EP0849350A1 - Procédé de transformation d'une coupe gazole pour produire un carburant à haut indice de cétane, désaromatisé et désulfuré - Google Patents
Procédé de transformation d'une coupe gazole pour produire un carburant à haut indice de cétane, désaromatisé et désulfuré Download PDFInfo
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- EP0849350A1 EP0849350A1 EP97402996A EP97402996A EP0849350A1 EP 0849350 A1 EP0849350 A1 EP 0849350A1 EP 97402996 A EP97402996 A EP 97402996A EP 97402996 A EP97402996 A EP 97402996A EP 0849350 A1 EP0849350 A1 EP 0849350A1
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Classifications
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Definitions
- the present invention relates to the field of fuels for combustion engines internal. It relates more particularly to the manufacture of a motor fuel compression ignition. In this field, the invention relates to a method of transformation of a diesel cut to produce a fuel with a high cetane number, flavored and desulfurized.
- Class II diesel fuel must not contain more than 50 ppm of sulfur and more than 10% by volume of aromatic compounds and that of class I more than 10 ppm of sulfur and 5% by volume of aromatic compounds.
- Class III diesel fuel must contain less than 500 ppm sulfur and less than 25% by volume of aromatic compounds. Similar limits are also to be observed for the sale of this type of fuel in California.
- the present invention therefore relates to a method of transformation of a diesel cut to produce a fuel with a high cetane number, flavored and desulphurized in at least two successive stages. It also concerns the fuel obtained by said process.
- the hydrogen is introduced at each of the first and second stages, and is optionally recycled at the level of the first and second stages, independently of each other, which means that there is no management common gas from said stages.
- the effluent from the first stage is subjected to a stripping with water vapor so as to separate at least partially the gaseous phase, which can be treated and optionally recycled at least in part to level of said step.
- At least part of the product from stripping is subjected to the second step of the process according to the invention.
- the effluent preferably leaving the last stage is stripped with steam, advantageously passes through a coalescer and is optionally dried.
- the operating conditions of the steps a) and b) are chosen according to the characteristics of the load which can be a direct distillation diesel cut, a diesel cut from cracking catalytic or diesel cut from coking or visbreaking (visbreaking) of residues or a mixture of two or more of these cuts so as to obtain a product containing less than 100 ppm of sulfur and less than 200 ppm, or better than 50 ppm of nitrogen and the conditions of step b) are chosen so as to obtain a product containing less than 10% by volume of aromatic compounds.
- the conditions of step a) include a temperature from about 300 ° C to about 450 ° C, a total pressure from about 2 MPa to about 20 MPa and an overall hourly space velocity of liquid charge of about 0.1 to about 10 and preferably 0.1 to 4 and that of step b) a temperature of about 200 ° C to about 400 ° C, a total pressure from about 2 MPa to about 20 MPa and a speed overall hourly liquid charge space from about 0.5 to about 10.
- step a1) When one wishes to remain in a relatively low pressure range while wishing to obtain excellent results it is possible to carry out a first step a1) under conditions allowing the sulfur content of the product to be reduced to a value about 500 to 800 ppm and then send this product in a subsequent step a2) under which conditions will be chosen to reduce the sulfur content to a less than about 100 ppm, preferably less than about 50 ppm and the product from this step a2) is then sent to step b).
- the conditions of step a2) are identical or preferably milder that when, for a given charge, we operate in a single step a), since the product sent in this step a2) already has a greatly reduced sulfur content.
- the catalyst of step a1) can be a conventional catalyst prior art such as that described in the text of patent applications in the name of the applicant FR-A-2197966 and FR-A-2538813 and that of step a2) is the one described above for step a). We would not go beyond the scope of this invention using in steps a1) and a2) the same catalyst.
- the catalyst support can be chosen from the group formed by alumina, silica, silica-aluminas, zeolites, titanium oxide, magnesia, zirconia, clays and mixtures of at least two of these compounds minerals.
- Alumina is very commonly used.
- the catalyst for these steps a), a1), a2) will comprise, deposited on the support, at least one metal or a compound of metal, advantageously chosen from the group formed by molybdenum and tungsten and at least one metal or a metal compound advantageously chosen in the group formed by nickel, cobalt and iron. Most often this catalyst includes molybdenum or a molybdenum compound and at least one metal or metal compound chosen from the group formed by nickel and cobalt.
