Title of Invention

A PROCESS FOR PRODUCING MEDICINAL OILS AND MIDDLE DISTILLATES FROM HYDROCARBON FEEDS AND AN APPARATUS THEREFORE

Abstract The invention concerns an improved process for the production of very high quality base oil optionally with simultaneous production of high quality middle distillates, comprising the steps of hydrotreatment, preferably hydrocracking, on a Y or beta zeolite, and atmospheric distillation. The effluent (which is not vacuum distilled) undergoes catalytic dewaxing, preferably using N"U-l 0, EU. 1, EU-13 or ferrierite zeolite. The process then comprises hydro finishing steps to hydrogenate the aromatic compounds, preferably using a catalyst comprising .at least one group VIII noble metal, chlorine and fluorine, and atmospheric and vacuum distillation steps. The qualities of the oils and middle distillates are improved (pour point, viscosit), index, aromatics content) and medicinal oil can be produced.
Full Text

The present invention relates to an improved process for the production of very high quality base oils, i.e., with a high viscosity index (VI), a low aromatic compound content, a good UV stability and a low pour point, from petroleum cuts with a boiling point of more than 340°C, optionally with simultaneous production of very high quality middle distillates (in particular gas oil and kerosine), i.e., with a low aromatic compound content and a low pour point. PRIOR ART
High quality lubricants are of vital importance for the correct operation of modern machines, automobiles and trucks.
Such lubricants are usually obtained by a succession of refining steps which can improve the properties of a petroleum cut. In particular, heavy petroleum fractions containing large amounts of linear paraffins or low paraffins with a small amount of branching must be treated to obtain good quality base oil in the best possible yields, by an operation which is aimed at eliminating the linear or very low branched paraffins from feeds which are then used as a base oil.
High molecular weight paraffins which are linear or with a very low amount of branching present in oils lead to high pour points and thus to congealing when used at low temperatures. In ' order to reduce the pour point, such paraffins which are linear or with a very low amount of branching must be completely or partially eliminated.
This operation can be carried out by extraction using solvents such as toluene/methyl ethyl ketone or methyl-isobutyl ketone mixtures, known as methyl ethyl ketone (MEK) or methyl-isobutyl ketone (MIBK) dewaxing. However, such techniques are expensive, not always easy to implement and lead to the formation of by-products, unrefined paraffins.
A further means is catalytic treatment in the presence or absence of hydrogen and, depending on their form selectivity, zeolites are among the most widely used catalysts.
Catalysts based on zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 have been described for their use in such processes. SUBJECT MATTER OF THE INVENTION
The Applicant's research has been concentrated on developing an improved process for producing very high quality lubricating oils.

The present invention relates to a sequence of processes for joint production of very high quality base oils and very high quality middle distillates (in particular gas oils). The oils produced have a high viscosity index (VI), a low aromatic compound content, low volatility, good UV stability and a low pour point, from petroleum cuts with a boiling point of more than 340°C.
In particular, and in contrast to the usual process sequences or those from the prior art, this process is not limited in the quality of the oil products which can be produced; in particular, a judicious choice of the operating conditions enables medicinal white oils (i.e. excellent qualities) to be produced. More precisely, the invention concerns a process for producing high quality oils and optionally high quality middle distillates from a hydrocarbon feed wherein at least 20% by volume boils above 340°C, the process comprising the following steps in succession:
(a) hydrotreatment carried out at a temperature of 330-450°C, at a pressure of 5-25 MPa, with a space velocity of 0.1-6 h" , in the presence of hydrogen in a hydrogen/hydrocarbon volume ratio of 100-2000, and in the presence of an amorphous catalyst comprising at least one group VIII metal and at least one group VIB metal;
(b) hydrocracking with no intermediate separation of the effluent obtained after hydrotreatment, hydrocracking being carried out at a temperature of 340-430°C, at a pressure of 5-25 MPa, at a space velocity of 0.1-5 h" , in the presence of hydrogen and in the presence of a catalyst containing at least one zeolite and also containing at least one group VIII element and at least one group VIB element;
(c) atmospheric distillation of the effluent obtained from hydrocracking to separate the gas from the liquid;
(d) catalytic dewaxing of at least one liquid fraction obtained by atmospheric distillation and which contains compounds with a boiling point of over 340°C, dewaxing being carried out at a temperature of 200-500°C, at a total pressure of 1-25 MPa, at an hourly space velocity of 0.05-50 h"1 with 50-2000 1 of hydrogen/1 of feed, in the presence of a catalyst also comprising at least one element with a hydro-dehydrogenating function, and at least one molecular sieve wherein the microporous system has at least one principal channel type with a pore opening containing 9 or 10 T atoms, T being selected from the group formed by Si/Al, P, B, Ti, Fe,

Ga, alternating with an equal number of oxygen atoms, the distance between two accessible pore openings containing 9 or 10 T atoms being equal to at most 0.75 mm, and said sieve having a 2-methylnonane/5-methylnonane ratio of more than 5 in the n-decane test;
(e) the dewaxed effluent undergoes a direct hydrofinishing treatment carried out at a temperature of 180-400°C, which is lower than the catalytic dewaxing temperature by at least 20°C and at most 200°C, at a total pressure of 1-25 MPa, with an hourly space velocity of 0.05-100 h"1, in the presence of 50-2000 litres of hydrogen/litre of feed, and in the presence of an amorphous aromatic compound hydrogenation catalyst comprising at least one metal selected from the group formed by group VIII metals and group VIB metals;
(f) the effluent from the hydrofinishing treatment undergoes a distillation step comprising atmospheric distillation and vacuum distillation so as to separate at least one oil fraction with a boiling point of more than 340°C, a pour point of less than -10°C, an aromatic compound content of less than 2% by weight, and a VI of more than 95, a viscosity of at least 3 cSt (i.e., 3 mm /s) at 100°C and so as to optionally separate at least one middle distillate with a pour point of -20°C or less, an aromatic compound content of at most 2% by weight and a polyaromatics content of at most 1% by weight.
DETAILED DESCRIPTION OF THE INVENTION
The process of the invention comprises the following steps: Step (a): hydrotreatment
The hydrocarbon feed from which the high quality oils and optional middle distillates are produced contains at least 20% by volume boiling above 340°C.
A wide variety of feeds can thus be treated by the process.
The feed can, for example, be a LCO (light cycle oil), a vacuum distillate from straight run crude distillation or from conversion units such as FCC, coker or visbreaking, or from aromatic compound extraction units, or originating from AR (atmospheric residue) desulphurisation or hydroconversion and/or VR (vacuum residues), or the feed can be a deasphalted oil, or any mixture of the feeds cited above. The above list is not limiting. In general, suitable feeds have an initial boiling point of more than 340°C, preferably more than 370°C.

