EP2184334A1 - Procédé et dispositif de recyclage de matériaux contenant de l'hydrocarbure - Google Patents

Procédé et dispositif de recyclage de matériaux contenant de l'hydrocarbure Download PDF

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Publication number
EP2184334A1
EP2184334A1 EP08019151A EP08019151A EP2184334A1 EP 2184334 A1 EP2184334 A1 EP 2184334A1 EP 08019151 A EP08019151 A EP 08019151A EP 08019151 A EP08019151 A EP 08019151A EP 2184334 A1 EP2184334 A1 EP 2184334A1
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EP
European Patent Office
Prior art keywords
reactor
tubular reactor
materials
tubular
pyrolysis
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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.)
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EP08019151A
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German (de)
English (en)
Inventor
Peter Spörri
Emin Sarial
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Individual
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Individual
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Priority to EP08019151A priority Critical patent/EP2184334A1/fr
Publication of EP2184334A1 publication Critical patent/EP2184334A1/fr
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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

Definitions

  • the invention relates to processes and systems for hydrocarbon-containing materials, in particular rubber-based materials (such as. Waste tires) to recycle by means of pyrolysis.
  • WO92 / 0176 a process for the recycling of car tires, in which in the presence of an oxygen-containing atmosphere at temperatures between 180 and 260 ° C car tires are pyrolyzed to form liquid and gaseous hydrocarbons.
  • This document further discloses a plant for carrying out this process, wherein the pyrolysis reactor is arranged vertically and is heated by partial combustion of the starting material autothermally.
  • US5505008 a discontinuous process for recycling hydrocarbon-containing materials, eg. Car tires, in which under inert atmosphere, reduced pressure of 0.1 - 40 mbar and temperatures of at least 200 ° C, the starting materials are reacted discontinuously.
  • This document further discloses a plant for carrying out this process, wherein the pyrolysis reactor is not specified more precisely.
  • GB2278606 also discloses a process for recycling rubber waste in which comminuted particles are reacted in the presence of 16-80% by weight of additives at 100-200 ° C in a stirred reactor to yield a rubber-like material as the final product. This Process causes no decomposition of the starting material but a return to reusable rubbery material. This document further discloses a plant for carrying out this process, wherein the reactor is designed as a stirred tank.
  • the present invention is therefore based on the object of providing an improved process for recycling hydrocarbon-containing materials, in particular rubber-based materials, and systems suitable therefor.
  • the invention relates to a continuous process for the pyrolysis of hydrocarbonaceous materials to form solid carbon (especially soot) and volatile hydrocarbons, characterized in that a) the hydrocarbonaceous materials under inert atmosphere, at normal or Underpressure in a tubular reactor containing means for conveying and mixing, subjected to a time and temperature graded treatment; b) the volatile hydrocarbons formed in step a) are removed at one or more points along the longitudinal axis of said tubular reactor; c) the solid carbon formed in step a) is removed after cooling at the end of said tubular reactor.
  • the inventive method is designed continuously, i. Starting material is constantly fed to the tubular reactor at one end and products (solid carbon and volatile hydrocarbons) are continuously withdrawn from the tube reactor.
  • the starting material is fed comminuted.
  • the method according to the invention is carried out in a time scale, i. the residence time of the materials in the various steps is predetermined and adapted to the particular situation.
  • the residence time can be determined or varied by the design of the tubular reactor, such as its dimenization or the design of a screw conveyor.
  • the process according to the invention is particularly suitable for recycling rubber-based materials, in particular rubber-based, vulcanized materials, for example old tires.
  • the inventive method is also particularly suitable for recycling hydrocarbon-containing materials, such as PS fittings.
  • An advantage of the process according to the invention is the resulting product mix of volatile hydrocarbons and solid carbon. Furthermore, it is to be regarded as advantageous that the method according to the invention is very flexible with regard to further components. Thus, the method is feasible with and without the addition of catalysts and with and without the addition of other auxiliaries.
  • the residence time in the tubular reactor can be varied within a wide range and can in principle be determined in simple series experiments. Residence times of from 0.5 to 24 hours, preferably from 4 to 10 hours, have proved to be advantageous. The residence times can be adjusted by the means for conveying and sizing the reactor.
  • the reaction temperatures in the reactor can be varied within a wide range.
  • the heating of the reactor takes place e.g. allothermic, preferably by means of a circulating carrier oil.
  • the temperatures realized are in the range between 20 ° C (room temperature) and about 1100 ° C (preferably: 20 - 500 ° C).
  • Reaction in the reactor is "temperature-graded", i. the temperature is varied along the reactor longitudinal axis.
