyst, in particular a bimetallic oxide or sulphide.

[00204] In one embodiment the sulphur removal catalyst is a termetallic sulphur removal catalyst, in particular a termetallic oxide or sulphide.

[00205] In one embodiment, the sulphur removal catalyst is a bimetallic sulphur removal catalyst supported on alumina, ΊΊΟ2, or a zeolite.

[00206] In one embodiment, the sulphur removal catalyst is a termetallic sulphur removal catalyst supported on alumina., ΊΊΟ2, or a zeolite.

[00207] In another embodiment, the sulphur removal catalyst comprises oxides/sulphides of cobalt and/or molybdenum on a support selected from alumina, HO2, and a zeolite. Suitably, the sulphur removal catalyst is a sulphide of cobalt or molybdenum on an AI2O3 support.

[00208] Suitable sulphur removal catalysts may have bimetallic catalytic components as follows: copper and zinc (CuZn), copper and nickel (CuNi), cobalt and molybdenum (C0M0), nickel and molybdenum (NiMo), nickel and tungsten (NiW).

[00209] Suitable sulphur removal catalysts may have catalytic components as follows: oxides of copper and zinc (CuZnOx), oxides of copper and nickel (CuNiOx), oxides of cobalt and molybdenum (CoMoOx),oxides of nickel and molybdenum (NiMoOx), oxides of nickel and tungsten (NiWOx), sulphides of copper and zinc (CuZnSx), sulphides of copper and nickel (CuNiSx), sulphides of cobalt and molybdenum (CoMoSx), sulphides of nickel and molybdenum (NiMoOx) and sulphides of nickel and tungsten (NiWSx).

[00210] In one embodiment, the sulphur removal catalyst has a catalytic component selected from CoMo/alumina, NiMo/alumina, NiW/zeolite, [00211 ] In another embodiment, the sulphur removal catalyst has a catalytic component selected from: oxides of nickel and molybdenum (NiMoOx), oxides of nickel and tungsten (NiWOx), and sulphides of cobalt and molybdenum (CoMoSx).

[00212] In another embodiment, the sulphur removal catalyst has a catalytic component selected from: oxides of nickel and molybdenum supported on alumina (NiMoOx/AI203), oxides of nickel and tungsten supported on ZSM-5 (NiWOx/ZSM-5), and sulphides of cobalt and molybdenum supported on alumina (C0M0SX/AI2O3).

[00213] In one embodiment, the sulphur removal catalyst is sulphurized. In another embodiment, the sulphur removal catalyst is used without sulphurization.

[00214] In one embodiment, the catalyst composition comprises a solid acid catalyst selected from an acidic aluminosilicate zeolite and an acidic silicon aluminium phosphate (SAPO) zeolite, and a sulphur removal catalyst comprising a catalytic component selected from CuZn, CuNi, CoMo, NiMo, NiW, CuZn, CuNi, CoMo, NiMo and NiW optionally on a support.

[00215] In one embodiment, the catalyst composition comprises a solid acid catalyst selected from an acidic aluminosilicate zeolite and an acidic silicon aluminium phosphate (SAPO) zeolite, and a sulphur removal catalyst comprising a catalytic component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[00216] In another embodiment, the catalyst composition comprises a solid acid catalyst selected from a mesoporous acidic aluminosilicate zeolite and a mesoporous acidic silicon aluminium phosphate (SAPO) zeolite, and a sulphur removal catalyst comprising a catalytic component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[00217] In another embodiment, the catalyst composition comprises H-ZSM-5, and a sulphur removal catalyst comprising a catalytic component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[00218] In another embodiment, the catalyst composition comprises mesoporous H-ZSM-5, and a sulphur removal catalyst comprising a catalytic component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[00219] In one embodiment, the ratio of solid acid catalyst to sulphur removal catalyst in the catalyst composition is from about 10:1 to about 1:1. In another embodiment, the ratio is about 10:1 to about 5:1, for example about 9:1.

[00220] In another embodiment, the catalyst composition comprises a mesoporous solid acid catalyst obtainable by treating H-ZSM-5 with Na2C03 solution and a CTAB solution, and a sulphur removal catalyst comprising a component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[00221] In another embodiment, the catalyst composition comprises a mesoporous solid acid catalyst obtainable by treating H-ZSM-5 with Na2C03 at concentration of about 0.01 to 1 M (suitably about 0.1 M) and a CTAB solution at a concentration of about 0.01 to about 1g of surfactant per 1g of catalyst (suitably about 0.1 g of surfactant per 1g of catalyst), and a sulphur removal catalyst comprising a component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[00222] In one embodiment, the catalyst composition is a mechanical mixture of solid acid catalyst and sulphur removal catalyst. That is to say the catalyst composition is a heterogeneous mixture of solid acid catalyst and sulphur removal catalyst. As such the sulphur removal catalyst is not chemically modified by the solid acid catalyst, they are simply in physical mixture.

[00223] In one embodiment, the catalyst composition comprises a solid acid catalyst and a sulphur removal catalyst, wherein the sulphur removal catalyst is not supported on the solid acid catalyst, i.e. chemically bonded to the solid acid catalyst.

Upgraded Petroleum Product [00224] As used herein, in each aspect of the invention, the term “upgraded” or “upgrading” used in relation to a petroleum product refers to removing or reducing the concentration of one or more unwanted substances in the petroleum product, and/or imparting or enriching the petroleum product with one or more desirable substances.

[00225] In one embodiment, the term “upgraded” or ’’upgrading” used in relation to a petroleum product refers to removing or reducing the concentration of one or more unwanted substances in the petroleum product. In another embodiment, the term “upgrading” or “upgraded” used in relation to a petroleum product refers to imparting or enriching the petroleum product with one or more desirable substances. Typically, upgraded is assessed relative to the petroleum product to be upgraded, i.e. the starting petroleum product prior to being subjected to the process of the invention (pre-reaction).

[00226] In one embodiment, the unwanted substances to be removed or reduced are selected from one or more of olefins and sulphur compounds. In another embodiment, the unwanted substances consist of olefins and sulphur compounds. In another embodiment, the unwanted substances consist of sulphur compounds. In another embodiment, the unwanted substances consist of olefins.

