EP0191388B1 - Preparation of a liquid carburettor fuel for otto engines - Google Patents

Preparation of a liquid carburettor fuel for otto engines Download PDF

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Publication number
EP0191388B1
EP0191388B1 EP86101331A EP86101331A EP0191388B1 EP 0191388 B1 EP0191388 B1 EP 0191388B1 EP 86101331 A EP86101331 A EP 86101331A EP 86101331 A EP86101331 A EP 86101331A EP 0191388 B1 EP0191388 B1 EP 0191388B1
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Prior art keywords
coal
dimethyl carbonate
phenol
phenols
subjected
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German (de)
French (fr)
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EP0191388A3 (en
EP0191388A2 (en
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Richard Dr. Wessendorf
Werner Dr. Döhler
Alfons Dr. Jankowski
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RAG AG
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Ruhrkohle AG
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition

Definitions

  • the invention relates to a method for producing a liquid gasoline for gasoline engines of the type specified in the preamble of the claim.
  • coal oils When working up by splitting hydrogenation or refining hydrogenation of hard coal or lignite or also by hydrogenating coal extracts, coal oils are obtained which contain phenol and various phenols, in particular alkylphenols, in varying amounts. Although phenol and its alkylated derivatives are excellent anti-knock agents for gasoline fuels, they have a strong corrosion effect and are physiologically questionable, so that they cannot be used as octane number improvers.
  • coal oils are refined to liquid gasoline fuels through a catalytic refining step with gaseous hydrogen (refining).
  • gaseous hydrogen gaseous hydrogen
  • the phenols contained in the coal oil are degraded to naphthenes and nitrogen and sulfur-containing hetero compounds are degraded to corresponding hydrocarbons, the heteroatoms 0, N and S being degraded to the simple hydrogen compounds.
  • This degradation proceeds without difficulty under suitable conditions.
  • the naphthenes are rearomatized or aromatics are formed from straight-chain paraffins, the hydrogen obtained in the reforming stage being used in part to cover the hydrogen requirement existing in the refining stage and in other conversion processes.
  • the conversion of the phenol mixture into an ether mixture is carried out according to the aforementioned US patent with dimethyl sulfate and includes the steps of extraction with aqueous sodium hydroxide, washing of the extract, removal of the detergent, re-acidification and addition of sodium chloride in order to separate the free phenols, washing those containing the phenols Phase, addition of aqueous sodium hydroxide and dimethyl sulfate to the isolated and purified phenol mixture, addition of excess aqueous sodium hydroxide for the hydrolysis of unreacted excess dimethyl sulfate and for the removal of unetherified phenols, separation of the aryl methyl ether phase, washing and working up of the reaction product by distillation.
  • the object of the invention is to avoid the costly isolation of the phenolic compounds of coal oil in a process of the type specified at the outset.
  • This object is achieved with the invention. It consists in treating this side stream with dimethyl carbonate as methylating agent under methylating conditions, but without the addition of a catalyst, in a process according to the preamble of claim 1, then removing the by-products methanol and carbon dioxide formed, and in that at least part of the thus obtained , Anisole and various methylaryl ethers containing side stream combined with at least part of the main stream subjected to the further treatment stages mentioned.
  • dialkyl carbonates preferably dimethyl carbonate and diethyl carbonate
  • This addition is aimed at increasing the knock resistance of such gasolines (EP-OS 0 082 688).
  • the desired etherification products can be obtained in a simple, one-step synthesis by reacting coal oil or fractions of the coal oil with preferably dimethyl carbonate at temperatures of about 150 to 180 ° C.
  • the reaction can be carried out in an autoclave or, in the case of a continuous configuration, in a reactor which is integrated in an overall system for producing gasoline fuels from coal oil.
  • the carbon dioxide obtained as a by-product when carrying out the process according to the invention can be removed from the process without difficulty.
  • the further working up of the reaction mixture of the reaction of the phenol-containing fraction with dimethyl carbonate preferably proceeds in such a way that the methanol also formed as a by-product is separated off in a preliminary fraction up to 65.degree.
  • the methanol present as a by-product is left in the bypass stream subjected to methylation with dimethyl carbonate.
  • the by-stream obtained by the present process and containing anisole and various methylaryl ethers and, if appropriate, methanol is also excellently suitable as an admixture component for mineral oil-derived refined petrol.
  • the method according to the invention includes a considerable relief of the refiner and reformer stage and also leads to considerable hydrogen savings.
  • reaction in the process according to the invention proceeds in high yields to the corresponding ethers, so that it is not necessary to separate unmethylated phenols if the product is used as an admixture.
  • the fraction boiling between 150 to 220 ° C. was isolated from the coal oil of a coal liquefaction plant operated as a test plant in Bottrop.
  • the gas chromatographic analysis for phenols showed the following components:
  • a mixture of 60 vol .-% super fuel (SVK) and 40 vol .-% of a total pyrolysis gasoline gave a value of the oxidation stability according to DIN 51 600 of 260 min.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines flüssigen Vergaserkraftstoffes für Otto-Motoren der im Oberbegriff des Patentanspruches bezeichneten Art.The invention relates to a method for producing a liquid gasoline for gasoline engines of the type specified in the preamble of the claim.

