EP0257260A1 - Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls - Google Patents

Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls Download PDF

Info

Publication number
EP0257260A1
EP0257260A1 EP87109958A EP87109958A EP0257260A1 EP 0257260 A1 EP0257260 A1 EP 0257260A1 EP 87109958 A EP87109958 A EP 87109958A EP 87109958 A EP87109958 A EP 87109958A EP 0257260 A1 EP0257260 A1 EP 0257260A1
Authority
EP
European Patent Office
Prior art keywords
oil
oils
alkali metal
hydrogenation
coal
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
EP87109958A
Other languages
German (de)
French (fr)
Other versions
EP0257260B1 (en
EP0257260B2 (en
Inventor
Werner Dr. Döhler
Rolf Dr. Holighaus
Klaus Dr. Niemann
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6304975&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0257260(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Veba Oel Technologie und Automatisierung GmbH filed Critical Veba Oel Technologie und Automatisierung GmbH
Priority to AT87109958T priority Critical patent/ATE68099T1/en
Publication of EP0257260A1 publication Critical patent/EP0257260A1/en
Publication of EP0257260B1 publication Critical patent/EP0257260B1/en
Application granted granted Critical
Publication of EP0257260B2 publication Critical patent/EP0257260B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00—Liquid purification or separation
    • Y10S210/902—Materials removed
    • Y10S210/908—Organic
    • Y10S210/909—Aromatic compound, e.g. pcb, phenol

Definitions

  • the invention relates to a process for the hydrogenating treatment of mineral oils contaminated with chlorobiphenyls, bromobiphenyls, chlorinated naphthalenes and terphenyls or other chloroaromatics as well as chlorinated paraffins or chloronaphthenes, in particular so-called waste oils and distillation residues of such mineral oils.
  • PCB-containing liquids or PCB-containing liquids mixed with oil residues after their use are to be regarded as special waste, which must be recorded, properly handled and disposed of or safely deposited.
  • thermal incineration processes therefore require extensive precautions to control and possibly treat the resulting exhaust gases and, if necessary, also to treat and landfill any solid residues that may occur. Even so, thermal combustion processes are the most developed and widely used. The remaining processes are partly only developed on a laboratory scale or on a semi-industrial scale.
  • the object of the invention is to provide a process which can be used on an industrial scale to indicate chlorine-containing waste oils, which bring about a breakdown, in particular of multiply chlorinated biphenyls, to values of up to 1 ppm and below, and in which the mineral base oils contained as the main constituent are recycled without being lost, for example, by incineration or other degradation processes.
  • this object is achieved in that the above-mentioned feed hydrogen pressurization under the typical conditions of a sump phase hydrogenation or a combined sump / gas phase hydrogenation at hydrogen pressures of 20 to 325 bar, temperatures of 250 to 500 ° C and gas-oil ratios of 100 to 3000 Nm3 / t are subjected.
  • This method is particularly suitable for waste oils containing PCB or with drilling oils, cutting oils, transformer oils, hydraulic oils and the like. Work up mixed used oils in a sump or combined sump / gas phase hydrogenation.
  • the feed oils are preferably used as such or in a mixture with residual oils, heavy oils or finely ground coal in the bottom phase hydrogenation, and if coal is used, a step is provided for preparing the mixture of finely ground coal and the oil components.
  • a finely divided, carbon-containing, surface-rich suspended material additive
  • additive which can optionally be mixed with heavy metal salts, especially iron (II ) -Sulfate can be impregnated as a single-use catalyst in the mixture preparation.
  • the feed mixture then goes through a compression stage and is charged with hydrogen-containing cycle gas and fresh hydrogen. After passing through heat exchangers, in which there is a heat exchange with product streams for heating the feed mixture, the mixture passes through a so-called preheater and enters the bottom phase reactor from below. They are generally vertical tubular reactors without internals.
  • the hydrogenation reaction takes place at elevated pressure, preferably at hydrogen pressures between 20 and 325 bar, and at elevated temperature, preferably between 250 and 500 ° C and at gas-oil ratios of preferably 100 to 3000 Nm3 / t, which is Gas is the hydrogenous hydrogenation gas.
  • Gas is the hydrogenous hydrogenation gas.
  • the reaction products are useful passed over a hot separator operated at reaction pressure and at a temperature which is preferably 20 to 50 ° C.
  • the uncondensed hydrocarbons are taken off overhead and the bottom products containing residues at the bottom.
  • Distillable heavy oil constituents can be separated in a downstream stripper and can be further processed by combining with the top product of the hot separator.
  • the residue behind the stripper can be used to generate hydrogen or energy.
  • a gas phase hydrogenation for further processing of the uncondensed reaction products which have been drawn off at the top of the hot separator can be coupled directly to the previously described bottom phase hydrogenation without reheating or depressurization.
  • the further hydrogenation, stabilization and removal in the gas phase hydrogenation, for example of heteroatoms such as sulfur or nitrogen, to obtain feedstocks with reformer feed specification or of middle distillate is carried out on fixed bed catalysts using commercially available catalysts.
  • the product streams After passing through the gas phase hydrogenation, the product streams are condensed and cooled by intensive heat exchange and separated into a liquid phase and a gas phase in a high-pressure cold separator. After relaxation of the Liquid phase is usually fed to a stabilizing column to remove the C4 products and to obtain a stabilized syncrude.
  • the gaseous products pass through a scrubber to remove, among others, H2S and NH3. Part of the purified hydrogen-rich gas is recycled as cycle gas into the bottom phase hydrogenation.
  • a scrubber to remove, among others, H2S and NH3.
  • Part of the purified hydrogen-rich gas is recycled as cycle gas into the bottom phase hydrogenation.
  • the separation takes place depending on the determination of the boiling sections in naphtha, middle distillate and vacuum gas oil. If coal and feed oil are used together, the ratio is preferably 1:20 to 1: 1, in particular 1: 5 to 4: 5.
  • a cold separator stage with subsequent expansion and separation of the liquid products into an aqueous phase and a mineral oil-containing phase and an atmospheric distillation of the oil-containing phase can also directly follow the bottom phase hydrogenation.
  • the additives in particular are the suspended lignite coke from shaft and hearth furnaces, lignite grit, soot from the gasification of heavy oil, hard coal, lignite or hydrogenation residues and activated coke, petroleum coke and dusts produced from the Winkler gasification and high-temperature Winkler gasification of coal, ie materials with a large inner surface and with a pore structure for demetallization and deasphalting as well as for the absorption of coke precursors when carrying out the bottom phase hydrogenation.
  • red masses, Bavarian masses, iron oxides and electrostatic filter dust and cyclone dust from metal / ore processing can also be used with advantage.
  • the proportion of these additives is preferably 0.5 to 5% by weight and, if carbon-containing additives are used, these can be mixed with salts of metals of 1. to 8th subgroup and the 4th main group of the periodic system of the elements, preferably iron, cobalt, nickel, vanadium, molybdenum, for example Fe (II) sulfate.
  • a compound which forms salts with hydrogen halide in particular hydrogen chloride by neutralization or cleaves hydroxide ions in aqueous solution
  • a compound which forms salts with hydrogen halide in particular hydrogen chloride by neutralization or cleaves hydroxide ions in aqueous solution
  • water in the effluent from the bottom phase reactor e.g. . B. inject the feed lines of the cold separator.
  • a compound which forms salts with hydrogen halide in particular hydrogen chloride by neutralization or cleaves hydroxide ions in aqueous solution
  • water in the effluent from the bottom phase reactor e.g. . B. inject the feed lines of the cold separator.
  • an alkali metal hydroxide, alkali metal carbonate, alkali metal acetate, alkali metal alcoholate, alkali metal sulfide, corresponding ammonium compounds insofar as they exist in bulk or in aqueous solution, or mixtures of the aforementioned compounds.
  • ammonium chloride When adding ammonium compounds or ammonia-water mixtures, ammonium chloride is suitable because of the tendency to sublimate Take precautionary measures to avoid clogging, for example of the cold separator product lines.
  • Alkaline earth compounds can also be used to neutralize the hydrogen halide and form water-soluble salts.
  • the sodium compounds for example sodium sulfide, are preferred.
  • PCB polychlorobiphenyl
  • the lubricating oil fraction in the raffinate (fracture 300 - 500 ° C) has a viscosity index of 120, making it a base oil component for the production of a quality motor oil.
  • a vacuum residue from Ba Ceiro crude oil with a residue content> 500 ° C. of 6% by weight is added with 15% by weight of a used industrial oil with a chlorine content of 10,000,000.
  • This mixture is hydrogenated after adding 1.8% active coke and 0.2% Na2S at 450 ° C and 220 bar in the bottom phase reactor.
  • the vacuum residue is converted to 9l% into low-boiling components and gaseous substances, whereby the liquid products produced are PCB-free, ie below the gas chromatographic detection limit.
  • the table shows the distribution of use and products.
  • the proposed method is therefore much more economical with regard to the practically complete degradation of PCB than the thermal combustion process for waste oils contaminated with PCB, which is also carried out on an industrial scale, and it also avoids the problems associated with combustion of the formation of non-harmless secondary products of the combustion of chlorinated hydrocarbons or Oils containing chlorobiphenyls.

