EP1194498B1 - Procede ameliore de desasphaltage de residus faisant appel a un recyclage reactif d'une matiere a point d'ebullition eleve - Google Patents
Procede ameliore de desasphaltage de residus faisant appel a un recyclage reactif d'une matiere a point d'ebullition eleve Download PDFInfo
- Publication number
- EP1194498B1 EP1194498B1 EP00925922.7A EP00925922A EP1194498B1 EP 1194498 B1 EP1194498 B1 EP 1194498B1 EP 00925922 A EP00925922 A EP 00925922A EP 1194498 B1 EP1194498 B1 EP 1194498B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solids
- residence time
- zone
- reaction zone
- fraction
- 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
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
- C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
-
- 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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
Definitions
- the present invention relates to an improved process for deasphalting a residua feedstock by use of a short vapor residence time process unit comprised of a horizontal moving bed of fluidized and/or stirred hot particles.
- the vapor phase product stream from said process unit is passed to a soaker drum where a high boiling fraction is separated and recycled to the process unit after undergoing reactions causing molecular weight growth.
- This reactive recycle using the soaker drum results in substantially improved qualities of the liquid products compared with what is achieved by once-through residua deasphalting process alternatives.
- crude oils are subjected to atmospheric distillation to separate lighter materials such as gas oils, kerosenes, gasolines, straight run naphtha, etc. from the heavier materials.
- the residue from the atmospheric distillation step is then distilled at a pressure below atmospheric pressure.
- This later distillation step produces a vacuum gas oil distillate and a vacuum reduced residual oil which often contains relatively high levels of asphaltene molecules.
- asphaltene molecules usually contain most of the Conradson Carbon residue and metal components of the resid. They also contain relatively high levels of heteroatoms, such as sulfur and nitrogen.
- Such feeds have little commercial value, primarily because they cannot be used as a fuel oil because of ever stricter environmental regulations.
- U.S. Patent No. 4,191,639 to Audeh et al teaches a process wherein hydrocarbon oils, such as residual petroleum oils, are deasphalted and demetallized by contact with a liquid mixture of at least two of the components selected from hydrogen sulfide, carbon dioxide, and propane.
- US Patent 5,714,056 teaches a process for deasphalting residua in a short vapor contact time thermal process unit comprised of a horizontal moving bed of fluidized hot particles. This is a once through process whereby the removal of feed contaminants is limited to what can be achieved in a single pass. There is no suggestion of separating a high boiling fraction from the vapor product fraction and recycling it to the reaction zone.
- a process for deasphalting an asphalt-containing feedstock in a deasphalting process unit comprised of:
- steam, C 4 minus gas, or both is injected into the soaker drum to maintain the solids in suspension and to strip out lower boiling range products.
- the soaker drum is operated at increased pressure and temperature to reduce reaction time and therefore the soaker drum size.
- the particles of the short contact time reaction zone are fluidized and/or stirred with the aid of a mechanical means.
- stream, C 4 minus gas, or both are injected into the vaporized fraction upstream of the soaker drum to reduce the partial pressure of the C 5 plus hydrocarbon to condense the high boiling fraction as per step (f) at a temperature which is lower than its initial boiling point of about 450-600°C.
- polymerization initiators are present in the soaker drum to increase reaction rates.
- the soaker drum can include a mechanical mixing device providing the advantages of self-cleaning to minimize coke deposits and to achieve substantially plug flow reaction conditions of the liquid phase.
- Residua feedstocks which are upgraded in accordance with the present invention are those petroleum fractions boiling above about 380°C, preferably above about 540°C, more preferably above about 560°C.
- Non-limiting examples of such fractions include vacuum resids, atmospheric resids, heavy and reduced petroleum crude oil; pitch; waste oils; asphalt; bitumen; solvent deasphalter residue; and tar sand oil. It is understood that such resids may also contain minor amounts of lower boiling material.
- These feedstocks cannot be fed in substantial quantities to refinery process units, such as FCC units, because they are typically high in Conradson Carbon and they usually contain an undesirable amount of metal-containing components.
- Conradson Carbon residues will deposit on the FCC cracking catalyst and cause excessive deactivation. Metals, such as nickel and vanadium will also deactivate the catalyst by acting as catalyst poisons. Such feeds will typically have a Conradson Carbon content of at least 5 wt.%, generally from about 5 to 50 wt.%. As to Conradson Carbon residue, see ASTM Test D189-165.
