Process for upgrading pyrolysis oil and upgrading solution used therein

Abstract

A process for upgrading pyrolysis oil, the process comprising treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof; and upgraded pyrolysis oil produced by the process.

Description

[0001] introduction

[0002] This paper describes a process for upgrading the quality of pyrolysis oil derived from plastics, rubber, or a combination thereof. The low-cost and efficient process utilizes sustainable resources to produce stable pyrolysis oil that can be used as a transportation fuel, for blending with fuels, and / or as a chemical feedstock. Background of the Invention

[0004] The total amount of plastic manufactured from 1950 to 2015 was approximately 8,300 Mt. Half of this was produced in the past 13 years alone. 2 If current production and waste management trends continue, around 12,000Mt of plastic waste will be in landfill or in the natural environment by 2050. 2 Between 1950 and 2015, the cumulative waste generation of primary (recycled) plastic waste and secondary (recycled) plastic waste amounted to 6300 Mt, of which approximately 800 Mt (12%) had been incinerated and 600 Mt (9%) had been recycled, of which only 10% had been recycled more than once. About 4900 Mt – 60% of all plastic ever produced – was discarded and accumulated in landfills or in the natural environment ( Figure 1 ) 2 .

[0005] Plastic items entering the waste stream come in a wide range of formats and are made from a variety of polymer types. The majority of this material is plastic film from commercial and household packaging sources and is sourced from municipal material recovery facilities (MRFs), with the remainder coming from composting and anaerobic digestion facilities. 1

[0006] The technology that is used to convert waste plastics and other solid hydrocarbon materials into oil is known. Gasification and pyrolysis technology of coal were commercialized in Germany during World War II, and were further developed in South Africa during the apartheid era. Plastic depolymerization technology was actively developed during the 1980s and 1990s, but because mechanical recovery methods developed rapidly, none of them were adopted commercially. In the past 10 years, as oil prices increased and waste collection and sorting methods improved, the amount of research on plastic conversion into oil has increased. In different parts of the world, there are now several technologies close to commercial feasibility operations.

[0007] The processes with the greatest technical and commercial potential fall into three categories: 1

[0008] Rapid gas-phase pyrolysis to produce synthetic crude oil blends;

[0009] Liquid phase catalytic depolymerization to produce mixed distillates; and

[0010] Gasification followed by chemical or biological synthesis to produce high-quality fuels.

[0011] Gasification processes with downstream synthesis of high-quality fuels are more capital intensive and require greater economies of scale than pyrolysis and catalytic depolymerization. These processes have lower product yields (30%-60% of the feedstock is recovered as liquid fuel), but recover energy in the form of electricity from the high-pressure, high-temperature process. 1

[0012] In contrast, pyrolysis and catalytic depolymerization processes have relatively low capital costs and relatively high yields (60%-70% of the feedstock is converted to liquids). However, the quality of these petroleum products is low and requires additional processing to give fuel products. Nevertheless, the high yields improve the environmental and economic viability of these processes. 1

[0013] The low quality of plastic pyrolysis oil is mainly due to solid residues, high olefin content and high heteroatom content.

[0014] The solid residue content may be due to inorganic content (e.g., dirt, soil, sand, SiO2, etc.) and / or coke / char content and / or unconverted plastic (e.g., HDPE, PP, etc.). 3 Therefore, pyrolysis oil cannot meet the standards required for transportation fuel because the solid residue will be very harmful to the cylinders of the internal combustion engine (ICE) and will easily clog the oil distribution lines and oil filters; thus resulting in inefficient combustion of the fuel.

[0015] Therefore, plastic pyrolysis oil upgrading processes tend to require the removal of solid residues by filtration or centrifugation.However, these upgrading processes significantly increase the capital and operating costs of the waste plastic to fuel process due to the large amount of feed stream required to be processed.

[0016] High concentrations of olefins are present in various plastic pyrolysis oils. As shown in the table below, the yield of the total olefin fraction from polyethylene (PE) is 42.6%, the yield of the total olefin fraction from polypropylene (PP) is 44.7%, and the yield of the total olefin fraction from municipal plastic waste is 37.3%. 4

[0017]

[0018]

[0019] The high olefin content in plastic pyrolysis oil leads to instability. In particular, during storage, the olefins react with oxygen and other components in the atmosphere. The subsequent polymerization reaction leads to the formation of a gel, which can adversely affect the physicochemical properties of the plastic pyrolysis oil. 5 These polymeric materials lead to deposits in the oil filter and the distribution lines of the engine.Therefore, plastic pyrolysis oil must undergo upgrading treatments, such as hydrogenation, to reduce the olefin levels. 5

[0020] Therefore, capital and operating costs will be increased significantly.A simpler approach is to blend the plastic pyrolysis oil into commercial gasoline / diesel to dilute the unstable olefin content. 6,7 However, even if the blend could meet the required fuel standards, it would certainly reduce the stability of the original fuel due to the increased olefin content and could result in higher emissions. 7

[0021] Plastics used as flame retardants, such as polyvinyl chloride (PVC) and acrylonitrile-butadiene-styrene (ABS), contain heteroatoms such as chlorine, nitrogen and bromine, which remain as organic compounds in the plastic pyrolysis oil during thermal degradation and also generate acids or toxic gases such as HCl, HBr, HCN, NH3 or polyhalogenated dibenzodioxins and dibenzofurans. 8-10 Their presence in pyrolysis oil is undesirable.

[0022] Thermal degradation of ABS produces oils which, besides large amounts of benzene derivatives, also contain organic nitrogen such as aliphatic and aromatic nitriles or nitrogen-containing heterocyclic compounds. 8,11 Brominated flame retardants in ABS also produce organic bromine compounds in the oil, among which bromophenol, bromobenzene and bromomethane are of note. 8,12

[0023] On the other hand, there have been many studies on individual PVCs. 13,14 or reports on the pyrolysis of PVC mixed with other polymers. 8,15 Hydrochloric acid and organic chlorine-containing compounds are formed during the initial stages of the process. 8,16,17

[0024] Therefore, the amount of these undesirable contents in plastic pyrolysis oil must be reduced as much as possible.

[0025] The removal of halogens and undesirable contents from plastics by catalytic conversion has been reported. Bhaskar et al. 12The development of calcium-based composites, iron-based composites, and potassium-based carbon composites for the capture of hydrogen chloride gas is reported. The calcium-based composites and the iron-based composites were found to be effective catalysts for the debromination of pyrolysis oil from polymers blended with high-impact polystyrene or brominated ABS. 18-20 The iron oxides and iron-carbon composites reduce the amount of nitrogen in the ABS pyrolysis oil and convert aromatic nitriles into light aliphatic nitriles as well as gaseous ammonia and hydrogen cyanide. 21

[0026] Brebu et al. reported the decomposition of a polymer mixture containing PE, PP, PS, ABS-Br, and PVC, and the effects of iron-based and calcium-based catalysts on the removal of bromine, chlorine, and nitrogen from plastic pyrolysis oil. 8 In their study, an iron-based catalyst and a calcium-based catalyst were used in vapor phase contacting (VPC) mode. 8 This means that the catalyst comes into contact with and reacts with the volatile products from the primary degradation of the plastic.

[0027] Brebu et al. observed that the oil product from the thermal decomposition of complex polymer mixtures contained significant amounts of bromine (1900 ppm), chlorine (5000 ppm), and nitrogen (1200 ppm) from the decomposition of brominated ABS and PVC. 8 The removal performance of bromine, chlorine, and nitrogen for various catalysts from the study by Brebu et al. is summarized in the table below.

[0028] Bromine (ppm) Chlorine (ppm) Nitrogen (ppm) Calories 1924 4972 1214 catalyst FeO(OH) 104 3370 840 <![CDATA[Fe3O4-based]]> 170 1014 981 <![CDATA[CaCO3-based]]> 418 113 1370 <![CDATA[CaCO3]]> 1161 335 1078

[0029] Iron oxyhydroxide produced the lowest amount of organic bromine (104 ppm) and nitrogen (840 ppm) in the plastic pyrolysis oil, and the CaCO3-based catalyst produced the lowest amount of organic chlorine (113 ppm) in the plastic pyrolysis oil. The authors concluded that pure iron oxyhydroxide and iron (II, III) oxide-based catalysts were found to be effective in removing more than 90 wt% of organic bromine from the degraded oil, while calcium carbonate-based catalysts and pure calcium carbonate produced the best results in terms of chlorine removal. 8

[0030] Although catalytic conversion can remove most heteroatoms, some heteroatom content is still present in the output fuel (<100 ppm) and makes it unsuitable for application in internal combustion engines.

[0031] There is a need in the art for alternative methods for upgrading pyrolysis oils, particularly pyrolysis oils derived from plastics, rubber, or combinations thereof. Suitably, the novel methods for upgrading provide higher quality pyrolysis oils having at least one or more advantages selected from the group consisting of lower olefin content, lower solid residue content, and lower heteroatom content. The upgraded pyrolysis oil product can be used as a transportation fuel, for blending with fuels, and / or as a chemical feedstock. SUMMARY OF THE INVENTION

[0033] In a first aspect, the present invention relates to a process for upgrading pyrolysis oil, the process comprising treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0034] In a second aspect, the present invention relates to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0035] (i) treating the pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0036] (ii) mixing the pyrolysis oil and the upgrading solution, and then allowing the mixture to form two phases consisting of a raffinate phase and an extract phase; and

[0037] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0038] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0039] In a third aspect, the present invention relates to the use of an upgrading solution for reducing the olefin content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0040] In a fourth aspect, the present invention relates to the use of an upgrading solution for reducing the solid residue content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent; and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0041] In a fifth aspect, the present invention relates to the use of an upgrading solution for increasing the stability of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent; and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0042] In a sixth aspect, the present invention relates to an upgraded pyrolysis oil obtainable by the process according to the first or second aspect of the invention.

[0043] Preferred features, suitable features and optional features of any particular aspect of the invention are also preferred features, suitable features and optional features of any other aspect. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 Provides details on global plastic use and the fate of millions of metric tons of plastic after use.

[0046] Figure 2 A schematic diagram of the pyrolysis unit is provided.

[0047] Figure 3 shows the colour of mixed pyrolysis oil (made of 25% LDPE, 25% PP, 25% PS and 25% rubber by weight) (a) and after paraffin washing (b) in sunlight (c).

[0048] FIG4 shows gasoline fractions after distillation of (a) original mixed pyrolysis oil and (b) upgraded pyrolysis oil.

[0049] FIG5 shows the colors of raw plastic pyrolysis oil (a) and pyrolysis oil after the purification process (b).

[0050] Figure 6 An apparatus for a catalytic upgrading process is shown. Detailed Description of the Invention

[0052] definition

[0053] As used herein, in each aspect of the invention, the terms "upgrading" and "upgraded" used in relation to pyrolysis oil refer to removing or reducing the concentration of one or more undesirable substances in the pyrolysis oil, and / or imparting or enriching the pyrolysis oil with one or more desired substances.

[0054] As used herein, the term "solid residue" refers to the solid material remaining after the pyrolysis oil has been heated to a high temperature (i.e., above about 400°C) and cooled to standard ambient temperature and pressure (SATP), i.e., at a temperature of about 298.15 K (25°C) and a pressure of about 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm).

[0055] As used herein, the term "hydrocarbon" refers to an organic compound composed of carbon and hydrogen.

[0056] For the avoidance of doubt, hydrocarbons include linear and branched, saturated and unsaturated aliphatic hydrocarbon compounds, including alkanes, alkenes and alkynes; and saturated and unsaturated cyclic aliphatic hydrocarbon compounds, including cycloalkanes, cycloalkenes and cycloalkynes; and hydrocarbon polymers, such as polyolefins.

[0057] Hydrocarbons also include aromatic hydrocarbons, ie hydrocarbons containing one or more aromatic rings. The aromatic rings may be monocyclic or polycyclic.

[0058] Aliphatic hydrocarbons substituted by one or more aromatic hydrocarbons and aromatic hydrocarbons substituted by one or more aliphatic hydrocarbons are of course also encompassed by the term "hydrocarbon" (such compounds consisting only of carbon and hydrogen), such as straight-chain or branched aliphatic hydrocarbons substituted by one or more cyclic aliphatic hydrocarbons and cyclic aliphatic hydrocarbons substituted by one or more straight-chain or branched aliphatic hydrocarbons.

[0059] “C n-m Hydrocarbons" or "C n -C m "Cn-Cm hydrocarbons" or "Cn-Cm hydrocarbons" (wherein n and m are integers) are hydrocarbons as defined above having from n to m carbon atoms. For example, C 1-150 Hydrocarbons are hydrocarbons as defined above having from 1 to 150 carbon atoms, and C 5-60 Hydrocarbons are hydrocarbons as defined above having from 5 to 60 carbon atoms.

[0060] As used herein, the term "alkane" refers to a straight or branched saturated hydrocarbon compound. Examples of alkanes are, for example, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and hexadecane. Alkanes such as dimethylbutane can be one or more possible isomers of this compound. Thus, dimethylbutane includes 2,3-dimethylbutane and 2,2-dimethylbutane. This also applies to all hydrocarbon compounds mentioned herein, including cycloalkanes, olefins, and cycloolefins.

[0061] As used herein, the term "cycloalkane" refers to a saturated cyclic aliphatic hydrocarbon compound. Examples of cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane, and cyclooctane. 5-8 Examples of cycloalkanes include cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane, and cyclooctane.The terms "cycloalkane" and "naphthene" may be used interchangeably.

[0062] As used herein, the term "alkene" refers to a straight or branched hydrocarbon compound containing one or more double bonds. Examples of alkene are butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, and tetradecene. Alkenes typically contain one or two double bonds. The terms "alkene" and "olefin" can be used interchangeably. One or more double bonds can be at any position in the hydrocarbon chain. Alkenes can be cis-olefins or trans-olefins (or as defined using E-nomenclature and Z-nomenclature). Alkenes containing terminal double bonds can be referred to as "alkane-1-ene" (e.g., hex-1-ene), "terminal alkene" (or "terminal olefin"), or "alpha-alkene" (or "alpha-olefin"). As used herein, the term "alkene" also often includes cycloolefins.

[0063] As used herein, the term "cycloolefin" refers to a partially unsaturated cyclic hydrocarbon compound. Examples of cycloolefins include cyclobutene, cyclopentene, cyclohexene, cyclohexa-1,3-diene, methylcyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene, and cyclooctene. Cycloolefins may contain one or two double bonds.

[0064] As used herein, the term "aromatic hydrocarbon" or "aromatic hydrocarbon compound" refers to a hydrocarbon compound containing one or more aromatic rings. The aromatic rings may be monocyclic or polycyclic. Typically, aromatic compounds contain benzene rings. Aromatic compounds may be, for example, C 6-14 Aromatic compounds, C 6-12 Aromatic compounds or C 6-10 Aromatic compounds. C 6-14 Examples of aromatic compounds are benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, naphthalene, methylnaphthalene, ethylnaphthalene and anthracene.

[0065] As used herein, the term "plastic" refers to a solid material comprising one or more thermoplastic polymers or thermosetting polymers. Suitably, the plastic consists (substantially) of one or more thermoplastic polymers or thermosetting polymers. Suitably, the plastic consists (substantially) of one or more thermoplastic polymers. Suitably, the plastic is waste plastic, which may be a mixture of multiple plastics. Plastics may be referred to by the name of the polymers from which they are composed. Examples of common plastics are polyethylene, polypropylene and polystyrene.

[0066] As used herein, the term "thermoplastic polymer" refers to a polymer that becomes flexible or moldable above a certain temperature and solidifies upon cooling, but can remelt upon heating. Typically, thermoplastic polymers have a melting temperature of from about 60°C to about 300°C, from about 80°C to about 250°C, or from about 100°C to about 250°C.

[0067] Suitably, thermoplastic polymers are thermoplastic polymers that are typically included in commercial plastic products. Suitable thermoplastic polymers typically include polyolefins, polyesters, polyamides, copolymers thereof, and combinations thereof. Examples of thermoplastic polymers include polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyamide-imide, polymethyl methacrylate (PMMA), polytetrafluoroethylene, polyethylene terephthalate (PET), natural rubber (NR), and polycarbonate (PC), polyvinylidene chloride (PVDC), acrylonitrile butadiene styrene (ABS), and polyurethane (PU).

[0068] As used herein, the term "thermosetting polymer" refers to a polymer that is irreversibly cured and cannot be reprocessed after reheating. Examples of thermosetting polymers are polyurethane and polyoxybenzyl methyl glycol anhydride (Bakelite TM ).

[0069] As used herein, the term "specific gravity (20 / 4)" refers to the true density of a sample at 20°C divided by the density of water at 4°C.

[0070] As used herein, the term "fluid" refers to a material that is a liquid or gas at standard ambient temperature and pressure (SATP), i.e., at a temperature of about 298.15 K (25°C) and a pressure of about 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm).

