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WO1988008020A1 - Process for the disposal of wastes of mixed polymeric materials and relevant equipment - Google Patents

Process for the disposal of wastes of mixed polymeric materials and relevant equipment Download PDF

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Publication number
WO1988008020A1
WO1988008020A1 PCT/EP1988/000169 EP8800169W WO8808020A1 WO 1988008020 A1 WO1988008020 A1 WO 1988008020A1 EP 8800169 W EP8800169 W EP 8800169W WO 8808020 A1 WO8808020 A1 WO 8808020A1
Authority
WO
WIPO (PCT)
Prior art keywords
pyrolysis
materials
products
polymeric
constituted
Prior art date
Application number
PCT/EP1988/000169
Other languages
English (en)
French (fr)
Inventor
Arturo Ferrari
Aldo Lucchesi
Giuseppe Maschio
Giuliano Nardini
Original Assignee
Arturo Ferrari
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 Arturo Ferrari filed Critical Arturo Ferrari
Publication of WO1988008020A1 publication Critical patent/WO1988008020A1/en

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Classifications

    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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

Definitions

  • An object of the present invention is a process for the disposal of wastes and/or scraps of mixed polymeric materials by thermal decomposition, or pyrolysis, with their energy content being taken advantage of, and from said wastes valuable and commercially useable products being winned.
  • Another object of the present invention is also an equipment for carrying out said process for the disposal, by pyrolysis, of said wastes of mixed polymeric materials.
  • plastics materials such as polyvinyl chloride, polyethylene, polyurethane resins, polyamides, polystyrene, polypropylene, polytetrafluoroethylene, phenolic resins, polyvinylidene fluoride, and the like, constitutes a serious problem from an environmental view point, in that the materials by which they are constituted, widely used in the most different fields, from the field of packaging, of electrotechnics, to the field of interior decoration, the car industry field, and so forth, are very inert from a chemical viewpoint, and very difficultly biodegradable.
  • the residues or scraps of filled and cured elastomeric materials such as, e.g., natural and/or synthetic rubbers, in particular car tyres, gaskets, couplings, sheats of electrical cables, and the like, can be "disposed of" by means of a treatment of thermal decomposition, or pyrolysis, substantially consisting in heating the rubber to temperatures of the order of from 400 to 600oC in the absence of oxygen, with a "depolymerization" of the material being thus accomplished, with lower molecular weight compounds being formed.
  • thermal decomposition substantially consisting in heating the rubber to temperatures of the order of from 400 to 600oC in the absence of oxygen
  • gaseous products which are prevailingly constituted by low molecular weight hydrocarbons
  • liquid products which are constituted as well by hydrocarbon blends, and/or by various aromatic products, according to the rubber type submitted to the pyrolysis
  • a solid residue which, in case of tyres, may represent up to 30-50% by weight of the initial material, and which is essentially constituted by the fillers initially used in the rubber compound, such as carbon black, silica, kaolin, calcium carbonate, zinc oxide, magnesium oxide, and the like, are obtained.
  • plastics material wastes like the mixed wastes of polymeric materials, i.e., the wastes wherein more or less considerable amounts of said plastics materials are contained, are simply dumped to landfills, wherein they accumulate, in that, as already said, they cannot undergo a biodegradation; and the problems of their disposal and elimination is still presently practical unsolved.
  • the purpose of the present invention is to provide a process for the disposal of the wastes or scraps or residues of various plastics materials, which does not involve the formation of also polluting byproducts, which are in their turn difficult to be eliminated and disposed of.
  • Another purpose of the present finding is to provide a process for the disposal of the residues of mixed polymeric materials, i.e., constituted by different and also non-homogeneous types of polymeric materials, comprising, e.g., plastics materials in mixture with one another, and also mixed with different elastomeric materials, such as rubber, and the like, without a preliminary sorting, separation and selection of the differentresidues having to be performed.
  • a further purpose of the present invention is to pruvide a process for cue disposal of mixed residues which originates the production of valuable, commercially useable materials, and with the simultaneous exploiting of the energy content of the same residues.
  • a still further purpose of the present finding is to provide an equipment capable of carrying out a process for the disposal of wastes of mixed plastics materials and/or mixed polymeric materials, with their energy content being taken advantage of, and withvaluable and commercially useable products beingsimultaneously produced.
  • said process of thermal breakdown by pyrolysis comprises the following steps:
  • pyrolysis oil being obtained; -cooling to a temperature lower than 50oC of a portion of said liquid product (i.e., the pyrolysis oil), and its use for the same quenching;