- the catalyst for these steps a), a1), a2) will comprise boron or at least one boron compound preferably in one quantity expressed by weight of boron trioxide relative to the weight of the support less than or equal to 10%, and preferably deposited on the support.
- the amount of metal or group VIB metal compound (preferred Mo) expressed by weight of metal relative to the weight of the finished catalyst will preferably be approximately 2 to 30% and more often about 5 to 25% and that of the metal or the compound of group VIII metal (Ni or Co preferred) will preferably be approximately 0.5 to 15% and the more often around 1 to 10%.
- a catalyst containing Ni, Mo, P is used, the proportions of these elements having been previously described, or better yet Ni, Mo, P, B.
- a particularly advantageous catalyst is that described in patent EP-297,949 whose teaching is included in this description.
- This catalyst comprises: a) a support comprising a porous mineral matrix, boron or a boron compound and phosphorus or a phosphorus compound, and b) at least one metal or metal compound from group VIB of the periodic table and at least one metal or metal compound from group VIII of said classification, in which the sum of the quantities of boron and phosphorus, expressed respectively by weight of boron trioxide (B 2 O 3 ) and phosphorus pentoxide (P 2 O 5 ) relative to the weight of the support is approximately 5 to 15%, preferably approximately 6 to 12% and advantageously approximately 8 to 11.5%, the atomic ratio boron on phosphorus (B / P) is d '' about 1.05: 1, to 2: 1 and preferably about 1.1: 1 to 1.8: 1.
- at least 40% and preferably at least 50% of the total pore volume of the finished catalyst is contained in pores with an average diameter greater than 13 nanometers.
- the catalyst preferably has a total pore volume of between 0.38 and 0.51 cm 3 xg -1 .
- the quantity of group VIB metal or metals contained in the catalyst is usually such as the phosphorus-to-metal atomic ratio or metals of the VIB group (P / VIB) is about 0.5: 1 to 1.5: 1 and preferably about 0.7: 1 to 0.9: 1.
- the respective quantities of group VIB metal or metals and of metal or metals of group VIII contained in the catalyst are usually such that the ratio atomic metal or metals of group VIII on metal or metals of group VIB (VIII / VIB) or from about 0.3: 1 to 0.7: 1 and preferably from about 0.3: 1 to about 0.45: 1.
- the quantity by weight of the metals contained in the finished catalyst expressed by weight of metal relative to the weight of the finished catalyst is usually, for metal or the metals of group VIB of approximately 2 to 30% and preferably of approximately 5 to 25%, and for the metal or metals of group VIII of about 0.1 to 15% and more particularly about 0.1 to 5% and preferably about 0.15 to 3% in the case of metals nobles of group VIII (Pt, Pd, Ru, Rh, Os, Ir) and about 0.5 to 15% and preferably about 1 to 10% in the case of non-noble metals from group VIII (Fe, Co, Ni).
- the mineral support can be chosen from the group formed by alumina, silica, silica-aluminas, zeolites, titanium oxide, magnesia, oxide of boron, zirconia, clays and mixtures of at least two of these compounds minerals.
- This support will preferably comprise at least one halogen chosen from the group formed by chlorine, fluorine, iodine and bromine and preferably chlorine and fluorine.
- this support will include chlorine and fluorine.
- the amount of halogen will most often be from about 0.5 to about 15% by weight relative to the weight of the support.
- the most commonly used medium is alumina.
- the halogen is usually introduced onto the support from corresponding acid halides and the noble metal, preferably platinum or palladium, for example from aqueous solutions of their salts or compounds such as for example hexachloroplatinic acid in the case of platinum.
- the noble metal preferably platinum or palladium, for example from aqueous solutions of their salts or compounds such as for example hexachloroplatinic acid in the case of platinum.
- the quantity of noble metal (Pt or Pd preferred) of this catalyst of step b) will be preferably about 0.01 to 10%, often about 0.01 to 5% and most often about 0.03 to 3% expressed by weight of metal relative to the weight of the catalyst finished.
- a particularly advantageous catalyst is described in patent FR-2,240,905, the teaching of which is included. It comprises a noble metal, alumina, a halogen, and it was prepared by mixing the aluminous support with a compound of the noble metal and a reducing agent of formula AlX y R 3-y where y is equal to 1.3 / 2 or 2, X is a halogen and R is a monovalent hydrocarbon radical.
