EP0662503A1 - Procédé et installation pour la préparation d'hydrocarbures liquides à partir de déchets de plastiques à composition variable - Google Patents

Procédé et installation pour la préparation d'hydrocarbures liquides à partir de déchets de plastiques à composition variable Download PDF

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Publication number
EP0662503A1
EP0662503A1 EP94120496A EP94120496A EP0662503A1 EP 0662503 A1 EP0662503 A1 EP 0662503A1 EP 94120496 A EP94120496 A EP 94120496A EP 94120496 A EP94120496 A EP 94120496A EP 0662503 A1 EP0662503 A1 EP 0662503A1
Authority
EP
European Patent Office
Prior art keywords
extruder
melt
stirred tank
discharge zone
mixed
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.)
Withdrawn
Application number
EP94120496A
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German (de)
English (en)
Inventor
Hans Dieter Zettler
Thomas Dr. Domschke
Gerd Dr. Ehrmann
Michael Dr. Bohn
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0662503A1 publication Critical patent/EP0662503A1/fr
Withdrawn legal-status Critical Current

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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 a method according to the preamble of claim 1 and an apparatus for performing the method.
  • a method of this type is known from WO 91/18960.
  • High-polymer waste products are then converted by melting them in an extruder and then decomposing the melt into gaseous and / or liquid fuels inside or outside the extruder.
  • This product degradation takes place by supplying heat and by adding reactive gases such as oxygen and / or hydrogen and / or water vapor.
  • reactive gases such as oxygen and / or hydrogen and / or water vapor.
  • the extruder due to the high temperatures of approximately 400 ° C., releases HCl and, due to abrasion, shows signs of corrosion relatively quickly.
  • plastic waste can only be processed separately according to fractions.
  • Visbreaking which is widespread in the petroleum industry in connection with a stirred tank, is also known for processing mixed plastic waste. Visbreaking is a pressure-free, thermal cracking process and enables the viscosity of highly viscous oily residues to be reduced (Ullmanns Encyklopadie der Technische Chemie, 4th edition, 1975, Verlag Chemie, Weinheim / Bergstr.). This process can also be carried out in a stirred tank in order to convert small-scale plastic waste of different composition into a recoverable oil (H. Hammer, G. Rauser, "Hydrogenating Liquefaction of Plastic Waste", lecture on May 6, 1992 at the German Plastic Recycling Congress Industry forum for technology in Würzburg).
  • the relatively long residence time of the melt in the stirred tank is disadvantageous in order to achieve the low viscosity required for stirring in the plastic waste. Due to dosing problems, the dissolution time and bonding phenomena, the plastic waste must also be reduced to a particle size of ⁇ 1 mm.
  • the invention is intended to create a process for the production of liquid hydrocarbons from plastic waste of different compositions, according to which problematic waste, in particular chlorine-containing plastic parts, is disposed of in an environmentally compatible and highly economical manner and the liquid hydrocarbons are fed directly to further petrochemical processing can be.
  • a device for performing the method is to be specified.
  • plastic waste of different compositions is melted in an extruder, for example plastic waste such as is accumulated in the collection of plastic packaging by the Dual System Germany or plastic parts from automobiles or electrical appliances.
  • plastic waste such as is accumulated in the collection of plastic packaging by the Dual System Germany or plastic parts from automobiles or electrical appliances.
  • Largely unpurified, shredded plastic waste in the size of about 10 to 30 mm can be used.
  • the plastic waste melts at ⁇ 350 ° C, so that only small amounts of HCl and pyrrolysis gases are formed.
  • a throughput-limiting degassing in the extruder is not necessary. Corrosion phenomena practically do not occur.
  • the melt formed in the extruder is subsequently passed into and through at least two stirred tanks and is decomposed there into gaseous and liquid components, the temperature of the melt in the first stirred tank being about 300 ° C. to 350 ° C. and in the second stirred tank being about 350 ° C. to 450 ° C is increased.
  • HCl and pyrolysis gases are removed in particular in the first stirred tank - seen in the product flow direction.
  • this stirred tank contains appropriate facilities, e.g. Strand degasser, stopper tube degasser, thin film evaporator or falling film evaporator.
  • An essential feature of the invention is that a partial flow of the degassed melt from the first stirred tank is returned to the discharge zone of the extruder and / or mixed with the melt discharged from the extruder.
  • already degraded, low-viscosity product is returned to the extruder.
