EP0354826B1 - Hydrocarbon fractionation and extraction process to obtain a petrol with a high octane number and a kerosene with an altered smoke point - Google Patents
Hydrocarbon fractionation and extraction process to obtain a petrol with a high octane number and a kerosene with an altered smoke point Download PDFInfo
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- EP0354826B1 EP0354826B1 EP89402119A EP89402119A EP0354826B1 EP 0354826 B1 EP0354826 B1 EP 0354826B1 EP 89402119 A EP89402119 A EP 89402119A EP 89402119 A EP89402119 A EP 89402119A EP 0354826 B1 EP0354826 B1 EP 0354826B1
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- 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
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- 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
- C10G61/00—Treatment of naphtha by at least one reforming process and at least one process of refining in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B3/00—Engines characterised by air compression and subsequent fuel addition
- F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition
Definitions
- the invention relates to a process for the fractionation and extraction of hydrocarbons, in particular a process for the production of gasolines with an improved octane number and kerosene with an improved smoke point and optionally a process for the production of gas oil with a cetane number. improved by selective extraction of suitable hydrocarbon cuts.
- Liquid effluents distilling between about 50 ° C and 130 ° C constitute a gasoline cut with a low octane number due to a majority of saturated hydrocarbons and to this cut can be added at least partially a cut of heavy gasoline 130 -220 ° C richer in aromatic hydrocarbons and interesting by its high octane number.
- This solution is even fully adopted in summer, some of the heavy petrol being used for aviation petrol. However, during the winter, the majority of heavy gasoline is mixed with the diesel cut to meet heating needs.
- patent FR 1424225 teaches the extraction of aromatic and non-aromatic constituents of recycling oil ((LCO) or light cycle oil) constituted by a distillation fraction of 204 to 316 ° C produced approximately by the catalytic cracking of oil in two successive zones.
- LCO recycling oil
- a mixture of dimethylformamide and approximately for example 10% of water is used as solvent for the aromatics while in the second one uses a mixture of naphtha rich in saturated hydrocarbons and xylene to extract a mixture containing the hydrocarbons aromatics and recycle the solvent to the first extraction zone.
- the mixture thus extracted is then passed through a distillation column. At the bottom, a concentrate of aromatic hydrocarbons is collected and at the top, at least part of the naphtha is recovered, which is recycled in the second extraction zone. This operation is costly in energy.
- One of the objects of the invention is therefore to remedy the above drawbacks.
- the process according to the invention has the advantage, by using a light gasoline cut 25-80 ° C as an auxiliary solvent for re-extracting the first solvent from aromatic hydrocarbons, of avoiding distillation, which is energy efficient. .
- the production of this light cut is accompanied by an increase in the quality of the gasoline obtained and simultaneously by the improvement in the quality of kerosene.
- the initial charge of hydrocarbons used is a charge of hydrocarbons the final boiling point of which is at least 220 ° C., charge for example comprised between its initial boiling point and a final point of 600 ° C., for example example 25 ° C to 350 ° C.
- This charge can come from a catalytic cracking, thermal cracking or hydrocracking process. It can also be a crude oil charge or a distillate containing at least petrol and kerosene fractions, and which has not undergone the above treatments.
- an effluent from a catalytic cracking unit in a fluid bed in English "Fluid Catalytic Cracking" (FCC) and whose starting charge has been cracked in the presence of a catalyst under known cracking conditions, will be used. of the Tradesman. This effluent, thus enriched in olefinic hydrocarbons, will help to improve the octane number of the gasoline cut (light).
- feedstock is fractionated by distillation according to known conventional means.
- the cuts obtained may, depending on the number of trays in the distillation column, have boiling point ranges which may interfere in part.
- the lighter gases can be collected separately as well as water and hydrogen sulfide.
- the light petrol cut generally contains less than 10% by weight of aromatic hydrocarbons and preferably from 0.1 to 5% by weight.
- the cut of heavy petrol generally contains from 25 to 75% by weight of aromatic hydrocarbons and in general approximately less than 15% by weight, preferably from 1 to 10% by weight approximately of dicyclic hydrocarbons having at least an aromatic cycle.
- the average gasoline cut can be reformed after hydrotreatment which usually makes it possible to reduce the nitrogen content to less than 1 ppm, before mixing it with the extract and the auxiliary solvent of step c), which will make it possible to further improve the octane number of the resulting mixture.
- the fractionation of the charge can reveal a boiling point cut above 220 ° C. intended to supply the engine diesel fuel tank (pool).
- This cut can be a Light Cycle Oil (L.C.O.) cut, if the charge comes from catalytic cracking.
- At least part of the raffinate from step b) according to the method of the invention can be mixed with at least part of the above cut to supply the engine diesel tank.
- the average gasoline cut of step a) usually containing from 5 to 50 ppm of nitrogen is hydrotreated in the presence of hydrogen in a hydrotreatment zone.
- the collected hydrotreatment effluent is subjected to catalytic reforming in the presence of hydrogen in a reforming zone under reforming conditions so to obtain a medium petrol cut with improved octane number.
- This medium essence can be mixed, at least in part and preferably in whole, with the aromatic extract which is itself in mixture with the 25-80 ° C cut according to step c) of the process and this is thus obtained a gasoline with a better octane number than that according to step c) of the process.
- the said mixture is then subjected to a hydrotreatment under hydrotreatment conditions such that the amount of nitrogen preferably does not exceed 1 ppm, then the hydrotreatment effluent is subjected to a catalytic reforming in the presence of hydrogen in a zone reforming, according to operating conditions such that a reforming gasoline with improved octane number is obtained.
- This reforming essence thus obtained can then be mixed at least in part and preferably in whole with at least a part and preferably all of the extract comprising the light gasoline cut 25-80 ° C. produced according to step c) of the process.
- hydrotreatment operation hydrodesulfurization and hydrodenitrogenation
- the hydrotreatment operation will be carried out under conditions such that there will generally remain only an amount of sulfur and nitrogen of less than 10 ppm and preferably less than 1 ppm. This operation will depend on the type of load. These conditions are known to those skilled in the art and are described, for example, in US patents 3,044,950.
- the solvents for extracting aromatic hydrocarbons from the heavy petrol fraction can be those described in US Pat. No. 3,627,671 and preferably dimethylsulfoxide, polyethylene glycol and dimethylformamide. These solvents can advantageously contain water, for example from 0.1 to 20% and preferably from 1 to 10% by weight to best adjust the selectivity of the separation.
- the auxiliary solvent, in this case the cut 25 ° C-80 ° C, used to separate the first extraction solvent in the second extraction zone may contain in particular when the original charge has been catalytically cracked, a quantity of olefins between 20 and 60% which will contribute to improving the octane number of the gasoline intended for the gasoline tank (pool).
- all the liquid-liquid extraction devices can be used for example columns with filling, plates or with mechanical agitation (RDC: rotating disc contactor) having in general from 3 to 20 stages and preferably from 5 to 10 stages at a temperature generally between 20 and 120 ° C, advantageously between 60 and 80 ° C and under a pressure allowing to operate in the liquid phase and therefore between 1 and 10 bars, preferably 1 and 3 bars.
- RDC rotating disc contactor
- the solvent volume ratio on heavy petrol cut is generally between 1 and 3 and preferably between 1.5 and 2, in the first extraction unit.
- the ratio between the volume of the light gasoline cut and the volume of the charge introduced, that is to say of the mixture comprising said solvent of first extraction and the extract enriched in hydrocarbons aromatics is generally between 0.5 and 2, preferably between 1 and 1.5.
- the determination of the engine and research octane numbers is carried out according to the standards ASTM D2699-D2700 while the determination of the smoke point and the cetane number is carried out according to the standards ASTM D1322 and ASTM D 613.
- a vacuum distillate for example, with boiling points of between about 350 and 550 ° C. is introduced by a line 1 into a catalytic cracking unit 2 where it is cracked under cracking conditions in the presence of a catalyst.
- the liquid catalytic cracking effluent or feed according to the invention for example 25-550 ° C, after separation of the catalyst is introduced by a line 3 at the base of a distillation unit 4 where it is fractionated.
