Title of Invention	AN IMPROVED PROCESS FOR PRODUCING VALUE ADDED PRODUCTS SUCH AS KEROSENE, GAS OILS, IUBRICATION OIL
Abstract	An improved process for producing value added products such as kerosene, gas oils, lubricating oil by hydro isomerizing heavy petroleum feeds with boiling points of essentially greater than about 3500 C, with a nitrogen content of less than about 200 ppm by weight and a metal content of less than about 50ppm by weight, the improvement comprising carrying out the hydro isomerization at a temperature of 200-4500C, at a partial pressure of hydrogen of 2-25 Mpa, at an hourly space velocity 0.1-10h-1 and a hydrogen feed volume ration of 100-2000, in the presence of a catalyst comprising 0.05-10% by weight of at least one metal from group VIII which is Pt, Pd, Ir, Rh,Ru, or as deposited on an amorphous silica-alumina support, said catalyst containing neither zeolite nor halogen, and having a constant silica content, wherein said support contains 5- 70% by weight of silica and has a BET specific surface are of 100-500 m 2tg, the catalyst having an average pore diameter of between 1-12 nm, a pore volume of pores with diameters between the average diameter reduced by 3nm and the average diameter increased by 3nm, of more than 40% of the total pore volume, a group VIII metal dispersion of between 20-100% a distribution coefficient for the group VIII metal of more than 0.1.

Title of Invention

AN IMPROVED PROCESS FOR PRODUCING VALUE ADDED PRODUCTS SUCH AS KEROSENE, GAS OILS, IUBRICATION OIL

Abstract

An improved process for producing value added products such as kerosene, gas oils, lubricating oil by hydro isomerizing heavy petroleum feeds with boiling points of essentially greater than about 3500 C, with a nitrogen content of less than about 200 ppm by weight and a metal content of less than about 50ppm by weight, the improvement comprising carrying out the hydro isomerization at a temperature of 200-4500C, at a partial pressure of hydrogen of 2-25 Mpa, at an hourly space velocity 0.1-10h-1 and a hydrogen feed volume ration of 100-2000, in the presence of a catalyst comprising 0.05-10% by weight of at least one metal from group VIII which is Pt, Pd, Ir, Rh,Ru, or as deposited on an amorphous silica-alumina support, said catalyst containing neither zeolite nor halogen, and having a constant silica content, wherein said support contains 5- 70% by weight of silica and has a BET specific surface are of 100-500 m 2tg, the catalyst having an average pore diameter of between 1-12 nm, a pore volume of pores with diameters between the average diameter reduced by 3nm and the average diameter increased by 3nm, of more than 40% of the total pore volume, a group VIII metal dispersion of between 20-100% a distribution coefficient for the group VIII metal of more than 0.1.

