ES2185445B1 - FLEXIBLE PROCEDURE FOR PRODUCTION OF OIL BASES AND MEDIUM DISTILLATES WITH A CONVERSION-HYDROISOMERIZATION FOLLOWED BY A CATALYTIC DEPARAFINING. - Google Patents

Abstract

Flexible process for the production of oil bases and middle distillates with a conversion-hydroisomerization followed by a catalytic dewaxing. The invention relates to an improved process for the manufacture of very high quality base oils and the simultaneous production of high quality medium distillates, comprising the successive stages of hydroisomerization and catalytic dewaxing. Hydroisomerization takes place in the presence of a catalyst containing at least one noble metal deposited on an amorphous acidic support, the metal dispersion being 20-100%. Preferably, the support is an amorphous silica-alumina. Catalytic dewaxing takes place in the presence of a catalyst containing at least one hydro-dehydrogenating element (group VII) and at least one molecular sieve (preferred zeolite). Preferably, the sieve is chosen from the zeolite NU-10, EU-1, EU-13 and ferrierite.

Description

Flexible procedure for the production of bases oils and middle distillates with a conversion-hydroisomerization followed by a catalytic dewaxing.

The present invention relates to a Improved process of manufacturing very high base oils quality, that is, they have a high viscosity index (VI), a Good UV stability and low pour point, from loads hydrocarbons (and preferably from loads coming from of the Fischer-Tropsch procedure or from hydrocracking waste), eventually with production simultaneous medium distillates (diesel, kerosene mainly) of very high quality, that is, they have a low yield point and a high cetane number.

Prior art

High quality lubricants are of one paramount importance for the proper functioning of the machines modern cars, and trucks.

These lubricants are obtained very often by a succession of refining stages that allow the improvement of properties of an oil fraction. In particular, it is necessary a treatment of heavy oil fractions with strong contained in linear or slightly branched paraffins in order to get good quality base oils and this with the best possible returns, for an operation that seeks to eliminate linear or very unbranched paraffins, of the charges that will be used below as base oils.

Indeed, high molecular weight paraffins that are linear or very weakly branched and that are present in oils they lead to high creep points and therefore to coagulation phenomena for low temperature uses. In order to decrease the values of creep points, these Linear paraffins nothing or very little branched should be removed Totally or partially.

Another means is catalytic treatment in presence or absence of hydrogen and, taking into account its shape selectivity, zeolites are among the catalysts most used.

\hbox{ZSM-38}

se han descrito para su utilización en estos procedimientos.Zeolite-based catalysts such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and

 \ hbox {ZSM-38} 

have been described for use in these procedures.

All catalysts currently used in hydroisomerization are of the bifunctional type that associate a function acidic to a hydrogenating function. The acid function is contributed by large surface supports (150 to 800 m 2 .g -1 generally) that have a superficial acidity, such as halogenated aluminas (mainly chlorinated or fluorinated), phosphorus aluminas, combinations of boron oxides and aluminum, amorphous silica-aluminas and silica-aluminas. The hydrogenating function is contributed either by one or several metals of group VIII of the periodic classification of the elements, such as iron, cobalt, nickel, ruthenium, palladium, osmium, iridium and platinum, or by an association of at least one group VI metal, such as chromium, molybdenum and tungsten and at least one metal of group VIII.

The balance between the two acidic functions and hydrogenator is the fundamental parameter that directs the activity and the selectivity of the catalyst. A low acid function and a strong hydrogenating function give little active catalysts and selective with respect to isomerization while a function strong acid and a low hydrogenation function give very catalysts active and selective regarding cracking. A third possibility is to use a strong acid function and a function strong hydrogenator in order to obtain a very active catalyst, but also very selective in relation to isomerization. It is possible, therefore, judiciously choosing each of the functions adjust the activity / selectivity pair of the catalyst.

The Requesting Firm therefore proposes according to the procedure described in the invention, produce jointly distilled media of very good quality, from the bases of VI oils and yield point at least equal to obtained with a hydrorefining procedure and / or hydrocracking

Object of the invention

The Requesting Firm has directed its efforts to research on the set-up of a procedure Improved manufacturing of very high quality lubricating oils and of high quality medium distillates from loads hydrocarbons and preferably from hydrocarbon charges from the Fischer-Tropsch procedure or to from hydrocracking waste.

The present invention is therefore based on a chain of procedures for the joint manufacture of base oils of very high quality and medium distillates (mainly diesel) of very high quality from fractions oil companies The oils obtained have a high index of viscosity (VI), low volatility, good UV stability and a low pour point.

More precisely, the invention relates to a procedure for the production of oils from a load hydrocarbon (preferably at least 20% of the volume of the it has a boiling temperature of at least 340 ° C), said procedure comprising the successive stages following:

(to)

conversion of the loading with simultaneous hydroisomerization of at least one part of the n-paraffins of the load, said load having a sulfur content of less than 1000 ppm by weight, a content of nitrogen less than 200 ppm by weight, a metal content less than 50 ppm by weight, a maximum oxygen content of 0.2%, said stage being developed at a temperature of 200-500 ° C, under a pressure of 2-25 MPa, at a spatial velocity of 0.1-10 h -1, in presence of hydrogen with an index generally between 100-2000 liters of hydrogen / liter load, and in presence of a catalyst that contains at least one noble metal deposited on an amorphous acidic support, the noble metal dispersion between 20-100%.

(b)

dewaxed catalytic of at least a part of the effluent from the stage (a), performed at a temperature of 200-500 ° C, under a pressure of 1-25 MPa, at a volumetric rate time of 0.05-50 h <-1>, in the presence of 50-200 liters of hydrogen / liter of effluent that enters stage (b) and in the presence of a catalyst comprising at least one hydro-dehydrogenating element and at less a molecular sieve.

Stage (a) is preceded, therefore, eventually by a hydrotreatment stage usually performed at a temperature of 200-450 ° C, under a pressure from 2 to 25Mpa, at a spatial velocity of 0.1-6 h -1 in the presence of hydrogen in the 100-2000 hydrogen / hydrocarbon volume ratio l / l, and in the presence of an amorphous catalyst comprising at least a metal of group VIII and at least one metal of group VI B.

The entire effluent from the stage (a) can be sent to step (b). Stage (a) can be followed possibly a separation of light gaseous compounds of the effluent obtained as a result of step (a).

Preferably, the effluent from the conversion-hydroisomerization treatment (a) is subjected to a distillation stage (preferably atmospheric) in order to separate compounds that have a point of boiling below 340ºC (gas, gasoline, kerosene, diesel) of products that have an initial boiling point higher than less at 340 ° C and they form the residue. It usually separates like this at minus an average distilled fraction that has a creep point maximum of -20 ° C, and a cetane number of at least 50.

The step (b) of catalytic dewaxing is then apply at least to the residue resulting from distillation containing compounds with a boiling point greater than at least 340 ° C. In another embodiment of the invention, the effluent from stage (a) is not distilled before carrying out the stage (b). At most, it is subjected to a separation of at least one part of the light gases (by flash ...) and is subjected to continuation to a catalytic dewaxing.