  • the present Rpplicant could surprisingly observe that the halogens initially contained in the polymeric materials used as the feedstock, in particular in polyvinyl chloride, when undergo the pyrolysis carried out according to the present invention, remain fixed in the solid product from the pyrolysis, and do not evolve as hydrogen halide, e.g.,hydrogen chloride in case of polyvinyl chloride.
  • the present Applicant was also able to observe that the solid products begins to appreciably relesse the fixed haloden, due to the effect of the heating in the absence of oxygen, only at temperatures of theorder of 1000oC, i.e., at temperatures by far higher than the maximum temperature of 800oC, at which the pyrolysis is made take place according to the presrnt invention.
  • halogens conventionally expressed as Cl
  • Their content of halogens may be as high as 4.5% by weight, referred to the total weight of the mixture submitted to the pyrolysis.
  • the gaseous product which is obtained from the pyrolysis results to be a mixture of permanent gases
  • the oxides of sulphur, rather small amounts of which are formed from the sulphur contained in the rubbers, are decreased, by means of an alkaline scrubbing, to levels lower than as detectable by means of the normal analytical procedures ( ⁇ 0.01% by volume).
  • Said gas mixture which has a heat value comprised within the range of from 5,000 to 8,000 kcal/m 3 , is used, as already said, in order to supply the heating fluid for the pyrolysis. Its combustion does not pose any problems and the produced fumes can be directly vented to atmosphere, because they are practically free from dusts, and, thanks to the above reported characteristics of the gases, have a content of polluting substances which is by far under the threshold values imposed by the regional regulations governing the facilities by which the special wastes are processed.
  • the liquid product which is obtained from pyrolysis results to be constituted by a mixture of aromatic, olefinic and saturated hydrocarbons.
  • carbon content results to be variable, but is anyway of approximately 85% by weight, hydrogen is approximately 10% by weight; the residual components thereof are nitrogen, oxygen; and sulphur and chlorine are contained at very low percentages, i.e., the chlorine content is of the order of 1,000 ppm, and the sulphur content is of the order of 1%.
  • the liquid product obtained from the pyrolysis results to be a material composed by the residues of very many types of elastomers, plastics materials and thermosetting resins, rubbers, copolymers, polymeric alloys, and the like.
  • the carbon content results to be variable, but anyway around 58-65% by weight; furthermore, small amounts of hydrogen (1-2%) and of nitrogen (0.3-0.4%) are present.
  • sulphur (1.5-2%) deriving from cured materials; and chlorine (3-4.5%), deriving from the chlorinated plastics and rubbers CPVC, isoprene rubbers and elastomeric copolymers
  • chlorine 3-4.5%)
  • an inorganic component, or residual ashes is present (20-35%), which is constituted by metals and metal salts originally added to the rubbers and to the plastics materials as fillers performing different functions (reinforcers, extenders, antioxidants, dyes, and so forth).
  • the metals mainly iron, aluminum, copper, magnesium, calcium, zinc, titanium, barium, have two origins:
  • metals and alloys as a powder, or small fragments (iron, aluminum, copper, magnesium), deriving from the crumbling of the metal structures initially associated with the plastics materials used as the feedstock to the process;
  • salts of calcium, barium, magnesium, zinc, aluminum, silicon, and titanium, which were originally present as fillers inside the feedstock to the process.
  • the coal powder obtained from the solid pyrolysis product by sieving and separation of the metal fractions according to known processes, can be used as a fuel.
  • the calorific value comprised within the range of from 4,800 to 5,600 kcal/kg, and can be burnt in thermal facilities equipped with coal powder burners, mixted with coal powder.
  • the sulphur content thereof is low, lower than the average content of mineral coals.
  • the solid product which is obtained from the pyrolysis is the residue left by the various materials undergoing the same pyrolysis, and is essentially constituted by coal powder, which can be also reused, after suitable treatments, known from the prior art, of sieving and separation of the metal fractions, and/or washing, as a filler in the field of the plastomeric materials and of vulcanized rubbers.
  • the ratio of the constituents of the mixture undergoing the pyrolysis, as well as the pyrolysis temperature can be varied of the amounts of the liquid products (the pyrolysis oil) to the gaseous products obtained from the process, according to the needs and/or the requirements from the market, for each type and composition of the mixture.
  • the process of the present invention is used in a particularly advantageous way in order to dispose of the polymeric materials deriving from the demolition and crumbling of cars.
  • non-metal materials constituted by various plastics materials, such as polyvinyl chloride, polyurethanes, polyester resinns, epoxy resins, polyamides and the like, and by various synthetic and natural rubbers, polyethylene, polypropylene, and the like, containing active or inert fillers, such as carbon black, calcium carbonate, z i nc oxide, silica, titanium dioxide, and the Iike.
