EP0191388B1 - Verfahren zur Herstellung eines flüssigen Vergaserkraftstoffes für Otto-Motoren - Google Patents

Verfahren zur Herstellung eines flüssigen Vergaserkraftstoffes für Otto-Motoren 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
Authority
EP
European Patent Office
Prior art keywords
coal
dimethyl carbonate
phenol
phenols
subjected
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86101331A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0191388A3 (en
EP0191388A2 (de
Inventor
Richard Dr. Wessendorf
Werner Dr. Döhler
Alfons Dr. Jankowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RAG AG
Original Assignee
Ruhrkohle AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ruhrkohle AG filed Critical Ruhrkohle AG
Publication of EP0191388A2 publication Critical patent/EP0191388A2/de
Publication of EP0191388A3 publication Critical patent/EP0191388A3/de
Application granted granted Critical
Publication of EP0191388B1 publication Critical patent/EP0191388B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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.

Landscapes

  • 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)
EP86101331A 1985-02-08 1986-02-01 Verfahren zur Herstellung eines flüssigen Vergaserkraftstoffes für Otto-Motoren Expired - Lifetime EP0191388B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3504529 1985-02-08
DE19853504529 DE3504529A1 (de) 1985-02-11 1985-02-11 Verfahren zur herstellung eines fluessigen vergaserkraftstoffes fuer otto-motoren

Publications (3)

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

Family

ID=6262149

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86101331A Expired - Lifetime EP0191388B1 (de) 1985-02-08 1986-02-01 Verfahren zur Herstellung eines flüssigen Vergaserkraftstoffes für Otto-Motoren

Country Status (4)

Country Link
EP (1) EP0191388B1 (ja)
JP (1) JPH068414B2 (ja)
DE (1) DE3504529A1 (ja)
ZA (1) ZA86918B (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899102A (zh) * 2012-10-30 2013-01-30 世纪国宏新能源科技（北京）有限公司 甲醇汽油速溶剂

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2729031A1 (de) * 1977-06-28 1979-01-18 Basf Ag Verfahren zur herstellung von aralkyl- und alkyl-phenolaethern
US4192949A (en) * 1977-06-28 1980-03-11 Basf Aktiengesellschaft Preparation of aralkyl phenyl ethers and alkyl phenyl ethers
IT1099572B (it) * 1978-07-21 1985-09-18 Snam Progetti Procedimento per la preparazione di eteri fenclici
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 (zh) * 2012-10-30 2013-01-30 世纪国宏新能源科技（北京）有限公司 甲醇汽油速溶剂

Also Published As

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

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