US20120217149A1 - Decomposition of waste plastics - Google Patents

Decomposition of waste plastics Download PDF

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Publication number
US20120217149A1
US20120217149A1 US13/496,217 US201013496217A US2012217149A1 US 20120217149 A1 US20120217149 A1 US 20120217149A1 US 201013496217 A US201013496217 A US 201013496217A US 2012217149 A1 US2012217149 A1 US 2012217149A1
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oil
reactor
plastic
process according
gas
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Myung Duck Ma
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Envion Inc
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Envion Inc
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
    • F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
    • F23G5/0276—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage using direct heating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/44—Details; Accessories
    • F23G5/46—Recuperation of heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/12—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of plastics, e.g. rubber
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the heat-conducting coefficient of typical waste plastic is low, it is difficult to conduct the heat into it from the heat source. But certain plastics absorb far infrared radiation easily, and when the waste plastics are heated by far infrared radiation, the heating rate and heating efficiency is increased. Consequently, the invention involves a process using far infrared radiation to decompose plastics to a liquid or liquid-gas mixture which can be further processed into useable oil products, fuels, or used to generate electrical power. In the process of the invention, melted plastic undergoes pyrrolysis to produce a gas-oil mixture.
  • the pyrrolysis produces coke, which is removed from the reactor, and the gas-oil mixture can be subjected to further processing to recover gas, a light oil and a heavy oil.
  • the invention thus involves a process for converting waste plastic into oil, comprising subjecting waste plastic to a plurality of far infrared radiation sources in intimate contact with said plastic in a reactor which contains an agitator which distributes the waste plastic past the radiation sources.
  • the energy source promoting decomposition of the plastic is internal to the reactor, and directly in contact with the plastic.
  • the plastic can be polypropylene, polyethylene, polyethylene terephthalate, polystyrene or a mixture thereof.
  • the plastic can further contain polyvinylchloride preferably in an amount of up to 2% by weight. Decomposition of the plastic takes place in the liquid phase. The plastic can be crushed and melted in a screw extruder prior to introduction to the reactor, or melted directly in the reactor where it will be decomposed.
  • the far infrared sources preferably comprise an electrical resistance heating element, a heat-absorbing material, a protective shell and thereon a far infrared radiation generating coating.
  • the far infrared radiation sources are preferably disposed about the reactor such that the radiation generated from each source intersects with that of another source.
  • the far infrared radiation has a frequency which is selected to maximize absorption by the plastic.
  • the frequency preferably is 4.0-1000 ⁇ m, more preferably 4.0-25 ⁇ m.
  • PP, PE, PVC, PS, PET and other plastics have their own special absorbing wavelength band, as is well known, and can all be processed in accordance with the invention.
  • the “FIR” heater can composite electrical resistance space, far infrared radiator, insulator, and protective shell.
  • the protective shell contains an isolation device that is made of metal, for example, iron or stainless. The isolation device, which separates the heater from the stream in the reactor, is preferably resistant to high temperature, high pressure and corrosion.
  • a layer of the far infrared radiator may cover the outer surface of the far infrared ray heater.
  • the far infrared ray radiator can be made into various shapes, for example, rod-shape, band-shape and other shapes, and on the outside can be encased by metal pipe, and finally painted with the far infrared radiator, whereby far infrared radiation can directly heat the plastics.
  • the protective shell is preferably in the form of a rod over the heating element and heat-absorbing material, although any shape is permissible.
  • the rod is bullet-shaped. When decomposed, the plastics will generate coke. This coke will cover the outer surface of the radiator, thus decreasing the heating efficiency.
  • an agitator is installed in the reactor.
  • the flowing liquid causes the coke to peel off the rods, and the heating efficiency is not affected or minimally affected.
  • the agitator may be a gate, propeller, combinatorial agitator or other shapes of agitator.
  • the sludge in the reactor may be discharged into a screw drier in which the heavy oil components in the sludge are re-cracked under high temperature and the gas products go back to the reactor. At the end of the drier, the dried sludge is cooled and crushed into pieces which can be collected as carbon residual.
