EP0938530A1 - Method for improving the pour-point of paraffin feedstock with a nu-86 zeolite based catalyst - Google Patents

Method for improving the pour-point of paraffin feedstock with a nu-86 zeolite based catalyst

Info

Publication number
EP0938530A1
EP0938530A1 EP97947123A EP97947123A EP0938530A1 EP 0938530 A1 EP0938530 A1 EP 0938530A1 EP 97947123 A EP97947123 A EP 97947123A EP 97947123 A EP97947123 A EP 97947123A EP 0938530 A1 EP0938530 A1 EP 0938530A1
Authority
EP
European Patent Office
Prior art keywords
zeolite
catalyst
charge
pour point
paraffins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97947123A
Other languages
German (de)
French (fr)
Other versions
EP0938530B1 (en
Inventor
Eric Benazzi
Nathalie George-Marchal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR9614627A external-priority patent/FR2756295B1/en
Priority claimed from FR9614628A external-priority patent/FR2756296B1/en
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP0938530A1 publication Critical patent/EP0938530A1/en
Application granted granted Critical
Publication of EP0938530B1 publication Critical patent/EP0938530B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the present invention relates to a method for improving the pour point of charges containing paraffins, linear and / or slightly branched, long (more than 10 carbon atoms), in particular for converting, with good efficiency, charges having high pour points in at least one section having a reduced pour point.
  • This cut can be a middle distillate and / or an oil base, which then has a high viscosity index.
  • This operation can be carried out by extraction with solvents such as propane or methyl ethyl ketone, this is known as dewaxing with propane or with methyl ethyl ketone (MEK).
  • solvents such as propane or methyl ethyl ketone
  • MEK methyl ethyl ketone
  • Another means is selective cracking of the longest linear paraffinic chains which leads to the formation of compounds of lower molecular weight, part of which can be removed by distillation.
  • zeolites are among the most used catalysts.
  • the idea which prevails in their use is that there are zeolitic structures whose pore openings are such that they allow the entry into their microporosity of long linear paraffins or very little branched but exclude branched paraffins, napthenes and aromatics. This phenomenon thus leads to a selective cracking of linear or very poorly branched paraffins.
  • Catalysts based on zeolites having intermediate pore sizes such as ZSM-5, ZSM-11, ZSM-12, ZSM22, ZSM-23, ZSM-35 and ZSM-38 have been described for use in these methods.
  • the Applicant has focused its research efforts on the development of an improved pour point reduction process using the catalyst based on zeolite NU-86. This process, applied to heavy cuts, makes it possible to produce both middle distillates with reduced pour point and a residue including oil bases with low pour point and high viscosity index.
  • the subject of the invention is a method for improving the pour point of a paraffinic charge comprising paraffins of more than 10 carbon atoms, in which the charge to be treated is brought into contact with a catalyst based on zeolite NU-86 and comprising at least one hydro-dehydrogenating element, at a temperature between 170 and 500 ° C, a pressure between 1 and 250 bar and an hourly volume speed between 0.05 and 100 h "1 , in the presence of hydrogen at a rate of 50 to 2000 l / l of charge
  • the product obtained is fractionated so as to obtain at least one cut including at least one medium distillate with reduced pour point and a residue including oil bases with reduced pour point and high viscosity index.
  • the NU-86 zeolite, in hydrogen form, designated by H-NU-86 and obtained by calcination and or ion exchanges of the crude synthetic NU-86 zeolite, used in the process according to the invention as well as its mode of synthesis are described in patent EP-0463768 A2.
  • This NU-86 zeolite is characterized by an X-ray diffraction table which is as follows:
  • the NU-86 zeolite has a three-dimensional microporous system
  • this three-dimensional microporous system consists of straight channels whose pore opening is delimited by 11 T atoms (tetrahedral atoms: Si, Al, Ga, Fe ..), straight channels delimited alternately by openings with 10 and 12 atoms T and sinusoidal channels also delimited alternately by openings with 10 and 12 T atoms.
  • pore opening with 10, 11 or 12 tetrahedral atoms (T) means pores made up of 10, 11 or 12 sides.
  • zeolites NU-86 comprising silicon and at least one element T chosen from the group formed by Al, Fe, Ga, B, and preferably aluminum.
  • the NU-86 zeolite used has been dealuminated or more generally, at least part of the element T has been removed, and it then has an overall atomic Si / T advantageously greater than about 20.
  • the extraction element T of the zeolitic framework (or network) is preferably carried out by at least one heat treatment, optionally carried out in the presence of water vapor, followed by at least one acid attack or else by a direct acid attack, with at least one solution of a mineral or organic acid.
  • the overall Si / T atomic ratio of said zeolite is greater than approximately 16 and advantageously approximately 20, preferably greater than approximately 22 and even more preferably between approximately 22 and approximately 300, or approximately 250.
  • the "dealuminated" NU-86 zeolite is at least in part, preferably practically totally, in acid form, that is to say in hydrogen form (H +).
  • the Na T atomic ratio is generally less than 0.7% and preferably less than 0.6% and even more preferably less than 0.4%.
  • this process makes it possible to convert a charge having a high pour point into a product having a lower pour point.
  • It can be a medium distillate type cup with a reduced pour point (gas oils for example) and / or an oil base with a reduced pour point and a high viscosity index.
  • the charge is composed, inter alia, of linear and / or sparingly branched paraffins comprising at least 10 carbon atoms, preferably from 15 to 50 carbon atoms and advantageously from 15 to 40 carbon atoms.
  • An advantage of the catalyst comprising the NU-86 molecular sieve is that it does not lead to the excessive formation of light products.
  • the catalyst comprises at least one hydro-dehydrogenating function, for example a metal from group VIII or a combination of at least one metal or compound from group VIII and at least one metal or compound from group VI, and the reaction is carried out under the conditions described below.
  • NU-86 zeolite according to the invention allows, in particular, the production of products with a low pour point and also of products with a high viscosity index, with good yields.
  • the NU-86 zeolite has an Si / T atomic ratio (preferred Al) of between 8 and 1000 and in particular between 8.5 and 16 for the zeolites obtained by synthesis, and a Si / T atomic ratio of more than 16 and advantageously more than 20 for zeolites in which at least part of the element T has been removed.
  • the first method known as direct acid attack comprises a first calcination step under dry air flow, at a temperature generally between about 450 and 550 ° C, which aims to remove the organic structuring present in the microporosity zeolite, followed by a step of treatment with an aqueous solution of a mineral acid such as HNO 3 or HCl or organic such as CH 3 CO 2 H. This last step can be repeated as many times as necessary to get the desired dealumination level. Between these two stages, it is possible to carry out one or more ion exchanges with at least one NH4NO3 solution, so as to eliminate at least in part, preferably practically completely, the alkaline cation, in particular sodium. Similarly, at the end of the dealumination treatment by direct acid attack, it is possible to carry out one or more ionic exchanges with at least one NH4NO3 solution, so as to eliminate the residual alkaline cations and in particular sodium.
  • the most critical parameters are the temperature of the treatment with the aqueous acid solution, the concentration of the latter, its nature, the ratio between the quantity of acid solution and the mass of zeolite treated, the duration of the treatment and the number of treatments performed.
  • the second method called thermal treatment (in particular with steam or "steaming") + acid attack comprises, firstly, calcination under dry air flow, at a temperature generally between approximately 450 and 550 ° C, which aims to eliminate the organic structuring agent occluded in the microporosity of the zeolite. Then the solid thus obtained is subjected to one or more ionic exchanges by at least one NH4NO3 solution, so as to eliminate at least in part, from preferably almost completely, the alkaline cation, in particular sodium, present in the cationic position in the zeolite.
  • the zeolite thus obtained is subjected to at least one structural dealumination cycle, comprising at least one heat treatment carried out, optionally and preferably in the presence of water vapor, at a temperature generally between 550 and 900 ° C., and optionally followed by at least one acid attack with an aqueous solution of a mineral or organic acid.
  • the calcination conditions in the presence of water vapor temperature, water vapor pressure and duration of the treatment
  • the post-calcination acid attack conditions are adapted so as to obtain the desired dealumination level.
  • the dealumination cycle of the frame comprising at least one heat treatment step, optionally and preferably carried out in the presence of water vapor, and at least one attack step in an acid medium.
  • NU-86 zeolite can be repeated as many times as necessary to obtain the dealuminated NU-86 zeolite having the desired characteristics.
  • the heat treatment possibly carried out and preferably in the presence of water vapor, several successive acid attacks, with acid solutions of different concentrations, can be carried out.
  • a variant of this second calcination method may consist in carrying out the heat treatment of the NU-86 zeolite containing the organic structuring agent, at a temperature generally between 550 and 850 ° C., optionally and preferably in the presence of water vapor.
  • the stages of calcination of the organic structuring agent and dealumination of the framework are carried out simultaneously.
  • the zeolite is optionally treated with at least one aqueous solution of a mineral acid (for example HNO3 or HCl) or organic (CH 3 CO 2 H for example).
  • the solid thus obtained can optionally be subjected to at least one ion exchange with at least one solution.
  • the sieve (zeolite NU-86) generally contains at least one hydro-dehydrogenating element, for example at least one metal from group VIII, preferably a noble metal and advantageously chosen from the group formed by Pt or Pd, which is introduced in the molecular sieve, for example by dry impregnation, by ion exchange or any other method known to those skilled in the art.
  • at least one hydro-dehydrogenating element for example at least one metal from group VIII, preferably a noble metal and advantageously chosen from the group formed by Pt or Pd, which is introduced in the molecular sieve, for example by dry impregnation, by ion exchange or any other method known to those skilled in the art.
  • the content of metal thus introduced is generally less than 5%, preferably less than 3% and generally of the order of 0.5% to 1% by weight.
  • the molecular sieve according to the invention is previously shaped.
  • the molecular sieve can be subjected to the deposition of at least one metal from group VIII preferably chosen from the group formed by platinum and palladium, and shaped by any technique known to those skilled in the art . It can in particular be mixed with a matrix, generally amorphous, for example with a wet powder of alumina gel. The mixture is then shaped, for example by extrusion through a die.
  • the molecular sieve content of the mixture thus obtained is generally between 0.5 and 99.9% and advantageously between 5 and 90% by weight relative to the mixture (molecular sieve + matrix).
  • support will be used to designate the molecular sieve + matrix mixture.
  • the shaping can be carried out with matrices other than alumina, such as for example magnesia, amorphous silica-aluminas, natural clays (kaolin, bentonite, sepiolite, attapulgite), silica, oxide of titanium, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, carbon and their mixtures.
  • matrices other than alumina such as for example magnesia, amorphous silica-aluminas, natural clays (kaolin, bentonite, sepiolite, attapulgite), silica, oxide of titanium, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, carbon and their mixtures.
  • Other techniques than extrusion such as pelletizing or coating, can be used.
  • the group VIII hydrogenating metal preferably Pt and / or Pd
  • the group VIII hydrogenating metal can also be deposited on the support by any process known to those skilled in the art and allowing the metal to be deposited on the molecular sieve.
  • the competitor is preferably ammonium nitrate
  • the competition ratio being at least equal to about 20 and advantageously from approximately 30 to 200.
  • platinum or palladium a tetramine complex of platinum or a tetramine complex of palladium is usually used: the latter will then be deposited almost entirely on the molecular sieve.
  • This cation exchange technique can also be used to deposit the metal directly on the molecular sieve powder, before possible mixing with a matrix.
  • the deposition of the group VIII metal (or metals) is generally followed by calcination in air or oxygen, usually between 300 and 600 ° C for 0.5 to 10 hours, preferably between 350 ° C and 550 ° C for 1 to 4 hours.
  • a reduction can then be carried out under hydrogen, generally at a temperature between 300 and 600 ° C for 1 to 10 hours, preferably one will operate between 350 ° and 550 ° C for 2 to 5 hours.
  • Platinum and / or palladium can also be deposited no longer directly on the molecular sieve, but on the matrix (the aluminum binder), before or after the shaping step, by implementing an anion exchange with l hexachloroplatinic acid, hexachloropalladic acid and / or palladium chloride in the presence of a competing agent, for example hydrochloric acid.
  • a competing agent for example hydrochloric acid.
  • the catalyst is as previously subjected to calcination and then reduced under hydrogen as indicated above.
  • the hydro-dehydrogenating element can also be a combination of at least one metal or compound of group VI (for example molybdenum or tungsten) and of at least one metal or compound of group VIII (for example nickel or cobalt).
  • the total concentration of metals of groups VI and VIII, expressed as metal oxides relative to the support, is generally between 5 and 40% by weight, preferably between 7 and 30% by weight.
  • the weight ratio (expressed as metal oxides) of Group VIII metals to Group VI metals is preferably between 0.05 and 0.8; preferably between 0.13 and 0.5.
  • the previous preparation methods can be used to deposit these metals.
  • This type of catalyst can advantageously contain phosphorus, the content of which, expressed as phosphorus oxide P2O5 relative to the support, will generally be less than 15% by weight, preferably less than 10% by weight.
  • the fillers which can be treated according to the process of the invention are advantageously fractions having relatively high pour points whose value it is desired to reduce.
  • the process according to the invention can be used to treat various charges ranging from relatively light fractions such as kerosene and jet fuels to charges having higher boiling points such as middle distillates, vacuum residues, diesel.
  • the load to be treated is in most cases a cut C- j n "1" with an initial boiling point greater than about 175 ° C, preferably a cut with an initial boiling point of at least 280 ° C .
  • heavy fillers are used, that is to say constituted for at least 80% by volume of compounds with boiling points of at least 350 ° C., preferably between 350-580 °. C, and advantageously at least 380 ° C.
  • the process according to the invention is particularly suitable for treating paraffinic distillates such as middle distillates which include gas oils, kerosene, jet fuels, for treating residues under vacuum and all other fractions whose pour point and viscosity must be adapted to fit within the specifications, and for example middle distillates from FCC (LCO and HCO) and hydrocracking residues.
  • paraffinic distillates such as middle distillates which include gas oils, kerosene, jet fuels
  • the fillers which can be treated according to the process of the invention can contain paraffins, olefins, naphthenes, aromatics and also heterocycles and with a large proportion of high molecular weight n-paraffins and paraffins which are also very little branched high molecular weight.
  • Typical fillers which can be advantageously treated according to the invention generally have a pour point above 0 ° C.
  • the products resulting from the treatment according to the method have pour points of less than 0 ° C and preferably less than about -10 ° C.
  • n-paraffins with more than 10 carbon atoms, of high molecular weight and in paraffins, with more than 10 carbon atoms, very little branched also of high molecular weight, higher than 30% and up to at around 90%, or in some cases even more than 90% by weight.
  • the process is particularly advantageous when this proportion is at least 60% by weight.
  • examples of other fillers which can be treated according to the invention and that are non-limiting, may be cited, bases for lubricating oils, synthetic paraffins obtained from the Fischer-Tropsch process, polyalphaolefins with high pour point, synthetic oils etc.
  • the process can also be applied to other compounds containing an n-alkane chain as defined above, for example n-alkylcycloalkane compounds, or comprising at least one aromatic group.
  • the reaction temperature is between 170 and 500 ° C and preferably between 180 and 470 ° C, preferably 190-450 ° C;
  • the pressure is between 1 and 250 bar and preferably between 10 and 200 bar;
  • the hourly volume speed (wh expressed in volume of charge injected per unit volume of catalyst and per hour) is between approximately 0.05 and approximately 100 and preferably between approximately 0.1 and approximately 30 h " 1.
  • the rate of hydrogen used and expressed in liters of hydrogen per liter of charge is between 50 and approximately 2000 liters of hydrogen per liter of charge and preferably between 100 and 1500 liters of hydrogen per liter of charge.
  • the feed to be treated preferably has a nitrogen compound content of less than about 200 ppm by weight and preferably less than 100 ppm by weight.
  • the sulfur content is less than 1000 ppm by weight, preferably less than 500 ppm and even more preferably less than 200 ppm by weight.
  • the content of metals in the filler, such as Ni or V, is extremely reduced, that is to say less than 50 ppm by weight, preferably less than 10 ppm by weight and even more preferably less than 2 ppm by weight .
  • the product obtained after treatment of the heavy filler with the catalyst based on zeolite NU-86, is fractionated into at least one section including at least one medium distillate. reduced pour point, and a residue including oil bases with reduced pour point and high viscosity index.
  • the middle distillate can be a kerosene (generally considered cut where boiling points 150 - less than 250 ° C), a gas oil (heavier cut than kerosene, generally considered at least 250 ° C and less than 400 C C, or less than 380 ° C).
  • the oil is then in the residue 380 + or 400+.
  • the cutting points can be more or less variable depending on the operator's constraints.
  • the raw material used is a NU-86 zeolite, which is prepared according to Example 2 of patent EP 0 463 768 A2 and has an overall Si / Al atomic ratio equal to 10.2 and an Na / Al atomic ratio equal to 0.25 .
  • This NU-86 zeolite first undergoes so-called dry calcination at 550 ° C. under a flow of dry air for 9 hours. Then the solid obtained is subjected to four ionic exchanges in a solution of NH4NO3 10N, at approximately 100 ° C. for 4 hours for each exchange.
  • the total area of the signal is measured for each sample over an angular range (2) of 6 to 40 °, then, in the same area, the area of the lines in number of pulses for a 3 second step recording with 0.02 ° steps (2).
  • the ratio of these two values, Line area / Total area, is characteristic of the amount of material crystallized in the sample. This ratio or "peak rate" is then compared, for each sample treated, with the peak rate of a standard reference arbitrarily considered to be totally (100%) crystallized.
  • the degree of crystallinity is therefore expressed as a percentage relative to a reference, which it is important to choose well, because the relative intensity of the lines varies according to the nature, the proportion and position of the different atoms in the structural unit, and in particular of the cations and of the structuring.
  • the reference chosen is the form calcined in dry air and exchanged 3 times, successively, with a solution of ammonium nitrate of the zeolite NU-86.
  • microporous volume from the quantity of nitrogen adsorbed at 77 K for a partial pressure P / Po equal to 0.19, for information only.
  • the crystallites of the NU-86 zeolite are in the form of crystals whose size varies from 0.4 ⁇ m to 2 ⁇ m.
  • the NH4-NU-86/1 zeolite is kneaded with alumina of the SB3 type supplied by the company Condisputeda.
  • the kneaded dough is then extruded through a die with a diameter of 1.2 mm.
  • the extrudates are then calcined at 500 ° C. for 2 hours in air, then impregnated to dryness with a solution of platinum chloride tetramine [Pt (NH3) 4JCl2, and finally calcined in air at 550 ° C.
  • the platinum content of the final catalyst C1 thus obtained is 0.7% by weight and the zeolite content expressed relative to the total mass of the catalyst is 20% by weight.
  • Example 2 Evaluation of the catalyst C1 on a hydrocracking residue
  • Catalyst C1 was evaluated to treat a hydrocracking residue from a vacuum distillate.
  • Catalyst C1 the preparation of which is described in Example 1, is used to prepare a base oil from the charge described above.
  • the catalyst is reduced beforehand under hydrogen at 450 ° C. before the catalytic test in situ in the reactor. This reduction is carried out in stages. It consists of a plateau at 150 ° C for 2 hours, then a rise in temperature to 450 ° C at the speed of 1 ° C / min, then a plateau for 2 hours at 450 ° C.
  • the hydrogen flow rate is 1000 liters of H2 per liter of catalyst.
  • the reaction takes place at 265 ° C, under a total pressure of 12 MPa, an hourly space velocity 2 h "1, and a hydrogen flow rate of 1000 liters of H2 per liter of feed.
  • the fractionation of the effluent allows collect a base oil as a residue and a medium distillate cut with boiling point 150-400 ° C. (400 ° C. being excluded) and light products. Under these operating conditions the net conversion into compounds 400- (having a boiling point below 400 ° C) is 25% by weight and the yield of base oil is 75% by weight.
  • the diesel pour point is -33 ° C.
  • This example shows all the advantage there is in using a catalyst according to the invention, which makes it possible to lower the pour point of the initial charge, in this case a hydrocracking residue, while retaining a high viscosity index (VI).
  • the zeolite of Example 1 is used.
  • the zeolite obtained is referenced NH4-NU-86/2. It has an overall Si / Ai atomic ratio equal to 34, and an Na / Al atomic ratio equal to 0.005. These crystallographic and adsorption characteristics are reported in Table 2, below.
  • the zeolite is kneaded with alumina of the SB3 type supplied by the company Condisputeda.
  • the kneaded dough is then extruded through a die with a diameter of 1.2 mm.
  • the extrudates are then calcined at 500 ° C. for 2 hours in air, then impregnated to dryness with a solution of platinum chloride tetramine [Pt (NH3) 4] Cl2, and finally calcined in air at 550 ° C.
  • the platinum content of the final catalyst thus obtained is 0.7% by weight and the zeolite content expressed relative to the total mass of the catalyst is 30% by weight.
  • the catalyst was evaluated on a hydrocracking residue from a vacuum distillate to prepare a base oil.
  • the catalyst is reduced beforehand under hydrogen at 450 ° C. before the catalytic test in situ in the reactor. This reduction is carried out in stages. It consists of a plateau at 150 ° C for 2 hours, then a rise in temperature to 450 ° C at the speed of 1 ° C / min, then a plateau for 2 hours at 450 ° C.
  • the hydrogen flow rate is 1000 liters of H2 per liter of catalyst.
  • the reaction takes place at 300 ° C, under a total pressure of 12 MPa, an hourly volume speed 1.8 h “" "and a hydrogen flow rate of 1000 liters of H2 per liter of charge. Under these operating conditions, the net conversion to 400 " compounds is 27% by weight and the yield of base oil is 73% by weight.
  • This example shows all the advantage there is in using a catalyst according to the invention, which makes it possible to lower the pour point of the initial charge, in this case a hydrocracking residue, while retaining a high viscosity index (VI).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Lubricants (AREA)

Abstract

The invention concerns a process for improving the pour point of a feed comprising paraffins containing more than 10 carbon atoms, in which process the feed to be treated is brought into contact with a catalyst comprising NU-86 zeolite, preferably dealuminated, and at least one hydro-dehydrogenating element, at a temperature which is in the range 170 DEG C. to 500 DEG C., a pressure in the range 1 to 250 bar and an hourly space velocity in the range 0.05 to 100 h-1, in the presence of hydrogen in a proportion of 50 to 2000 l/l of feed. The product from heavy feeds is fractionated to produce at least one cut including at least one middle distillate with a reduced pour point, and a residue including oil bases with a reduced pour point and a high viscosity index.

Description

PROCEDE POUR L'AMELIORATION DU POINT D'ECOULEMENT DE CHARGES PARAFFINIQUES AVEC UN CATALYSEUR A BASE DE ZÉOLITHE NU-86PROCESS FOR IMPROVING THE FLOW POINT OF PARAFFINIC LOADS WITH A NU-86 ZEOLITE CATALYST
La présente invention concerne un procédé pour améliorer le point d'écoulement de charges contenant des paraffines, linéaires et/ou peu ramifiées, longues (plus de 10 atomes de carbone), en particulier pour convertir, avec un bon rendement, des charges possédant des points d'écoulement élevés en au moins une coupe présentant un point d'écoulement réduit. Cette coupe peut être un distillât moyen et/ou une base huile, qui présente alors un indice de viscosité élevé.The present invention relates to a method for improving the pour point of charges containing paraffins, linear and / or slightly branched, long (more than 10 carbon atoms), in particular for converting, with good efficiency, charges having high pour points in at least one section having a reduced pour point. This cut can be a middle distillate and / or an oil base, which then has a high viscosity index.
Art antérieurPrior art
Les lubrifiants de haute qualité sont d'une importance primordiale pour le bon fonctionnement des machines modernes, des automobiles, et des camions. Cependant, la quantité de paraffines issues directement du pétrole, non traitées, et possédant les propriétés adéquates pour constituer des bons lubrifiants est très faible par rapport à la demande croissante dans ce secteur.High quality lubricants are of paramount importance for the proper functioning of modern machines, automobiles, and trucks. However, the quantity of paraffins directly obtained from petroleum, untreated, and having the adequate properties to constitute good lubricants is very low compared to the growing demand in this sector.
Le traitement des fractions pétrolières lourdes à fortes teneurs en paraffines linéaires ou peu ramifiées est nécessaire afin d'obtenir des huiles de base de bonne qualité et ce avec les meilleurs rendements possibles, par une opération qui vise à éliminer les paraffines linéaires ou très peu branchées, des charges qui seront ensuite utilisées en tant que huiles de base ou en tant que kérosène ou carburéacteur (jet fuel).The treatment of heavy petroleum fractions with high contents of linear or slightly branched paraffins is necessary in order to obtain good quality base oils and this with the best possible yields, by an operation which aims to eliminate linear or very branched paraffins , fillers which will then be used as base oils or as kerosene or jet fuel.
En effet, ies paraffines de haut poids moléculaire qui sont linéaires ou très faiblement branchées et qui sont présentes dans les huiles ou dans le kérosène ou carburéacteur conduisent à des points d'écoulement hauts et donc à des phénomènes de figeage pour des utilisations à basse température. Afin de diminuer les valeurs des points d'écoulement, ces paraffines linéaires pas ou très peu branchées doivent être entièrement ou partiellement éliminées.Indeed, high molecular weight paraffins which are linear or very weakly branched and which are present in oils or in kerosene or jet fuel lead to high pour points and therefore to freezing phenomena for uses at low temperature. . In order to decrease the pour point values, these linear paraffins with little or no branching must be entirely or partially removed.
Cette opération peut s'effectuer par extraction par des solvants tels que le propane ou la méthyl-éthyl cétone, on parle alors de déparaffinage au propane ou à la méthyl éthyl-cétone (MEK). Cependant, ces techniques sont coûteuses, longues et pas toujours aisées à mettre en oeuvre. Un autre moyen est un craquage sélectif des chaînes paraffiniques linéaires les plus longues qui conduit à la formation de composés de poids moléculaire plus faible dont une partie peut être éliminée par distillation.This operation can be carried out by extraction with solvents such as propane or methyl ethyl ketone, this is known as dewaxing with propane or with methyl ethyl ketone (MEK). However, these techniques are expensive, time-consuming and not always easy to implement. Another means is selective cracking of the longest linear paraffinic chains which leads to the formation of compounds of lower molecular weight, part of which can be removed by distillation.
Compte tenu de leur sélectivité de forme les zeolithes sont parmi les catalyseurs les plus utilisés. L'idée qui prévaut à leur utilisation est qu'il existe des structures zéolithiques dont les ouvertures de pores sont telles qu'elles permettent l'entrée dans leur microporosité des paraffines linéaires longues ou très peu branchées mais en excluent les paraffines ramifiées, les napthènes et les aromatiques. Ce phénomène conduit ainsi à un craquage sélectif des paraffines linéaires ou très peu branchées.Given their shape selectivity, zeolites are among the most used catalysts. The idea which prevails in their use is that there are zeolitic structures whose pore openings are such that they allow the entry into their microporosity of long linear paraffins or very little branched but exclude branched paraffins, napthenes and aromatics. This phenomenon thus leads to a selective cracking of linear or very poorly branched paraffins.
Des catalyseurs à base de zeolithes ayant des tailles de pores intermédiaires telles que les ZSM-5, ZSM-11 , ZSM-12, ZSM22, ZSM-23, ZSM-35 et ZSM-38 ont été décrits pour leur utilisation dans ces procédés.Catalysts based on zeolites having intermediate pore sizes such as ZSM-5, ZSM-11, ZSM-12, ZSM22, ZSM-23, ZSM-35 and ZSM-38 have been described for use in these methods.
Les procédés utilisant certaines de ces zeolithes permettent d'obtenir des huiles par craquage de charges contenant des quantités de paraffines linéaires ou très peu branchées inférieures à 50 % poids. Cependant, pour des charges contenant des quantités supérieures de ces composés il est apparu que leur craquage par lesdites zeolites conduit à la formation de quantités importantes de produits légers de poids moléculaires faibles, tels que du butane, propane, éthane et méthane, ce qui réduit considérablement le rendement en produits recherchés. D'autres zeolithes (SZM-22 par ex.) favorisent une isomérisation de ces composés et sont plus dédiées à la production d'huiles avec de forts rendements.The processes using some of these zeolites make it possible to obtain oils by cracking fillers containing quantities of linear or very slightly branched paraffins less than 50% by weight. However, for fillers containing higher quantities of these compounds, it has been found that their cracking by said zeolites leads to the formation of large quantities of light products of low molecular weight, such as butane, propane, ethane and methane, which reduces considerably the yield of sought-after products. Other zeolites (SZM-22 for example) promote isomerization of these compounds and are more dedicated to the production of oils with high yields.
La demanderesse a porté ses efforts de recherche sur la mise au point d'un procédé amélioré de réduction du point d'écoulement grâce à l'emploi de catalyseur à base de zéolithe NU-86. Ce procédé, appliqué à des coupes lourdes, permet de produire à la fois des distillats moyens à point d'écoulement réduit et un résidu incluant les bases huiles à bas point d'écoulement réduit et indice de viscosité élevé.The Applicant has focused its research efforts on the development of an improved pour point reduction process using the catalyst based on zeolite NU-86. This process, applied to heavy cuts, makes it possible to produce both middle distillates with reduced pour point and a residue including oil bases with low pour point and high viscosity index.
Objet de l'inventionSubject of the invention
L'invention a pour objet un procédé pour l'amélioration du point d'écoulement d'une charge paraffinique comportant des paraffines de plus de 10 atomes de carbone, dans lequel la charge à traiter est mise au contact d'un catalyseur à base de zéolithe NU-86 et comprenant au moins un élément hydro-déshydrogénant, à une température comprise entre 170 et 500°C, une pression entre 1 et 250 bar et une vitesse volumique horaire entre 0,05 et 100 h"1 , en présence d'hydrogène à raison de 50 à 2000 l/l de charge. Dans le cas de traitement de charge lourde, le produit obtenu est fractionné de façon à obtenir au moins une coupe incluant au moins un distillât moyen à point d'écoulement réduit et un résidu incluant les bases huile à point d'écoulement réduit et indice de viscosité élevé.The subject of the invention is a method for improving the pour point of a paraffinic charge comprising paraffins of more than 10 carbon atoms, in which the charge to be treated is brought into contact with a catalyst based on zeolite NU-86 and comprising at least one hydro-dehydrogenating element, at a temperature between 170 and 500 ° C, a pressure between 1 and 250 bar and an hourly volume speed between 0.05 and 100 h "1 , in the presence of hydrogen at a rate of 50 to 2000 l / l of charge In the case of treatment of heavy charge, the product obtained is fractionated so as to obtain at least one cut including at least one medium distillate with reduced pour point and a residue including oil bases with reduced pour point and high viscosity index.
La zéolithe NU-86, sous forme hydrogène, désignée par H-NU-86 et obtenue par calcination et ou échanges ioniques de la zéolithe NU-86 brute de synthèse, employée dans le procédé selon l'invention ainsi que son mode de synthèse sont décrits dans le brevet EP-0463768 A2. Cette zéolithe NU-86 est caractérisée par un tableau de diffraction des rayons X qui est le suivant :The NU-86 zeolite, in hydrogen form, designated by H-NU-86 and obtained by calcination and or ion exchanges of the crude synthetic NU-86 zeolite, used in the process according to the invention as well as its mode of synthesis are described in patent EP-0463768 A2. This NU-86 zeolite is characterized by an X-ray diffraction table which is as follows:
Tableau de diffraction des rayons X de la zéolithe H-NU-86X-ray diffraction table for zeolite H-NU-86
l/lo représente les intensités relatives des pics graduées selon l'échelle suivante f = faible (l/lo compris entre 0 et 20), m = moyen (l/lo compris entre 20 et 40),l / lo represents the relative intensities of the peaks graduated according to the following scale f = low (l / lo between 0 and 20), m = medium (l / lo between 20 and 40),
F = Fort (l/lo compris entre 40 et 60), TF = Très Fort (l/lo compris entre 60 et 100). (1 ) indique qu'il s'agit d'une raie large et asymétrique contenant un certain nombre de pics, parmi lesquels les majeurs sont ceux situés à des équidistances réticulaires dhkl de 11 ,80, 11 ,10 et 10,60.F = Strong (l / lo between 40 and 60), TF = Very Strong (l / lo between 60 and 100). (1) indicates that it is a broad and asymmetrical line containing a number of peaks, among which the major ones are those located at reticular equidistances dhkl of 11, 80, 11, 10 and 10.60.
(2) indique que la raie est constituée d'un doublet. Néanmoins, dans certains cas il peut s'avérer que sur le diffractogramme le doublet ne soit pas résolu et que par conséquent il apparaisse sous forme d'un seul pic non résolu.(2) indicates that the line consists of a doublet. However, in some cases it may turn out that on the diffractogram the doublet is not resolved and that consequently it appears in the form of a single unresolved peak.
Le type structural de cette zéolithe n'a pas encore été officiellement attribué par la commission de synthèse de l'IZA (International Zeolite Association). Cependant, suite aux travaux publiés au 9ieme Congrès International sur les Zeolithes par J.L. Casci, P.A. Box et M.D. Shannon ("Proceedings of the 9th International Zeolite Conférence, Montréal 1992, Eds R. Von Ballmoos et al., 1993 by Butterworth) il apparaît que :The structural type of this zeolite has not yet been officially assigned by the synthesis committee of the International Zeolite Association (IZA). However, following the work published at the 9th International Congress on Zeoliths by JL Casci, PA Box and MD Shannon ("Proceedings of the 9th International Zeolite Conférence, Montréal 1992, Eds R. Von Ballmoos et al., 1993 by Butterworth) it appears than :
- la zéolithe NU-86 possède un système microporeux tridimensionnel;- the NU-86 zeolite has a three-dimensional microporous system;
- ce système microporeux tridimensionnel est constitué de canaux droits dont l'ouverture de pore est délimitée par 11 atomes T (atomes tétraédriques : Si, Al, Ga, Fe..), de canaux droits délimités alternativement par des ouvertures à 10 et 12 atomes T et des canaux sinusoïdaux aussi délimités de façon alternative par des ouvertures à 10 et 12 atomes T.- this three-dimensional microporous system consists of straight channels whose pore opening is delimited by 11 T atoms (tetrahedral atoms: Si, Al, Ga, Fe ..), straight channels delimited alternately by openings with 10 and 12 atoms T and sinusoidal channels also delimited alternately by openings with 10 and 12 T atoms.
On entend par le terme ouverture de pores à 10, 1 1 ou 12 atomes tétraédriques (T) des pores constitués de 10, 11 ou 12 côtés.The term “pore opening with 10, 11 or 12 tetrahedral atoms (T)” means pores made up of 10, 11 or 12 sides.
On comprendra également dans ce texte par « zeolite NU-86 » les zeolithes NU-86 comprenant du silicium et au moins un élément T choisi dans le groupe formé par Al, Fe, Ga, B, et de préférence l'aluminium.Also understood in this text by "zeolite NU-86" the zeolites NU-86 comprising silicon and at least one element T chosen from the group formed by Al, Fe, Ga, B, and preferably aluminum.
De préférence, la zéolithe NU-86 utilisée a été désaluminée ou de façon plus générale, une partie au moins de l'élément T a été enlevée, et elle possède alors un Si/T atomique global avantageusement supérieur à environ 20. L'extraction d'élément T de la charpente (ou réseau) zéolithique est effectuée de préférence, par au moins un traitement thermique, réalisé éventuellement en présence de vapeur d'eau, suivi d'au moins une attaque acide ou bien par une attaque acide directe, par au moins une solution d'un acide minéral ou organique. De préférence, le rapport Si/T atomique global de ladite zéolithe est supérieur à environ 16 et avantageusement à environ 20, de préférence supérieur à environ 22 et de manière encore plus préférée compris entre environ 22 et environ 300, ou environ 250.Preferably, the NU-86 zeolite used has been dealuminated or more generally, at least part of the element T has been removed, and it then has an overall atomic Si / T advantageously greater than about 20. The extraction element T of the zeolitic framework (or network) is preferably carried out by at least one heat treatment, optionally carried out in the presence of water vapor, followed by at least one acid attack or else by a direct acid attack, with at least one solution of a mineral or organic acid. Preferably, the overall Si / T atomic ratio of said zeolite is greater than approximately 16 and advantageously approximately 20, preferably greater than approximately 22 and even more preferably between approximately 22 and approximately 300, or approximately 250.
La zéolithe NU-86 "désaluminée" est au moins en partie, de préférence pratiquement totalement, sous forme acide, c'est-à-dire sous forme hydrogène (H+). Le rapport atomique Na T est généralement inférieur à 0,7 % et de préférence inférieur à 0,6 % et de manière encore plus préférée inférieur à 0, 4 %.The "dealuminated" NU-86 zeolite is at least in part, preferably practically totally, in acid form, that is to say in hydrogen form (H +). The Na T atomic ratio is generally less than 0.7% and preferably less than 0.6% and even more preferably less than 0.4%.
Avantageusement ce procédé permet de convertir une charge possédant un haut point d'écoulement en un produit possédant un point d'écoulement plus bas. Ce peut être une coupe de type distillât moyen à point d'écoulement réduit (gazoles par exemple) et/ou une base huile à point d'écoulement réduit et indice de viscosité élevé.Advantageously, this process makes it possible to convert a charge having a high pour point into a product having a lower pour point. It can be a medium distillate type cup with a reduced pour point (gas oils for example) and / or an oil base with a reduced pour point and a high viscosity index.
La charge est composée, entre autres, de paraffines linéaires et/ou peu ramifiées comportant au moins 10 atomes de carbone, de préférence de 15 à 50 atomes de carbone et avantageusement de 15 à 40 atomes de carbone.The charge is composed, inter alia, of linear and / or sparingly branched paraffins comprising at least 10 carbon atoms, preferably from 15 to 50 carbon atoms and advantageously from 15 to 40 carbon atoms.
Un avantage du catalyseur comportant le tamis moléculaire NU-86 est qu'il ne conduit pas à la formation trop importante de produits légers.An advantage of the catalyst comprising the NU-86 molecular sieve is that it does not lead to the excessive formation of light products.
D'autre part le catalyseur comporte au moins une fonction hydro-déshydrogénante, par exemple un métal du groupe VIII ou une combinaison d'au moins un métal ou composé du groupe VIII et d'au moins un métal ou composé du groupe VI, et la réaction est réalisée dans les conditions décrites ci-après.Furthermore, the catalyst comprises at least one hydro-dehydrogenating function, for example a metal from group VIII or a combination of at least one metal or compound from group VIII and at least one metal or compound from group VI, and the reaction is carried out under the conditions described below.
L'utilisation de zéolithe NU-86 selon l'invention dans les conditions décrites ci-dessus permet, notamment, la production de produits à faible point d'écoulement et également de produits à haut indice de viscosité, avec de bons rendements.The use of NU-86 zeolite according to the invention under the conditions described above allows, in particular, the production of products with a low pour point and also of products with a high viscosity index, with good yields.
Description détaillée de l'inventionDetailed description of the invention
La zéolithe NU-86 présente un rapport atomique Si/T (Al préféré) compris entre 8 et 1000 et en particulier entre 8,5 et 16 pour les zeolithes obtenues par synthèse, et un rapport atomique Si/T de plus de 16 et avantageusement de plus de 20 pour les zeolithes dans laquelle une partie au moins d'élément T a été ôtée.The NU-86 zeolite has an Si / T atomic ratio (preferred Al) of between 8 and 1000 and in particular between 8.5 and 16 for the zeolites obtained by synthesis, and a Si / T atomic ratio of more than 16 and advantageously more than 20 for zeolites in which at least part of the element T has been removed.
Pour préparer la zéolithe NU-86 désaluminée selon l'invention, dans le cas préféré où T est Al, deux méthodes de désalumination peuvent être employées, à partir de la zéolithe NU-86 brute de synthèse comprenant du structurant organique. Elles sont décrites ci-après. Mais toute autre méthode connue de l'homme du métier entre aussi dans le cadre de l'invention, ainsi que toute méthode applicable lorsque T est différent de Al.To prepare the dealuminated NU-86 zeolite according to the invention, in the preferred case where T is Al, two dealumination methods can be used, starting from the synthetic crude NU-86 zeolite comprising organic structuring agent. They are described below. But any other method known to a person skilled in the art also falls within the scope of the invention, as well as any method applicable when T is different from Al.
La première méthode dite de l'attaque acide directe comprend une première étape de calcination sous flux d'air sec, à une température généralement comprise entre environ 450 et 550°C, qui a pour but d'éliminer le structurant organique présent dans la microporosité de la zéolithe, suivie d'une étape de traitement par une solution aqueuse d'un acide minéral tel que HNO3 ou HCI ou organique tel que CH3CO2H. Cette dernière étape peut être répétée autant de fois qu'il est nécessaire afin d'obtenir le niveau de désalumination voulue. Entre ces deux étapes il est possible de réaliser un ou plusieurs échanges ioniques par au moins une solution NH4NO3, de manière à éliminer au moins en partie, de préférence pratiquement totalement, le cation alcalin, en particulier le sodium. De même, à la fin du traitement de désalumination par attaque acide directe, il est possible de réaliser un ou plusieurs échanges ioniques par au moins une solution NH4NO3, de manière à éliminer les cations alcalins résiduels et en particulier le sodium.The first method known as direct acid attack comprises a first calcination step under dry air flow, at a temperature generally between about 450 and 550 ° C, which aims to remove the organic structuring present in the microporosity zeolite, followed by a step of treatment with an aqueous solution of a mineral acid such as HNO 3 or HCl or organic such as CH 3 CO 2 H. This last step can be repeated as many times as necessary to get the desired dealumination level. Between these two stages, it is possible to carry out one or more ion exchanges with at least one NH4NO3 solution, so as to eliminate at least in part, preferably practically completely, the alkaline cation, in particular sodium. Similarly, at the end of the dealumination treatment by direct acid attack, it is possible to carry out one or more ionic exchanges with at least one NH4NO3 solution, so as to eliminate the residual alkaline cations and in particular sodium.
Pour atteindre le rapport Si/Ai désiré, il est nécessaire de bien choisir les conditions opératoires ; de ce point de vue les paramètres les plus critiques sont la température du traitement par la solution aqueuse d'acide, la concentration de ce dernier, sa nature, le rapport entre la quantité de solution acide et la masse de zéolithe traitée, la durée du traitement et le nombre de traitement réalisés.To achieve the desired Si / Ai ratio, it is necessary to choose the operating conditions carefully; from this point of view the most critical parameters are the temperature of the treatment with the aqueous acid solution, the concentration of the latter, its nature, the ratio between the quantity of acid solution and the mass of zeolite treated, the duration of the treatment and the number of treatments performed.
La deuxième méthode dite de traitement thermique (en particulier à la vapeur d'eau ou "steaming") + attaque acide, comprend, dans un premier temps, la calcination sous flux d'air sec, à une température généralement comprise entre environ 450 et 550°C, qui a pour but d'éliminer le structurant organique occlus dans la microporosité de la zéolithe. Puis le solide ainsi obtenu est soumis à un ou plusieurs échanges ioniques par au moins une solution NH4NO3, de manière à éliminer au moins en partie, de préférence pratiquement totalement, le cation alcalin, en particulier le sodium, présent en position cationique dans la zéolithe. La zéolithe ainsi obtenue est soumise à au moins un cycle de désalumination de charpente, comportant au moins un traitement thermique réalisé, éventuellement et de préférence en présence de vapeur d'eau, à une température généralement comprise entre 550 et 900°C, et éventuellement suivie d'au moins une attaque acide par une solution aqueuse d'un acide minéral ou organique. Les conditions de calcination en présence de vapeur d'eau (température, pression de vapeur d'eau et durée du traitement) ainsi que les conditions d'attaque acide post-calcination (durée de l'attaque, concentration de l'acide, nature de l'acide utilisé et le rapport entre le volume d'acide et la masse de zéolithe), sont adaptées de manière à obtenir le niveau de désalumination souhaité. Dans le même but on peut aussi jouer sur le nombre de cycles traitement thermique-attaque acide qui sont effectués.The second method called thermal treatment (in particular with steam or "steaming") + acid attack, comprises, firstly, calcination under dry air flow, at a temperature generally between approximately 450 and 550 ° C, which aims to eliminate the organic structuring agent occluded in the microporosity of the zeolite. Then the solid thus obtained is subjected to one or more ionic exchanges by at least one NH4NO3 solution, so as to eliminate at least in part, from preferably almost completely, the alkaline cation, in particular sodium, present in the cationic position in the zeolite. The zeolite thus obtained is subjected to at least one structural dealumination cycle, comprising at least one heat treatment carried out, optionally and preferably in the presence of water vapor, at a temperature generally between 550 and 900 ° C., and optionally followed by at least one acid attack with an aqueous solution of a mineral or organic acid. The calcination conditions in the presence of water vapor (temperature, water vapor pressure and duration of the treatment) as well as the post-calcination acid attack conditions (duration of the attack, acid concentration, nature of the acid used and the ratio between the volume of acid and the mass of zeolite), are adapted so as to obtain the desired dealumination level. For the same purpose we can also play on the number of heat treatment-acid attack cycles that are performed.
Dans le cas préféré où T est Al, le cycle de désalumination de la charpente, comportant au moins une étape de traitement thermique, réalisé éventuellement et de préférence en présence de vapeur d'eau, et au moins une étape d'attaque en milieu acide de la zéolithe NU-86, peut être répété autant de fois qu'il est nécessaire pour obtenir la zéolithe NU-86 désaluminée possédant les caractéristiques désirées. De même, suite au traitement thermique, réalisé éventuellement et de préférence en présence de vapeur d'eau, plusieurs attaques acides successives, avec des solutions en acide de concentrations différentes, peuvent être opérées.In the preferred case where T is Al, the dealumination cycle of the frame, comprising at least one heat treatment step, optionally and preferably carried out in the presence of water vapor, and at least one attack step in an acid medium. NU-86 zeolite, can be repeated as many times as necessary to obtain the dealuminated NU-86 zeolite having the desired characteristics. Similarly, following the heat treatment, possibly carried out and preferably in the presence of water vapor, several successive acid attacks, with acid solutions of different concentrations, can be carried out.
Une variante de cette deuxième méthode de calcination peut consister à réaliser le traitement thermique de la zéolithe NU-86 contenant le structurant organique, à une température généralement comprise entre 550 et 850°C, éventuellement et de préférence en présence de vapeur d'eau. Dans ce cas les étapes de calcination du structurant organique et de désalumination de la charpente sont réalisées simultanément. Puis, la zéolithe est éventuellement traitée par au moins une solution aqueuse d'un acide minéral (par exemple de HNO3 ou de HCI) ou organique(CH3CO2H par exemple). Enfin, le solide ainsi obtenu peut être éventuellement soumis à au moins un échange ionique par au moins une solutionA variant of this second calcination method may consist in carrying out the heat treatment of the NU-86 zeolite containing the organic structuring agent, at a temperature generally between 550 and 850 ° C., optionally and preferably in the presence of water vapor. In this case, the stages of calcination of the organic structuring agent and dealumination of the framework are carried out simultaneously. Then, the zeolite is optionally treated with at least one aqueous solution of a mineral acid (for example HNO3 or HCl) or organic (CH 3 CO 2 H for example). Finally, the solid thus obtained can optionally be subjected to at least one ion exchange with at least one solution.
NH4NO3, de manière à éliminer pratiquement tout cation alcalin, en particulier le sodium, présent en position cationique dans la zéolithe. Le tamis (zéolithe NU-86) contient généralement au moins un élément hydro- déshydrogénant, par exemple au moins un métal du groupe VIII, de préférence un métal noble et avantageusement choisi dans le groupe formé par le Pt ou le Pd, qui est introduit dans le tamis moléculaire par exemple par imprégnation à sec, par échange ionique ou toute autre méthode connue de l'homme du métier.NH4NO3, so as to eliminate practically any alkaline cation, in particular sodium, present in the cationic position in the zeolite. The sieve (zeolite NU-86) generally contains at least one hydro-dehydrogenating element, for example at least one metal from group VIII, preferably a noble metal and advantageously chosen from the group formed by Pt or Pd, which is introduced in the molecular sieve, for example by dry impregnation, by ion exchange or any other method known to those skilled in the art.
La teneur en métal ainsi introduit, exprimée en % poids par rapport à la masse de tamis moléculaire engagée, est généralement inférieure à 5 %, de préférence inférieure à 3 % et généralement de l'ordre de 0,5 % à 1 % poids.The content of metal thus introduced, expressed in% by weight relative to the mass of molecular sieve engaged, is generally less than 5%, preferably less than 3% and generally of the order of 0.5% to 1% by weight.
Dans le cas du traitement d'une charge réelle le tamis moléculaire selon l'invention est préalablement mis en forme. Selon une première variante, le tamis moléculaire peut être soumis au dépôt d'au moins un métal du groupe VIII de préférence choisi dans le groupe formé par le platine et le palladium, et mis en forme par toute technique connue de l'homme du métier. Il peut en particulier être mélangé à une matrice, généralement amorphe, par exemple à une poudre humide de gel d'alumine. Le mélange est ensuite mis en forme, par exemple par extrusion au travers d'une filière. La teneur en tamis moléculaire du mélange ainsi obtenu est généralement comprise entre 0,5 et 99,9 % et avantageusement comprise entre 5 et 90 % en poids par rapport au mélange (tamis moléculaire + matrice).In the case of the treatment of an actual charge, the molecular sieve according to the invention is previously shaped. According to a first variant, the molecular sieve can be subjected to the deposition of at least one metal from group VIII preferably chosen from the group formed by platinum and palladium, and shaped by any technique known to those skilled in the art . It can in particular be mixed with a matrix, generally amorphous, for example with a wet powder of alumina gel. The mixture is then shaped, for example by extrusion through a die. The molecular sieve content of the mixture thus obtained is generally between 0.5 and 99.9% and advantageously between 5 and 90% by weight relative to the mixture (molecular sieve + matrix).
Dans la suite du texte on désignera par le terme support le mélange tamis moléculaire + matrice.In the remainder of the text, the term support will be used to designate the molecular sieve + matrix mixture.
La mise en forme peut être réalisée avec d'autres matrices que l'alumine, telles que par exemple la magnésie, les silice-alumines amorphes, les argiles naturelles (kaolin, bentonite, sepiolite, attapulgite), la silice, l'oxyde de titane, l'oxyde de bore, la zircone, les phosphates d'aluminium, les phosphates de titane, les phosphates de zirconium, le charbon et leurs mélanges. D'autres techniques que l'extrusion, telles que le pastillage ou la dragéification, peuvent être utilisées.The shaping can be carried out with matrices other than alumina, such as for example magnesia, amorphous silica-aluminas, natural clays (kaolin, bentonite, sepiolite, attapulgite), silica, oxide of titanium, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates, carbon and their mixtures. Other techniques than extrusion, such as pelletizing or coating, can be used.
Le métal hydrogénant du groupe VIII, de préférence Pt et/ou Pd, peut également être déposé sur le support par tout procédé connu de l'homme de l'art et permettant le dépôt du métal sur le tamis moléculaire. On peut utiliser la technique d'échange cationique avec compétition où le compétiteur est de préférence le nitrate d'ammonium, le rapport de compétition étant au moins égal à environ 20 et avantageusement d'environ 30 à 200. Dans le cas du platine ou du palladium, on utilise habituellement un complexe tétramine du platine ou un complexe tétramine du palladium : ces derniers se déposeront alors pratiquement en totalité sur le tamis moléculaire. Cette technique d'échange cationique peut également être utilisée pour déposer directement le métal sur la poudre de tamis moléculaire, avant son mélange éventuel avec une matrice.The group VIII hydrogenating metal, preferably Pt and / or Pd, can also be deposited on the support by any process known to those skilled in the art and allowing the metal to be deposited on the molecular sieve. One can use the cation exchange technique with competition where the competitor is preferably ammonium nitrate, the competition ratio being at least equal to about 20 and advantageously from approximately 30 to 200. In the case of platinum or palladium, a tetramine complex of platinum or a tetramine complex of palladium is usually used: the latter will then be deposited almost entirely on the molecular sieve. This cation exchange technique can also be used to deposit the metal directly on the molecular sieve powder, before possible mixing with a matrix.
Le dépôt du métal (ou des métaux) du groupe VIII est suivi en général d'une calcination sous air ou oxygène, usuellement entre 300 et 600°C durant 0,5 à 10 heures, de préférence entre 350°C et 550°C durant 1 à 4 heures. On peut procéder ensuite à une réduction sous hydrogène, généralement à une température comprise entre 300 et 600°C pendant 1 à 10 heures, de préférence on opérera entre 350° et 550°C pendant 2 à 5 heures.The deposition of the group VIII metal (or metals) is generally followed by calcination in air or oxygen, usually between 300 and 600 ° C for 0.5 to 10 hours, preferably between 350 ° C and 550 ° C for 1 to 4 hours. A reduction can then be carried out under hydrogen, generally at a temperature between 300 and 600 ° C for 1 to 10 hours, preferably one will operate between 350 ° and 550 ° C for 2 to 5 hours.
On peut également déposer le platine et/ou le palladium non plus directement sur le tamis moléculaire, mais sur la matrice (le liant aluminique), avant ou après l'étape de mise en forme, en mettant en œuvre un échange anionique avec de l'acide hexachloroplatinique, de l'acide hexachloropalladique et/ou du chlorure de palladium en présence d'un agent compétiteur, par exemple l'acide chlorhydrique. En générai après le dépôt de platine et/ou de palladium, le catalyseur est comme précédemment soumis à une calcination puis réduit sous hydrogène comme indiqué ci-dessus.Platinum and / or palladium can also be deposited no longer directly on the molecular sieve, but on the matrix (the aluminum binder), before or after the shaping step, by implementing an anion exchange with l hexachloroplatinic acid, hexachloropalladic acid and / or palladium chloride in the presence of a competing agent, for example hydrochloric acid. In general after the deposition of platinum and / or palladium, the catalyst is as previously subjected to calcination and then reduced under hydrogen as indicated above.
L'élément hydro-déshydrogénant peut également être une combinaison d'au moins un métal ou composé du groupe VI (par exemple le molybdène ou le tungstène) et d'au moins un métal ou composé du groupe VIII (par exemple le nickel ou le cobalt). La concentration totale en métaux des groupes VI et VIII, exprimée en oxydes de métaux par rapport au support, est généralement comprise entre 5 et 40 % poids, de préférence entre 7 et 30 % poids. Le rapport pondéral (exprimé en oxydes métalliques) métaux du groupe VIII sur métaux du groupe VI est de préférence compris entre 0,05 et 0,8; de préférence entre 0,13 et 0,5.The hydro-dehydrogenating element can also be a combination of at least one metal or compound of group VI (for example molybdenum or tungsten) and of at least one metal or compound of group VIII (for example nickel or cobalt). The total concentration of metals of groups VI and VIII, expressed as metal oxides relative to the support, is generally between 5 and 40% by weight, preferably between 7 and 30% by weight. The weight ratio (expressed as metal oxides) of Group VIII metals to Group VI metals is preferably between 0.05 and 0.8; preferably between 0.13 and 0.5.
Les méthodes de préparation précédentes sont utilisables pour déposer ces métaux.The previous preparation methods can be used to deposit these metals.
Ce type de catalyseur peut avantageusement contenir du phosphore, dont la teneur, exprimée en oxyde de phosphore P2O5 par rapport au support, sera généralement inférieure à 15 % poids, de préférence inférieure à 10 % poids. Les charges qui peuvent être traitées selon le procédé de l'invention sont avantageusement des fractions possédant des points d'écoulement relativement hauts dont on désire diminuer la valeur.This type of catalyst can advantageously contain phosphorus, the content of which, expressed as phosphorus oxide P2O5 relative to the support, will generally be less than 15% by weight, preferably less than 10% by weight. The fillers which can be treated according to the process of the invention are advantageously fractions having relatively high pour points whose value it is desired to reduce.
Le procédé selon l'invention peut être utilisé pour traiter des charges variées allant de fractions relativement légères telles que les kérosènes et carburéacteurs jusqu'à des charges possédant des points d'ébullition plus élevés telles que les distillats moyens, les résidus sous vide, les gazoles.The process according to the invention can be used to treat various charges ranging from relatively light fractions such as kerosene and jet fuels to charges having higher boiling points such as middle distillates, vacuum residues, diesel.
La charge à traiter est dans la majeure partie des cas une coupe C-j n"1" de point d'ébullition initial supérieur à environ 175 °C, de préférence une coupe à point d'ébullition initial d'au moins 280°C. Pour la production d'huiles, on emploie des charges lourdes, c'est-à-dire constituées pour au moins 80 % en volume de composés à points d'ébullition d'au moins 350°C, de préférence entre 350-580°C, et avantageusement à au moins 380°C. Le procédé selon l'invention est particulièrement adapté pour traiter des distillats paraffiniques tels que les distillats moyens qui englobent les gazoles, les kérosènes, les carburéacteurs, pour traiter les résidus sous vide et toutes autres fractions dont le point d'écoulement et la viscosité doivent être adaptés pour rentrer dans le cadre des spécifications, et par exemple les distillats moyens issus du FCC (LCO et HCO) et les résidus d'hydrocraquage.The load to be treated is in most cases a cut C- j n "1" with an initial boiling point greater than about 175 ° C, preferably a cut with an initial boiling point of at least 280 ° C . For the production of oils, heavy fillers are used, that is to say constituted for at least 80% by volume of compounds with boiling points of at least 350 ° C., preferably between 350-580 °. C, and advantageously at least 380 ° C. The process according to the invention is particularly suitable for treating paraffinic distillates such as middle distillates which include gas oils, kerosene, jet fuels, for treating residues under vacuum and all other fractions whose pour point and viscosity must be adapted to fit within the specifications, and for example middle distillates from FCC (LCO and HCO) and hydrocracking residues.
Les charges qui peuvent être traitées selon le procédé de l'invention peuvent contenir des paraffines, des oléfines, des naphtènes, des aromatiques et aussi des hétérocycles et avec une proportion importante de n-paraffines de haut poids moléculaire et de paraffines très peu branchées également de haut poids moléculaire.The fillers which can be treated according to the process of the invention can contain paraffins, olefins, naphthenes, aromatics and also heterocycles and with a large proportion of high molecular weight n-paraffins and paraffins which are also very little branched high molecular weight.
Des charges typiques qui peuvent être traitées avantageusement selon l'invention possèdent en générai un point d'écoulement au dessus de 0°C. Les produits résultant du traitement selon le procédé ont des points d'écoulement inférieurs à 0°C et de préférence inférieurs à environ -10°C.Typical fillers which can be advantageously treated according to the invention generally have a pour point above 0 ° C. The products resulting from the treatment according to the method have pour points of less than 0 ° C and preferably less than about -10 ° C.
Ces charges possèdent des teneurs en n-paraffines, à plus de 10 atomes de carbone, de haut poids moléculaire et en paraffines, à plus de 10 atomes de carbone, très peu branchées également de haut poids moléculaire, supérieures à 30 % et jusqu'à environ 90 %, voire dans certains cas supérieures à 90 % poids. Le procédé est particulièrement intéressant lorsque cette proportion est d'au moins 60 % poids. On peut citer comme exemples d'autres charges traitables selon l'invention et à titre non limitatif, les bases pour huiles lubrifiantes, les paraffines de synthèse issues du procédé Fischer-Tropsch, les polyalphaoléfines à haut point d'écoulement, les huiles de synthèse etc.. Le procédé peut également s'appliquer à d'autres composés contenant une chaîne n-alcane tels que définis précédemment, par exemple des composés n-alkylcycloalcanes, ou comportant au moins un groupe aromatique.These charges have contents of n-paraffins, with more than 10 carbon atoms, of high molecular weight and in paraffins, with more than 10 carbon atoms, very little branched also of high molecular weight, higher than 30% and up to at around 90%, or in some cases even more than 90% by weight. The process is particularly advantageous when this proportion is at least 60% by weight. Examples of other fillers which can be treated according to the invention and that are non-limiting, may be cited, bases for lubricating oils, synthetic paraffins obtained from the Fischer-Tropsch process, polyalphaolefins with high pour point, synthetic oils etc. The process can also be applied to other compounds containing an n-alkane chain as defined above, for example n-alkylcycloalkane compounds, or comprising at least one aromatic group.
Les conditions opératoires dans lesquelles s'opère le procédé de l'invention sont les suivantes:The operating conditions under which the process of the invention operates are as follows:
- la température de réaction est comprise entre 170 et 500°C et de préférence entre 180 et 470°C, avantageusement 190-450°C ;- The reaction temperature is between 170 and 500 ° C and preferably between 180 and 470 ° C, preferably 190-450 ° C;
- la pression est comprise entre 1 et 250 bar et de préférence entre 10 et 200 bar;- the pressure is between 1 and 250 bar and preferably between 10 and 200 bar;
- la vitesse volumique horaire (wh exprimée en volume de charge injectée par unité de volume de catalyseur et par heure) est comprise entre environ 0,05 et environ 100 et de préférence entre environ 0,1 et environ 30 h"1.- The hourly volume speed (wh expressed in volume of charge injected per unit volume of catalyst and per hour) is between approximately 0.05 and approximately 100 and preferably between approximately 0.1 and approximately 30 h " 1.
Le contact entre la charge et le catalyseur est réalisé en présence d'hydrogène. Le taux d'hydrogène utilisé et exprimé en litres d'hydrogène par litre de charge est compris entre 50 et environ 2000 litres d'hydrogène par litre de charge et de préférence entre 100 et 1500 litres d'hydrogène par litre de charge.Contact between the feed and the catalyst is carried out in the presence of hydrogen. The rate of hydrogen used and expressed in liters of hydrogen per liter of charge is between 50 and approximately 2000 liters of hydrogen per liter of charge and preferably between 100 and 1500 liters of hydrogen per liter of charge.
La charge à traiter possède de préférence une teneur en composés azotés inférieure à environ 200 ppm poids et de préférence inférieure à 100 ppm poids. La teneur en soufre est inférieure à 1000 ppm poids, de préférence inférieure à 500 ppm et de manière encore plus préférée inférieure à 200 ppm poids. La teneur en métaux de la charge, tels que Ni ou V, est extrêmement réduite, c'est-à-dire inférieure à 50 ppm poids, de manière préférée inférieure à 10 ppm poids et de manière encore plus préférée inférieure à 2 ppm poids.The feed to be treated preferably has a nitrogen compound content of less than about 200 ppm by weight and preferably less than 100 ppm by weight. The sulfur content is less than 1000 ppm by weight, preferably less than 500 ppm and even more preferably less than 200 ppm by weight. The content of metals in the filler, such as Ni or V, is extremely reduced, that is to say less than 50 ppm by weight, preferably less than 10 ppm by weight and even more preferably less than 2 ppm by weight .
Dans le cas où une charge lourde est traitée pour fournir une base huile, le produit obtenu, après traitement de la charge lourde par le catalyseur à base de zéolithe NU-86, est fractionné en au moins une coupe incluant au moins un distillât moyen à point d'écoulement réduit, et en un résidu incluant les bases huiles à point d'écoulement réduit et indice de viscosité élevé.In the case where a heavy filler is treated to provide an oil base, the product obtained, after treatment of the heavy filler with the catalyst based on zeolite NU-86, is fractionated into at least one section including at least one medium distillate. reduced pour point, and a residue including oil bases with reduced pour point and high viscosity index.
Le distillât moyen peut être un kérosène (coupe généralement considérée où points d'ébullition 150 - moins de 250°C), un gasoil (coupe plus lourde que le Kérosène, généralement considérée à au moins 250°C et moins de 400CC, ou moins de 380°C). L'huile est alors dans le résidu 380 + ou 400+. les points de coupe peuvent être plus ou moins variables selon les contraintes de l'exploitant.The middle distillate can be a kerosene (generally considered cut where boiling points 150 - less than 250 ° C), a gas oil (heavier cut than kerosene, generally considered at least 250 ° C and less than 400 C C, or less than 380 ° C). The oil is then in the residue 380 + or 400+. the cutting points can be more or less variable depending on the operator's constraints.
Les exemples qui suivent illustrent l'invention sans toutefois en limiter la portée.The following examples illustrate the invention without, however, limiting its scope.
Exemple 1Example 1
La matière première utilisée est une zéolithe NU-86, qui est préparée selon l'exemple 2 du brevet EP 0 463768 A2 et possède un rapport Si/Ai atomique global égal à 10,2 et un rapport atomique Na/AI égal 0,25.The raw material used is a NU-86 zeolite, which is prepared according to Example 2 of patent EP 0 463 768 A2 and has an overall Si / Al atomic ratio equal to 10.2 and an Na / Al atomic ratio equal to 0.25 .
Cette zéolithe NU-86 subit tout d'abord une calcination dite sèche à 550°C sous flux d'air sec durant 9 heures. Puis le solide obtenu est soumis à quatre échanges ioniques dans une solution de NH4NO3 10N, à environ 100°C pendant 4 heures pour chaque échange. Le solide ainsi obtenu est référencé NH4-NU-86/I et possède un rapport Si/Ai = 10,4 et un rapport Na/AI = 0,013. Ses autres caractéristiques physicochimiques sont regroupées dans le tableau 1.This NU-86 zeolite first undergoes so-called dry calcination at 550 ° C. under a flow of dry air for 9 hours. Then the solid obtained is subjected to four ionic exchanges in a solution of NH4NO3 10N, at approximately 100 ° C. for 4 hours for each exchange. The solid thus obtained is referenced NH4-NU-86 / I and has a Si / Al ratio = 10.4 and an Na / Al ratio = 0.013. Its other physicochemical characteristics are grouped in Table 1.
Les valeurs ont été déterminées de la façon suivante :The values were determined as follows:
A partir des diagrammes de diffraction des rayons X, on mesure, pour chaque échantillon, la surface totale du signal sur une plage angulaire (2) de 6 à 40°, puis, dans la même zone, la surface des raies en nombre d'impulsions pour un enregistrement pas à pas de 3 secondes avec des pas de 0,02°(2). Le rapport de ces deux valeurs, Surface des raies/Surface totale, est caractéristique de la quantité de matière cristallisée dans l'échantillon. On compare ensuite ce rapport ou "taux de pics", pour chaque échantillon traité, au taux de pics d'une référence étalon considérée arbitrairement comme totalement (100%) cristallisée. Le taux de cristallinité est donc exprimé en pourcentage par rapport à une référence, qu'il importe de bien choisir, car l'intensité relative des raies varie en fonction de la nature, de la proportion et de la position des différents atomes dans l'unité de structure, et en particulier des cations et du structurant. Dans le cas des mesures effectuées dans les exemples de la présente description, la référence choisie est la forme calcinée sous air sec et échangée 3 fois, successivement, par une solution de nitrate d'ammonium de la zéolithe NU-86.From the X-ray diffraction diagrams, the total area of the signal is measured for each sample over an angular range (2) of 6 to 40 °, then, in the same area, the area of the lines in number of pulses for a 3 second step recording with 0.02 ° steps (2). The ratio of these two values, Line area / Total area, is characteristic of the amount of material crystallized in the sample. This ratio or "peak rate" is then compared, for each sample treated, with the peak rate of a standard reference arbitrarily considered to be totally (100%) crystallized. The degree of crystallinity is therefore expressed as a percentage relative to a reference, which it is important to choose well, because the relative intensity of the lines varies according to the nature, the proportion and position of the different atoms in the structural unit, and in particular of the cations and of the structuring. In the case of the measurements carried out in the examples of the present description, the reference chosen is the form calcined in dry air and exchanged 3 times, successively, with a solution of ammonium nitrate of the zeolite NU-86.
Il est aussi possible d'estimer le volume microporeux à partir de la quantité d'azote adsorbée à 77 K pour une pression partielle P/Po égale à 0,19, à titre indicatif.It is also possible to estimate the microporous volume from the quantity of nitrogen adsorbed at 77 K for a partial pressure P / Po equal to 0.19, for information only.
Tableau 1Table 1
Les cristallites de la zéolithe NU-86 se présentent sous forme de cristaux dont la taille varient de 0,4 μm à 2 μm.The crystallites of the NU-86 zeolite are in the form of crystals whose size varies from 0.4 μm to 2 μm.
La zéolithe NH4-NU-86/1 est malaxée avec de l'alumine de type SB3 fournie par la société Condéa. La pâte malaxée est ensuite extrudée à travers une filière de diamètre 1 ,2 mm. Les extrudés sont ensuite calcinés à 500°C durant 2 heures sous air puis imprégnés à sec par une solution de chlorure de platine tétramine [Pt(NH3)4JCl2, et enfin calcinés sous air à 550°C. La teneur en platine du catalyseur final C1 ainsi obtenu est de 0,7 % poids et la teneur en zéolithe exprimée par rapport à l'ensemble de la masse du catalyseur est de 20 % poids.The NH4-NU-86/1 zeolite is kneaded with alumina of the SB3 type supplied by the company Condéa. The kneaded dough is then extruded through a die with a diameter of 1.2 mm. The extrudates are then calcined at 500 ° C. for 2 hours in air, then impregnated to dryness with a solution of platinum chloride tetramine [Pt (NH3) 4JCl2, and finally calcined in air at 550 ° C. The platinum content of the final catalyst C1 thus obtained is 0.7% by weight and the zeolite content expressed relative to the total mass of the catalyst is 20% by weight.
Exemple 2 : Evaluation du catalyseur C1 sur un résidu d'hydrocraquageExample 2: Evaluation of the catalyst C1 on a hydrocracking residue
Le catalyseur C1 a été évalué pour traiter un résidu d'hydrocraquage issu d'un distillât sous vide.Catalyst C1 was evaluated to treat a hydrocracking residue from a vacuum distillate.
Les caractéristiques de cette charge sont les suivantes The characteristics of this charge are as follows
Le catalyseur C1 dont la préparation est décrite exemple 1 est utilisé pour préparer une huile de base à partir de la charge décrite ci-dessus.Catalyst C1, the preparation of which is described in Example 1, is used to prepare a base oil from the charge described above.
Le catalyseur est préalablement réduit sous hydrogène à 450°C avant le test catalytique in situ dans le réacteur. Cette réduction s'effectue par paliers. Elle consiste en un palier à 150°C de 2 heures, puis une montée en température jusqu'à 450°C à la vitesse de 1°C/min, puis un palier de 2 heures à 450°C. Durant ce protocole de réduction, le débit d'hydrogène est de 1000 litres d'H2 par litre de catalyseur.The catalyst is reduced beforehand under hydrogen at 450 ° C. before the catalytic test in situ in the reactor. This reduction is carried out in stages. It consists of a plateau at 150 ° C for 2 hours, then a rise in temperature to 450 ° C at the speed of 1 ° C / min, then a plateau for 2 hours at 450 ° C. During this reduction protocol, the hydrogen flow rate is 1000 liters of H2 per liter of catalyst.
La réaction a lieu à 265°C, sous une pression totale de 12 MPa, une vitesse volumique horaire 2 h"1 et un débit d'hydrogène de 1000 litres d'H2 par litre de charge. Le fractionnement de l'effiuent permet de recueillir une huile de base en tant que résidu et une coupe distillât moyen à point d'ébullition 150-400°C (400°C étant exclu) et des produits légers. Dans ces conditions opératoires la conversion nette en composés 400- (ayant un point d'ébullition inférieur à 400°C) est de 25 % poids et le rendement en huile de base est de 75 % poids.The reaction takes place at 265 ° C, under a total pressure of 12 MPa, an hourly space velocity 2 h "1, and a hydrogen flow rate of 1000 liters of H2 per liter of feed. The fractionation of the effluent allows collect a base oil as a residue and a medium distillate cut with boiling point 150-400 ° C. (400 ° C. being excluded) and light products. Under these operating conditions the net conversion into compounds 400- (having a boiling point below 400 ° C) is 25% by weight and the yield of base oil is 75% by weight.
Les caractéristiques de l'huile obtenue sont reportées dans le tableau ci-après.The characteristics of the oil obtained are given in the table below.
Le point d'écoulement du gazole est de -33°C. Cet exemple montre tout l'intérêt qu'il y a à utiliser un catalyseur selon l'invention, qui permet d'abaisser le point d'écoulement de la charge initiale, dans ce cas un résidu d'hydrocraquage, tout en conservant un haut indice de viscosité (VI).The diesel pour point is -33 ° C. This example shows all the advantage there is in using a catalyst according to the invention, which makes it possible to lower the pour point of the initial charge, in this case a hydrocracking residue, while retaining a high viscosity index (VI).
Exemple 3Example 3
La zéolithe de l'exemple 1 est utilisée.The zeolite of Example 1 is used.
Cette zéolithe NU-86 subit tout d'abord une calcination dite sèche à 550°C sous flux d'air sec durant 9 heures. Puis le solide obtenu est soumis à quatre échanges ioniques dans une solution de NH4NO3 10N, à environ 100°C pendant 4 heures pour chaque échange. Le solide ainsi obtenu est référencé NH4-NU-86 et possède un rapport Si/Ai = 10,4 et un rapport Na/AI = 0,013. Ses autres caractéristiques physicochimiques sont regroupées dans le tableau 1 . La zéolithe NU-86 est alors soumise à un traitement par une solution d'acide nitrique 6N, à environ 100°C, pendant 5 heures. Le volume V de la solution d'acide nitrique engagé (en ml) est égal à 10 fois le poids P de zéolithe NU-86 sèche (V/P = 10).This NU-86 zeolite first undergoes so-called dry calcination at 550 ° C. under a flow of dry air for 9 hours. Then the solid obtained is subjected to four ionic exchanges in a solution of NH4NO3 10N, at approximately 100 ° C. for 4 hours for each exchange. The solid thus obtained is referenced NH4-NU-86 and has a Si / Al ratio = 10.4 and an Na / Al ratio = 0.013. Its other physicochemical characteristics are grouped in Table 1. The NU-86 zeolite is then subjected to a treatment with a 6N nitric acid solution, at approximately 100 ° C., for 5 hours. The volume V of the nitric acid solution used (in ml) is equal to 10 times the weight P of dry NU-86 zeolite (V / P = 10).
A l'issue de ces traitements, la zéolithe obtenue est référencée NH4-NU-86/2. Elle possède un rapport Si/Ai atomique global égal à 34, et un rapport atomique Na/AI égal à 0,005. Ces caractéristiques cristallographiques et d'adsorption sont reportées dans le tableau 2, ci-après.At the end of these treatments, the zeolite obtained is referenced NH4-NU-86/2. It has an overall Si / Ai atomic ratio equal to 34, and an Na / Al atomic ratio equal to 0.005. These crystallographic and adsorption characteristics are reported in Table 2, below.
Tableau 2Table 2
La zéolithe est malaxée avec de l'alumine de type SB3 fournie par la société Condéa. La pâte malaxée est ensuite extrudée à travers une filière de diamètre 1 ,2 mm. Les extrudés sont ensuite calcinés à 500°C durant 2 heures sous air puis imprégnés à sec par une solution de chlorure de platine tétramine [Pt(NH3)4]Cl2, et enfin calcinés sous air à 550°C. La teneur en platine du catalyseur final ainsi obtenu est de 0,7 % poids et la teneur en zéolithe exprimée par rapport à l'ensemble de la masse du catalyseur est de 30 % poids.The zeolite is kneaded with alumina of the SB3 type supplied by the company Condéa. The kneaded dough is then extruded through a die with a diameter of 1.2 mm. The extrudates are then calcined at 500 ° C. for 2 hours in air, then impregnated to dryness with a solution of platinum chloride tetramine [Pt (NH3) 4] Cl2, and finally calcined in air at 550 ° C. The platinum content of the final catalyst thus obtained is 0.7% by weight and the zeolite content expressed relative to the total mass of the catalyst is 30% by weight.
Exemple 4Example 4
Le catalyseur a été évalué sur un résidu d'hydrocraquage issu d'un distillât sous vide pour préparer une huile de base.The catalyst was evaluated on a hydrocracking residue from a vacuum distillate to prepare a base oil.
Les caractéristiques de la charge utilisée sont reportées ci-après :The characteristics of the load used are reported below:
Le catalyseur est préalablement réduit sous hydrogène à 450°C avant le test catalytique in situ dans le réacteur. Cette réduction s'effectue par paliers. Elle consiste en un palier à 150°C de 2 heures, puis une montée en température jusqu'à 450°C à la vitesse de 1 °C/min, puis un palier de 2 heures à 450°C. Durant ce protocole de réduction, le débit d'hydrogène est de 1000 litres d'H2 par litre de catalyseur.The catalyst is reduced beforehand under hydrogen at 450 ° C. before the catalytic test in situ in the reactor. This reduction is carried out in stages. It consists of a plateau at 150 ° C for 2 hours, then a rise in temperature to 450 ° C at the speed of 1 ° C / min, then a plateau for 2 hours at 450 ° C. During this reduction protocol, the hydrogen flow rate is 1000 liters of H2 per liter of catalyst.
La réaction a lieu à 300°C, sous une pression totale de 12 MPa, une vitesse volumique horaire 1 ,8 h""' et un débit d'hydrogène de 1000 litres d'H2 par litre de charge. Dans ces conditions opératoires la conversion nette en composés 400" est de 27 % poids et le rendement en huile de base est de 73 % poids.The reaction takes place at 300 ° C, under a total pressure of 12 MPa, an hourly volume speed 1.8 h "" "and a hydrogen flow rate of 1000 liters of H2 per liter of charge. Under these operating conditions, the net conversion to 400 " compounds is 27% by weight and the yield of base oil is 73% by weight.
Les caractéristiques de l'huile obtenue sont reportées dans le tableau ci-après.The characteristics of the oil obtained are given in the table below.
Cet exemple montre tout l'intérêt qu'il y a à utiliser un catalyseur selon l'invention, qui permet d'abaisser le point d'écoulement de la charge initiale, dans ce cas un résidu d'hydrocraquage, tout en conservant un haut indice de viscosité (VI). This example shows all the advantage there is in using a catalyst according to the invention, which makes it possible to lower the pour point of the initial charge, in this case a hydrocracking residue, while retaining a high viscosity index (VI).

Claims

REVENDICATIONS
1 . Procédé pour l'amélioration du point d'écoulement d'une charge comportant des paraffines de plus de 10 atomes de carbone, dans lequel la charge à traiter est mise au contact d'un catalyseur à base de zéolithe NU-86 et au moins un élément hydro-déshydrogénant, à une température comprise entre 170 et 500°C, une pression entre 1 et 250 bar et une vitesse volumique horaire entre 0,05 et 100 h"1 , en présence d'hydrogène à raison de 50 à 2000 l/l de charge.1. Process for improving the pour point of a charge comprising paraffins of more than 10 carbon atoms, in which the charge to be treated is brought into contact with a catalyst based on zeolite NU-86 and at least one hydro-dehydrogenating element, at a temperature between 170 and 500 ° C, a pressure between 1 and 250 bar and an hourly volume speed between 0.05 and 100 h "1 , in the presence of hydrogen at a rate of 50 to 2000 l / l of charge.
2. Procédé selon la revendication 1 , dans lequel le catalyseur est à base de zéolithe NU-86 comprenant du silicium et au moins un élément T choisi dans le groupe formé par l'aluminium, le fer, le gallium et le bore, dans laquelle une partie au moins de l'élément T a été ôtée et possédant un rapport Si/T atomique global supérieur à 20.2. Method according to claim 1, in which the catalyst is based on zeolite NU-86 comprising silicon and at least one element T chosen from the group formed by aluminum, iron, gallium and boron, in which at least part of the element T has been removed and having an overall Si / T atomic ratio greater than 20.
3. Procédé selon la revendication 1 , dans lequel l'élément hydro-déshyrogénant appartient au groupe VIII.3. Method according to claim 1, wherein the hydro-dehyrogenating element belongs to group VIII.
4. Procédé selon la revendication 1 , dans lequel l'élément hydro-déshyrogénant est une combinaison d'au moins un métal ou un composé du groupe VI et d'au moins un métal ou un composé du groupe VIII.4. The method of claim 1, wherein the hydro-dehyrogenating element is a combination of at least one metal or a group VI compound and at least one metal or a group VIII compound.
5. Procédé selon l'une des revendications 1 à 3, dans lequel l'élément T est l'aluminium.5. Method according to one of claims 1 to 3, wherein the element T is aluminum.
6. Procédé selon l'une des revendications 1 à 4, dans lequel le rapport molaire Si/T est supérieur à 22.6. Method according to one of claims 1 to 4, in which the Si / T molar ratio is greater than 22.
7. Procédé selon l'une des revendications 1 à 5, dans lequel le rapport molaire Si/T est compris entre 22 et 300.7. Method according to one of claims 1 to 5, wherein the Si / T molar ratio is between 22 and 300.
8. Procédé selon l'une des revendications 1 à 6, dans lequel la zéolithe est en partie sous forme acide.8. Method according to one of claims 1 to 6, wherein the zeolite is partly in acid form.
9. Procédé selon la revendication 1 , dans lequel le catalyseur contient au moins une matrice choisie parmi les éléments du groupe formé par les argiles, la magnésie, I' alumine, la silice, l'oxyde de titane, l'oxyde de bore, la zircone, les phosphates d'aluminium, les phosphates de titane, les phosphates de zirconium et les silices- alumines et le charbon.9. The method of claim 1, wherein the catalyst contains at least one matrix chosen from the elements of the group formed by clays, magnesia, Alumina, silica, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, zirconium phosphates and silica-aluminas and carbon.
10. Procédé selon l'une des revendications précédentes, dans lequel la teneur en zéolithe dans le catalyseur est comprise entre 0,5 et 99,9% poids.10. Method according to one of the preceding claims, in which the zeolite content in the catalyst is between 0.5 and 99.9% by weight.
1 1. Procédé selon l'une des revendications précédentes, dans lequel la charge a un point d'ébullition initial supérieur à 175°C.1 1. Method according to one of the preceding claims, wherein the charge has an initial boiling point above 175 ° C.
12. Procédé selon l'une des revendications précédentes, dans lequel la charge a un point d'ébullition initial d'au moins 280°C.12. Method according to one of the preceding claims, in which the charge has an initial boiling point of at least 280 ° C.
13. Procédé selon l'une des revendications précédentes, dans lequel la charge est constituée pour au moins 80 % en volume de composés à point d'ébullition d'au moins 350°C.13. Method according to one of the preceding claims, in which the feedstock consists for at least 80% by volume of compounds with a boiling point of at least 350 ° C.
14. Procédé selon l'une des revendications précédentes, dans lequel le composé à traiter est présent dans une charge hydrocarbonée choisie dans le groupe formé par les kérosènes, les carburéacteurs, les gazoles, les résidus sous vide, les résidus d'hydrocraquage, les paraffines issues du procédé Fischer-Tropsch, les huiles de synthèse, les distillats moyens issus du FCC, les bases pour huiles, les polyalphaoléfines.14. Method according to one of the preceding claims, in which the compound to be treated is present in a hydrocarbon feedstock chosen from the group formed by kerosene, jet fuels, gas oils, vacuum residues, hydrocracking residues, paraffins from the Fischer-Tropsch process, synthetic oils, middle distillates from FCC, bases for oils, polyalphaolefins.
15. Procédé selon la revendication 13, dans lequel le produit obtenu, après traitement de la charge lourde par le catalyseur à base de zéolithe NU-86, est fractionné en au moins une coupe incluant au moins un distillât moyen à point d'écoulement réduit, et en un résidu incluant les bases huiles à point d'écoulement réduit et indice de viscosité élevé. 15. The method of claim 13, wherein the product obtained, after treatment of the heavy load with the catalyst based on zeolite NU-86, is fractionated into at least one section including at least one medium distillate with reduced pour point , and a residue including oil bases with reduced pour point and high viscosity index.
EP97947123A 1996-11-27 1997-11-21 Method for improving the pour-point of paraffin feedstock with a nu-86 zeolite based catalyst Expired - Lifetime EP0938530B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9614627 1996-11-27
FR9614627A FR2756295B1 (en) 1996-11-27 1996-11-27 PROCESS FOR IMPROVING THE FLOW POINT OF PARAFFINIC LOADS WITH A NU-86 ZEOLITE CATALYST
FR9614628 1996-11-27
FR9614628A FR2756296B1 (en) 1996-11-27 1996-11-27 PROCESS FOR IMPROVING THE FLOW POINT OF PARAFFINIC LOADS WITH A CATALYST BASED ON DEALUMINATED ZEOLITHE NU-86
PCT/FR1997/002113 WO1998023706A1 (en) 1996-11-27 1997-11-21 Method for improving the pour-point of paraffin feedstock with a nu-86 zeolite based catalyst

Publications (2)

Publication Number Publication Date
EP0938530A1 true EP0938530A1 (en) 1999-09-01
EP0938530B1 EP0938530B1 (en) 2003-05-21

Family

ID=26233128

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97947123A Expired - Lifetime EP0938530B1 (en) 1996-11-27 1997-11-21 Method for improving the pour-point of paraffin feedstock with a nu-86 zeolite based catalyst

Country Status (14)

Country Link
US (1) US5932088A (en)
EP (1) EP0938530B1 (en)
JP (1) JP3906366B2 (en)
KR (1) KR100530712B1 (en)
CN (1) CN1098334C (en)
AT (1) ATE240997T1 (en)
AU (1) AU733124B2 (en)
BR (1) BR9713447A (en)
CA (1) CA2272143A1 (en)
DE (1) DE69722235T2 (en)
ES (1) ES2199376T3 (en)
NZ (1) NZ335893A (en)
RU (1) RU2178451C2 (en)
WO (1) WO1998023706A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2755958B1 (en) * 1996-11-19 1999-01-08 Inst Francais Du Petrole DESALUMINATED ZEOLITHE NU-86 AND ITS USE IN HYDROCARBON CONVERSION
ES2205717T3 (en) * 1998-02-26 2004-05-01 Institut Francais Du Petrole CATALYST THAT INCLUDES A SELECTED ZEOLITE BETWEEN THE GROUP FORMED BY THE NU-85, AND NU-87 ZEOLITES AND ITS USE IN HYDROCONVERSION HYDROCONVERSION CARGO HYDROCONVERSION.
FR2779072B1 (en) * 1998-05-28 2000-07-13 Inst Francais Du Petrole CATALYST INCLUDING A ZEOLITH CHOSEN FROM THE GROUP FORMED BY ZEOLITHES NU-85, NU-86 AND NU-87, AN ELEMENT OF GROUP VB AND ITS USE IN HYDROCONVERSION OF HYDROCARBON OIL FEEDS
JP4267936B2 (en) * 2003-02-24 2009-05-27 新日本石油株式会社 Hydrocracking catalyst and method for producing liquid hydrocarbon
FR2984759B1 (en) * 2011-12-22 2013-12-20 IFP Energies Nouvelles CATALYST COMPRISING AT LEAST ONE NU-86 ZEOLITE, AT LEAST ONE USY ZEOLITE AND A POROUS MINERAL MATRIX AND METHOD OF HYDROCONVERSION OF HYDROCARBON LOADS USING THE CATALYST
RU2502787C1 (en) * 2012-08-27 2013-12-27 Федеральное государственное бюджетное учреждение науки Институт проблем переработки углеводородов Сибирского отделения Российской академии наук Fuel oil viscosity reduction method
RU2530000C1 (en) * 2013-07-01 2014-10-10 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук Heavy oil stock processing method
FR3049954A1 (en) * 2016-04-08 2017-10-13 Ifp Energies Now USE OF ZEOLITHE NU-86 FOR CATALYTIC CRACKING PROCESS OF NAPHTHA

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4574043A (en) * 1984-11-19 1986-03-04 Mobil Oil Corporation Catalytic process for manufacture of low pour lubricating oils
CN1016193B (en) * 1988-11-16 1992-04-08 钱任 Equipment for manufacturing elastic paper by tooth difference method
GB9013916D0 (en) * 1990-06-22 1990-08-15 Ici Plc Zeolites

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9823706A1 *

Also Published As

Publication number Publication date
RU2178451C2 (en) 2002-01-20
BR9713447A (en) 2000-03-28
EP0938530B1 (en) 2003-05-21
AU733124B2 (en) 2001-05-10
US5932088A (en) 1999-08-03
JP3906366B2 (en) 2007-04-18
WO1998023706A1 (en) 1998-06-04
KR100530712B1 (en) 2005-11-24
AU5228398A (en) 1998-06-22
CN1098334C (en) 2003-01-08
NZ335893A (en) 2000-09-29
DE69722235T2 (en) 2003-12-04
ATE240997T1 (en) 2003-06-15
CA2272143A1 (en) 1998-06-04
ES2199376T3 (en) 2004-02-16
JP2001506677A (en) 2001-05-22
KR20000069140A (en) 2000-11-25
CN1245522A (en) 2000-02-23
DE69722235D1 (en) 2003-06-26

Similar Documents

Publication Publication Date Title
EP0789739B1 (en) Selective hydroisomerisation method for straight and/or slightly branched long paraffins, using a molecular sieve catalyst
EP1265705A1 (en) Zeolite zsm-48 catalyst and method for improving paraffinic feedstock flow point
EP0863198B1 (en) Molecular sieve-based catalyst and process for the selective hydroisomeration of long straight chain and/or branched chain paraffins using this catalyst
EP0515256A1 (en) Process for the isomerisation of Fischer-Tropsch paraffins with a catalyst based on zeolite H-Y
FR2926087A1 (en) MULTI-PROCESS PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES BY HYDROISOMERIZATION AND HYDROCRACKING OF AN EFFLUENT PRODUCED BY THE FISCHER-TROPSCH PROCESS
EP0214042B1 (en) Omega structure zeolite
FR2926086A1 (en) PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES BY HYDROISOMERIZATION AND HYDROCRACKING SEQUENCES OF AN EFFLUENT PRODUCED BY THE FISCHER-TROPSCH PROCESS
EP0911380B1 (en) Process for improving the pour point of paraffinic feedstocks with zeolite IM-5 based catalysts
EP0938530B1 (en) Method for improving the pour-point of paraffin feedstock with a nu-86 zeolite based catalyst
FR2743733A1 (en) CATALYST INCLUDING A ZEOLITH OF FAUJASITE TYPE AND A ZEOLITH OF TON TYPE AND PROCESS FOR HYDROCONVERSION OF HYDROCARBON OIL FEEDS
EP1462168B1 (en) Catalyst and its use for improving the pour point of hydrocarbon feedstocks
FR2758817A1 (en) PROCESS FOR CRACKING HYDROCARBON CHARGES USING A CATALYST COMPRISING A POTENTIALLY DESALUMINATED IM-5 ZEOLITE
FR2765206A1 (en) ZEOLITHE EU-1, CATALYST AND METHOD FOR IMPROVING THE FLOW POINT CONTAINING PARAFFINS
EP0962251B1 (en) Process for improving the pour point and catalyst based on at least a MTT, TON, or FER zeolite
FR2765236A1 (en) PROCESS FOR IMPROVING THE FLOW POINT OF LOADS CONTAINING PARAFFINS WITH A MODIFIED ZEOLITH NU-87 CATALYST
FR2765207A1 (en) ZEOLITHE NU-85, CATALYST AND METHOD FOR IMPROVING THE FLOW POINT CONTAINING PARAFFINS
FR2765209A1 (en) Modified zeolite, for improving setting point of charge comprising paraffin(s)
EP1462166B1 (en) Catalyst and its use for improving the pour point of hydrocarbon feedstocks
FR2610539A1 (en) ZEOLITHE-BASED CATALYST, PREPARATION AND USE THEREOF IN PROCESSES FOR CONVERTING HYDROCARBONS
FR2758567A1 (en) PROCESS FOR CRACKING HYDROCARBON CHARGES USING A CATALYST COMPRISING A DEALUMINATED NU-86 ZEOLITE
FR2756296A1 (en) Improving flowing point of paraffin feed with zeolite based catalyst
WO2013153317A1 (en) Method for the dewaxing of hydrocarbon feedstocks using an izm-2 zeolite-based catalyst
EP0967013B1 (en) Catalyst containing a zeolite MTT, TON or FER and an element of the group VB and the use thereof for improving the pour point of hydrocarbon feedstocks
FR2765237A1 (en) Improving the setting point of paraffin charge
FR2756295A1 (en) Improving flowing point of paraffin feed with zeolite based catalyst

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990628

AK Designated contracting states

Kind code of ref document: A1

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

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20020208

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RIN1 Information on inventor provided before grant (corrected)

Inventor name: GEORGE-MARCHAL, NATHALIE

Inventor name: BENAZZI, ERIC

AK Designated contracting states

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

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

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030521

Ref country code: GB

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030521

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030521

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030521

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: FRENCH

REF Corresponds to:

Ref document number: 69722235

Country of ref document: DE

Date of ref document: 20030626

Kind code of ref document: P

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

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030821

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030821

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030821

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20030821

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

Ref country code: ES

Payment date: 20031110

Year of fee payment: 7

GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

Effective date: 20030521

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

Ref country code: LU

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

Effective date: 20031121

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

Ref country code: NL

Payment date: 20031128

Year of fee payment: 7

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

Ref country code: MC

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

Effective date: 20031130

Ref country code: LI

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

Effective date: 20031130

Ref country code: CH

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

Effective date: 20031130

Ref country code: BE

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

Effective date: 20031130

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

Ref country code: DE

Payment date: 20031204

Year of fee payment: 7

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

Ref document number: 0938530E

Country of ref document: IE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2199376

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

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

26N No opposition filed

Effective date: 20040224

BERE Be: lapsed

Owner name: INSTITUT FRANCAIS DU *PETROLE

Effective date: 20031130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: ES

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

Effective date: 20041122

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

Ref country code: NL

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

Effective date: 20050601

Ref country code: DE

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

Effective date: 20050601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20050601

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

Ref country code: IT

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

Effective date: 20051121

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20041122

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

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

Ref country code: FR

Payment date: 20101103

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20120731

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

Ref country code: FR

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

Effective date: 20111130