The feed first undergoes hydrotreatment during which it is brought into contact, in the presence of hydrogen, with at least one catalyst comprising an amorphous support and at least one metal with a hydro-dehydrogenating function provided, for example, by at least one group VIB element and at least one group VIII element, at a temperature in the range 330°C to 450°C, preferably 360-420°C, at a pressure in the range 5 to 25 MPa, preferably less than 20 MPa, the space velocity being in the range 0.1 to 6 h" , preferably 0.3-3 h" , and the quantity of hydrogen introduced is such that the hydrogen/hydrocarbon volume ratio is in the range 100 to 2000.
During the first step, the use of a catalyst encouraging hydrogenation over cracking, used under suitable thermodynamic and kinetic conditions, substantially reduces the amount of condensed polycyclic aromatic compounds. Under these conditions, the major portion of the nitrogen-containing and sulphur-containing products of the feed are also transformed. This operation can thus eliminate two types of compounds which are known to inhibit the zeolitic catalyst used in the rest of the process.
By pre-cracking the feed to be treated, this first step enables the properties of the base oil to be adjusted at the outlet from the first step as a function of the quality of the base oil which is to be * obtained from the process. Advantageously, this adjustment can be made by adjusting the nature and the quality of the catalyst used in the first step and/or adjusting the temperature of this first step, to raise the viscosity index for the base oil, the fraction with a boiling point of more than 340°C, at the outlet from this stage. The viscosity index obtained before dewaxing is preferably in the range 80 to 150, more preferably in the range 90 to 140, or even 90 to 130.
The support is generally based on (and preferably is essentially constituted by) amorphous alumina or silica-alumina; it can also comprise boron oxide, magnesia, zirconia, titanium oxide or a combination of these oxides. The hydro-dehydrogenating function is preferably fulfilled by at least one metal or compound of a metal from groups VIII and VI, preferably selected from molybdenum, tungsten, nickel and cobalt.
This catalyst can advantageously contain phosphorous; this compound is known to have two advantages for hydrotreatment catalysts: facility of preparation in particular when impregnating with nickel and molybdenum solutions, and better hydrogenation activity.

Preferred catalysts are NiMo and/or Ni/W on alumina catalysts, as well as NiMo and/or NiW on alumina catalysts doped with at least one element selected from the group formed by phosphorous, boron, silicon and fluorine, or NiMo and/or NiW on silica-alumina catalysts, or on silica-alumina-titanium oxide doped or not doped with at least one element selected from the group formed by atoms formed by phosphorous, boron, fluorine and silicon.
The total concentration of oxides of group VI and VIII metals is in the range 5% to 40% by weight, preferably in the range 7% to 30% and the weight ratio, expressed as the metal oxide, of the group VI metal (or metals) to the group VIII metal (or metals) is preferably in the range 20 to 1.25, more preferably in the range 10 to 2. The concentration of phosphorous oxide P2O5 is less than 15% by weight, preferably less than 10% by weight.
The product obtained at the end of this first step is sent to a second catalyst in a second step with no intermediate separation of ammonia (NH3) and hydrogen sulphide (H2S), nor any distillation. Step (b): hydrocracking
All of the effluent from the first step (a) is introduced into the catalyst for the second step (b) ■ in the presence of hydrogen where it is hydrocracked in the presence of a Afunctional catalyst comprising an acidic zeolitic function and a metallic hydro-dehydrogenating function.
During this step the polyaromatic and polynaphthenoaromatic compounds which have been partially and/or completely hydrogenated during the first step are hydrocracked on the acidic sites to produce paraffins. In the presence of a Afunctional catalyst, these paraffins can undergo isomerisation then possibly hydrocracking to lead to the formation of isoparaffms and lighter cracking products respectively.
Converting the polyaromatic compounds containing a plurality of rings necessitates hydrogenation prior to cracking.
The catalyst for the second step comprises a zeolite, a support and a hydro-dehydrogenating function.
The hydro-dehydrogenating function is advantageously obtained by a combination of metals from group VIB (for example molybdenum and/or tungsten) and/or metals from group VIII of the

periodic table, preferably non noble metals (for example cobalt and/or nickel). This catalyst can preferably also contain at least one promoter element deposited on the catalyst surface, which element is selected from the group formed by phosphorous, boron and silicon, advantageously phosphorous.
The total concentration of group VIB and VIII metals, expressed as the metal oxides with •espect to the support, is generally in the range 5% to 40% by weight, preferably in the range 7% to !0% by weight. The weight ratio (expressed as the metal oxides) of the group VIII metals to the ^roup VIB metals is preferably in the range 0.05 to 0.8; more preferably, it is in the range 0.13 to 15.
This type of catalyst can advantageously contain phosphorous, the content of which, :xpressed as phosphorous oxide P205 with respect to the support, is generally less than 15% by veight, preferably less than 10% by weight.
The quantities of boron and silicon are less than 15% by weight, preferably less than 10% by veight (expressed as the oxide).
The amorphous or low crystallinity support is selected from the group formed by alumina, ilica, silica alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide and lay, used alone or as a mixture.
The zeolite is advantageously selected from the group formed by Y zeolite (FAU, faujasite tructure type) and beta zeolite (structure type BEA) using the nomenclature developed in the "Atlas f zeolite structure types" by W. M. Meier, D. H. Olson and Ch. Baerlocher, 4th revised edition, 996, Elsevier.
The amount of zeolite is in the range 2% to 80% by weight, preferably in the range 3% to 0% with respect to the final catalyst, and advantageously in the range 3-25%.
The zeolite can optionally be doped with metallic elements such as metals from the rare earth imily, in particular lanthanum or cerium, or noble or non noble group VIII metals, such as latinum, palladium, ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc or lagnesium.

