EP0078951A1 - Process for the preparation of technical white oils by hydrogenation - Google Patents
Process for the preparation of technical white oils by hydrogenation Download PDFInfo
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- EP0078951A1 EP0078951A1 EP82109747A EP82109747A EP0078951A1 EP 0078951 A1 EP0078951 A1 EP 0078951A1 EP 82109747 A EP82109747 A EP 82109747A EP 82109747 A EP82109747 A EP 82109747A EP 0078951 A1 EP0078951 A1 EP 0078951A1
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- oil
- hydrogenation
- technical white
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
Definitions
- the present invention relates to a method for producing technical white oils.
- unrefined or raw mineral oils for the production of technical white oils are catalytically hydrogenated in one step without the usual use of noble metal catalysts.
- Technical white oils are highly refined petroleum fractions that are largely free of oxygen, nitrogen and sulfur compounds and, depending on the intended use, contain only small amounts of aromatics.
- Technical white oils are widely used as carrier oils for insecticides and herbicides and as components for printing inks for textiles or textile fibers.
- Older processes for the production of white oils are based on suitable petroleum fractions which are refined either directly or after prior partial dearomatization by solvent extraction, for example with furfural, SO 2 , phenol or with highly concentrated sulfuric acid or oleum.
- Multi-stage catalytic refining processes for the production of white oils are also known in order to avoid the sulfuric acid treatment which was customary in the past.
- the published German application 16 45 791 describes a two-stage catalytic process in which a low-aromatic petroleum fraction is hydrogenated in a first catalytic process stage on a sulfur-resistant hydrogenation catalyst and in a second hydrogenation stage on a catalyst containing noble metal.
- the object was therefore to develop a process for the catalytic refining of white oil precursors to technical white oils, in which the disadvantages described do not occur.
- the present invention is based on a process for the production of industrial white oils from petroleum fractions containing aromatics, nitrogen, oxygen and sulfur compounds with a boiling range from 200 to 580 ° C., which have optionally been subjected to solvent extraction and solvent dewaxing, by catalytic hydrogenation in Presence of a sulfurized catalyst containing nickel and molybdenum.
- the advantage of the process according to the invention is that, in addition to the light stripping oil, an additional fraction with the properties of technical white oil is obtained from the distillation of the more volatile hydrogenation constituents by separating off the parts boiling from approx. 150 ° C. when stripping in the distillation column after the hydrogenation reactor .
- Sulfurized catalysts which contain nickel and molybdenum and advantageously also phosphoric acid and which have been prepared by impregnating a support with a phosphoric acid nickel molybdate solution are used as hydrogenation catalysts.
- a sulfidic catalyst which, in the oxidic state, based on the catalyst weight, contains 3 to 6% nickel oxide, 10 to 15% molybdenum oxide and 3 to 6% o-phosphoric acid on a support consisting in particular of ⁇ -aluminum oxide.
- the carrier consists, for example, of 100 to 95% by weight ⁇ -aluminum oxide and up to 5% by weight Si0 2 .
- the preparation of the catalyst differs from the usual production methods for, for example, cobalt / molybdenum, nickel / molybdenum and nickel / tungsten-containing catalysts by the impregnation with a phosphoric acid nickel molybdate solution.
- This special catalyst containing nickel, molybdenum and phosphoric acid is expediently used under the following conditions: pressure range 140 to 160 at, preferably 150 at; Temperature range 250 to 370 ° C, preferably 300 to 350 ° C; Gas: oil ratio greater than 1.0 Nm 3 , advantageously 1.2 Nm 3 hydrogen per kg of oil; Catalyst load 0.15 to 1.0 kg of oil per liter of catalyst per hour.
- Active diluents are used to reduce the nickel-molybdenum content of the catalyst.
- “Active diluents” are to be understood as meaning large-area aluminum oxides or aluminum oxide / silicon dioxide mixtures which, because of their surface properties, are themselves catalytically active and further increase the activity of the catalyst.
- the activity of the catalyst can additionally be changed in a known manner by introducing MgO, C aO, ZnO, B 2 0 3 and TiO 2 in amounts of 1 to 10% by weight.