  • FIG. 1 shows the structure of the far infrared ray-heating rods.
  • FIG. 2 shows the structure of the reactor
  • FIG. 3 represents another view of a reactor with far infrared ray-heating rods.
  • FIG. 4 is a flow chart of a process involving further processing of the oil from plastic.
  • FIG. 5 is a detailed process flow diagram.
  • FIG. 6 is a process flow diagram of the desulfurization aspect of the invention.
  • FIG. 1 shows the basic structure of a “FIR” heating rod.
  • the heating element ( 3 ) is located in the center of the pipe ( 5 ), then from the inside to outside are located the far IR generator ( 4 ), e.g., carborundum, ( 4 ), metal pipe ( 5 ) and far infrared generating coating ( 6 ) in turn.
  • AC power is introduced into the rod though pole ( 2 ) to the heating element ( 3 ). Heated by the heating element ( 3 ), the temperature of the carborundum ( 4 ) can reach 600° or above, and it transfers the heat to the pipe ( 5 ).
  • FIG. 1 shows a view of one embodiment of the present invention with a reactor, in which 21 far infrared ray-heating rods that are the same like the above far infrared ray-heating rod are installed. Among the 21 rods in the reactor, 9 rods are installed on the upper head.
  • the waste plastics are fed into the reactor through the feeding inlet ( 16 ), then absorb the heat from the bottom rods ( 15 ) and top rods ( 17 ), and are melted and decomposed.
  • the reactor is preferably operated under vacuum, in the absence of oxygen.
  • the agitator ( 13 ) the coke subsides slowly into the bottom of the reactor, and drained out together with the plastics liquor from the reactor through the sludge outlet ( 20 ) into the screw drier (not shown in this patent). This mixture of coke and plastic is called sludge at this point.
  • the cracked gas from the decomposing plastic flows through the oil gas outlet ( 12 ) to another unit, for example, the scrubber (not indicated) where the hydrogen chloride gas can be neutralized, the fraction tower where the gas can be separated into light oil and heavy oil, or the second reactor where the catalyst is packed and the heavy component can be cracked further into light components.
  • the reactor can have many accessories, such as, motor reducer ( 10 ), manhole ( 18 ), thermocouple well ( 19 ), level gauge nozzle ( 24 ), pressure gauge nozzle ( 21 ), gage hatch ( 21 ), safety valve nozzle ( 22 ), manual emergency vent ( 23 ), coupling ( 11 ), lug support ( 14 ).
  • FIG. 3 shows a view of one embodiment of the present invention with the reactor ( 34 ), in which the similar far infrared ray-heating rods ( 27 ) are installed, but the type of the agitator is different.
  • the reactor in which the similar far infrared ray-heating rods ( 27 ) are installed, but the type of the agitator is different.
  • the reactor in which the similar far infrared ray-heating rods ( 27 ) are installed, but the type of the agitator is different.
  • the reactor there are two agitators that are separately drawn by their own motor reducer ( 28 ) and ( 29 ).
  • One is a column form impeller ( 25 )
  • another is a gate paddle impeller ( 26 ).
  • the reactor has plastic inlet ( 31 ), oil gas outlet ( 30 ), sludge outlet ( 32 ) and other accessories (not shown in the diagram).
  • the hot-splitting technique of high-molecular compounds is the course that produces flammable legit oil, thereby breaking the long chains of high-molecules and the chains of complex molecules. This produces a part of light oil and meanwhile some coke from the process. This coke together with some heavy pyrolytic product will be discharged as sludge from the reactor constantly.
  • Both dry and wet methods can be used for treatment of the sludge. For both methods, discharging of the hot-slitting sludge is performed in a closed system, that this method guarantees the safety to discharge residuals.
  • the invention optionally involves further processing into qualified automotive diesel.
