EP0978552B1 - 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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Publication number
EP0978552B1
EP0978552B1 EP99114579A EP99114579A EP0978552B1 EP 0978552 B1 EP0978552 B1 EP 0978552B1 EP 99114579 A EP99114579 A EP 99114579A EP 99114579 A EP99114579 A EP 99114579A EP 0978552 B1 EP0978552 B1 EP 0978552B1
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heavy
metal compounds
heavy oils
metal
fraction
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French (fr)
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EP0978552A2 (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 generally be below 440 ° C in order to prevent excessive coke formation, which would lead to the reactor systems becoming blocked.
  • Methods for removing or concentrating metal compounds from heavy oils in the presence of water near the critical point are described, for example, in US Patents 3983027, 3453206, 3733259, 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.
  • US Pat. No. 4,444,012 describes a non-catalytic process in which Boscan heavy oil from Venezuela was used as a feed at a temperature of 410 ° C. and a pressure of 140 ⁇ 10 5 Pa (140 bar), which has a density (API) of 10.3 and had a vanadium and nickel content of 1500 and 100 ppm, respectively.
  • API density
  • the draining oil was separated into two fractions, one with a boiling point below 343 ° C and soluble in pentane, which made up 64.6% by weight of the starting fraction and was the light fraction after conversion , and a second fraction with a boiling point above 343 ° C., insoluble in pentane, which represented 22.2% by weight of the starting fraction and was called the heavy fraction.
  • the untreated heavy starting oil originally contained about 15% by weight, which corresponded to the definition as light fraction.
  • vanadium or nickel contents of 7.8 ppm or 1.2 ppm were found in the light fraction, while the heavy fraction had concentrated vanadium or nickel to 5900 ppm or 600 ppm.
  • US-A-4,381,993 describes a method for removing Impurities from hydrocarbons described in which the Hydrocarbons at a temperature between 260 and 455 ° C with a gas containing water and carbon monoxide in the presence of a Treated catalyst, which is a base metal component of group VIII of the periodic table, activated alumina and a Contains phosphorus component.
  • a Treated catalyst which is a base metal component of group VIII of the periodic table, activated alumina and a Contains phosphorus component.
  • a gas for Treatment of the hydrocarbons makes this process expensive.
  • carbon monoxide is toxic, so its use is a Represents a source of danger.
  • a method is proposed in which a catalyst containing a metal from group IVB and a metal from group IA of the periodic table at temperatures between 300 to 500 ° C. and a pressure between 101 ⁇ 10 5 Pa and 304 ⁇ 10 5 Pa (100 to 300 atm) is used and in which zirconium oxide impregnated with potassium carbonate in the form of granules or tablets is used as a fixed bed catalyst in the reactor.
  • 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 group IA compounds to that Group IVB should be in the range of about 0.01: 1 to 0.5: 1.
  • 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 demetallization was carried out at a pressure of 225 ⁇ 10 5 Pa (225 bar) and a temperature of 480 ° C for a period of 30 minutes, the oil feed (LHSV) being 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.
  • a residue from a petroleum distillation under atmospheric pressure and water in a weight ratio of 0.9: 1 was introduced.
  • the distillation residue had a density (API) of 12.6 and a vanadium content of 7.0 ppm and a nickel content of 2.0 ppm.
  • the demetalization was carried out at a pressure of 225.10 6 Pa (225 bar) and a temperature of 460 ° C over a period of 30 minutes.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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 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. Since the metals predominantly on the catalysts to be put down, the consumption of catalysts is also very high large.

Speziell zur Entfernung von Metallverbindungen 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; 221·105 Pa (218,3 atm)) die Eigenschaften des Wasser sich als Funktion von Temperatur und Druck sehr schnell ändern. Dieses "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 the water (374.1 ° C .; 221 · 10 5 Pa (218.3 atm)) Properties of water change very quickly as a function of temperature and pressure. This "supercritical water" has completely different solution properties than normal water; Particularly noteworthy is the fact that the solubility behavior compared to non-polar organic compounds such as heavy hydrocarbons increases sharply, because these are soluble in water under supercritical conditions. This is of great importance for chemical reactions since only one phase exists in the reactions 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 generally be below 440 ° C in order to prevent excessive coke formation, which would lead to the reactor systems becoming blocked. Methods for removing or concentrating metal compounds from heavy oils in the presence of water near the critical point are described, for example, in US Patents 3983027, 3453206, 3733259, 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 140·105 Pa (140 bar) eingesetzt wurde, das eine Dichte (API) 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, US Pat. No. 4,444,012 describes a non-catalytic process in which Boscan heavy oil from Venezuela was used as a feed at a temperature of 410 ° C. and a pressure of 140 · 10 5 Pa (140 bar), which has a density (API) of 10.3 and had a vanadium and nickel content of 1500 and 100 ppm, respectively. After treatment with water at supercritical conditions, the draining oil was separated into two fractions, one with a boiling point below 343 ° C and soluble in pentane, which made up 64.6% by weight of the starting fraction and was the light fraction after conversion , and a second fraction with a boiling point above 343 ° C., insoluble in pentane, which represented 22.2% by weight of the starting fraction and was called the heavy fraction. The untreated heavy starting oil originally contained about 15% by weight, which corresponded to the definition as light fraction. After the treatment, vanadium or nickel contents of 7.8 ppm or 1.2 ppm were found in the light fraction, while the heavy fraction had concentrated vanadium or nickel to 5900 ppm or 600 ppm.

