EP1307526B1 - Flexible method for producing oil bases and distillates from feedstock containing heteroatoms - Google Patents

Flexible method for producing oil bases and distillates from feedstock containing heteroatoms Download PDF

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EP1307526B1
EP1307526B1 EP01958156A EP01958156A EP1307526B1 EP 1307526 B1 EP1307526 B1 EP 1307526B1 EP 01958156 A EP01958156 A EP 01958156A EP 01958156 A EP01958156 A EP 01958156A EP 1307526 B1 EP1307526 B1 EP 1307526B1
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Prior art keywords
pipe
effluent
catalyst
separation
removal
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German (de)
French (fr)
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EP1307526A1 (en
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Eric Benazzi
Christophe Gueret
Pierre Marion
Alain Billon
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority to FR0009812A priority patent/FR2812301B1/en
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Priority to PCT/FR2001/002390 priority patent/WO2002008363A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton

Description

  • The present invention describes an improved process for manufacturing base oils of very high quality that is to say having a high viscosity index (VI), a low aromatic content, good UV stability and a low pour point from petroleum fractions having an initial boiling point of 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 aromatic and a low pour point.
  • More specifically, the invention relates to a flexible process for the production of base oils and middle distillates from a feedstock containing heteroatoms (eg N, S, O ... and preferably free of metals), that is, containing more than 200 ppm of nitrogen and more than 500 ppm of sulfur. The process comprises at least one hydrorefining step, at least one catalytic zeolite dewaxing step and at least one hydrofinishing step.
  • Prior art
  • The patent US-5,976,354 discloses a process for producing oils comprising these 3 steps.
  • The first step carries out denitrogenation and desulfurization of the feedstock in the presence of a non-noble metal catalyst of groups VIII and / or VI B and of alumina or silica-alumina support, the preferred catalysts being prepared by impregnation of the support. preformed.
    The effluent obtained, after stripping the gases, is treated in the catalytic dewaxing step based on zeolite ZSM-5, ZSM-35 or SAPO type molecular sieve, the catalyst also containing at least one catalytic metal hydrogenating. The process ends with a hydrofinishing step to saturate the aromatics with a catalyst comprising Pt and Pd oxides on alumina, or with the aid of a preferred catalyst based on zeolite Y.
  • In a communication from DV Law at the 7th Refinery Technology Meeting in Bombay, 6-8 December 1993 a process for producing oils and middle distillates is described.
  • It comprises a first hydrocracking step performing denitrogenation, cracking of low VI components (viscosity index) and a rearrangement (aromatic saturation, naphthenic ring opening) producing high VI compounds.
    This step is conducted in the presence of a cogel type catalyst having a high uniform dispersion of hydrogenating element and a unique distribution of pore sizes. Such catalysts are said to be clearly superior to the catalysts obtained by impregnating the support. One example is the catalyst ICR106. The effluent obtained is distilled, the naphtha, jet fuel, diesel sections are separated as well as the gases, and the remaining fractions (neutra oils and bright stock) are treated with catalytic dewaxing.
  • In this step is carried out an isomerization of n-paraffins on an ICR 404 catalyst. The process also ends with a hydrofinishing step.
  • Other information is given on the implementation of the dewaxing and hydrofinishing stages. It is stated that the VI of the final oil increases with the wax content of the feed and the severity of the hydrocracking.
  • The patent US 4,699,707 describes a process for producing oil bases from a particular charge of the "shale oil" type. The method successively implements catalytic dewaxing and hydrogenation hydrotreatment steps. In the catalytic dewaxing step, the catalyst used is based on silicalite or ZSM-5 type zeolite.
  • Object of the invention
  • The applicant has focused its research efforts on the development of an improved process for the manufacture of lubricating oils and in particular of very high quality oils.
    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, from petroleum fractions having an initial boiling point greater than 340 ° C. The oils obtained have a high viscosity index VI, a low aromatic content, low volatility, good UV stability and a low point. flow.
    The present application proposes an alternative process to the processes of the prior art which, by a particular choice of catalysts and conditions, makes it possible to produce oils and middle distillates of good quality, under mild conditions and with important cycle times. .
