WO2003035804A1 - Procede de traitement thermique de residus contenant du vanadium - Google Patents
Procede de traitement thermique de residus contenant du vanadium Download PDFInfo
- Publication number
- WO2003035804A1 WO2003035804A1 PCT/EP2002/011236 EP0211236W WO03035804A1 WO 2003035804 A1 WO2003035804 A1 WO 2003035804A1 EP 0211236 W EP0211236 W EP 0211236W WO 03035804 A1 WO03035804 A1 WO 03035804A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- residues
- gasification
- water
- reactor
- temperature
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/466—Entrained flow processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/482—Gasifiers with stationary fluidised bed
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/024—Dust removal by filtration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/02—Dust removal
- C10K1/026—Dust removal by centrifugal forces
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0943—Coke
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0956—Air or oxygen enriched air
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
- C10J2300/1838—Autothermal gasification by injection of oxygen or steam
Definitions
- the invention relates to a process for the thermal treatment of vanadium-containing residues consisting of at least 30% by weight (anhydrous) carbon from the gasification of liquid hydrocarbons or petroleum coke in a reactor in which the carbon partially oxidizes to gaseous compounds and the formation of vanadium (V) oxide is prevented.
- Residues containing vanadium arise, for example, from the gasification of viscous residues in oil refineries.
- Another example of such residues is soot, which is formed during the partial oxidation of hydrocarbons and is obtained during the rough cleaning of the raw gas generated by the partial oxidation, for example in the form of soot water.
- soot and soot water is described in detail in Ullmann 's Encyclopedia of Industrial Chemistry, 5th edition, volume A 12, pages 207 to 209.
- EP-B-0 542 322 discloses a process for the treatment of vanadium-containing residues which consist of at least 5% by weight (anhydrous) of carbon and are thermally treated in an oven at temperatures of 500 to 1300 ° C., the residues are passed in the furnace through a temperature range above 700 ° C., the oxygen partial pressure in this range is at most 10 "2 bar and the formation of vanadium (V) oxide is suppressed.
- the solid mixture withdrawn from the furnace contains at least 5% by weight % Vanadium oxide in the form of vanadium (III) and / or vanadium (V) oxide.
- the exhaust gas containing carbon monoxide formed in this process requires extensive treatment in order to be able to release it into the atmosphere without damage. Another disadvantage is that to see that the oven must be comparatively large and complex if the process is to be operated, in particular in the low temperature range up to 800 ° C.
- This object is achieved in that the amount of the residues and the added oxidizing agent are fed to the reactor in such a ratio that reaction temperatures of 950 to 1600 ° C., preferably 1300 to 1500 ° C., and that a gas is generated, that at least 70 vol .-% (water and nitrogen free) consists of carbon monoxide and hydrogen. Only so much oxygen is added to the residues that the carbon contained in the residues is essentially converted into carbon monoxide and hydrogen and only a little carbon dioxide is produced. In order to promote the partial oxidation of the carbon contained in the residues and to form hydrogen, steam is additionally fed to the reactor.
- the partial oxidation of the residues is expediently carried out in reactors such as fluidized bed reactors with a stationary or circulating fluidized bed or entrained-flow reactors.
- soot gasification with the soot producing System is spatially connected to use the same gasification agent as in the main system.
- This is usually an oxygen-vapor mixture.
- the residues are expediently predried by reducing the residual moisture to 0 to 200% (based on the dry substance) in order to maintain the free-flowing properties of the residues.
- the residual moisture is preferably 30 to 70% (based on the dry substance), since, depending on the nature of the residues for the subsequent partial oxidation, this is close to the optimum and thus the need for external steam supply is reduced to a minimum.
- the gaseous compounds produced are cooled either indirectly to temperatures of 25 to 800 ° C. or directly to temperatures of 150 to 300 ° C.
- the ash is separated off at a temperature above the dew point of the gaseous compounds in order to prevent the ash from sticking.
- the gas generated by the method according to the invention has such a high calorific value that it can be used either as a direct heating gas or after further treatment as a synthesis gas
- the method according to the invention also offers the possibility of achieving a significant simplification of an entire oil gasification system in that the solids are obtained dry directly from the gas phase in the oil gasification. As a result, the complex washing water cycle from the known process for oil gasification can be avoided.
- the method according to the invention permits further processing of dry soot by pneumatically conveying the soot into the subsequent reactor without further processing steps, this not precluding intermediate storage in a closed container.