Full Text	The present invention relates to an improved process for producing high added value products such as kerosene, gas oils lubricating oil by hydroisomerizing heavy petroleum feeds. The present invention also relates to a catalyst for hydroisomerizing. The present invention also concerns a hydroconversion and hydroisomerisation process for feeds with boiling points which are essentially above 350OC and with reduced metal contents. The process is particularly advantageous for the ' hydroisoitierisation treatment of feeds (such as hydrocracking residues) to obtain very high added value products such as kerosine, gas oils and lubricating oils. A number of catalysts can be used to carry out the hydroisomerisation reaction. United States patent US-A-4 929 795, for example, describes the use of a catalyst composed of 0.6% by weight of platinum deposited on a halogenated alumina containing 7.2% by weight of fluorine to obtain lubricating oils from paraffins. We have developed a halogen-free catalyst which can be used in a simpler process since the catalyst just described requires continuous injection of the fluorinated compound into the catalytic unit. United States patent US-A-4 428 819 describes a catalyst.containing a zeolite which is used to carry out the isomerisat ion of a mixture of paraffins from oil mixed with a lubricating oil obtained by catalytic deparaffination with a view to improving the cloud point. Finalliy. United States patent US-A-4 547 283 describes; a hydroisomerisation catalyst for paraffins from oil containing at least one active metal from group 2a, 3a, 5 4a and/or 4b of the periodic classification of the elements on a support which is preferably silica. We have developed a catalyst which is easier to use by avoiding the use of the zeolite or addition of supplemental elements during manufacture of the catalyst. 10 All the catalysts which are currently used for hydroconversion are bifunctional, combining an acidic function with a hydroqenating function. The acidic function is provided by supports with large surface areas (generally 150 to 800 m2.g"-1) with surface acidity, such 15 as halogenated aluminas (in particular chlorinated or fluorinated), phosphorous-containing aluminas, combinations of boron oxides and aluminium, amorphous silica-aluminas and silica-aluminas. The hydrogenating function is provided either by one or more metals from 20 group VIII of the periodic classification of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by combination of at least one metal from, group V] such as chromium, molybdenum and tungsten with at least one metal 2"! from group VIII. The balance between acidic and hydroqenat i nq functions is a fundamental parameter which qoverns rhe activity and selectivity of the catalyst. A weak acidic function and a strong hydrogenating function produces catalysts which are less active and selective as regards isomerisation while a strong acidic function and a weak hydrogenating function produces very active and selective catalysts as regards cracking. A third possibility is to use a strong acidic function and a strong hydrogenating function to obtain a very active but also very selective isomerisation catalyst. It is thus possible, by judicious choice of each of the functions, to adjust the activity/selectivity balance of the catalyst. Our research on a number of silica-aluminas has led to the discovery that, surprisingly, the use or a catalyst comprisinq a particular silica-alumina can produce catalysts which are very active but also very selective in certain reactions such as isomerisation of feeds as defined below. More precisely, the catalyst of the invention is essentially constituted by 0.05-10%. by weight of at least one precious metal from group VIII deposited on an amorphous s ilica alumina support which contains ^J-7'J; by weight ot silica and has a BET specific surface area of an average pore diameter of between 1-12 nm, a pore volume cr pores with diameters between the average diameter as defined above reduced by 3 nm and the average diameter as defined above increased by 3 nm, of more than 40% of the total pore volume, a precious metal dispersion of between 20-100%, a distribution coefficient for the precious metal of more than 0.1. In more detail, these characteristics are: Silica content: the support used to prepare the catalyst described in this patent is composed of silica SiQ2 and alumina AI2O3. The silica content, expressed as the percentage by weight, is between 5% and 70',, preferably betv;een 20% and 60%, more preferably between 22% and 4b%. This content can be accurately measured using X ray fluerescence. It is constant over the whole of the catalyst, i.e., the silica concentration is not higher at the catalyst surface, for example. The silica in the catalyst is homogeneous. Nature. of precious metal precious metal: for this particular reaction type, the metallic function is provided by a precious metal from group VIII of the periodic classification of the elements, in particular platinum. precious metal content;the precious metal 1 content, .•■> ■ ' '■:■-':.: : r. weight of metal with respect to the catalyst, is between0.05 and 10, preferably between 0.1 and b . Precious metel dispersion The dispersion, representing the fraction of the metal which is accessible to the 5 reactant with respect to the total quantity of metal in the catalyst, can be measured, for example, by H2/O2 titration. the metal is first reduced, i.e., it undergoes treatment in a hydrogen stream at high temperature under conditions which transform all the 10 platinum atoms accessible to hydrogen to the metal. An oxygen stream is then passed under operating conditions which oxidise all the reduced platinum atoms which are accessible to oxygen to Pt02. By calculating the difference between the quantity of oxygen introduced and 15 the quantity of oxygen leaving, the amount of oxygen consumed can be deduced. This value allows the quantity of platinum which is accessible to oxygen