    In particular and contrary to conventional process sequences or from the state of the prior art, this process is not limited in the quality of the oil products it provides; in particular, a judicious choice of the operating conditions makes it possible to obtain medicinal white oils (that is to say excellent qualities).
  • The subject of the request is defined in the independent claims language.
  • The dependent claims contain additional features of the invention.
  • More specifically, the invention relates to a process for the production of oils and middle distillates from a feedstock containing more than 200ppm nitrogen weight and more than 500ppm sulfur weight, and of which at least 20% by volume above 340 ° C, the feedstock is selected from the group consisting of vacuum distillates from direct distillation of crude or conversion units, hydrocracking residues, vacuum distillates from desulfurization or hydroconversion of atomospheric residues or vacuum residues of deasphalted oils or mixtures thereof, comprising the following steps:
  1. (a) hydrorefining of the feed, carried out at a temperature of 330 ° -450 ° C, under a pressure of 5-25 MPa, with a space velocity of 0.1-10h -1 in the presence of hydrogen in the volumetric ratio hydrogen / hydrocarbon of 100-2000, and in the presence of an amorphous catalyst comprising a support and at least one non-noble group VIII metal, at least one Group VI B metal, and at least one doping element chosen from the group formed by phosphorus, boron and silicon,
  2. (b) from the effluent obtained in step (a) separation of at least gases and compounds with a boiling point below 150 ° C, optionally including vacuum distillation,
  3. (c) catalytic dewaxing of at least a portion of the effluent at the end of step (b) and which contains compounds with a boiling point greater than 340 ° C., produced at a temperature of 200-500 C., under a total pressure of 1-25 MPa, with an hourly space velocity of 0.054-50 h -1 , with 50-2000 l of hydrogen / l of filler, and in the presence of a catalyst comprising at least one hydro-dehydrogenating element and at least one molecular sieve, selected from the group of zeolites formed by Ferrierite, NU-10, EU-13, EU-1, ZSM-48,
  4. (d) hydrofinishing at least a portion of the effluent from step (c) carried out at a temperature of 180-400 ° C, under a pressure of 1-25 MPa, with an hourly space velocity of 0.05 -100h -1 , in the presence of 50-2000 l of hydrogen / l of filler, and in the presence of an amorphous catalyst for the hydrogenation of aromatics comprising at least one hydro-dehydrogenating metal and at least one halogen.
  5. (e) separating the effluent obtained in step (d) to obtain at least one oil fraction, said separation including vacuum distillation.
  • Generally, the effluent resulting from the hydrofinishing treatment is subjected to a distillation step comprising an atmospheric distillation and a vacuum distillation so as to separate at least one initial boiling point oil fraction greater than 340 ° C., and which of Preferably, has a pour point of less than -10 ° C, a weight content of aromatic compounds of less than 2%, and a VI greater than 95, a viscosity at 100 ° C of at least 3cSt (ie 3mm 2 / s ) and optionally separating at least one preferably distillate middle fraction having a pour point less than or equal to -10 ° C and preferably -20 ° C, an aromatics content of at most 2 wt% and a polyaromatic content of not more than 1% by weight.
  • Detailed description of the invention
  • The method according to the invention comprises the following steps:
  • Step (a): Hydrifrocessing
  • 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, vacuum distillates obtained from the distillation directly from the crude or from conversion units such as FCC, coker or visbreaking, or from desulphurization or hydroconversion of RAT (atmospheric residues) and / or RSV (residues under vacuum), hydrocracking residues or the charge may be a deasphalted oil, or any mixture of the aforementioned fillers. The list above is not exhaustive. In general, the fillers suitable for the objective oils have an initial boiling point above 340 ° C, and more preferably above 370 ° C.
  • The nitrogen content of the filler is generally greater than 200 ppm by weight, preferably greater than 400 ppm by weight and even more preferably greater than 500 ppm by weight. The sulfur content of the filler is generally greater than 500 ppm by weight and most often greater than 1% by weight.