[00227] As used herein, the term “sulphur compounds” refers to molecules containing sulphur which are commonly found in petroleum products. Governments of numerous countries have adopted regulations which aim at a drastic reduction of sulphur emissions by vehicles thus requiring a very low concentration of this element in fuels. The EU presently requires that member states only allow gasoline (petrol) or diesel to be placed on the market within their territory if the sulphur content is 10 ppm or less. The new regulations make it necessary to remove sulphur compounds from gasoline and diesel almost completely.

[00228] In one embodiment, the sulphur compounds reduced/removed by the process of the invention comprise organic sulphur compounds (OSCs). In another embodiment, the sulphur compounds consist of organic sulphur compounds. In another embodiment, the sulphur compounds reduced/removed comprise compounds selected from thiols, thioethers, disulphides, thiophenes and benzothiophenes. In another embodiment, the sulphur compounds reduced/removed are selected from thiols, thioethers, disulphides, thiophenes and benzothiophenes.

[00229] As used herein, the term “olefins” refers to unsaturated hydrocarbons. The EU imposes restrictions on the amount of olefins in gasoline due to health and environmental concerns. The term “olefin” may be used interchangeably with “alkene”. In one embodiment, the olefins removed are olefins commonly found in petroleum products. In another embodiment, the olefins reduced/removed by the process of the invention are linear or branched C2 to Ci8 olefins. In another embodiment, the olefins reduced/removed are linear, branched or cyclic C4 to Ci4 olefins. In another embodiment, the olefins reduced/removed are linear, branched or cyclic C4 to C12 olefins. In another embodiment, the olefins reduced/removed are linear, branched or cyclic C4 to C10 olefins.

[00230] Examples of olefins which may be reduced/removed by the process of the invention include butene, pentene, methylbutene, hexene, methylpentene, dimethylbutene, heptene, methylhexene, dimethylpentene, octene, methylheptene, nonene, decene, undecene, dodecene, cyclobutene, cyclopentene, cyclohexene, cyclohexa-1,3-diene, methylcyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene and cyclooctene.

[00231] In another embodiment, the desirable substances enriched comprise/essentially consist of/consist of paraffins (also referred to as alkanes interchangeably).

[00232] In one embodiment, the paraffins enriched/imparted are selected from one or more of one or more C1-12 alkanes. For instance, one or more C4-12 alkanes. Thus, the alkanes may comprise one or more C6-12 alkanes, or more typically, for example, one or more C6-10 alkanes, or for instance one or more C6-8 alkanes. Often, the one or more alkanes, include a C8 alkane. Often, they include octane, for instance n-octane.

[00233] In another embodiment, the desirable substances enriched comprise/essentially consist of/consist of aromatic hydrocarbons.

[00234] In one embodiment, the aromatic hydrocarbons enriched/imparted are selected from one or more of C6-14 aromatic compounds. More typically, the aromatic hydrocarbon compounds are one or more aromatic hydrocarbon compounds selected from C6-12 aromatic compounds, for instance from C6-10 aromatic compounds. The aromatic hydrocarbon compounds may for instance comprise one or more aromatic hydrocarbon compounds selected from benzene, toluene, xylene, ethylbenzene, methylethylbenzene, trimethylbenzene, diethylbenzene, naphthalene, methylnaphthalene and ethylnaphthalene.

[00235] In one embodiment the upgraded petroleum product is upgraded gasoline.

[00236] The term “gasoline”, as used herein, refers to a composition comprising hydrocarbons that may be used as fuel, for instance in an internal combustion engine. Typically, a gasoline product comprises alkanes, alkenes, cyloalkanes and aromatic compounds (also known as paraffinic, olefinic, naphthenic and aromatic hydrocarbons respectively). Gasoline typically comprises hydrocarbon compounds containing from 4 to 12 carbon atoms. Gasoline may comprise one or more C4-12 alkane compounds, one or more C4-12 alkene compounds, one or more C4-10 cycloalkane compounds, or one or more C6-12 aromatic hydrocarbon compounds.

[00237] In one embodiment the gasoline product has a boiling point of less than or equal to about 225¾. In another embodiment, the gasoline product has a boiling point of less than or equal to about 220¾. In another embodiment, the gasoline product has a boiling point of less than or equal to about 200¾. In another embodiment, the gasoline product has a boiling point of less than or equal to about 180¾. In another embodiment, the gasoline product has a boiling point of less than or equal to about 160¾.

[00238] In one embodiment, gasoline product comprises hydrocarbons having a boiling point of from about 30¾ to about 225¾. In another embodiment, gasoline product essentially consists of hydrocarbons having a boiling point of from about 30¾ to about 225¾. In another embodiment, gasoline product consists of hydrocarbons having a boiling point of from about 30¾ to about 225¾.

[00239] In one embodiment, gasoline product comprises hydrocarbons having a boiling point of from about 30¾ to about 220¾. In another embodiment, gasoline product essentially consists of hydrocarbons having a boiling point of from about 30°C to about 220°C. In another embodiment, gasoline product consists of hydrocarbons having a boiling point of from about 30¾ to about 220 °C.

[00240] In one embodiment, the gasoline product comprises hydrocarbons having a boiling point of from about 30°C to about 200°C. In another embodiment, gasoline product essentially consists of hydrocarbons having a boiling point of from about 30¾ to about 200 °C. In another embodiment, gasoline product consists of hydrocarbons having a boiling point of from about 30¾ to about 200 °C.

[00241 ] In one embodiment, gasoline product comprises hydrocarbons having a boiling point of from about 30°C to about 180*^0. In another embodiment, gasoline product essentially consists of hydrocarbons having a boiling point of from about 30°C to about 180°C. In another embodiment, gasoline product consists of hydrocarbons having a boiling point of from about 30¾ to about 180°C.

[00242] In one embodiment, gasoline product comprises hydrocarbons having a boiling point of from about 30°C to about 160*^0. In another embodiment, gasoline product essentially consists of hydrocarbons having a boiling point of from about 30 °C to about 160°C. In another embodiment, gasoline product consists of hydrocarbons having a boiling point of from about 30 ¾ to about 160°C.

[00243] Reference to “boiling point” made herein is a reference to the boiling at standard pressure, unless otherwise stated.

