[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP0287796B1 - Process for the hydroconversion of heavy and residual oils - Google Patents

Process for the hydroconversion of heavy and residual oils Download PDF

Info

Publication number
EP0287796B1
EP0287796B1 EP88103755A EP88103755A EP0287796B1 EP 0287796 B1 EP0287796 B1 EP 0287796B1 EP 88103755 A EP88103755 A EP 88103755A EP 88103755 A EP88103755 A EP 88103755A EP 0287796 B1 EP0287796 B1 EP 0287796B1
Authority
EP
European Patent Office
Prior art keywords
weight
oils
process according
solid
heavy
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.)
Expired - Lifetime
Application number
EP88103755A
Other languages
German (de)
French (fr)
Other versions
EP0287796A1 (en
Inventor
Ludwig Dr. Merz
Klaus Dr. Niemann
Klaus Kretschmer
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.)
Filing date
Publication date
Application filed by Veba Oel Technologie und Automatisierung GmbH filed Critical Veba Oel Technologie und Automatisierung GmbH
Publication of EP0287796A1 publication Critical patent/EP0287796A1/en
Application granted granted Critical
Publication of EP0287796B1 publication Critical patent/EP0287796B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
    • C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries

Definitions

  • EP-A-0 263 522 with its priority DE-A 3634275.0 describes a process for the hydrogenative conversion of heavy and residual oils, waste and waste oils and, if appropriate, their mixtures with ground brown and hard coal in the sump or combined bottom and gas phase with hydrogen-containing gases at a hydrogen partial pressure of 50 to 300 bar, preferably 150 to 200 bar, a temperature of 250 to 500 ° C, preferably 400 to 490 ° C, a gas-oil ratio of 100 to 10 000 Nm3 / t, preferably 1 000 to 5 000 Nm3 / t liquid and solid feed products with addition of at least one additive in amounts of 0.5 to 5.0 wt .-% based on the total amount of liquid and solid feed products proposed and in order to increase the specific throughput of the bottom phase reactors added in two different grain size ranges.
  • the invention relates to a.
  • the present method of admixing waste oils or waste materials, ie organic or synthetic, uncrosslinked or also crosslinked Substances containing carbon chains to the feed stream of hydrogenation systems consisting, for example, of residual oil, heavy oil or vacuum residue or admixture as a side stream into the hydrogenation reactor have the following advantages.
  • the heat of hydrogenation that is generated during the conversion of the heavy oils is used for the conversion and decontamination of the waste oils or waste materials under the conditions of the phase-phase hydrogenation.
  • the hydrating treatment of such waste oils or waste materials only a slight exotherm is normally to be expected. This significantly reduces the load on the preheater system of a typical sump phase hydrogenation system.
  • the bubble column maintained in the hydrogenation reactors during operation is suitable for processing waste oils containing solids as well, by using the stable fluid dynamics of the mixture of residual oil or heavy oil based on mineral oil with the hydrogenation gas as a "supporting" component.
  • waste oils or waste materials that are classified as hazardous waste can be disposed of in such a way that the carbon-containing components contained in these substances, hydrocarbon chains in particular are retained.
  • heteroatoms in particular oxygen, sulfur, nitrogen and halogens are largely removed by conversion into the corresponding hydrogen compounds, transition into the gas phase and their discharge with the waste water, in which the hydrogen halides and ammonia and hydrogen sulfide dissolve in whole or in part.
  • the contents of heavy metals or ash-forming constituents in the feed materials are effectively transferred to the residue in the hot separator systems following the bottom phase hydrogenation.
  • the amounts involved are different, for example, in the case of waste oils or sewage sludge containing solids, increased amounts of ash formers and heavy metals have to be discharged via the residue.
  • the feed materials mentioned, which form the condensed phase can also be used with coal in a weight ratio of 20: 1 to 1: 1.5, preferably 5: 1 to 5: 4.
  • the carbon-containing solids used with two grain size ranges can advantageously be impregnated with solutions of metal salts, of metals from subgroups 1 to 8 and the fourth main group of the periodic system of the elements, preferably iron, cobalt, nickel, vanadium or molybdenum.
  • the solid with two grain size ranges in two fractions which are sharply separated according to the grain spectrum, but it can also be used in a continuous grain size distribution with the corresponding coarse grain fraction of 100 »m or larger.
  • a sewage sludge In the hydrogenation of mixtures of heavy or residual oils, waste or waste oils with sewage sludge, the weight ratio of oil to sewage sludge being preferably from 10: 1 to 1: 1.5, a sewage sludge can be used which has a corresponding proportion of coarse grain fraction of 100 »m or larger.
  • the proportion of the coarse grain fraction can be 20% by weight or more of the added solid with two grain size ranges, this being understood to mean both carbon-containing, surface-rich, suspended solids and the aforementioned red masses, iron oxides, electrostatic filter dust and cyclone dust.
  • weight ratios of oil to coal from 5: 1 to 1: 1.5 are advantageous, with a part of the coal corresponding to the proportion of the coarse grain fraction of the solid to be added with two grain size ranges Grain sizes of 100 »m or larger can be used.
  • neutralizing agents which is necessary due to the halogen constituents of the waste oils or waste materials used to neutralize the hydrogen halides formed, is preferably carried out in amounts of 0.01 to 5.0% by weight of compounds which salts with hydrogen halide by neutralization form or split off hydroxide ions in aqueous solution.
  • the compounds to be added for this purpose are preferably injected together with water at a suitable point in the effluent from the bottom phase reactor and can be discharged from the process in the so-called cold separators as an aqueous solution of the corresponding halides, for example by phase separation.
  • sodium sulfide in the form of the aqueous solution, in suspension with oils or the like, as the compound which forms salts with hydrogen halide by neutralization or which releases hydroxide ions in aqueous solution.
  • sewage sludge as a preferred embodiment of the present process, it is advisable to dry to a water content of less than 10.0% by weight, preferably less than 2.0% by weight and, if necessary, by grinding, sieving and / or screening processes from coarse foreign bodies and brought to a grain size of less than 1.0 mm, preferably less than 0.5 mm.
  • the sewage sludge treated in this way acts as a solid with two grain size ranges.
  • the added solid with two grain size ranges is selected according to the desired conversion rate and the tendency of the feed material to form coke according to the type and amount added.
  • the present process for the hydrogenative conversion of heavy and residual oils, in a mixture with municipal or also industrial sewage sludge in the bottom or combined bottom and gas phase is expediently carried out in such a way that a high-pressure pump contains the oil or the oil / solid mixture including the Solids with two grain size ranges in the high pressure part of the plant.
  • Hydrogen-containing cycle gas and fresh hydrogen are heated up and mixed, for example, with the residual oil in the high-pressure section.
  • the reaction mixture flows through a regenerator battery and a peak heater to utilize the heat of reaction of the reaction products and then reaches the bottom phase reactors.
  • the reactor system consists, for example, of three vertical empty tube reactors connected in series, which are fed with the flow direction from bottom to top.
  • the conversion takes place at temperatures between preferably 400 to 490 ° C and a hydrogen partial pressure of 50 to 350 bar.
  • a quasi-isothermal operation of the reactors is possible by feeding in cold gas.
  • downstream hot separators which are operated at approximately the same temperature level as the reactors, the unconverted portion of the heavy and residual oils used as well as the solids is separated from the gaseous reaction products under process conditions.
  • the bottom product of the hot separator is expanded in a multi-stage flash unit.
  • the top product of the hot separators, the flash distillates and any crude oil distillate fractions to be processed are combined and fed to the downstream gas phase reactors.
  • Hydrotreating or mild hydrocracking is carried out on a catalytic fixed bed, for example under what are known as trickle flow conditions, under preferably the same total pressure as in the bottom phase.
  • gas and liquid are separated in a high-pressure cold separator. After phase separation, the wastewater can be discharged from the process at this point.
  • the liquid product is decompressed and processed in standard refinery processes.
  • the gaseous reaction products (C1 - to C4 gases, H2S, NH3, hydrogen halides) accumulate in the process gas, the water-soluble components with the waste water and the C1- to C4 gases are expediently discharged in an oil wash according to their solubility.
  • the hydrogen remaining in the process gas with small amounts of inert gases and other gaseous constituents is recycled as recycle gas.
  • a vacuum residue from Middle East crude oil is mixed with 15% by weight of a used industrial cleaning solution with a chlorine content of 4% by weight and 15% by weight sewage sludge (dried to less than 2% by weight). -% residual moisture) with 1.5 m3 H2 per kg of mash used at 210 bar hydrogen partial pressure.
  • the sewage sludge was ground in such a way that 90% of the material in the grain spectrum was less than 90 »m and 10% between 100 and 150» m.
  • To incorporate the chlorine 1% by weight Na2S based on the mash was metered in continuously. At 465 ° C.
  • the vacuum residue was converted to 91% by weight into low-boiling products.
  • These products contain less than 1 wt .-% ppm chlorine, the organic part of the sewage sludge is more than 75 wt .-% in liquid Products implemented.
  • a Venezuelan vacuum residue is reacted together with 30% by weight (based on vacuum residue), corresponding to 22.7% by weight based on the total mash used, of a used metal degreasing solution.
  • the aromatic and phenol-containing degreasing solution has a chlorine content of 1.02% by weight and oxygen contents of 3.7% by weight, nitrogen of 0.92% by weight and sulfur of 0.98% by weight.
  • the fraction boiling below 200 ° C is 44% by weight
  • the fraction of the fraction 200 to 350 ° C is 22% by weight.
  • the reaction in the bottom phase hydrogenation is carried out with the addition of 2% by weight of a brown coal coke with grain sizes of 1.5% by weight less than 90 »m and 0.5% by weight from 100 to 400» m with a specific throughput of 0.5 kg / lh (based on vacuum residue), an H2 / oil ratio of 2000 Nm3 / t and a hydrogen partial pressure of 200 bar.
  • the vacuum residue used was converted to 90% by weight into low-boiling products (less than 500 ° C).
  • the primary product of the bottom phase hydrogenation has a chlorine content of less than 1% by weight ppm.
  • the chlorine contained in the metal degreasing solution becomes sodium chloride with a Hot separator solid discharged.
  • the primary product of the bottom phase hydrogenation is subjected to a catalytic fixed bed refining in a commercially available refining contact in the directly coupled gas phase hydrogenation at 380 ° C and a catalyst load of 2.0 kg / kg.h.
  • the total product produced after the gas phase hydrogenation is phenol-free and free of chlorine, the sulfur and nitrogen content is less than 0.1% by weight.
  • a Venezuelan vacuum residue together with 10% by weight of a distillation residue from solvent recycling (dried at 100 ° C. in vacuo, ground and sieved to less than 150 »m, of which 75% by weight a particle size less than 90 and 25 wt .-% have a particle size of 100 to 150 »m) with a specific throughput of 0.5 kg mash / lh, an H2 / oil ratio of 3000 Nm3 / t and a hydrogen partial pressure of 200 bar implemented.
  • 94% by weight of the vacuum residue used is converted into low-boiling products.
  • the organic fraction of the distillation residue (ash content: 17% by weight, carbon content: 54% by weight, hydrogen content: 6.5% by weight, sulfur content: 0.2% by weight, balance: nitrogen and oxygen) becomes over 80% by weight converted into liquid products and gases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Sludge (AREA)
  • Catalysts (AREA)
  • Processing Of Solid Wastes (AREA)
  • Fats And Perfumes (AREA)

