EP0138213A2 - Procédé de pyrolyse de résidus d'hydrogénation du charbon - Google Patents

Procédé de pyrolyse de résidus d'hydrogénation du charbon Download PDF

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Publication number
EP0138213A2
EP0138213A2 EP84112303A EP84112303A EP0138213A2 EP 0138213 A2 EP0138213 A2 EP 0138213A2 EP 84112303 A EP84112303 A EP 84112303A EP 84112303 A EP84112303 A EP 84112303A EP 0138213 A2 EP0138213 A2 EP 0138213A2
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EP
European Patent Office
Prior art keywords
hydrogenation
screw machine
smoldering
residue
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
EP84112303A
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German (de)
English (en)
Other versions
EP0138213B1 (fr
EP0138213A3 (en
Inventor
Lothar Ing. Grad. Winckler
Klaus Dr. Dipl.-Chem. Fuhrmann
Ulrich Dr. Dipl.-Ing. Graeser
Peter Dipl.-Ing. Wenning
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.)
Veba Oel Technologie und Automatisierung GmbH
Original Assignee
Veba Oel Technologie und Automatisierung GmbH
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.)
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Publication date
Application filed by Veba Oel Technologie und Automatisierung GmbH filed Critical Veba Oel Technologie und Automatisierung GmbH
Publication of EP0138213A2 publication Critical patent/EP0138213A2/fr
Publication of EP0138213A3 publication Critical patent/EP0138213A3/de
Application granted granted Critical
Publication of EP0138213B1 publication Critical patent/EP0138213B1/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
    • C10G1/02—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
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
    • C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws

Definitions

  • coal is hydrogenated by reaction with hydrogen at temperatures of 250-550 ° C., preferably 350-490 ° C. and pressures of 50-700 bar, preferably 100-350 bar, in particular in the presence of catalysts becomes.
  • the products produced are solid or viscous hydrogenation residues at room temperature.
  • Both hard coal and lignite can be used in the hydrogenation (see W. Krönig, "The catalytic hydrogenation of coal, tars and mineral oils", Springer Verlag, Berlin, Göttingen, Heidelberg 1950).
  • the corresponding technologies were developed and used for technical maturity in the years 1920-1945.
  • the hydrogenation technologies according to BERGIUS-PIER and POTT-BROCHE are to be mentioned as basic processes.
  • the oils obtained can be used as grinding oils or grinding oil components for the coal. Smoldering was carried out in ball ovens or screw ovens. During the smoldering process, even the per se vaporizable oils are broken down pyrolytically, so that there is a loss of valuable hydrogenation products.
  • the evaporable oils can be removed by vacuum distillation of the hydrogenation residue.
  • the oils obtained are high-quality rubbing oils or can be further hydrated under relatively mild conditions. However, handling the vacuum residue poses considerable problems. The discharge from the vacuum is particularly effective umkolonne and the transport for further processing extremely difficult due to the high toughness of the highly solids-enriched material.
  • the object of the present invention is to overcome these difficulties and to improve the overall liquid product yield of the process. According to the invention, this is done by subjecting the residue of the carbon hydrogenation to distillation under reduced pressure in a single- or multi-shaft screw machine, in this case the evaporable components are drawn off and the remaining material is then smelted in the screw machine.
  • the hydrogenation residue which constantly increases its viscosity during the distillation and smoldering, is continuously circulated by screws and thereby passed through the distillation zone and the smoldering zone of the screw machine, the evaporable constituents first being withdrawn, then the volatile constituents obtainable by pyrolysis.
  • Single- or multi-shaft screw machines with gas or steam discharge are known, for. B. from US Pat. Nos. 1,156,096 and 2,615,199. They are used especially in plastics production, and are used there, inter alia, for gas or monomer removal from polymerization mixtures (see M. Herrmann, "Snail machines in process engineering", Springer Verlag, Berlin, Heidelberg, New York 1972). Although carried out on a technical scale since the beginning ten coal hydrogenation, the difficulties associated with oil separation were known, vacuum screw machines have not been used for processing carbohydrate residues.
  • the processing of hydrogenation residues has different objectives than in the production of plastics:
  • the screw machine is part of the polymerization reactor, whereby the polymerization reaction is terminated by removing the monomers in the vacuum zone, whereas in the case of coal hydrogenation, the enrichment of solids in the hydrogenation residue is effective is.
  • pressures of 0.01 to 0.6 bar preferably 0.02 to 0.1 bar
  • the pressure drops from 0.6, preferably 0.1 bar to 0.01, preferably 0.02, over the length of the screw machine from the entry of the hydrogenation sludge to its exit. This measure reduces the risk of disturbances in the distillation process in the screw machine.
  • the distillation of the hydrogenation residue in the screw machine is carried out in particular at temperatures of 200-400 ° C., preferably 250-350 ° C.
  • the temperature increases over the length of the screw machine from the entry to the exit of the hydrogenation residue from 200, preferably 250 ° C to 400, preferably 350 ° C under constant or falling over the length of the screw machine pressure. This shortens the time during which the hydrogenation residue assumes high temperatures which favor changes and facilitates the further processing of the residue freed from the volatile constituents.
  • the non-evaporated material is heated to higher temperatures, preferably 350-600 ° C., and smelted at these temperatures, in particular at atmospheric pressure or at a pressure below it.
  • the screw machine expediently has a smoldering zone in addition to the distillation zone, into which the hydrogenation residue is conveyed through the screws after passing through the former.
  • the resulting sulfur fumes are extracted separately from the oil vapors.
  • the resulting coke can finally z. B. can be used as fuel. Residues up to a final viscosity of approximately 2000 mPas (250 ° C.) can be handled in the distillate removal by the process according to the invention.
  • the gaseous oils withdrawn from the screw machine are expediently used as grating oils or with the other hydrogenating oils, e.g. B. combines the hot separator leaving gaseous hydrogenation products and together with these further treatment, for. B. subjected to a hydrogenation.
  • the present method is suitable for processing all hydrogenation residues which occur in high-pressure coal hydrogenation processes in which coal is mashed with grinding oil and reacted together with hydrogen hydrogen and, if appropriate, in the presence of a catalyst at elevated pressure and elevated temperature, for example by the so-called Bergius-Pier process .
  • a typical gas flame coal of the Ruhr area is mashed with a grinding oil returned from the process and fed together with the hydrogenation hydrogen and with the addition of an iron catalyst at 300 bar and 470 ° C after preheating via line 1 under process pressure hydrogenation reactor 2.
  • the reaction product leaves the reactor 2 via line 3 and is fed to the hot separator 4, in which, under process pressure and at 460 ° C., the products volatile under the prevailing conditions are separated from the solid or liquid reaction products.
  • a vacuum of 0.1 bar is generated in the screw machine 7, which is equipped with a twin screw, via a vacuum line 14.
  • the hydrogenation residue used, which is fed via nozzle 8 to the screw machine 7, contained 0.5 t of oil with a boiling point of 325 ° C. or above, 0.15 t of higher molecular components, which were about 0.1 t as asphaltenes and about 0 , 05 t were determined as pre-asphaltenes, and 0.35 t of inorganic components composed of 0.24 t of ash and 0.11 t of unreacted coal.
  • the ash content was determined to be 32% by weight of SiO 2 , 26% by weight of A1 2 0 3 , 25% by weight of Fe 2 0 3 and 17% by weight of other components.
  • distillate was separated off at the pressure of 0.1 bar, the hydrogenation residue in the vacuum twin-screw machine 7 being heated from 350 to 450 ° C. during the distillate separation. 0.40 t of distillable components of the oil portion evaporated, which were drawn off via the connecting pieces 9 from the evaporation zone 18 and, after cooling (not shown), via line 10 and via condensate container 13 by means of line 15.
  • the softening point of the residue after passing through the evaporation zone 18 was 180 ° C.
  • the viscosity of the same residue at 250 ° C was determined to be 1500 mPas.
  • the distillable constituents drawn off via line 15 can be returned to the hydrogenation as valuable grinding oil components.
  • Evaporation zone 18 and smoldering zone 19 are separated by a mechanical compression stage 11, which is realized in a known manner by suitable design of the screw and the arrangement of suitable screw elements in this area. This results in a compression of the residue, which contains only 0.1 t of residual oil in addition to inorganic constituents and higher molecular weight intermediate products, before it enters the smoldering zone 19 and is heated to 600 ° C. here.
  • a mechanical compression stage 11 which is realized in a known manner by suitable design of the screw and the arrangement of suitable screw elements in this area.
  • the residue after the smoldering consisted of 87% by weight of inorganic components and 13% by weight of other residue components, in particular coke-like products, and was drawn off after passing through a compression zone 12 via connection piece 20 and line 21.
  • the screw machine was heated by means of jacket heating of the screw machine using superheated steam in the evaporation zone and flue gas in the smoldering zone.
  • the heating can also be carried out by means of electrically heated heating jaws or by induction heating or, in the case of jacket heating, by heat transfer oils.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP84112303A 1983-10-15 1984-10-12 Procédé de pyrolyse de résidus d'hydrogénation du charbon Expired EP0138213B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3337622 1983-10-15
DE19833337622 DE3337622A1 (de) 1983-10-15 1983-10-15 Verfahren zur schwelung von rueckstaenden der kohlehydrierung