[00244] The invention will now be further described by way of the following numbered paragraphs: 1. A process for producing an upgraded petroleum product which comprises contacting a feedstock with a catalyst composition; wherein the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol; and wherein the catalyst composition comprises a solid acid catalyst. 2. A process according to paragraph 1 wherein the feedstock is contacted with the catalyst composition at a temperature of equal to or above about 100°C, suitably equal to or above about 250°C, suitably equal to or above about 300°C, suitably equal to or above about 350 °C, suitably equal to or above about 400¾. 3. A process according to any preceding paragraph wherein the feedstock is contacted with the catalyst composition at a temperature of from about 200 eC to 800 eC, for example from about 200 eC to about 700 eC, for example from about 200 eC to 600 eC, for example from about 200 eC to 500 eC. 4. A process according to any preceding paragraph wherein the feedstock is contacted with the catalyst composition at a temperature of from about 400 eC to 800 eC, for example from about 400 eC to about 700 eC, for example from about 400 eC to 600 eC, for example from about 400 eC to 500 eC. 5. A process according to any preceding paragraph wherein the feedstock is contacted with the catalyst composition at a temperature of about 450 SC. 6. A process according to any preceding paragraph wherein the feedstock is contacted with the catalyst composition at a pressure of equal to or greater than about 125 KPa, for example greater than about 150 KPa, for example greater than about 175 KPa, for example greater than about 200 KPa, for example greater than about 225 KPa, for example greater than about 250 KPa, for example greater than about 275 KPa. 7. A process according to any preceding paragraph wherein feedstock is contacted with the catalyst composition at a pressure from about 250 KPa to about 500 KPa, for example, a pressure of between about 250 KPa and about 475 KPa, for example, a pressure of between about 250 KPa and about 450 KPa, for example, a pressure of between about 250 KPa and about 425 KPa, for example, a pressure of between about 250 KPa and about 400 KPa, for example, a pressure of between about 250 KPa and about 375 KPa, for example, a pressure of between about 250 KPa and about 350 KPa. 8. A process according to any preceding paragraph wherein feedstock is contacted with the catalyst composition at a pressure from about 300 KPa to about 500 KPa, for example, a pressure of between about 300 KPa and about 475 KPa, for example, a pressure of between about 300 KPa and about 450 KPa, for example, a pressure of between about 250 KPa and about 425 KPa, for example, a pressure of between about 300 KPa and about 400 KPa, for example, a pressure of between about 300 KPa and about 375 KPa, for example, a pressure of between about 300 KPa and about 350 KPa, for example, a pressure of between about 300 KPa and about 340 KPa, for example, a pressure of between about 300 KPa and about 330 KPa, for example, a pressure of between about 300 KPa and about 320 KPa, for example, a pressure of between about 300 KPa and about 310 KPa. 9. A process according to any preceding paragraph wherein the process comprises contacting the feedstock with a catalyst at a temperature of from about 350 SC to 500 eC and a pressure of from about 250 KPa to about 400 KPa. 10. A process according to any preceding paragraph wherein the process comprises contacting the feedstock with a catalyst at a temperature of from about 425 SC to 475 eC and a pressure of from about 275 KPa to about 325 KPa. 11. A process according to any preceding paragraph wherein the process comprises contacting the feedstock with a catalyst at a temperature of about 450SC and a pressure of about 300 KPa. 12. A process according to any preceding paragraph wherein the feedstock is treated with catalyst at a WHSV of equal to or greater than about 0.1 hr1, for example, equal to or greater than about 0.5 hr1, for example, equal to or greater than about 1.0 hr1, for example, equal to or greater than about 1.5 hr1, or for example equal to or greater than about 2.0 hr1. 13. A process according to any preceding paragraph wherein the feedstock is treated with catalyst at a WHSV of about 1.5 hr1 to about 2.5 hr1. 14. A process according to any preceding paragraph wherein the feedstock essentially consists of petroleum product or at least one component thereof, a pyrolysis oil and methanol. 15. A process according to any preceding paragraph wherein the feedstock consists of petroleum product or at least one component thereof, a pyrolysis oil and methanol. 16. A process according to any preceding paragraph wherein the petroleum product is FCC gasoline or at least one component thereof. 17. A process according to any preceding paragraph wherein petroleum product or at least one component thereof is selected from paraffins, aromatic hydrocarbons, olefins and organic sulphur compounds. 18. A process according to any preceding paragraph wherein the petroleum product or at least one component thereof is selected from olefins and organic sulphur compounds. 19. A process according to any preceding paragraph wherein the petroleum product or at least one component thereof is selected from one of more C2-18 alkenes and C4-10 cycloalkenes, for example, one or more C4-m alkenes and C4-10 cycloalkenes, for example one or more C4-12 alkenes and C4-10 cycloalkenes. 20. A process according to any preceding paragraph wherein the petroleum product or at least one component thereof is selected from one of more one or more substituted or unsubstituted C4-18 organosulfur compounds, for example one or more substituted or unsubstituted C4-12 organosulfur compounds. 21. A process according to any preceding paragraph wherein the petroleum product or at least one component thereof is obtained/obtainable by extracting FCC gasoline with a polar organic solvent, for example, methanol. 22. A process according to any preceding paragraph wherein the pyrolysis oil is obtained/obtainable from biomass. 23. A process according to any preceding paragraph wherein the pyrolysis oil is a pyrolysis bio-oil. 24. A process according to any preceding paragraph wherein the feedstock comprises a further solvent, for example, a solvent selected from ethanol, propanol, isopropanol, butanol, sec-butanol, iso-butanol, water, ethylene glycol, propylene glycol, and propane-1,3-diol. 25. A process according to any preceding paragraph wherein the feedstock comprises a further solvent selected from water and ethylene glycol, for example water. 26. A process according to any preceding paragraph wherein the feedstock comprises a pyrolysis oil in an amount of about 5 wt. % to about 60 wt. %. 27. A process according to any preceding paragraph wherein the feedstock comprises a pyrolysis oil in an amount of about 10 wt. % to about 20 wt. %. 28. A process according to any preceding paragraph wherein the feedstock comprises methanol is an amount of about 40 wt. % to about 95 wt. %. 29. A process according to any preceding paragraph wherein the feedstock comprises methanol in an amount of about 80 wt. % to about 95 wt. %. 30. A process according to any preceding paragraph wherein the feedstock comprises a pyrolysis oil in an amount of between about 5 to about 50 wt. %, and methanol in an amount of about 95 to about 50 wt. %. 31. A process according to any preceding paragraph wherein the feedstock comprises the petroleum product or at least one component thereof in an amount of less than or equal to 50 wt. %, for example less than 40 wt. %, for example less than 30 wt. %, for example less than about 20 wt. %, for example less than about 10 wt. %, for example less than about 5 wt. %, for example less than about 2.5 wt. %, for example less than about 1 wt. %. 32. A process according to any preceding paragraph wherein the feedstock is obtained/obtainable by extracting FCC gasoline with an extraction solution wherein said extraction solution comprises/essentially consists of/consists of a pyrolysis oil and methanol. 33. A process according to paragraph 32 wherein the pyrolysis oil is obtained/obtainable from fossil fuels, plastic, rubber and biomass. 34. A process according to any one of paragraphs 32 to 33 where the pyrolysis oil is obtained/obtainable from biomass. 35. A process according to any one of paragraphs 32 to 34 where the biomass is selected from wood, crops, agricultural residues and domestic and industrial waste and mixtures thereof. 