Upgrading residues, heavy oils and plastics

Abstract

The present invention relates to upgrading heavy petroleum oils, their residues, and/or polymeric materials. More specifically the present invention relates to a method for upgrading heavy petroleum oils, their residues, and/or polymeric materials by hydrothermal treatment with an aqueous solvent.

1 . A method for upgrading heavy oil or heavy oil residue, the method comprising the stages of:
 treating a mixture of the oil and an aqueous solvent at a temperature of more than 370° C. and at a pressure of more than 20 bar for a suitable time period, and   depressurising the mixture to obtain an upgraded product,   wherein the upgraded product has any one or more of a lower boiling point, reduced viscosity, lower specific gravity, and/or lower density compared to the heavy oil.   
     
     
         2 . The method according to  claim 1 , wherein the heavy oil has a viscosity of more than 100 centipoise, more than 200 centipoise, more than 1000 centipoise, more than 5000 centipoise, more than 10,000 centipoise, more than 100,000 centipoise or more than 1,000,000 centipoise at 40° C. 
     
     
         3 . The method according to  claim 1  or  claim 2 , wherein the heavy oil has an API (American Petroleum Institute) gravity of less than 25°, less than 20°, less than 15°, less than 10°, less than 5°, less than 4°, less than 3°, or less than 2°. 
     
     
         4 . The method according to any one of  claims 1  to  3 , wherein the atmospheric equivalent boiling point (AEBP) of the heavy oil is more than 300° C., more than 350° C., more than 400° C., more than 450° C., more than 500° C., or more than 550° C. 
     
     
         5 . The method according to any one of  claims 1  to  4 , wherein the heavy oil comprises re-refined Vacuum Tower Bottoms (RVTB), waste engine oil residue (WEOR), waste engine oil (WEO) residue, waste oil distillation bottoms (WODB), re-refined heavy vacuum distillation oil (RHVDO), asphalt flux, Processed Fuel Oil (PFO) sludge by-products of the production of Processed Fuel Oil (PFO) from waste oils, heavy oil residue of re-refined oil, heavy oil residue from distillation of coal, heavy oil residue from distillation of liquid or tar derived from processing coal, heavy oil and/or tar derived from hydrothermal processing of lignite or sub-bituminous coal or peat, distillation residues of products from hydrothermal processing of lignite or sub-bituminous coal, distillation residues of products from hydrothermal processing of biomass, lube oil residue (LOR), or any combination thereof. 
     
     
         6 . The method according to any one of  claims 1  to  5 , wherein the heavy oil comprises bitumen, tar/oil sands, oil shale, shale oil, plant oil, or any combination thereof. 
     
     
         7 . The method according to any one of  claims 1  to  6 , wherein the heavy oil comprises used oil, used lubricating oil, used motor oil, used transformer oil, used cooking oil, heavy oil residue of re-refined oil, heavy oil residue from distillation of coal, heavy oil residue from distillation of liquid or tar derived from processing coal, oil and/or tar derived from hydrothermal processing of lignite or sub-bituminous coal or peat, distillation residues of products from hydrothermal processing of lignite or sub-bituminous coal, distillation residues of products from hydrothermal processing of biomass, or any combination thereof. 
     
     
         8 . The method according to any one of  claims 1  to  7 , wherein the mixture comprises any one or more of lignite, lignocellulosic biomass, plant gum, plant resin, plant tar, plant pitch, or any combination thereof. 
     
     
         9 . The method according to any one of  claims 1  to  8 , wherein the temperature is between 370° C. and 500° C., between 370° C. and 480° C., between 374° C. and 500° C., 380° C. and 500° C., between 380° C. and 450° C., between 400° C. and 480° C., or between 440° C. and 480° C. 
     
     
         10 . The method according to any one of  claims 1  to  9 , wherein the pressure is:
 (i) between 20 bar and 400 bar; 
 (ii) between 40 bar and 300 bar; 
 (iii) above 200 bar; or 
 (iv) above 221 bar. 
 
     
     
         11 . The method according to any one of  claims 1  to  10 , wherein the mixture is a slurry or emulsion under continuous flow during said treating. 
     
     
         12 . The method according to any one of  claims 1  to  11 , wherein the mixture comprises an additive catalyst selected from the group consisting of: a base catalyst; an acid catalyst; a water-gas-shift catalyst; an alumino-silicate catalyst; a sulphide catalyst; and any combination thereof, wherein the additive catalyst is not derived from: any other component of the mixture or a reactor apparatus component. 
     