  • the temperatures are selected so that the steps "carbonization", “finishing” and “post-treatment” occur in successive zones of the tubular reactor.
  • the temperature is chosen so that the refining takes place at higher temperatures and the aftertreatment at lower temperatures than the carbonization.
  • the following temperature ranges have proven to be advantageous: For the carbonization to 500 ° C (preferably: 350 ° C); for refining up to 1100 ° C (preferably: 450 ° C).
  • the aftertreatment is conducted in an advantageous embodiment so that the solid reaction product leaves the reactor at a maximum of 100.degree. Suitable reaction temperatures are naturally related to the (sub) pressure of the plant, wherein a lower pressure in the system also allows lower reaction temperatures.
  • a temperature profile can likewise be impressed, for example, fluctuating between 80 and 300 ° C. during the carbonization and continuously decreasing from 400 ° C. to 80 ° C. in the after-treatment.
  • the reaction pressure in the reactor can be varied in a wider range.
  • a suitable reaction pressure the range of -100 - +800 mbar, in particular 400 - 600 mbar has been found.
  • the reaction pressure can be generated by vacuum pumps, which with the Points communicate to remove the liquid hydrocarbons.
  • the invention in a second aspect , relates to a plant for the pyrolysis of rubber-based materials, comprising one or more tubular reactors, these tubular reactors being equipped with i) means for supplying comminuted rubber-based materials; ii) means for conveying and mixing said rubber-based materials through the tubular reactor; iii) means for removing formed gaseous hydrocarbons disposed along the longitudinal axis of the tubular reactor; (iv) means of removal of solid carbon formed; v) means for indirect temperaturgraduften heating and wherein said tubular reactors are designed so that they can be operated under inert atmosphere, at normal or negative pressure.
  • Suitable reactors are known per se, for example rotary kilns or screw reactors. Particularly suitable are screw reactors. Such reactors may have baffles which cause a promotion and mixing. In the case of screw reactors, mixing and conveying takes place exclusively or additionally through the central auger. The pitch of the screw can be constant over the entire length or vary, so as to adjust the residence time.
  • the supply of the starting material and the removal of the solid carbon can be done by common devices, such as cyclo and other equipment.
  • the removal of the volatile hydrocarbons can also be done by conventional devices, for example. Via valves that communicate with capacitors and vacuum pumps. Suitable devices and equipment are known in the art and may be selected and designed by those skilled in the art.
  • the tubular reactor is arranged horizontally or nearly horizontally (i.e., +/- 10 °). Such an arrangement has the advantage over a vertical arrangement that a controlled homogenized process is achieved.
  • the tubular reactor is subdivided into three or more interconnected partial reactors.
  • the subdivision preferably takes place in three partial reactors.
  • the carbonization is carried out in the first part reactor, the refining in the second part reactor and the aftertreatment in the third part reactor.
  • means for removing volatile hydrocarbons are provided only in the first and second part of the reactor. Further, only the first part reactor contains means for feeding crushed rubber-based materials and only the third part reactor means for removing formed solid carbons.
  • the tubular reactor is subdivided into three or more interconnected partial reactors (phases), these partial reactors being arranged one below the other, such that the feed takes place at the upper part reactor and the removal takes place at the lower part reactor.
  • the pyrolysis plant according to the invention are assigned further secondary plants in order to carry out the process described here. Particular mention should be made of: devices for generating the desired reaction pressure (over-, under-, normal pressure); Apparatus for isolating and separating the generated liquid hydrocarbons; Storage container for the starting material; Reservoir for the generated solid carbon. These individual devices are known per se and can be designed and adapted by the person skilled in the art.
  • means for recovering energy e.g., heat exchangers
  • the energy for heating the plant can be obtained from the recovered volatile hydrocarbons.
  • FIG. 1 Showing: 1 Pyrolysis plant for rubber-based materials 2 Screw reactor consisting of three partial reactors, Schwelung 21, finishing 22 and after-treatment 23 24 Volatile hydrocarbon removal agent and vacuum connection 25 Means for feeding shredded rubber-based materials 26 Snail for conveying and mixing 27 Means for removing formed solid carbons 28 Double-walled version for indirect heating 3 Plant for the supply of rubber-based materials 31 reservoir 32 conveyor belt 33 intermediate container 4 Plant for storage and delivery of the soot formed 41 reservoir 42 Auger 43 Auger
  • a corresponding plant for the processing of hydrocarbon-containing materials is similar to the one in Fig. 1 shown construction, wherein (3) and (25) are modified accordingly.
  • a plant according to Fig. 1 In a plant according to Fig. 1
  • two identically dimensioned tubular reactors in each case 10 tons of shredded old tires, are continuously converted per day. This typically gives: 7 t of soot; 10 t volatile hydrocarbons (1 t gas, 9 t liquid hydrocarbons); 3 t of waste steel. While preferred embodiments of the invention are described in the present application, it is to be understood that the invention is not limited thereto and may be embodied otherwise within the scope of the following claims.