  • the waste plastics are thermally decomposed using far infrared ray heating technology
  • the vapor products of the decomposition can be fractionated into gas, light oil and crude diesel oil, and the crude diesel oil can be subjected to ultrasonic desulphurization and solvent-extraction treatments to obtain qualified automobile diesel.
  • the sludge produced in plastic decomposition can be re-cracked to remove the heavy oil components, crushed into pieces, and collected as carbon residual byproduct.
  • the oil products further used to produce fuels or electricity.
  • a facility employing the process of the invention can include, for example, preprocessing unit, reaction unit, fractionation unit, HCl adsorption unit, diesel desulfurization and refining unit, sludge drying unit, circulation water unit and/or waste water collection unit.
  • the noncondensable gas which is produced in this facility can be burned in electricity generator to produce electricity.
  • the quality of diesel oil which can be produced meets the requirements of Australian auto-diesel oil standard.
  • plastic is introduced into preprocessing unit, where it is firstly crushed into pieces of desired size and then loaded to a screw extruder feeding machine.
  • the waste plastics are molten in the extruder cylinder and are about 200-300° C. at the inlet of the reaction unit.
  • plastic of an appropriate size can be melted directly in the reactor.
  • Far infrared radiation is used to provide energy for thermal cracking of the plastics.
  • far infrared heating rods are inserted to the reactor vessel, and emit far infrared ray of a desired wavelength, which can be intensively absorbed by the plastic mixture.
  • the waste plastic can be decomposed at a temperature from about 360° C. to 420° C.
  • An agitator in the reactor e.g., which rotates in the rate of approximately 30 rpm, mixes the plastic liquor and makes it homogeneous.
  • oil gas flows up into the fraction tower (FT- 1 ).
  • the sludge which is produced in the reactor and often mixed with some the melted plastic, can be drained from the bottom of the reactor into a sludge-drying unit.
  • FT- 1 fractionation tower
  • the oil gas is separated, e.g., by passing through an umbrella-shaped cap and an upside-down cone. Because of the change of velocity and direction, droplets of some heavy oil and most of the melted plastic will be separated from the oil gas and flow back into the reactor. Then the oil gas goes up into the packing bed and exchanges heat and mass with top reflux. The heavy oil will be separated from the oil gas and can be recycled to the reactor to be decomposed again.
  • the oil gas is the mixture of non-condensable gas, a gasoline component, a diesel component and some heavy oil.
  • the reflux is the bottom liquid of (FT- 2 ).
  • the oil gas from the top of (FT- 1 ) enters (FT- 2 ) from the bottom inlet.
  • the oil gas is distillated into light oil and middle oil.
  • the oil gas from the top of (FT- 2 ) is mixed with some caustic sodium solution and then is cooled in the heat exchanger (HE- 1 ) to 40° C. or so.
  • HE- 1 heat exchanger
  • GOS- 1 gas/oil separator
  • the liquid is also called light oil.
  • the sweet gas from the top of (GOS- 1 ) is conveyed to the gas storage tank (GST- 1 ) as fuel of generator (G- 1 ).
  • the middle oil from the bottom of the stripping tower (STT- 1 ) is crude diesel oil. It is cooled, e.g., to 50° C. by water box (HE- 2 ) and sent to desulfurization and solvent-extraction unit for further refining.
  • the bottom liquid of (FT- 2 ) is by (P- 3 ) to the top of (FT- 1 ) as a reflux.
  • the oil gas from the top of (FT- 2 ) is mixed with some caustic sodium solution which is injected directly into the top oil/gas pipe.
  • the crude diesel oil from the bottom of middle oil tank (MT- 1 ) and the oxidant in the oxidant storage tank (OST- 1 ) are pumped to the ultrasonic reactor (UR- 1 ) by (P- 7 ) and (P- 12 ), respectively.
  • the sulphur organic compounds are transformed to sulfoxide, sulfone or sulfosalt under the ultrasonic energy.
