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US20140155661A1 - Production of hydrocarbons from copyrolysis of plastic and tyre material with microwave heating - Google Patents

Production of hydrocarbons from copyrolysis of plastic and tyre material with microwave heating Download PDF

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US20140155661A1
US20140155661A1 US14/007,236 US201214007236A US2014155661A1 US 20140155661 A1 US20140155661 A1 US 20140155661A1 US 201214007236 A US201214007236 A US 201214007236A US 2014155661 A1 US2014155661 A1 US 2014155661A1
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pyrolysis
pfu
plastic materials
dephlegmator
benzene
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Piero Frediani
Luca Rosi
Marco Frediani
Andrea Undri
Silvio Occhialini
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COOPERATIVA AUTOTRASPORTATORI FIORENTINI CAF- COOPERATIVA A RL Soc
COOPERATIVA AUTOTRASPORTATORI FIORENTINI CAF- 'COOPERATIVAARL Soc
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COOPERATIVA AUTOTRASPORTATORI FIORENTINI CAF- 'COOPERATIVAARL Soc
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Assigned to COOPERATIVA AUTOTRASPORTATORI FIORENTINI C.A.F.- SOCIETA COOPERATIVA A R.L. reassignment COOPERATIVA AUTOTRASPORTATORI FIORENTINI C.A.F.- SOCIETA COOPERATIVA A R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FREDIANI, Marco, FREDIANI, Piero, OCCHIALINI, Silvio, ROSI, Luca, UNDRI, Andrea
Publication of US20140155661A1 publication Critical patent/US20140155661A1/en
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    • 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
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B19/00—Heating of coke ovens by electrical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • 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
    • C10G15/00—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs
    • C10G15/08—Cracking of hydrocarbon oils by electric means, electromagnetic or mechanical vibrations, by particle radiation or with gases superheated in electric arcs by electric means or by electromagnetic or mechanical vibrations
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics

Definitions

  • the present invention relates to the field of methods of recycling plastic materials, in particular to recycling of tyres at their end-of-cycle (PFU), polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyvinyl chloride (PVC) and their mixtures.
  • PFU end-of-cycle
  • PE polyethylene
  • PP polypropylene
  • PS polystyrene
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • Polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyvinylchloride (PVC), polyurethanes (PU) represent up to 90% of the waste in plastics, specifically 60 to 65% by weight are polyolefins PE and PP, between 10 to 20% by weight is PS and a quantity from 12 to 17% is PVC.
  • a first major problem concerns the variable composition of the waste, both for polymers types and for the presence of additives and other substances such as glues, inks, labels, and organic residues.
  • thermoplastic materials are immiscible with each other and recycling by simple reprocessing cannot lead to obtaining a material with good properties.
  • remelting polymer mixtures worsens their physical properties, stability and processing.
  • a recycle that is efficient with this type of approach provides use of homogeneous plastic materials or, when possible, use of large amounts of compatibilisers.
  • the technologies for recycling of plastic materials can be divided into four categories:
  • the tertiary recycling comprises all the heat treatments of plastic waste that lead to chemical or petrochemical products of interest.
  • pyrolysis gasification, and hydrogenation.
  • Heat treatments are extremely versatile and can be used in the recycling of all those materials otherwise difficult to recover such as, for example, contaminated medical waste, polymeric residues of motorcars, and many other types of waste of complex formulation.
  • Selection of the recycling technique is made on the basis of the purity of the waste, the chemical composition, and the nature of the additives.
  • Pyrolysis processes convert the PE, PP, PS, PET, and PVC in oils to be used both by the petrochemical industry and in the existing refining processes.
  • pyrolysis By the term pyrolysis, reference is made to all those processes wherein energy is supplied, generally in the form of heat, to an organic compound to facilitate decomposition. This type of thermochemical degradation is an approach of considerable interest in the recovery and appreciation of post-consumer plastic materials. Pyrolysis is an endothermic process and is carried out at temperatures from 250° C. up to over 1,000° C. It leads into obtaining liquid and gaseous products, while certain solid products are constituted by carbon residues or inorganic non-pyrolisable fillers. These general considerations can be applied both to the treatment of plastic materials and to the PFU
  • the five main categories of plastic materials, identifiable in urban solid waste, are polyethylene (HDPE and LDPE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), and polyvinyl chloride (PVC).
