EP0132612A1 - Procédé pour la production d'hydrocarbures liquides - Google Patents

Procédé pour la production d'hydrocarbures liquides Download PDF

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Publication number
EP0132612A1
EP0132612A1 EP84107378A EP84107378A EP0132612A1 EP 0132612 A1 EP0132612 A1 EP 0132612A1 EP 84107378 A EP84107378 A EP 84107378A EP 84107378 A EP84107378 A EP 84107378A EP 0132612 A1 EP0132612 A1 EP 0132612A1
Authority
EP
European Patent Office
Prior art keywords
solvent
liquid hydrocarbons
pressure
waste
bar
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP84107378A
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German (de)
English (en)
Other versions
EP0132612B1 (fr
Inventor
Hubert Dr. Coenen
Rainer Hagen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fried Krupp AG
Original Assignee
Fried Krupp AG
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 Fried Krupp AG filed Critical Fried Krupp AG
Priority to AT84107378T priority Critical patent/ATE30045T1/de
Publication of EP0132612A1 publication Critical patent/EP0132612A1/fr
Application granted granted Critical
Publication of EP0132612B1 publication Critical patent/EP0132612B1/fr
Expired legal-status Critical Current

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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
    • C10G1/10—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

  • the invention relates to a process for the production of liquid hydrocarbons from used tires, cable, polyethylene and / or polypropylene waste.
  • the liquid hydrocarbons that are produced by this process include alkanes, cycloalkanes and aromatics, which have a boiling point of 20 to about 350 ° C and whose molecules contain 5 to about 30 carbon atoms.
  • the liquid hydrocarbons produced by the process can contain organic sulfur and chlorine compounds.
  • the liquid hydrocarbons can be used as heating oil or for blending heating oil or as a chemical raw material.
  • Used tires belong to the waste products of the automotive industry and consist of one or more rubber compounds, a bead ring and a fabric.
  • the rubber mixture contains rubber, soot, oils and resins, zinc oxide, vulcanization accelerators, anti-aging agents and sulfur.
  • the rubber is composed of chain-like macromolecules which interengage 29lun g en and are additionally linked by sulfur atoms.
  • the tires are manufactured using natural rubber and synthetic rubber, with the synthetic rubbers being polymerized by the polymerization of isoprene, butadiene, chlorobutadiene and the copolymerization of butadiene Styrene or iso-butene can be produced with isoprene.
  • the carbon black serves as a filler and to improve the rubber properties, because it forms a very close bond with the rubber during tire manufacture.
  • the oils and resins act as plasticizers and improve the processability of the rubber mixture.
  • the zinc oxide serves as a filler and as an activator for the vulcanization accelerators.
  • the bead ring stabilizes the tire against radial forces and is made of steel wire or steel cable.
  • the fabric in the tire consists of synthetic fibers or steel wires.
  • the weight proportion of the rubber compound in the old tires is usually between 75 and 80%.
  • Cable waste arises from the processing and renewal of cables that consist of a metallic electrical conductor, a plastic insulation and a plastic jacket and are used for the transmission of messages or electrical energy.
  • Polyethylene and polypropylene waste is produced in the manufacture and processing of plastics and accumulates there in a relatively pure form. These pure wastes can be processed into liquid hydrocarbons by the process according to the invention, while the polyethylene and polypropylene wastes contained in the household waste cannot be fed to the process according to the invention, since they are difficult to separate from the other plastics contained in the household waste, in particular polyvinyl chloride.
  • Polyethylene and polypropylene are produced by polymerizing ethene or propene and, in addition to the polymers, also contain fillers.
  • used tires are usually removed by incineration, which takes place either in specially designed ovens or in waste incineration plants.
  • the exhaust gases from the incineration plants, in which used tires are burned, must be dedusted and desulphurized, in particular due to the high ZnO and S0 2 content.
  • used tires can be removed by pyrolysis processes and processed into reusable products.
  • the pyrolysis of old tires produces a pyrolysis coke, a flammable pyrolysis gas that mostly serves to cover the energy requirements of the pyrolysis process, and a pyrolysis oil that is used as heating oil.
  • the polyethylene and polypropylene waste is mostly incinerated.
  • the cable waste is usually deposited in a landfill.
  • the combustion processes have the disadvantage that they are difficult to carry out due to the nature of the old tires and plastic waste and that the combustion exhaust gases have to be cleaned using complex processes.
  • the disadvantage of the pyrolysis process is that a very large part of the organic compounds, which are valuable per se, is coked and thus converted into a less valuable state.