- a light petrol fraction 25-80 ° C is collected at the head by a line 5, which will be sent, as will be seen below, to the base of a second extraction unit 19, an average petrol fraction of points d boiling between 80 and 150 ° C and which is sent by a line 6 to a gasoline storage tank (pool) 15.
- This medium gasoline can be reformed in a reforming unit 12 in the presence of hydrogen supplied by a line 13 and a reforming catalyst.
- this pretreatment is carried out in a hydrotreatment unit 9, upstream of the reforming unit 12, in the presence of hydrogen supplied by a line 10 and of a hydrotreatment catalyst, and under conditions which make it possible to reach these amounts of nitrogen and sulfur.
- the hydrotreatment effluent is then sent via a line 11 to the reforming unit.
- a heavy petrol fraction is also collected, with a boiling point of between approximately 150 ° C. and 220 ° C., which is sent by a line 7 to a first extraction unit 16 supplied with solvent. for the extraction of aromatic hydrocarbons, for example, dimethyl sulfoxide.
- the refined fraction enriched in non-aromatic hydrocarbons or raffinate is collected at least partly in the upper part of the unit, washed to remove traces of extraction solvent (device not shown diagrammatically in the figure) and it is supplied via a line 18 the kerosene storage tank 23. This fraction has a smoke point improved.
- a part of this same refined fraction can feed via a line 22 the line 6 for supplying the medium petrol cut upstream of the hydrotreatment 9 and reforming units 12.
- the amount of raffinate thus mixed with the medium petrol cut is such that the mixture thus obtained has an amount of nitrogen of less than 50 ppm and that it can therefore be hydrotreated in a conventional manner and then subjected to a reforming process, as indicated above to increase its octane number.
- the hydrotreatment carried out on this mixture makes it possible, as explained above, in particular to lower the sulfur and nitrogen contents to approximately at most 1 ppm and moreover hydrogenate at least part of the olefins of this mixture which can be a poison for the reforming catalyst.
- the extracted fraction enriched in aromatic hydrocarbons and mixed with the first extraction solvent is drawn off via line 17 and then sent via this line 17 to the top of a second extraction unit 19. It is introduced against the current at the base from this unit a light gasoline cut 25-80 ° C (second auxiliary solvent).
- This light gasoline is capable of dissolving aromatic hydrocarbons but unable to dissolve a substantial amount of the first extraction solvent, that is to say incapable of dissolving more than 5% and preferably more than 1% of its weight of said solvent .
- the first extraction solvent is collected at the base of the unit 19 and recycled by a line 21 at the top of the first extraction unit 16.
- the second extraction effluent of improved octane number, mixed with the light petrol cup is in turn sent to the petrol storage tank 15 by a line 20 after having been freed from the traces of the first extraction solvent by conventional means not shown in the figure.
- the distillation charge for example from the catalytic cracking unit 2 contains a fraction of boiling point above 220 ° C capable of constituting a light cycle oil fraction (LCO) to supply a line 8 to a motor fuel storage tank (pool 8), it is possible to improve its cetane number by mixing with said LCO cut at least part (for example 80%) of the raffinate of the heavy petrol cut coming from the first extraction unit 16, thanks to a line 24.
- LCO light cycle oil fraction
- distillation residue (350 ° C +) is collected at the base of the distillation unit 4 via line 26.
- the liquid catalytic cracking effluent is subjected to a distillation delivering at least four cuts (Tab. I) E l , E m , E L , and LCO
- the extraction of the heavy petrol cut is carried out in an extraction unit of the R.D.C. type. at 6 stages, against the current in the presence of dimethyl sulfoxide containing 2% of water, at a temperature of approximately 70 ° C. and at a pressure substantially equal to 2 bars so as to maintain the mixture in the liquid phase.
- the solvent to charge ratio is approximately 1.6 by volume.
- the so-called raffinate part is washed with water so that the amount of solvent does not exceed 5 ppm and feeds the kerosene tank or the gas oil.
- the extract mixed with dimethyl sulfoxide is extracted against the current by the light petrol cut in a second extraction unit of the same type as the first at a pressure substantially equal to 2 bars and at a temperature of around 70 ° C.
- the solvent (light petrol cut) to charge ratio in the second unit is approximately 1.2 by volume.
- the undissolved dimethyl sulfoxide is recycled in the first unit while the mixture of aromatic extract and light essence with improved octane number (95) is collected, washed so that there is substantially no more dimethyl sulfoxide and introduced into the tank. petrol storage.
- the operation is carried out at constant production in gasoline, in kerosene and in diesel.
- case A where we operate according to the prior art, that is to say the case where a gasoline is conventionally constituted from all of the light and medium gasoline cuts and a part of the heavy gasoline, the other part of the heavy gasoline being intended to supply the engine diesel or kerosene storage tank and case B according to the present invention, without hydrotreating or reforming.
- a fuel storage tank is supplied by the light petrol cutter and the so-called extract part (EL1) of the heavy petrol cutter which leaves the second extraction unit (46% of the heavy fuel cut, i.e. 7% of the load) as well as the medium fuel cut.
- an amount of gasoline (37%) of octane number 93 is obtained which can be compared to the same amount of gasoline obtained according to the prior art (the number 7 representing the same amount of heavy gasoline added), or 37%, of octane number 90.
- Example 2 is carried out according to the conditions of Example 1 according to the method of the invention (case D). However, two modes of implementation are determined, one for winter and the other for summer.
- the diesel tank is supplied by the L.C.O. while the petrol tank is supplied by the light petrol fraction serving as a solvent for the second extraction, the extract enriched with aromatic hydrocarbons (EL1) according to the process of the invention and the medium petrol as well as the raffinate (ELR) of l heavy gasoline.
- the raffinate instead of supplying the kerosene or diesel tank, is mixed with the medium petrol cut. This raffinate contains approximately 30 ppm nitrogen. The mixture formed is subjected, after washing intended to rid it of traces of dimethylsulfoxide, to a hydrotreatment and then to reforming under the following conditions described in Table III.
- the petrol tank is supplied by the light petrol cut, the extract according to the invention and the medium petrol cut subjected to the above hydrotreatment and reforming while the diesel tank is supplied by the LCO cut and the raffinate obtained according to the invention.
- the diesel fuel tank is conventionally supplied (case C), for the winter, by the LCO cut and part of the heavy petrol (the same quantity as that according to the invention), and supplies the petrol tank with the light petrol cutter, the medium petrol cutter, which has been subjected to the hydrotreatment and reforming processes under substantially the same conditions as those described above, and the additional part of the heavy petrol .
- the fuel tank is supplied with the light fuel cut, the medium fuel cut which has been subjected to the hydrotreatment and reforming processes as above, and the fuel cut. heavy petrol.
- Table IV show that the quality of the products obtained is improved when operating according to the process of the invention.
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Description
L'invention concerne un procédé de fractionnement et d'extraction d'hydrocarbures, particulièrement un procédé de production d'essences à indice d'octane amélioré et de kérosène à point de fumée amélioré et éventuellement un procédé de production de gasole à indice de cétane amélioré par extraction sélective de coupes d'hydrocarbures appropriées.The invention relates to a process for the fractionation and extraction of hydrocarbons, in particular a process for the production of gasolines with an improved octane number and kerosene with an improved smoke point and optionally a process for the production of gas oil with a cetane number. improved by selective extraction of suitable hydrocarbon cuts.
Il est connu de l'Homme de Métier de produire des essences à partir de la distillation atmosphérique d'une charge d'hydrocarbures. Les effluents liquides distillant entre environ 50°C et 130°C constituent une coupe essence à indice d'octane peu élevé dû à une majorité d'hydrocarbures saturés et à cette coupe peut être ajoutée au moins en partie une coupe d'essence lourde 130-220°C plus riche en hydrocarbures aromatiques et intéressante par son haut indice d'octane. Cette solution est même totalement adoptée en été, une partie de l'essence lourde étant dévolue à l'essence d'aviation. Par contre, durant l'hiver, la majorité de l'essence lourde est mélangée à la coupe gasole pour satisfaire les besoins en chauffage.It is known to those skilled in the art to produce gasolines from the atmospheric distillation of a hydrocarbon charge. Liquid effluents distilling between about 50 ° C and 130 ° C constitute a gasoline cut with a low octane number due to a majority of saturated hydrocarbons and to this cut can be added at least partially a cut of heavy gasoline 130 -220 ° C richer in aromatic hydrocarbons and interesting by its high octane number. This solution is even fully adopted in summer, some of the heavy petrol being used for aviation petrol. However, during the winter, the majority of heavy gasoline is mixed with the diesel cut to meet heating needs.
