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
  • 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
  • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
• • 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 internal combustion engines. It relates more particularly to the manufacture of a fuel for a compression ignition engine and the fuel thus obtained.
• Class II diesel fuel must not contain more than 50 ppm of sulfur and more than 10% by weight of aromatic compounds
• Class I diesel fuel must not contain more than 10 ppm of sulfur and 5% by weight of aromatic compounds.
• Class III diesel fuel must contain less than 500 ppm of sulfur and less than 25% by weight of aromatic compounds. Similar limits must also be observed for the sale of this type of fuel in California.
• diesel cuts come either from direct distillation of crude or from catalytic cracking: that is to say, light distillery cuts (Anglo-Saxon initials LCO for Light Cycle Oil), heavy fraction cuts (Anglo-Saxon initials HCO for Heavy Cycle Oil), or another conversion process (coking, visbreaking, residue hydroconversion, etc.) or even gas oils obtained from the distillation of aromatic or naphthenoaromatic crude oil such as Hamaca, Zuata, El Pao. It is particularly important to produce an effluent directly and fully recoverable as a very high quality fuel cutter.
• the present invention differs from the prior art in that it combines hydrocracking with hydrogenation.
• the charge treated contains at least 50% by weight of constituents boiling above 375 ° C. and the aim of the process is to convert at least 70% vol. of these heavy constituents into constituents with boiling points below 375 ° C.
• the light compounds are obviously separated (residual H2, C1-C4, H2S, NH3 .7)
• this process comprising a hydrotreatment step followed by a hydrocracking step on a zeolitic catalyst converts a heavy fraction into diesel (250-375 ° C) and gasoline (150-250 ° C) with the highest possible yield. .
• the invention relates to a process for converting a diesel cut into a fuel with a high cetane number, which is flavored, desulphurized and having good cold qualities, this process comprising the following steps:
• a catalyst comprising a mineral support partly zeoiithic, at least one metal or metal compound of group VIB of the periodic table of the elements in an amount expressed by weight of metal relative to the weight of the finished catalyst of approximately 0.5 to 40% and at least one non-noble metal or compound of non-noble metal from group VIII in an amount expressed by weight of metal relative to the weight of the finished catalyst of approximately 0.01 to 20%, the hydrocracking effluent being subjected to separation of the light compounds.
• This two-stage process essentially comprises a significant or controlled hydrogenation of the aromatic compounds - depending on the content of aromatic compounds which it is desired to obtain in the final product -, then a hydrocracking intended to open the naphthenes produced in the first stage so form paraffins.
• These charges are treated with hydrogen in the presence of catalysts, this treatment makes it possible to hydrogenate the aromatic compounds present in the charge, it also makes it possible to simultaneously carry out hydrodesulphuration and hydrodenitrogenation.
• the operating conditions for the hydrogenation (or hydrotreatment) are as follows: the space velocity (VVH) is between 0.1 and 30 volumes of liquid charge per volume of catalyst and per hour and preferably between 0.2 and 10; the inlet temperature to the reactor is between 250 and 450 ° C and preferably between 320 and 400 ° C; the pressure in the reactor is between 0.5 and 20 MPa and preferably between 4 and 15 MPa; the recycling of pure hydrogen is between 100 and 2,500 Nm3 / m3 of charge and preferably between 200 and 2,100 Nm3 / m3, and even more advantageously lower at 2000 Nm3 / m3.
• the hydrogen consumption in the process can go up to around 5% by weight of the charge (0.5-4.5% in general).
• the hydrogenation catalyst comprises, on an amorphous mineral support, at least one metal or compound of metal from group VIB of the periodic table of elements such as molybdenum or tungsten, in an amount expressed by weight of metal relative to the weight of the finished catalyst of between 0.5 and 40% and preferably between 2 to 30%, at least one metal or compound of non-noble metal from group VIII of said periodic classification such as nickel, cobalt or iron in an amount expressed by weight of metal relative to the weight of the finished catalyst of between 0.01 and 30% and preferably between 0.1 and 10%, of phosphorus or at least one phosphorus compound in an amount expressed by weight of pentoxide of phosphorus relative to the weight of the support between 0.001 and 20%.
• group VIB of the periodic table of elements such as molybdenum or tungsten
• the catalyst can also contain boron or at least one boron compound in an amount expressed by weight of boron trioxide relative to the weight of the support of between 0.001 and 10%.
• the amorphous mineral support will be, for example, alumina or silica-alumina. According to a particular form of the invention, cubic gamma alumina will be used which preferably has a specific surface of approximately 50 to 500 m 2 / g.
• the hydrogenation catalyst used in the present invention is preferably subjected to a sulphurization treatment making it possible to transform, at least in part, the metallic species into sulphide before they are brought into contact with the charge to be treated.
• This sulfurization activation treatment is well known to those skilled in the art and can be carried out by any method already described in the literature.
• a conventional sulfurization method well known to those skilled in the art consists in heating the catalyst in the presence of hydrogen sulfide or of a hydrogen sulfide precursor at a temperature between 150 and 800 ° C., preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
• hydrogen sulfide precursor within the meaning of the present description, is meant any compound capable of reacting, under the operating conditions of the reaction to give hydrogen sulfide.