A particularly advantageous H-Y acid zeolite is characterized by different specifications: a S1O2/AI2O3 molar ratio in the range about 6 to 70, preferably in the range about 12 to 50: a sodium content of less than 0.15% by weight determined for the zeolite calcined at 1100°C; a lattice parameter a for the unit cell in the range 24.58 x 10"10 m to 24.24 x 10'10 m, preferably in the range 24.38 x 10"lQ m to 24.26 x 10" m; a sodium ion take-up capacity CNa, expressed in grams of Na per 100 grams of modified, neutralised then calcined zeolite of more than about 0.85; a specific surface area, determined using the BET method, of more than about 400 m /g, preferably more than 550 m /g, a water vapour adsorption capacity of more than about 6% at 25°C at a partial pressure of 2,6 torrs (i.e., 34.6 MPa), a pore distribution, determined by nitrogen physisorption, in the range 5 to 45%, preferably in the range 5% to 40% of the total pore volume of the zeolite contained in pores with a diameter in the range 20 x 10" m to 80 x 10" m, and between 5% and 45% and preferably in the range 5% to 40% of the total pore volume of the zeolite contained in pores with a diameter of more than 80 x 10"10 m and generally less than 1000 x 10"10 m, the remainder of the pore volume being contained in pores with a diameter of less than 20 x 10" m.
One preferred catalyst essentially consists of at least one group VI metal and/or at least one -non noble group VIII metal, Y zeolite and alumina.
A more preferred catalyst essentially contains nickel, molybdenum, a Y zeolite as defined above and alumina.
The operating conditions under which this second step (b) is carried out are important.
The pressure is kept between 5 and 25 MPa, advantageously between 5 and 20 MPa and preferably between 7 and 15 MPa; the space velocity is in the range 0.1 h" to 5 h", preferably in the range 0.5 h"1 to 4.0 h'1.
The temperature is adjusted during the second step (b) so as to obtain the desired viscosity in that and VI. It is in the range 340°C to 430°C, in general and advantageously in the range 370°C to 420°C.
These two steps (a) and (b) can be carried out using two catalyst types in two (two or more) different reactors, or preferably using at least two catalytic beds installed in the same reactor.

Hydrogen is separated from the effluent leaving the hydrocracker and the effluent then undergoes direct atmospheric distillation (step (c)) to separate the gas (such as ammonia and hydrogen sulphide (H2S) formed, and the other light gases which are present, any possible hydrogen...). At least one liquid fraction containing products with a boiling point of more than 340° C is obtained.
Advantageously, atmospheric distillation is carried out to obtain several fractions (gasoline, kerosine, gas oil, for example) with a boiling point of at most 340°C and a fraction (residue) with an initial boiling point of more than 340°C (or preferably more than 370°C).
The VI of this fraction before dewaxing is in the range 95 to 165, preferably at least 110.
In accordance with the invention, this fraction (residue) is then treated in the catalytic dewaxing step, i.e., without undergoing vacuum distillation.
In a variation of the process, aromatic compounds are extracted from the residue before catalytic dewaxing (constituting a step (c')).
This extraction is carried out using any known means; the solvents usually used are furfural and N-methylpyrrolidone.
The naphthenoaromatic compounds are thus extracted, and the raffinate obtained has a viscosity index which is higher than that of the residue entering the extraction step. This operation further increases the VI of the product obtained from the hydrofmishing step.
In a further implementation which is more closely attuned to the production of middle distillates, the cut point is reduced, and instead of cutting at 340°C as before, gas oils and possibly kerosines can be included in the fraction containing compounds boiling above 340°C. As an example, a fraction with an initial boiling point of at least 150°C is produced.
In contrast, aromatic compounds can be extracted from the residue before catalytic dewaxing. This extraction is carried out using any known means, furfural usually being used. Visual operating conditions are used.
The raffinate obtained has a higher viscosity index than the index of the incoming residue. Thus the VI of the product obtained after hydrofmishing is further increased.

The fraction obtained which contains said compounds is treated directly by catalytic dewaxing; the other fractions (150°C") may or may not be separately treated by catalytic dewaxing in this implementation.
In general, the present text defines middle distillates as fraction(s) with an initial boiling point of at least 150°C and an end point just before the residue, i.e., generally up to 340°C or preferably 370°C.
One advantage of this conversion process (hydrotreatment and hydrocracking) described (using a zeolite type catalyst) is that in general it enables lubricant base oil to be produced with a viscosity which is higher than that obtained with an amorphous catalyst at the same conversion. During the hydrocracking process, the viscosity at 100°C of the unconverted fraction with a boiling point of more than 340°C is a decreasing function of the conversion obtained.
When this level of conversion is high (above 70%), the viscosity of the residue obtained with an amorphous catalyst is such that it cannot be used to produce more viscous lubricating oil grades (500 N and bright stock). This limitation disappears when the zeolite catalyst described above is used.
Thus the ratio between the viscosity at 100°C of the 370°C+ residue, obtained by a process using only non zeolitic catalysts (V10OA) and the viscosity at 100°C of the 370°C+ hydrocracking residue, obtained using our process (V10oz) and at the same conversion, (VIOOA^VIOOZ)? is strictly less than 1, preferably in the range 0.95 to 0.4. Step (d): catalytic hydrodewaxing (CHDW)
At least part, preferably all of the fraction containing compounds boiling above 340°C as defined above from the second step and from atmospheric distillation (c) then undergoes a catalytic dewaxing step in the presence of hydrogen and a hydrodewaxing catalyst comprising an acidic function, a metallic hydro-dehydrogenating function and at least one matrix. ■ -
It should be noted that compounds boiling above 340°C always undergo catalytic dewaxing.
The acid function is provided by at least one molecular sieve with a microporous system with at least one principal channel type with openings formed by rings containing 10 or 9 T atoms. The T atoms are tetrahedral constituent atoms of the molecular sieve and can be at least one of the elements