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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)
EP08019151A 2008-10-31 2008-10-31 Procédé et dispositif de recyclage de matériaux contenant de l'hydrocarbure Withdrawn EP2184334A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08019151A EP2184334A1 (fr) 2008-10-31 2008-10-31 Procédé et dispositif de recyclage de matériaux contenant de l'hydrocarbure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08019151A EP2184334A1 (fr) 2008-10-31 2008-10-31 Procédé et dispositif de recyclage de matériaux contenant de l'hydrocarbure

Publications (1)

Publication Number Publication Date
EP2184334A1 true EP2184334A1 (fr) 2010-05-12

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EP08019151A Withdrawn EP2184334A1 (fr) 2008-10-31 2008-10-31 Procédé et dispositif de recyclage de matériaux contenant de l'hydrocarbure

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013187788A2 (fr) 2012-06-12 2013-12-19 DAGAS Sp. z.o.o. Procédé de pyrolyse de déchets de matière et/ou de caoutchouc et/ou organiques et installation de mise en œuvre de ce procédé
CN106701131A (zh) * 2015-11-13 2017-05-24 张瑞永 具有三段式反应炉系统的连续式热脱附及裂解设备
CN112973578A (zh) * 2021-03-16 2021-06-18 江西诺邦生物科技有限公司 一种消毒剂生产用低温干馏提取装置
IT202100033053A1 (it) 2021-12-30 2023-06-30 Versalis Spa Processo di pirolisi per la produzione di un olio di pirolisi adatto al riciclo a ciclo chiuso (“closed loop recycling”), relativo apparato, prodotto ed uso del medesimo
IT202100033044A1 (it) 2021-12-30 2023-06-30 Versalis Spa Procedimento per la pirolisi di materiale sostanzialmente plastico di composizione non costante, relativo reattore, apparato e prodotto ottenuto
IT202100033059A1 (it) 2021-12-30 2023-06-30 Versalis Spa Metodo per monitorare un parametro di controllo su un materiale sostanzialmente plastico, relativo apparato e processo di pirolisi che impiega detto metodo

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US689768A (en) * 1901-04-29 1901-12-24 James A Wathen Continuous vacuum distilling, drying, and evaporating machine.
US3787292A (en) * 1971-08-13 1974-01-22 E Keappler Apparatus for pyrolysis of wastes
WO1992001767A2 (fr) 1990-07-26 1992-02-06 Munger Joseph H Procede de recyclage, appareil et produit fabrique au moyen de ce procede, et fabrication d'un agent diluant/plastifiant a partir de pneumatiques de voitures usages
WO1994010507A1 (fr) * 1992-10-28 1994-05-11 Alf Johansson Procede de recuperation en continu de materiau tel que le caoutchouc et installation d'exploitation de ce procede
GB2278606A (en) 1993-06-04 1994-12-07 Yu Chun An Dry process for recycling rubber waste
US5389691A (en) * 1993-09-07 1995-02-14 Univ. Of Wyoming Process for co-recycling tires and oils
US5505008A (en) 1993-06-29 1996-04-09 Leybold Durferrit Gmbh Method for recycling materials containing plastic, rubber or lacquer
WO2000053385A1 (fr) * 1999-03-09 2000-09-14 Svedala Industries, Inc. Processus de pyrolyse permettant de recuperer des matieres souhaitables de pneus de vehicules
WO2002031082A1 (fr) * 2000-10-10 2002-04-18 Rj Lee Group, Inc. Appareil d'alimentation et de collecte discontinues en tandem pour pyrolyse continue du caoutchouc et/ou d'un autre materiau a base d'hydrocarbure -
WO2005078049A1 (fr) * 2004-02-18 2005-08-25 Technologie Ekologiczne Procede et dispositif pour la conversion continue de dechets organiques
WO2006119594A1 (fr) * 2005-05-09 2006-11-16 Dimitar Nikolaev Kolev Procede et installation pour la pyrolyse de pneus
US20060280669A1 (en) * 2005-06-10 2006-12-14 Jones Fred L Waste conversion process

