EP0068231B1 - Process for the hydrogenation of coal, heavy oil, bitumen and the like - Google Patents
Process for the hydrogenation of coal, heavy oil, bitumen and the like Download PDFInfo
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- EP0068231B1 EP0068231B1 EP82105119A EP82105119A EP0068231B1 EP 0068231 B1 EP0068231 B1 EP 0068231B1 EP 82105119 A EP82105119 A EP 82105119A EP 82105119 A EP82105119 A EP 82105119A EP 0068231 B1 EP0068231 B1 EP 0068231B1
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- bar
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- hydrogenation
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- hot
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- 238000000034 method Methods 0.000 title claims description 22
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 15
- 239000003245 coal Substances 0.000 title claims description 8
- 239000000295 fuel oil Substances 0.000 title claims description 6
- 239000010426 asphalt Substances 0.000 title claims description 5
- 239000007789 gas Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 16
- 239000010802 sludge Substances 0.000 claims description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 235000013844 butane Nutrition 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000571 coke Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000005360 mashing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- HOWJQLVNDUGZBI-UHFFFAOYSA-N butane;propane Chemical compound CCC.CCCC HOWJQLVNDUGZBI-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- 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
Definitions
- the invention relates to the separation of liquid products from the hot separator residues of the bottom or combined bottom and gas phase hydrogenation of coal, heavy oil, bitumen and similar starting products, such as residues from top or vacuum distillation of crude oil.
- coal, heavy oils, bitumen and other residues can be converted into low-boiling hydrocarbon mixtures by hydrogenation and catalyst, optionally also mixed with a mashing oil originating from the product and this mixture heated at a pressure of 50-700 bar, preferably 100-325 bar in a heater to 200-500 ° C, preferably 350-450 ° C.
- the mixture After passing through a preheater, the mixture is passed from below through a reactor system in which hydrocracking reactions take place at temperatures between 250 and 550 ° C, preferably 380-480 ° C, which lead to the cleavage of large molecules and their partial desulfurization, denitrification and deoxygenation .
- Disposable catalysts are preferably used as catalysts.
- these are, for example, molybdic acid, tin oxalate / ammonium chloride, Bayer mass and lux mass.
- catalysts are used which contain catalytically active metal compounds, for example tungsten, molybdenum, lead, tin, chromium, cobalt and nickel, in particular iron, on a carrier such as active carbon or in particular coke.
- the catalysts are used in amounts of up to 10% by weight, in particular 1 to 6% by weight, based on the starting product.
- the reaction mixture passes into a hot separator, from the top of which gaseous and vaporous reaction products, which contain the major part of the liquid product yield, from the base of which unreacted feed, asphaltenes, catalyst and a certain amount of heavy and medium oil are drawn off as hot sludge.
- the hot separator which can also consist of a system of several separators connected in series, is operated at temperatures which are up to 100 ° C., preferably 20 to 40 ° C., below the reactor temperature.
- FR-A-23 74401 describes, in a process for converting a solid fuel into a liquid fuel, in which a mixture of solid fuel particles and solvent is produced, heating the mixture at elevated pressure and elevated temperature and the liquid part of the effluent from the heating zone to enter in a stripping zone.
- a gas containing hydrogen gas is used as a stripping agent in countercurrent contact with the entire liquid reaction product.
- the gaseous or vaporous products drawn off at the top of the hot separator are either regulated in a cold relaxation system and fed to further processing, or are passed under reaction pressure from a short distance from above into a system of reactors in which the gaseous or vaporous products are carried by fixed bed catalysts desulphurized, denitrified, deoxygenated and split (cf. W. Urban “Petroleum processing in the Scholvener 300 at combi hydrogenation chamber" in Petroleum and Coal, 8 (1955), pp. 780 - 782).
- the products of this "combi-hydrogenation" are regulated by a cold separator system and sent for further processing.
- the liquid product yield of the bottom or combined bottom and gas phase hydrogenation is increased in that part of the liquid constituents are separated from the base product of the hot separator with the aid of process gases and stripped.