     
         13 . The method according to  claim 12 , wherein the additive catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium formate, potassium formate, an iron salt, or any combination thereof. 
     
     
         14 . The method according to any one of  claims 1  to  13 , wherein the additive catalyst is added to the mixture after the mixture has been heated to more than 300° C., more than 350° C., more than 360° C., more than 370° C., more than 370° C., or more than 374° C. 
     
     
         15 . The method according to any one of  claims 1  to  14 , wherein the additive catalyst is added to the mixture after the mixture has been pressurised to more than 50 bar, more than 100 bar, more than 150 bar, or more than 200 bar, more than 200 bar, or more than 221 bar. 
     
     
         16 . The method according to any one of  claims 1  to  15 , comprising:
 (i) heating and pressuring the aqueous solvent to supercritical temperature and pressure; and 
 (ii) contacting the heavy oil with the supercritical aqueous solvent to form the mixture. 
 
     
     
         17 . The method according to any one of  claims 1  to  16 , wherein the mixture comprises a solid substrate that is either or both of:
 (i) solid or substantially solid at the temperature and the pressure; 
 (ii) inert or substantially inert at the temperature and the pressure. 
 
     
     
         18 . The method according  claim 17 , wherein the solid substrate is:
 (i) a carbonaceous material comprising at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight carbon; or   (ii) is a non-carbonaceous material comprising no more than 10%, no more than 5%, no more than 1%, or no carbon.   
     
     
         19 . The method according to  claim 17  or  claim 18 , wherein the solid substrate is selected from the group consisting of: coals, anthracitic coal, meta-anthracite, anthracite semianthracite, bituminous coal, subbituminous coal, lignite (i.e. brown coal), coking coal, coal tar, coal tar derivatives, coal char, coke, high temperature coke, foundry coke, low and medium temperature coke, pitch coke, petroleum coke, coke oven coke, coke breeze, gas coke, brown coal coke, semi coke, charcoal, pyrolysis char, hydrothermal char, carbon black, graphite fine particles, amorphous carbon, carbon nanotubes, carbon nanofibers, vapor-grown carbon fibers, fly ash, a mineral, calcium carbonate, calcite, a silicate, silica, quartz, an oxide, a metal oxide, an insoluble or substantially insoluble metal salt, iron ore, a clay mineral, talc, gypsum, carbonates of calcium, carbonates of magnesium, carbonates of calcium and magnesium, calcite, limestone, dolomite, hydroxides of calcium, hydroxides of magnesium, oxides of calcium, oxides of magnesium, hydrogen carbonates of calcium, hydrogen carbonates of magnesium, 
     
     
         20 . The method according to any one of  claims 17  to  19 , wherein the solid substrate is present in the mixture at a concentration of more than 0.5%, more than 1%, more than 3%, more than 5%, more than 10%, more than 15%, more than 20%, more than 25%, or more than 30% by weight. 
     
     
         21 . The method according to any one of  claims 1  to  20 , wherein gases released during said depressurising are used as syngas for production of hydrocarbons. 
     
     
         22 . The method according to any one of  claims 1  to  21 , wherein polar and non-polar liquids in the upgraded product are separated by distillation followed by physical means. 
     
     
         23 . The method according to  claim 22 , wherein the distillation is fractional distillation and the physical means are any one or more of decantation, centrifugation or gravitational means. 
     
     
         24 . The method according to any one of  claims 1  to  23  comprising recycling the upgraded product or a component thereof into the heavy oil prior to said treating. 
     
     
         25 . The method according to  claim 24 , wherein the component thereof is heavy oil residue generated from distillation of the upgraded product. 
     
     
         26 . The method according to any one of  claims 1  to  25 , wherein the upgraded product has a viscosity that is at least 50 centipoise lower, at least 100 centipoise lower, at least 200 centipoise lower, at least 500 centipoise lower least 1,000 centipoise lower, at least 1500 centipoise lower, at least 2,000 centipoise lower, at least 3,000 centipoise lower, at least 4,000 centipoise lower, at least 5,000 centipoise lower, or at least 10,000 centipoise lower or at least 50,000 centipoise lower than the viscosity of the heavy oil at 40° C. 
     
