DE1067160B

DE1067160B -

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Publication number: DE1067160B
Application number: DENDAT1067160D
Authority: DE

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DEUTSCHESGERMAN

Es ist bereits bekannt, schwefelhaltige ungesättigte Benzine in Gegenwart von Katalysatoren mit Wasserstoff unter Druck bei erhöhter Temperatur zu raffinieren. Es wurde auch schon vorgeschlagen, derartige Ausgangsstoffe zunächst in einer ersten Stufe einer Vorhydrierung zu unterwerfen und das dabei erhaltene Produkt dann in einer zweiten Stufe mit Wasserstoff katalytisch zu raffinieren. Weiterhin wurde bereits vorgeschlagen, Ausgangsstoffe mit leichtpolymerisierbaren Verbindungen vor der Raffination zu verdampfen, nur die verdampften Anteile zusammen mit Wasserstoff der katalytischen Raffination zu unterwerfen und den kleineren, nichtverdampften Anteil aus dem Reaktionssystem zu entfernen. Mit Hilfe dieser Maßnahmen soll verhindert werden, daß sich schädigende Ablagerungen auf dem Katalysator in der eigentlichen Raffinationsstufe bilden.It is already known to use sulfur-containing unsaturated gasolines in the presence of catalysts with hydrogen to refine under pressure at elevated temperature. It has also been suggested that such Submitting starting materials first in a first stage of a pre-hydrogenation and the thereby obtained The product is then catalytically refined in a second stage with hydrogen. Furthermore has already been suggested starting materials with readily polymerizable compounds before refining evaporate, only the evaporated fractions together with hydrogen for catalytic refining and remove the smaller, non-evaporated portion from the reaction system. With The aim of these measures is to prevent damaging deposits from forming on the catalytic converter form in the actual refining stage.

Es hat sich nun gezeigt, daß für die Raffination schwefelhaltiger ungesättigter Benzine, die größere Mengen aromatischer 'Kohlenwasserstoffe enthalten, ao weder die Vorhydrierung der Ausgangsstoffe noch die Abtrennung polymerisierbarer Anteile allein ausreichen, um eine Raffination im kontinuierlichen, störungsfreien Betrieb für lange Zeit zu gewährleisten. It has now been shown that for refining unsaturated gasoline containing sulfur, the larger Amounts of aromatic 'hydrocarbons contain, ao neither the pre-hydrogenation of the starting materials nor the Separation of polymerizable fractions alone is sufficient to enable refining in a continuous, to ensure trouble-free operation for a long time.

Es wurde nun gefunden, daß man schwefelhaltige ungesättigte Benzine, die aromatische Kohlenwasserstoffe enthalten, kontinuierlich mit gutem Erfolg raffinieren kann, wenn man den Ausgangsstoff zunächst unter Druck auf mindestens IOO⁰ C erwärmt und zusammen mit einer kleinen Menge Wasserstoff, z. B. 20 bis 500 1 je kg Ausgangsstoff, im Temperaturbereich zwischen 100 und 250° C in vorwiegend flüssiger Phase über einem Katalysator vorhydriert, darauf den vorhydrierten Ausgangsstoff in einem Verdampfer zweckmäßig unter dem gleichen Druck mit einer großen Menge erhitztem Wasserstoff, z. B. 0,5 bis 3 m³ je kg Ausgangsstoff, weitgehend verdampft und die nichtverdampften hochsiedenden Anteile am Boden des Verdampfers abzieht, anschließend die verdampften Anteile zusammen mit Wasserstoff weitererhitzt und im Temperaturbereich zwischen 300 und 450° C katalytisch raffiniert und anschließend die Reaktionsprodukte zusammen mit dem Wasserstoff abkühlt, die gasförmigen von den flüssigen Anteilen in einem Abscheider abtrennt, das wasserstoffhaltige Gas in das Verfahren zurückführt und die flüssigen Anteile entspannt.It has now been found that sulfur-containing unsaturated gasolines which contain aromatic hydrocarbons, can continuously refine with good success when first heated under pressure to the starting material at least IOO ⁰ C and together with a small amount of hydrogen, z. B. 20 to 500 1 per kg of starting material, pre-hydrogenated in the temperature range between 100 and 250 ° C in the predominantly liquid phase over a catalyst. B. 0.5 to 3 m ³ per kg of starting material, largely evaporated and the non-evaporated high-boiling fractions are removed at the bottom of the evaporator, then the evaporated fractions are further heated together with hydrogen and catalytically refined in the temperature range between 300 and 450 ° C and then the reaction products together cools with the hydrogen, separates the gaseous from the liquid components in a separator, recirculates the hydrogen-containing gas to the process and relaxes the liquid components.