contained in the following set of atoms (Si, Al, P, B, Ti, Fe, Ga). Atoms T, defined above, alternate with an equal number of oxygen atoms in the constituent rings of the channel openings. Thus it can also be said that the openings are formed from rings containing 10 or 9 oxygen atoms or formed by rings containing 10 or 9 T atoms.
The molecular sieve forming part of the composition of the hydrodewaxing catalyst can also include other channel types but with openings formed from rings containing less than 10 T atoms or oxygen atoms.
The molecular sieve forming part of the catalyst composition also has a bridging distance, the distance between two pore openings, as defined above, which is at most 0.75 nm (1 nm = 10"9 m), preferably in the range 0.50 nm to 0.75 nm, more preferably in the range 0.52 nm to 0.73 nm.
The Applicant has discovered that one of the determining factors for producing good catalytic performances in the third step (hydrodewaxing step) is the use of molecular sieves with a bridging distance of at most 0.75 nm, preferably in the range 0.50 nm to 0.75 nm, preferably in the range 0.52 nm to 0.73 nm.
The bridging distance is measured using a molecular modelling tool such as Hyperchem or ^Biosym, which enables the surface of the molecular sieves under consideration to be constructed using the ionic radii of the elements present in the sieve framework, to measure the bridging distance.
The catalyst which is suitable for this process is characterized by a catalytic test known as a standard pure n-decane transformation test which is carried out at a partial pressure of 450 kPa of hydrogen and a partial pressure of n-Cio of 1.2 kPa, giving a total pressure of 451.2 kPa in a fixed bed with a constant n-Cio flow rate of 9.5 mlh, a total flow rate of 3.6 1/h and a catalyst mass of 0.2 g. The reaction is carried out in upflow mode. The degree of conversion is adjusted by the temperature at which the reaction is carried out. The test catalyst is constituted by pelletised pure zeolite and 0.5% by weight of platinum.
In the presence of a molecular sieve and a hydro-dehydrogenating function, n-decane undergoes hydroisomerisation reactions which produce isomerised products containing 10 carbon

atoms, and hydrocracking reactions leading to the formation of products containing less than 10 , carbon atoms.
Under these conditions, a molecular sieve used in the hydrodewaxing step of the invention must have the physico-chemical characteristics described above and lead, for a yield of isomerised n-Cio products of the order of 5% by weight (the degree of conversion is regulated by the temperature), to a 2-methylnonane/5-methylnonane ratio of more than 5 and preferably more than 7.
The use of molecular sieves selected in this manner and under the conditions described above from the numerous molecular sieves already in existence enables products with a low pour point and a high viscosity index to be produced in good yields in the process of the invention.
Examples of molecular sieves which can be used in the composition of the catalytic hydrodewaxing catalyst are the following zeolites: ferrierite, NU-10, EU-13, EU-1 and zeolites with the same structure type.
Preferably, the molecular sieves used in the composition of the hydrodewaxing catalyst are included in the set formed by ferrierite and EU-1 zeolite.
The quantity of molecular sieve in the hydrodewaxing catalyst is in the range 1% to 90% by * weight, preferably in the range 5% to 90% by weight and more preferably in the range 10% to 85% by weight.
Non limiting examples of matrices used to produce the catalyst are alumina gel, alumina, magnesia, amorphous silica-alumina and mixtures thereof. Techniques such as extrusion, pelletisation or bowl granulation can be used to carry out the forming operation.
The catalyst also comprises a hydro-dehydrogenating function ensured, for example, by at least one group VIII element and preferably at least one element selected from the group formed by platinum and palladium. The amount of non noble group VIII metal with respect to the final catalyst is in the range 1% to 40%, preferably in the range 10% to 30%. In this case, the non noble metal is often associated with at least one group VIB metal (preferably Mo and W). If at least one noble group VIII metal is used, the quantity with respect to the final catalyst, is less than 5% by weight, preferably less than 3% and more preferably less than 1.5%.

When using noble group VIII metals, the platinum and/or palladium are preferably localised m the matrix as defined above.
The hydrodewaxing catalyst of the invention can also contain 0 to 20%, preferably 0 to 10% )y weight (expressed as the oxides) of phosphorous. The combination of group VIB metal(s) and/or *roup VIII metal(s) with phosphorous is particularly advantageous.
The hydrocracking residue (i.e., the fraction with an initial boiling point of more than 340°C) obtained from step (c) of the invention and which is treated in this hydrodewaxing step (d) has the following characteristics: it has an initial boiling point of more than 340°C and preferably more than 370°C, a pour point of at least 15°C, a nitrogen content of less than 10 ppm by weight and a sulphur content of less than 50 ppm by weight, preferably less than 10 ppm by weight, a viscosity index of 35 to 165 (before dewaxing), preferably at least 110 and more preferably less than 150, an aromatic :ompound content of less than 10%) by weight, and a viscosity at 100°C of 3 cSt (mm /s) or more.
These characteristics are also those of the residue which would be obtained by atmospheric distillation of a sample of a liquid fraction containing the compounds with a boiling point of more than 340°C, said fraction having an initial boiling point of 340°C or less and undergoing catalytic dewaxing.
The operating conditions for the hydrodewaxing step of the process of the invention are as follows:
• the reaction temperature is in the range 200°C to 500°C, preferably in the range 250°C to 470°C, advantageously 270-430°C;
• the pressure is in the range 0.1 to 25 MPa (10 Pa), preferably in the range 1.0 to 20 MPa;
• the hourly space velocity (HSV, expressed as the volume of feed injected per unit volume of catalyst per hour) is in the range from about 0.05 to about 50, preferably in the range about 0.1 to about 20 h"1, more preferably in the range 0.2 to 10 h"1.
They are selected to produce the desired pour point.
The feed entering the dewaxing step and the catalyst are brought into contact in the presence of hydrogen. The amount of hydrogen used, expressed in litres of hydrogen per litre of feed, is in the

range 50 to about 2000 litres of hydrogen per litre of feed, preferably in the range 100 to 1500 litres of hydrogen per litre of feed.
The skilled person is aware that the improvement in the pour point of base oil. whether obtained by the solvent dewaxing (SDW) process or by a catalytic hydrodewaxing process (CHDW), causes a drop in the viscosity index (VI).
One of the characteristics of the process of the invention is that:
• the variation in VI during the catalytic hydrodewaxing (CHDW) step is preferably 0 or more, for
the same pour point;
or
• when a reduction in VI is observed during the catalytic hydrodewaxing step (CHDW) this drop is
smaller than that which can be observed in the case of solvent dewaxing (SDW) to obtain the
same pour point. Thus the ratio between the variation in VI, the base oil, during the catalytic
dewaxing step, and the variation in VI of the base oil during solvent dewaxing step, AVICHDW/A
VISDW is strictly less than 1 for the same pour point.
Step (e): hydrofinishing
The whole of the effluent from the outlet from the catalytic hydrodewaxing step is sent, with no intermediate distillation, over a hydrofinishing catalyst in the presence of hydrogen to carry out deep hydrogenation of the aromatic compounds which have a deleterious effect on the stability of the oils and distillates. However, the acidity of the catalyst must be sufficiently weak so as not to lead to the formation of a cracking product with a boiling point of less than 340°C so as not to degrade the final yields, in particular the oil yields.
The catalyst used in this step comprises at least one group VIII metal and/or at least one element from group VIB of the periodic table. The strong metallic functions: platinum and/or palladium, or nickel-tungsten, nickel-molybdenum combinations are advantageously used to carry out deep hydrogenation of the aromatic compounds.
These metals are deposited and dispersed on an amorphous or crystalline support, such as aluminas, silicas and silica-aluminas.