  • the invention has for its object to provide a method with which old tires, cable, polyethylene and / or polypropylene waste can be removed without damage and processed into valuable reusable liquid hydrocarbons, the formation of gaseous and coke-like decomposition products should be largely avoided.
  • the object underlying the invention is achieved in that the shredded old tires, cable, polyethylene and / or polypropylene waste at a temperature of 150 to 500 ° C and a pressure of 20 to 300 bar with a liquid at 1 bar and 20 ° C.
  • Solvents are treated, that the solvent phase laden with the liquid hydrocarbons is separated off and broken down into its constituents by lowering the pressure or by lowering the pressure and temperature, and that the solvent is circulated.
  • the polymer molecules are cleaved under the influence of the high pressure and the high temperature, liquid hydrocarbons in particular having about 5 to 30 carbon atoms being formed without any noticeable coking occurring.
  • the liquid hydrocarbons are absorbed and removed comparatively quickly by the solvent.
  • the plasticizers and anti-aging agents are released from the solvent and only slightly decomposed under the influence of pressure and temperature.
  • the carbon black, the fillers, the metals and the fabric remain as a solid, insoluble residue, which also contains the small amounts of coking products that may arise during the process.
  • the process has the advantage that the majority of the organic compounds present in the waste materials are converted into liquid reusable hydrocarbons.
  • the process according to the invention can be carried out particularly successfully if gasoline, benzene, toluene, xylene, ethyl bezole and / or water is used as the solvent, the weight ratio of the waste materials to the solvent being between 1: 3 and 1:30.
  • the organic solvents to be used according to the invention have an optimal dissolving power for the liquid hydrocarbons formed, while the water to be used according to the invention provides products with a lower molecular weight.
  • the pressure and temperature are reduced in several stages and that the constituents of the loaded solvent phase are obtained in several fractions. This procedure allows the liquid hydrocarbons to be broken down into fractions suitable for various purposes.
  • a suitable fraction can be returned to the process according to the invention as a solvent.
  • the reactor 1 there is a bed of shredded old tires, cable, polyethylene and / or polypropylene waste.
  • the sulfur and chlorine content of the old tires is advantageously diluted by the polyethylene and polypropylene waste.
  • the solvent is heated in the heat exchanger 6 to the process temperature of 150 to 500 ° C and brought to a process pressure of 20 to 300 bar by the compressor 5 and conveyed into the reactor 1.
  • the solvent flows through the reactor 1 and removes the liquid hydrocarbons formed in the reactor 1 and the gaseous reaction products formed in a small amount.
  • the solvent phase laden with the liquid hydrocarbons is removed, expanded in the expansion valve 2, cooled in the heat exchanger 7, freed from the gaseous reaction products in the separation vessel 8 and then fed to the distillation column 3.
  • the higher-boiling hydrocarbons are taken off at the bottom of the distillation column 3, while the low-boiling hydrocarbons are taken off together with the solvent at the top of the distillation column 3.
  • the low-boiling fraction is then cooled in the heat exchanger 9 and, after liquefaction, is returned from the compressor 5 to the reactor 1. It is possible to carry out the expansion and cooling of the solvent phase laden with the liquid hydrocarbons in several stages, which is not shown in the drawing.
  • the solid residue which contains the insoluble constituents of the waste materials used and the coking products is removed from the reactor 1.
  • Used tires and cable waste were shredded so that particles with an edge length of approx. 2 cm were obtained. 602 g of these particles were treated with toluene at 350 ° C. and 80 bar for 4 hours.
  • the solvent phase laden with the liquid hydrocarbons was then separated off and let down to 10 bar and cooled to 310 ° C.
  • a separation was carried out into a toluene-containing liquid phase and into a gas phase, which mainly consisted of toluene.
  • the liquid phase which contained about 85% toluene, was distilled to remove the toluene and the low-boiling liquid hydrocarbons after relaxing to atmospheric pressure.
  • the solid residue obtained after the toluene treatment was powdery and mainly consisted of carbon black, ZnO, other tire fillers and pieces of metal. Its sulfur content was 2.37%, while the sulfur content of the particles used was 1.70%.
  • 12 kg of toluene were used for 1 kg of starting material, and these can largely be recovered and recycled.
  • the metals present in the starting material were found in the residue in unchanged form. This is an advantage over pyrolysis carried out at higher temperatures. There, the metals present in the old tires and cable waste melt together in an undesirable manner, while in the process according to the invention they can be reduced at a low rate with mechanical separation processes! Energy expenditure can be sorted out and recycled.