- Another catalyst which is very suitable is that described in US Pat. No. 4,225,461. he includes a noble metal and a halogen and has been specially prepared.
- the first step is carried out in a pilot hydrotreating unit.
- This includes two reactors in series which can contain up to 20 l. of catalyst in a fixed bed.
- Unity includes a hydrogen recycling compressor.
- the flow of fluids is descending in each of the reactors.
- the unit has a row column of steam stripping which allows stripping the reaction effluent which is thus completely free of the H2S and NH3 formed during the reaction.
- This pilot unit is loaded with 5 l. of the same catalyst in each of the reactors.
- a deeply desulphurized product is thus obtained (sulfur content less than 50 ppm) and very deeply denitrogenized (nitrogen content less than 6 ppm).
- the effluent is kept for second stage pilot tests.
- the second step is carried out in a smaller pilot unit comprising a 1 l reactor with upward flow of fluids.
- the unit has no recycling compressor.
- the first step is carried out in a pilot hydrotreating unit.
- This includes two reactors in series which can contain up to 20 l. of catalyst.
- the unit has a hydrogen recycling compressor.
- the flow of fluids is descending in each of the reactors.
- the unit has an in-line stripping column vapor which strikes the reaction effluent which is thus completely freed from H2S and NH3 formed during the reaction.
- This pilot unit is loaded with 5 l. of the same catalyst in each of the reactors.
- the effluent is kept for second stage pilot tests.
- the second step is carried out in a smaller pilot unit comprising a 1 l reactor with upward flow of fluids.
- the unit has no recycling compressor.
- Example 2 The same charge is treated as that mentioned in Example 2, under the same VVH conditions, total pressure, recycling H 2 and temperature in each of the stages, the only difference being that in the 1st stage, a catalyst is used containing, under oxide form, approximately 3% nickel, 15% molybdenum, 6% P 2 O 5 and 3.5% B 2 O 3 on alumina and in the 2nd stage a catalyst containing approximately 0.6% of platinum , 1% chlorine and 1% fluorine on alumina.
- Table 4 The analysis of the effluent from 1st stage and from 2nd is reported in the table below.
- This example clearly shows the effect of using a boron-containing catalyst in the 1st stage and it also shows the influence of the use of a catalyst containing both chlorine and fluorine in 2nd stage.
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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)
- Catalysts (AREA)
Abstract
Description
De préférence, selon le procédé, l'effluent issu de la première étape est soumis à un strippage à la vapeur d'eau de façon à séparer au moins en partie la phase gazeuse, qui pourra être traité et éventuellement recyclé au moins en partie au niveau de ladite étape. Au moins une partie du produit issu du strippage est soumis à la deuxième étape du procédé selon l'invention.
L'effluent sortant de la dernière étape de préférence, est strippé à la vapeur, passe avantageusement dans un coalesceur et est éventuellement séché.
On traite cette coupe gazole selon un schéma en 2 étapes :
- une première étape sur un catalyseur contenant sous forme d'oxyde environ 3 % de nickel, 16,5 % de molybdène et 6 % de P2O5sur alumine. Cette première étape vise à la désulfuration et à la déazotation profonde de la coupe gazole
- une deuxième étape sur un catalyseur contenant environ 0,6 % de platine sur alumine. Cette deuxième étape vise essentiellement à la désaromatisation profonde de l'effluent de la première étape, mais permet également de diminuer encore la teneur en soufre.