Bei der Aufarbeitung durch spaltende Hydrierung oder raffinierende Hydrierung von Steinkohle oder Braunkohle oder auch durch Hydrierung von Kohleextrakten fallen Kohleöle an, die Phenol und verschiedene Phenole, insbesondere Alkylphenole, in wechselnden Mengen enthalten. Phenol und seine alkylierten Abkömmlinge sind zwar hervorragende Antiklopfmittel für Vergaserkraftstoffe, besitzen aber starke Korrosionswirkung und sind physiologisch bedenklich, so daß sie als Oktanzahlverbesserer nicht einsetzbar sind.When working up by splitting hydrogenation or refining hydrogenation of hard coal or lignite or also by hydrogenating coal extracts, coal oils are obtained which contain phenol and various phenols, in particular alkylphenols, in varying amounts. Although phenol and its alkylated derivatives are excellent anti-knock agents for gasoline fuels, they have a strong corrosion effect and are physiologically questionable, so that they cannot be used as octane number improvers.

Im allgemeinen werden Kohleöle durch eine katalytische Raffinationsstufe mit gasförmigem Wasserstoff (Refining) auf flüssige Vergaserkraftstoffe aufgearbeitet. In dieser Stufe erfolgt der Abbau der in dem Kohleöl enthaltenen Phenole zu Naphthenen sowie der Abbau stickstoff- und schwefelhaltiger Heteroverbindungen zu entsprechenden Kohlenwasserstoffen, wobei die Heteroatome 0, N sowie S zu den einfachen Wasserstoffverbindungen abgebaut werden. Dieser Abbau verläuft unter geeigneten Bedingungen ohne Schwierigkeiten. Bei der anschließenden Reformierung erfolgt unter anderem eine Rearomatisierung der Naphthene oder auch eine Aromatenbildung aus geradkettigen Paraffinen, wobei der in der Reformingstufe anfallende Wasserstoff zum Teil zur Deckung des in der Raffinationsstufe und in anderen Umwandlungsverfahren bestehenden Wasserstoffbedarfes dient. Aufgrund des hohen Phenolgehaltes der rohen Kohleöle resultieren bei der Raffination hohe Naphthengehalte, insbesondere Cyclohexan. Im Reforming-Prozeß führt dies zu hohen Benzolgehalten im kohlestämmigen Benzin, so daß ein solches Verfahren für die Herstellung von Kraftstoffen für Otto-Motoren zu unerwünscht hohen Benzolgehalten führt.In general, coal oils are refined to liquid gasoline fuels through a catalytic refining step with gaseous hydrogen (refining). In this stage, the phenols contained in the coal oil are degraded to naphthenes and nitrogen and sulfur-containing hetero compounds are degraded to corresponding hydrocarbons, the heteroatoms 0, N and S being degraded to the simple hydrogen compounds. This degradation proceeds without difficulty under suitable conditions. In the subsequent reforming, among other things, the naphthenes are rearomatized or aromatics are formed from straight-chain paraffins, the hydrogen obtained in the reforming stage being used in part to cover the hydrogen requirement existing in the refining stage and in other conversion processes. Due to the high phenol content of the raw coal oils, high naphthen contents result in refining, especially cyclohexane. In the reforming process, this leads to high benzene contents in coal-derived gasoline, so that such a process for the production of fuels for Otto engines leads to undesirably high benzene contents.

