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
  • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
  • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation 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
  • 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

Definitions

• the ground coal is generally rubbed with a mixture of medium and heavy oil. Catalysts are added to the ground coal if such substances are not already sufficiently present in the coal.
• the coal pulp obtained in this way is then pressurized together with hydrogen and / or cycle gas, heated and passed through one or more reection rooms in which the so-called bottom phase hydrogenation (1st hydrogenation stage) takes place.
• the products leaving the bottom phase hydrogenation are passed into a hot separator which is kept slightly below the reaction temperature, where a separation into a bottom product (sludge) on the one hand and gaseous and vaporous products on the other hand takes place.
• the sludge contains the heaviest oil components, asphalt, unreacted coal particles and possibly other solids.
• the sludge can, for example, be thickened (flopped) in a flash evaporation followed by a vacuum stage, for example to a solids content (insoluble in benzene) of approximately 40 to 60%.
• the resulting distillate oil can be used to rub the Coal can be used.
• the topped sludge can be gasified by partial oxidation in the presence of steam at 1100 to 1500 ° C to a mixture of carbon oxides and hydrogen, which can be worked up for hydrogen.
• the gaseous and vaporous products leaving the hot separator are exchanged for incoming coal in heat exchangers. porridge and then cooled in a final cooling to near room temperature and fed to a stripper, where the separation into liquid and gaseous products takes place and the gaseous products are recycled as recycle gas.
• the liquid products are let down to atmospheric pressure and, after the aqueous phase has been separated off, subjected to distillation at atmospheric pressure, giving petrol, medium oil and heavy oil. Part of the heavy oil and the middle oil / generally used to grind the coal.
• the remaining parts and the gasoline, which together constitute the oil production, are generally further hydrogenated in the gas phase on fixed catalysts.
• a process has now been found for the production of liquid hydrocarbons from coal by splitting pressure hydrogenation, in which ground coal, optionally together with catalysts, is rubbed with a mixture of medium oil and heavy oil obtained in the process and the coal pulp thus obtained is mixed with hydrogen
• the pressure is heated and passed through one or more reaction spaces, the reaction products are passed into a hot separator which is kept slightly below the reaction temperature, the bottom product from the hot separator is separated into a distillate oil for grinding the coal and a residue which is converted to synthesis gas, and the gases and vapors withdrawing at the head of the hot separator are optionally passed through a second hot separator and then cooled in series-connected heat exchangers, which is characterized in that the condensates occurring between and behind the heat exchangers are collected in wipers, from these condensates a portion for the grinding oil and subtracts a portion as oil gain and supplies both portions without intermediate distillation for grinding coal or for hydrogenation in the gas phase or mixed phase.
• the coal pulp can be produced, for example, by grinding practically asphalt-free medium and heavy oils in the process in a coal: oil ratio of 1: 1 to 1: 3.
• Suitable catalysts are, for example, mixtures containing iron compounds, such as Bayer mass or lux mass (the latter also in used form), iron ores or iron salts.
• Bayer mass or lux mass are the residues which result from the digestion of bauxite with sodium hydroxide solution or soda, for example 48.6% Fe203, 20% A1 2 0 3 , 9.2% Si0 2 , 6.0% TiO 2 , 0.2 % MnO 2 , 1.2% CaO, 0.5% MgO, 6.2% Na 2 0, 0.2% K 2 0 and 13 to 15% H 2 0 (see Ullmann, Encyclopedia of Technical Chemistry , Volume 10, page 499 (1958)).
• Ferrosulfate for example, can be used as the iron salt, which can be impregnated onto the coal in aqueous solution.
• the catalysts can be added, for example, in amounts of 0.5 to 5.0% by weight, based on the water-free and ash-free coal (pure coal). If the coal already contains such catalyst components, the addition of catalysts to the coal slurry can also be omitted.
• Coal for the process according to the invention is, for example, a wide variety of hard or brown coals Mining areas suitable. Lignite is preferably used together with a catalyst.
• the coal pulp is pressurized together with hydrogen, which generally consists of fresh hydrogen and cycle gas.
• hydrogen which generally consists of fresh hydrogen and cycle gas.
• pressures in the range of 100 to 400 bar are suitable.
• coal pulp and hydrogen can be heated to 380 to 420 ° C.
• the reaction space or the reaction spaces for the hydrogenation in the bottom phase can, for example, be kept at 420 to 490 ° C.
• the reaction products from the bottom phase hydrogenation are fed to a hot separator which is kept at a temperature slightly below the temperature of the bottom phase hydrogenation, for example 10 to 50 ° C. below the temperature of the bottom phase hydrogenation.