Abstract

Halogen-containing oils and hydrocarbons are treated on an industrial scale whereby the mineral base oils comprising the main component of the oils hydrocarbons can be reused. The oils are subjected to a high pressure hydrogenation under typical conditions of liquid phase hydrogenation or of combined liquid-phase and gas-phase hydrogenation, at hydrogen pressures of 20-325 bar, temperatures of 250 DEG -500 DEG C., and gas/oil ratios of 100-300 m3 per metric ton at STP.

Description

Die Erfindung betrifft ein Verfahren zur hydrierenden Behandlung von mit Chlorbiphenylen, Brombiphenylen, chlorierten Naphthalinen und Terphenylen oder anderen Chloraromaten sowie Chlorparaffinen bzw. Chlornaphthenen kontaminierten Mineralölen, insbesondere sogenannten Altölen sowie von Destillationsrückständen solcher Mineralöle.The invention relates to a process for the hydrogenating treatment of mineral oils contaminated with chlorobiphenyls, bromobiphenyls, chlorinated naphthalenes and terphenyls or other chloroaromatics as well as chlorinated paraffins or chloronaphthenes, in particular so-called waste oils and distillation residues of such mineral oils.

Bei den vorgenannten Chlorkohlenwasserstoffen sind in dem vorliegenden Zusammenhang die meist mehrfach chlorierten Biphenyle, häufig auch als PCB bezeichnet, an erster Stelle hinsichtlich der Möglichkeiten zu ihrer gefahrlosen Beseitigung zu untersuchen. Diese Verbindungen, für die inzwischen MAK-Werte je nach Chlorgehalt von 0,5 bis l,0 mg/m³ festgesetzt wurden und für deren Herstellung und Weiterverwendung weitgehende behördliche Beschränkungen erlassen worden sind, wurden wegen ihrer thermischen und chemischen Stabilität und ihrer dielektrischen Eigenschaften als Isolier- und Kühlflüssigkeiten beim Bau von Starkstromkondensatoren, Trafos und Gleichrichtern, als Weichmacher für Lackharze und Kunststoffe, Sperrflüssigkeiten, Tränkmittel für Dichtungen, Hydrauliköle und Wärmeübertragungsmittel eingesetzt (vgl. Römpps Chemielexikon, 8. Auflage, Seite 7l5).In the case of the aforementioned chlorinated hydrocarbons, the mostly multiply chlorinated biphenyls, often also referred to as PCBs, are to be examined in the first place with regard to the possibilities for their safe removal. These compounds, for which meanwhile MAK values of 0.5 to 1.0 mg / m³ have been determined depending on the chlorine content and for the manufacture and further use of which extensive official restrictions have been imposed, were considered to be due to their thermal and chemical stability and their dielectric properties Insulating and cooling liquids used in the construction of high-voltage capacitors, transformers and rectifiers, as plasticizers for paint resins and plastics, sealing liquids, impregnating agents for seals, hydraulic oils and heat transfer agents (see Römpps Chemielexikon, 8th edition, page 7l5).

Wegen ihrer geringen Abbaubarkeit und wegen der Notwendigkeit, die Chlorbiphenyle und verwandte sonstige Chlorkohlenwasserstoffe sicher zu beseitigen, besteht ein Bedürfnis nach einem hierfür geeigneten industriell durchführbaren Verfahren.Because of their low degradability and because of the need to safely remove the chlorobiphenyls and related other chlorinated hydrocarbons, there is a need for a suitable industrially feasible process.

Insbesondere sind PCB-haltige Flüssigkeiten oder nach ihrem Gebrauch mit Ölresten vermengte PCB-haltige Flüssigkeiten als Sondermüll anzusehen, der erfaßt, sachgemäß behandelt und beseitigt bzw. sicher deponiert werden muß.In particular, PCB-containing liquids or PCB-containing liquids mixed with oil residues after their use are to be regarded as special waste, which must be recorded, properly handled and disposed of or safely deposited.

Zur Beseitigung von Chlorbiphenylen sind thermische Verbrennungsverfahren, Adsorbtionsverfahren oder Verfahren zur Lösungsmittelextraktion, Verfahren zur katalytischen Behandlung mit Wasserstoff in Gegenwart organischer Lösungsmittel, Chlorolyseverfahren unter Behandlung mit Chlor in der Dampfphase, Verfahren zur Dehalogenierung mittels Natrium oder natrium-organischer Substanzen, Mikrowellen-Plasma-Verfahren, Ozonisierungsverfahren, Verfahren zur Reaktion mit einem in Gegenwart von Sauerstoff aus Natriummetall und Polyethylenglykolen hergestellten Reagenz, Verfahren zur Spaltung des PCB-Moleküls in Biphenyl und Chlor sowie Verfahren der direkten Oxidation von Chlorbiphenylen mittels Luft oder Sauerstoff in wäßriger Phase in Gegenwart von Säuren bei erhöhten Temperaturen entwickelt worden (vgl. D. G. Ackerman et al "Distruction and Disposal of PCBs by Thermal and Non-Thermal Methods", Noyes Data Corporation, Park Ridge, New Jersey, U.S.A., l983).For the removal of chlorobiphenyls are thermal combustion processes, adsorption processes or processes for solvent extraction, processes for catalytic treatment with hydrogen in the presence of organic solvents, chlorolysis processes with treatment with chlorine in the vapor phase, processes for dehalogenation using sodium or sodium-organic substances, microwave-plasma processes , Ozonization processes, processes for reaction with a reagent prepared in the presence of oxygen from sodium metal and polyethylene glycols, processes for cleaving the PCB molecule into biphenyl and chlorine and processes for direct oxidation of chlorobiphenyls by means of air or oxygen in the aqueous phase in the presence of acids at elevated temperatures Temperatures have been developed (cf. DG Ackerman et al "Distruction and Disposal of PCBs by Thermal and Non-Thermal Methods", Noyes Data Corporation, Park Ridge, New Jersey, USA, l983).