- the process gas is passed through the product at temperatures between 20 and 300 ° C., preferably 50 to 200 ° C. and a pressure between 10 and 300 bar, preferably 50 to 200 bar.
- Any gas obtained in the process preferably a fraction enriched by washing from the process gas and containing methane, ethane, propane, butanes and pentanes, in particular high contents of propane, butene and / or pentane, can be used as stripping gas.
- the treatment of the hot sludge with the process gases expediently takes place continuously in that a pressure vessel coupled to the hot separator system is charged from above with the hot sludge and from below with the process gases.
- the weight ratio hot blowdown: process gas is 1:10, preferably 1: 3, the throughput 0.2 to 2.0 m 3 , preferably 0.3 to 0.6 m 3 blowdown per m 3 pressure vessel volume and per hour.
- the stripping gas can be from the entrained components of the hydrogenation residue by reducing the pressure to 100 to 1 bar, preferably 70 to 30 bar or increasing the temperature by 20 to 150 ° C, preferably 50 to 100 0 C or a combination of both measures, for example increasing the temperature by 20 up to 70 ° C with a pressure reduction to 100 to 50 bar.
- the liquid products are refined or split in the gas phase reactor; in the case of coal hydrogenation, they serve as asphaltene-free mashing oil components.
- the stripping gas can be used again for separation after pressure increase by means of a compressor or a fan or after cooling.
- the solid-containing residue, enriched in metals and asphaltenes, from the treatment of hot sludge with the process gases is removed from the process by the gas pressure via a lock system and can be fed to gasification, in order to cover the hydrogen requirement of the hydrogenation process.
- This hot sludge was placed in a downstream 5 l container with fittings for gas and liquid distribution at 200 bar and 150 ° C with 4.8 kg / h of a propane-butane mixture (propane: butane weight ratio 3: 2). treated.
- the gaseous product was let down to 40 bar, 0.9 kg / h of a liquid product with a boiling end of 520 ° C. separating.
- the product was free of asphaltenes and metals, its H / C ratio was 1.3; the sulfur content was 1.5% by weight.
- the solids in the residue were enriched to 28% by weight; the residue contained all metals which had been introduced into the process with the oil and the single-use catalyst.
Landscapes
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Working-Up Tar And Pitch (AREA)
Description
Die Erfindung bezieht sich auf die Abtrennung von Flüssigprodukten aus den Heißabscheider-Rückständen der Sumpf- oder kombinierten Sumpf- und Gasphasenhydrierung von Kohle, Schweröl, Bitumen und ähnlichen Ausgangsprodukten, wie Rückständen der Top-oder Vakuumdestillation von Rohöl.The invention relates to the separation of liquid products from the hot separator residues of the bottom or combined bottom and gas phase hydrogenation of coal, heavy oil, bitumen and similar starting products, such as residues from top or vacuum distillation of crude oil.
Es ist zum Beispiel aus W. Krönig "Die katalytische Druckhydrierung von Kohlen, Teeren und Mineralölen", Berlin/Göttingen/Heidelberg 1950 bekannt, daß Kohle, Schweröle, Bitumen sowie andere Rückstände sich in leicht siedende Kohlenwasserstoffgemische umwandeln lassen, indem man sie mit Wasserstoff und Katalysator, gegebenenfalls auch mit einem aus dem Produkt stammenden Anmaischöl mischt und diese Mischung beim Druck von 50 - 700 bar, vorzugsweise 100 - 325 bar in einem Erhitzer auf 200 - 500° C, vorzugsweise 350 - 450° C erhitzt. Nach Durchlaufen eines Vorheizers wird die Mischung von unten durch ein Reaktorsystem geführt, in dem bei Temperaturen zwischen 250 und 550° C, vorzugsweise 380 - 480° C Hydrocrackreaktionen ablaufen, die zu einer Spaltung großer Moleküle sowie zu deren partieller Entschwefelung, Denitrifizierung und Entoxigenierung führen.For example, it is known from W. Krönig "The catalytic pressure hydrogenation of coal, tars and mineral oils", Berlin / Göttingen / Heidelberg 1950 that coal, heavy oils, bitumen and other residues can be converted into low-boiling hydrocarbon mixtures by hydrogenation and catalyst, optionally also mixed with a mashing oil originating from the product and this mixture heated at a pressure of 50-700 bar, preferably 100-325 bar in a heater to 200-500 ° C, preferably 350-450 ° C. After passing through a preheater, the mixture is passed from below through a reactor system in which hydrocracking reactions take place at temperatures between 250 and 550 ° C, preferably 380-480 ° C, which lead to the cleavage of large molecules and their partial desulfurization, denitrification and deoxygenation .
