Title of Invention	A PROCESS FOR CONVERTING A HEAVY HYDROCARBON FRACTION USING AN EBULLATED BED HYDRODEMETALLIZATION CATALYST
Abstract	A process for converting a heay hydrocarbon fraction comprises treating the hydrocarbon feed in a hydroconversion section in the presence of hydrogen, the section comprising at least one three-phase reactor containing at least one ebullated bed hYdroconversion catalyst, operating in liquid and gas riser mode, said reactor comprising at least one means for removing catalyst from said reactor and at least one means for adding fresh catalyst to said reactor. At least a portion of the hydroconverted liquid effluent is sent to at) atmospheric distillation zone from which a distillate and an atmospheric residue are recovered; at least a portion of the atmospheric residue is sent to a vacuum distillation zone from which a vacuum distillate and a vacuum residue are recovered; at least a portion of the vacuum residue is sent to a deasphalting section from which a deasphalted hydrocarbon cut and residual asphalt are recovered; and at least a portion of the deasphalted hydrocarbon cut is sent to a hydrotreatment section from which a gas fraction, an atmospheric distillate and a heavier liquid fraction of the hydro treated feed are produced by atmospheric distillation separation.

Title of Invention

A PROCESS FOR CONVERTING A HEAVY HYDROCARBON FRACTION USING AN EBULLATED BED HYDRODEMETALLIZATION CATALYST

Abstract

A process for converting a heay hydrocarbon fraction comprises treating the hydrocarbon feed in a hydroconversion section in the presence of hydrogen, the section comprising at least one three-phase reactor containing at least one ebullated bed hYdroconversion catalyst, operating in liquid and gas riser mode, said reactor comprising at least one means for removing catalyst from said reactor and at least one means for adding fresh catalyst to said reactor. At least a portion of the hydroconverted liquid effluent is sent to at) atmospheric distillation zone from which a distillate and an atmospheric residue are recovered; at least a portion of the atmospheric residue is sent to a vacuum distillation zone from which a vacuum distillate and a vacuum residue are recovered; at least a portion of the vacuum residue is sent to a deasphalting section from which a deasphalted hydrocarbon cut and residual asphalt are recovered; and at least a portion of the deasphalted hydrocarbon cut is sent to a hydrotreatment section from which a gas fraction, an atmospheric distillate and a heavier liquid fraction of the hydro treated feed are produced by atmospheric distillation separation.