- Particularly suitable surface-rich aluminum oxides are obtained by precipitation of aluminum oxide hydrates from aqueous solutions containing aluminum salts.
- Suitable starting products for the production of white oils of technical quality are oils with a boiling range between 200 and 550 ° C, e.g. Gas oil fractions with a boiling range of 220 to 340 ° C, spindle oil or lubricating oil fractions. Higher boiling starting products generally require stricter refining conditions.
- the aromatic content of the raw materials is not particularly critical since the aromatics can be largely reduced by the hydrogenation. Only in particularly stored cases when the aromatic content of the raw material has considerable values, e.g. over 30%, it may be appropriate to remove some of the aromatics beforehand by extraction.
- FIG. 1 shows a diagram for the implementation of the method according to the invention.
- a hydrocarbon feed which boils in the range of 200 to 550 ° C, is led from line (1) together with fresh hydrogen from line (2) and the circulating hydrogen from line (3) into the reaction and there over a sulfur-resistant hydrogenation catalyst, the nickel and Contains molybdenum, implemented.
- the hydrocarbons are hydrogenated in (4) at 360 ° C and at 140 bar.
- the stream coming from the reactor (4) is passed through line (5) into the separation zone (6), in which the gas phase is separated from the liquid phase.
- the liquid phase is then passed through line (7) into the separation zone (8), which can be a distillation zone and there into a light stripping oil fraction which is loaded with gaseous components and which is removed through line (9) and a heavy product which Line (11) is withdrawn, separated.
- the separation zone (8) can be operated so that in addition to the heavy product with white oil quality from line (11) from line (10) as a further product only heavy stripping oil can be removed, which also has the quality of a technical white oil.
- the catalyst is prepared as follows and sulfurized before use.
- An aluminum oxide hydrate is precipitated from an Al 2 (SO 4 ) 3 solution (7.5% A12 0 3 ) with 25% NH 4 OH at a pH of 6.5 and a temperature of 85 ° C. 0.25% (NH 4 ) 2 CO 3 solution washed sulfate-free and dried at 120 ° C.
- extrudates with a diameter of 1.5 mm are produced from the aluminum oxide which has been calcined at 500.degree. 1,000 g of catalyst are sprayed with 755 g of a solution which contains the equivalent of 22.1% Mo03, 8.5% NiO and 6.8% by weight phosphoric acid.
- Mo03 sublimate is digested by heating with the calculated amount of an o-phosphoric acid solution.
- the required amount of Ni (NO 3 ) 2 .6 H 2 0 is then added to this solution, a clear solution being obtained.
- the impregnated extrusions are dried at 120 ° C. for 12 hours and then calcined at 350 ° C. for 2 hours.
- the finished catalyst contains 5% NiO, 13% Mo03 and 4% H 3 PO 4 .
- Table 1 compares the properties of the starting material with those of the raffinates.
- Hydrogenation stage can be used for the production of medical white oil.
- the process also makes it possible to adjust the viscosity and flash point of the end products by varying the process conditions.
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von technischen Weißölen. Hierbei werden unraffinierte bzw. rohe Mineralöle zur Herstellung von technischen Weißölen katalytisch in einer Stufe ohne die übliche Verwendung von Edelmetallkatalysatoren hydriert.The present invention relates to a method for producing technical white oils. Here, unrefined or raw mineral oils for the production of technical white oils are catalytically hydrogenated in one step without the usual use of noble metal catalysts.
Technische Weißöle sind stark raffinierte Erdölfraktionen, die weitgehend frei von Sauerstoff-, Stickstoff- und Schwefelverbindungen sind und je nach dem vorgesehenen Verwendungszweck nur noch geringe Anteile an Aromaten enthalten. Technische Weißöle finden vielfältige Verwendung als Trägeröle für Insektizide und Herbizide und als Komponenten für Druckfarben von Textilien bzw. Textilfasern.Technical white oils are highly refined petroleum fractions that are largely free of oxygen, nitrogen and sulfur compounds and, depending on the intended use, contain only small amounts of aromatics. Technical white oils are widely used as carrier oils for insecticides and herbicides and as components for printing inks for textiles or textile fibers.