- FIG. 1 shows a process flow diagram for processing soot water from an oil gasification.
- FIG. 2 shows a process flow diagram for processing soot from a dry gas filtration
- a soot-containing wastewater is created, which is fed via line (1) to a filter (2), from which the soot-free water is drawn off via line (3) and returned to the oil gasification.
- the filter cake formed is fed via line (4) to a steam-heated fluidized bed dryer (5), in which the soot is brought to a residual moisture of 50% (based on the dry matter) in order to remain free-flowing.
- the dried residue is fed via line (6) to the entrained flow reactor (8).
- the moisture removed from the residue is discharged from the fluidized bed dryer (5) via line (7).
- the entrained flow reactor (8) is charged with oxygen via line (9) and hydrogen via line (10).
- the carbon in the residue reacts with oxygen and hydrogen to form synthesis gas, which essentially consists of hydrogen and carbon monoxide.
- the vanadium oxide present in the residue in the form of vanadium (III) oxide and vanadium (IV) oxide remains unchanged and solid, ie it does not become liquid at these temperatures.
- the synthesis gas generated in the entrained flow reactor (8) has a temperature of 950 to 1600 ° C and is cooled via indirect heat exchange by means of a cooling coil (12) arranged in the entrained flow reactor (8).
- the syngas cooled to a temperature of 25 to 800 ° C leaves the entrained flow reactor (8) via line (11) and arrives in the solids separator (13), which is a ceramic filter, sintered metal candle filter, bag filter and cyclone, for example, by removing the soot-poor ash from the Syngas removed and discharged via line (15).
- the synthesis gas delivered via line (14) is used.
- residual oil is fed via line (21) together with oxygen via line (22) and water vapor via line (23) to a reactor (24) in which the residual oil is gasified.
- the synthesis gas thus formed loaded with ash and soot, passes via line (25) into the gas cooler (26), in which cooling to a temperature of 150 to 800 ° C takes place. It is important that the cooling does not fall below the dew point of the gas, because otherwise the soot will become sticky and may clog the downstream solids filter (28).
- the cooled synthesis gas is fed via line (27) to the solids filter (28) and freed of soot and ash in this.
- the gas is discharged from the solids filter (28) via line (29).
- the soot is fed via line (30) together with the oxygen supplied via line (32) and water vapor supplied via line (33) to the soot gasification reactor (31), the ratio of these components being adjusted so that a reaction temperature of 950 to 1600 ° C.
- This in the soot gasification reactor (31) gas enters via a neck (34) into the quench part (35) of the soot gasification reactor (31), in which the gas is heated to a temperature of 150 to 300 ° C. by adding water supplied via line (36) is cooled.
- the water vapor-saturated gas freed from ash emerges via line (37) and is used for other purposes.
- the quench water loaded with low-ashes ash is fed via line (38) to a filter system (39) in which the ash is separated from the water.
- the ash is discharged via line (40); the quench water leaves the filter device (39) via line (41) and is returned to the quench.
- 70 t / h of heavy oil are gasified at a pressure of 60 bar and a temperature of 1300 ° C.
- the soot water produced in a quantity of 50 m 3 / h contains 350 kg / h carbon and 90 kg / h ash.
- the soot water is passed over the filter (2) and the 80% by weight water-formed filter cake which, in addition to carbon, also contains 9.55% by weight vanadium, 2.54% by weight nickel, 0.81% by weight.
- % Iron and 6.75% by weight of other substances is fed to the fluidized bed dryer (5), in which most of the water is expelled.
- the discharge (6) of the fluidized bed dryer has a residual moisture content of 50% by weight (based on the dry matter), ie 660 kg / h of residue are discharged, of which 220 kg / h of water, 350 kg / h of carbon and 90 kg / h Ash.
- This residue is gasified with 189 m 3 n / h (dry) oxygen at atmospheric pressure and a temperature of 1450 ° C. in the entrained flow reactor (8). 870 m 3 n / h (dry) of useful gas are produced which, after flowing through the solids separator (13), are discharged via line (14) and have the composition given in table (1).
- 94.4 kg / h of ash which has the composition given in Table 2, are drawn off from the solids separator (13).
- Residual oil is gasified in the reactor (24) in the presence of oxygen and hydrogen in such a way that, at a pressure of 60 bar, 225,000 m 3 n / h moist raw gas containing 350 kg / h soot and 90 kg / h ash is produced become.
