EP1406990B1 - Verfahren zur herstellung von mitteldestillaten durch zweistufige hydroisomerisation und hydrocracking von reaktionsprodukten aus dem fischer-tropsch verfahren - Google Patents

Verfahren zur herstellung von mitteldestillaten durch zweistufige hydroisomerisation und hydrocracking von reaktionsprodukten aus dem fischer-tropsch verfahren Download PDF

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EP1406990B1
EP1406990B1 EP02751285A EP02751285A EP1406990B1 EP 1406990 B1 EP1406990 B1 EP 1406990B1 EP 02751285 A EP02751285 A EP 02751285A EP 02751285 A EP02751285 A EP 02751285A EP 1406990 B1 EP1406990 B1 EP 1406990B1
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Prior art keywords
catalyst
fraction
effluent
weight
hydrocracking
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French (fr)
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EP1406990A1 (de
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Eric Benazzi
Christophe Gueret
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IFP Energies Nouvelles IFPEN
Agip Petroli SpA
Eni Tecnologie SpA
Eni SpA
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IFP Energies Nouvelles IFPEN
Agip Petroli SpA
Eni Tecnologie SpA
Eni SpA
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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
    • C10G65/12—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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C10G2400/06—Gasoil
    • 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
    • C10G2400/08—Jet fuel

Definitions

  • the present invention relates to a process and a treatment plant with hydrocracking and hydroisomerization, feedstock from the Fischer-Tropsch process, for obtaining middle distillates (gas oil, kerosene).
  • the synthesis gas (CO + H 2 ) is catalytically converted into oxygenates and substantially linear hydrocarbons in gaseous, liquid or solid form.
  • These products are generally free of heteroatomic impurities such as, for example, sulfur, nitrogen or metals. They also contain practically little or no aromatics, naphthenes and more generally cycles especially in the case of cobalt catalysts.
  • they may have a significant content of oxygenated products which, expressed by weight of oxygen, is generally less than about 5% by weight and also an unsaturated content (olefinic products in general) generally less than 10% by weight.
  • these products mainly paraffins normal, can not be used as such, in particular because of their cold-holding properties not compatible with the usual uses of oil cuts.
  • the pour point of a linear hydrocarbon containing 20 carbon atoms per molecule is +37 ° C about what makes its use impossible, the specification being -15 ° C for diesel.
  • the hydrocarbons resulting from the Fischer-Tropsch process comprising mainly n-paraffins must be converted into more valuable products such as, for example, gas oil, kerosene, which are obtained after catalytic reactions of hydroisomerization.
  • the patent EP-583,836 discloses a process for the production of middle distillates from filler obtained by Fischer-Tropsch synthesis.
  • the filler is treated in its entirety, at most it is possible to remove the fraction C 4 minus and obtain the fraction C 5 + boiling at near 100 ° C.
  • Said feed is subjected to a hydrotreatment and then to a hydroisomerisation with a conversion (products boiling above 370 ° C in lower boiling products) by at least 40% by weight.
  • a catalyst that can be used in hydroconversion is a platinum-silica-alumina formulation. The conversions described in the examples are at most 60% by weight.
  • the results obtained show that it is more profitable to send said gasoline cut (C 5 to at most 200 ° C) to a steam cracker to make olefins that to treat it in the process according to the invention, where it has been found that the quality of this cut is only slightly improved. In particular, its engine and search octane numbers remain too low for this cut to be integrated into the gasoline pool.
  • the process according to the invention allows the production of middle distillates (kerosene, diesel) with a minimum of gasoline obtained.
  • the yields of middle distillates (kerosene + gas oil) of the process according to the invention are higher than those of the prior art, in particular because the kerosene cut (generally initial boiling point of 150 to 160 ° C.
  • the catalytic performances (activity, selectivity) and / or the cycle time of the hydrotreatment and hydroisomerization / hydrocracking catalysts used in the process according to the invention could be improved.
  • the effluent from the Fischer-Tropsch synthesis unit comprises mainly paraffins but also contains olefins and oxygenated compounds such as alcohols. It also contains water, CO 2 , CO and unreacted hydrogen as well as light hydrocarbon compounds C1 to C4 in the form of gas.
  • the effluent from the Fischer-Tropsch synthesis unit is fractionated (for example by distillation) into at least two fractions: at least one light fraction and at least one heavy-point fraction. initial boiling equal to a temperature between 120 and 200 ° C and preferably between 130 and 180 ° C and even more preferably at a temperature of about 150 ° C, in other words the cutting point is between 120 and 200 ° C.
  • the heavy fraction generally has paraffin contents of at least 50% by weight.
  • This fractionation can be carried out by methods well known to those skilled in the art such as flash, distillation, etc.
  • the effluent from the Fischer-Tropsch synthesis unit will be subject to flash, decantation to remove water and distillation to obtain at least the 2 fractions described above.
  • the light fraction is not treated according to the process of the invention but may for example constitute a good load for petrochemicals and more particularly for a steam cracking unit. At least one heavy fraction previously described is treated according to the method of the invention.