Full Text	The present invention concerns refining and converting heavy hydrocarbon fractions containing, among others, asphaltenes and sulphur-containing and metal-containing impurities. More particularly, it concerns a process for converting at least part of a feed with a Conradson carbon of more than 10, usually more than 15 and normally more than 20, for example a vacuum residue of a crude, to a product with a Conradson carbon which is sufficiently low and metal and sulphur contents which are sufficiently low for it to be used, for example, as a feed for the production of gas oil and gasoline by catalytic cracking in a conventional fluid bed cracking unit and/or in a fluid bed catalytic cracking unit comprising a double regeneration system, and optionally a catalyst cooling system in the regeneration step. The present invention also concerns a process for the production of gasoline and/or gas oil comprising at least one fluidised bed catalytic cracking step. As refiners increase the proportion of heavier crude oil of lower quality in the feed to be treated, it becomes ever more necessary to have particular processes available which are specially adapted to treatment of these residual heavy fractions from oil, shale oil, or similar materials containing asphaltenes and with a high Conradson carbon. Thus European patent EP-B-0 435 242 describes a process for the treatment of a feed of this type comprising a hydrotreatment step using a single catalyst under conditions which reduce the amount of sulphur and metallic impurities, bringing all the effluent with a reduced sulphur content from the hydrotreatment step into contact with a solvent under asphaltene extraction conditions to recover an extract which is relatively depleted in asphaltene and metallic impurities and sending that extract to a catalytic cracking unit to produce low molecular weight hydrocarbon products. In a preferred implementation in that patent, the product from the first step undergoes visbreaking and the product from the visbreaking step is sent to the asphaltene solvent extraction step. In Example 1 of that patent, the treated feed is an atmospheric residue. According to the teaching of that patent, it appears to be difficult to produce a feed with the characteristics which are necessary to enable treatment in a conventional catalytic cracking reactor with a view to producing a fuel from vacuum residues with a very high metal content (more than 50 ppm, usually more than 100 ppm and normally more than 200 ppm) and with a high Conradson carbon. The current limit on metal content in industrial feeds is about 20 to 25 ppm of metal, and the limit for the Conradson carbon is about 3% for a conventional catalytic cracking unit and about 8% for a unit which is specially adapted for cracking heavy feeds. The use of feeds in which the metallic impurity content is on the upper limit or higher than those mentioned above causes the catalyst to be considerably deactivated, requiring substantial addition of fresh catalyst, and is thus prohibitive for the process and can even render it unworkable. Further, such a process implies the use of substantial quantities of solvent for deasphalting since all the hydrotreated and preferably visbroken product is deasphalted. The use of a single hydrotreatment catalyst limits the performances as regards elimination of metallic impurities to values of less than 75% (Table I, Example II) and/or those of desulphurization to values of no more than 85% (Table I Example II). That technique cannot produce a feed which can be treated using conventional FCC unless the hydrotreated oil, which may have been visbroken, is deasphalted with a C3 type solvent, thus severely limiting the yield. The present invention aims to overcome the disadvantages described above and produce, from feeds containing large amounts of metals and with high Conradson carbons and sulphur contents, a product which has been more than 80% demetallized, normally at least 90% demetallized, more than 80% and normally more than 85% desulphurized and with a Conradson carbon which is no more than 8, allowing the product to be sent to a residue catalytic cracking reactor are important factors which are selected as a function of the characteristics of the feed to be treated and the conversion desired. Normally, the liquid HSV is about 0.1 h'1 to about 5 h'1, preferably about 0.15 h'1 to about 2 h"1. Used catalyst is replaced in part by fresh catalyst by extraction from the bottom of the reactor and introduction of fresh or new catalyst to the top of the reactor at regular intervals, for example in batches or quasi continuously. Fresh catalyst can, for example, b6 introduced daily. The rate of replacement of used catalyst by fresh catalyst can, for example, be about 0.05 kilograms to about 10 kilograms per cubic metre of feed. Extraction and replacement are effected using apparatus which allows continuous operation of this step of the hydroconversion. The unit normally comprises a recirculating pump which can keep the catalyst in an ebullated bed by continuous recycling of at least a portion of the liquid extracted overhead from the reactor and re-injected at the bottom of the reactor. In step a), at least one catalyst can be used to ensure both demetallization and desulphurization, under conditions such that a liquid feed is produced which has a reduced metal content, a reduced Conradson carbon and a reduced sulphur content and which can produce good conversion to light products, in particular gasoline fractions and gas oil fuel fractions. In the atmospheric distillation zone of step b), the conditions are generally selected such that the cut point is about 300°C to about 400°C, preferably about 340°C to about 380°C. The distillate produced is normally sent to the corresponding gasoline pools, generally after separation into a gasoline fraction and a gas oil fraction. In a particular implementation, at least a portion, possibly all, of the gas oil fraction of the atmospheric distillate is sent to hydrotreatment step e). The atmospheric residue can be sent at least in part to the refinery's gasoline pool. In the vacuum distillation zone of step c) where the atmospheric residue from step b) is treated, the conditions are generally selected such that the cut point is about 450°C to 600°C, normally about 500°C to 550°C. The distillate produced is normally sent at least in part to hydrotreatment step e) and the vacuum residue is sent at least in part to deasphalting step d). In a particular implementation of the invention, at least a portion of the vacuum residue is sent to the refinery's heavy gasoline pool. It is also possible to recycle at least a portion of the vacuum residue to hydroconversion step a). Solvent deasphalting step d) is carried out under conventional conditions which are well known to the skilled person. Reference should be made in this respect to the article by BILLON et al, published in 1994, volume 49, number 5 of the review by the INSTITUT FRANCAIS DU PETROLE, pages 495-507, or to the description given in our patent FR-B-2 480 773 or FR-B-2 681 871, or in our United States patent US-A-4 715 946, the descriptions of which are hereby considered to be incorporated by reference. Deasphalting is normally carried out at a temperature of 60°C to 250°C with at least one hydrocarbon solvent containing 3 to 7 carbon atoms, which may contain at least one additive. Suitable solvents and additives have been widely described in the documents cited above and in US-A-1 948 296, US-A-2 081 473, US-A-2 587 643, US-A-2 882 219, US-A-3 278 415 and US-A-3 331 394, for example. The solvent can be recovered using the opticritical process, i.e., using a solvent under supercritical conditions. That process can substantially improve the overall economy of the process. Deasphalting can be carried out in a mixer settler or in an extraction column. In the present invention, at least one extraction column is preferably used. Step e) for hydrotreatment of the deasphalted hydrocarbon cut is carried out under conventional conditions for fixed bed hydrotreatment of a liquid hydrocarbon fraction. An absolute pressure of 5 MP a to 25 MP a is normally used, more often 5 MPa to 12 MPa, at a temperature of about 300°C to about 500°C, usually about 350°C to about 430°C. The hourly space velocity (HSV) and partial pressure of hydrogen are important factors which are selected as a function of the characteristics of the feed to be treated and the desired conversion. Normally, the HSV is in a range from about 0.1 h~l to about 10 h\ preferably about 0.3 h"1 to about 1 h" . The quantity of hydrogen mixed with the feed is normally about 50 to about 5000 normal cubic metres (Nm ) per cubic metre (mJ) of liquid feed, normally about 100 to about 3000 Nm3/m . A conventional catalyst can be used, such as a catalyst containing cobalt and molybdenum on an alumina based support: see, for example, ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, Volume A 18, 1991, page 67, Table 4. As an example, one of the catalysts sold by PROCATALYSE with reference number HR306C or HR316C, which contain cobalt and molybdenum, or that with reference HR348, which contains nickel and molybdenum, can be used. The scope of the present invention includes in this