EP0441677A1 - Process for stabilising catalytically cracked gasoils, obtained gasoils and compositions containing this stabilised gasoil - Google Patents

Process for stabilising catalytically cracked gasoils, obtained gasoils and compositions containing this stabilised gasoil Download PDF

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Publication number
EP0441677A1
EP0441677A1 EP91400204A EP91400204A EP0441677A1 EP 0441677 A1 EP0441677 A1 EP 0441677A1 EP 91400204 A EP91400204 A EP 91400204A EP 91400204 A EP91400204 A EP 91400204A EP 0441677 A1 EP0441677 A1 EP 0441677A1
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Prior art keywords
weight
diesel
lco
alcohol
gasoils
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EP91400204A
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German (de)
French (fr)
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EP0441677B1 (en
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André Ciais
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Elf Antar France
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Elf Antar France
Elf France SA
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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
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
    • 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
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
    • C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step

Definitions

  • This invention relates to a method for stabilizing gas oils from catalytic cracking.
  • Heavy distillates from petroleum refineries cannot be used as is. These heavy distillates are subjected to a treatment by catalytic cracking in a fluidized bed. This treatment makes it possible to recover a fraction of liquefied petroleum gas or LPG, a large fraction of petrol, then an intermediate fraction corresponding to a diesel cut.
  • This cut of diesel, from catalytic cracking is usually called LCO, after the English name "light cycle oil”. For simplicity we will use the abbreviation LCO.
  • the LCO is lower in the distillation range and less viscous than direct distillation diesel. Because of its high aromatic content, it is also denser.
  • LCOs According to their sulfur content, LCOs are classified as LCO-BTS or low sulfur content and LCO-HTS or high sulfur content. Products with a sulfur content of less than 1% are usually classified in LCO-BTS. Traditionally, LCO was used to dilute distillation residues intended to constitute heavy fuel oils and to adjust their viscosity to the value of the specifications. In France this value must be less than or equal to 4.10 ⁇ 6m2 / s at 100 ° C for fuel oil n ° 2.
  • LCOs with a high sulfur content are still mainly used as diluents or fluxes for heavy fuel oils, LCOs with low sulfur content are starting to enter the composition of gas oils.
  • Diesel fuels have two main uses, the first is thermal use, as domestic fuel intended to be burned in boilers, the second is the use as fuels in Diesel engines. They are then marketed under the name of diesel fuel.
  • diesel fuels require meeting stringent specifications so that the combustion and ignition in the engines are satisfactory.
  • the diesel fuel must have a cetane number of at least 48, which limits the introduction of large quantities of LCO into the diesel fuel, the LCOs having too low a cetane number.
  • LCOs are therefore mainly used in the composition of heating oil, where in principle their use is limited only by their sulfur content.
  • Condensed rings can contain heteroatoms, such as indole, isoindazole, benzoxazole, carbazole and anthranile.
  • the precipitation of the gums is accentuated when mixing the LCO with gas oils.
  • the highly aromatic nature of LCO makes it possible to dissolve aromatic heterocycles, even already oxidized.
  • the highly coloring compounds insoluble in alkanes precipitate.
  • Non-aromatic secondary or tertiary amines are generally used, with which metal deactivators, such as N, N′-disalicylidene propane-1,2-diamine and / or dispersants such as polyacrylates or polymethacrylates.
  • metal deactivators such as N, N′-disalicylidene propane-1,2-diamine and / or dispersants such as polyacrylates or polymethacrylates.
  • FOA 3 9 and 310 from DUPONT de NEMOURS
  • KEROPON 5257 from BASF
  • HITEC 4235 from ETHYL CORP.
  • the gas oils treated according to the invention are more resistant to oxidation, which results in a reduction in the precipitates and in the development of the color.
  • the treated diesel also loses its foul odor. It is usually more stable when mixed with paraffinic cups.
  • the treatment of LCO has a favorable effect on the quality of mixtures, such as diesel and domestic fuel oils. These mixtures have a cetane number and a combustion quality in better diesel engines.
  • the stability of the LCOs treated according to the invention can be further improved by the usual additives.
  • the treatment makes LCO more sensitive to the action of antioxidant and stabilizing additives, which greatly reduce the formation of precipitates and also improve color.
  • This process can also be used for the treatment of already oxidized gas oils, for example from long-term storage. These oxidized gas oils regain their original appearance and quality.
  • the stabilization process according to the invention of gas oils from catalytic cracking, already oxidized or not consists of a liquid-liquid extraction of said gas oil with a mixture of alcohol and water followed by the separation of the gas oil and the extract alcoholic.
  • the alcohol used is generally a linear or branched Cip to C6 aliphatic alcohol.
  • methanol is used.
  • This alcohol-water mixture represents 15 to 35% by weight and preferably 20 to 30% by weight of diesel.
  • the water content of the alcohol is variable depending on the composition of the diesel to be treated.
  • the alcohol-water mixture generally contains 1 to 10% by weight and preferably between 3 and 7% by weight of water.
  • the effectiveness of the treatment can be increased by replacing the water with an aqueous sodium hydroxide solution.
  • This aqueous solution contains between 10 and 30% by weight and preferably between 15 and 25% by weight of soda.
  • the extraction according to the invention can be combined with other treatments, such as meroxing or hydrotreating.