Landscapes

  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP84107378A 1983-07-21 1984-06-27 Procédé pour la production d'hydrocarbures liquides Expired EP0132612B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84107378T ATE30045T1 (de) 1983-07-21 1984-06-27 Verfahren zur herstellung fluessiger kohlenwasserstoffe.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3326284 1983-07-21
DE3326284A DE3326284C2 (de) 1983-07-21 1983-07-21 Verfahren zur Herstellung flüssiger Kohlenwasserstoffe

Publications (2)

Publication Number Publication Date
EP0132612A1 true EP0132612A1 (fr) 1985-02-13
EP0132612B1 EP0132612B1 (fr) 1987-09-30

Family

ID=6204535

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107378A Expired EP0132612B1 (fr) 1983-07-21 1984-06-27 Procédé pour la production d'hydrocarbures liquides

Country Status (6)

Country Link
US (1) US4642401A (fr)
EP (1) EP0132612B1 (fr)
JP (1) JPS6040193A (fr)
AT (1) ATE30045T1 (fr)
DE (1) DE3326284C2 (fr)
ES (1) ES8504897A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020590A2 (fr) * 1993-03-10 1994-09-15 The University Of Wyoming Research Corporation Doing Business As Western Research Institute Procede de recyclage de dechets plastiques
FR2706168A1 (fr) * 1993-04-01 1994-12-16 Yamasaki Nakamichi Procédé pour la conversion en huiles de caoutchoucs vulcanisés.
US6861568B1 (en) 1998-05-15 2005-03-01 Wyoming Research Corporation Process for waste plastic recycling
EP1770148A1 (fr) * 2005-10-03 2007-04-04 CHUNG BONG, ChOON Procédé et appareil de production d'huile à partir de déchets plastiques

