EP0068231A2 - Process for the hydrogenation of coal, heavy oil, bitumen and the like - Google Patents
Process for the hydrogenation of coal, heavy oil, bitumen and the like Download PDFInfo
- Publication number
- EP0068231A2 EP0068231A2 EP82105119A EP82105119A EP0068231A2 EP 0068231 A2 EP0068231 A2 EP 0068231A2 EP 82105119 A EP82105119 A EP 82105119A EP 82105119 A EP82105119 A EP 82105119A EP 0068231 A2 EP0068231 A2 EP 0068231A2
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- Prior art keywords
- bar
- hydrogenation
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- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
Definitions
- the invention relates to the separation of liquid products from the hot separator residues of the bottom or combined bottom and gas phase hydrogenation of coal, heavy oil, bitumen and similar starting products, such as residues from top or vacuum distillation of crude oil.
- the mixture After passing through a preheater, the mixture is passed from below through a reactor system in which hydrocracking reactions take place at temperatures between 250 and 550 ° C, preferably 380-480 ° C, which lead to the cleavage of large molecules and their partial desulfurization, denitrification and deoxygenation .
- Disposable catalysts are preferably used as catalysts.
- these are, for example, molybdic acid, tin oxalate / ammonium chloride, Bayer mass and lux mass.
- catalysts are used which contain catalytically active metal compounds, for example tungsten, molybdenum, lead, tin, chromium, cobalt and nickel, in particular iron, on a carrier such as active carbon or in particular coke.
- the catalysts are used in amounts of up to 10% by weight, based on the starting product, in particular 1 to 6% by weight.
- the reaction mixture passes into a hot separator, from the top of which gaseous and vaporous reaction products, from the foot of unreacted feed, asphaltenes, catalyst and a certain amount of heavy and medium oil are drawn off as hot sludge.
- the hot separator which can also consist of a system of several separators connected in series, is operated at temperatures which are up to 100 K, preferably 20 to 40 K below the reactor temperature.
- the gaseous or vaporous products drawn off at the top of the hot separator are either regulated in a cold relaxation system and fed to further processing, or are passed under reaction pressure from a short distance from above into a system of reactors in which the gaseous or vaporous products are carried by fixed bed catalysts desulphurized, denitrified, deoxygenated and split (cf. W. Urban “Petroleum processing in the Scholvener 300 at combi hydrogenation chamber" in Petroleum and Coal, 8 (1955), pp. 780 - 782).
- the products of this "combi-hydrogenation" are regulated by a cold separator system and sent for further processing.
- the liquid product yield of the bottom or combined bottom and gas phase hydrogenation is increased in that part of the liquid constituents are separated from the base product of the hot separator with the aid of process gases and stripped.
- the process gas is passed through the product at temperatures between 20 and 300 ° C., preferably 50 to 200 ° C. and a pressure between 10 and 300 bar, preferably 50 to 200 bar.
- Any gas obtained in the process preferably a fraction enriched by washing from the process gas and containing methane, ethane, propane, butanes and pentanes, in particular high contents of propane, butane and / or pentane, can be used as stripping gas.
- the treatment of the hot sludge with the process gases expediently takes place continuously in that a pressure vessel coupled to the hot separator system is charged from above with the hot sludge and from below with the process gases.
- the weight ratio of hot blowdown: process gases is 1:10, preferably 1: 3, the throughput is 0.2 to 2.0 m 3 , preferably 0.3 to 0.6 m 3 blowdown per m 3 pressure vessel volume and per hour.
- the stripping gas can be removed from the entrained constituents of the hydrogenation residue by reducing the pressure to 100 to 1 bar, preferably 70 to 30 bar or increasing the temperature by 20 up to 150 K, preferably 50 to 100 K or a combination of both measures, for example a temperature increase of 20 to 70 K with a pressure reduction to 100 to 50 bar.
- the liquid products are refined or split in the gas phase reactor; in the case of coal hydrogenation, they serve as asphaltene-free mashing oil components.
- the stripping gas can be used again for separation after pressure increase by means of a compressor or a fan or after cooling.
- the solid-containing residue, enriched in metals and asphaltenes, from the treatment of the hot sludge with the process gases is removed from the process by the gas pressure via a lock system and can be fed to gasification, in order to cover the hydrogen requirement of the hydrogenation process.
- This hot sludge was placed in a downstream 5 l container with fittings for gas and liquid distribution at 200 bar and 150 ° C with 4.8 kg / h of a propane-butane mixture (propane: butane weight ratio 3: 2). treated.
