EP0257260B1 - 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

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Publication number
EP0257260B1
EP0257260B1 EP87109958A EP87109958A EP0257260B1 EP 0257260 B1 EP0257260 B1 EP 0257260B1 EP 87109958 A EP87109958 A EP 87109958A EP 87109958 A EP87109958 A EP 87109958A EP 0257260 B1 EP0257260 B1 EP 0257260B1
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Prior art keywords
process according
weight
oil
hydrogenation
oils
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German (de)
French (fr)
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EP0257260A1 (en
EP0257260B2 (en
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Werner Dr. Döhler
Rolf Dr. Holighaus
Klaus Dr. Niemann
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Veba Oel Technologie und Automatisierung GmbH
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Veba Oel Technologie und Automatisierung GmbH
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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 hazardous waste, which must be recorded, properly handled and disposed of or safely disposed of.
  • 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 rest of the processes are only partially developed on a laboratory scale or on a semi-industrial scale.
  • EP-0 178 001 A describes a further process for working up by refining and / or eliminating halogen, nitrogen and / or sulfur-containing compounds which are difficult to biodegrade in hydrocarbon feed streams.
  • the feed stream is first passed together with hydrogen gas over a pre-column filled with an absorbent and then over a fixed bed contact preferably made of nickel or cobalt plus molybdenum on a support.
  • the object of the invention is to provide a further process which can be used on an industrial scale for working up chlorine-containing waste oils. This process enables degradation, especially of multiply chlorinated biphenyls, to values of up to 1 ppm and below.
  • the mineral base oils contained as the main component can be reused without being lost, for example, by incineration or other mining processes.
  • this object is achieved in that the above-mentioned starting materials of pressure hydrogenation 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 Nm 3 / 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 'also finely ground coal in the bottom phase hydrogenation, a step for preparing the mixture of finely ground coal and the oil components being provided in the case of the use of coal. It is advantageous to add 30 to 95% by weight, preferably 50 to 95% by weight of residual oil or heavy oil to the bottoms hydrogenation.
  • an amount between 0.5 and 5% by weight of a finely divided carbon-containing surface-rich suspended material (additive), which is optionally impregnated with heavy metal salts, in particular iron (II) sulfate can be added 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.
  • 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, at hydrogen pressures between 20 and 325 bar, and at elevated temperature, between 250 and 500 ° C and at gas-oil ratios of 100 to 3,000 Nm 3 / t, with the gas is the hydrogen-containing hydrogenation gas.
  • the desired degree of conversion and the required limit for the degradation of the chlorobiphenyls determine the flow rate of the feed products. Typical values are 0.4 to 1.0 tlm 3 h.
  • the reaction products are expediently passed over a heat separator operated at reaction pressure and at a temperature which is preferably 20 to 50 ° C. lower than the reaction temperature.
  • 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 directly coupled 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 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, this is usually fed to a stabilizing column to remove the Ca products and to obtain a stabilized syncrude.
  • the gaseous products pass through a gas scrubber to remove, among other things, H 2 S and NH 3 .
  • Part of the purified hydrogen-rich gas is recycled as cycle gas into the bottom phase hydrogenation.
  • the separation is then carried out in an atmospheric distillation, depending on the determination of the boiling cuts 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 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 from subgroups 1 to 8 and 4.
  • Main group of the periodic system of the elements preferably iron, cobalt, nickel, vanadium, molybdenum, for example Fe (II) sulfate.
  • 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.
  • a used motor oil with I 100 ppm polychlorobiphenyl (PCB) is contacted in a continuous hydrogenation system at 430 ° C and a pressure of 280 bar with 1500 Nm 3 / t hydrogen.
  • I% by weight of Fe-containing (Fe 2 0 3 ) dust from iron ore processing and 0.2% by weight of Na 2 S are added to the oil.
  • the PCBs are broken down below the analytical detection limit of I ppm, while the waste oil undergoes a shift in the boiling point according to the table below.
  • the lubricating oil fraction in the raffinate (Frakt. 300 -500 ° C) has a viscosity index of 120, it is therefore 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 ppm.
  • This mixture is hydrogenated after adding 1.8% activated coke and 0.2% Na 2 S at 450 C and 220 bar in the bottom phase reactor.
  • the vacuum residue is converted to 91% into low-boiling components and gaseous substances, whereby the liquid products generated 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 I,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 715).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 / m 3, depending on the chlorine content, have been set and for which production and further use extensive regulatory restrictions have been imposed, were due to their thermal and chemical stability and their dielectric properties used as insulating and cooling liquids in the construction of high-voltage capacitors, transformers and rectifiers, as plasticizers for coating resins and plastics, sealing liquids, impregnating agents for seals, hydraulic oils and heat transfer agents (cf.Römpps Chemielexikon, 8th edition, page 715).