Keines der aufgeführten Verfahren kann als für alle Einsatzfälle geeignetes, ohne Einschränkungen anwendbares Verfahren angesehen werden. So erfordern die thermischen Verbrennungsverfahren umfangreiche Vorkehrungen zur Kontrolle und eventuellen Nachbehandlung der entstehenden Abgase und ggf. auch zur Behandlung und Deponie eventuell anfallender fester Rückstände. Trotzdem sind die Verfahren zur thermischen Verbrennung die am weitesten entwickelten und am meisten verbreiteten Verfahren. Die übrigen Verfahren sind teilweise erst im Labormaßstab oder im halbtechnischen Maßstab ausgearbeitet.None of the listed methods can be regarded as suitable for all applications and can be used without restrictions. The thermal incineration processes therefore require extensive precautions to control and possibly treat the resulting exhaust gases and, if necessary, also to treat and landfill any solid residues that may occur. Even so, thermal combustion processes are the most developed and widely used. The remaining processes are partly only developed on a laboratory scale or on a semi-industrial scale.

Als Beispiel seien die Untersuchungen von W. L. Kranich et al, "Process for Hydrodechlorination of Polychlorinated Hydrocarbons", l977, Presented at the American Chemical Society Div. of Pestizide Chemistry, l94th National Meeting, Chicago, Illinois, angeführt. Für dieses Verfahren sind Wasserstoffdrucke von 30 bis 50 bar, Nickel auf Kieselgur oder Palladium auf einem Kohlenstoffträger als Katalysator und Temperaturen im Bereich von etwa l00 bis l20 °C genannt worden. Als Lösungsmittel wird NaOH in Ethanol eingesetzt. Derartige Verfahren erfordern umfangreiche Lösungsmittelrückläufe und Lösungsmittelaufarbeitungen. Aus diesem Grunde ist eine großtechnische Realisierung noch nicht bekannt geworden.As an example, the studies by W. L. Kranich et al, "Process for Hydrodechlorination of Polychlorinated Hydrocarbons", l777, Presented at the American Chemical Society Div. of Pesticides Chemistry, l94th National Meeting, Chicago, Illinois. Hydrogen pressures of 30 to 50 bar, nickel on kieselguhr or palladium on a carbon support as catalyst and temperatures in the range of approximately 100 to 120 ° C. have been mentioned for this process. NaOH in ethanol is used as solvent. Such processes require extensive solvent refluxes and solvent workups. For this reason, a large-scale implementation has not yet become known.

Aufgabe der Erfindung ist es, ein im industriellen Maßstab anwendbares Verfahren zur Aufarbeitung chlorhaltiger Altöle anzugeben, welches einen Abbau insbesondere von mehrfach chlorierten Biphenylen auf Werte von bis zu l ppm und darunter bewirkt und bei dem die als Hauptbestandteil enthaltenen mineralischen Grundöle einer Wiederverwendung zugeführt werden ohne daß diese etwa durch Verbrennung oder andere Abbauverfahren verloren gehen würden.The object of the invention is to provide a process which can be used on an industrial scale to indicate chlorine-containing waste oils, which bring about a breakdown, in particular of multiply chlorinated biphenyls, to values of up to 1 ppm and below, and in which the mineral base oils contained as the main constituent are recycled without being lost, for example, by incineration or other degradation processes.

Gemäß der Erfindung wird diese Aufgabe dadurch gelöst, daß die vorgenannten Einsatzstoffe einer Druckhydrierung unter den typischen Bedingungen einer Sumpfphasenhydrierung oder einer kombinierten Sumpf-/Gasphasenhydrierung bei Wasserstoffdrucken von 20 bis 325 bar, Temperaturen von 250 bis 500 °C und Gas-Öl-Verhältnissen von l00 bis 3000 Nm³/t unterworfen werden.According to the invention, this object is achieved in that the above-mentioned feed hydrogen pressurization under the typical conditions of a sump phase hydrogenation or a combined sump / gas phase hydrogenation at hydrogen pressures of 20 to 325 bar, temperatures of 250 to 500 ° C and gas-oil ratios of 100 to 3000 Nm³ / t are subjected.

Dieses Verfahren ist insbesondere geeignet, PCB enthaltende Altöle oder mit Bohrölen, Schneidölen, Transformatorenölen, Hydraulikölen u. dgl. vermischte Altöle in einer Sumpf- bzw. kombinierten Sumpf-/Gasphasenhydrierung aufzuarbeiten.This method is particularly suitable for waste oils containing PCB or with drilling oils, cutting oils, transformer oils, hydraulic oils and the like. Work up mixed used oils in a sump or combined sump / gas phase hydrogenation.

Die Einsatzöle werden bevorzugt als solche oder in Mischung mit Rückstandsölen, Schwerölen oder auch feingemahlener Kohle in die Sumpfphasenhydrierung eingesetzt, wobei im Falle des Miteinsatzes von Kohle eine Stufe zur Bereitung des Gemisches aus feingemahlener Kohle und den Ölbestandteilen vorgesehen ist.The feed oils are preferably used as such or in a mixture with residual oils, heavy oils or finely ground coal in the bottom phase hydrogenation, and if coal is used, a step is provided for preparing the mixture of finely ground coal and the oil components.

Abhängig von dem gewünschten Umsatzgrad und der Tendenz der eingesetzten Öle zur Koksbildung kann es vorteilhaft sein, eine Menge zwischen 0,5 und 5 Gew.-% eines fein verteilten kohlenstoffhaltigen oberflächenreichen suspendierten Materials (Additiv), welches wahlweise mit Schwermetallsalzen, insbesondere Eisen(II)-Sulfat getränkt sein kann, als Einwegkatalysator in der Gemischzubereitung zuzusetzen. Das Einsatzgemisch durchläuft anschließend eine Kompressionsstufe und wird mit wasserstoffhaltigem Kreislaufgas und Frischwasserstoff beaufschlagt. Nach Durchlaufen von Wärmeaustauschern, bei dem ein Wärmeaustausch mit Produktströmen zur Aufheizung des Einsatzgemisches erfolgt, durchläuft das Gemisch einen sogenannten Vorheizer und tritt von unten in den Sumpfphasereaktor ein. Es handelt sich im allgemeinen um vertikale Rohrreaktoren ohne Einbauten. Die Hydrierreaktion läuft bei erhöhtem Druck, vorzugsweise bei Wasserstoffdrucken zwischen 20 und 325 bar, und erhöhter Temperatur, vorzugsweise zwischen 250 und 500 °C und bei Gas-Öl-Verhältnissen von vorzugsweise l00 bis 3000 Nm³/t, ab, wobei es sich bei dem Gas um das wasserstoffhaltige Hydriergas handelt. Der gewünschte Umsatzgrad und der geforderte Grenzwert für den Abbau beispielsweise der Chlorbiphenyle bestimmt die Strömungsgeschwindigkeit der Einsatzprodukte. Typische Werte sind 0,4 bis l,0 t/m³h. Im Falle des gemeinsamen Einsatzes von Ölbestandteilen und Kohle oder auch der Anwesenheit eines Additivs oder sonstiger Rückstände, z. B. von Bohrspänen, werden die Reaktionsprodukte zweckmäßig über einen bei Reaktionsdruck und bei einer um vorzugsweise 20 bis 50 °C gegenüber der Reaktionstemperatur erniedrigten Temperatur betriebenen Heißabscheider geleitet. Hier werden die nichtkondensierten Kohlenwasserstoffe über Kopf und die rückstandshaltigen Sumpfprodukte am Boden abgezogen. Destillierbare Schwerölbestandteile können in einem nachgeschalteten Stripper abgetrennt und durch Vereinigung mit dem Kopfprodukt des Heißabscheiders der weiteren Aufarbeitung zugeführt werden. Der hinter dem Stripper verbleibende Rückstand kann zur Wasserstoff- oder Energieerzeugung genutzt werden.Depending on the desired degree of conversion and the tendency of the oils used to form coke, it can be advantageous to add an amount between 0.5 and 5% by weight of a finely divided, carbon-containing, surface-rich suspended material (additive), which can optionally be mixed with heavy metal salts, especially iron (II ) -Sulfate can be impregnated as a single-use catalyst in the mixture preparation. The feed mixture then goes through a compression stage and is charged with hydrogen-containing cycle gas and fresh hydrogen. After passing through heat exchangers, in which there is a heat exchange with product streams for heating the feed mixture, the mixture passes through a so-called preheater and enters the bottom phase reactor from below. They are generally vertical tubular reactors without internals. The hydrogenation reaction takes place at elevated pressure, preferably at hydrogen pressures between 20 and 325 bar, and at elevated temperature, preferably between 250 and 500 ° C and at gas-oil ratios of preferably 100 to 3000 Nm³ / t, which is Gas is the hydrogenous hydrogenation gas. The desired degree of conversion and the required limit for the degradation of the chlorobiphenyls, for example, determine the flow rate of the feed products. Typical values are 0.4 to 1.0 t / m³h. In the case of the joint use of oil components and coal or the presence of an additive or other residues, e.g. B. drilling chips, the reaction products are useful passed over a hot separator operated at reaction pressure and at a temperature which is preferably 20 to 50 ° C. lower than the reaction temperature. Here, the uncondensed hydrocarbons are taken off overhead and the bottom products containing residues at the bottom. Distillable heavy oil constituents can be separated in a downstream stripper and can be further processed by combining with the top product of the hot separator. The residue behind the stripper can be used to generate hydrogen or energy.