- the gaseous product was let down to 40 bar, 0.9 kg / h of a liquid product with a boiling point of 520 ° C. separating.
- the product was free of asphaltenes and metals, its H / C ratio was 1.3; the sulfur content was 1.5% by weight.
- the solids in the residue were enriched to 28% by weight; the residue contained all metals that had been introduced into the process with the oil and the single-use catalyst.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Description
Die Erfindung bezieht sich auf die Abtrennung von Flüssigprodukten aus den Heißabscheider-Rückständen der Sumpf-oder kombinierten Sumpf- und Gasphasenhydrierung von Kohle, Schweröl, Bitumen und ähnlichen Ausgangsprodukten, wie Rückständen der Top- oder Vakuumdestillation von Rohöl.The invention relates to the separation of liquid products from the hot separator residues of the bottom or combined bottom and gas phase hydrogenation of coal, heavy oil, bitumen and similar starting products, such as residues from top or vacuum distillation of crude oil.
Es ist zum Beispiel aus W. Krönig "Die katalytische Druckhydrierung von Kohlen, Teeren und Mineralölen", Berlin/ Göttingen/Heidelberg 1950 bekannt, daß Kohle, Schweröle, Bitumen sowie andere Rückstände sich in leicht siedende Kohlenwasserstoffgemische umwandeln lassen, indem man sie mit Wasserstoff und Katalysator, gegebenenfalls auch mit einem aus dem Produkt stammenden Anmaischöl mischt und diese Mischung beim Druck von 50 - 700 bar, vorzugsweise 100 - 325 bar in einem Erhitzer auf 200 - 500 °C, vorzugsweise 350 - 450 °C erhitzt. Nach Durchlaufen eines Vorheizers wird die Mischung von unten durch ein Reaktorsystem geführt, in dem bei Temperaturen zwischen 250 und 550 °C, vorzugsweise 380 - 480 °C Hydrocrackreaktionen ablaufen, die zu einer Spaltung großer Moleküle sowie zu deren partieller Entschwefelung, Denitrifizierung und Entoxigenierung führen.It is known, for example, from W. Krönig "The catalytic pressure hydrogenation of coal, tars and mineral oils", Berlin / Göttingen / Heidelberg 1950 that coal, heavy oils, bitumen and other residues can be converted into low-boiling hydrocarbon mixtures by hydrogenation and catalyst, optionally also mixed with a mashing oil originating from the product and this mixture heated at a pressure of 50-700 bar, preferably 100-325 bar in a heater to 200-500 ° C, preferably 350-450 ° C. After passing through a preheater, the mixture is passed from below through a reactor system in which hydrocracking reactions take place at temperatures between 250 and 550 ° C, preferably 380-480 ° C, which lead to the cleavage of large molecules and their partial desulfurization, denitrification and deoxygenation .
Als Katalysatoren werden vorzugsweise Einwegkatalysatoren verwendet. Bei der Hydrierung von Kohle sind dies zum Beispiel Molybdänsäure, Zinnoxalat/Ammonchlorid, Bayermasse und Luxmasse. Für die Hydrierung von Schweröl und Bitumen werden Katalysatoren eingesetzt, die auf einem Träger, wie aktiver Kohle oder insbesondere Koks katalytisch wirksame Metallverbindungen zum Beispiel von Wolfram, Molybdän, Blei, Zinn, Chrom, Kobalt und Nickel, insbesondere von Eisen enthalten. Die Katalysatoren werden in Mengen bis 10 Gew.%, bezogen auf das Einsatzprodukt, insbesondere 1 bis 6 Gew.% eingesetzt. Als besonders wirksam haben sich Eisenverbindungen, die unter den Reaktionsbedingungen in Eisensulfid übergehen, wie Eisensulfat in Mengen von 2 bis 7 Gew.% auf aktiver Kohle oder Koks erwiesen.Disposable catalysts are preferably used as catalysts. In the hydrogenation of coal, these are, for example, molybdic acid, tin oxalate / ammonium chloride, Bayer mass and lux mass. For the hydrogenation of heavy oil and bitumen, catalysts are used which contain catalytically active metal compounds, for example tungsten, molybdenum, lead, tin, chromium, cobalt and nickel, in particular iron, on a carrier such as active carbon or in particular coke. The catalysts are used in amounts of up to 10% by weight, based on the starting product, in particular 1 to 6% by weight. Iron compounds which change into iron sulfide under the reaction conditions, such as iron sulfate in amounts of 2 to 7% by weight on active carbon or coke, have proven to be particularly effective.
