EP1421157B1 - Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking aus zwei fraktionen der reaktionsprodukte aus dem fischer-tropsch verfahren - Google Patents

Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking aus zwei fraktionen der reaktionsprodukte aus dem fischer-tropsch verfahren Download PDF

Info

Publication number
EP1421157B1
EP1421157B1 EP02755093A EP02755093A EP1421157B1 EP 1421157 B1 EP1421157 B1 EP 1421157B1 EP 02755093 A EP02755093 A EP 02755093A EP 02755093 A EP02755093 A EP 02755093A EP 1421157 B1 EP1421157 B1 EP 1421157B1
Authority
EP
European Patent Office
Prior art keywords
fraction
catalyst
hydrocracking
process according
products
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.)
Expired - Lifetime
Application number
EP02755093A
Other languages
English (en)
French (fr)
Other versions
EP1421157A1 (de
Inventor
Eric Benazzi
Christophe Gueret
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Agip Petroli SpA
Eni Tecnologie SpA
Eni SpA
Original Assignee
IFP Energies Nouvelles IFPEN
Agip Petroli SpA
Eni Tecnologie SpA
Eni SpA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN, Agip Petroli SpA, Eni Tecnologie SpA, Eni SpA filed Critical IFP Energies Nouvelles IFPEN
Publication of EP1421157A1 publication Critical patent/EP1421157A1/de
Application granted granted Critical
Publication of EP1421157B1 publication Critical patent/EP1421157B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
    • 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
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S208/00—Mineral oils: processes and products
    • Y10S208/95—Processing of "fischer-tropsch" crude

