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 - 71 . (canceled) 
     
     
         72 . A method for converting a polymeric feedstock into a product, the method comprising the stages of:
 treating a mixture of   (i) the polymeric feedstock,   (ii) any one or more of lignite, lignocellulosic biomass, plant gum, plant resin, plant tar, plant pitch, and   (iii) 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, wherein:   the reaction mixture comprises at least 40% wt/wt of the polymeric material, and   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) (ENAL), 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.   
     
     
         73 . The method according to  claim 72 , 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. 
     
     
         74 . The method according to  claim 72 , 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.   
     
     
         75 . The method according to  claim 72 , wherein the mixture is a slurry or emulsion under continuous flow during said treating. 
     
     
         76 . The method according to  claim 72 , 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. 
     
     
         77 . The method according to  claim 76 , 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. 
     
     
         78 . The method according to  claim 72 , 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. 
     
     
         79 . The method according to  claim 72 , wherein the additive catalyst is added to the mixture after the mixture has been pressurized to more than 50 bar, more than 100 bar, more than 150 bar, or more than 200 bar, or more than 221 bar. 
     
     
         80 . The method according to  claim 72 , 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.   
     
     
         81 . The method according to  claim 72 , 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.   
     
     
         82 . The method according to  claim 81 , 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.   
     
     
         83 . The method according to  claim 81 , 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. 
     
     
         84 . The method according to  claim 81 , 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. 
     
     
         85 . The method according to  claim 72 , wherein:
 (i) gases released during said depressurizing are used as syngas for production of hydrocarbons and/or   (ii) polar and non-polar liquids in the product are separated by distillation followed by physical means; and/or   (iii) polar and non-polar liquids in the product are separated by fractional distillation followed by any one or more of decantation, centrifugation or gravitational means.   
     
     
         86 . The method according to  claim 72 , wherein the polymeric feedstock is ground prior to inclusion in the mixture. 
     
     
         87 . The method according to  claim 72 , wherein mixture is emulsified after inclusion of the polymeric feedstock. 
     
     
         88 . The method according to  claim 72 , wherein:
 the temperature is between about 370° C. and 480° C. and the pressure is between bar and 300 bar;   the temperature is between about 370° C. and 420° C. and the pressure is between bar and 300 bar;   the temperature is between about 380° C. and 450° C. and the pressure is between bar and 300 bar;   the temperature is between about 440° C. and 480° C. and the pressure is between bar and 300 bar; or   the temperature is between about 400° C. and 460° C. and the pressure is between bar and 300 bar.   
     
     
         89 . The method according to  claim 72 , wherein:
 (i) the temperature is between about 390° C. and 410° C. and the pressure is between 40 bar and 300 bar;   (ii) the temperature is about 400° C. and the pressure is between 40 bar and 300 bar; and/or   (iii) 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.   
     
     
         90 . The method according to  claim 72 , wherein the feedstock does not contain heavy oil or heavy oil residue. 
     
     
         91 . The method according to  claim 72 , wherein the mixture is pressurized and/or heated by an extruder.