to be deduced. The dispersion is thus equal to the ratio of the quantity of platinum which is accessible to oxygen over the total 20 quantity of platinum in the catalyst. In our case, the dispersion is between 20% and 100%, preferably between 30% and 100%. Precious metal distribution: distribution ot the precious metal rrepresents- the distribution of the metal inside a . grain of the catalyat the metal being well or poorly dispersed. Thus it is possible to obtain poorly distributed platinum (detected, for example, in a ring in which the thickness is substantially lower than the radius of the grain) but v.'hich is well dispersed, i.e., 5 all the platinum atoms in the ring are accessible to the reactants. In our case, the platinum distribution is good, i.e., the platinum profile, measured using the Castaing microprobe analysis method, has a distribution coefficient for more than 0.1, preferably more than 0.2. 10 BET surface area: the BET surface area of the support is between 100 m2/g and 500 m2g, preferably between 250 m2/g and 450 m2/g, more preferably between 310 m2/g and 450 m2/g. Average pore diameter; the average pore diameter of the 15 catalyst is measured from a pore distribution profile obtained using a mercury porosimeter. The average pore diameter is defined as the diameter corresponding to the 2ero point of the curve derived from the mercury porosity curve. The average pore diameter, as defined, is between 20 1 nm (1 X 109 metre) and 12 nm (12 x 10-9 metre), preferably between 2.5 nm ?2.5 x 10-9 mietre) and 11 nm (11 X 10-9 metre), more pretcrably between 4 nm (4 x 10-9 metre) and 1(J . 5 nm (10.5 x 10-9 metre), and advantageously between2and 9 nm. pre distribution the catalyst of this patent has a pore distribution but Ion such that the pore volume of the pores with diameter between the average diameter as defined above reduced by 3 nm and the average diameter as defined above increased by 3 nm (i.e., the average diameter ± 3 nm) is more than 40% of the total pore volume, preferably between 50% and 90% of the total pore volume, more advantageously between 50% and 80% of the total pore volume and most advantageously between 50% and 70% of the total pore volume. The catalyst thus has a uniform pore distribution, more monomodal than bimodal. Total pore volume of support this is generally less than 1 ml/g, preferably between 0.3 and 0.9 m]/g, and more advantageously less than 0.85 ml/g. In general, the support has a total pore volume of more than 0.55 ml/g, preferably at least 0. 6 ml/g , The silica-alumina is prepared and formed using the usual methods which are well known to the skilled person. Advantageously, the support is calcined prior to impregnation of the metal, for example by heat treatment ar 300-750Oc (preferably 600°C) for 0.25-10 hours (preferably 2 hours) in 2-30% by volume of steam ('preferably 7.5%). the metal salt is introduced using oneof the usual r-r rn;;^;r 'or depositing metal (preferably c^atinur; on support surface. one of the preferred methods is dry impregnation which consists in introducing the metai salt in a volume of solution which is equal to the pore volume of the catalyst mass to be impregnated. Before 5 reduction, the catalyst can be calcined, for example by treatment in dry air at 300-750°C (preferably 520°C) for 0.25-10 hours (preferably 2 hours). Before its use in the conversion reaction, the metal contained in the catalyst must be reduced. One preferred 10 method for reducing the metal is treatment in hydrogen at a temperature of between 150OC and 650OC at a total pressure of betv;een 0.1 and 25 MPa. Reduction consists, for example, of a 2 hour stage at 150"c followed by raising the temperature to 4 50Oc at a rate of 1OC/min 15 then a 2 hour stage at 450OC: during the whole of this reduction step, the hydrogen flow rate is 1OC 1 hydrogen/ 1. catalyst. It should also be noted that any ex-situ reduction method is suitable. The catalyst described is active, for example, for 20 hydroisomerisation of feeds such as those described below, to obtain a large quantity of products resulting from hydroisoraerisation of the molecules present in the initial feed. It is of particular interest to produce products which can then be used as components of 21 lubricating products. Any clean feed can be used, for example vacuum distillates, vacuum residues, atmospheric residues or paraffin products from deparaffination or an oil feed, for example when the feed is a deasphalted vacuum 5 residue. These feeds contain molecules containing at least about 10 carbon atoms. They may contain paraffin fragments or they may be entirely paratfinic, and the aromatic carbon content is at most 20% by weight of the total carbon atoms in the feed. The term clean feed 10 means feeds in which the sulphur content is less than 1000 ppm by weight, preferably less than 500 ppm by weight, more preferably less than 300 ppm by weight, and the nitrogen content is less than 200 ppm by weight, preferably less than 100 ppm by weight, more preferably lb less than 50 ppm by weight. The metal content of the feed, such as nickel and vanadium, is extremely low, i.e., less than 50 ppm by weight, more advantageously less than 10 ppm by weight. Heavy feeds are preferably hydroisorrerised, such as 20 hydrocracking residues, i.e., those with boiling points of essentially more than 350Oc. These feeds contain molecules with at least about 20 carbon atoms containing paraffinic fragments or which are entirely paraffinic molecules. Hydroisomerisati on essentially concerns paraffins, in particular n-paraffms, and produce isoparaffms. The operating conditions employed for this hydroisomerisation reaction are a temperature of 200°C to 450Oc preferably 250°C to 430°C. advantageously above 340°C, a hydrogen partial pressure of 2 Mpa, to 25 Mpa, preferably between 3 Mpa and 20 Mpa, an hourly space velocity of between 0.1 and 10 h-1 preferably between 0.2 and 2 h'-1 and a hydrogen ratio of between 100 and 2000 litres of hydrogen per litre of