- Residuum feedstocks are upgraded in accordance with the present invention in a short vapor residence time process unit which is comprised of a heating zone, a short vapor residence time horizontal fluidized and/or stirred bed reaction zone and a stripping zone.
- a short vapor residence time process unit which is comprised of a heating zone, a short vapor residence time horizontal fluidized and/or stirred bed reaction zone and a stripping zone.
- a residual feedstock which is high in Conradson Carbon and/or metal-components is fed via line 10 to one or more short vapor residence time reaction zone 1 which contains a horizontal moving bed of fluidized and/or stirred hot solids. It is preferred that the solids in the short vapor residence time reactor are fluidized and/or stirred with assistance of mechanical means.
- the reactor may be stripped by use of a stripping gas, such as steam, or C 4 minus gas, or by the vapors resulting from the vaporization of a fraction of the feed-stock.
- a stripping gas such as steam, or C 4 minus gas
- the mechanical means be a self cleaning mechanical mixing system characterized as having a relatively high radial mixing efficiency with only minor amounts of axial backmixing. Such a mixing system acts like a plug flow system with a flow pattern which ensures that the residence time is nearly equal for all particles.
- the most preferred mechanical mixer is the mixer referred to by Lurgi AG of Germany as the LR-Mixer or LR-Flash Coker which was originally designed for processing oil shale, coal, and tar sands.
- the LR-Mixer consists of two or more horizontally oriented rotating screws which mix the feed and hot solids while stirring and transporting the mixture through the reactor.
- the solid particles be coke particles, they may be any other suitable refractory particulate material.
- suitable refractory materials include those selected from the group consisting of silica, alumina, zirconia, magnesia, mullite, synthetically prepared or naturally occurring material such as pumice, clay, kieselguhr, diatomaceous earth, bauxite, and the like.
- the solids be inert or have catalytic properties.
- the solids will preferably have an average particle size of about 40 microns to 2,000 microns, more preferably from about 200 microns to about 1000 microns.
- the feedstock is contacted with the hot solids at a temperature from about 450°C to about 700°C, preferably from about 500°C to 600°C, more preferably from about 520°C to 600°C.
- a substantial portion of the high Conradson Carbon and metal-containing components will deposit on the hot solid particles in the form of high molecular weight carbon and metal moieties.
- the remaining portion will be vaporized on contact with the hot solids.
- the residence time of vapor products in reaction zone 1 will be an effective amount of time so that substantial secondary cracking does not occur. This amount of time will typically be less than about 5 seconds, preferably less than about 2 seconds.
- the residence time of solids in the reaction zone will be from about 5 to 60 seconds, preferably from about 10 to 30 seconds.
- One novel aspect of the present invention is that the residence time of the solids and the residence time of the vapor products, in the reaction zone, are independently controlled. Most fluidized bed processes are designed so that the solids residence time, and the vapor residence time cannot be independently controlled, especially at relatively short vapor residence times. It is preferred that the short vapor residence time process unit be operated so that the ratio of solids to feed be from about 30 to 1 to 3 to 1, preferably about 5 to 1. It is to be understood that the precise ratio of solids to feed will primarily depend on the heat balance requirement of the short vapor residence time reaction zone and the temperature of the solids. Associating the oil to solids ratio with heat balance requirements is within the skill of those having ordinary skill in the art, and thus will not be elaborated herein any further.
- the vaporized fraction is passed via line 11 to soaker drum 2 which is maintained at effective conditions so that the highest boiling materials are condensed out. Typically these conditions will include controlled quenching of the vapor fraction just below the dewpoint.
- the condensate is maintained in the soaker drum for an effective amount of time and reaction severity to initiate polymerization to coke precursors.
- a quench stream can also be passed into soaker drum via line 21.
- the quench stream will typically be an oil stream ranging from naphtha (C 5 /150°C) to residuum stream (550°C+).
- Preferred quench streams are fractionator bottoms having a boiling range of 300°C to 700°C.
- Coke or polymerization initiators which include those selected from the group consisting of elemental sulfur, peroxides, and spent cracking catalysts can be added to the soaker drum via line 19.
