EP0978552A2 - Process for the catalytic removal of metal compounds from heavy oils - Google Patents

Process for the catalytic removal of metal compounds from heavy oils Download PDF

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EP0978552A2
EP0978552A2 EP99114579A EP99114579A EP0978552A2 EP 0978552 A2 EP0978552 A2 EP 0978552A2 EP 99114579 A EP99114579 A EP 99114579A EP 99114579 A EP99114579 A EP 99114579A EP 0978552 A2 EP0978552 A2 EP 0978552A2
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metal
heavy
metal compounds
heavy oils
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EP0978552B1 (en
EP0978552A3 (en
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Kjeld Andersen
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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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • 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
    • C10G45/24—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 with hydrogen-generating compounds
    • C10G45/26—Steam or water

Definitions

  • the invention relates to a process for the catalytic removal of Metal compounds from heavy oils.
  • Heavy oils usually contain metal compounds, often in large quantities Amounts, especially vanadium and nickel. Based on these Metal compounds is based on the recovery of heavy oils in general limited use as a fuel.
  • the upper temperature limit must therefore usually be below 440 ° C
  • Methods for removing or concentrating metal compounds from heavy oils in the presence of water near the critical point are described, for example, in U.S. Patents 3983027, 3453206, 3733 259, 3586621, 4446012 or 4743357.
  • the metals from the unprocessed heavy oil are usually found in the heaviest part of the oil product that flows off after treatment in unconverted form. This can be determined from the refractive properties of the organometallic compounds.
  • U.S. Patent 4,444,012 describes a non-catalytic process described, in which Boscan uses heavy oil from Venezuela as a feed Temperature of 410 ° C and a pressure of 140 bar was used a density (APl) of 10.3 and a vanadium and nickel content of 1500 or 100 ppm. After treatment with water at supercritical Under conditions, the draining oil was separated into two fractions one with a boiling point below 343 ° C and soluble in pentane, the 64.6% by weight the starting fraction and the light fraction after conversion and a second fraction with a boiling point above 343 ° C, insoluble in pentane, the 22.2 wt .-% starting fraction and as Heavy fraction was designated.
  • APl density
  • the untreated heavy starting oil originally contained about 15% by weight, which is defined as a light fraction corresponded. After treatment, the light fraction was found Vanadium and nickel contents of 7.8 ppm and 1.2 ppm, while in the heavy fraction a concentration of vanadium or nickel to 5900 ppm or 600 ppm was done.
  • a method which is characterized in that a catalyst containing a metal of Group IVB and with a metal from Group IA of the periodic table Temperatures between 300 to 550 ° C and a pressure between 100 to 300 atm is used.
  • Catalysts from compounds of group IVB and IA of the periodic table are known per se from EP 0 402 405, but for use in Gasification process for organic substances.
  • group IVB is preferably zirconium oxide, which is used in the relatively high Temperatures is stable.
  • the preferred compound from the group IA is potassium carbonate, but it can be replaced by other potassium salts.
  • Other metal compounds of group IA or group IVB can also be used use, the ratio of the compounds of group IA to that Group IVB should be in the range of about 0.01: 1 to 0.5: 1.
  • the methods according to the invention are preferably carried out with a Fixed bed catalyst carried out in the reactor, in such a way that with Potassium impregnated zirconium oxide in the form of granules or tablets is used.
  • the invention offers the advantage that effective metal removal takes place and no enrichment of the metal compounds in the heavy fraction of the draining oil takes place. The separate treatment and disposal of this Difficult phase is therefore eliminated.
  • the catalytic demetalization was carried out at a pressure of 225 bar and a temperature of 480 ° C for a period of 30 minutes, wherein the oil feed (LHSV) was 1000 ml / h.
  • the outflowing oil fraction was not separated, but from it Total fraction performed a metal analysis that contained vanadium or nickel of 6 ppm or 2 ppm.
  • the yield was more than 99% in terms of metal removal.
  • the vanadium and nickel determinations were carried out in a manner known per se by atomic absorption spectroscopy.
  • the effluent fraction was not divided into a light and a heavy fraction separated, but made a metal analysis of the total fraction, which found a content of vanadium or nickel of 0.2 or 0.1 ppm.