Zur Abtrennung von Phenolen, allerdings mit anderer Zielsetzung als beim erfindungsgemäßen Verfahren, wird im US Patent 4 319 981 folgender Weg vorgeschlagen: Abtrennung einer phenolhaltigen Fraktion des Kohleöls und Umwandlung des Phenols und seiner alkylierten Abkömmlinge in ein korrespondierendes Gemisch von Methylarylethern und Wiederzusatz dieses Gemisches zu dem raffinierten und reformierten Kohlebenzin. In einer grundlegenden Arbeit von G. M. Singermann, Gulf Research and Development Co., wurde die Eignung derartig erhaltener Mischungen von Methylarylethern als Kraftstoffzusatz und Oktanverbesserer aufgezeigt (C.A. 95: 153 300j).For the separation of phenols, but with a different objective than in the process according to the invention, the following route is proposed in US Pat. No. 4,319,981: separation of a phenol-containing fraction of the coal oil and conversion of the phenol and its alkylated derivatives into a corresponding mixture of methylaryl ethers and re-addition of this mixture the refined and reformed coal gasoline. A fundamental work by G.M. Singermann, Gulf Research and Development Co., demonstrated the suitability of mixtures of methylaryl ethers obtained in this way as fuel additives and octane improvers (C.A. 95: 153 300j).

Ein Zusatz von 5 Vol.-% dieser Methylarylethermischung bewirkt z.B. eine Erhöhung der Research Oktanzahl (ROZ) um 0,6.An addition of 5% by volume of this methylaryl ether mixture causes e.g. an increase in Research Octane Number (RON) by 0.6.

Die Überführung des Phenolgemisches in ein Ethergemisch wird nach dem genannten US Patent mit Dimethylsulfat durchgeführt und beinhaltet die Stufen Extraktion mit wäßrigem Natriumhydroxid, Waschen des Extraktes, Entfernen des Waschmittels, Wiederansäuern und Zusatz von Natriumchlorid, um die freien Phenole abzuscheiden, Waschen der die Phenole enthaltenden Phase, Zusatz von wäßrigem Natriumhydroxid und Dimethylsulfat zu der isolierten und gereinigten Phenolmischung, Zusatz von überschüssigem wäßrigen Natriumhydroxid zur Hydrolyse von nicht umgesetztem überschüssigen Dimethylsulfat und zur Beseitigung nicht veretherter Phenole, Abtrennen der Arylmethylether-Phase, Waschen und Aufarbeitung des Reaktionsproduktes durch Destillation.The conversion of the phenol mixture into an ether mixture is carried out according to the aforementioned US patent with dimethyl sulfate and includes the steps of extraction with aqueous sodium hydroxide, washing of the extract, removal of the detergent, re-acidification and addition of sodium chloride in order to separate the free phenols, washing those containing the phenols Phase, addition of aqueous sodium hydroxide and dimethyl sulfate to the isolated and purified phenol mixture, addition of excess aqueous sodium hydroxide for the hydrolysis of unreacted excess dimethyl sulfate and for the removal of unetherified phenols, separation of the aryl methyl ether phase, washing and working up of the reaction product by distillation.

Diese Isolierung und Veretherung der erhaltenen Phenole ist langwierig und materialaufwendig.This isolation and etherification of the phenols obtained is lengthy and expensive.

Demgemäß besteht die Erfindungsaufgabe darin, bei einem Verfahren der eingangs angegebenen Art, die aufwendige Isolierung der phenolischen Verbindungen des Kohleöls zu vermeiden.Accordingly, the object of the invention is to avoid the costly isolation of the phenolic compounds of coal oil in a process of the type specified at the outset.

Diese Aufgabe wird mit der Erfindung gelöst. Sie besteht darin, daß man bei einem Verfahren nach dem Oberbegriff des Patentanspruches 1 diesen Nebenstrom mit Dimethylcarbonat als Methylierungsmittel unter methylierenden Bedingungen, aber ohne Zusatz eines Katalysators, behandelt, anschließend die entstandenen Nebenprodukte Methanol und Kohlendioxid entfernt und daß man mindestens einen Teil des so erhaltenen, Anisol sowie verschiedene Methylarylether enthaltenden, Nebenstromes mit mindestens einem Teil des den genannten Weiterbehandlungsstufen unterworfenen Hauptstromes vereinigt.This object is achieved with the invention. It consists in treating this side stream with dimethyl carbonate as methylating agent under methylating conditions, but without the addition of a catalyst, in a process according to the preamble of claim 1, then removing the by-products methanol and carbon dioxide formed, and in that at least part of the thus obtained , Anisole and various methylaryl ethers containing side stream combined with at least part of the main stream subjected to the further treatment stages mentioned.