     
         27 . The method according to any one of  claims 1  to  26 , wherein the upgraded product has an API gravity that is at least 1°, at least 2°, at least 5°, at least 10°, at least 15°, or at least 20° higher than the API gravity of the heavy oil. 
     
     
         28 . The method according to any one of  claims 1  to  27 , wherein the upgraded product has an AEBP that is at least 20° C., at least 30° C., at least 40° C., at least 250° C., at least 60° C., at least 70° C., at least 80° C., at least 90° C., at least 100° C., at least 150° C., or at least 200° C. lower than the AEBP of the heavy oil. 
     
     
         29 . The method according to any one of  claims 1  to  28 , wherein the upgraded product has a density that is at least 0.5%, at least 1%, at least 2%, at least 5%, at least 10%, at least 15%, or at least 20% lower than the density of the heavy oil when measured at the same temperature between 15° C. and 60° C. 
     
     
         30 . The method according to any one of  claims 1  to  29 , wherein the proportion of the upgraded product capable of being distilled at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% more than the proportion of the heavy oil capable being distilled. 
     
     
         31 . The method according to any one of  claims 1  to  30 , wherein the heavy oil constitutes at least 5% wt/wt, at least 10% wt/wt, at least 15% wt/wt, at least 20% wt/wt, at least 25% wt/wt, at least 30% wt/wt, at least 40% wt/wt, at least 50% wt/wt, at least 60% wt/wt, at least 70% wt/wt, at least 80% wt/wt, at least 90% wt/wt, at least 95% wt/wt, at least 96% wt/wt, at least 97% wt/wt, at least 98% wt/wt, or at least 99% wt/wt, of the mixture during said treating. 
     
     
         32 . The method according to any one of  claims 1  to  31 , wherein the mixture comprises at least: 1% wt/wt, 2% wt/wt, 3% wt/wt, 4% wt/wt, 5% wt/wt, 10% wt/wt, 15% wt/wt, 20% wt/wt, 25% wt/wt, 30% wt/wt, 35% wt/wt, 40% wt/wt, 45% wt/wt, 50% wt/wt, 60% wt/wt, 70% wt/wt, 80% wt/wt, 90% wt/wt, 95% wt/wt, or 98% wt/wt, polymeric material. 
     
     
         33 . The method according to any one of  claims 1  to  31 , wherein the mixture comprises less than: 98% wt/wt, 95% wt/wt, 90% wt/wt, 80% wt/wt, 70% wt/wt, 60% wt/wt, 50% wt/wt, 45% wt/wt, 40% wt/wt, 35% wt/wt, 30% wt/wt, 25% wt/wt, 20% wt/wt, 15% wt/wt, 10% wt/wt, 5% wt/wt, 4% wt/wt, 3% wt/wt, 2% wt/wt, or 1% wt/wt, polymeric material. 
     
     
         34 . The method according to  claim 32  or  claim 33 , wherein the polymeric material is selected from the group consisting of Polyethylene (PE), Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE), Polypropylene (PP), Polyester, Poly(ethylene terephthalate) (PET), poly(lactic acid) PLA, Poly (vinyl chloride) (PVC), Polystyrene (PS), Polyamide, Nylon, Nylon 6, Nylon 6,6, Acrylonitrile-Butadiene-Styrene (ABS), Poly(Ethylene vinyl alcohol) (E/VAL), Poly(Melamine formaldehyde) (MF), Poly(Phenol-formaldehyde) (PF), Epoxies, Polyacetal, (Acetal), Polyacrylates (Acrylic), Polyacrylonitrile (PAN), Polyamide-imide (PAI), Polyaryletherketone (PAEK), Polybutadiene (PBD), Polybutylene (PB), Polycarbonate (PC), Polydicyclopentadiene (PDCP), Polyketone (PK), polycondensate, Polyetheretherketone (PEEK), Polyetherimide (PEI), Polyethersulfone (PES), Polyethylenechlorinates, (PEC), Polyimide, (PI), Polymethylpentene (PMP), Poly(phenylene Oxide) (PPO), Polyphenylene Sulfide (PPS), Polyphthalamide, (PTA), Polysulfone (PSU), Polyurethane, (PU), Poly(vinylidene chloride) (PVDC), Poly(tetrafluoroethylene) PTFE, Poly(fluoroxy alkane), Poly(siloxanes), silicones, thermosplastics, thermosetting polymers, natural rubbers, tyre rubbers, ethylene propylene diene monomer rubbers EPDM, chloroprene rubbers, acrylonitrile butadiene (nitrile) rubbers, polyacrylate rubbers, Ethylene Acrylic rubbers, Styrene-butadiene rubbers, Polyester urethane rubbers, Polyether urethane rubbers, Fluorosilicone rubbers, silicone rubbers, and copolymers and mixtures thereof. 
     