Abstract

Metal compounds are removed from heavy oils using a catalyst containing a group IVB metal and a group IA metal at temperatures of 300-550oC and at a pressure of 100-300 atm.

Description

Die Erfindung betrifft ein Verfahren zum katalytischen Entfernen von Metallverbindungen aus Schwerölen.The invention relates to a process for the catalytic removal of Metal compounds from heavy oils.

Ein großer Teil der bekannten Weltölreserven liegt in Form von sogenannten Schwerölen vor; als Beispiel sei darauf hingewiesen, daß nur für Venezuela die Menge an gewinnbarem Schweröl auf 270 Milliarden Barrel geschätzt wird.A large part of the known world oil reserves is in the form of so-called Heavy oils before; As an example, it should be noted that only for Venezuela the The amount of recoverable heavy oil is estimated at 270 billion barrels.

Schweröle enthalten in der Regel Metallverbindungen, und zwar oft in großen Mengen, und zwar insbesondere Vanadium und Nickel. Aufgrund dieser Metallverbindungen ist die Verwertung von Schwerölen im allgemeinen auf den Einsatz als Brennstoff beschränkt.Heavy oils usually contain metal compounds, often in large quantities Amounts, especially vanadium and nickel. Based on these Metal compounds is based on the recovery of heavy oils in general limited use as a fuel.

Es gibt eine ganze Reihe von kommerziellen Verfahren zur Reduktion bzw. zum Aufkonzentrieren von Metallen in Schwerölen. Diese Verfahren können unterteilt werden in thermische Verfahren wie Visbreaking, Coking, delayed Coking zusammen mit mildem Hydrotreating oder Überführung in Brenngase, und andererseits in katalytische Prozesse wie Hydrocracking und katalytisches Cracking.There are a number of commercial processes for reduction or for concentrating metals in heavy oils. These procedures can are divided into thermal processes such as visbreaking, coking, delayed Coking along with mild hydrotreating or conversion to fuel gases, and on the other hand in catalytic processes such as hydrocracking and catalytic Cracking.

Bei thermischen Verfahren werden Temperaturen von mehr als 500°C benötigt; außerdem führen diese Verfahren zur Produktion großer Mengen von Koks. Bei den thermischen Verfahren werden die Metalle in dem sich bildenden Koks aufkonzentriert. In den katalytischen Verfahren ist der Bedarf an Wasserstoff unter hohem Druck sehr groß und die Kosten für die Anlagen sind daher ebenfalls hoch. Da die Metalle überwiegend auf den Katalysatoren niedergeschlagen werden, ist auch der Verbrauch an Katalysatoren sehr groß.Temperatures of more than 500 ° C are required for thermal processes; in addition, these processes lead to the production of large quantities of coke. At The thermal process uses the metals in the coke that forms concentrated. In the catalytic processes there is a need for hydrogen very high under high pressure and the cost of the equipment is therefore high also high. Because the metals predominantly on the catalysts to be put down, the consumption of catalysts is also very high.

Speziell zur Entfernung von Metallerbindungen aus Schwerölen werden Verfahren unter Einsatz von superkritischem Wasser kommerziell durchgeführt, die darauf basieren, daß in der Nähe des kritischen Punktes des Wassers (374,1°C; 218,3 atm) die Eigenschaften des Wasser sich als Funktion von Temperatur und Druck sehr schnell ändern. Dieses