Abstract

Heavy and residual oils, spent and waste oils are hydroconverted by liquid-phase hydrogenation. <??>The mixing of waste oils or waste materials with the hydrogenation feed products is intended to allow re-use in place of disposal in landfills or combustion. <??>Mixtures of heavy or residual oils with spent and waste oils and also waste materials containing organic constituents are used in certain weight ratios, an additive within certain grain size ranges being present.

Description

In der älteren Patentanmeldung EP-A-0 263 522 mit ihrer Priorität DE-A 3634275.0 wird ein Verfahren zur hydrierenden Konversion von Schwer- und Rückstandsölen, Alt- und Abfallölen sowie ggf. deren Mischungen mit gemahlenen Braun- und Steinkohlen in der Sumpf- bzw. kombinierten Sumpf- und Gasphase mit wasserstoffhaltigen Gasen bei einem Wasserstoffpartialdruck von 50 bis 300 bar, vorzugsweise 150 bis 200 bar, einer Temperatur von 250 bis 500 °C, vorzugsweise 400 bis 490 °C, einem Gas-Öl-Verhältnis von 100 bis 10 000 Nm³/t, vorzugsweise 1 000 bis 5 000 Nm³/t flüssiger und fester Einsatzprodukte unter Zusatz wenigstens eines Additivs in Mengen von 0,5 bis 5,0 Gew.-% bezogen auf die Gesamtmenge flüssiger und fester Einsatzprodukte vorgeschlagen und zwecks Erhöhung des spezifischen Durchsatzes der Sumpfphasereaktoren das Additiv in zwei unterschiedlichen Korngrößenbereichen zugesetzt.The older patent application EP-A-0 263 522 with its priority DE-A 3634275.0 describes a process for the hydrogenative conversion of heavy and residual oils, waste and waste oils and, if appropriate, their mixtures with ground brown and hard coal in the sump or combined bottom and gas phase with hydrogen-containing gases at a hydrogen partial pressure of 50 to 300 bar, preferably 150 to 200 bar, a temperature of 250 to 500 ° C, preferably 400 to 490 ° C, a gas-oil ratio of 100 to 10 000 Nm³ / t, preferably 1 000 to 5 000 Nm³ / t liquid and solid feed products with addition of at least one additive in amounts of 0.5 to 5.0 wt .-% based on the total amount of liquid and solid feed products proposed and in order to increase the specific throughput of the bottom phase reactors added in two different grain size ranges.

Ein Verfahren zur Aufarbeitung von kohlenstoffenthaltenden Abfällen und Biomasse durch Hydrierung derselben bei erhöhter Temperatur und einem Wasserstoffdruck von wenigstens 1 bar ist in der EP-A-0 182 309, beschrieben.A process for processing carbon-containing wastes and biomass by hydrogenating them at elevated temperature and a hydrogen pressure of at least 1 bar is described in EP-A-0 182 309.

Bei der hydrierenden Konversion von Schwer- und Rückstandsölen, Alt- und Abfallölen, insbesondere in Mischung mit organischen oder synthetischen Stoffen, die in eine feindisperse Verteilung gebracht werden müssen, bevor sie in die Sumpfphasenhydrierung eingespeist werden, zeigte sich, daß es Schwierigkeiten bereitet, eine ausreichende Füllung der Sumpfphasereaktoren, wie sie sich in dem beobachteten Druckabfall über die Reaktorhöhe ausdrückt, zu erreichen.In the hydrogenating conversion of heavy and residual oils, waste and waste oils, especially in a mixture with organic or synthetic substances, which have to be brought into a finely dispersed distribution before they are fed into the bottom phase hydrogenation, it has been found that it is difficult to achieve a sufficient filling of the bottom phase reactors, as is expressed in the pressure drop observed above the reactor height.

Ausgehend von dieser Erkenntnis ist es ein Ziel der Erfindung, durch Zumischung der Abfallöle oder Abfallstoffe zu den Einsatzprodukten der Hydrierung von Rückstandsöl oder Schweröl auf Mineralölbasis, ggf. in Mischung mit feingemahlener Kohle, in der Hydrierung ein Syncrude herzustellen, dessen Eigenschaften im wesentlichen durch die Produkte aus dem Rückstandsöl bestimmt sind. Damit sollen die mit der Entsorgung der vorgenannten Abfallöle oder Abfallstoffe durch Deponie oder thermische Verbrennungsverfahren verbundenen evidenten Probleme vermieden werden.On the basis of this knowledge, it is an object of the invention to produce a syncrude in the hydrogenation by adding the waste oils or waste materials to the feed products for the hydrogenation of residual oil or heavy oil based on mineral oil, possibly in a mixture with finely ground coal, the properties of which are essentially determined by the Products from which residual oil are determined. This is to avoid the evident problems associated with the disposal of the aforementioned waste oils or waste materials by landfill or thermal incineration processes.

Weitere Merkmale, Ziele und die verschiedenen Vorteile der Erfindung sind aus der folgenden Beschreibung und den Patentansprüchen ersichtlich.Further features, objects and the various advantages of the invention will be apparent from the following description and the claims.

Gegenstand der Erfindung ist ein.The invention relates to a.