• the sludge separated in the hot separator can be processed further using known methods. For example, a distillate can be obtained from it by flash evaporation with a subsequent vacuum stage, which can be used to grind the coal and a topped sludge which is suitable for the production of hydrogen.
• the first, previously described hot separator can optionally be followed by a second hot separator which can be operated, for example, 10 to 30 ° C. lower than the first hot separator.
• a second hot separator which can be operated, for example, 10 to 30 ° C. lower than the first hot separator.
• entrained small portions of solids and asphalts can be separated.
• the substances separated in the second hot separator are generally added to the sludge from the first hot separator.
• the gases and vapors present after the hot separator (s) are cooled in series-connected heat exchangers. It is an essential feature of the method according to the invention that the condensates obtained between and behind the heat exchangers are collected in wipers. For example, 3 or more heat exchangers can be used.
• Heat exchangers can be operated, for example, in such a way that heat exchange takes place in the first heat exchangers or the first heat exchanger between the gases and vapors from the hot separator (s) on the one hand and the coal slurry used in the first hydrogenation stage and / or the recycle gas on the other.
• the last or the last heat exchanger is preferably operated with water or air as the coolant.
• two heat exchangers are used for the heat exchange between the outgoing gases and vapors and the incoming feedstocks coal pulp and cycle gas and one or more air and / or water coolers in the further cooling path. Between or after individual or all heat exchangers, the respective condensates are separated, for example in wipers.
• the heat exchangers are preferably operated in this way and the condensates are separated off in such a way that at least three different condensates are collected. It is preferably carried out in such a way that a heavy oil condensate which boils substantially above 325 ° C, a medium oil condensate which boils substantially between 180 and 325 ° C and a gasoline condensate which boils substantially between 30 and 180 ° C are collected.
• it is also possible to separate more than the three aforementioned condensates for example two heavy oil condensates, two medium oil condensates and / or two gasoline condensates.
• the above-mentioned boiling ranges for individual condensates relate to normal pressure and are approximate values, from which larger deviations are possible.
• the gaseous fractions which remain after the separation of the condensates and contain substantial amounts of hydrogen are preferably recycled as recycle gas before the bottom phase hydrogenation.
• Water occurs almost exclusively in the gasoline condensate, separates there as the lower insoluble phase and can be drawn off separately from the hydrocarbon phase. If necessary, the aqueous phase can also be separated off in a downstream settling tank.
• the boiling limits of the condensates can be regulated in various ways. For example, the boiling limits of the condensates can be influenced by the design of the heat exchanger.
• the separated, high-boiling and still hot condensates or parts thereof can be cooled by heat exchange for hydrogen and the hydrogen thus heated can be fed to the coal pulp in quantities which are matched to the requirements, for example before the first heat exchanger or passes the first heat exchanger.
• the portion of the heavy oil condensate which is recycled to the coal is preferably used for heating the circulating gas.
• the selectivity between the individual condensates can be increased if the condensates are separated in separators and then individually cooled against recycle gas in reflux coolers. If the heat exchange between the heavy oil condensate or the parts thereof and the cycle gas does not yet result in the heavy oil condensate or parts thereof for further use, for example as grinding oil for the coal has cooled sufficiently, the heavy oil condensate or parts thereof, for example by air cooling, can be cooled further.
• the amounts of grind oil provided are generally taken from the heavy oil and medium oil condensates obtained as described above.
• the remaining portions of the heavy oil and medium oil condensate are available together with the gasoline condensate as oil gain for further processing.
• the oil gain can be fed to the hydrogenation in the gas phase or mixed phase without significant pressure relief and temperature reduction.
• the combined oil gain as a whole will be used in the further hydrogenation. If these are to be operated under aromatizing hydrogenation conditions, it is advantageous to hydrogenate the gasoline condensate separately in a refining manner.
• the hydrogenation in the gas phase or mixed phase is preferably carried out on fixed-bed catalysts.
• This hydrogenation can be carried out, for example, at 100 to 400 bar and as a refining hydrogenation at 340 to 420 ° C. or as a splitting hydrogenation at 420 to 480 ° C.
• Suitable catalysts for the second hydrogenation stage are oxides, sulfides or phosphates of the metals of VI. or VIII. group of the periodic system, such as tungsten or mclybdenum, optionally in a mixture with Oxides or sulfides of the iron group, expediently applied to supports such as aluminum oxide and its spinels, natural or synthetic bleaching earths, in particular zeolites. Platinum and rhenium are also suitable as hydrogenation catalysts. Highly active catalysts are preferably used in this hydrogenation, for example nickel / tungsten sulfide on supports. A certain H 2 S partial pressure is necessary during this hydrogenation in order to maintain the high activity over longer periods of time for such catalysts.