Ältere Verfahren zur Herstellung von Weißölen gehen von geeigneten Erdölfraktionen aus, die entweder direkt oder nach vorheriger teilweiser Entaromatisierung durch eine Solventextraktion, z.B. mit Furfurol, S02, Phenol oder mit hochkonzentrierter Schwefelsäure bzw. Oleum raffiniert werden.Older processes for the production of white oils are based on suitable petroleum fractions which are refined either directly or after prior partial dearomatization by solvent extraction, for example with furfural, SO 2 , phenol or with highly concentrated sulfuric acid or oleum.
Es sind auch mehrstufige katalytische Raffinationsverfahren zur Herstellung von Weißölen bekannt, um die früher übliche Schwefelsäurebehandlung zu vermeiden. So wird in der offengelegten deutschen Anmeldung 16 45 791 ein zweistufiges katalytisches Verfahren beschrieben, bei dem eine aromatenarme Erdölfraktion in einer ersten katalytischen Verfahrensstufe an einem schwefelfesten Hydrierkatalysator und in einer zweiten Hydrierstufe an einem Edelmetall enthaltenden Katalysator hydriert wird.Multi-stage catalytic refining processes for the production of white oils are also known in order to avoid the sulfuric acid treatment which was customary in the past. For example, the published German application 16 45 791 describes a two-stage catalytic process in which a low-aromatic petroleum fraction is hydrogenated in a first catalytic process stage on a sulfur-resistant hydrogenation catalyst and in a second hydrogenation stage on a catalyst containing noble metal.
Bei Verwendung von Nichtedelmetallkatalysatoren war es erforderlich, den Aromatengehalt in der zu hydrierenden Erdölfraktion durch Solventextraktion auf vorzugsweise weniger als 5 % herabzusetzen (vgl. DE-OS 20 50 908).When using non-noble metal catalysts, it was necessary to reduce the aromatic content in the petroleum fraction to be hydrogenated to preferably less than 5% by solvent extraction (cf. DE-OS 20 50 908).
Ein weiteres Problem bei der Hydrierung von aromatenreicheren Weißölvorprodukten ist die bei der Aromatenhydrierung freiwerdende Hydrierwärme. Man ist gezwungen, durch den Einbau von Quenchzonen in den Reaktor den Temperaturanstieg während der Hydrierung zu begrenzen, da bei gegebenem Druck durch einen zu starken Temperaturanstieg das thermodynamische Gleichgewicht nach der Seite der Dehydrierung der Aromaten verschoben würde. Ein Einbau von Quenchzonen würde die Anlagekosten erheblich erhöhen.Another problem with the hydrogenation of white oil precursors rich in aromatics is the heat of hydrogenation released during the aromatization hydrogenation. It is necessary to limit the temperature rise during the hydrogenation by installing quench zones in the reactor, since at a given pressure the thermodynamic equilibrium would be shifted to the side of the dehydrogenation of the aromatics. The installation of quench zones would increase the investment costs considerably.
Es bestand daher die Aufgabe, ein Verfahren zur katalytischen Raffination von Weißölvorprodukten zu technischen Weißölen zu entwickeln, bei dem die geschilderten Nachteile nicht auftreten.The object was therefore to develop a process for the catalytic refining of white oil precursors to technical white oils, in which the disadvantages described do not occur.
Die vorliegende Erfindung geht aus von einem Verfahren zur Herstellung von technischen Weißölen aus Aromaten, Stickstoff-, Sauerstoff- und Schwefelverbindungen enthaltenden Erdölfraktionen mit einem Siedebereich von 200 bis 580°C, die gegebenenfalls einer Solventextraktion und einer Solvententparaffinierung unterzogen worden sind, durch katalytische Hydrierung in Gegenwart eines geschwefelten Katalysators der Nickel und Molybdän enthält.The present invention is based on a process for the production of industrial white oils from petroleum fractions containing aromatics, nitrogen, oxygen and sulfur compounds with a boiling range from 200 to 580 ° C., which have optionally been subjected to solvent extraction and solvent dewaxing, by catalytic hydrogenation in Presence of a sulfurized catalyst containing nickel and molybdenum.