Preferably, step (b) is performed with a catalyst containing at least one molecular sieve, whose system microporous presents at least one main type of channels of pore openings having 9 or 10 T atoms, T being chosen in the group formed by Si / Al, P, B, Ti, Fe, Ga, alternating with a equal number of oxygen atoms, the distance between two being accessible pore openings and comprising 9 or 10 T atoms as maximum equal to 0.75 mm, and presenting said sieve in the test with n-dean a relationship 2-methylnonano / 5-netilnonano superior to 5.

Advantageously, the effluent from the Dewaxing treatment is subjected to a distillation stage, which advantageously comprises an atmospheric distillation and a vacuum distillation in order to separate at least a fraction of oil of a boiling point greater than at least 340 ° C. Presents very often a creep point below -10 ° C and a higher VI at 95, a viscosity at 100 ° C of at least 3 cSt (or 3mm2 / s). This distillation stage is essential when there is no distillation between stages (a) and (b).

Advantageously, the effluent from the dewaxing treatment, possibly distilled, is subjected to a hydro-finishing treatment.

Detailed description of the invention

The method according to the invention comprises the following stages:

Load

The hydrocarbon load, from which it they obtain the oils and eventually the high distilled media quality, preferably contains at least 20% by volume of compounds that boil above 340 ° C, preferably at least 350 ° C and advantageously at least 380 ° C. This does not mean that the boiling point is 380ºC and more, but 380ºC or more.

The load contains n-paraffins. Preferably, the charge is an effluent from a unit of Fischer-Tropsch Very varied loads can be treated by the procedure

The load can also be for example distillates under vacuum from direct distillation of crude oil or from conversion units such as the FCC, the coker or the viscorreduction, or that come from extraction units of aromatic, or that come from hydrotreatment or hydroconversion RAT (atmospheric waste) and / or RSV (vacuum waste), or even the load can be a deasphalted oil, or even a hydrocracking residue for example from DSV or any mixture of the aforementioned loads. The above list is not limiting

In general, the charges that are appropriate for the target oils have a higher initial boiling point at least at 340 ° C and better even at least at 370 ° C.

The load introduced in step (a) of Conversion-hydroisomerization should be adequate. I know understood as adequate cargo charges whose sulfur content is less than 1000 ppm by weight preferably less than 500 ppm in weight and even more preferably less than 300 ppm by weight or better at 100 ppm by weight. The nitrogen content is less than 200 ppm by weight and preferably less than 100 ppm by weight and so even more preferred less than 500 ppm by weight. The content in charge metals such as nickel and vanadium is extreme reduced, that is, less than 50 ppm by weight and more advantageously less than 10 ppm by weight, or better less than 2 ppm in weight.

In the case where the contents in products unsaturated or oxygenated are likely to produce a very important deactivation of the catalytic system, the load (for example from the procedure of Fischer-Tropsch) must submit, before entering in the hydroisomerization zone, to hydrotreatment in an area Hydrotreatment Hydrogen is reacted with the charge in contact with a hydrotreatment catalyst, whose role is that of reduce the content of unsaturated hydrocarbon molecules and oxygenated (produced for example during synthesis Fischer-Tropsch).

The oxygen content is reduced, therefore up to 0.2% by weight.

In the case where the load to be treated is not adequate in the sense defined above, it is submitted at first to a previous stage of hydrotreatment, during which, it is put into contact, in the presence of hydrogen, with at least one catalyst that it comprises an amorphous support and at least one metal that has a guaranteed hydro-dehydrogenating function for example by at least one element of group VI B and at least one element of group VIII, at a temperature between 200 and 450 ° C, preferably 250-450 ° C advantageously 330-450 ° C or 360-420 ° C, under one pressure between 5 and 25 MPa or better than 20 MPa, preferably between 5 and 20 MPa, the speed being included spacing between 0.1 and 6 h -1, preferably 0.3-3 h -1, and the amount of hydrogen introduced is such that the hydrogen / hydrocarbon volume ratio It is between 100 and 2000 liters / liter.

The support is usually based (preferably essentially constituted) of alumina or of amorphous silica-alumina; may also contain boron oxide, magnesium, zirconium, titanium oxide or a combination of these oxides. The function hydro-dehydrogenating is preferably fulfilled by at least one metal or metal compound of groups VIII and VIB preferably chosen (s) from; molybdenum, tungsten, nickel and cobalt.

This catalyst may advantageously contain match; indeed, it is known in the prior art that the compound provides two advantages to the catalysts of hydrotreatment: an ease of preparation mainly during the impregnation of nickel and molybdenum solutions, and better hydrogenation activity.

Preferred catalysts are those NiMo and / or NiW catalysts on alumina, also the NiMo and / or NiW catalysts on bonded alumina with at least one element included in the group of atoms formed by the phosphorus, boron, silicon and fluorine, or even catalysts NiMo and / or NiW on silica-alumina, or on silica-alumina-titanium oxide bonded or not by at least one element included in the group of atoms formed by phosphorus, boron, fluoride and silicon.

The total concentration in metal oxides of Groups VIB and VIII are between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed in metal oxide between metal (or metals) of group VI on metal (or metals) of group VIII is preferably between 20 and 1.25 and even more preferred between 10 and 2. The concentration in oxide of phosphorus P 2 O 5 will be less than 15% by weight and preferably at 10% by weight.

Before being sent to stage (a), the product obtained as a result of hydrotreatment is submitted, if it is necessary, at an intermediate separation of water (H2O, H2S, NH3) in order to reduce the water content, in H2S and in NH 3 in the charge introduced in step (a) to values, respectively, less than a maximum of 100 ppm, 200 ppm, 50 ppm. An eventual separation of the products that have a boiling point below 340ºC with the in order to treat in step (a) only a residue.

In the case where a hydrocracking residue is treated, it is then in the presence of a load that has been already subjected to hydrotreatment and hydrocracking. Load suitable can then be treated directly in step (a).

Generally, hydrocracking takes place with a zeolitic catalyst, very often based on zeolite Y, and in particular of zeolites and desaluminadas.

         \ newpage
      

The catalyst also contains at least one non-noble GVIII group metal and at least one metal of the VIB group.

Stage (a) Hydroisomerization-Conversion Catalyst

Stage (a) takes place in the presence of hydrogen and in the presence of a bifunctional catalyst comprising an amorphous acidic support (preferably a amorphous silica-alumina) and a metallic function hydro-dehydrogenator secured by at least one noble metal The dispersion in noble metal is of 20-100%

The support is called amorphous, that is, devoid of molecular sieve, and in particular of zeolite, as well as the catalyst The amorphous acidic support is advantageously a amorphous silica-alumina, but others are usable brackets When it is a silica-alumina, the Catalyst generally does not contain added halogen, except the that could be introduced for the impregnation of the noble metal by example.