     
         35 . The method according to any one of  claims 32  to  34 , wherein the polymeric material comprises any one or more of:
 less than about 5% w/w nitrogen, less than about 1% w/w nitrogen, less than about 0.5% w/w nitrogen, or less than about 0.1% w/w nitrogen; 
 less than about 1% w/w total halogens, less than about 1% w/w total halogens, less than about 0.5% w/w total halogens, less than about 0.1% w/w total halogens, or less than about 0.05% total halogens; 
 a molar ratio of hydrogen to carbon (H/C) of greater than 2.15, greater than 2.0, greater than 1.8, greater than 1.6, greater than 14, greater than 1.2, greater than 1.0, or greater than 0.8. 
 
     
     
         36 . The method according to any one of  claims 32  to  35 , wherein the polymeric material is ground prior to inclusion in the mixture. 
     
     
         37 . The method according to any one of  claims 32  to  36 , wherein mixture is emulsified after inclusion of the polymeric material. 
     
     
         38 . The method according to any one of  claims 1  to  37 , wherein:
 the temperature is between about 370° C. and 480° C. and the pressure is between 40 bar and 300 bar; 
 the temperature is between about 380° C. and 450° C. and the pressure is between 40 bar and 300 bar; 
 the temperature is between about 390° C. and 410° C. and the pressure is between 40 bar and 300 bar; or 
 the temperature is about 400° C. and the pressure is between 40 bar and 300 bar. 
 
     
     
         39 . The method according to any one of  claims 1  to  38 , wherein the temperature is between about 390° C. and 430° C. and the heavy oil residue comprises or consists of lubricating oil residue (LOR). 
     
     
         40 . The method according to any one of  claims 1  to  39 , wherein the temperature is between about 420° C. and 460° C. and the mixture comprises:
 any one or more of lignite, lignocellulosic biomass, plant gum, plant resin, plant tar, plant pitch, or any combination thereof; and/or 
 polymeric material (e.g. polyethylene). 
 
     
     
         41 . The method according to any one of  claims 1  to  40 , wherein the suitable time period is less than about: 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes or 5 minutes; more than about: 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, 5 minutes, or 2 minutes; or between about: 1 minute and 60 minutes, 5 minutes and 45 minutes, 5 minutes and 35 minutes, 10 minutes and 35 minutes, 15 minutes and about 30 minutes, or 20 minutes and 30 minutes. 
     
     
         42 . A method for converting a polymeric feedstock into a product, the method comprising the stages of:
 treating a mixture of the polymeric feedstock and an aqueous solvent at a temperature of more than 370° C. and at a pressure of more than 20 bar for a suitable time period, and   depressurising the mixture to obtain a product,   wherein the product comprises bio oil.   
     
     
         43 . The method according to  claim 42 , wherein the mixture comprises any one or more of lignite, lignocellulosic biomass, plant gum, plant resin, plant tar, plant pitch, or any combination thereof. 
     
     
         44 . The method according to  claim 42  or  claim 43 , wherein the temperature is between 370° C. and 500° C., between 370° C. and 480° C., between 374° C. and 500° C., 380° C. and 500° C., between 380° C. and 450° C., between 400° C. and 480° C., or between 440° C. and 480° C. 
     
     
         45 . The method according to any one of  claims 42  to  44 , wherein the wherein the pressure is:
 (i) between 20 bar and 400 bar; 
 (ii) between 40 bar and 300 bar; 
 (iii) above 200 bar; or 
 (iv) above 221 bar. 
 
     
     
         46 . The method according to any one of  claims 42  to  45 , wherein the mixture is a slurry or emulsion under continuous flow during said treating. 
     
     
         47 . The method according to any one of  claims 42  to  46 , wherein the mixture comprises an additive catalyst selected from the group consisting of: a base catalyst; an acid catalyst; a water-gas-shift catalyst; an alumino-silicate catalyst; a sulphide catalyst; and any combination thereof, wherein the additive catalyst is not derived from any other component of the mixture or a reactor apparatus component. 
     