Definitions

  • the present invention relates to a process for hydrocracking and hydroisomerization treatment, 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 mainly comprise n-paraffins which must be converted into more valuable products such as, for example, diesel fuel, kerosene, which are obtained, for example, after catalytic hydroisomerisation reactions.
  • the patent EP-635, 557 discloses a process for producing middle distillates having good low temperature properties from a feed which is a Fischer-Tropsch process effluent.
  • the process comprises separating said feedstock into at least one light fraction boiling below 260 ° C and a heavy fraction boiling above 260 ° C. Light and heavy fractions are treated separately.
  • the light fraction undergoes hydrotreatment to remove the heteroatoms and then hydroisomerization.
  • the heavy fraction optionally undergoes hydrotreatment (but preferably there is no hydrotreatment), followed by hydroisomerization of the fraction obtained by hydrotreatment.
  • the conversion of 371 ° C + products to 371 ° C is 35-80% by weight.
  • EP1101813 describes conversions higher than 80% for a step of hydrocracking / hydroisomerization on heavy, resulting in a higher yield of middle distillates.
  • the present invention provides an alternative process for the production of middle distillates.
  • the yields of middle distillates (kerosene + diesel) according to the invention are higher than those of the prior art, in particular because the kerosene cut (generally the initial boiling point of 150 to 160 ° C - final boiling point of 260 to 280 ° C) has could be optimized (and even maximized compared to the prior art EP-635, 557 ), and more, without the detriment of the diesel cut. Moreover, this kerosene cut unexpectedly has excellent cold properties (freezing point for example).
  • 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.
  • a cut between a boiling point T1 of between 120 - 200 ° C and T2 of above 300 ° C and below 370 ° C is preferred.
  • the cut at 370 ° C is even more preferred, ie the heavy fraction is a 370 ° C + cut.
  • Cutting at 370 ° C separates at least 90% by weight oxygenates and olefins, and most often at least 95% wt.
  • the heavy cut to be treated is then purified and removal of the heteroatoms or unsaturated by hydrotreating is then not necessary.
  • Fractionation is obtained here by distillation, but it can be carried out in one or more steps and by other means than distillation.
  • 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 a petrochemical unit and more particularly for a steam cracker (steam cracking unit 6).
  • Said intermediate fraction is admitted via line (4), in the presence of hydrogen supplied by the pipe (7), in a hydrotreatment zone (8) containing a hydrotreatment catalyst.
  • the objective of this hydrotreatment is to reduce the content of olefinic and unsaturated compounds as well as to hydrotreat the oxygenates (alcohols) present.
  • 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 provides two advantages to hydrotreatment catalysts: an ease of preparation, particularly in the impregnation of 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 Group VIII metal (or metals) on metal (or metals) is between 1.25 and 20 and preferably between 2 and 10.
  • the concentration of phosphorus oxide P205 will be less than 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%.
  • Another particularly advantageous catalyst contains promoter silicon deposited on the support.
  • An interesting catalyst contains BSi or PSi.
  • 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.
  • 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.
  • These metals are deposited on 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.
  • 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 which 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 2000 Nl / 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 10h -1 , preferably between 0.2 and 5h -1 and even more preferably between 0.2 and 3h -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 from the hydrotreatment reactor is optionally introduced into a zone (9) of water removal which aims to remove at least a portion of 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 achieved by all methods and techniques known to those skilled in the art, for example by drying, passing on a desiccant, flash, decantation ....
  • the fraction thus possibly dried is then introduced (line 10), as well as possibly a stream of hydrogen (line 11) into the zone (12) containing the hydroisomerization / hydrocracking catalyst.
  • Another possibility of the process also according to the invention consists in sending all the effluent leaving the hydrotreating reactor (without drying) into the reactor containing the amorphous hydroisomerization / hydrocracking catalyst and preferably at the same time as a flow of hydrogen.
  • 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 hydroisomerization and hydrocracking step (d) is advantageously carried out under conditions such that the pass conversion into dot products boiling point greater than or equal to 150 ° C. in products having boiling points below 150 ° C. is as low as possible, preferably less than 50%, even more preferably less than 30%, and makes it possible to to obtain middle distillates (diesel and kerosene) with cold properties (pour point and freezing point) sufficiently good to meet the specifications in force for this type of fuel.
  • step (d) it is sought to promote hydroisomerization rather than hydrocracking.
  • Said heavy fraction whose boiling points are higher than the previously defined cutting point T2 is introduced via line (5) into a zone (13) where it is placed, in the presence of hydrogen (26), in contact with an amorphous hydroisomerization / hydrocracking catalyst to produce a middle distillate cut (kerosene + gas oil) with good cold properties.