Vom Kopf des Reaktorsystems gelangt die Reaktionsmischung in einen Heißabscheider, von dessen Kopf gas- und dampfförmige Reaktionsprodukte, von dessen Fuß nicht umgesetztes Einsatzmaterial, Asphaltene, Katalysator sowie ein gewisser Schwer- und Mittelölanteil als Heißabschlamm abgezogen werden. Der Heißabscheider, der auch aus einem System von mehreren in Serie geschalteten Abscheidern bestehen kann, wird bei Temperaturen-betrieben, die bis zu 100 K, vorzugsweise 20 bis 40 K unterhalb der Reaktortemperatur liegen.From the top of the reactor system, the reaction mixture passes into a hot separator, from the top of which gaseous and vaporous reaction products, from the foot of unreacted feed, asphaltenes, catalyst and a certain amount of heavy and medium oil are drawn off as hot sludge. The hot separator, which can also consist of a system of several separators connected in series, is operated at temperatures which are up to 100 K, preferably 20 to 40 K below the reactor temperature.
Die am Kopf des Heißabscheiders abgezogenen gas- bzw. dampfförmigen Produkte werden entweder in einem Kaltentspannungssystem abgeregelt und der weiteren Verarbeitung zugeführt, oder unter Reaktionsdruck auf kurzem Weg von oben in ein System von Reaktoren geleitet, in denen die gas- bzw. dampfförmigen Produkte an Festbettkatalysatoren weiterentschwefelt, denitrifiziert, entoxigeniert sowie gespalten werden (vgl. W. Urban "Erdölverarbeitung in der Scholvener 300 at-Kombi-Hydrierkammer" in Erdöl und Kohle, 8 (1955), S. 780 - 782). Auch die Produkte dieser "Kombi-Hydrierung" werden über ein Kaltabscheidersystem abgeregelt und der Weiterverarbeitung zugeführt.The gaseous or vaporous products drawn off at the top of the hot separator are either regulated in a cold relaxation system and fed to further processing, or are passed under reaction pressure from a short distance from above into a system of reactors in which the gaseous or vaporous products are carried by fixed bed catalysts desulphurized, denitrified, deoxygenated and split (cf. W. Urban "Petroleum processing in the Scholvener 300 at combi hydrogenation chamber" in Petroleum and Coal, 8 (1955), pp. 780 - 782). The products of this "combi-hydrogenation" are regulated by a cold separator system and sent for further processing.
Es ist bekannt, das am Fuße des Heißabscheiders abgezogene Produkt zur Erhöhung der Flüssigproduktausbeute zu nutzen, indem dieses Produkt einer Vakuumdestillation bzw. einer Schwelung unterworfen wird. Es kann auch teilweise in den Sumpfphasereaktor zurückgeführt werden. Diese Rückführung hat den Nachteil, daß der Asphaltenspiegel im Reaktor ansteigt, wodurch die Verkokungsneigung des Reaktionsgutes größer wird. Destillation bzw. Schwelung sind wegen der speziellen Art der Abschlämme schwer zu beherrschen und ermöglichen zum Teil auch aus prinzipiellen Gründen - Schwelung - eine nur begrenzte Flüssigproduktausbeute.It is known to use the product drawn off at the foot of the hot separator to increase the liquid product yield by subjecting this product to vacuum distillation or smoldering. It can also be partially returned to the bottom phase reactor. This recycling has the disadvantage that the asphaltene level in the reactor rises, as a result of which the tendency towards coking of the reaction mixture increases. Distillation or smoldering are difficult to control due to the special nature of the sludge and sometimes also allow for limited reasons - smoldering - only a limited yield of liquid products.
Erfindungsgemäß wird die Flüssigproduktausbeute der Sumpf- bzw. kombinierten Sumpf- und Gasphasehydrierung dadurch erhöht, daß vom Fußprodukt des Heißabscheiders ein Teil der flüssigen Bestandteile mit Hilfe von Prozeßgasen abgetrennt, gestrippt wird. Hierfür wird das Prozeßgas bei Temperaturen zwischen 20 und 300 °C, vorzugsweise 50 bis 200 °C und einem Druck zwischen 10 und 300 bar, vorzugsweise 50 bis 200 bar durch das Produkt geleitet. Als Strippgas kann jedes im Verfahren anfallende Gas, vorzugsweise eine durch Waschen aus dem Prozeßgas angereicherte, Methan, Ethan, Propan, Butane und Pentane, insbesondere hohe Gehalte an Propan, Butan und/oder Pentan enthaltende Fraktion verwendet werden.According to the invention, the liquid product yield of the bottom or combined bottom and gas phase hydrogenation is increased in that part of the liquid constituents are separated from the base product of the hot separator with the aid of process gases and stripped. For this purpose, the process gas is passed through the product at temperatures between 20 and 300 ° C., preferably 50 to 200 ° C. and a pressure between 10 and 300 bar, preferably 50 to 200 bar. Any gas obtained in the process, preferably a fraction enriched by washing from the process gas and containing methane, ethane, propane, butanes and pentanes, in particular high contents of propane, butane and / or pentane, can be used as stripping gas.