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DE3710021A1 (de) * 1987-03-30 1988-10-20 Veba Oel Entwicklungs Gmbh Verfahren zur hydrierenden konversion von schwer- und rueckstandsoelen
US5099086A (en) * 1989-06-28 1992-03-24 Universite Laval Extraction of commercially valuable chemicals from tire-derived pyrolytic oils
US5158982A (en) * 1991-10-04 1992-10-27 Iit Research Institute Conversion of municipal waste to useful oils
US5158983A (en) * 1991-10-04 1992-10-27 Iit Research Institute Conversion of automotive tire scrap to useful oils
US5230777A (en) * 1991-12-13 1993-07-27 James Jarrell Apparatus for producing fuel and carbon black from rubber tires
US5296515A (en) * 1992-06-03 1994-03-22 Phillips Petroleum Company Hydrovisbreaking of hydrocarbon polymers
US5364996A (en) * 1992-06-09 1994-11-15 Texaco Inc. Partial oxidation of scrap rubber tires and used motor oil
US5569801A (en) * 1992-08-27 1996-10-29 Fina Research, S.A. Polymer conversion process
US5288934A (en) * 1992-08-27 1994-02-22 Petrofina, S.A. Process for the conversion of polymers
US5301834A (en) * 1993-01-21 1994-04-12 The Lift Ticket Card vending machine
US5799626A (en) * 1993-01-28 1998-09-01 Ponsford; Thomas E. Methods for using styrene oil (as heat transfer fluid, hydraulic fluid, lubricant)
US5406010A (en) * 1993-01-28 1995-04-11 Ponsford; Thomas E. Method of reclaiming styrene and other products from polystyrene based products
US5639934A (en) * 1993-04-01 1997-06-17 Nakamichi Yamasaki Process for the desulfurization of sulfur-containing compositions by hydrothermal reaction
DE4411483C2 (de) * 1993-04-01 2002-10-24 Nakamichi Yamasaki Verfahren zur Entschwefelung von schwefelhaltigen Zusammensetzungen durch hydrothermale Reaktion
DE4447937C2 (de) * 1993-04-01 2002-12-05 Nakamichi Yamasaki Verfahren zur Umwandlung vulkanisierter Kautschuke in Öle unter Verwendung überkritischer wässriger Flüssigkeiten
US5395404A (en) * 1993-08-27 1995-03-07 The Jerrold Corporation Apparatus for pyrolyzing tires
US5445659A (en) * 1993-10-04 1995-08-29 Texaco Inc. Partial oxidation of products of liquefaction of plastic materials
EP0722480B1 (fr) * 1993-10-04 2000-04-19 Texaco Development Corporation Liquefaction et oxydation partielle de materiaux plastiques
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US5824193A (en) * 1997-03-27 1998-10-20 Edwards; Raymond S. Method of thermally treating plastics material
US5977294A (en) * 1997-05-13 1999-11-02 Prs, Llc Polymer deformulation by solvent solution filtration
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US6143940A (en) * 1998-12-30 2000-11-07 Chevron U.S.A. Inc. Method for making a heavy wax composition
JP2003041045A (ja) * 2001-07-26 2003-02-13 Yokohama Rubber Co Ltd:The ゴム成形品からの材料回収方法および回収材料
US7048832B2 (en) * 2002-01-07 2006-05-23 Material Conversion Corp. Method and system for extracting hydrocarbon fuel products from plastic material
US6822126B2 (en) * 2002-04-18 2004-11-23 Chevron U.S.A. Inc. Process for converting waste plastic into lubricating oils
US6774272B2 (en) 2002-04-18 2004-08-10 Chevron U.S.A. Inc. Process for converting heavy Fischer Tropsch waxy feeds blended with a waste plastic feedstream into high VI lube oils
US6703535B2 (en) * 2002-04-18 2004-03-09 Chevron U.S.A. Inc. Process for upgrading fischer-tropsch syncrude using thermal cracking and oligomerization
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EA010464B1 (ru) * 2004-02-26 2008-08-29 Игорь Антонович Рожновский Устройство для переработки углеродсодержащих отходов
US7893307B2 (en) * 2007-02-23 2011-02-22 Smith David G Apparatus and process for converting feed material into reusable hydrocarbons
US20090007484A1 (en) * 2007-02-23 2009-01-08 Smith David G Apparatus and process for converting biomass feed materials into reusable carbonaceous and hydrocarbon products
US7834226B2 (en) * 2007-12-12 2010-11-16 Chevron U.S.A. Inc. System and method for producing transportation fuels from waste plastic and biomass
US8664458B2 (en) * 2010-07-15 2014-03-04 Greenmantra Recycling Technologies Ltd. Method for producing waxes and grease base stocks through catalytic depolymerisation of waste plastics
RU2603965C2 (ru) 2011-01-05 2016-12-10 Игнайт Ресорсиз Пти Лтд Переработка органического материала
US8480880B2 (en) 2011-01-18 2013-07-09 Chevron U.S.A. Inc. Process for making high viscosity index lubricating base oils
AT511772B1 (de) 2011-05-05 2018-03-15 Omv Refining & Marketing Gmbh Verfahren und vorrichtung zur energieeffizienten aufbereitung sekundärer lagerstätten
CA3229291A1 (fr) 2013-01-17 2014-07-24 Greenmantra Recycling Technologies Ltd. Depolymerisation catalytique de matieres polymeres
US10472487B2 (en) 2015-12-30 2019-11-12 Greenmantra Recycling Technologies Ltd. Reactor for continuously treating polymeric material
BR112018016499B1 (pt) 2016-02-13 2022-03-29 Greenmantra Recycling Technologies Ltd Método para formar uma cera e empregar a referida cera para modificar asfalto
BR112018068992B1 (pt) 2016-03-24 2023-01-31 Greenmantra Recycling Technologies Ltd Método para produzir um polímero modificado com um índice de fluidez melhorado a partir de uma cera despolimerizada
EP3519487A4 (fr) 2016-09-29 2020-07-29 GreenMantra Recycling Technologies Ltd Réacteur pour le traitement de matériau de polystyrène
US10723858B2 (en) 2018-09-18 2020-07-28 Greenmantra Recycling Technologies Ltd. Method for purification of depolymerized polymers using supercritical fluid extraction
CA3164216A1 (fr) 2019-12-23 2021-07-01 Chevron U.S.A. Inc. Economie circulaire de dechets plastiques en polypropylene par l'intermediaire d'une unite fcc de raffinerie
MX2022007132A (es) 2019-12-23 2022-09-19 Chevron Usa Inc Economia circular para residuos plasticos en polipropileno a traves de craqueo catalitico de fluidos (fcc) de refineria y unidades de alquilacion.
MX2022007303A (es) 2019-12-23 2022-10-21 Chevron Usa Inc Economia circular para residuos plasticos en polietileno a traves de una unidad de crudo de refineria.
BR112022011773A2 (pt) 2019-12-23 2022-08-30 Chevron Usa Inc Economia circular para resíduos de plástico para polietileno e produtos químicos via unidade de cru de refinaría
US11518945B2 (en) 2019-12-23 2022-12-06 Chevron U.S.A. Inc. Circular economy for plastic waste to polypropylene and lubricating oil via refinery FCC and isomerization dewaxing units
JP2023508353A (ja) 2019-12-23 2023-03-02 シェブロン ユー．エス．エー． インコーポレイテッド 精製ｆｃｃ及びアルキレーションユニットを介したポリエチレンへの廃プラスチックのサーキュラーエコノミー
CA3164223A1 (fr) 2019-12-23 2021-07-01 Chevron U.S.A. Inc. Economie circulaire de dechets plastiques en polyethylene et huile lubrifiante par l'intermediaire d'unites de brut et de deparaffinage par isomerisation
US11566182B2 (en) 2020-03-30 2023-01-31 Chevron U.S.A. Inc. Circular economy for plastic waste to polyethylene via refinery FCC feed pretreater and FCC units
US11306253B2 (en) 2020-03-30 2022-04-19 Chevron U.S.A. Inc. Circular economy for plastic waste to polyethylene via refinery FCC or FCC/alkylation units
WO2021216873A1 (fr) 2020-04-22 2021-10-28 Chevron U.S.A. Inc. Économie circulaire de déchets plastiques en polypropylène par raffinage d'huile avec filtration et traitement d'oxyde métallique d'huile de pyrolyse
KR20230004713A (ko) 2020-04-22 2023-01-06 셰브런 유.에스.에이.인크. 열분해 오일의 여과 및 금속 산화물 처리가 있는 오일 정제를 통한 플라스틱 폐기물의 폴리에틸렌으로의 순환 경제
WO2024133944A1 (fr) 2022-12-23 2024-06-27 Borealis Ag Procédé de recyclage de plastique

