EP1002853A1 - Procédé de production d'essences à faible teneur en soufre - Google Patents
Procédé de production d'essences à faible teneur en soufre Download PDFInfo
- Publication number
- EP1002853A1 EP1002853A1 EP99402792A EP99402792A EP1002853A1 EP 1002853 A1 EP1002853 A1 EP 1002853A1 EP 99402792 A EP99402792 A EP 99402792A EP 99402792 A EP99402792 A EP 99402792A EP 1002853 A1 EP1002853 A1 EP 1002853A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrodesulfurization
- fraction
- catalyst
- light
- sulfur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
-
- 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
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
- C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
Definitions
- the present invention relates to a method for producing gasolines with low sulfur content, which makes it possible to recover the entire petrol cut containing sulfur, to reduce the total sulfur and mercaptan contents of said petrol cut at very low levels, with no appreciable reduction in fuel efficiency, and minimizing the decrease in the octane number.
- Patent application EP-A-0 725 126 describes a hydrodesulfurization process of a cracked gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in compounds easy to desulfurization and a second fraction rich in compounds difficult to desulfurize. Before to carry out this separation, it is first necessary to determine the distribution of the products sulfur by means of analyzes. These analyzes are necessary to select apparatus and separation conditions.
- the charge of the process according to the invention is a petrol cut containing sulfur, preferably a petrol cut from a catalytic cracking unit, whose range of boiling points typically extends from about the points boiling of hydrocarbons with 5 carbon atoms (C5) up to about 220 ° C.
- the end point of the gasoline cut depends on the refinery from which it comes and constraints of the market, but generally remains within the limits indicated above.
- the method according to the invention comprises a separation of the gasoline in two fractions: a light fraction (also called hereinafter light cut or essence light) whose end point is generally less than or equal to about 160 ° C, preferably less than 140 ° C and more preferably less than 120 ° C, a fraction heavy (also called hereinafter heavy cut or heavy petrol) which is constituted by the heavy fraction complementary to light petrol.
- a light fraction also called hereinafter light cut or essence light
- a fraction heavy also called hereinafter heavy cut or heavy petrol
- the cutting point is chosen so as to maximize the olefin content in the light cut.
- This content can be easily determined, for example by means of the determination of the bromine index, generally available on the site.
- Hydrodesulfurization also called hydrotreatment
- Hydrodesulfurization of light gasoline is carried out on a nickel-based catalyst described in a patent application deposited simultaneously, and the hydrodesulfurization of the heavy fraction on a catalyst conventional hydrotreatment (hydrodesulfurization) comprising a metal from the group VIII and a metal from group Vlb.
- gasoline to be desulfurized contains polyolefins (dienes), to achieve a selective hydrogenation of gasoline before fractionation.
- the sulfur content of gasoline cuts produced by catalytic cracking depends on the sulfur content of the feed treated with FCC, as well as the point end of the cut. Light fractions naturally have a higher sulfur content weaker than heavier cuts.
- This catalyst operates under a pressure of 0.4 to 5 MPa, at a temperature of 50 to 250 ° C, with an hourly space velocity of the liquid from 1 to 10 h -1 .
- Another metal can be combined to form a bimetallic catalyst, such as for example molybdenum or tungsten.
- the light fraction of the catalytic cracked petrol cut may contain up to a few% by weight of diolefins.
- the diolefin content is generally reduced to less than 3000 ppm or even less than 2500 ppm and more preferably less than 1500 ppm. In some cases it can be obtained less than 500 ppm.
- the content of dienes after selective hydrogenation can even if necessary be reduced to less than 250 ppm.
- This separation can be carried out by any known technique of those skilled in the art, such as for example distillation or adsorption.
- the nickel content of the catalyst used according to the invention is generally between about 1 and about 80% by weight, preferably between 5 and 70% by weight and, even more preferably, between 10 and 50% by weight.
- the catalyst is generally shaped, preferably in the form of beads, extrudates, lozenges, or trilobes.
- Nickel can be incorporated into the catalyst on the preformed support, it can also be mixed with the support before the step of shaping.
- Nickel is generally introduced in the form of a precursor salt, generally soluble in water, such as for example nickel nitrate. This mode of introduction is not specific to the invention. Any other known mode of introduction skilled in the art is suitable for the invention.