- Steam, C 4 minus, air, or a mixture thereof, can also be used in the soaker drum to increase reaction rates, strip lower boiling components, and to keep the solids suspended in a slurry.
- the soaker drum may be continuously cleaned by mechanical means to minimize coke deposits.
- the soaker drum is operated at effective temperatures and residence times to initiate coking reactions, but not to the extent that coke deposits significantly build-up in the soaker drum.
- Conditions include temperatures from about 350°C to about 520°C, preferably from about 400°C to about 450°C and residence times of from about 1 to 60 minutes, preferably from about 5 to 30 minutes, depending on the feed properties and desired feed decontamination rates.
- Proper use of the soaker drum will selectively condense only the highest boiling vapor products and produce a pre-polymerized heavy oil which is recycled to reaction zone 1 via line 9. This will result in an increased metals rejection rate from about 90% for once-through to 95% or greater with extinction recycle.
- Use of the soaker drum also enables increased rejection of other feed contaminants, such as Conradson Carbon, sulfur, and nitrogen.
- the resulting liquid product quality is substantially improved and of higher value as feed to refinery conversion processes.
- the vapor fraction from soaker drum 2 is passed via line 14 to cyclone 20 where most of the entrained solids, or dust, are removed.
- the dedusted vapors are then passed to quench zone 13 via line 24 where the vapors are reduced to temperatures below which substantial thermal cracking occurs. This temperature will preferably be below about 450°C, more preferably below about 340°C.
- Solids, having carbonaceous material deposited thereon, are passed from reaction zone 1 via line 15 to the bed of solids 17 in stripper 3.
- the solids pass downwardly through the stripper and past a stripping zone at the bottom section where any remaining volatiles, or vaporizable material, are stripped from the solids with use of a stripping gas, preferably steam, introduced into the stripping zone via line 16.
- a stripping gas preferably steam
- Stripped vapor products pass upwardly in stripper vessel 3 to quench zone 13 where a light product is removed overhead via line 28.
- the light product will typically be a 550°C minus product stream.
- a 550°C plus stream will also be collected from the quench zone via line 26.
- the stripped solids are passed via line 18 to heater 4 which contains a heating zone.
- the heating zone is operated in an oxidizing gas environment, preferably air, at an effective temperature. That is, at a temperature that will meet the heat requirements of the reaction zone.
- the heating zone will typically be operated at a temperature of about 40°C to 200°C, preferably from about 50°C to 175°C, more preferably from about 50°C to 120°C in excess of the operating temperature of reaction zone 1.
- preheated air can be introduced into the heater. While some carbonaceous residue will be burned from the solids in the heating zone, it is preferred that only partial combustion take place so that the solids, after passing through the heater, will have value as a fuel.
- Excess solids can be removed from the process unit via line 50. Flue gas is removed overhead from heater 4 via line 40. The flue gas is passed through a cyclone system 36, 39, and 38 to remove most solid fines. Dedusted flue gas will be passed to a co-boiler for waste heat recovery (not shown), scrubbed to remove contaminants and particulates, and passed to atmosphere. The hot inert solids are then recycled via lines 12 to thermal zone 1.