Als Katalysatoren werden vorzugsweise Einwegkatalysatoren verwendet. Bei der Hydrierung von Kohle sind dies zum Beispiel Molybdänsäure, Zinnoxalat/Ammonchlorid, Bayermasse und Luxmasse. Für die Hydrierung von Schweröl und Bitumen werden Katalysatoren eingesetzt, die auf einem Träger, wie aktiver Kohle oder insbesondere Koks katalytisch wirksame Metallverbindungen zum Beispiel von Wolfram, Molybdän, Blei, Zinn, Chrom, Kobalt und Nickel, insbesondere von Eisen enthalten. Die Katalysatoren werden in Mengen bis 10 Gew.0/o, bezogen auf das Einsatzprodukt, insbesondere 1 bis 6 Gew.% eingesetzt. Als besonders wirksam haben sich Eisenverbindungen, die unter den Reaktionsbedingungen in Eisensulfid übergehen, wie Eisensulfat in Mengen von 2 bis 7 Gew.% auf aktiver Kohle oder Koks erwiesen.Disposable catalysts are preferably used as catalysts. In the hydrogenation of coal, these are, for example, molybdic acid, tin oxalate / ammonium chloride, Bayer mass and lux mass. For the hydrogenation of heavy oil and bitumen, catalysts are used which contain catalytically active metal compounds, for example tungsten, molybdenum, lead, tin, chromium, cobalt and nickel, in particular iron, on a carrier such as active carbon or in particular coke. The catalysts are used in amounts of up to 10% by weight, in particular 1 to 6% by weight, based on the starting product. Iron compounds which change into iron sulfide under the reaction conditions, such as iron sulfate in amounts of 2 to 7% by weight on active carbon or coke, have proven to be particularly effective.
Vom Kopf des Reaktorsystems gelangt die Reaktionsmischung in einen Heißabscheider, von dessen Kopf gas- und dampfförmige Reaktionsprodukte, die den wesentlichen Teil der Flüssigproduktausbeute enthalten, von dessen Fuß nicht umgesetztes Einsatzmaterial, Asphaltene, Katalysator sowie ein gewisser Schwer- und Mittelölanteil als Heißabschlamm abgezogen werden. Der Heißabscheider, der auch aus einem System von mehreren in Serie geschalteten Abscheidern bestehen kann, wird bei Temperaturen betrieben, die bis zu 100°C, vorzugsweise 20 bis 40° C unterhalb der Reaktortemperatur liegen.From the top of the reactor system, the reaction mixture passes into a hot separator, from the top of which gaseous and vaporous reaction products, which contain the major part of the liquid product yield, from the base of which unreacted feed, asphaltenes, catalyst and a certain amount of heavy and medium oil are drawn off as hot sludge. The hot separator, which can also consist of a system of several separators connected in series, is operated at temperatures which are up to 100 ° C., preferably 20 to 40 ° C., below the reactor temperature.
In FR-A-23 74401 ist beschrieben, bei einem Verfahren zur Umwandlung eines Festbrennstoffes in einen Flüssigbrennstoff, bei dem eine Mischung aus Festbrennstoffteilchen und Lösungsmittel hergestellt wird, die Mischung bei erhöhtem Druck und erhöhter Temperatur zu erhitzen und den flüssigen Teil des Abstroms der Heizzone in eine Strippzone einzugeben. Hierbei wird ein Wasserstoffgas enthaltendes Gas als Strippmittel im Gegenstromkontakt zu dem gesamten flüssigen Reaktionsprodukt angewendet.FR-A-23 74401 describes, in a process for converting a solid fuel into a liquid fuel, in which a mixture of solid fuel particles and solvent is produced, heating the mixture at elevated pressure and elevated temperature and the liquid part of the effluent from the heating zone to enter in a stripping zone. Here, a gas containing hydrogen gas is used as a stripping agent in countercurrent contact with the entire liquid reaction product.