[0071] As used herein, the term "liquid" suitably refers to a liquid at standard ambient temperature and pressure (SATP), ie at a temperature of about 298.15 K (25°C) and a pressure of about 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm).

[0072] As used herein, the term "desulfurization catalyst" refers to a catalyst typically used in hydrodesulfurization reactions. Desulfurization catalysts may also be referred to as HDS catalysts. Examples of desulfurization catalysts are well known to those skilled in the art. For example, desulfurization catalysts typically comprise a transition metal. For example, desulfurization catalysts typically comprise a transition metal capable of forming bonds with sulfur or oxygen, such as Ni, Mo, Co, Cu, Zn, Fe, W, Pd, Pt, Rh, Ru.

[0073] Extraction process

[0074] In one aspect, the present invention relates to a process for upgrading pyrolysis oil, the process comprising treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber, or a combination thereof.

[0075] In another aspect, the present invention relates to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0076] (i) treating the pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0077] (ii) mixing the pyrolysis oil and the upgrading solution, and then allowing the mixture to form at least two phases including a raffinate phase and an extract phase; and

[0078] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0079] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0080] In another aspect, the present invention relates to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0081] (i) treating the pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0082] (ii) mixing the pyrolysis oil and the upgrading solution, and then allowing the mixture to form two phases consisting of a raffinate phase and an extract phase; and

[0083] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0084] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0085] In another aspect, the present invention relates to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0086] (i)(a) treating pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0087] (i)(b) optionally treating the product of (i)(a) with a hydrocarbon fluid;

[0088] (ii) mixing the pyrolysis oil and the upgraded solution obtained from (i)(a) or optionally (i)(b), and then allowing the mixture to form at least two phases comprising a raffinate phase and an extract phase; and

[0089] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0090] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0091] In one embodiment, "upgrading" and "upgraded" as used in relation to pyrolysis oil refer to removing or reducing the concentration of one or more undesirable substances in the pyrolysis. In another embodiment, the terms "upgrading" and "upgraded" as used in relation to pyrolysis refer to imparting one or more desirable substances to the pyrolysis oil or enriching the pyrolysis oil with one or more desirable substances. Typically, upgrading / upgrading is assessed relative to the pyrolysis oil to be upgraded, i.e., the starting pyrolysis oil before undergoing the process of the present invention.

[0092] In one embodiment, the unwanted substances to be removed or reduced are selected from one or more of solid residues (e.g., inorganic materials, coke, char), olefins, and compounds containing heteroatoms such as sulfur, nitrogen, or halogens. In another embodiment, the unwanted substances consist of solid residues, olefins, and sulfur compounds.

[0093] In another embodiment, the undesirable species consists of compounds comprising heteroatoms, suitably the heteroatom-containing compounds are selected from sulphur compounds, nitrogen compounds and halogen compounds or combinations thereof.

[0094] In one embodiment, the sulfur compounds reduced / removed by the process of the present invention comprise organosulfur compounds (OSCs). In another embodiment, the sulfur compounds consist of organosulfur compounds. In another embodiment, the sulfur compounds reduced / removed comprise compounds selected from the group consisting of mercaptans, sulfides, disulfides, thiophenes, and benzothiophenes. In another embodiment, the sulfur compounds reduced / removed are selected from the group consisting of mercaptans, sulfides, disulfides, thiophenes, and benzothiophenes.

[0095] In one embodiment, the halogen compound is a halogen compound commonly found in plastic or rubber pyrolysis oil. These compounds include, for example, halogenated acids (such as HCl and HBr) and halogenated aromatic compounds, such as polyhalogenated dibenzodioxins and dibenzofurans.

[0096] In one embodiment, nitrogen compounds are nitrogen-containing molecules commonly found in pyrolysis products.In one embodiment, nitrogen compounds reduced / removed by the process of the present invention include organic nitrogen compounds, such as ammonia and organic amines and imines.

[0097] In another embodiment, the undesirable material consists of olefins, suitably alpha-olefins. In another embodiment, the olefins reduced / removed by the process of the present invention are linear or branched C2 to C 18In another embodiment, the olefins reduced / removed are linear, branched or cyclic C4 to C 14 In another embodiment, the olefins reduced / removed are linear, branched or cyclic C4 to C 12 In another embodiment, the olefins reduced / removed are linear, branched or cyclic C4 to C 10 Olefins.

[0098] In one embodiment, desirable substances that can be enriched / imparted to the upgraded pyrolysis oil include oxygenates. Oxygenates are desirable in fuels such as gasoline because they increase octane rating and thus allow for a reduction in carcinogenic aromatic compounds. Thus, oxygenates in fuels contribute to policies aimed at reducing CO emissions and particulates in exhaust gases.

[0099] In another embodiment, the desired substance that is enriched / imparted consists of oxygenates. As used herein, the term "oxygenate" refers to a hydrocarbon containing one or more oxygen atoms. In one embodiment, the oxygenates that are enriched / imparted are selected from one or more of ethers, esters, ketones, carboxylic acids, aldehydes, and alcohols. In another embodiment, the oxygenates are selected from one or more of ethers, esters, aldehydes, ketones, and alcohols. In another embodiment, the oxygenates are selected from one or more of ethers, aldehydes, ketones, and alcohols. In another embodiment, the oxygenates are selected from one or more of ethers, suitably alpha ethers.

[0100] Examples of oxygenates that may be enriched / imparted into / into the pyrolysis oil / raffinate phase include methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), tert-amyl methyl ether (TAME), and diisopropyl ether (DIPE).

[0101] The pyrolysis oil and the upgrading solution can be mixed by any means known in the art. For example, the pyrolysis oil and the upgrading solution can be added to a container, reactor, or mixer commonly used in the art, and the two components can be mixed. Mixing can include vigorously stirring the two components using a mixing device. For example, the two components can be mixed together by stirring or by shaking.

[0102] The mixing of the two components may occur more than once. For example, after the first mixing of the pyrolysis oil and the upgrading solution, the resulting two phases may be mixed again, possibly multiple times. The steps of contacting and forming the two phases may be continuous. Thus, the two components may pass through a mixing device before entering a separation chamber where the first and second phases are formed. The contact of the two components may be achieved using a propeller, a countercurrent flow device, a stirring device, column, Column or centrifugal extractor.

[0103] The pyrolysis oil can be repeatedly mixed with fresh batches of upgrading solution multiple times. For example, the pyrolysis oil can be mixed with a first batch of upgrading solution to provide a first raffinate phase and a first extract phase. After the raffinate phase is separated from the extract phase, the raffinate phase can be mixed with a second batch of upgrading solution to provide a second raffinate phase and a second extract phase. This cycle can be repeated multiple times.

[0104] In one embodiment, the cycle of mixing the pyrolysis oil and its raffinate with the upgrading solution is repeated between 1 and 9 times. In another embodiment, the cycle is repeated between 1 and 4 times. In another embodiment, the cycle is repeated 1, 2, 3, or 4 times. In another embodiment, the cycle is repeated 4 times.

[0105] Typically, the pyrolysis oil and the upgrading solution are mixed to an extent that allows for efficient extraction of the pyrolysis oil by the upgrading solution. For two immiscible solutions, the skilled person will understand that typically these solutions are intimately mixed until an emulsion is formed, which is then allowed to separate into two phases.

[0106] In one embodiment, mixing is carried out at ambient temperature and pressure. Typically, at a temperature between about 18°C ​​and 28°C, more typically between about 21°C and 25°C, and a pressure of about 100 kPa. Thus, the costs and other problems associated with high temperature or high pressure conditions are avoided.

[0107] Alternatively, mixing is carried out at a temperature between about 0°C and about 70°C, suitably about 15°C to about 50°C.

[0108] Typically, the mass ratio of pyrolysis oil to upgrading solution is from about 95:5 to about 10:90. In one embodiment, the mass ratio of pyrolysis oil to upgrading solution is from about 95:5 to about 50:50, or suitably from about 95:5 to about 60:40, or suitably from about 95:5 to about 70:30, or suitably from about 95:5 to about 80:20. In one embodiment, the mass ratio of pyrolysis oil to upgrading solution is about 90:10.

[0109] As used herein, the term "raffinate phase" refers to a phase comprising / consisting essentially of / consisting of upgraded pyrolysis oil.

[0110] In one embodiment, the raffinate phase / upgraded pyrolysis oil will have a reduced concentration of undesirable species compared to the pyrolysis oil prior to mixing with the upgrading solution.

[0111] In one embodiment, the raffinate phase / upgraded pyrolysis oil will have a reduced concentration of one or more of sulfur compounds, olefins, and solid residues compared to the pyrolysis oil prior to mixing with the upgrading solution.

[0112] In one embodiment, the concentration of sulfur compounds in the raffinate / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 80% (wt.%) relative to the concentration of sulfur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulfur compounds in the raffinate / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 70% (wt.%) relative to the concentration of sulfur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulfur compounds in the raffinate / upgraded pyrolysis oil is reduced by about 30% (wt.%) to about 80% (wt.%) relative to the concentration of sulfur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulfur compounds in the raffinate / upgraded pyrolysis oil is reduced by about 30% (wt.%) to about 70% (wt.%) relative to the concentration of sulfur compounds in the starting pyrolysis oil. In another embodiment, the concentration of sulfur compounds in the raffinate / upgraded pyrolysis oil is reduced by about 40% (wt.%) to about 60% (wt.%) relative to the concentration of sulfur compounds in the starting pyrolysis oil.

[0113] In one embodiment, the raffinate phase / upgraded pyrolysis oil will have a reduced concentration of olefins compared to the pyrolysis oil prior to mixing with the upgrading solution.

[0114] In one embodiment, the concentration of olefins in the raffinate / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 80% (wt.%) relative to the concentration of olefins in the starting pyrolysis oil. In another embodiment, the concentration of olefins in the raffinate / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 70% (wt.%) relative to the concentration of olefins in the starting pyrolysis oil. In another embodiment, the concentration of olefins in the raffinate / upgraded pyrolysis oil is reduced by about 30% (wt.%) to about 80% (wt.%) relative to the concentration of olefins in the starting pyrolysis oil. In another embodiment, the concentration of olefins in the raffinate / upgraded pyrolysis oil is reduced by about 30% (wt.%) to about 70% (wt.%) relative to the concentration of olefins in the starting pyrolysis oil. In another embodiment, the concentration of olefins in the raffinate / upgraded pyrolysis oil is reduced by about 40% (wt.%) to about 60% (wt.%) relative to the concentration of olefins in the starting pyrolysis oil.

[0115] In one embodiment, the raffinate phase / upgraded pyrolysis oil will have a reduced concentration of chlorides compared to the pyrolysis oil prior to mixing with the upgrading solution.

[0116] In one embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 80% (wt.%) relative to the chloride concentration in the starting pyrolysis oil. In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 70% (wt.%) relative to the chloride concentration in the starting pyrolysis oil. In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 10% (wt.%) to about 60% (wt.%) relative to the chloride concentration in the starting pyrolysis oil.

[0117] In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 30% (wt. %) to about 80% (wt. %) relative to the chloride concentration in the starting pyrolysis oil. In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 30% (wt. %) to about 70% (wt. %) relative to the chloride concentration in the starting pyrolysis oil. In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 30% (wt. %) to about 60% (wt. %) relative to the chloride concentration in the starting pyrolysis oil.

[0118] In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 40% (wt. %) to about 60% (wt. %) relative to the chloride concentration in the starting pyrolysis oil. In another embodiment, the chloride concentration in the raffinate phase / upgraded pyrolysis oil is reduced by about 50% (wt. %) to about 60% (wt. %) relative to the chloride concentration in the starting pyrolysis oil.

[0119] In one embodiment, the raffinate phase / upgraded pyrolysis oil will have reduced concentrations of sulfur compounds and olefins compared to the pyrolysis oil before mixing with the upgrading solution. Suitably, the concentrations of sulfur compounds and olefins will be reduced to the extent as described in any of the embodiments above.

[0120] In the process of the present invention, the raffinate phase tends to have a lower density than the extract phase, and therefore the raffinate phase will generally be the upper phase and the extract phase will generally be the lower phase.

[0121] Typically, the process also includes separating the raffinate phase to produce an upgraded pyrolysis oil.

[0122] The raffinate phase can be separated by any means used in the art, and is typically separated by a physical process. The separation typically involves physically isolating the raffinate phase or at least some of the raffinate phase. Thus, the separation typically involves separating at least some of the raffinate phase from the extract phase.

[0123] Since the two phases will typically have separated in the same vessel due to their immiscibility, the separation may simply comprise removing (e.g., by draining or decanting) at least a portion of the extract phase from the vessel containing the extract and raffinate phases. Alternatively, the raffinate phase may be removed from the vessel (e.g., by draining or decanting) to leave the extract phase.

[0124] In one aspect, the present invention relates to a raffinate phase obtainable by a process as defined in any of the above embodiments.

[0125] In another aspect, the present invention relates to a raffinate phase obtained by a process as defined in any of the above embodiments.

[0126] As used herein, the term "extract phase" refers to a phase that typically contains an upgrading solution, such as the upgrading solution after it has been mixed with the pyrolysis oil. Typically, after mixing with the pyrolysis oil, the extract phase will contain the majority of the upgrading solution. Typically, the extract phase will be denser than the raffinate phase and will form the lower layer. In addition to the upgrading solution, the extract phase may contain one or more undesirable substances extracted from the pyrolysis oil.

[0127] In another aspect, the present invention relates to an upgraded pyrolysis oil obtained by a process as defined in any one of the embodiments above. In one embodiment, the upgraded pyrolysis oil obtained / obtainable by the process of the present invention is suitable as a fuel (e.g. gasoline) or for blending with a fuel (e.g. gasoline).

[0128] Pyrolysis oil

[0129] Pyrolysis oil is a substance known to those skilled in the art. Pyrolysis oil can be obtained from a variety of sources. The present invention relates to pyrolysis oil derived from plastics, rubber, or a combination thereof. In one embodiment, the pyrolysis oil to be upgraded is obtainable or obtained by pyrolysis of plastics, rubber, or a combination thereof. Typically, pyrolysis is carried out at high temperatures (greater than 400° C.) and in the absence of oxygen at very high heating rates.

[0130] In another embodiment, the pyrolysis oil is obtainable or obtained by pyrolysis of plastic. In another embodiment, the pyrolysis oil is obtainable or obtained by pyrolysis of rubber. In another embodiment, the pyrolysis oil is obtainable or obtained by pyrolysis of a combination of plastic and rubber.

[0131] In one embodiment, the combination of rubber and plastic comprises at least about 50% w / w plastic and rubber, suitably at least about 60% w / w plastic and rubber, suitably at least about 70% w / w plastic and rubber, suitably at least about 80% w / w plastic and rubber, suitably at least about 90% w / w plastic and rubber, suitably at least about 95% w / w plastic and rubber.

[0132] In another embodiment, the combination of plastic and rubber comprises about 50% (w / w) to about 100% (w / w) plastic and rubber, suitably about 60% (w / w) to about 100% (w / w) plastic and rubber, about 70% (w / w) to about 100% (w / w) plastic and rubber, about 80% (w / w) to about 100% (w / w) plastic and rubber, about 90% (w / w) to about 100% (w / w) plastic and rubber.

[0133] Suitably, in each of the above mentioned embodiments, the rubber is obtained from a tyre.

[0134] Suitably, in each of the above embodiments, the plastic consists (substantially) of one or more thermoplastic polymers. Suitably, the plastic is waste plastic, which may be a mixture of multiple plastics. Plastics may be referred to by the name of the polymers from which they are composed. Examples of common plastics are polyethylene, polypropylene and polystyrene.

[0135] In one embodiment, the pyrolysis oil is obtainable or obtained by pyrolysis of waste plastics. In another embodiment, the pyrolysis oil is obtainable or obtained by pyrolysis of plastics comprising one or more of polyethylene, polypropylene, and polystyrene.

[0136] In one embodiment, the waste plastic comprises at least about 50% w / w plastic, suitably at least about 60% w / w plastic, suitably at least about 70% w / w plastic, suitably at least about 80% w / w plastic, suitably at least about 90% w / w plastic, suitably at least about 95% w / w plastic.

[0137] In another embodiment, the waste plastic comprises about 50% (w / w) to about 100% (w / w) plastic, suitably about 60% (w / w) to about 100% (w / w) plastic, about 70% (w / w) to about 100% (w / w) plastic, about 80% (w / w) to about 100% (w / w) plastic, about 90% (w / w) to about 100% (w / w) plastic.

[0138] In one embodiment, the pyrolysis oil to be upgraded has a specific gravity (20 / 4) of about 1 or less, suitably about 0.95 or less, or about 0.90 or less. In one embodiment, the pyrolysis oil to be upgraded has a specific gravity (20 / 4) of from about 0.7 to about 0.95, suitably about 0.8 to about 0.95, or about 0.7 to about 0.85.

[0139] In one embodiment, the pyrolysis oil to be upgraded is immiscible with water at standard ambient temperature and pressure (SATP), ie, at a temperature of 298.15 K (25° C.) and at 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm).