Zwar ist aus der EP-A-0 000 162 die Methylierung von Phenol durch Dimethylcarbonat in Gegenwart eines Katalysators bekannt. Die Methylierung ohne einen Katalysator ist dadurch jedoch nicht nahegelegt.The methylation of phenol by dimethyl carbonate in the presence of a catalyst is known from EP-A-0 000 162. However, this does not suggest methylation without a catalyst.

Es ist auch der Zusatz von Dialkylcarbonaten, vorzugweise Dimethylcarbonat und Diethylcarbonat zu verbleiten oder unverbleiten Benzinen als Kraftstoff für Verbrennungsmaschinen vorgeschlagen worden. Durch diesen Zusatz wird eine Erhöhung der Klopffestigkeit derartiger Benzine angestrebt (EP-OS 0 082 688).It has also been proposed to add dialkyl carbonates, preferably dimethyl carbonate and diethyl carbonate, to lead or unleaded gasoline as a fuel for internal combustion engines. This addition is aimed at increasing the knock resistance of such gasolines (EP-OS 0 082 688).

Es wurde gefunden, daß man mit einer einfachen, einstufigen Synthese zu den gewünschten Veretherungsprodukten gelangt, indem man Kohleöl oder Fraktionen des Kohleöls mit vorzugsweise Dimethylcarbonat bei Temperaturen von etwa 150 bis 180°C umsetzt. Die Umsetzung kann im Autoklaven oder auch bei kontinuierlicher Ausgestaltung in einem in eine Gesamtanlage zur Herstellung von Otto-Kraftstoffen aus Kohleöl integrierten Reaktor durchgeführt werden.It has been found that the desired etherification products can be obtained in a simple, one-step synthesis by reacting coal oil or fractions of the coal oil with preferably dimethyl carbonate at temperatures of about 150 to 180 ° C. The reaction can be carried out in an autoclave or, in the case of a continuous configuration, in a reactor which is integrated in an overall system for producing gasoline fuels from coal oil.

Als Reaktionsprodukt fällt ein Gemisch der veretherten Phenole mit Methanol nach folgender Reaktionsgleichung an:

Figure imgb0001
A mixture of the etherified phenols with methanol is obtained as the reaction product according to the following reaction equation:
Figure imgb0001

Das bei Durchführung des erfindungsgemäßen Verfahrens als Nebenprodukt anfallende Kohlendioxid kann ohne Schwierigkeiten aus dem Verfahren ausgeschleust werden. Die weitere Aufarbeitung des Reaktionsgemisches der Umsetzung der phenolhaltigen Fraktion mit Dimethylcarbonat verläuft vorzugsweise so, daß in einer Vorlauffraktion bis 65°C das ebenfalls als Nebenprodukt gebildete Methanol .abgetrennt wird.The carbon dioxide obtained as a by-product when carrying out the process according to the invention can be removed from the process without difficulty. The further working up of the reaction mixture of the reaction of the phenol-containing fraction with dimethyl carbonate preferably proceeds in such a way that the methanol also formed as a by-product is separated off in a preliminary fraction up to 65.degree.

Bei dem in dem erfindungsgemäßen Verfahren eingesetzten Dimethylcarbonat handelt es sich um ein Großprodukt der chemischen Industrie, das von verschiedenen Herstellern angeboten wird. Die Synthese von Dimethylcarbonat erfolgt beispielsweise nach folgender Gleichung:

  • 2 CH3OH + CO +½ O2 → (H3CO)2CO + H2O
The dimethyl carbonate used in the process according to the invention is a large product of the chemical industry, which is offered by various manufacturers. For example, dimethyl carbonate is synthesized using the following equation:
  • 2 CH 3 OH + CO + ½ O 2 → (H 3 CO) 2 CO + H 2 O