Die Behandlung des Heißabschlammes mit den Prozeßgasen erfolgt zweckmäßig kontinuierlich dadurch, daß ein mit dem Heißabscheidersystem gekoppelter Druckbehälter von oben mit dem Heißabschlamm und von unten mit den Prozeßgasen beschickt wird. Das Gewichtsverhältnis Heißabschlamm : Prozeßgasen beträgt 1 : 10, vorzugsweise 1 : 3, der Durchsatz 0,2 bis 2,0 m3, vorzugsweise 0,3 bis 0,6 m3 Abschlamm pro m3 Druckbehälter-Volumen und pro Stunde.The treatment of the hot sludge with the process gases expediently takes place continuously in that a pressure vessel coupled to the hot separator system is charged from above with the hot sludge and from below with the process gases. The weight ratio of hot blowdown: process gases is 1:10, preferably 1: 3, the throughput is 0.2 to 2.0 m 3 , preferably 0.3 to 0.6 m 3 blowdown per m 3 pressure vessel volume and per hour.
Das Strippgas kann von den mitgeführten Bestandteilen des Hydrierrückstandes durch Druckminderung auf 100 bis 1 bar, vorzugsweise 70 bis 30 bar oder Temperaturerhöhung um 20 bis 150 K, vorzugsweise 50 bis 100 K bzw. eine Kombination beider Maßnahmen, zum Beispiel eine Temperaturerhöhung um 20 bis 70 K bei einer Druckminderung auf 100 bis 50 bar befreit werden. Die Flüssigprodukte werden nach Aufwärmung im Gasphasereaktor raffiniert bzw. gespalten; im Falle der Kohlehydrierung dienen sie als asphaltenfreie Anmaisch- ölkomponente. Das Strippgas kann nach Druckerhöhung mittels eines Kompressors oder eines Gebläses bzw. nach Kühlung erneut zur Abtrennung verwendet werden.The stripping gas can be removed from the entrained constituents of the hydrogenation residue by reducing the pressure to 100 to 1 bar, preferably 70 to 30 bar or increasing the temperature by 20 up to 150 K, preferably 50 to 100 K or a combination of both measures, for example a temperature increase of 20 to 70 K with a pressure reduction to 100 to 50 bar. After heating, the liquid products are refined or split in the gas phase reactor; in the case of coal hydrogenation, they serve as asphaltene-free mashing oil components. The stripping gas can be used again for separation after pressure increase by means of a compressor or a fan or after cooling.
Der feststoffhaltige, an Metallen und Asphaltenen angereicherte Rückstand der Behandlung des Heißabschlammes mit den Prozeßgasen wird durch den Gasdruck über ein Schleusensystem aus dem Prozeß entfernt und kann einer Vergasung zugeführt werden, um so den Wasserstoffbedarf des Hydrierprozesses abzudecken.The solid-containing residue, enriched in metals and asphaltenes, from the treatment of the hot sludge with the process gases is removed from the process by the gas pressure via a lock system and can be fed to gasification, in order to cover the hydrogen requirement of the hydrogenation process.
In einem senkrecht stehenden Rohrreaktor von 4,5 1 Inhalt wurden 4,0 kg/h eines Rückstandes der Vakuumdestillation von Arabian-Light-Rohöl mit 3 Nm3/h Wasserstoff bei 450 °C und 280 bar hydriert. Dem Vakuumrückstahd waren 5 Gew.% eines feinteiligen Kokses zugesetzt, auf den 50 g FeS04/kg Koks aufgetragen waren. Von dem am Kopf des Reaktors abgeführten Hydrierprodukt wurden in einem bei 420 °C gefahrenen Heißabscheider 1,6 kg/h Heißabschlamm abgezogen.4.0 kg / h of a residue from the vacuum distillation of Arabian light crude oil were hydrogenated with 3 Nm 3 / h of hydrogen at 450 ° C. and 280 bar in a vertical tubular reactor with a capacity of 4.5 l. 5% by weight of a finely divided coke to which 50 g of FeSO 4 / kg of coke had been applied were added to the vacuum residue. 1.6 kg / h of hot sludge were drawn off from the hydrogenation product carried off at the top of the reactor in a hot separator operated at 420 ° C.