[0140] Suitably, the pyrolysis oil to be upgraded is immiscible with water at standard ambient temperature and pressure (SATP), i.e. at a temperature of 298.15 K (25° C.) and at 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm), and has a specific gravity (20 / 4) of from about 0.7 to about 0.95, suitably from about 0.8 to about 0.95, or from about 0.7 to about 0.85.

[0141] Quality improvement solution

[0142] The process of the present invention utilizes an upgrading solution. As used herein, an upgrading solution refers to a solution or liquid mixture that is capable of reducing / removing one or more undesirable substances from pyrolysis oil.

[0143] In one embodiment, the upgrading solution is capable of removing or reducing the concentration of undesirable substances in the pyrolysis oil, wherein the undesirable substances are selected from one or more of solid residues, heteroatom compounds, and olefins. Suitably, the undesirable substances are selected from one or more of solid residues, sulfur compounds, halogen compounds (e.g., chlorides), nitrogen compounds, and olefins.

[0144] The upgrading solution comprises a polar organic solvent. As used herein, the term polar organic solvent refers to an organic solvent that generally has a dipole moment (D) greater than or equal to about 1.5 at 298°K. For example, methanol has a dipole moment (D) of 1.7 (at 298°K). Tables of dipole moments of solvents are readily available to those skilled in the art.

[0145] In one embodiment, the polar organic solvent has a dipole moment (D) at 298°K of about 1.5 or greater, suitably about 2.0 or greater, suitably about 2.5 or greater, suitably about 3 or greater, suitably about 3.5 or greater.

[0146] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 1.5 to about 6.0, suitably from about 1.5 to about 5.5, suitably from about 1.5 to about 5.0.

[0147] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 2.0 to about 6.0, suitably from about 2.0 to about 5.5, suitably from about 2.0 to about 5.0.

[0148] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 2.5 to about 6.0, suitably from about 2.5 to about 5.5, suitably from about 2.5 to about 5.0.

[0149] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 2.5 to about 6.0, suitably from about 2.5 to about 5.5, suitably from about 2.5 to about 5.0.

[0150] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 3.0 to about 6.0, suitably from about 3.0 to about 5.5, suitably from about 3.0 to about 5.0.

[0151] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 3.5 to about 6.0, suitably from about 3.5 to about 5.5, suitably from about 3.5 to about 5.0.

[0152] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 4.0 to about 6.0, suitably from about 4.0 to about 5.5, suitably from about 4.0 to about 5.0.

[0153] In another embodiment, the polar organic solvent has a dipole moment (D) at 298°K of from about 4.5 to about 6.0, suitably from about 4.5 to about 5.5, suitably from about 4.5 to about 5.0.

[0154] In one embodiment, the polar organic solvent is selected from one or more of an alcohol, a carbonate, an amide, an organosulfur compound, a nitrile, and a heterocyclic compound. In another embodiment, the polar organic solvent is selected from one or more of an alcohol, a carbonate, an amide, and an organosulfur compound. In another embodiment, the polar organic solvent is selected from one or more of an alcohol, a carbonate, and an organosulfur compound.

[0155] In one embodiment, the polar organic solvent is an alcohol. Suitably, the polar organic solvent may be any C 1-10 Alcohol, typically C 1-4 Alcohols. The alcohol may have the structure alkyl-OH, OH-alkylene-OH, alkenyl-OH, OH-alkenylene-OH, cycloalkyl-OH, or OH-cycloalkylene-OH.

[0156] In one embodiment, the polar organic solvent is an alcohol selected from the group consisting of methanol, ethanol and n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol, pentanol, methyl glycol, glycerol, ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol) and sorbitol.

[0157] In another embodiment, the polar organic solvent comprises / consists essentially of / consists of methanol or ethanol. In another embodiment, the polar organic solvent comprises / consists essentially of / consists of methanol.

[0158] In another embodiment, the polar organic solvent is a carboxylic acid.Examples of carboxylic acids that the upgrading solution may comprise include methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid, butyric acid, and valeric acid.

[0159] In another embodiment, the polar organic solvent is a carbonate. The carbonate that the upgrading solution may also contain may be any C 3-10 Carbonates. Carbonates typically have the structure alkyl-OC(O)O-alkyl. Examples of carbonates that the upgrading solution may comprise include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, and trimethylene carbonate. Suitably, the upgrading solution comprises propylene carbonate.

[0160] In one embodiment, the polar organic solvent is an amide. Suitably, the polar organic solvent may be C 2-10 Amides. Amides typically have the structure alkyl-CONH2, alkyl-CONH(alkyl), or alkyl-CON(alkyl)2.

[0161] Examples of amides that the upgrading solution may comprise include formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide (DMA), N-vinylacetamide, pyrrolidone, N-methylpyrrolidone (NMP) (also known as N-methyl-2-pyrrolidone), and N-vinylpyrrolidone.

[0162] In one embodiment, the polar organic solvent is an organic sulfur compound. Suitably, a sulfoxide or a sulfone. The sulfone / sulfoxide compound that the upgrading solution may also contain may be C 2-10 Sulfone / sulfoxide compounds. For example, the upgrading solution may comprise dimethyl sulfoxide (DMSO) or sulfolane. Suitably, the upgrading solution comprises sulfolane.

[0163] In one embodiment, the polar organic solvent is a heterocyclic compound. The heterocyclic compound that the upgrading solution may contain may be any C 3-10Heterocyclic compounds. The heterocyclic compound can be any compound having from 3 to 10 carbon atoms and comprising a ring containing a heteroatom selected from N, P, O, and S. The upgrading solution can comprise a heterocyclic compound selected from furan, tetrahydrofuran, thiophene, pyrrole, pyrroline, pyrrolidine, dioxolane, oxazole, thiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, isoxazole, isothiazole, oxadiazole, pyran, pyridine, piperidine, pyridazine, and piperazine. For example, the upgrading solution can comprise pyridine.

[0164] In one embodiment, the polar organic solvent is a nitrile compound. The nitrile that the upgrading solution may also contain may be C 2-10 Nitrile. For example, the upgrading solution may comprise acetonitrile or propionitrile.

[0165] In one embodiment, the polar organic solvent is selected from methanol, ethanol, ethylene glycol, propylene carbonate, sulfolane, acetic acid, propionic acid, DMSO, NMP, DMF, DMA and pyridine. Suitably, the polar organic solvent is selected from methanol, ethanol, ethylene glycol, propylene carbonate, sulfolane, acetic acid and propionic acid. Suitably, the polar organic solvent is selected from methanol, ethanol, ethylene glycol, propylene carbonate and sulfolane. Suitably, the upgrading solution comprises one or more of sulfolane and propylene carbonate.

[0166] Suitably, the polar organic solvent is selected from methanol, ethanol, ethylene glycol, propylene carbonate, NMP, sulfolane, acetic acid and propionic acid. Suitably, the polar organic solvent is selected from methanol, ethanol, ethylene glycol, NMP, propylene carbonate and sulfolane. Suitably, the upgrading solution comprises one or more of NMP, sulfolane and propylene carbonate.

[0167] The upgrading solution may contain additional solvents such as alcohols, aldehydes, ketones, ethers, carboxylic acids, esters, carbonates, anhydrides, amides, amines, heterocyclic compounds, imines, imides, nitriles, nitro compounds, sulfoxides, and halogenated alkanes.

[0168] In another embodiment, the upgrading solution may further comprise one or more of another solvent, an acid, a base, or an organometallic compound.

[0169] In another embodiment, the upgrading solution may further comprise an additional solvent selected from the group consisting of alcohols, aldehydes, ketones, ethers, esters, carbonates, amides, amines, heterocyclic compounds, imines, nitriles, nitro compounds, halogenated alkanes, and sulfoxides.

[0170] The alcohol that the upgrading solution may also contain may be any C 1-10 Alcohol, typically C 1-4Alcohol. Examples of alcohols that the upgrading solution may include: monohydric alcohols such as methanol, ethanol, propanol, isopropyl alcohol (propan-2-ol), butanol (butan-1-ol), sec-butanol (butan-2-ol), isobutyl alcohol (2-methylpropan-1-ol), tert-butyl alcohol (2-methylpropan-2-ol), cyclopentanol, pentanol, cyclohexanol, hexanol, heptanol, and octanol; and polyhydric alcohols such as ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), propane-1,3-diol, propane-1,2,3-triol (glycerol), isopropylene glycol, butanediol, isobutylene glycol, tert-butylene glycol, butanetriol, pentanediol, methylbutanediol, hexanediol, hexanetriol. For compounds where the position of the hydroxyl group is not specified, alcohols with every possible position are encompassed. Thus, butanediol includes butane-1,2-diol, butane-1,3-diol, butane-1,4-diol and butane-2,3-diol.Ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), propane-1,3-diol, isopropylene glycol and butanediol are examples of diols.

[0171] The upgraded solution may also contain an aldehyde which may be any C 1-10 Aldehydes, typically C 3-6 Aldehydes. Aldehydes typically have the structure alkyl-CHO. Examples of aldehydes that the upgrading solution may contain include methanal (formaldehyde), ethanal (acetaldehyde), propionaldehyde, butyraldehyde, valeraldehyde, and hexanal.

[0172] The upgraded solution may also contain ketones which may be any C 3-10 Ketones. Ketones typically have the structure alkyl-C(O)-alkyl, cycloalkyl-C(O)-alkyl, or aryl-C(O)-alkyl. Ketones can be linear, branched, or cyclic. Examples of ketones that the upgrading solution may include propanone (acetone), butanone, pentan-2-one, pentan-3-one, ethyl isopropyl ketone, hexan-2-one, and hexan-3-one.

[0173] The upgrading solution may also contain ethers which may be any C 2-10 Ethers, i.e., ethers containing from 2 to 10 carbon atoms. Ethers typically have the structure alkyl-O-alkyl or alicyclic ether. Ethers can be linear, branched, or cyclic. Examples of ethers that may also be included in the upgrading solution include diethyl ether, ethyl isopropyl ether, dipropyl ether, diisopropyl ether, and tetrahydrofuran.

[0174] The upgraded solution may also contain esters which may be any C 2-10 For example, the ester can be C 1-5 Formic acid C 1-5Alkyl esters. Esters typically have the structure alkyl-COO-alkyl. Examples of esters that the upgrading solution may include include methyl formate, ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, and ethyl isopropionate.

[0175] The carbonate ester that the upgrading solution may also contain may be any C 3-10 Carbonates. Carbonates typically have the structure alkyl-OC(O)O-alkyl. Examples of carbonates that the upgrading solution may contain include dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate. The carbonate may be propylene carbonate or trimethylene carbonate. The anhydride that the upgrading solution may contain may be any C 4-8 Anhydrides. An example of an anhydride that the upgrading solution may comprise is acetic anhydride.

[0176] The upgrading solution may also contain amides which are any C 2-10 Amides. Amides typically have the structure alkyl-CONH2, alkyl-CONH(alkyl), or alkyl-CON(alkyl)2.

[0177] Examples of amides that the upgrading solution may further comprise include formamide, N-methylformamide, dimethylformamide, dimethylacetamide, N-vinylacetamide, pyrrolidone, N-methylpyrrolidone, and N-vinylpyrrolidone.

[0178] The upgrading solution may also contain an amine which may be any C 2-15 Amines. Amines generally have the structures RNH2, R2NH, R3N, and H2NR'NH2, where R can be selected from C 2-10 Alkyl, C 2-10 Alkenyl, C 2-12 Alkynyl, C 6-10 Aryl and C 6-12 Arylalkyl, and R' can be selected from C 2-10 Alkylene, C 2-10 Alkenylene, C 2-10 Alkynylidene, C 5-10 Cycloalkylene and C 6-10 Arylene. The amine may be a primary amine, a secondary amine or a tertiary amine. The amine may contain one or more or two or more amine groups. The amine may be selected from mono-C 2-15 -alkylamine, di-C 1-7 -alkylamine and tri-C 1-5 -alkylamine. The amine can be C 2-10 - Alkylenediamines. Examples of amines that the upgrading solution may comprise include ethylamine, triethylamine, tripropylamine, tributylamine, ethylenediamine, propylenediamine, diethylenetriamine, morpholine, piperidine and quinoline.

[0179] The upgraded solution may also contain heterocyclic compounds which may be any C 3-10 Heterocyclic compounds. The heterocyclic compound can be any compound having from 3 to 10 carbon atoms and comprising a ring containing a heteroatom selected from N, P, O, and S. The upgrading solution can comprise a heterocyclic compound selected from furan, tetrahydrofuran, thiophene, pyrrole, pyrroline, pyrrolidine, dioxolane, oxazole, thiazole, imidazole, imidazoline, imidazolidine, pyrazole, pyrazoline, pyrazolidine, isoxazole, isothiazole, oxadiazole, pyran, pyridine, piperidine, pyridazine, and piperazine. For example, the upgrading solution can also comprise pyridine, furan, or tetrahydrofuran.

[0180] The upgrading solution may also contain an imine which may be C 4-10 Imine. The imide that the upgrading solution may also contain may be C 4-10 imide.

[0181] The upgraded solution may also contain nitrites which may be C 2-10 Nitrile. For example, the upgrading solution may comprise acetonitrile or propionitrile.

[0182] The nitro compound that the upgrading solution may also contain may be C 1-10 Nitro compounds. For example, the upgrading solution may comprise nitromethane, nitroethane, nitropropane, or nitrobenzene.

[0183] The sulfoxide compound that the upgrading solution may further comprise may be C 2-10 Sulfoxide compounds. For example, the upgrading solution may comprise dimethyl sulfoxide (DMSO). The upgrading solution may also comprise diethyl sulfoxide or methyl ethyl sulfoxide.

[0184] The upgraded solution may also contain halogenated alkanes which may be any C 1-10 Halogenated alkanes. For example, the upgrading solution may further comprise dichloromethane (DCM), chloroform, tetrachloromethane or dichloroethane.

[0185] In certain embodiments, the upgrading solution may further comprise a solvent selected from the group consisting of methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, and propane-1,3-diol.

[0186] The acid that the upgrading solution may also contain may be any C 1-8 Carboxylic acids. Carboxylic acids generally have the structure alkyl-COOH. Carboxylic acids can be linear, branched, or cyclic. Examples of carboxylic acids that the upgrading solution may contain include formic acid, ethanoic acid, propionic acid, butyric acid, and valeric acid.

[0187] Suitably, the acid is present in an amount from about 0.5 wt.% to about 20 wt.%, suitably about 0.5 wt.% to about 15 wt.%, 0.5 wt.% to about 10 wt.%, 0.5 wt.% to about 5 wt.%. Suitably, the acid is present in an amount from about 1 wt.% to about 20 wt.%, suitably about 1 wt.% to about 15 wt.%, 1 wt.% to about 10 wt.%, 1 wt.% to about 5 wt.%, suitably about 1 wt.%.

[0188] The base that the upgrading solution may further comprise may be any alkali metal hydroxide or alkali metal carbonate. Examples include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate. Suitably, the base is selected from potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate. Suitably, the base is selected from potassium hydroxide and sodium hydroxide.

[0189] Suitably, the base is present in an amount from about 0.5 wt.% to about 20 wt.%, suitably about 0.5 wt.% to about 15 wt.%, 0.5 wt.% to about 10 wt.%, 0.5 wt.% to about 5 wt.%. Suitably, the base is present in an amount from about 1 wt.% to about 20 wt.%, suitably about 1 wt.% to about 15 wt.%, 1 wt.% to about 10 wt.%, 1 wt.% to about 5 wt.%, suitably about 1 wt.%.

[0190] The organometallic compound that the upgrading solution may further comprise may be any alkali metal salt. Examples include potassium acetate, sodium acetate, potassium formate, and sodium formate. In one embodiment, the organometallic compound is potassium acetate or sodium acetate.

[0191] Suitably, the organometallic compound is present in an amount from about 0.5 wt.% to about 20 wt.%, suitably about 0.5 wt.% to about 15 wt.%, 0.5 wt.% to about 10 wt.%, 0.5 wt.% to about 5 wt.%. Suitably, the organometallic compound is present in an amount from about 1 wt.% to about 20 wt.%, suitably about 1 wt.% to about 15 wt.%, 1 wt.% to about 10 wt.%, 1 wt.% to about 5 wt.%, suitably about 1 wt.%.

[0192] In one embodiment, the upgrade solution has a specific gravity (20 / 4) of about 0.95 or greater, suitably about 1.00 or greater, suitably about 1.05 or greater.

[0193] In one embodiment, the upgrading solution comprises a polar organic solvent selected from one of NMP, DMF, DMSO, sulfolane and propylene carbonate. Suitably, the upgrading solution comprises at least about 50% wt. of one or more of NMP, DMF, DMSO, sulfolane and propylene carbonate, suitably sulfolane or propylene carbonate.