Nach einer weiteren Ausgestaltung der Erfindung wird in dem der Methylierung mit Dimethylcarbonat unterworfenen Nebenstrom das als Nebenprodukt enthaltene Methanol belassen. Der nach dem vorliegenden Verfahren erhaltene, Anisol sowie verschiedene Methylarylether sowie ggf. Methanol enthaltende, Nebenstrom eignet sich auch ausgezeichnet als Zumischkomponente für mineralölstämmiges Raffineriebenzin.According to a further embodiment of the invention, the methanol present as a by-product is left in the bypass stream subjected to methylation with dimethyl carbonate. The by-stream obtained by the present process and containing anisole and various methylaryl ethers and, if appropriate, methanol is also excellently suitable as an admixture component for mineral oil-derived refined petrol.

Die O-Methylierung von Phenol mit Dimethylcarbonat als solche ist bekannt, wobei die in der Literatur beschriebenen Reaktionen in Gegenwart von Katalysatoren wie tertiären Aminen, tertiären Phosphinen oder einem Gemisch von Natriumhydroxid und Kaliumjodid durchgeführt werden.The O-methylation of phenol with dimethyl carbonate as such is known, the reactions described in the literature being carried out in the presence of catalysts such as tertiary amines, tertiary phosphines or a mixture of sodium hydroxide and potassium iodide.

Überraschend wurde gefunden, daß die Umsetzung von mit Phenol und alkylierten Abkömmlingen des Phenols angereicherten Fraktionen aus Kohleöl mit Dimethylcarbonat keine zusätzlichen und bei der anschließenden Aufarbeitung wieder zu entfernenden Katalysatoren benötigt.Surprisingly, it was found that the reaction of fractions enriched with phenol and alkylated derivatives of phenol from coal oil with dimethyl carbonate does not require any additional catalysts which have to be removed in the subsequent workup.

Das erfindungsgemäße Verfahren beinhaltet eine beträchtliche Entlastung der Refiner- sowie Reformerstufe und führt auch zu einer erheblichen Wasserstoffeinsparung.The method according to the invention includes a considerable relief of the refiner and reformer stage and also leads to considerable hydrogen savings.

Die Umsetzung bei dem erfindungsgemäßen Verfahren verläuft in hohen Ausbeuten zu den entsprechenden Ethern, so daß man auf eine Abtrennung nicht methylierter Phenole verzichten kann, wenn das Produkt als Zumischkomponente eingesetzt wird.The reaction in the process according to the invention proceeds in high yields to the corresponding ethers, so that it is not necessary to separate unmethylated phenols if the product is used as an admixture.

Das erfindungsgemäße Verfahren wird anhand der folgenden Beispiele weiter erläutert.The process according to the invention is further explained using the following examples.

Beispiel 1example 1

Aus dem Kohleöl einer in Bottrop als Versuchsanlage betriebenen Kohleverflüssigungsanlage wurde durch fraktionierte Destillation die zwischen 150 bis 220°C siedende Fraktion isoliert. Die gaschromatographische Analyse auf Phenole ergab folgende Bestandteile:

Figure imgb0002
The fraction boiling between 150 to 220 ° C. was isolated from the coal oil of a coal liquefaction plant operated as a test plant in Bottrop. The gas chromatographic analysis for phenols showed the following components:
Figure imgb0002

200 g dieser Kohleölfraktion wurden mit 72 g Dimethylcarbonat in einem Rührautoklav auf 160°C erwärmt. Dabei stieg der Druck innerhalb von 4,5 Stunden auf 19 bar. Nach dem Erkalten wurde der Autoklav über eine Gasuhr entspannt. Dieser Vorgang wurde noch zweimal wiederholt. Insgesamt fielen 13,8 I Gas an (99,6 Vol.-% CO2, Gasdichte bei 20°C 1,842 g/I). Die Auswaage ergab 242 g Flüssigprodukt und 25,3 g gasförmiges Produkt. Das Reaktionsprodukt enthielt noch 1,7 Gew.-% phenolische Substanzen. Es wurde ohne weitere Aufarbeitung der reformierten Fraktion zugesetzt. Der Benzolgehalt dieses Vergaserkraftstoffes betrug 3,6 Gew.-%.200 g of this coal oil fraction were heated to 160 ° C. in a stirred autoclave with 72 g of dimethyl carbonate. The pressure rose to 19 bar within 4.5 hours. After cooling, the autoclave was depressurized using a gas meter. This process was repeated two more times. A total of 13.8 l of gas was obtained (99.6% by volume of CO 2 , gas density at 20 ° C. 1.842 g / l). The weight resulted in 242 g of liquid product and 25.3 g of gaseous product. The reaction product still contained 1.7% by weight of phenolic substances. It was added to the reformed faction without further elaboration. The benzene content of this gasoline was 3.6% by weight.