During this stage, the n-paraffins in the presence of a catalyst bifunctional undergo isomerization, then eventually a hydrocracking to lead, respectively, to the formation of isoparaffins and lighter cracking products such as diesel and kerosene. The conversion usually varies between 5 and 90%, but is generally at least 20% or greater than 20%.

In a preferred embodiment of the invention, a catalyst comprising a particular silica-alumina that allows to obtain very active catalysts, but also very selective in the isomerization of charges such as those defined above.

A preferred catalyst comprises (and preferably it consists essentially of) 0.05-10% by weight of at least one noble metal of the group VIII deposited on an amorphous support of silica-alumina (preferably containing 5-70% by weight of silica) that has a BET specific surface area of 100-500 m 2 / g and the catalyst presents:

-

an average diameter of pores between 1-12 nm,

-

a porous volume of the pores, whose diameter is between the average diameter as defined above decreased 3 nm and the diameter medium as defined above increased by 3 nm is greater than 40% of the total porous volume,

-

a dispersion of noble metal between 20-100%,

-

a coefficient of noble metal distribution greater than 0.1.

The characteristics of the catalyst according to the invention are more in detail:

Silica content : the preferred support used for the preparation of the catalyst described in the framework of this patent is composed of silica SiO2 and alumina Al2O3. The silica content of the support, expressed as a percentage by weight, is generally between 1 and 95%, advantageously even between 5 and 95% and preferably between 10 and 80% and even more preferably between 20 and 70% and between 22 and 45%. This silica content is perfectly measured with the help of X fluorescence.

Nature of the noble metal : for this particular type of reaction, the metallic function is contributed by a noble metal of group VIII of the periodic classification of the elements and more particularly platinum and / or palladium.

Noble metal content: the noble metal content, expressed in% by weight of metal in relation to the catalyst, is between 0.05 to 10 and more preferably between 0.1 and 5.

Noble metal dispersion: the dispersion, which represents the fraction of metal accessible to the reagent in relation to the total amount of metal in the catalyst, can be measured, for example, by titration H 2 / O 2. The previously reduced metal, that is to say, which is subjected to a treatment under high temperature hydrogen flow under such conditions in which all platinum atoms accessible with hydrogen are transformed in metallic form. Next, an oxygen flow is sent under suitable operating conditions so that all reduced platinum atoms accessible to oxygen are oxidized in the form of PtO2. By calculating the difference between the amount of oxygen introduced and the amount of oxygen exiting, the amount of oxygen consumed is accessed; thus, the amount of platinum accessible to oxygen can be deduced from this last value. The dispersion is then equal to the ratio of the amount of platinum accessible to oxygen over the total platinum amount of the catalyst. In our case, the dispersion is between 20% and 100% and preferably between 30% and 100%.

         \ newpage
      

Distribution of the noble metal : the distribution of the noble metal represents the distribution of the metal inside the catalyst grain, the metal may be well or poorly dispersed. Thus, it is possible to obtain the badly distributed platinum (for example detected in a crown, whose thickness is clearly less than the radius of the grain), but well dispersed, that is, that all platinum atoms, located in the crown, will be accessible to reagents In our case, the distribution of platinum is good, that is, that the platinum profile, measured according to the Castaing microwave method, has a distribution coefficient greater than 0.1 and preferably greater than 0.2.

BET surface : the BET surface of the support is between 100 m 2 / g and 500 m 2 / g and preferably is between 250 m 2 / g and 450 m 2 / g and for the supports based on silica-alumina, even more preferably between 310 m2 / g and 450 m2 / g.

Average pore diameter : for preferred silica-alumina-based catalysts, the average pore diameter of the catalyst is measured from the porous distribution profile obtained with the aid of a mercury porosimeter. The average pore diameter is defined as the diameter that corresponds to the cancellation of the derived curve obtained from the mercury porosity curve. The mean pore diameter, thus defined, is between 1 nm (1x10 -9 meters) and 12 nm (12x10 -9 meters) and is preferably between 1 nm (1x10 -9) meters) and 11 nm (11x10 -9 meters) and even more preferably between 3 nm (4 x 10-9 meters) and 10.5 nm (10.5x10 -9 meters).

Porous distribution : the preferred catalyst in question in this patent has a porous distribution such that the porous volume of the pores, whose diameter is comprised between the average diameter as defined above decreased by 3 nm and the average diameter such as the defined above increased by 3 nm (or the average diameter ± 3 nm) is greater than 40% of the total porous volume and preferably is between 50% and 90% of the total porous volume and more advantageously even between 50% and 70% of the total porous volume.

Overall porous volume of the support : for the preferred silica-alumina-based catalyst, it is generally less than 1.0 ml / g and is preferably between 0.3 and 0.9 ml / g and even more advantageously it is less than 0.85 ml / g

The preparation and configuration of the support, and in particular silica-alumina (mainly used in the preferred embodiment) is done by methods usual well known to the technician. Advantageously, prior to the impregnation of the metal, the support may be subjected to a calcination, such as a heat treatment to 300-750 ° C (600 ° C preferred) during 0.25-10 hours (2 hours preferably) under 0-30% by volume of water vapor (for silica alumina, 7.5% is preferred).

The noble metal salt is introduced by one of the usual methods used to deposit the metal (preferably platinum and / or palladium, platinum even being preferred) in the surface of a support. One of the preferred methods is the dry impregnation consisting of the introduction of salt metal in a solution volume that is equal to the porous volume of the mass of catalyst to impregnate. Before the reduction operation, The catalyst may undergo calcination, such as a treatment under dry air at 300-750ºC (520ºC preferred) for 0.25-10 hours (2 hours with preference).

Before use in the hydroisomerization-conversion reaction, the metal contained in the catalyst must be reduced. One of the preferred methods for carrying out the reduction of the metal is the treatment under hydrogen at a temperature comprised between 150 ° C and 650 ° C and a total pressure comprised between 0.1 and 25 Mpa. For example, a reduction consists of a 2-hour plateau at 150 ° C, then a temperature rise to 450 ° C at the rate of 1 ° C / min., Then a 2-hour plateau at 450 ° C; During this entire reduction stage, the hydrogen flow rate is 1000 liters hydrogen / liter catalyst. It should also be noted that any ex-situ reduction method is convenient.

The operating conditions in which it is carried out This stage (a) are important.

The pressure will generally be maintained between 2 and 25 MPa (more often at least 5 MPa) and preferably 2 (or 3) at 20 MPa and advantageously from 2 to 18 MPa, the space velocity will be usually between 0.1 h -1 and 10 h -1 and preferably between 0.2 and 10 h -1, with 0.1 being advantageous or 0.5 h -1 and 5.0 h -1, and a hydrogen index generally between 100 and 2000 liters of hydrogen per liter of charge and preferably between 150 and 1500 liters of hydrogen per liter of load.

The temperature used in this stage is most often between 200 and 500 ° C (or 450 ° C) and preferably from 250 ° C to 450 ° C, advantageously from 300 to 450 ° C, and even more advantageously higher than 340 ° C, for example between 320-450 ° C.