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 hazardous waste, which must be recorded, properly handled and disposed of or safely disposed of.

Zur Beseitigung von Chlorbiphenylen sind thermische Verbrennungsverfahren, Adsorptionsverfahren 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., 1983).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 (see DG Ackerman et al "Distruction and Disposal of PCBs by Thermal and Non-Thermal Methods", Noyes Data Corporation, Park Ridge, New Jersey, USA, 1983).

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, 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 rest of the processes are only partially 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", 1977, Presented at the American Chemical Society Div. of Pestizide Chemistry, 194th National Meeting, Chicago, Illinois, angeführt. Für dieses Verfahren sind Wasserstoffdrükke von 30 bis 50 bar, Nickel auf Kieselgur oder Palladium auf einem Kohlenstoffträger als Katalysator und Temperaturen im Bereich von etwa 100 bis 120 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", 1977, Presented at the American Chemical Society Div. of Pesticides Chemistry, 194th National Meeting, Chicago, Illinois. Hydrogen pressures of 30 to 50 bar, nickel on diatomaceous earth 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.

In der Druckschrift EP-0 178 001 A ist ein weiteres Verfahren zur Aufarbeitung durch Raffination und/oder Eliminierung von biologisch schwer abbaubaren halogen-, stickstoff- und/oder schwefelhaltigen Verbindungen in Kohlenwasserstoffeinsatzströmen mitgeteilt. Der Einsatzstrom wird zunächst zusammen mit Wasserstoffgas über eine mit einem Absorbens gefüllte Vorkolonne und anschließend über einen vorzugsweise aus Nickel oder Cobalt plus Molybdän auf einem Träger aufgebrachten Festbettkontakt geleitet.EP-0 178 001 A describes a further process for working up by refining and / or eliminating halogen, nitrogen and / or sulfur-containing compounds which are difficult to biodegrade in hydrocarbon feed streams. The feed stream is first passed together with hydrogen gas over a pre-column filled with an absorbent and then over a fixed bed contact preferably made of nickel or cobalt plus molybdenum on a support.

Aufgabe der Erfindung ist es, ein weiteres im industriellen Maßstab anwendbares Verfahren zur Aufarbeitung chlorhaltiger Altöle anzugeben. Dieses Verfahren ermöglicht einen Abbau insbesondere von mehrfach chlorierten Biphenylen auf Werte von bis zu 1 ppm und darunter. Die als Hauptbestandteil enthaltenen mineralischen Grundöle können 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 further process which can be used on an industrial scale for working up chlorine-containing waste oils. This process enables degradation, especially of multiply chlorinated biphenyls, to values of up to 1 ppm and below. The mineral base oils contained as the main component can be reused without being lost, for example, by incineration or other mining 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 Wasserstoffdrücken von 20 bis 325 bar, Temperaturen von 250 bis 500 C und Gas-ÖI-Verhältnissen von 100 bis 3000 Nm3/t unterworfen werden.According to the invention, this object is achieved in that the above-mentioned starting materials of pressure hydrogenation 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 Nm 3 / 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. Es ist vorteilhaft, der Sumpfhasenhydrierung 30 bis 95 Gew.-%, vorzugsweise 50 bis 95 Gew.-% Rückstandsöl oder Schweröl zuzusetzen.The feed oils are preferably used as such or in a mixture with residual oils, heavy oils or 'also finely ground coal in the bottom phase hydrogenation, a step for preparing the mixture of finely ground coal and the oil components being provided in the case of the use of coal. It is advantageous to add 30 to 95% by weight, preferably 50 to 95% by weight of residual oil or heavy oil to the bottoms hydrogenation.