The hydrofmishing (HDF) catalyst can also contain at least one element from group VIIA of the periodic table. Preferably, these catalysts contain fluorine and/or chlorine.
The metal contents are in the range 10% to 30% in the case of non noble metals and less than 2%, preferably in the range 0.1% to 1.5%, more preferably in the range 0.1% to 1.0% in the case of noble metals.
The total quantity of halogen is in the range 0.02% to 30% by weight, advantageously 0.01% to 15%, or 0.01% to 10%, preferably 0.01% to 5%.
Catalysts containing at least one noble group VIII metal (for example platinum) and at least one halogen (chlorine and/or fluorine), a combination of chlorine and fluorine being preferred, can be cited as catalysts suitable for use in this HDF step, and lead to excellent performances in particular for the production of medicinal oils.
The following conditions are employed for the hydrofmishing step of the process of the invention:
• the reaction temperature is in the range 180°C to 400°C, preferably in the range 210°C to 350°C, advantageously 230-320°C;
• the pressure is in the range 0.1 to 25 MPa (106 Pa), preferably in the range 1.0 to 20 MPa;
• the hourly space velocity (HSV, expressed as the volume of feed injected per unit volume of catalyst per hour) is in the range from about 0.05 to about 100, preferably in the range about 0.1 to about 30 h"1.
Contact between the feed and the catalyst is carried out in the presence of hydrogen. The amount of hydrogen used and expressed in litres of hydrogen per litre of feed is in the range 50 to about 2000 litres of hydrogen per litre of feed, preferably in the range 100 to 1500 litres of hydrogen per litre of feed.
One of the characteristics of the process of the invention is that the temperature of the HDF step is lower than the temperature of the catalytic hydrodewaxing step (CHDW). The difference TCHDW-THDF is generally in the range 20°C to 200°C, preferably in the range 30°C to 100°C.
The effluent at the outlet from the HDF step is sent to the distillation train which integrates atmospheric distillation and vacuum distillation, with the aim of separating the conversion products

with a boiling point of less than 340°C and preferably less than 370°C (and including those formed . during the catalytic hydrodewaxing step (CHDW)), from the fraction which constitutes the base oil and with an initial boiling point of more than 340°C, preferably more than 370°C.
Further, this vacuum distillation section can separate different grades of oils.
The base oils obtained using this process have a pour point of less than -10°C, an aromatic compound content of less than 2% by weight, a VI of more than 95, preferably more than 110 and more preferably more than 120, a viscosity of at least 3.0 cSt at 100°C, an ASTM colour of less than 1 and a UV stability such that the increase in the ASTM colour is in the range 0 to 4, preferably in the range 0.5 to 2.5.
The UV stability test, adapted from the ASTM D925-55 and Dl 148-55 processes, is a rapid method for comparing the stability of lubricating oils exposed to a source of ultraviolet radiation. The test chamber is constituted by a metal chamber provided with a rotary plate which receives the oil samples. A bulb producing the same ultraviolet radiation as that of solar radiation placed in the top of the test chamber is directed towards the bottom onto the samples. The samples include a standard oil with known UV characteristics. The ASTM D1500 colour of the samples is determined *at t=0 then after 45 h of exposure at 55°C. The results for the standard sample and the test samples are transcribed as follows:
a) initial ASTM D1500 colour;
b) final ASTM D1500 colour;
c) increase in colour;
d) cloudiness;
e) precipitate.
A further advantage of the process of the invention is that it is possible to achieve very low aromatic compound contents of less than 2% by weight, preferably 1% by weight and more preferably less than 0.05% by weight) and even of producing medicinal quality white oils with aromatic compound contents of less than 0.01% by weight. The UV absorbance values of these oils at 275, 295 and 300 nanometres are less than 0.8, 0.4 and 0.3 respectively (ASTM D2008 method) and have a Saybolt colour in the range 0 to 30.

The fact that the process of the invention can also produce medicinal quality white oils is of particular interest. Medicinal white oils are mineral oils obtained by deep refining of petroleum; their quality is subject to different regulations which are aimed at guaranteeing their harmlessness for pharmaceutical applications. They are non toxic and are characterized by their density and viscosity. Medicinal white oils essentially comprise saturated hydrocarbons, they are chemically inert and they have a low aromatic hydrocarbon content. Particular attention is paid to aromatic compounds in particular those containing 6 polycyclic aromatic hydrocarbons (PAH) which are toxic and present in concentrations of one part per million by weight of aromatic compounds in white oil. The total aromatic content can be monitored using the ASTM D2008 method, this UV absorption test at 275,292 and 300 nanometres enabling an absorbance of less than 0.8, 0.4 and 0.3 respectively to be monitored (i.e., the white oils have aromatic compound contents of less than 0.01% by weight). These measurements are made with concentrations of 1 g of oil per litre, in a 1 cm cell. Commercially available white oils are distinguished by their viscosity and also by their crude of origin which may be paraffmic or naphthenic, these two parameters causing differences both in the physico-chemical properties of the white oils and in their chemical composition.
Currently, oil cuts whether originating from straight run distillation of a crude petroleum followed by extraction of aromatic compounds by a solvent, or from a catalytic hydrorefining or hydrocracking process, still contain non negligible quantities of aromatic compounds. Current legislation in the majority of industrialised nations requires that medicinal white oils must have an aromatic compound content below a threshold imposed by the legislation in each of the countries. The absence of these aromatic compounds in oil cuts results in a Saybolt colour specification which must be substantially at least 30 (+30), a maximum UV adsorption which must be less than 1.60 at 275 nm on a pure product in a 1 centimetre cell and a maximum absorption specification for products extracted by DMSO which must be less than 0.1 for the American market (Food and Drug Administration, standard n° 1211145). This latter test consists of specifically extracting polycyclic aromatic hydrocarbons using a polar solvent, usually DMSO, and checking their content in the extract by measuring the UV absorption in the 260-350 nm range.