Verfahren zur hydrierenden Konversion von

  • Schwer- und Rückstandsölen,
  • Alt- und Abfallölen sowie
  • ggf. deren Mischungen mit gemahlenen Braun- und Steinkohlen
in der Sumpf- bzw. kombinierten Sumpf- und Gasphase mit wasserstoffhaltigen Gasen bei
  • einem Wasserstoffpartialdruck von 50 bis 350 bar, vorzugsweise 150 bis 200 bar,
  • einer Temperatur von 250 bis 500 °C, vorzugsweise 400 bis 490 °C,
  • einem Gas-Öl-Verhältnis von 100 bis 10 000 Nm³/t, vorzugsweise 1 000 bis 5 000 Nm³/t flüssiger und fester Einsatzprodukte
dadurch gekennzeichnet, daß
wenigstens ein Feststoff
  • in Mengen von 0,1 bis 15 Gew.-% - bezogen auf die Gesamtmenge flüssiger und fester Einsatzprodukte - und mit den Korngrößenbereichen
    • · 90 »m oder weniger und
    • · 100 »m bis 1 000 »m, vorzugsweise 100 bis 500 »m,
    die jeweils entweder innerhalb einer kontinuierlichen Korngrößenverteilung oder bevorzugt als zwei scharf getrennte Fraktionen vorliegen,
zugesetzt wird und
Mischungen von
  • a) Schwer- oder Rückstandsölen
  • b)
    • · Alt- und Abfallölen, nämlich
      • PCB-haltige bzw. halogenhaltige Altöle, die auch feststoffhaltig sein können
      • Transformatoren-Öle
      • Hydraulik-Öle
      • Deponie-Sickeröle
      • Bilgenöle
    • · Klärschlämmen aus
      • Vorklärbecken
      • biologischer Klärung
      • Faultürmen
    • · Lackschlämmen
    • · halogenhaltigen Lösungsmitteln
    • · organischen Rückständen aus
      • chemisch-Reiniger-Betrieben
      • der Teileentfettung
      • Reinigungsbädern
      • der Tankreinigung
      • der Destillation halogenhaltiger Lösungsmittel oder aus Recycling-Prozessen
      oder
    • · Kunststoffen, Altkunststoffen, Kunststoff-Produktionsabfällen
    bei einem Durchsatz von 0,1 bis 2 t/m³h - bezogen auf Schwer- oder Rückstandsöl - und im Gewichtsverhältnis von 100 : 1 bis 1 : 1,5 eingesetzt werden.
Process for the hydrogenative conversion of
  • Heavy and residual oils,
  • Waste and waste oils as well
  • where appropriate, their mixtures with ground brown and hard coal
in the bottom or combined bottom and gas phase with hydrogen-containing gases
  • a hydrogen partial pressure of 50 to 350 bar, preferably 150 to 200 bar,
  • a temperature of 250 to 500 ° C, preferably 400 to 490 ° C,
  • a gas-oil ratio of 100 to 10,000 Nm³ / t, preferably 1,000 to 5,000 Nm³ / t liquid and solid feed products
characterized in that
at least one solid
  • in quantities of 0.1 to 15% by weight - based on the total quantity of liquid and solid feed products - and with the grain size ranges
    • · 90 »m or less and
    • · 100 »m to 1,000» m, preferably 100 to 500 »m,
    which are either present within a continuous grain size distribution or preferably as two sharply separated fractions,
is added and
Mixtures of
  • a) Heavy or residue oils
  • b)
    • · Waste and waste oils, namely
      • PCB-containing or halogen-containing waste oils, which can also contain solids
      • Transformer oils
      • Hydraulic oils
      • Landfill seepage oils
      • Bilge oils
    • · Sewage sludge
      • Pre-clarifier
      • biological clarification
      • Digestion towers
    • · Paint sludge
    • · Halogenated solvents
    • · Organic residues
      • chemical cleaning companies
      • parts degreasing
      • Cleaning baths
      • the tank cleaning
      • the distillation of halogenated solvents or from recycling processes
      or
    • · Plastics, waste plastics, plastic production waste
    at a throughput of 0.1 to 2 t / m³h - based on heavy or residual oil - and in a weight ratio of 100: 1 to 1: 1.5.

Das vorliegende Verfahren der Zumischung von Abfallölen oder Abfallstoffen, d. h. organischen oder synthetischen, unvernetzte oder auch vernetzte Kohlenstoffketten aufweisenden Stoffen zu dem beispielsweise aus Rückstandsöl, Schweröl oder Vakuumrückstand bestehenden Einsatzstrom von Hydrieranlagen bzw. der Zumischung als Seitenstrom in den Hydrierreaktor hat die folgenden Vorteile.The present method of admixing waste oils or waste materials, ie organic or synthetic, uncrosslinked or also crosslinked Substances containing carbon chains to the feed stream of hydrogenation systems consisting, for example, of residual oil, heavy oil or vacuum residue or admixture as a side stream into the hydrogenation reactor have the following advantages.

Die Hydrierwärme, die bei der Konversion der schweren Öle entsteht, wird zur Umwandlung und Dekontamination der Abfallöle oder Abfallstoffe unter den Bedingungen der Sumpfphasenhydrierung genutzt. Bei der hydrierenden Behandlung solcher Abfallöle oder Abfallstoffe ist im Normalfall nur eine geringe Wärmetönung zu erwarten. Dadurch wird das Vorheizersystem einer typischen Anlage zur Sumpfphasenhydrierung signifikant entlastet.The heat of hydrogenation that is generated during the conversion of the heavy oils is used for the conversion and decontamination of the waste oils or waste materials under the conditions of the phase-phase hydrogenation. In the case of the hydrating treatment of such waste oils or waste materials, only a slight exotherm is normally to be expected. This significantly reduces the load on the preheater system of a typical sump phase hydrogenation system.

Die in den Hydrierreaktoren beim Betrieb aufrechterhaltene Blasensäule ist geeignet, auch feststoffhaltige Abfallöle zu verarbeiten, indem die stabile Fluiddynamik der Mischung von Rückstandsöl oder Schweröl auf Mineralölbasis mit dem Hydriergas als "tragende" Komponente genutzt wird.The bubble column maintained in the hydrogenation reactors during operation is suitable for processing waste oils containing solids as well, by using the stable fluid dynamics of the mixture of residual oil or heavy oil based on mineral oil with the hydrogenation gas as a "supporting" component.

Bei Zumischung der Abfallöle oder Abfallstoffe zum Rückstandsöl auf Mineralölbasis entsteht in der Hydrieranlage ein Syncrude, das in gängigen Raffineriestrukturen weiter verarbeitet werden kann.When the waste oils or waste materials are added to the mineral oil-based residual oil, a syncrude is created in the hydrogenation system, which can be further processed in common refinery structures.

Mit dem vorgeschlagenen Verfahren gelingt es, Abfallöle oder Abfallstoffe, die als Sondermüll einzustufen sind, derartig zu entsorgen, daß die in diesen Stoffen enthaltenen kohlenstoffhaltigen Bestandteile, insbesondere auch Kohlenwasserstoffketten erhalten bleiben.With the proposed method, waste oils or waste materials that are classified as hazardous waste can be disposed of in such a way that the carbon-containing components contained in these substances, hydrocarbon chains in particular are retained.

Gleichzeitig erfolgt eine weitgehende Entfernung sogenannter Heteroatome, insbesondere Sauerstoff, Schwefel, Stickstoff sowie von Halogenen durch Überführung in die entsprechenden Wasserstoffverbindungen, Übergang in sie Gasphase und deren Ausschleusung mit dem Abwasser, in dem sich die Halogenwasserstoffe sowie Ammoniak und Schwefelwasserstoff ganz oder teilweise lösen.At the same time, so-called heteroatoms, in particular oxygen, sulfur, nitrogen and halogens are largely removed by conversion into the corresponding hydrogen compounds, transition into the gas phase and their discharge with the waste water, in which the hydrogen halides and ammonia and hydrogen sulfide dissolve in whole or in part.

Die Gehalte der Einsatzstoffe an Schwermetallen oder aschebildenden Bestandteilen werden in den an die Sumpfphasenhydrierung anschließenden Heißabscheidersystemen wirksam in den Rückstand überführt. Je nach Art der Einsatzstoffe handelt es sich um unterschiedliche Mengen, beispielsweise sind bei feststoffhaltigen Altölen oder Klärschlämmen erhöhte Mengen an Aschebildnern und Schwermetallen über den Rückstand auszuschleusen.The contents of heavy metals or ash-forming constituents in the feed materials are effectively transferred to the residue in the hot separator systems following the bottom phase hydrogenation. Depending on the type of input material, the amounts involved are different, for example, in the case of waste oils or sewage sludge containing solids, increased amounts of ash formers and heavy metals have to be discharged via the residue.