  • this fraction or at least part of the initial charge is admitted via line (1) in the presence of hydrogen (supplied via line (2)) to an area (3) containing a hydrotreatment catalyst which has aim is to reduce the content of olefinic and unsaturated compounds as well as to hydrotreat the oxygenates (alcohols) present in the heavy fraction described above.
  • the catalysts used in this step (b) are hydrotreating catalysts which are non-crunchy or slightly crisp and comprise at least one metal of group VIII and / or group VI of the periodic table of elements.
  • the catalyst comprises at least one metal of the metal group formed by nickel, molybdenum, tungsten, cobalt, ruthenium, indium, palladium and platinum and comprising at least one support.
  • the hydro-dehydrogenating function is preferably provided by at least one metal or group VIII metal compound such as nickel and cobalt in particular.
  • a combination of at least one metal or group VI metal compound (especially molybdenum or tungsten) and at least one metal or group VIII metal compound (especially cobalt and nickel) of the classification may be used periodic elements.
  • the non-noble group VIII metal concentration, when used, is 0.01-15% by weight based on the finished catalyst.
  • At least one element selected from P, B, Si is deposited on the support.
  • This catalyst may advantageously contain phosphorus; indeed, this compound brings two advantages to hydrotreatment catalysts: an ease in particular during the impregnation of the nickel and molybdenum solutions, and a better hydrogenation activity.
  • the total concentration of metals of groups VI and VIII, expressed as metal oxides is between 5 and 40% by weight and preferably between 7 and 30% by weight and the weight ratio expressed as metal oxide. (or metals) of group VI on metal (or metals) of group VIII is between 1.25 and 20 and preferably between 2 and 10.
  • the concentration of phosphorus oxide P2O5 will be lower 15% by weight and preferably less than 10% by weight.
  • boron and phosphorus are promoter elements deposited on the support, and for example the catalyst according to the patent. EP-297.949 .
  • the sum of the amounts of boron and phosphorus, expressed respectively by weight of boron trioxide and phosphorus pentoxide, relative to the weight of support, is about 5 to 15% and the atomic ratio boron on phosphorus is about 1 1 to 2: 1 and at least 40% of the total pore volume of the finished catalyst is contained in pores with an average diameter greater than 13 nanometers.
  • the amount of Group VI metal such as molybdenum or tungsten is such that the phosphorus atomic ratio on Group VIB metal is about 0.5: 1 to 1.5: 1; the amounts of Group VIB metal and Group VIII metal, such as nickel or cobalt, are such that the atomic ratio of Group VIII metal to Group VIB metal is about 0.3: 1 to 0.7 1.
  • the amounts of Group VIB metal expressed in weight of metal relative to the weight of finished catalyst is about 2 to 30% and the amount of Group VIII metal expressed as weight of metal relative to the weight of finished catalyst is about 0.01 to 15%.
  • Ni alumina, NiMo on alumina, NiMo on alumina doped with boron and phosphorus and NiMo on silica-alumina catalysts are also preferred.
  • eta or gamma alumina will be chosen.
  • Another particularly advantageous catalyst contains promoter silicon deposited on the support.
  • An interesting catalyst contains BSi or PSi.
  • the metal content is between 0.05 and 3% by weight relative to the finished catalyst and preferably between 0.1 and 2% by weight.
  • catalyst preferably an alumina, but which may also be boron oxide, magnesia, zirconia, titanium oxide, a clay or a combination of these oxides.
  • a support which is preferably an alumina, but which may also be boron oxide, magnesia, zirconia, titanium oxide, a clay or a combination of these oxides.
  • These catalysts can be prepared by any method known to those skilled in the art or can be acquired from companies specializing in the manufacture and sale of catalysts.
  • the feedstock is contacted in the presence of hydrogen and the catalyst at operating temperatures and pressures for carrying out the hydrodeoxygenation (HDO) of the alcohols and the hydrogenation of the olefins present in the load.
  • the reaction temperatures used in the hydrotreatment reactor are between 100 and 350, preferably between 150 and 300 ° C, even more preferably between 150 and 275 ° C and more preferably between 175 and 250 ° C.
  • the total pressure range used varies from 5 to 150 bar, preferably from 10 to 100 bar and even more preferably from 10 to 90 bar.
  • the hydrogen that feeds the hydrotreatment reactor is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 100 to 3000 Nl / l / h, preferably between 100 and 2000Ml / l / h and even more preferred between 250 and 1500 Nl / l / h.
  • the charge rate is such that the hourly volume velocity is between 0.1 and 10 h -1 , preferably between 0.2 and 5 h -1 and even more preferably between 0.2 and 3 h -1 . Under these conditions, the content of unsaturated and oxygenated molecules is reduced to less than 0.5% and to less than 0.1% in general.
  • the hydrotreatment step is conducted under conditions such that conversion to products having boiling points greater than or equal to 370 ° C to products having boiling points below 370 ° C is limited to 30% wt. preferably, less than 20% and even more preferably less than 10%.