Publications (3)

Publication Number Publication Date
EP0138213A2 true EP0138213A2 (fr) 1985-04-24
EP0138213A3 EP0138213A3 (en) 1986-10-01
EP0138213B1 EP0138213B1 (fr) 1989-01-18

Family

ID=6211989

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84112303A Expired EP0138213B1 (fr) 1983-10-15 1984-10-12 Procédé de pyrolyse de résidus d'hydrogénation du charbon

Country Status (5)

Country Link
US (1) US4584060A (fr)
EP (1) EP0138213B1 (fr)
CA (1) CA1226840A (fr)
DD (1) DD232719A5 (fr)
DE (2) DE3337622A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686008A (en) * 1985-10-08 1987-08-11 Gibson Harry T Pyrolytic decomposition apparatus
EP0379705A1 (fr) * 1988-12-28 1990-08-01 Apv Chemical Machinery Inc. Procédé pour la carbonisation continue d'un mélange composé principalement de déchets organiques
GB2527830A (en) * 2014-07-03 2016-01-06 Dps Bristol Holdings Ltd Waste processing apparatus
US10421919B2 (en) 2014-07-03 2019-09-24 Pyrocore S.A. Gasifier

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3829986A1 (de) * 1988-09-03 1990-03-15 Enka Ag Verfahren zur erhoehung des mesophasenanteils in pech
US4908104A (en) * 1988-12-28 1990-03-13 Apv Chemical Machinery Inc. Method of continuously carbonizing a mixture of primarily organic waste material
EP1405895A1 (fr) * 2002-10-04 2004-04-07 Danieli Corus Technical Services BV Dispositif et procédé pour le traitement pyrolytique d'une matière, et son utilisation
CA2539012C (fr) 2006-03-10 2013-07-09 John Flottvik Systeme de reacteur a charbon a cornue fermee
CN100439449C (zh) * 2006-03-30 2008-12-03 中国科学院山西煤炭化学研究所 一种道路沥青改性剂及其应用方法
BRPI0720677A2 (pt) * 2006-12-26 2014-03-18 Nucor Corp Aparelho e método para produzir carvão.
US9045693B2 (en) 2006-12-26 2015-06-02 Nucor Corporation Pyrolyzer furnace apparatus and method for operation thereof
EP2769148A4 (fr) 2011-10-21 2015-11-04 Therma Flite Inc Système et procédé de gazéification, et système et procédé de traitement des déchets les comprenant
FI129499B (en) * 2018-02-26 2022-03-31 Teknologian Tutkimuskeskus Vtt Oy Procedure for performing thermolysis and thermolysis equipment
US11920099B2 (en) * 2021-11-23 2024-03-05 Saudi Arabian Oil Company Extruder systems and processes for production of petroleum coke
US11959022B2 (en) * 2021-11-23 2024-04-16 Saudi Arabian Oil Company Extruder systems and processes for production of petroleum coke and mesophase pitch

