EP1157084B1 - Procede flexible de production d'huiles medicinales et eventuellement de distillats moyens - Google Patents

Procede flexible de production d'huiles medicinales et eventuellement de distillats moyens Download PDF

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Publication number
EP1157084B1
EP1157084B1 EP99950885A EP99950885A EP1157084B1 EP 1157084 B1 EP1157084 B1 EP 1157084B1 EP 99950885 A EP99950885 A EP 99950885A EP 99950885 A EP99950885 A EP 99950885A EP 1157084 B1 EP1157084 B1 EP 1157084B1
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Prior art keywords
line
catalyst
effluent
hydrocracking
process according
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EP99950885A
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German (de)
English (en)
French (fr)
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EP1157084A1 (fr
Inventor
Eric Benazzi
Pierre Marion
Alain Billon
Christophe Gueret
Jean-Claude Hipeaux
Jean-Paul Gouzard
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority claimed from FR9813995A external-priority patent/FR2785616B1/fr
Priority claimed from FR9814814A external-priority patent/FR2785617B1/fr
Priority claimed from FR9910222A external-priority patent/FR2797270B1/fr
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    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/304—Pour point, cloud point, cold flow properties
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4012—Pressure
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/14—White oil, eating oil

Definitions

  • the subject of the present invention is an improved process for producing base oils of very high quality, ie having a high viscosity index (VI), a low aromatic content, good UV stability and a low d from petroleum fractions with a boiling point greater than 340 ° C, possibly simultaneously with the production of middle distillates (especially gas oils, kerosene) of very high quality, that is to say having a low in aromatics and a low pour point.
  • VI viscosity index
  • lubricants are most often obtained by a succession of refining steps to improve the properties of a petroleum cut.
  • a treatment of heavy petroleum fractions with high levels of linear paraffins or little branched is necessary in order to obtain base oils of good quality and with the best possible yields, by an operation which aims to eliminate linear paraffins or very poorly connected, loads that will then be used as base oils.
  • This operation may be carried out by extraction with solvents such as toluene / methyl-ethyl ketone or methyl-isobutyl ketone mixtures, this being known as methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) dewaxing.
  • solvents such as toluene / methyl-ethyl ketone or methyl-isobutyl ketone mixtures, this being known as methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) dewaxing.
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • zeolites are among the most used catalysts.
  • Zeolite catalysts such as ZSM-5, ZSM-11, ZSM-12, ZSM22, ZSM-23, ZSM-35 and ZSM-38 have been described for use in these processes.
  • the applicant has focused its research efforts on the development of an improved process for manufacturing lubricating oils of very high quality.
  • the present invention therefore relates to a series of processes for the joint production of very high quality base oils and middle distillates (including gas oils) of very high quality.
  • the oils obtained have a high viscosity index VI), a low aromatic content, a low volatility, a good UV stability and a low pour point, from petroleum fractions having a boiling point greater than 340 ° C. .
  • the method according to the invention comprises the following steps:
  • the hydrocarbon feedstock from which the oils and possibly the middle distillates of high quality are obtained contains at least 20% boiling volume above 340 ° C.
  • Very varied loads can therefore be processed by the process.
  • the feedstock may be, for example, LCOs (light cycle oil), vacuum distillates obtained from the direct distillation of crude oil or from conversion units such as FCC, coker or visbreaking, or from extraction units. of aromatics, or derived from desulphurization or hydroconversion of RAT (atmospheric residues) and / or RSV (vacuum residues), or the charge may be a deasphalted oil, or any mixture of the aforementioned fillers.
  • LCOs light cycle oil
  • RAT atmospheric residues
  • RSV vacuum residues
  • the charge may be a deasphalted oil, or any mixture of the aforementioned fillers.
  • the fillers suitable for the objective oils have an initial boiling point above 340 ° C, and more preferably above 370 ° C.
  • the feedstock is first subjected to a hydrotreatment, during which it is brought into contact, in the presence of hydrogen, with at least one catalyst comprising an amorphous support and at least one metal having a hydro-dehydrogenating function provided, for example by at least one element of group VI B and at least one element of group VIII, at a temperature of between 330 and 450 ° C, preferably 360-420 ° C, at a pressure of 5 to 25 MPa, preferably lower at 20 MPa, the space velocity being between 0.1 and 6 h -1 , preferably 0.3-3 h -1 , and the quantity of hydrogen introduced is such that the volume ratio hydrogen / hydrocarbon is between 100 and 2000.
  • a hydrotreatment during which it is brought into contact, in the presence of hydrogen, with at least one catalyst comprising an amorphous support and at least one metal having a hydro-dehydrogenating function provided, for example by at least one element of group VI B and at least one element of group VIII, at a temperature of between 330 and 450 ° C
  • This first step makes it possible, by performing a precracking of the load to be treated, to adjust the properties of the oil base at the exit of this first step depending on the quality of the oil base that we want to obtain at the output of the process.
  • this adjustment can be made by varying the nature and quality of the catalyst used in the first step and / or the temperature of this first step, so as to raise the viscosity number for the oil base, point fraction. boiling above 340 ° C, at the exit of this step.
  • the viscosity index obtained, before dewaxing is preferably between 80 and 150, and more preferably between 90 and 140, or even 90 and 130.
  • the support generally is based on (preferably consists essentially of) alumina or amorphous silica-alumina; it may also contain boron oxide, magnesia, zirconia, titanium oxide or a combination of these oxides.
  • the hydro-dehydrogenating function is preferably filled with at least one metal or group VIII and VI metal compound preferably chosen from; molybdenum, tungsten, nickel and cobalt.
  • This catalyst may advantageously contain phosphorus; in fact, it is known in the prior art that the compound provides two advantages to hydrotreatment catalysts: an ease of preparation, especially when impregnating the nickel and molybdenum solutions, and a better hydrogenation activity.
  • the preferred catalysts are the NiMo and / or NiW catalysts on alumina, also the NiMo and / or NiW catalysts on alumina doped with at least one element included in the group of atoms formed by phosphorus, boron, silicon and fluorine, or alternatively NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-titanium oxide doped or not doped with at least one element included in the group of atoms formed by phosphorus, boron, fluorine and silicon .
  • the total concentration of metal oxides of groups VI and VIII is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of group VI on metal (or metals) of group VIII is preferably between 20 and 1.25 and even more preferably between 10 and 2.
  • the concentration of phosphorus oxide P 2 O 5 will be less than 15% by weight and preferably 10% by weight.
  • the product obtained at the end of this first step is sent to a second catalyst in a second step without intermediate separation of ammonia (NH 3 ) and hydrogen sulfide (H 2 S), nor distillation.
  • NH 3 ammonia
  • H 2 S hydrogen sulfide
  • the effluent from the first step (a) is entirely introduced onto the catalyst of the second step (b) in the presence of hydrogen where it is hydrocracked in the presence of a bifunctional catalyst comprising a zeolitic acid function and a metal function hydrodehydrogenating.
  • the polyaromatic and polynaphthoaromatic compounds partially and / or totally hydrogenated during the first step are hydrocracked on the acidic sites to give rise to the formation of paraffins.
  • These paraffins in the presence of a bifunctional catalyst can undergo isomerization and then optionally hydrocracking to lead respectively to the formation of isoparaffins and lighter cracking products.
  • the second stage catalyst comprises a zeolite, a support and a hydro-dehydrogenating function.
  • the hydro-dehydrogenating function is advantageously obtained by a combination of Group VI B metals (for example molybdenum and / or tungsten) and / or preferably non-noble Group VIII metals (for example cobalt and / or nickel) of the classification. periodic elements.
  • this catalyst may also contain at least one promoter element deposited on the surface of the catalyst, element comprised in the group formed by phosphorus, boron and silicon and advantageously phosphorus.
  • the total concentration of metals of groups VI B 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 B metals is preferably between 0.05 and 0.8; preferably between 0.13 and 0.5.
  • This type of catalyst may advantageously contain phosphorus, the content of which, expressed as phosphorus oxide P 2 O 5 relative to the support, will generally be less than 15% by weight, preferably less than 10% by weight.
  • the boron and silicon contents are less than 15% by weight and preferably less than 10% by weight (expressed as oxide).
  • the amorphous or poorly crystallized support is chosen from the group formed by alumina, silica, silica-alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, silica, clay, alone or in mixtures.
  • the zeolite is advantageously chosen from the group formed by zeolite Y (structural type FAU, faujasite) and zeolite Beta (structural type BEA) according to the nomenclature developed in "Atlas of zeolites structure types", WM Meier, DH Olson and Ch. Baerlocher, 4 th revised Edition 1996, Elsevier.
  • the weight content of zeolite is between 2 and 80% and preferably between 3 and 50% relative to the final catalyst, and advantageously between 3-25%.
  • the zeolite may optionally be doped with metal elements such as, for example, rare earth metals, especially lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium or ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
  • metal elements such as, for example, rare earth metals, especially lanthanum and cerium, or noble or non-noble metals of group VIII, such as platinum, palladium or ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
  • a particularly advantageous HY acid zeolite is characterized by various specifications: an SiO 2 / Al 2 O 3 molar ratio of between about 6 and 70 and preferably between about 12 and 50: a sodium content of less than 0.15% by weight on zeolite calcined at 1100 ° C; a crystalline parameter has elemental mesh of between 24.58 x 10 -10 m and 24.24 x 10 -10 m, and preferably between 24.38 x 10 -10 m and 24.26 ⁇ 10 -10 m; a sodium recovery CNa capacity, expressed in grams of Na per 100 grams of modified zeolite, neutralized and then calcined, greater than about 0.85; a specific surface area determined by the BET method of greater than about 400 m 2 / g and preferably greater than 550 m 2 / g, a water vapor adsorption capacity at 25 ° C.
  • a porous distribution determined by nitrogen physisorption, comprising between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores of diameter between 20 x 10 -10 m and 80 x 10 -10 m, and between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in pores of diameter greater than 80 x 10 -10 m and generally less than 1000 x 10 -10 m. the remainder of the pore volume being contained in pores with a diameter of less than 20 ⁇ 10 -10 m.
  • a preferred catalyst essentially contains at least one Group VI metal, and / or at least one non-noble Group VIII metal, zeolite Y, and alumina.
  • An even more preferred catalyst essentially contains nickel, molybdenum, zeolite Y as previously defined and alumina.
  • the pressure will be maintained between 5 and 25 MPa, advantageously between 5 and 20 MPa and preferably 7 to 15 MPa, the space velocity will be between 0.1 h -1 and 5 h -1 and preferably between 0.5 and 4 , 0 h -1 .
  • the temperature is adjusted to the second step (b), so as to obtain the desired viscosity and V.I. It is between 340 and 430 ° C, and in general it is advantageously between 370 and 420 ° C.
  • step c the effluent leaving the hydrocracker, the hydrogen is separated, the effluent is then subjected directly to an atmospheric distillation (step c) so as to separate the gases (such as ammonia and hydrogen sulphide ( H 2 S) formed, as well as other light gases that would be present, possibly hydrogen ).
  • gases such as ammonia and hydrogen sulphide ( H 2 S) formed, as well as other light gases that would be present, possibly hydrogen .
  • At least one liquid fraction containing products whose boiling point is greater than 340 ° C. is obtained.
  • This fraction has a VI, before dewaxing, of between 95 and 165 and preferably of at least 110.
  • this fraction (residue) will then be treated in the catalytic dewaxing step, that is to say without undergoing distillation under vacuum.
  • the residue undergoes, before being catalytically dewaxed, an extraction of the aromatic compounds (constituting a step (c ').
  • This extraction is carried out by any known means, the most used solvents are furfurol and N-methylpyrrolidone.
  • the naphthenoaromatic compounds are thus extracted, and the raffinate obtained has a viscosity index greater than that of the residue entering the extraction step.
  • an increases the VI of the product obtained at the end of the hydrofinishing step.
  • the cutting point is lowered, and instead of cutting at 340 ° C as before, it can for example include gas oils and possibly kerosene in the fraction containing compounds boiling above 340 ° C. For example, an initial boiling fraction of at least 150 ° C is obtained.
  • the residue can be extracted from the aromatic compounds before being catalytically dewaxed.
  • This extraction is carried out by any known means, furfurol being most often used.
  • the visual operating conditions are used.
  • the raffinate obtained has a viscosity index higher than the index of the incoming residue. This further increases the VI of the product obtained after the hydrofinition.
  • the fraction thus obtained containing the said compounds will be handled directly by catalytic dewaxing, the other fractions (150 ° C -) being or not being processed separately by catalytic dewaxing in this embodiment.
  • the fraction (s) with initial boiling point of at least 150 ° C and final up to the residue ie say generally up to 340 ° C, or preferably 370 ° C.
  • An advantage of this conversion process (hydrotreating and hydrocracking) described is that it generally makes it possible to manufacture lubricating oil bases having a viscosity greater than that obtained by an amorphous catalyst at the same conversion.
  • the viscosity at 100 ° C of the fraction of boiling point above 340 ° C unconverted, and preferably above 370 ° C is a decreasing function of the conversion level obtained.
  • this ratio is strictly less than 1, preferably between 0.95 and 0.4.
  • the fraction containing the compounds boiling above 340 ° C., as defined above, resulting from the second stage and the atmospheric distillation (c) is then subjected, at least in part, and preferably entirely, to a catalytic dewaxing step in the presence of hydrogen and a hydrodewaxing catalyst comprising an acid function and a hydro-dehydrogenating metal function and at least one matrix.
  • the acid function is provided by at least one molecular sieve whose microporous system has at least one main type of channel whose openings are formed of rings containing 10 or 9 atoms T.
  • the T atoms are the constituent tetrahedral atoms of the molecular sieve and may be at least one of the elements contained in the following set of atoms (Si, Al, P, B, Ti, Fe, Ga).
  • the atoms T In the rings constituting the channel openings, the atoms T, defined above, alternate with an equal number of oxygen atoms. It is therefore equivalent to say that the openings are formed of rings which contain 10 or 9 oxygen atoms or rings which contain 10 or 9 atoms T.
  • the molecular sieve used in the composition of the hydrodewaxing catalyst may also comprise other types of channels but the openings of which are formed of rings which contain less than 10 T atoms or oxygen atoms.
  • one of the determining factors for obtaining good catalytic performance in the third step is the use of molecular sieves having a bridge width of at most 0.75 nm, preferably between 0.50 nm and 0.75 nm, preferably between 0.52 nm and 0.73 nm.
  • the bridge width measurement is carried out using a graphic design and molecular modeling tool such as Hyperchem or Biosym, which makes it possible to construct the surface of the molecular sieves in question and, taking into account the ionic rays of the elements present in the framework of the sieve, to measure the bridge width.
  • a graphic design and molecular modeling tool such as Hyperchem or Biosym
  • the catalyst suitable for this process is characterized by a catalytic test said standard pure n-decane transformation test which is carried out under a partial pressure of 450 kPa of hydrogen and a partial pressure of 10 nC 1.2 kPa is a pressure total 451.2 kPa in a stationary bed and at a rate of 10 nC constant of 9.5 ml / h, a total flow of 3.6 l / h and a catalyst mass of 0.2 g.
  • the reaction is carried out in downflow.
  • the conversion rate is set by the temperature at which the reaction takes place.
  • the catalyst subjected to said test consists of pure zeolite and 0.5% by weight of platinum.
  • n-decane in the presence of the molecular sieve and a hydro-dehydrogenating function will undergo hydroisomerization reactions which will produce isomerized products with 10 carbon atoms, and hydrocracking reactions leading to the formation of products containing less than 10 carbon atoms.
  • a molecular sieve used in the hydrodewaxing step according to the invention must have the physicochemical characteristics described above and lead, for a yield of isomerized products of nC 10 of the order of 5% by weight (the conversion rate is controlled by the temperature) at a ratio of 2-methylnonane / 5-methylnonane greater than 5 and preferably greater than 7.
  • molecular sieves thus selected, under the conditions described above, from among the numerous molecular sieves already in existence, makes it possible in particular to produce low pour point and high viscosity index products with good yields in the context of process according to the invention.
  • the molecular sieves that may be included in the composition of the catalytic hydrodewaxing catalyst are, by way of examples, the following zeolites: Ferrierite, NU-10, EU-13, EU-1 and zeolites of the same structural type.
  • the molecular sieves used in the composition of the hydrodewaxing catalyst are included in the group formed by ferrierite and zeolite EU-1.
  • the weight content of molecular sieves in the hydrodewaxing catalyst is between 1 and 90%, preferably between 5 and 90% and even more preferably between 10 and 85%.
  • the matrices used to carry out the shaping of the catalyst are, by way of examples and in a nonlimiting manner, alumina gels, aluminas, magnesia, amorphous silica-aluminas, and mixtures thereof. Techniques such as extrusion, pelletizing or coating may be used to perform the shaping operation.
  • the catalyst also comprises a hydro-dehydrogenating function ensured, for example, by at least one group VIII element and preferably at least one element comprised in the group consisting of platinum and palladium.
  • the weight content of non-noble metal of group VIII, relative to the final catalyst, is between 1 and 40%, preferably between 10 and 30%.
  • the non-noble metal is often associated with at least one Group VIB metal (Mo and W preferred).
  • the weight content, relative to the final catalyst is less than 5%, preferably less than 3% and even more preferably less than 1.5. %.
  • platinum and / or palladium are preferably located on the matrix, defined as above.
  • the hydrodewaxing catalyst according to the invention may also contain from 0 to 20%, preferably from 0 to 10% by weight (expressed as oxides) phosphorus.
  • the combination of Group VIB metal (s) and / or Group VIII metal (s) with phosphorus is particularly advantageous.
  • the hydrocracking residue (that is to say the fraction with an initial boiling point greater than 340 ° C.) obtained in step (c) of the process according to the invention and which is to be treated in this stage ( d) of hydrodewaxing, has the following characteristics: it has, an initial boiling point greater than 340 ° C and preferably greater than 370 ° C, a pour point of at least 15 ° C, a content of nitrogen less than 10 ppm weight a sulfur content of less than 50 ppm by weight, or better still 10 ppm by weight, a viscosity number of 35 to 165 (before dewaxing), preferably at least 110 and even more preferably less than 150, an aromatic content of less than 10% by weight, a viscosity at 100 ° C of greater than or equal to 3 cSt (mm 2 / s).
  • the contact between the feed entering dewaxing and the catalyst is carried out in the presence of hydrogen.
  • the level of hydrogen used and expressed in liters of hydrogen per liter of filler is between 50 and about 2000 liters of hydrogen per liter of filler and preferably between 100 and 1500 liters of hydrogen per liter of filler.
  • the effluent leaving the catalytic hydrodewaxing step is, in its entirety and without intermediate distillation, sent to a hydrofinishing catalyst in the presence of hydrogen so as to carry out a thorough hydrogenation of the aromatic compounds which adversely affect the stability oils and distillates.
  • the acidity of the catalyst must be low enough not to lead to the formation of cracking product boiling point below 340 ° C so as not to degrade the final yields including oils.
  • the catalyst used in this step comprises at least one Group VIII metal and / or at least one Group VIB element of the Periodic Table.
  • amorphous or crystalline oxide type support such as, for example, aluminas, silicas, silica-aluminas.
  • the hydrofinishing catalyst (HDF) may also contain at least one element of group VII A of the periodic table of elements.
  • these catalysts contain fluorine and / or chlorine.
  • the weight contents of metals are between 10 and 30% in the case of non-noble metals and less than 2%, preferably between 0.1 and 1.5%, and even more preferably between 0.1. and 1.0% in the case of noble metals.
  • the total amount of halogen is between 0.02 and 30 wt.%, Advantageously 0.01 to 15 wt.%, Or even 0.01 to 10 wt.%, Preferably 0.01 to 5 wt.
  • group VIII platinum for example
  • halogen chlorine and / or fluorine
  • the contact between the feedstock and the catalyst is carried out in the presence of hydrogen.
  • the level of hydrogen used and expressed in liters of hydrogen per liter of filler is between 50 and about 2000 liters of hydrogen per liter of filler and preferably between 100 and 1500 liters of hydrogen per liter of filler.
  • the temperature of the HDF step is lower than the temperature of the catalytic hydrodewaxing step (HDPC).
  • the difference T HDPC -T HDF is generally between 20 and 200, and preferably between 30 and 100 ° C.
  • the effluent leaving the HDF stage is sent to the distillation train, which incorporates atmospheric distillation and vacuum distillation, the purpose of which is to separate the conversion products with a boiling point below 340. ° C and preferably below 370 ° C, (and including in particular those formed during the catalytic hydrodewaxing step (HDPC)), the fraction which constitutes the oil base and whose initial boiling point is greater than 340 ° C and preferably greater than 370 ° C.
  • the distillation train which incorporates atmospheric distillation and vacuum distillation, the purpose of which is to separate the conversion products with a boiling point below 340. ° C and preferably below 370 ° C, (and including in particular those formed during the catalytic hydrodewaxing step (HDPC)), the fraction which constitutes the oil base and whose initial boiling point is greater than 340 ° C and preferably greater than 370 ° C.
  • this vacuum distillation section makes it possible to separate the different grades of oils.
  • the base oils obtained according to this process have a pour point of less than -10 ° C, a weight content of aromatic compounds of less than 2%, a VI greater than 95, preferably greater than 110 and even more preferably higher than at 120, a viscosity of at least 3.0 cSt at 100 ° C, an ASTM color of less than 1 and a UV stability such that the increase in color ASTM is between 0 and 4 and preferably between 0, 5 and 2.5.
  • Another advantage of the process according to the invention is that it is possible to achieve very low aromatics contents, less than 2% by weight, preferably 1% by weight and better still less than 0.05% by weight, and even of go to the production of medicinal grade white oils with aromatic contents of less than 0.01% by weight.
  • These oils have UV absorbance values at 275, 295 and 300 nanometers respectively less than 0.8, 0.4 and 0.3 (ASTM D2008 method) and a Saybolt color between 0 and 30.
  • the process according to the invention also makes it possible to obtain medicinal white oils.
  • Medical white oils are mineral oils obtained by advanced petroleum refining, their quality is subject to various regulations that aim to ensure their safety for pharmaceutical applications, they are devoid of toxicity and are characterized by their density and viscosity.
  • White medicinal oils mainly comprise saturated hydrocarbons, they are chemically inert and their content of aromatic hydrocarbons is low. Particular attention is paid to aromatic compounds and in particular to 6 polycyclic aromatic hydrocarbons (PAHs for the abbreviation of polycyclic aromatic hydrocarbons) which are toxic and present at concentrations of one part per billion by weight of aromatic compounds in the form of polycyclic aromatic hydrocarbons. white oil.
  • PAHs polycyclic aromatic hydrocarbons
  • the control of the total aromatic content can be carried out by the ASTM D 2008 method, this UV adsorption test at 275, 292 and 300 nanometers makes it possible to control an absorbance less than 0.8, 0.4 and 0.3 respectively. (That is, the white oils have aromatic contents of less than 0.01% by weight). These measurements are made with concentrations of 1g of oil per liter, in a 1 cm tank.
  • the white oils marketed differ in their viscosity but also in their original crude which can be paraffinic or naphthenic, these two parameters will induce differences both in the physicochemical properties of the white oils considered but also in their chemical composition .
  • oil cuts whether from direct distillation of a crude oil followed by extraction of the aromatic compounds by a solvent, or from catalytic hydrorefining or hydrocracking processes, still contain significant amounts of aromatic compounds.
  • medicinal white oils must have an aromatic content lower than a threshold imposed by the legislation of each country.
  • the absence of these aromatic compounds in the oil cuts results in a Saybolt color specification which must be substantially at least 30 (+30), a maximum UV adsorption specification which must be less than 1.60-275. nm on a 1 centimeter pure vessel product and a maximum specification of DMSO extraction product absorption which must be less than 0.1 for the US market (Food and Drug Administration, standard 1211145).
  • the latter test consists in extracting polycyclic aromatic hydrocarbons specifically using a polar solvent, often DMSO, and controlling their content in the extract by a UV absorption measurement in the range 260-350 nm.
  • the average distillates obtained have improved pour points (less than or equal to -20 ° C.), low aromatics contents (at most 2% by weight), polyaromatic (di and more) contents of less than 1% by weight and for gas oils, a cetane number greater than 50, and even greater than 52.
  • Another advantage of the process according to the invention is that the total pressure can be the same in all reactors hence the possibility of working in series and use a single unit and thus generate cost savings.
  • FIGS. 1 and 2 The process is illustrated in FIGS. 1 and 2, FIG. 1 representing the treatment of the entire liquid fraction in hydrodewaxing and FIG. 2 that of a hydrocracking residue.
  • the charge enters via the pipe (1) in a hydrotreatment zone (2) (Which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts) in which hydrogen enters (for example via line (3)) and where step (a) is carried out. ) hydrotreatment.
  • a hydrotreatment zone (2) Which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts in which hydrogen enters (for example via line (3)) and where step (a) is carried out. ) hydrotreatment.
  • the hydrotreated feed is transferred via line (4) to the hydrocracking zone (5) (which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts) where, in the presence of hydrogen is hydrocracking step (b).
  • the hydrocracking zone (5) which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts
  • the effluent from the zone (5) is sent via a pipe (6) into a flask (7) for separating the hydrogen which is extracted via a pipe (8), the effluent is then distilled at atmospheric pressure in the column (9) from which is extracted at the top by the pipe (10) the gaseous fraction. Step (c) of the process is thus carried out.
  • a liquid fraction containing the compounds with a boiling point greater than 340 ° C. is obtained at the bottom of the column. This fraction is evacuated via line (11) to the catalytic dewaxing zone (12).
  • the catalytic dewaxing zone (12) (comprising one or more reactors, one or more than one catalytic bed of one or more catalysts) also receives hydrogen through a line (13) to perform step (d) of the process.
  • the effluent leaving this zone via a pipe (14) is sent directly to the hydrofinishing zone (15) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) from which it emerges from driving (16). Hydrogen may be added if necessary in the zone (15) where step (e) of the process is carried out.
  • the effluent obtained is separated in a distillation train (process step f) comprising in addition to the flask (17) to separate the hydrogen by a line (18), an atmospheric distillation column (19) and a vacuum column ( 20) which treats the atmospheric distillation residue transferred via line (21), which has an initial boiling point of greater than 340 ° C.
  • FIG. 2 shows the markings of FIG. 1.
  • the difference lies in the distillation of the effluent resulting from the hydrocracking step (b) which leaves via the pipe (6). After separation of the hydrogen in the flask (7), it is removed by atmospheric distillation in a column (9) gases which are extracted by the pipe (10). The distillation is carried out so as to obtain a residue with an initial boiling point greater than 340 ° C. leaving via the pipe (11), and to obtain the gasoil (line 28), kerosene (line 29) and gasoline (line 30) fractions. ).
  • the operator will adapt the recycling rate to its "products" objective to favor obtaining oils or rather that of middle distillates.
  • hydrotreating and hydrocracking zones are in the same reactor. Therefore, the transfer of the hydrotreated effluent is done directly in the absence of pipe (4). Recycling the effluent is still possible either to the hydrotreatment zone (upstream of a catalyst bed) or to the hydrocracking zone.
  • the residue leaving the line (11) and having an initial boiling point greater than 340 ° C. is sent at least in part in an additional hydrocracking zone (32) different from the zone (5) (comprising one or more reactors, one or more catalytic beds of one or more catalysts).
  • This other hydrocracking zone may contain the same catalyst as zone (5) or another catalyst.
  • the resulting effluent is recycled to the atmospheric distillation step.
  • the remaining portion of the initial boiling point residue greater than 340 ° C is transferred to the catalytic dewaxing step.
  • the residue leaving the column (9) through the pipe (11) is sent to the other zone (32) of hydrocracking, from which emerges an effluent in a pipe (33) which is recycled in the column (9) .
  • a line (34) connected to the line (11) delivers the residue that is sent to the dewaxing zone (12).
  • FIG. 3 also shows the production in the same reactor (31) of zones (2) for hydrotreatment and (5) hydrocracking, but separate zones are quite possible in combination with the additional zone (32). hydrocracking.
  • the conversion assembly of FIG. 3 can thus substitute for the conversion assembly of FIG. 2, the hydrodewaxing, hydrofinishing and distillation train stages being unchanged. All the complementary possibilities (recycling H2 ..) are transposable.
  • the residue leaving the pipe (11) is sent to the aromatics extraction unit (35) provided with a pipe (36) for the entry of the solvent, d. a line (37) for the exit of the solvent and a line (38) through which the raffinate flows into the catalytic dewaxing zone (12).
  • This variant (corresponding to step (c ') of the process) is shown in FIG. 4.
  • the upstream and downstream treatments are those of the process such as for example illustrated in FIGS. 2 or 3.
  • the invention thus also relates to an installation in which zones (2) and (3) are located in the same reactor provided with at least one a pipe (1) for the entry of the feedstock, at least one pipe (3) for the entry of hydrogen, and at least one pipe (6) for the outlet of the hydrocracked effluent, said plant further comprising at least one additional hydrocracking zone (32) provided with at least one pipe (11) for admitting the residue from the atmospheric distillation column (9), and at least one pipe (33). ) for the outlet of the effluent thus hydrocracked, said pipe (33) opening into the pipe (6) for recycling said effluent, and furthermore the installation comprises at least one pipe (34) located on the pipe (11) for transfer the residue to the extraction unit (35).
  • the hydrocracking residue is obtained by hydrocracking of a vacuum distillate whose composition is given in Table 1.
  • the space velocity is then 1 h -1 on this catalyst.
  • the reaction temperature is 315 ° C.
  • a second reactor located after this first reactor a catalyst containing 1% by weight of pI, 1% by weight of IC on alumina is charged.
  • the product from the first reactor is introduced into the second reactor which is maintained at a temperature of 220 ° C.
  • the pressure is 14 MPa and the product circulates at a space velocity of 0.5h -1
  • the effluent is recovered and then distilled under vacuum.
  • Table 1 The characteristics of the residue 375 ° C + are reported in Table 1.
  • Example 2 The test of the carbonizable materials on the dewaxed and hydrofini residue produced in Example 2 obeys the standard in force. In addition, the UV absorption at 275 nm on pure product, in 1 cm vat, is 1.2 therefore lower than the norm.

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  • Chemical & Material Sciences (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)
  • Lubricants (AREA)
  • Catalysts (AREA)
EP99950885A 1998-11-06 1999-10-29 Procede flexible de production d'huiles medicinales et eventuellement de distillats moyens Expired - Lifetime EP1157084B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FR9813995A FR2785616B1 (fr) 1998-11-06 1998-11-06 Procede flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite
FR9813995 1998-11-06
FR9814814A FR2785617B1 (fr) 1998-11-06 1998-11-24 Procede flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite
FR9814814 1998-11-24
FR9910222 1999-08-02
FR9910222A FR2797270B1 (fr) 1999-08-02 1999-08-02 Procede et flexible de production de bases huiles et eventuellement de distillats moyens de tres haute qualite
PCT/FR1999/002654 WO2000027950A1 (fr) 1998-11-06 1999-10-29 Procede flexible de production d'huiles medicinales et eventuellement de distillats moyens

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EP1157084B1 true EP1157084B1 (fr) 2006-06-28

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KR (1) KR100603225B1 (zh)
CN (1) CN100457866C (zh)
BR (1) BR9915120B1 (zh)
CZ (1) CZ303253B6 (zh)
DE (1) DE69932186T2 (zh)
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CN102226104A (zh) * 2011-05-23 2011-10-26 大连理工大学 一种利用废润滑油生产汽柴油的方法
CZ303253B6 (cs) * 1998-11-06 2012-06-20 Institut Francais Du Petrole Zpusob výroby oleju a stredních destilátu vysoké kvality a zarízení k provádení tohoto zpusobu

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FR2812301B1 (fr) * 2000-07-26 2003-04-04 Inst Francais Du Petrole Procede flexible de production de bases huiles et de distillats moyens a partir de charge contenant des heteroatomes
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WO2005085394A1 (en) * 2004-03-02 2005-09-15 Shell Internationale Research Maatschappij B.V. Process to continuously prepare two or more base oil grades and middle distillates
JP4850472B2 (ja) * 2005-09-21 2012-01-11 出光興産株式会社 プロセスオイルの製造方法
CN101210195B (zh) * 2006-12-27 2012-05-30 中国石油化工股份有限公司 一种由劣质重质原料多产化工轻油的加氢裂化方法
US7594991B2 (en) 2007-12-28 2009-09-29 Exxonmobil Research And Engineering Company All catalytic medicinal white oil production
US8394255B2 (en) * 2008-12-31 2013-03-12 Exxonmobil Research And Engineering Company Integrated hydrocracking and dewaxing of hydrocarbons
US9334451B2 (en) 2010-03-15 2016-05-10 Saudi Arabian Oil Company High quality middle distillate production process
CN103949280B (zh) * 2014-05-14 2016-04-13 武汉凯迪工程技术研究总院有限公司 适于生物质费托合成油生产航空煤油的催化剂及其制备方法
FR3071849A1 (fr) * 2017-09-29 2019-04-05 IFP Energies Nouvelles Procede de production amelioree de distillats moyens par hydrocraquage deux etapes de distillats sous vide

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CZ303253B6 (cs) * 1998-11-06 2012-06-20 Institut Francais Du Petrole Zpusob výroby oleju a stredních destilátu vysoké kvality a zarízení k provádení tohoto zpusobu
CN102226104A (zh) * 2011-05-23 2011-10-26 大连理工大学 一种利用废润滑油生产汽柴油的方法

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BR9915120A (pt) 2002-01-08
ES2267296T3 (es) 2007-03-01
KR100603225B1 (ko) 2006-07-24
CN100457866C (zh) 2009-02-04
CZ20011573A3 (cs) 2001-11-14
KR20010100987A (ko) 2001-11-14
EP1157084A1 (fr) 2001-11-28
WO2000027950A1 (fr) 2000-05-18
CZ303253B6 (cs) 2012-06-20
DE69932186D1 (de) 2006-08-10
JP4496647B2 (ja) 2010-07-07
DE69932186T2 (de) 2006-11-23
JP2002539277A (ja) 2002-11-19
BR9915120B1 (pt) 2010-12-14

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