feed, preferably between 150 and 2500 1kitres of hydrogen per litre of feed. The use of the catalyst is not limited to hydroisomerisation, but it is generally suitable for conversion of hydrocarbons under suitable conditions to obtain the desired conversion. An improved process for producing value added products such as kerosene, gas oils, lubricating oil by hydroisomerizing heavy petroleum feeds with boiling points of essentially greater than about 350°C, with a nitrogen content of less than about 200 ppm by weight and a metal content of less than about 50 ppm by weight, the improvement comprising carrying out the hydroisomerization at a temperature of 200-450°C,at a partial pressure of hydrogen of 2-25Mpa, at an hourly space velocity 0. H0h-1'and a hydrogen feed volume ratio of 100-2000, in the presence of a catalyst comprising 0.05-10% by weight of at least one metal from group VIII which is Pt, Pd, Ir, Rh, Ru, or Os deposited on an amorphous silica-alumina support, said catalyst containing neither zeolite nor halogen, and having a constant silica content, wherein said support contains 5-70% by weight of silica and has a BET specific surface area of 100-500 m2/g, the catalyst having an average pore diameter of between 1-12 nm, a pore volume of pores with diameters between the average diameter reduced by 3nm and the average diameter increased by 3nm, of more than 40% of the total pore volume, a group VIII metal dispersion of between 20-100%, a distribution coefficient for the group VIII metal of more than 0.1. EXAMPLE The Example described below illustrates the features of the invention without in any way limiting its scope-Preparation of catalyst: The support was a silica-alumina in the form of extrudates. It contained 29.1% by weight of silica Sio2 and 70.9% by weight of alumina AI2O3. Before addition of the precious metal, the silica-alumina had a surface area of 389 m2/g and an average pore diameter of 6.6 nm. The total pore volume of the support was 0.76 ml/g. The corresponding catalyst was obtained after impregnation of the precious metal into the support. The 5 platinum salt Pt(NH3)4Cl2 was dissolved in a volume of solution which corresponded to the total pore volume to be impregnated. The solid was then calcined for 2 hours in dry air at 520OC. The platinum content was 0.60% by weight. The platinum dispersion was 60% and the 10 distribution was uniform across the grain. The catalyst had a pore volume of 0.75 ml/g, a BET surface area of 332 m2/g and an average pore diameter of 6.5 nm. The pore volume corresponding to pores with diameters between 3.5 nm and 9.5 nm was 0.46 ml/g, i.e., 59% of the total pore 15 volume. The pore distribution of this catalyst was as follows: Pore diameter'6 nm pore volume-Q. 16 ml/g = 21% of total 20 6-15 nm 0.36 ml/g = 48% 15-60 nm 0.06 ml/g - 8% >60 nm 0.17 ml/g = 2 3%. feed characteristics: The table below lists the physico-chemical characteristics of the feed used for the hydroisomerisation reaction. This was a hydrocracking residue from a vacuum distillation cut. 5 10 15 20 25 30 Pro_duction of lubricating oil after reaction: The catalyst prepared as described above was used to prepare a lubricating oil by hydroisoinerisation of the feed described. The reaction took place at 3b5"C, ar a total pressure of 12 MPa, an hourly space velocity of 1 h-1 and a hydrogen t low rate of 1000 I nyaroqen/i feed. Under these operation conditions, the net conversion to 400 was 55% by weight and the lubricating oil yield was 85% by weight. The recovered oil had a VI of 135. The following table compares the characteristics of the oil after hydroisomerisation with those of the oil extracted from a hydrocracking residue using a conventional solvent extraction method (MEK/Tol). It can be seen that the two oils are very close as regards density and viscosity. On the other hand, the VIS, pour points and above all the oil/residue yields are better for the hydroisomerised product. WE CLAIM; 1. An improved process for producing value added products such as kerosene, gas oils, lubricating oil by hydroisomerizing heavy petroleum feeds with boiling points of essentially greater than about 350°C, with a nitrogen content of less than about 200 ppm by weight and a metal content of less than about 50 ppm by weight, the improvement comprising carrying out the hydroisomerization at a temperature of 200-450°C,at a partial pressure of hydrogen of 2-25Mpa, at an hourly space velocity 0. 1-10h'-1and a hydrogen feed volume ratio of 100-2000, in the presence of a catalyst comprising 0.05-10% by weight of at least one metal from group VIII which is Pt, Pd, Ir, Rh, Ru, or Os deposited on an amorphous silica-alumina support, said catalyst containing neither zeolite nor halogen, and having a constant silica content, wherein said support contains 5-70% by weight of silica and has a BET specific surface area of 100-500 m2/g, the catalyst having an average pore diameter of between 1-12 nm, a pore volume of pores with diameters between the average diameter reduced by 3nm and the average diameter increased by 3nm, of more than 40% of the total pore volume, a group VIII metal dispersion of between 20-100%, a distribution coefficient for the group VIII metal of more than 0.1. 2. The process according to claim 1, wherein the group VIII metal is Platinum. 3. The process according to claim 1, wherein the support has a average pore diameter between 2.5 and 11 nm. 4. The process according to claim 1, wherein the pore volume of pores with diameters between the average diameter reduced by 3 nm and the average diameter increased by 3 nm is between 50% and 90% of the total pore volume. 5. The process according to claim 1, wherein the support contains 20-60% by weight of silica. 6. The process according to claim 1, wherein the support has a BET surface area of between 250 and 450 mVg. 7. An improved process for producing value added products such as kerosene, gas oils, lubricating oil substantially as herein above described and exemplified.