  • DOS- 1 oil water separator
  • the separated diesel is further pumped to static mixer (SM- 1 ) and mixed there with the solvent from the solvent storage tank (SST- 1 ). Then the mixture enters the settling tank (ST- 1 / 2 ) consequently for complete separation of solvent from the diesel.
  • the refined diesel is sent out as product, and the solvent in (ST- 1 / 2 ) flows to solvent distillation tower (SFT- 1 ) for flash distillation.
  • the recovered solvent is sent to solvent storage tank SST- 1 and reused.
  • the waste solvent with high content of deposits is sent to (DOST- 1 ) by (P- 8 ) and further recycled to (R- 1 ) by (P- 1 ).
  • the solvent is evaporated in (R- 1 ) and recovered in (GOS- 1 ) at time intervals (equipment not shown in the diagram), and the compounds containing S is transferred into the carbon residuals.
  • the sludge in the bottom of reactor (R- 1 ) is drained to the screw drier (SD- 1 ) with jacketed heater.
  • Waste water tank (WWT- 1 ) is used to collect the waste oxidant from (DOS- 1 ), the waste caustic solution, the oily water accumulating in some tanks (HE- 2 ), (GOS- 1 ), (MDT- 1 ), (GOT- 1 ) and (DOT- 1 ), or emitted oil/water.
  • the waste water in (WWT- 1 ) is pumped by (P- 9 ) to water oil separator (WOS- 1 ).
  • the separated oil in (WOS- 1 ) is pumped to dirty oil/solvent tank (DOST- 1 ) by (P- 8 ) at time intervals and sent back to (R- 1 ) by (P- 1 ). Intermittently, the waste water in (WOS- 1 ) is drained out and sent to the wastewater treatment plant.
  • the oil produced in the present process may be rich with sulfur components, e.g. thiols, thioethers, didulfides, and thiophenes which lower the quality of the oils.
  • the oil is typically desulfurized.
  • the oil is pumped to an ultrasonic chamber together with peroxide solution and reacts in the presence of ultrasound energy. After separation with the oxidant solution, the oil is further mixed with polar solvent for extraction of the oxidized of the sulfur components. After separation with the polar solvent, the oil is desulfurized oil which is adequate to automotive uses.
  • FIG. 6 shows the basic flow diagram of this embodiment of invention.
  • the oil A which can be light oil, diesel oil, heavy oil produced from the decomposition of waste plastics, continuously flows into the middle tank ( 61 ) with heating device.
  • tank ( 61 ) the oil is preheated to about 50° C. and sent to ultrasonic reactor ( 65 ) by pump ( 62 ).
  • the oxidizing solution B is preferably a mixture of peroxide solution (e.g., approximate mass percent 27%) and formic acid at the volume ratio of 2:1 ⁇ 10:1, and preferably 2:1 ⁇ 3:1.
  • the peroxide and the formic acid are used as the oxidant and catalyst for the oxidation reaction, respectively.
  • the oxidizing solution is prepared in corrosion resisting tank ( 63 ) and conveyed to ultrasonic reactor ( 65 ) by corrosion resisting pump ( 64 ).
  • the volume ratio of the oxidizing solution and the oil is 1:100 ⁇ 1:10, preferably 2:100 ⁇ 3:100.
  • the oil and the oxidizing solution is intensely mixed and the sulfur organic compounds in the oil are transformed to sulfoxide, sulfone or sulfosalt under ultrasonic energy.
  • An effective ultrasound frequency range for the oxidation reaction is from 20 kHz to 100 kHz and from 20 kHz to 40 kHz the highest reaction efficiency is obtained.
  • the preferable intensity is 60 ⁇ 50 watt/cm 2 .
  • the temperature for the reaction to generate best result is about 60° C. Because the reaction generates heat, in order to control the temperature inner cooling device is preferably installed on the device, e.g. coiled pipe.
  • the coolant can be water or other liquid coolant and is cycled between the reactor and an external heat-exchanging device.
  • the reaction can be completed in very short time.
  • the retention time of the oil flow should be less than 30 mins in the reactor, and preferably it is 10 ⁇ 15 mins.