36. A process according to any one of paragraphs 32 to 35 where the pyrolysis oil is pyrolysis bio-oil. 37. A process according to any one of paragraphs 32 to 36 where the ratio of FCC gasoline to extraction solution is from about 20:1 to about 1:20. 38. A process according to any one of paragraphs 32 to 36 where the ratio of FCC gasoline to extraction solution is from about 5:1 to 1:1. 39. A process according to any one of paragraphs 32 to 38 where the extraction solution further comprises a solvent selected from water, an alcohol, an aldehyde, a ketone, an ether, a carboxylic acid, an ester, a carbonate, an acid anhydride, an amide, an amine, a heterocyclic compound, an imine, an imide, a nitrile, a nitro compound, a sulfoxide, and a haloalkane. 40. A process according to any one of paragraphs 32 to 39 where the extraction solution further comprises a solvent selected from water and an alcohol. 41. A process according to any one of paragraphs 32 to 40 where the extraction solution further comprises a solvent selected from water, ethylene glycol, propylene glycol, and propane-1,3-diol. 42. A process according to any one of paragraphs 32 to 41 where the extraction solution comprises (i) a pyrolysis bio-oil, (ii) methanol and (iii) water. 43. A process according to any one of paragraphs 32 to 42 where the extraction solution comprises the pyrolysis oil in an amount of about 10 wt. % and methanol in an amount of about 80%. 44. A process according to any one of paragraphs 32 to 43 where the extraction solution comprises pyrolysis oil in an amount of about 10 wt. %, a polar organic solvent in an amount of about 80%, and water in an amount of about 10 wt. %. 45. A process according to any preceding paragraph wherein the catalyst composition essentially consists of/consists of a solid acid catalyst. 46. A process according to any preceding paragraph wherein the solid acid catalyst is selected from an acidic aluminosilicate zeolite or an acidic silicon aluminium phosphate (SAPO) zeolite. 47. A process according any preceding paragraph wherein the solid acid catalyst is selected from a hydrogen zeolite (an H-zeolite), for example, H-ZSM-5, Η-Beta, H-Y or H-Mordenite. 48. A process according to any preceding paragraph wherein the solid acid catalyst is H-ZSM-5. 49. A process according to any preceding paragraph wherein the solid acid catalyst is a mesoporous solid acid catalyst. 50. A process according to any preceding paragraph wherein the solid acid catalyst is a non-ordered or ordered mesoporous solid acid catalyst. 51. A process according to any preceding paragraph wherein the solid acid catalyst is a crystalline mesoporous solid acid catalyst. 52. A process according to any preceding paragraph wherein the solid acid catalyst is obtained/obtainable by treating a solid acid catalyst with a base and optionally a surfactant. 53. A process according to paragraph 52 wherein the base is selected from carbonate and hydroxide-based bases, for example Na2C03, NaHC03, NaOH, KOH, Ba(OH)2 and Ca(OH)2. 54. A process according to any one of paragraphs 52 to 53 wherein the base is Na2C03. 55. A process according to any one of paragraphs 52 to 54 wherein the surfactant is selected from a cationic surfactant and a non-ionic surfactant. 56. A process according to any one of paragraphs 52 to 55 wherein the surfactant is selected from cetyl trimethyl ammonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride and dioctadecyldimethylammonium bromide (DODAB), suitably cetyltrimethylammonium bromide (CTAB). 57. A process according to any preceding paragraph wherein the catalyst composition further comprises a sulphur removal catalyst. 58. A process according to paragraph 57 wherein the sulphur removal catalyst is selected from a transition metal oxide or sulphide optionally supported on a carrier. 59. A process according to any one of paragraphs 57 and 58 wherein the sulphur removal catalyst is a bimetallic sulphur removal catalyst comprising a catalytic component selected from oxides of copper and zinc (CuZnOx), oxides of copper and nickel (CuNiOx), oxides of cobalt and molybdenum (CoMoOx),oxides of nickel and molybdenum (NiMoOx), oxides of nickel and tungsten (NiWOx), sulphides of copper and zinc (CuZnSx), sulphides of copper and nickel (CuNiSx), sulphides of cobalt and molybdenum (CoMoSx), sulphides of nickel and molybdenum (NiMoOx) and sulphides of nickel and tungsten (NiWSx). 60. A process according to any one of paragraphs 57 to 59 wherein the sulphur removal catalyst is supported on alumina, Ti02 or a zeolite. 61. An upgraded petroleum product obtainable/obtained by a process according to any of paragraphs 1 to 60. 62. An upgraded petroleum product according to paragraph 60 which is an upgraded gasoline or diesel product. 63. A catalyst composition comprising a solid acid catalyst and a sulphur removal catalyst wherein said composition is a heterogeneous mixture of the solid acid catalyst and the sulphur removal catalyst. 64. A catalyst composition to paragraph 63 wherein the catalyst composition essentially consists of/consists of a solid acid catalyst and a sulphur removal catalyst. 65. A catalyst composition according to any one of paragraphs 63 and 64 wherein the solid acid catalyst is selected from an acidic aluminosilicate zeolite or an acidic silicon aluminium phosphate (SAPO) zeolite. 66. A catalyst composition according to any one of paragraphs 63 to 65 wherein the solid acid catalyst is selected from a hydrogen zeolite (an H-zeolite), for example, H-ZSM-5, H-Beta, H-Y or H-Mordenite. 67. A catalyst composition according to any one of paragraphs 63 to 66 wherein the solid acid catalyst is H-ZSM-5. 68. A catalyst composition according to any one of paragraphs 63 to 67 wherein the solid acid catalyst is a mesoporous solid acid catalyst. 69. A catalyst composition according to any one of paragraphs 63 to 68 wherein the solid acid catalyst is a non-ordered or ordered solid acid catalyst. 70. A catalyst composition according to any one of paragraphs 63 to 69 wherein the solid acid catalyst is a crystalline solid acid catalyst. 71. A catalyst composition according to any one of paragraphs 63 to 70 wherein the sulphur removal catalyst is selected from a sulphur removal catalyst comprising transition metal oxide or sulphide, optionally supported on a carrier. 72. A catalyst composition according to any one of paragraphs 63 to 71 wherein the sulphur removal catalyst is a bimetallic sulphur removal catalyst comprising a catalytic component selected from oxides of copper and zinc (CuZnOx), oxides of copper and nickel (CuNiOx), oxides of cobalt and molybdenum (CoMoOx), oxides of nickel and molybdenum (NiMoOx), oxides of nickel and tungsten (NiWOx), sulphides of copper and zinc (CuZnSx), sulphides of copper and nickel (CuNiSx), sulphides of cobalt and molybdenum (CoMoSx), sulphides of nickel and molybdenum (NiMoOx) and sulphides of nickel and tungsten (NiWSx). 73. A catalyst composition according to any one of paragraphs 63 to 72 wherein the sulphur removal catalyst is supported on alumina, Ti02 or a zeolite. 74. A catalyst composition according to any one of paragraphs 63 to 73 wherein the solid acid catalyst is obtained/obtainable by treating a solid acid catalyst with a base and optionally a surfactant. 75. A catalyst composition according to any one of paragraphs 63 to 74 wherein the base is selected from carbonate and hydroxide-based bases, for example Na2C03, NaHC03, NaOH, KOH, Ba(OH)2 and Ca(OH)2. 76. A catalyst composition according to any one of paragraphs 63 to 75 wherein the base is Na2C03. 77. A catalyst composition according to any one of paragraphs 63 to 76 wherein the surfactant is a cationic or non-ionic surfactant. 78. A catalyst composition according to any one of paragraphs 63 to 77 wherein the surfactant is cetyltrimethylammonium bromide (CTAB). 79. A process for preparing a catalyst according to any one of claims 63 to 78 comprising mechanically mixing a solid acid catalyst and a sulphur removal catalyst. 80. Use of a catalyst composition according to any one of paragraphs 63 to 79 for upgrading a feedstock wherein the feedstock comprises one or more of a petroleum product or at least one component thereof, a pyrolysis oil and methanol. 81. Use according to paragraph 80 wherein the feedstock comprises two or more of a petroleum product or at least one component thereof, a pyrolysis oil and methanol. 82. Use according to any one of paragraphs 80 and 81 wherein the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol. 83. Use according to any one of paragraphs 80 to 82 wherein the pyrolysis oil is pyrolysis bio-oil. 84. Use according to any one of paragraphs 80 to 83 wherein the petroleum product is FCC gasoline or at least one component thereof.