• the products used in the hydrogenation should therefore have a sulfur content of the order of about 0.1 to 1%. Such a sulfur content can optionally also be maintained by adding sulfur or sulfur compounds.
• reaction products from this hydrogenation can be worked up in a customary manner, in particular by decomposing them into the desired fractions by distillation at atmospheric pressure.
• the products consist of hydrogen-rich hydrocarbons free of secondary components such as oxygen, nitrogen or sulfur compounds. They can be used as finished products, but are also fully suitable for further processing in the processes customary in the petroleum industry, such as catalytic cracking and reforming, hydrocracking, thermal and pyrolytic cracking.
• the advantages of the process according to the invention are, in particular, that after the first hydrogenation stage, the distillation of the condensed gases and vapors, which is carried out at normal pressure according to the prior art, is avoided. Pumping can also be responsive pressure for those fractions from the first hydrogenation stage which are used in the second hydrogenation stage.
• substantial energy savings occur when heating up to the reaction temperature.
• the removal of the aqueous phase is much easier because of the greater density differences than in the one-stage condensation of the condensable products from the gases and vapors of the hot separator.
• products can be obtained after the gas phase hydrogenation which are practically free of nitrogen, oxygen and sulfur and in which the gasoline fraction over 13.4, the middle oil fraction over 12.6 and the heavy oil fraction over 11.8% by weight hydrogen contain.
• Such products are particularly suitable for pyrolytic cracking for the production of chemical raw materials, primarily olefins and aromatics.
• the coal pulp is brought to the operating pressure of 300 bar and, together with fresh hydrogen and cycle gas, heated to 430 ° C via a heat exchanger and a preheater and introduced into the hydrogenation reactor, where the hydrogenation takes place at 470 ° C with a hydrogen absorption of 4.5 t
• the reaction products enter a hot separator kept at 435 ° C, where the separation takes place in a bottom phase product (sludge), which is converted into vacuum distillate and topped sludge by flash evaporation, and the gases and vapors withdrawing from the upper part, some of which give off their latent heat in two heat exchangers connected in series to the incoming mixture of coal pulp, cycle gas and fresh hydrogen.
• sludge bottom phase product
• the gases and vapors are cooled to 350 ° C, with 96.2 t of heavy oil condensing, which are taken up in a first stripper.
• cooling to 225 ° C takes place, with 72.3 t of medium oil condensing, which are taken up in a second stripper.
• the temperature is reduced to 40 ° C., with 7.5 t of gasoline condensing, which are taken up in a third wiper.
• 10 t of gaseous hydrocarbon are generated substances C 1 to C 4 .
• the heavy oil condensate are removed and after cooling in a heat exchanger against circulating gas and subsequent air cooling to normal pressure, are released and used as part of the grinding oil.
• 45.1 t are used as the grinding oil component after cooling and relaxation.
• the three wipers are used to extract oil: 12.2 t heavy oil, 27.2 t medium oil and 7.5 t gasoline and without pressure relief and temperature reduction to the second hydrogenation stage with a fixed catalyst.
• the hydrogenation of the combined oil gain (46.9 t) in the second hydrogenation stage takes place in the hydrogen cycle gas at 420 ° C. and 290 bar over nickel / tungsten sulfide on aluminum oxide with a hydrogen uptake of 1.6 t.
• After cooling to 40 ° C and separating the cycle gas in a further scraper the following are obtained: 12.1 t of gasoline, 21.7 t of medium oil and 10.7 t of heavy oil.
• the 12.1 t of gasoline, 21.7 t of medium oil and 10.7 t of heavy oil obtained according to Example 1 are separately subjected to pyrolysis (steam cracking), in separate cracking furnaces and condensation.
• the pyrolysis conditions are as follows:
• the yields obtained from pyrolysis (steam cracking) are as follows (for the entire use of 44.5 t):
• the ratio of the olefins to the aromatics can be shifted in favor of the aromatics if the gasoline fraction from the hydrogenation is previously catalytically reformed, the aromatics are obtained from the reformate by extraction and the raffinate is introduced into the pyrolysis. It is advisable to split the hydrocarbons ethane, propane and n-butane from both hydrogenation stages into olefins in a known manner by steam cracking.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1979
  • 1979-10-27 DE DE2943494A patent/DE2943494C2/de not_active Expired
• 1980
  • 1980-10-16 DE DE8080106290T patent/DE3069069D1/de not_active Expired
  • 1980-10-16 EP EP80106290A patent/EP0027962B1/fr not_active Expired
  • 1980-10-23 AU AU63636/80A patent/AU538950B2/en not_active Ceased
  • 1980-10-24 JP JP14826580A patent/JPS5667392A/ja active Pending
  • 1980-10-24 ZA ZA00806545A patent/ZA806545B/xx unknown

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