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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• • 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
• • 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
  • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
  • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/78—High-pressure apparatus
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/093—Coal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0973—Water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0983—Additives
  • C10J2300/0986—Catalysts

Definitions

• the invention relates to a method for producing lower molecular hydrocarbons from higher molecular hydrocarbons, in particular a method for liquefying coal.
• Solid and liquid fossil energy raw materials such as. B. understood coal, bitumen, mineral oil, tar sand or oil shale.
• the object of the invention to favor the conversion of high molecular weight hydrocarbon mixtures into lower molecular ones by using auxiliaries in corresponding processes and thereby to achieve a higher added value due to the more favorable C: H ratios in the end products.
• the invention is intended to provide an improved process for liquefying coal.
• guanidinium compounds as auxiliaries is proposed according to the invention in a method for obtaining relatively low molecular weight hydrocarbons from higher molecular weight hydrocarbons.
• guanidinium compounds means the use of only one guanidinium compound alone or the use of a combination of different guanidinium compounds.
• auxiliary substances here are meant substances which, like catalysts, are added to the starting material to be converted in relatively small amounts, but, unlike catalysts, do not act solely by their presence, but rather when the corresponding process or the physical and / or chemical reaction on which it is based is carried out changed or consumed.
• guanidinium compounds used according to the invention as auxiliaries in the usual treatment of the hydrocarbons to be reacted under pressure and elevated temperature have the pronounced effect of stabilizing the binding forces in the high molecular weight hydrocarbons and / or to break up and thereby direct the processes towards an enrichment of lighter, lower molecular hydrocarbons.
• binding forces are to be understood in a broad sense; they can be physical, chemical and / or as transitional forms between the two existing binding forces.
• the stabilization or loosening up to the complete breakdown of the binding forces immediately facilitates the initially outlined generation of low molecular weight hydrocarbons.
• solubility of the hydrocarbons treated is increased by the guanidinium compounds used according to the invention, which obviously also directly facilitates the recovery process.
• the amount of coal released or dissolved can cover up to 30% by weight of the coal supplied, in contrast to 1 or 2% in many known processes.
• the use of the guanidinium compounds in substance or in dissolved form is provided, for. B. dissolved in water in the case of guanidinium carbonate.
• the case used in each case total amounts of guanidinium compounds amount up to 10 wt .-% and lie p en preferably between 0.1 and 3 wt .-%, each based on the starting material. If the guanidinium compounds are used in dissolved form, up to 10% by weight, preferably between 0.01 and 3% by weight, can be used, in each case based on the solvent. In detail, the amount used will be determined from an economic point of view.
• guanidinium carbonate is particularly suitable as an adjuvant because it is the cheapest of all guanidinium compounds. It also has other important advantages. Guanidinium carbonate is neither corrosive still polluting, its decay is also very controllable and can therefore be used in a targeted manner. In addition, the basic character of the carbonate part of the guanidine carbonate gives additional reactivity, which can be utilized in Umsetzun- g s having acidic groups in an advantageous manner.
• the guanidinium carbonate in combination with other guanidinium compounds particularly in conjunction with carboxylic acids, preferably fatty acid guanidinium salts such as palmitates, oleates or stearates, and / or used together with guanidinium phenolates. It is not absolutely necessary to produce the corresponding guanidinium compounds in exact stoichiometric ratios and then to add them to the corresponding reaction mixture in exact weight ratios. Rather, the composition and dosage of the optimal formulation are always based on economic principles. This is an essential advantage of the invention, namely that the amounts and mixing ratios of the guanidinium compounds used in accordance with the invention can be varied within a wide range primarily according to economic considerations without sacrificing efficiency.
• a further, very economical use lends itself to the fact that the guanidinium carbonate is used in excess or in excess with added acids or free acids already present in the hydrocarbon mixture, such as carboxylic acids, in particular fatty acids, sulfonic acids and / or phenols, or also with use acidic alcohols can.
• the weight ratio of guanidinium carbonate to free acids can be between 0.1: 1 and 10: 1.
• guanidinium carbonate is used in the deficit, a mixture of unreacted starting chemical and corresponding guanidinium compound is produced, which then acts as an auxiliary according to the invention.