EXAMPLES

Materials [00245] Methanol with purity of 99.9% was purchased from Sigma Aldrich Company. Pyrolysis bio-oil was purchased from Future Blends Limited, UK. FCC gasoline was purchased from Petroineos Manufacturing Scotland LTD, UK. These agents were used without further purification. HZSM-5 with a Si/AI ratio of 60 was purchased from ZEOLYST international Company, USA. Sulphur Removal catalyst, RMS-IB (CoMo/AI203) was obtained from Qimao Catalysts, China and used directly without sulphurization.

Preparation of Modified HZSM-5 Catalyst [00246] Zeolite HZSM-5 was treated with 0.1 M of Na2C03 (about 15mL/g of zeolite) and cetrimonium bromide (CTAB) (0.1g CTAB/g of zeolite) solution for 3 hours at 75°C. The sample was filtered and washed with de-ionized water until the pH of water wash was neutral. Fresh Na2C03and CTAB solutions of the same primary concentration were added and the treatment repeated.

[00247] After washing with water and drying overnight at 80°C the sample was ion exchanged by treating with a 1.0 M solution of ammonium nitrate NH4NO3 (about 15 mL/g of zeolite) for 3 hours at 75¾. The sample was filtered and washed with de-ionized water until pH of water wash was neutral. Fresh NH4NO3 solution of the same primary concentration was added and treatment repeated.

[00248] After washing with water then drying overnight at 80°C, the sample was calcinated at 500 °C for 6 hours to obtain protonated sample. The latter was labelled as 0.10C60, which represents the HZSM-5 with the Si/AI ratio of 60 sample treated with 0.1 M solution of Na2C03 and 0.1g CTAB/g of zeolite as described above.

[00249] During the catalytic conversion process, 0.10C60 HZSM-5 was mechanically mixed with sulphur removal catalyst with catalytic component CoMo/AI203 (RMS-1 B) with 9:1 ratio in weight to form a catalyst composition. The latter was labelled as 0.10C60+HDS.

Preparation of Feedstock [00250] An extraction solution was prepared consisting of methanol (80%, wt), Bio-oil (10%, wt) and distilled water (10%, wt). FCC gasoline and the extraction solution were fed into a separating funnel in a ratio (wt.%) of 5:1 FCC gasoline to extraction solution. The two phases were mixed well by vigorously shaking the separating funnel. The mixture was allow to stand and two liquid phases were observed in the mixture, the mixture was stabilized for another 5 minutes (Figure 2). The upper phase and lower extract phase were separated, and fresh extraction solution was added into the upper phase with 5:1 ratio (wt.%) upper phase to extraction solution. This process was repeated another 4 times and the upper phase was isolated. The extract phases (also referred to as LPM or LPM feedstock herein) comprising products extracted from FCC, methanol and bio-oil were retained for use as the feedstock in the catalytic upgrading process.

Catalytic Upgrading Process [00251] A fixed bed microreactor system was used in the catalytic conversion process as depicted in Figure 1. In this process, as feedstock, the extract phase referred to above comprising products extracted from FCC, methanol and bio-oil (LPM) was pumped into the microreactor by a HPLC pump. The pumping flow rate of these mixtures into the reactor was 4g/hour. The carrier gas for the conversion process was nitrogen and the flow rate was set to 20ml/min. During the reaction preparation of each test, 2 gram of unmodified HZSM-5 (HZSM-5) or 0.10C60+HDS mixed catalyst was added into the reactor tube with the carborundum sand and quartz wool in order to prevent the catalyst being blown away by the carrier gas. The weight hour space velocity (WHSV) of the system was calculated to be about 2 hour1. The temperature of the system was maintained at 450¾ and the pressure was varied as described below.