  • the hydrotreatment may be milder and require a lower hydrogen pressure than the hydrotreatment of a feedstock not previously extracted.
  • the hydrogen pressure being lower, the coking of the catalyst decreases and its lifetime increases at the same time.
  • hydrogen consumption will also be lower.
  • the extraction is carried out in an extractor operating at cocurrent or countercurrent, continuously or discontinuously.
  • the operating parameters are the temperature, the pressure, the duration of the extraction and the quantity of the solvent.
  • the efficiency of the extractor must correspond to at least 10 theoretical stages.
  • the mixture After extraction, the mixture is sent to a decanter, where it separates into two phases.
  • the supernatant phase consists of the alcoholic extract of polar aromatic compounds, sources of instability. It also contains water or aqueous soda.
  • the decanted phase consists of stabilized LCO containing traces of methanol.
  • the supernatant phase is subjected in a column to a "flash" distillation to remove the methanol. Then the water or the aqueous sodium hydroxide are separated by decantation. After washing followed by decantation, the aromatic extract can be added to heavy fuel oils. If aqueous sodium hydroxide is used for extraction, the latter is sent to a column to remove the volatile compounds. The aqueous sodium hydroxide recovered at the bottom of this column is recycled in the process with the addition of fresh sodium hydroxide.
  • the decanted phase consisting of LCO
  • the decanted phase is washed to remove traces of methanol. After decantation, the stabilized LCO is recovered. The washing water is subjected to "flash" distillation to recover the methanol. All of the methanol recovered in the process can be recycled.
  • the proportions of stabilized LCO and aromatic extract vary depending on the composition of the treated LCO. In general, the amount of aromatic compounds eliminated varies between 3 and 5%. 95 to 97% by weight of stabilized LCO is therefore recovered.
  • the stabilized LCO according to the invention is added to the direct distillation diesel.
  • the compositions contain a major proportion of direct distillation diesel and 10 to 30% by weight and preferably 15 to 25% by weight of a diesel fuel produced from catalytic cracking, stabilized according to the invention.
  • compositions have good oxidation stability during storage.
  • compositions are very sensitive to the action of additives.
  • compositions according to the invention are more stable and respond better to the effect of antioxidants than that formed with LCO untreated.
  • antioxidants generally between 0.0001 and 1% and preferably between 0.001 and 0.02% by weight are sufficient.
  • Table 1 shows the characteristics of the LCO before treatment:
  • the solvent contains 97% methanol and 3% 5N aqueous sodium hydroxide.
  • the extractor is a rotating cone device using liquid-liquid thin film exchange. It is used discontinuously.
  • the temperature in the extractor is 20 ° C, the residence time is 1 minute.
  • the mixture is sent to the decanter where it separates into two phases.
  • the supernatant phase is separated and subjected to "flash" distillation to recover the methanol.
  • Compounds aromatic extracts are separated by decantation from the aqueous sodium hydroxide. After washing with water, followed by separation by decantation, 30 g of aromatic compounds are recovered.
  • the decanted phase is washed with water to recover the traces of methanol. After decantation, 768 g of LCO are recovered.
  • Table 2 summarizes the contents of basic nitrogen (NB), total nitrogen (NT) and sulfur (S) of the LCO before and after extraction, as well as the same contents for the aromatic extract.
  • the color is measured by comparison with a color scale, according to standard ASTM-D-1500.
  • the total nitrogen and especially the basic nitrogen, responsible for the instability is concentrated in the extract.
  • compositions containing 70% of direct distillation diesel (GO) and 30% of untreated LCO and of LCO treated according to the invention are subjected to an accelerated aging process to measure their stability.
  • This accelerated aging process is derived from the ASTM D-2274 method.
  • the 350 ml sample is subjected in a glass tube to oxidation at 120 ° C for two hours, under a flow of pure oxygen of 3 l / h. Oxygen bubbled through the sample. After which the tube is cooled to room temperature and its contents filtered through a cellulose acetate filter whose diameter is 4.7 cm and the porosity of 800nm (8.10 ⁇ 7m).
  • the weighing after washing with pentane and drying gives the amount of insoluble gums in the sample, which is brought back to a value in mg / 100l.
  • the tube rinsed with pentane is then washed with a trisolvent (toluene, acetone, methanol, one third of each) intended to dissolve the gums which have adhered to the tube.
  • a trisolvent toluene, acetone, methanol, one third of each
  • the residue obtained is weighed. It corresponds to the quantity of adherent gums for 350ml of diesel. This value is reduced to 100ml of diesel.
  • the sum (insoluble gums + adherent gums) is called potential gums or total gums.
  • the antioxidant used in our experiments is a mixture of 36 ppm of an additive consisting of non-aromatic amines, FOA-3 from DUPONT and 4 ppm of a metal deactivator, DMD from DUPONT.
  • Table 3 shows the stability of the LCO treated according to the invention, both alone and as a mixture with direct distillation gas oils.
  • the treated LCO also reacts better to the effect of antioxidants.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Abstract

Process for stabilising gas oils originating from catalytic cracking, by extraction with an alcohol-water mixture. A linear or branched C1-C6 aliphatic alcohol is generally employed, and preferably methanol. The treated gas oils are more resistant to oxidation and more stable as a mixture with paraffinic cuts.

Description

Cette invention concerne un procédé de stabilisation des gazoles issus du craquage catalytique.This invention relates to a method for stabilizing gas oils from catalytic cracking.

Les schémas de raffinage ont fortement évolué ces dernières années avec la généralisation des craqueurs catalytiques et viscoréducteurs.Refining schemes have evolved considerably in recent years with the spread of catalytic crackers and visbreakers.