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US689768A (en) * 1901-04-29 1901-12-24 James A Wathen Continuous vacuum distilling, drying, and evaporating machine.
US3787292A (en) * 1971-08-13 1974-01-22 E Keappler Apparatus for pyrolysis of wastes
WO1992001767A2 (fr) 1990-07-26 1992-02-06 Munger Joseph H Procede de recyclage, appareil et produit fabrique au moyen de ce procede, et fabrication d'un agent diluant/plastifiant a partir de pneumatiques de voitures usages
WO1994010507A1 (fr) * 1992-10-28 1994-05-11 Alf Johansson Procede de recuperation en continu de materiau tel que le caoutchouc et installation d'exploitation de ce procede
GB2278606A (en) 1993-06-04 1994-12-07 Yu Chun An Dry process for recycling rubber waste
US5505008A (en) 1993-06-29 1996-04-09 Leybold Durferrit Gmbh Method for recycling materials containing plastic, rubber or lacquer
US5389691A (en) * 1993-09-07 1995-02-14 Univ. Of Wyoming Process for co-recycling tires and oils
WO2000053385A1 (fr) * 1999-03-09 2000-09-14 Svedala Industries, Inc. Processus de pyrolyse permettant de recuperer des matieres souhaitables de pneus de vehicules
WO2002031082A1 (fr) * 2000-10-10 2002-04-18 Rj Lee Group, Inc. Appareil d'alimentation et de collecte discontinues en tandem pour pyrolyse continue du caoutchouc et/ou d'un autre materiau a base d'hydrocarbure -
WO2005078049A1 (fr) * 2004-02-18 2005-08-25 Technologie Ekologiczne Procede et dispositif pour la conversion continue de dechets organiques
WO2006119594A1 (fr) * 2005-05-09 2006-11-16 Dimitar Nikolaev Kolev Procede et installation pour la pyrolyse de pneus
US20060280669A1 (en) * 2005-06-10 2006-12-14 Jones Fred L Waste conversion process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013187788A2 (fr) 2012-06-12 2013-12-19 DAGAS Sp. z.o.o. Procédé de pyrolyse de déchets de matière et/ou de caoutchouc et/ou organiques et installation de mise en œuvre de ce procédé
EP2679654A1 (fr) 2012-06-12 2014-01-01 DAGAS Sp. z o.o. Procédé de conduite d'un processus de pyrolyse de déchets de matières plastiques et/ou de caoutchouc et/ou organiques et installation pour la mise en oeuvre du procédé
CN106701131A (zh) * 2015-11-13 2017-05-24 张瑞永 具有三段式反应炉系统的连续式热脱附及裂解设备
CN106701131B (zh) * 2015-11-13 2020-10-30 张瑞永 具有三段式反应炉系统的连续式热脱附及裂解设备
CN112973578A (zh) * 2021-03-16 2021-06-18 江西诺邦生物科技有限公司 一种消毒剂生产用低温干馏提取装置
IT202100033053A1 (it) 2021-12-30 2023-06-30 Versalis Spa Processo di pirolisi per la produzione di un olio di pirolisi adatto al riciclo a ciclo chiuso (“closed loop recycling”), relativo apparato, prodotto ed uso del medesimo
IT202100033044A1 (it) 2021-12-30 2023-06-30 Versalis Spa Procedimento per la pirolisi di materiale sostanzialmente plastico di composizione non costante, relativo reattore, apparato e prodotto ottenuto
IT202100033059A1 (it) 2021-12-30 2023-06-30 Versalis Spa Metodo per monitorare un parametro di controllo su un materiale sostanzialmente plastico, relativo apparato e processo di pirolisi che impiega detto metodo

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