  • The filler, optionally comprising a mixture of the abovementioned fillers, is first subjected to hydrorefining, 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 group VI B element and at least one group VIII element, at a temperature between 330 and 450 ° C, preferably 360-420 ° C under a pressure between 5 and 25 MPa, preferably less than 20 MPa, the space velocity being between 0.1 and 10 h -1 and advantageously between 0.1 and 6 h -1 , preferably between 0.3 and 3 h -1 , and the amount of hydrogen introduced is such that the volume ratio hydrogen / hydrocarbon is between 100 and 2000.
  • During the first stamp, the use of a catalyst favoring hydrogenation over cracking, used under appropriate thermodynamic and kinetic conditions, allows a significant reduction in the content of condensed polycyclic aromatic hydrocarbons. Under these conditions, most of the nitrogen and sulfur products in the feed are also processed. This operation therefore makes it possible to largely eliminate two types of compounds; the aromatic compounds and the organic nitrogen compounds initially present in the feedstock.
  • Given the presence of organic sulfur and nitrogen present in the The charge of the catalyst of step (a) will operate in the presence of significant amounts of NH 3 and H 2 S respectively from the hydrodenitrogenation and hydrodesulfurization of the organic and organic sulfur compounds present in the feed.
  • In this first step, which performs hydrodenitrogenation, hydrodesulphurization, hydrogenation of the aromatics and cracking of the feedstock to be treated, the feed is purified while simultaneously making it possible to adjust the properties of the oil base at the outlet of this first step. depending on the quality of the oil base that we want to obtain at the end of the process. Advantageously, 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 cracking and therefore the viscosity number of the oil base. . If we consider the fraction of initial boiling point greater than 340 ° C (or 370 ° C), at the exit of this step, its viscosity index obtained after solvent dewaxing (methyl isobutyl ketone) to about -20 ° C, is preferably between 80 and 150, and better still between 90 and 140, or even 90 and 135. To obtain such indices, in general the conversion of the feedstock into cracking products, with boiling points below 340 ° C. C (see 370 ° C.) is at most equal to approximately 60% by weight, or even at most 50% by weight.
  • 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. Preferably, the support is acidic. The hydro-dehydrogenated functional group is preferably filled with at least one metal or group VIII and VI metal compound, preferably chosen from among; molybdenum, tungsten, nickel and cobalt.
  • This catalyst may advantageously contain at least one element comprised in the assembly formed by the elements phosphorus, boron and silicon.
  • 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, or the NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-titanium oxide doped with at least one element included in the group of atoms formed by phosphorus, boron and silicon .
  • The most preferred catalysts are those containing phosphorus, those containing phosphorus and boron, those containing phosphorus, boron and silicon, as well as those containing boron and silicon. The catalysts which are suitable for carrying out the process according to the invention may also advantageously contain at least one element of the VB group (Niobium for example) and / or at least one element of group VII A (for example fluorine) and / or least one element of group VII B (rhenium, manganese for example).
  • Preferably, phosphorus, boron, silicon are introduced as a promoter element.
  • The promoter element, and in particular the silicon introduced on the support according to the invention, is mainly located on the matrix of the support and may be characterized by techniques such as the Castaing microprobe (distribution profile of the various elements), transmission electron microscopy coupled with X analysis of the catalyst components, or even by mapping the distribution of the elements present in the catalyst by electron microprobe. These local analyzes will provide the location of the various elements, in particular the location of the promoter element, in particular the location of the amorphous silica due to the introduction of silicon onto the matrix of the support. The localization of the silicon in the framework of the zeolite contained in the support is also revealed. In addition, a quantitative estimate of the local silicon contents and other elements can be made.
    On the other hand, the magnetic NMR of the 29 Si spinning at the magic angle is a technique that can detect the presence of amorphous silica introduced into the catalyst.
  • The total concentration of metal oxides of groups VIB (W, Mo preferred) and VIII (Co, Ni preferred) is between 1-40%, or even 5 and 40% by weight and preferably between 7 and 30% and the ratio weight expressed as oxide Group VIII metal (or metals) metal group (or metals) is preferably between 20 and 1.25 and even more preferably between 10 and 2. The content of the doping element catalyst is at least 0, 1% weight and is less than 60%. The content of the phosphorus (oxide) catalyst is generally at most 20% by weight, preferably 0.1-15%, the boron (oxide) content is generally at most 20% by weight, preferably 0% by weight. , 1-15%, and the silicon content (oxidized and off-matrix) is generally at most 20% by weight, preferably 0.1-15%.