- the catalyst supports used in the process of the invention are generally porous solids chosen from refractory oxides, such as, for example, aluminas, silicas and silica-aluminas, magnesia, as well as titanium oxide and zinc oxide, the latter oxides can be used alone or as a mixture with alumina or silica-alumina.
- the supports are transition aluminas or silicas whose specific surface is between 25 and 350 m 2 / g.
- the supports chosen from natural compounds for example kieselguhr or kaolin may also be suitable as supports for the catalysts of the process according to the invention.
- the catalyst is in a first step activated.
- This activation can correspond either to a oxidation, then reduction, either direct reduction, or calcination only.
- the calcination step is generally carried out at temperatures ranging from about 100 to about 600 ° C and preferably between 200 and 450 ° C, under air flow.
- the reduction step is carried out under conditions allowing convert at least some of the oxidized forms of nickel to metal. Usually, it consists in treating the catalyst under a stream of hydrogen at a temperature at less than 300 ° C.
- the reduction can also be achieved in part by means of chemical reducers.
- the catalyst is preferably reduced under the conditions described above, then sulphurized by passing a charge containing at least one sulfur compound, which once decomposed leads to the fixing of sulfur on the catalyst.
- This charge can be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur-containing compound.
- the sulfur-containing compound is added to the catalyst ex situ.
- a sulfur-containing compound can be introduced onto the catalyst in the optional presence of another compound.
- the catalyst is then dried, then transferred to the reactor used to carry out the process of the invention. In this reactor, the catalyst is then treated under hydrogen in order to transform at least part of the nickel into sulphide.
- a procedure which is particularly suitable for the invention is that described in patents FR-B- 2,708,596 and FR-B- 2,708,597.
- the sulfur content of the catalyst is generally understood between 0.5 and 25% by weight, preferably between 4 and 20% by weight.
- the hydrodesulfurization of the light fraction is carried out in the presence of hydrogen, with the nickel-based catalyst at a temperature between about 160 ° C and about 420 ° C, under a low to moderate pressure, generally between about 0, 5 and around 8 MPa.
- the space velocity of the liquid is between approximately 0.5 and approximately 10 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 1 and 8 h -1 .
- the H 2 / HC ratio is adjusted as a function of the desired hydrodesulfurization rates in the range between approximately 100 and approximately 600 liters per liter.
- the heavy fraction thus desulfurized has the same distillation range and a slightly lower octane number than before hydrotreatment, due to saturation total olefins. This loss of octane is limited because the heavy fraction (petrol heavy) has an olefin content generally less than 20% by weight and preferably less than 10% by weight.
- the operating conditions of the hydrotreatment reactor according to the present invention must be adjusted in order to reach the desired level of desulfurization. At least 90% of the sulfur compounds present in heavy petrol are generally converted into H 2 S.
- the heavy fraction is subjected to hydrotreatment, in the presence of hydrogen, with a catalyst containing at least one group VIII metal and / or at least one Vlb group metal, at a temperature between about 160 ° C and about 420 ° C, under a pressure generally between approximately 0.5 and approximately 8 MPa.
- the space velocity of the liquid is between approximately 0.5 and approximately 10 h -1 (expressed in volume of liquid per volume of catalyst and per hour), preferably between 1 and 6 h -1 .
- the H 2 / HC ratio is adjusted as a function of the desulfurization rates desired in the range of 100 to 600 liters per liter and preferably from 300 to 600 liters per liter.
- the temperature is between 200 ° C and 300 ° C.
- the pressure is between 2 and 4 MPa.
- At least one conventional hydrodesulfurization catalyst comprising at least one group VIII metal (metals of groups 8, 9 and 10 of the new classification, i.e. iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium or platinum) and / or at least one metal of group Vlb (metals of group 6 of the new classification, i.e. chromium, molybdenum or tungsten), on a suitable support.
- Group VIII metal when is present, is usually nickel or cobalt
- the metal of group Vlb when is present, is usually molybdenum or tungsten.
- the catalyst support is usually a porous solid, such as for example an alumina, a silica-alumina or other porous solids, such as, for example, magnesia, silica or titanium oxide, alone or as a mixture with alumina or silica-alumina.