Die am Kopf des Heißabscheiders abgezogenen gas- bzw. dampfförmigen Produkte werden entweder in einem Kaltentspannungssystem abgeregelt und der weiteren Verarbeitung zugeführt, oder unter Reaktionsdruck auf kurzem Weg von oben in ein System von Reaktoren geleitet, in denen die gas- bzw. dampfförmigen Produkte an Festbettkatalysatoren weiterentschwefelt, denitrifiziert, entoxigeniert sowie gespalten werden (vgl. W. Urban "Erdölverarbeitung in der Scholvener 300 at-Kombi-Hydrierkammer" in Erdöl und Kohle, 8 (1955), S. 780 - 782). Auch die Produkte dieser "Kombi-Hydrierung" werden über ein Kaltabscheidersystem abgeregelt und der Weiterverarbeitung zugeführt.The gaseous or vaporous products drawn off at the top of the hot separator are either regulated in a cold relaxation system and fed to further processing, or are passed under reaction pressure from a short distance from above into a system of reactors in which the gaseous or vaporous products are carried by fixed bed catalysts desulphurized, denitrified, deoxygenated and split (cf. W. Urban "Petroleum processing in the Scholvener 300 at combi hydrogenation chamber" in Petroleum and Coal, 8 (1955), pp. 780 - 782). The products of this "combi-hydrogenation" are regulated by a cold separator system and sent for further processing.
Es ist bekannt, das am Fuße des Heißabscheiders abgezogene Produkt zur Erhöhung der Flüssigproduktausbeute zu nutzen, indem dieses Produkt einer Vakuumdestillation bzw. einer Schwelung unterwerfen wird. Es kann auch teilweise in den Sumpfphasereaktor zurückgeführt werden. Diese Rückführung hat den Nachteil, daß der Asphaltenspiegel im Reaktor ansteigt, wodurch die Verkokungsneigung des Reaktionsgutes größer wird. Destillation bzw. Schwelung sind wegen der speziellen Art der Abschlämme schwer zu beherrschen und ermöglichen zum Teil auch aus prinzipiellen Gründen - Schwelung - eine nur begrenzte Flüssigproduktausbeute.It is known to use the product drawn off at the foot of the hot separator to increase the liquid product yield by subjecting this product to vacuum distillation or smoldering. It can also be partially returned to the bottom phase reactor. This recycling has the disadvantage that the asphaltene level in the reactor rises, as a result of which the tendency towards coking of the reaction mixture increases. Distillation or smoldering are difficult to control due to the special nature of the sludge and sometimes also allow for limited reasons - smoldering - only a limited yield of liquid products.
Erfindungsgemäß wird die Flüssigproduktausbeute der Sumpf- bzw. kombinierten Sumpf- und Gasphasehydrierung dadurch erhöht, daß vom Fußprodukt des Heißabscheiders ein Teil der flüssigen Bestandteile mit Hilfe von Prozeßgasen abgetrennt, gestrippt wird. Hierfür wird das Prozeßgas bei Temperaturen zwischen 20 und 300°C, vorzugsweise 50 bis 200°C und einem Druck zwischen 10 und 300 bar, vorzugsweise 50 bis 200 bar durch das Produkt geleitet. Als Strippgas kann jedes im Verfahren anfallende Gas, vorzugsweise eine durch Waschen aus dem Prozeßgas angereicherte, Methan, Ethan, Propan, Butane und Pentane, insbesondere hohe Gehalte an Propan, Buten und/oder Pentan enthaltende Fraktion verwendet werden.According to the invention, the liquid product yield of the bottom or combined bottom and gas phase hydrogenation is increased in that part of the liquid constituents are separated from the base product of the hot separator with the aid of process gases and stripped. For this purpose, the process gas is passed through the product at temperatures between 20 and 300 ° C., preferably 50 to 200 ° C. and a pressure between 10 and 300 bar, preferably 50 to 200 bar. Any gas obtained in the process, preferably a fraction enriched by washing from the process gas and containing methane, ethane, propane, butanes and pentanes, in particular high contents of propane, butene and / or pentane, can be used as stripping gas.
Die Behandlung des Heißabschlammes mit den Prozeßgasen erfolgt zweckmäßig kontinuierlich dadurch, daß ein mit dem Heißabscheidersystem gekoppelter Druckbehälter von oben mit dem Heißabschlamm und von unten mit den Prozeßgasen beschickt wird. Das Gewichtsverhältnis Heißabschlamm : Prozeßgas beträgt 1 : 10, vorzugsweise 1 : 3, der Durchsatz 0,2 bis 2,0 m3, vorzugsweise 0,3 bis 0,6 m3 Abschlamm pro m3 Druckbehälter-Volumen und pro Stunde.The treatment of the hot sludge with the process gases expediently takes place continuously in that a pressure vessel coupled to the hot separator system is charged from above with the hot sludge and from below with the process gases. The weight ratio hot blowdown: process gas is 1:10, preferably 1: 3, the throughput 0.2 to 2.0 m 3 , preferably 0.3 to 0.6 m 3 blowdown per m 3 pressure vessel volume and per hour.
Das Strippgas kann von den mitgeführten Bestandteilen des Hydrierrückstandes durch Druckminderung auf 100 bis 1 bar, vorzugsweise 70 bis 30 bar oder Temperaturerhöhung um 20 bis 150° C, vorzugsweise 50 bis 1000 C bzw. eine Kombination beider Maßnahmen, zum Beispiel eine Temperaturerhöhung um 20 bis 70° C bei einer Druckminderung auf 100 bis 50 bar befreit werden. Die Flüssigprodukte werden nach Aufwärmung im Gasphasereaktor raffiniert bzw. gespalten; im Falle der Kohlehydrierung dienen sie als asphaltenfreie Anmaischölkomponente. Das Strippgas kann nach Druckerhöhung mittels eines Kompressors oder eines Gebläses bzw. nach Kühlung erneut zur Abtrennung verwendet werden.The stripping gas can be from the entrained components of the hydrogenation residue by reducing the pressure to 100 to 1 bar, preferably 70 to 30 bar or increasing the temperature by 20 to 150 ° C, preferably 50 to 100 0 C or a combination of both measures, for example increasing the temperature by 20 up to 70 ° C with a pressure reduction to 100 to 50 bar. After heating, the liquid products are refined or split in the gas phase reactor; in the case of coal hydrogenation, they serve as asphaltene-free mashing oil components. The stripping gas can be used again for separation after pressure increase by means of a compressor or a fan or after cooling.
Der feststoffhaltige, an Metallen und Asphaltenen angereicherte Rückstand der Behandlung Heißabschlammes mit den Prozeßgasen wird durch den Gasdruck über ein Schleusensystem aus dem Prozeß entfernt und kann einer Vergasung zugeführt werden, um so den Wasserstoffbedarf des Hydrierprozesses abzudecken.The solid-containing residue, enriched in metals and asphaltenes, from the treatment of hot sludge with the process gases is removed from the process by the gas pressure via a lock system and can be fed to gasification, in order to cover the hydrogen requirement of the hydrogenation process.
In einem senkrecht stehenden Rohrreaktor von 4,5 I Inhalt wurden 4,0 kg/h eines Rückstandes der Vakuumdestillation von Arabian-Light-Rohöl mit 2 Nm3/h Wasserstoff bei 450°C und 280 bar hydriert. Dem Vakuumrückstand waren 5 Gew.% eines feinteiligen Kokses zugesetzt, auf den 50 g FeSOJkg Koks aufgetragen waren. Von dem am Kopf des Reaktors abgeführten Hydrierprodukt wurden in einem bei 420° C gefahrenen Heißabscheider 1,6 kg/h Heißabschlamm abgezogen.In a vertical tube reactor with a capacity of 4.5 l, 4.0 kg / h of a residue from the vacuum distillation of Arabian light crude oil were hydrogenated with 2 Nm 3 / h of hydrogen at 450 ° C. and 280 bar. 5% by weight of a finely divided coke to which 50 g of FeSO4 kg of coke had been applied were added to the vacuum residue. 1.6 kg / h of hot sludge were drawn off from the hydrogenation product carried off at the top of the reactor in a hot separator operated at 420 ° C.