Figure 00020001
superkritische Wasser" hat völlig andere Lösungseigenschaften als normales Wasser; besonders bemerkenswert ist die Tatsache, daß das Lösungsverhalten gegenüber nichtpolaren organischen Verbindungen wie beispielsweise schweren Kohlenwasserstoffen stark ansteigt, denn diese sind unter superkritischen Bedingungen in Wasser löslich. Dies ist für chemische Reaktionen von großer Bedeutung, da bei den Reaktionen von Schwerölen in Wasser nur eine Phase existiert. Es gibt bei der Behandlung von Schwerölen mit Wasser allerdings einen begrenzenden Faktor, denn Schweröle enthalten Verbindungen, die sehr schnell Koks bilden. Die Temperaturobergrenze muß daher in der Regel unter 440°C liegen, um eine übermäßige Koksbildung zu verhindern, die zum Verstopfen der Reaktorsysteme führen würde. Verfahren zum Entfernen bzw. Aufkonzentrieren von Metallverbindungen aus Schwerölen in Gegenwart von Wasser nahe dem kritischen Punkt sind beispielsweise in den US-Patenten 3983027, 3453206, 3733259, 3586621, 4446012 oder 4743357 beschrieben. In diesen Verfahren finden sich die Metalle aus dem unbearbeiteten Schweröl nach der Behandlung in nicht umgewandelter Form meist im schwersten Anteil des abfließenden Ölproduktes. Dies läßt sich anhand der Brechungseigenschaften der Organometallverbindungen feststellen. Especially for the removal of metal compounds from heavy oils, processes using supercritical water are carried out commercially, which are based on the fact that in the vicinity of the critical point of water (374.1 ° C .; 218.3 atm) the properties of the water change as a function of Change temperature and pressure very quickly. This
Figure 00020001
supercritical water "has completely different solubility properties than normal water. Particularly noteworthy is the fact that the solubility behavior compared to non-polar organic compounds such as heavy hydrocarbons increases greatly, because these are soluble in water under supercritical conditions. This is of great importance for chemical reactions, since there is only one phase in the reaction of heavy oils in water. However, there is a limiting factor in the treatment of heavy oils with water, because heavy oils contain compounds that form coke very quickly. The upper temperature limit must therefore usually be below 440 ° C To prevent excessive coke formation that would clog the reactor systems Methods for removing or concentrating metal compounds from heavy oils in the presence of water near the critical point are described, for example, in U.S. Patents 3983027, 3453206, 3733 259, 3586621, 4446012 or 4743357. In these processes, the metals from the unprocessed heavy oil are usually found in the heaviest part of the oil product that flows off after treatment in unconverted form. This can be determined from the refractive properties of the organometallic compounds.

Im US-Patent 4446012 wird beispielsweise ein nichtkatalytisches Verfahren beschrieben, bei dem als Speisung Boscan Schweröl aus Venezuela bei einer Temperatur von 410°C und einem Druck von 140 bar eingesetzt wurde, das eine Dichte (APl) von 10,3 und einen Vanadium- und Nickelgehalt von 1500 bzw. 100 ppm aufwies. Nach der Behandlung mit Wasser bei superkritischen Bedingungen wurde das abfließende Öl in zwei Fraktionen getrennt, und zwar eine mit einem Siedepunkt unter 343°C und löslich in Pentan, die 64,6 Gew.% der Ausgangsfraktion ausmachte und die leichte Fraktion nach Umwandlung darstellte, und eine zweite Fraktion mit einem Siedepunkt von über 343°C, unlöslich in Pentan, die 22,2 Gew.-% Ausgangsfraktion darstellte und als Schwerfraktion bezeichnet wurde. Das unbehandelte schwere Ausgangsöl enthielt ursprünglich etwa 15 Gew.-%, die der Definition als leichte Fraktion entsprachen. Nach der Behandlung fanden sich in der leichten Fraktion Vanadium- bzw. Nickelgehalte von 7,8 ppm bzw. 1,2 ppm, während in der schweren Fraktion eine Aufkonzentrierung an Vanadium bzw. Nickel auf 5900 ppm bzw. 600 ppm erfolgt war.For example, U.S. Patent 4,444,012 describes a non-catalytic process described, in which Boscan uses heavy oil from Venezuela as a feed Temperature of 410 ° C and a pressure of 140 bar was used a density (APl) of 10.3 and a vanadium and nickel content of 1500 or 100 ppm. After treatment with water at supercritical Under conditions, the draining oil was separated into two fractions one with a boiling point below 343 ° C and soluble in pentane, the 64.6% by weight the starting fraction and the light fraction after conversion and a second fraction with a boiling point above 343 ° C, insoluble in pentane, the 22.2 wt .-% starting fraction and as Heavy fraction was designated. The untreated heavy starting oil originally contained about 15% by weight, which is defined as a light fraction corresponded. After treatment, the light fraction was found Vanadium and nickel contents of 7.8 ppm and 1.2 ppm, while in the heavy fraction a concentration of vanadium or nickel to 5900 ppm or 600 ppm was done.