  • the catalyst used in the zone (13) of step (f) to carry out the hydrocracking and hydrideisomerization reactions of the heavy fraction, defined according to the invention, is of the same type as that present in the reactor (12). ). However, it should be noted that the catalysts used in the reactors (12) and (13) may be identical or different.
  • step (f) the fraction entering the reactor undergoes in contact with the catalyst and in the presence of hydrogen essentially hydrocracking reactions which, accompanied by hydroisomerization reactions of n-paraffins, will allow to improve the quality of the formed products and more particularly the cold properties of kerosene and diesel, and also to obtain very good yields of distillates.
  • the conversion to products having boiling points greater than or equal to 370 ° C. in products with a boiling point of less than 370 ° C. is greater than 80% by weight, often at least 85% and preferably greater than or equal to 88%.
  • conversions of products with a boiling point greater than or equal to 260 ° C to boiling point products less than 260 ° C is at most 90% by weight, generally at most 70% or 80%, and preferably at most 60% by weight.
  • step (f) it will therefore seek to promote hydrocracking, but preferably by limiting the cracking of diesel fuel.
  • the choice of operating conditions makes it possible to finely adjust the quality of the products (diesel, kerosene) and in particular the cold properties of kerosene, while maintaining a good yield of diesel and / or kerosene.
  • the method according to the invention makes it quite interesting to produce both kerosene and gas oil and which are of good quality.
  • the effluent at the outlet of the reactor (12), step (d), is sent to a distillation train, which incorporates an atmospheric distillation and optionally a vacuum distillation, and whose purpose is to separate, on the one hand, the light products inevitably formed during step (d), for example gases (C 1 -C 4 ) (line 14) and a petrol section (line 19), and distilling at least one gasoil section (line 17) and kerosene (line 16). ).
  • gases C 1 -C 4
  • petrol section line 19
  • the gas oil and kerosene fractions can be recycled (line 25) partly, jointly or separately, at the top of the hydroisomerization / hydrocracking reactor (12) step (d).
  • the effluent leaving step (f) is subjected to a separation step in a distillation train so as to separate, on the one hand, the light products inevitably formed during step (f), for example the gases (C 1 -C 4 ) (line 18) and a petrol cut (line 19), to distil a diesel cut (line 21) and kerosene (line 20) and to distil the fraction (line 22) boiling over diesel fuel that is, the compounds which constitute it have boiling points higher than those of middle distillates (kerosene + gas oil).
  • This fraction, called the residual fraction generally has an initial boiling point of at least 350 ° C., preferably greater than 370 ° C.
  • This non-hydrocracked fraction is advantageously recycled at the top of the reactor (line 13) hydroisomerization / hydrocracking step (f).
  • step (d), step (f) or both may also be advantageous to recycle a portion of the kerosene and / or diesel in step (d), step (f) or both.
  • at least one of the kerosene and / or diesel fractions is recycled in part (line 25) in step (d) (zone 12). It has been found that it is advantageous to recycle a portion of the kerosene to improve its cold properties.
  • the non-hydrocracked fraction is partially recycled in step (f) (zone 13).
  • 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 catalysts may be the same or different.
  • they will be selected from the preferred catalysts described below.
  • 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 hydrogenating function is provided either by one or more metals of group VIII of the periodic table of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by a combination of at least one Group VI metal such as chromium, molybdenum and tungsten and at least one Group VIII metal.
  • group VIII of the periodic table of the elements such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by a combination of at least one Group VI metal such as chromium, molybdenum and tungsten and at least one Group VIII metal.
  • 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 give catalysts which are not very active and selective towards 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, 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 silicone 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 the platinum atoms accessible to hydrogen are converted into 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 still most preferred between 3 nm (4x10 -9 meters) and 10.5 nm (10.5x10 -9 meters).
  • the preferred catalyst has a porous distribution such that the pore volume of the pores whose diameter is between the mean diameter as defined above decreased by 3 nm and the average diameter as defined previously increased by 3 nm (ie the average 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%.
  • catalysts 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 can be carried out after any one 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 and micro / mesoporous silica-alumina gel with a pore size. controlled, 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 , a silicon compound which can be hydrolyzed to SiO 2 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 hydrolysable aluminum compound preferably being a trialkoxide aluminum alloy 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.
  • the trialkoxide of 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 chosen 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 hydrogen / l 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.