An die vorbeschriebene Sumpfphasenhydrierung kann eine Gasphasenhyrierung zur Weiterverarbeitung der nichtkondensierten Reaktionsprodukte, die am Kopf des Heißabscheiders abgezogen worden sind, ohne Wiederaufheizung oder Druckentspannung direkt angekoppelt werden. Die in der Gasphasenhydrierung erfolgende weitere Hyrierung, Stabilisierung und Entfernung beispielsweise von Heteroatomen wie Schwefel oder Stickstoff zur Gewinnung von Einsatzprodukten mit Reformereinsatzspezifikation oder von Mitteldestillat erfolgt an Festbettkatalysatoren unter Einsatz von handelsüblichen Katalysatoren. Die Produktströme werden nach Durchlaufen der Gasphasenhydrierung durch intensiven Wärmeaustausch kondensiert und abgekühlt und in einem Hochdruck-Kaltabscheider in eine flüssige Phase und eine Gasphase aufgetrennt. Nach Entspannung der Flüssigphase wird diese üblicherweise einer Stabilisierkolonne zur Entfernung der C₄-Produkte und zum Erhalt eines stabilisierten Syncrudes zugeführt. Die gasförmigen Produkte durchlaufen einen Gaswäscher zur Entfernung von u. a. H₂S und NH₃. Ein Teil des gereinigten wasserstoffreichen Gases wird als Kreislaufgas in die Sumpfphasenhydrierung zurückgeführt. In einer atomosphärischen Destillation erfolgt dann die Auftrennung je nach Festlegung der Siedeschnitte in Naphtha, Mitteldestillat und Vakuumgasöl. Im Falle des gemeinsamen Einsatzes von Kohle und Einsatzöl liegt das Verhältnis vorzugsweise bei l : 20 bis l : l, insbesondere bei l : 5 bis 4 : 5.A gas phase hydrogenation for further processing of the uncondensed reaction products which have been drawn off at the top of the hot separator can be coupled directly to the previously described bottom phase hydrogenation without reheating or depressurization. The further hydrogenation, stabilization and removal in the gas phase hydrogenation, for example of heteroatoms such as sulfur or nitrogen, to obtain feedstocks with reformer feed specification or of middle distillate is carried out on fixed bed catalysts using commercially available catalysts. After passing through the gas phase hydrogenation, the product streams are condensed and cooled by intensive heat exchange and separated into a liquid phase and a gas phase in a high-pressure cold separator. After relaxation of the Liquid phase is usually fed to a stabilizing column to remove the C₄ products and to obtain a stabilized syncrude. The gaseous products pass through a scrubber to remove, among others, H₂S and NH₃. Part of the purified hydrogen-rich gas is recycled as cycle gas into the bottom phase hydrogenation. In an atomic distillation, the separation takes place depending on the determination of the boiling sections in naphtha, middle distillate and vacuum gas oil. If coal and feed oil are used together, the ratio is preferably 1:20 to 1: 1, in particular 1: 5 to 4: 5.

An die Sumpfphasenhydrierung kann sich aber auch direkt eine Kaltabscheiderstufe mit nachfolgender Entspannung und Auftrennung der Flüssigprodukte in eine wäßrige Phase und eine mineralölhaltige Phase sowie eine atmosphärische Destillation der ölhaltigen Phase anschließen.However, a cold separator stage with subsequent expansion and separation of the liquid products into an aqueous phase and a mineral oil-containing phase and an atmospheric distillation of the oil-containing phase can also directly follow the bottom phase hydrogenation.

Als Additive sind insbesondere die suspendierten Braunkohlenkokse aus Schacht- und Herdöfen, Braunkohlengrude, Ruße aus der Vergasung von Schweröl, Steinkohle, Braunkohle oder Hydrierrückständen und daraus erzeugte Aktivkokse, Petrolkoks sowie Stäube aus der Winklervergasung und Hochtemperatur-Winkler-Vergasung von Kohle, d. h. Materialien mit einer großen inneren Oberfläche und mit einer Porenstruktur zur Demetallisierung und Deasphaltierung sowie zur Aufnahme von Koksvorläufern bei der Durchführung der Sumpfphasenhydrierung, geeignet. Es können aber auch Rotmassen, Bayermasse, Eisenoxide sowie Elektrofilterstäube und Zyklonstäube aus der Metall/Erzaufarbeitung mit Vorteil eingesetzt werden. Der Anteil dieser Additive beträgt vorzugsweise 0,5 bis 5 Gew.-% und im Falle des Einsatzes kohlenstoffhaltiger Additive können diese mit Salzen von Metallen der l. bis 8. Nebengruppe sowie der 4. Hauptgruppe des periodischen Systems der Elemente, vorzugsweise Eisen, Kobalt, Nickel, Vanadium, Molybdän beladen sein, beispielsweise Fe(II)-Sulfat.The additives in particular are the suspended lignite coke from shaft and hearth furnaces, lignite grit, soot from the gasification of heavy oil, hard coal, lignite or hydrogenation residues and activated coke, petroleum coke and dusts produced from the Winkler gasification and high-temperature Winkler gasification of coal, ie materials with a large inner surface and with a pore structure for demetallization and deasphalting as well as for the absorption of coke precursors when carrying out the bottom phase hydrogenation. However, red masses, Bavarian masses, iron oxides and electrostatic filter dust and cyclone dust from metal / ore processing can also be used with advantage. The proportion of these additives is preferably 0.5 to 5% by weight and, if carbon-containing additives are used, these can be mixed with salts of metals of 1. to 8th subgroup and the 4th main group of the periodic system of the elements, preferably iron, cobalt, nickel, vanadium, molybdenum, for example Fe (II) sulfate.