The middle distillates obtained have improved pour points (-20°C or less), low aromatic compound contents (at most 2% by weight), polyaromatic compound contents (di- and above) of less than 1% by weight and for gas oils, a cetane number of more than 50, and even more than 52.
A further advantage of the process of the invention is that the total pressure can be the same in all reactors, hence the possibility of operating in series and of using a single unit and thus of cutting costs.
The process is illustrated in Figures 1 and 2, Figure 1 showing the treatment of the whole of the liquid fraction as regards hydrodewaxing; Figure 2 shows that of a hydrocracking residue.
In Figure 1, the feed enters via line (1) into a hydrotreatment zone (2) (which can be composed of one or more reactors, and comprises one or more catalytic beds of one or more catalysts) into which the hydrogen enters (for example via line (3)) and where hydrotreatment step (a) is carried out.
The hydrotreated feed is transferred via line (4) into a hydrocracking zone (5) (which can be composed of one or more reactors, and comprises one or more catalytic beds of one or more catalysts) where hydrocracking step (b) is carried out in the presence of hydrogen.
The effluent from zone (5) is sent via a line (6) to a drum (7) to separate hydrogen which is extracted via a line (8); the effluent is then distilled at atmospheric pressure in a column (9) from which the gas fraction is extracted overhead via a line (10). Step (c) of the process is then carried out.
A liquid fraction containing compounds with a boiling point of over 340°C is obtained from the column bottom. This fraction is evacuated via line (11) to a catalytic dewaxing zone (12).
Catalytic dewaxing zone (12) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) also receives hydrogen via a line (13) to carry out step (d) of the process.
The effluent leaving this zone via a line (14) is sent directly to a hydrofmishing zone (15) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) from which it leaves via a line (16). Hydrogen can be added to zone (15) if necessary where step (e) of the process is carried out.

The effluent obtained is separated in a distillation train (step (f) of the process) comprising, in addition to the drum (17) to separate hydrogen via a line (18), an atmospheric distillation column (19) and a vacuum column (20) which treats the atmospheric distillation residue transferred via line (21), the residue with an initial boiling point of more than 340°C.
The products obtained after the distillations are an oil fraction (line 22), and lower boiling fractions such as gas oil (line 23), kerosine (line 24), gasoline (line 25); light gases eliminated via line (26) of the atmospheric column and gases eliminated via column (27) of the vacuum distillation.
In order not to complicate the figure, the hydrogen recycle has not been shown, either from drum (7) to the hydrotreatment and/or hydrocracking, and/or from drum (17) to the dewaxing and/or hydrofinishing.
Figure 2 uses the same reference numerals as Figure 1. The difference is in the distillation of the effluent from hydrocracking step (b) which leaves via line (6). After separating the hydrogen in drum (7), the gases are separated by atmospheric distillation in a column (9) and extracted via line (10). Distillation is carried out so as to obtain a residue with an initial boiling point of more than 340°C leaving via line (11), and to obtain gas oil (line 28), kerosine (line 29) and gasoline (line 30) * fractions.
Only the residue is treated in dewaxing zone (12).
The recycles described above are completely transposable.
This shows all the overall conversion with 2 reactors with no recycling of the effluent leaving the hydrocracker (5).
It is also possible to recycle a portion of this effluent to the hydrotreatment step carried out in zone (2) and/or to the hydrocracking step carried out in zone (5).
The operator will adjust the recycle ratio to his "products" to encourage the production of oils or middle distillates.
Quite often, the hydrotreatment and hydrocracking zones are found in the same reactor. The transfer of hydrotreated effluent is then carried out directly without a line (4). The effluent can always be recycled either to the hydrotreatment zone (upstream of the catalyst bed) or to the hydrocracking zone.

In a further implementation of this conversion step (hydrocracking in two steps), at least a portion of the residue leaving via line (11) with an initial boiling point of more than 340°C (as shown in Figure 2) is sent to a supplemental hydrocracking zone (32), different from zone (5) (comprising one or more reactors or one or more catalytic beds of one or more catalysts). This other hydrocracking zone can contain the same catalyst as that of zone (5) or a further catalyst.
The resulting effluent is recycled to the atmospheric distillation step.
The other portion of the residue with an initial boiling point of more than 340°C is transferred to the catalytic dewaxing step.
Figure 3 shows these possible features of the conversion, where reference numerals which are the same as Figure 2 will not be described again.
The residue leaving column (9) via line (11) is sent to a further hydrocracking zone (32), from which an effluent leaves via a line (33) which is recycled to column (9). A line (34) branching offline (11) carries the residue which is sent to dewaxing zone (12).
Figure 3 also shows the use of the same reactor (31) for hydrotreatment zone (2) and for hydrocracking zone (5), but separate zones are possible in combination with the supplemental hydrocracking zone (32).
The conversion ensemble of Figure 3 can thus be substituted for the conversion ensemble of Figure 2, the hydrodewaxing and hydrofmishing steps and the distillation train being unchanged. All of the complementary possibilities (H2 recycle,...) are transposable.
In a further variation of Figures 2 or 3, the residue leaving line (11) is sent to an aromatic compound extraction unit (35) provided with a solvent inlet line (36), a solvent outlet line (37) and a line (38) from which the raffmate leaves to be sent to the catalytic dewaxing zone (12).
This variation (corresponding to step (c') of the process) is shown in Figure 4. The upstream and downstream treatments are those of the process shown, for example, in Figures 2 or 3.
Thus the invention also concerns a facility for the production of high quality oils and optionally of high quality middle distillates, comprising:
• at least one hydrotreatment zone (2) containing at least one hydrotreatment catalyst and provided with at least one line (1) for introducing feed and at least one line (3) for introducing hydrogen;