The two stages of hydrotreatment and of hydroisomerization-conversion can be performed on the two types of catalysts in (two or several) reactors different, or / and on at least two catalytic beds installed in The same reactor.

As this has been shown in the patent US 5,879,539, the use of the catalyst described earlier in step (a) it has the effect of increasing the rate of viscosity (VI) of +10 points. More generally, it is found that the VI increase is at least 2 points, the VI being measured over a charge (residue) dewaxed in the solvent and on the product from step (a) also dewaxed in the solvent, pretending a creep point temperature between -15 and -20ºC.

An increase in LV of at minus 5 points, and very often more than 5 points, even more than 10 points.

It is possible to control the increase in VI mainly from the measurement of the conversion. It will be possible thus optimize production towards oils with high VI or towards higher oil yields but with less elevated VI.

Parallel to the increase in VI, most of the sometimes you get a decrease in the yield point that can go from a few degrees to 10-15 ° C, even more (25 ° C for example). The extent of the decrease varies depending on of the conversion and, therefore, of the operating conditions and of load.

Treatment of the effluent resulting from step (a)

In a preferred embodiment, the effluent from stage (a) of hydroisomerization-conversion can be treated in its whole in stage (b) dewaxing. In a variant, you can undergo a separation of at least one part (and preferably of at least a major part) of light gases comprising the hydrogen and eventually also hydrocarbon compounds of as maximum 4 carbon atoms. Hydrogen can separate previously. The embodiment (out of variant) with step a stage (b) of the entire effluent of stage (a), is economically interesting, because a single distillation unit is use at the end of the procedure. In addition, in the final distillation (after catalytic dewaxing or previous treatments) You get a very cold diesel.

Advantageously in another embodiment, the effluent from step (a) is distilled in order to separate light gases and also separate at least one residue which contains compounds with a boiling point higher than less at 340 ° C. It is preferably a distillation atmospheric

It can be advantageously distilled to obtain several fractions (gasoline, kerosene, diesel for example), with boiling point at a maximum of 340 ° C and a fraction (called residue) with an initial boiling point above at least 340 ° C and better than 350 ° C and preferably at least 370 ° C or 380 ° C

According to a preferred variant of the invention, this fraction (residue) will be treated next in the stage of catalytic dewaxing, that is, without distillation empty. But in another variant, a distillation can be used to empty.

In a more focused embodiment on a objective of production of middle distillates, and always according to the invention, it is possible to recycle a part of the residue from the separation stage towards the reactor containing the catalyst of hydroisomerization in order to convert and increase the middle distillate production.

In a general way, they are called in this text middle distillates, the boiling fraction (s) initial of at least 150ºC and final that goes until before the residue, is that is, generally up to 340 ° C, 350 ° C or preferably less than 370 ° C or 380 ° C.

The effluent from stage (a) can undergo, before or after distillation, other treatments such as for example an extraction of at least one part of the aromatic compounds

Stage (b) Catalytic Hydro Dewaxing

At least one part of the effluent from the step (a), effluent that has been eventually subjected to separations and / or treatments described above, undergoes then at a stage of catalytic dewaxing in the presence of hydrogen and a hydrodeparaffinized catalyst comprising an acid function, a hydrodehydrogen metal function and at less a matrix.

It should be noted that the compounds that boil above at least 340 ° C they are always subjected to dewaxing catalytic.

Catalyst

The acid function is assured by at least one molecular sieve and preferably a molecular sieve, whose system microporous presents at least one main type of channels, whose openings are formed of rings containing 10 or 9 atoms of T. The atoms of T are the tetrahedral atoms constituting the molecular sieve and can be at least one of the elements contained in the following set of atoms (Si, Al, P, B, Ti, Faith, Ga). In the constituent rings of the channel openings, the atoms of T, defined above, alternate with a number Equal oxygen atoms. It is therefore equivalent to say that the openings are formed by rings containing 10 or 9 atoms of oxygen or are formed by rings containing 10 or 9 atoms of T.

The molecular sieve that enters the composition of the hydrodewax catalyst may also comprise other types of channels, but whose openings are formed by rings containing less than 10 T atoms or oxygen atoms.

The molecular sieve that enters the composition of the preferred catalyst also has a bridge width, distance between two pore openings, as defined above, which is at most 0.75 nm (1nm = 10-9 m) preferably it is between 0.50 nm and 0.75 nm, so even more preferred between 0.52 nm and 0.73 nm; allowing such sieves obtaining good catalytic results at the stage of hydrodeparaffin.

The width measurement of the bridge is made using a graphing and molecular modeling instrument such as Hyperchem or Biosym, which allows you to build the surface of the molecular sieves in question and, taking into account the radii ionic elements present in the sieve structure, measure bridge width

The preferred catalyst that is suitable for this procedure can also be characterized by an essay catalytic called standard transformation test of pure n-dean that is performed under a pressure partial of 450 kPa of hydrogen and a partial pressure of n-C 10 of 1.2 kPa or a total pressure of 451.2 kPa in fixed bed and with a flow of constant n-C10 of 9.5 ml / h, a total flow of 3.6 l / h and a catalyst mass of 0.2 g. The reaction is carried out. in downward flow. The conversion rate is regulated by the temperature at which the reaction develops. Catalyst undergoing said test consists of pure zeolite in form of tablet and 0.5% by weight of platinum.

The n-dean in the presence of molecular sieve and a hydrodehydrogenating function is going to experience hydroisomerization reactions that will produce products isomerized with 10 carbon atoms, and reactions of hydrocracking that lead to the formation of products that contain less than 10 carbon atoms.

Under these conditions, a molecular sieve used in the hydrodewaxing stage with the catalyst preferred according to the invention must have the characteristics physicochemical described above and drive, for a performance in isomerized products of n-C 10 of the order of 5% by weight (the index of conversion is regulated by temperature), at a ratio 2-methylnonano / 5-methyltilano superior to 5 and preferably greater than 7.

The use of molecular sieves as well selected, under the conditions described above, among the numerous already existing molecular sieves, mainly allows the production of products with low yield point and high index of viscosity with good yields under the procedure according to the invention.

Molecular sieves that can enter the composition of the preferred hydrodeparaffin catalyst Catalytic are, by way of examples, the following zeolites: Ferrierita, NU-10, EU-13, EU-1.

Preferably molecular sieves that enter the composition of the hydrodewax catalyst are included in the set formed by ferrierite and zeolite EU-1.

\hbox{ISI-1,}

KZ-2, ISI-4, KZ-1.In general, the hydrodeparaffinate catalyst comprises a zeolite chosen in the group consisting of NU-10, EU-1, EU-13, ferrierite, ZSM-22, Theta-1, ZSM-50, ZSM-23, NU- 23, ZSM-35, ZSM-38, ZSM-48,

 \ hbox {ISI-1,} 

KZ-2, ISI-4, KZ-1.