Es ist bevorzugt, 0,5 bis 5 Gew.-% einer Verbindung, die mit Halogenwasserstoff, insbesondere Chlorwasserstoff durch Neutralisation Salze bildet oder in wäßriger Lösung Hydroxidionen abspaltet den Einsatzprodukten der Sumpfphasenhydrierung zuzusetzen oder diese Verbindungen zusammen mit Wasser in den Abstrom des Sumpfphasereaktors, z. B. die Zuführungsleitungen des Kaltabscheiders, einzuspritzen. Hierfür werden vorzugsweise 0,5 bis 5 Gew.-% eines Alkalihydroxids, Alkalicarbonats, Alkaliacetats, Alkalialkoholats, Alkalisulfids, entsprechender Ammoniumverbindungen, soweit in Substanz oder in wäßriger Lösung existent, oder von Mischungen der vorgenannten Verbindungen zugegeben.It is preferred to add 0.5 to 5% by weight of a compound which forms salts with hydrogen halide, in particular hydrogen chloride by neutralization or cleaves hydroxide ions in aqueous solution to the feedstocks of the bottom phase hydrogenation, or these compounds together with water in the effluent from the bottom phase reactor, e.g. . B. inject the feed lines of the cold separator. For this purpose, preferably 0.5 to 5% by weight of an alkali metal hydroxide, alkali metal carbonate, alkali metal acetate, alkali metal alcoholate, alkali metal sulfide, corresponding ammonium compounds, insofar as they exist in bulk or in aqueous solution, or mixtures of the aforementioned compounds.

Bei der Zugabe von Ammoniumverbindungen oder Ammoniak-Wasser-Gemischen sind wegen der Sublimationsneigung von Ammoniumchlorid geeignete Vorsichtsmaßnahmen zur Vermeidung von Verstopfungen beispielsweise der Produktleitungen des Kaltabscheiders zu ergreifen. Auch Erdalkaliverbindungen können zur Neutralisation des Halogenwasserstoffs und Bildung wasserlöslicher Salze eingesetzt werden. Bevorzugt sind die Natriumverbindungen, beispielsweise Natriumsulfid.When adding ammonium compounds or ammonia-water mixtures, ammonium chloride is suitable because of the tendency to sublimate Take precautionary measures to avoid clogging, for example of the cold separator product lines. Alkaline earth compounds can also be used to neutralize the hydrogen halide and form water-soluble salts. The sodium compounds, for example sodium sulfide, are preferred.

Beispiel lExample 1

Ein gebrauchtes Motorenöl mit l l00 ppm Polychlorbiphenyl (PCB) wird in einer kontinuierlichen Hydrieranlage bei 430 °C und einem Druck von 280 bar mit l500 Nm³/t Wasserstoff kontaktiert. Dem Öl wird vor der Reaktion l Gew.-% Fe-haltiger (Fe₂O₃) Staub aus der Eisenerzaufarbeitung und 0,2 Gew,-% Na₂S zugesetzt. Nach einer Verweilzeit von l,5 h im Hydrierreaktor sind die PCBs bis unter die analytische Nachweisgrenze von l ppm abgebaut, während das Altöl eine Siedelagenverschiebung gemäß nachfolgender Tabelle erfährt.

Figure imgb0001
A used motor oil with 100 ppm polychlorobiphenyl (PCB) is contacted in a continuous hydrogenation system at 430 ° C and a pressure of 280 bar with 1500 Nm³ / t hydrogen. Before the reaction, 1% by weight of Fe-containing (Fe₂O₃) dust from iron ore processing and 0.2% by weight of Na₂S is added to the oil. After a residence time of 1.5 hours in the hydrogenation reactor, the PCBs are degraded to below the analytical detection limit of 1 ppm, while the waste oil is shifted according to the table below.
Figure imgb0001

Die Schmierölfraktion im Raffinat (Frakt. 300 - ­500 °C) weist einen Viskositätsindex von l20 auf, sie stellt somit eine Grundölkomponente für die Herstellung eines Qualitätsmotorenöls dar.The lubricating oil fraction in the raffinate (fracture 300 - 500 ° C) has a viscosity index of 120, making it a base oil component for the production of a quality motor oil.

Beispiel 2Example 2

Einem Vakuumrückstand aus Bachaquero-Rohöl mit einem Rückstandsgehalt > 500 °C von 6 Gew.-% werden l5 Gew.-% eines gebrauchten Industrieöls mit einem Chlorgehalt von l0 000 ppm zugesetzt. Diese Mischung wird nach Zugabe von l,8 % Aktivkoks und 0,2 % Na₂S bei 450 °C und 220 bar im Sumpfphasereaktor hydriert. Dabei wird der Vakuumrückstand zu 9l % in leichtsiedende Komponenten und gasförmige Substanzen konvertiert, wobei die erzeugten Flüssigprodukte PCB-frei, d. h. unter der gaschromatografischen Nachweisgrenze sind. Die Tabelle zeigt die Verteilung von Einsatz und Produkten.

Figure imgb0002
A vacuum residue from Bachaquero crude oil with a residue content> 500 ° C. of 6% by weight is added with 15% by weight of a used industrial oil with a chlorine content of 10,000,000. This mixture is hydrogenated after adding 1.8% active coke and 0.2% Na₂S at 450 ° C and 220 bar in the bottom phase reactor. The vacuum residue is converted to 9l% into low-boiling components and gaseous substances, whereby the liquid products produced are PCB-free, ie below the gas chromatographic detection limit. The table shows the distribution of use and products.
Figure imgb0002

Das vorgeschlagene Verfahren ist damit hinsichtlich des praktisch vollständigen Abbaus von PCB wesentlich ökonomischer als das ebenfalls im industriellen Maßstab ausgeübte thermische Verbrennungsverfahren für PCB-belastete Altöle und es vermeidet auch die mit einer Verbrennung einhergehende Problematik der Bildung von ebenfalls nicht unbedenklichen Folgeprodukten der Verbrennung von Chlorkohlenwasserstoffe oder Chlorbiphenyle enthaltenden Ölen.The proposed method is therefore much more economical with regard to the practically complete degradation of PCB than the thermal combustion process for waste oils contaminated with PCB, which is also carried out on an industrial scale, and it also avoids the problems associated with combustion of the formation of non-harmless secondary products of the combustion of chlorinated hydrocarbons or Oils containing chlorobiphenyls.