[00252] Four sets of conditions were investigated in the microreactor. In each case the reaction time was 6 hours.

[00253] Condition 1: Feedstock = bio-oil and methanol 1:7 (wt.) mixture; catalyst = HZSM-5; reaction condition = 450°C and atmospheric pressure.

[00254] Condition 2: Feedstock = LPM; catalyst = HZSM-5; reaction condition = 450¾ and atmospheric pressure.

[00255] Condition 3: Feedstock = LPM; catalyst = HZSM-5; reaction condition = 450¾ and 301 KPa; [00256] Condition 4: Feedstock = LPM; catalyst: 0.10C60+HDS, reaction condition: 450¾ and 301 KPa.

Analysis of the Upgraded Petroleum Product [00257] A SHIMADZU GC2014 gas chromatography (GC) spectrometer was linked to the gas outlet of the microreactor to analyse the gaseous product from the conversion process (Figure 1). The gaseous product was injected into the GC analyser each hour during the conversion process. The main operating parameters of GC spectrometer were: Column Oven Temperature 45^ Injection Temperature 300^ the system was held at 45¾ for 4 minutes, then increased from 45 to 200¾ at 50^min, then at 200¾ the system held for another 7.8 minutes. The temperature was then increased at 10^min, until it reached 300¾.

[00258] The GC results showed that the hydrogen and carbon monoxide yield of condition 2, i.e. employing LPM as feedstock, were higher than when the feedstock consisted of a bio-oil and methanol mixture (condition 1) (Figure 3). The higher production of hydrogen is likely to lead to better hydrogenation performance during the catalytic upgrading process.

[00259] Comparing the results of conditions 2 and 3, GC (TCD) demonstrated that the hydrogen yield of the conversion at a pressure of 301 KPa is higher than the conversion at atmospheric pressure, whereas the carbon monoxide yield is similar (Figure 7).

[00260] Comparing the results of conditions 3 and 4, GC (TCD) demonstrated that the hydrogen yield of the conversion when using the 0.10C60+HDS mixed catalyst is higher than the conversion using unmodified HZSM-5, whereas the carbon monoxide yield is similar (Figure 11).

[00261] Further, GC analysis also demonstrated that the yields of gaseous paraffins are higher when LPM is used as a feedstock (condition 2) compared to the feedstock consisting of bio-oil and methanol only (condition 1) (Figure 4). Consequently, the upgrading process using LPM as the feedstock provides more gasoline range hydrocarbon product.

[00262] Also, the yield of gaseous olefins was found to be lower when LPM is used as the feedstock (condition 2) compared to the feedstock consisting of bio-oil and methanol only (condition 1) (Figure 4). This may be due to the higher H2 yield when LPM is used as the feedstock in the conversion process.

[00263] A comparison of the GC (TCD) outcome of conditions 2 and 3 showed the yield of gaseous paraffin C2-C4 and C4 olefin are higher when the conversion is performed 301 KPa. Meanwhile, the yields of methane, ethylene and propylene under condition 3 are lower than when condition 2 is employed (Figure 8).

[00264] A comparison of the GC (TCD) outcome of conditions 3 and 4 showed the yield of gaseous methane, ethylene, ethane and propylene are higher when the conversion is performed with the 0.10C60+HDS mixed catalyst (condition 4). The yields of propane, butanes and butylenes are higher when the conversion is performed with the unmodified HZSM-5 catalyst (condition 3) (Figure 12).

[00265] Liquid product was collected from the liquid outlet of the microreactor. Two phases were observed in the liquid product, the oil phase at the top and water phase at the bottom. The two phases were separated and the weight and volume of the oil phase measured.

[00266] Figure 5 shows that a 61% increase in yield of the oil phase (wt. %) was observed when LPM was used as the feedstock (condition 2) as opposed to a feedstock consisting of bio-oil/methanol mixture (condition 1).

[00267] Figure 9 shows that a 24% increase in yield of the oil phase (wt. %) was observed when the conversion of LPM was carried out at 301 KPa (condition 3) compared to atmospheric pressure (condition 2).

[00268] Figure 13 shows that a 2.6% increase in yield of the oil phase (wt. %) was observed when the conversion of LPM was carried with a 0.10C60+HDS mixed catalyst (condition 4) compared to an unmodified HZSM-5 catalyst (condition 3).

[00269] The oil phase was sent to the GCMS analyser to quantify the aromatic hydrocarbons content therein. The main operating parameters of GCMS analyser were: Column Oven Temperature 35^3/308 K; Injection Temperature 205°C/478 K; Injection Mode direct. The temperature was increased from 35 to 40¾ at a rate of 1 °C/min, and after 40°C the rate was changed to lO'C/min, until the temperature reached 180°C/453 K.

[00270] The GCMS spectra showed that the concentration of a range of aromatic hydrocarbons was higher in the oil phase when conditions employing LPM as feedstock (condition 2) were used as opposed to a feedstock consisting of a bio-oil and methanol mixture (condition 1) (Figure 6). The increase in aromatics concentration is likely to result in a desirable increase in octane number of the oil phase product prepared from LPM compared to the oil phase product prepared from the bio-oil/methanol mixture.

[00271] On comparison of the oil phases produced under conditions 2 and 3, GCMS showed that the concentration of aromatic hydrocarbons in the oil phase was higher when the conversion was carried out at 301 KPa (condition 3) than at atmospheric conditions (condition 2) (Figure 10).

[00272] On comparison of the oil phases produced under conditions 3 and 4, GCMS showed that the concentration of aromatic hydrocarbons in the oil phase was higher when the conversion was carried out with 0.10C60+FIDS mixed catalyst (condition 4) compared to an unmodified FIZSM-5 catalyst (condition 3) (Figure 14).

[00273] In summary, the use of a feedstock comprising a petroleum product or component thereof, bio-oil and methanol, and/or performing the catalytic conversion at pressure and/or using a 0.10C60+FIDS mixed catalyst leads to improvements in hydrogen generation, increased yield of the oil phase, increased proportion of gasoline product hydrocarbons, reduced levels of olefins and increased levels of aromatic hydrocarbons. Consequently, these process conditions provide an improved upgraded petroleum product.