Beispiel 2Example 2

Von einem Kohleöl gleicher Herkunft wie nach Beispiel 1 wurde die unterhalb einer Temperatur von 150°C siedende Fraktion abgetrennt.The fraction boiling below a temperature of 150 ° C. was separated from a coal oil of the same origin as in Example 1.

2.127 g der Kohleölfraktion im Siedebereich von 150 bis 220°C und 319 g Dimethylcarbonat wurden in einem Autoklav nach Stickstoffabdeckung unter Rühren auf 185°C erwärmt. Innerhalb von 10 Stunden stieg dabei der Druck auf 40 bar an, der nach der anschließenden Abkühlung auf 25°C auf 16 bar abfiel. Der Autoklav wurde über eine Gasuhr entspannt, wobei 91 I Gas mit 98,6 Vol.-% C02 mit einer Gasdichte (20°C) von 1,832 g/I anfielen.

  • Die Auswaage an Flüssigprodukt betrug 2.311 g.
  • Die GC-Analyse ergab, daß
  • 95,6 Gew.-% Phenol zu Anisol
  • 75,8 Gew.-% o-Kresol zu o-Kresylmethylether
  • 83,8 Gew.-% m-Kresol zu m-Kresylmethylether und
  • 97,0 Gew.-% p-Kresol zu p-Kresylmethylether umgesetzt worden waren.
2,127 g of the coal oil fraction in the boiling range from 150 to 220 ° C and 319 g of dimethyl carbonate were in an autoclave heated to 185 ° C after stirring with nitrogen. The pressure rose to 40 bar within 10 hours, which dropped to 16 bar after the subsequent cooling to 25.degree. The autoclave was depressurized via a gas meter, 91 l of gas with 98.6% by volume of CO 2 having a gas density (20 ° C.) of 1.832 g / l being obtained.
  • The liquid product weighed 2,311 g.
  • GC analysis showed that
  • 95.6% by weight phenol to anisole
  • 75.8% by weight of o-cresol to o-cresyl methyl ether
  • 83.8% by weight of m-cresol to m-cresyl methyl ether and
  • 97.0% by weight of p-cresol had been converted to p-cresyl methyl ether.

Beispiel 3Example 3

Nachfolgend sind einige Untersuchungsergebnisse von drei Fraktionen von nach dem erfindungsgemäßen Verfahren erhaltenen veretherten Kohleölen mitgeteilt:

Figure imgb0003
Below are some test results of three fractions of etherified coal oils obtained by the process according to the invention:
Figure imgb0003

In Abmischung von 10 Vol.-% der oben bezeichneten Fraktionen zu handelsüblichem, verbleitem Superkraftstoff wurden folgende Mischoktanzahlen ermittelt;

Figure imgb0004
The following mixed octane numbers were determined by mixing 10% by volume of the fractions described above into commercial leaded super fuel;
Figure imgb0004

Eine Abmischung von 60 Vol.-% Superkraftstoff (SVK) und 40 Vol.-% eines Pyrolyse-Gesamtbenzins ergab einen Wert der Oxidationsstabilität nach DIN 51 600 von 260 min.A mixture of 60 vol .-% super fuel (SVK) and 40 vol .-% of a total pyrolysis gasoline gave a value of the oxidation stability according to DIN 51 600 of 260 min.

Durch Abmischung von jeweils 10 Vol.-% der Fraktionen A bis C zu der oben bezeichneten 60: 40-Abmischung erhöhte sich die Oxidationsstabilität in allen Fällen auf einen Wert von >960 min.Mixing each 10% by volume of fractions A to C into the above-mentioned 60:40 mixture increased the oxidation stability in all cases to a value of> 960 min.