Die vorliegende Erfindung betrifft ein Verfahren dieser Art, bei dem man die Hydrierung bei Drücken oberhalb 140 at und einem Gas-zu-Ölverhältnis von = 1,0 Nm3 Wasserstoff pro kg Öl ausführt und bei der nachfolgenden Trennung des Hydrierproduktes neben der höhersiedenden Fraktion des technischen Weißöls zusätzlich ein niedriger siedendes ab 150°C entnimmt.The present invention relates to a method of this type in which the hydrogenation is carried out at pressures above 140 at and a gas-to-oil ratio of = 1.0 Nm 3 of hydrogen per kg of oil and in the subsequent separation of the hydrogenation product in addition to the higher-boiling fraction of technical white oil also takes a lower boiling from 150 ° C.
Der Vorteil des erfindungsgemäßen Verfahrens besteht darin, daß man neben dem leichten Strippöl eine zusätzliche Fraktion mit den Eigenschaften von technischem Weißöl aus der Destillation der leichter flüchtigen Hydrierbestandteile durch Abtrennung der ab ca. 150°C siedenden Anteile beim Strippen in der Destillationskolonne nach dem Hydrierreaktor erhält.The advantage of the process according to the invention is that, in addition to the light stripping oil, an additional fraction with the properties of technical white oil is obtained from the distillation of the more volatile hydrogenation constituents by separating off the parts boiling from approx. 150 ° C. when stripping in the distillation column after the hydrogenation reactor .
Als Hydrierkatalysatoren dienen geschwefelte Katalysatoren, die Nickel und Molybdän und vorteilhaft auch Phosphorsäure enthalten und durch Tränkung eines Trägers mit einer phosphorsauren Nickelmolybdatlösung hergestellt worden sind.Sulfurized catalysts which contain nickel and molybdenum and advantageously also phosphoric acid and which have been prepared by impregnating a support with a phosphoric acid nickel molybdate solution are used as hydrogenation catalysts.
Für die katalytische Hydrierung wird ein sulfidischer Katalysator verwendet, der im oxidischen Zustand, bezogen auf das Katalysatorgewicht, 3 bis 6 % Nickeloxid, 10 bis 15 % Molybdänoxid und 3 bis 6 % o-Phosphorsäure auf einem insbesondere aus γ-Aluminiumoxid bestehenden Träger enthält. Der Träger besteht z.B. aus 100 bis 95 Gew.% γ-Aluminiumoxid und bis zu 5 Gew.% Si02. Die Herstellung des Katalysators unterscheidet sich von den üblichen Herstellungsmethoden für z.B. Kobalt/Molybdän, Nickel/Molybdän und Nickel/Wolfram enthaltende Katalysatoren durch die Tränkung mit einer phosphorsauren Nickelmolybdatlösung.For the catalytic hydrogenation, a sulfidic catalyst is used which, in the oxidic state, based on the catalyst weight, contains 3 to 6% nickel oxide, 10 to 15% molybdenum oxide and 3 to 6% o-phosphoric acid on a support consisting in particular of γ-aluminum oxide. The carrier consists, for example, of 100 to 95% by weight γ-aluminum oxide and up to 5% by weight Si0 2 . The preparation of the catalyst differs from the usual production methods for, for example, cobalt / molybdenum, nickel / molybdenum and nickel / tungsten-containing catalysts by the impregnation with a phosphoric acid nickel molybdate solution.
Dieser spezielle, Nickel, Molybdän und Phosphorsäure enthaltende Katalysator wird zweckmäßig unter den nachfolgend genannten Bedingungen eingesetzt: Druckbereich 140 bis 160 at, vorzugsweise 150 at; Temperaturbereich 250 bis 370°C, vorzugsweise 300 bis 350°C; Gas:Öl-Verhältnis größer als 1,0 Nm3, vorteilhaft 1,2 Nm3 Wasserstoff pro kg Öl; Katalysatorbelastung 0,15 bis 1,0 kg Öl pro Liter Katalysator und Stunde.This special catalyst containing nickel, molybdenum and phosphoric acid is expediently used under the following conditions: pressure range 140 to 160 at, preferably 150 at; Temperature range 250 to 370 ° C, preferably 300 to 350 ° C; Gas: oil ratio greater than 1.0 Nm 3 , advantageously 1.2 Nm 3 hydrogen per kg of oil; Catalyst load 0.15 to 1.0 kg of oil per liter of catalyst per hour.