Full Text

The present invention relates to an improved process for producing high added value products such as kerosene, gas oils lubricating oil by hydroisomerizing heavy petroleum feeds. The present invention also relates to a catalyst for hydroisomerizing.
The present invention also concerns a hydroconversion and hydroisomerisation process for feeds with boiling points which are essentially above 350OC and with reduced metal contents.
The process is particularly advantageous for the ' hydroisoitierisation treatment of feeds (such as hydrocracking residues) to obtain very high added value products such as kerosine, gas oils and lubricating oils.
A number of catalysts can be used to carry out the hydroisomerisation reaction. United States patent US-A-4 929 795, for example, describes the use of a catalyst composed of 0.6% by weight of platinum deposited on a halogenated alumina containing 7.2% by weight of fluorine to obtain lubricating oils from paraffins. We have developed a halogen-free catalyst which can be used in a simpler process since the catalyst just described requires continuous injection of the fluorinated compound into the catalytic unit.
United States patent US-A-4 428 819 describes a catalyst.containing a zeolite which is used to carry out the isomerisat ion of a mixture of paraffins from oil mixed with a lubricating oil obtained by catalytic

deparaffination with a view to improving the cloud point. Finalliy. United States patent US-A-4 547 283 describes; a hydroisomerisation catalyst for paraffins from oil containing at least one active metal from group 2a, 3a, 5 4a and/or 4b of the periodic classification of the elements on a support which is preferably silica.
We have developed a catalyst which is easier to use by avoiding the use of the zeolite or addition of supplemental elements during manufacture of the catalyst.
10 All the catalysts which are currently used for hydroconversion are bifunctional, combining an acidic function with a hydroqenating function. The acidic function is provided by supports with large surface areas (generally 150 to 800 m2.g"-1) with surface acidity, such
15 as halogenated aluminas (in particular chlorinated or fluorinated), phosphorous-containing aluminas, combinations of boron oxides and aluminium, amorphous silica-aluminas and silica-aluminas. The hydrogenating function is provided either by one or more metals from
20 group VIII of the periodic classification of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by combination of at least one metal from, group V] such as chromium, molybdenum and tungsten with at least one metal
2"! from group VIII.

The balance between acidic and hydroqenat i nq functions is a fundamental parameter which qoverns rhe activity and selectivity of the catalyst. A weak acidic function and a strong hydrogenating function produces catalysts which are less active and selective as regards isomerisation while a strong acidic function and a weak hydrogenating function produces very active and selective catalysts as regards cracking. A third possibility is to use a strong acidic function and a strong hydrogenating function to obtain a very active but also very selective isomerisation catalyst. It is thus possible, by judicious choice of each of the functions, to adjust the activity/selectivity balance of the catalyst.
Our research on a number of silica-aluminas has led to the discovery that, surprisingly, the use or a catalyst comprisinq a particular silica-alumina can produce catalysts which are very active but also very selective in certain reactions such as isomerisation of feeds as defined below.
More precisely, the catalyst of the invention is essentially constituted by 0.05-10%. by weight of at least one precious metal from group VIII deposited on an amorphous s ilica alumina support which contains ^J-7'J; by weight ot silica and has a BET specific surface area of

an average pore diameter of between 1-12 nm, a pore volume cr pores with diameters between the average diameter as defined above reduced by 3 nm and the average diameter as defined above increased by 3 nm, of more than 40% of the total pore volume, a precious metal dispersion of between 20-100%, a distribution coefficient for the precious metal of more than 0.1.
In more detail, these characteristics are: Silica content: the support used to prepare the catalyst described in this patent is composed of silica SiQ2 and alumina AI2O3. The silica content, expressed as the percentage by weight, is between 5% and 70',, preferably betv;een 20% and 60%, more preferably between 22% and 4b%. This content can be accurately measured using X ray fluerescence. It is constant over the whole of the catalyst, i.e., the silica concentration is not higher at the catalyst surface, for example. The silica in the catalyst is homogeneous.
Nature. of precious metal precious metal: for this particular reaction
type, the metallic function is provided by a precious metal from group VIII of the periodic classification of the elements, in particular platinum.
precious metal content;the precious metal 1 content, .•■> ■ ' '■:■-':.: : r. weight of metal with respect to the