  • the settling tank ( 66 ) (corrosion resistant) is used for separation of the oil from the aqueous solution after the ultrasound treatment.
  • the aqueous phase settled to the bottom of tank ( 66 ) contains no peroxide but contains formic acid. It is pumped back to tank ( 63 ) by pump ( 67 ) and recycled. Some insoluble oxidation product E is discharged at time intervals.
  • the oxidized oil C from the top of settling tank ( 66 ) is sent to static mixer ( 611 ), in which it mixes intensely with the polar solvent F powered by pump ( 610 ). In static mixer ( 611 ), the solvent or the oil is dispersed into fine droplets of diameter less than 100 ⁇ m and two phase extraction occurs.
  • the effective solvents can be dimethyl formamide (DMF), N-methylpyrrolidone, furaldehyde, acetonitrile or some other solvent, and DMF is preferred.
  • DMF dimethyl formamide
  • good result is generated when the volume ratio of the solvent and the oil is 1:5 to 10:1, and for both efficiency and economy consideration, the ratio of 1:1 is preferred.
  • the best temperature for the extraction is 60-80° C.
  • the mixture of oil and solvent is pressured out of the static mixer 11 and flows to settling tank ( 612 ) for separation of the oil and the solvent.
  • the best settling time is 20 ⁇ 30 mins
  • the oil is sent out from top of tank ( 612 ) as desulphurized product G, and the bottom solvent H is sent by pump ( 613 ) to flash distillation tower ( 614 ) for recovery.
  • flash distillation tower ( 614 ) the solvent is evaporated and the vapor I is condensed in condenser ( 615 ).
  • the condensed solvent flows back to solvent storage tank 9 and is recycled.
  • the bottom sludge J of flash distillation tower ( 614 ) contains high content of sulfur and is discharged for further treatment.
  • Waste plastic cement bags of polypropylene are cut into pieces and the sand sediment removed (298.5/g). They are then put into the cracking reactor and subjected to far IR radiation. The pieces begin to melt and are turning into a liquid state when the temperature of the bottom part of the reactor rises to 110° C. and fuel oil appears at the exit of the condenser behind the reactor when the temperature reaches a specified range and the top temperature is 75° C. After 20 minutes the oil flow increases when the temperature in the bottom increases and the top temperature reaches 95° C. After 10 minutes at this stage, the oil flow accelerates and produces a great quantity of cracking gas, which is ignited after passing through a water-sealed tank.
  • the bottom temperature is increased and the top temperature reaches 242° C. and cracking is carried on for 35 minutes. Ten minutes after this stage, the reaction phase finishes with a top temperature of 147° C.
  • the cracking fuel oil distilled out of the top of the reactor is 196.5/g.
  • the yield of fuel oil is 65.83% from the cement bag and the heavy oil that contains wax at the bottom of the reactor is 62.5/g or 29.93%. Total yield of high quality fuel oil is 86.76%.
  • Cracking gas and loss amounts to 30.54/g or 10.23% and coke is 8.96/g or 3.01%.

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  • Life Sciences & Earth Sciences (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
US13/496,217 2009-09-16 2010-09-16 Decomposition of waste plastics Abandoned US20120217149A1 (en)

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CN108714310A (zh) * 2018-06-12 2018-10-30 金结娥 一种制药用外循环真空蒸馏器
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WO2020178599A1 (fr) * 2019-03-07 2020-09-10 Oxford Sustainable Fuels Limited Procédé de valorisation d'une huile de pyrolyse et solution de valorisation utilisée dans celui-ci
WO2021163094A1 (fr) * 2020-02-10 2021-08-19 Eastman Chemical Company Recyclage chimique de flux de déchets plastiques mélangés traités
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EP2478070A4 (fr) 2014-07-16
WO2011034989A2 (fr) 2011-03-24
EP2478070A2 (fr) 2012-07-25
BR112012005516A2 (pt) 2016-04-19

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