Es ist daher möglich und bekannt, Metallverbindungen in den schweren Fraktionen von Schweröl aufzukonzentrieren, wenn das Öl mit Wasser in der Nähe des kritischen Punktes behandelt wird.It is therefore possible and known to use metal compounds in the heavy Concentrate fractions of heavy oil when the oil is mixed with water in the Near the critical point.

Ein Nachteil dieser bekannten Verfahren besteht allerdings darin, daß eben der Großteil der Metalle sich in der schweren Fraktion ansammelt, was bedeutet, daß diese Schwerfraktion in spezieller und aufwendiger Weise weiter behandelt werden muß, bevor sie in irgendeiner Weise kommerziell eingesetzt werden kann. Derartige mit Metallen angereicherte Fraktionen stellen auch unter Aspekten des Umweltschutzes ein schwieriges Problem dar. A disadvantage of these known methods, however, is that Most of the metals accumulate in the heavy fraction, which means that this heavy fraction is treated in a special and complex manner must be used before they are used commercially in any way can. Such fractions enriched with metals are also included Environmental issues are a difficult problem.

Es besteht daher noch ein Bedarf an Verfahren zum katalytischen Entfernen von Metallverbindungen aus Schwerölen, das die Probleme der vorbekannten Verfahren vermeidet.There is therefore still a need for processes for the catalytic removal of Metal compounds from heavy oils, which the problems of the known Avoids proceedings.

Zur Lösung dieser Aufgabe wird ein Verfahren vorgeschlagen, das dadurch gekennzeichnet ist, daß ein Katalysator mit einem Gehalt an einem Metall der Gruppe IVB und mit einem Metall aus der Gruppe IA des Periodensystems bei Temperaturen zwischen 300 bis 550°C und einem Druck zwischen 100 bis 300 atm eingesetzt wird.To solve this problem, a method is proposed which is characterized in that a catalyst containing a metal of Group IVB and with a metal from Group IA of the periodic table Temperatures between 300 to 550 ° C and a pressure between 100 to 300 atm is used.

Völlig überraschend wurde jetzt festgestellt, daß sich Schwermetallverbindungen aus Schwerölen mit hervorragenden Ausbeuten, einer wirksamen Verringerung der Metallgehalte und unter Vermeidung des Übertritts der Metallverbindungen in die Schwerfraktion des abfließenden Öls enternen lassen, wenn ein bestimmter Katalysatortyp eingesetzt wird.Quite surprisingly, it has now been found that Heavy metal compounds from heavy oils with excellent yields, an effective reduction in metal levels while avoiding the Transfer of the metal compounds into the heavy fraction of the oil that flows away get boarded if a certain type of catalyst is used.