De plus, il est connu d'améliorer l'indice d'octane de la coupe essence par reformage par le brevet US 3044950 mais la teneur en azote de la charge ne doit pas excéder 50 ppm, ce qui interdit de traiter directement les coupes essences lourdes 130-220°C plus riches en azote et particulièrement les essences lourdes de craquage catalytique.In addition, it is known to improve the octane number of the gasoline cut by reforming by US patent 3,044,950 but the nitrogen content of the feed should not exceed 50 ppm, which prohibits directly treating gasoline cuts heavy 130-220 ° C richer in nitrogen and particularly heavy gasolines of catalytic cracking.
Pour pallier cet inconvénient, il est nécessaire de prétraiter par un hydrotraitement sévère cette coupe d'essence lourde, ce prétraitement s'avérant difficile et coûteux.To overcome this drawback, it is necessary to pretreat this heavy gasoline cut with severe hydrotreatment, this pretreatment proving difficult and costly.
Par ailleurs, il est connu par le brevet FR 1421273 un procédé d'extraction des hydrocarbures (par exemple le benzène, toluène et xylène et/ou des hydrocarbures aromatiques polycycliques) par un solvant d'extraction comme le diméthylsulfoxyde dans une première zone d'extraction. Mais son emploi s'est heurté à de nombreuses difficultés en raison de sa stabilité médiocre vis-à-vis de la chaleur et des traitements de distillation. Pour éviter une distillation lors de la séparation du mélange comprenant l'extrait enrichi en hydrocarbures aromatiques et le diméthylsulfoxyde, il a été recommandé d'utiliser un solvant auxiliaire dans une deuxième zone d'extraction, capable de dissoudre les hydrocarbures de la charge mais incapable de dissoudre une quantité substantielle (plus de 5% de son poids) de diméthylsulfoxyde. Ce dernier peut ainsi être séparé puis recyclé dans la première zone d'extraction.Furthermore, it is known from patent FR 1421273 a process for the extraction of hydrocarbons (for example benzene, toluene and xylene and / or polycyclic aromatic hydrocarbons) by a extraction solvent such as dimethyl sulfoxide in a first extraction zone. However, its use has encountered many difficulties due to its poor stability with respect to heat and distillation treatments. To avoid distillation during the separation of the mixture comprising the extract enriched in aromatic hydrocarbons and dimethyl sulfoxide, it was recommended to use an auxiliary solvent in a second extraction zone, capable of dissolving the hydrocarbons in the feed but incapable dissolve a substantial amount (more than 5% by weight) of dimethyl sulfoxide. The latter can thus be separated and then recycled in the first extraction zone.
Afin de récupérer la coupe aromatique extraite et sensiblement purifiée, on est amené à passer par une série d'opérations telles qu'un lavage à l'eau pour entraîner les traces de diméthylsulfoxyde suivi d'une distillation du mélange restant, c'est-à-dire des hydrocarbures aromatiques et du solvant auxiliaire qui est ainsi séparé puis recyclé dans la deuxième zone d'extraction.In order to recover the extracted and substantially purified aromatic cut, it is necessary to go through a series of operations such as washing with water to remove the traces of dimethyl sulfoxide followed by distillation of the remaining mixture, ie aromatic hydrocarbons and auxiliary solvent which is thus separated and then recycled in the second extraction zone.
De plus, le brevet FR 1424225 enseigne l'extraction des constituants aromatiques et non aromatiques d'huile de recyclage ((L.C.O.) ou light cycle oil) constituée par une fraction de distillation de 204 à 316°C environ produite par le craquage catalytique du pétrole dans deux zones successives. Dans la première, on utilise un mélange de diméthylformamide et d'environ par exemple 10% d'eau comme solvant des aromatiques tandis que dans la seconde on utilise un mélange de naphta riche en hydrocarbures saturés et de xylène pour extraire un mélange contenant les hydrocarbures aromatiques et recycler le solvant vers la première zone d'extraction.In addition, patent FR 1424225 teaches the extraction of aromatic and non-aromatic constituents of recycling oil ((LCO) or light cycle oil) constituted by a distillation fraction of 204 to 316 ° C produced approximately by the catalytic cracking of oil in two successive zones. In the first one, a mixture of dimethylformamide and approximately for example 10% of water is used as solvent for the aromatics while in the second one uses a mixture of naphtha rich in saturated hydrocarbons and xylene to extract a mixture containing the hydrocarbons aromatics and recycle the solvent to the first extraction zone.
Le mélange ainsi extrait est ensuite passé dans une colonne de distillation. En queue, on recueille un concentrat d'hydrocarbures aromatiques et en tête on récupère une partie au moins du naphta qui est recyclé dans la seconde zone d'extraction. Cette opération-là est coûteuse en énergie.The mixture thus extracted is then passed through a distillation column. At the bottom, a concentrate of aromatic hydrocarbons is collected and at the top, at least part of the naphtha is recovered, which is recycled in the second extraction zone. This operation is costly in energy.
L'art antérieur est enfin illustré par le brevet US 3044950 qui décrit un double traitement d'une charge 25-220°C combinant un hydrotraitement suivi d'une extraction par solvant. Cet hydrotraitement est effectué soit sur toute la charge soit sur la fraction la plus lourde de la charge obtenue par distillation.The prior art is finally illustrated by US patent 3,044,950 which describes a double treatment of a load 25-220 ° C combining a hydrotreatment followed by a solvent extraction. This hydrotreatment is carried out either on the entire charge or on the heaviest fraction of the charge obtained by distillation.
Il s'ensuit que l'hydrogénation de la fraction la plus légère de la charge entraîne une perte en indice d'octane et l'hydrogénation de la fraction la plus lourde ne peut être exécutée que dans de conditions très sévères de pression étant donné la grande quantité d'azote dans cette fraction. De plus, l'hydrogénation de la fraction la plus lourde et par conséquent des hydrocarbures aromatiques qu'elle contient entraîne une diminution de son indice d'octane.It follows that the hydrogenation of the lightest fraction of the charge causes a loss in octane number and the hydrogenation of the heaviest fraction can only be carried out under very severe pressure conditions given the large amount of nitrogen in this fraction. In addition, the hydrogenation of the heaviest fraction and consequently of the aromatic hydrocarbons which it contains leads to a reduction in its octane number.
Un des objets de l'invention est donc de remédier aux inconvénients ci-dessus.One of the objects of the invention is therefore to remedy the above drawbacks.
On a découvert en effet qu'il n'était pas nécessaire de redistiller le solvant dit auxiliaire rajouté dans la seconde étape d'extraction du brevet FR 1424225. Plus particulièrement, on a découvert et ceci constitue un autre objet de la présente invention, un procédé de fractionnement et d'extraction d'hydrocarbures permettant d'obtenir des résultats sensiblement améliorés vis-à-vis des procédés de l'art antérieur.It has in fact been discovered that it was not necessary to redistill the so-called auxiliary solvent added in the second extraction step of patent FR 1424225. More particularly, it has been discovered and this constitutes another object of the present invention, a process for the fractionation and extraction of hydrocarbons making it possible to obtain substantially improved results with respect to the processes of the prior art.