Bei Anwendung dieser speziellen Arbeitsweise gelingt es, Ausgangsstoffe, wie Benzine, die 50 bis 95 Gewichtsprozent aromatische Kohlenwasserstoffe enthalten und durch Spaltung schwefelhaltiger Erdöle oder Teere bei Temperaturen oberhalb 500° C, z. B. 650 bis 1000° C oder darüber, oder durch VerkokungWhen using this special procedure, it is possible to use starting materials, such as gasoline, the 50 to Contains 95 percent by weight of aromatic hydrocarbons and by splitting sulfur-containing petroleum or tars at temperatures above 500 ° C, e.g. B. 650 to 1000 ° C or above, or by coking

Verfahren zur katalytischer! Raffination schwefelhaltiger ungesättigter BenzineProcess for catalytic! Refining of unsaturated gasoline containing sulfur

Anmelder:Applicant:

Badlsche Anilin- & Soda-Fabrik
Aktiengesellschaft,
Ludwigshafen/RheinBadlsche aniline & soda factory
Corporation,
Ludwigshafen / Rhine

Dr. Helmut Nonnenmacher und Dr. Wilhelm Himmler, Ludwigshaf en/Rhein,
sind als Erfinder genannt wordenDr. Helmut Nonnenmacher and Dr. Wilhelm Himmler, Ludwigshafen / Rhine,
have been named as inventors

oder Verschwelung fester Brennstoffe erhalten weiden, in gut raffinierte Produkte überzuführen. Di· genannten Ausgangsstoffe sind im allgemeinen reiel an aromatischen Verbindungen, die ungesättigt Seitenketten enthalten und bei der Aufheizung bzw der Raffination besonders leicht höhermolekular Polymerisationsprodukte bilden.or carbonization of solid fuels will get past to be converted into well-refined products. Tue The starting materials mentioned are generally rich in aromatic compounds that are unsaturated Contain side chains and particularly slightly higher molecular weight when heated or refined Form polymerization products.

Da die Aufheizung und Vorhydrierung dieser StolT in vorwiegend flüssiger Phase durchgeführt werdei soll, benötigt man Drücke von 10 bis 200 at, ζ. Β. 2ι bis 100 at. Die Ausgangsstoffe werden unter diesen Druck auf Temperaturen von 100 bis etwa 250° < erhitzt. Es ist ratsam, bei der Aufheizung nur sch wenig Gas zuzusetzen, damit ein möglichst hohe Anteil dieser Stoffe, vorteilhaft etwa 60 bis 90 Gc wichtsprozent, flüssig bleibt.Since the heating and pre-hydrogenation of this StolT are mainly carried out in the liquid phase you need pressures of 10 to 200 at, ζ. Β. 2ι to 100 at. The starting materials are among these Pressure heated to temperatures of 100 to about 250 ° <. It is advisable to only shine when heating Add little gas so that the highest possible proportion of these substances, advantageously about 60 to 90 Gc weight percent, remains liquid.

Mitunter kann man diese Phase der Aufheizun: auch ohne Zugabe von Wasserstoff durchführen. Nac' der Aufheizung gibt man dem Ausgangsstoff zweck mäßig eine weitere kleine Menge Wasserstoff zu, de vorteilhaft auf 150 bis etwa 250° C erhitzt ist. Di Menge an Wasserstoff oder an freien Wasserstoff ent haltenden Gasen, die vor und bzw. oder nach der Er hitzung insgesamt zugegeben wird, beträgt 20 bi 5001, insbesondere 50 bis 3001, je kg Ausgangsstofi Bei Anwendung dieser Reaktionsbedingungen bleil; ein großer Teil des Ausgangsbenzins, z. B. etwa 5C 60 oder 75 Gewichtsprozent, flüssig und wird an schließend mit Wasserstoff über einen an sich bekann ten Hydrierkatalysator der VI. bis VIII. Gruppe de Periodischen Systems mit einem Durchsatz von 1 bi 10 kg, insbesondere 2 bis 8 kg, Benzin je Liter Kata lysator und Stunde geleitet. Als geeignete Katalysa toren haben sich z. B. die Oxyde oder Sulfide—vo Molybdän, Wolfram, Chrom,_t Vanadin, Kobalt od/Sometimes this phase of heating can also be carried out without adding hydrogen. After the heating, a further small amount of hydrogen is expediently added to the starting material, which is advantageously heated to 150 to about 250.degree. The amount of hydrogen or gases containing free hydrogen, which is added in total before and or or after heating, is 20 to 5001, in particular 50 to 3001, per kg of starting material. When these reaction conditions are used, lead; a large part of the starting gasoline, e.g. B. about 5C 60 or 75 percent by weight, liquid and is then closed with hydrogen over a well-known hydrogenation catalyst VI. to VIII. Group de Periodic System with a throughput of 1 to 10 kg, in particular 2 to 8 kg, gasoline per liter of catalyst and hour passed. Suitable catalysts have z. As the oxides or Sul fide vo molybdenum, tungsten, chromium, vanadium _t, cobalt od /

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Claims

STickel and mixtures of these, e.g. B. cobalt and molybdenum or tungsten and nickel, have been proven.