Katalysatoren aus Verbindungen der Gruppe IVB und IA des Periodensystems sind an sich aus der EP 0 402 405 bekannt, allerdings zur Verwendung in Gasifizierungsverfahren für organische Stoffe. Als Verbindung aus der Gruppe IVB wird vorzugsweise Zirkonoxid eingesetzt, das bei den relativ hohen Temperaturen stabil ist. Die bevorzugt eingesetzte Verbindung aus der Gruppe IA ist Kaliumcarbonat, das aber durch andere Kaliumsalze ersetzt werden kann. Ebenso lassen sich andere Metallverbindungen der Gruppe IA bzw. Gruppe IVB verwenden, wobei das Verhältnis der Verbindungen der Gruppe IA zu der Gruppe IVB etwa im Bereich von 0,01 : 1 bis 0,5 : 1 liegen sollte. Catalysts from compounds of group IVB and IA of the periodic table are known per se from EP 0 402 405, but for use in Gasification process for organic substances. As a connection from the group IVB is preferably zirconium oxide, which is used in the relatively high Temperatures is stable. The preferred compound from the group IA is potassium carbonate, but it can be replaced by other potassium salts. Other metal compounds of group IA or group IVB can also be used use, the ratio of the compounds of group IA to that Group IVB should be in the range of about 0.01: 1 to 0.5: 1.

Die erfindungsgemäßen Verfahren werden vorzugsweise mit einem Festbettkatalysator im Reaktor durchgeführt, und zwar in der Weise, daß mit Kaliumcarbonat imprägniertes Zirkonoxid in Form von Granulat oder Tabletten eingesetzt wird.The methods according to the invention are preferably carried out with a Fixed bed catalyst carried out in the reactor, in such a way that with Potassium impregnated zirconium oxide in the form of granules or tablets is used.

Die Erfindung bietet den Vorteil, daß eine wirksame Metallentfernung stattfindet und keine Anreicherung der Metallverbindungen in der Schwerfraktion des abfließenden Öls erfolgt. Die separate Behandlung und Entsorgung dieser Schwerphase entfällt daher.The invention offers the advantage that effective metal removal takes place and no enrichment of the metal compounds in the heavy fraction of the draining oil takes place. The separate treatment and disposal of this Difficult phase is therefore eliminated.

Die Erfindung wird nunmehr anhand von Beispielen näher erläutert:The invention will now be explained in more detail by means of examples:

Beispiel 1example 1

In einen Reaktor mit einem Volumen von 0,5 l und mit einem Festbettkatalysator aus Zirkonoxid, das mit Kaliumcarbonat imprägniert war, wurden Wasser und Schweröl im Gewichtsverhältnis 2 : 1 eingebracht. Die Dichte des Schweröles (APl) betrug 10,8; der Vanadium- bzw. Nickelgehalt lag bei 790 bzw. 85 ppm.In a reactor with a volume of 0.5 l and with a Fixed bed catalyst made of zirconium oxide impregnated with potassium carbonate water and heavy oil were introduced in a weight ratio of 2: 1. The Heavy oil density (APl) was 10.8; the vanadium or nickel content was at 790 and 85 ppm.

Die katalytische Demetallisierung erfolgte bei einem Druck von 225 bar und einer Temperatur von 480°C während einer Zeitspanne von 30 Minuten, wobei die Öleinspeisung (LHSV) 1000 ml/h betrug.The catalytic demetalization was carried out at a pressure of 225 bar and a temperature of 480 ° C for a period of 30 minutes, wherein the oil feed (LHSV) was 1000 ml / h.

Die abfließende Ölfraktion wurde nicht aufgetrennt, sondern von dieser Gesamtfraktion eine Metallanalyse durchgeführt, die einen Gehalt an Vanadium bzw. Nickel von 6 ppm bzw. 2 ppm ergab. The outflowing oil fraction was not separated, but from it Total fraction performed a metal analysis that contained vanadium or nickel of 6 ppm or 2 ppm.

Die Ausbeute betrug mehr als 99% in bezug auf Metallentfernung.The yield was more than 99% in terms of metal removal.

Die Vanadium- und Nickelbestimmungen erfolgten in an sich bekannter Weise durch Atomabsorbtionspektroskopie.The vanadium and nickel determinations were carried out in a manner known per se by atomic absorption spectroscopy.