Abhängig von dem gewünschten Umsatzgrad und der Tendenz der eingesetzten Öle zur Koksbildung wird 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 zugesetzt. 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, bei Wasserstoffdrücken zwischen 20 und 325 bar, und erhöhter Temperatur, zwischen 250 und 500 ° C und bei Gas-ÖI-Verhältnissen von 100 bis 3 000 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 1,0 tlm3h. Im Falle des gemeinsamen Einsatzes von Ölbestandteilen und Kohle oder auch der Anwesenheit eines Additives 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, an amount between 0.5 and 5% by weight of a finely divided carbon-containing surface-rich suspended material (additive), which is optionally impregnated with heavy metal salts, in particular iron (II) sulfate can be added 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, at hydrogen pressures between 20 and 325 bar, and at elevated temperature, between 250 and 500 ° C and at gas-oil ratios of 100 to 3,000 Nm 3 / t, with the gas is the hydrogen-containing 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 tlm 3 h. In the case of the joint use of oil components and coal or the presence of an additive or other residues, e.g. B. from drilling chips, the reaction products are expediently passed over a heat 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 Hydrierung, 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 Ca-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 atmosphärischen 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 1 : 20 bis 1 : 1, insbesondere bei 1 : 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 directly coupled 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 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, this is usually fed to a stabilizing column to remove the Ca products and to obtain a stabilized syncrude. The gaseous products pass through a gas scrubber to remove, among other things, H 2 S and NH 3 . Part of the purified hydrogen-rich gas is recycled as cycle gas into the bottom phase hydrogenation. The separation is then carried out in an atmospheric distillation, depending on the determination of the boiling cuts 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 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 1. 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 from subgroups 1 to 8 and 4. 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, aber auch 0,01 bis 5 Gew.-% einer Verbindung, die mit Halogenwasserstoff, insbesondere Chlorwasserstoff durch Neutralisation Salze bildet oder in wäßriger Lösung Hydroxidionen abspaltet den Einsatzprodukten der Sumpfphasehydrierung 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, aber auch 0,01 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, but also 0.01 to 5% by weight of a compound which forms salts with hydrogen halide, in particular hydrogen chloride, by neutralization or which releases hydroxide ions in aqueous solution, to the bottom phase hydrogenation feedstocks, or to add 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, but also 0.01 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 ammonium compounds or ammonia-water mixtures are added, due to the tendency of ammonium chloride to sublimate, suitable precautionary measures must be taken to avoid clogging, for example of the product lines of the cold separator. 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 IExample I

Ein gebrauchtes Motorenöl mit I 100 ppm Polychlorbiphenyl (PCB) wird in einer kontinuierlichen Hydrieranlage bei 430 °C und einem Druck von 280 bar mit 1500 Nm3/t Wasserstoff kontaktiert. Dem Öl wird vor der Reaktion I Gew.-% Fe-haltiger (Fe203) Staub aus der Eisenerzaufarbeitung und 0,2 Gew,-% Na2S zugesetzt. Nach einer Verweilzeit von 1,5 h im Hydrierreaktor sind die PCBs bis unter die analytische Nachweisgrenze von I ppm abgebaut, während das Altöl eine Siedelagenverschiebung gemäß nachfolgender Tabelle erfährt.