  • the pyrolysis process of these macromolecules leads into obtaining a gas, a liquid, and generally a solid residue.
  • the proportions among these products are directly related to the type of treated material, but also to the type of reactor and the process conditions, in particular on the temperature and heating rate used.
  • Most research has focused on the study of the pyrolysis processes of single polymers or mixtures thereof, to simulate the true composition of the MSW.
  • the microwave-induced pyrolysis is a process of new concept and was introduced for the first time by Tech—En Ltd (U.S. Pat. No. 5,387,321; U.S. Pat. No. 5,330,623).
  • the plastic materials have very small dielectric constant and loss factor. This implies that generally they do not absorb microwaves and therefore cannot heat at the pyrolysis temperature.
  • the problem can be circumvented if in the mixture of plastics, which are transparent to microwaves, an absorbent material such as carbon is added.
  • This type of pyrolysis then takes the name of microwave-assisted pyrolysis.
  • the energy transfer from the absorbing material (carbon) to the polymer can be very efficient. This type of heating causes formation of oxygenated organic compounds only for the quantities of oxygen present in plasticisers, additives, paints, inks, paper or other materials that make part of the treated products.
  • the present invention relates to this context on the research for new and always more efficient methods of recycling and reuse of plastic materials and of end-of-use tyres, which has as first objective, proposing the production of hydrocarbons.
  • Purpose of the present invention is therefore a microwave pyrolysis process for the conversion of this waste into solid, liquid, and gaseous products which may find new use in various industrial sectors: from the production of electrical energy for combustion to the synthesis of plastic materials for polymerisation.
  • liquid products characterised qualitatively and quantitatively
  • liquid products possibly even direct, such as petroleum fractions, or for the extraction of their majority components (for example limonene, benzene, toluene, xylene, or other hydrocarbons prevailing therein).
  • V M % Mean percentage pyrolysis rate
  • V M ⁇ % 100 ⁇ ( M - M r ) * M - 1 t
  • V M Structure : Mean heating rate of the mass undergoing pyrolysis.
  • V M ⁇ ⁇ ist T f - T i t
  • T f and T i are the final and initial temperatures of the pyrolysis process and t is the duration of the experiment.
  • the present invention solves the above-mentioned problems by a copyrolysis process of plastic materials selected among PE, PP, PS, PVC, PET, and mixtures thereof in the presence of end-of-life tyres (PFU), or their pyrolysis residues or other material of carbon nature, through microwave (MW), said method characterised in that:
  • (B) delivery of the MW is at such a power level as to obtain a mean percentage pyrolysis rate (V M % ) less than or equal to 1.0/min and/or a mean heating rate (V M risc ) less than or equal to 10° C./min., in the case pyrolysis induced by PFU; or delivery of the MW is at such a power level as to obtain a mean percentage pyrolysis rate (V M % ) less than or equal to 2.0/min and/or a mean heating rate (V M ist ) less than or equal to 15° C./min, in the case of pyrolysis induced by PFU pyrolysis residues.
  • pyrolysis oils are obtained having a sulphur content ⁇ 1% by weight and a fraction greater than 50% by weight of distillable hydrocarbons comprised between 20 and 250° C.
  • the oils obtained by the process of the present invention appear straw yellow in colour and are transparent, while those obtained under conditions other than the process of the invention appear brown in colour and are turbid, or actually they solidify at room temperature clogging the entire condensation system, but above all their hydrocarbon content with boiling points less than or equal to 250° C., do not exceed 30 to 40% by weight of the collected liquid fraction.
  • oils obtained by means of the process of the invention can be used for the recovery, through further refining, of raw materials such as for example, limonene, benzene, toluene, xylene, or other hydrocarbons prevailing therein.
  • the oils obtained from the process of the invention could be used directly as fuel for motor vehicles, or be mixed with commercial fuels.
  • FIG. 1 Experimental apparatus (Set-up A) used for the pyrolysis of tyre fragments and other plastic materials.
  • FIG. 2 Example apparatus with fractionation (Set-up B) used for the pyrolysis of tyre fragments and other plastic materials.
  • the pyrolysis oils obtainable by the process according to the present invention also have PCS and PCI comprised between 33 and 48 MJ/kg; viscosity comprised between 0.49 and 2.80 cps; density less than or equal to 0.932 gr/cm 3 .
  • the density of the pyrolysis oils obtained by the process is less than 0.850 gr/cm 3 and the viscosity comprised between 0.80 and 2.20 cps.