[00274] The stability of the oil phase produced under conditions 1 and 2 was assessed by storing it for one month at ambient temperature and pressure in sealed glass amber bottles. The oil phase was then reanalysed by GCMS.

[00275] Before storage the oil phase from condition 1 was visually assessed as brown in colour and transparent (Figure 15a). One month later, the oil phase product became black and non-transparent (Figure 15b). Content change was observed in the GCMS analysis results (Figure 15c). Without being bound by theory, this may be the result of the presence of unconverted oxy-organics (oxygenates) in the oil phase produced by condition 1, and insufficient generation of hydrogen from methanol during the catalytic conversion.

[00276] A similar but less pronounced change in oil phase composition was observed visually when the oil phases of conditions 2 and 3 (Figures 16a,b and 17a,b) were stored for one month. GCMS analysis also indicated a change in product composition (Figures 16c and 17c).

[00277] Flowever, when the oil phase produced using the 0.10C60+FIDS mixed catalyst (condition 4) was stored for two months no obvious colour change was observed (Figure 18). Furthermore, GCMS analysis also did not show any obvious change in the composition of the oil phase. Without being bound by theory, this may be due to the oxy-organics (oxygenates) in the LPM feedstock being converted through FIDO processes as a result of hydrogen generated during the reaction.

[00278] Gasoline is formed of a complex mixture of paraffins, isoparaffins, olefins, naphthenics, aromatics and some amount of other compounds, with chains containing 4 to 12 atoms of carbon, and the range of ebullition from 30 to 225^0. In order to establish that the oil phase product produced under condition 4 can be treated as a gasoline product, the boiling point under atmosphere was analysed.

[00279] The analyser used was a TA Instruments SDT Analyzer Model Q600. The analysis program was: 100ml/min carrier gas flow rate (N2), 5°C/min heating rate, final temperature is 600 °C.

[00280] TGA analysis indicated that all the content evaporated before the temperature of the furnace reached 180°C (Figure 19). The oil phase consisted of a two part mixture with different ebullition temperature. Before 105°C the major part (71.31% wt.) of the oil phase evaporated, and from 105°C to 180°C the remaining part of the oil phase evaporated (Figure 19).

[00281] In summary, the gasoline products produced by the exemplified processes have improved stability compared to petroleum products produced by upgrading bio-oil/methanol mixtures. Further improvements in stability of the upgraded petroleum products are possible when a 0.10C60+FIDS mixed catalyst is used in the upgrading process.

Analysis of the Catalyst [00282] X-ray Diffraction (XRD) patterns were used to identify the phase and assess the crystallinity of the powder samples. XRD patterns were recorded using a PANalytical (X’Pert PRO model) diffractometer with Cu Ka radiation in the 2Θ range of 2-60°.

[00283] Figure 20 shows the XRD pattern of pre-reaction 0.10C60 catalyst in comparison with pre-reaction unmodified HZSM-5. The diffractograms show that both of the samples consist of a major MFI crystalline phase. Accordingly, the crystallinity is well preserved for both 0.10C60 modified catalyst and unmodified samples, even though the (101) peak of the alkaline treated zeolite is slightly reduced. The desilication treatment changes the zeolite structure slightly, in particular, a slight decrease in the intensities of the signals and therefore in crystallinity was detected. Moreover, no reflections were observed in the low angle 20-region (Figure 20), indicating that the mesopores for 0.10C60 are not ordered.

[00284] The reproducibility of the modified 0.10C60 catalyst has also been assessed. Three batches of the 0.10C60 catalyst were produced at different times. XRD analysis of each batch showed that all three batches of catalyst were found to have the same XRD pattern (Figure 21).

[00285] Fourier Transform Infrared Spectroscopy (FT-IR) experiments were performed using a Perkin Elmer FT-IR Spectrum RXI spectrometer to investigate the possible changes of the catalyst active sites during the modification of the catalyst from the parent FIZSM-5. Catalyst samples were prepared as pills with 3 mg of catalyst per 997 mg KBr. The infrared spectra were obtained under the scanning conditions of wavelength range 400-4000 cm-1, resolution of 1 cnr1 and scanned 10 times.

[00286] Figure 22 shows the FTIR spectra of the unmodified FIZSM-5 and 0.10C60 catalyst. Both samples have well separated bands. Characteristic peaks are present near 450 cm'1, 550 cm'1, 800 cm'1, 1100 cm1, 1200 cm1, 1650 cm1, 3440 cm1, 3660 cm1 for each catalyst indicating the persistence of the framework of the ZSM-5 phase. The peak at 3660 cnr1 represents Si-OH groups commonly located on the external surface of the zeolite. The peak near 3450 cm'1 is related to nearly free Si-OFI sites inside the structure. The asymmetric T-O stretching vibration of the band at 1225 cm"1, has been assigned to external linkages between TCU tetrahedral. The peaks near 1100 cm 1 (internal asymmetric stretch), 800 cm 1 (external symmetric stretch), 550 cnr1 (ring vibration) and 450 cnr1 (T-O connection) were present for all catalyst samples and belong to the usual FTIR fingerprint of the ZSM-5 phase.

[00287] Compared to the unmodified HZSM-5, 0.10C60 catalyst showed an increased intensity of all characteristic peaks (Figure 22). As intensity of the peaks increases with the increase of specific surface area, it is concluded that the 0.10C60 modified catalyst has bigger surface area than unmodified HZSM-5.

[00288] To investigate the stability of the catalysts, samples of the pre-reaction unmodified HZSM-5 and pre-reaction 0.10C60+HDS mixed catalyst were compared by XRD to samples of each catalyst after reaction with LPM at a pressure of 301 KPa and at 450 °C (conditions 3 and 4 respectively (above)).

[00289] It was found that the intensity of the characteristic peaks between post-reaction HZSM-5 and post-reaction 0.10C60+HDS mixed catalyst varied only slightly to the respective pre-reaction catalysts (Figures 26 and 27). That means the crystallinity of the post-reaction catalysts was conserved. The slight decrease of the peak intensity (highlighted in Figures 26 and 27) is due to the coke deposition on the post-reaction catalysts. However, on comparison of the characteristic peaks around 45°(2Θ) of both post-reaction 0.10C60+HDS mixed catalyst and post-reaction unmodified HZSM-5 catalyst it can be seen that the peaks of the 0.10C60+HDS mixed catalyst are of higher intensity and sharper. This is indicative of the higher crystallinity of the post-reaction 0.10C60+HDS mixed catalyst, which suggests that during the conversion less coke deposition takes place on the 0.10C60+HDS mixed catalyst than the unmodified HZSM-5 catalyst.