Beispiel 2Example 2

In einem Reaktor mit einem Volumen von 0,5 l und mit einem Festkatalysator aus Zirkonoxid, das mit Kaliumcarbonat imprägniert war, wurde ein Rückstand aus einer Erdöldestillation unter atmosphärischem Druck und Wasser im Gewichtsverhältnis 0,9 : 1 eingebracht. Der Destillationsrückstand wies eine Dichte (APl) von 12,6 und einen Vanadingehalt von 7,0 ppm und einen Nickelgehalt von 2,0 ppm auf. Die Demetallisierung erfolgte bei einem Druck von 225 bar und einer Temperatur von 460°C während einer Zeitspanne von 30 Minuten.In a reactor with a volume of 0.5 l and with a solid catalyst a residue became from zirconium oxide impregnated with potassium carbonate from a petroleum distillation under atmospheric pressure and water in Weight ratio 0.9: 1 introduced. The distillation residue showed one Density (APl) of 12.6 and a vanadium content of 7.0 ppm and one Nickel content of 2.0 ppm. The demetallization was carried out with one print of 225 bar and a temperature of 460 ° C for a period of 30 minutes.

Die abfließende Fraktion wurde nicht in eine leichte und eine schwere Fraktion aufgetrennt, sondern von der Gesamtfraktion eine Metallanalyse gemacht, die einen Gehalt an Vanadin bzw. Nickel von 0,2 bzw. 0,1 ppm ergab.The effluent fraction was not divided into a light and a heavy fraction separated, but made a metal analysis of the total fraction, which found a content of vanadium or nickel of 0.2 or 0.1 ppm.

Dieses Beispiel zeigt, daß auch Fraktionen mit einem relativ bescheidenen Gehalt an Organo-Metallverbindungen erfindungsgemäß behandelt werden können, wobei eine praktisch vollständige Entfernung der störenden Organo-Metallverbindungen, insbesondere Vanadin- und Nickelverbindungen erfolgt.This example shows that factions with a relatively modest Content of organometallic compounds are treated according to the invention can, with a practically complete removal of the interfering organometallic compounds, in particular vanadium and nickel compounds.

Besonders ist hervorzuheben, daß bei Durchführung des erfindungsgemäßen Verfahrens auch bei Verwendung unterschiedlicher Ausgangsfraktionen praktisch keine Koksbildung erfolgt, während die Metallverbindungen in effizienter Weise abgetrennt werden.It should be particularly emphasized that when carrying out the invention Procedure even when using different starting fractions practically no coke formation takes place while the metal compounds in be separated efficiently.

Claims (5)

