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 broken down into naphthenes and Degradation of nitrogen and sulfur-containing hetero compounds to corresponding hydrocarbons, the heteroatoms O, N and S being broken down to the simple hydrogen compounds.
• This degradation proceeds without difficulty under suitable conditions.
• the subsequent reforming involves, among other things, rearomatizing the naphthenes or also forming aromatics from straight-chain paraffins, the hydrogen produced 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 U.S. 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 to separate the free phenols, washing the phenols containing 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 ° C.
• dimethyl carbonate used in the process according to the invention is a large product of the chemical industry, which is offered by various manufacturers.
• dimethyl carbonate is synthesized using the following equation:
• 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 additive component.
• the fraction boiling between 150 to 220 ° C. was isolated from the coal oil of a coal liquefaction plant operated in Bottrop as a test facility.
• the gas chromatographic analysis for phenols showed the following components: 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 liters of gas were obtained (99.6% by volume of CO 2 , gas density at 20 ° C. 1.842 g / l). The balance gave 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.
• 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)

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Citations (3)

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• 1985
  • 1985-02-11 DE DE3504529A patent/DE3504529C2/de not_active Expired
• 1986
  • 1986-02-01 EP EP86101331A patent/EP0191388B1/fr not_active Expired - Lifetime
  • 1986-02-07 JP JP61024280A patent/JPH068414B2/ja not_active Expired - Lifetime
  • 1986-02-07 ZA ZA86918A patent/ZA86918B/xx unknown

Patent Citations (3)

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