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- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Working-Up Tar And Pitch (AREA)
Claims (9)
- Procédé de désasphaltage d'une charge contenant de l'asphalte dans une unité de traitement de désasphaltage composée de :(i) une zone de chauffage (4) dans laquelle des matières solides contenant des dépôts carbonés sont reçues depuis une zone d'épuisement (3) et chauffées en présence d'un gaz de chauffage qui peut contenir de l'oxygène à des fins de combustion partielle ;(ii) une zone de réaction à court temps de résidence de vapeur (1) contenant un lit mobile horizontal de matières solides chaudes agitées recyclées depuis la zone de chauffage et une charge, laquelle zone de réaction est exploitée à une température de 450 à 700 °C et dans des conditions telles que le temps de résidence des matières solides et le temps de résidence de la vapeur sont contrôlés indépendamment, lequel temps de résidence de la vapeur est inférieur à 5 secondes, et lequel temps de résidence des matières solides est de 5 à 60 secondes ; et(iii) une zone d'épuisement (3) à travers laquelle des matières solides ayant des dépôts carbonés sur elles sont acheminées depuis la zone de réaction et dans laquelle des hydrocarbures supplémentaires à point d'ébullition inférieur et des composants volatils sont récupérés avec un gaz d'épuisement ;
lequel procédé comprend :(a) l'introduction de la charge contenant de l'asphalte dans la zone de réaction à court temps de résidence de vapeur (1) dans laquelle elle entre en contact avec les matières solides chaudes fluidisées et/ou agitées pour donner ainsi naissance à des composants à indice de Conradson élevé et des composants contenant des métaux étant déposés sur lesdites matières solides chaudes, et une fraction vaporisée ;(b) la séparation de la fraction vaporisée des matières solides ; et(c) l'acheminement des matières solides jusqu'à ladite zone d'épuisement (3) où elles sont mises en contact avec un gaz d'épuisement, pour en retirer ainsi les composants volatils ;(d) l'acheminement des matières solides épuisées jusqu'à une zone de chauffage (4) où elles sont chauffées jusqu'à une température efficace qui maintiendra la température de fonctionnement de la zone de réaction ;(e) le recyclage des matières solides chaudes de la zone de chauffage à la zone de réaction où elles sont mises en contact avec une charge fraîche ;
caractérisé en ce que ledit procédé comprend en outre :(f) l'acheminement de la fraction vaporisée issue de l'étape (b) au-dessus d'un maturateur (2) fonctionnant à une température de 350 à 520 °C et un temps de résidence de 1 à 60 minutes où elle est refroidie rapidement pour générer une fraction de vapeur bouillant à moins de 450-600 °C et un condensat à point d'ébullition élevé ayant un point d'ébullition initial de 450 à 600 °C, pour permettre à des réactions d'augmentation du poids moléculaire de se produire ;(g) le recyclage de ladite fraction à point d'ébullition élevé du maturateur (2) à la zone de réaction à court temps de résidence de vapeur (1) ; et(h) la récupération de la fraction de vapeur ayant une concentration inférieure de contaminants issue de l'étape (g). - Procédé de la revendication 1, dans lequel la charge résiduaire est choisie dans le groupe constitué par les résidus sous vide, les résidus atmosphériques, le pétrole brut lourd et réduit ; le brai ; les huiles usagées ; l'asphalte ; le bitume ; le résidu du désasphaltage au solvant, et le pétrole extrait des sables bitumineux.
- Procédé de la revendication 2, dans lequel la charge résiduaire est un résidu sous vide.
- Procédé de la revendication 1, dans lequel on fait fonctionner le maturateur à une pression de 1 à 10 bar.
- Procédé de la revendication 4, dans lequel on fait fonctionner le maturateur à une température de 400 à 450 °C et une pression de 1 à 3 bar.
- Procédé de la revendication 1, dans lequel des initiateurs de polymérisation sont ajoutés au maturateur pour accroître les vitesses de réaction.
- Procédé de la revendication 6, dans lequel les initiateurs de polymérisation sont choisis dans le groupe constitué par le soufre élémentaire, les peroxydes, un catalyseur épuisé, les particules de coke, et l'air.
- Procédé de la revendication 1, dans lequel de la vapeur d'eau, des fractions en C4 et moins, de l'air, ou des mélanges de ceux-ci sont injectés dans le maturateur pour maintenir les matières solides en suspension épaisse et pour extraire les produits à point d'ébullition inférieur.