Figure imgb0001
A used motor oil with I 100 ppm polychlorobiphenyl (PCB) is contacted in a continuous hydrogenation system at 430 ° C and a pressure of 280 bar with 1500 Nm 3 / t hydrogen. Before the reaction, I% by weight of Fe-containing (Fe 2 0 3 ) dust from iron ore processing and 0.2% by weight of Na 2 S are added to the oil. After a dwell time of 1.5 h in the hydrogenation reactor, the PCBs are broken down below the analytical detection limit of I ppm, while the waste oil undergoes a shift in the boiling point according to the table below.
Figure imgb0001

Die Schmierölfraktion im Raffinat (Frakt. 300 -500 ° C) weist einen Viskositätsindex von 120 auf, sie stellt somit eine Grundölkomponente für die Herstellung eines Qualitätsmotorenöls dar.The lubricating oil fraction in the raffinate (Frakt. 300 -500 ° C) has a viscosity index of 120, it is therefore 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 15 Gew.-% eines gebrauchten Industrieöls mit einem Chlorgehalt von 10 000 ppm zugesetzt. Diese Mischung wird nach Zugabe von 1,8 % Aktivkoks und 0,2 % Na2S bei 450 C und 220 bar im Sumpfphasereaktor hydriert. Dabei wird der Vakuumrückstand zu 91 % 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 ppm. This mixture is hydrogenated after adding 1.8% activated coke and 0.2% Na 2 S at 450 C and 220 bar in the bottom phase reactor. The vacuum residue is converted to 91% into low-boiling components and gaseous substances, whereby the liquid products generated 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 (10)

1. A process for the hydrogenating treatment of mineral oils contaminated with chloro biphenyls, bromo biphenyls, chlorinated naphthalenes and terphenyls or other chloro aromatics and also chloro paraffin waxes or chloro naphthenes, more particularly waste oils and distillation residues of such mineral oils, characterized in that the aforementioned batch materials are subjected to a semi-solid phase hydrogenation or a combined semi-solid/gaseous 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, 0.5 to 5% by weight of a carbon-containing surface-rich suspended solid are used in the semi-solid phase hydrogenation.
2. A process according to claim 1, characterized in that the semi-solid phase hydrogenation is performed in a mixture with residue oil, heavy oil or finely ground coal.
3. A process according to claim 2, characterized in that 30 to 95% by weight, preferably 50 to 95% by weight of residual oil or heavy oil are added.
4. A process according to claim 1, characterized in that coal and oil are used in the ratio by weight of 1 : 20 to 1 : 1, preferably 1 : 5 to 4 : 5.
5. A process according to claim 1, characterized in that use is made of lignite cokes from shaft and hearth furnaces, soots from the gasification of heavy oil, pit coal, hydrogenation residues, lignite and the activated cokes produced therefrom, petroleum coke, dusts from the Winkler gasification of coal.
6. A process according to claim 5, characterized in that the carbon-containing additives used are impregnated with a metal salt of subsidiary groups 1 to 8 and main group 4 of the periodic table of elements, preferably iron, cobalt, nickel, vanadium, molybdenum.
7. A process according to claim 1, characterized in that use is made of 0.5 to 5% by weight of red bodies, iron oxides, electric filter dusts and cyclone dusts from metal/ore dressing.
8. A process according to claim 1, characterized in that 0.01 to 5% by weight of a compound which with halides forms salts by neutralization or splits off hydroxide ions in aqueous solution is added with the batch products.
9. A process according to claim 8, characterized in that 0.01 to 5% by weight of an alkaline hydroxide, an alkaline carbonate an alkaline acetate, an alkaline alcoholate, an alkaline sulphide, corresponding ammonium compounds, if existent in substance or in aqueous solution, or mixtures of the aforementioned compounds are added.
10. A process according to claim 8 or 9, characterized in that the compound to be added is sprayed together with water into the discharge flow of the semi-solid phase reactor.
EP87109958A 1986-07-11 1987-07-10 Process for the hydrogenation treatment of mineral oils contaminated by chlorobiphenyls Expired - Lifetime EP0257260B2 (en)

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US4810365A (en) 1989-03-07

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