Die genannten, die kondensierte Phase bildenden Einsatzstoffe können in einer speziellen Fahrweise auch mit Kohle im Gewichtsverhältnis von 20 : 1 bis 1 : 1,5, vorzugsweise 5 : 1 bis 5 : 4 eingesetzt werden.In a special procedure, the feed materials mentioned, which form the condensed phase, can also be used with coal in a weight ratio of 20: 1 to 1: 1.5, preferably 5: 1 to 5: 4.

Bei Einsatz eines Feststoffs mit zwei Korngrößenbereichen in Form eines kohlenstoffhaltigen, oberflächenreichen suspendierten Feststoffes in die Sumpfphasenhydrierung in Mengen von 0,1 bis 10, vorzugsweise 0,5 bis 5,0 Gew.-% ist es bevorzugt, Braunkohlenkokse aus Schacht- und Herdöfen, Ruße aus der Vergasung von Schweröl, Steinkohle, Hydrierrückständen oder Braunkohle und die daraus erzeugten Aktivkokse, Petrolkoks sowie Stäube aus der Winklervergasung von Kohle Verwendung finden zu lassen.When using a solid with two particle size ranges in the form of a carbon-containing, surface-rich suspended solid in the bottom phase hydrogenation in amounts of 0.1 to 10, preferably 0.5 to 5.0% by weight, it is preferred to use brown coal coke from shaft and hearth furnaces, soot from the gasification of heavy oil, hard coal, hydrogenation residues or brown coal and the activated coke, petroleum coke and dusts from the Winkler gasification of coal produced therefrom.

Mit Vorteil können die eingesetzten kohlenstoffhaltigen Feststoffe mit zwei Korngrößenbereichen mit Lösungen von Metallsalzen, von Metallen der 1. bis 8. Nebengruppe sowie der 4. Hauptgruppe des periodischen Systems der Elemente, vorzugsweise Eisen, Kobalt, Nickel, Vanadium oder Molybdän imprägniert sein.The carbon-containing solids used with two grain size ranges can advantageously be impregnated with solutions of metal salts, of metals from subgroups 1 to 8 and the fourth main group of the periodic system of the elements, preferably iron, cobalt, nickel, vanadium or molybdenum.

Es kann auch zweckmäßig sein, als Feststoffe mit zwei Korngrößenbereichen 0,1 bis 10, vorzugsweise 0,5 bis 5,0 Gew.-% Rotmasse, Eisenoxide, Elektrofilterstäube und Zyklonstäube aus der Metall- oder Erzaufarbeitung einzusetzen. Diese Massen können als solche oder auch nach Vorbehandlung, beispielsweise Sulfidierung u. dgl. eingesetzt werden.It can also be expedient to use as solids with two grain size ranges 0.1 to 10, preferably 0.5 to 5.0% by weight of red mass, iron oxides, electrostatic filter dusts and cyclone dusts from metal or ore processing. These masses as such or after pretreatment, for example sulfidation and. Like. Be used.

Durch die Zugabe der kohlenstoffhaltigen, oberflächenreichen Feststoffe mit zwei Korngrößenbereichen in die Sumpfphasenhydrierung werden auch Reaktionen der Hydrodemetallisation und der Hydrodesulfurierung begünstigt, die zu einer Ausschleusung der metallhaltigen oder aschebildenden Bestandteile mit dem Heißabscheiderrückstand führen. In dieser Form erfahren diese Bestandteile eine Überführung in einen Zustand, der leichter zu handhaben ist, als in dem Ausgangsmaterial. Darüber hinaus sind diese Bestandteile im Heißabscheiderrückstand soweit angereichert, daß sie beispielsweise auch nach metallurgischen Verfahren wiedergewonnen werden können.The addition of the carbon-containing, surface-rich solids with two grain size ranges to the bottom phase hydrogenation also favors reactions of hydrodemetallization and hydrodesulfurization, which lead to the removal of the metal-containing or ash-forming constituents with the hot separator residue. In this form, these components are brought into a state that is easier to handle than in the starting material. In addition, these components are so far enriched in the hot separator residue that they can also be recovered, for example, by metallurgical processes.

Bevorzugt ist es, den Feststoff mit zwei Korngrößenbereichen in zwei scharf nach dem Kornspektrum getrennten Fraktionen einzusetzen, er kann aber auch in einer kontinuierlichen Korngrößenverteilung mit dem entsprechenden Grobkornanteil von 100 »m oder größer eingesetzt werden.It is preferred to use the solid with two grain size ranges in two fractions which are sharply separated according to the grain spectrum, but it can also be used in a continuous grain size distribution with the corresponding coarse grain fraction of 100 »m or larger.

Bei der Hydrierung von Mischungen aus Schwer- oder Rückstandsölen, Alt- oder Abfallölen mit Klärschlämmen, wobei das Gewichtsverhältnis Öl zu Klärschlamm, vorzugsweise von 10 : 1 bis 1 : 1,5 liegt, kann ein Klärschlamm eingesetzt werden, der einen entsprechenden Anteil an Grobkornfraktion von 100 »m oder größer enthält.In the hydrogenation of mixtures of heavy or residual oils, waste or waste oils with sewage sludge, the weight ratio of oil to sewage sludge being preferably from 10: 1 to 1: 1.5, a sewage sludge can be used which has a corresponding proportion of coarse grain fraction of 100 »m or larger.

Der Anteil der Grobkornfraktion kann 20 Gew.-% oder mehr des zugesetzten Feststoffs mit zwei Korngrößenbereichen betragen, wobei hierunter sowohl kohlenstoffhaltige, oberflächenreiche, suspendierte Feststoffe als auch die vorgenannten Rotmassen, Eisenoxide, Elektrofilterstäube und Zyklonstäube verstanden sein sollen.The proportion of the coarse grain fraction can be 20% by weight or more of the added solid with two grain size ranges, this being understood to mean both carbon-containing, surface-rich, suspended solids and the aforementioned red masses, iron oxides, electrostatic filter dust and cyclone dust.

Aufgrund der während der Betriebsphase auftretenden Anreicherung des Grobkornanteils des zugesetzten Feststoffs mit zwei Korngrößenbereichen kann hier ein Anteil von kleiner oder gleich 20 Gew.-% Grobkornanteil der laufend zuzusetzenden Menge besagten Feststoffes ausreichend sein.Due to the enrichment of the coarse grain fraction of the added solid with two grain size ranges that occurs during the operating phase, a proportion of less than or equal to 20% by weight of coarse grain fraction of the quantity of said solid to be continuously added may be sufficient here.

Bei der hydrierenden Konversion von Mischungen von Schwer- oder Rückstandsölen, Alt- oder Abfallölen in Mischung mit den genannten weiteren Einsatzstoffen sowie in Gegenwart von Braun- oder Steinkohlen im Sinne der sogenannten Coprocessing-Fahrweise sind Gewichtsverhältnisse von Öl zu Kohle von 5 : 1 bis 1 : 1,5 vorteilhaft, wobei ein dem zuzusetzenden Anteil der Grobkornfraktion des Feststoffs mit zwei Korngrößenbereichen entsprechender Teil der Kohle in Korngrößen von 100 »m oder größer eingesetzt werden kann.In the hydrogenating conversion of mixtures of heavy or residual oils, waste or waste oils in a mixture with the other feedstocks mentioned and in the presence of brown or hard coal in the sense of the so-called coprocessing procedure, weight ratios of oil to coal from 5: 1 to 1: 1.5 are advantageous, with a part of the coal corresponding to the proportion of the coarse grain fraction of the solid to be added with two grain size ranges Grain sizes of 100 »m or larger can be used.

Die Zugabe von Neutralisationsmitteln, die aufgrund der evtl. vorhandenen Halogenbestandteile der eingesetzten Abfallöle oder Abfallstoffe zur Neutralisation der gebildeten Halogenwasserstoffe erforderlich ist, erfolgt bevorzugt in Mengen von 0,01 bis 5,0 Gew.-% von Verbindungen, die mit Halogenwasserstoff durch Neutralisation Salze bilden oder in wäßriger Lösung Hydroxidionen abspalten.The addition of neutralizing agents, which is necessary due to the halogen constituents of the waste oils or waste materials used to neutralize the hydrogen halides formed, is preferably carried out in amounts of 0.01 to 5.0% by weight of compounds which salts with hydrogen halide by neutralization form or split off hydroxide ions in aqueous solution.