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994020590A2 (fr) * 1993-03-10 1994-09-15 The University Of Wyoming Research Corporation Doing Business As Western Research Institute Procede de recyclage de dechets plastiques
WO1994020590A3 (fr) * 1993-03-10 1994-11-10 Univ Wyoming Procede de recyclage de dechets plastiques
US5753086A (en) * 1993-03-10 1998-05-19 The University Of Wyoming Research Corp. Process for waste plastic recycling
FR2706168A1 (fr) * 1993-04-01 1994-12-16 Yamasaki Nakamichi Procédé pour la conversion en huiles de caoutchoucs vulcanisés.
US6861568B1 (en) 1998-05-15 2005-03-01 Wyoming Research Corporation Process for waste plastic recycling
EP1770148A1 (fr) * 2005-10-03 2007-04-04 CHUNG BONG, ChOON Procédé et appareil de production d'huile à partir de déchets plastiques

Also Published As

Publication number Publication date
ES534485A0 (es) 1985-04-16
JPS6040193A (ja) 1985-03-02
EP0132612B1 (fr) 1987-09-30
DE3326284C2 (de) 1985-08-14
ES8504897A1 (es) 1985-04-16
ATE30045T1 (de) 1987-10-15
DE3326284A1 (de) 1985-02-21
US4642401A (en) 1987-02-10

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