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US1428458A (en) * 1919-09-15 1922-09-05 Carey W Thompson Process and apparatus for recovery of hydrocarbons from oil shale
DE326227C (de) * 1919-10-21 1920-12-03 Koeln Rottweil Akt Ges Liegende Retorte zur fortlaufenden Destillation von Kohle, Holz, Torf o. dgl. bei gewoehnlichem Druck, UEberdruck oder Vakuum
GB188686A (en) * 1921-05-17 1922-11-17 Herman Plauson Improvements in the extraction of hydrocarbons from wood
GB288148A (en) * 1927-03-31 1929-06-28 Ig Farbenindustrie Ag Improvements in the production of low boiling point and other hydrocarbons and derivatives thereof by the destructive hydrogenation of coals, oils and the like and in the treatment of the residues thereof
US1810828A (en) * 1927-05-16 1931-06-16 Coal Carbonization Company Method of carbonizing coal
US1817926A (en) * 1928-02-03 1931-08-11 Consolidation Coal Products Co Distillation of pitch into coke
DE619298C (de) * 1934-01-25 1935-09-27 Edwin M F Guignard Vorrichtung zum Verdampfen und Destillieren
US2072721A (en) * 1935-02-01 1937-03-02 Albert M Barr Low temperature carbonization
DE704444C (de) * 1940-02-13 1941-03-31 Hydrierwerk Scholven Akt Ges Verfahren zum Aufarbeiten von oelhaltigen Schleuderrueckstaenden der Druckhydrierung aschehaltiger Brennstoffe
DE737780C (de) * 1940-09-01 1943-07-23 Dr Edwin M F Guignard Kessel zur fraktionierten Destillation von Fluessigkeiten
US2615199A (en) * 1945-05-15 1952-10-28 Welding Engineers Material treating apparatus
US3075912A (en) * 1958-09-18 1963-01-29 Texaco Inc Hydroconversion of solid carbonaceous materials
US3691019A (en) * 1970-02-16 1972-09-12 Ray S Brimhall Retorting apparatus with hood-shaped unitary coolant jacket disposed over screw conveyor
US3947256A (en) * 1971-05-10 1976-03-30 Kabushiki Kaisha Niigata Tekrosho Method for decomposition of polymers into fuels
US3787292A (en) * 1971-08-13 1974-01-22 E Keappler Apparatus for pyrolysis of wastes
DE2407217A1 (de) * 1974-02-15 1975-09-04 Kloeckner Humboldt Deutz Ag Verfahren und vorrichtung zur thermischen behandlung von koernigen feststoffen
GB1501729A (en) * 1974-05-06 1978-02-22 Redker Young Processes Inc Conversion of organic waste material
JPS5331642B2 (fr) * 1975-02-10 1978-09-04
NL8201824A (nl) * 1982-05-04 1983-12-01 Tno Werkwijze en inrichting voor het bereiden van een vloeibaar koolwaterstofprodukt uit steenkool.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686008A (en) * 1985-10-08 1987-08-11 Gibson Harry T Pyrolytic decomposition apparatus
EP0379705A1 (fr) * 1988-12-28 1990-08-01 Apv Chemical Machinery Inc. Procédé pour la carbonisation continue d'un mélange composé principalement de déchets organiques
GB2527830A (en) * 2014-07-03 2016-01-06 Dps Bristol Holdings Ltd Waste processing apparatus
US10421919B2 (en) 2014-07-03 2019-09-24 Pyrocore S.A. Gasifier

Also Published As

Publication number Publication date
DD232719A5 (de) 1986-02-05
CA1226840A (fr) 1987-09-15
DE3337622A1 (de) 1985-04-25
EP0138213B1 (fr) 1989-01-18
DE3476219D1 (en) 1989-03-02
EP0138213A3 (en) 1986-10-01
US4584060A (en) 1986-04-22

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