Claims (11)

1. Verfahren zur hydrierenden Behandlung von mit Chlorbiphenylen, Brombiphenylen, chlorierten Naphthalinen und Terphenylen oder anderen Chloraromaten sowie Chlorparaffinen bzw. Chlornaphthenen kontaminierten Mineralölen, insbesondere sogenannten Altölen sowie von Destillationsrückständen solcher Mineralöle, dadurch gekennzeichnet, daß die vorgenannten Einsatzstoffe einer Druckhydrierung unter den typischen Bedingungen einer Sumpfphasenhydrierung oder einer kombinierten Sumpf-/Gasphasenhydrierung bei Wasserstoffdrucken von 20 bis 325 bar, Temperaturen von 250 bis 500 °C und Gas-Öl-Verhältnissen von l00 bis 3000 Nm³/t unterworfen werden.1. A process for the hydrogenating treatment of mineral oils contaminated with chlorobiphenyls, bromobiphenyls, chlorinated naphthalenes and terphenyls or other chloroaromatics and chlorinated paraffins or chloronaphthenes, in particular so-called waste oils and distillation residues of such mineral oils, characterized in that the above-mentioned starting materials are pressurized under the typical conditions of a Bottom phase hydrogenation or a combined bottom / gas phase hydrogenation at hydrogen pressures from 20 to 325 bar, temperatures from 250 to 500 ° C and gas-oil ratios from 100 to 3000 Nm³ / t are subjected. 2. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß die Sumpfphasenhydrierung in Mischung mit Rückstandsöl, Schweröl oder feingemahlener Kohle durchgeführt wird.2. The method according to claim l, characterized in that the bottom phase hydrogenation is carried out in a mixture with residual oil, heavy oil or finely ground coal. 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß 30 bis l00 Gew.-%, vorzugsweise 50 bis 95 Gew.-% Rückstandsöl oder Schweröl zugesetzt werden.3. The method according to claim 2, characterized in that 30 to 100% by weight, preferably 50 to 95% by weight of residual oil or heavy oil are added. 4. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß Kohle und Einsatzöl im Gewichtsverhältnis von l : 20 bis l : l, vorzugsweise l : 5 bis 4 : 5 eingesetzt werden.4. The method according to claim 2, characterized in that coal and feed oil in a weight ratio of l: 20 to l: l, preferably l: 5 to 4: 5 are used. 5. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß in der Sumpfphasenhydrierung 0,5 bis 5 Gew.-% eines kohlenstoffhaltigen, oberflächenreichen suspendierten Feststoffes eingesetzt werden.5. The method according to claim l, characterized in that 0.5 to 5 wt .-% of a carbon-containing, surface-rich suspended solid are used in the bottom phase hydrogenation. 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß Braunkohlenkokse aus Schacht- und Herdöfen, Ruße aus der Vergasung von Schweröl, Steinkohle, Hydrierrückständen, Braunkohle und die daraus erzeugten Aktivkokse, Petrolkoks, Stäube aus der Winklervergasung von Kohle Verwendung finden.6. The method according to claim 5, characterized in that brown coal coke from shaft and hearth furnaces, soot from the gasification of heavy oil, hard coal, hydrogenation residues, lignite and the activated coke, petroleum coke and dusts produced therefrom from the Winkler gasification of coal are used. 7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß die eingesetzten kohlenstoffhaltigen Additive mit Metallsalz der l. bis 8. Nebengruppe sowie der 4. Hauptgruppe des periodischen Systems der Elemente, vorzugsweise Eisen, Kobalt, Nickel, Vanadium, Molybdän getränkt sind.7. The method according to claim 6, characterized in that the carbon-containing additives used with metal salt of l. to 8th subgroup and the 4th main group of the periodic system of the elements, preferably iron, cobalt, nickel, vanadium, molybdenum. 8. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß 0,5 bis 5 Gew.-% Rotmassen, Eisenoxide, Elektrofilterstäube und Zyklonstäube aus der Metall-/Erzaufarbeitung eingesetzt werden.8. The method according to claim l, characterized in that 0.5 to 5 wt .-% red masses, iron oxides, electrostatic filter dust and cyclone dust from the metal / ore processing are used. 9. Verfahren nach Anspruch l, dadurch gekennzeichnet, daß 0,0l bis 5 Gew.-% einer Verbindung, die mit Halogenwasserstoff durch Neutralisation Salze bildet oder in wäßriger Lösung Hydroxidionen abspaltet, mit den Einsatzprodukten zugegeben werden.9. The method according to claim l, characterized in that 0.0l to 5 wt .-% of a compound which forms salts with hydrogen halide by neutralization or cleaves hydroxide ions in aqueous solution, are added with the starting products. l0. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß 0,0l bis 5 Gew.-% eines Alkalihydroxids, Alkalicarbonats, Alkaliacetats, Alkalialkoholats, Alkalisulfids, entsprechender Ammoniumverbindungen, soweit in Substanz oder in wäßriger Lösung existent, oder von Mischungen der vorgenannten Verbindungen zugegeben werden.l0. Process according to Claim 9, characterized in that 0.0l to 5% by weight of an alkali metal hydroxide, alkali metal carbonate, alkali metal acetate, alkali metal alcoholate, alkali metal sulfide, corresponding ammonium compounds, insofar as they exist in bulk or in aqueous solution, or mixtures of the aforementioned compounds are added. 11. Verfahren nach Anspruch 9 oder l0, dadurch gekennzeichnet, daß die zuzugebende Verbindung zusammen mit Wasser in den Abstrom des Sumpfphasereaktors eingespritzt wird.11. The method according to claim 9 or l0, characterized in that the compound to be added is injected together with water into the effluent of the bottom phase reactor.
EP87109958A 1986-07-11 1987-07-10 Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls Expired - Lifetime EP0257260B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87109958T ATE68099T1 (en) 1986-07-11 1987-07-10 PROCESS FOR THE HYDRATING TREATMENT OF WITH CHLORBIPHENYLENE AND THE LIKE. CONTAMINATED MINERAL OILS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863623430 DE3623430A1 (en) 1986-07-11 1986-07-11 METHOD FOR HYDROGENATING TREATMENT WITH CHLORBIPHENYLENE AND THE LIKE CONTAMINATED MINERAL OILS
DE3623430 1986-07-11

Publications (3)

Publication Number Publication Date
EP0257260A1 true EP0257260A1 (en) 1988-03-02
EP0257260B1 EP0257260B1 (en) 1991-10-09
EP0257260B2 EP0257260B2 (en) 1996-08-07

Family

ID=6304975

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87109958A Expired - Lifetime EP0257260B2 (en) 1986-07-11 1987-07-10 Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls

Country Status (8)

Country Link
US (1) US4810365A (en)
EP (1) EP0257260B2 (en)
JP (1) JP2544391B2 (en)
AT (1) ATE68099T1 (en)
CA (1) CA1297063C (en)
DE (2) DE3623430A1 (en)
ES (1) ES2025597T5 (en)
GR (2) GR3002876T3 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3723607A1 (en) * 1987-07-17 1989-01-26 Ruhrkohle Ag METHOD FOR HYDROGENATING WORKOUT OF ALTOELS
EP0371201A1 (en) * 1988-12-01 1990-06-06 Ruhrkohle Aktiengesellschaft Process for the hydrogenation of chloroorganic compounds and neutralisation of the resulting hydrogen chloride, and neutralising agent for hydrogen chloride resulting from chloroorganic compounds
DE3839799A1 (en) * 1988-11-25 1990-07-05 Rwe Entsorgung Ag METHOD FOR PROCESSING CONTAMINATED OILS
FR2687684A1 (en) * 1992-02-24 1993-08-27 Font Pierre Improvement in the treatments of spent oils and the like