- VVH=1,5 h-1
- pression totale=50 bar (10 bar = 1 MPa)
- Recyclage H2 = 400 Normaux litre H2/litre de charge (NI/I)
- Température=340 °C
- VVH=6 h-1
- Pression totale=50 bar
- Débit H2 = 400 NI. H2 /l. de charge
- Température =300 °C
Analyse charge et effluent 1ère et 2ème étape | |||
propriétés | Charge Gazole SR | 1ère étape | 2ème étape |
Densité 15/4 | 0,852 | 0,830 | 0,824 |
Indice Refraction | 1,4748 | 1.4600 | 1,454 |
Pt.Ecoulement °C | -3 | -3 | -6 |
Pt. Aniline °C | 71,7 | 79.1 | 86,7 |
Soufre ppm | 14400 | 30 | 4 |
Azote ppm | 110 | 6 | 6 |
Aromatiques %p | 30 | 22 | 2 |
Indice Cétane moteur | 56 | 61 | 65 |
D86 : PI °C | 223 | 205 | 205 |
D86 : 95%v °C | 375 | 365 | 359 |
(D86 signifie selon la méthode ASTM-D86) |
Bilan matière 1ère et 2ème étape | ||
% pds/charge | 1ère étape | 2ème étape |
H2S | 1,53 | 0,01 |
NH3 | 0,01 | 0,00 |
C1 | 0,01 | 0,00 |
C2 | 0,01 | 0,00 |
C3 | 0,02 | 0,00 |
C4 | 0,02 | 0,00 |
C5+ | 99,14 | 100,49 |
Total | 100,74 | 100,50 |
On traite cette coupe gazole selon un schéma en 2 étapes :
- une première étape sur un catalyseur contenant sous forme d'oxyde environ 3 % de nickel, 16,5 % de molybdène et 6 % de P2O5 sur alumine . Cette première étape vis à la désulfuration et à la déazotation profonde de la coupe gazole
- une deuxième étape sur un catalyseur contenant environ 0,6 % de platine sur alumine. Cette deuxième étape vise essentiellement à la désaromatisation profonde de l'effluent de la première étape, mais permet également de diminuer encore la teneur en soufre et en azote.
- VVH=1 h-1
- pression totale=80 bar (10 bar = 1 MPa)
- Recyclage H2 = 400 NI H2/l de charge
- Température=375 °C
Ses caractéristiques sont reportées sur le tableau N° 3. Le bilan matière est reporté dans le tableau 4.
- VVH=4 h-1
- Pression totale=50 bar
- Débit H2 = 400 l. H2 /l. de charge
- Température =300 °C
Analyse charge et effluent 1ère et 2ème étape | |||
propriétés | Charge LCO | 1ère étape | 2ème étape |
Densité 15/4 | 0,942 | 0,873 | 0,857 |
Indice Refraction | 1.5417 | 1.4818 | 1,4676 |
Pt.Ecoulement °C | 3 | 3 | 3 |
Pt. Aniline °C | 37 | 62 | 76 |
Soufre ppm | 15600 | 30 | 5 |
Azote ppm | 1089 | 16 | 8 |
Aromatiques %p | 72 | 32 | 4 |
Indice Cétane moteur | 27 | 45 | 54 |
D86 :PI °C | 184 | 147 | 174 |
D86 :95%v °C | 394 | 382 | 380 |
Bilan matière 1ère et 2ème étape | ||
%pds/charge | 1ère étape | 2ème étape |
H2S | 1,66 | 0,00 |
NH3 | 0,13 | 0,00 |
C1 | 0,08 | 0,00 |
C2 | 0,08 | 0,00 |
C3 | 0,06 | 0,00 |
C4 | 0,05 | 0,00 |
C5+ | 100,36 | 100,92 |
Total | 102,42 | 100,93 |
Propriétés | Charge LCO | 1ère étape | 2ème étape |
Densité 15/4 | 0,942 | 0,873 | 0,856 |
Indice réfraction | 1,5417 | 1,4816 | 1,4666 |
Pt d'écoulement °C | 3 | 3 | 3 |
Pt d'aniline °C | 37 | 62 | 77 |
Soufre ppm | 15 600 | 21 | 4 |
Azote ppm | 1 089 | 8 | 4 |
Aromatiques % poids | 72 | 32 | 3 |
Indice cétane moteur | 27 | 45 | 45 |
D86 PI °C | 184 | 147 | 174 |
D86 95 % °C | 394 | 382 | 380 |
Claims (14)
- Procédé de transformation d'une coupe gazole en un carburant à haut indice de cétane, désaromatisé et désulfuré caractérisé en ce qu'il comprend les étapes suivantes avec introduction d'hydrogène et éventuel recyclage d'hydrogène au niveau de chacune des première et deuxième étapes indépendamment entre elles :a) au moins une première étape dite de désulfuration et de déazotation profonde dans laquelle on fait passer ladite coupe gazole et de l'hydrogène sur un catalyseur comprenant un support minéral, au moins un métal ou composé de métal du groupe VIB de la classification périodique des éléments en une quantité exprimée en poids de métal par rapport au poids du catalyseur fini d'environ 0,5 à 40%, au moins un métal ou composé de métal du groupe VIII de ladite classification périodique en une quantité exprimée en poids de métal par rapport au poids du catalyseur fini d'environ 0,1 à 30% et du phosphore ou au moins un composé de phosphore en quantité exprimée en poids de pentoxyde de phosphore par rapport au poids du support d'environ 0,001 à 20 % etb) au moins une deuxième étape subséquente dite de désaromatisation dans laquelle on fait passer au moins une partie du produit issu du strippage à la vapeur de l'éffluent obtenu à l'issue de la première étape, produit qui est au moins en partie désulfuré et déazoté, et de l'hydrogène sur un catalyseur comprenant, sur un support minéral au moins un métal noble ou composé de métal noble du groupe VIII en une quantité exprimée en poids de métal par rapport au poids du catalyseur fini d'environ 0,01 à 20%.
