WO2004072163A1 - A method and a device for continuous conversion of polyolefinic plastics wastes - Google Patents

A method and a device for continuous conversion of polyolefinic plastics wastes Download PDF

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Publication number
WO2004072163A1
WO2004072163A1 PCT/PL2003/000032 PL0300032W WO2004072163A1 WO 2004072163 A1 WO2004072163 A1 WO 2004072163A1 PL 0300032 W PL0300032 W PL 0300032W WO 2004072163 A1 WO2004072163 A1 WO 2004072163A1
Authority
WO
WIPO (PCT)
Prior art keywords
heat exchanger
charge
pipe heat
stage
reactor
Prior art date
Application number
PCT/PL2003/000032
Other languages
English (en)
French (fr)
Inventor
Zbigniew Tokarz
Marek Stelmachowski
Original Assignee
Zbigniew Tokarz
Marek Stelmachowski
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zbigniew Tokarz, Marek Stelmachowski filed Critical Zbigniew Tokarz
Priority to EP20030815872 priority Critical patent/EP1594916A1/en
Priority to AU2003303917A priority patent/AU2003303917A1/en
Publication of WO2004072163A1 publication Critical patent/WO2004072163A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00Recovery or working-up of waste materials
    • C08J11/04Recovery or working-up of waste materials of polymers
    • C08J11/10Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16Recovery 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 treatment with inorganic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07Destructive 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04Disintegrating plastics, e.g. by milling
    • B29B2017/0424Specific disintegrating techniques; devices therefor
    • B29B2017/0496Pyrolysing the materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/141Feedstock
    • Y02P20/143Feedstock the feedstock being recycled material, e.g. plastics
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling

Definitions

  • the present invention concerns a method for continuous conversion of polyolefinic plastics wastes such as for example polyethylene or polypropylene, to the form of liquid mixture of non-saturated and saturated hydrocarbons, constituting the high quality paraffin.
  • polyolefinic plastics wastes such as for example polyethylene or polypropylene
  • the present invention relates to the single-stage industrial scale process for the continuous thermo-catalytic conversion of highly contaminated polyolefinic plastics wastes in a single vessel.
  • the present invention relates also to a device to realize the said method.
  • the Polish patent application P 336,773 teaches a method for conversion of plastics wastes comprising thermic or catalytic cracking of plastics wastes in the presence of the waste catalysts from fluidal catalytic cracking or natural aluminosilicates in the reactor, wherein gaseous or liquid products of cracking are directed to an evaporator directly after cracking, where they are mixed with hydrogen, evaporated and sent to a hydrogenation reactor.
  • polish patent application P 314,409 presents a method for recycling waste thermoplastic materials, in particular polyolefines, polystyrene, polycarbonates, saturated polyesters, polyacetals, polyphenylene oxide, polyacrylic esters, polyvinyl chloride and their copolymers and thermopolymers and their mixtures. It comprises melting comminuted and mechanically cleaned waste thermoplastic materials, containing at least 20% by weight polyolefines (or with addition of polyolefines), preferably polyethylene or polypropylene, with high-molecular compounds of 2-oxazoline, preferably methylmaleate of ricynyl-2-oxazoline and organic superoxides.
  • the mixture of waste thermoplastic materials does not contain any polyolefines it can be recycled in a two-stage process.
  • polyolefines are melted with high-molecular compounds of 2- oxazoline, preferably methylmaleate of ricynyl-2-oxazoline and organic superoxides.
  • polyolefines are melted with comminuted and mechanically cleaned waste thermoplastic materials.
  • polish patent application P 339,821 discloses a method for manufacturing aliphatic hydrocarbons from a preselected mixture of waste plastics, particularly from unreusable packaging.
  • This method for manufacturing aliphatic hydrocarbons in a thermic decomposition reaction comprises heating the mixed mass of waste thermoplastic materials, preferably after separating its lighter than water fraction and (possibly) the preliminary cleaning, to the temp. 320-400 °C at the pressure 0.008-3.5 MPa and subsequently distillating it under the same conditions.
  • the obtained product can be separated and purified by known methods.
  • the US 4,108,730 patent (Chen et al.) describes a process for converting relatively ash-free solid polymeric wastes to more valuable liquid, solid, and gaseous products which comprises mixing rubber and/or plastic wastes at high temperatures in a refractory petroleum stream and catalytically cracking the mixture.
  • a disclosed set up comprises : a shredder, a grinder, a metals separation unit, a mixer/dissolver, a reactor, a catalyst regenerator and a distillation vessel.
  • the international publication WO 01/05908 (Xing) relates to a process for producing gasoline and diesel from waste plastics and/or heavy oil and comprises the steps of a) a mixing waste plastics and/or heavy oil with a first catalyst in a pyrolysis reactor at high temperature to carry out a pyrolysis and a first catalytic cracking; and (b) introducing the products in step (a) into a fixed bed to perform a second catalytic cracking with a second catalyst.
  • the process -f-urther comprises the step (c) recycling the first catalyst in the reaction.
  • the European Patent Specification EP) 276081 discloses a process for preparing a normally liquid hydrocarbon product which comprises thermally cracking a plastics material in the molten liquid phase and catalytically convertion the vaporous product thereby generated by contact at 200-350 ° C with a zeolite having a constraint index between 1 and 12.
  • a catalytic reactor includes a reactor vessel, a catalyst bed and at least two heat exchangers.
  • the catalyst bed and heat exchangers are arranged coaxially with the central axis of a reactor vessel and substantially at the same height.
  • the Polish patent PL 99,486 describes the device for conversion of plastics wastes comprising a boiler for melting the waste, a reactor, provided with a mixer and a supply pomp, for the thermic decomposition of the waste and product storage tank having a cooler and a burner, wherein the device is also equipped with the cooling tank to cool the product directed to the burner.
  • the realized processes for the conversion of plastics wastes have the process of catalytic conversion carried out exclusively in the reactor. Such processes require maintaining high pressure and using large quantities of catalyst.
  • the charge treated by those processes requires preliminary comminution, purification, phase separation, addition of hydrogen or mixing with depolymerization facilitation agents.
  • the chemical plant hardware is exposed to strongly corrosive agents.
  • Most of the disclosed methods have never been executed in the form of industrial scale production, as witnessed by the laboratory scale examples given in the publications.
  • the disclosed catalytic methods require costly catalysts and do not allow for the direct conversion into high grade mixture of non-saturated and saturated hydrocarbons.
  • the known devices for the conversion of plastics wastes do not have an integrated modular construction nor are they suitable for conducting the whole process of the conversion of plastics wastes on the industrial scale (small or medium) in a single reaction vessel.
  • the known devices are susceptible to corrosion. They are usually very complex and require many auxiliary tanks, pumps, heaters etc. for each active apparatus in the plant.
  • a method for continuous conversion of plastics wastes comprising continuous loading the charge, plastifying it, bringing it to the liquid state and converting it catalytically, as expressed in claim 1, characterized in that the whole process, from charge loading to collecting the gaseous product and removing impurities, is conducted in a single stage and in a single internal vessel of an integrated, melting box- heat exchanger - reactor device with a vertical arrangement, wherein plastified and liquefied charge forms a uniform block of the charge mass moving downwards gravitationally.
  • a device for continuous conversion of plastics wastes as expressed in claim 14, characterized in that it constitutes a modular integrated melting box - heat exchanger - reactor device with a vertical arrangement, for a single stage conducting of the whole process of thermo-catalytic conversion of plastics wastes, from the charge loading to collecting the gaseous product and removing impurities in a single internal vessel.
  • Fig.l shows the front section view of the present device