As hydrogenation gas, in addition to pure "hydrogen", gases containing free hydrogen, such as coke-soap gas, Town gas or water gas can be used. These gases should deialize at least 30%> · hydrogen.

After this pre-hydrogenation, the mixture (s) of starting materials and hydrogen is passed into an evaporator, which can be seen entirely or partially with packing elements. It is beneficial to use circulation steamers. By adding large quantities of hydrogen or gases containing free hydrogen, e.g. B. 0.5 to 3 m ³ per kg of starting material, the vast majority of the starting material is evaporated. The pressure in the evaporator is usually the same as in the pre-hydration. But you can also use another, e.g. B.: Select a pressure lower by 10 to 100 atmospheres, in which the reaction participants introduced into the evaporator are relaxed to a lower pressure. The newly supplied hydrogen is compressed to the pressure of the evaporator or a pressure slightly higher and heated to 200 to 450 ° C before entering the evaporator. In general, it is advantageous to work in such a way that the hydrogen is at a higher temperature than the leaking material from the prehydrogenation. At the bottom of the evaporator a small amount, e.g. B. about 0.5) is 5 percent by weight, deducted and optionally processed luf special products such as coumarone or cyclopentadiene.

The vaporized starting material is then brought together with the hydrogen in a preheater to approximately the reaction temperature, e.g. B. 250 to 400 ° C ₁ air-heated and with a throughput of 0.5 to 6 kg, ns especially 1 to 3 kg, gasoline per liter of catalyst in hour fed to the reaction vessel, which is filled with hydrogenation catalysts known per se. ^ .Is such come z. B. the oxides or sulfides of the V to VIII. Group as well as the platinum metals or some of these into consideration. They can be applied to carriers such as silica, silicates, alumina, titanium oxide, zirconium oxide, magnesia, which may have been pretreated with chlorine, iodine, fluorine or their compounds. The products released from the reaction vessel are passed through a heat exchanger in which they use their heat e.g. B. to heat up to approximately the reaction temperature-Ien release starting materials. They then enter: a separator in which the liquid taffinate is separated from the gases. The gases are, if necessary after previous washing, the / experience, z. B. in the evaporator and upstream of the Vorlydrierungsgefäß supplied. The raffinate is expanded and released from dissolved gases, which can also be recycled.

example

10 kg of a gasoline obtained in the thermal cleavage of id oil to olefin-rich gases, boiling between 50 and 150 ° C, the 0.7 percent by weight sulfur, 80 percent by weight aromatic,

Contains hydrocarbons partially provided with unsaturated side chains and has a bromine number of 50, are ^{heated together with 2.5 m 8} hydrogen per hour under a pressure of 30 atm in a heated preheater to 160 ° C., with only 20 percent by weight of the gasoline evaporating. The reaction material is then pre-hydrogenated over tungsten sulfide with a throughput of 8 kg of gasoline per liter of catalyst per hour. The pre-hydrogenated mixture is ^{fed to a circulation evaporator together with 20 m 3} of hydrogen heated to 200 ° C. per hour. The gasoline evaporates to a large extent. The non-evaporated liquid portion is drawn off in an amount of 4.5 percent by weight (based on the gasoline used) at the bottom of the vessel. The vaporized gasoline is heated together with the hydrogen in a heat exchanger to 370 ° C and passed over cobalt molybdate with a throughput of 2 kg per liter of catalyst per hour.

The resulting refined gasoline contains less than 0.001 weight percent sulfur and a bromine number of 1. Nuclear hydrogenation of the aromatics did not occur.

Patentanspruch:Claim:

Process for the catalytic refining of unsaturated gasolines containing sulfur and containing aromatic hydrocarbons in the presence of hydrogen under pressure at elevated temperature, characterized in that the starting material is first heated to at least 100 ° C. at a pressure between 10 and 200 atm and together with a small amount of hydrogen, e.g. B. 20 to 5001 per kg of starting material, in the temperature range between 100 and 250 ° C in pre- // L predominantly liquid phase over a catalyst / pre-hydrogenated, then the pre-hydrogenated starting material in one. Evaporator conveniently under the same pressure with a large amount of heated hydrogen, e.g. B. 0.5 to 3 m ³ per kg of starting material, largely evaporated and the non-evaporated high-boiling fractions are removed at the bottom of the evaporator, then the evaporated fractions are further heated together with hydrogen and catalytically refined in the temperature range between 300 and 450 ° C and then the reaction products together cools with the hydrogen, separates the gaseous from the liquid components in a separator, recirculates the hydrogen-containing gas to the process and relaxes the liquid components.

Considered publications:

German Patent Nos. 869198, 933 648;

German Auslegeschrift No. 1 041 620;

Patent specification No. 12 392 of the Office for Invention and Patents in the Soviet Zone of Occupation Germany;

U.S. Patent No. 2,061,845;

J. Chem. Soc. Japan, in d. Chem. Sect., 60, 61-64, Jan. 1957, ref. i. Chem. Zentralbl., 1957, p. 5150 (Ichirö Yoshikawa).

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