- Procédé selon la revendication 1 dans lequel les conditions opératoires de l'étape a) sont choisies de manière à obtenir un produit contenant moins de 100 ppm de soufre et moins de 200 ppm d'azote et les conditions de l'étape b) sont choisies de manière à obtenir un produit contenant moins de 10 % en volume de composés aromatiques.
- Procédé selon la revendication 1 ou 2 dans lequel les conditions opératoires de l'étape a) comprennent une température de 300 °C à 450 °C, une pression totale de 2 MPa à 20 MPa et une vitesse spatiale horaire globale de charge liquide de 0,1 à 10 h-1 et celle de l'étape b) une température de 200 C à 400 °C, une pression totale de 2 MPa à 20 MPa et une vitesse spatiale horaire globale de charge liquide de 0,5 à 10 h-1.
- Procédé selon l'une des revendications 1 à 3 dans lequel le catalyseur de l'étape a) comprend au moins un métal ou un composé de métal choisi dans le groupe formé par le molybdène et le tungstène et au moins un métal ou un composé de métal choisi dans le groupe formé par le nickel, le cobalt et le fer.
- Procédé selon l'une des revendications 1 à 4 dans lequel le catalyseur de l'étape a) comprend du molybdène ou un composé de molybdène en une quantité exprimée en poids de métal par rapport au poids du catalyseur fini d'environ 2 à 30% et un métal ou un composé de métal choisi dans le groupe formé par le nickel et le cobalt en une quantité exprimée en poids de métal par rapport au poids du catalyseur fini d'environ 0,5 à 15%.
- Procédé selon l'une des revendications 1 à 5 dans lequel le métal du GVIII est le nickel et le métal du GVIB le molybdène.
- Procédé selon l'une des revendications 1 à 6 dans lequel le catalyseur de l'étape a) comprend en outre du bore ou au moins un composé de bore en une quantité exprimée en poids de trioxyde de bore par rapport au poids du support inférieure ou égale à 10 %.
- Procédé selon l'une des revendications 1 à 7 dans lequel le support des catalyseurs employés dans l'étape a) et dans l'étape b) sont choisis indépendamment l'un de l'autre dans le groupe formé par l'alumine, la silice, les silices-alumines, les zéolites, l'oxyde de titane, la magnésie l'oxyde de bore, la zircone, les argiles et les mélanges d'au moins deux de ces composés minéraux.
- Procédé selon l'une des revendications 1 à 8 dans lequel le support du catalyseur de l'étape b) comprend au moins un halogène.
- Procédé selon l'une des revendications 1 à 9 dans lequel le support du catalyseur de l'étape b) comprend une quantité d'halogène d'environ 0,5 à environ 15 % en poids par rapport au poids du support.
- Procédé selon la revendication 9 ou 10 dans lequel le support du catalyseur de l'étape b) comprend au moins un halogène choisi dans le groupe formé par le chlore et le fluor.
- Procédé selon l'une des revendications 9 à 11 dans lequel le support du catalyseur de l'étape b) comprend du chlore et du fluor.
- Procédé selon l'une des revendications 1 à 12 dans lequel le catalyseur de l'étape b) comprend au moins un métal ou un composé de métal choisi dans le groupe formé par le palladium et le platine en une quantité exprimée en poids de métal par rapport au poids du catalyseur fini d'environ 0,01 à 10%.