Die für diesen Zweck zuzugebenden Verbindungen werden vorzugsweise zusammen mit Wasser an geeigneter Stelle in den Abstrom des Sumpfphasenreaktors eingespritzt und können als wäßrige Lösung der entsprechenden Halogenide, beispielsweise durch Phasentrennung, in den sogenannten Kaltabscheidern aus dem Verfahren ausgeschleust werden.The compounds to be added for this purpose are preferably injected together with water at a suitable point in the effluent from the bottom phase reactor and can be discharged from the process in the so-called cold separators as an aqueous solution of the corresponding halides, for example by phase separation.

Es ist bevorzugt, als Verbindung, die mit Halogenwasserstoff durch Neutralisation Salze bildet oder in wäßriger Lösung Hydroxidionen abspaltet, 0,01 bis 5,0 Gew.-% Natriumsulfid in Form der wäßrigen Lösung, in Suspension mit Ölen oder dgl. zuzugeben.It is preferred to add 0.01 to 5.0% by weight of sodium sulfide in the form of the aqueous solution, in suspension with oils or the like, as the compound which forms salts with hydrogen halide by neutralization or which releases hydroxide ions in aqueous solution.

Im Falle der Zugabe von Klärschlamm als einer bevorzugten Ausführungsform des vorliegenden Verfahrens wird zweckmäßig bis auf Wassergehalte von kleiner 10,0 Gew.-%, vorzugsweise kleiner 2,0 Gew.-% getrocknet und falls notwendig, durch Mahl-, Sieb- und/oder Sichtungsprozesse von groben Fremdkörpern befreit und auf eine Körnung von kleiner 1,0 mm, vorzugsweise kleiner 0,5 mm gebracht. Der so behandelte Klärschlamm wirkt als Feststoff mit zwei Korngrößenbereichen. Der zugesetzte Feststoff mit zwei Korngrößenbereichen, wird je nach angestrebter Konversionsrate und Koksbildungsneigung des Einsatzmaterials nach Art und Zusatzmenge ausgewählt.In the case of the addition of sewage sludge as a preferred embodiment of the present process, it is advisable to dry to a water content of less than 10.0% by weight, preferably less than 2.0% by weight and, if necessary, by grinding, sieving and / or screening processes from coarse foreign bodies and brought to a grain size of less than 1.0 mm, preferably less than 0.5 mm. The sewage sludge treated in this way acts as a solid with two grain size ranges. The added solid with two grain size ranges is selected according to the desired conversion rate and the tendency of the feed material to form coke according to the type and amount added.

Das vorliegende Verfahren zur hydrierenden Konversion von Schwer- und Rückstandsölen, in Mischung mit kommunalen oder auch industriellen Klärschlämmen in der Sumpf- bzw. kombinierten Sumpf- und Gasphase wird zweckmäßig so durchgeführt, daß eine Hochdruckpumpe das Öl bzw. das Öl-/Feststoffgemisch einschließlich des Feststoffs mit zwei Korngrößenbereichen in den Hochdruckteil der Anlage fördert. Wasserstoffhaltiges Kreislaufgas und Frischwasserstoff werden aufgeheizt und beispielsweise dem Rückstandsöl im Hochdruckteil zugemischt. Las Reaktionsgemisch durchströmt zur Ausnutzung der Reaktionswärme der Reaktionsprodukte eine Regeneratorbatterie und einen Spitzenerhitzer und gelangt dann in die Sumpfphasereaktoren. Das Reaktorsystem besteht beispielsweise aus drei in Reihe geschalteten, senkrechtstehenden Leerrohrreaktoren, die mit Flußrichtung von unten nach oben beschickt werden. Hier erfolgt die Konversion bei Temperaturen zwischen vorzugsweise 400 bis 490 °C und einem Wasserstoffpartialdruck von 50 bis 350 bar. Durch Kaltgaseinspeisung ist eine quasi-isotherme Fahrweise der Reaktoren möglich.The present process for the hydrogenative conversion of heavy and residual oils, in a mixture with municipal or also industrial sewage sludge in the bottom or combined bottom and gas phase is expediently carried out in such a way that a high-pressure pump contains the oil or the oil / solid mixture including the Solids with two grain size ranges in the high pressure part of the plant. Hydrogen-containing cycle gas and fresh hydrogen are heated up and mixed, for example, with the residual oil in the high-pressure section. The reaction mixture flows through a regenerator battery and a peak heater to utilize the heat of reaction of the reaction products and then reaches the bottom phase reactors. The reactor system consists, for example, of three vertical empty tube reactors connected in series, which are fed with the flow direction from bottom to top. Here the conversion takes place at temperatures between preferably 400 to 490 ° C and a hydrogen partial pressure of 50 to 350 bar. A quasi-isothermal operation of the reactors is possible by feeding in cold gas.

In nachgeschalteten Heißabscheidern, die auf annähernd gleichem Temperaturniveau betrieben werden wie die Reaktoren, wird der nichtkonvertierte Anteil der eingesetzten Schwer- und Rückstandsöle sowie der Feststoffe von den unter Prozeßbedingungen gasförmigen Reaktionsprodukten getrennt. Das Sumpfprodukt der Heißabscheider wird in einer mehrstufigen Flash-Einheit entspannt. Im Falle des kombinierten Betriebes von Sumpf- und Gasphase werden das Kopfprodukt der Heißabscheider, die Flash-Destillate sowie evtl. mitzuverarbeitende Rohöldestillatfraktionen vereinigt und den nachgeschalteten Gasphasereaktoren zugeführt. Unter vorzugsweise gleichem Gesamtdruck wie in der Sumpfphase erfolgt ein Hydrotreating oder auch mildes Hydrocracken an einem katalytischen Festbett beispielsweise unter sogenannten trickle flow-Bedingungen. Nach intensiver Kühlung und Kondensation werden Gas und Flüssigkeit in einem Hochdruck-Kaltabscheider getrennt. Nach Phasentrennung kann an dieser Stelle das Abwasser aus dem Verfahren ausgeschleust werden. Das Flüssigprodukt wird entspannt und in raffinerieüblichen Prozessen weiterverarbeitet.In downstream hot separators, which are operated at approximately the same temperature level as the reactors, the unconverted portion of the heavy and residual oils used as well as the solids is separated from the gaseous reaction products under process conditions. The bottom product of the hot separator is expanded in a multi-stage flash unit. In the case of combined operation of the bottom and gas phases, the top product of the hot separators, the flash distillates and any crude oil distillate fractions to be processed are combined and fed to the downstream gas phase reactors. Hydrotreating or mild hydrocracking is carried out on a catalytic fixed bed, for example under what are known as trickle flow conditions, under preferably the same total pressure as in the bottom phase. After intensive cooling and condensation, gas and liquid are separated in a high-pressure cold separator. After phase separation, the wastewater can be discharged from the process at this point. The liquid product is decompressed and processed in standard refinery processes.

Die gasförmigen Reaktionsprodukte (C₁ - bis C₄-Gase, H₂S, NH₃, Halogenwasserstoffe) reichern sich in dem Prozeßgas an, wobei die wasserlöslichen Bestandteile mit dem Abwasser und die C₁- bis C₄-Gase entsprechend ihrer Löslichkeit zweckmäßig in einer Ölwäsche ausgeschleust werden. Der in dem Prozeßgas verbleibende Wasserstoff mit geringen Mengen an Inertgasen und sonstigen gasförmigen Bestandteilen wird als Kreislaufgas zurückgeführt.The gaseous reaction products (C₁ - to C₄ gases, H₂S, NH₃, hydrogen halides) accumulate in the process gas, the water-soluble components with the waste water and the C₁- to C₄ gases are expediently discharged in an oil wash according to their solubility. The hydrogen remaining in the process gas with small amounts of inert gases and other gaseous constituents is recycled as recycle gas.