catalyst, is between0.05 and 10, preferably between 0.1 and b .
Precious metel dispersion The dispersion, representing the fraction of the metal which is accessible to the 5 reactant with respect to the total quantity of metal in the catalyst, can be measured, for example, by H2/O2 titration. the metal is first reduced, i.e., it undergoes treatment in a hydrogen stream at high temperature under conditions which transform all the
10 platinum atoms accessible to hydrogen to the metal. An oxygen stream is then passed under operating conditions which oxidise all the reduced platinum atoms which are accessible to oxygen to Pt02. By calculating the difference between the quantity of oxygen introduced and
15 the quantity of oxygen leaving, the amount of oxygen consumed can be deduced. This value allows the quantity of platinum which is accessible to oxygen to be deduced. The dispersion is thus equal to the ratio of the quantity of platinum which is accessible to oxygen over the total
20 quantity of platinum in the catalyst. In our case, the dispersion is between 20% and 100%, preferably between 30% and 100%.
Precious metal distribution: distribution ot the precious metal rrepresents- the distribution of the metal inside a
. grain of the catalyat the metal being well or poorly

dispersed. Thus it is possible to obtain poorly distributed platinum (detected, for example, in a ring in which the thickness is substantially lower than the radius of the grain) but v.'hich is well dispersed, i.e., 5 all the platinum atoms in the ring are accessible to the reactants. In our case, the platinum distribution is good, i.e., the platinum profile, measured using the Castaing microprobe analysis method, has a distribution coefficient for more than 0.1, preferably more than 0.2.
10 BET surface area: the BET surface area of the support is between 100 m2/g and 500 m2g, preferably between 250 m2/g and 450 m2/g, more preferably between 310 m2/g and 450 m2/g. Average pore diameter; the average pore diameter of the
15 catalyst is measured from a pore distribution profile obtained using a mercury porosimeter. The average pore diameter is defined as the diameter corresponding to the 2ero point of the curve derived from the mercury porosity curve. The average pore diameter, as defined, is between
20 1 nm (1 X 109 metre) and 12 nm (12 x 10-9 metre), preferably between 2.5 nm ?2.5 x 10-9 mietre) and 11 nm (11 X 10-9 metre), more pretcrably between 4 nm (4 x 10-9 metre) and 1(J . 5 nm (10.5 x 10-9 metre), and advantageously between2and 9 nm.

pre distribution the catalyst of this patent has a pore distribution but Ion such that the pore volume of the pores with diameter between the average diameter as defined above reduced by 3 nm and the average diameter as defined above increased by 3 nm (i.e., the average diameter ± 3 nm) is more than 40% of the total pore volume, preferably between 50% and 90% of the total pore volume, more advantageously between 50% and 80% of the total pore volume and most advantageously between 50% and 70% of the total pore volume. The catalyst thus has a uniform pore distribution, more monomodal than bimodal.
Total pore volume of support this is generally less than 1 ml/g, preferably between 0.3 and 0.9 m]/g, and more advantageously less than 0.85 ml/g. In general, the support has a total pore volume of more than 0.55 ml/g, preferably at least 0. 6 ml/g ,
The silica-alumina is prepared and formed using the usual methods which are well known to the skilled person. Advantageously, the support is calcined prior to impregnation of the metal, for example by heat treatment ar 300-750Oc (preferably 600°C) for 0.25-10 hours (preferably 2 hours) in 2-30% by volume of steam ('preferably 7.5%).
the metal salt is introduced using oneof the usual r-r rn;;^;r 'or depositing metal (preferably c^atinur; on

support surface. one of the preferred methods is dry impregnation which consists in introducing the metai salt in a volume of solution which is equal to the pore volume of the catalyst mass to be impregnated. Before 5 reduction, the catalyst can be calcined, for example by treatment in dry air at 300-750°C (preferably 520°C) for 0.25-10 hours (preferably 2 hours).
Before its use in the conversion reaction, the metal contained in the catalyst must be reduced. One preferred
10 method for reducing the metal is treatment in hydrogen at a temperature of between 150OC and 650OC at a total pressure of betv;een 0.1 and 25 MPa. Reduction consists, for example, of a 2 hour stage at 150"c followed by raising the temperature to 4 50Oc at a rate of 1OC/min
15 then a 2 hour stage at 450OC: during the whole of this reduction step, the hydrogen flow rate is 1OC 1 hydrogen/ 1. catalyst. It should also be noted that any ex-situ reduction method is suitable.
The catalyst described is active, for example, for
20 hydroisomerisation of feeds such as those described below, to obtain a large quantity of products resulting from hydroisoraerisation of the molecules present in the initial feed. It is of particular interest to produce products which can then be used as components of
21 lubricating products.