[0194] In another embodiment, the upgraded solution comprises at least about 50% wt. of one or more of sulfolane and propylene carbonate, suitably at least about 60% wt., suitably at least about 70% wt., suitably at least about 80% wt., suitably at least about 90% wt. of one or more of sulfolane and propylene carbonate.

[0195] In another embodiment, the upgraded solution comprises at least about 50% wt. of one or more of NMP, sulfolane, and propylene carbonate, suitably at least about 60% wt., suitably at least about 70% wt., suitably at least about 80% wt., suitably at least about 90% wt. of one or more of NMP, sulfolane, and propylene carbonate.

[0196] In one embodiment, the upgrading solution comprises at least about 50% wt. of one or more of sulfolane and propylene carbonate, and further comprises an alcohol selected from the group consisting of methanol, ethanol, and ethane-1,2-diol.

[0197] In one embodiment, the upgrading solution comprises at least about 50% by weight of one or more of sulfolane and propylene carbonate, and further comprises an alcohol selected from methanol, ethanol, and ethane-1,2-diol, and a base or an organometallic compound. Suitably, the base is potassium carbonate, and the organometallic compound is potassium acetate.

[0198] In another embodiment, the upgrading solution comprises at least about 50% wt. of one or more of sulfolane and propylene carbonate, and further comprises an acid selected from the group consisting of ethanoic acid (acetic acid) and propionic acid.

[0199] In one embodiment, the upgrade solution comprises sulfolane, methanol, and potassium hydroxide; or sulfolane, ethylene glycol, and potassium hydroxide; or propylene carbonate and acetic acid; or propylene carbonate, ethylene glycol, and potassium acetate.

[0200] In one embodiment, the upgrading solution comprises NMP and water. In another embodiment, the upgrading solution consists essentially of NMP and water. In another embodiment, the upgrading solution consists of NMP and water. In another embodiment, the upgrading solution is a mixture of NMP and water.

[0201] Suitably, the mixture of NMP and water comprises at least about 50% (v / v) NMP. Alternatively, at least about 60% (v / v) NMP, at least about 70% (v / v) NMP, at least about 80% (v / v) NMP, at least about 90% (v / v) NMP or at least about 95% (v / v) NMP.

[0202] In one embodiment, the upgrading solution comprises NMP and water, wherein the ratio of NMP to water (v / v) is from about 1:1 to about 10:1, suitably from about 2:1 to about 10:1, suitably from about 3:1 to about 10:1, suitably from about 4:1 to about 10:1, suitably from about 5:1 to about 10:1.

[0203] In another embodiment, the upgrading solution comprises NMP and water, wherein the ratio of NMP to water (v / v) is from about 1:1 to about 9:1, suitably from about 2:1 to about 9:1, suitably from about 3:1 to about 9:1, suitably from about 4:1 to about 90:1, suitably from about 5:1 to about 9:1.

[0204] In one embodiment, the upgrading solution comprises about 90% NMP and about 10% water. In another embodiment, the upgrading solution consists essentially of about 90% NMP and about 10% water. In another embodiment, the upgrading solution consists of about 90% NMP and about 10% water. In another embodiment, the upgrading solution is a mixture of about 90% NMP and about 10% water.

[0205] Optionally, after the upgrading solution has been added to the pyrolysis oil, the resulting mixture may be treated with a hydrocarbon fluid to assist in phase separation. In one embodiment, the hydrocarbon fluid is an alkane or an alkene or a mixture thereof. Suitably, the hydrocarbon fluid is a saturated hydrocarbon fluid. In one embodiment, the hydrocarbon fluid comprises a hydrocarbon selected from the group consisting of C5-C 16 One or more hydrocarbons of alkanes and olefins.

[0206] Suitably, the hydrocarbon fluid may be C1-C 20 Alkanes or alkenes or mixtures thereof; suitably C2-C 20 Alkanes or alkenes or mixtures thereof; suitably C3-C 20 Alkanes or alkenes or mixtures thereof; suitably C4-C 20 Alkanes or alkenes or mixtures thereof; suitably C5-C 20 Alkanes or alkenes or mixtures thereof; suitably C5-C 16 Alkanes or alkenes or mixtures thereof.

[0207] In one embodiment, the hydrocarbon fluid is a liquid at standard temperature and pressure.

[0208] In one embodiment, the hydrocarbon fluid is selected from the group consisting of propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and tetradecane, hexadecane (cetane), cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane and cyclooctane, and mixtures thereof.

[0209] In another embodiment, the hydrocarbon fluid is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and tetradecane, hexadecane (cetane), cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane and cyclooctane, and mixtures thereof.

[0210] In another embodiment, the hydrocarbon fluid is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and hexadecane (cetane), and mixtures thereof.

[0211] In one aspect, the present invention relates to the use of an upgrading solution for reducing the heteroatom content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0212] In one aspect, the present invention relates to the use of an upgrading solution for reducing the olefin content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0213] In another aspect, the present invention relates to the use of an upgrading solution for reducing the solid residue content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent; and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0214] Suitably, the upgrading solution is as defined in each of the above mentioned embodiments.

[0215] Washing steps

[0216] In one embodiment, the pyrolysis oil may be treated with an aqueous solution prior to treating the pyrolysis oil with the upgrading solution.

[0217] Thus, in one embodiment, the present invention is directed to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0218] (i) treating the pyrolysis oil with an aqueous solution to provide a mixture comprising an organic phase and an aqueous phase, and separating the organic phase;

[0219] (ii) treating the separated organic phase of step (i) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase;

[0220] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0221] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0222] In another embodiment, the pyrolysis oil may be treated with an aqueous solution and a hydrocarbon fluid prior to being treated with the upgrading solution. Suitably, the pyrolysis oil is treated with the aqueous solution and the hydrocarbon fluid simultaneously.

[0223] Thus, in one embodiment, the present invention is directed to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0224] (i) treating the pyrolysis oil with an aqueous solution and a hydrocarbon fluid to provide a mixture comprising an organic phase and an aqueous phase, and separating and optionally filtering the organic phase;

[0225] (ii) treating the separated organic phase of step (i) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase;

[0226] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0227] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0228] In another embodiment, the present invention is a process for producing an upgraded pyrolysis oil product, the process comprising:

[0229] (i) treating the pyrolysis oil with an aqueous solution to form a mixture consisting of an organic phase and an aqueous phase, and separating the organic phase from the aqueous phase;

[0230] (ii) treating the organic phase with a hydrocarbon fluid, and optionally filtering the treated organic phase;

[0231] (iii) treating the filtered organic phase of step (ii) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase;

[0232] (iv) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0233] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0234] In another embodiment, the present invention is a process for producing an upgraded pyrolysis oil product, the process comprising:

[0235] (i) treating the pyrolysis oil with a hydrocarbon fluid and optionally filtering the mixture;

[0236] (ii) treating the mixture of step (i) with an aqueous solution to form a second mixture consisting of an organic phase and an aqueous phase, and separating the organic phase from the aqueous phase;

[0237] (iii) treating the separated organic phase of step (ii) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase;

[0238] (iv) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0239] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0240] The pyrolysis oil and the aqueous solution can be mixed by any means known in the art. For example, the pyrolysis oil and the aqueous solution can be added to a container, reactor, or mixer commonly used in the art, and the two components can be mixed. Mixing can include vigorously stirring the two components using a mixing device. For example, the two components can be mixed together by stirring or by shaking.

[0241] The mixing of the two components may occur more than once. For example, after the first mixing of the pyrolysis oil and the aqueous solution, the resulting two phases may be mixed again, possibly multiple times. The steps of contacting and forming the two phases may be continuous. Thus, the two components may pass through a mixing device before entering a separation chamber where the first and second phases are formed. The contact of the two components may be achieved using a propeller, a countercurrent flow device, a stirring device, column, Column or centrifugal extractor.

[0242] The pyrolysis oil can be repeatedly mixed with fresh batches of aqueous solution multiple times. For example, the pyrolysis oil can be mixed with a first batch of aqueous solution to provide a first organic phase and a first aqueous phase. After the organic phase is separated from the aqueous phase, the organic phase can be mixed with a second batch of aqueous solution to provide a second organic phase and a second aqueous phase. This cycle can be repeated multiple times.

[0243] In one embodiment, the cycle of mixing the pyrolysis oil / separated organic phase with the aqueous solution is repeated between 1 and 9 times. In another embodiment, the cycle is repeated between 1 and 4 times. In another embodiment, the cycle is repeated 1, 2, 3, or 4 times. In another embodiment, the cycle is repeated 4 times.

[0244] Typically, the pyrolysis oil and the aqueous solution are mixed to an extent that allows for effective washing of the pyrolysis oil by the aqueous solution. For two immiscible solutions, the skilled person will understand that typically these solutions are intimately mixed until an emulsion is formed, which is then allowed to separate into two phases.

[0245] In one embodiment, mixing is carried out at ambient temperature and pressure. Typically, at a temperature between about 18°C ​​and 28°C, more typically between about 21°C and 25°C, and a pressure of about 100 kPa. Thus, the costs and other problems associated with high temperature or high pressure conditions are avoided.

[0246] Alternatively, mixing is carried out at a temperature between about 0°C and about 70°C, suitably about 15°C to about 50°C.

[0247] Typically, the mass ratio of pyrolysis oil to aqueous solution is from about 95:5 to about 10:90. In one embodiment, the mass ratio of pyrolysis oil to aqueous solution is from about 95:5 to about 50:50, or suitably from about 95:5 to about 60:40, or suitably from about 95:5 to about 70:30, or suitably from about 95:5 to about 80:20. In one embodiment, the mass ratio of pyrolysis oil to aqueous solution is about 90:10.

[0248] In another embodiment, the mass ratio of pyrolysis oil to aqueous solution is from about 70:30 to about 30:70, or suitably about 60:40 to about 40:60, or suitably about 50:50.

[0249] In one embodiment, the organic phase will have a reduced concentration of salts, acids, and other water-soluble components compared to the pyrolysis oil prior to mixing with the upgrading solution. In another embodiment, the organic phase will have a reduced concentration of solid residues compared to the pyrolysis oil prior to mixing with the upgrading solution.

[0250] In the process of the present invention, the organic phase tends to have a lower density than the extract phase, and therefore the organic phase will generally be the upper phase and the aqueous phase will generally be the lower phase.

[0251] Typically, the process also includes separating the organic phase. The organic phase can be separated by any means used in the art, and is usually separated by physical processes. The separation usually includes physically isolating the organic phase or at least some of the organic phases. Therefore, the separation usually includes separating at least some of the organic phases from the aqueous phase.

[0252] Since the two phases will usually have separated in the same container due to their immiscibility, the separation can simply comprise removing (e.g., by draining or decanting) at least a portion of the aqueous phase from the container containing the aqueous and organic phases. Alternatively, the organic phase can be removed from the container (e.g., by draining or decanting) to leave the aqueous phase.

[0253] In one embodiment, the pyrolysis oil is treated with the aqueous solution prior to treatment with the hydrocarbon fluid. In another embodiment, the pyrolysis oil is treated with the aqueous solution separately from treatment with the hydrocarbon fluid. In another embodiment, the pyrolysis oil is treated with the aqueous solution prior to and separately from treatment with the hydrocarbon fluid. In another embodiment, the pyrolysis oil is treated simultaneously with the aqueous solution and the hydrocarbon fluid.

[0254] The (washed) pyrolysis oil and the hydrocarbon fluid can be mixed by any means known in the art. For example, the (washed) pyrolysis oil and the hydrocarbon fluid can be added to a container, reactor, or mixer commonly used in the art, and the two components can be mixed. Mixing can include vigorously stirring the two components using a mixing device. For example, the two components can be mixed together by stirring or by shaking.

[0255] In one embodiment, mixing is carried out at ambient temperature and pressure. Typically, at a temperature between about 18°C ​​and 28°C, more typically between about 21°C and 25°C, and a pressure of about 100 kPa. Thus, the costs and other problems associated with high temperature or high pressure conditions are avoided.

[0256] Alternatively, mixing is carried out at a temperature between about 0°C and about 70°C, suitably about 15°C to about 50°C.

[0257] Typically, the mass ratio of (washed) pyrolysis oil to hydrocarbon fluid is from about 95:5 to about 10:90. In one embodiment, the mass ratio of pyrolysis oil to upgrading solution is from about 70:30 to about 30:70, or suitably from about 60:40 to about 40:60, or suitably about 50:50.

[0258] In one embodiment, the organic phase / hydrocarbon mixture is treated to remove any solid particles. This can be accomplished by any suitable means known in the art. A skilled artisan will appreciate suitable techniques for removing any solid particles, such as filtration. Suitably, the organic phase / hydrocarbon mixture is filtered.

[0259] In one embodiment, the organic phase / hydrocarbon mixture will have a reduced concentration of solid residues, such as coke or asphaltenes, compared to the pyrolysis oil prior to mixing with the hydrocarbon fluid.

[0260] aqueous solution

[0261] In one embodiment, the aqueous solution has a pH of about 5 to about 10, suitably a pH of about 5 to about 9, suitably a pH of about 5 to 8. In another embodiment, the aqueous solution has a pH of about 6 to about 10, suitably a pH of about 6 to about 9, suitably a pH of about 6 to 8.

[0262] In one embodiment, the aqueous solution may comprise an acid, suitably C 1-8 Carboxylic acids. Carboxylic acids generally have the structure alkyl-COOH. Carboxylic acids can be linear, branched, or cyclic. Examples of carboxylic acids that the aqueous solution may contain include methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid, butyric acid, and valeric acid.

[0263] Suitably, the acid is present in an amount from about 0.5 wt.% to about 20 wt.%, suitably about 0.5 wt.% to about 15 wt.%, 0.5 wt.% to about 10 wt.%, 0.5 wt.% to about 5 wt.%. Suitably, the acid is present in an amount from about 1 wt.% to about 20 wt.%, suitably about 1 wt.% to about 15 wt.%, 1 wt.% to about 10 wt.%, 1 wt.% to about 5 wt.%, suitably about 1 wt.%.

[0264] In one embodiment, the aqueous solution may contain a base. The base may be any alkali metal hydroxide or alkali metal carbonate. Examples include potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate. Suitably, the base is selected from potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate. Suitably, the base is selected from potassium hydroxide and sodium hydroxide.

[0265] Suitably, the base is present in an amount from about 0.5 wt.% to about 20 wt.%, suitably about 0.5 wt.% to about 15 wt.%, 0.5 wt.% to about 10 wt.%, 0.5 wt.% to about 5 wt.%. Suitably, the base is present in an amount from about 1 wt.% to about 20 wt.%, suitably about 1 wt.% to about 15 wt.%, 1 wt.% to about 10 wt.%, 1 wt.% to about 5 wt.%, suitably about 1 wt.%.

[0266] In one embodiment, the aqueous solution may comprise an organometallic compound, suitably an alkali metal salt. Examples include potassium acetate, sodium acetate, potassium formate and sodium formate. In one embodiment, the organometallic compound is potassium acetate or sodium acetate.

[0267] Suitably, the organometallic compound is present in an amount from about 0.5 wt.% to about 20 wt.%, suitably about 0.5 wt.% to about 15 wt.%, 0.5 wt.% to about 10 wt.%, 0.5 wt.% to about 5 wt.%. Suitably, the organometallic compound is present in an amount from about 1 wt.% to about 20 wt.%, suitably about 1 wt.% to about 15 wt.%, 1 wt.% to about 10 wt.%, 1 wt.% to about 5 wt.%, suitably about 1 wt.%.

[0268] In one embodiment, the aqueous solution consists essentially of water. In another embodiment, the aqueous solution is water.

[0269] hydrocarbon fluids

[0270] In one embodiment, the hydrocarbon fluid is an alkane, an alkene or a mixture thereof. In one embodiment, the hydrocarbon fluid is a saturated hydrocarbon fluid. Suitably, the hydrocarbon fluid is an alkane or a cycloalkane or a mixture thereof. In another embodiment, the hydrocarbon fluid comprises a hydrocarbon selected from the group consisting of C5-C 16 Alkanes and C5-C 16 Olefins One or more hydrocarbons.

[0271] Suitably, the alkane may be C1-C 20 Alkanes, suitably C2-C 20 Alkanes, suitably C3-C 20 Alkanes, suitably C4-C 20 Alkanes, suitably C5-C 20 Alkanes, suitably C5-C 16 Alkanes.

[0272] Suitably, the cycloalkane may be C3-C 20 Cycloalkanes, suitably C4-C 20 Cycloalkanes, suitably C5-C 20 Cycloalkanes, suitably C5-C 16 Cycloalkanes.

[0273] Suitably, the olefin may be a C3-C 20 Olefins, suitably C4-C 20 Olefins, suitably C5-C 20 Olefins, suitably C5-C 16 Olefins.

[0274] In one embodiment, the hydrocarbon fluid is selected from C3-C 20 Alkanes or alkenes or mixtures thereof; suitably C4-C 20 Alkanes or alkenes or mixtures thereof; suitably C5-C 20 Alkanes or alkenes or mixtures thereof; suitably C5-C 16 Alkanes or alkenes or mixtures thereof.