  • the melt reaches the nozzle plate of the strand degasser with an adjustable or adjustable viscosity and temperature and thus into the first stirred tank. In this way, an optimal strand thickness and a significantly better stirrability than without backmixing can be achieved, the process is more reliable.
  • it has proven to be expedient if up to 95% by weight of melt is returned from the first stirred tank into this and / or into the extruder.
  • degassed melt can also be returned from the second stirred tank into the discharge zone of the extruder and / or mixed with the melt discharged from the extruder or with degassed melt from the first stirred tank.
  • the degassing of the melt is carried out in the form of strand degassing. It is advantageous that a viscosity of 10 - 50 Pas, a temperature of 300 - 350 ° C and a strand diameter of 1 - 3 mm can be set by appropriate selection of the nozzle geometry and the return ratio.
  • the device for carrying out the method according to the invention is characterized in that there is no need for finely divided grinding of the plastic waste, the cleaning effort remains low and the viscosity is quickly reduced by premature mixing with the degradation product.
  • the device shown in the drawing comprises an extruder (1), two stirred tanks (4) and (14), a mixer (11, 13) being arranged in front of the stirred tanks, of which the mixer (13) is heatable , and a filter (21).
  • Mixed, unpurified plastic waste with a particle size of ⁇ 30 mm is metered into the extruder (1).
  • the extruder (1) is designed in the feed zone (2) as a counter-rotating, positive-feeding twin screw and in the melting and discharge zone (3) as a single screw. This arrangement ensures good feed behavior, which is necessary to cope with the DSD feed material due to its low density.
  • the worm shafts have a diameter of 50-600 mm, preferably 100-400 mm; their speed is about 5 - 100 min ⁇ 1, preferably 10 - 50 min ⁇ 1.
  • the feed zone (2) is generally heated to 0-60 ° C., preferably 10-40 ° C.
  • the temperature of the melting and discharge zone (3) is between 200 and 350 ° C, preferably 250 - 300 ° C.
  • the throughput is 50 to 50,000 kg / h, preferably 100 to 20,000 kg / h.
  • the plastic wastes melted in the extruder are fed to the first stirred tank (4) and thermally broken down, degassed and largely dechlorinated in the latter, with strand degassing (5) being carried out in the stirred tank.
  • the strand degassing area per kg of plastic melt is between 10 ⁇ 4 and 2 ⁇ 10 ⁇ 4 m2.
  • the residence time of the melt in the stirred tank is 5-60 min, preferably 10-40 min.
  • Pressure control is carried out at the top of the stirred tank the released HCl and pyrrolysis gases are drawn off, subjected to a neutralizing gas scrubber and then used for process energy generation (not shown in the drawing).
  • the stirred tank (4) is pressure-resistant, heatable and provided with a wall-mounted stirrer (6), e.g. Speed of 5 - 50 min ⁇ 1 ensures good vertical mixing. It is heated to 300 - 350 ° C, whereby a pressure of 100 - 900 mbar is set.
  • the melt is discharged via a heatable pump (7), for example via a thick matter pump.
  • a partial flow of the melt from the first stirred tank is returned via the return lines (8) and (9) and / or (10) to the discharge zone (3) of the extruder or mixed with the melt discharged from the extruder.
  • a mixer (11) is provided in the pipeline (12) connecting the extruder (1) to the stirred tank (4). Such mixers are commercially available.
  • the type SMR mixing reactors from Gebrüder Sulzer Aktiengesellschaft, Winterthur, Switzerland are particularly suitable.
  • the ratio between the returned partial flow of the melt and the total melt discharge from the first stirred tank can vary within wide limits. Up to 95% of the melt discharge can be returned.
  • the melt portion which is not returned is conveyed via the heatable mixer (13) into the second stirred tank (14).
  • the melt is heated by 10-100 ° C, preferably 10-60 ° C and optionally mixed with melt from the second stirred tank.
  • the melt mixture is then thermally broken down in the second stirred tank (14), i.e. freed of volatile constituents at a temperature of about 350-450 ° C.
  • the pressure-resistant and heatable stirred tank contains a stirrer (15) which can be passed through the wall, e.g. Helix, the angular speed of which is about 5 - 50 min ⁇ 1.
  • the pressure in the stirred tank (14) is approximately 600-900 mbar, the residence time of the melt is approximately 5-60 min, preferably 10-40 min.
  • the gases released in the stirred tank are removed at (16).
  • the melt is discharged from the stirred tank (14) with the aid of a heatable pump (17), for example a thick matter pump, with up to 95% by weight of melt being returned to the extruder (1) via the pipes (18, 20, 10) and / or can be mixed with melt from the extruder and / or the pipes (18, 19) with melt from the first stirred tank via the pipes (18, 20, 9).
  • the melt which is not returned is discharged through the filter (21).
  • the melt has a thin consistency. Its viscosity is approximately 0.1 - 10 Pa ⁇ s at a temperature of around 370 - 430 ° C.
  • gap filters or separating heads can be considered as filters.