- Procédé de la revendication 1, dans lequel de la vapeur d'eau, des gaz en C4 et moins, ou des mélanges de ceux-ci sont ajoutés à la fraction vaporisée provenant de la zone de réaction à court temps de résidence pour réduire sa pression partielle dans le maturateur et permettre la condensation d'une fraction à point d'ébullition supérieur.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US293029 | 1989-01-03 | ||
US29302999A | 1999-04-16 | 1999-04-16 | |
PCT/US2000/009607 WO2000063320A1 (fr) | 1999-04-16 | 2000-04-11 | Procede ameliore de desasphaltage de residus faisant appel a un recyclage reactif d'une matiere a point d'ebullition eleve |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1194498A1 EP1194498A1 (fr) | 2002-04-10 |
EP1194498A4 EP1194498A4 (fr) | 2011-02-16 |
EP1194498B1 true EP1194498B1 (fr) | 2015-11-11 |
Family
ID=23127326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00925922.7A Expired - Lifetime EP1194498B1 (fr) | 1999-04-16 | 2000-04-11 | Procede ameliore de desasphaltage de residus faisant appel a un recyclage reactif d'une matiere a point d'ebullition eleve |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1194498B1 (fr) |
JP (1) | JP4590108B2 (fr) |
CN (1) | CN1347442A (fr) |
AR (1) | AR023503A1 (fr) |
AU (1) | AU771590B2 (fr) |
CA (1) | CA2370591C (fr) |
ES (1) | ES2559272T3 (fr) |
WO (1) | WO2000063320A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020038778A1 (en) | 2000-05-01 | 2002-04-04 | Maa Peter S. | Process for upgrading residua |
US7033486B2 (en) | 2002-04-01 | 2006-04-25 | Exxonmobil Research And Engineering Company | Residuum conversion process |
JP5239226B2 (ja) * | 2007-06-28 | 2013-07-17 | 株式会社Ihi | 重質燃料の改質方法及びその改質装置 |
CN109328215B (zh) * | 2016-06-14 | 2021-06-25 | 理查德·斯通 | 湍动的中间相沥青工艺和产品 |
US10508240B2 (en) | 2017-06-19 | 2019-12-17 | Saudi Arabian Oil Company | Integrated thermal processing for mesophase pitch production, asphaltene removal, and crude oil and residue upgrading |
US10913901B2 (en) | 2017-09-12 | 2021-02-09 | Saudi Arabian Oil Company | Integrated process for mesophase pitch and petrochemical production |
SG11202001475YA (en) * | 2017-09-12 | 2020-03-30 | Saudi Arabian Oil Co | An integrated process for mesophase pitch and petrochemical production |
DE102018213210A1 (de) | 2018-08-07 | 2020-02-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Reinigung mineralischer Feststoffe und Holzmaterialien, Vorrichtung für dieses Verfahren und deren Verwendung |
KR102481197B1 (ko) * | 2020-08-13 | 2022-12-27 | 최창균 | 원료피치의 연속 공급 및 개질된 전구체피치의 연속 배출이 가능한 피치 개질수단 및 연속개질장치 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3334043A (en) * | 1965-09-29 | 1967-08-01 | Sun Oil Co | Neopentane separation of bituminous materials |
US4054512A (en) * | 1976-10-22 | 1977-10-18 | Exxon Research And Engineering Company | Deasphalting with liquid hydrogen sulfide |
US4191639A (en) * | 1978-07-31 | 1980-03-04 | Mobil Oil Corporation | Process for deasphalting hydrocarbon oils |
US4277324A (en) * | 1979-04-13 | 1981-07-07 | Exxon Research & Engineering Co. | Treatment of pitches in carbon artifact manufacture |
US5714056A (en) * | 1995-07-17 | 1998-02-03 | Exxon Research And Engineering Company | Process for deasphalting residua (HEN9511) |
-
2000
- 2000-04-11 CN CN 00806321 patent/CN1347442A/zh active Pending
- 2000-04-11 CA CA2370591A patent/CA2370591C/fr not_active Expired - Fee Related
- 2000-04-11 JP JP2000612401A patent/JP4590108B2/ja not_active Expired - Fee Related
- 2000-04-11 WO PCT/US2000/009607 patent/WO2000063320A1/fr active Application Filing
- 2000-04-11 AU AU44542/00A patent/AU771590B2/en not_active Ceased
- 2000-04-11 ES ES00925922.7T patent/ES2559272T3/es not_active Expired - Lifetime
- 2000-04-11 EP EP00925922.7A patent/EP1194498B1/fr not_active Expired - Lifetime
- 2000-04-14 AR ARP000101746 patent/AR023503A1/es unknown
Also Published As
Publication number | Publication date |
---|---|
EP1194498A4 (fr) | 2011-02-16 |
AU4454200A (en) | 2000-11-02 |
JP4590108B2 (ja) | 2010-12-01 |
CA2370591C (fr) | 2011-01-11 |
AU771590B2 (en) | 2004-03-25 |
JP2002542375A (ja) | 2002-12-10 |
EP1194498A1 (fr) | 2002-04-10 |
CA2370591A1 (fr) | 2000-10-26 |
CN1347442A (zh) | 2002-05-01 |
ES2559272T3 (es) | 2016-02-11 |
AR023503A1 (es) | 2002-09-04 |
WO2000063320A1 (fr) | 2000-10-26 |
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