  • The content of the Group VII A element catalyst is at most 20% by weight, preferably 0.1-15%, the Group VII B element content is at most 50% by weight, preferably 0% by weight. , 01-30% and the element content of Group VB of at most 60% by weight, preferably 0.1-40%.
  • Thus advantageous catalysts according to the invention contain at least one element chosen from Co and Ni, at least one element chosen from Mo and W, and at least one doping element chosen from P, B, Si, said elements being deposited on a support .
    Other preferred catalysts contain, as doping elements, phosphorus and boron deposited on an alumina-based support.
    Other preferred catalysts contain, as doping elements, boron and silicon deposited on an alumina-based support.
  • Other preferred catalysts also contain phosphorus in addition to boron and / or silicon.
    Preferably, all these catalysts contain at least one element of GVIII selected from Co and Ni, and at least one element of GVIB selected from W and Mo.
  • Step (b): Separation step of the formed products
  • The effluent obtained at the end of this first step is sent (step b) to a separation train comprising a gas separation means (for example a gas-liquid separator) for separating gases such as hydrogen, hydrogen sulphide (H 2 S), ammonia (NH 3 ) formed, and gaseous hydrocarbons up to 4 carbon atoms. At least one effluent containing the products with a boiling point above 340 ° C. is then recovered.
  • Advantageously, after the gas-liquid separation, the effluent undergoes a separation of compounds with a boiling point below 150 ° C. (gasoline), generally carried out by stripping and / or atmospheric distillation.
    Preferably, the separation step (b) is terminated by vacuum distillation.
  • The separation train can therefore be realized in different ways.
    It may for example comprise a stripper to separate the gasoline formed during step (a) and the resulting effluent is sent to a vacuum distillation column to recover at least one oil fraction and also the middle distillates.
  • In another embodiment, the separation train may comprise before atmospheric distillation, an atmospheric distillation of the effluent from the separator or stripper.
    At the level of the atmospheric distillation, at least one middle distillate fraction is recovered. At least one gasoline fraction is obtained at the level of the stripper or the atmospheric distillation. The atmospheric distillation residue is sent to vacuum distillation.
    The vacuum distillation makes it possible to obtain the oil fraction or fractions of different grades according to the needs of the operator.
  • There is thus obtained at least one oil fraction whose initial boiling point is greater than 340 ° C, and more preferably greater than 370 ° C, or 380 ° C, or 400 ° C.
  • This fraction has, after solvent dewaxing (methyl isobutyl ketone) at about -20 ° C, an IV of at least 80 and generally between 80 and 150 and more preferably between 90 and 140 or even 90 and 135.
  • According to the invention, this fraction (residue) will then be treated alone or mixed with one or more other fractions in the catalytic dewaxing step.
  • Step (a) also leads to the production of compounds having lower boiling points which can be advantageously recovered during step (b) of separation. They comprise at least one gasoline cut and at least one middle distillate cut (for example 150-380 °) which generally has a pour point of less than -20 ° C and a cetane number greater than 48.
  • In another embodiment more focused on an objective of producing middle distillates with a very low pour point, the cutting point is lowered, and for example instead of cutting at 340 ° C, it can for example include gasoils and optionally the kerosines in the fraction containing the compounds boiling above 340 ° C. For example, an initial boiling point fraction of at least 150 ° C is obtained. This fraction will then be sent to dewaxing.
  • In general terms, this term is used to mean the fraction (s) having an initial boiling point of at least 150 ° C. and a final product up to the level of the oil (the residue). that is, generally up to 340 ° C, or preferably about 380 ° C.
  • Step (c): Catalytic Hydrodewaxing (HDPC)
  • At least one fraction containing the compounds boiling above 340 ° C., as defined above, resulting from stage (b) is then subjected alone or as a mixture with other fractions resulting from the sequence of stages. (a) and (b) of the process according to the invention, in 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.
  • Note that compounds boiling above 340 ° C are preferably always subjected to catalytic dewaxing, regardless of the mode of separation chosen in step (b).
  • 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 can be at least one of the elements contained in the following set of atoms (Si, Al, P, B, Ti, Fe, Ga). 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.
  • The molecular sieve used in the composition of the catalyst also has a bridge width, distance between two pore openings, as defined above, which is at most 0.75 nm (1 nm = 10 -9 m), preferably between 0.50 nm and 0.75 nm, even more 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.
  • The catalyst suitable for this process is characterized by a catalytic test said standard transformation test pure n-decane which is performed 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 I / 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.
  • The n-decane in the presence of the molecular sieve and a hydro-dehydrogenating function will undergo hydroisomerization reactions which will produce products isomerized to 10 carbon atoms, and reactions hydrocracking leading to the formation of products containing less than 10 carbon atoms.
    Under these conditions, 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.
  • The use of molecular sieves thus selected, under the conditions described above, among the numerous molecular sieves already in existence, makes it possible in particular to produce products with a low pour point and a high viscosity index with good yields in the context of process according to the invention.
  • The molecular sieves used in the composition of the catalytic hydrodewaxing catalyst are the following zeolites: Ferrierite, NU-10, EU-13, EU-1, ZSM-48 and zeolites of the same structural type.
  • Preferably 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 hydns-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%. In this case, the non-noble metal is often associated with at least one Group VIB metal (Mo and W preferred). If it is at least one noble metal of group VIII, the weight content, relative to the final catalyst, is less than 5%, preferably less than 3% and even more preferably less than 1.5. %.
  • In the case of the use of noble metals of group VIII, 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.
  • Considering the fraction of the effluent with initial boiling point greater than 340 ° C which can be obtained at the end of steps (a) and. (b) the process according to the invention which is to be treated in this step (c) hydrodewaxing, it has the following characteristics: an initial boiling point greater than 340 ° C and preferably greater than 370 ° C, a pour point of at least 15 ° C, a nitrogen content of less than 10 ppm by weight, a sulfur content of less than 50 ppm by weight, preferably less than 20 ppm, or even more preferably 10 ppm by weight, an index viscosity obtained after solvent dewaxing (methyl isobutyl ketone) at about -20 ° C, which is at least 80, preferably between 80 and 150, and more preferably between 90 and 140, or even 90 and 135, a content of in aromatic compounds less than 15% and preferably less than 10% by weight, a viscosity at 100 ° C greater than or equal to 3 cSt (mm 2 / s) .
  • The operating conditions in which the hydrodeparaffinization step of the process of the invention takes place are as follows:
    • the reaction temperature is between 200 and 500 ° C and preferably between 250 and 470 ° C, preferably 270-430 ° C;
    • the pressure is between 0.1 (or 0.2) and 25 MPa (10 6 Pa) and preferably between 0.5 (1.0) and 20 MPa;
    • the hourly volume velocity (wh expressed as volume of feed injected per unit volume of catalyst per hour) is between about 0.05 and about 50 and preferably between about 0.1 and about 20 h -1 and still most preferred between 0.2 and 10 h -1 .
    They are chosen to obtain the desired pour point.
  • 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.
  • Step (d): Hydrofinishing
  • The effluent leaving the catalytic hydrodewaxing step is preferably 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 of oils and distillates. However, the acidity of the catalyst must be sufficiently low not to lead to the excessive formation of cracking products with a boiling point below 340 ° C. so as not to degrade the final yields, especially of 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. The strong metal functions: platinum and / or palladium, or nickel-tungsten, nickel-molybdenum combinations will advantageously be used to carry out a thorough hydrogenation of the aromatics.
  • These metals are deposited and dispersed on an amorphous or crystalline oxide type support, such as, for example, aluminas, silicas, silica-aluminas. The carrier does not contain zeolite.
  • The hydrofinishing catalyst (HDF) may also contain at least one element of group VII A of the periodic table of elements. Preferably, 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% by weight, advantageously 0.01 to 15%, or else 0.01 to 10%; preferably 0.01 to 5%.
  • Among the catalysts that can be used in this HDF step, and leading to excellent performance, and especially for obtaining medicinal oils, catalysts containing at least one noble metal of group VIII (platinum for example) and at least one halogen (chlorine and / or fluorine), the combination of chlorine and fluorine being preferred. A preferred catalyst is noble metal, chlorine, fluorine and alumina.
  • The operating conditions in which the hydrofinishing step of the process of the invention takes place are as follows:
    • the reaction temperature is between 180 and 400 ° C and preferably between 210 and 350 ° C, preferably 220-320 ° C;
    • the pressure is between 0.1 and 25 MPa (10 6 Pa) and preferably between 1.0 and 20 MPa;
    • the hourly volume velocity (wh expressed as the volume of feed injected per unit volume of catalyst per hour) is from about 0.05 to about 100 and preferably from about 0.1 to about 30 h -1 .
  • 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.
  • Generally, 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.
  • Step (e): Separation
  • The effluent leaving the HDF stage is sent to a separation or distillation train, which comprises a separation of the gases (for example by means of a gas-liquid separator) making it possible to separate liquid products from them. gases such as hydrogen and gaseous hydrocarbons having from 1 to 4 carbon atoms. This separation train may also comprise a separation of compounds with a boiling point below 150 ° C. (gasoline) formed during the preceding steps (for example stripping and / or atmospheric distillation). The separation step (e) terminates with vacuum distillation to recover at least one oil fraction. The middle distillates formed during the preceding steps are also recovered during the separation of step (e).
  • The separation train can be realized in different ways.
    It may for example comprise a stripper to separate the gasoline formed during step (a) and the resulting effluent is sent to a vacuum distillation column to recover at least one oil fraction and also the middle distillates.
    In another embodiment, the separation train may comprise before atmospheric distillation, an atmospheric distillation of the effluent from the separator or stripper.
    At the level of the atmospheric distillation, at least one middle distillate fraction is recovered (these are the distillates formed during the preceding steps). At least one gasoline fraction is obtained at the level of the stripper or the atmospheric distillation. The atmospheric distillation residue is sent to vacuum distillation.
    The vacuum distillation makes it possible to obtain the oil fraction or fractions of different grades according to the needs of the operator.
  • All combinations are possible, the cutting points being adjusted by the operator according to his needs (eg product specifications).
    This separation also makes it possible to refine the characteristics of the oil fraction such as, for example, NOACK, viscosity, by choosing the cutting point between the gas oil and the oil fraction.
  • The base oils obtained by this process are most often pour point less than -10 ° C, a content by weight of aromatics of less than 2%, a VI greater than 95, preferably greater than 105 and even more preferably greater than 120, a viscosity of at least 3 At 100 ° C, an ASTM D1500 color of less than 1 and preferably less than 0.5, and a UV stability such as ASTM D1500 color increase is 0 to 4 and preferably 0, 5 and 2.5.
  • The UV stability test, adapted from ASTM D925-55 and D1148-55, provides a quick method for comparing the stability of lubrication oils exposed to an ultraviolet light source. The test chamber consists of a metal enclosure equipped with a turntable which receives the oil samples. A bulb producing the same ultraviolet rays as that of sunlight and placed at the top of the test chamber is directed downwards on the samples. Included in the samples is a standard oil with known UV characteristics. The ASTM D1500 color of the samples is determined at t = 0 and after 45 hours of exposure at 55 ° C. The results are transcribed for the standard sample and the test samples as follows:
    1. a) initial color ASTM D1500,
    2. b) ASTM D1500 final color,
    3. c) increase in color,
    4. d) trouble,
    5. e) precipitated.
  • Another advantage of the process according to the invention is that it 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 Anglo-Saxon polycyclic aromatic hydrocarbons) which are toxic and present at concentrations of one part per billion by weight of aromatic compounds in the white oil. 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. . These measurements are made with concentrations of 1 g 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 .
    At present, 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. In the current legislative framework of the majority of the industrialized countries, the so-called 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.
  • In addition, medicinal white oils must also meet the test for carbonizable materials (ASTM D565). It consists of heating and stirring a mixture of white oil and concentrated sulfuric acid. After decantation of the phases, the acidic layer should have a less intense coloration than that of a reference colored solution or that resulting from the combination of two yellow and red colored glasses.
  • The middle distillates resulting from the sequence of the steps of the process according to The invention has pour points less than or equal to -10 ° C and generally -20 ° C, low aromatics contents (at most 2% weight), aromatic poly (di and higher) contents less than 1% 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 the reactors of steps (c) and (d) hence the possibility of working in series and thus generating cost savings.
  • The present invention also relates to an installation that can be used for carrying out the method described above.
    The installation includes:
    • a hydrorefining zone (2) containing a hydrorefining catalyst, and having at least one pipe (1) for bringing the charge to be treated
    • a separation train comprising at least one gas separation means (4) provided with a pipe (3) supplying the effluent from the zone (2), said means being provided with at least one pipe (5) for the evacuation of the gases, at least one means (7) for separating the compounds with a boiling point below 150 ° C., said means being provided with at least one pipe (8) for the outlet of the fraction containing the compounds boiling below 150 ° C, and at least one pipe (9) for discharging an effluent containing compounds boiling at least 150 ° C, said train also comprising at least one vacuum distillation column (10) for treating said effluent, said column being provided with at least one pipe (11) for the outlet of at least one oil fraction,
    • a catalytic dewaxing zone (15) with a catalyst comprising at least one hydro-dehydrogenating element and at least one molecular sieve selected from the group of zeolites formed by Ferrierite, NU-10, EU-13, EU-1, ZSM-48 for treating at least one oil fraction, and provided with at least one line (16) for discharging the dewaxed effluent,
    • a hydrofinishing zone (17) for treating the dewaxed effluent of the pipe (16), and provided with at least one pipe (18) for discharging the hydrofini effluent,
    • a final separation train comprising at least one gas separation means (19) provided with at least one pipe (18) supplying the hydrofini effluent, said means being provided with at least one pipe (20) for evacuation of the at least one means (22) for separating the compounds with a boiling point below 150 ° C., said means being at least one pipe (24) for the outlet of the fraction containing the compounds that boil below 150 ° C, and at least one line (25) for discharging an effluent containing compounds boiling at least 150 ° C, said train also comprising at least one vacuum distillation column (26) for treating said effluent, said column being provided with at least one pipe (28) for the outlet of at least one oil fraction.
  • We will follow the description better from the figure 1 .
    The feed enters via the pipe (1) in the hydrorefining zone (2) which comprises one or more catalytic beds of hydrorefining catalyst, arranged in one or more reactors.
    The effluent leaving the line (3) of the hydrorefining zone is sent into a separation train. According to figure 1 , this train comprises a separation means (4) for separating the light gases (H 2 S, H 2 , NH 3 ... C1-C4) discharged through the pipe (5).
    The effluent "degassed" is fed via line (6) into a means for separating compounds with a boiling point of less than 150 ° C., which is, for example, a stripper (7) provided with a pipe (8) for evacuate the fraction 150- and a line (9) to bring the stripped effluent into a vacuum distillation column (10).
    Said column separates at least one oil fraction discharged for example by the pipe (11) and at least one pipe (12), it leaves at least a middle distillate fraction. Optionally, depending on the needs of the operator, it can be separated from the fractions light oils with different grades coming out on the figure 1 in the lines (13) (14).
    The oil fraction obtained in line (11) is sent to the catalytic dewaxing zone (15) which comprises one or more catalytic catalytic dewax catalyst beds, arranged in one or more reactors.
    The oil fractions of the lines (13) (14) can also be sent in the zone (12), alone or mixed with one another or with the heavier oil of the pipe (11).
    The dewaxed effluent thus obtained is discharged in its entirety from the zone (15) through the pipe (16).
    It is then treated in the hydrofinishing zone (17) which comprises one or more catalytic beds of hydrofinishing catalyst, arranged in one or more reactors.
    The hydrofini effluent thus obtained is discharged through line (18) to the final separation train.
    On the figure 1 , this train comprises a separation means (19) for separating the light gases discharged through the pipe (20).