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Claims (11)

  1. Verfahren zur Herstellung von Mitteldestillaten aus einer mittels Fischer-Tropsch-Synthese hergestellten Paraffinbeschickung, das die folgenden Schritte umfasst:
    1.) Fraktionieren (Schritt a) der Beschickung in mindestens 3 Fraktionen:
    - mindestens eine Zwischenfraktion mit einem Anfangssiedepunkt T1 im Bereich zwischen 120 und 200 °C und einem Endsiedepunkt T2 oberhalb von 300 °C und unterhalb von 410 °C,
    - mindestens eine leichte Fraktion, die unterhalb der Zwischenfraktion siedet,
    - mindestens eine schwere Fraktion, die oberhalb der Zwischenfraktion siedet,
    2.) Hydrobehandeln (Schritt b) mindestens eines Teils der Zwischenfraktion, dann Übertragen (Schritt d) mindestens eines Teils der hydrobehandelten Fraktion auf einen amorphen Hydroisomerisierungs-/Hydrocrackingkatalysator.
    3.) Übertragen (Schrittf) mindestens eines Teils der schweren Fraktion auf einen amorphen Hydrocracking- /Hydroisomerisierungskatalysator mit einer Umwandlung der Produkte 370 °C+ in 370 °C-Minus-Produkte von mehr als 80 Gew.-%.
    4.) Destillieren (Schritte e und g) mindestens eines Teils der hydrogecrackten/hydroisomerisierten Fraktionen, um Mitteldestillate zu erhalten.
  2. Verfahren nach Anspruch 1, wobei die Temperatur T2 unterhalb von 370 °C und oberhalb von 300 °C liegt.
  3. Verfahren nach einem der vorhergehenden Ansprüche, wobei die leichte Fraktion zum Dampfcracken geschickt wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei mindestens ein Teil des Wassers nach der Hydrobehandlung entfernt wird (Schritt c).
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Kontakte mit den Hydroisomerisierungs-/Hydrocrackingkatalysatoren der Schritte (d) und (f) unter einem Druck von 2 bis 150 Bar, mit einer Raumgeschwindigkeit von 0,1 bis 10 h-1 durchgeführt werden, wobei der Wasserstoffanteil im Bereich zwischen 100 und 2.000 NI/I Beschickung und pro Stunde und die Temperatur bei 200 bis 450 °C liegt.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei für Schritt (d) die Umwandlung der Produkte mit Siedepunkten oberhalb von oder gleich 150°C in Produkte mit Siedepunkten oberhalb von 150°C weniger als 50 Gew.-% beträgt.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei für Schritt (f) die Umwandlung der Produkte mit Siedepunkten oberhalb von oder gleich 260°C in Produkte mit Siedepunkten unterhalb von 260 °C bei höchstens 90 Gew.-% liegt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei im Schritt zur Destillation, die Restfraktion, die oberhalb von Diesel siedet, zu Schritt (f) zurückgeführt wird, um auf den Hydrocracking- /Hydroisomerisierungskatalysator übertragen zu werden.
  9. Verfahren nach einem der vorhergehenden Ansprüche, wobei im Schritt zur Destillation, mindestens eine der Kerosin-, Dieselfraktionen teilweise zu mindestens einem der Schritte (d) oder (f) zurückgeführt wird, um auf den (die) Hydrocracking-/Hydroisomerisierungskatalysator(en) übertragen zu werden.
  10. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Katalysatoren der Schritte (d) (f) Katalysatoren sind, die mindestens ein Edelmetall und einen Siliciumdioxid-Aluminiumoxidträger umfassen.
  11. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Hydrobehandlung auf einem geträgerten Katalysator durchgeführt wird, der mindestens ein Metall der Gruppe VIII und/oder der Gruppe VI und mindestens ein Element umfasst, das auf dem Träger abgelagert und aus Phosphor, Bor und Silicium ausgewählt ist.
EP02755093A 2001-07-06 2002-06-26 Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking aus zwei fraktionen der reaktionsprodukte aus dem fischer-tropsch verfahren Expired - Lifetime EP1421157B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0108971A FR2826973B1 (fr) 2001-07-06 2001-07-06 Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de 2 fractions issues de charges provenant du procede fischer-tropsch
FR0108971 2001-07-06
PCT/FR2002/002207 WO2003004584A1 (fr) 2001-07-06 2002-06-26 Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de 2 fractions issues de charges provenant du procede fischer-tropsch

Publications (2)

Publication Number Publication Date
EP1421157A1 EP1421157A1 (de) 2004-05-26
EP1421157B1 true EP1421157B1 (de) 2012-08-15

Family

ID=8865186

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02755093A Expired - Lifetime EP1421157B1 (de) 2001-07-06 2002-06-26 Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking aus zwei fraktionen der reaktionsprodukte aus dem fischer-tropsch verfahren

Country Status (7)

Country Link
US (1) US7156978B2 (de)
EP (1) EP1421157B1 (de)
FR (1) FR2826973B1 (de)
MY (1) MY141718A (de)
NO (1) NO335525B1 (de)
RU (1) RU2283858C2 (de)
WO (1) WO2003004584A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10190063B2 (en) 2014-07-28 2019-01-29 Sasol Technology Proprietary Limited Production of oilfield hydrocarbons