Die Verwendung des genannten Katalysators bietet bei-der Raffination von Vorprodukten für die Weißölherstellung einen erheblichen technischen Vorteil gegenüber den üblichen Raffinationskatalysatoren, da dieser bei gleichem Entschwefelungsgrad wesentlich mehr Aromaten hydriert. Es ist damit möglich, technische Weißöle, Druckfarbenöle oder Trägeröle für Insektizide in einer Stufe herzustellen.The use of the catalyst mentioned offers a considerable technical advantage over the conventional refining catalysts in the refining of preliminary products for white oil production, since it hydrogenates considerably more aromatics with the same degree of desulfurization. It is thus possible to produce technical white oils, printing ink oils or carrier oils for insecticides in one step.
Zur Herabsetzung des Nickel-Molybdän-Gehaltes des Katalysators dienen aktive Verdünnungsmittel. Unter "aktiven Verdünnungsmitteln" sollen verstanden werden großoberflächige Aluminiumoxide oder Aluminiumoxid/Siliciumdioxidgemische, die aufgrund ihrer Oberflächenbeschaffenheit selbst katalytisch wirksam sind und die Aktivität des Katalysators noch verstärken. Die Aktivität des Katalysators kann zusätzlich noch durch Einbringen von MgO, CaO, ZnO, B203 und TiO2 in Mengen von 1 bis 10 Gew.% in bekannter Weise verändert werden.Active diluents are used to reduce the nickel-molybdenum content of the catalyst. “Active diluents” are to be understood as meaning large-area aluminum oxides or aluminum oxide / silicon dioxide mixtures which, because of their surface properties, are themselves catalytically active and further increase the activity of the catalyst. The activity of the catalyst can additionally be changed in a known manner by introducing MgO, C aO, ZnO, B 2 0 3 and TiO 2 in amounts of 1 to 10% by weight.
Besonders geeignete oberflächenreiche Aluminiumoxide werden durch Ausfällen von Aluminiumoxidhydraten aus Aluminiumsalze enthaltenden wäßrigen Lösungen gewonnen. Man kann dabei von sauren Aluminiumsalzlösungen oder von Aluminatlösungen ausgehen und im ersten Fall mit Laugen, wie Ammoniak, im zweiten Fall mit Säuren, z.B. C02, oder sauren Aluminiumsalzlösungen, die bekannten Zwischenstufen der Oxidhydrate, wie Bayerit, Hydrargillit oder Böhmit, und aus diesen nach bekannten Verfahren - bzw. -Aluminiumoxide herstellen.Particularly suitable surface-rich aluminum oxides are obtained by precipitation of aluminum oxide hydrates from aqueous solutions containing aluminum salts. One can start from acidic aluminum salt solutions or from aluminate solutions and in the first case with alkalis, such as ammonia, in the second case with acids, for example C0 2 , or acidic aluminum salt solutions, and the known intermediate stages of the oxide hydrates, such as bayerite, hydrargillite or boehmite, and from these by known methods - or - produce aluminum oxides.
Geeignete Ausgangsprodukte zur Herstellung von Weißölen technischer Qualität sind öle mit einem Siedebereich zwischen 200 und 550°C, wie z.B. Gasölfraktionen mit einem Siedebereich von 220 bis 340°C, Spindelöl- oder Schmier- ölfraktionen. Höhersiedende Ausgansprodukte erfordern dabei allgemein schärfere Raffinationsbedingungen. Der Aromatengehalt der Rohstoffe ist nicht besonders kritisch, da die Aromaten durch die Hydrierung weitgehend reduziert werden können. Nur in besonders gelagerten Fällen, wenn der Aromatengehalt des Rohstoffs beträchtliche Werte, z.B. über 30 %, annimmt, ist es gegebenenfalls zweckmäßig, die Aromaten zuvor durch eine Extraktion teilweise zu entfernen.Suitable starting products for the production of white oils of technical quality are oils with a boiling range between 200 and 550 ° C, e.g. Gas oil fractions with a boiling range of 220 to 340 ° C, spindle oil or lubricating oil fractions. Higher boiling starting products generally require stricter refining conditions. The aromatic content of the raw materials is not particularly critical since the aromatics can be largely reduced by the hydrogenation. Only in particularly stored cases when the aromatic content of the raw material has considerable values, e.g. over 30%, it may be appropriate to remove some of the aromatics beforehand by extraction.