step one or more catalytic keeper beds in the head of the reactor, or one or more keeper reactors, to trap the last traces of metals still present in the product introduced into step e). One or more catalysts can be used, either in the same reactor, or in a plurality of reactors, generally in series. The products obtained during this step are normally sent to a separation zone from which a gas fraction and a liquid fraction are recovered. The liquid fraction can be sent to a second separation zone in which it can be separated into light fractions, for example gasoline and gas oil, which can be sent at least in part to gasoline pools, and into a heavier fraction. The heavier fraction normally has an initial boiling point of at least 340°C, normally at least 370°C. This heavier fraction can be sent at least in part to a refinery's heavy gasoline pool with a very low sulphur content (normally less than 0.5% by weight). In one particular embodiment of the invention, at least one means which can improve the viscosity of the overall feed which is treated in ebullated bed hydroconversion step a) is advantageously provided. A low viscosity means that the pump used to recirculate the liquid can be used more efficiently. Further, dilution of the fresh feed with a hydrocarbon fraction can reduce the gas/liquid ratio and thus greatly reduce the risk of unpriming the liquid recirculating pump inside the reactor. In this particular embodiment, at least a portion of the distillate obtained by atmospheric distillation in step b), and/or at least a portion of the distillate obtained by vacuum distillation in step c), and/or at least a portion of the fuel fraction (atmospheric distillate) obtained in step e), and/or at least a portion of the heavy liquid fraction obtained in step e), can be sent to step a). Finally, in the variation mentioned above, in a catalytic cracking step f) at least a portion of the heavier fraction of the hydro treated feed produced in step e) can be sent to a conventional catalytic cracking section in which is it catalytically cracked in conventional fashion under conditions which are known to the skilled person, to produce a fuel fraction (comprising a gasoline fraction and a gas oil fraction) which is normally sent at least in part to the gasoline pools, and into a slurry fraction which is, for example, at least in part or even all sent to a heavy gasoline pool or is at least in part, or all, recycled to catalytic cracking step f). In a particular implementation of the invention, a portion of the gas oil fraction produced during step f) is recycled either to step a) or to step e) or to step f) mixed with the feed introduced into catalytic cracking step f). In the present description, the term "a portion of the gas oil fraction" means a fraction which is less than 100%. The scope of the present invention includes recycling a portion of the gas oil fraction to step a), a further portion to step f) and a third portion to step e), the sum of these three portions not necessarily representing the whole of the gas oil fraction. It is also possible, within the scope of the invention, to recycle all of the gas oil obtained by catalytic cracking either to step a), or to step f), or to step e), or a fraction to each of these steps, the sum of these fractions representing 100% of the gas oil fraction produced in step f) At least a portion of the gasoline fraction obtained in catalytic cracking step f) can also be recycled to step f). As an example, a summary description of catalytic cracking (first industrial use as far back as 1936 [HOUDRY process] or 1942 for the use of a fluidised bed catalyst) is to be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A18,1991, pages 61 to 64. Normally, a conventional catalyst is used which comprises a matrix, possibly an additive and at least one zeolite. The quantity of zeolite can vary but is normally about 3% to 60% by weight, usually about 6% to 50% by weight and most often about 10% to 45% by weight. The zeolite is normally dispersed in the matrix. The quantity of additive is usually about 0 to 30% by weight, more often 0 to 20% by weight. The quantity of matrix represents the complement to 100% by weight. The additive is generally selected from the group formed by oxides of metals from group HA of the periodic classification of the elements, for example magnesium oxide or calcium oxide, rare-earth oxides and titanates of metals from group HA. The matrix is usually a silica, an alumina, a silica-alumina, a silica-magnesia, a clay or a mixture of two or more of these substances. Y zeolite is most frequently used. Cracking is carried out in a reactor which is substantially vertical, either in riser or in dropper mode. The choice of catalyst and operating conditions are a function of the desired products, dependent on the feed which is treated as described, for example, in the article by M MARCILLY, pages 990-991 published in the review by the INSTITUT FRANCAIS DU PETROLE, Nov-Dec 1975, pages 969-1006. A temperature of about 450°C to about 600°C is normally used and the residence times in the reactor are less than 1 minute, generally about 0.1 to about 50 seconds. Catalytic cracking step f) can also be a fluidised bed catalytic cracking step, for example the process developed by ourselves known as R2R. This step can be carried out conventionally in a fashion which is known to the skilled person under suitable residue cracking conditions to produce hydrocarbon products with a lower molecular weight. Descriptions of the operation and suitable catalysts for fluidised bed catalytic cracking in step f) are described, for example, in US-A-4 695 370, EP-B-0 184 517, US-A-4 959 334? EP-B-0 323 297, US-A-4 965 232, US-A-5 120 691, US-A-5 344 554, US-A-5 449 496, EP-A-0 485 259, US-A-5 286 690, US-A-5 324 696 and EP-A-0 699 224, the descriptions of which are considered to be hereby incorporated by reference. In this particular implementation, it is possible in step 0 to introduce catalytic cracking of at least a portion of the atmospheric residue obtained from step b). The fluidised bed catalytic cracking reactor may operate in riser or dropper mode. Although it does not constitute a preferred implementation of the present invention, it is also possible to carry out catalytic cracking in a moving bed reactor. Particularly preferred catalytic cracking catalysts are those containing at least one zeolite which is normally mixed with a suitable matrix such as alumina, silica or silica-alumina. In a particular implementation when the treated feed is a vacuum residue from vacuum distillation or an atmospheric distillation residue of a crude oil, it is advantageous to recover the vacuum distillate and send at least part or all of it to step e) in which it is hydrotreated mixed with the deasphalted hydrocarbon cut produced in step d). When only part of the vacuum distillate is sent to step e), the other portion is preferably sent to hydroconversion step a). In a further variation, a portion of the deasphalted hydrocarbon cut produced in step d) is recycled to hydroconversion step a). In a preferred form of the invention, the residual asphalt produced in step d) is sent to an oxyvapogasification section in which it is transformed into a gas containing hydrogen and carbon monoxide. This gaseous mixture can be used to synthesise methanol or hydrocarbons using the Fischer-Tropsch reaction. Within the context of the present invention, this mixture is preferably sent to a shift conversion section in which it is converted to hydrogen and carbon dioxide in the presence of steam. The hydrogen obtained can be used in steps a) and e) of the present invention. The residual asphalt can also be used as a solid fuel, or after fluxing, as a liquid fuel. In a further implementation, at least a portion of the residual asphalt is recycled to hydroconversion step a). The following example illustrates the invention without limiting its scope. EXAMPLE A pilot hydrotreatment unit was used with an ebullated bed catalyst. The pilot unit simulated an industrial residue hydroconversion process and produced identical performances to those of industrial units. The catalyst was replaced at a rate of 0.5kg/m of feed. The reactor volume was 3 litres. A Safaniya vacuum residue was treated in the pilot unit; its characteristics are shown in Table 1, column 1. A specific ebullated bed residue hydroconversion catalyst was used as described in Example 2 of US-A-4 652 545 under reference HDS-1443 B. The operating conditions were as follows: HSV = 1 with respect to catalyst P= 150 bar T - 420°C Hydrogen recycle = 500 1 H2/l of feed All yields were calculated from a base of 100 (by weight) of VR. The characteristics of the total C$+ liquid effluent from the reactor are shown in Table 1, column 2. The product was then fractionated, in succession, in an atmospheric distillation column from which an atmospheric residue (AR) was collected as a bottoms product, then the AR was fractionated in a vacuum distillation column producing a vacuum distillate (VD) and a vacuum residue (VR). The yields and characteristics of these products are shown in Table 1 in columns 3, 5 and 4 respectively. In the atmospheric distillation step, a distillate was recovered which was sent to gasoline pools after separation of a gasoline fraction and a gas oil fraction. The vacuum residue was then deasphalted in a pilot unit which simulated the SOLVAHL® deasphalting process. The pilot unit operated with a vacuum residue flow rate of 3 1/h, the solvent was a pentane cut used in a ratio of 5/1 by volume with respect to the feed. A deasphalted oil cut (DAO) was produced - the yield and characteristics are shown in Table 1 column 6; a residual asphalt was also produced. The DAO cut was remixed with the VD cut from the preceding step. The VD + DAO mixture was then catalytically hydrotreated in a pilot unit. The catalyst was HR348 from Procatalyse. Table 1 shows the characteristics of the VD + DAO mixture (column 7) and the characteristics of the product obtained at the hydrotreatment outlet (column 8). This time, the operating conditions were as follows: HSV - 0.5 P = 80 bar T = 380°C Hydrogen recycle = 600 1 H2/l of feed The vacuum distillate and deasphalted oiL (DAO) mixture from the hydrotreatment unit had the characteristics shown in column 8 of Table 1. The feed, preheated to 140°C, was brought into contact at the bottom of a vertical pilot reactor with a hot regenerated catalyst from a pilot regenerator. The inlet temperature of the catalyst in the reactor was 730°C. The ratio of the catalyst flow rate to the feed flow rate was 6.64. The heat added by the catalyst at 730°C allowed the feed to vaporise and allowed the cracking reaction, which is endothermic, to take place. The average residence time of the catalyst in the reaction zone was about 3 seconds. The operating pressure was 1.8 bars absolute. The temperature of the catalyst, measured at the riser flow fluidised bed reactor outlet, was 520°C. The cracked hydrocarbons and the catalyst were separated using cyclones located in a stripper zone where the catalyst was stripped. The catalyst, which was coked during the reaction and stripped in the stripping zone, was then sent to the regenerator. The coke content in the solid (delta coke) at the regenerator inlet was about 95%. The coke was burned off by air injected into the regenerator. The highly exothermic combustion raised the temperature of the solid from 520°C to 730°C. The hot regenerated catalyst left the regenerator and was returned to the bottom of the reactor. The hydrocarbons separated from the catalyst left the stripping zone; they were cooled in exchangers and sent to a stabilising column which separated the gas and the liquids. The (C$+) liquid was also sampled then fractionated in a further column to recover a gasoline fraction, a gas oil fraction and a heavy fuel or slurry fraction (360°C+). Tables 2 and 3 show the yields of gasoline and gas oil and principal characteristics of these products produced over the whole of the process. 1. A process for converting a heavy hydrocarbon fraction with a Conradson carbon of at least 10, a metal content of at least 50 ppm, a C7 asphaltene content of at least 1%, and a sulphur content of at least 0.5%, characterized in that it comprises the following steps: a) treating the hydrocarbon feed in a hydroconversion section in the presence of hydrogen, the section comprising at least one three-phase reactor containing at least one ebullated bed hydroconversion catalyst operating in liquid and gas riser mode, said reactor comprising at least one means for removing catalyst from said reactor and at least one means for adding fresh catalyst to said reactor, under conditions which will produce a liquid effluent with a reduced Conradson carbon, metal content and sulphur content; b) sending at least a portion of the hydroconverted liquid effluent from step a) to an atmospheric distillation zone, from which an atmospheric distillate and an atmospheric residue are recovered; c) sending at least a portion of the atmospheric residue from step b) to a vacuum distillation zone from which a vacuum distillate and a vacuum residue are recovered; d) sending at least a portion of the vacuum residue from step c) to a deasphalting section in which it is treated in an extraction section using a solvent under conditions such that a deasphalted hydrocarbon cut and residual asphalt are produced; e) sending at least a portion of the deasphalted hydrocarbon cut from step d) to a hydrotreatment section in which it is hydrotreated under conditions such that, in particular, the metal content, sulphur content and Conradson carbon are reduced, and after separation, a gas fraction, an atmospheric distillate and a heavier liquid fraction of the hydrotreated feed are produced by atmospheric distillation. A process according to claim 1, in which at least a portion of the heavier liquid fraction of the hydrotreated feed from step e) is sent to a catalytic cracking section (step f)) in which it is treated under conditions such that a gaseous fraction, a gasoline fraction, a gas oil fraction and a slurry fraction are produced. A process according to claim 1 or claim 2, in which during step a), treatment in the presence of hydrogen is carried out at an absolute pressure of 5 to 35 MPa, at a temperature of about 300°C to 500°C with an hourly space velocity of about 0.1 h"1 to 5 h"1. A process according to claim 2 or claim 3, in which at least a portion of the gas oil fraction recovered in catalytic cracking step f) is returned to step a). A process according to any one of claims 1 to 4, in which deasphalting is carried out at a temperature of 60°C to 250°C with at least one hydrocarbon solvent containing 3 to 7 carbon atoms. A process according to any one of claims 1 to 5, in which the distillate obtained by vacuum distillation in step c) is sent at least in part to hydrotreatment step e). 7. A process according to any one of claims 1 to 6, in which hydrotreatment step e) is carried out at an absolute pressure of about 5 MPa to 25 MPa, at a temperature of about 300°C to 500°C with an hourly space velocity of about 0.1 h" to 10 h1 and the quantity of hydrogen mixed with the feed is about 50 to 5000 Nm3/m3. 8. A process according to any one of claims 2 to 7, in which catalytic cracking step f) is carried out under conditions in which a gasoline fraction is produced which is sent at least in part to the gasoline pool, also a gas oil fraction is produced which is sent at least in part to the gas oil pool, and a slurry fraction is produced which is sent at least in part to the heavy gasoline pool. 9. A process according to any one of claims 1 to 8, in which at least a portion of the vacuum residue produced in step c) is recycled to step a). 10. A process according to any one of claims 1 to 9 in which at least a portion of the heavier liquid fraction of the hydrotreated feed produced in step e) is sent to a very low sulphur content heavy fuel pool. 11. A process according to any one of claims 2 to 10, in which at least a portion of the gas oil fraction and/or the gasoline fraction produced in catalytic cracking step f) is recycled to the inlet to said step f). 12. A process according to any one of claims 2 to 11, in which at least a portion of the slurry fraction produced in catalytic cracking step f) is recycled to the inlet to said step f). A process according to any one of claims 1 to 12, in which a portion of the deasphalted hydrocarbon cut produced in step d) is recycled to hydroconversion step a). A process according to any one of claims 1 to 13, in which the treated feed is a vacuum residue from vacuum distillation of an atmospheric distillation residue of a crude oil and at least part of the vacuum distillate is sent to hydrotreatment step e). A process according to any one of claims 1 to 14, in which the distillate produced in step b) and/or step e) are separated into a gasoline fraction and a gas oil fraction which are sent at least in part to their respective gasoline pools. A process according to any one of claims 1 to 15, in which a portion of the residual asphalt produced in step d) is recycled to hydroconversion step a). A process according to any one of claims 1 to 16, in which a portion of the slurry fraction produced in catalytic cracking step f) is recycled to hydroconversion step a). A process according to any one of claims 1 to 17, in which the atmospheric distillate produced in step b) is separated into a gasoline fraction and a gas oil fraction of which at least a portion is sent to hydrotreatment step e). 19. A process according to any one of claims 14 to 18, in which at least a portion of the vacuum distillate is sent to hydroconversion step a). 20. A process according to any one of claims 1 to 19, in which at least a portion of the distillate obtained by atmospheric distillation in step b) is sent to hydroconversion step a). 21. A process according to any one of claims 1 to 20, in which at least a portion of the distillate obtained by vacuum distillation in step c) is sent to hydroconversion step a). 22. A process according to any one of claims 1 to 21, in which at least a portion of the fuel fraction obtained in step e) is sent to hydroconversion step a). 23. A process according to any one of claims 1 to 22, in which at least a portion of the heavy liquid fraction obtained in step e) is sent to hydroconversion step a). 24. A process for converting a heaw hydrocarbon fraction substantially as herein descrih, s ml exemplified.

Full Text

The present invention concerns refining and converting heavy hydrocarbon fractions containing, among others, asphaltenes and sulphur-containing and metal-containing impurities. More particularly, it concerns a process for converting at least part of a feed with a Conradson carbon of more than 10, usually more than 15 and normally more than 20, for example a vacuum residue of a crude, to a product with a Conradson carbon which is sufficiently low and metal and sulphur contents which are sufficiently low for it to be used, for example, as a feed for the production of gas oil and gasoline by catalytic cracking in a conventional fluid bed cracking unit and/or in a fluid bed catalytic cracking unit comprising a double regeneration system, and optionally a catalyst cooling system in the regeneration step. The present invention also concerns a process for the production of gasoline and/or gas oil comprising at least one fluidised bed catalytic cracking step.
As refiners increase the proportion of heavier crude oil of lower quality in the feed to be treated, it becomes ever more necessary to have particular processes available which are specially adapted to treatment of these residual heavy fractions from oil, shale oil, or similar materials containing asphaltenes and with a high Conradson carbon.
Thus European patent EP-B-0 435 242 describes a process for the treatment of a feed of this type comprising a hydrotreatment step using a single catalyst under conditions which reduce the amount of sulphur and metallic impurities, bringing all the effluent with a reduced sulphur content from the hydrotreatment step into contact with a solvent under asphaltene extraction conditions to recover an extract which is relatively depleted in asphaltene and metallic impurities and sending that extract to a catalytic cracking unit to produce low molecular weight hydrocarbon products. In a preferred implementation in that patent, the product from the first step undergoes visbreaking and the product from the visbreaking step is sent to the asphaltene solvent extraction step. In

Example 1 of that patent, the treated feed is an atmospheric residue. According to the teaching of that patent, it appears to be difficult to produce a feed with the characteristics which are necessary to enable treatment in a conventional catalytic cracking reactor with a view to producing a fuel from vacuum residues with a very high metal content (more than 50 ppm, usually more than 100 ppm and normally more than 200 ppm) and with a high Conradson carbon. The current limit on metal content in industrial feeds is about 20 to 25 ppm of metal, and the limit for the Conradson carbon is about 3% for a conventional catalytic cracking unit and about 8% for a unit which is specially adapted for cracking heavy feeds. The use of feeds in which the metallic impurity content is on the upper limit or higher than those mentioned above causes the catalyst to be considerably deactivated, requiring substantial addition of fresh catalyst, and is thus prohibitive for the process and can even render it unworkable. Further, such a process implies the use of substantial quantities of solvent for deasphalting since all the hydrotreated and preferably visbroken product is deasphalted. The use of a single hydrotreatment catalyst limits the performances as regards elimination of metallic impurities to values of less than 75% (Table I, Example II) and/or those of desulphurization to values of no more than 85% (Table I Example II). That technique cannot produce a feed which can be treated using conventional FCC unless the hydrotreated oil, which may have been visbroken, is deasphalted with a C3 type solvent, thus severely limiting the yield.
The present invention aims to overcome the disadvantages described above and produce, from feeds containing large amounts of metals and with high Conradson carbons and sulphur contents, a product which has been more than 80% demetallized, normally at least 90% demetallized, more than 80% and normally more than 85% desulphurized and with a Conradson carbon which is no more than 8, allowing the product to be sent to a residue catalytic cracking reactor

are important factors which are selected as a function of the characteristics of the feed to be treated and the conversion desired. Normally, the liquid HSV is about 0.1 h'1 to about 5 h'1, preferably about 0.15 h'1 to about 2 h"1. Used catalyst is replaced in part by fresh catalyst by extraction from the bottom of the reactor and introduction of fresh or new catalyst to the top of the reactor at regular intervals, for example in batches or quasi continuously. Fresh catalyst can, for example, b6 introduced daily. The rate of replacement of used catalyst by fresh catalyst can, for example, be about 0.05 kilograms to about 10 kilograms per cubic metre of feed. Extraction and replacement are effected using apparatus which allows continuous operation of this step of the hydroconversion. The unit normally comprises a recirculating pump which can keep the catalyst in an ebullated bed by continuous recycling of at least a portion of the liquid extracted overhead from the reactor and re-injected at the bottom of the reactor.
In step a), at least one catalyst can be used to ensure both demetallization and desulphurization, under conditions such that a liquid feed is produced which has a reduced metal content, a reduced Conradson carbon and a reduced sulphur content and which can produce good conversion to light products, in particular gasoline fractions and gas oil fuel fractions.
In the atmospheric distillation zone of step b), the conditions are generally selected such that the cut point is about 300°C to about 400°C, preferably about 340°C to about 380°C. The distillate produced is normally sent to the corresponding gasoline pools, generally after separation into a gasoline fraction and a gas oil fraction. In a particular implementation, at least a portion, possibly all, of the gas oil fraction of the atmospheric distillate is sent to hydrotreatment step e). The atmospheric residue can be sent at least in part to the refinery's gasoline pool.

In the vacuum distillation zone of step c) where the atmospheric residue from step b) is treated, the conditions are generally selected such that the cut point is about 450°C to 600°C, normally about 500°C to 550°C. The distillate produced is normally sent at least in part to hydrotreatment step e) and the vacuum residue is sent at least in part to deasphalting step d). In a particular implementation of the invention, at least a portion of the vacuum residue is sent to the refinery's heavy gasoline pool. It is also possible to recycle at least a portion of the vacuum residue to hydroconversion step a).
Solvent deasphalting step d) is carried out under conventional conditions which are well known to the skilled person. Reference should be made in this respect to the article by BILLON et al, published in 1994, volume 49, number 5 of the review by the INSTITUT FRANCAIS DU PETROLE, pages 495-507, or to the description given in our patent FR-B-2 480 773 or FR-B-2 681 871, or in our United States patent US-A-4 715 946, the descriptions of which are hereby considered to be incorporated by reference. Deasphalting is normally carried out at a temperature of 60°C to 250°C with at least one hydrocarbon solvent containing 3 to 7 carbon atoms, which may contain at least one additive. Suitable solvents and additives have been widely described in the documents cited above and in US-A-1 948 296, US-A-2 081 473, US-A-2 587 643, US-A-2 882 219, US-A-3 278 415 and US-A-3 331 394, for example. The solvent can be recovered using the opticritical process, i.e., using a solvent under supercritical conditions. That process can substantially improve the overall economy of the process. Deasphalting can be carried out in a mixer settler or in an extraction column. In the present invention, at least one extraction column is preferably used.
Step e) for hydrotreatment of the deasphalted hydrocarbon cut is carried out under conventional conditions for fixed bed hydrotreatment of a liquid hydrocarbon fraction. An absolute pressure of 5 MP a to 25 MP a is normally used,

more often 5 MPa to 12 MPa, at a temperature of about 300°C to about 500°C, usually about 350°C to about 430°C. The hourly space velocity (HSV) and partial pressure of hydrogen are important factors which are selected as a function of the characteristics of the feed to be treated and the desired conversion. Normally, the HSV is in a range from about 0.1 h~l to about 10 h*\ preferably about 0.3 h"1 to about 1 h" . The quantity of hydrogen mixed with the feed is normally about 50 to about 5000 normal cubic metres (Nm ) per cubic metre (mJ) of liquid feed, normally about 100 to about 3000 Nm3/m . A conventional catalyst can be used, such as a catalyst containing cobalt and molybdenum on an alumina based support: see, for example, ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, Volume A 18, 1991, page 67, Table 4. As an example, one of the catalysts sold by PROCATALYSE with reference number HR306C or HR316C, which contain cobalt and molybdenum, or that with reference HR348, which contains nickel and molybdenum, can be used. The scope of the present invention includes in this step one or more catalytic keeper beds in the head of the reactor, or one or more keeper reactors, to trap the last traces of metals still present in the product introduced into step e). One or more catalysts can be used, either in the same reactor, or in a plurality of reactors, generally in series. The products obtained during this step are normally sent to a separation zone from which a gas fraction and a liquid fraction are recovered. The liquid fraction can be sent to a second separation zone in which it can be separated into light fractions, for example gasoline and gas oil, which can be sent at least in part to gasoline pools, and into a heavier fraction. The heavier fraction normally has an initial boiling point of at least 340°C, normally at least 370°C. This heavier fraction can be sent at least in part to a refinery's heavy gasoline pool with a very low sulphur content (normally less than 0.5% by weight).

In one particular embodiment of the invention, at least one means which can improve the viscosity of the overall feed which is treated in ebullated bed hydroconversion step a) is advantageously provided. A low viscosity means that the pump used to recirculate the liquid can be used more efficiently. Further, dilution of the fresh feed with a hydrocarbon fraction can reduce the gas/liquid ratio and thus greatly reduce the risk of unpriming the liquid recirculating pump inside the reactor. In this particular embodiment, at least a portion of the distillate obtained by atmospheric distillation in step b), and/or at least a portion of the distillate obtained by vacuum distillation in step c), and/or at least a portion of the fuel fraction (atmospheric distillate) obtained in step e), and/or at least a portion of the heavy liquid fraction obtained in step e), can be sent to step a).
Finally, in the variation mentioned above, in a catalytic cracking step f) at least a portion of the heavier fraction of the hydro treated feed produced in step e) can be sent to a conventional catalytic cracking section in which is it catalytically cracked in conventional fashion under conditions which are known to the skilled person, to produce a fuel fraction (comprising a gasoline fraction and a gas oil fraction) which is normally sent at least in part to the gasoline pools, and into a slurry fraction which is, for example, at least in part or even all sent to a heavy gasoline pool or is at least in part, or all, recycled to catalytic cracking step f). In a particular implementation of the invention, a portion of the gas oil fraction produced during step f) is recycled either to step a) or to step e) or to step f) mixed with the feed introduced into catalytic cracking step f). In the present description, the term "a portion of the gas oil fraction" means a fraction which is less than 100%. The scope of the present invention includes recycling a portion of the gas oil fraction to step a), a further portion to step f) and a third portion to step e), the sum of these three portions not necessarily representing the whole of the gas oil fraction. It is also possible, within the scope of the invention, to recycle all of the

gas oil obtained by catalytic cracking either to step a), or to step f), or to step e), or a fraction to each of these steps, the sum of these fractions representing 100% of the gas oil fraction produced in step f) At least a portion of the gasoline fraction obtained in catalytic cracking step f) can also be recycled to step f).
As an example, a summary description of catalytic cracking (first industrial use as far back as 1936 [HOUDRY process] or 1942 for the use of a fluidised bed catalyst) is to be found in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY VOLUME A18,1991, pages 61 to 64. Normally, a conventional catalyst is used which comprises a matrix, possibly an additive and at least one zeolite. The quantity of zeolite can vary but is normally about 3% to 60% by weight, usually about 6% to 50% by weight and most often about 10% to 45% by weight. The zeolite is normally dispersed in the matrix. The quantity of additive is usually about 0 to 30% by weight, more often 0 to 20% by weight. The quantity of matrix represents the complement to 100% by weight. The additive is generally selected from the group formed by oxides of metals from group HA of the periodic classification of the elements, for example magnesium oxide or calcium oxide, rare-earth oxides and titanates of metals from group HA. The matrix is usually a silica, an alumina, a silica-alumina, a silica-magnesia, a clay or a mixture of two or more of these substances. Y zeolite is most frequently used. Cracking is carried out in a reactor which is substantially vertical, either in riser or in dropper mode. The choice of catalyst and operating conditions are a function of the desired products, dependent on the feed which is treated as described, for example, in the article by M MARCILLY, pages 990-991 published in the review by the INSTITUT FRANCAIS DU PETROLE, Nov-Dec 1975, pages 969-1006. A temperature of about 450°C to about 600°C is normally used and the residence times in the reactor are less than 1 minute, generally about 0.1 to about 50 seconds.

Catalytic cracking step f) can also be a fluidised bed catalytic cracking step, for example the process developed by ourselves known as R2R. This step can be carried out conventionally in a fashion which is known to the skilled person under suitable residue cracking conditions to produce hydrocarbon products with a lower molecular weight. Descriptions of the operation and suitable catalysts for fluidised bed catalytic cracking in step f) are described, for example, in US-A-4 695 370, EP-B-0 184 517, US-A-4 959 334? EP-B-0 323 297, US-A-4 965 232, US-A-5 120 691, US-A-5 344 554, US-A-5 449 496, EP-A-0 485 259, US-A-5 286 690, US-A-5 324 696 and EP-A-0 699 224, the descriptions of which are considered to be hereby incorporated by reference. In this particular implementation, it is possible in step 0 to introduce catalytic cracking of at least a portion of the atmospheric residue obtained from step b).
The fluidised bed catalytic cracking reactor may operate in riser or dropper mode. Although it does not constitute a preferred implementation of the present invention, it is also possible to carry out catalytic cracking in a moving bed reactor. Particularly preferred catalytic cracking catalysts are those containing at least one zeolite which is normally mixed with a suitable matrix such as alumina, silica or silica-alumina.
In a particular implementation when the treated feed is a vacuum residue from vacuum distillation or an atmospheric distillation residue of a crude oil, it is advantageous to recover the vacuum distillate and send at least part or all of it to step e) in which it is hydrotreated mixed with the deasphalted hydrocarbon cut produced in step d). When only part of the vacuum distillate is sent to step e), the other portion is preferably sent to hydroconversion step a).
In a further variation, a portion of the deasphalted hydrocarbon cut produced in step d) is recycled to hydroconversion step a).

In a preferred form of the invention, the residual asphalt produced in step d) is sent to an oxyvapogasification section in which it is transformed into a gas containing hydrogen and carbon monoxide. This gaseous mixture can be used to synthesise methanol or hydrocarbons using the Fischer-Tropsch reaction. Within the context of the present invention, this mixture is preferably sent to a shift conversion section in which it is converted to hydrogen and carbon dioxide in the presence of steam. The hydrogen obtained can be used in steps a) and e) of the present invention. The residual asphalt can also be used as a solid fuel, or after fluxing, as a liquid fuel. In a further implementation, at least a portion of the residual asphalt is recycled to hydroconversion step a).
The following example illustrates the invention without limiting its scope.
EXAMPLE
A pilot hydrotreatment unit was used with an ebullated bed catalyst. The pilot unit simulated an industrial residue hydroconversion process and produced identical performances to those of industrial units. The catalyst was replaced at a rate of 0.5kg/m of feed. The reactor volume was 3 litres.
A Safaniya vacuum residue was treated in the pilot unit; its characteristics are shown in Table 1, column 1.
A specific ebullated bed residue hydroconversion catalyst was used as
described in Example 2 of US-A-4 652 545 under reference HDS-1443 B. The
operating conditions were as follows:
HSV = 1 with respect to catalyst
P= 150 bar
T - 420°C
Hydrogen recycle = 500 1 H2/l of feed
All yields were calculated from a base of 100 (by weight) of VR. The characteristics of the total C$+ liquid effluent from the reactor are shown in Table 1, column 2. The product was then fractionated, in succession, in

an atmospheric distillation column from which an atmospheric residue (AR) was collected as a bottoms product, then the AR was fractionated in a vacuum distillation column producing a vacuum distillate (VD) and a vacuum residue (VR). The yields and characteristics of these products are shown in Table 1 in columns 3, 5 and 4 respectively. In the atmospheric distillation step, a distillate was recovered which was sent to gasoline pools after separation of a gasoline fraction and a gas oil fraction.
The vacuum residue was then deasphalted in a pilot unit which simulated the SOLVAHL® deasphalting process. The pilot unit operated with a vacuum residue flow rate of 3 1/h, the solvent was a pentane cut used in a ratio of 5/1 by volume with respect to the feed. A deasphalted oil cut (DAO) was produced - the yield and characteristics are shown in Table 1 column 6; a residual asphalt was also produced.
The DAO cut was remixed with the VD cut from the preceding step. The
VD + DAO mixture was then catalytically hydrotreated in a pilot unit. The
catalyst was HR348 from Procatalyse. Table 1 shows the characteristics of the
VD + DAO mixture (column 7) and the characteristics of the product obtained at
the hydrotreatment outlet (column 8).
This time, the operating conditions were as follows: HSV - 0.5 P = 80 bar T = 380°C Hydrogen recycle = 600 1 H2/l of feed
The vacuum distillate and deasphalted oiL (DAO) mixture from the hydrotreatment unit had the characteristics shown in column 8 of Table 1.
The feed, preheated to 140°C, was brought into contact at the bottom of a vertical pilot reactor with a hot regenerated catalyst from a pilot regenerator. The

inlet temperature of the catalyst in the reactor was 730°C. The ratio of the catalyst flow rate to the feed flow rate was 6.64. The heat added by the catalyst at 730°C allowed the feed to vaporise and allowed the cracking reaction, which is endothermic, to take place. The average residence time of the catalyst in the reaction zone was about 3 seconds. The operating pressure was 1.8 bars absolute. The temperature of the catalyst, measured at the riser flow fluidised bed reactor outlet, was 520°C. The cracked hydrocarbons and the catalyst were separated using cyclones located in a stripper zone where the catalyst was stripped. The catalyst, which was coked during the reaction and stripped in the stripping zone, was then sent to the regenerator. The coke content in the solid (delta coke) at the regenerator inlet was about 95%. The coke was burned off by air injected into the regenerator. The highly exothermic combustion raised the temperature of the solid from 520°C to 730°C. The hot regenerated catalyst left the regenerator and was returned to the bottom of the reactor.
The hydrocarbons separated from the catalyst left the stripping zone; they were cooled in exchangers and sent to a stabilising column which separated the gas and the liquids. The (C$+) liquid was also sampled then fractionated in a further column to recover a gasoline fraction, a gas oil fraction and a heavy fuel or slurry fraction (360°C+).
Tables 2 and 3 show the yields of gasoline and gas oil and principal characteristics of these products produced over the whole of the process.

1. A process for converting a heavy hydrocarbon fraction with a Conradson carbon of at least 10, a metal content of at least 50 ppm, a C7 asphaltene content of at least 1%, and a sulphur content of at least 0.5%, characterized in that it comprises the following steps:
a) treating the hydrocarbon feed in a hydroconversion section in the presence of hydrogen, the section comprising at least one three-phase reactor containing at least one ebullated bed hydroconversion catalyst operating in liquid and gas riser mode, said reactor comprising at least one means for removing catalyst from said reactor and at least one means for adding fresh catalyst to said reactor, under conditions which will produce a liquid effluent with a reduced Conradson carbon, metal content and sulphur content;
b) sending at least a portion of the hydroconverted liquid effluent from step a) to an atmospheric distillation zone, from which an atmospheric distillate and an atmospheric residue are recovered;
c) sending at least a portion of the atmospheric residue from step b) to a
vacuum distillation zone from which a vacuum distillate and a vacuum
residue are recovered;
d) sending at least a portion of the vacuum residue from step c) to a deasphalting section in which it is treated in an extraction section using a solvent under conditions such that a deasphalted hydrocarbon cut and residual asphalt are produced;
e) sending at least a portion of the deasphalted hydrocarbon cut from step d) to a hydrotreatment section in which it is hydrotreated under conditions such that, in particular, the metal content, sulphur content

and Conradson carbon are reduced, and after separation, a gas fraction, an atmospheric distillate and a heavier liquid fraction of the hydrotreated feed are produced by atmospheric distillation.
A process according to claim 1, in which at least a portion of the heavier liquid fraction of the hydrotreated feed from step e) is sent to a catalytic cracking section (step f)) in which it is treated under conditions such that a gaseous fraction, a gasoline fraction, a gas oil fraction and a slurry fraction are produced.
A process according to claim 1 or claim 2, in which during step a), treatment in the presence of hydrogen is carried out at an absolute pressure of 5 to 35 MPa, at a temperature of about 300°C to 500°C with an hourly space velocity of about 0.1 h"1 to 5 h"1.
A process according to claim 2 or claim 3, in which at least a portion of the gas oil fraction recovered in catalytic cracking step f) is returned to step a).
A process according to any one of claims 1 to 4, in which deasphalting is carried out at a temperature of 60°C to 250°C with at least one hydrocarbon solvent containing 3 to 7 carbon atoms.
A process according to any one of claims 1 to 5, in which the distillate obtained by vacuum distillation in step c) is sent at least in part to hydrotreatment step e).

7. A process according to any one of claims 1 to 6, in which hydrotreatment step e) is carried out at an absolute pressure of about 5 MPa to 25 MPa, at a temperature of about 300°C to 500°C with an hourly space velocity of about 0.1 h" to 10 h*1 and the quantity of hydrogen mixed with the feed is about 50 to 5000 Nm3/m3.
8. A process according to any one of claims 2 to 7, in which catalytic cracking step f) is carried out under conditions in which a gasoline fraction is produced which is sent at least in part to the gasoline pool, also a gas oil fraction is produced which is sent at least in part to the gas oil pool, and a slurry fraction is produced which is sent at least in part to the heavy gasoline pool.
9. A process according to any one of claims 1 to 8, in which at least a portion of the vacuum residue produced in step c) is recycled to step a).

10. A process according to any one of claims 1 to 9 in which at least a portion of the heavier liquid fraction of the hydrotreated feed produced in step e) is sent to a very low sulphur content heavy fuel pool.
11. A process according to any one of claims 2 to 10, in which at least a portion of the gas oil fraction and/or the gasoline fraction produced in catalytic cracking step f) is recycled to the inlet to said step f).
12. A process according to any one of claims 2 to 11, in which at least a portion of the slurry fraction produced in catalytic cracking step f) is recycled to the inlet to said step f).

A process according to any one of claims 1 to 12, in which a portion of the deasphalted hydrocarbon cut produced in step d) is recycled to hydroconversion step a).
A process according to any one of claims 1 to 13, in which the treated feed is a vacuum residue from vacuum distillation of an atmospheric distillation residue of a crude oil and at least part of the vacuum distillate is sent to hydrotreatment step e).
A process according to any one of claims 1 to 14, in which the distillate produced in step b) and/or step e) are separated into a gasoline fraction and a gas oil fraction which are sent at least in part to their respective gasoline pools.
A process according to any one of claims 1 to 15, in which a portion of the residual asphalt produced in step d) is recycled to hydroconversion step a).
A process according to any one of claims 1 to 16, in which a portion of the slurry fraction produced in catalytic cracking step f) is recycled to hydroconversion step a).
A process according to any one of claims 1 to 17, in which the atmospheric distillate produced in step b) is separated into a gasoline fraction and a gas oil fraction of which at least a portion is sent to hydrotreatment step e).

19. A process according to any one of claims 14 to 18, in which at least a portion of the vacuum distillate is sent to hydroconversion step a).
20. A process according to any one of claims 1 to 19, in which at least a portion of the distillate obtained by atmospheric distillation in step b) is sent to hydroconversion step a).
21. A process according to any one of claims 1 to 20, in which at least a portion of the distillate obtained by vacuum distillation in step c) is sent to hydroconversion step a).
22. A process according to any one of claims 1 to 21, in which at least a portion of the fuel fraction obtained in step e) is sent to hydroconversion step a).
23. A process according to any one of claims 1 to 22, in which at least a portion of the heavy liquid fraction obtained in step e) is sent to hydroconversion step a).
24. A process for converting a heaw hydrocarbon fraction substantially as herein descrih, s ml exemplified.

Documents:

2180-mas-1997-abstract.pdf

2180-mas-1997-claims filed.pdf

2180-mas-1997-claims granted.pdf

2180-mas-1997-correspondnece-others.pdf

2180-mas-1997-correspondnece-po.pdf

2180-mas-1997-description(complete)filed.pdf

2180-mas-1997-description(complete)granted.pdf

2180-mas-1997-form 1.pdf

2180-mas-1997-form 26.pdf

2180-mas-1997-form 3.pdf

2180-mas-1997-form 4.pdf

2180-mas-1997-form 5.pdf

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Patent Number

210066

Indian Patent Application Number

2180/MAS/1997

PG Journal Number

50/2007

Publication Date

14-Dec-2007

Grant Date

17-Sep-2007

Date of Filing

01-Oct-1997

Name of Patentee

M/S. INSTITUT FRANCAIS DU PETROLE

Applicant Address

4 AVENUE DE BOIS PREAU, 92502 RUEIL MALMAISON,

Inventors:

#	Inventor's Name	Inventor's Address
1	MOREL FREDERIC (ET.AL.)	16, RUE DOUBLINE 69340 FRANCHEVILLE,

PCT International Classification Number

C10 G 49/12

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	96/12.103	1996-10-02	France