In Abmischung von 10 Vol.-% Zusatz zu handelsüblichem Superkraftstoff wurden für die drei Fraktionen folgende Werte des Abdampfrückstands ermittelt (DIN 51 600 max. 5 mg/100 ml Abadampfrückstand nach DIN EN 5).

Figure imgb0005
In a mixture of 10 vol.% Addition to commercially available super fuel, the following values of the evaporation residue were determined for the three fractions (DIN 51 600 max. 5 mg / 100 ml of evaporation residue according to DIN EN 5).
Figure imgb0005

Alle Fraktionen A, B, C waren weinbrandfarben, A war heller als C, B war heller als A. Die Fraktionen hatten folgende Dichten:

Figure imgb0006
All fractions A, B, C were brandy-colored, A was lighter than C, B was lighter than A. The fractions had the following densities:
Figure imgb0006

In 10 Vol.-%iger Abmischung mit Superkraftstoff traten bis -25°C keine Trübungen auf.In 10 vol.% Blending with super fuel, no turbidity occurred down to -25 ° C.

Claims (2)

1. A method of manufacturing a liquid carburettor fuel for spark-ignition engines, in which a naphtha fraction of coal origin obtained by liquefaction of coal is separated by distillation into a main flow, which is subjected to a refining process and to a subsequent reforming process, and into a subsidiary flow enriched with phenol and with various alkyl phenols and wherein, possibly afterfurther isolation, the subsidiary flow containing the enriched phenols is treated with dimethyl carbonate as methylating agent under methylating conditions, but without addition of a catalyst, thereafter the resultant byproducts methanol and carbon dioxide are removed and that at least a portion of the thus obtained subsidiary flow, containing anisole and various methyl aryl ethers, is combined with at least a portion of the main flow subjected to the aforementioned further treatment steps.
2. A method according to Claim 1, characterized in that the methanol produced as byproduct is left in the subsidiary flow subjected to the methylation with dimethyl carbonate.
EP86101331A 1985-02-08 1986-02-01 Preparation of a liquid carburettor fuel for otto engines Expired - Lifetime EP0191388B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3504529 1985-02-08
DE3504529A DE3504529C2 (en) 1985-02-11 1985-02-11 Process for producing a liquid carburettor fuel for Otto engines

Publications (3)

Publication Number Publication Date
EP0191388A2 EP0191388A2 (en) 1986-08-20
EP0191388A3 EP0191388A3 (en) 1988-03-23
EP0191388B1 true EP0191388B1 (en) 1990-04-25

Family

ID=6262149

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86101331A Expired - Lifetime EP0191388B1 (en) 1985-02-08 1986-02-01 Preparation of a liquid carburettor fuel for otto engines

Country Status (4)

Country Link
EP (1) EP0191388B1 (en)
JP (1) JPH068414B2 (en)
DE (1) DE3504529C2 (en)
ZA (1) ZA86918B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899102A (en) * 2012-10-30 2013-01-30 世纪国宏新能源科技（北京）有限公司 Methanol gasoline instantizer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729031A1 (en) * 1977-06-28 1979-01-18 Basf Ag Aralkyl- and alkyl-phenol-ether prepn. - by reacting phenol and di:aralkyl- or di:alkyl-carbonate using tert. amine or phosphine catalyst
US4192949A (en) * 1977-06-28 1980-03-11 Basf Aktiengesellschaft Preparation of aralkyl phenyl ethers and alkyl phenyl ethers
IT1099572B (en) * 1978-07-21 1985-09-18 Snam Progetti PROCEDURE FOR THE PREPARATION OF PHENCLIC ETHERS
US4319981A (en) * 1980-11-12 1982-03-16 The United States Of America As Represented By The United States Department Of Energy Process for preparing a liquid fuel composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899102A (en) * 2012-10-30 2013-01-30 世纪国宏新能源科技（北京）有限公司 Methanol gasoline instantizer

Also Published As

Publication number Publication date
EP0191388A3 (en) 1988-03-23
JPH068414B2 (en) 1994-02-02
EP0191388A2 (en) 1986-08-20
ZA86918B (en) 1986-11-26
DE3504529A1 (en) 1986-08-14
JPS61200198A (en) 1986-09-04
DE3504529C2 (en) 1987-02-12

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