at least one hydrocracking zone (5) containing at least one hydrocracking catalyst, to treat the hydrotreated effluent from zone (2), the hydrocracked effluent leaving zone (5) via a line (6); at least one atmospheric distillation column (9) to treat the hydrocracked effluent, and provided with at least one line (10) to withdraw the gaseous fraction, at least one line (11) to withdraw a liquid fraction (residue) containing compounds with boiling points of more than 340°C, and at least one line (28, 29 or 30) to withdraw at least one distillate;
at least one unit for extracting aromatic compounds (35) to treat the residue, provided with at least one line (35) to supply the solvent, at least one outlet line (36), and at least one line (38) to withdraw a raffinate; > at least one catalytic dewaxing zone (12) containing at least one dewaxing catalyst, into which the raffinate enters, hydrogen being admitted via at least one line (13), the zone (12) being provided with at least one line (14) for withdrawing the dewaxed effluent; » at least one hydrofmishing zone (15) for treating the dewaxed effluent with a hydrofmishing
catalyst, the effluent leaving via at least one line (16); • at least one distillation zone comprising at least one atmospheric distillation column (19) and at least one vacuum distillation column (20), the column (19) being provided with at least one line (26) to withdraw light gases, at least one line (23, 24 or 25) to withdraw at least one distillate, and at least one line (21) to recover a residue, the column (20) comprising at least one line (22) to withdraw the oil fraction and at least one line (27) to withdraw other compounds.
In a further embodiment, the invention also concerns a facility in which zones (2) and (3) are located in the same reactor provided with at least one line (1) to admit a feed, at least one line (3) to admit hydrogen, and at least one line (6) to withdraw the hydrocracked effluent, said facility also comprising at least one supplemental hydrocracking zone (32) provided with at least one line (11) to admit the residue from the atmospheric distillation column (9), and at least one line (33) to withdraw cracked effluent, said line (33) opening into the line (6) for recycling said effluent, and the facility further comprises at least one line (34) located on line (11) to transfer the residue to an extraction unit (35).

EXAMPLE 1
The hydrocracking residue is obtained by hydrocracking a vacuum distillate the composition of which is given in Table 1.
The feed described in Table 1 and hydrogen under a pressure of 14 MPa were introduced into a reactor containing a bed of amorphous catalyst (15% M0O3, 5% NiO, 80% alumina). The H2/HC ratio was 1000 Ni/Ni by volume. The space velocity was 0.75 h"1 over the amorphous catalyst. The reaction temperature was 380°C.
A second reactor located after the first reactor was charged with a catalyst of 12% M0O3, 4% NiO, and 20% of Y zeolite on alumina. The product from the first reactor was introduced into the second reactor. The pressure was 14 MPa and the product circulated at a space velocity of 1.5 h"1. The effluent was recovered then vacuum distilled. The characteristics of the 375°C+ residue are shown in Table 1.
EXAMPLE 2
The 375°C+ residue of Example 1 was then introduced into a reactor containing a bed of hydrodewaxing catalyst (0.5% Pt, 80% ferrierite, the remainder being AI2O3) and hydrogen at a * pressure of 14 MPa and in a H2/HC volume ratio of 1000 Ni/Ni. The space velocity was 1 h"1 over this catalyst. The reaction temperature was 315°C.
A catalyst containing 1% by weight of Pt and 1% by weight of CI on alumina was charged into a second reactor located after the first reactor. The product from the first reactor was introduced into the second reactor which was maintained at a temperature of 220°C. The pressure was 14 MPa and the product circulated at a space velocity of 0.5 h" . The effluent was recovered then vacuum distilled. The characteristics of the 375°C+ residue are shown in Table 1.
The carbonisable material test carried out on the dewaxed and hydrofmished residue in Example 2 satisfied the current regulations.
Further, the UV absorption at 275 nm over the pure product in a 1 cm cell was 1.2, i.e., below the regulations.
As a result, the dewaxed and hydro finished residue of Example 2 constituted a medicinal oil.






CLAIMS
A process for producing medicinal oils and optionally high quality middle distillates from a hydrocarbon feed wherein at least 20% by volume boils above 340°C5 the medicinal oils having a Saybolt colour of substantially at least 30, a maximum UV absorption of less than 1.60 at 275 nm over a pure product in a 1 cm cell and a maximum DMSO extracted products absorption value of less than 0.1, the process comprising the following steps in succession: hydrotreatment carried out at a temperature of 330-450°C5 at a pressure of 5-25 MPa, with a space velocity of 0.1-6 h* , in the presence of hydrogen in a hydrogen/hydrocarbon volume ratio of 100-2000, and in the presence of an amorphous catalyst comprising at least one group VIII metal and at least one group VIB metal;
hydrocracking with no intermediate separation of the effluent obtained after hydrotreatment, hydrocracking being carried out at a temperature of 340-430°C, at a pressure of 5-25 MPa, at a space velocity of 0.1-5 h" , in the presence of hydrogen and in the presence of a catalyst containing at least one zeolite and also containing at least one group VIII element and at least one group VIB element;
atmospheric distillation of the effluent obtained from hydrocracking to separate the gas from the liquid;
catalytic dewaxing of at least one liquid fraction obtained by atmospheric distillation and which contains compounds with a boiling point of over 340°C, dewaxing being carried out at a temperature of 200-500°C, at a total pressure of 1-25 MPa, at an hourly space velocity of 0.05-50 h_i with 50-2000 1 of hydrogen/1 of feed, in the presence of a catalyst also comprising at least one element with a hydro-dehydrogenating function, and at least one molecular sieve wherein the microporous system has at least one principal channel type with a pore opening containing 9 or 10 T atoms, T being selected from the group formed by Si/Al, P, B, Ti, Fe, Ga, alternating with an equal number of oxygen atoms, the distance between two accessible pore openings containing 9 or 10 T atoms being equal to at most 0.75 mm, and said sieve having a 2-methylnonane/5-methylnonane ratio of more than 5 in the n-decane test;