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2826972B1 (fr) * 2001-07-06 2007-03-23 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent produit par le procede fischer-tropsch
FR2826971B1 (fr) * 2001-07-06 2003-09-26 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de charges issues du procede fischer-tropsch
US6949180B2 (en) * 2002-10-09 2005-09-27 Chevron U.S.A. Inc. Low toxicity Fischer-Tropsch derived fuel and process for making same
NL1026215C2 (nl) * 2003-05-19 2005-07-08 Sasol Tech Pty Ltd Koolwaterstofsamenstelling voor gebruik in CI motoren.
US7354507B2 (en) * 2004-03-17 2008-04-08 Conocophillips Company Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons
US7323100B2 (en) * 2004-07-16 2008-01-29 Conocophillips Company Combination of amorphous materials for hydrocracking catalysts
US20080194901A1 (en) * 2004-12-23 2008-08-14 Michiel Cramwinckel Process To Prepare Two Iso Paraffinic Products From A Fischer-Tropsch Derived Feed
FR2888584B1 (fr) * 2005-07-18 2010-12-10 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de charges issues du procede fischer-tropsch utilisant un lit de garde multifonctionnel
DE102005035988B4 (de) * 2005-07-28 2009-01-02 Wolf, Bodo Max, Dr.-Ing. Verfahren zur Erzeugung von flüssigen Kohlenwasserstoffen aus Gas
WO2008043066A2 (en) * 2006-10-05 2008-04-10 Syntroleum Corporation Process to produce middle distillate
WO2008124852A2 (en) * 2007-04-10 2008-10-16 Sasol Technology (Pty) Ltd Fischer-tropsch jet fuel process
US20080260631A1 (en) 2007-04-18 2008-10-23 H2Gen Innovations, Inc. Hydrogen production process
FR2917419B1 (fr) 2007-06-12 2014-10-24 Inst Francais Du Petrole Procede de production de distillats moyens par hydroisomerisation et hydrocraquage d'une fraction lourde issue d'un effluent fischer-tropsch
EP2188352A1 (de) 2007-09-10 2010-05-26 Shell Internationale Research Maatschappij B.V. Verfahren zum hydrocracking und zur hydroisomerisierung eines paraffinierten rohmaterials
FR2934794B1 (fr) * 2008-08-08 2010-10-22 Inst Francais Du Petrole Procede de production de distillats moyens par hydrocraquage de charges issues du procede fischer-trospch en presence d'un catalyseur comprenant un solide izm-2
KR102321624B1 (ko) * 2014-05-23 2021-11-04 에스케이이노베이션 주식회사 디젤 수율을 극대화할 수 있는 rfcc 공정용 접촉분해촉매 및 이의 제조방법
US10472581B2 (en) * 2016-06-30 2019-11-12 Uop Llc Process and apparatus for hydrocracking and hydroisomerizing a hydrocarbon stream

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4832819A (en) 1987-12-18 1989-05-23 Exxon Research And Engineering Company Process for the hydroisomerization and hydrocracking of Fisher-Tropsch waxes to produce a syncrude and upgraded hydrocarbon products
US4919786A (en) * 1987-12-18 1990-04-24 Exxon Research And Engineering Company Process for the hydroisomerization of was to produce middle distillate products (OP-3403)
GB9119505D0 (en) * 1991-09-12 1991-10-23 Shell Int Research Process for the preparation of middle distillates
MY108862A (en) * 1992-08-18 1996-11-30 Shell Int Research Process for the preparation of hydrocarbon fuels
CA2104044C (en) * 1992-08-25 2004-11-02 Johan W. Gosselink Process for the preparation of lower olefins
US5378348A (en) * 1993-07-22 1995-01-03 Exxon Research And Engineering Company Distillate fuel production from Fischer-Tropsch wax
EP0848992B1 (de) * 1996-12-17 2002-03-27 Institut Francais Du Petrole Bor und Silicium enthaltender Katalysator und Anwendung dieses in der Hydrobehandlung von Kohlenwasserstoffeinsätzen
US6113775A (en) * 1997-12-05 2000-09-05 Uop Llc Split end hydrocracking process
JP3848086B2 (ja) * 1999-04-06 2006-11-22 サゾル テクノロジー（プロプライアタリー）リミティド 合成ナフサ燃料を製造する方法およびその方法により製造された合成ナフサ燃料
FR2792851B1 (fr) * 1999-04-29 2002-04-05 Inst Francais Du Petrole Catalyseur a base de metal noble faiblement disperse et son utilisation pour la conversion de charges hydrocarbonees
EP1101813B1 (de) * 1999-11-19 2014-03-19 ENI S.p.A. Verfahren zur Herstellung von Mitteldestillaten aus geradkettigen Paraffinen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10190063B2 (en) 2014-07-28 2019-01-29 Sasol Technology Proprietary Limited Production of oilfield hydrocarbons