The molecular sieve weight content in the hydrodewax catalyst is between 1 and 90%, preferably between 5 and 90% and even more preferably between 10 and 85%.

The matrices used to perform the catalyst configuration are by way of examples and so non-limiting, alumina gels, aluminas, magnesia, amorphous silica-aluminas, and mixtures thereof. Techniques such as extrusion, tablet formation or formation of dragees, can be used to perform the operation of setting.

The catalyst also comprises a function hydro-dehydrogenating assured, for example, by the at least one element of group VIII and preferably at least one noble element included in the set formed by platinum and Palladium The non-noble metal weight content of group VII, in relation to the final catalyst, it is between 1 and 40%, preferably between 10 and 30%. In this case, the non-noble metal is associated with at least one metal of group VIB (Mo and W preferred). I know it is at least one noble metal of group VIII, whose content weight, in relation to the final catalyst, is less than 5%, preferably less than 3% and even more preferably less than 1.5%.

In the case of the use of noble metals Group VIII, platinum and / or palladium are located preferably on the matrix.

The hydrodeparaffinate catalyst according to the invention may also contain from 0 to 20%, preferably from 0 to 10% by weight (expressed in oxides) of phosphorus. Combining metal (s) of group VI B and / or metal (s) of group VII with Phosphorus is particularly advantageous.

The treatment

A residue obtained as a result of the stage (a) and distillation and what is interesting to deal with in this stage (b) of hydrodewaxing, has the characteristics following: it has an initial boiling point higher than 340ºC and preferably greater than 370 ° C, a creep point of at least 15 ° C, a viscosity index of 35 to 165 (before dewaxing), preferably at least equal to 110 and even more so preferred below 150, a viscosity at 100 ° C greater than or equal to 3 cSt (mm2 / s), a lower aromatic compound content at 10% by weight, a nitrogen content of less than 10 ppm by weight, a sulfur content of less than 50 ppm by weight or better than 10 ppm in weight.

The operating conditions in which it operates in The catalytic stage of the process of the invention are the following:

-

the temperature of reaction is between 200 and 500 ° C and preferably between 250 and 470 ° C, advantageously 270-430 ° C;

-

the pressure is between 0.1 (or 0.2) and 25 MPa (10 6 Pa) and preferably between 1.0 and 20 MPa;

-

speed hourly volume (wh expressed in volume of cargo injected by unit volume of catalyst and per hour) is between about 0.05 and about 50 and preferably between about 0.1 and about 20 h -1 and in a way even more preferred between 0.2 and 10 h -1.

They are chosen to obtain the yield point wanted.

The contact between the charge and the catalyst is performed in the presence of hydrogen. The hydrogen index used and expressed in liters of hydrogen per liter of charge is between 50 and approximately 2000 liters of hydrogen per liter of cargo and preferably between 100 and 1500 liters of hydrogen per liter of charge.

The tributary obtained

The effluent at the exit of stage (b) of hydrodeparaffin, is sent to the distillation train, which integrates preferably an atmospheric distillation and a distillation at void, which aims to separate conversion products from boiling point below 340 ° C and preferably below 370 ° C (and that mainly includes those formed during the stage of catalytic hydrodeparaffinate), and separate the fraction that constitutes the oil base and, therefore, the initial boiling point is greater than at least 340 ° C and preferably greater than or equal to 370 ° C.

On the other hand, this distillation section a vacuum allows to separate the different grades of oils.

Preferably, before being distilled, the effluent at the exit of hydrodesparaffinating stage (b) catalytic is sent, at least in part and preferably in its whole, on a hydro-finishing (hydro-finishing) catalyst in presence of hydrogen in order to perform hydrogenation driven aromatic compounds that impair stability of oils and distillates. However, the acidity of catalyst must be low enough not to lead to Boiling point cracking product formation less than 340 ° C not to degrade the final yields mainly in oils

The catalyst used in this stage comprises at least one metal of group VIII and / or at least one element of the group VIB of the periodic classification. The strong metallic functions: platinum and / or palladium, or combinations nickel-tungsten, nickel-molybdenum, they will be used advantageously to carry out a hydrogenation Aromatic driven.

These metals are deposited and dispersed on an amorphous or crystalline oxide type support, such as by example, aluminas, silicas, silica-aluminas.

The hydro-finishing catalyst (HDF) can also contain at least one element of group VII A of the Periodic clasification of the elements. Preferably, these Catalysts contain fluorine and / or chlorine.

The weight contents in metals are between 10 and 30% in the case of non-noble metals and less than 2%, preferably between 0.1 and 1.5%, and even more preferably between 0.1 and 1.0% in the case of noble metals

The total amount of halogen is comprised between 0.02 and 30%, by weight advantageously 0.01 to 15% or even of 0.01 to 10%, preferably 0.01 to 5%.

They can be cited among the catalysts usable at this stage of hydro-finishing, and that lead to excellent results, and mainly for obtaining oils medicinal, catalysts that contain at least one noble metal of group VIII (platinum and VIII for example) and at least one halogen (chlorine and / or fluorine), the combination chlorine and fluorine.

The operating conditions in which it is performed The hydro-finishing stage of the process of the invention are the following:

- the reaction temperature is included between 180 and 400 ° C and preferably between 210 and 350 ° C, advantageously 230-320 ° C;

- the pressure is between 0.1 and 25 Mpa (106 Pa) and preferably between 1.0 and 20 Mpa;

- hourly volumetric speed (Wh expressed in load volume injected per unit volume of catalyst and per hour) is between approximately 0.05 and about 100, and preferably between about 0.1 and approximately 30 h -1.

The contact between the charge and the catalyst is performed in the presence of hydrogen. The hydrogen index used and expressed in liters of hydrogen per liter of charge is between 50 and approximately 2000 liters of hydrogen per liter of cargo and preferably between 100 and 1500 liters of hydrogen per liter of charge.

Advantageously, the temperature of the stage of Hydrofinishing (HDF) is lower than the stage temperature of catalytic hydrodeparaffin (HDPC). The difference T_ {HDPC} -T_ {HDF} is generally comprised between 20 and 200, and preferably between 30 and 100 ° C. The effluent in The HDF output is then sent to the distillation train.

The products

The base oils obtained according to this procedure have a creep point below -10 ° C, a VI greater than 95, preferably greater than 110 and even more preferred greater than 120, a viscosity of at least 3.0 cSt at 100 ° C, an ASTM color less than 1 and a UV stability such that the ASTM color increase is between 0 and 4 and preferably between 0.5 and 2.5.

The UV stability test, adapted from ASTM D925-55 procedures and D1148-55, provides a quick method to compare the stability of lubrication oils exposed to a source of ultraviolet rays. The test chamber is constituted by a metal enclosure provided with a rotating tray that receives the oil samples. A blister that produces the same rays ultraviolet than those of sunlight and placed on top of the Test chamber is directed down onto the samples. Between the Samples include a standard oil with U.V. known. The ASTM D1500 color of the samples is determined at t = 0, after 45 hours of exposure at 55 ° C. The results are transcribed for the standard sample and the test samples of the Following way:

a) ASTM D1500 initial color,

b) ASTM D1500 final color,

c) color increase,

d) cloudy,

e) precipitate.