Any clean feed can be used, for example vacuum distillates, vacuum residues, atmospheric residues or paraffin products from deparaffination or an oil feed, for example when the feed is a deasphalted vacuum 5 residue. These feeds contain molecules containing at least about 10 carbon atoms. They may contain paraffin fragments or they may be entirely paratfinic, and the aromatic carbon content is at most 20% by weight of the total carbon atoms in the feed. The term clean feed
10 means feeds in which the sulphur content is less than 1000 ppm by weight, preferably less than 500 ppm by weight, more preferably less than 300 ppm by weight, and the nitrogen content is less than 200 ppm by weight, preferably less than 100 ppm by weight, more preferably
lb less than 50 ppm by weight. The metal content of the feed, such as nickel and vanadium, is extremely low, i.e., less than 50 ppm by weight, more advantageously less than 10 ppm by weight.
Heavy feeds are preferably hydroisorrerised, such as
20 hydrocracking residues, i.e., those with boiling points of essentially more than 350Oc. These feeds contain molecules with at least about 20 carbon atoms containing paraffinic fragments or which are entirely paraffinic molecules. Hydroisomerisati on essentially concerns

paraffins, in particular n-paraffms, and produce isoparaffms.
The operating conditions employed for this hydroisomerisation reaction are a temperature of 200°C to 450Oc preferably 250°C to 430°C. advantageously above 340°C, a hydrogen partial pressure of 2 Mpa, to 25 Mpa, preferably between 3 Mpa and 20 Mpa, an hourly space velocity of between 0.1 and 10 h-1 preferably between 0.2 and 2 h'-1 and a hydrogen ratio of between 100 and 2000 litres of hydrogen per litre of feed, preferably between 150 and 2500 1kitres of hydrogen per litre of feed.
The use of the catalyst is not limited to hydroisomerisation, but it is generally suitable for conversion of hydrocarbons under suitable conditions to obtain the desired conversion.
An improved process for producing value added products such as kerosene, gas oils, lubricating oil by hydroisomerizing heavy petroleum feeds with boiling points of essentially greater than about 350°C, with a nitrogen content of less than about 200 ppm by weight and a metal content of less than about 50 ppm by weight, the improvement comprising carrying out the hydroisomerization at a temperature of 200-450°C,at a partial pressure of hydrogen of 2-25Mpa, at an hourly space velocity 0. H0h-1'and a hydrogen feed volume ratio of 100-2000, in the presence of a catalyst comprising 0.05-10% by weight of at least one metal from group VIII which is Pt, Pd, Ir, Rh, Ru, or Os deposited on an amorphous silica-alumina support, said catalyst containing neither zeolite nor halogen, and having a

constant silica content, wherein said support contains 5-70% by weight of silica and has a BET specific surface area of 100-500 m2/g, the catalyst having an average pore diameter of between 1-12 nm, a pore volume of pores with diameters between the average diameter reduced by 3nm and the average diameter increased by 3nm, of more than 40% of the total pore volume, a group VIII metal dispersion of between 20-100%, a distribution coefficient for the group VIII metal of more than 0.1.
EXAMPLE The Example described below illustrates the features of the invention without in any way limiting its scope-Preparation of catalyst:
The support was a silica-alumina in the form of extrudates. It contained 29.1% by weight of silica Sio2 and 70.9% by weight of alumina AI2O3. Before addition of the precious metal, the silica-alumina had a surface area

of 389 m2/g and an average pore diameter of 6.6 nm. The total pore volume of the support was 0.76 ml/g.
The corresponding catalyst was obtained after impregnation of the precious metal into the support. The 5 platinum salt Pt(NH3)4Cl2 was dissolved in a volume of solution which corresponded to the total pore volume to be impregnated. The solid was then calcined for 2 hours in dry air at 520OC. The platinum content was 0.60% by weight. The platinum dispersion was 60% and the
10 distribution was uniform across the grain. The catalyst had a pore volume of 0.75 ml/g, a BET surface area of 332 m2/g and an average pore diameter of 6.5 nm. The pore volume corresponding to pores with diameters between 3.5 nm and 9.5 nm was 0.46 ml/g, i.e., 59% of the total pore
15 volume.
The pore distribution of this catalyst was as follows:
Pore diameter'6 nm pore volume-Q. 16 ml/g = 21% of total
20 6-15 nm 0.36 ml/g = 48%
15-60 nm 0.06 ml/g - 8%
>60 nm 0.17 ml/g = 2 3%.
feed characteristics:

The table below lists the physico-chemical
characteristics of the feed used for the
hydroisomerisation reaction. This was a hydrocracking
residue from a vacuum distillation cut. 5
10
15
20
25
30 Pro_duction of lubricating oil after reaction:
The catalyst prepared as described above was used to prepare a lubricating oil by hydroisoinerisation of the feed described.
The reaction took place at 3b5"C, ar a total
pressure of 12 MPa, an hourly space velocity of 1 h-1 and
a hydrogen t low rate of 1000 I nyaroqen/i feed. Under
these operation conditions, the net conversion to 400

was 55% by weight and the lubricating oil yield was 85% by weight. The recovered oil had a VI of 135.
The following table compares the characteristics of the oil after hydroisomerisation with those of the oil extracted from a hydrocracking residue using a conventional solvent extraction method (MEK/Tol). It can be seen that the two oils are very close as regards density and viscosity. On the other hand, the VIS, pour points and above all the oil/residue yields are better for the hydroisomerised product.

WE CLAIM;
1. An improved process for producing value added products such as kerosene, gas oils, lubricating oil by hydroisomerizing heavy petroleum feeds with boiling points of essentially greater than about 350°C, with a nitrogen content of less than about 200 ppm by weight and a metal content of less than about 50 ppm by weight, the improvement comprising carrying out the hydroisomerization at a temperature of 200-450°C,at a partial pressure of hydrogen of 2-25Mpa, at an hourly space velocity 0. 1-10h'-1and a hydrogen feed volume ratio of 100-2000, in the presence of a catalyst comprising 0.05-10% by weight of at least one metal from group VIII which is Pt, Pd, Ir, Rh, Ru, or Os deposited on an amorphous silica-alumina support, said catalyst containing neither zeolite nor halogen, and having a constant silica content, wherein said support contains 5-70% by weight of silica and has a BET specific surface area of 100-500 m2/g, the catalyst having an average pore diameter of between 1-12 nm, a pore volume of pores with diameters between the average diameter reduced by 3nm and the average diameter increased by 3nm, of more than 40% of the total pore volume, a group VIII metal dispersion of between 20-100%, a distribution coefficient for the group VIII metal of more than 0.1.
2. The process according to claim 1, wherein the group VIII metal is Platinum.

3. The process according to claim 1, wherein the support has a
average pore diameter between 2.5 and 11 nm.
4. The process according to claim 1, wherein the pore volume of
pores with diameters between the average diameter reduced by 3 nm and the
average diameter increased by 3 nm is between 50% and 90% of the total
pore volume.
5. The process according to claim 1, wherein the support contains
20-60% by weight of silica.
6. The process according to claim 1, wherein the support has a
BET surface area of between 250 and 450 mVg.
7. An improved process for producing value added products such
as kerosene, gas oils, lubricating oil substantially as herein above described
and exemplified.

Documents:

362-mas-95 claims.pdf

362-mas-95 correspondence-others.pdf

362-mas-95 correspondence-po.pdf

362-mas-95 description-complete.pdf

362-mas-95 form-1.pdf

362-mas-95 form-26.pdf

362-mas-95 form-4.pdf

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Patent Number

188244

Indian Patent Application Number

362/MAS/1995

PG Journal Number

30/2009

Publication Date

24-Jul-2009

Grant Date

02-May-2003

Date of Filing

24-Mar-1995

Name of Patentee

M/S. INSTITUT FRANCAIS FRANCAIS DU PETROLE

Applicant Address

4 AVENUE DE BOIS PREAU, 92502 RUEIL MALMAISON,

Inventors:

#	Inventor's Name	Inventor's Address
1	BIGEARD PIERRE-HENRI	LES CHARAVELLS-BT-E CHEMIN DE CHARAVEL LA CERISAIE 38200 VIENNE
2	BILLON ALAIN	48 BOULEVARD DES ETATS-UNIS 78110 LE VESINET
3	MIGNARD SAMUEL	22, AVENUE GUY DE MAUPASSANT 78400 CHATOU
4	MARCHAL NATHALIE	62 RUE GAY-LUSSAC 75005 PARIS
5	KASZTELAN SLAVIK	57, RUE CRAMAIL 92500 RUEIL MALMAISON

PCT International Classification Number

B01J 35/10

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA