[go: up one dir, main page]

EP0263522B1 - Procédé d'hydroconversion d'huiles lourdes et résiduelles - Google Patents

Procédé d'hydroconversion d'huiles lourdes et résiduelles Download PDF

Info

Publication number
EP0263522B1
EP0263522B1 EP87114725A EP87114725A EP0263522B1 EP 0263522 B1 EP0263522 B1 EP 0263522B1 EP 87114725 A EP87114725 A EP 87114725A EP 87114725 A EP87114725 A EP 87114725A EP 0263522 B1 EP0263522 B1 EP 0263522B1
Authority
EP
European Patent Office
Prior art keywords
particle size
weight
oils
fraction
process according
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
EP87114725A
Other languages
German (de)
English (en)
Other versions
EP0263522A2 (fr
EP0263522A3 (en
Inventor
Klaus Kretschmar
Ludwig Dr. Merz
Klaus Dr. Niemann
José Guitian
Julio Dr. Krasuk
Franzo Dr. Marruffo
Klaus Kurzeja
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.)
Veba Oel Technologie und Automatisierung GmbH
Intevep SA
Original Assignee
Veba Oel Technologie und Automatisierung GmbH
Intevep SA
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 Veba Oel Technologie und Automatisierung GmbH, Intevep SA filed Critical Veba Oel Technologie und Automatisierung GmbH
Priority to EP92112758A priority Critical patent/EP0516187B1/fr
Priority to AT87114725T priority patent/ATE94583T1/de
Publication of EP0263522A2 publication Critical patent/EP0263522A2/fr
Publication of EP0263522A3 publication Critical patent/EP0263522A3/de
Application granted granted Critical
Publication of EP0263522B1 publication Critical patent/EP0263522B1/fr
Priority to GR950402920T priority patent/GR3017825T3/el
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00—Working-up tar
    • C10C1/20—Refining by chemical means inorganic or organic compounds
    • C10C1/205—Refining by chemical means inorganic or organic compounds refining in the presence of hydrogen
    • 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
    • C10G1/086—Characterised by the catalyst used
    • 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
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries

Definitions

  • the invention relates to a process for the hydrogenative conversion of heavy and residual oils, waste and waste oils in the sump or combined sump and gas phase with hydrogen-containing gases at a hydrogen partial pressure of 50 to 300 bar, preferably 150 to 200 bar, one Temperature of 250 to 500 ° C, preferably 400 to 490 ° C, a gas-oil ratio of 100 to 10,000 Nm3 / t, preferably 1,000 to 5,000 Nm3 / t liquid and solid feed products with the addition of at least one component from the Group of activated coke from hard coal or lignite, soot, red mud, ferric oxide, blast furnace dust, ash from the gasification process of crude oils, natural inorganic ferrous minerals, laterites and limonites in an amount of 0.5 to 15% by weight based on the total amount liquid and solid feed products.
  • the feedstocks are characterized by a high metal, sulfur and asphalt content as well as a high tendency to form coke.
  • the invention particularly relates to a catalytic process for converting hydrocarbon-containing feedstocks such as Orinoco Belt Crudes, Maracaibo Lake Crudes, tar sands from Athabasca and Canada crude oils such as Gold Lake in the sump phase in the presence of hydrogen.
  • feedstocks have a sulfur content between 2 and 6%, a metal content (vanadium and nickel) of 200 to 1400 ppm and more, a density of less than 20 ° API, a coking residue of more than 2% and a residue content of more than 40 % By weight (500 ° C +).
  • hydrocracking conditions pressure, temperature, gas / oil ratio, etc.
  • a component such as activated coke made from hard coal or lignite, soot, red mud, iron III oxide, blast furnace dust, ash from gasification processes of the aforementioned crude oils , natural, inorganic ferrous minerals such as laterite and limonite, in an amount of 0.5 to 15 wt .-% based on the liquid or liquid and solid use added to the hydrogenation process.
  • Document CA-A-1,117,887 describes a hydrocracking process for converting heavy oil into lighter hydrocarbons under high pressure and high temperature.
  • the heavy oil is mixed with a finely divided brown coal additive with a grain size of less than 149 ⁇ m, which is loaded with at least one metal from element group IVa or VIII of the periodic table.
  • Document US-A-4,591,426 also describes a hydroconversion process for heavy feedstocks with a metal content of at least 200 ppm at temperatures above 400 ° C. and a total hydrogen pressure of 1022 bar using a natural inorganic material such as laterite or limonite.
  • a natural inorganic material such as laterite or limonite.
  • 1 to 15% by weight of particles with particle sizes between 1270 and 12700 ⁇ m, based on the feed are supplied, these making up 20 to 80% by weight of the content of the reaction zone.
  • Document GB-A-2 135 691 describes a process for hydrocracking heavy oils in the presence of an additive made from finely ground coal or another carbon-containing material with the addition of a compound of a catalytically active metal such as iron, cobalt or molybdenum. Particle sizes of the additive of less than 74 ⁇ m are disclosed.
  • the invention has for its object to avoid excessive foam formation in a method of the type mentioned.
  • Another object of the invention is the improved utilization of the reaction zone of the hydrogenation reactor or reactors.
  • the component is added in two different grain size distributions from separate grindings, such that a fine grain fraction with a grain size of 90 ⁇ m or less and a coarse grain fraction with a grain size of 90 to 1,000 ⁇ m, preferably 100 Up to 500 microns is present and the latter makes up a share of 5 - 80 wt .-% of the added component.
  • One embodiment of the method according to the invention is that the proportion of the coarse grain fraction is between 10 and 30 and in particular between 20 and 30% by weight of the added component.
  • a preferred embodiment for the start-up phase of the present method is that the coarse grain fraction is more than 20% by weight of the amount of the component added.
  • the invention can also be used for the hydrogenation of mixtures of heavy or residual oils or waste oils with ground brown coal and / or hard coal, the oil / coal weight ratio being between 5: 1 and 1: 1.5.
  • the coal can be used as a coarse grain fraction with a corresponding proportion of a grain size of 100 ⁇ m and more.
  • the amount of liquid in the hydrocracking zone of the reactor initially increases for a given gas velocity when larger particles are used.
  • the present invention enables improved utilization of the reaction zone by using two metering streams of the catalyst with two different particle size distributions.
  • An embodiment of the present invention discloses a conversion process for heavy crude oils with a density of less than 20 ° API, more than 200 ppm metal content and more than 5% by weight Conradson coal in the presence of hydrogen and a catalyst in a bottom phase reactor in which an upward three-phase flow is formed.
  • the catalyst can comprise metals from element group Va, VIa or VIIIa of the periodic table, with or without a porous support, on which metals also contained in the crude oil are deposited.
  • the present invention discloses that for very high conversion rates (90% and more) of fractions boiling above 500 ° C. at moderately high flow rates (0.5 t / m3h or more), a considerable proportion of small particles (below 50 ⁇ m) are required because this brings significant advantages for the hydrogenation capacity of the catalyst system.
  • thermodynamic, fluid dynamic and kinetic relationships in the bottom phase hydrogenation with the addition of additives or catalysts in a bottom-flow tube reactor have not yet been completely clarified, it is assumed that the coarse grain fraction limits the foam formation or the gas residence time and that the amount of liquid is limited to Cost of the gas portion within the reactor, which is reflected by the differential pressure across the reactor height as well expresses the conversion rate and the preheating temperature. This phenomenon is noticeable at gas velocities in the reactor of more than 3 cm / s, temperatures of more than 250 ° C and pressures between 50 and 300 bar.
  • the highly active fine grain fraction preferably having a grain size of less than 50 ⁇ m by means of a metering system and the coarse grain fraction of a less active catalyst by means of a second metering system or inert material with a grain size of 100 to 1000 microns, preferably 150 to 1000 microns is fed, which serves to adapt the system to the fluid dynamic requirements, the amount of liquid in the bottom phase reactor is maximized.
  • the corresponding catalyst mixture which is formed from components of two different particle size distributions, can also be prepared beforehand in another separate apparatus, in order then to be brought into contact with the oil insert via a single metering system.
  • a remarkable aspect of the present invention is that two separate particle size distributions of the catalyst are used, where both fractions can consist of the same or different materials.
  • FIG. 1 shows the hydroconversion process according to the invention with subsequent distillation and hydrodesulfurization in a flow diagram.
  • the fine-grain fraction is introduced via line 1, from the storage vessel 2 discontinuously via valve 3 into a weighing container 4, from which the desired amount of the added component is fed via line 6 to the mixing container 13 via a continuous screw conveyor 5.
  • the coarse grain fraction of the single-use catalyst or additive fed.
  • the coarse grain fraction is provided via line 7 in the storage vessel 8 and fed discontinuously to the weighing container 10 via valve 9.
  • the desired amount of coarse grain fraction is introduced into the mixing container 13 via a continuous screw conveyor 11 and mixed with the heavy oil and the fine grain fraction supplied via line 16.
  • the invention is not limited to the illustrated embodiment with the two dosing systems described.
  • the different grain fractions of the catalyst can also be supplied in other ways.
  • the heavy oil and the two grain fractions of the catalyst are fed from the mixing tank 13 via line 14 to a high-pressure pump 15 and via line 15 'to the heat exchangers 49 and 50, in which this material flow is preheated using the heat of reaction of the reaction products.
  • the fresh hydrogen is fed via line 61, the hydrogen-containing cycle gas via line 59 to the cycle gas preheater 63, where the gas is heated to 200 to 500 ° C. and is fed to the heater 18 together with the preheated feed stream from line 50 ′.
  • the reactor system consists of one or at least two reactors connected in series. To be favoured three reactors connected in series.
  • the reactors 20, 24 and 27 are vertical tubular reactors with or without internals, which are operated with the flow direction from bottom to top. Here the conversion takes place at temperatures between 400 and 490 ° C, preferably 430 and 480 ° C, a hydrogen partial pressure between 50 and 300 bar and a circulating gas volume of 100 Nm3 / t to 10000 Nm3 / t.
  • a quasi-isothermal mode of operation of the reactors is possible by supplying cold gas via lines 21, 23 and 26.
  • downstream hot separators which are operated at approximately the same temperature level as the reactors, the unconverted portion of the heavy and residual oils used as well as the solids is separated from the gaseous reaction products under process conditions.
  • the bottom product of the hot separator is expanded in a multi-stage flash unit.
  • the top product of the hot separators, the flash stills and any crude oil distillate fractions to be processed are combined and fed to the downstream gas phase reactors. Hydrotreating or mild hydrocracking is carried out on a fixed catalytic bed under trickle-flow conditions under the same total pressure as in the sump phase.
  • the gaseous reaction products (C1 to C4 gases, H2S, NH3) are largely separated from the process gas, the remaining hydrogen is recycled as recycle gas.
  • the amount of liquid in the reactor can be optimized so that the conversion of the heavy crude oil in the reaction system increases while the preheating temperature is reduced, thereby reducing the investment and operating costs of the preheater system.
  • the process according to the invention has particular advantages in the event that the gas velocity in the Reactor under reaction conditions is greater than 3 cm / s based on the reactor cross section, which is normally true for gas velocities in industrial reactors.
  • the same material is added as a fine grain and a coarse grain fraction.
  • material of different compositions for the fine and coarse grain fraction e.g. B. Fe2O3 as a fine grain fraction with a particle size with an upper limit of 30 microns and for the coarse grain fraction activated coke from lignite with a lower grain size of 100 microns.
  • the two catalyst fractions do not necessarily have to be fed to the catalyst-oil mixing container 13 (FIG. 1) via two separate metering systems. but can also be mixed beforehand and added directly as a catalyst mixture.
  • the only decisive factor is the use of two different particle size distributions of the catalyst or additive from the same or different chemical species. The use of these two catalyst fractions leads to the unexpected result described in the invention.
  • the hydrocracking product is fed via line 28 into the first hot separator 29 in order to separate the gas / vapor phase from the heavier liquid products which contain unconverted residues (catalyst).
  • the temperature of the hot separators 29 and 33 is regulated in a range from 300 to 450 ° C. by supplying quench gas via lines 32 and 34, which is fed in at the bottom.
  • the second hot separator 33 mainly serves as a scraper for the gas phase reactors 40 and 46.
  • the top product of the second hot separator 33 is combined via line 36, the flash distillate 77 as well as the crude oil distillate 36 ', which is produced elsewhere, and the gas phase reactors 40 and 46 at the same total pressure and approximately the same or fed to a somewhat reduced temperature as in the bottom phase reactor.
  • the operating conditions of these reactors are according to the invention for the pressure between 50 and 300 bar, for the temperature between 300 and 450 ° C and for the gas / liquid ratio between 50 and 10000 Nm3 / t.
  • Hydrotreating or mild is carried out in this conventional reactor Hydrocracking at fixed bed reaction zones under trickle flow conditions using a conventional hydrodesulfurization catalyst or a mild hydrocracking catalyst from groups VIa or VIIIa of the periodic table on an alumina support.
  • the product is fed via line 47 to intensive cooling and condensation (49, 50).
  • the heat of reaction is used to preheat the fresh insert.
  • the gas / liquid mixture is fed to the high-pressure cold separator 52 via line 51.
  • the liquid product is relaxed and can then be fed to the standard refinery technology.
  • the gaseous reaction product After passing through the cold separator 52, the gaseous reaction product is separated as much as possible from the process gas which is discharged via line 56. The remaining hydrogen is fed to the compressor 58 via line 57 and returned to the process via line 59.
  • the bottom product of the hot separators 29 and 33 is fed via lines 32 and 34 to a multi-stage flash unit 65 and 72, decompressed and the residue of the used catalysts or additives is removed for workup, for example by carbonization, gasification or solids separation, via line 73 in order to be used again later can.
  • a vertical bubble column reactor without internals the temperature of which is controlled via the outlet temperature of a preheater system and via a cold gas quench system, is charged with a specific throughput of 1.5 t / m3h with vacuum residue from a conventional residual oil of Venezuelan origin at a hydrogen partial pressure of 190 bar, whereby 2000 Nm3 of hydrogen can be used per ton of residue.
  • the gas velocity is 6 cm / s. 2% by weight of lignite coke with a sharp upper grain limit at 90 ⁇ m are added to the feed product.
  • a temperature in the reactor of 455 ° C. is reached at a preheater outlet temperature of 447 ° C.
  • the differential pressure across the reactor height is about 100 mbar. A residue conversion of approximately 45% is achieved under these conditions.
  • the system was then operated with two different dosing systems.
  • the total amount of catalyst was again 2% by weight.
  • the differential pressure increased from 100 mbar to approximately 300 mbar, while the preheater outlet temperature decreased from 447 ° C to 438 ° C.
  • the conversion rate (RU) of the residue rose from 45 to 62%.
  • H middle Temperature ° C Conversion% A 100% by weight 30 ⁇ m 0.5 461 90 B 75% by weight 30 ⁇ m 0.5 455 90 25% by weight 90-130 ⁇ m C. like B 0.75 455 78 D like B 0.75 461 90

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)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Lubricants (AREA)

Claims (7)

  1. Procédé d'hydroconversion d'huiles lourdes et résiduelles, d'huiles usées et de déchets d'huile en phase liquide ou en phase combinée liquide et gazeuse avec des gaz contenant de l'hydrogène à une pression partielle d'hydrogène de 50 à 300 bars de préférence de 150 à 200 bars, une température de 250 à 500°C, de préférence de 400 à 490°C, une proportion gaz/huile de 100 à 10 000 Nm3/t, de préférence de 1 000 à 5 000 Nm3/t de produits mis en oeuvre liquides et solides en ajoutant au moins un composant du groupe coke actif de houille ou de lignite, noir de carbone, boue rouge, oxyde de fer III, poussière de haut fourneau, cendres de procédés de gazéification d'huiles brutes, minéraux naturels contenant du fer, latérite et limonite, à une concentration de 0,5 à 15 % en poids par rapport à la quantité totale de produits liquides et solides mis en oeuvre, caractérisé en ce qu'on ajoute les composants en deux répartitions granulométriques différentes provenant de deux broyages différents, de sorte qu'il existe une fraction granulométrique fine avec une taille de grain de 90 µm ou inférieure et une fraction granulométrique grossière avec une taille de grain de 90 à 1 000 µm et que, celle-ci représente une proportion de 5 à 80 % en poids du composant ajouté.
  2. Procédé selon la revendication 1, caractérisé en ce que la fraction à grain grossier a une granulométrie comprise entre 100 et 500 µm
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la proportion de la fraction grossière est comprise entre 10 et 30, notamment entre 20 et 30 % en poids du composant ajouté.
  4. Procédé selon la revendication 1 ou 2, caractérisé en ce que la fraction grossière représente, dans la phase de démarrage plus de 20 % en poids de la quantité des composants ajoutés.
  5. Procédé selon au moins l'une des revendications précédentes, caractérisé en ce qu'on utilise deux répartitions granulométriques séparées du composant ajouté, les deux fractions pouvant être constituées du même matériau ou de matériaux différents.
  6. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des mélanges d'huiles lourdes ou résiduelles, des huiles usagées ou des déchets d'huile avec de la houille ou du lignite, la proportion pondérale de l'huile au charbon étant comprise entre 5 : 1 et 1 : 1,5.
  7. Procédé selon la revendication 6, caractérisé en ce qu'on utilise une partie du lignite ou du charbon correspondant à la fraction grossière du composant à une granulométrie de 100 µm ou supérieure.
EP87114725A 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles Expired - Lifetime EP0263522B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP92112758A EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles
AT87114725T ATE94583T1 (de) 1986-10-08 1987-10-08 Verfahren zur hydrierenden konversion von schwer- und rueckstandsoelen.
GR950402920T GR3017825T3 (en) 1986-10-08 1995-10-20 Process for the hydroconversion of heavy and residual oils.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3634275 1986-10-08
DE19863634275 DE3634275A1 (de) 1986-10-08 1986-10-08 Verfahren zur hydrierenden konversion von schwer- und rueckstandsoelen

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP92112758.5 Division-Into 1987-10-08
EP92112758A Division-Into EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles

Publications (3)

Publication Number Publication Date
EP0263522A2 EP0263522A2 (fr) 1988-04-13
EP0263522A3 EP0263522A3 (en) 1989-04-12
EP0263522B1 true EP0263522B1 (fr) 1993-09-15

Family

ID=6311311

Family Applications (2)

Application Number Title Priority Date Filing Date
EP92112758A Expired - Lifetime EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles
EP87114725A Expired - Lifetime EP0263522B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP92112758A Expired - Lifetime EP0516187B1 (fr) 1986-10-08 1987-10-08 Procédé d'hydroconversion d'huiles lourdes et résiduelles

Country Status (8)

Country Link
US (1) US4851107A (fr)
EP (2) EP0516187B1 (fr)
JP (1) JPH0696710B2 (fr)
AT (1) ATE128174T1 (fr)
CA (1) CA1302332C (fr)
DE (3) DE3634275A1 (fr)
ES (2) ES2078610T3 (fr)
NO (1) NO171219C (fr)

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5166118A (en) * 1986-10-08 1992-11-24 Veba Oel Technologie Gmbh Catalyst for the hydrogenation of hydrocarbon material
DE3737370C1 (de) * 1987-11-04 1989-05-18 Veba Oel Entwicklungs Gmbh Verfahren zur hydrierenden Konversion von Schwer- und Rueckstandsoelen,Alt- und Abfalloelen in Mischung mit Klaerschlaemmen
DE3806365C1 (fr) * 1988-02-27 1989-07-20 Veba Oel Entwicklungs-Gesellschaft Mbh, 4650 Gelsenkirchen, De
DE3912807A1 (de) * 1989-04-19 1990-11-08 Gfk Kohleverfluessigung Gmbh Katalysator bzw. additiv zur hydrierenden behandlung von schweren erdoelen bzw. schweren erdoelfraktionen sowie verfahren zur gewinnung des katalysators
US5755955A (en) * 1995-12-21 1998-05-26 Petro-Canada Hydrocracking of heavy hydrocarbon oils with conversion facilitated by control of polar aromatics
US5721186A (en) * 1996-09-06 1998-02-24 The United States Of America As Represented By The United States Department Of Energy Method for producing catalysis from coal
US5922191A (en) * 1996-10-04 1999-07-13 Intevep, S.A. Foam control using a fluidized bed of particles
US5922190A (en) * 1996-10-04 1999-07-13 Intevep, S.A. Process for suppressing foam formation in a bubble column reactor
DE19742266A1 (de) * 1997-09-25 1999-05-06 Ludger Dr Steinmann Aufwertung von Chemie- und Energierohstoffen durch Reaktion mit geringwertigen Rohstoffen
US7745369B2 (en) 2003-12-19 2010-06-29 Shell Oil Company Method and catalyst for producing a crude product with minimal hydrogen uptake
US20100098602A1 (en) * 2003-12-19 2010-04-22 Opinder Kishan Bhan Systems, methods, and catalysts for producing a crude product
US20050150818A1 (en) 2003-12-19 2005-07-14 Bhan Opinder K. Systems, methods, and catalysts for producing a crude product
ES2585891T3 (es) 2004-04-28 2016-10-10 Headwaters Heavy Oil, Llc Métodos y sistemas de hidroprocesamiento en lecho en ebullición
US10941353B2 (en) 2004-04-28 2021-03-09 Hydrocarbon Technology & Innovation, Llc Methods and mixing systems for introducing catalyst precursor into heavy oil feedstock
BRPI0510346A (pt) * 2004-04-28 2007-10-30 Headwaters Heavy Oil Llc métodos e sistemas de hidroprocessamento de leito fixo para beneficiamento de um sistema de leito fixo existente
PL1753844T3 (pl) * 2004-04-28 2016-12-30 Sposób obróbki wodorem i instalacja do uszlachetniania oleju ciężkiego
US7422904B2 (en) * 2005-02-04 2008-09-09 Exxonmobil Chemical Patents Inc. Method of operating a fixed bed reactor under predetermined hydraulic conditions
EP1874897A1 (fr) 2005-04-11 2008-01-09 Shell Internationale Research Maatschappij B.V. Procede et catalyseur destines a produire un produit brut presentant une teneur en mcr reduite
BRPI0609411A2 (pt) * 2005-04-11 2011-10-11 Shell Int Research método para produzir um produto bruto
EP1874896A1 (fr) 2005-04-11 2008-01-09 Shell International Research Maatschappij B.V. Procede et catalyseur pour produire un produit brut a teneur reduite en azote
US20080083650A1 (en) 2006-10-06 2008-04-10 Bhan Opinder K Methods for producing a crude product
WO2008043785A1 (fr) * 2006-10-10 2008-04-17 Bioecon International Holding N.V. Procédé en deux étapes pour la conversion de sable bitumeux en combustibles liquides et produits chimiques de spécialité
US8034232B2 (en) * 2007-10-31 2011-10-11 Headwaters Technology Innovation, Llc Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker
US9688934B2 (en) 2007-11-23 2017-06-27 Bixby Energy Systems, Inc. Process for and processor of natural gas and activated carbon together with blower
US8142645B2 (en) * 2008-01-03 2012-03-27 Headwaters Technology Innovation, Llc Process for increasing the mono-aromatic content of polynuclear-aromatic-containing feedstocks
US8679322B2 (en) 2009-11-24 2014-03-25 Intevep, S.A. Hydroconversion process for heavy and extra heavy oils and residuals
US9168506B2 (en) 2010-01-21 2015-10-27 Intevep, S.A. Additive for hydroconversion process and method for making and using same
US9334452B2 (en) 2010-06-30 2016-05-10 Chevron U.S.A. Inc. Two-stage, close-coupled, dual-catalytic heavy oil hydroconversion process
US9039890B2 (en) 2010-06-30 2015-05-26 Chevron U.S.A. Inc. Two-stage, close-coupled, dual-catalytic heavy oil hydroconversion process
US20120157726A1 (en) * 2010-12-15 2012-06-21 Air Liquide Large Industries U.S. Lp Process For The Production Of Cellulose Based Biofuels
EP2654948A4 (fr) 2010-12-20 2015-02-11 Chevron Usa Inc Catalyseurs d'hydrotraitement et leurs procédés de fabrication
WO2012170167A1 (fr) * 2011-06-10 2012-12-13 4Crgroup, Llc Procédé d'hydroconversion d'huile lourde à deux catalyseurs, à couplage étroit, à deux étages
US9790440B2 (en) 2011-09-23 2017-10-17 Headwaters Technology Innovation Group, Inc. Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker
WO2013126364A2 (fr) 2012-02-21 2013-08-29 4CRGroup LLC Procédé d'hydroconversion de pétrole lourd à double catalyse, monobloc, à deux zones, utilisant un hydrotraitement amélioré
WO2013126362A2 (fr) 2012-02-21 2013-08-29 4CRGroup LLC Procédé d'hydroconversion de pétrole lourd monobloc à deux zones, utilisant une première zone à lit bouillonnant
US9644157B2 (en) 2012-07-30 2017-05-09 Headwaters Heavy Oil, Llc Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking
US8999145B2 (en) * 2012-10-15 2015-04-07 Uop Llc Slurry hydrocracking process
EP2970777B1 (fr) * 2013-03-14 2018-02-07 BP Europa SE Procédé d'introduction d'additifs fins et grossiers pour l'hydroconversion d'hydrocarbures lourds
CN106102908A (zh) * 2014-02-12 2016-11-09 Bp欧洲公司 加氢裂化重油和残渣油的方法
US11414608B2 (en) 2015-09-22 2022-08-16 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor used with opportunity feedstocks
US11414607B2 (en) 2015-09-22 2022-08-16 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor with increased production rate of converted products
US11421164B2 (en) 2016-06-08 2022-08-23 Hydrocarbon Technology & Innovation, Llc Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product
US11118119B2 (en) 2017-03-02 2021-09-14 Hydrocarbon Technology & Innovation, Llc Upgraded ebullated bed reactor with less fouling sediment
US11732203B2 (en) 2017-03-02 2023-08-22 Hydrocarbon Technology & Innovation, Llc Ebullated bed reactor upgraded to produce sediment that causes less equipment fouling
CA3057131C (fr) 2018-10-17 2024-04-23 Hydrocarbon Technology And Innovation, Llc Reacteur a lit bouillonnant ameliore sans accumulation liee au recyclage d'asphaltenes dans des residus de tour sous vide
FI128237B (en) * 2018-12-21 2020-01-15 Neste Oyj METHOD FOR UPGRADING GAME OILS
CN114425273B (zh) * 2020-10-10 2022-11-18 中国石油化工股份有限公司 碳二加氢反应器的控制方法及应用

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635943A (en) * 1969-10-16 1972-01-18 Cities Service Res & Dev Co Hydrotreating process with coarse and fine catalysts
CA965767A (en) * 1970-05-18 1975-04-08 Council Of Scientific And Industrial Research Preparation of iron catalysts for hydrogenation of coal
US3844933A (en) * 1972-10-16 1974-10-29 Hydrocarbon Research Inc Hydroconversion of coal-derived oils
US3975259A (en) * 1975-07-10 1976-08-17 Air Products And Chemicals, Inc. Hydrodesulfurization of liquid hydrocarbon utilizing a suspended catalyst particle of less than 10 microns
CA1079663A (fr) * 1976-08-13 1980-06-17 Maurice M. Mitchell (Jr.) Procede pour l'hydrodesulfurisation de matieres carbonees a l'aide d'un catalyseur en suspension
CA1094492A (fr) * 1977-10-24 1981-01-27 Ramaswami Ranganathan Hydrocraquage d'huiles lourdes avec un catalyseur fer- charbon
JPS54106506A (en) * 1978-02-08 1979-08-21 Yamagata Daigakuchiyou Coal direct liquefication reaction method and apparatus
CA1124194A (fr) * 1979-03-05 1982-05-25 Ramaswami Ranganathan Hydrocraquage de suspensions de cendres volantes dans des huiles lourdes
CA1163222A (fr) * 1981-02-12 1984-03-06 Her Majesty The Queen, In Right Of Canada As Represented By The Minister Of Natural Resources Canada Demetallisation et hydrofractionnement en simultane des hydrocarbures lourds
US4370221A (en) * 1981-03-03 1983-01-25 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Energy, Mines And Resources Catalytic hydrocracking of heavy oils
JPS57174384A (en) * 1981-04-21 1982-10-27 Canada Majesty In Right Of Hydrogenolysis of bitumen-coal slurry
JPS5832193B2 (ja) * 1981-06-17 1983-07-11 工業技術院長 反応副生コ−クスを触媒とする重質炭化水素の水素化分解法
FR2511389A1 (fr) * 1981-08-11 1983-02-18 Inst Francais Du Petrole Procede d'hydroconversion catalytique d'hydrocarbures lourds en phase liquide et en presence d'un catalyseur disperse et de particules charbonneuses
DD210295A1 (de) * 1981-09-02 1984-06-06 Rheinische Braunkohlenw Ag Verfahren zum hydrieren von schwer- und rueckstandsoelen und dafuer verwendete katalysatoren
CA1151579A (fr) * 1981-10-07 1983-08-09 Ramaswami Ranganathan Hydrocraquage d'hydrocarbures lourds avec fort taux de converssion des brais
US4396495A (en) * 1982-01-25 1983-08-02 Uop Inc. Reduction of foaming in a slurry catalyst hydrocarbon conversion process
JPS58219292A (ja) * 1982-06-14 1983-12-20 カナダ国 重質炭化水素油の水素添加分解方法
CA1202588A (fr) * 1983-02-10 1986-04-01 Theodore J.W. Debruijn Hydrofractionnement des petroles lourds par intervention d'additifs secs
US4613427A (en) * 1984-10-03 1986-09-23 Intevep, S.A. Process for the demetallization and hydroconversion of heavy crudes and residues using a natural clay catalyst

Also Published As

Publication number Publication date
ES2078610T3 (es) 1995-12-16
NO171219C (no) 1993-02-10
EP0263522A2 (fr) 1988-04-13
NO874205L (no) 1988-04-11
EP0516187B1 (fr) 1995-09-20
NO874205D0 (no) 1987-10-07
EP0263522A3 (en) 1989-04-12
EP0516187A3 (en) 1992-12-09
DE3634275A1 (de) 1988-04-28
EP0516187A2 (fr) 1992-12-02
DE3751534D1 (de) 1995-10-26
JPH0696710B2 (ja) 1994-11-30
DE3787434D1 (de) 1993-10-21
CA1302332C (fr) 1992-06-02
JPS63146989A (ja) 1988-06-18
NO171219B (no) 1992-11-02
US4851107A (en) 1989-07-25
ATE128174T1 (de) 1995-10-15
ES2043629T3 (es) 1994-01-01

Similar Documents

Publication Publication Date Title
EP0263522B1 (fr) Procédé d'hydroconversion d'huiles lourdes et résiduelles
DE69701088T2 (de) Wasserstoffbehandlung von schweren kohlenwasserstoffölen mit kontrolle der verteilung der teilchenförmigen additiven
CA2131261C (fr) Hydrocraquage de bruts lourds avec recyclage des hydrocarbures lourds
DE69609355T2 (de) Hydrocracken von schweren kohlenwasserstoffölen mit kontrolle von polare aromaten
DE2932488C2 (de) Verfahren zur Gewinnung einer Kohlenwasserstofffraktion
DE69215481T2 (de) Methode zur Behandlung eines schweren Kohlenwasserstofföls
DE2215664C3 (fr)
DE3737370C1 (de) Verfahren zur hydrierenden Konversion von Schwer- und Rueckstandsoelen,Alt- und Abfalloelen in Mischung mit Klaerschlaemmen
DE3780275T2 (de) Verfahren zum hydrocracken von schweroelen.
DE1645826B1 (de) Verfahren zur Umwandlung eines Kohlenwasserstoffeinsatzmaterials
DE112007001743T5 (de) Hydrocracking-Verfahren
DE1119438B (de) Verfahren zum Raffinieren von schwefelhaltigen schweren OElen
DE3903144A1 (de) Hydrocracken von schweroelen in gegenwart einer eisen-kohle-aufschlaemmung
DE60115372T2 (de) Verfahren zur Behandlung einer Kohlenwasserstoffbeschickung durch eine Gegenstrom-Hydrobehandlung in einem Festbett
DE2835123A1 (de) Umwandlungsverfahren fuer feste, kohlenwasserstoffhaltige materialien
DE3233344A1 (de) Verfahren zur verfluessigung von kohle
DE1770264A1 (de) Verfahren zur Reinigung von Erdoel
DE2730159C2 (fr)
DE1954004A1 (de) Verfahren zur Umwandlung und Entschwefelung eines schwefelhaltigen Kohlenwasserstoff-Einsatzmaterials
DE3151614A1 (de) Verfahren zur qualitaetsverbesserung eines kohlenwasserstoffhaltigen oels
DE3237037A1 (de) Verfahren zum hydroprocessing eines schweren kohlenwasserstoffhaltigen oelausgangsmaterials
DE2344251C3 (de) Verfahren zur katalytischen Hydrokrackung einer Schwefel, Asche und Asphaltene enthaltenden Kohlenwasserstoffbeschickung
DE69022858T2 (de) Kohlenwasserstoffbehandlung eines gas enthaltenden zulaufes in einem gegenstromkatalysatorfliessbett.
EP0209665B1 (fr) Procédé d'hydrogénation de charbon en phase liquide et en lit fixe avec catalyseur
DE3734011A1 (de) Verfahren zur hydrierenden konversion von schwer- und rueckstandsoelen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19871022

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INTEVEP S.A.

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INTEVEP S.A.

Owner name: VEBA OEL ENTWICKLUNGS-GESELLSCHAFT MBH

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KURZEJA, KLAUS

Inventor name: MARRUFFO, FRANZO, DR.

Inventor name: KRASUK, JULIO, DR.

Inventor name: GUITIAN, JOSE

Inventor name: NIEMANN, KLAUS, DR.

Inventor name: MERZ, LUDWIG, DR.

Inventor name: KRETSCHMAR, KLAUS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INTEVEP S.A.

Owner name: VEBA OEL TECHNOLOGIE GMBH

17Q First examination report despatched

Effective date: 19901005

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INTEVEP S.A.

Owner name: VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG GMBH

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 94583

Country of ref document: AT

Date of ref document: 19931015

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3787434

Country of ref document: DE

Date of ref document: 19931021

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19930928

EPTA Lu: last paid annual fee
ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2043629

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3010623

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 87114725.2

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20010926

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20010928

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20011003

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20011008

Year of fee payment: 15

Ref country code: GB

Payment date: 20011008

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20011011

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20011016

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20011031

Year of fee payment: 15

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20020104

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021008

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021008

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021009

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021009

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021030

Year of fee payment: 16

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021031

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20021114

Year of fee payment: 16

BERE Be: lapsed

Owner name: S.A. *INTEVEP

Effective date: 20021031

Owner name: *VEBA OEL TECHNOLOGIE UND AUTOMATISIERUNG G.M.B.H.

Effective date: 20021031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030506

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20021008

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030501

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20031112

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051008