- Each of the two fractions is then subjected to hydrodesulfurization, in the conditions described above, in order to almost completely remove the sulfur from the fraction heavy and eliminating part of the sulfur present in the light fraction, limiting itself preferably to reach the sulfur content necessary for the product obtained by mixing the two hydrodesulfurized cuts has a sulfur content corresponding to the specifications sought.
- Another possibility is to place the reaction zones where the hydrodesulfurization reactions of light and heavy fractions of gasoline to outside the distillation area but to use as charge areas hydrodesulfurization reaction of the liquid fractions sampled on the distillation zone, with recycling of the desulphurized effluents to said distillation, at one or more levels above or below, preferably at neighborhood, levy levels.
- hydrotreatment catalysts aimed at treating light and heavy fractions petrol are placed directly in the distillation zone allowing the separation of the light fraction from the heavy fraction.
- Example 1 hydrodesulfurization of unfractionated gasoline.
- HR306C® catalyst sold by the company Procatalyse
- the catalyst is first sulfurized with treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a charge consisting of 2% sulfur in the form of dimethyldisulfide in n-heptane.
- Example 2 hydrodesulfurization of fractionated gasoline.
- the heavy fraction of gasoline is subjected to hydrodesulfurization on a conventional hydrotreating catalyst in an insulated tubular reactor.
- 25 ml of HR306C® catalyst, sold by the company Procatalyse, are placed in the hydrodesulfurization reactor.
- the catalyst is first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a load consisting of 2% sulfur in the form of dimethyldisulfide in n-heptane.
- the catalyst is prepared from a transition alumina of 140 m 2 / g in the form of beads 2 mm in diameter.
- the pore volume is 1 ml / g of support.
- 1 kilogram of support is impregnated with 1 liter of nickel nitrate solution.
- the catalyst is then dried at 120 ° C and calcined in an air stream at 400 ° C for one hour.
- the nickel content of the catalyst is 20% by weight.
- the catalyst (100 ml) is then sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a feed containing 4% sulfur in the form of dimethyldisulphide in n-heptane.
- Hydrodesulfurization of light gasoline is then carried out.
- the temperature is 280 ° C
- the charge rate is 200 ml / hour.
- the H 2 / charge ratio expressed in liters of hydrogen per liter of charge is 400, the operating pressure is 2.7 MPa.
- the gasoline whose characteristics are described in Table 1 is divided into two cuts, one with an end point of 110 ° C (light cut) the other with a point initial temperature of 110 ° C (heavy cut).
- the characteristics of distilled essences and the yield of each cut are described in Table 3 of Example 2.
- the light fraction of petrol is subjected to hydrodesulfurization on the HR306C® catalyst in isothermal tubular reactor.
- the catalyst is first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, at contact of a charge consisting of 2% sulfur in the form of dimethyldisulfide in n-heptane.
- the light gasoline and the heavy gasoline desulfurized separately are then mixed.
- the product obtained has the following characteristics: Characteristics of the light petrol - heavy petrol mixture after hydrodesulfurization Charge Desulfurized gasoline S total (ppm) 4500 315 S ex mercaptans (ppm) 0 113 Olefins (% vol.) 25 16 MY 82 78.6 RON 95 88.6 (RON + MON) / 2 88.5 83.6 Octane loss - 4.9 % HDS 93.1 % HDO 36
Abstract
Description
- une fraction légère, dont les points intitial et final sont par exemple de 20 °C et 160 °C respectivement, et qui renferme la plus grande partie des oléfines et une partie des composés soufrés,
- une fraction lourde, dont le point initial est par exemple supérieur à 160 °C, et qui renferme les composés soufrés les plus lourds et, comme composés insaturés, peu d'oléfines mais principalement des composés aromatiques.
- chromatographie en phase gaz (CPG) pour les constituants hydrocarbonés ;
- méthode NF M 07022/ASTM D 3227 pour les mercaptans ;
- méthode NF M 07052 pour le soufre total ;
- méthode NF EN 25164/M 07026-2/ISO 5164/ASTM D 2699 pour l'indice d'octane recherche ;
- méthode NF EN 25163/M 07026-1/ISO 5163/ASTM D 2700 pour l'indice d'octane moteur.