De façon plus précise, l'invention concerne un procédé de fractionnement et d'extraction d'hydrocarbures permettant l'obtention d'une essence à indice d'octane amélioré et d'un kérosène à point de fumée amélioré, à partir d'une charge d'hydrocarbures dont le point d'ébullition final est d'au moins 220°C, de préférence de points d'ébullition compris entre 25 et 350°C. Le procédé comprend:
- a) Une étape de fractionnement de ladite charge dans des conditions de fractionnement délivrant au moins trois coupes:
- 1― Une coupe essence légère de point d'ébullition compris entre 25°C et 80°C et contenant environ moins de 10% en poids d'hydrocarbures aromatiques,
- 2― Une coupe essence moyenne de point d'ébullition compris entre 80°C et au plus 150°C, ayant une teneur en azote inférieure à environ 50 ppm,
- 3― Une coupe essence lourde de point d'ébullition final au plus égal à environ 220°C par exemple de points d'ébullition compris entre 150°C et au plus 220°C ayant une teneur en hydrocarbures aromatiques, généralement comprise entre 25 et 75% en poids,
- b) Une étape d'extraction de la majeure partie des hydrocarbures aromatiques de ladite coupe essence lourde dans des conditions d'extraction par un premier solvant des hydrocarbures aromatiques, dans une première zone d'extraction produisant un raffinat désaromatisé et un mélange comprenant ledit solvant et un extrait enrichi en lesdits hydrocarbures aromatiques, le rapport en volume dudit premier solvant sur ladite coupe essence lourde étant compris entre 1 et 3;
- c) Une étape d'extraction dudit mélange par un second solvant auxiliaire dans des conditions d'extraction dans une seconde zone d'extraction, produisant d'une part ledit extrait comprenant ledit second solvant auxiliaire et d'autre part ledit premier solvant que l'on recycle à l'étape b), le rapport en volume du solvant auxiliaire et dudit mélange étant compris entre 0,5 et 2.
Le procédé est caractérisé en ce que ledit solvant auxiliaire est ladite coupe essence légère (25°C-80°C) et en ce que: - d) On recueille au moins une partie du raffinat désaromatisé de l'étape b) de façon à obtenir un kérosène ayant un point de fumée amélioré.
- a) A step of fractionating said charge under fractionation conditions delivering at least three cuts:
- 1― A light petrol cup with a boiling point between 25 ° C and 80 ° C and containing approximately less than 10% by weight of aromatic hydrocarbons,
- 2― A medium petrol cup with a boiling point between 80 ° C and at most 150 ° C, having a nitrogen content of less than about 50 ppm,
- 3― A heavy petrol cut with a final boiling point at most equal to about 220 ° C, for example boiling points between 150 ° C and at most 220 ° C having an aromatic hydrocarbon content, generally between 25 and 75% by weight,
- b) A step of extracting the major part of the aromatic hydrocarbons from said heavy gasoline cut under conditions of extraction with a first solvent of the aromatic hydrocarbons, in a first extraction zone producing a dearomatized raffinate and a mixture comprising said solvent and an extract enriched in said aromatic hydrocarbons, the volume ratio of said first solvent to said heavy petrol cut being between 1 and 3;
- c) A step of extracting said mixture with a second auxiliary solvent under extraction conditions in a second extraction zone, producing on the one hand said extract comprising said second auxiliary solvent and on the other hand said first solvent than l 'is recycled in step b), the volume ratio of the auxiliary solvent and said mixture being between 0.5 and 2.
The method is characterized in that said auxiliary solvent is said light gasoline cut (25 ° C-80 ° C) and in that: - d) at least a portion of the dearomatized raffinate of step b) is collected so as to obtain a kerosene having an improved smoke point.
Le procédé selon l'invention présente l'avantage, par l'utilisation d'une coupe essence légère 25-80°C comme solvant auxiliaire de réextraction du premier solvant des hydrocarbures aromatiques, d'éviter une distillation, ce qui est économe en énergie. Par ailleurs, la production de cette coupe légère s'accompagne d'une augmentation de la qualité de l'essence obtenue et simultanément de l'amélioration de la qualité du kérosène.The process according to the invention has the advantage, by using a light gasoline cut 25-80 ° C as an auxiliary solvent for re-extracting the first solvent from aromatic hydrocarbons, of avoiding distillation, which is energy efficient. . In addition, the production of this light cut is accompanied by an increase in the quality of the gasoline obtained and simultaneously by the improvement in the quality of kerosene.
La charge initiale d'hydrocarbures utilisée est une charge d'hydrocarbures dont le point d'ébullition final est d'au moins 220°C, charge par exemple comprise entre son point d'ébullition initial et un point final de 600°C, par exemple 25°C à 350°C. Cette charge peut provenir d'un procédé de craquage catalytique, de craquage thermique ou d'hydrocraquage. Ce peut être aussi une charge de pétrole brut ou un distillat contenant au moins des fractions essence et kérosène, et qui n'a pas subi les traitements ci-dessus. De préférence, on utilisera un effluent provenant d'une unité de craquage catalytique en lit fluide, en anglais "Fluid Catalytic Cracking" (F.C.C.) et dont la charge de départ a été craquée en présence d'un catalyseur dans des conditions de craquage connues de l'Homme de Métier. Cet effluent ainsi enrichi en hydrocarbures oléfiniques va contribuer à améliorer l'indice d'octane de la coupe essence (légère).The initial charge of hydrocarbons used is a charge of hydrocarbons the final boiling point of which is at least 220 ° C., charge for example comprised between its initial boiling point and a final point of 600 ° C., for example example 25 ° C to 350 ° C. This charge can come from a catalytic cracking, thermal cracking or hydrocracking process. It can also be a crude oil charge or a distillate containing at least petrol and kerosene fractions, and which has not undergone the above treatments. Preferably, an effluent from a catalytic cracking unit in a fluid bed, in English "Fluid Catalytic Cracking" (FCC) and whose starting charge has been cracked in the presence of a catalyst under known cracking conditions, will be used. of the Tradesman. This effluent, thus enriched in olefinic hydrocarbons, will help to improve the octane number of the gasoline cut (light).
La charge de départ ou l'effluent ci-dessus, dénommée charge par la suite est fractionnée par distillation selon des moyens conventionnels connus.The above feedstock or effluent, hereinafter referred to as feedstock, is fractionated by distillation according to known conventional means.
Les coupes obtenues peuvent en fonction du nombre de plateaux de la colonne de distillation, avoir des gammes de point d'ébullition qui peuvent interférer en partie.The cuts obtained may, depending on the number of trays in the distillation column, have boiling point ranges which may interfere in part.
Dans la zone de distillation, les gaz les plus légers peuvent être recueillis séparément ainsi que l'eau et l'hydrogène sulfuré.In the distillation zone, the lighter gases can be collected separately as well as water and hydrogen sulfide.
La coupe d'essence légère contient généralement moins de 10% en poids d'hydrocarbures aromatiques et de préférence de 0,1 à 5% en poids.The light petrol cut generally contains less than 10% by weight of aromatic hydrocarbons and preferably from 0.1 to 5% by weight.
La coupe d'essence moyenne a généralement une teneur en azote inférieure à environ 50 ppm (1 ppm = partie par million), par exemple comprise entre 5 et 50 ppm et de préférence comprise entre 20 et 40 ppm, et cette teneur détermine le point d'ébullition final de ladite coupe.The average fuel cut generally has a nitrogen content of less than about 50 ppm (1 ppm = parts per million), for example between 5 and 50 ppm and preferably between 20 and 40 ppm, and this content determines the point final boiling of said cup.
Enfin, la coupe d'essence lourde contient en général de 25 à 75% en poids d'hydrocarbures aromatiques et en général environ moins de 15% en poids, de préférence de 1 à 10% en poids environ d'hydrocarbures dicycliques ayant au moins un cycle aromatique.Finally, the cut of heavy petrol generally contains from 25 to 75% by weight of aromatic hydrocarbons and in general approximately less than 15% by weight, preferably from 1 to 10% by weight approximately of dicyclic hydrocarbons having at least an aromatic cycle.
On pourra avantageusement reformer la coupe essence moyenne après un hydrotraitement permettant habituellement d'abaisser la teneur en azote à moins de 1 ppm, avant de la mélanger avec l'extrait et le solvant auxiliaire de l'étape c), ce qui permettra d'améliorer encore plus l'indice d'octane du mélange résultant.Advantageously, the average gasoline cut can be reformed after hydrotreatment which usually makes it possible to reduce the nitrogen content to less than 1 ppm, before mixing it with the extract and the auxiliary solvent of step c), which will make it possible to further improve the octane number of the resulting mixture.