In Figur 1 ist ein Schema für die Durchführung des erfindungsgemäßen Verfahrens wiedergegeben. Eine Kohlenwasserstoffbeschickung, die im Bereich von 200 bis 550°C siedet, wird aus Leitung (1) zusammen mit Frischwasserstoff aus Leitung (2) und dem Kreislaufwasserstoff aus Leitung (3) in die Reaktion geführt und dort über einen schwefelfesten Hydrierkatalysator, der Nickel und Molybdän enthält, umgesetzt.FIG. 1 shows a diagram for the implementation of the method according to the invention. A hydrocarbon feed, which boils in the range of 200 to 550 ° C, is led from line (1) together with fresh hydrogen from line (2) and the circulating hydrogen from line (3) into the reaction and there over a sulfur-resistant hydrogenation catalyst, the nickel and Contains molybdenum, implemented.
Die Hydrierung der Kohlenwasserstoffe wird bei 360°C und bei 140 bar in (4) vorgenommen. Der aus dem Reaktor (4) kommende Strom wird durch Leitung (5) in die Trennzone (6) geleitet, in der die Gasphase von der Flüssigphase getrennt wird. Die Flüssigphase wird dann durch Leitung (7) in die Trennzone (8) geleitet, die eine Destillationszone sein kann und dort in eine Leichtstrippölfraktion, die mit gasförmigen Anteilen beladen ist und die durch Leitung (9) entfernt wird und ein schweres Produkt, das durch Leitung (11) abgezogen wird, getrennt.The hydrocarbons are hydrogenated in (4) at 360 ° C and at 140 bar. The stream coming from the reactor (4) is passed through line (5) into the separation zone (6), in which the gas phase is separated from the liquid phase. The liquid phase is then passed through line (7) into the separation zone (8), which can be a distillation zone and there into a light stripping oil fraction which is loaded with gaseous components and which is removed through line (9) and a heavy product which Line (11) is withdrawn, separated.
Beim Einsatz einer schwerem Fraktion durch Leitung (1) kann die Trennzone (8) so betrieben werden, daß neben dem schweren Produkt mit Weißölqualität aus Leitung (11) aus Leitung (10) als weiteres Produkt nur schweres Strippöl entnommen werden kann, welches ebenfalls die Qualität eines technischen Weißöles besitzt.When using a heavy fraction through line (1), the separation zone (8) can be operated so that in addition to the heavy product with white oil quality from line (11) from line (10) as a further product only heavy stripping oil can be removed, which also has the quality of a technical white oil.
Zur Herstellung eines technischen Weißöls wird von einer Erdölfraktion mit einem Siedebereich von 340 bis 500°C, einer Dichte von 0,901 (15°C), einer Viskosität von 47,50 cSt/50°C und einem Schwefelgehalt von 1,1 Gew.% ausgegangen. Der Aromatengehalt beträgt 17 Gew.%. Dieses öl wird an einem geschwefelten Katalysator, dessen Herstellung nachfolgend beschrieben wird, unter bestimmten Verfahrensbedingungen bei 150 at hydriert.To produce a technical white oil, a petroleum fraction with a boiling range of 340 to 500 ° C, a density of 0.901 (15 ° C), a viscosity of 47.50 cSt / 50 ° C and a sulfur content of 1.1% by weight went out. The aromatic content is 17% by weight. This oil is hydrogenated over a sulfurized catalyst, the preparation of which is described below, under certain process conditions at 150 at.