  • Fig.2 shows the cross-section view of the present device.
  • the charge is placed in the chute 20 of the loading press 21 and then, through the connection 19, in the transport conduit 18 connected to the melting box 10 of the internal vessel la.
  • the charge material is compacted and formed in the way enabling its transporting into the device with the simultaneous removal, from it, of air and water.
  • the transport conduit 18 after having been filled with the compressed charge material ensures the sufficient sealing for the hydrocarbon vapours.
  • the melting box 10 passes through the heating chamber 17 of the charge intake, where its walls are heated to the temperature of, preferably, 120 °C.
  • the charge material is then supplied to the space between the head 11 a ⁇ d the Il-nd stage pipe heat exchanger chamber unit 14. In this space it is heated and partially dissolved by the hydrocarbon vapours filling the whole interior of the device.
  • the surface of the pipes of the Il-nd stage pipe heat exchanger chamber unit 14 is heated by means of the combustion gasses to the temperature of, preferably, 420 °C.
  • the heated and partially melted charge material is divided into a number of narrow streams with the width of, preferably, 50 to 70 mm. After this division the charge material is moved towards the pipes of the I-st stage pipe heat exchanger chamber unit L5 by means of the forces of gravitation and the press pushing.
  • Both the I-st and the Il-nd stage of the charge material melting comprise, preferably, two rows each of horizontal pipes with an external diameter, preferably, 120 to 140 mm and the wall thickness, preferably, 3 to 4 mm.
  • the temperature of the pipes of the I-st stage pipe heat exchanger chamber unit 15 is, preferably, 440 to 490 °C.
  • the distances between the pipes at this stage are also, preferably, 50 to 70 mm.
  • the pipes belonging to the consecutive rows in the exchanger are shifted in relation to the pipes of previous rows so that the axis of symmetry of each shifted pipe is placed exactly in the middle of the distance between the two pipes placed above it.
  • the bi-convex bottom 32 of the reactor chamber 8 is constructed out of two 120 degrees cylindrical sections with the diameter of, preferably, 600 mm and the length 1200 mm, which are made of the nickel alloy HAYNES HR-120 with the thickness of, preferably, 10 mm and are separated with the stiffener partition 29.
  • agitators 22 driven by the separate moto-reductor 24 each and they rotate with the constant speed of 15 to 20 rpm.
  • the stability of the bottom temperature and the steady collection of heat from its surface is ensured by a layer of liquid metal 33 with the temperature of melting, preferably, 270 to 300 °C.
  • the thickness of metal layer in the hollows of the sections of the bottom 32 is, preferably, no more than 50 to 70 mm.
  • the removal of impurities introduced into the device together with the charge material is enabled by two cleaning units each comprising the impurities feeder 30, displaceable partition 31, the screw conveyer with its housing 25 for removing the impurities from the reactor chamber 8, connecting lock 26 and impurities receptable 28.
  • the screw conveyer with its housing 25 is driven by the hand crank 27.
  • the heat, necessary to carry out the process in the heat exchanger chambers 14, _15 and the reactor chamber 8, is provided by the system comprising a burner fed for example with the generator gas obtained out of the bio-mass gas generator.
  • a local brand combustion gas generator (designated AZS-automatic wood combustion unit) with the power output of lOOkW was used, having the combustion chamber 2 with the roof 4 constituting a heat equalizing baffle.
  • the roof 4 contains the bores 3, preferably 16 to 20 of them, with a diameter, preferably 80 to 100mm.
  • the combustion gases pass through the bores 3 from the combustion chamber 2 to the heat distributing chamber 5, which is supporting the module of the reactor chamber 8.
  • the combustion gases after giving away some of their heat to the interior of the reactor chamber 8, move by means of the passage 7 to the heat exchanger giving away their heat in the heat exchanger pipe chamber units 14 and 15. Then they heat the melting box 10 placed in the heating chamber 17 before getting into the chimney conduit 12.
  • the flow regulating throttle 9 enables maintaining the required pipe surface temperatures.
  • the process thermal stability and limiting the heat losses are provided by the heating unit housing 1, thermal side isolation 6 and thermal top isolation 13.
  • Cleaning of the module of the heat exchanger and the module of the reactor chamber 8 are eanbled and provided by the system of clamps 16. Removal of the clamps 16 enables separating the head H from the module of the heat exchanger and the module of the heat exchanger from the module of the reactor chamber 8.
  • the housing of the reactor chamber 8 is constructed in the form of a cuboid with dimensions 2670x1250x1120mm. Its sides are made of heat- and acid-resistant steel H25N20S2 with the thickness, preferably, 8 to 10mm.
  • the rigidity of this construction is provided by the external skeleton 34 in the form of a grid made of steel sheet H20N12S2, with the thickness, preferably, of 8 to 10mm and the dimensions 130x130x100mm.
  • the module of the heat exchanger is constructed similarly to the module of the reactor chamber 8 housing and is in the form of a cuboid with dimensions 1450x1250x940mm and walls made of steel sheet H20N12S2, with the thickness, preferably, of 8mm.
  • the rigidity of this construction is provided by the external skeleton 23 in the form of a grid made of steel sheet 18G2A, with the thickness of 8mm and the dimensions 130x130x100mm.
  • the transport conduit 18 of the charge inlet has got the rectangular cross-section with dimensions, preferably, 200x400mm and the length 500 to 700mm. It ends with the connection 19 and is made of steel sheet 1H18N9T, with the thickness, preferably, of 8mm.
  • the connection 19 leads to the loading press 2 feeding the charge to the present device.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Sustainable Development (AREA)
  • Materials Engineering (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processing Of Solid Wastes (AREA)
PCT/PL2003/000032 2003-02-17 2003-04-02 A method and a device for continuous conversion of polyolefinic plastics wastes WO2004072163A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20030815872 EP1594916A1 (en) 2003-02-17 2003-04-02 A method and a device for continuous conversion of polyolefinic plastics wastes
AU2003303917A AU2003303917A1 (en) 2003-02-17 2003-04-02 A method and a device for continuous conversion of polyolefinic plastics wastes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PLP.358774 2003-02-17
PL358774A PL199825B1 (pl) 2003-02-17 2003-02-17 Sposób ciągłego przetwarzania odpadów z tworzyw sztucznych i urządzenie do ciągłego przetwarzania odpadów z tworzyw sztucznych