Les distillats lourds des raffineries de pétrole ne peuvent pas être utilisés en l'état. Ces distillats lourds sont soumis à un traitement par craquage catalytique en lit fluidisé. Ce traitement permet de récupérer une fraction de gaz de pétrole liquéfié ou GPL, une fraction importante d'essence, puis une fraction intermédiaire correspondant à une coupe gazole. Cette coupe de gazole, issu de craquage catalytique est appelé habituellement LCO, d'après la dénomination anglaise "light cycle oil". Pour plus de simplicité nous utiliserons l'abréviation LCO.Heavy distillates from petroleum refineries cannot be used as is. These heavy distillates are subjected to a treatment by catalytic cracking in a fluidized bed. This treatment makes it possible to recover a fraction of liquefied petroleum gas or LPG, a large fraction of petrol, then an intermediate fraction corresponding to a diesel cut. This cut of diesel, from catalytic cracking is usually called LCO, after the English name "light cycle oil". For simplicity we will use the abbreviation LCO.

De façon générale le LCO est plus bas en intervalle de distillation et moins visqueux que le gazole de distillation directe. A cause de sa haute teneur en aromatique, il est également plus dense.In general, the LCO is lower in the distillation range and less viscous than direct distillation diesel. Because of its high aromatic content, it is also denser.

Selon leur teneur en soufre, les LCO sont classés en LCO-BTS ou basse teneur en soufre et en LCO-HTS ou haute teneur en soufre. On classe habituellement dans les LCO-BTS des produits dont la teneur en soufre est inférieure à 1%.
Traditionnellement, le LCO était utilisé pour diluer des résidus de distillation destinés à constituer les fiouls lourds et ajuster leur viscosité à la valeur des spécifications. En France cette valeur doit être inférieure ou égale à 4.10⁻⁶m²/s à 100°C pour le fioul n°2.According to their sulfur content, LCOs are classified as LCO-BTS or low sulfur content and LCO-HTS or high sulfur content. Products with a sulfur content of less than 1% are usually classified in LCO-BTS.
Traditionally, LCO was used to dilute distillation residues intended to constitute heavy fuel oils and to adjust their viscosity to the value of the specifications. In France this value must be less than or equal to 4.10⁻⁶m² / s at 100 ° C for fuel oil n ° 2.

Aujourd'hui, on assiste conjointement à l'augmentation de la capacité de craquage catalytique et surtout des quantités de distillat lourd traitées et à la diminution du marché du fioul lourd.Today, we are jointly witnessing an increase in catalytic cracking capacity and especially the quantities of heavy distillate processed and a decrease in the heavy fuel oil market.

Ainsi, si les LCO à haute teneur en soufre sont toujours surtout utilisés comme diluants ou fluxants des fiouls lourds, les LCO à basse teneur en soufre commencent à entrer dans la composition des gazoles.Thus, if LCOs with a high sulfur content are still mainly used as diluents or fluxes for heavy fuel oils, LCOs with low sulfur content are starting to enter the composition of gas oils.

Les gazoles ont deux utilisations principales, la première est l'utilisation thermique, comme fioul domestique destiné à être brûlé dans les chaudières, la seconde est l'utilisation comme carburants dans les moteurs Diesel. Ils sont alors commercialisés sous le nom de gazole moteur.Diesel fuels have two main uses, the first is thermal use, as domestic fuel intended to be burned in boilers, the second is the use as fuels in Diesel engines. They are then marketed under the name of diesel fuel.

L'utilisation des gazoles comme carburant impose de répondre à des spécifications contraignantes pour que la combustion et l'inflammation dans les moteurs soient satisfaisantes. Pour cela, le carburant Diesel doit posséder un indice de cétane d'au moins 48, ce qui limite l'introduction de grandes quantités de LCO dans le gazole moteur, les LCO possédant un trop faible indice de cétane.The use of diesel fuels as a fuel requires meeting stringent specifications so that the combustion and ignition in the engines are satisfactory. For this, the diesel fuel must have a cetane number of at least 48, which limits the introduction of large quantities of LCO into the diesel fuel, the LCOs having too low a cetane number.

Les LCO entrent donc principalement dans la composition des fiouls domestiques où en principe leur utilisation n'est limitée que par leur teneur en soufre.LCOs are therefore mainly used in the composition of heating oil, where in principle their use is limited only by their sulfur content.

Cependant, l'incorporation des LCO aussi bien dans les gazoles que dans les fiouls domestiques pose un problème sérieux à cause du manque de stabilité de ces produits. En effet, les coupes LCO s'avèrent être évolutives. Lors de leur stockage, des réactions d'oxydation qui se produisent se manifestent par la formation de gommes et l'évolution de la couleur du jaune clair ou brun foncé ou même noir.However, the incorporation of LCOs in both diesel and domestic fuel oils poses a serious problem due to the lack of stability of these products. Indeed, LCO cuts are proving to be scalable. During their storage, oxidation reactions that occur are manifested by the formation of gums and the development of the color of light yellow or dark brown or even black.

Les gommes formées précipitent et sédimentent partiellement et sont alors appelées gommes insolubles ou se déposent sur les parois des éléments de stockage, elles sont alors désignées sous le nom de gommes adhérentes. La somme de ces deux catégories de gommes est appelée gomme totale.The gums formed precipitate and partially sediment and are then called insoluble gums or are deposited on the walls of the storage elements, they are then designated under the name of adherent gums. The sum of these two categories of gum is called total gum.