- Carburant obtenu selon le procédé de l'une quelconque des revendications 1 à 13.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9615929A FR2757532B1 (fr) | 1996-12-20 | 1996-12-20 | Procede de transformation d'une coupe gazole pour produire un carburant a haute indice de cetane, desaromatise et desulfure |
FR9615929 | 1996-12-20 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0849350A1 true EP0849350A1 (fr) | 1998-06-24 |
EP0849350B1 EP0849350B1 (fr) | 2005-04-13 |
Family
ID=9499065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97402996A Expired - Lifetime EP0849350B1 (fr) | 1996-12-20 | 1997-12-10 | Procédé de transformation d'une coupe gazole pour produire un carburant à haut indice de cétane, désaromatisé et désulfuré |
Country Status (9)
Country | Link |
---|---|
US (3) | US6042716A (fr) |
EP (1) | EP0849350B1 (fr) |
JP (1) | JP4134345B2 (fr) |
KR (1) | KR100536016B1 (fr) |
CN (1) | CN1134529C (fr) |
BR (1) | BR9706404A (fr) |
DE (1) | DE69732998T2 (fr) |
ES (1) | ES2242209T3 (fr) |
FR (1) | FR2757532B1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1063275A1 (fr) * | 1999-06-25 | 2000-12-27 | Institut Francais Du Petrole | Procédé d'hydrotraitement d'un distillat moyen dans deux zones comprenant une zone intermédiaire de stripage |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4225461A (en) * | 1978-01-02 | 1980-09-30 | Institut Francais Du Petrole | Process for manufacturing a group VIII noble metal catalyst of improved resistance to sulfur, and its use for hydrogenating aromatic hydrocarbons |
US4875992A (en) * | 1987-12-18 | 1989-10-24 | Exxon Research And Engineering Company | Process for the production of high density jet fuel from fused multi-ring aromatics and hydroaromatics |
US5110444A (en) * | 1990-08-03 | 1992-05-05 | Uop | Multi-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3356608A (en) * | 1967-12-05 | Hydrotreating process with hzs removal from the effluent | ||
US3236764A (en) * | 1964-11-27 | 1966-02-22 | Standard Oil Co | Jet fuel manufacture |
FR2197967B1 (fr) * | 1972-09-01 | 1975-01-03 | Inst Francais Du Petrole | |
US4427534A (en) * | 1982-06-04 | 1984-01-24 | Gulf Research & Development Company | Production of jet and diesel fuels from highly aromatic oils |
FR2617412B1 (fr) * | 1987-07-01 | 1993-05-14 | Inst Francais Du Petrole | Catalyseur comprenant un support mineral, du phosphore et du bore, methodes de preparation et utilisation en hydroraffinage de coupes petrolieres |
US4828675A (en) * | 1987-12-04 | 1989-05-09 | Exxon Research And Engineering Company | Process for the production of ultra high octane gasoline, and other fuels from aromatic distillates |
US5114562A (en) * | 1990-08-03 | 1992-05-19 | Uop | Two-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons |
US5462651A (en) * | 1994-08-09 | 1995-10-31 | Texaco Inc. | Hydrodearomatization of hydrocarbon oils using novel "phosphorus treated carbon" supported metal sulfide catalysts |
FR2757532B1 (fr) * | 1996-12-20 | 1999-02-19 | Inst Francais Du Petrole | Procede de transformation d'une coupe gazole pour produire un carburant a haute indice de cetane, desaromatise et desulfure |
-
1996
- 1996-12-20 FR FR9615929A patent/FR2757532B1/fr not_active Expired - Lifetime
-
1997
- 1997-12-10 DE DE69732998T patent/DE69732998T2/de not_active Expired - Lifetime
- 1997-12-10 ES ES97402996T patent/ES2242209T3/es not_active Expired - Lifetime
- 1997-12-10 EP EP97402996A patent/EP0849350B1/fr not_active Expired - Lifetime
- 1997-12-18 US US08/992,486 patent/US6042716A/en not_active Expired - Lifetime