Publications (1)

Publication Number Publication Date
WO2004072163A1 true WO2004072163A1 (en) 2004-08-26

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Application Number Title Priority Date Filing Date
PCT/PL2003/000032 WO2004072163A1 (en) 2003-02-17 2003-04-02 A method and a device for continuous conversion of polyolefinic plastics wastes

Country Status (4)

Country Link
EP (1) EP1594916A1 (pl)
AU (1) AU2003303917A1 (pl)
PL (1) PL199825B1 (pl)
WO (1) WO2004072163A1 (pl)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7285186B2 (en) 2003-12-11 2007-10-23 Zbigniew Tokarz Transverse-flow catalytic reactor for conversion of waste plastic material and scrap rubber
US11597690B2 (en) 2020-05-29 2023-03-07 Braskem America, Inc. Molten salt catalytic compositions and methods for the cracking of carbon-containing feedstocks

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106009A1 (de) 2009-03-16 2010-09-23 Vit Environmentsystems Ag Vorrichtung zur thermischen behandlung, insbesondere thermolyse von altöl-gemischen
WO2010117284A1 (en) 2009-04-09 2010-10-14 Przedsiębiorstwo EKONAKS Sp. z o.o. Method of processing plastics waste, especially polyolefines and a device for processing plastics waste, especially polyolefines

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2613721A1 (fr) * 1987-04-07 1988-10-14 Gensac Patrice Procede de fabrication de cires artificielles
WO1996001298A1 (en) * 1994-07-01 1996-01-18 Dynamic Structures Corp. S.A. The method of obtaining liquid fuels from polyolefins wastes
WO2001005908A1 (en) * 1999-07-16 2001-01-25 Enercon Technologies, Inc. A process for producing gasoline and diesel from waste plastics and/or heavy oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2613721A1 (fr) * 1987-04-07 1988-10-14 Gensac Patrice Procede de fabrication de cires artificielles
WO1996001298A1 (en) * 1994-07-01 1996-01-18 Dynamic Structures Corp. S.A. The method of obtaining liquid fuels from polyolefins wastes
WO2001005908A1 (en) * 1999-07-16 2001-01-25 Enercon Technologies, Inc. A process for producing gasoline and diesel from waste plastics and/or heavy oil

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7285186B2 (en) 2003-12-11 2007-10-23 Zbigniew Tokarz Transverse-flow catalytic reactor for conversion of waste plastic material and scrap rubber
US7563345B2 (en) 2003-12-11 2009-07-21 Zbigniew Tokarz Transverse-flow pyrocatalytic reactor for conversion of waste plastic material and scrap rubber
US7977518B2 (en) 2003-12-11 2011-07-12 Zbigniew Tokarz Transverse-flow pyrocatalytic reactor for conversion of waste plastic material and scrap rubber
US11597690B2 (en) 2020-05-29 2023-03-07 Braskem America, Inc. Molten salt catalytic compositions and methods for the cracking of carbon-containing feedstocks
US11834397B1 (en) 2020-05-29 2023-12-05 Braskem America, Inc. Molten salt catalytic compositions and methods for the cracking of carbon-containing feedstocks

Also Published As

Publication number Publication date
EP1594916A1 (en) 2005-11-16
AU2003303917A1 (en) 2004-09-06
PL358774A1 (pl) 2004-08-23
PL199825B1 (pl) 2008-11-28

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