Selon un mode de mise en oeuvre du procédé, le fractionnement de la charge peut faire apparaître une coupe de point d'ébullition supérieur à 220°C destinée à alimenter le réservoir (pool) gasole moteur. Cette coupe peut être une coupe Light Cycle Oil (L.C.O.), si la charge provient du craquage catalytique. Une partie au moins du raffinat de l'étape b) selon le procédé de l'invention peut être mélangée avec une partie au moins de la coupe ci-dessus pour alimenter le réservoir gasole moteur.According to one embodiment of the method, the fractionation of the charge can reveal a boiling point cut above 220 ° C. intended to supply the engine diesel fuel tank (pool). This cut can be a Light Cycle Oil (L.C.O.) cut, if the charge comes from catalytic cracking. At least part of the raffinate from step b) according to the method of the invention can be mixed with at least part of the above cut to supply the engine diesel tank.
On peut également avec cette partie au moins du raffinat de l'étape b) selon l'invention alimenter directement le réservoir (pool) de stockage de gasole moteur, de façon à améliorer son indice de cétane.It is also possible with this part at least of the raffinate from step b) according to the invention to directly supply the engine diesel storage tank (pool), so as to improve its cetane number.
Selon un autre mode de réalisation du procédé, la coupe essence moyenne de l'étape a) contenant habituellement de 5 à 50 ppm d'azote est hydrotraitée en présence d'hydrogène dans une zone d' hydrotraitement.According to another embodiment of the method, the average gasoline cut of step a) usually containing from 5 to 50 ppm of nitrogen is hydrotreated in the presence of hydrogen in a hydrotreatment zone.
Dans des conditions d'hydrotraitement telles que la quantité résiduelle d'azote est inférieure à 1 ppm puis l'effluent d'hydrotraitement recueilli est soumis à un reformage catalytique en présence d'hydrogène dans une zone de reformage dans des conditions de reformage de façon à obtenir une coupe essence moyenne à indice d'octane amélioré.Under hydrotreatment conditions such that the residual quantity of nitrogen is less than 1 ppm then the collected hydrotreatment effluent is subjected to catalytic reforming in the presence of hydrogen in a reforming zone under reforming conditions so to obtain a medium petrol cut with improved octane number.
Cette essence moyenne peut être mélangée, au moins en partie et de préférence en totalité à l'extrait aromatique qui est lui-même en mélange avec la coupe 25-80°C selon l'étape c) du procédé et l'on obtient ainsi une essence à meilleur indice d'octane que celle selon l'étape c) du procédé.This medium essence can be mixed, at least in part and preferably in whole, with the aromatic extract which is itself in mixture with the 25-80 ° C cut according to step c) of the process and this is thus obtained a gasoline with a better octane number than that according to step c) of the process.
Selon un autre mode de réalisation particulièrement avantageux du procédé, on peut mélanger une partie au moins du raffinat de l'étape b) par exemple de 5 à 80%, de préférence de 10 à 20% en poids, avec la coupe essence moyenne 80-150°C, dans une proportion telle que la quantité d' azote du mélange ainsi obtenu reste inférieure à 50 ppm (1 ppm = 1 partie par million). On soumet ensuite ledit mélange à un hydrotraitement dans des conditions d'hydrotraitement telles que la quantité d'azote ne dépasse pas de préférence 1 ppm, puis on soumet l'effluent d'hydrotraitement à un reformage catalytique en présence d'hydrogène dans une zone de reformage, selon des conditions opératoires telles que l'on obtient une essence de reformage à indice d'octane amélioré.According to another particularly advantageous embodiment of the process, it is possible to mix at least part of the raffinate from step b) for example from 5 to 80%, preferably from 10 to 20% by weight, with the average gasoline cut 80 -150 ° C, in a proportion such that the quantity of nitrogen in the mixture thus obtained remains less than 50 ppm (1 ppm = 1 part per million). The said mixture is then subjected to a hydrotreatment under hydrotreatment conditions such that the amount of nitrogen preferably does not exceed 1 ppm, then the hydrotreatment effluent is subjected to a catalytic reforming in the presence of hydrogen in a zone reforming, according to operating conditions such that a reforming gasoline with improved octane number is obtained.
Cette essence de reformage ainsi obtenue peut alors être mélangée au moins en partie et de préférence en totalité avec au moins une partie et de préférence la totalité de l'extrait comprenant la coupe essence légère 25-80°C produit selon l'étape c) du procédé.This reforming essence thus obtained can then be mixed at least in part and preferably in whole with at least a part and preferably all of the extract comprising the light gasoline cut 25-80 ° C. produced according to step c) of the process.
Ainsi par rapport à l'art antérieur (US 3044950), on n'hydrotraite avant le reformage que le raffinat de la coupe la plus lourde appauvri en aromatiques et non pas l'intégralité de la coupe la plus lourde, ce qui évite d'opérer selon des conditions opératoires très sévères d'hydrotraitement et de reformage.Thus compared to the prior art (US 3044950), only the raffinate of the heaviest cut depleted in aromatics and not the entirety of the heaviest cut is hydrotreated before reforming, which avoids operate under very severe hydrotreating and reforming operating conditions.
L'opération d'hydrotraitement (hydrodésulfuration et hydrodéazotation) sera réalisée dans des conditions telles qu'il ne restera en général qu'une quantité de soufre et d'azote inférieure à 10 ppm et de préférence, inférieure à 1 ppm. Cette opération sera fonction du type de charge. Ces conditions sont connues de l'Homme de Métier et sont décrites par exemple dans les brevets US 3044950.The hydrotreatment operation (hydrodesulfurization and hydrodenitrogenation) will be carried out under conditions such that there will generally remain only an amount of sulfur and nitrogen of less than 10 ppm and preferably less than 1 ppm. This operation will depend on the type of load. These conditions are known to those skilled in the art and are described, for example, in US patents 3,044,950.
Elles sont généralement les suivantes:
- Température:
- = 300-350°C
- Pression:
- = 20-30 bar
- H₂/charge:
- 30-80 en volume
- VVH:
- 2-10
- Catalyseur:
- alumine +CO - MO (Procatalyse)
They are generally as follows:
- Temperature:
- = 300-350 ° C
- Pressure:
- = 20-30 bar
- H₂ / load:
- 30-80 in volume
- VVH:
- 2-10
- Catalyst:
- alumina + CO - MO (Procatalyse)
Les conditions de reformage ont été largement décrites dans les brevets US 3044950, US 3627671, US 4172027, US 4133733 US 4210519 et US 4233288.The reforming conditions have been widely described in US Patents 3,044,950, US 3,627,671, US 4,172,027, US 4,133,733 US 4,210,519 and US 4,232,288.
Elles sont généralement les suivantes:
- Température:
- à l'entrée 480-520°C
- Pression:
- 3,5-10 bar
- H₂/charge:
- 2-6 (mode)
- V.V.H.:
- 1,5-3
- Catalyseur:
- alumine + (Pt +Sn) ou (Pt +Re) (Procatalyse)
They are generally as follows:
- Temperature:
- at the input 480-520 ° C
- Pressure:
- 3.5-10 bar
- H₂ / load:
- 2-6 (mode)
- VVH:
- 1.5-3
- Catalyst:
- alumina + (Pt + Sn) or (Pt + Re) (Procatalysis)
Les solvants d'extraction des hydrocarbures aromatiques de la coupe essence lourde peuvent être ceux décrits dans le brevet US 3627671 et de préférence le diméthylsulfoxyde, le polyéthylèneglycol et la diméthylformamide. Ces solvants peuvent contenir avantageusement de l'eau, par exemple de 0,1 à 20% et de préférence de 1 à 10% en poids pour ajuster au mieux la sélectivité de la séparation.The solvents for extracting aromatic hydrocarbons from the heavy petrol fraction can be those described in US Pat. No. 3,627,671 and preferably dimethylsulfoxide, polyethylene glycol and dimethylformamide. These solvents can advantageously contain water, for example from 0.1 to 20% and preferably from 1 to 10% by weight to best adjust the selectivity of the separation.