the dewaxed effluent undergoes a direct hydrofinishing treatment carried out at a temperature
of 180-400°C, which is lower than the catalytic dewaxing temperature by at least 20°C and at
most 200°C, at a total pressure of 1-25 MPa, with an hourly space velocity of 0.05-100 h"1, in
the presence of 50-2000 litres of hydrogen/litre of feed, and in the presence of an amorphous
aromatic compound hydrogenation catalyst, comprising at least one metal selected from the
group formed by group VIII metals and group VIB metals;
the effluent from the hydrofinishing treatment undergoes a distillation step comprising
atmospheric distillation and vacuum distillation so as to separate at least one oil fraction with
a boiling point of more than 340°C, a pour point of less than -10°C5 an aromatic compound
content of less than 2% by weight, and a VI of more than 95, a viscosity of at least 3 cSt (i.e.,
3 mm Is) at 100°C and so as to optionally separate at least one middle distillate with a pour
point of -20°C or less, an aromatic compound content of at most 2% by weight and a
polyaromatics content of at most 1% by weight.
A process according to claim 1, in which the molecular sieve in dewaxing step (d) is selected
from the group formed by ferrierite, NU-10, EU-1 and EU-13 zeolites.
A process according to any one of the preceding claims, in which the element with the hydro-
dehydrogenating function in the dewaxing catalyst of step (d) is selected from the group
formed by group VIII elements and group VIB elements, said catalyst also containing
phosphorous.
A process according to any one of the preceding claims, in which the hydrofinishing catalyst
of step (e) comprises an amorphous support, at least one noble group VIII element, chlorine
and fluorine.
A process according to any one of the preceding claims, in which hydrotreatment step (a) and
hydrocracking step (b) are carried out in the same reactor.
A process according to any one of claims 1 to 4, in which hydrotreatment step (a) and
hydrocracking step (b) are carried out in different reactors.

A process according to any one of the preceding claims, in which during atmospheric
distillation step (c), a residue with an initial boiling point of more than 340°C is obtained
which then undergoes catalytic dewaxing in step (d).
A process according to claim 7, in which at least a portion of the hydrocracking residue is
recycled to the hydrotreatment step and/or to the hydrocracking step.
A process according to claim 7, in which at least a portion of the hydrocracking residue
undergoes a supplementary hydrocracking step different from step (b), the effluent obtained
being recycled to atmospheric distillation step (c), the other portion of the residue being
treated in dewaxing step (d).
A process according to any one of claims 7 to 9, in which the residue from the atmospheric
distillation step of step (c) undergoes aromatic compound extraction (step c') and the
raffmate obtained is catalytically dewaxed in step (d).
A process according to any one of the preceding claims for the production of white oils with
aromatic compound contents of less than 0.01% by weight.
A facility for the production of high quality oils and optionally of high quality middle
distillates, comprising:
• at least one hydrotreatment zone (2) containing at least one hydrotreatment catalyst and provided with at least one line (1) for introducing feed and at least one line (3) for introducing hydrogen;
• at least one hydrocracking zone (5) containing at least one hydrocracking catalyst, to treat the hydrotreated effluent from zone (2), the hydrocracked effluent leaving zone (5) via a line (6);
• at least one atmospheric distillation column (9) to treat the hydrocracked effluent, and provided with at least one line (10) to withdraw the gaseous fraction, at least one line (11) to withdraw a liquid fraction (residue) containing compounds with boiling points of more than 340°C, and at least one line (28, 29 or 30) to withdraw at least one distillate;
• at least one unit for extracting aromatic compounds (35) to treat the residue provided with at least one line (35) to supply the solvent, at least one line (36) for withdrawal, and at least one line (38) to withdraw a raffmate;

at least one catalytic dewaxing zone (12) containing at least one dewaxing catalyst, into which the raffinate enters, hydrogen being admitted via at least one line (13), the zone (12) being provided with at least one line (14) for withdrawing the dewaxed effluent;
at least one hydrofmishing zone (15) for treating the dewaxed effluent with a hydro finishing catalyst, the effluent leaving via at least one line (16);
» at least one distillation zone comprising at least one atmospheric distillation column (19) and at least one vacuum distillation column (20), the column (19) being provided with at least one line (26) to withdraw light gases, at least one line (23, 24 or 25) to withdraw at least one distillate, and at least one line (21) to recover a residue, the column (20) comprising at least one line (22) to withdraw the oil fraction and at least one line (27) to withdraw other compounds.
A facility according to claim 12, in which zones (2) and (3) are located in the same reactor provided with at least one line (1) to admit a feed, at least one line (3) to admit hydrogen, and at least one line (6) to withdraw the hydrocracked effluent, said facility also comprising at least one supplemental hydrocracking zone (32) provided with at least one line (11) to admit the residue from the atmospheric distillation column (9), and at least one line (33) to withdraw cracked effluent, said line (33) opening into the line (6) for recycling said effluent, and the facility further comprises at least one line (34) located on line (11) to transfer the residue to an extraction unit (35).

A process for producing medicinal oils
substantially as hereinbefore described with reference to the accompanying drawings.
. A facility for the production of high quality oils substantially as hereinbefore described with reference to the accompanying drawings.


Documents:

in-pct-2001-621-che- abstract.pdf

in-pct-2001-621-che- claims duplicate.pdf

in-pct-2001-621-che- claims original.pdf

in-pct-2001-621-che- correspondence others.pdf

in-pct-2001-621-che- correspondence po.pdf

in-pct-2001-621-che- descripition complete duplicate.pdf

in-pct-2001-621-che- descripition complete original .pdf

in-pct-2001-621-che- drawings.pdf

in-pct-2001-621-che- form 1.pdf

in-pct-2001-621-che- form 19.pdf

in-pct-2001-621-che- form 26.pdf

in-pct-2001-621-che- form 3.pdf

in-pct-2001-621-che- form 5.pdf

in-pct-2001-621-che- pct.pdf


Patent Number 207412
Indian Patent Application Number IN/PCT/2001/621/CHE
PG Journal Number 26/2007
Publication Date 29-Jun-2007
Grant Date 13-Jun-2007
Date of Filing 03-May-2001
Name of Patentee INSTITUT FRANCAIS DU PETROLE
Applicant Address 1 et 4, avenue de Bois Préau F-92852 Rueil Malmaison Cedex.
Inventors:
# Inventor's Name Inventor's Address
1 MARION Pierre 15, rue Louis Berthou F-92160 Antony
2 BILLON Alain 24, boulevard d'Angleterre F-78110 Le Vésinet
3 GUERET Christophe 43, Grande rue de la Plaine F-69560 Saint Romain en Gal
4 HIPEAUX Jean-Claude; 22, rue de la Fraternité F-92700 Colombes
5 BENAZZI Eric 44, rue le Val Sablons F-78400 Chatou
6 GOUZARD Jean-Paul 11 ter, rue Edeline F-92500 Rueil Malmaison
PCT International Classification Number C10G65/12
PCT International Application Number PCT/FR1999/002654
PCT International Filing date 1999-10-29
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 98/14814 1998-11-24 France
2 98/13995 1999-11-06 France
3 99/10222 1999-08-02 France