[0275] In one embodiment, the hydrocarbon fluid is a liquid at standard temperature and pressure.

[0276] In one embodiment, the hydrocarbon fluid is selected from the group consisting of propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and tetradecane, hexadecane (cetane), cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane and cyclooctane, or mixtures thereof.

[0277] In another embodiment, the hydrocarbon fluid is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and tetradecane, hexadecane (cetane), cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane and cyclooctane, or mixtures thereof.

[0278] In another embodiment, the hydrocarbon fluid is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and hexadecane (cetane), or mixtures thereof.

[0279] In another embodiment, the hydrocarbon fluid is selected from pentane, hexane and heptane or a mixture thereof. Suitably, the hydrocarbon fluid comprises pentane. Suitably, the hydrocarbon fluid consists essentially of pentane. Suitably, the hydrocarbon fluid is pentane.

[0280] Catalytic quality improvement

[0281] In one embodiment, after treating the pyrolysis oil with the upgrading solution, the raffinate may be treated with a mixture comprising C 1-4 The raw material is treated with a blending agent of alcohol, and the obtained raw material is contacted with a catalyst composition; wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst.

[0282] Thus, in one embodiment, the present invention is directed to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0283] (i) treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, and separating the raffinate phase, wherein the upgrading solution comprises a polar organic solvent;

[0284] (ii) Using a 1-4 treating the separated raffinate phase of step (i) with a blending agent of an alcohol and contacting the resulting feedstock with a catalyst composition at a temperature of about 10° C. to about 250° C. to produce an upgraded pyrolysis oil product; wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst; and

[0285] The pyrolysis oil comes from the pyrolysis of plastic or rubber or a mixture.

[0286] In another embodiment, the present invention is a process for producing an upgraded pyrolysis oil product, the process comprising:

[0287] (i) treating the pyrolysis oil with an aqueous solution and optionally a hydrocarbon fluid to provide a mixture comprising an organic phase and an aqueous phase, and separating and optionally filtering the organic phase;

[0288] (ii) treating the separated organic phase of step (i) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, and separating the raffinate phase, wherein the upgrading solution comprises a polar organic solvent;

[0289] (iii) Using a 1-4 treating the separated raffinate phase of step (ii) with a blending agent of an alcohol and contacting the resulting feedstock with a catalyst composition at a temperature of about 10° C. to about 250° C. to produce an upgraded pyrolysis oil product; wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst; and

[0290] The pyrolysis oil comes from the pyrolysis of plastic or rubber or a mixture.

[0291] In another embodiment, the present invention is a process for producing an upgraded pyrolysis oil product, the process comprising:

[0292] (i) treating the pyrolysis oil with an aqueous solution to form a mixture consisting of an organic phase and an aqueous phase, and separating the organic phase from the aqueous phase;

[0293] (ii) treating the organic phase with a hydrocarbon fluid, and optionally filtering the treated organic phase;

[0294] (iii) treating the treated organic phase of step (ii) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, and separating the raffinate phase, wherein the upgrading solution comprises a polar organic solvent;

[0295] (iv) Using a C 1-4 treating the separated raffinate phase of step (iii) with a blending agent of an alcohol and contacting the resulting feedstock with a catalyst composition to produce an upgraded pyrolysis oil product; wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst; and

[0296] The pyrolysis oil comes from the pyrolysis of plastic or rubber or a mixture.

[0297] In another embodiment, the present invention is a process for producing an upgraded pyrolysis oil product, the process comprising:

[0298] (i) treating the pyrolysis oil with a hydrocarbon fluid and optionally filtering the mixture;

[0299] (ii) treating the mixture of step (i) with an aqueous solution to form a second mixture consisting of an organic phase and an aqueous phase, and separating the organic phase from the aqueous phase;

[0300] (iii) treating the separated organic phase of step (ii) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, and separating the raffinate phase, wherein the upgrading solution comprises a polar organic solvent;

[0301] (iv) Using a C 1-4 treating the separated raffinate phase of step (iii) with a blending agent of an alcohol and contacting the resulting feedstock with a catalyst composition to produce an upgraded pyrolysis oil product; wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst; and

[0302] The pyrolysis oil comes from the pyrolysis of plastic or rubber or a mixture.

[0303] The raffinate / upgraded pyrolysis oil can be treated with the blending agent by any means known in the art, wherein some mixing occurs. For example, the raffinate / upgraded pyrolysis oil and the blending agent can be added to a container, reactor, or mixer commonly used in the art, and the two components can be mixed. Mixing can be achieved by a mixing device that stirs the two components. For example, the two components can be mixed together by stirring or by shaking.

[0304] In one embodiment, the treatment with the blending agent is carried out at ambient temperature and pressure. Typically, the temperature is between about 18°C ​​and 28°C, more typically between about 21°C and 25°C, and the pressure is about 100 kPa. Thus, the costs and other problems associated with high temperature or high pressure conditions are avoided.

[0305] Alternatively, mixing is carried out at a temperature between about 0°C and about 70°C, suitably about 15°C to about 50°C.

[0306] The process of contacting the feedstock with the catalyst composition can be carried out at ambient temperature or, typically, at elevated temperature. Thus, the process typically involves contacting the feedstock with the catalyst composition at a temperature above ambient temperature. For example, the temperature is typically about 25°C or higher.

[0307] In one embodiment, the feedstock is contacted with the catalyst composition at a temperature of about 40°C or higher, such as 50°C or higher, such as about 60°C or higher, such as about 70°C or higher, such as about 80°C or higher.

[0308] In one embodiment, the feedstock is contacted with the catalyst composition at a temperature of about 100°C or higher, such as about 250°C or higher, such as about 300°C or higher, such as about 350°C or higher, such as about 400°C or higher.

[0309] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature from about 40°C to about 500°C, such as from about 40°C to about 400°C, such as from about 40°C to about 300°C, such as from about 40°C to 200°C, such as from about 40°C to 150°C.

[0310] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature from about 60°C to about 500°C, such as from about 60°C to about 400°C, such as from about 60°C to about 300°C, such as from about 60°C to 200°C, such as from about 60°C to 150°C.

[0311] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature from about 80°C to about 500°C, such as from about 80°C to about 400°C, such as from about 80°C to about 300°C, such as from about 80°C to 200°C, such as from about 80°C to 150°C.

[0312] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature from about 100°C to about 500°C, such as from about 100°C to about 400°C, such as from about 100°C to about 300°C, such as from about 100°C to 200°C, such as from about 100°C to 150°C.

[0313] In one embodiment, the process includes contacting the feedstock with the catalyst composition at or above ambient pressure. For example, the process may include 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 include contacting the feedstock with the catalyst composition at a pressure greater than about 1 atmosphere (atm) or about 101 kPa.

[0314] In one embodiment, the process includes 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.

[0315] Although the process can be carried out in batches, a continuous mode can be used. Therefore, the process generally includes continuously feeding the raw materials to the catalyst composition. In one embodiment, the process is carried out using a microreactor. A suitable microreactor is a fixed bed microreactor.

[0316] Any suitable space velocity can be used to feed the feedstock onto the catalyst composition. For example, the feedstock can be fed at a space velocity equal to or greater than about 0.1 hour. -1 The feedstock may be fed to the catalyst composition at a weight hourly space velocity (WHSV) of about 0.5 hours. -1 A weight hourly space velocity (WHSV) of 1.0 hr is fed to the catalyst composition. Suitably, the weight hourly space velocity is equal to or greater than about 1.0 hr -1 , such as equal to or greater than about 1.5 hours -1 , or for example, equal to or greater than about 2.0 hours -1 .

[0317] In one embodiment, the WHSV is from about 0.1 hours -1 About 10 hours -1 For example, from about 0.1 hours -1 About 5.0 hours -1 For example, from about 0.1 hours -1 About 4 hours -1 For example, from about 0.1 hours -1 About 3.5 hours -1 For example, from about 0.1 hours -1 About 3 hours -1 For example, from about 0.1 hours -1 About 2.5 hours -1 WHSV.

[0318] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of greater than about 40°C to about 150°C and a pressure of about 101 KPa.

[0319] In one embodiment, the process comprises contacting the feedstock with the catalyst composition at a temperature of greater than about 60°C to about 120°C and a pressure of about 101 KPa.

[0320] raw material

[0321] The feedstock for use in the catalytic upgrading step may comprise any of the raffinate products from the first aspect of the invention. Typically, the feedstock comprises upgraded pyrolysis oil obtainable by treating pyrolysis oil derived from the pyrolysis of plastic, rubber, or a combination thereof with an upgrading solution. The upgrading solution may be as described in any of the above-mentioned embodiments.

[0322] The raw material also contains one or more C 1-4 The blending agent comprises one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol and tert-butanol. Suitably, the blending agent comprises one or more of methanol, ethanol, n-propanol and n-butanol. Suitably, the blending agent comprises one or more of methanol and ethanol.

[0323] In one embodiment, the blending agent comprises methanol in an amount greater than or equal to about 40 wt.%. In another embodiment, the blending agent comprises methanol in an amount from about 40 wt.% to about 95 wt.%. In another embodiment, the blending agent comprises methanol in an amount from about 50 wt.% to about 95 wt.%. In another embodiment, the blending agent comprises methanol in an amount from about 60 wt.% to about 95 wt.%. In another embodiment, the blending agent comprises methanol in an amount from about 70 wt.% to about 95 wt.%. In another embodiment, the blending agent comprises methanol in an amount from about 80 wt.% to about 95 wt.%. In another embodiment, the blending agent comprises methanol in an amount of about 80 wt.%.

[0324] In one embodiment, the mass ratio of raffinate / upgraded pyrolysis oil to blending agent in the feedstock is from about 99:1 to about 1:99, suitably from about 90:10 to about 10:90, suitably from about 80:20 to about 20:80, suitably from about 70:30 to about 30:70.

[0325] In another embodiment, the mass ratio of raffinate / upgraded pyrolysis oil to blending agent in the feedstock is about 60:40 to about 10:90, suitably about 60:40 to about 20:80, suitably about 60:40 to about 30:70, suitably about 60:40 to about 40:60. In another embodiment, the mass ratio of raffinate / upgraded pyrolysis oil to blending agent in the feedstock is about 50:50.

[0326] Catalyst composition

[0327] In one embodiment, the process of the present invention comprises contacting a feedstock with a catalyst composition, wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst.

[0328] Solid acid catalysts are well known to the skilled person. Well-known examples include zeolites and aluminum silicates.

[0329] In one embodiment, the solid acid catalyst may be an acidic zeolite. As will be appreciated by those skilled in the art, aluminosilicate zeolites comprise SiO4 and AlO4 tetrahedra, and each AlO4 tetrahedron and its trivalent aluminum has an additional negative charge that is balanced by monovalent, divalent, or trivalent cations. Such zeolites are typically prepared in their sodium form. However, surface acidity can be increased by treating with H + Replace Na + To generate (to produce acidic zeolites). Protons can be introduced into the structure by ion exchange, hydrolysis of water, or hydration of cations or reduction of cations to lower valence states. In the case of hydrogen zeolites, protons associated with the negatively charged framework aluminum are the source of Bronsted acid activity, and a linear relationship between catalytic activity and the concentration of proton sites associated with the framework aluminum has been demonstrated (WO Haag et al., Nature, 309, 589, 1984).

[0330] In one embodiment, the solid acid catalyst is a hydrogen zeolite (H-zeolite), for example, H-ZSM-5, H-beta, HY, or H-mordenite.

[0331] In another embodiment, acidic silicoaluminophosphate (SAPO) zeolites, such as SAPO-34, may also be used. SBA is also a suitable zeolite catalyst that may be used.

[0332] In another embodiment, the solid acid catalyst can be used in combination with a mixed metal oxide. Examples of metal oxides and acidic mixed metal oxides that can be suitably employed are ZnO, VOPO4 (e.g., VOPO4.2H2O), ZrO2 / WO3 2- 、ZrO2 / SO4 2- 、Al2O3 / PO4 3- , Al2O3 / TiO2 / ZnO, Al2O3 / ZrO2 / WO3 and TiO2 / SO4 2- .

[0333] In another embodiment, the solid acid catalyst can be a solid heteropoly acid. Suitable solid heteropoly acids include, for example, Cs x H x -3PW 12 O 40 、H3PW 12 O 40 .6H2O、H3PW 12 O 40 / K-10 clay, Ag 0.5 H 2.5 PW 12 O 40 、Zr 0.7 H0.2 PW 12 O 40 and H3PW 12 O 40 / ZrO2.

[0334] In one embodiment, the solid acid catalyst is selected from acidic aluminosilicate zeolites or acidic silicoaluminophosphate (SAPO) zeolites.

[0335] In another embodiment, the solid acid catalyst is an acidic aluminosilicate zeolite having the general formula (I):

[0336] [M n+ ] x / n [(AlO2 - ) x (SiO2) y ] (I)

[0337] in

[0338] M is H + , or M is two or more different cations, one of which is H + ;as well as

[0339] The Si / Al ratio y / x is from 1 to 300.

[0340] In one embodiment, the Si / Al ratio y / x can be, for example, from about 20 to about 90, such as from about 30 to about 90, such as from about 40 to about 80, or such as from about 50 to about 70, or from about 55 to about 65. In one embodiment, the Si / Al ratio y / x is about 60.

[0341] When M is two or more different cations, one of which is H + When H + The charge ratio with other cations M is usually equal to or greater than 1. In other words, the charge ratio of all M n+ At least half of the positive charge produced by the cation is typically due to protons.

[0342] In one embodiment, the solid acid catalyst is H-ZSM-5.

[0343] Typically, the solid acid catalyst is H-ZSM-5 having a Si / Al ratio of from 20 to 90, e.g., from 30 to 90, e.g., from 40 to 80, or e.g., from 50 to 70, or from 55 to 65. In one embodiment, the solid acid catalyst is H-ZSM-5 having a Si / Al ratio of about 60. Such H-ZSM-5 catalysts are commercially available from ZEOLYST International.

[0344] In one embodiment, the catalyst composition comprises a mesoporous solid acid catalyst. The term "mesoporous" in the context of catalysis is well known in the art. For example, the UPAC Goldbook defines mesopores as pores of intermediate size between micropores and macropores, particularly pores having a width between 2 nm and 0.05 μm.

[0345] As used herein, the term "desulfurization catalyst" refers to a catalyst commonly used in hydrodesulfurization reactions. Desulfurization catalysts may also be referred to as HDS catalysts. Examples of desulfurization catalysts are well known to those skilled in the art. For example, desulfurization catalysts are typically based on metals from Groups VIB and VIII of the Periodic Table of Elements. For example, desulfurization catalysts typically comprise transition metals capable of forming bonds with sulfur or oxygen, such as Ni, Mo, Co, Cu, Zn, W, Fe, Pd, Pt, Rh, Ru.

[0346] Therefore, the desulfurization catalyst can be a desulfurization catalyst comprising an oxide and / or sulfide of a transition metal such as Ni, Mo, Co, Cu, Zn, W, Fe, Pd, Pt, Rh, Ru as a catalytic component. The transition metal catalyst can be supported on a material with a high surface area such as alumina, TiO2, zeolite, etc.

[0347] In one embodiment, the desulfurization catalyst is a bimetallic desulfurization catalyst, particularly a bimetallic oxide or sulfide.

[0348] In one embodiment, the desulfurization catalyst is a trimetallic desulfurization catalyst, particularly a trimetallic oxide or sulfide.

[0349] In one embodiment, the desulfurization catalyst is a bimetallic desulfurization catalyst supported on alumina, TiO2, or zeolite.

[0350] In one embodiment, the desulfurization catalyst is a trimetallic desulfurization catalyst supported on alumina, TiO2, or zeolite.

[0351] In another embodiment, the desulfurization catalyst comprises cobalt and / or molybdenum oxide / sulfide on a support selected from alumina, TiO2 and zeolite. Suitably, the desulfurization catalyst is a cobalt or molybdenum sulfide on an Al2O3 support.

[0352] Suitable desulfurization catalysts may have bimetallic catalytic components such as copper and zinc (CuZn), copper and nickel (CuNi), cobalt and molybdenum (CoMo), nickel and molybdenum (NiMo), nickel and tungsten (NiW).

[0353] Suitable desulfurization catalysts may have a catalytic component comprising one or more of oxides of copper, zinc, iron, nickel, cobalt, tungsten, and / or molybdenum.

[0354] Suitable desulfurization catalysts may have the following catalytic components: copper and zinc oxides (CuZnOx), copper and nickel oxides (CuNiOx), cobalt and molybdenum oxides (CoMoOx), nickel and molybdenum oxides (NiMoOx), nickel and tungsten oxides (NiWOx), copper and zinc sulfides (CuZnSx), copper and nickel sulfides (CuNiSx), cobalt and molybdenum sulfides (CoMoSx), nickel and molybdenum sulfides (NiMoOx) and nickel and tungsten sulfides (NiWSx).