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)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
EP94120496A 1994-01-07 1994-12-23 Procédé et installation pour la préparation d'hydrocarbures liquides à partir de déchets de plastiques à composition variable Withdrawn EP0662503A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944400327 DE4400327A1 (de) 1994-01-07 1994-01-07 Verfahren und Vorrichtung zur Herstellung flüssiger Kohlenwasserstoffe aus Kunststoffabfall unterschiedlicher Zusammensetzung
DE4400327 1994-01-07

Publications (1)

Publication Number Publication Date
EP0662503A1 true EP0662503A1 (fr) 1995-07-12

Family

ID=6507573

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94120496A Withdrawn EP0662503A1 (fr) 1994-01-07 1994-12-23 Procédé et installation pour la préparation d'hydrocarbures liquides à partir de déchets de plastiques à composition variable

Country Status (2)

Country Link
EP (1) EP0662503A1 (fr)
DE (1) DE4400327A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737649A2 (fr) * 1995-04-15 1996-10-16 Buna Sow Leuna Olefinverbund GmbH Procédé d'élimination de PVC, afin d'extraire de préférence du gaz hydrochlorique épuré et/ou pur
EP0812899A2 (fr) * 1996-06-11 1997-12-17 Nkk Corporation Procédé et dispositif pour l'élimination d'une matière synthétique résineuse
WO2005028593A1 (fr) * 2003-09-25 2005-03-31 Beijing Dragon New Energy Technology Ltd. Procede industrialise et dispositif servant a la production d'essence et de gazole a partir de dechets de plastique
WO2009086908A1 (fr) * 2008-01-05 2009-07-16 Relux Umwelt Gmbh Procédé et dispositif de production de distillat moyen à partir de porteurs d'énergie renfermant des hydrocarbures
WO2010106399A3 (fr) * 2009-03-14 2010-12-23 Clariter Poland Sp. Zo. O. Appareil pour réaliser la thermolyse de déchets plastiques et procédé de thermolyse en continu
WO2023049040A1 (fr) * 2021-09-21 2023-03-30 Eastman Chemical Company Contact direct d'effluent de pyrolyse et de matières plastiques liquéfiées dans des installations chimiques
US11801140B2 (en) 2019-11-14 2023-10-31 Evalve, Inc. Catheter assembly with coaptation aid and methods for valve repair

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2137664A1 (fr) * 1971-05-10 1972-12-29 Niigata Engineering Co Ltd
WO1991018960A1 (fr) * 1990-05-26 1991-12-12 Georg Menges Procede et dispositif de recuperation de dechets organiques
WO1993018112A1 (fr) * 1992-03-13 1993-09-16 Rwe Entsorgung Aktiengesellschaft Procede de fabrication d'olefines

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2137664A1 (fr) * 1971-05-10 1972-12-29 Niigata Engineering Co Ltd
WO1991018960A1 (fr) * 1990-05-26 1991-12-12 Georg Menges Procede et dispositif de recuperation de dechets organiques
WO1993018112A1 (fr) * 1992-03-13 1993-09-16 Rwe Entsorgung Aktiengesellschaft Procede de fabrication d'olefines

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0737649A2 (fr) * 1995-04-15 1996-10-16 Buna Sow Leuna Olefinverbund GmbH Procédé d'élimination de PVC, afin d'extraire de préférence du gaz hydrochlorique épuré et/ou pur
EP0737649A3 (fr) * 1995-04-15 1997-02-05 Buna Sow Leuna Olefinverb Gmbh Procédé d'élimination de PVC, afin d'extraire de préférence du gaz hydrochlorique épuré et/ou pur
EP0812899A2 (fr) * 1996-06-11 1997-12-17 Nkk Corporation Procédé et dispositif pour l'élimination d'une matière synthétique résineuse
EP0812899A3 (fr) * 1996-06-11 1998-11-18 Nkk Corporation Procédé et dispositif pour l'élimination d'une matière synthétique résineuse
US6048380A (en) * 1996-06-11 2000-04-11 Nkk Corporation Method for disposing synthetic resinous material
US6221311B1 (en) 1996-06-11 2001-04-24 Nkc Corporation Apparatus for disposing synthetic resinous materials
WO2005028593A1 (fr) * 2003-09-25 2005-03-31 Beijing Dragon New Energy Technology Ltd. Procede industrialise et dispositif servant a la production d'essence et de gazole a partir de dechets de plastique
WO2009086908A1 (fr) * 2008-01-05 2009-07-16 Relux Umwelt Gmbh Procédé et dispositif de production de distillat moyen à partir de porteurs d'énergie renfermant des hydrocarbures
WO2010106399A3 (fr) * 2009-03-14 2010-12-23 Clariter Poland Sp. Zo. O. Appareil pour réaliser la thermolyse de déchets plastiques et procédé de thermolyse en continu
US8680349B2 (en) 2009-03-14 2014-03-25 Clariter Ip S.A. Apparatus for conducting thermolysis of plastic waste in a continuous manner
US9376632B2 (en) 2009-03-14 2016-06-28 Clariter Ip S.A. Apparatus for conducting thermolysis of plastic waste and method of thermolysis in continuous manner
US11801140B2 (en) 2019-11-14 2023-10-31 Evalve, Inc. Catheter assembly with coaptation aid and methods for valve repair
WO2023049040A1 (fr) * 2021-09-21 2023-03-30 Eastman Chemical Company Contact direct d'effluent de pyrolyse et de matières plastiques liquéfiées dans des installations chimiques

Also Published As

Publication number Publication date
DE4400327A1 (de) 1995-07-13

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