Caractéristiques de la charge utilisée. | |
Charge | |
Densité | 0,75 |
Point initial (°C) | 80°C |
Point final (°C) | 240°C |
teneur en oléfines (% vol.) | 25 |
S total (ppm) | 4500 |
S ex mercaptans (ppm) | 0 |
RON | 95 |
MON | 82 |
(RON + MON)/2 | 88.5 |
Comparaison des caractéristiques de la charge et de l'effluent désulfuré. | ||
Charge | Effluent | |
S total (ppm) | 4500 | 315 |
S ex mercaptans (ppm) | 0 | 150 |
Oléfines (% vol.) | 25 | 8 |
MON | 82 | 76 |
RON | 95 | 85 |
(RON + MON)/2 | 88.5 | 80.5 |
Perte en octane | -- | 8 |
% HDS | 93.1 | |
% HDO | 68 |
Caractéristiques des essences distillées et rendement de chaque coupe | |||
Charge | Essence légère | Essence lourde | |
Volume (%) | 45 | 55 | |
S total (ppm) | 4500 | 1600 | 6900 |
S ex mercaptans (ppm) | 0 | 0 | 0 |
Oléfines (% vol.) | 25 | 46 | 7.5 |
Point initial (°C) | 80 | 80 | 110 |
Point final (°C) | 240 | 110 | 240 |
Hydrodésulfuration de l'essence légère sur catalyseur au Nickel | ||
Essence légère | Essence légère désulfurée | |
S total (ppm) | 1600 | 700 |
S ex mercaptans (ppm) | 0 | 20 |
Oléfines (% vol.) | 46 | 43 |
Point initial (°C) | 80 | 80 |
Point final (°C) | 110 | 110 |
Caractéristiques du mélange essence légère - essence lourde après hydrodésulfurations | ||
Charge | Essence désulfurée | |
S total (ppm) | 4500 | 315 |
S ex mercaptans (ppm) | 0 | 9 |
Oléfines (% vol.) | 25 | 19.5 |
MON | 82 | 81.2 |
RON | 95 | 92 |
(RON + MON)/2 | 88.5 | 86.6 |
Perte en octane | -- | 1.9 |
% HDS | 93.1 | |
% HDO | 22 |
Hydrodésulfuration de l'essence légère sur catalyseur HR 306C® | ||
Essence légère | Essence légère désulfurée | |
S total (ppm) | 1600 | 700 |
S ex mercaptans (ppm) | 0 | 250 |
Oléfines (% vol.) | 46 | 36 |
Point initial (°C) | 80 | 80 |
Point final (°C) | 110 | 110 |
Caractéristiques du mélange essence légère - essence lourde après hydrodésulfurations | ||
Charge | Essence désulfurée | |
S total (ppm) | 4500 | 315 |
S ex mercaptans (ppm) | 0 | 113 |
Oléfines (% vol.) | 25 | 16 |
MON | 82 | 78.6 |
RON | 95 | 88.6 |
(RON + MON)/2 | 88.5 | 83.6 |
Perte en octane | -- | 4.9 |
% HDS | 93.1 | |
% HDO | 36 |
Claims (10)
- Procédé de production d'essence à faible teneur en soufre, dans lequel ledit procédé comprend :une séparation d'une essence contenant du soufre en une fraction légère et une fraction lourde, le point de coupe étant choisi de façon à maximiser la teneur en oléfines dans la coupe légère,une hydrodésulfuration de la fraction légère sur un catalyseur à base de nickel,une hydrodésulfuration de la fraction lourde sur un catalyseur comprenant au moins un métal du groupe VIII et/ou au moins un métal du groupe Vlb, etle mélange des fractions désulfurées.
- Procédé selon la revendication 1 dans lequel l'essence contenant du soufre est issue d'un procédé de craquage catalytique.
- Procédé selon l'une des revendications précédentes dans lequel le catalyseur utilisé pour l'hydrodésulfuration de la fraction lourde comprend également un métal du groupe Vlb.
- Procédé selon la revendication 3 dans lequel le métal du groupe Vlb est le molybdène ou le tungstène et le métal du groupe VIII est le nickel ou le cobalt.
- Procédé selon l'une des revendications précédentes dans lequel on effectue, avant la séparation, une hydrogénation des diènes présents dans la coupe essence contenant du soufre.
- Procédé selon l'une des revendications précédentes dans lequel le point de coupe entre la fraction légère et la fraction lourde se situe à une température inférieure à 160°C.
- Procédé selon l'une des revendications précédentes dans lequel la fraction lourde présente une teneur en oléfine inférieure à 20% poids.