[0355] In one embodiment, the desulfurization catalyst has a catalytic component selected from CoMo / alumina, NiMo / alumina, NiW / zeolite.

[0356] In another embodiment, the desulfurization catalyst has a catalytic component selected from the group consisting of nickel and molybdenum oxides (NiMoOx), nickel and tungsten oxides (NiWOx), and cobalt and molybdenum sulfides (CoMoSx).

[0357] In another embodiment, the desulfurization catalyst has a catalytic component selected from the group consisting of nickel and molybdenum oxides supported on alumina (NiMoOx / Al2O3), nickel and tungsten oxides supported on ZSM-5 (NiWOx / ZSM-5), and cobalt and molybdenum sulfides supported on alumina (CoMoSx / Al2O3).

[0358] In one embodiment, the desulfurization catalyst is sulfided. In another embodiment, the desulfurization catalyst is used without sulfidation.

[0359] In one embodiment, the catalyst composition comprises a solid acid catalyst selected from acidic aluminosilicate zeolites and acidic silicoaluminophosphate (SAPO) zeolites, and a desulfurization catalyst comprising a catalytic component selected from CuZn, CuNi, CoMo, NiMo, NiW, CuZn, CuNi, CoMo, NiMo and NiW, optionally on a support.

[0360] In one embodiment, the catalyst composition comprises a solid acid catalyst selected from acidic aluminosilicate zeolites and acidic silicoaluminophosphate (SAPO) zeolites, and a desulfurization catalyst comprising a catalytic component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[0361] In another embodiment, the catalyst composition comprises a solid acid catalyst selected from mesoporous acidic aluminosilicate zeolites and mesoporous acidic silicoaluminophosphate (SAPO) zeolites, and a desulfurization catalyst comprising a catalytic component selected from CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx and NiWSx, optionally on a support.

[0362] In another embodiment, the catalyst composition comprises H-ZSM-5, and a desulfurization catalyst comprising a catalytic component selected from the group consisting of CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx, and NiWSx, optionally on a support.

[0363] In another embodiment, the catalyst composition comprises mesoporous H-ZSM-5, and a desulfurization catalyst comprising a catalytic component selected from the group consisting of CuZnOx, CuNiOx, CoMoOx, NiMoOx, NiWOx, CuZnSx, CuNiSx, CoMoSx, NiMoOx, and NiWSx, optionally on a support.

[0364] In one embodiment, the ratio of solid acid catalyst to desulfurization catalyst in the catalyst composition is from about 10: 1 to about 1: 10. In another embodiment, the ratio is from about 5: 1 to about 1:2, such as about 1: 1.

[0365] In one embodiment, the catalyst composition includes a solid acid catalyst and a desulfurization catalyst, wherein the desulfurization catalyst is not supported on the solid acid catalyst, ie, chemically bonded to the solid acid catalyst.

[0366] In another embodiment, the catalyst composition may further include a dehalogenation catalyst. Suitable dehalogenation catalysts include metal oxides (e.g., ZnO, CaO, FeO X ), alkali and alkaline earth metal bases (e.g. KOH, K2CO3, Ca(OH)2, CaCO3), metal hydroxides (e.g. Fe(OH) X ) and metal-carbon composite (Fe-C or Ca-C) catalysts.

[0367] In another embodiment, the catalyst composition may further comprise an ion exchange resin. Suitably, the ion exchange resin is a cation exchange resin, suitably a sulfonic acid based ion exchange resin.

[0368] In one embodiment, the catalyst composition consists of a solid acid catalyst, an ion exchange resin, a desulfurization catalyst, and a dehalogenation catalyst, suitably in a mass ratio of about 2:2:1:1.

[0369] In one embodiment, the catalyst composition consists of a zeolite, at least one metal oxide, and an ion exchange resin.

[0370] In one embodiment, the catalyst composition consists of zeolite, ion exchange resin, iron oxide, zinc oxide, suitably in a mass ratio of about 2:2:1:1.

[0371] In one embodiment, the catalyst composition is a mechanical mixture of the components. That is, the catalyst composition is a heterogeneous mixture of individual catalyst / resins. Thus, the catalyst and resin are not chemically modified with each other; they are merely in a physical mixture.

[0372] absorb

[0373] In another embodiment, after treating the pyrolysis oil with the upgrading solution, the raffinate may be treated with an absorbent.

[0374] Thus, in one embodiment, the present invention is directed to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0375] (i) treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, and separating the raffinate phase, wherein the upgrading solution comprises a polar organic solvent;

[0376] (ii) treating the separated raffinate phase of step (i) with an absorbent;

[0377] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0378] In another aspect, the present invention relates to a process for producing an upgraded pyrolysis oil product, the process comprising:

[0379] (i)(a) treating pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0380] (i)(b) optionally treating the product of (i)(a) with a hydrocarbon fluid;

[0381] (ii) mixing the mixture obtained from (i)(a) or optionally (i)(b), and then allowing the mixture to form at least two phases comprising a raffinate phase and an extract phase; and

[0382] (iii) separating the raffinate phase from the extract phase;

[0383] (iv) treating the separated raffinate phase of step (iii) with an absorbent;

[0384] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0385] The raffinate / upgraded pyrolysis oil can be treated with the absorbent by any means known in the art. For example, the raffinate / upgraded pyrolysis oil and absorbent can be combined and allowed to stand, stirred, or shaken together, or a combination thereof. Alternatively, the raffinate / upgraded pyrolysis oil can be passed through a bed of absorbent.

[0386] In one embodiment, the treatment with the absorbent is carried out at a temperature between about 0°C and about 300°C, more typically between about 15°C and about 250°C, and a pressure between about 100 KPa and about 500 KPa, suitably about 100 KPa to about 250 KPa.

[0387] Alternatively, the treatment is carried out at a temperature between about 0°C and about 70°C, suitably about 15°C to about 50°C.

[0388] In one embodiment, the treatment with the absorbent is carried out at ambient temperature and pressure, typically between about 18°C ​​and about 28°C, more typically between about 21°C and about 25°C, and at a pressure of about 100 kPa.

[0389] Suitably, the absorbent is capable of absorbing one or more heteroatoms (suitably sulphur and / or chlorine) from the raffinate / upgraded pyrolysis oil.Specific examples of suitable absorbents are zeolites, aluminosilicates, activated carbon and mixtures thereof.

[0390] In one embodiment, the absorbent is a commercially available molecular sieve. Suitably, the absorbent is a microporous molecular sieve (ie, pore size of 2 nm or less).

[0391] In one embodiment, the absorbent is a zeolite molecular sieve suitably selected from 3A, 4A, 5A, 10X, 13X. Suitably, the absorbent is zeolite molecular sieve 13X.

[0392] In one embodiment the zeolite is a zeolite of the faujasite series, suitably zeolite Y (eg zeolite Na-Y or La-Y).

[0393] In one embodiment, the absorbent is selected from zeolite molecular sieve 3A, 4A, 5A, 10X, 13X or zeolite Na-Y and La-Y. In another embodiment, the absorbent is selected from zeolite molecular sieve 13X and zeolite Na-Y or La-Y. In another embodiment, the absorbent is selected from zeolite molecular sieve 13X and zeolite Na-Y. The present invention will now be further described by way of the following numbered paragraphs:

[0394] 1. A process for upgrading pyrolysis oil, the process comprising treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0395] 2. A process for producing an upgraded pyrolysis oil product, the process comprising:

[0396] (i) treating the pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0397] (ii) mixing the pyrolysis oil and the upgrading solution, and then allowing the mixture to form two phases consisting of a raffinate phase and an extract phase; and

[0398] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0399] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0400] 3. A process for producing an upgraded pyrolysis oil product, the process comprising:

[0401] (i)(a) treating pyrolysis oil with an upgrading solution, wherein the upgrading solution comprises a polar organic solvent;

[0402] (i)(b) optionally treating the product of (i)(a) with a hydrocarbon fluid;

[0403] (ii) mixing the pyrolysis oil and the upgraded solution obtained from (i)(a) or optionally (i)(b), and then allowing the mixture to form at least two phases comprising a raffinate phase and an extract phase; and

[0404] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0405] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0406] 4. The process according to any one of paragraphs 1 to 3, wherein the upgrading solution comprises at least one polar organic solvent having a dipole moment (D) of about 1.5 or greater, suitably about 2.0 or greater, suitably about 2.5 or greater.

[0407] 5. The process according to any of the preceding paragraphs, wherein the upgrading solution comprises at least one polar organic solvent having a dipole moment (D) of about 3.5 to about 6.0, suitably about 3.5 to about 5.5, suitably about 3.5 to about 5.0.

[0408] 6. A process according to any one of the preceding paragraphs, wherein the polar organic solvent is selected from one or more of alcohols, carbonates, amides, organosulfur compounds, nitriles and heterocyclic compounds, suitably carbonates and organosulfur compounds.

[0409] 7. A process according to any one of the preceding paragraphs, wherein the polar organic solvent is selected from methanol, ethanol, ethylene glycol, propylene carbonate, sulfolane, acetic acid, propionic acid, DMSO, NMP, DMF, DMA and pyridine, suitably NMP, propylene carbonate and sulfolane.

[0410] 8. A process according to any of the preceding paragraphs, wherein the upgrading solution has a specific gravity (20 / 4) of about 0.95 or greater, suitably 1 or greater.

[0411] 9. The process of any of the preceding paragraphs, wherein the upgrading solution further comprises one or more of another solvent, an acid, a base, or an organometallic compound.

[0412] 10. A process according to paragraph 9, wherein the additional solvent is selected from alcohols, aldehydes, ketones, ethers, carboxylic acids, esters, carbonates, anhydrides, amides, amines, heterocyclic compounds, imines, imides, nitriles, nitro compounds, sulfoxides and halogenated alkanes.

[0413] 11. A process according to any of paragraphs 9 and 10, wherein the additional solvent is selected from methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol and propane-1,3-diol, suitably methanol.

[0414] 12. A process according to any preceding paragraph, wherein the upgrading solution comprises at least about 50% wt. (suitably at least about 90% wt.) of one or more of NMP, sulfolane and propylene carbonate.

[0415] 13. A process according to any of the preceding paragraphs, wherein the upgrading solution comprises at least about 50% wt. (suitably at least about 90% wt.) of one or more of sulfolane and propylene carbonate, and further comprises an alcohol selected from methanol, ethanol and ethane-1,2-diol, and optionally a base or an organometallic compound.

[0416] 14. The process according to any one of paragraphs 9 to 11, wherein the acid is selected from methanoic acid (formic acid), ethanoic acid (acetic acid), propionic acid, butyric acid and valeric acid, suitably acetic acid or propionic acid.

[0417] 15. A process according to any one of paragraphs 9 to 14, wherein the base is a metal alkali metal hydroxide or carbonate, suitably potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate.

[0418] 16. A process according to any one of paragraphs 9 to 13, wherein the organometallic compound is an alkali metal salt, suitably potassium acetate, sodium acetate, sodium formate or potassium formate; more suitably potassium acetate or sodium acetate.

[0419] 17. The process of any of paragraphs 1 to 12, wherein the upgrading solution comprises NMP and water.

[0420] 18. The process of any of paragraphs 1 to 12, wherein the upgrading solution consists of about 90% NMP and about 10% water.

[0421] 19. The process according to any of the preceding paragraphs, wherein the mass ratio of pyrolysis oil to upgrading solution is from about 95:5 to about 10:90, suitably from about 95:5 to about 50:50, more suitably about 90:10.

[0422] 20. A process according to any preceding paragraph, wherein the pyrolysis oil is derived from the pyrolysis of a thermoplastic, suitably one or more of polyethylene, polypropylene and polystyrene.

[0423] 21. The process of any of paragraphs 1 to 19, wherein the pyrolysis oil is derived from the pyrolysis of rubber.

[0424] 22. A process according to any preceding paragraph, wherein the pyrolysis oil has a specific gravity (20 / 4) of about 1 or less, suitably about 0.7 to about 0.95.

[0425] 23. The process of any of the preceding paragraphs, wherein the pyrolysis oil is treated with an aqueous solution prior to treating the pyrolysis oil with the upgrading solution.

[0426] 24. The process of any of the preceding paragraphs, comprising:

[0427] (i) treating pyrolysis oil with an aqueous solution to provide a mixture comprising an organic phase and an aqueous phase, and separating the organic phase;

[0428] (ii) treating the separated organic phase of step (i) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase;

[0429] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0430] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0431] 25. The process according to any of the preceding paragraphs, wherein the mass ratio of pyrolysis oil to aqueous solution is from about 95:5 to about 10:90, or suitably about 60:40 to about 40:60, or suitably about 50:50.

[0432] 26. The process of any one of paragraphs 24 to 25, wherein the aqueous solution has a pH of about 5 to about 10, suitably about 6 to 8.

[0433] 27. The process of any of paragraphs 24 to 26, wherein the aqueous solution comprises an acid, a base, or an organometallic compound.

[0434] 28. A process according to paragraph 27, wherein the acid is a carboxylic acid, suitably selected from methanoic acid (formic acid), ethanoic acid (acetic acid), propanoic acid, butyric acid and valeric acid.

[0435] 29. A process according to paragraph 27, wherein the base is an alkali metal hydroxide or carbonate, suitably potassium hydroxide, sodium hydroxide, sodium carbonate and potassium carbonate.

[0436] 30. The process of paragraph 27, wherein the organometallic compound is an alkali metal salt, such as potassium acetate or sodium acetate.

[0437] 31. The process of any of the preceding paragraphs, wherein the pyrolysis oil is treated with a hydrocarbon fluid prior to treating the pyrolysis oil with the upgrading solution.

[0438] 32. The process of any of the preceding paragraphs, comprising:

[0439] (i) treating the pyrolysis oil with an aqueous solution and optionally a hydrocarbon fluid to provide a mixture comprising an organic phase and an aqueous phase, and separating and optionally filtering the organic phase;

[0440] (ii) treating the separated organic phase of step (i) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase;

[0441] (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product;

[0442] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0443] 33. The process of any of paragraphs 31 and 32, wherein the mass ratio of pyrolysis oil to hydrocarbon fluid is from about 95:5 to about 10:90, suitably about 60:40 to about 40:60, or suitably about 50:50.

[0444] 34. The process of any one of paragraphs 3 to 33, wherein the hydrocarbon fluid is C3 to C 20 Alkanes, suitably C5 to C 16 Alkanes.

[0445] 35. The process of any of paragraphs 3 to 34, wherein the hydrocarbon fluid is selected from pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and hexadecane (cetane).

[0446] 36. The process of any of the preceding paragraphs, wherein the raffinate phase is treated with an absorbent.

[0447] 37. The process of paragraph 36, wherein the absorbent is a zeolite, an aluminosilicate, or activated carbon.

[0448] 38. The process of any of paragraphs 36 or 37, wherein the absorbent is selected from zeolite molecular sieve 13X and zeolite Na-Y or La-Y.

[0449] 39. The process according to any one of paragraphs 1 to 35, wherein the raffinate phase is treated with a mixture comprising C 1-4 The method comprises treating the raw material with a blending agent of an alcohol and contacting the obtained raw material with a catalyst composition; and wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst.

[0450] 40. A process for producing an upgraded pyrolysis oil product, the process comprising:

[0451] (i) treating the pyrolysis oil with an aqueous solution and optionally a hydrocarbon fluid to provide a mixture comprising an organic phase and an aqueous phase, and separating and optionally filtering the organic phase;

[0452] (ii) treating the separated organic phase of step (i) with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, and separating the raffinate phase, wherein the upgrading solution comprises a polar organic solvent;

[0453] (iii) Using a 1-4 treating the separated raffinate phase of step (ii) with a blending agent of an alcohol and contacting the resulting feedstock with a catalyst composition to produce an upgraded pyrolysis oil product; wherein the catalyst composition comprises a combination of a solid acid catalyst and a desulfurization catalyst; and

[0454] The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0455] 41. The process of any of paragraphs 39 and 40, wherein the feedstock is contacted with the catalyst composition at a temperature of about 40°C to 200°C, such as from about 40°C to 150°C.

[0456] 42. The process of any of paragraphs 39 to 41, wherein the feedstock is contacted with the catalyst composition at a pressure of about 101 KPa to about 350 KPa, suitably about 101 KPa.

[0457] 43. The process of any one of paragraphs 39 to 42, wherein the -1 About 10 hours -1 , suitably about 0.1 hours -1 About 2.5 hours -1 The feedstock is contacted with the catalyst composition at a weight hourly space velocity (WHSV) of 1.5 wt %.

[0458] 44. The process of any of paragraphs 39 to 43, wherein the blending agent comprises methanol.

[0459] 45. The process of any of paragraphs 39 to 44, wherein the blending agent comprises at least about 50% wt.% methanol, suitably at least about 90% wt.% methanol.