     
         48 . The method according to  claim 47 , wherein the additive catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium formate, potassium formate, an iron salt, or any combination thereof. 
     
     
         49 . The method according to any one of  claims 42  to  48 , wherein the additive catalyst is added to the mixture after the mixture has been heated to more than 300° C., more than 350° C., more than 360° C., more than 370° C., or more than 374° C. 
     
     
         50 . The method according to any one of  claims 42  to  48 , wherein the additive catalyst is added to the mixture after the mixture has been pressurised to more than 50 bar, more than 100 bar, more than 150 bar, or more than 200 bar, or more than 221 bar. 
     
     
         51 . The method according to any one of  claims 42  to  50 , comprising:
 (i) heating and pressuring the aqueous solvent to supercritical temperature and pressure; and 
 (ii) contacting the polymeric feedstock with the supercritical aqueous solvent to form the mixture. 
 
     
     
         52 . The method according to any one of  claims 42  to  51 , wherein the mixture comprises a solid substrate that is either or both of:
 (i) solid or substantially solid at the temperature and the pressure; 
 (ii) inert or substantially inert at the temperature and the pressure. 
 
     
     
         53 . The method according  claim 52 , wherein the solid substrate is.
 (i) a carbonaceous material comprising at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% by weight carbon; or   (ii) is a non-carbonaceous material comprising no more than 10%, no more than 5%, no more than 1%, or no carbon.   
     
     
         54 . The method according to  claim 52  or  claim 53 , wherein the solid substrate is selected from the group consisting of: coals, anthracitic coal, meta-anthracite, anthracite semianthracite, bituminous coal, subbituminous coal, lignite (i.e. brown coal), coking coal, coal tar, coal tar derivatives, coal char, coke, high temperature coke, foundry coke, low and medium temperature coke, pitch coke, petroleum coke, coke oven coke, coke breeze, gas coke, brown coal coke, semi coke, charcoal, pyrolysis char, hydrothermal char, carbon black, graphite fine particles, amorphous carbon, carbon nanotubes, carbon nanofibers, vapor-grown carbon fibers, fly ash, a mineral, calcium carbonate, calcite, a silicate, silica, quartz, an oxide, a metal oxide, an insoluble or substantially insoluble metal salt, iron ore, a clay mineral, talc, gypsum, carbonates of calcium, carbonates of magnesium, carbonates of calcium and magnesium, calcite, limestone, dolomite, hydroxides of calcium, hydroxides of magnesium, oxides of calcium, oxides of magnesium, hydrogen carbonates of calcium, hydrogen carbonates of magnesium. 
     
     
         55 . The method according to any one of  claims 52  to  54 , wherein the solid substrate is present in the mixture at a concentration of more than 0.5%, more than 1%, more than 3%, more than 5%, more than 10%, more than 15%, more than 20%, more than 25%, or more than 30% by weight. 
     
     
         56 . The method according to any one of  claims 42  to  55 , wherein gases released during said depressurising are used as syngas for production of hydrocarbons. 
     
     
         57 . The method according to any one of  claims 42  to  56 , wherein polar and non-polar liquids in the product are separated by distillation followed by physical means. 
     
     
         58 . The method according to  claim 57 , wherein the distillation is fractional distillation and the physical means are any one or more of decantation, centrifugation or gravitational means. 
     
     
         59 . The method according to any one of  claims 42  to  58 , wherein the mixture comprises at least: 1% wt/wt, 2% wt/wt, 3% wt/wt, 4% wt/wt, 5% wt/wt, 10% wt/wt, 15% wt/wt, 20% wt/wt, 25% wt/wt, 30% wt/wt, 35% wt/wt, 40% wt/wt, 45% wt/wt, 50% wt/wt, 60% wt/wt, 70% wt/wt, 80% wt/wt, 90% wt/wt, 95% wt/wt, or 98% wt/wt, polymeric feedstock. 
     
     
         60 . The method according to any one of  claims 42  to  58 , wherein the mixture comprises less than: 98% wt/wt, 95% wt/wt, 90% wt/wt, 80% wt/wt, 70% wt/wt, 60% wt/wt, 50% wt/wt, 45% wt/wt, 40% wt/wt, 35% wt/wt, 30% wt/wt, 25% wt/wt, 20% wt/wt, 15% wt/wt, 10% wt/wt, 5% wt/wt, 4% wt/wt, 3% wt/wt, 2% wt/wt, or 1% wt/wt, polymeric feedstock. 
     