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3932927A1 (en) * 1989-10-03 1991-04-18 Hansjoerg Prof Dr Sinn Dehalogenating organo-halogen-contg. hydrocarbon - by passing vaporous educts through with sodium-vapour pressure corresp. to temp. and measuring residence time
US5051030A (en) * 1990-06-05 1991-09-24 Roy F. Weston, Inc. Chemical detoxification process for treatment of soils contaminated with halogenated organic compounds
US5316663A (en) * 1992-01-13 1994-05-31 Uop Process for the treatment of halogenated hydrocarbons
EP0675864A4 (en) * 1992-12-23 1995-12-20 Commw Scient Ind Res Org Destruction of halide containing organics and solvent purification.
US5397459A (en) * 1993-09-10 1995-03-14 Exxon Research & Engineering Co. Process to produce lube oil basestock by low severity hydrotreating of used industrial circulating oils
US5951852A (en) * 1993-12-23 1999-09-14 Commonwealth Scientific And Industrial Research Organisation Et Al. Destruction of halide containing organics and solvent purification
EP0643123A3 (en) * 1994-11-21 1995-08-23 Dow Chemical Co Process for the treatment of halogenated hydrocarbons.
US5849172A (en) * 1997-06-25 1998-12-15 Asarco Incorporated Copper solvent extraction and electrowinning process
IT1292420B1 (en) * 1997-06-26 1999-02-08 Enel Spa PROCESS FOR REMOVING POLYCHLOROBIPHENYLS FROM MINERAL OILS
DE19742266A1 (en) * 1997-09-25 1999-05-06 Ludger Dr Steinmann Upgrading of chemical and energy raw materials by reaction with low-value raw materials
US7444305B2 (en) * 2001-02-15 2008-10-28 Mass Connections, Inc. Methods of coordinating products and service demonstrations
JP3758537B2 (en) 2001-07-23 2006-03-22 豊田合成株式会社 Method for producing group III nitride compound semiconductor
US20060289340A1 (en) * 2003-12-19 2006-12-28 Brownscombe Thomas F Methods for producing a total product in the presence of sulfur
US7745369B2 (en) * 2003-12-19 2010-06-29 Shell Oil Company Method and catalyst for producing a crude product with minimal hydrogen uptake
US7763160B2 (en) * 2003-12-19 2010-07-27 Shell Oil Company Systems and methods of producing a crude product
US20070000810A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method for producing a crude product with reduced tan
US20070012595A1 (en) * 2003-12-19 2007-01-18 Brownscombe Thomas F Methods for producing a total product in the presence of sulfur
US7807046B2 (en) * 2003-12-19 2010-10-05 Shell Oil Company Systems, methods, and catalysts for producing a crude product
US20070000808A1 (en) * 2003-12-19 2007-01-04 Bhan Opinder K Method and catalyst for producing a crude product having selected properties
TW200602591A (en) * 2004-07-08 2006-01-16 hong-yang Chen Gas supply device by gasifying burnable liquid
TWI415930B (en) * 2005-04-06 2013-11-21 Shell Int Research A process for reducing the total acid number (tan) of a liquid hydrocarbonaceous feedstock
RU2424275C2 (en) 2005-04-11 2011-07-20 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Procedure for production of semi-finished product with reduced content of micro-carbon residue and catalyst for its implementation
US7678264B2 (en) * 2005-04-11 2010-03-16 Shell Oil Company Systems, methods, and catalysts for producing a crude product
WO2006110546A2 (en) * 2005-04-11 2006-10-19 Shell Internationale Research Maatschappij B.V. Systems, methods, and catalysts for producing a crude product
EP1869144A1 (en) * 2005-04-11 2007-12-26 Shell International Research Maatschappij B.V. Method and catalyst for producing a crude product having a reduced nitrogen content
WO2007149923A2 (en) * 2006-06-22 2007-12-27 Shell Oil Company Method for producing a crude product with a long-life catalyst
CA2655581A1 (en) * 2006-06-22 2007-12-27 Shell Internationale Research Maatschappij B.V. Methods for producing a crude product from selected feed
CA2655576A1 (en) * 2006-06-22 2007-12-27 Shell Internationale Research Maatschappij B.V. Methods for producing a total product with selective hydrocarbon production
US20080085225A1 (en) * 2006-10-06 2008-04-10 Bhan Opinder K Systems for treating a hydrocarbon feed
JP5070169B2 (en) * 2008-09-18 2012-11-07 Ｊｘ日鉱日石エネルギー株式会社 Method for producing hydrocarbon oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917456A (en) * 1956-12-13 1959-12-15 American Cyanamid Co Process for hydrodesulfurizing crude oil in the presence of coke
DE3004968A1 (en) * 1980-02-11 1981-08-20 Sante M Cundari Fuel compsn. contg. iron oxide - in form of by=product waste obtd. in steel prodn. and a metallic reducer
US4351978A (en) * 1980-07-21 1982-09-28 Osaka Prefectural Government Method for the disposal of polychlorinated biphenyls
EP0178001A1 (en) * 1984-09-14 1986-04-16 Kinetics Technology International B.V. Process for cleaning of waste materials by refining and/or elimination of biologically Difficult to degrade halogen-, nitrogen- and/or sulfur compounds

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE474915A (en) * 1941-12-26
US2377546A (en) * 1943-08-30 1945-06-05 Phillips Petroleum Co Process for treating hydrocarbon containing organically combined fluorine
US2409372A (en) * 1944-01-03 1946-10-15 Phillips Petroleum Co Removal of organic fluorine
US2412220A (en) * 1944-01-03 1946-12-10 Phillips Petroleum Co Treatment of fluorine-containing hydrocarbon mixtures
US2413871A (en) * 1945-07-24 1947-01-07 Phillips Petroleum Co Process of removing organically combined chlorine from hydrocarbons
US2535735A (en) * 1945-10-23 1950-12-26 Phillips Petroleum Co Method of removing aluminum halides in hydrocarbon conversion processes
NL300450A (en) * 1962-11-16
US3355376A (en) * 1965-11-15 1967-11-28 Consolidation Coal Co Hydrocracking of polynuclear hydrocarbons
US3595931A (en) * 1968-05-28 1971-07-27 Gulf Research Development Co Hydrogenolysis of aromatic halides
US3855347A (en) * 1972-09-15 1974-12-17 Badger Co Process for hydrogenating halogenated hydrocarbons
US3935295A (en) * 1973-01-23 1976-01-27 Catalysts And Chemicals, Inc. Process for removing chlorine-containing compounds from hydrocarbon streams
US3925193A (en) * 1974-10-10 1975-12-09 Phillips Petroleum Co Removal of fluorides from catalytic reactor feed
CA1156449A (en) * 1979-11-30 1983-11-08 Oscar L. Norman Method of destruction of polychlorinated biphenyls
US4601817A (en) * 1984-09-21 1986-07-22 Globus Alfred R Treatment of hazardous materials
US4623448A (en) * 1985-03-12 1986-11-18 Moreco Energy, Inc. Removing halogenated polyphenyl materials from used oil products
US4599472A (en) * 1985-06-27 1986-07-08 Phillips Petroleum Company Purification of iodine-containing mixtures and compositions useful therefor
US4719007A (en) * 1986-10-30 1988-01-12 Uop Inc. Process for hydrotreating a hydrocarbonaceous charge stock
JPH101847A (en) * 1996-06-12 1998-01-06 Tsudakoma Corp Operational stabilization of change-over valve in water jet loom