  • plastics materials such as polyvinyl chloride, polyurethanes, polyester resinns, epoxy resins, polyamides and the like
  • active or inert fillers such as carbon black, calcium carbonate, z i nc oxide, silica, titanium dioxide, and the Iike.
  • the polymeric material coming from car demolition, as above said already practically contains all the components, plastics materials and rubbers which constitute the mixture of polymeric material to be submitted to the pyrolysis according to the present finding.
  • such a material results to be substantially cons ituted by the following components:
  • the material used as the feedstock was constituted by the wastes coming from the crushing processes, and contained approximately 80% of pyrolysable substances according to the present finding (rubber, plastics materials and wood), with the remainder 20% being constituted by inert substances; the characteristics (expressed as percentages by weight, referred to the dry matter) of the processed materials were as follows:
  • the pyrolysis oil shows optimum characteristics: a high fluidity, a high calorific value, a low sulphur content, a high content of aromatics.
  • the solid product obtained by the pyrolysis after a sieving carried out in order to remove metal fractions and other inert materials, can be powdered for being used as a solid fuel.
  • the ash content is rather high, but not excessive, in that mineral coals containing from 20 to 25% of ashes are normally used.
  • the coal can also be used in manufacturing industry, as a filler for various types of blends. Samples of produced coal were tested by specialized industries for the production of plastics films and electrical cables, with satisfactory results. The gas obtained is partially used in order to supply the necessary heat to the process; the residual amount can be used for energy supply for other purposes.
  • a mill of a traditional type known from the prior art, suitable for grinding plastics materials of various kinds, such as bakelite, polyethylene, polyvinyl chloride, and the like, and elastomeric materials such as filled vulcanized rubbers, down to a particle. size comprised within the range of from 2 to 5 cm;
  • a hopper for storing the ground polymeric material, and feeding the material to the pyrolysis reactor, by means of a loading device intercepted by two gate valves, which prevent air from entering the furnace, and the reaction products from escaping to the external environment;
  • -a pyrolysis reactor made from special thermal steels capable of withstanding temperatures of up to 900oC, provided with an indirect heating means, inside which the hot flue gases are circulated;
  • -a tower for quenching the gases, and condensing the vapours Leaving the pyrolysis reactor by spray ⁇ recycling the pre-cooled liquid product
  • -a cooling device of heat exchanger type, for pre ⁇ cooling the liquid product to be delivered to the quenching tower;
  • the facility is maintained slightly pressurized under a head of 50-80 mm of water, and through it nitrogen, or another inert gas is suitably flown.
  • the system is furthermore equipped with a hydraulic sealing system performing an antiburst function.
  • FIG. 1 a simplified diagram is depicted, which shows the process and the relevant equipment according to a preferred, non-exclusive form of practical embodiment of the invention.
  • the residues of plastics material and the residues or scraps of filled rubber are mixed and blended with one another inside 1, and are then stored inside the hopper 2.
  • From said hopper by means of a feeding and metering screw 3, they are fed to the pyrolysis reactor 4, of a tubular type, equipped with an indirect heating system.
  • the heating of the reactor takes place through the jacket 5 and the central element 6, by means of the hot gases produced inside the burner 7 by means of the combustion of the pyrolysis gases coming from the scrubbing tower 8, possibly through compression and storage devices not shown in Figure, with air 9.
  • the gases are scrubbed with an alkaline solution 10.
  • the pyrolysis products in gas or vapour form leaving the reactor 4 enter the quenching tower 11, inside which the higher-molecular-weight products condense. From the separator 12, the non-condensed products are sent to the scrubbing tower 8, whilst the liquid products are collected inside 13, and are cooled inside the heat exchanger 14. From this latter, a portion of the liquid products are sent to the quenching tower 11 for quenching the products Leaving the reactor 4, and the remainder of the products is sent to the storage tank 15.
  • the flue gases used for heating the pyrolysis reactor are vented to the atmosphere trhough 16.
  • the solid products are discharged from 17, are cooled inside 18 down to temperatures lower than 200oC, and are then collected and stored inside the tank 19.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
PCT/EP1988/000169 1987-04-07 1988-03-05 Process for the disposal of wastes of mixed polymeric materials and relevant equipment WO1988008020A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT20007A/87 1987-04-07
IT20007/87A IT1203869B (it) 1987-04-07 1987-04-07 Procedimento per lo smaltimento di scarti e/o rifiuti di materiali polimerici misti mediante pirolisi e relativa apparecchiatura