Beispiel 1example 1

In einer kontinuierlich betriebenen Hydrieranlage mit drei hintereinandergeschalteten vertikalen Sumpfphasereaktoren ohne Einbauten wurde der Vakuumrückstand eines venezolanischen Schweröls unter Zusatz von 2,0 Gew.-% Braunkohlenkoks, entsprechend 1,8 Gew.-% bezogen auf die Gesamtmenge flüssiger und fester Einsatzprodukte mit einer Kornobergrenze bei 40 »m und Zumischung von 10 Gew.-% Klärschlamm, entsprechend 8,9 Gew.-% bezogen auf die Gesamtmenge flüssiger und fester Einsatzprodukte (getrocknet auf kleiner 2,0 % Gew.-Restfeuchte, gemahlen und abgesiebt auf kleiner 150 »m) mit 1,5 m³H₂ pro kg Rückstand und einem Wasserstoffpartialdruck von 190 bar umgesetzt. Zur Erzielung einer Rückstandskonversionsrate (Umsatz) von 90 % wurde eine mittlere Temperatur über die hintereinandergeschalteten Sumpfphasenreaktoren von 465 °C eingestellt. Der spezifische Durchsatz betrug 0,54 kg/l. h (500 °C⁺).In a continuously operated hydrogenation plant with three vertical sump phase reactors connected in series without internals, the vacuum residue of a Venezuelan heavy oil was added with the addition of 2.0% by weight of brown coal coke, corresponding to 1.8% by weight based on the total amount of liquid and solid feed products with an upper grain limit 40 »m and admixture of 10% by weight sewage sludge, corresponding to 8.9% by weight based on the total amount of liquid and solid feed products (dried to less than 2.0% residual weight by weight, ground and sieved to less than 150» m ) with 1.5 m³H₂ per kg of residue and a hydrogen partial pressure of 190 bar. In order to achieve a residue conversion rate (conversion) of 90%, an average temperature of 465 ° C. was set via the sump phase reactors connected in series. The specific throughput was 0.54 kg / l. h (500 ° C⁺).

In der nachfolgenden Tabelle sind die Ergebnisse zusammengefaßt. Betriebsbedingungen Temperatur LPH 465 °C spez. Durchsatz 0,54 t/m³h Öl mit Siedebereich 500 °C⁺ Braunkohlenkoks 2,0 Gew.-% bezogen auf Öleinsatz, entsprechend Klärschlammeinsatz 10,0 Gew.-% bezogen auf Öleinsatz, 1,8 Gew.-% entsprechend 8,9 Gew.-%, jeweils bezogen auf die Gesamtmenge flüssiger und fester Einsatzprodukte Ausbeute Konversion 500 °C⁺ Öl 90,2 % C₁-C₄ Gase 7,6 % v. E. Konversion Klärschlamm (organischer Anteil) größer 70 % The results are summarized in the table below. Operating conditions LPH temperature 465 ° C spec. Throughput 0.54 t / m³h oil with boiling range 500 ° C⁺ Lignite coke 2.0% by weight based on the use of oil, accordingly Sewage sludge 10.0% by weight based on oil input, 1.8% by weight accordingly 8.9% by weight, based on the total amount of liquid and solid feed products yield Conversion 500 ° C⁺ oil 90.2% C₁-C₄ gases 7.6% of E. Sludge conversion (organic fraction) greater than 70%

Beispiel 2: Example 2 :

In einer kontinuierlich betriebenen Hydrieranlage mit einem Sumpfphasereaktor ohne Einbauten wird ein Vakuumrückstand aus Nahost-Rohöl zusammen mit 15 Gew.-% einer gebrauchten Industriereinigerlösung mit einem Chlorgehalt von 4 Gew.-% und 15 Gew.-% Klärschlamm (getrocknet auf kleiner 2 Gew.-% Restfeuchte) mit 1,5 m³ H₂ pro kg eingesetzter Maische bei 210 bar Wasserstoffpartialdruck umgesetzt. Der Klärschlamm wurde so aufgemahlen, daß 90 % des Materials im Kornspektrum kleiner 90 »m und 10 % zwischen 100 und 150 »m haben. Zur Einbindung des Chlors wurden 1 Gew.-% Na₂S bezogen auf Maische kontinuierlich zudosiert. Bei 465 °C im Sumpfphasereaktor wurde der Vakuumrückstand zu 91 Gew.-% in leichtersiedende Produkte umgewandelt. Diese Produkte enthalten weniger als 1 Gew.-% ppm Chlor, der organische Anteil des Klärschlammes ist zu mehr als 75 Gew.-% in flüssige Produkte umgesetzt. Eine Kohlenwasserstoffgasbildung (C₁ - C₄) von 8,1 Gew.-% bezogen auf eingesetzte Maische wurde dabei beobachtet.In a continuously operated hydrogenation plant with a bottom phase reactor without internals, a vacuum residue from Middle East crude oil is mixed with 15% by weight of a used industrial cleaning solution with a chlorine content of 4% by weight and 15% by weight sewage sludge (dried to less than 2% by weight). -% residual moisture) with 1.5 m³ H₂ per kg of mash used at 210 bar hydrogen partial pressure. The sewage sludge was ground in such a way that 90% of the material in the grain spectrum was less than 90 »m and 10% between 100 and 150» m. To incorporate the chlorine, 1% by weight Na₂S based on the mash was metered in continuously. At 465 ° C. in the bottom phase reactor, the vacuum residue was converted to 91% by weight into low-boiling products. These products contain less than 1 wt .-% ppm chlorine, the organic part of the sewage sludge is more than 75 wt .-% in liquid Products implemented. A hydrocarbon gas formation (C₁ - C₄) of 8.1 wt .-% based on the mash used was observed.

Beispiel 3:Example 3:

In einer kontinuierlich betriebenen Hydrieranlage mit einer kombinierten Sumpf-/Gasphasenhydrierung wird ein venezolanischer Vakuumrückstand zusammen mit 30 Gew.-% (bezogen auf Vakuumrückstand), entsprechend 22,7 Gew.-% bezogen auf insgesamt eingesetzte Maische einer gebrauchten Metallentfettungslösung umgesetzt. Die aromatische und phenolhaltige Entfettungslösung weist einen Chlorgehalt von 1,02 Gew.-% auf und Gehalte an Sauerstoff von 3,7 Gew.-%, an Stickstoff von 0,92 Gew.-% und Schwefel von 0,98 Gew.-%, der Anteil kleiner 200 °C siedend beträgt 44 Gew.-%, der Anteil der Fraktion 200 bis 350 °C 22 Gew.-%. Die Umsetzung in der Sumpfphasenhydrierung erfolgt unter Zusatz von 2 Gew.-% eines Braunkohlenkokses mit Korngrößen von 1,5 Gew.-% kleiner als 90 »m und 0,5 Gew.-% von 100 bis 400 »m bei einem spezifischen Durchsatz von 0,5 kg/l.h (bezogen auf Vakuumrückstand), einem H₂/Öl-Verhältnis von 2000 Nm³/t und einem Wasserstoffpartialdruck von 200 bar. Bei 465 °C wurde der eingesetzte Vakuumrückstand zu 90 Gew.-% in leichtersiedende Produkte (weniger als 500 °C) umgewandelt. Das Primärprodukt der Sumpfphasenhydrierung weist einen Chlorgehalt von weniger als 1 Gew.-% ppm auf. Durch Zusatz der doppelt stöchiometrischen Menge von Natriumsulfid wird das in der Metallentfettungslösung enthaltene Chlor als Natriumchlorid mit einem Heißabscheiderfeststoff ausgetragen. Das Primärprodukt der Sumpfphasenhydrierung wird in der direkt angekoppelten Gasphasenhydrierung bei 380 °C und einer Katalysatorbelastung von 2,0 kg/kg.h einer katalytischen Festbettraffination an einem handelsüblichen Raffinationskontakt unterworfen. Das erzeugte Gesamtprodukt nach der Gasphasenhydrierung ist phenolfrei und frei von Chlor, der Gehalt an Schwefel und Stickstoff ist kleiner 0,1 Gew.-%.In a continuously operated hydrogenation system with a combined bottom / gas phase hydrogenation, a Venezuelan vacuum residue is reacted together with 30% by weight (based on vacuum residue), corresponding to 22.7% by weight based on the total mash used, of a used metal degreasing solution. The aromatic and phenol-containing degreasing solution has a chlorine content of 1.02% by weight and oxygen contents of 3.7% by weight, nitrogen of 0.92% by weight and sulfur of 0.98% by weight. , the fraction boiling below 200 ° C is 44% by weight, the fraction of the fraction 200 to 350 ° C is 22% by weight. The reaction in the bottom phase hydrogenation is carried out with the addition of 2% by weight of a brown coal coke with grain sizes of 1.5% by weight less than 90 »m and 0.5% by weight from 100 to 400» m with a specific throughput of 0.5 kg / lh (based on vacuum residue), an H₂ / oil ratio of 2000 Nm³ / t and a hydrogen partial pressure of 200 bar. At 465 ° C, the vacuum residue used was converted to 90% by weight into low-boiling products (less than 500 ° C). The primary product of the bottom phase hydrogenation has a chlorine content of less than 1% by weight ppm. By adding twice the stoichiometric amount of sodium sulfide, the chlorine contained in the metal degreasing solution becomes sodium chloride with a Hot separator solid discharged. The primary product of the bottom phase hydrogenation is subjected to a catalytic fixed bed refining in a commercially available refining contact in the directly coupled gas phase hydrogenation at 380 ° C and a catalyst load of 2.0 kg / kg.h. The total product produced after the gas phase hydrogenation is phenol-free and free of chlorine, the sulfur and nitrogen content is less than 0.1% by weight.