[0460] 46. ​​The process of any one of paragraphs 39 to 45, wherein the mass ratio of raffinate to blending agent in the feedstock is from about 60:40 to about 10:90, suitably from about 60:40 to about 40:60.

[0461] 47. A process according to any one of paragraphs 39 to 46, wherein the solid acid catalyst is selected from a hydrogen zeolite (H-zeolite), suitably H-ZSM-5, H-beta, HY or H-mordenite.

[0462] 48. The process according to any one of paragraphs 39 to 47, wherein the desulfurization catalyst is selected from oxides, hydroxides and / or sulfides of transition metals such as Ni, Mo, Co, Cu, Zn, W, Fe, W, Pd, Pt, Rh, Ru.

[0463] 49. The process of any of paragraphs 39 to 48, wherein the desulfurization catalyst is selected from oxides of copper, zinc, iron, nickel, cobalt, tungsten, and / or molybdenum.

[0464] 50. A process according to any one of paragraphs 39 to 49, wherein the catalyst composition further comprises a dehalogenation catalyst suitably selected from metal oxides (e.g. ZnO, CaO, FeO X ), alkali and alkaline earth metal bases (e.g. KOH, K2CO3, Ca(OH)2, CaCO3), metal hydroxides (e.g. Fe(OH) X) and metal-carbon composite (Fe-C or Ca-C) catalysts.

[0465] 51. The process of any of paragraphs 39 to 50, wherein the catalyst composition further comprises an ion exchange resin, suitably selected from sulfonic acid based ion exchange resins.

[0466] 52. Use of an upgrading solution for reducing the olefin content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent, and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0467] 53. Use of an upgrading solution for reducing the solid residue content of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent; and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0468] 54. Use of an upgrading solution for increasing the stability of a pyrolysis oil, wherein the upgrading solution comprises a polar organic solvent; and wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

[0469] 55. An upgraded pyrolysis oil obtainable by the process according to any one of paragraphs 1 to 51. Example

[0470] A. Preparation of pyrolysis oil

[0471] Solvents and chemicals were purchased from Sigma Aldrich and Fisher Scientific.

[0472] Plastic pyrolysis oils from different plastics (LDPE, PP, PS, rubber, blends) were produced on a laboratory-scale pyrolysis unit ( Figure 2 ). LDPE, PP, PS for the production of pyrolysis oil were used in the form of pellets (Sigma Aldrich). Rubber for the production of pyrolysis oil was also used in the form of pellets obtained from scrap tires.

[0473] Each material (LDPE, PP, PS and rubber) and the mixture were subjected to pyrolysis. The raw materials for producing the mixed rubber / plastic pyrolysis oil (hereinafter "mixed pyrolysis oil") included 25% LDPE, 25% PP, 25% PS and 25% rubber (in weight %). Pyrolysis was carried out in batches in a 10L batch unit. Before pyrolysis, the pyrolysis unit was purged with nitrogen to create an inert atmosphere in the unit. Pyrolysis was carried out in the absence of a catalyst and at various temperatures depending on the raw materials and at atmospheric pressure. LDPE was pyrolyzed at 450°C, PP at 450°C, PS at 400°C, rubber at 500°C, and the mixed raw materials at 450°C. Water (at a temperature of about 15°C) was used in the condenser to cool the pyrolysis vapors. Pyrolysis oil was collected after each pyrolysis process, and non-condensable gases were discharged.

[0474] B. Aqueous Washing of Pyrolysis Oil

[0475] B1. Water washing

[0476] Each sample of pyrolysis oil and distilled water (pH 7) is fed into a separating funnel with a mass ratio of pyrolysis oil to water of 10:1. Mixing is carried out by shaking the funnel hole. After observing complete phase separation (two liquid phases) in the mixture, the mixture is allowed to stabilize for another 5 minutes. Then, the pyrolysis oil layer and the water layer are separated and analyzed. The pH level of the aqueous phase after water washing is analyzed by a pH meter (Table 2).

[0477] Table 2: pH of water wash

[0478]

[0479] All aqueous phase samples from the water washing process appeared weakly acidic, indicating that the acidic contents from the pyrolysis oil had been extracted by the water washing process.

[0480] In addition, asphaltenes / coke and other solid residues are retained in the aqueous phase. Therefore, asphaltenes can be easily separated from the organic phase.

[0481] B2. Alkane washing

[0482] Isoalkanes or normal alkanes (paraffins) with 5-16 carbon atoms have been used as paraffin feed streams in the tests. 99% pure n-pentane, 97% pure n-hexane, 99.8% pure isooctane, 99% pure isododecane, 99% pure n-dodecane, and 99% pure n-hexadecane were purchased from Sigma Aldrich and used in the following treatments.

[0483] The mixed pyrolysis oil and each of the above paraffin waxes were mixed in a glass container at a weight ratio of 1:1 pyrolysis oil to paraffin wax by shaking and rotating. During mixing, flocculation was observed in the mixture, and black flocs separated from the liquid mixture. After mixing, each mixture was stabilized for an additional 5 minutes. The liquid mixture and flocs were then separated by filtration and analyzed.

[0484] The color and clarity of each pyrolysis oil before and after paraffin washing were directly compared with and without a light source (sunlight). Specifically, for consistency, the same amount of oil samples were prepared and placed in 15 ml clear glass vials.

[0485] The color change after the purification process is significant. The original mixed pyrolysis oil (made from 25% LDPE, 25% PP, 25% PS, and 25% rubber by weight) is very dark in color and opaque even under strong flashlight light (Figure 3). However, after washing with paraffin wax in n-hexane, the pyrolysis oil becomes clear under sunlight (Figure 3c).

[0486] Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied to the output of the water wash followed by the paraffin wash. The analyzer was a TA Instruments SDT analyzer model Q600. The analysis procedure was: 100 ml / min carrier gas flow (N2), 10°C / min heating rate, a final temperature of 500°C held for 5 minutes, then the carrier gas was changed to air and heated to 800°C to burn off the residue in the sample holder. As can be seen in Table 3, a water wash followed by an n-hexadecane wash was able to reduce the residue above 400°C to 0.44% by weight (76.09% total reduction).

[0487] Table 3. Residue analysis of different pyrolysis oil samples

[0488] Pyrolysis oil samples Residue above 400°C (wt%) Original mixed pyrolysis oil 1.84 After water / n-pentane washing 0.59 After water / hexane washing 0.55 After water / isooctane washing 0.54 After water / isododecane washing 0.46 After water / n-dodecane washing 0.46 After water / n-hexadecane washing 0.44

[0489] The olefin content of the raw mixed pyrolysis oil and the paraffin wash product was analyzed by gas chromatography-mass spectrometry (GCMS). The GCMS analyzer was a Perkin Elmer Clarus 500 GCMS gas chromatograph-mass spectrometer. The main operating parameters of the GCMS analyzer were: column oven temperature 35°C / 308K; injection temperature 205°C / 478K; direct injection mode; and a heating rate of 3°C / min from 35°C to 200°C / 473K.

[0490] The results are shown in Table 4. Washing with n-hexadecane reduced the olefin content in the mixed pyrolysis oil from 36.10% to 16.97% by GCMS area (52.99% total reduction).

[0491] Table 4. Olefin content in different pyrolysis oil samples

[0492] Oil samples Olefin content (GCMS area %) Original mixed pyrolysis oil 36.10 After washing with water / n-pentane 19.29 After washing with water / n-hexane 18.09 After washing with water / isooctane 17.94 After washing with water / isododecane 17.84 After washing with water / n-dodecane 17.77 After washing with water / n-hexadecane 16.97

[0493] The heteroatom content (ie sulfur, nitrogen, chlorine, bromine) in the mixed pyrolysis oil and the output of the paraffin wash has also been analyzed by GCMS. Table 5 shows the heteroatom content in the mixed pyrolysis oil before and after the n-hexadecane wash.

[0494] Table 5. Heteroatom content in mixed pyrolysis oils

[0495]

[0496]

[0497] Compared to the original mixed pyrolysis oil, the sulfur content was reduced by 70.83%, the nitrogen content was reduced by 78.70%, the chlorine content was reduced by 100%, and the bromine content was also reduced by 100%. In total, the heteroatom content in the pyrolysis oil was reduced by 79.59%.

[0498] Since the high boiling residues and olefin content in the pyrolysis oil has been significantly reduced, this makes the oil much more stable and causes less fouling when stored for long periods of time or when subjected to thermal treatments such as distillation (heat exchangers).

[0499] The original mixed pyrolysis oil and the upgraded pyrolysis oil after water / paraffin washing were distilled up to 225°C to separate the gasoline fraction from the pyrolysis oil. The distillation was carried out in a round-bottomed glass flask and heated by an electric heating mantle. The product vapor was then cooled and condensed by cold water (about 15°C) in a condenser and collected in another round-bottomed flask placed in an ice-water bath (0°C). In order to remove any air in the system during the distillation, nitrogen was used as a carrier gas in the distillation system.

[0500] Fig. 4 shows the gasoline fraction yield after the distillation of the pyrolysis oil of original mixing and the mixing of upgrading.In the gasoline yield of the pyrolysis oil of original mixing, can observe white flocculent (Fig. 4 a), but in the gasoline yield of the pyrolysis oil of upgrading, can't observe solid (Fig. 4 b).White flocculent is because the heat of alkene promotes polymerization, therefore causes the formation of jelly.The pyrolysis oil of upgrading has much lower olefin content, so it does not have a large amount of jelly formations during still.

[0501] C. Extraction with upgrading solution

[0502] The raw mixed pyrolysis oil was washed with water as stated above in B 1. Subsequently, the organic phase was subjected to extraction with an upgrading solution.

[0503] The process was carried out under ambient conditions. 99.9% pure methanol, 99.8% pure ethanol, 99% pure ethylene glycol, 99.5% pure tetraethylene glycol, 99.5% pure propylene carbonate, 99% pure sulfone, 99.8% pure acetic acid, 99.5% pure propionic acid, 99.0% pure potassium hydroxide, and 99% pure potassium acetate were used in the following extractions.

[0504] The pyrolysis oil mixed and the upgrading solution (upgrading solution 4) consisting of 99wt.% propylene carbonate and 1wt.% propionic acid are fed into a separating funnel with a mass ratio of 10:1 pyrolysis oil and upgrading solution. The mixture is then mixed well by shaking the funnel. After observing complete phase separation (two liquid phases) in the mixture, the mixture is stabilized for another 5 minutes. Based on their vertical order, raffinate is an upper phase mixture and extraction agent is a lower phase mixture. Raffinate and extraction agent are separated.

[0505] Fresh upgrading solution was added to the raffinate at a mass ratio of raffinate to upgrading solution of 10:1, and the extractive purification process was repeated 4 times.

[0506] The color and clarity of pyrolysis oil were compared before and after extraction with an upgrading solution. Using the same volume of pyrolysis oil, samples of the original mixed pyrolysis oil and raffinate were placed in a 15 ml clear glass tube. The color change after treatment with the upgrading solution was significant. The original plastic pyrolysis oil was very dark in color and opaque even under strong flashlight light (Figure 5a). After purification with the upgrading solution, the pyrolysis oil became clear and bright (Figure 5b).

[0507] Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied to the raffinate. The analyzer was a TA Instruments SDT analyzer, model Q600. The analysis procedure was: 100 ml / min carrier gas flow (N2), 10°C / min heating rate, a final temperature of 500°C held for 5 minutes, then the carrier gas was changed to air and heated to 800°C to burn off the residue in the sample holder. As can be seen in Table 5b, extraction with the upgrading solution was able to reduce the residue (above 400°C) to as low as 0.14% by weight (92.39% total reduction).

[0508] Table 5b. Residue analysis of different pyrolysis oil samples

[0509]

[0510]

[0511] The olefin content of the original mixed pyrolysis oil and the product extracted with the upgrading solution was analyzed by gas chromatography-mass spectrometry (GCMS). The GCMS analyzer was a Perkin Elmer Clarus 500 GCMS. The main operating parameters of the GCMS analyzer were: column oven temperature of 35°C / 308K; injection temperature of 205°C / 478K; direct injection mode; and a heating rate of 3°C / min from 35°C to 200°C / 473K.

[0512] The results are shown in Table 6. Upgrading solution 4 reduced the olefin content in the plastic pyrolysis oil to 11.85% by area on a GCMS basis (67.17% total reduction).

[0513] Table 6. Olefin content in different pyrolysis oil samples

[0514]

[0515] The heteroatom content (i.e. sulfur, nitrogen, chlorine, bromine) in the combined pyrolysis oil and the output extracted with upgrading solution has also been analyzed by GCMS. Table 7 shows the heteroatom content in the combined pyrolysis oil before and after extraction with upgrading solution 4.

[0516] Table 7. Heteroatom content in mixed pyrolysis oils

[0517]

[0518]

[0519] Compared to the original mixed pyrolysis oil, the sulfur content was reduced by 58.33%, the nitrogen content was reduced by 91.71%, the chlorine content was reduced by 94.12%, and the bromine content was reduced by 100%. After the purification process, the heteroatom content in the upgraded pyrolysis oil was reduced by a total of 90.68%.

[0520] D. Catalytic upgrading of pyrolysis oil

[0521] Ethers, in particular the tertiary ethers, MTBE (methyl tert-butyl ether, 2-methoxy-2-methylpropane), TAME (tert-amyl methyl ether, 2-methoxy-2-methylbutane) and ETBE (ethyl tert-butyl ether, 2-ethoxy-2-methylpropane) have become important components of reformulated gasoline due to strict legislation on fuels.

[0522] Ethers improve fuel combustion and thus significantly reduce exhaust hydrocarbon and carbon monoxide emissions. In addition, they improve cold weather drivability and have a high blending octane rating. 22

[0523] During the catalytic upgrading process, the blended alcohols are reacted with the olefin content (eg, diolefins, alpha olefins, etc.) to form ethers / stable olefin isomers (eg, 2-olefins, etc.). The scheme below shows an example of the reaction of methanol with the olefin content during the catalytic upgrading process.

[0524]

[0525] A mixture of methanol and pyrolysis oil (40 g) was used as a feedstock for the catalytic upgrading process. Methanol and pyrolysis oil were blended in a weight ratio of 1:9.

[0526] The raw materials were fed into a glass tube reactor ( Figure 6 The mixture was pumped to the reactor at a flow rate of 40 g / h, and the LHSV of the reaction was 0.5 h. -1 -4h -1 The catalyst is a multifunctional catalyst composition, which consists of a solid acid catalyst, a heat-sensitive macroporous sulfonic acid ion exchange resin catalyst, a desulfurization catalyst / sulfur absorbent, and a dehalogenation catalyst.

[0527] Specifically, the multifunctional catalyst composition used in the following studies was prepared by mixing Hβ zeolite (purchased from Fisher Scientific) with a 360:1 Si:Al ratio, Amberlyst 35 wet catalyst (purchased from Sigma Aldrich), 99.0% pure zinc oxide, and iron (III) oxide powder (purchased from Sigma Aldrich). The catalyst composition had a mixing ratio of Hβ zeolite:Amberlyst 15:zinc oxide:iron oxide of 2:2:1:1. The reaction temperature was between 60°C and 120°C, and the reaction was carried out at atmospheric pressure.

[0528] The product of the reaction was cooled by a water condenser and collected in a round bottom flask placed in an ice bath and the yield was weighed after the completion of the reaction. In order to evaluate the performance of the upgrading process, a GCMS method was employed to quantify the levels of various compounds in the oil produced after the upgrading process.

[0529] During the experiment, 40 grams of feedstock (methanol + pyrolysis oil) were input, and the yield of the reaction was 39 grams (97.50% yield by weight). According to the literature, etherification and isomerization reactions are very selective, and the conversion of methanol is very high. The selectivity of etherification and isomerization should exceed 98% on average. Side reactions are the etherification of methanol to dimethyl ether, the formation of alcohols from olefins and water, which are impurities (wet) from the reactants and catalyst and also from the formation of dimethyl ether, and the dimerization of olefins. 22 Since the dimethyl ether formed has a relatively low boiling point of -24°C, dimethyl ether is evaporated even if the product is cooled in an ice bath (0°C). This is why the yield of etherification is 97.50% by weight instead of 100% by weight.

[0530] The olefin and ether contents of the pyrolysis oils and the catalytic upgrading products were analyzed by gas chromatography-mass spectrometry (GCMS) (Table 8). The GCMS analyzer was a Perkin Elmer Clarus 500 GCMS. The main operating parameters of the GCMS analyzer were: column oven temperature, 35°C / 308K; injection temperature, 205°C / 478K; direct injection mode; and a heating rate of 3°C / min from 35°C to 200°C / 473K.

