EP0441677A1 - Verfahren zur Stabilisierung von Gasölen von katalytischen Krackverfahren, hergestelltes Gasöl und Zusammensetzungen, die sie erhalten - Google Patents

Verfahren zur Stabilisierung von Gasölen von katalytischen Krackverfahren, hergestelltes Gasöl und Zusammensetzungen, die sie erhalten 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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EP
European Patent Office
Prior art keywords
weight
diesel
lco
alcohol
gasoils
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.)
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Application number
EP91400204A
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English (en)
French (fr)
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EP0441677B1 (de
Inventor
André Ciais
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elf Antar France
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Elf Antar France
Elf France SA
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Publication of EP0441677A1 publication Critical patent/EP0441677A1/de
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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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
EP19910400204 1990-01-30 1991-01-29 Verfahren zur Stabilisierung von Gasölen von katalytischen Krackverfahren, hergestelltes Gasöl und Zusammensetzungen, die sie erhalten Expired - Lifetime EP0441677B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9001050A FR2657620B1 (fr) 1990-01-30 1990-01-30 Procede de stabilisation de gazoles issus de craquage catalytique, gazole ainsi obtenu et compositions renfermant ledit gazole stabilise.
FR9001050 1990-01-30

Publications (2)

Publication Number Publication Date
EP0441677A1 true EP0441677A1 (de) 1991-08-14
EP0441677B1 EP0441677B1 (de) 1992-12-23

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910400204 Expired - Lifetime EP0441677B1 (de) 1990-01-30 1991-01-29 Verfahren zur Stabilisierung von Gasölen von katalytischen Krackverfahren, hergestelltes Gasöl und Zusammensetzungen, die sie erhalten

Country Status (4)

Country Link
EP (1) EP0441677B1 (de)
JP (1) JPH04348187A (de)
DE (1) DE69100013D1 (de)
FR (1) FR2657620B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0900837A1 (de) * 1997-08-21 1999-03-10 Her Majesty in Right of Canada as represented by the Minister of Natural Resources Canada Entfernung von Kontaminierungsstoffen aus thermisch gecrackten gebrauchten Ölen durch Methanolextraktion
EP2147966A1 (de) * 2008-07-25 2010-01-27 Total Raffinage Marketing Zusatzstoff für flüssigen Brennstoff, der ihn enthaltende flüssige Brennstoff und seine Anwendung für Energieerzeugungsgeräte und/oder Heizgeräte und/oder Kochgeräte

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 (de) * 1997-08-21 1999-03-10 Her Majesty in Right of Canada as represented by the Minister of Natural Resources Canada Entfernung von Kontaminierungsstoffen aus thermisch gecrackten gebrauchten Ölen durch Methanolextraktion
EP2147966A1 (de) * 2008-07-25 2010-01-27 Total Raffinage Marketing Zusatzstoff für flüssigen Brennstoff, der ihn enthaltende flüssige Brennstoff und seine Anwendung für Energieerzeugungsgeräte und/oder Heizgeräte und/oder Kochgeräte
FR2934276A1 (fr) * 2008-07-25 2010-01-29 Total France Additif pour combustible liquide, combustible liquide le contenant et son utilisation pour les appareils de production d'energie et/ou de chauffage et/ou de cuisson

Also Published As

Publication number Publication date
DE69100013D1 (de) 1993-02-04
FR2657620A1 (fr) 1991-08-02
JPH04348187A (ja) 1992-12-03
EP0441677B1 (de) 1992-12-23
FR2657620B1 (fr) 1992-04-17

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