[00290] During the post-reaction analysis of catalysts, Laser Raman Spectroscopy was also used to analyse coke deposition on the catalysts by subtracting the fluorescence caused by coke. The measurements were carried out using 3 to 5 mg of post-reaction catalyst. Laser Raman spectra were obtained from a Perkin Elmer Raman Station 400F spectrometer. The sample was assessed under the following conditions: temperature = -49^: exposure time = 5 seconds, exposure was done 4 times while minimizing exposure to air to avoid coke oxidation.

[00291] For both the post-reaction unmodified HZSM-5 and the 0.10C60+HDS mixed catalyst, two major peaks were observed in the spectra (Figure 23): (i) 1425 cm-1, “breathing” vibrational mode of not-well-structured aromatics (D-band coke); (ii) 1600 cm-1, in-plane stretching vibrational modes of well-structured aromatics (G-band coke).

[00292] Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) was also used to analyse the coke deposition on the post-reaction catalysts. The catalyst after each reaction was collected and 30-50 mg of catalyst sample was analysed by the TGA/DSC analyser. The analyser was a TA Instruments SDT Analyzer Model Q600. The analysis program was: 100ml/min carrier gas flow rate (Air), 10°C/min heating rate, final temperature was 1000°C.

[00293] The post-reaction samples of unmodified HZSM-5 and 0.10C60+HDS mixed catalyst from conversions under conditions 3 and 4 above were analysed.

[00294] The results indicated that the HZSM-5 catalyst was 15.48 wt.% coke postreaction (Figure 24). Under the same reaction conditions, 0.10C60+HDS mixed catalyst was 12.07 wt.% coke post-reaction (Figure 25). Accordingly, 0.10C60+HDS mixed catalyst has better anti-coke performance during the conversion process than unmodified HZSM-5, and can be expected to have a longer catalytic lifetime.

[00295] In summary, the 0.10C60+HDS mixed catalyst has improved anti-coke performance than unmodified HZSM-5 catalyst in the upgrading process. Both unmodified HZSM-5 catalyst and 0.10C60+HDS mixed catalyst present good stability during the upgrading process.

Conclusion [00296] The process of the present invention provides higher yields of upgraded petroleum products and higher yields of gasoline range hydrocarbons compared to upgrading processes wherein the feedstock consists of a mixture of bio-oil and methanol. Product storage analysis has shown that the upgraded petroleum products of the present invention have improved storage stability.

[00297] Moreover, by employing a catalytic composition comprising a modified HZSM-5 catalyst mixed with a sulphur removal catalyst the oil phase yield and gasoline range product yield is improved. Furthermore, the stability of the upgraded petroleum product is further improved.

[00298] Also, it has been shown that a catalytic composition comprising a modified HZSM-5 catalyst mixed with a sulphur removal catalyst has improved anticoke properties.

[00299] The present invention provides an improved method for pyrolysis oil upgrading/utilization, and/or a more sustainable FCC gasoline/diesel upgrading process, and/or a novel modified catalyst with improved upgrading performance.

[00300] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference in their entirety and to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein (to the maximum extent permitted by law).

[00301] All headings and sub-headings are used herein for convenience only and should not be construed as limiting the invention in any way.

[00302] The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise paragraphed. No language in the specification should be construed as indicating any non-paragraphed element as essential to the practice of the invention.

[00303] The citation and incorporation of patent documents herein is done for convenience only and does not reflect any view of the validity, patentability, and/or enforceability of such patent documents.

[00304] This invention includes all modifications and equivalents of the subject matter recited in the paragraphs appended hereto as permitted by applicable law.

Claims

1. A process for producing an upgraded petroleum product which comprises contacting a feedstock with a catalyst composition; wherein the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol; and wherein the catalyst composition comprises a solid acid catalyst.

2. A process according to claim 1 wherein the petroleum product is FCC gasoline or at least one component thereof.

3. A process according to any preceding claim wherein the pyrolysis oil is pyrolysis bio oil.

4. A process according to any preceding claim wherein the feedstock is obtainable by extracting FCC gasoline with an extraction solution comprising pyrolysis bio-oil and methanol.

5. A process according to any preceding claim wherein the feedstock is contacted with the catalyst composition at pressure of between about 150 KPa and about 500 KPa.

6. A process according to any preceding claim wherein the feedstock is contacted with the catalyst composition at pressure of about 300 KPa.

7. A process according to any preceding claim wherein the catalyst composition comprises a combination of a solid acid catalyst and a sulphur removal catalyst.

8. A process according to any preceding claim wherein the solid acid catalyst is FI-ZSM- 5.

9. A process according to any preceding claim wherein the solid acid catalyst is obtainable by treating H-ZSM-5 with a Na2C03 and CTAB solution.

10. A process according to any one of claims 7 to 9 wherein the sulphur removal catalyst is selected from a sulphur removal catalyst having bimetallic catalytic components selected from copper and zinc (CuZn), copper and nickel (CuNi), cobalt and molybdenum (CoMo), nickel and molybdenum (NiMo), nickel and tungsten (NiW).

11. An upgraded petroleum product obtainable according to the process of any one of claims 1 to 10.

12. A catalyst composition comprising a solid acid catalyst and a sulphur removal catalyst wherein said composition is a heterogeneous mixture of the solid acid catalyst and the sulphur removal catalyst.

13. A catalyst composition according to claim 12 wherein the solid acid catalyst is obtainable by treating H-ZSM-5 with a Na2C03 and CTAB solution.

14. A catalyst composition according to any one of claims 12 and 13 wherein the sulphur removal catalyst is selected from a sulphur removal catalyst having bimetallic catalytic components selected from copper and zinc (CuZn), copper and nickel (CuNi), cobalt and molybdenum (CoMo), nickel and molybdenum (NiMo), nickel and tungsten (NiW).

15. Use of a catalyst composition according to any one of claims 12 to 14 for upgrading a feedstock wherein the feedstock comprises one or more of (i) a petroleum product or at least one component thereof, (ii) a pyrolysis oil and (iii) methanol.

16. Use according to claim 15 wherein the feedstock comprises a petroleum product or at least one component thereof, a pyrolysis oil and methanol.