- the raw gas which has a dew point of 150 ° C., is cooled to 340 ° C. with the generation of steam at a pressure of 100 bar in the synthesis gas cooler (26) and then fed to the filter (28).
- the solids separated in the filter are conveyed to the soot gasification reactor (31) by means of 345 m 3 n / h nitrogen, in which the solids with 217 m 3 n / h oxygen and 213 kg / h steam at a pressure of 5 bar and a temperature of 1500 ° C.
- the composition of the cooled useful gas discharged via line (41) and cleaned of solids is given in Table 3.
- the amount of useful gas is 1233 m 3 n / h. 94.2 kg / h of ash product having the composition given in Table 4 are drawn off from the filter (39).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Industrial Gases (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2001152686 DE10152686B4 (de) | 2001-10-19 | 2001-10-19 | Verfahren zur thermischen Behandlung von Vanadium enthaltenden Rückständen |
DE10152686.5 | 2001-10-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003035804A1 true WO2003035804A1 (fr) | 2003-05-01 |
Family
ID=7703684
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/011236 WO2003035804A1 (fr) | 2001-10-19 | 2002-10-08 | Procede de traitement thermique de residus contenant du vanadium |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE10152686B4 (fr) |
WO (1) | WO2003035804A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010033935B4 (de) | 2010-08-10 | 2013-01-17 | Lurgi Gmbh | Brenner und Verfahren für die partielle Oxidation von flüssigem, kohlenstoffhaltigem Brennstoff |
DE102011014221A1 (de) | 2011-03-17 | 2012-09-20 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Verfahren zur Gewinnung von Schwermetallen aus Rußwasser |
EP3438042A1 (fr) * | 2017-08-03 | 2019-02-06 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Captage du noir de carbon dans la production de gaz de synthèse |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0542322A1 (fr) * | 1991-11-13 | 1993-05-19 | METALLGESELLSCHAFT Aktiengesellschaft | Procédé pour le traitement d'un résidu contenant du vanadium |
EP0606957A1 (fr) * | 1993-01-14 | 1994-07-20 | Shell Internationale Researchmaatschappij B.V. | Procédé d'élimination de carbone par grillage |
EP0686598A2 (fr) * | 1994-05-11 | 1995-12-13 | Norsk Hydro A/S | Procédé pour l'oxydation partielle d'une charge d'hydrocarbures |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE8400092L (sv) * | 1984-01-10 | 1985-07-11 | T G Owe Berg | Forfarande for forbrenning av kol utan utslepp av kolets skadliga emnen |
DE4017089C3 (de) * | 1990-05-26 | 1996-10-17 | Menges Georg | Verfahren und Vorrichtung zum Vegasen von Kunststoffen zur Erzeugung von Synthesegas |
DE4114171A1 (de) * | 1991-04-30 | 1992-11-05 | Loesche Gmbh | Spiralstromfeuerung |
ES2154316T3 (es) * | 1994-05-11 | 2001-04-01 | Norsk Hydro As | Procedimiento para la oxidacion parcial de un material de alimentacion de hidrocarburos. |
DE4446803C2 (de) * | 1994-12-24 | 1998-05-28 | Krc Umwelttechnik Gmbh | Verfahren und Vorrichtung zur thermischen und stofflichen Verwertung von Rest- und Abfallstoffen |
DE19622153A1 (de) * | 1996-06-01 | 1997-12-04 | Krupp Uhde Gmbh | Verfahren zur Erzeugung eines metallurgischen Rohstoffs |
-
2001
- 2001-10-19 DE DE2001152686 patent/DE10152686B4/de not_active Expired - Fee Related
-
2002
- 2002-10-08 WO PCT/EP2002/011236 patent/WO2003035804A1/fr not_active Application Discontinuation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0542322A1 (fr) * | 1991-11-13 | 1993-05-19 | METALLGESELLSCHAFT Aktiengesellschaft | Procédé pour le traitement d'un résidu contenant du vanadium |
EP0606957A1 (fr) * | 1993-01-14 | 1994-07-20 | Shell Internationale Researchmaatschappij B.V. | Procédé d'élimination de carbone par grillage |
EP0686598A2 (fr) * | 1994-05-11 | 1995-12-13 | Norsk Hydro A/S | Procédé pour l'oxydation partielle d'une charge d'hydrocarbures |
Also Published As
Publication number | Publication date |
---|---|
DE10152686A1 (de) | 2003-05-08 |
DE10152686B4 (de) | 2004-09-23 |
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