Beispiel 4:Example 4:

In einer kontinuierlich betriebenen Hydrieranlage mit einem Sumpfphasereaktor ohne Einbauten wird ein venezolanischer Vakuumrückstand zusammen mit 10 Gew.-% eines Destillationsrückstandes aus dem Lösungsmittelrecycling (bei 100 °C im Vakuum getrocknet, gemahlen und abgesiebt auf kleiner 150 »m, wovon 75 Gew.-% eine Teilchengröße kleiner 90 und 25 Gew.-% eine Teilchengröße von 100 bis 150 »m aufweisen) bei einem spezifischen Durchsatz von 0,5 kg Maische/l.h, einem H₂/Öl-Verhältnis von 3000 Nm³/t und einem Wasserstoffpartialdruck von 200 bar umgesetzt. Bei 456 °C wird der eingesetzte Vakuumrückstand zu 94 Gew.-% in leichtersiedende Produkte umgesetzt. Der organische Anteil des Destillationsrückstandes (Aschegehalt: 17 Gew.-%, Kohlenstoffgehalt: 54 Gew.-%, Wasserstoffgehalt: 6,5 Gew.-%, Schwefelgehalt: 0,2 Gew.-%, Rest: Stickstoff und Sauerstoff) wird zu über 80 Gew.-% in Flüssigprodukte und Gase umgesetzt.In a continuously operated hydrogenation plant with a bottom phase reactor without internals, a Venezuelan vacuum residue together with 10% by weight of a distillation residue from solvent recycling (dried at 100 ° C. in vacuo, ground and sieved to less than 150 »m, of which 75% by weight a particle size less than 90 and 25 wt .-% have a particle size of 100 to 150 »m) with a specific throughput of 0.5 kg mash / lh, an H₂ / oil ratio of 3000 Nm³ / t and a hydrogen partial pressure of 200 bar implemented. At 456 ° C, 94% by weight of the vacuum residue used is converted into low-boiling products. The organic fraction of the distillation residue (ash content: 17% by weight, carbon content: 54% by weight, hydrogen content: 6.5% by weight, sulfur content: 0.2% by weight, balance: nitrogen and oxygen) becomes over 80% by weight converted into liquid products and gases.

Claims (13)

  1. Process for the hydroconversion of
    - heavy and residual oils,
    - used and waste oils, and
    - optionally their mixtures with ground brown or hard coals
    in the liquid phase or combined liquid and gas phase with water-containing gases at
    - a hydrogen partial pressure of 50 to 350 bar, preferably 150 to 200 bar,
    - a temperature of 250 to 500°C, preferably 400 to 490°C,
    - a gas/oil ratio of 100 to 10 000 Nm³/t, preferably 1000 to 5000 Nm³/t, of liquid and solid charge stocks,
    characterized in that
    at least one solid is added
    - in amounts of 0.1 to 15% by weight, based on the total amount of liquid and solid charge stocks, and with the particle size ranges
    · 90 »m or less and
    · 100 »m to 1000 »m, preferably 100 to 500 »m
    which are each present either within a continuous particle size distribution or preferably as two sharply separated fractions,
    and
    mixtures of
    a) heavy or residual oils,
    b)
    · used and waste oils, namely,
    - PCB-containing or halogen-containing used oils which may also contain solids,
    - transformer oils,
    - hydraulic fluids,
    - landfill seepage oils,
    - bilge oils
    · sewage sludges from
    - preliminary clarification tanks,
    - biological clarification,
    - digesting towers,
    · paint sludges,
    · halogen-containing solvents,
    · organic residues from
    - chemical-cleaner establishments,
    - parts degreasing,
    - cleaning baths,
    - tank cleaning,
    - the distillation of halogen-containing solvents or from recycling processes,
    or
    · plastics materials, used plastics materials, plastics production wastes
    are used at a throughput of 0.1 to 2 t/m³ h, based on heavy or residual oil, and in a ratio by weight of 100:1 to 1:1.5.
  2. Process according to Claim 1, characterized in that coal and the other feedstocks are used in a proportion by weight of 1:20 to 1.5:1, preferably 1:5 to 4:5.
  3. Process according to Claim 1 or 2, characterized in that a portion of the coal equivalent to the proportion to be used of the coarse particle fraction of the solid with two particle size ranges is used in particle sizes of 100 »m or greater.
  4. Process according to at least one of the preceding claims, characterized in that 0.5 to 5.0% by weight of a carbon-containing, large-surface suspended solid with two particle size ranges is used in the liquid-phase hydrogenation.
  5. Process according to at least one of the preceding claims, characterized in that brown-coal cokes from shaft and hearth-type furnaces, soots from the gasification of heavy oil, hard coal, hydrogenation residues or brown coal and the active cokes produced therefrom, petroleum cokes and dusts from the Winkler gasification of coal are used as solid with two particle size ranges.
  6. Process according to at least one of the preceding claims, characterized in that the carbon-containing solids with two particle size ranges used are impregnated with metal-salt solutions of subgroup 1 to 8 and of main group 4 of the periodic system of elements, preferably iron, cobalt, nickel, vanadium, molybdenum.
  7. Process according to at least one of Claims 1 to 3, characterized in that 0.5 to 5.0% by weight of red mud, iron oxide, electrostatic filter dusts and cyclone dusts from metal-ore processing are used as solid with two particle size ranges.
  8. Process according to at least one of the preceding claims, characterized in that the proportion of the coarse particle fraction is 20% by weight or more of the solid with two particle size ranges added.
  9. Process according to at least one of the preceding claims, characterized in that 0.01 to 5.0% by weight of a compound which forms salts with hydrogen halide by neutralization or cleaves hydroxide ions in aqueous solution is added with the charge stocks.
  10. Process according to Claim 9, characterized in that the compound which forms salts with hydrogen halide by neutralization or detaches hydroxide ions in aqueous solution is injected together with water into the outflow of the liquid-phase reactor.
  11. Process according to Claim 9 or 10, characterized in that 0.01 to 5.0% by weight of Na₂S is added.
  12. Process according to at least one of the preceding claims, characterized in that, in the hydrogenation of mixtures of heavy and residual oils, or used or waste oils together with sewage sludge, the ratio by weight of oil to sewage sludge being 10:1 to 1:1.5, a sewage sludge is used which contains an appropriate proportion of coarse particle fraction of 100 »m or greater.
  13. Process according to Claim 12, characterized in that the sewage sludge used is dried to water contents of less than 10.0, preferably less than 2.0% by weight and, if necessary, freed of coarse foreign bodies by grinding, screening and/or classifying processes and converted to a particle size of less than 1.0, preferably less than 0.5 mm.
EP88103755A 1987-03-30 1988-03-10 Process for the hydroconversion of heavy and residual oils Expired - Lifetime EP0287796B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873710021 DE3710021A1 (en) 1987-03-30 1987-03-30 METHOD FOR HYDROGENATING CONVERSION OF HEAVY AND RESIDUAL OILS
DE3710021 1987-03-30

Publications (2)

Publication Number Publication Date
EP0287796A1 EP0287796A1 (en) 1988-10-26
EP0287796B1 true EP0287796B1 (en) 1995-12-06

Family

ID=6324069

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88103755A Expired - Lifetime EP0287796B1 (en) 1987-03-30 1988-03-10 Process for the hydroconversion of heavy and residual oils

Country Status (11)