Another advantage of the process according to the invention is that it is possible to reach very low aromatic contents, less than 2% by weight preferably 1% by weight and better less than 0.05% by weight) and even go to the production of medicinal grade white oils that have contents in aromatic less than 0.01% by weight. These oils have values UV absorption at 275, 295 and 300 nanometers, respectively, below 0.8, 0.4 and 0.3 (ASTM D2008 method) and a Saybolt color between 0 and 30.

In a particularly interesting way, so therefore, the process according to the invention also allows obtaining white medicinal oils White medicinal oils are mineral oils obtained by a refined petroleum driven, its quality is subject to different regulations that are intended guarantee its safety for pharmaceutical applications, they are devoid of toxicity and are characterized by their density and their viscosity. White medicinal oils essentially comprise saturated hydrocarbons, are chemically inert and their content in aromatic hydrocarbons is low. A particular attention is paid to aromatic compounds and mainly 6 hydrocarbons polycyclic aromatics (P.A.H for short Anglo-Saxon polycyclic aromatic hydrocarbons) which are toxic and are present in concentrations of one part per billion by weight of aromatic compounds in the oil White. The control of the total aromatic content can be carried out by the ASTM D 2008 method, where this adsorption test UV at 275, 292 and 300 nanometers allows to control absorption lower, respectively, at 0.8, 0.4 and 0.3 (that is, the white oils have aromatic contents of less than 0.01% in weigh). These measurements are made with concentrations of 1 g of oil per liter, in a 1 cm bowl. White oils marketed differ by viscosity, but also by its crude oil of origin that can be paraffinic or naphthenic, and these two parameters will induce differences in properties at the same time physicochemical of the white oils considered, but also in its chemical composition.

Currently the oil fractions, which they come either from the direct distillation of a crude oil followed by an extraction of the aromatic compounds by a solvent, or that come from the hydrorefining process catalytic or hydrocracking, they contain even quantities not negligible aromatic compounds. In the legislative framework Current of most industrial countries, white oils called medicinal must have an aromatic content less than a threshold imposed by the legislation of each of the countries The absence of these aromatic compounds in the fractions of oils is translated by a Saybolt color specification that must be at least 30 (+30), a specification maximum absorption U.V. which should be less than 1.60 at 275 nm above a pure product in Cuba of 1 centimeter and a specification maximum absorption of DMSO extraction products that must be be less than 0.1 for the American market (Food and Drug Administration, norm nº 1211145). This last essay consists of specifically extract polycyclic aromatic hydrocarbons with the help of a polar solvent, often the DMSO, and in controlling its content in the extract by a measure of UV absorption in the 260-350 nm range.

The invention will be illustrated with figures 1 to 3, which represent different embodiments modes for the treatment of a load, for example, from the procedure Fischer-Tropsch or a hydrocracking residue.

Figure 1

In figure 1, the load enters the duct (1) to a hydrotreatment zone (2) (which may be composed by one or several reactors, and comprises one or several layers catalysts of one or more catalysts) into which hydrogen enters (for example through the duct (3)) and where the stage of hydrotreatment

The hydrotreated load is transferred by the conduit (4) to the hydroisomerization zone (7) (which may be composed of one or several reactors and comprises one or several beds catalysts of one or more catalysts) where it is carried out, in presence of hydrogen, the step (a) of hydroisomerization. The Hydrogen can be introduced through the conduit (8).

In this figure, before being introduced in the zone (7), a large part of the hydroisomerize is removed from the cargo its water in the flask (5), water flowing out of the duct (6) and possibly ammonia and hydrogen sulfide H2S, in the case where the charge entering through conduit 1 contains sulfur and nitrogen.

The effluent from zone (7) is sent through a conduit (9) to a flask (10) for the separation of the hydrogen that is extracted through a conduit (11), the effluent is then distilled at atmospheric pressure in the column (12), where a fraction is extracted from the head through the duct (13) light containing the compounds of a maximum of 4 atoms of carbon and those that boil at the bottom.

At least a fraction of gasoline (14) and at least a fraction of medium distillate (kerosene (15) and diesel (16) for example).

A fraction is obtained at the bottom of the column which contains compounds with a boiling point higher than less at 340 ° C. This fraction is evacuated through the duct (17) towards the zone (18) of catalytic dewaxing.

The catalytic dewaxing zone (18) (which it comprises one or more reactors, one or several catalytic beds of one or more catalysts) also receives hydrogen by a conduit (19) to perform step (b) of the procedure.

The effluent obtained leaving the duct (20) is separated in a distillation train comprising, in addition, the flask (21) to separate hydrogen through a conduit (22), a atmospheric distillation column (23) and a vacuum column (24) which treats the atmospheric distillation residue transferred by the duct (25), a residue with an initial boiling point greater than 340 ° C.

It is obtained as products that come from the distillations, a fraction of oil (conduit 26) and fractions that boil at a lower temperature, such as diesel (duct 27), kerosene (conduit 28) gasoline (conduit 29); light gases are eliminated by the duct (30) of the atmospheric column and by the duct (31) of the vacuum distillation column.

The effluent that goes out through the duct (20) can also advantageously sent to a hydro-finished area (not represented) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) before being injected into the separation train. Hydrogen can be added if It is necessary in that area. The effluent that leaves is transferred then to the flask (21) and to the distillation train described.

In order not to reload the figure, it has not been represented hydrogen recycling, either at the level of the flask (10) towards the hydrotreatment and / or hydroisomerization, and / or at the level of the flask (21) towards dewaxing and / or hydro-finishing.

Figure 2

It will be recognized that the references of figure 1. In this embodiment, the all effluent from zone (7) of hydroisomerization-conversion (step a) passes directly through the duct (9) to the dewaxing zone (18) catalytic (stage b).

Figure 3

In the same way as before, they have retained the references in figure 1. In this mode of embodiment, the effluent from zone (7) of hydroisomerization-conversion (step a) is subjected to the flask (32) at a separation of at least one part of the gases lightweight (hydrogen and hydrocarbon compounds up to 4 carbon atoms) for example by flash. The separated gases are extracted through the duct (33) and the residual effluent is sent by the conduit (34) to the zone (18) of catalytic dewaxing.

It will be noted that in Figures 1, 2 and 3 it has been planned a separation on the effluent from the area (18) Catalytic dewaxing. This separation may not take place. when said effluent is subsequently treated in an area of hydro-finishing, then the separation taking place after said treatment.

This is about the separation made in the flasks or columns 21, 23, 24.

Example 1 Preparation of catalyst A1 according to the invention

Catalyst A1 is prepared from a silica-alumina support used in the form of extruded It contains 29.3% by weight of silica SiO2 and 70.7% in alumina weight Al 2 O 3. Silica alumina before adding noble metal it has a surface area of 330 m2 / g and its total porous volume is 0.87 ml / g.