• the hydrogenated products coming from the first stage may or may not undergo a treatment chosen from the group formed by gas-liquid separations and distillations.
• the liquid phase then undergoes hydrocracking according to step b) of the present invention.
• the operating conditions for hydrocracking are as follows: the space velocity (VVH) is approximately 0.1 to 30 volumes of liquid charge per volume of catalyst and per hour and preferably between 0.2 and 10, the inlet temperature into the reactor is between 250 to 450 ° C and preferably between 300 and 400 ° C; the reactor pressure is between 0.5 and 20 MPa and preferably between 4 and 15 MPa and even more preferably between 7 and 15 MPa; the recycling of pure hydrogen is between 100 to 2200 Nm3 / m3 of charge. Under these conditions, the conversion is adjusted according to the cetane number and the other properties (density, T95, etc.) to be obtained.
• the total conversion (hydrocracking b) + that obtained during the hydrogenation step a)) can be greater than 50% or less than 50% (5-50% for example) depending on the cut to be treated.
• the catalyst of the second stage generally comprises at least one zeolite, at least one support and at least one hydro-dehydrogenating function.
• An acidic zeolite is particularly advantageous in this type of embodiment, for example a zeolite of faujasite type, and preferably a Y zeolite, will be used.
• the zeolite content by weight is between 0.5 and 80% and preferably between 3 and 50 % relative to the finished catalyst.
• a zeolite Y with a crystalline parameter 24.14 x 10 "10 m to 24.55 x 10 " 10 m will be used.
• the catalyst contains at least one metal oxide or sulfide of group VIB such as molybdenum or tungsten in an amount expressed by weight of metal by relative to the weight of the finished catalyst of between 0.5 to 40% and at least one non-noble metal or compound of non-noble metal from group VIII such as nickel, cobalt or iron in an amount expressed by weight of metal relative by weight of the finished catalyst of between 0.01 and 20% and preferably between 0.1 and 10%.
• group VIB such as molybdenum or tungsten
• group VIII such as nickel, cobalt or iron
• hydrocracking catalyst used in the present invention is preferably subjected to a sulphurization treatment making it possible to transform, at least in part, the metallic species into sulphides before they are brought into contact with the feed to be treated.
• This sulfurization activation treatment is well known to those skilled in the art and can be carried out by any method already described in the literature.
• a conventional sulfurization method well known to those skilled in the art consists in heating the catalyst in the presence of hydrogen sulfide or of a hydrogen sulfide precursor at a temperature between 150 and 800 ° C., preferably between 250 and 600 ° C, generally in a crossed-bed reaction zone.
• a particularly advantageous acidic zeolite HY is characterized by different specifications: a Si ⁇ 2 / Al2 ⁇ 3 molar ratio of between 8 and 70 and preferably between 12 and 40: a sodium content of less than 0.15% by weight determined on the zeolite calcined at 1100 ° C; a crystalline parameter "a" of the elementary mesh comprised between 24.55 x 10 " 10 m and
• the Y-Na zeolite from which the HY zeolite is prepared has a Si ⁇ 2 / Al2 ⁇ 3 molar ratio of between approximately 4 and 6; it should first be lowered the sodium content (weight) to a value of the order of 1 to 3% and preferably to less than 2.5%; the Y-Na zeolite also generally has a specific surface of between 750 m 2 / g and 950 m 2 / g approximately.
• the effluent obtained at the end of the hydrocracking is obviously fractionated to separate the light products (cracked), that is to say the products boiling below 150 ° C in general, or even below 180 ° C or other temperature chosen by the refiner. At least one diesel cut 150 ° C + or even 180 ° C + is thus obtained. If the feeds contain compounds with a boiling point above 370 ° C., it is advantageously possible to separate them so as to preferably recycle them towards the hydrogenation step and / or the hydrocracking step. Instead of cutting at 370 ° C, we can cut lower, at 350 ° C for example, according to the refiner's request.
• the present invention makes it possible to obtain diesel cuts whose cetane number, and possibly the content of aromatic compounds, are improved in such a way that these cuts can reach current and future specifications. These diesel cuts are directly marketable.
• the present invention makes it possible to make the most of all the products contained in the treated petroleum cut.
• the yield of recoverable products is close to 99% compared to the quantity of hydrocarbons; unlike other conventional processes, there is no liquid or solid waste to be incinerated.
• the diesel feedstocks to be treated are preferably light diesel oils, such as for example direct distillation gas oils, fluid catalytic cracking gas oils (English initials FCC for Fluid Catalytic Cracking) or (LCO). They generally have an initial boiling point of at least 180 ° C and a final boiling point of at most 370 ° C. More broadly, the invention is applicable to diesel cuts with an initial boiling point of at least 150 ° C, of which at least 80% by weight at at most 370 ° C, and advantageously at least 90% by weight at at most 370 ° C The weight composition of these charges by families of hydrocarbons is variable according to the intervals.