• guanidinium carbonate is used in excess, a mixture of guanidinium carbonate and corresponding guanidinium compound is formed, which acts accordingly.
• Maximum economy is achieved when the above-mentioned raw chemicals are waste or residue products.
• the waste fatty acids or the crude tar acids which are obtained in large quantities are particularly suitable as extremely economical starting products for reaction with guanidinium carbonate
• the invention essentially includes the fact that guanidinium compounds have a fragmenting effect on high-molecular hydrocarbon mixtures due to the chemical structure of the guanidinium cation and thereby favor the extraction of lower molecular hydrocarbons. In addition and overlapping, there is also an effect of the guanidinium compound which promotes the solubility of the hydrocarbon mixtures.
• a particularly preferred field of application of the invention is sawn in in g solid hydrocarbons and here especially the liquefaction or gasification of coal including such Ver g a-making procedures, in which the coal is placed in aqueous solution to the reaction.
• guanidinium compounds as auxiliary material makes it possible to increase the economic efficiency.
• the guanidinium compounds used according to the invention have essentially the effect that they facilitate the desired formation of binding forces within the molecular lattice of the coal and accelerate the subsequent saturation of the fractures with hydrogen in the molecular reaction process.
• This has the advantage that the use of catalysts envisaged in most of the process variants is reduced or even made completely unnecessary, and that it is also possible, instead of pure molecular hydrogen, to use at least partially cheaper hydrogenation gases for the liquefaction or gasification of the To use coal. Both relieve the known methods directly in terms of costs.
• guanidinium compounds used according to the invention decompose at elevated temperatures to give highly reactive decomposition products which, in turn, can favor the hydrogenation reaction in a very desirable manner. This effect is particularly pronounced with guanidinium carbonate.
• chloride, sulfate or nitrate is the guanidine carbonate orrisionsverhi appris from the previously mentioned reasons, the K, environmental protection and a better tax superior "cash decay. It is also, as also indicated, particularly inexpensive.
• the guanidinium carbonate can also be used as an auxiliary in coal liquefaction alone.
• use in conjunction with fatty acid guanidinium salts is particularly advantageous here. This, in particular by stearates, improves the interaction of the guanidinium carbonate with the hydrocarbon mixture in the sense of a dissolving aid, especially in the range of low temperatures, for example below 150 ° C. This advantageously contributes to the stabilization of the coal-rubbing oil suspension processed during coal liquefaction and directs the heterogeneous hydrogen / coal reaction more towards a homogeneous reaction.
• the ratio of guanidinium carbonate to the guanidinium compound (s), which acts as a solvent, depends on the particular liquefaction process and the properties of the starting materials.
• the preferred ratio of guanidinium carbonate to fatty acid guanidinium salt, in particular stearate, is between 0.3: 1 and 3: 1, with approximately 3: 1 being very particularly preferred.
• the guanidine compounds according to the invention at the input of Verfatun g s- or gasification process the starting materials, preferably in substance, impose.
• the addition can be carried out together with any catalysts still used.
• a suitable addition point in the coal liquefaction process according to DE-OS? 8 03 985 and DE-OS 27 11 105, for which the invention is particularly suitable, is in the DE-OS with regard to its other function and its Arrangement of mixing containers 2 explained in more detail
• a suspension of the finely ground coal to be treated is provided in this mixing container.
• the suspension arrives directly in a reaction zone in which low molecular weight, liquid hydrocarbons are produced by treating the suspension under elevated pressure of typically 10 to 300 bar and at an elevated reaction temperature of typically 250 to 500 ° C.
• the invention achieves that under the most varied reaction conditions there is an increased release and / or dissolution of hydrocarbons and, accordingly, an increased conversion. This also makes it possible to carry out the hydrogenation under milder conditions than were indicated in the known processes to date.
• This is the following
• reaction mixtures obtained in the various experiments were worked up in 30-o parts. The portions were washed out under reflux of 100 ml of THF. After filtration, the Au was f insectssgrad the coal on the basis of analytical measured enrichment of the ash content of the residue determined charcoal. The following were found

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 1980
  • 1980-11-27 WO PCT/EP1980/000140 patent/WO1981001576A1/fr not_active Ceased
  • 1980-11-27 US US06/290,812 patent/US4388170A/en not_active Expired - Fee Related
  • 1980-11-28 DE DE8080107459T patent/DE3060453D1/de not_active Expired
  • 1980-11-28 EP EP80107459A patent/EP0030020B1/fr not_active Expired
  • 1980-12-03 NO NO803649A patent/NO803649L/no unknown
  • 1980-12-03 CA CA000365999A patent/CA1155409A/fr not_active Expired

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