  • the process of the invention allows delivering the MW at maximum power in case of the presence of a separation system or anyhow to a power such as to obtain a V M % greater than 0.5 min ⁇ 1 and/or a mean heating rate (V M risc ) greater than 3.5° C./min.
  • a power such as to obtain a V M % greater than 0.5 min ⁇ 1 and/or a mean heating rate (V M risc ) greater than 3.5° C./min.
  • V M ist mean heating rate
  • one or more generators are used, operating at a frequency of 2.45 GHz.
  • the quantity of distillable hydrocarbons in the range of 20 to 250° C. may reach and exceed 85% by weight of the pyrolysis oil.
  • the ratio by weight between plastic materials and PFU varies between 1:1.5 and 1:4.0, while in the case of solid PFU pyrolysis residue, use of said ratio varies between 1:0.5 and 1:1.
  • the yield of the pyrolysis process is always 100%.
  • yields of pyrolysis oil in the process of the invention may vary between 5 and 90%.
  • the yields of the solid product vary between 10 and 60%, while those of the gaseous product vary between 4 and 75%.
  • the sulphur content of the pyrolysis oils does not exceed 1.0%: these liquid products, therefore, may fall into the class of low sulphur content fuel oils (BTZ, the limit of the sulphur content being 1% by weight), and also the results with respect to the heat power allow to insert the liquid products in this class of commercial products.
  • BTZ low sulphur content fuel oils
  • the possible use as diesel fuels for motor vehicles of liquid products is limited in the light of the new regulation provisions on the subject of fuel quality (from 1 Jan. 2009, the maximum sulphur content in fuels for motor vehicles is set at 10 mg/Kg).
  • a sulphurated compounds sequestering agent e.g. Ca(OH) 2 , is used, causing a reduction of the sulphur content of the pyrolysis oils.
  • test 2 corresponds with test 9
  • test 5 corresponds with test 10 (Table 3).
  • the pyrolysis process with microwave heating has proved to be an effective, selective, and environmentally friendly method for the thermal degradation of plastic materials in a mixture with tyres or their pyrolysis residues.
  • the process provides for all the collection and dumping, incineration, waste-to-energy and conventional pyrolysis processes. It preserves the energy and chemical content of polymeric materials by not oxidizing, but by depolymerising the macromolecules that constitute the charge by transforming them into a potential substrate for the petrochemical industry. There is no dispersion in the environment either of waste or of hazardous or potentially hazardous burning residues, such as sulphurous compounds and heavy metals.
  • the pyrolysis experiments were carried out by means of a microwave laboratory oven manufactured by Bi.Elle s.r.I. Company (No. 6, via Ho Chi Min, Modena, Italy).
  • the oven consists of a sealed chamber, inside of which there is a turntable, four microwave generators outside the oven (characterised by a total power absorption of 8 KW (4 ⁇ 2 KW), that deliver a maximum power of 6 KW as an electromagnetic field operating at a frequency of 2,450 MHz) which communicate with the interior of the chamber through small windows located at half height of the chamber.
  • the position and the method adopted of the microwave generators, of the magnetron type ensure uniformity of the MW field inside of the entire chamber.
  • the oven has a 40 mm diameter hole for the escape of gases and vapours.
  • an infrared sensor and a pyrometer were installed in the centre of one of the inner walls.
  • the oven is operated by an electronic system which allows adjusting the delivery of microwaves, even in continuity, by varying the electrical power absorbed individually by each generator.
  • the system allows the creation of heating programmes, characterised by temperature steps, monitored by the infrared probe, with the control of the delivered power and the duration of the step for each value of temperature.
  • the plastic materials subjected to pyrolysis process have been selected on the basis of their presence in the RSU: polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP), polyethylene terephthalate (PET) and polyvinylchloride (PVC).
  • PS polystyrene
  • HDPE high-density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PVC polyvinylchloride
  • the PS necessary for the tests was derived from foam PS used in packaging of materials. This was first heated to above its softening temperature, about 60° C., and reduced in volume to be able to handle higher quantities in a lesser volume.
  • the HDPE was recovered from a tank for solvents, suitably fragmented for easy handling and durability in time thereof.
  • the PP was obtained from a container often dedicated to the disposal of contaminated material available in many laboratories.
  • the PET was obtained from 0.5 L bottles of mineral water.