• light diesel oils such as for example direct distillation gas oils, fluid catalytic cracking gas oils (English initials FCC for Fluid Catalytic Cracking) or (LCO). They generally have an initial boiling point of at least 180 ° C and a final boiling point of at most 370 ° C. More broadly, the invention is applicable to diesel cuts with an initial boiling point of at least 150 ° C, of which at
• the paraffin contents are between 5.0 and 30.0%, naphthenes between 5.0 and 40.0% and aromatic compounds between 40.0 and 80.0% .
• Less aromatic fillers can also be treated having less than 40% of aromatics and generally from 20% to less than 40% of aromatics, the naphthene contents being able to go up to 60%.
• the catalyst used in the hydrogenation stage has the following characteristics: nickel content in the form of oxides of 3%, a molybdenum content in the form of oxides of 16.5% and 6% phosphorus pentoxide on alumina.
• a catalyst is advantageously used, the support of which is alumina. This catalyst contains by weight 12% of molybdenum, 4% of nickel in the form of oxides and 10% of zeolite Y, this catalyst is described in example 2 of US Pat. No. 5,525,209.
• These catalysts are sulfurized by an n-hexane mixture / DMDS + aniline up to 320 ° C. After 3000 hours of continuous operation, no deactivation of the catalysts as described in the example was observed.
• the charge is treated in a pilot unit comprising two reactors in series, under the following conditions: the space speed in the two reactors is 0.29 volume of liquid charge per volume of catalyst and per hour, the temperature of entry into the first reactor is 380 ° C for hydrogenation and it is 390 ° C for hydrocracking, the pressure in the two reactors is 14 MPa. In each reactor, the hydrogen recycling is 2000 Nm 3 per m 3 of feed. The characteristics of the feed and of the 190 ° C. + product obtained after each step are recorded in Table 1, after the hydrocracking step and after distillation.
• the charge was treated in a pilot unit comprising two reactors in series, under the following conditions, the space speed in the two reactors is 0.25 volume of liquid charge per volume of catalyst and per hour, the inlet temperature into the first reactor is 385 ° C for hydrogenation and in the second reactor, it is 375 ° C for hydrocracking, the pressure in the two reactors is 14 MPa. In each reactor, the hydrogen recycling is 2000 Nm 3 per m 3 of feed. The characteristics of the fillers and of the products obtained after each step are recorded in Table 2.
• the feed was treated in a pilot unit comprising the two reactors in series in Example 1, under the following conditions, the space speed in the two reactors is 0.25 volume of liquid feed per volume of catalyst and per hour, the inlet temperature in the first reactor is 360 ° C. for the hydrogenation and in the second reactor, it is 367 ° C. for the hydrocracking, the pressure in the two reactors is 14 MPa. In each reactor, the hydrogen recycling is 2000 Nm 3 per m 3 of feed. The characteristics of the fillers and of the products obtained after each step are recorded in Table 3. 11
• This example 3 shows the contribution of the hydrocracking stage with regard to the quality of the products, the gains obtained on the hydrocracking catalyst alone are 39 / 1000th in density, 22 ° C. at 95% point and 11 cetane points.
• the invention has two major advantages: it saves hydrogen since less hydrogenation is carried out to obtain the same cetane number; it also allows the constitution of a reserve of aromatic compounds that 12
• the hydrogenation step is carried out with any known hydrogenation catalyst, and in particular those containing at least one noble metal deposited on an amorphous support of refractory oxide (alumina for example).
• a preferred catalyst contains at least one noble metal (preferred platinum), at least one halogen (and preferably 2 halogens: chlorine and fluorine) and a matrix (preferred alumina)
• the hydrogenation step can be carried out on the total effluent leaving the hydrocracking step, a separation of the compounds 150- (or preferably 180-) then taking place after this hydrogenation.
• the hydrogenation stage can also be carried out on the 150+ section (or 180+ depending on the fractionation chosen), optionally followed by separation of the compounds 150- (or 180-).
• fuels having sulfur contents of less than 500 ppm, and even contents of less than 50 ppm or even less than 10 ppm are obtained.
• the cetane numbers remain at least 49 or at least 50.
• the aromatics content is generally at most 20% (5- 20%) and that in polyaromatics lowered below 1% .
• the gain is the difference observed between the property values for the product and for the starting cut.
• Density at 15 ° C gain generally around 100 / 1000th and more cetane (cut 150+): gain of at least 20 or 25 which can go up to + 35 or more against approximately 20 in the point 95 hydrogenation processes %: gains ranging from 25 to 60 ° C or more, instead of 10-20 ° C maximum for hydrogenation

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• 1998
  • 1998-04-09 FR FR9804605A patent/FR2777290B1/fr not_active Expired - Lifetime
• 1999
  • 1999-04-09 US US09/445,573 patent/US6814856B1/en not_active Expired - Fee Related
  • 1999-04-09 WO PCT/FR1999/000817 patent/WO1999052993A1/fr not_active Application Discontinuation
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  • 1999-04-09 KR KR1020007011223A patent/KR100601822B1/ko not_active IP Right Cessation
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• 2004
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