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2917456A (en) * 1956-12-13 1959-12-15 American Cyanamid Co Process for hydrodesulfurizing crude oil in the presence of coke
DE3004968A1 (en) * 1980-02-11 1981-08-20 Sante M Cundari Fuel compsn. contg. iron oxide - in form of by=product waste obtd. in steel prodn. and a metallic reducer
US4351978A (en) * 1980-07-21 1982-09-28 Osaka Prefectural Government Method for the disposal of polychlorinated biphenyls
EP0178001A1 (en) * 1984-09-14 1986-04-16 Kinetics Technology International B.V. Process for cleaning of waste materials by refining and/or elimination of biologically Difficult to degrade halogen-, nitrogen- and/or sulfur compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Band 81, Nr. 3, 22. Juli 1974, Seite 314, Zusammenfassung Nr. 13319h, Columbus, Ohio, US; & JP-A-74 13 155 (KUREHA CHEMICAL INDUSTRY CO. LTD) 05-02-1974 *
CHEMICAL ABSTRACTS, Band 89, Nr. 13, 25. September 1978, Seite 257, Zusammenfassung Nr. 101844w, Columbus, Ohio, US; W.L. KRANICH et al.: "Catalytic hydrodechlorination of polychlorinated hydrocarbons", & ACS SYMP. SER. 1978, 73(Disposal Decontam. Pestic.) 24-34 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3723607A1 (en) * 1987-07-17 1989-01-26 Ruhrkohle Ag METHOD FOR HYDROGENATING WORKOUT OF ALTOELS
DE3839799A1 (en) * 1988-11-25 1990-07-05 Rwe Entsorgung Ag METHOD FOR PROCESSING CONTAMINATED OILS
EP0371201A1 (en) * 1988-12-01 1990-06-06 Ruhrkohle Aktiengesellschaft Process for the hydrogenation of chloroorganic compounds and neutralisation of the resulting hydrogen chloride, and neutralising agent for hydrogen chloride resulting from chloroorganic compounds
US5015457A (en) * 1988-12-01 1991-05-14 Ruhrkohle Ag Process for the hydrogenation of organochlorine compounds, neutralization of the hydrochloric acid obtained and a neutralization agent for hydrochloric acid obtained from organochlorine compounds
FR2687684A1 (en) * 1992-02-24 1993-08-27 Font Pierre Improvement in the treatments of spent oils and the like

Also Published As

Publication number Publication date
ATE68099T1 (en) 1991-10-15
ES2025597T3 (en) 1992-04-01
JPS6323989A (en) 1988-02-01
DE3623430A1 (en) 1988-01-28
EP0257260B1 (en) 1991-10-09
JP2544391B2 (en) 1996-10-16
US4810365A (en) 1989-03-07
GR3021219T3 (en) 1997-01-31
CA1297063C (en) 1992-03-10
DE3623430C2 (en) 1989-02-23
GR3002876T3 (en) 1993-01-25
EP0257260B2 (en) 1996-08-07
DE3773586D1 (en) 1991-11-14
ES2025597T5 (en) 1996-11-01

Similar Documents

Publication Publication Date Title
EP0257260B2 (en) Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls
DE69914145T2 (en) Integrated hydrogen treatment and hydrocracking process
EP0073355B1 (en) Production of liquid hydrocarbons
EP0377606B1 (en) Process for purifying and regenerating used oils
DE2215665C3 (en) Process for producing gasoline and refined liquid hydrocarbons
DE3437374A1 (en) METHOD FOR RECOVERING HYDROGEN
DE2850540C2 (en) Process for processing waste oil
DD268477A5 (en) METHOD FOR THE HYDRAULIC CONVERSION OF HEAVY AND REINFORCING SOLE
EP0372276B1 (en) Process for the recuperation of contaminated oils
EP0314992A2 (en) Process for the hydroconversion of heavy oils, residual oils and waste oils, mixed with sewage sludge
EP0299149A2 (en) Process for working up used lubricants by hydrogenation
EP0330757B1 (en) Process for reprocessing waste materials or the like by pyrolysis, and subsequent further processing of the pyrolysis oil
DE3033259A1 (en) METHOD FOR SOLVENT REFINING OF COAL
DE102019133911B4 (en) Methods of co-processing
DE3232683A1 (en) METHOD FOR RERAFFINATING ALTOEL
DE3529795A1 (en) METHOD FOR LIQUIDIZING COAL
DE3325128A1 (en) METHOD FOR SOLVENT REFINING OF COAL
DE2259959C3 (en) Process for the production of heating oils by asphaltene separation and two-stage catalytic hydrogenative desulphurisation
EP0027962B1 (en) Process for the production of liquid hydrocarbons from coal
EP0209665B1 (en) Coal hydrogenation process by liquid phase and fixed-bed catalyst hydrogenation
DE3329222A1 (en) METHOD FOR COOLING LIQUID WITH AN ACTIVATED ZINC SULFIDE CATALYST
DD156920A5 (en) PROCESS FOR THE CONVERSION OF STURDY CARBON COAL
DE1275234B (en) Process for the hydrocracking of a predominantly polynuclear aromatic hydrocarbonaceous feed to gasoline
DE2910334A1 (en) PROCESS FOR GASIFICATION OF LIQUID AND SOLID HYDROCARBONS AND A CATALYST TO CARRY OUT THIS PROCESS
DE2415627C2 (en) Process for the desulphurization of crude oils, heavy heating oils and similar heavy oils

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

17P Request for examination filed

Effective date: 19870718

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

17Q First examination report despatched

Effective date: 19890807

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

Owner name: VEBA OEL TECHNOLOGIE GMBH

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: 68099

Country of ref document: AT

Date of ref document: 19911015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3773586

Country of ref document: DE

Date of ref document: 19911114

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2025597

Country of ref document: ES

Kind code of ref document: T5

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: RWE ENTSORGUNG AKTIENGESELLSCHAFT

Effective date: 19920429

NLR1 Nl: opposition has been filed with the epo

Opponent name: RWE ENTSORGUNG AG.

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3002876

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG GMBH

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG GMBH TE G

EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 87109958.6

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: RWE ENTSORGUNG AKTIENGESELLSCHAFT

Effective date: 19920429

NLR1 Nl: opposition has been filed with the epo

Opponent name: RWE ENTSORGUNG AKTIENGESELLSCHAFT

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 19960807

AK Designated contracting states

Kind code of ref document: B2

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

ET3 Fr: translation filed ** decision concerning opposition
GBTA Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977)

Effective date: 19960807

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

NLR2 Nl: decision of opposition
NLR3 Nl: receipt of modified translations in the netherlands language after an opposition procedure
NLT1 Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1

Owner name: VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG GMBH

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

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19961002

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Kind code of ref document: T5

Effective date: 19960925

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3021219

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

Ref country code: ES

Payment date: 19990702

Year of fee payment: 13

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

Ref country code: GR

Payment date: 20000426

Year of fee payment: 14

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

Ref country code: AT

Payment date: 20000508

Year of fee payment: 14

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

Ref country code: SE

Payment date: 20000614

Year of fee payment: 14

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

Ref country code: BE

Payment date: 20000703

Year of fee payment: 14

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

Ref country code: GB

Payment date: 20000706

Year of fee payment: 14

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

Ref country code: LU

Payment date: 20000710

Year of fee payment: 14

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

Ref country code: FR

Payment date: 20000728

Year of fee payment: 14

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

Ref country code: NL

Payment date: 20000731

Year of fee payment: 14

Ref country code: DE

Payment date: 20000731

Year of fee payment: 14

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

Ref country code: CH

Payment date: 20000928

Year of fee payment: 14

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: 20010710

Ref country code: GB

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

Effective date: 20010710

Ref country code: AT

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

Effective date: 20010710

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: 20010711

Ref country code: ES

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

Effective date: 20010711

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: 20010731

Ref country code: CH

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

Effective date: 20010731

Ref country code: BE

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

Effective date: 20010731

BERE Be: lapsed

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

Effective date: 20010731

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: 20020201

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

Effective date: 20010710

EUG Se: european patent has lapsed

Ref document number: 87109958.6

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: 20020329

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

Effective date: 20020201

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

Ref country code: DE

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

Effective date: 20020501

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: 20020810

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: 20050710