Le solvant auxiliaire, en l'occurence la coupe 25°C-80°C, utilisé pour séparer le premier solvant d'extraction dans la seconde zone d'extraction peut contenir notamment quand la charge d'origine a été craquée catalytiquement, une quantité d'oléfines comprise entre 20 et 60% qui va contribuer à améliorer l'indice d'octane de l'essence destinée au réservoir (pool) essence.The auxiliary solvent, in this case the
Pour la mise en oeuvre du présent procédé, tous les dispositifs d'extraction liquide-liquide, de préférence à contre-courant peuvent être utilisés par exemple des colonnes à remplissage, à plateaux ou à agitation mécanique (R.D.C.: rotating disc contactor) ayant en général de 3 à 20 étages et de préférence de 5 à 10 étages à une température généralement comprise entre 20 et 120°C, avantageusement entre 60 et 80°C et sous une pression permettant d'opérer en phase liquide et donc comprise entre 1 et 10 bars, de préférence 1 et 3 bars. Le rapport en volume solvant sur coupe essence lourde est en général compris entre 1 et 3 et de préférence entre 1,5 et 2, dans la première unité d'extraction. Par contre, dans la seconde unité d'extraction, le rapport entre le volume de la coupe essence légère et le volume de la charge introduite c'est-à-dire du mélange comprenant ledit solvant de première extraction et l'extrait enrichi en hydrocarbures aromatiques est généralement compris entre 0,5 et 2, de préférence entre 1 et 1,5.For the implementation of the present process, all the liquid-liquid extraction devices, preferably against the current, can be used for example columns with filling, plates or with mechanical agitation (RDC: rotating disc contactor) having in general from 3 to 20 stages and preferably from 5 to 10 stages at a temperature generally between 20 and 120 ° C, advantageously between 60 and 80 ° C and under a pressure allowing to operate in the liquid phase and therefore between 1 and 10 bars, preferably 1 and 3 bars. The solvent volume ratio on heavy petrol cut is generally between 1 and 3 and preferably between 1.5 and 2, in the first extraction unit. On the other hand, in the second extraction unit, the ratio between the volume of the light gasoline cut and the volume of the charge introduced, that is to say of the mixture comprising said solvent of first extraction and the extract enriched in hydrocarbons aromatics is generally between 0.5 and 2, preferably between 1 and 1.5.
La détermination des indices d'octane moteur et recherche est effectuée selon les normes ASTM D2699-D2700 tandis que la détermination du point de fumée et de l'indice de cétane est réalisée selon les normes ASTM D1322 et ASTM D 613.The determination of the engine and research octane numbers is carried out according to the standards ASTM D2699-D2700 while the determination of the smoke point and the cetane number is carried out according to the standards ASTM D1322 and ASTM D 613.
L'invention sera mieux comprise au vu de la figure unique représentant à titre illustratif le procédé.The invention will be better understood in view of the single figure illustrating the process by way of illustration.
Un distillat sous vide par exemple, de points d'ébullition compris entre environ 350 et 550°C est introduit par une ligne 1 dans une unité de craquage catalytique 2 où elle est craquée dans des conditions de craquage en présence d'un catalyseur.A vacuum distillate, for example, with boiling points of between about 350 and 550 ° C. is introduced by a line 1 into a
L'effluent liquide de craquage catalytique ou charge selon l'invention, par exemple 25-550°C, après séparation du catalyseur est introduit par une ligne 3 à la base d'une unité de distillation 4 où il est fractionné. On recueille en tête par une ligne 5 une fraction essence légère 25-80°C, qui sera envoyée, comme on le verra ci-dessous, à la base d'une seconde unité d'extraction 19, une fraction essence moyenne de points d'ébullitions compris entre 80 et 150°C et qui est envoyée par une ligne 6 vers un réservoir (pool) de stockage d'essence 15. Cette essence moyenne peut être reformée dans une unité de reformage 12 en présence d'hydrogène amené par une ligne 13 et d'un catalyseur de reformage. Cependant, il peut s'avérer nécessaire de prétraiter l'essence de façon à ce que cette coupe avant reformage ne présente pas une quantité d'azote supérieure à 1 ppm (1 partie par million) et une quantité de soufre supérieure à 1 ppm. Ce prétraitement est réalisé dans une unité d'hydrotraitement 9, en amont de l'unité de reformage 12, en présence d'hydrogène apporté par une ligne 10 et d'un catalyseur d'hydrotraitement, et dans des conditions qui permettent d'atteindre ces quantités d'azote et de soufre. L'effluent d'hydrotraitement est ensuite envoyé par une ligne 11 vers l'unité de reformage.The liquid catalytic cracking effluent or feed according to the invention, for example 25-550 ° C, after separation of the catalyst is introduced by a
De l'unité de fractionnement 4, on recueille aussi une fraction essence lourde, de point d'ébullition compris entre 150°C et 220°C environ, qui est envoyée par une ligne 7 vers une première unité d'extraction 16 alimentée en solvant d'extraction des hydrocarbures aromatiques par exemple, du diméthylsulfoxyde. La fraction raffinée enrichie en hydrocarbures non aromatiques ou raffinat est recueillie au moins en partie dans la partie supérieure de l'unité, lavée pour éliminer les traces de solvant d'extraction (dispositif non schématisé sur la figure) et elle alimente par une ligne 18 le réservoir de stockage de kérosène 23. Cette fraction présente un point de fumée amélioré. Une partie de cette même fraction raffinée peut alimenter par une ligne 22 la ligne 6 d'alimentation de la coupe essence moyenne en amont des unités d'hydrotraitement 9 et de reformage 12. La quantité de raffinat ainsi mélangée à la coupe essence moyenne est telle que le mélange ainsi obtenu présente une quantité d'azote inférieure à 50 ppm et qu'il peut donc être hydrotraité de manière conventionnelle puis soumis à un procédé de reformage, comme indiqué ci-dessus pour augmenter son indice d'octane. L'hydrotraitement réalisé sur ce mélange permet, comme expliqué ci-dessus, notamment d'abaisser les teneurs en soufre et en azote jusqu'à environ au plus 1 ppm et par ailleurs d'hydrogéne une partie au moins des oléfines de ce mélange qui peuvent être un poison pour le catalyseur de reformage.From the fractionation unit 4, a heavy petrol fraction is also collected, with a boiling point of between approximately 150 ° C. and 220 ° C., which is sent by a
La fraction extraite enrichie en hydrocarbures aromatiques et en mélange au premier solvant d'extraction est soutirée par la ligne 17 et envoyée ensuite par cette ligne 17 vers le sommet d'une seconde unité d'extraction 19. On introduit à contre courant à la base de cette unité une coupe essence légère 25-80°C (second solvant auxiliaire). Cette essence légère est capable de dissoudre les hydrocarbures aromatiques mais incapable de dissoudre une quantité substantielle du premier solvant d'extraction, c'est-à-dire incapable de dissoudre plus de 5% et de préférence plus de 1% de son poids dudit solvant. Le premier solvant d'extraction est recueilli à la base de l'unité 19 et recyclé par une ligne 21 au sommet de la première unité d'extraction 16. L'effluent de seconde extraction d'indice d'octane amélioré, en mélange avec la coupe d'essence légère, est envoyée à son tour sur le réservoir (pool) de stockage d'essence 15 par une ligne 20 après avoir été débarrassé des traces du premier solvant d'extraction par des moyens conventionnels non représentés sur la figure.The extracted fraction enriched in aromatic hydrocarbons and mixed with the first extraction solvent is drawn off via
Lorque la charge de distillation par exemple en provenance de l'unité de craquage catalytique 2 contient une fraction de point d'ébullition supérieur à 220°C susceptible de constituer une coupe light cycle oil (L.C.O.) pour alimenter par une conduite 8 un réservoir (pool) de stockage de gasole moteur 25, il est possible d'améliorer son indice de cétane en mélangeant à ladite coupe L.C.O. une partie au moins (par exemple 80%) du raffinat de la coupe essence lourde provenant de la première unité d'extraction 16, grâce à une ligne 24.When the distillation charge for example from the catalytic cracking
Enfin le résidu de distillation (350°C+) est recueilli à la base de l'unité de distillation 4 par la conduite 26.Finally, the distillation residue (350 ° C +) is collected at the base of the distillation unit 4 via
L'exemple qui suit illustre de façon non limitative le procédé selon la présente invention.The example which follows illustrates in a nonlimiting manner the method according to the present invention.