- Procédé selon l'une des revendications précédentes dans lequel l'hydrodésulfuration de la fraction légère et l'hydrodésulfuration de la fraction lourde sont effectuées en présence d'hydrogène, à une température comprise entre 160°C et 420°C, sous une pression comprise entre environ 0,5 et environ 8 MPa, avec une vitesse spatiale du liquide comprise entre environ 0,5 et environ 10 h-1 et un rapport H2/HC compris entre environ 100 et environ 600 litres par litre.
- Procédé selon l'une des revendications précédentes dans lequel la séparation est effectuée dans une colonne de distillation et dans lequel les charges des réacteurs d'hydrodésulfurations sont prélevées à deux niveaux différents de ladite colonne et les effluents desdits réacteurs sont renvoyés dans ladite colonne.
- Procédé selon l'une des revendications précédentes dans lequel la séparation est effectuée dans une colonne de distillation et dans lequel les catalyseurs d'hydrodésulfuration sont placés à l'intérieur de ladite colonne.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9814480A FR2785908B1 (fr) | 1998-11-18 | 1998-11-18 | Procede de production d'essences a faible teneur en soufre |
FR9814480 | 1998-11-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1002853A1 true EP1002853A1 (fr) | 2000-05-24 |
EP1002853B1 EP1002853B1 (fr) | 2006-06-14 |
Family
ID=9532861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99402792A Expired - Lifetime EP1002853B1 (fr) | 1998-11-18 | 1999-11-09 | Procédé de production d'essences à faible teneur en soufre |
Country Status (8)
Country | Link |
---|---|
US (1) | US6334948B1 (fr) |
EP (1) | EP1002853B1 (fr) |
JP (1) | JP4547745B2 (fr) |
KR (1) | KR100626623B1 (fr) |
CN (1) | CN1158378C (fr) |
DE (1) | DE69931876T2 (fr) |
ES (1) | ES2267238T3 (fr) |
FR (1) | FR2785908B1 (fr) |
Cited By (1)
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FR2900157A1 (fr) * | 2006-04-24 | 2007-10-26 | Inst Francais Du Petrole | Procede de desulfuration d'essences olefiniques comprenant au moins deux etapes distinctes d'hydrodesulfuration |
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FR2993569B1 (fr) | 2012-07-17 | 2015-12-04 | IFP Energies Nouvelles | Procede de desulfuration d'une essence |
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FR2997415B1 (fr) | 2012-10-29 | 2015-10-02 | IFP Energies Nouvelles | Procede de production d'une essence a basse teneur en soufre |
FR3000964B1 (fr) | 2013-01-14 | 2016-01-01 | IFP Energies Nouvelles | Procede de production d'une essence basse teneur en soufre |
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- 1999-11-09 ES ES99402792T patent/ES2267238T3/es not_active Expired - Lifetime
- 1999-11-09 DE DE69931876T patent/DE69931876T2/de not_active Expired - Lifetime
- 1999-11-17 KR KR1019990051003A patent/KR100626623B1/ko not_active IP Right Cessation
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EP1849850A1 (fr) * | 2006-04-24 | 2007-10-31 | Ifp | Procédé de désulfuration d'essences oléfiniques comprenant au moins deux étapes distinctes d'hydrodésulfuration |
US7651606B2 (en) | 2006-04-24 | 2010-01-26 | Institut Francais Du Petrole | Process for desulphurizing olefinic gasolines, comprising at least two distinct hydrodesulphurization steps |
Also Published As
Publication number | Publication date |
---|---|
DE69931876T2 (de) | 2006-10-05 |
ES2267238T3 (es) | 2007-03-01 |
FR2785908B1 (fr) | 2005-12-16 |
CN1253993A (zh) | 2000-05-24 |
KR100626623B1 (ko) | 2006-09-25 |
JP4547745B2 (ja) | 2010-09-22 |
DE69931876D1 (de) | 2006-07-27 |
KR20000035520A (ko) | 2000-06-26 |
CN1158378C (zh) | 2004-07-21 |
FR2785908A1 (fr) | 2000-05-19 |
EP1002853B1 (fr) | 2006-06-14 |
US6334948B1 (en) | 2002-01-01 |
JP2000160169A (ja) | 2000-06-13 |
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