- 1997-12-18 BR BR9706404A patent/BR9706404A/pt not_active IP Right Cessation
- 1997-12-19 JP JP35061197A patent/JP4134345B2/ja not_active Expired - Fee Related
- 1997-12-19 KR KR1019970070486A patent/KR100536016B1/ko not_active IP Right Cessation
- 1997-12-20 CN CNB971297231A patent/CN1134529C/zh not_active Expired - Fee Related
-
2000
- 2000-01-10 US US09/480,628 patent/US6221239B1/en not_active Expired - Lifetime
-
2001
- 2001-03-22 US US09/813,946 patent/US6451198B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4225461A (en) * | 1978-01-02 | 1980-09-30 | Institut Francais Du Petrole | Process for manufacturing a group VIII noble metal catalyst of improved resistance to sulfur, and its use for hydrogenating aromatic hydrocarbons |
US4875992A (en) * | 1987-12-18 | 1989-10-24 | Exxon Research And Engineering Company | Process for the production of high density jet fuel from fused multi-ring aromatics and hydroaromatics |
US5110444A (en) * | 1990-08-03 | 1992-05-05 | Uop | Multi-stage hydrodesulfurization and hydrogenation process for distillate hydrocarbons |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1063275A1 (fr) * | 1999-06-25 | 2000-12-27 | Institut Francais Du Petrole | Procédé d'hydrotraitement d'un distillat moyen dans deux zones comprenant une zone intermédiaire de stripage |
FR2795420A1 (fr) * | 1999-06-25 | 2000-12-29 | Inst Francais Du Petrole | Procede d'hydrotraitement d'un distillat moyen dans deux zones successives comprenant une zone intermediaire de stripage de l'effluent de la premiere zone avec condensation des produits lourds sortant en tete du strippeur |
US6623628B1 (en) | 1999-06-25 | 2003-09-23 | Institut Francais Du Petrole | Process for hydrotreating a middle distillate in two successive zones comprising an intermediate zone for stripping effluent from the first zone with condensation of the heavy products leaving overhead from the stripper |
KR100730969B1 (ko) * | 1999-06-25 | 2007-06-22 | 앵스띠뛰 프랑세 뒤 뻬뜨롤 | 스트립퍼의 정상부에서 배출되는 중질 탄화수소를 응축시키면서 제1 구간의 유출물을 스트립핑시키기 위한 중간 구간을 포함하고 있는 2 연속 구간에서 중간 증류물을 히드로 처리하는 방법 및 이 방법으로부터 얻어지는 부분 탈황되고 부분 탈방향족된 탄화수소 분획 |
EP1240942A1 (fr) * | 1999-08-30 | 2002-09-18 | Cosmo Oil Co., Ltd | Catalyseur destine a l'hydrotraitement du gas-oil, et procede d'hydrotraitement du gas-oil |
EP1240942A4 (fr) * | 1999-08-30 | 2003-08-06 | Cosmo Oil Co Ltd | Catalyseur destine a l'hydrotraitement du gas-oil, et procede d'hydrotraitement du gas-oil |
US6821412B1 (en) | 1999-08-30 | 2004-11-23 | Cosmo Oil Co., Ltd. | Catalyst for hydrotreating of gas oil and method for hydrotreating of gas oil |
EP1244761A1 (fr) * | 1999-12-08 | 2002-10-02 | Exxonmobil Oil Corporation | Procede permettant d'extraire du soufre d'une charge d'hydrocarbure |
EP1244761A4 (fr) * | 1999-12-08 | 2004-03-24 | Exxonmobil Oil Corp | Procede permettant d'extraire du soufre d'une charge d'hydrocarbure |
Also Published As
Publication number | Publication date |
---|---|
CN1189526A (zh) | 1998-08-05 |
DE69732998D1 (de) | 2005-05-19 |
ES2242209T3 (es) | 2005-11-01 |
JPH10183144A (ja) | 1998-07-14 |
MX9710346A (es) | 1998-08-30 |
FR2757532A1 (fr) | 1998-06-26 |
US20010013485A1 (en) | 2001-08-16 |
JP4134345B2 (ja) | 2008-08-20 |
US6221239B1 (en) | 2001-04-24 |
US6042716A (en) | 2000-03-28 |
CN1134529C (zh) | 2004-01-14 |
DE69732998T2 (de) | 2005-09-01 |
BR9706404A (pt) | 1999-06-08 |
EP0849350B1 (fr) | 2005-04-13 |
US6451198B2 (en) | 2002-09-17 |
FR2757532B1 (fr) | 1999-02-19 |
KR100536016B1 (ko) | 2006-04-20 |
KR19980064338A (ko) | 1998-10-07 |
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