Un distillat sous vide Brent de point d'ébullition compris entre environ 350°C et 550°C est introduit dans une unité de craquage catalytique opérant dans les conditions suivantes en présence d'un catalyseur de craquage catalytique à base de zéolithe Y (Octacat (R) marque déposée):
- Temps de contact =
- 2-3 s.
- Rapport pondéral catalyseur
- sur charge:
- 6
- Température du riser:
- 520°C
- Température du régénérateur:
- 750°C
- Conversion (% poids):
- 77%
A Brent vacuum distillate with a boiling point of between approximately 350 ° C. and 550 ° C. is introduced into a catalytic cracking unit operating under the following conditions in the presence of a catalytic cracking catalyst based on zeolite Y (Octacat ( R) registered trademark):
- Contact time =
- 2-3 s.
- Catalyst weight ratio
- on load:
- 6
- Riser temperature:
- 520 ° C
- Regenerator temperature:
- 750 ° C
- Conversion (% weight):
- 77%
L'effluent liquide de craquage catalytique est soumis à une distillation délivrant au moins quatre coupes (Tab. I) El, Em, EL, et L.C.O.
L'extraction de la coupe essence lourde est réalisée dans une unité d'extraction du type R.D.C. à 6 étages, à contre courant en présence de diméthylsulfoxyde contenant 2% d'eau, à une température de 70°C environ et à pression sensiblement égale à 2 bars de façon à maintenir le mélange en phase liquide.The extraction of the heavy petrol cut is carried out in an extraction unit of the R.D.C. type. at 6 stages, against the current in the presence of dimethyl sulfoxide containing 2% of water, at a temperature of approximately 70 ° C. and at a pressure substantially equal to 2 bars so as to maintain the mixture in the liquid phase.
Le rapport solvant sur charge est d'environ 1,6 en volume. La partie dite raffinat est lavée à l'eau de façon à ce que la quantité de solvant ne dépasse pas 5 ppm et alimente le réservoir de kérosène ou le gasole.The solvent to charge ratio is approximately 1.6 by volume. The so-called raffinate part is washed with water so that the amount of solvent does not exceed 5 ppm and feeds the kerosene tank or the gas oil.
L'extrait mélangé au diméthylsulfoxyde est extrait à contre courant par la coupe essence légère dans une seconde unité d'extraction de même type que la première à une pression sensiblement égale à 2 bars et à une température d'environ 70°C.The extract mixed with dimethyl sulfoxide is extracted against the current by the light petrol cut in a second extraction unit of the same type as the first at a pressure substantially equal to 2 bars and at a temperature of around 70 ° C.
Le rapport solvant (coupe essence légère) sur charge dans la seconde unité est d'environ 1,2 en volume. Le diméthylsulfoxyde non dissous est recyclé dans la première unité tandis que le mélange extrait aromatique et essence légère à indice d'octane amélioré (95) est recueilli, lavé de façon à ce qu'il ne reste sensiblement plus de diméthylsulfoxyde et introduit dans le réservoir de stockage d'essence.The solvent (light petrol cut) to charge ratio in the second unit is approximately 1.2 by volume. The undissolved dimethyl sulfoxide is recycled in the first unit while the mixture of aromatic extract and light essence with improved octane number (95) is collected, washed so that there is substantially no more dimethyl sulfoxide and introduced into the tank. petrol storage.
Pour bien illustrer l'intérêt du procédé selon l'invention, et faciliter la comparaison des résultats selon l'art antérieur et l'invention, on opère à production constante en essence, en kérosène et en gasole.To illustrate the advantage of the process according to the invention, and to facilitate the comparison of the results according to the prior art and the invention, the operation is carried out at constant production in gasoline, in kerosene and in diesel.
Les résultats sont présentés dans le tableau II.The results are presented in Table II.
On considère le cas A où l'on opère selon l'art antérieur c'est-à-dire le cas où l'on constitue de manière conventionnelle une essence à partir de l'intégralité des coupes essences légère et moyenne et d'une partie de l'essence lourde, l'autre partie de l'essence lourde étant destinée à alimenter le réservoir de stockage de gasole moteur ou de kérosène et le cas B selon la présente invention, sans hydrotraitement ni reformage.We consider case A where we operate according to the prior art, that is to say the case where a gasoline is conventionally constituted from all of the light and medium gasoline cuts and a part of the heavy gasoline, the other part of the heavy gasoline being intended to supply the engine diesel or kerosene storage tank and case B according to the present invention, without hydrotreating or reforming.
On alimente, selon l'invention (cas B), un réservoir de stockage d'essence par la coupe essence légère et la partie dite extrait (EL1) de la coupe essence lourde qui quittent la seconde unité d'extraction (46% de la coupe essence lourde, soit 7% de la charge) ainsi que la coupe d'essence moyenne. On obtient finalement une quantité d'essence (37%) d'indice d'octane 93 que l'on peut comparer à une même quantité d'essence obtenue selon l'art antérieur (le chiffre 7 représentant la même quantité d'essence lourde ajoutée), soit 37%, d'indice d'octane 90.According to the invention (case B), a fuel storage tank is supplied by the light petrol cutter and the so-called extract part (EL1) of the heavy petrol cutter which leaves the second extraction unit (46% of the heavy fuel cut, i.e. 7% of the load) as well as the medium fuel cut. Finally, an amount of gasoline (37%) of octane number 93 is obtained which can be compared to the same amount of gasoline obtained according to the prior art (the
Le reste de l'essence lourde, c'est-à-dire le raffinat enrichi en hydrocarbures non aromatiques (ELR = 8%) est introduit soit dans le réservoir (pool) kérosène soit dans le réservoir (pool) gasole et l'on observe des qualités de carburant améliorées par comparaison avec le cas A selon l'art antérieur, à un même niveau de production (rajout du complément d'essence lourde, soit 8%, dans le réservoir (pool) kérosène ou gasole).The rest of the heavy petrol, i.e. the raffinate enriched in non-aromatic hydrocarbons (ELR = 8%), is introduced either into the kerosene tank (pool) either in the diesel tank (pool) and improved fuel qualities are observed by comparison with case A according to the prior art, at the same production level (addition of the additional heavy fuel, or 8%, in the kerosene or diesel tank).
On réalise l'exemple 2 selon les conditions de l'exemple 1 d'après le procédé de l'invention (cas D). On détermine cependant deux modes de mise en oeuvre, l'un pour l'hiver, l'autre pour l'été.Example 2 is carried out according to the conditions of Example 1 according to the method of the invention (case D). However, two modes of implementation are determined, one for winter and the other for summer.
Pour l'été, le réservoir de gasole est alimenté par la coupe L.C.O. alors que le réservoir essence est alimenté par la fraction essence légère servant de solvant de seconde extraction, l'extrait enrichi en hydrocarbures aromatiques (EL1) selon le procédé de l'invention et l'essence moyenne ainsi que le raffinat (ELR) de l'essence lourde. Mais contrairement à l'exemple 1, le raffinat au lieu d'alimenter le réservoir de kérosène ou de gasole, est mélangé à la coupe d'essence moyenne. Ce raffinat contient environ 30 ppm d'azote. Le mélange constitué est soumis, après un lavage destiné à le débarrasser des traces de diméthylsulfoxyde à un hydrotraitement puis à un reformage dans les conditions suivantes décrites dans le tableau III.For the summer, the diesel tank is supplied by the L.C.O. while the petrol tank is supplied by the light petrol fraction serving as a solvent for the second extraction, the extract enriched with aromatic hydrocarbons (EL1) according to the process of the invention and the medium petrol as well as the raffinate (ELR) of l heavy gasoline. But unlike Example 1, the raffinate, instead of supplying the kerosene or diesel tank, is mixed with the medium petrol cut. This raffinate contains approximately 30 ppm nitrogen. The mixture formed is subjected, after washing intended to rid it of traces of dimethylsulfoxide, to a hydrotreatment and then to reforming under the following conditions described in Table III.