On ne connait pas la nature exacte des composés évolutifs, responsables de l'évolution de la couleur et de la formation de gommes. Il s'agit surement, au moins en partie, de composés aromatiques à cycles condensés, comme l'indène, le phenalène ou l'azulène. Les cycles condensés peuvent renfermer des hetéroatomes, comme l'indole, l'isoindazole, le benzoxazole, le carbazole et l'anthranile.We do not know the exact nature of the evolutionary compounds responsible for the development of color and the formation of gums. It is surely, at least in part, aromatic compounds with condensed rings, such as indene, phenalene or azulene. Condensed rings can contain heteroatoms, such as indole, isoindazole, benzoxazole, carbazole and anthranile.

Ces composés, surtout ceux renfermant des hetéroatomes sont sensibles à l'oxydation et peuvent être responsables de l'instabilité des LCO.These compounds, especially those containing heteroatoms, are sensitive to oxidation and may be responsible for the instability of LCOs.

La précipitation des gommes s'accentue lors de mélanges du LCO avec des gazoles. La nature fortement aromatique du LCO permet de solubiliser les hétérocycles aromatiques, même déjà oxydés. Par contre, lors de mélanges du LCO avec des coupes paraffiniques, comme les gazoles, les composés très colorants insolubles dans les alcanes précipitent.The precipitation of the gums is accentuated when mixing the LCO with gas oils. The highly aromatic nature of LCO makes it possible to dissolve aromatic heterocycles, even already oxidized. On the other hand, when mixing the LCO with paraffinic cuts, such as gas oils, the highly coloring compounds insoluble in alkanes precipitate.

Il est possible de stabiliser le LCO par hydrotraitement. Ce procédé suppose la disponibilité de capacités d'hydrotraitement et d'importantes quantités d'hydrogène, ce qui peut poser un problème dans certaines raffineries.It is possible to stabilize the LCO by hydrotreatment. This process assumes the availability of hydrotreatment capacities and large quantities of hydrogen, which can pose a problem in certain refineries.

Il est également possible d'augmenter la stabilité des LCO par l'utilisation d'additifs à effet antioxydant.It is also possible to increase the stability of LCO by the use of additives with antioxidant effect.

On utilise en général des mélanges d'amines secondaires ou tertiaires non-aromatiques, auxquels sont parfois associés des désactivateurs de métaux, comme la N,N′-disalicylidène propane-1,2-diamine et/ou des dispersants comme les polyacrylates ou les polyméthacrylates. On peut citer parmi les additifs commerciaux utilisés les FOA 3, 11 et 310 de DUPONT de NEMOURS, le KEROPON 5257 de BASF et l'HITEC 4235 d'ETHYL CORP.Mixtures of non-aromatic secondary or tertiary amines are generally used, with which metal deactivators, such as N, N′-disalicylidene propane-1,2-diamine and / or dispersants such as polyacrylates or polymethacrylates. Among the commercial additives used, mention may be made of FOA 3, 11 and 310 from DUPONT de NEMOURS, KEROPON 5257 from BASF and HITEC 4235 from ETHYL CORP.

Les additifs retardent mais n'empêchent pas la formation et la précipitation des gommes. Ils sont pratiquement sans effet sur l'évolution de la couleur.Additives delay but do not prevent the formation and precipitation of gums. They have practically no effect on the evolution of color.

Nous avons trouvé maintenant un procédé de stabilisation des gazoles issus de craquage catalytique. Les gazoles traités selon l'invention sont plus résistants à l'oxydation, ce qui se traduit par une diminution des précipités et de l'évolution de la couleur. Le gazole traité perd aussi son odeur nauséabonde. Il est généralement plus stable en mélange avec des coupes paraffiniques. Le traitement des LCO a un effet favorable sur la qualité des mélanges, comme les gazoles moteur et les fiouls domestiques.
Ces mélanges ont un indice de cétane et une qualité de combustion dans les moteurs diesel meilleurs.We have now found a process for stabilizing gas oils from catalytic cracking. The gas oils treated according to the invention are more resistant to oxidation, which results in a reduction in the precipitates and in the development of the color. The treated diesel also loses its foul odor. It is usually more stable when mixed with paraffinic cups. The treatment of LCO has a favorable effect on the quality of mixtures, such as diesel and domestic fuel oils.
These mixtures have a cetane number and a combustion quality in better diesel engines.

En absence d'impuretés, l'action des additifs de comportement à froid est amélioré, la durée de vie des filtres diesel augmente et le gommage des injecteurs diminue.In the absence of impurities, the action of cold behavior additives is improved, the service life of diesel filters increases and the gumming of the injectors decreases.

La stabilité des LCO traités selon l'invention peut encore être améliorée par les additifs usuels. Le traitement rend les LCO plus sensible à l'action des additifs antioxydants et stabilisants qui diminuent fortement la formation des précipités et améliorent également la couleur.The stability of the LCOs treated according to the invention can be further improved by the usual additives. The treatment makes LCO more sensitive to the action of antioxidant and stabilizing additives, which greatly reduce the formation of precipitates and also improve color.

Nous avons vu que les additifs sont sans effet sur l'évolution de la couleur des LCO non traités selon l'invention.We have seen that the additives have no effect on the development of the color of the LCOs not treated according to the invention.

Ce procédé peut également être utilisé pour le traitement de gazoles déjà oxydés, par exemple issus de stockage longue durée. Ces gazoles oxydés retrouvent leur aspect et qualité d'origine.This process can also be used for the treatment of already oxidized gas oils, for example from long-term storage. These oxidized gas oils regain their original appearance and quality.