     
         61 . The method according to  claim 59  or  claim 60 , wherein the polymeric feedstock is selected from the group consisting of Polyethylene (PE), Low Density Polyethylene (LDPE), High Density Polyethylene (HDPE), Polypropylene (PP), Polyester, Poly(ethylene terephthalate) (PET), poly(lactic acid) PLA, Poly (vinyl chloride) (PVC), Polystyrene (PS), Polyamide, Nylon, Nylon 6, Nylon 6,6, Acrylonitrile-Butadiene-Styrene (ABS), Poly(Ethylene vinyl alcohol) (E/VAL), Poly(Melamine formaldehyde) (MF), Poly(Phenol-formaldehyde) (PF), Epoxies, Polyacetal, (Acetal), Polyacrylates (Acrylic), Polyacrylonitrile (PAN), Polyamide-imide (PAI), Polyaryletherketone (PAEK), Polybutadiene (PBD), Polybutylene (PB), Polycarbonate (PC), Polydicyclopentadiene (PDCP), Polyketone (PK), polycondensate, Polyetheretherketone (PEEK), Polyetherimide (PEI), Polyethersulfone (PES), Polyethylenechlorinates, (PEC), Polyimide, (PI), Polymethylpentene (PMP), Poly(phenylene Oxide) (PPO), Polyphenylene Sulfide (PPS), Polyphthalamide, (PTA), Polysulfone (PSU), Polyurethane, (PU), Poly(vinylidene chloride) (PVDC), Poly(tetrafluoroethylene) PTFE, Poly(fluoroxy alkane) PFA, Poly(siloxanes), silicones, thermosplastics, thermosetting polymers, natural rubbers, tyre rubbers, ethylene propylene diene monomer rubbers EPDM, chloroprene rubbers, acrylonitrile butadiene (nitrile) rubbers, polyacrylate rubbers, Ethylene Acrylic rubbers, Styrene-butadiene rubbers, Polyester urethane rubbers, Polyether urethane rubbers, Fluorosilicone rubbers, silicone rubbers, and copolymers and mixtures thereof. 
     
     
         62 . The method according to any one of  claims 42  to  61 , wherein the polymeric feedstock is ground prior to inclusion in the mixture. 
     
     
         63 . The method according to any one of  claims 42  to  62 , wherein mixture is emulsified after inclusion of the polymeric feedstock. 
     
     
         64 . The method according to any one of  claims 42  to  63 , wherein:
 the temperature is between about 370° C. and 480° C. and the pressure is between 40 bar and 300 bar; 
 the temperature is between about 370° C. and 420° C. and the pressure is between 40 bar and 300 bar; 
 the temperature is between about 380° C. and 450° C. and the pressure is between 40 bar and 300 bar; 
 the temperature is between about 440° C. and 480° C. and the pressure is between 40 bar and 300 bar; or 
 the temperature is between about 400° C. and 460° C. and the pressure is between 40 bar and 300 bar. 
 
     
     
         65 . The method according to any one of  claims 42  to  64 , wherein the temperature is between about 390° C. and 410° C. and the pressure is between 40 bar and 300 bar. 
     
     
         66 . The method according to any one of  claims 42  to  65 , wherein the temperature is about 400° C. and the pressure is between 40 bar and 300 bar. 
     
     
         67 . The method according to any one of  claims 42  to  66 , wherein the suitable time period is less than about: 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes or 5 minutes; more than about: 60 minutes, 45 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 10 minutes, 2 minutes, or 5 minutes; or between about: 1 minute and 60 minutes, 5 minutes and 45 minutes, 5 minutes and 35 minutes, 10 minutes and 35 minutes, 15 minutes and about 30 minutes, or 20 minutes and 30 minutes. 
     
     
         68 . The method according to any one of  claims 42  to  67 , wherein the feedstock does not contain heavy oil or heavy oil residue. 
     
     
         69 . The method according to any one of  claims 1  to  68 , wherein the mixture is pressurized and/or heated by an extruder. 
     
     
         70 . Upgraded product obtained or obtainable from the method of any one of  claim 1  to  41  or  69 . 
     
     
         71 . A product obtained or obtainable from the method of any one of  claims 42  to  69 .