Der Katalysator wird folgendermaßen hergestellt und vor seiner Verwendung geschwefelt. Aus einer Al2(SO4)3-Lösung (7,5 % A1203) wird mit 25 %igem NH4OH bei einem pH--Wert von 6,5 und einer Temperatur von 850C ein Aluminiumoxidhydrat gefällt, mit 0,25 %iger (NH4)2CO3-Lösung sulfatfrei gewaschen und bei 120°C getrocknet. Zur Herstellung des Katalysators werden Strangpreßlinge mit 1,5 mm Durchmesser aus dem Aluminiumoxid, das bei 500 C calciniert wurde, hergestellt. 1 000 g Katalysator werden mit 755 g einer Lösung übersprüht, die umgerechnet 22,1 % Mo03, 8,5 % NiO und 6,8 Gew.% Phosphorsäure enthält. Zur Herstellung dieser Lösung wird Mo03-Sublimat durch Erhitzen mit der berechneten Menge einer o-Phosphorsäure--Lösung aufgeschlossen. Zu dieser Lösung wird anschliessend die erforderliche Menge Ni(NO3)2 · 6 H20 gegeben, wobei man eine klare Lösung erhält. Die imprägnierten Strangpreßlinge werden 12 Stunden bei 120°C getrocknet und anschließend 2 Stunden bei 350°C calciniert. Der fertige Katalysator enthält 5 % NiO, 13 % Mo03 und 4 % H3PO4. Für den Hydrierversuch werden 100 ml des zuvor geschwefelten Katalysators in einer Testapparatur bei 360°C, 150 at Wasserstoffpartialdruck und einem Gas-zu-ölverhältnis von 1,6 Nm3 Wasserstoff pro kg Öl mit 200 g einer Erdölfraktion (mit einem Siedebereich von 340 bis 580°C) pro Liter Katalysator und Stunde beaufschlagt.The catalyst is prepared as follows and sulfurized before use. An aluminum oxide hydrate is precipitated from an Al 2 (SO 4 ) 3 solution (7.5% A12 0 3 ) with 25% NH 4 OH at a pH of 6.5 and a temperature of 85 ° C. 0.25% (NH 4 ) 2 CO 3 solution washed sulfate-free and dried at 120 ° C. To produce the catalyst, extrudates with a diameter of 1.5 mm are produced from the aluminum oxide which has been calcined at 500.degree. 1,000 g of catalyst are sprayed with 755 g of a solution which contains the equivalent of 22.1% Mo03, 8.5% NiO and 6.8% by weight phosphoric acid. To prepare this solution, Mo03 sublimate is digested by heating with the calculated amount of an o-phosphoric acid solution. The required amount of Ni (NO 3 ) 2 .6 H 2 0 is then added to this solution, a clear solution being obtained. The impregnated extrusions are dried at 120 ° C. for 12 hours and then calcined at 350 ° C. for 2 hours. The finished catalyst contains 5% NiO, 13% Mo03 and 4% H 3 PO 4 . For the hydrogenation run, 100 ml of the previously sulfurized catalyst in a test apparatus at 360 ° C, 150 at hydrogen partial pressure, and a gas-to-oil ratio of 1, 6 Nm 3 of hydrogen per kg of oil with 200 g of a petroleum fraction (with a boiling range of 340 to 580 ° C) per liter of catalyst per hour.
In Tabelle 1 sind die Eigenschaften des Ausgangsstoffes denen der Raffinate gegenübergestellt.