  • the effluent (line 4) from the hydrotreating reactor (3) is optionally introduced into a zone (5) of water removal which is intended to eliminate at least partly the water produced during the hydrotreatment reactions.
  • This removal of water can be carried out with or without eliminating the C 4 less gas fraction which is generally produced during the hydrotreating step.
  • the elimination of water is understood to mean the elimination of the water produced by the hydrodeoxygenation (HDO) reactions of the alcohols, but it may also include the elimination at least partly of the saturation water of the hydrocarbons.
  • the removal of water can be carried out by all the methods and techniques known to those skilled in the art, for example by drying, passage on a desiccant, flash, decantation ....
  • At least part and preferably all of the hydrocarbon fraction (at least part of the feed or at least part of the heavy fraction of step a) or at least part of the hydrotreated fraction or feed and optionally dried) is then introduced (line 6) and possibly a stream of hydrogen (line 7) into the zone (8) containing said first hydroisomerization / hydrocracking catalyst.
  • Another possibility of the process also according to the invention consists in sending part or all of the effluent leaving the hydrotreating reactor (without drying) into the reactor containing the hydroisomerization / hydrocracking catalyst and preferably at the same time. time as a flow of hydrogen.
  • the metal contained in the catalyst Before use in the reaction, the metal contained in the catalyst must be reduced.
  • One of the preferred methods for conducting the reduction of the metal is hydrogen treatment at a temperature of from 150 ° C to 650 ° C and a total pressure of 0.1 to 25 MPa.
  • a reduction consists of a stage at 150 ° C. for 2 hours then a rise in temperature up to 450 ° C. at the rate of 1 ° C./min and then a plateau of 2 hours at 450 ° C. throughout this reduction step, the hydrogen flow rate is 1000 liters hydrogen / liter catalyst. Note also that any ex-situ reduction method is suitable.
  • the temperature used in this stage is between 200 and 450.degree. C. and preferably from 250.degree. C. to 450.degree. C., advantageously from 300 to 450.degree. C., and even more advantageously above 320.degree. C. or, for example, between 320.degree.-420.degree. .
  • the two stages, hydrotreatment and hydroisomerization-hydrocracking, can be carried out on the two types of catalysts in two or more different reactors, and / or in the same reactor.
  • the hydroisomerized / hydrocracked effluent leaving the reactor (8), step (d), is sent to a distillation train (9) which incorporates an atmospheric distillation and optionally a vacuum distillation which is intended to separate the conversion products.
  • a distillation train (9) which incorporates an atmospheric distillation and optionally a vacuum distillation which is intended to separate the conversion products.
  • boiling point below 340 ° C and preferably below 370 ° C and including including those formed in step (d) in the reactor (8), and to separate the residual fraction whose initial point of boiling is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C.
  • the process according to the invention uses a second zone (16) containing a hydroisomerization / hydrocracking catalyst (called second catalyst). It passes on this catalyst, in the presence of hydrogen (line 15) an effluent chosen from a part of the kerosene produced (line 12), part of the gas oil (line 13) and the residual fraction and preferably the residual fraction whose initial boiling point is generally greater than at least 370 ° C.
  • the catalyst present in the reactor (16) of step (f) of the process according to the invention is in the same way as for stage d), of amorphous acid type and based on at least one noble metal of group VIII; however it may be the same or different from that of step d).
  • the fraction entering the reactor (16) undergoes, in the presence of hydrogen, hydroisomerization and / or hydrocracking reactions in the reactor, which will make it possible to improve the quality of the products formed and more particularly the properties cold kerosene and diesel, and obtain distillate yields improved over the prior art.
  • the temperature used in this stage is between 200 and 450.degree. C. and preferably from 250.degree. C. to 450.degree. C., advantageously from 300 to 450.degree. C., and even more advantageously above 320.degree. C. or, for example, between 320.degree.-420.degree. .
  • the operator will adjust the operating conditions on the first and second hydrocracking / hydroisomerization catalyst so as to obtain the desired product qualities and yields.
  • the conversion by pass in Products having a boiling point greater than or equal to 150 ° C. in products with a boiling point below 150 ° C. are less than 50% by weight, preferably less than 30% by weight.
  • the conversion by pass to products with boiling points greater than or equal to 370 ° C in products with boiling points lower than 370 ° C is superior. at 40% by weight, preferably above 50% by weight, or better at 60% by weight. It can even be advantageous to have conversions of at least 80% by weight.
  • the pass conversion into products with boiling points greater than or equal to 150 ° C into products with boiling points below 150 ° C is lower. at 50% by weight, preferably less than 30% by weight.
  • the operating conditions applied in the reactors (8) and (16) may be different or identical.
  • the operating conditions used in the 2 hydroisomerization / hydrocracking reactors are chosen to be different in terms of operating pressure, temperature, contact time (wh) and H 2 / feed ratio. This embodiment allows the operator to adjust the qualities and / or yields of kerosene and diesel.
  • the effluent from the reactor (16) is then sent via line (17) in the distillation train so as to separate the conversion products, gasoline, kerosene and diesel.