Also Published As

Publication number Publication date
RU2004103463A (ru) 2005-08-10
EP1421157A1 (de) 2004-05-26
US20030057133A1 (en) 2003-03-27
FR2826973A1 (fr) 2003-01-10
US7156978B2 (en) 2007-01-02
RU2283858C2 (ru) 2006-09-20
NO20035837L (no) 2004-03-04
NO335525B1 (no) 2014-12-22
MY141718A (en) 2010-06-15
FR2826973B1 (fr) 2005-09-09
WO2003004584A1 (fr) 2003-01-16

Similar Documents

Publication Publication Date Title
EP1406990B1 (de) Verfahren zur herstellung von mitteldestillaten durch zweistufige hydroisomerisation und hydrocracking von reaktionsprodukten aus dem fischer-tropsch verfahren
EP1406989B1 (de) Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking aus einer schwerfraktion der reaktionsprodukte aus dem fischer-tropsch verfahren
EP1421157B1 (de) Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking aus zwei fraktionen der reaktionsprodukte aus dem fischer-tropsch verfahren
EP1406988B1 (de) Verfahren zur herstellung von mitteldestillaten durch hydroisomerisation und hydrocracking von reaktionsprodukten aus dem fischer-tropsch verfahren
EP1048346B1 (de) Katalysator mit schwach dispergiertem Edelmetall und seine Verwendung für die Umwandlung von Kohlenwasserstoffeneinsätzen
FR2718145A1 (fr) Procédé de traitement avec hydroisomérisation de charges issues du procédé fischer-tropsch.
EP1346010B2 (de) Verbessertes flexibles verfahren zur herstellung von grundölen und destillaten durch hydroisomerisierung-konversion an einem schwach dispergierten katalysator und anschliessende katalytische entparaffinierung
FR2926087A1 (fr) Procede multietapes de production de distillats moyens par hydroisomerisation et hydrocraquage d'un effluent produit par le procede fischer-tropsch
WO2009106704A2 (fr) Procede de production de distillats moyens par hydroisomerisation et hydrocraquage sequences d'un effluent produit par le procede fischer-tropsch
EP1462168A1 (de) Katalysator und seine Verwendung zur Verbesserung des Fliesspunktes von Kohlenwasserstoffen
FR2989381A1 (fr) Production de distillats moyens a partir d'un effluent issu de la synthese fischer-tropsch comprenant une etape de reduction de la teneur en composes oxygenes
FR2805543A1 (fr) Procede flexible de production de bases huiles et distillats moyens avec une conversion-hydroisomerisation suivie d'un deparaffinage catalytique
FR2805542A1 (fr) Procede flexible de production de bases huiles et de distillats par une conversion-hydroisomerisation sur un catalyseur faiblement disperse suivie d'un deparaffinage catalytique
WO2005012461A1 (fr) Procede d'amelioration du point d'ecoulement de charges hydrocarbonees issues du procede fischer-tropsch utilisant un catalyseur a base d'un melange de zeolithes
FR2950896A1 (fr) Procede de production de distillats moyens par hydroisomerisation et hydrocraquage de charges issues du procede fischer-tropsch mettant en oeuvre un catalyseur a base de carbure de silicium
WO2005012460A1 (fr) Procede d'amelioration du point d'ecoulement de charges hydrocarbonees issues du procede fischer-tropsch, utilisant un catalyseur a base de zeolithe zbm-30
EP1462166A1 (de) Katalysator und seine Verwendung zur Verbesserung des Fliesspunktes von Kohlenwasserstoffen
FR2792946A1 (fr) Procede de production de bases huiles et de distillats moyens a partir de charges hydrocarbonees par une conversion-hydroisomerisation sur un catalyseur faiblement disperse suivie d'un deparaffinage catalytique
FR3084084A1 (fr) Procede de production d'olefines et de distillats moyens a partir d'un effluent hydrocarbone issu de la synhtese fischer-tropsch
FR2989380A1 (fr) Procede optimise de production de distillats moyens a partir d'une charge issue du procede fischer-tropsch contenant une quantite limitee de composes oxygenes

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040206

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17Q First examination report despatched

Effective date: 20110419

REG Reference to a national code

Ref country code: DE

Ref legal event code: R108

Effective date: 20110426

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): IT

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20130516

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20180629

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190626