Publications (1)

Publication Number Publication Date
WO1988008020A1 true WO1988008020A1 (en) 1988-10-20

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IT (1) IT1203869B (it)
WO (1) WO1988008020A1 (it)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993000449A1 (en) * 1991-06-21 1993-01-07 Universite Laval Treatment of automobile shredder residue by vacuum pyrolysis
WO1994020590A2 (en) * 1993-03-10 1994-09-15 The University Of Wyoming Research Corporation Doing Business As Western Research Institute Process for waste plastic recycling
EP0670360A1 (de) * 1992-10-31 1995-09-06 RWE Entsorgung Aktiengesellschaft Verfahren zur thermischen Behandlung thermoplastischer, organischer Abfälle
US6861568B1 (en) 1998-05-15 2005-03-01 Wyoming Research Corporation Process for waste plastic recycling
GB2446797A (en) * 2006-12-19 2008-08-27 Used Tyre Distillation Res Ltd Recycling carbon-containing material
US20110083953A1 (en) * 2009-10-14 2011-04-14 Reklaim, Inc. Pyrolysis process and products
WO2021165923A1 (en) * 2020-02-21 2021-08-26 3M Innovative Properties Company Upcycling perfluoropolymers into fluorinated olefins
WO2023144520A1 (en) * 2022-01-26 2023-08-03 Plastic Energy Limited System and method for removing contaminants from a pyrolysis fluid
EP4379021A1 (en) * 2022-11-30 2024-06-05 Covestro Deutschland AG Pyrolysis of scrap, fiber reinforced polyurethane-poly(meth)acrylate composite material for recovery of recyclates
EP4424798A1 (en) * 2023-03-01 2024-09-04 OMV Downstream GmbH Process for producing hydrocarbon products from plastic material containing a triarylphosphite compound

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171345A (en) * 1977-07-26 1979-10-16 Vish Chimiko-Technologicheski Institute Method of manufacture of reinforcing carbon black
US4515659A (en) * 1982-09-30 1985-05-07 Ford Motor Company Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalysts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171345A (en) * 1977-07-26 1979-10-16 Vish Chimiko-Technologicheski Institute Method of manufacture of reinforcing carbon black
US4515659A (en) * 1982-09-30 1985-05-07 Ford Motor Company Pyrolytic conversion of plastic and rubber waste to hydrocarbons with basic salt catalysts

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993000449A1 (en) * 1991-06-21 1993-01-07 Universite Laval Treatment of automobile shredder residue by vacuum pyrolysis
US5451297A (en) * 1991-06-21 1995-09-19 Universite Laval Treatment of automobile shredder residue by vacuum pyrolysis
EP0670360A1 (de) * 1992-10-31 1995-09-06 RWE Entsorgung Aktiengesellschaft Verfahren zur thermischen Behandlung thermoplastischer, organischer Abfälle
WO1994020590A2 (en) * 1993-03-10 1994-09-15 The University Of Wyoming Research Corporation Doing Business As Western Research Institute Process for waste plastic recycling
WO1994020590A3 (en) * 1993-03-10 1994-11-10 Univ Wyoming Process for waste plastic recycling
US5753086A (en) * 1993-03-10 1998-05-19 The University Of Wyoming Research Corp. Process for waste plastic recycling
US6861568B1 (en) 1998-05-15 2005-03-01 Wyoming Research Corporation Process for waste plastic recycling
US8795475B2 (en) 2006-12-19 2014-08-05 Used Tyre Distillation Research Limited System and method for recycling of carbon-containing materials
GB2446797B (en) * 2006-12-19 2012-02-29 Used Tyre Distillation Res Ltd Recycling of carbon-containig material
GB2446797A (en) * 2006-12-19 2008-08-27 Used Tyre Distillation Res Ltd Recycling carbon-containing material
US20110083953A1 (en) * 2009-10-14 2011-04-14 Reklaim, Inc. Pyrolysis process and products
US8888961B2 (en) * 2009-10-14 2014-11-18 Reklaim, Inc. Pyrolysis process and products
US9777159B2 (en) 2009-10-14 2017-10-03 Reklaim, Inc. Pyrolysis process and products
WO2021165923A1 (en) * 2020-02-21 2021-08-26 3M Innovative Properties Company Upcycling perfluoropolymers into fluorinated olefins
US11795126B2 (en) 2020-02-21 2023-10-24 3M Innovative Properties Company Upcycling perfluoropolymers into fluorinated olefins
WO2023144520A1 (en) * 2022-01-26 2023-08-03 Plastic Energy Limited System and method for removing contaminants from a pyrolysis fluid
EP4379021A1 (en) * 2022-11-30 2024-06-05 Covestro Deutschland AG Pyrolysis of scrap, fiber reinforced polyurethane-poly(meth)acrylate composite material for recovery of recyclates
WO2024115297A1 (en) * 2022-11-30 2024-06-06 Covestro Deutschland Ag Pyrolysis of scrap, fiber reinforced polyurethane-poly(meth) acrylate composite material for recovery of recyclates
EP4424798A1 (en) * 2023-03-01 2024-09-04 OMV Downstream GmbH Process for producing hydrocarbon products from plastic material containing a triarylphosphite compound
WO2024180205A1 (en) 2023-03-01 2024-09-06 OMV Downstream GmbH Process for producing hydrocarbon products

Also Published As

Publication number Publication date
IT8720007A0 (it) 1987-04-07
IT1203869B (it) 1989-02-23

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