  • FIG. 1 there is shown an embodiment with the residual fraction (line 14) passing through the hydroisomerization / hydrocracking zone (16) (step f), the effluent obtained being sent (line 17) to the zone (9) of separation.
  • the kerosene and / or diesel fuel may be partly recycled (line 18) in the hydroisomerization / hydrocracking zone (8) (step d) on the first catalyst.
  • the invention is not limited to these 2 embodiments.
  • the gas oil (s) obtained has a pour point of at most 0 ° C, generally below -10 ° C and often below -15 ° C.
  • the cetane number is greater than 60, generally greater than 65, often greater than 70.
  • the resulting kerosene (s) has a freezing point of not more than -35 ° C, generally less than -40 ° C.
  • the smoke point is greater than 25 mm, usually greater than 30 mm.
  • the yield of gasoline will always be less than 50% by weight, preferably less than 40% by weight; advantageously less than 30% by weight or 20% by weight or even 15% by weight.
  • the installation comprises a pipe (14) for sending said residual fraction into the zone (16) containing the second catalyst, and a pipe (18) for recycling a portion of the kerosene and / or diesel fuel produced in the zone (8) containing the first catalyst.
  • the installation comprises a pipe (12, 13) for feeding a portion of the kerosene and / or diesel fuel produced in the zone (16) containing the second catalyst, and a pipe (14) for recycling. said residual fraction in the zone (8) containing the first catalyst.
  • the majority of catalysts currently used in hydroisomerization / hydrocracking are of the bifunctional type associating an acid function with a hydrogenating function.
  • the acid function is provided by supports with large surface areas (generally 150 to 800 m 2 .g -1 ) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), phosphorus aluminas, combinations of oxides of boron and aluminum, silica-aluminas.
  • the equilibrium between the two acid and hydrogenating functions is the fundamental parameter which governs the activity and the selectivity of the catalyst.
  • a weak acidic function and a strong hydrogenating function result in weakly active and selective catalysts in the isomerization whereas a strong acid function and a low hydrogenating function give very active and cracking-selective catalysts.
  • a third possibility is to use a strong acid function and a strong hydrogenating function to obtain a very active catalyst but also very selective towards isomerization. It is therefore possible, by judiciously choosing each of the functions to adjust the activity / selectivity couple of the catalyst.
  • the hydroisomerization-hydrocracking catalysts are bifunctional catalysts comprising an amorphous acid support (preferably a silica-alumina) and a hydro-dehydrogenating metal function provided by at least one noble metal.
  • the support is said to be amorphous, that is to say devoid of molecular sieves, and in particular of zeolite, as well as the catalyst.
  • the amorphous acidic support is advantageously a silica-alumina but other supports are usable.
  • the catalyst preferably does not contain added halogen, other than that which could be introduced for the impregnation of the noble metal, for example. More generally, and preferably, the catalyst does not contain added halogen, for example fluorine.
  • the support has not been impregnated with a silicon compound.
  • a catalyst comprising a particular silica-alumina is used which makes it possible to obtain very active catalysts that are also very selective in the isomerization of effluents from Fischer-Synthesis units. Tropsch.
  • the metal function is provided by a noble metal of group VIII of the periodic table of elements and more particularly platinum and / or palladium.
  • the noble metal content expressed in% by weight of metal relative to the catalyst, is between 0.05 to 10 and more preferably between 0.1 and 5.
  • the dispersion representing the reagent-accessible metal fraction based on the total amount of catalyst metal, can be measured, for example, by H 2 / O 2 titration.
  • the metal is reduced beforehand, that is to say that it undergoes treatment under hydrogen flow at high temperature under conditions such that all Hydrogen-accessible platinum atoms are converted to metallic form.
  • a flow of oxygen is sent under suitable operating conditions so that all the reduced platinum atoms accessible to oxygen is oxidized in PtO 2 form.
  • the dispersion is then equal to the ratio of the quantity of platinum accessible to oxygen to the total amount of platinum of the catalyst. In our case, the dispersion is between 20% and 100% and preferably between 30% and 100%.
  • the distribution of the noble metal represents the distribution of the metal within the catalyst grain, the metal being able to be well or poorly dispersed.
  • the platinum poorly distributed for example detected in a ring whose thickness is significantly less than the radius of the grain
  • the platinum distribution is good, that is to say that the platinum profile, measured according to the Castaing microprobe method, has a distribution coefficient greater than 0.1 and preferably greater than 0.1. 0.2.
  • the BET surface of the support is between 100 m 2 / g and 500 m 2 / g and preferably between 250 m 2 / g and 450 m 2 / g and for silica-alumina-based supports, even more preferably between 310 m 2 / g and 450 m 2 / g.
  • the average pore diameter of the catalyst is measured from the porous distribution profile obtained with a mercury porosimeter.
  • the average pore diameter is defined as the diameter corresponding to the cancellation of the derived curve obtained from the mercury porosity curve.
  • the mean diameter of the pores, thus defined, is between 1 nm (1x10 -9 meters) and 12 nm (12x10 -9 meters) and preferably between 1 nm (1x10 -9 meters) and 11 nm (11x10 -9 meters). ) and even more preferably between 3 nm (4x10 -9 meters) and 10.5 nm (10.5x10 -9 meters).
  • the preferred catalyst has a porous distribution such as the pore volume of the pores whose diameter is between the mean diameter as defined previously decreased by 3 nm and the average diameter as defined above increased by 3 nm (ie the mean diameter ⁇ 3 nm) is greater than 40% of the total pore volume and preferably between 50% and 90% of the total pore volume and more preferably between 50% and 70% of the total pore volume.
  • silica-alumina catalyst it is generally less than 1.0 ml / g and preferably between 0.3 and 0.9 ml / g and even more preferably less than 0.85 ml / g.
  • the preparation and shaping of the support, and in particular of the silica-alumina (especially used in the preferred embodiment) is made by usual methods well known to those skilled in the art.
  • the support may undergo calcination, for example a heat treatment at 300-750 ° C. (preferred 600 ° C.) for 0.25-10 hours (preferred 2 hours) under 0. -30% volume of water vapor (for the silica alumina 7.5% preferred).
  • the noble metal salt is introduced by one of the usual methods used to deposit the metal (preferably platinum and / or palladium, platinum being still preferred) on the surface of a support.
  • One of the preferred methods is dry impregnation which consists of introducing the metal salt into a volume of solution which is equal to the pore volume of the catalyst mass to be impregnated.
  • the catalyst Prior to the reduction operation, the catalyst may be calcined such as, for example, in dry air at 300-750 ° C (520 ° C preferred) for 0.25-10 hours (preferred 2 hours).
  • the bifunctional catalyst comprises at least one noble metal deposited on an amorphous acid support, the noble metal dispersion being less than 20%.
  • the fraction of the noble metal particles having a size of less than 2 nm represents at most 2% by weight of the noble metal deposited on the catalyst.
  • At least 70% preferably at least 80%, and more preferably at least 90%
  • noble metal particles have a size greater than 4 nm (% number).
  • the support is amorphous, it does not contain molecular sieve; the catalyst does not contain molecular sieves either.
  • the amorphous acid support is generally chosen from the group formed by a silica-alumina, a halogenated alumina (preferably fluorinated), a silicon-doped alumina (deposited silicon), a titanium oxide alumina mixture, a sulphated zirconia, a doped zirconia with tungsten, and mixtures thereof with one another or with at least one amorphous matrix chosen from the group formed by alumina, titanium oxide, silica, boron oxide, magnesia, zirconia, clay by example.
  • the support consists of an amorphous silica alumina.
  • a preferred catalyst comprises (preferably consists essentially of) from 0.05 to 10% by weight of at least one Group VIII noble metal deposited on an amorphous silica-alumina support.
  • the metal function is provided by at least one noble metal of group VIII of the periodic table of elements and more particularly platinum and / or palladium.
  • the noble metal content expressed in% by weight of metal relative to the catalyst, is between 0.05 to 10 and more preferably between 0.1 and 5.
  • the dispersion (measured in the same manner as above) is less than 20%, it is generally greater than 1% or better at 5%.
  • the catalyst sample is finely ground in an agate mortar and is then ethanol-dispersed. Samples at different locations to ensure good representativeness in size are made and deposited on a copper grid covered with a thin carbon film. The grids are then air dried under infra-red light before being introduced into the microscope for observation. In order to estimate the average size of noble metal particles, several hundred measurements are made from dozens of shots. All of these measurements make it possible to produce a histogram of distribution of the particle size. Thus, we can accurately estimate the proportion of particles corresponding to each particle size domain.
  • the distribution of platinum is good that is to say that the platinum profile, measured according to the method of the microprobe of Castaing, has a distribution coefficient greater than 0.1 advantageously greater than 0.2 and preferably greater than 0.5.
  • the BET surface of the support is generally between 100 m 2 / g and 500m 2 / g and preferably between 250 m 2 / g and 450 m 2 / g and the silica alumina carriers, even more preferably 310 m 2 / g.
  • silica-based alumina supports it is generally less than 1.2 ml / g and preferably between 0.3 and 1.1 ml / g and even more advantageously less than 1.05 ml / g.
  • the preparation and shaping of the silica-alumina and of any support in general is made by usual methods well known to those skilled in the art.
  • the support may undergo calcination, for example a heat treatment at 300-750 ° C. (600 ° C. preferred) for a period of between 0.25 and 10 hours (2 hours). preferred) under 0-30% volume of water vapor (about 7.5% preferred for a silica-alumina).
  • the metal salt is introduced by one of the usual methods used to deposit the metal (preferably platinum) on the surface of a support.
  • One of the preferred methods is dry impregnation which consists of introducing the metal salt into a volume of solution which is equal to the pore volume of the catalyst mass to be impregnated.
  • the catalyst Prior to the reduction operation and to obtain the size distribution of the metal particles, the catalyst is calcined in humidified air at 300-750 ° C (550 ° C preferred) for 0.25-10 hours (preferred 2 hours).
  • the partial pressure of H2O during the calcination is for example 0.05 bar to 0.50 bar (0.15 bar preferred).
  • Other known methods of treatment making it possible to obtain the dispersion of less than 20% are suitable within the scope of the invention.
  • the support may consist of pure silica-alumina or result from mixing with said silica-alumina a binder such as silica (SiO 2 ), alumina (Al 2 O 3 ), clays, titanium oxide (TiO 2 ), boron oxide (B 2 O 3 ) and zirconia (ZrO 2 ) and any mixture of binders previously mentioned.
  • the preferred binders are silica and alumina and even more preferably alumina in all these forms known to those skilled in the art, for example gamma-alumina.
  • the weight content of binder in the catalyst support is between 0 and 40%, more particularly between 1 and 40% and even more preferably between 5% and 20%. As a result, the weight content of silica-alumina is 60 - 100%.
  • the catalysts according to the invention whose support consists solely of silica-alumina without any binder are preferred.
  • the support may be prepared by shaping the silica-alumina in the presence or absence of binder by any technique known to those skilled in the art.
  • the shaping can be carried out for example by extrusion, pelletizing, by the method of coagulation in drop (oil-drop), by rotating plate granulation or by any other method well known to those skilled in the art.
  • At least one calcination may be carried out after any of the steps of the preparation, it is usually carried out under air at a temperature of at least 150 ° C, preferably at least 300 ° C.
  • the catalyst is a bifunctional catalyst in which a noble metal is supported by a support consisting essentially of an amorphous silica-alumina gel and micro / mesoporous membrane with a controlled pore size, having an area of at least 500 m 2 / g and an SiO 2 / Al 2 O 3 molar ratio of between 30/1 and 500/1, preferably between 40/1 and 150/1.
  • the noble metal supported on the support may be chosen from metals of Groups 8, 9 and 10 of the Periodic Table, in particular Co, Ni, Pd and Pt. Palladium and platinum are preferably used.
  • the proportion of noble metals is normally between 0.05 and 5.0% by weight relative to the weight of the support. Particularly advantageous results have been obtained using palladium and platinum in proportions of between 0.2 and 1.0% by weight.
  • Said support is generally obtained from a mixture of tetra-alkylated ammonium hydroxide, an aluminum compound which can be hydrolysed to Al 2 O 3 of a silicon compound which can be hydrolyzed to SiO 2 and a sufficient amount of water to dissolve and hydrolyze these compounds, said tetra-alkylated ammonium hydroxide having 2 to 6 carbon atoms in each alkyl residue, said hydrolyzable aluminum compound being preferably a trialkoxide of aluminum having 2 to 4 carbon atoms in each alkoxide residue and said hydrolysable silicon compound being a tetraalkylorthosilicate having 1 to 5 carbon atoms for each alkyl residue.
  • the tetra-alkylated ammonium hydroxide which may be used in the context of the present invention is, for example, chosen from hydroxides of tetraethylammonium, propylammonium, isopropylammonium, butylammonium, isobutylammonium, terbutylammonium and pentylammonium, and preferably from the hydroxides of tetrapropylammonium, tetraisopropylammonium and tetrabutylammonium.
  • Trialkoxide aluminum is for example chosen from triethoxide, propoxide, isopropoxide, butoxide, isobutoxide and aluminum tertbutoxide, preferably from tripropoxide and tri-isopropoxide of aluminum.
  • the tetra-alkylated orthosilicate is chosen, for example, from tetramethyl-, tetraethyl-, propyl-, isopropyl-, butyl-, isobutyl-, terbutyl- and pentyl-orthosilicate, tetraethylorthosilicate being used preferably.
  • an aqueous solution containing tetra-alkylated ammonium hydroxide and aluminum trialkoxide is first prepared at a temperature sufficient to ensure effective dissolution of the aluminum compound.
  • the tetra-alkylated orthosilicate is added to said aqueous solution.
  • This mixture is brought to a temperature suitable for the activation of the hydrolysis reaction. This temperature depends on the composition of the reaction mixture (generally 70 to 100 ° C).
  • the hydrolysis reaction is exothermic, which guarantees a self-sustaining reaction after activation.
  • the proportions of the constituents of the mixture are such that they respect the following molar ratios: SiO 2 / Al 2 O 3 of 30/1 to 500/1, tetra-alkylated ammonium hydroxide / SiO 2 of 0.05 / 1 to 0.2 / 1, and H 2 O / SiO 2 from 5/1 to 40/1.
  • the preferred values for these molar ratios are as follows: SiO 2 / Al 2 O 3 from 40/1 to 150/1, tetra-alkylated ammonium hydroxide / SiO 2 from 0.05 / 1 to 0.2 / 1, and H 2 O / SiO 2 from 10/1 to 25/1.
  • the hydrolysis of the reagents and their gelling are carried out at a temperature equal to or higher than the boiling point, at atmospheric pressure, of any alcohol developed as a by-product of said hydrolysis reaction, without any significant elimination or elimination. of these alcohols of the reaction medium.
  • the hydrolysis and gelling temperature is therefore critical and is suitably maintained at values above about 65 ° C, of the order of about 110 ° C.
  • the hydrolysis and gelling are carried out in the presence of an amount of alcohol greater than that developed as a by-product.
  • a free alcohol preferably ethanol, is added to the reaction mixture in a proportion up to a maximum molar ratio of added alcohol / SiO 2 of 8/1.
  • the time required to carry out the hydrolysis and gelling under the conditions indicated above is normally between 10 minutes and 3 hours, preferably between 1 and 2 hours.
  • the alcohol is finally extracted from the gel which is then dried, preferably under a reduced pressure (from 3 to 6 kPa for example), at a temperature of 110 ° C.
  • the dried gel is then subjected to a calcination process under an oxidizing atmosphere (normally in air), at a temperature between 500 and 700 ° C for 4 to 20 hours, preferably at 500-600 ° C for 6 to 10 hours.
  • the silica gel and alumina thus obtained has a composition which corresponds to that of the reagents used, if it is considered that the reaction yields are practically complete.
  • the molar ratio SiO 2 / Al 2 O 3 is therefore between 30/1 and 500/1, preferably between 40/1 and 150/1, the preferred values being of the order of 100/1.
  • This gel is amorphous, when subjected to X-ray powder diffraction analysis, it has an area of at least 500 m 2 / g, generally between 600 and 850 m 2 / g, and a pore volume of 0.4 to 0.8 cm 3 / g .
  • a metal selected from the noble metals of groups 8, 9 or 10 of the periodic table is supported on the micro / mesoporous amorphous silica-alumina gel obtained as described above. As indicated above, this metal is preferably chosen from platinum or palladium, platinum being preferably used.
  • the proportion of noble metal, especially platinum, in the catalyst thus supported is between 0.4 and 0.8%, preferably between 0.6 and 0.8% by weight relative to the weight of the support.
  • the porous support having the characteristics of the acid carrier (a) described above is brought into contact with an aqueous or alcohol solution of a compound of the desired metal for a time sufficient to allow a homogeneous distribution of the metal in the solid. This operation normally requires a few minutes to several hours, preferably with stirring.
  • H 2 PtF 6 , H 2 PtCl 6 , [Pt (NH 3 ) 4] Cl 2 , [Pt (NH 3 ) 4 ] (OH) 2 are, for example, soluble salts suitable for this purpose, as well as salts of palladium; mixtures of salts of different metals are also used in the context of the invention. It is advantageous to use the minimum amount of aqueous liquid (usually water or an aqueous mixture with a second inert liquid or with an acid in a proportion of less than 50% by weight) necessary for dissolving the salt and impregnating uniformly said support, preferably with a solution / support ratio of between 1 and 3. The amount of metal used is chosen according to the desired concentration in the catalyst, the entire metal being fixed on the support.
  • the solution is evaporated and the solid obtained is dried and calcined under an inert or reducing atmosphere, under conditions of temperature and time similar to those previously described for the calcination of the support.
  • Another method of impregnation is by means of an ion exchange.
  • the support consisting of amorphous silica-alumina gel is brought into contact with an aqueous solution of a salt of the metal used, as in the previous case, but the deposition is carried out by ion exchange, under conditions made basic (pH between 8.5 and 11) by the addition of a sufficient amount of an alkaline compound, usually an ammonium hydroxide.
  • the suspended solid is then separated from the liquid by filtration or decantation, and then dried and calcined as described above.
  • the salt of the transition metal may be included in the silica-alumina gel during the preparation phase, for example before hydrolysis for the formation of the wet gel, or before its calcination.
  • the latter method is advantageously easier to implement, the catalyst thus obtained is slightly less active and selective than that obtained with the two previous methods.
  • the supported catalyst described above can be used as it is during the hydrocracking step of the process according to the present invention, after activation according to one of the known methods and / or described below.
  • said supported catalyst is reinforced by the addition with mixing of a suitable amount of an inert mineral solid capable of improving its mechanical properties.
  • the catalyst is preferably used in granular form rather than in powder form with a relatively tight particle distribution.
  • Extrusion and shaping methods are also known which use a suitable inert additive (or binder) capable of providing the properties mentioned above, for example according to the methods described in the European patent applications.
  • EP-A 550,922 and EP-A 665.055 are also known which use a suitable inert additive (or binder) capable of providing the properties mentioned above, for example according to the methods described in the European patent applications.
  • EP-A 550,922 and EP-A 665.055 being preferably implemented, their contents being mentioned here by way of reference.
  • Plasticizers such as methylcellulose are also preferably added during step (b) to promote the formation of a homogeneous, easily treated mixture.
  • a granular acidic support comprising from 30 to 70% by weight of inert inorganic binder is thus obtained, the remaining proportion consisting of amorphous silica-alumina having essentially the same characteristics of porosity, surface and structure as those described above for the same gel without binder.
  • the granules are advantageously in the form of pellets approximately 2-5 mm in diameter and 2-10 mm long.