Country Link
US (1) US4941966A (en)
EP (1) EP0287796B1 (en)
JP (1) JPS63260984A (en)
AT (1) ATE131203T1 (en)
CA (1) CA1304310C (en)
DD (1) DD268477A5 (en)
DE (2) DE3710021A1 (en)
ES (1) ES2081283T3 (en)
GR (1) GR3018806T3 (en)
NO (1) NO174933C (en)
RU (1) RU1836408C (en)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5166118A (en) * 1986-10-08 1992-11-24 Veba Oel Technologie Gmbh Catalyst for the hydrogenation of hydrocarbon material
DE3737370C1 (en) * 1987-11-04 1989-05-18 Veba Oel Entwicklungs Gmbh Process for the hydroconversion of heavy and residual soils, waste and waste allogols mixed with sewage sludge
US5374348A (en) * 1993-09-13 1994-12-20 Energy Mines & Resources - Canada Hydrocracking of heavy hydrocarbon oils with heavy hydrocarbon recycle
US5849172A (en) * 1997-06-25 1998-12-15 Asarco Incorporated Copper solvent extraction and electrowinning process
US5904838A (en) * 1998-04-17 1999-05-18 Uop Llc Process for the simultaneous conversion of waste lubricating oil and pyrolysis oil derived from organic waste to produce a synthetic crude oil
US7444305B2 (en) * 2001-02-15 2008-10-28 Mass Connections, Inc. Methods of coordinating products and service demonstrations
US7615196B2 (en) 2003-12-19 2009-11-10 Shell Oil Company Systems for producing a crude product
US7745369B2 (en) 2003-12-19 2010-06-29 Shell Oil Company Method and catalyst for producing a crude product with minimal hydrogen uptake
US7811445B2 (en) 2003-12-19 2010-10-12 Shell Oil Company Systems and methods of producing a crude product
TW200602591A (en) * 2004-07-08 2006-01-16 hong-yang Chen Gas supply device by gasifying burnable liquid
US7678264B2 (en) 2005-04-11 2010-03-16 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US7918992B2 (en) 2005-04-11 2011-04-05 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US20080087578A1 (en) 2006-10-06 2008-04-17 Bhan Opinder K Methods for producing a crude product and compositions thereof
TW201026837A (en) * 2008-09-17 2010-07-16 Bdi Bio Diesel Internat Ag Process for obtaining combustibles and fuels, respectively
US9168506B2 (en) 2010-01-21 2015-10-27 Intevep, S.A. Additive for hydroconversion process and method for making and using same
GB2478332A (en) 2010-03-04 2011-09-07 Grimley Smith Associates Method of metals recovery from refinery residues
US8999145B2 (en) 2012-10-15 2015-04-07 Uop Llc Slurry hydrocracking process
WO2014142874A1 (en) 2013-03-14 2014-09-18 Bp Europa Se Process for introducing fine and coarse additives for hydroconversion of heavy hydrocarbons
US10745629B2 (en) 2017-01-16 2020-08-18 Council Of Scientific And Industrial Research Process for upgradation of heavy crude oil/residue using waste plastic as hydrogen donating agent
CN111909719A (en) * 2020-06-19 2020-11-10 张家港保税区慧鑫化工科技有限公司 Production system and production method for heavy oil to produce naphtha in large quantity
CN111849554A (en) * 2020-07-03 2020-10-30 张家港保税区慧鑫化工科技有限公司 Garbage liquid-phase suspension bed hydrotreatment system and technology
CN111808632A (en) * 2020-07-17 2020-10-23 张家港保税区慧鑫化工科技有限公司 Method for processing mixture of oil and organic waste
CN111808636A (en) * 2020-07-17 2020-10-23 张家港保税区慧鑫化工科技有限公司 Sludge heavy oil treatment method
CN111849555A (en) * 2020-07-21 2020-10-30 张家港保税区慧鑫化工科技有限公司 System and method for hydrotreating halogen-containing waste oil
EP4032963A1 (en) 2021-01-21 2022-07-27 Basell Poliolefine Italia S.r.l. Process for hydrodepolymerization of polymeric waste material

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3704108A (en) * 1970-09-25 1972-11-28 Hydrocarbon Research Inc Hydroconversion of waste natural and synthetic rubbers
CA1079663A (en) * 1976-08-13 1980-06-17 Maurice M. Mitchell (Jr.) Process for hydrodesulfurization of carbonaceous stocks using suspended catalyst
US4089773A (en) * 1976-12-01 1978-05-16 Mobil Oil Corporation Liquefaction of solid carbonaceous materials
DE2654635B2 (en) * 1976-12-02 1979-07-12 Ludwig Dr. 6703 Limburgerhof Raichle Process for the continuous production of hydrocarbon oils from coal by cracking pressure hydrogenation
JPS5458704A (en) * 1977-10-20 1979-05-11 Bridgestone Corp Hydrocracking of waste rubber
US4370221A (en) * 1981-03-03 1983-01-25 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources Catalytic hydrocracking of heavy oils
CA1151579A (en) * 1981-10-07 1983-08-09 Ramaswami Ranganathan Hydrocracking of heavy hydrocarbon oils with high pitch conversion
US4448665A (en) * 1982-12-30 1984-05-15 Exxon Research And Engineering Co. Use of ammonia to reduce the viscosity of bottoms streams produced in hydroconversion processes
DE3326284C2 (en) * 1983-07-21 1985-08-14 Fried. Krupp Gmbh, 4300 Essen Process for the production of liquid hydrocarbons
DE3442506C2 (en) * 1984-11-22 1987-04-16 Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln Process for the processing of carbon-containing waste
US4623448A (en) * 1985-03-12 1986-11-18 Moreco Energy, Inc. Removing halogenated polyphenyl materials from used oil products
JP3153350B2 (en) * 1992-07-28 2001-04-09 日本電子株式会社 Electron microscope with automatic focusing

Also Published As

Publication number Publication date
JPS63260984A (en) 1988-10-27
US4941966A (en) 1990-07-17
DD268477A5 (en) 1989-05-31
NO881408D0 (en) 1988-03-29
GR3018806T3 (en) 1996-04-30
RU1836408C (en) 1993-08-23
EP0287796A1 (en) 1988-10-26
NO174933C (en) 1994-08-03
DE3710021A1 (en) 1988-10-20
CA1304310C (en) 1992-06-30
ATE131203T1 (en) 1995-12-15
NO881408L (en) 1988-10-03
ES2081283T3 (en) 1996-03-01
NO174933B (en) 1994-04-25
DE3854747D1 (en) 1996-01-18

Similar Documents

Publication Publication Date Title
EP0287796B1 (en) Process for the hydroconversion of heavy and residual oils
EP0182309B1 (en) Process for the hydrotreatment of carbon-containing wastes of primarily synthetic origin
EP0236701B1 (en) Process for the recovery of carbon-containing wastes
EP0263522B1 (en) Process for the hydroconversion of heavy and residual oils
DE68908205T2 (en) Recycling of oil-containing refining residues.
DE3737370C1 (en) Process for the hydroconversion of heavy and residual soils, waste and waste allogols mixed with sewage sludge
EP0257260B2 (en) Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls
DE69201276T2 (en) Process for reactivating exhausted hydrotreatment catalysts with alumina supports.
EP0377606B1 (en) Process for purifying and regenerating used oils
DE2729533A1 (en) METHOD FOR HYDROCONVERTING AN OIL / COAL MIXTURE
EP0330757B1 (en) Process for reprocessing waste materials or the like by pyrolysis, and subsequent further processing of the pyrolysis oil
DE10215679B4 (en) Direct thermochemical conversion of high molecular weight organic substances into low viscosity liquid fuels
EP0249748B1 (en) Process for the destructive hydrogenation of carbon-containing wastes in a fluidized bed
DE1212662B (en) Process for removing metallic and nitrogenous impurities from hydrocarbon oils
EP0291698B1 (en) Improved process for the hydrocracking of carbon containing synthetic wastes
EP0534046B1 (en) Process for the disintegration of contaminated plastics
DE4447317C2 (en) Moldings, their production and their use
CN111808632A (en) Method for processing mixture of oil and organic waste
DE19547259A1 (en) Production of hydrocarbon(s) from thermoplastic waste plastic
DE4412360C2 (en) Process for the combined recycling of mixed and contaminated plastic waste
DD249036A5 (en) Process for the treatment of waste containing carbon
DE3504183A1 (en) Coal liquefaction process
DE3320410A1 (en) Process for the two-stage treatment of solid shale materials containing shale oil

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19881122

17Q First examination report despatched

Effective date: 19890828

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: VEBA OEL TECHNOLOGIE GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG GMBH

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KRETSCHMER, KLAUS

Inventor name: NIEMANN, KLAUS, DR.

Inventor name: MERZ, LUDWIG, DR.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 131203

Country of ref document: AT

Date of ref document: 19951215

Kind code of ref document: T

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19951207

REF Corresponds to:

Ref document number: 3854747

Country of ref document: DE

Date of ref document: 19960118

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: TROESCH SCHEIDEGGER WERNER AG

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2081283

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3018806

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20020211

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20020218

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20020222

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20020225

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20020228

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20020308

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020311

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20020325

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20020329

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20020331

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20020607

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030310

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030310

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030310

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030311

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030331

BERE Be: lapsed

Owner name: *VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG G.M.B.H.

Effective date: 20030331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031001

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031002

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20030310

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031127

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20031001

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030311

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050310