Diese Ergebnisse zeigen, daß man auch bei einstufiger Fahrweise dank der gewählten Betriebsbedingungen technische Weißöle von ausgezeichneter Qualität gewinnt. überraschend ist es, daß die aus dem Strippöl abgezweigte Fraktion des schweren Teils des Strippöles die Qualitätsanforderungen für technische Weißöle erfüllt, womit eine Ausbeuteverbesserung verbunden ist. Dieser Effekt wird durch eine mäßige Druckerhöhung und durch ein höheres Gas/Öl-Verhältnis erzielt. Weiterhin können die beiden Fraktionen das schwere Produkt (11) und das schwere Strippöl (10),wegen ihres niedrigen S-Gehaltes ( <5 ppm) in einer zweitenThese results show that even with a one-step procedure, technical white oils of excellent quality can be obtained thanks to the selected operating conditions. It is surprising that the fraction of the heavy part of the stripping oil branched off from the stripping oil fulfills the quality requirements for technical white oils, which is associated with an improvement in yield. This effect is achieved by a moderate increase in pressure and a higher gas / oil ratio. Furthermore, the two fractions can the heavy product (11) and the heavy stripping oil (10), because of their low S content (<5 ppm) in a second
Hydrierstufe zur Herstellung von medizinischem Weißöl verwendet werden. Das Verfahren ermöglicht es auch, Viskosität und Flammpunkt der Endprodukte durch Variierung der Verfahrensbedingungen einzustellen.Hydrogenation stage can be used for the production of medical white oil. The process also makes it possible to adjust the viscosity and flash point of the end products by varying the process conditions.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813143869 DE3143869A1 (en) | 1981-11-05 | 1981-11-05 | METHOD FOR PRODUCING TECHNICAL WHITE OILS BY HYDRATION |
| DE3143869 | 1981-11-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0078951A1 true EP0078951A1 (en) | 1983-05-18 |
| EP0078951B1 EP0078951B1 (en) | 1986-03-05 |
Family
ID=6145643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP82109747A Expired EP0078951B1 (en) | 1981-11-05 | 1982-10-22 | Process for the preparation of technical white oils by hydrogenation |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0078951B1 (en) |
| DE (2) | DE3143869A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5976353A (en) * | 1996-06-28 | 1999-11-02 | Exxon Research And Engineering Co | Raffinate hydroconversion process (JHT-9601) |
| US6096189A (en) * | 1996-12-17 | 2000-08-01 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
| US6099719A (en) * | 1996-12-17 | 2000-08-08 | Exxon Research And Engineering Company | Hydroconversion process for making lubicating oil basestocks |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1645791A1 (en) * | 1966-08-16 | 1970-05-21 | Sinclair Research Inc | Process for the production of a white mineral oil |
| DE2300038A1 (en) * | 1973-01-02 | 1974-07-04 | Basf Ag | PROCESS FOR MANUFACTURING TECHNICAL OR MEDICAL WHITE OILS |
| FR2235997A1 (en) * | 1973-07-03 | 1975-01-31 | Shell Int Research | |
| US3959122A (en) * | 1972-02-24 | 1976-05-25 | Sun Oil Company Of Pennsylvania | Making a white oil by hydrogenation with a sulfided nickel and molybdenum catalyst |
| DE2813571A1 (en) * | 1977-03-30 | 1978-10-05 | Exxon France | WHITE OIL AND METHOD FOR PRODUCING IT |
-
1981
- 1981-11-05 DE DE19813143869 patent/DE3143869A1/en not_active Withdrawn
-
1982
- 1982-10-22 EP EP82109747A patent/EP0078951B1/en not_active Expired
- 1982-10-22 DE DE8282109747T patent/DE3269677D1/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1645791A1 (en) * | 1966-08-16 | 1970-05-21 | Sinclair Research Inc | Process for the production of a white mineral oil |
| US3959122A (en) * | 1972-02-24 | 1976-05-25 | Sun Oil Company Of Pennsylvania | Making a white oil by hydrogenation with a sulfided nickel and molybdenum catalyst |
| DE2300038A1 (en) * | 1973-01-02 | 1974-07-04 | Basf Ag | PROCESS FOR MANUFACTURING TECHNICAL OR MEDICAL WHITE OILS |
| FR2235997A1 (en) * | 1973-07-03 | 1975-01-31 | Shell Int Research | |
| DE2813571A1 (en) * | 1977-03-30 | 1978-10-05 | Exxon France | WHITE OIL AND METHOD FOR PRODUCING IT |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5976353A (en) * | 1996-06-28 | 1999-11-02 | Exxon Research And Engineering Co | Raffinate hydroconversion process (JHT-9601) |
| US6096189A (en) * | 1996-12-17 | 2000-08-01 | Exxon Research And Engineering Co. | Hydroconversion process for making lubricating oil basestocks |
| US6099719A (en) * | 1996-12-17 | 2000-08-08 | Exxon Research And Engineering Company | Hydroconversion process for making lubicating oil basestocks |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3143869A1 (en) | 1983-05-11 |
| DE3269677D1 (en) | 1986-04-10 |
| EP0078951B1 (en) | 1986-03-05 |
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