  • the deposition step of the noble metal on the granular acidic support is then carried out according to the same procedure as that described above.
  • the metal contained in the catalyst must be reduced.
  • One of the preferred methods for conducting the reduction of the metal is hydrogen treatment at a temperature of from 150 ° C to 650 ° C and a total pressure of 0.1 to 25 MPa.
  • a reduction consists of a stage at 150 ° C. for 2 hours then a rise in temperature up to 450 ° C. at the rate of 1 ° C./min and then a plateau of 2 hours at 450 ° C. throughout this reduction step, the hydrogen flow rate is 1000 l hydrogen / catalyst. Note that any in situ or ex-situ reduction method is suitable.
  • the pressure in the reactor is maintained between 30 and 80 atm.

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Claims (8)

  1. Verfahren zur Herstellung von Mitteldestillaten aus einer Paraffincharge, die mittels Fischer-Tropsch-Synthese erzeugt wurde, wobei es die folgenden Schritte aufweist, die nacheinander durchgeführt werden:
    a) gegebenenfalls Fraktionierung der Charge in mindestens eine Schwerfraktion mit einen anfänglichen Siedepunkt im Bereich von 120 bis 200 °C, und mindestens eine Leichtfraktion, die unterhalb der Schwerfraktion siedet,
    b) gegebenenfalls Hydrobehandlung mindestens eines Teils der Charge oder der Schwerfraktion, woraufhin gegebenenfalls (Schritt c) die Entfernung mindestens eines Teils des Wassers folgt,
    d) Aufgeben mindestens eines Teils des Stoffstroms oder der gegebenenfalls hydrobehandelten Fraktion auf einen ersten Hydroisomerisierungs/Hydrocrack-Katalysator, wobei es sich um einen amorphen Katalysator handelt, der mindestens ein Edelmetall aus der Gruppe VIII enthält,
    e) Destillation des hydroisomerisierten/hydrogecrackten Stoffstroms, um Mitteldestillate (Kerosin, Diesel) und eine restlichen Fraktion, die oberhalb der Mitteldestillate siedet, zu erhalten,
    f) Aufgabe mindestens eines Teils der restlichen Schwerfraktion und/oder eines Teils der Mitteldestillate auf einen zweiten Hydroisomerisierungs/Hydrocrack-Katalysator, wobei es sich um einen amorphen Katalysator handelt, der mindestens ein Edelmetall aus der Gruppe VIII enthält, und Destillation des erhaltenen Stoffstroms, um Mitteldestillate zu erhalten, wobei mindestens ein Teil der Mitteldestillate zum Bereich (16), welcher den zweiten Katalysator enthält, oder zum Bereich (8), welcher den ersten Katalysator enthält, zurückgeführt wird.
  2. Verfahren nach Anspruch 1, wobei mindestens eine der Fraktionen Kerosin, Dieselkraftstoff aus Schritt e) teilweise zum Schritt d) zurückgeführt wird und die restliche Fraktion dem Schritt f) unterzogen wird.
  3. Verfahren nach Anspruch 1, wobei mindestens eine der Fraktionen Kerosin, Dieselkraftstoff aus Schritt e) dem Schritt f) unterzogen wird, und die restliche Fraktion zum Schritt d) zurückgeführt wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Verfahren den Schritt a) umfasst und die Leichtfraktion, welche in Schritt a) abgetrennt wird, dem Dampfcrackverfahren zugeführt wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Hydroisomerisierungs/Hydrocrack-Katalysatoren kein zugesetztes Halogen enthalten.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei am ersten Katalysator eine Umwandlung von weniger als 50 Gew.-% erzielt wird, wobei Stoffe mit Siedepunkten von mindestens 150 °C in Stoffe mit Siedepunkten von weniger als 150 °C umgewandelt werden.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei am zweiten Katalysator die restliche Fraktion derart behandelt wird, dass eine Umwandlung von mehr als 40 Gew,-% erzielt wird, wobei Stoffe mit Siedepunkten von mindestens 370 °C in Stoffe mit Siedepunkten von weniger als 370 °C umgewandelt werden.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei am zweiten Katalysator ein Teil des Kerosins und/oder des Dieselkraftstoffs derart behandelt wird, dass eine Umwandlung von weniger als 50Gew.-% erzielt wird, wobei Stoffe mit Siedepunkten von mindestens 150 °C in Stoffe mit Siedepunkten von weniger als 150 °C umgewandelt werden.
EP02751285A 2001-07-06 2002-06-26 Verfahren zur herstellung von mitteldestillaten durch zweistufige hydroisomerisation und hydrocracking von reaktionsprodukten aus dem fischer-tropsch verfahren Expired - Lifetime EP1406990B1 (de)

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FR0108972 2001-07-06
PCT/FR2002/002206 WO2003004587A1 (fr) 2001-07-06 2002-06-26 Procede de production de distillats moyens par hydroisomerisation et hydrocraquage en 2 etapes de charges issues du procede fischer-tropsch

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