  • the polymeric materials before being subjected to the pyrolysis process were characterised through FT-IR and by means of CHN analysis.
  • a tyre consists of several portions, characterised by relative quantities of reinforcement materials (steel) and different compounds, in relation to its function.
  • cross sections of about 200 to 350 gr. of the tyre, further fragmented into pieces with sides of about 2 cm, were subjected to pyrolysis: a cross section can be considered a representative sample of an entire tyre since within the sample, all the portions of the tyre (tread, sides and bead) are found in the same proportions with respect to the entire tyre.
  • the plastic materials were fragmented in pieces with sides of 2 cm to enable introducing them easily into the pyrolysis apparatus, and to have sufficient homogeneity of the treated sample.
  • FIG. 1 a system (Set-up of the A type) of the experimental apparatus used for the execution of the pyrolysis experiments, while in FIG. 2 is shown the fractionation system (Set-up B)
  • the tyre fragments were introduced, after drying in an oven at 65° C. for 48 hours, within a 1 dm 3 Pyrex glass flask, used as a reaction vessel ( 1 ): this latter was housed in the centre of the oven chamber, at a height corresponding to that of the emission windows of the MW field and of the infrared sensor.
  • the reaction vessel was connected, by means of Pyrex glass joints ( 2 ) to a Claisen head ( 3 ) with a thermometer ( 4 ) located outside the oven chamber.
  • a straight Pyrex glass joint ( 5 ) connected the Claisen head to a water-cooled straight cooler ( 6 ) (at room temperature), in turn connected by a bend fitting ( 7 ) to a cooling coil ( 8 ) cooled at ⁇ 10° C., and with a thermostat.
  • a liquid nitrogen trap ( 10 ) was connected to the flask collection system of the liquid phase allowing condensation of the vapours of the substances which possibly, despite being liquid at room temperature, were dragged by the gas stream. Finally, the non-condensable part was collected in a gas counter ( 11 ).
  • the experimental apparatus used for the execution of the pyrolysis fractionation experiments of the vapours in outlet from the MW oven had a set-up of the B type, which was similar to the system of the A type, but differed for a glass Pyrex vertical joint (2/a), located above the joint ( 2 ) in outlet from the oven immediately before the Claisen head, filled with 4 mm diameter glass beads, or with another fractionation system among those reported in the paragraph on the fractionation systems, with the purpose, precisely, of fractionising the vapours in outlet from the oven.
  • These vapours, passing through the fractionation column were deprived from that component which had a boiling temperature higher than the temperature of the vapours. This system thus allowed dropping back into the reaction vessel the higher boiling compounds that had been dragged by the vapour stream.
  • the degradation process started on average 30 seconds after the ignition of the microwave generators regardless of the delivered power.
  • the vapours in outlet initially were white, which, with the increase of the flow of material in outlet from the oven became coloured up to yellow-brown. Initially, only a minimum fraction of the vapours condensed before reaching the coolers.
  • the liquid products were centrifuged at 3,000 rpm for eliminating any solid materials in suspension. Samples of liquid products were transferred into 2 cm 3 vials and sent to the determinations of the upper heat power and elemental composition (CHNS analysis). The liquid products were also characterised by infrared spectroscopy and nuclear magnetic resonance spectroscopy, determinations of the density and composition by GC-MS analysis, also carried out on the centrifuged and homogenised liquid.
  • the solid residues were taken from the reaction vessel (a 1 dm 3 Pyrex glass flask), fragmented, and homogenised in a mortar until obtaining a powder. Dust samples were then transferred into 2 cm 3 vials and used for determining the upper heat power and the elemental composition (CHNS analysis).
  • the gaseous mixtures produced during the pyrolysis process were collected in a gas counter, connected to the nitrogen liquid trap located immediately upstream in the process system.
  • the volume of gas was measured by means of a GFW Luzern water counter installed upstream of the sampling system.
  • the sampling of the gaseous mixtures for the subsequent characterisations was carried out directly by the gas counter through a single 250 ⁇ L Hamilton Gastight syringe.
  • Measurement of the pyrolysis oil density was carried out by weighing the mass of oil contained in a known volume under standard conditions (25.00° C., 1 atm.). Measurement of viscosity was determined on the liquid products by means of an Ostwlad viscometer thermostat at 25.00° C. in a silicone oil bath Julabo thermostat, ME-18V model.