Dieser Heißabschlamm wurde in einem nachgeschalteten, mit Einbauten zur Gas- und Flüssigkeitsverteilung versehenen Behälter von 5 1 Inhalt bei 200 bar und 150 °C mit 4,8 kg/h einer Propan-Butan-Mischung (Propan : Butan-Gewichtsverhältnis 3 : 2) behandelt. Das gasförmige Produkt wurde auf 40 bar entspannt, wobei sich 0,9 kg/h eines Flüssigproduktes mit einem Siedeende von 520 °C abschied. Das Produkt war frei von Asphaltenen und Metallen, sein H/C-Verhältnis betrug 1,3; der Gehalt an Schwefel lag bei 1,5 Gew.%.This hot sludge was placed in a downstream 5 l container with fittings for gas and liquid distribution at 200 bar and 150 ° C with 4.8 kg / h of a propane-butane mixture (propane: butane weight ratio 3: 2). treated. The gaseous product was let down to 40 bar, 0.9 kg / h of a liquid product with a boiling point of 520 ° C. separating. The product was free of asphaltenes and metals, its H / C ratio was 1.3; the sulfur content was 1.5% by weight.
Im Rückstand waren die Feststoffe auf 28 Gew.% angereichert; der Rückstand enthielt alle Metalle, die mit dem Öl und dem Einwegkatalysator in den Prozeß eingetragen worden waren.The solids in the residue were enriched to 28% by weight; the residue contained all metals that had been introduced into the process with the oil and the single-use catalyst.
Claims (9)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813123535 DE3123535A1 (en) | 1981-06-13 | 1981-06-13 | METHOD FOR HYDROGENATING COAL, HEAVY OIL, BITUMEN AND THE LIKE. |
DE3123535 | 1981-06-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0068231A2 true EP0068231A2 (en) | 1983-01-05 |
EP0068231A3 EP0068231A3 (en) | 1984-09-12 |
EP0068231B1 EP0068231B1 (en) | 1987-04-08 |
Family
ID=6134663
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82105119A Expired EP0068231B1 (en) | 1981-06-13 | 1982-06-11 | Process for the hydrogenation of coal, heavy oil, bitumen and the like |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0068231B1 (en) |
CA (1) | CA1171013A (en) |
DE (2) | DE3123535A1 (en) |
NO (1) | NO162864C (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3914057A1 (en) * | 1989-04-28 | 1990-10-31 | Ruhrkohle Ag | STRIPING OF RESIDUES |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB892113A (en) * | 1957-05-08 | 1962-03-21 | Apv Co Ltd | Separation of low boiling point impurities from hydrocarbons |
FR2374401A1 (en) * | 1976-12-15 | 1978-07-13 | Texaco Development Corp | PROCESS FOR TRANSFORMATION OF SOLID FUELS INTO FLUID FUELS |
-
1981
- 1981-06-13 DE DE19813123535 patent/DE3123535A1/en not_active Withdrawn
-
1982
- 1982-06-03 NO NO821844A patent/NO162864C/en unknown
- 1982-06-11 CA CA000405046A patent/CA1171013A/en not_active Expired
- 1982-06-11 EP EP82105119A patent/EP0068231B1/en not_active Expired
- 1982-06-11 DE DE8282105119T patent/DE3276003D1/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB892113A (en) * | 1957-05-08 | 1962-03-21 | Apv Co Ltd | Separation of low boiling point impurities from hydrocarbons |
FR2374401A1 (en) * | 1976-12-15 | 1978-07-13 | Texaco Development Corp | PROCESS FOR TRANSFORMATION OF SOLID FUELS INTO FLUID FUELS |
Also Published As
Publication number | Publication date |
---|---|
DE3123535A1 (en) | 1982-12-30 |
NO162864C (en) | 1990-02-28 |
DE3276003D1 (en) | 1987-05-14 |
NO162864B (en) | 1989-11-20 |
NO821844L (en) | 1982-12-14 |
CA1171013A (en) | 1984-07-17 |
EP0068231B1 (en) | 1987-04-08 |
EP0068231A3 (en) | 1984-09-12 |
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