Catalyst A1 is obtained after impregnation of the noble metal on the support. Platinum salt H2 PtCl6 is dissolved in a volume of solution that corresponds to the total porous volume to impregnate. The solid is calcined next for 2 hours under dry air at 500 ° C. The Platinum content is 0.60% by weight. Measure on the catalyst, the BET surface is equal to 312 m 2 / g. The Platinum dispersion measured by titration H 2 / O 2 is of 99% By Transmission Electron Microscope, platinum is Hard to put in evidence. When it is displayed, it is fit of very small particles of 0.7 to 1.0 nm.

Example 2 Evaluation of catalyst A1 in hydroisomerization of a charge Fischer-Tropsch followed by a separation and a catalytic dewaxing

The catalyst, whose preparation is described in Example 1 is used in order to hydroisomerize a charge of paraffins from the Fischer-Tropsch synthesis with the aim of obtaining oils. In order to be able to use directly the hydroisomerization catalysts, the charge has previously hydrotreated and the oxygen content has been reduced below 0.1% by weight. The main characteristics of the Hydrotreated cargo are as follows:

starting point 170 ° C point 10% 197 ° C 50% point 350ºC 90% point 537 ° C point final 674 ° C fraction 380 + (% by weight) 42 Point of creep + 73 ° C density (20/4) 0.787

The catalytic test unit comprises a fixed bed reactor, with upward load circulation (`` up-flow ''), in which 80 ml of catalyst. The catalyst is then subjected to an atmosphere of pure hydrogen at a pressure of 10 MPa in order to ensure the reduction of platinum oxide in metallic platinum after the load is finally injected. The total pressure is 10 MPa, the Hydrogen flow rate is 1000 liters of gaseous hydrogen per liter of injected load, the hourly volumetric speed is 2 h <-1> and the reaction temperature of 350 ° C. After the reaction, the effluents are divided into light products (gasoline PI-150ºC), middle distillates (150-380 ° C) and residue (380 ° C).

\hbox{Si/A1=10,2}

y 20% en peso de alúmina así como 0,6% en peso de Pt. El catalizador es sometido entonces a una atmósfera de hidrógeno puro a una presión de 10 MPa con el fin de asegurar la reducción del óxido de platino en platino metálico, después que la carga es por último inyectada. La presión total es de 10 MPa, el caudal de hidrógeno es de 1000 litros de hidrógeno gaseoso por litro de carga inyectada, la velocidad volúmica horaria es de 2 h^{-1} y la temperatura de reacción de 350ºC. Después de la reacción, los efluentes son fraccionados en productos ligeros (gasolina PI-150ºC), destilados medios (150-380ºC) y residuo (380ºC+).The residue is then dewaxed in a second reactor with up-flow of the load (`` up-flow ''), in which 80 ml of catalyst containing 80% by weight of a zeolite Ferrierite ratio is introduced

 \ hbox {Si / A1 = 10.2} 

and 20% by weight of alumina as well as 0.6% by weight of Pt. The catalyst is then subjected to an atmosphere of pure hydrogen at a pressure of 10 MPa in order to ensure the reduction of platinum oxide in metallic platinum, after the load is finally injected. The total pressure is 10 MPa, the hydrogen flow rate is 1000 liters of hydrogen gas per liter of injected load, the hourly volumetric rate is 2 h -1 and the reaction temperature is 350 ° C. After the reaction, the effluents are fractionated into light products (gasoline PI-150ºC), medium distillates (150-380ºC) and waste (380ºC +).

The characteristics of the oil obtained are measurements.

The following table shows the yields for the different fractions and the characteristics of oils obtained directly with the load and with the effluents hydroisomerized on catalyst A1 (according to the invention), then catalytically dewaxed.

Load Hydroisomerized effluent and hydrotreated catalytically dewaxed Catalyst / A1 Dewaxed in the dewaxed catalytically solvent -20ºC * according to the example Density of effluents a 15ºC 0.790 0.781 % in weight 380 - / effluents 58 67 % in weigh 380 + / effluents 42 33 Residue quality 380 + Performance of dewaxed 6 53 (% in weight) Performance oil / load 2.5 17.5 Oil quality VI (index of Viscosity) 143 137 Distribution by fractions PI-150 0 10 150-380 58 58 380 + 42 32 Net conversion in 380 - (%) / 21.4 * the solvent used is the methyl isobutyl ketone.

It indicates, more clearly, that the load does not hydroisomerized and dewaxed in the solvent at -20 ° C, it has an extremely low oil yield while after of the operation of hydroisomerization and catalytic dewaxing, the oil yield is higher.

Example 3 High quality oil production

The hydrocracking residue described in the Table above is introduced into a reactor that contains a bed of hydroisomerization catalyst A2 as well as hydrogen under a total pressure of 7 MPa and in a volume ratio H2 / HC = 600 NI / NI. The space velocity is then 1h-1 over this catalyst. The reaction temperature is 326 ° C.

Catalyst A2 contains a support that has 28% by weight of SiO2 and 72% by weight of Al2O3 over the which has deposited 0.6% by weight of Pt. The dispersion in Pt is of 56%

The effluent is recovered, then distilled to vacuum in order to recover a fraction 380 ° C +, whose Features are represented in the following table.

The fraction 250-380 ° C, which corresponds to a fraction of diesel and resulting from the conversion hydroisomerization of the hydrofisuration residue, it has a yield point of -20ºC and a cetane number of 58, For this reason it is an excellent diesel.

The 380 ° C + fraction prepared above is then introduced into a reactor containing a bed of hydrodeparaffinate catalyst (0.5% PT deposited on a support containing 75% ferrierite and 25% Al 2 O 3) and hydrogen under a pressure of 14 MPa and in a volume ratio H2 / HC = 1000 NI / NI. The spatial velocity is then 1 h <-1> About this catalyst. The reaction temperature is 315 ° C.

It is loaded in a second reactor located waters below this first reactor a hydro-finishing catalyst that contains 1% by weight of Pt, 1% by weight of F and 1% by weight of Cl over alumina. The product resulting from the first reactor is introduced into the second reactor that is maintained at a temperature of 220 ° C. The pressure is 14 MPa and the product circulates at a spatial speed of 0.5h -1.

The effluent is recovered, then distilled to empty. The characteristics of the residue 380 ° C + are represented in the board.

This example shows that the combination of a conversion-hydroisomerization stage (stage a) and of a stage of catalytic dewaxing, leads to products of high quality. In particular, it shows that step (a) allows increase the viscosity index of the oil fraction (380 ° C +) from 98 to 131 without sufficiently decreasing the creep point (see table, columns 1 and 2). This decrease is made during the stage (b) on the catalytic dewaxing catalyst and a yield point of -18ºC as well as a Saybolt color of +30 which gives the product the quality of medicinal oil (see table, columns 2 and 3).