Dieser Heißabschlamm wurde in einem nachgeschalteten, mit Einbauten zur Gas- und Flüssigkeitsverteilung versehenen Behälter von 5 1 Inhalt bei 200 bar und 150° C mit 4,8 kg/h einer Propan-Butan-Mischung (Propan : Butan-Gewichtsverhältnis 3 : 2) behandelt. Das gasförmige Produkt wurde auf 40 bar entspannt, wobei sich 0,9 kg/h eines Flüssigproduktes mit einem Siedeende von 520°C abschied. Das Produkt war frei von Asphaltenen und Metallen, sein H/C-Verhältnis betrug 1,3; der Gehalt an Schwefel lag bei 1,5 Gew.%.This hot sludge was placed in a downstream 5 l container with fittings for gas and liquid distribution at 200 bar and 150 ° C with 4.8 kg / h of a propane-butane mixture (propane: butane weight ratio 3: 2). treated. The gaseous product was let down to 40 bar, 0.9 kg / h of a liquid product with a boiling end of 520 ° C. separating. The product was free of asphaltenes and metals, its H / C ratio was 1.3; the sulfur content was 1.5% by weight.
Im Rückstand waren die Feststoffe auf 28 Gew.% angereichert; der Rückstand enthielt alle Metalle, die mit dem Öi und dem Einwegkatalysator in den Prozeß eingetragen worden waren.The solids in the residue were enriched to 28% by weight; the residue contained all metals which had been introduced into the process with the oil and the single-use catalyst.
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19813123535 DE3123535A1 (en) | 1981-06-13 | 1981-06-13 | METHOD FOR HYDROGENATING COAL, HEAVY OIL, BITUMEN AND THE LIKE. |
DE3123535 | 1981-06-13 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0068231A2 EP0068231A2 (en) | 1983-01-05 |
EP0068231A3 EP0068231A3 (en) | 1984-09-12 |
EP0068231B1 true EP0068231B1 (en) | 1987-04-08 |
Family
ID=6134663
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82105119A Expired EP0068231B1 (en) | 1981-06-13 | 1982-06-11 | Process for the hydrogenation of coal, heavy oil, bitumen and the like |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0068231B1 (en) |
CA (1) | CA1171013A (en) |
DE (2) | DE3123535A1 (en) |
NO (1) | NO162864C (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3914057A1 (en) * | 1989-04-28 | 1990-10-31 | Ruhrkohle Ag | STRIPING OF RESIDUES |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB892113A (en) * | 1957-05-08 | 1962-03-21 | Apv Co Ltd | Separation of low boiling point impurities from hydrocarbons |
GB1527570A (en) * | 1976-12-15 | 1978-10-04 | Texaco Development Corp | Coal liquefaction |
-
1981
- 1981-06-13 DE DE19813123535 patent/DE3123535A1/en not_active Withdrawn
-
1982
- 1982-06-03 NO NO821844A patent/NO162864C/en unknown
- 1982-06-11 CA CA000405046A patent/CA1171013A/en not_active Expired
- 1982-06-11 EP EP82105119A patent/EP0068231B1/en not_active Expired
- 1982-06-11 DE DE8282105119T patent/DE3276003D1/en not_active Expired
Also Published As
Publication number | Publication date |
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NO162864C (en) | 1990-02-28 |
DE3276003D1 (en) | 1987-05-14 |
NO821844L (en) | 1982-12-14 |
EP0068231A3 (en) | 1984-09-12 |
EP0068231A2 (en) | 1983-01-05 |
CA1171013A (en) | 1984-07-17 |
DE3123535A1 (en) | 1982-12-30 |
NO162864B (en) | 1989-11-20 |
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