  • the upper heating power level (U.H.P.) was determined for the pyrolysis products in the condensed phase, pyrolysis oil, and solid residue.
  • the lower heating power level L.H.P.
  • the determination of the heat power of the condensed phases was carried out by the ESSE.TI.A. s.r.l. Company, at No. 121/123, viale dell'Arte della Paglia, 50058 Signa (FI), Italy, through a method which consists in measuring the temperature before and after combustion, with excess oxygen, of a known mass sample in a calorimetric bomb completely immersed in a calorimeter.
  • the GC-MS analyses of the liquid products, for the identification of the substances constituting the mixtures were carried out through the GC-MS QP5050A Shimadzu instrument, equipped with a quadruple mass analyser, and having a Supelco Equity 5 capillary column or 100 m. Petrocol.
  • the pyrolysis experiments are shown below with unique identifying numbers: the pyrolysis products will be indicated by preceding the identifying number of the experiment with letter G for gases, with letter L for liquids, and with letter S for solid residues.
  • the substances attributed to gas chromatographic peaks for L15 are easily attributable to processes of degradation of the polymer chain of PET.
  • the high presence of benzene may be attributed to the aromatic part of the polymer.
  • the presence of such species as biphenyl or 4-methyl-acetophenone is explained by the coupling of two radicals; respectively between two phenyl radicals, and between the acetophenone radical and a methyl radical.
  • Table 8 are shown the results of the GC-MS analysis of the two fractions obtained by the pyrolysis of HDPE with the experimental set-up of the B type.
  • the products obtained by pyrolysis with the experimental set-up of the A type are not shown because they are solid products at room temperature.
  • the second fraction was sampled with all generators ignited at full power.
  • the two collected fractions are composed, in addition to the same substances identified for the pyrolysis oils L1 and L2, by increasing chain olefins and their hydrogenated equivalents, i.e., linear hydrocarbons from O 5 to O 36 .
  • the distilled fractions regardless of the distilled amounts, have boiling temperatures typical of commercial petrol.
  • the solid products obtained from copyrolysis of polymeric materials and tyres in appearance are identical to those obtained by simple tyre pyrolysis, that is, the solid residue in the reaction vessel at the end of the experiment, is a friable material, black in colour, of the same sizes of the initial tyre fragments.
  • the material after fragmentation and homogenisation is as a black powder mixed with metal wires removable with a simple magnet.
  • the solid residue of tests 2 to 10, and 12, therefore, is the same as that obtained from a pyrolysis test of only tyres (test 1).
  • Solid S11 is a single solid compact block, but fragile. Notwithstanding, the different appearance from other friable solid products, the conversion of PET is practically total; the amount of solid residue is only increased by 2%, compared to the initial PET.
  • the solid products after having been deprived of the metal wires with a magnet, are composed mainly of carbon (Table 24).
  • the presence of hydrogen is minimal and in samples from S2 to S6 is attributable to the incomplete volatilisation of all the substances containing hydrogen.
  • samples from S9 to S13 the majority concentration of hydrogen can be explained by the presence of oil which, in the last phase of the experiment, was present in the dephlegmator and returned to the reaction flask

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Electromagnetism (AREA)
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  • Wood Science & Technology (AREA)
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  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)
US14/007,236 2011-02-18 2012-02-20 Production of hydrocarbons from copyrolysis of plastic and tyre material with microwave heating Abandoned US20140155661A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITFI2011A000029A IT1404131B1 (it) 2011-02-18 2011-02-18 Produzione di idrocarburi da co-pirolisi di materiali plastici e pneumatici con riscaldamento a microonde.
ITFI2011A000029 2011-02-18
PCT/IB2012/050747 WO2012110990A1 (en) 2011-02-18 2012-02-20 Production of hydrocarbons from copyrolysis of plastic and tyre material with microwave heating

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US11591523B2 (en) 2018-04-20 2023-02-28 Resynergi, Inc. Distillation system and method using microwave-assisted pyrolysis
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US12195674B2 (en) 2021-09-21 2025-01-14 Eastman Chemical Company Using spent caustic solution from pygas treatment to neutralize halogens from liquified waste plastic
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WO2025028007A1 (ja) * 2023-08-03 2025-02-06 国立大学法人東北大学 熱分解によるオイル回収用の架橋済みゴム組成物、オイル、及びオイルの製造方法
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