Verfahren zur katalytischen Entfernung von Metallverbindungen aus Schwerölen, dadurch gekennzeichnet, daß ein Katalysator mit einem Gehalt an einem Metall der Gruppe IVB und einem Metall der Gruppe IA des Periodensystems bei Temperaturen zwischen 300 bis 550°C und einem Druck zwischen 100 bis 300 atm eingesetzt wird.Process for the catalytic removal of metal compounds Heavy oils, characterized in that a catalyst with a Group IVB metal and Group metal content IA of the periodic table at temperatures between 300 and 550 ° C and a pressure between 100 and 300 atm is used. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als Metallverbindung der Gruppe IVB des Periodensystems Zircondioxid eingesetzt wird.A method according to claim 1, characterized in that as Metal compound of group IVB of the periodic table zirconium dioxide is used. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Metallverbindung der Gruppe IA des Periodensystems eine Kaliumverbindung verwendet wird.A method according to claim 1 or 2, characterized in that as Group IA metal compound of the periodic table one Potassium compound is used. Verfahren nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß die Kaliumverbindung während der Reaktion kontinuierlich dem Einsatzöl zugeführt wird.A method according to claim 1 to 3, characterized in that the Potassium compound continuously added to the feed oil during the reaction is fed. Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, daß die Umsetzung bei Temperaturen zwischen 400 bis 500°C und einem Druck zwischen 150 bis 250 atm erfolgt.A method according to claim 1 to 4, characterized in that the Implementation at temperatures between 400 to 500 ° C and one Pressure between 150 to 250 atm occurs.
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US9039889B2 (en) 2010-09-14 2015-05-26 Saudi Arabian Oil Company Upgrading of hydrocarbons by hydrothermal process
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US10752847B2 (en) 2017-03-08 2020-08-25 Saudi Arabian Oil Company Integrated hydrothermal process to upgrade heavy oil
US10703999B2 (en) 2017-03-14 2020-07-07 Saudi Arabian Oil Company Integrated supercritical water and steam cracking process
CA3024814C (en) 2018-01-20 2023-04-25 Indian Oil Corporation Limited A process for conversion of high acidic crude oils
US10526552B1 (en) 2018-10-12 2020-01-07 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3733259A (en) * 1971-11-10 1973-05-15 Texaco Inc Treatment of heavy petroleum oils
US4381993A (en) * 1981-10-14 1983-05-03 Standard Oil Company (Indiana) Process for treating hydrocarbon feedstocks with CO and H2 O in the presence of steam stable catalysts
US4446012A (en) * 1982-12-17 1984-05-01 Allied Corporation Process for production of light hydrocarbons by treatment of heavy hydrocarbons with water
WO1989008138A1 (en) * 1988-03-02 1989-09-08 Kjeld Andersen Gasification process

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3453206A (en) 1966-06-24 1969-07-01 Universal Oil Prod Co Multiple-stage hydrorefining of petroleum crude oil
US3586621A (en) 1968-09-03 1971-06-22 Phillips Petroleum Co Hydrocarbon steam reforming,conversion and refining
US3983027A (en) 1974-07-01 1976-09-28 Standard Oil Company (Indiana) Process for recovering upgraded products from coal
US4743357A (en) 1983-12-27 1988-05-10 Allied Corporation Catalytic process for production of light hydrocarbons by treatment of heavy hydrocarbons with water
US5236882A (en) * 1991-01-22 1993-08-17 Mobil Oil Corp. Catalyst comprising a hydrogenation metal and a delaminated layered silicate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3733259A (en) * 1971-11-10 1973-05-15 Texaco Inc Treatment of heavy petroleum oils
US4381993A (en) * 1981-10-14 1983-05-03 Standard Oil Company (Indiana) Process for treating hydrocarbon feedstocks with CO and H2 O in the presence of steam stable catalysts
US4446012A (en) * 1982-12-17 1984-05-01 Allied Corporation Process for production of light hydrocarbons by treatment of heavy hydrocarbons with water
WO1989008138A1 (en) * 1988-03-02 1989-09-08 Kjeld Andersen Gasification process

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009073442A2 (en) * 2007-11-28 2009-06-11 Saudi Arabian Oil Company Process to reduce acidity of crude oil
WO2009073442A3 (en) * 2007-11-28 2009-11-05 Saudi Arabian Oil Company Process to reduce acidity of crude oil
CN101983227B (en) * 2007-11-28 2013-08-14 沙特阿拉伯石油公司 Process to reduce acidity of crude oil
US9295957B2 (en) 2007-11-28 2016-03-29 Saudi Arabian Oil Company Process to reduce acidity of crude oil
US9656230B2 (en) 2007-11-28 2017-05-23 Saudi Arabian Oil Company Process for upgrading heavy and highly waxy crude oil without supply of hydrogen
US10010839B2 (en) 2007-11-28 2018-07-03 Saudi Arabian Oil Company Process to upgrade highly waxy crude oil by hot pressurized water

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US6325921B1 (en) 2001-12-04
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DE59910380D1 (en) 2004-10-07
EP0978552A3 (en) 2000-04-05
DE19835479B4 (en) 2007-06-06

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