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 in water 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 is, however, that the majority of the metals accumulate in the heavy fraction, which means that this heavy fraction in special and complex Way needs to be dealt with before going in any way can be used commercially. Such enriched with metals Fractions also hire from an environmental perspective difficult problem.

Weiterhin wird in US-A- 4 381 993 ein Verfahren zur Entfernung von Verunreinigungen aus Kohlenwasserstoffen beschrieben, bei dem die Kohlenwasserstoffe bei einer Temperatur zwischen 260 und 455 °C mit einem Wasser- und Kohlenmonoxid-haltigen Gas in der Gegenwart eines Katalysators behandelt werden, der eine Nichtedelmetallkomponente aus der Gruppe VIII des Periodensystems, aktiviertes Aluminiumoxid und eine Phosphorkomponente enthält. Die Verwendung eines Gases zur Behandlung der Kohlenwasserstoffe macht dieses Verfahren kostspielig. Weiterhin ist Kohlenmonoxid giftig, so daß seine Verwendung eine Gefahrenquelle darstellt.Furthermore, US-A-4,381,993 describes a method for removing Impurities from hydrocarbons described in which the Hydrocarbons at a temperature between 260 and 455 ° C with a gas containing water and carbon monoxide in the presence of a Treated catalyst, which is a base metal component of group VIII of the periodic table, activated alumina and a Contains phosphorus component. The use of a gas for Treatment of the hydrocarbons makes this process expensive. Furthermore, carbon monoxide is toxic, so its use is a Represents a source of danger.

Es besteht daher noch ein Bedarf an Verfahren zum katalytischen Entfemen von Metallverbindungen aus Schweröl, das die Probleme der vorbekannten Verfahren vermeidet.There is therefore still a need for catalytic processes Removal of metal compounds from heavy oil, which the problems of avoids known methods.

Zur Lösung wird ein Verfahren vorgeschlagen, bei dem ein Katalysator mit einem Gehalt an einem Metall der Gruppe IVB und einem Metall der Gruppe IA des Periodensystems bei Temperaturen zwischen 300 bis 500 °C und einem Druck zwischen 101·105 Pa und 304·105 Pa (100 bis 300 atm) eingesetzt wird und bei dem mit Kaliumcarbonat imprägniertes Zirkonoxid in Form von Granulat oder Tabletten als Festbettkatalysator im Reaktor eingesetzt wird.To solve this problem, a method is proposed in which a catalyst containing a metal from group IVB and a metal from group IA of the periodic table at temperatures between 300 to 500 ° C. and a pressure between 101 · 10 5 Pa and 304 · 10 5 Pa (100 to 300 atm) is used and in which zirconium oxide impregnated with potassium carbonate in the form of granules or tablets is used as a fixed bed catalyst in the reactor.

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 entfernen 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 and below Avoiding the passage of the metal compounds into the heavy fraction of the draining oil, if a certain one Catalyst type 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 group IA compounds to that Group IVB should be in the range of about 0.01: 1 to 0.5: 1.

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 (API) 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 (API) was 10.8; the vanadium or nickel content was at 790 and 85 ppm.

Die katalytische Demetallisierung erfolgte bei einem Druck von 225·105 Pa (225 bar) und einer Temperatur von 480°C während einer Zeitspanne von 30 Minuten, wobei die Öleinspeisung (LHSV) 1000 ml/h betrug.The catalytic demetallization was carried out at a pressure of 225 · 10 5 Pa (225 bar) and a temperature of 480 ° C for a period of 30 minutes, the oil feed (LHSV) being 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 (API) 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 225.106 Pa (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 made of zirconium oxide impregnated with potassium carbonate, a residue from a petroleum distillation under atmospheric pressure and water in a weight ratio of 0.9: 1 was introduced. The distillation residue had a density (API) of 12.6 and a vanadium content of 7.0 ppm and a nickel content of 2.0 ppm. The demetalization was carried out at a pressure of 225.10 6 Pa (225 bar) and a temperature of 460 ° C over 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 (2)

  1. A method for the catalytic elimination of metal compounds from heavy oils, in which a catalyst containing a metal from group IVB and a metal from group IA of the periodic table is used at temperatures between 300 to 500 °C and a pressure between 101 x 105 Pa and 304 x 105 Pa (100 to 300 atm), characterised in that potassium-carbonate-impregnated zirconium oxide in the form of granulate or pellets is used in the reactor as a fixed-bed catalyst.
  2. A method according to Claim 1, characterised in that the reaction takes place at temperatures between 400 to 500 °C and a pressure between 151 x 105 Pa and 253 x 105 Pa (150 to 250 atm).
EP99114579A 1998-08-06 1999-07-24 Process for the catalytic removal of metal compounds from heavy oils Expired - Lifetime EP0978552B1 (en)

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US6325921B1 (en) 2001-12-04
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DE59910380D1 (en) 2004-10-07
EP0978552A3 (en) 2000-04-05
DE19835479A1 (en) 2000-02-10

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