Par contre, pour l'hiver, le réservoir essence est alimenté par la coupe essence légère, l'extrait selon l'invention et la coupe essence moyenne soumise à l'hydrotraitement et au reformage ci-dessus tandis que le réservoir de gasole est alimenté par la coupe L.C.O. et le raffinat obtenu selon l'invention.
A titre de comparaison, on alimente de manière conventionnelle (cas C), pour l'hiver, le réservoir de gasole par la coupe L.C.O. et une partie de l'essence lourde (la même quantité que celle selon l'invention), et on alimente le réservoir d'essence par la coupe essence légère, la coupe essence moyenne, qui a été soumise aux procédés d'hydrotraitement et de reformage sensiblement dans les mêmes conditions que celles décrites ci-haut, et la partie complémentaire de l'essence lourde. En revanche, pour l'été on alimente le réservoir d'essence par la coupe d'essence légère, la coupe d'essence moyenne qui a été soumise aux procédés d'hydrotraitement et de reformage comme ci-dessus, et la coupe d'essence lourde. Les résultats présents dans le tableau IV montrent que l'on gagne en qualité des produits obtenus lorsqu'on opère selon le procédé de l'invention.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8810545 | 1988-08-02 | ||
FR8810545A FR2635112B1 (en) | 1988-08-02 | 1988-08-02 | PROCESS FOR FRACTIONATION AND EXTRACTION OF HYDROCARBONS FOR OBTAINING AN ESSENCE WITH IMPROVED OCTANE INDEX AND AN IMPROVED SMOKE POINT KEROSENE |
Publications (2)
Publication Number | Publication Date |
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EP0354826A1 EP0354826A1 (en) | 1990-02-14 |
EP0354826B1 true EP0354826B1 (en) | 1991-12-04 |
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ID=9369111
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Application Number | Title | Priority Date | Filing Date |
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EP89402119A Expired - Lifetime EP0354826B1 (en) | 1988-08-02 | 1989-07-26 | Hydrocarbon fractionation and extraction process to obtain a petrol with a high octane number and a kerosene with an altered smoke point |
Country Status (6)
Country | Link |
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US (1) | US5021143A (en) |
EP (1) | EP0354826B1 (en) |
JP (1) | JPH0275698A (en) |
DE (1) | DE68900503D1 (en) |
ES (1) | ES2038427T3 (en) |
FR (1) | FR2635112B1 (en) |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2004058920A1 (en) * | 2002-12-27 | 2004-07-15 | Council Of Scientific And Industrial Research | Process for extraction of aromatics from petroleum streams |
CN100378197C (en) * | 2003-11-07 | 2008-04-02 | 丁冉峰 | Catalytic hydrocarbon recombinant treating method |
ATE551413T1 (en) * | 2003-07-04 | 2012-04-15 | Beijing Grand Golden Bright Engineering & Technologies Co Ltd | METHOD FOR RECOMBINATION OF CATALYTIC HYDROCARBONS |
JP2011503264A (en) * | 2007-11-09 | 2011-01-27 | 丁冉峰 | System and method for producing high quality gasoline by recombining hydrocarbons by catalytic action |
US8940154B2 (en) * | 2007-11-09 | 2015-01-27 | Ranfeng Ding | System and process for producing high quality gasoline by catalytic hydrocarbon recombination |
US8246811B2 (en) * | 2009-05-26 | 2012-08-21 | IFP Energies Nouvelles | Process for the production of a hydrocarbon fraction with a high octane number and a low sulfur content |
US9334451B2 (en) * | 2010-03-15 | 2016-05-10 | Saudi Arabian Oil Company | High quality middle distillate production process |
US8741127B2 (en) | 2010-12-14 | 2014-06-03 | Saudi Arabian Oil Company | Integrated desulfurization and denitrification process including mild hydrotreating and oxidation of aromatic-rich hydrotreated products |
US8741128B2 (en) | 2010-12-15 | 2014-06-03 | Saudi Arabian Oil Company | Integrated desulfurization and denitrification process including mild hydrotreating of aromatic-lean fraction and oxidation of aromatic-rich fraction |
US9005433B2 (en) | 2011-07-27 | 2015-04-14 | Saudi Arabian Oil Company | Integrated process for in-situ organic peroxide production and oxidative heteroatom conversion |
EP2737030A1 (en) | 2011-07-29 | 2014-06-04 | Saudi Arabian Oil Company | Integrated selective hydrocracking and fluid catalytic cracking process |
CN103781883B (en) | 2011-07-29 | 2016-03-23 | 沙特阿拉伯石油公司 | Selectivity two-stage hydrotreating systems and method |
US8852426B2 (en) | 2011-07-29 | 2014-10-07 | Saudi Arabian Oil Company | Integrated hydrotreating and isomerization process with aromatic separation |
CN103781881A (en) | 2011-07-29 | 2014-05-07 | 沙特阿拉伯石油公司 | Selective single-stage hydroprocessing system and method |
JP6057999B2 (en) | 2011-07-29 | 2017-01-11 | サウジ アラビアン オイル カンパニー | Integrated isomerization and hydroprocessing processes |
US9145521B2 (en) | 2011-07-29 | 2015-09-29 | Saudi Arabian Oil Company | Selective two-stage hydroprocessing system and method |
WO2013019590A2 (en) | 2011-07-29 | 2013-02-07 | Saudi Arabian Oil Company | Selective series-flow hydroprocessing system and method |
KR101947849B1 (en) | 2011-07-29 | 2019-02-13 | 사우디 아라비안 오일 컴퍼니 | Selective series-flow hydroprocessing system and method |
CN103827265B (en) | 2011-07-29 | 2016-08-17 | 沙特阿拉伯石油公司 | The hydrotreating of aromatics extracting hydrocarbon stream |
US9284237B2 (en) | 2013-12-13 | 2016-03-15 | Uop Llc | Methods and apparatuses for processing hydrocarbons |
US10711208B2 (en) | 2017-06-20 | 2020-07-14 | Saudi Arabian Oil Company | Process scheme for the production of optimal quality distillate for olefin production |
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US2773006A (en) * | 1955-03-04 | 1956-12-04 | Union Oil Co | Separation of hydrocarbons |
US3044950A (en) * | 1958-12-15 | 1962-07-17 | Gulf Research Development Co | Process for upgrading catalytically cracked gasoline |
FR1424225A (en) * | 1964-02-10 | 1966-01-07 | Marathon Oil Co | Aromatic hydrocarbon extraction process |
BE757343A (en) * | 1969-10-09 | 1971-03-16 | Chevron Res | COMBINED PROCESS OF CATALYTIC REFORMING AND EXTRACTION |
US3793192A (en) * | 1972-04-14 | 1974-02-19 | Exxon Research Engineering Co | Catalytic cracking process |
US4209383A (en) * | 1977-11-03 | 1980-06-24 | Uop Inc. | Low benzene content gasoline producing process |
-
1988
- 1988-08-02 FR FR8810545A patent/FR2635112B1/en not_active Expired - Fee Related
-
1989
- 1989-07-26 DE DE8989402119T patent/DE68900503D1/en not_active Expired - Fee Related
- 1989-07-26 ES ES198989402119T patent/ES2038427T3/en not_active Expired - Lifetime
- 1989-07-26 EP EP89402119A patent/EP0354826B1/en not_active Expired - Lifetime
- 1989-08-02 JP JP1201144A patent/JPH0275698A/en active Pending
- 1989-08-02 US US07/388,033 patent/US5021143A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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ES2038427T3 (en) | 1993-07-16 |
US5021143A (en) | 1991-06-04 |
EP0354826A1 (en) | 1990-02-14 |
FR2635112B1 (en) | 1990-09-28 |
DE68900503D1 (en) | 1992-01-16 |
FR2635112A1 (en) | 1990-02-09 |
JPH0275698A (en) | 1990-03-15 |
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