TABLE

one two 3 Load = Residue Stage (a) Stage (b) + from hydrocracking (Hydroisomerization) hydro-finished (Dewaxed + hydro finish catalytic) Reaction temperature ºC / 326 315 220 Total p (bars) / 80 140 140 Conversion 380 ° C (% in / Four. Five / weight) Sulfur (ppm weight) 150 / / Nitrogen (ppm in weight) 9 / / d15 / 4 of the load or of the 0.8535 0.8360 / effluent total Content at 380 ° C + in 81 / / the load 380º fraction + Creep point (ºC) +40 +26 -18 ASTM color D1500 3.0 /

TABLE (continued)

one two 3 Load = Residue Stage (a) Stage (b) + from hydrocracking (Hydroisomerization) hydro-finished (Dewaxed + hydro finish catalytic) Fraction 380 ° C + 380ºC fraction + 380ºC fraction + Fraction 380 ° C + after treatment of the residue from of the hydroisomerized of the hydroisomerized, hydrocracking Y dewaxed dewaxed dewaxed in solvent and hydro-finished in solvent catalytically SAW 98 131 129 Creep point ºC -fifteen -fifteen -18 Color Saybolt / 7 +30 UV absorption (D2008) / 260-280 nm / / 0.0007 280-290 nm / / 0.0006 290-300 nm / / 0.0004 300-360 nm / / 0.0002 360-400 nm / / <0.0001 300-330 nm / / 0.0002 330-350 nm / / <0.0001

This procedure also appears as a very flexible procedure that allows to reach a large range of yields and qualities of oils and diesel due to the possibility of modulating the viscosity index (or conversion) on the catalyst of step (a) of hydroisomerization-conversion and at the same time the presence or not of a distillation after step (a).

In this way, stage (a) allows to carry the VI at a high level and thereby partially compensate for the loss of VI produced during the catalytic dewaxing stage.

Claims (14)

1. A procedure for the preparation of a oil from a hydrocarbon filler, said comprising procedure the following stages:

(to)

conversion of the loading with simultaneous hydroisomerization of at least part of the n-paraffins of the load, said load having a sulfur content of less than 1000 ppm by weight, a content of nitrogen less than 200 ppm by weight, and a metal content less than 50 ppm by weight, a maximum oxygen content of 0.2% by weight, at a temperature of 200-500 ° C, at a pressure of 2-25 MPa, at a spatial speed of 0.1-10 h -1, in the presence of hydrogen, and in presence of a catalyst that contains at least one noble metal deposited on an amorphous acidic support, the noble metal dispersion between 20-100%, followed by

(b)

dewaxed catalytic of at least a part of the effluent from the step a), at a temperature of 200-500 ° C, at a pressure of 1-25 MPa, with a volumetric velocity time of 0.05-50 h <-1>, and in the presence of 50-2000 liters of hydrogen / liter of effluent that enters stage (b) and in the presence of a selected catalyst from the group formed by ferrierita, NU-10, EU-13, EU-1, comprising at least a hydrodehydrogenating element and at least one sieve molecular.

2. A method according to claim 1, in  which for stage (a) uses a catalyst that contains the minus a noble metal deposited on a amorphous silica-alumina. 3. A procedure for the preparation of a oil from a hydrocarbon filler, said comprising procedure the following stages: (a) load conversion with simultaneous hydroinsomerization of at least part of the n-paraffins of the load, said load having a sulfur content of less than 1000 ppm by weight, a content of nitrogen less than 200 ppm by weight, and a metal content less than 50 ppm by weight, a maximum oxygen content of 0.2% by weight, at a temperature of 200-500 ° C, at a pressure of 2-25 MPa, at a spatial speed of 0.1-10 h -1, in the presence of hydrogen, and in presence of a catalyst that contains a noble metal at the hands deposited on an amorphous acidic support, the noble metal dispersion between 20-100%, where the catalyst comprises 0.05-10% by weight of at least a noble metal of group VIII deposited on an amorphous support of silica-alumina containing 5-90% by weight of silica and has a specific BET surface of 100-500 m2 / g, and the catalyst has:

-

an average diameter of pores between 1-12 nm,

-

a porous volume of the pores, whose diameter is between the average diameter as defined above decreased 3 nm and the diameter medium as defined above increased by 3 nm is greater than 40% of the total porous volume,

-

a dispersion of noble metal between 20-100%,

-

a coefficient of noble metal distribution greater than 0.1, followed by

(b) catalytic dewaxing of at least a part of the effluent from stage a), at a temperature of

 \ hbox {200-500 ° C,} 

at a pressure of 1-25 MPa, with an hourly volumetric velocity of 0.05-50 h -1, and in the presence of

 \ hbox {50-2000} 

liters of hydrogen / liter of effluent entering stage (b) and in the presence of a catalyst selected from the group consisting of ferrierite, NU-10, EU-13 and EU-1, comprising at least one hydrodehydrogenating element and at least a molecular sieve 4. A method according to claim 1 in that the noble metal of the catalyst in step (a) is platinum and / or palladium. 5. A method according to claim 1 in that the entire effluent of stage (a) is treated in the stage (b). 6. A method according to claim 1, in  which the effluent resulting from step (a) is distilled from so that light gases are separated and at least one residue that contains the boiling compounds greater than at least 340 ° C, said residue being subjected to step (b). 7. A method according to claim 1, in  which the effluent resulting from step (b) is distilled from form that separates an oil that contains the compounds of the point boiling above at least 340 ° C. 8. A method according to claim 7, where said effluent is distilled by atmospheric distillation followed vacuum distillation of atmospheric distillation residue resulting. 9. A method according to claim 1, in  the one that before stage (a) the load is subjected to a hydrotreatment, followed by optional separation of water, from ammonia, and hydrogen sulphide. 10. A method according to claim 1, wherein the catalyst of step (b) comprises at least one molecular sieve, whose microporous system has at least one type main pore opening channels that have 9 6 10 atoms of T, being chosen T from the group formed by Si, Al, P, B, Ti, Fe, Ga, alternating with an equal number of oxygen atoms, the distance between the two accessible pore openings of 9 or 10 T atoms at most 0.75 mm, and presenting said sieve in the n-dean assay, a ratio of 2-methylnonano / 5-methylnonano greater than 5. 11. A method according to claim 6, wherein the effluent resulting from step (b) is subjected to a hydro-finishing stage followed by a distillation stage. 12. A method according to claim 1, wherein the charge contains at least 20% by volume of compounds boiling above 340 ° C. 13. A method according to claim 1, in which the charge is an effluent resulting from the unit Fischer-Tropsch, the resulting vacuum distillates of direct distillation of crude oil, vacuum distillates resulting from conversion unit, vacuum distillates that they come from aromatic extraction units, the distillates to vacuum that come from desulfurization or hydroconversion of atmospheric waste and / or vacuum waste, oils deasphalted, hydrocracking waste or any mixture of such charges. 14. A method according to claim 1, wherein the charge contains at least 20% by volume of compounds boiling above 370 ° C.