Le procédé de stabilisation selon l'invention des gazoles issus de craquage catalytique, déjà oxydé ou non, consiste en une extraction liquide-liquide dudit gazole avec un mélange d'alcool et d'eau suivi de la séparation du gazole et de l'extrait alcoolique.The stabilization process according to the invention of gas oils from catalytic cracking, already oxidized or not, consists of a liquid-liquid extraction of said gas oil with a mixture of alcohol and water followed by the separation of the gas oil and the extract alcoholic.

Les gazoles issus de craquage catalytiques sont très fortement aromatiques. Une extraction complète de leur teneur en aromatiques avec un alcool pur ne serait pas une opération économiquement viable.Gas oils from catalytic cracking are very strongly aromatic. A complete extraction of their aromatic content with pure alcohol would not be an economically viable operation.

La présence de l'eau permet de limiter le pouvoir solvant de l'alcool. La quantité d'eau doit être ajustée de façon à n'extraire que des composés aromatiques fortement polaires, responsables de l'instabilité et à éviter des pertes de composés aromatiques qui ne contribuent pas à cette instabilité.The presence of water limits the solvent power of the alcohol. The amount of water must be adjusted so as to extract only strongly polar aromatic compounds responsible for instability and to avoid losses of aromatic compounds which do not contribute to this instability.

L'alcool utilisé est en général un alcool aliphatique linéaire ou ramifié en C₁ à C₆. On utilise avantageusement le méthanol.The alcohol used is generally a linear or branched Cip to C₆ aliphatic alcohol. Advantageously, methanol is used.

Ce mélange alcool-eau représente 15 à 35% poids et de préférence 20 à 30% poids du gazole.This alcohol-water mixture represents 15 to 35% by weight and preferably 20 to 30% by weight of diesel.

La teneur en eau de l'alcool est variable en fonction de la composition du gazole à traiter. Le mélange alcool-eau renferme en général en 1 à 10% poids et de préférence entre 3 et 7% poids d'eau.The water content of the alcohol is variable depending on the composition of the diesel to be treated. The alcohol-water mixture generally contains 1 to 10% by weight and preferably between 3 and 7% by weight of water.

L'efficacité du traitement peut être augmenté par le remplacement de l'eau par une solution aqueuse de soude. Cette solution aqueuse renferme entre 10 et 30% poids et de préférence entre 15 et 25% poids de soude.The effectiveness of the treatment can be increased by replacing the water with an aqueous sodium hydroxide solution. This aqueous solution contains between 10 and 30% by weight and preferably between 15 and 25% by weight of soda.

Si les charges renferment des quantités très importantes de produits soufrés, ce qui est le cas pour les LCO-HTS, l'extraction selon l'invention peut être combinée avec d'autres traitements, comme le meroxage ou l'hydrotraitement.
Dans ce cas, l'hydrotraitement pourra être plus doux et nécessiter une pression d'hydrogène plus faible que l'hydrotraitement d'une charge non-extraite au préalable.
La pression d'hydrogène étant plus faible, le cokage du catalyseur diminue et sa durée de vie augmente en même temps. Bien évidemment, la consommation d'hydrogène sera également plus faible.If the fillers contain very large quantities of sulfur-containing products, which is the case for LCO-HTS, the extraction according to the invention can be combined with other treatments, such as meroxing or hydrotreating.
In this case, the hydrotreatment may be milder and require a lower hydrogen pressure than the hydrotreatment of a feedstock not previously extracted.
The hydrogen pressure being lower, the coking of the catalyst decreases and its lifetime increases at the same time. Of course, hydrogen consumption will also be lower.

L'extraction est mise en oeuvre dans un extracteur fonctionnant à cocourant ou à contrecourant, de façon continu ou discontinu.The extraction is carried out in an extractor operating at cocurrent or countercurrent, continuously or discontinuously.

Diverses technologies peuvent être appliquées, comme les colonnes à plateaux, le colonnes à remplissage ou les extracteurs utilisant le principe de l'échange liquide-liquide en film mince.Various technologies can be applied, such as tray columns, filling columns or extractors using the principle of liquid-liquid exchange in thin film.

Pour un extracteur donné, les paramètres opératoires sont la température, la pression, la durée de l'extraction et la quantité du solvant.For a given extractor, the operating parameters are the temperature, the pressure, the duration of the extraction and the quantity of the solvent.

Afin d'éviter les pertes de calories, on s'efforce en général d'utiliser le LCO à la température de sortie du craqueur.
Dans ce cas les autres paramètres sont ajustés en fonction des spécifications visées.In order to avoid loss of calories, efforts are generally made to use the LCO at the outlet temperature from the cracker.
In this case the other parameters are adjusted according to the targeted specifications.

L'efficacité de l'extracteur doit correspondre à environ 10 étages théoriques au moins.The efficiency of the extractor must correspond to at least 10 theoretical stages.

Après extraction, le mélange est envoyé dans un décanteur, ou il se sépare en deux phases. La phase surnageante est constituée par l'extrait alcoolique des composés aromatiques polaires, sources d'instabilité. Elle renferme également l'eau ou la soude aqueuse. La phase décantée est constituée du LCO stabilisé contenant des traces de méthanol.After extraction, the mixture is sent to a decanter, where it separates into two phases. The supernatant phase consists of the alcoholic extract of polar aromatic compounds, sources of instability. It also contains water or aqueous soda. The decanted phase consists of stabilized LCO containing traces of methanol.

La phase surnageante est soumise dans une colonne à une distillation "flash" pour éliminer le méthanol. Ensuite l'eau ou la soude aqueuse sont séparées par décantation. Après un lavage suivi de décantation, l'extrait aromatique peut être ajouté aux fiouls lourds. En cas d'utilisation de soude aqueuse pour l'extraction, cette dernière est envoyée dans une colonne pour éliminer les composés volatils. La soude aqueuse récupéré en bas de cette colonne est recyclé dans le procédé avec un rajout de soude fraîche.The supernatant phase is subjected in a column to a "flash" distillation to remove the methanol. Then the water or the aqueous sodium hydroxide are separated by decantation. After washing followed by decantation, the aromatic extract can be added to heavy fuel oils. If aqueous sodium hydroxide is used for extraction, the latter is sent to a column to remove the volatile compounds. The aqueous sodium hydroxide recovered at the bottom of this column is recycled in the process with the addition of fresh sodium hydroxide.

La phase décantée, constituée de LCO, est lavée pour éliminer les traces de méthanol. Après décantation, on récupère le LCO stabilisé. L'eau de lavage est soumise à une distillation "flash" pour récupérer le méthanol. Tout le méthanol récupéré dans le procédé peut être recyclé.The decanted phase, consisting of LCO, is washed to remove traces of methanol. After decantation, the stabilized LCO is recovered. The washing water is subjected to "flash" distillation to recover the methanol. All of the methanol recovered in the process can be recycled.

Les proportions de LCO stabilisé et d'extrait aromatique varient en fonction de la composition du LCO traité. En général la quantité de composés aromatiques éliminée varie entre 3 et 5%. On récupère donc 95 à 97% poids de LCO stabilisé.The proportions of stabilized LCO and aromatic extract vary depending on the composition of the treated LCO. In general, the amount of aromatic compounds eliminated varies between 3 and 5%. 95 to 97% by weight of stabilized LCO is therefore recovered.

Le LCO stabilisé selon l'invention est ajouté au gazole de distillation directe. Les compositions renferment une proportion majeur de gazole de distillation directe et 10 à 30% poids et de préférence 15 à 25% poids d'un gazole issu de craquage catalytique, stabilisé selon l'invention.The stabilized LCO according to the invention is added to the direct distillation diesel. The compositions contain a major proportion of direct distillation diesel and 10 to 30% by weight and preferably 15 to 25% by weight of a diesel fuel produced from catalytic cracking, stabilized according to the invention.

Ces compositions présentent une bonne stabilité à l'oxydation pendant le stockage.These compositions have good oxidation stability during storage.

Toutefois, si la stabilité de cette composition était insuffisante, il est possible d'utiliser les additifs antioxydant habituels. Selon un aspect particulièrement avantageux de l'invention, ces compositions sont très sensibles à l'action des additifs.However, if the stability of this composition was insufficient, it is possible to use the usual antioxidant additives. According to a particularly advantageous aspect of the invention, these compositions are very sensitive to the action of additives.

Nous avons vu que les additifs étaient peu efficaces pour éviter l'évolution de la couleur des compositions renfermant du LCO.We have seen that the additives were not very effective in preventing the color development of the compositions containing LCO.

Si nous comparons l'évolution de la couleur ou la quantité de gommes formées après un traitement d'oxydation accélérée, nous constatons que les compositions selon l'invention sont plus stables et répondent mieux à l'effet des antioxydants que celle formée avec du LCO non-traité.If we compare the change in color or the quantity of gums formed after an accelerated oxidation treatment, we find that the compositions according to the invention are more stable and respond better to the effect of antioxidants than that formed with LCO untreated.

De très faibles quantités d'antioxydants, en général entre 0,0001 et 1% et de préférence entre 0,001 et 0,02% poids sont suffisantes.Very small amounts of antioxidants, generally between 0.0001 and 1% and preferably between 0.001 and 0.02% by weight are sufficient.

L'exemple suivant illustre l'invention sans toutefois la limiter. Sauf indication contraire tous les pourcentages sont en poids.The following example illustrates the invention without however limiting it. Unless otherwise indicated, all percentages are by weight.

EXEMPLEEXAMPLE

Le tableau 1 regroupe les caractéristiques du LCO avant traitement :

Figure imgb0001
Table 1 shows the characteristics of the LCO before treatment:
Figure imgb0001

On introduit dans l'extracteur 800g de LCO et 200g de solvant. Le solvant renferme 97% de méthanol et 3% de soude aqueuse 5N.800g of LCO and 200g of solvent are introduced into the extractor. The solvent contains 97% methanol and 3% 5N aqueous sodium hydroxide.

L'extracteur est un appareil à cône tournant utilisant l'échange liquide-liquide en film mince. Il est utilisé en discontinu.The extractor is a rotating cone device using liquid-liquid thin film exchange. It is used discontinuously.

La température dans l'extracteur est de 20°C, le temps de séjour est de 1 minute.The temperature in the extractor is 20 ° C, the residence time is 1 minute.

Après extraction, le mélange est envoyé dans le décanteur où il se sépare en deux phases.After extraction, the mixture is sent to the decanter where it separates into two phases.

La phase surnageante est séparée et soumise à une distillation "flash" pour récupérer le méthanol. Les composés aromatiques extraits sont séparés par décantation de la soude aqueuse. Après lavage à l'eau, suivi d'une séparation par décantation, on récupère 30g de composés aromatiques.The supernatant phase is separated and subjected to "flash" distillation to recover the methanol. Compounds aromatic extracts are separated by decantation from the aqueous sodium hydroxide. After washing with water, followed by separation by decantation, 30 g of aromatic compounds are recovered.

La phase décantée est lavée à l'eau pour récupérer les traces de méthanol. Après décantation on récupère 768g de LCO.The decanted phase is washed with water to recover the traces of methanol. After decantation, 768 g of LCO are recovered.

Le tableau 2 résume les teneurs en azote basique (NB), en azote totale (NT) et en soufre (S) du LCO avant et après extraction, ainsi que les mêmes teneurs pour l'extrait aromatique.Table 2 summarizes the contents of basic nitrogen (NB), total nitrogen (NT) and sulfur (S) of the LCO before and after extraction, as well as the same contents for the aromatic extract.

La couleur est mesurée par comparaison avec une échelle de couleur, selon la norme ASTM-D-1500.

Figure imgb0002
The color is measured by comparison with a color scale, according to standard ASTM-D-1500.
Figure imgb0002

L'azote total et surtout l'azote basique, responsable de l'instabilité se concentre dans l'extrait.The total nitrogen and especially the basic nitrogen, responsible for the instability is concentrated in the extract.

Nous avons préparé des compositions renfermant 70% de gazole de distillation directe (GO) et 30% de LCO non-traité et de LCO traité selon l'invention. Ces compositions sont soumises à un procédé de vieillissement accéléré pour mesurer leur stabilité. Ce procédé de vieillissement accéléré, dérive de la méthode ASTM D-2274. L'échantillon de 350ml est soumis dans un tube de verre à une oxydation à 120°C pendant deux heures, sous un débit d'oxygène pur de 3 l/h. L'oxygène barbote dans l'échantillon. Après quoi le tube est refroidi à la température ambiante et son contenu filtré sur un filtre acétate de cellulose dont le diamètre est de 4,7cm et la porosité de 800nm (8.10⁻⁷m). La pesée après lavage au pentane et séchage donne la quantité de gommes insolubles dans l'échantillon, qui est ramenée à une valeur en mg/100l.We have prepared compositions containing 70% of direct distillation diesel (GO) and 30% of untreated LCO and of LCO treated according to the invention. These compositions are subjected to an accelerated aging process to measure their stability. This accelerated aging process is derived from the ASTM D-2274 method. The 350 ml sample is subjected in a glass tube to oxidation at 120 ° C for two hours, under a flow of pure oxygen of 3 l / h. Oxygen bubbled through the sample. After which the tube is cooled to room temperature and its contents filtered through a cellulose acetate filter whose diameter is 4.7 cm and the porosity of 800nm (8.10⁻⁷m). The weighing after washing with pentane and drying gives the amount of insoluble gums in the sample, which is brought back to a value in mg / 100l.

Le tube rincé au pentane est ensuite lavé par un trisolvant (toluène, acétone, méthanol, un tiers de chaque) destiné à dissoudre les gommes ayant adhéré au tube. Après évaporation du trisolvant dans une coupelle, le résidu obtenu est pesé.
Il correspond à la quantité de gommes adhérentes pour 350ml de gazole. Cette valeur est ramenée à 100ml de gazole. La somme (gommes insolubles + gommes adhérentes) est appelée gommes potentielles ou gommes totales.The tube rinsed with pentane is then washed with a trisolvent (toluene, acetone, methanol, one third of each) intended to dissolve the gums which have adhered to the tube. After evaporation of the trisolvent in a dish, the residue obtained is weighed.
It corresponds to the quantity of adherent gums for 350ml of diesel. This value is reduced to 100ml of diesel. The sum (insoluble gums + adherent gums) is called potential gums or total gums.

Nous avons également mesuré l'effet des antioxydants sur ces compositions.We also measured the effect of antioxidants on these compositions.

L'antioxydant utilisé dans nos expériences est un mélange de 36ppm d'un additif constitué d'amines non aromatiques, le FOA-3 de DUPONT et de 4ppm d'un désactivateur de métaux, le DMD de DUPONT.The antioxidant used in our experiments is a mixture of 36 ppm of an additive consisting of non-aromatic amines, FOA-3 from DUPONT and 4 ppm of a metal deactivator, DMD from DUPONT.

Dans le tableau 3 nous comparons l'effet du vieillissement accéléré sur le LCO et les compositions renfermant du LCO avant et après traitement selon l'invention.

Figure imgb0003
In Table 3 we compare the effect of accelerated aging on LCO and the compositions containing LCO before and after treatment according to the invention.
Figure imgb0003

Le tableau 3 montre la stabilité du LCO traité selon l'invention, aussi bien seul qu'en mélange avec des gazoles de distillation directe. Le LCO traité réagit également mieux à l'effet des antioxydants.Table 3 shows the stability of the LCO treated according to the invention, both alone and as a mixture with direct distillation gas oils. The treated LCO also reacts better to the effect of antioxidants.

Claims (11)

1 - Procédé de stabilisation des gazoles issus de craquage catalytique, déjà oxydés ou non, caractérisé en ce qu'il consiste en une extraction liquide-liquide dudit gazole avec un mélange d'alcool et d'eau, suivi de la séparation du gazole stabilisé et de l'extrait alcoolique. 1 - Method for stabilizing gas oils from catalytic cracking, already oxidized or not, characterized in that it consists of a liquid-liquid extraction of said gas oil with a mixture of alcohol and water, followed by the separation of the stabilized gas oil and alcoholic extract. 2 - Procédé selon la revendication 1 caractérisé en ce que l'alcool est un alcool aliphatique linéaire ou ramifié en C₁ à C₆. 2 - Process according to claim 1 characterized in that the alcohol is a linear or branched Cip to C₆ aliphatic alcohol. 3 - Procédé selon la revendication 2 caractérisé en ce que l'alcool aliphatique est le méthanol. 3 - Process according to claim 2 characterized in that the aliphatic alcohol is methanol. 4 - Procédé selon l'une des revendications 1 à 3 caractérisé en ce que le mélange alcool-eau représente 15 à 35% poids et de préférence entre 20 et 30% poids du gazole. 4 - Method according to one of claims 1 to 3 characterized in that the alcohol-water mixture represents 15 to 35% by weight and preferably between 20 and 30% by weight of diesel. 5 - Procédé selon l'une des revendications 1 à 4 caractérisé en ce que le mélange alcool-eau renferme entre 1 à 10% poids et de préférence entre 3 et 7% poids d'eau. 5 - Method according to one of claims 1 to 4 characterized in that the alcohol-water mixture contains between 1 to 10% by weight and preferably between 3 and 7% by weight of water. 6 - Procédé selon l'une des revendications 1 à 5 caractérisé en ce que l'eau renferme entre 10 et 30% poids et de préférence entre 15 et 25% poids de soude. 6 - Method according to one of claims 1 to 5 characterized in that the water contains between 10 and 30% by weight and preferably between 15 and 25% by weight of soda. 7 - Procédé selon l'une des revendications 1 à 6 caractérisé en ce que l'extraction est mise en oeuvre dans un extracteur fonctionnant à cocourant ou à contrecourant, en continu ou en discontinu. 7 - Method according to one of claims 1 to 6 characterized in that the extraction is carried out in an extractor operating in cocurrent or countercurrent, continuously or discontinuously. 8 - Procédé selon l'une des revendications 1 à 7 caractérisé en ce que l'efficacité de l'extracteur correspond à environ 10 étages théoriques au moins. 8 - Method according to one of claims 1 to 7 characterized in that the efficiency of the extractor corresponds to about 10 theoretical stages at least. 9 - Gazoles issus de craquage catalytique caractérisé en ce qu'ils sont stabilisés par le procédé décrit dans les revendications 1 à 8. 9 - Diesel oils from catalytic cracking, characterized in that they are stabilized by the process described in claims 1 to 8. 10- Composition renfermant une proportion majeure de gazole de distillation directe et entre 10 et 30% poids et de préférence entre 15 et 25% poids d'un gazole selon la revendication 9. 10- Composition containing a major proportion of direct distillation diesel and between 10 and 30% by weight and preferably between 15 and 25% by weight of a diesel according to claim 9. 11- Composition selon la revendication 10 caractérisé en ce qu'elle renferme entre 0,0001 et 1% poids et de préférence entre 0,001 et 0,02% poids d'additifs à effet antioxydant et/ou stabilisant. 11- Composition according to claim 10 characterized in that it contains between 0.0001 and 1% by weight and preferably between 0.001 and 0.02% by weight of additives with antioxidant and / or stabilizing effect.
EP19910400204 1990-01-30 1991-01-29 Process for stabilising catalytically cracked gasoils, obtained gasoils and compositions containing this stabilised gasoil Expired - Lifetime EP0441677B1 (en)

Applications Claiming Priority (2)

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FR9001050 1990-01-30
FR9001050A FR2657620B1 (en) 1990-01-30 1990-01-30 PROCESS FOR THE STABILIZATION OF GAS OILS DERIVED FROM CATALYTIC CRACKING, GAS OIL OBTAINED THEREBY AND COMPOSITIONS CONTAINING SAID GAS OIL.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0900837A1 (en) * 1997-08-21 1999-03-10 Her Majesty in Right of Canada as represented by the Minister of Natural Resources Canada Methanol extraction of contaminating substances from thermally cracked waste oils
EP2147966A1 (en) * 2008-07-25 2010-01-27 Total Raffinage Marketing Additive for liquid fuel, liquid fuel containing same and its use for energy generation and/or heating and/or cooking devices

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB257270A (en) * 1925-08-20 1928-02-20 Ig Farbenindustrie Ag Improvements in the purification of the liquid complex hydrocarbon products of the destructive hydrogenation of carbonaceous materials
US3847800A (en) * 1973-08-06 1974-11-12 Kvb Eng Inc Method for removing sulfur and nitrogen in petroleum oils
US4761222A (en) * 1985-12-20 1988-08-02 Phillips Petroleum Company Method for separating normally liquid organic compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB257270A (en) * 1925-08-20 1928-02-20 Ig Farbenindustrie Ag Improvements in the purification of the liquid complex hydrocarbon products of the destructive hydrogenation of carbonaceous materials
US3847800A (en) * 1973-08-06 1974-11-12 Kvb Eng Inc Method for removing sulfur and nitrogen in petroleum oils
US4761222A (en) * 1985-12-20 1988-08-02 Phillips Petroleum Company Method for separating normally liquid organic compounds

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0900837A1 (en) * 1997-08-21 1999-03-10 Her Majesty in Right of Canada as represented by the Minister of Natural Resources Canada Methanol extraction of contaminating substances from thermally cracked waste oils
EP2147966A1 (en) * 2008-07-25 2010-01-27 Total Raffinage Marketing Additive for liquid fuel, liquid fuel containing same and its use for energy generation and/or heating and/or cooking devices
FR2934276A1 (en) * 2008-07-25 2010-01-29 Total France LIQUID FUEL ADDITIVE, LIQUID FUEL CONTAINING THE SAME, AND USE THEREOF FOR ENERGY AND / OR HEATING AND / OR COOKING APPARATUS

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EP0441677B1 (en) 1992-12-23
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DE69100013D1 (en) 1993-02-04
FR2657620B1 (en) 1992-04-17

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