[0531] Table 8. Olefin and ether contents in different oil samples

[0532]

[0533]

[0534] The results are shown in Table 8. The catalytic upgrading process reduced the olefin content in polypropylene (PP) pyrolysis oil to 42.38% (by GCMS area) (10.12% total reduction), while 5.14% (by GCMS area) of ether was produced by the process. The olefin content in low-density polyethylene (LDPE) pyrolysis oil was reduced by 22.64% (by GCMS area), and 3.93% (by GCMS area) of ether was produced after the catalytic upgrading process. The olefin content in polystyrene (PS) pyrolysis oil was reduced by 38.41% (by GCMS area), and 12.78% (by GCMS area) of ether was produced after the process. The olefin content in waste tire (rubber) pyrolysis oil was reduced by 28.31% (by GCMS area), and 6.70% (by GCMS area) of ether was produced by the process. The olefin content in the mixed pyrolysis oil had been reduced by 27.25% (by GCMS area), and 3.41% (by GCMS area) of ether had been produced by conversion.

[0535] The total GCMS area percentage of the most unstable components of the pyrolysis oils, namely, multi-double-bond olefins (e.g., diolefins, triolefins, etc.), was quantified by GCMS before and after the catalytic upgrading process. The results are shown in Table 9. As can be seen, between approximately 41% and 83% of the multi-double-bond olefins were removed from various pyrolysis oils during the catalytic upgrading process.

[0536] Table 9. Content of multiple olefins in different oil samples

[0537]

[0538] Compared to other olefins, α-olefins have the lowest octane rating and are more susceptible to polymer / gums formation during storage or heating processes. Therefore, the total GCMS area % of the pyrolysis oil of the two main species was analyzed before and after the catalytic upgrading process to determine the impact on the α-olefin content.

[0539] The results are shown in Table 10. Total α-olefins were significantly reduced in both samples tested. The blended pyrolysis oil had a 76.85% reduction in total α-olefins, while the rubber pyrolysis oil had a 35.19% reduction. Compared to the blended pyrolysis oil, the upgraded rubber pyrolysis oil had a relatively higher content of beta olefins and an increase in other olefin isomers relative to the original oil. This can be attributed to differences in methanol levels in the feedstock.

[0540] Table 10. Olefin content in different oil samples

[0541]

[0542] These results indicate that the catalytic upgrading process can effectively reduce the unstable α-olefin content and convert it to much more stable, higher value, high octane ethers and other olefin isomers under relatively mild conditions (about 60-120°C and atmospheric pressure).

[0543] Solid residues in the output of catalytic upgrading processes

[0544] Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied to the upgraded pyrolysis oil. The analyzer was a TA Instruments SDT analyzer, model Q600. The analysis procedure was: 100 ml / min carrier gas flow (N2), 10°C / min heating rate, a final temperature of 500°C held for 5 minutes, then the carrier gas was changed to air and heated to 800°C to burn off any residue in the sample holder.

[0545] Table 11 shows a comparison of the residue (above 400°C) of the original mixed pyrolysis oil and rubber pyrolysis oil with the output of the catalytic upgrading process. The catalytic upgrading process significantly reduced the residue above 400°C in the rubber pyrolysis oil to 0.33% by weight (95.90% total reduction), and in the mixed pyrolysis oil, the residue was reduced by 78.80% (Table 11).

[0546] Table 11. Residue analysis of different oil samples

[0547]

[0548] The heteroatom content (i.e. sulfur, nitrogen, chlorine, bromine) in the mixed pyrolysis oil and rubber pyrolysis oil and the output of catalytic upgrading was analyzed by GCMS. Table 12 shows the heteroatom content in the mixed pyrolysis oil and rubber pyrolysis oil before and after the catalytic upgrading process.

[0549] Table 12. Heteroatom content in oil samples before and after catalytic upgrading process

[0550]

[0551] Compared to the original mixed pyrolysis oil, the sulfur content decreased by 64.29%, and the other heteroatom content decreased by 64.86%. The sulfur content in the rubber pyrolysis oil decreased by 44.71%, and the other heteroatom content decreased by 74.42%. After the catalytic upgrading process, the total heteroatom content in the mixed pyrolysis oil decreased by 64.41%, and the total heteroatom content in the rubber pyrolysis oil decreased by 66%.

[0552] The octane number of the product is another important factor affecting the economics of the overall upgrading process. Gasoline products with higher octane numbers provide higher value products and improve process economics. The octane number of the original mixed pyrolysis oil and the yield from the catalytic upgrading process were analyzed, and the results are shown in Table 13. Compared to the original mixed pyrolysis oil, the calculated octane number of the yield from the catalytic upgrading process showed an improvement of 10.03% (RON) or 20.73% (MON).

[0553] Table 13. Octane number analysis results

[0554]

[0555] The above describes various upgrading steps for improving the quality of pyrolysis oil derived from plastics and / or rubber. Using mild conditions and sustainable materials, excellent olefin reduction (stabilization), heteroatom content reduction, and solid residue removal can be achieved. Various washing, extraction, and catalytic upgrading processes can be used individually or in combination to provide high-quality, high-value, stable fuel products / chemical feedstocks with a low carbon footprint and low cost.

[0556] E. Upgrading of commercially available waste plastic pyrolysis oil

[0557] Waste plastic pyrolysis oil was obtained from a commercial rotary kiln batch pyrolysis unit in Thailand. The waste plastic used as the pyrolysis feedstock comes from municipal waste and primarily consists of low-grade low-density polyethylene (LDPE) film, with smaller amounts of scrap tires / rubber and other plastics such as polyvinyl chloride (PVC). The pyrolysis process was operated at approximately 450°C and atmospheric pressure.

[0558] X-ray fluorescence (XRF) analysis was performed using an XOS Petra Max multi-element HD XRF analyzer to analyze the concentrations of 14 different elements in the pyrolysis oil (see Table 14). The analytical methods applied were ASTM D4294, ISO 8754 & IP336, with a scan time of 300 seconds.

[0559] Table 14. Elemental analysis of commercial crude pyrolysis oil

[0560] element Concentration (ppm) count Ca 20 ND 0.0 Cl 17 228.2 20.8 Co 27 ND 0.0 Cr 24 ND 0.0 Cu 29 ND 1.8 Fe 26 6.10 65.0 K 19 ND 0.4 Mn 25 ND 0.4 Ni 28 0.13 2.5 P 15 ND 0.0 S 16 602.3 21.1 Ti 22 ND 0.6 V 23 ND 0.0 Zn 30 ND 0.0

[0561] In addition, GCMS analysis of the pyrolysis oil was performed to determine the ratio of aromatic and olefinic groups in the oil, among other factors (Table 15). The GCMS analyzer was a Perkin Elmer Clarus 500 GCMS gas chromatograph-mass spectrometer. The main operating parameters of the GCMS analyzer were: column oven temperature 35°C / 308K; injection temperature 205°C / 478K; direct injection mode; and a heating rate of 3°C / min from 35°C to 200°C / 473K.

[0562] Table 15. GCMS analysis of commercial crude pyrolysis oil

[0563] family compounds GCMS area % paraffin 51.70 Olefins 31.08 Naphthalene 0.08 Aromatic compounds 6.43 Diolefins 0.39 oxygen-containing compounds 9.00 other 1.32

[0564] An upgrading solution 6 consisting of 90 wt.% NMP (N-methyl-2-pyrrolidone) and 10 wt.% water was used in the extraction of the above pyrolysis oil.

[0565] Upgrading solution 6 and pyrolysis oil were fed into a separatory funnel at a mass ratio of pyrolysis oil to upgrading solution of 2:1. The mixture was then mixed well by shaking the funnel. After complete phase separation (two liquid phases) was observed in the mixture, the mixture was stabilized for another 5 minutes. Based on their vertical order, the raffinate was the upper phase mixture and the extractant was the lower phase mixture. The raffinate and the extractant were separated. Fresh upgrading solution was added to the raffinate at a mass ratio of raffinate to upgrading solution of 10:1, and the extraction purification process was repeated 4 times.

[0566] The raffinate was analyzed by XRF using the same technique as before. Details of the elemental analysis are provided in Table 16.

[0567] Table 16. Elemental analysis after extraction with upgrading solution 6

[0568]

[0569]

[0570] In the upgraded pyrolysis oil (raffinate), the chlorine level was reduced from 228.2 ppm to 101.2 ppm (56% reduction). The sulfur level was reduced from 602.3 ppm to 213.2 ppm (65% reduction). This shows that upgrading solution 6 (90 wt.% NMP + 10 wt.% water) can significantly reduce the heteroatom and sulfur levels in commercial plastic pyrolysis oil.

[0571] The raffinate was analyzed by GCMS using the same method as described above (Table 17).

[0572] Table 17. GCMS analysis after extraction with Upgrading Solution 6

[0573] family compounds GCMS area % paraffin 58.32 Olefins 30.81 Naphthalene 0.03 Aromatic compounds 4.53 Diolefins 0.02 oxygen-containing compounds 5.80 other 0.48

[0574] Higher levels of diolefins result in reduced stability (e.g., oxidative stability) of the oil, and in the case of higher diolefin levels, the oil is more likely to form a jelly, which means lower oil quality. In the upgraded oil, diolefins have been reduced from 0.39 GCMS area % to 0.02 GCMS area % (95% reduction). Naphthalene has been reduced from 0.08 GCMS area % to 0.03 GCMS area % (63% reduction). Oxygenates have been reduced from 9.00 GCMS area % to 5.80 GCMS area % (36% reduction).

[0575] The raffinate was further treated with an absorbent. Specifically, the absorption process was carried out by a fixed bed reactor that had been preloaded with 10 grams of absorbent. The WHSV during the absorption process was 1 h -1 The process was operated at room temperature (20° C.) and under atmospheric pressure.

[0576] The resulting upgraded oil was analyzed using XRF as before. Tables 18 and 19 show the results using molecular sieve 5A and molecular sieve 13X as absorbents, respectively.

[0577] Table 18. Elemental analysis of pyrolysis oil upgraded after absorption with molecular sieve 5A

[0578]

[0579]

[0580] After the absorption step with molecular sieve 5A, the chlorine level in the upgraded oil had been reduced from 101.2 ppm to 17.36 ppm (83% reduction).The sulfur level had been reduced from 213.2 ppm to 130.0 ppm (39% reduction).

[0581] Table 19. Elemental analysis of pyrolysis oil upgraded after absorption with molecular sieve 13X

[0582] element Concentration (ppm) count Ca 20 ND 0.0 Cl 17 ND 0.0 Co 27 ND 0.0 Cr 24 ND 0.0 Cu 29 ND 2.7 Fe 26 ND 0.0 K 19 ND 0.0 Mn 25 ND 0.8 Ni 28 ND 1.1 P 15 ND 0.0 S 16 ND 0.5 Ti 22 ND 0.0 V 23 ND 0.3 Zn 30 ND 0.0

[0583] After the absorption step with molecular sieve 13X, the chlorine level in the upgraded oil had been reduced from 101.2 ppm to undetectable 0 ppm (100% reduction), and the sulfur level had been reduced from 213.2 ppm to undetectable (100% reduction).

[0584] All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference in their entirety 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).

[0585] All headings and sub-headings are used herein for convenience only and should not be construed as limiting the invention in any way.

[0586] Unless otherwise indicated in the paragraph, the use of any and all examples or exemplary language (e.g., "such as") provided herein is intended merely to better illustrate the invention and does not impose a limitation on the scope of the invention. No language in this specification should be construed as indicating that any non-paragraph element is essential to the practice of the invention.

[0587] The citation and incorporation of patent documents herein is done for convenience only and does not reflect any view regarding the validity, patentability, and / or enforceability of such patent documents.

[0588] This invention includes all modifications and equivalents of the subject matter recited in the paragraphs appended hereto as permitted by applicable law.

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Claims

1. A process for upgrading pyrolysis oil, the process comprising treating the pyrolysis oil with an upgrading solution to provide a mixture comprising an extract phase and a raffinate phase, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof, and wherein the upgrading solution (i) consists of NMP and water; or (ii) comprises methanol and a base.

2. The process according to claim 1, comprising: (i) treating pyrolysis oil with the upgrading solution; (ii) mixing the pyrolysis oil and the upgrading solution, and then allowing the mixture to form two phases consisting of a raffinate phase and an extract phase; as well as (iii) separating the raffinate phase from the extract phase to produce an upgraded pyrolysis oil product; The pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof.

3. The process of claim 1 , wherein the upgrading solution consists of NMP and water.

4. The process of claim 2, wherein the upgrading solution consists of NMP and water.

5. The process of claim 3, wherein the mixture of NMP and water is from 50% v / v NMP to 95% v / v NMP.

6. The process of claim 4, wherein the mixture of NMP and water is from 50% v / v NMP to 95% v / v NMP.

7. The process of claim 5, wherein the upgrading solution is 90 wt% NMP and 10 wt% water.

8. The process of claim 6, wherein the upgrading solution is 90 wt% NMP and 10 wt% water.

9. The process of claim 1, wherein the base is potassium hydroxide or sodium hydroxide.

10. The process of claim 2, wherein the base is potassium hydroxide or sodium hydroxide.

11. The process according to any one of claims 1 to 10, wherein the mass ratio of the pyrolysis oil to the upgrading solution is from 95:5 to 10:

90.

12. The process of any one of claims 1 to 10, wherein the pyrolysis oil is treated with an aqueous solution prior to treating the pyrolysis oil with the upgrading solution.

13. The process of claim 11, wherein the pyrolysis oil is treated with an aqueous solution prior to treating the pyrolysis oil with the upgrading solution.

14. The process of claim 12, wherein the aqueous solution comprises a base.

15. The process of claim 13, wherein the aqueous solution comprises a base.

16. The process of any one of claims 1-10 and 13-15, wherein the pyrolysis oil is treated with a hydrocarbon fluid prior to treating the pyrolysis oil with the upgrading solution.

17. The process of claim 11, wherein the pyrolysis oil is treated with a hydrocarbon fluid prior to treating the pyrolysis oil with the upgrading solution.

18. The process of claim 12, wherein the pyrolysis oil is treated with a hydrocarbon fluid prior to treating the pyrolysis oil with the upgrading solution.

19. The process of claim 16, wherein the hydrocarbon fluid comprises a hydrocarbon selected from the group consisting of C5-C 16 Alkanes and C5-C 16 Olefins One or more hydrocarbons.

20. The process of claim 17, wherein the hydrocarbon fluid comprises a hydrocarbon selected from the group consisting of C5-C 16 Alkanes and C5-C 16 Olefins One or more hydrocarbons.

21. The process of claim 18, wherein the hydrocarbon fluid comprises a hydrocarbon selected from the group consisting of C5-C 16 Alkanes and C5-C 16 Olefins One or more hydrocarbons.

22. The process according to any one of claims 1 to 10, 13 to 15 and 17 to 21, comprising the further step of treating the raffinate phase with an absorbent.

23. The process of claim 11 comprising the further step of treating the raffinate phase with an absorbent.

24. The process of claim 12, comprising the further step of treating the raffinate phase with an absorbent.

25. The process of claim 16, comprising the further step of treating the raffinate phase with an absorbent.

26. The process of claim 22, wherein the absorbent is zeolite molecular sieve 13X or zeolite Na-Y.

27. The process of any one of claims 23 to 25, wherein the absorbent is zeolite molecular sieve 13X or zeolite Na-Y.

28. A process for producing an upgraded pyrolysis oil product, the process comprising: (i) (a) treating pyrolysis oil with an upgrading solution; (ii) mixing the pyrolysis oil obtained from step (i)(a) and the upgrading solution, and then allowing the mixture to form at least two phases comprising a raffinate phase and an extract phase; as well as (iii) separating the raffinate phase from the extract phase; (iv) treating the separated raffinate phase of step (iii) with an absorbent; wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof, and wherein the upgrading solution (i) consists of NMP and water; or (ii) comprises methanol and a base.

29. The process of claim 28, wherein the process further comprises (i)(b) treating the product of (i)(a) with a hydrocarbon fluid.

30. The process of claim 28, wherein the upgrading solution consists of NMP and water.

31. The process of claim 29, wherein the upgrading solution consists of NMP and water.

32. The process of claim 29 or 31, wherein the hydrocarbon fluid comprises a hydrocarbon selected from the group consisting of C5-C 16 Alkanes and C5-C 16 Olefins One or more hydrocarbons.

33. The process of any one of claims 28 to 31 , wherein the absorbent is molecular sieve 13X.

34. The process of claim 32, wherein the absorbent is molecular sieve 13X.

35. Use of an upgrading solution for reducing the olefin content of a pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastics or rubber or a combination thereof, and wherein the upgrading solution (i) consists of NMP and water; or (ii) comprises methanol and a base.

36. Use of an upgrading solution for reducing the solid residue content of pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof, and wherein the upgrading solution (i) consists of NMP and water; or (ii) comprises methanol and a base.

37. Use of an upgrading solution for increasing the stability of pyrolysis oil, wherein the pyrolysis oil is derived from the pyrolysis of plastic or rubber or a combination thereof, and wherein the upgrading solution (i) consists of NMP and water; or (ii) comprises methanol and a base.

38. An upgraded pyrolysis oil obtained by the process according to any one of claims 1 to 34.

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