    The effluent "degassed" is fed through line (21) into a distillation column. On the figure 1 it is an atmospheric distillation column (22) for separating one or more middle distillate fractions evacuated by, for example, a line (23) and optionally a gasoline fraction discharged via a line (24).
    On the figure 1 the residue of the atmospheric distillation discharged through line (25) is sent to a vacuum distillation column (26) which separates one or more light oil fractions (according to the needs of the operator) discharged through at least one pipe, for example, a pipe (27) and allows to recover a base oil fraction by the pipe (28).
    On the figure 2 another embodiment of the separation has been shown. We will not describe all the elements that will be recognized by the reference signs, but only the separations.
    In the figure 2 , the effluent from the zone (2) which has been degassed is fed via line (6) into a distillation column (30) which is here an atmospheric distillation column.
    In this column are separated one or more gasoline fractions and / or middle distillates leaving via the pipes (31), (32) on the figure 2 and the residue containing the heavy products (boiling point generally greater than 340 ° C, or even 370 ° C or more) is discharged through the pipe (33).
  • This residue is, according to figure 2 , sent to a vacuum distillation column (10) from which an oil fraction is separated by the line (11) and optionally by one or more ducts (34) (35) for example carry one or more fractions of light oils of different grades when the operator wished to obtain them.
    In the figure 2 , the final separation train comprises a gas separation means (19) in which between the hydrofini effluent through the pipe (18) and spring "degassed" through the pipe (21).
    This degassed effluent is sent to a stripper (36) provided with a pipe (37) to evacuate the fraction 150 and a pipe (38) through which the stripped effluent. Said effluent is sent to a vacuum distillation column (26) which separates an oil base fraction through the line (28) and at least a lighter fraction. Here, these lighter fractions are for example light oils discharged through the lines (39) (40) and a single fraction discharged through the line (41) and containing gasoline and middle distillates.
  • It will be understood that all combinations of the separating trains are possible provided that the train comprises a means for evacuating the light gases, a means for separating the fraction 150 (stripper, atmospheric distillation) and a vacuum distillation to separate the fraction containing the products. Boiling point greater than 340 ° C (oil fraction or oil base). Generally, vacuum columns used directly after the stripper are set to separate overhead boiling point fractions lower than 340 ° C, or 370 ° C or higher (380 ° C for example). In fact, the operator will adjust the cutting points according to the products to be obtained and for example if he wants to produce light oils.
    The more conventional sequence separator, atmospheric distillation column and vacuum distillation column is more often used for the final separation train.
    The combination of figure 1 is particularly interesting in the quality of the separation (and thus the products obtained) for a very optimized (saving a column).
  • Claims (18)

    1. Process for the production of oils and middle distillates from a charge containing more than 200 ppm by weight of nitrogen and more than 500 ppm by weight of sulphur, of which at least 20% by volume boils above 340°C, the charge is selected from the group formed by the vacuum distillates produced by direct distillation of the crude or conversion units, hydrocracking residues, vacuum distillates produced by desulphuration or hydroconversion of atmospheric residues or vacuum residues; deasphalted oils or mixtures of these, comprising the following stages:
      (a) hydrorefining of the charge, carried out at a temperature of 330°C-450°C, under a pressure of 5-25 MPa, at a spatial velocity of 0.1-10h-1, in the presence of hydrogen in the hydrogen/hydrocarbon volume ratio of 100-2000, in the presence of an amorphous catalyst comprising a support, at least one non-noble metal of Group VIII and at least one metal of Group VI B, and at least one doping element selected from the group formed by phosphorus, boron and silicon, conversion being 60% by weight maximum.
      (b) from the effluent obtained in stage (a), separation of the gases and compounds with a boiling point below 150°C including optionally a vacuum distillation.
      (c) catalytic dewaxing of at least part of the effluent from stage (b), which contains compounds with a boiling point above 340°C, carried out at a temperature of 200-500°C, under a total pressure of 1-25MPa, at an hourly volume rate of 0.05-50h-1, with 50-20001 of hydrogen/l of charge, and in the presence of a catalyst comprising at least one hydro-dehydrogenating element and at least one molecular sieve selected from the group of zeolites formed by Ferrierite, NU-10, EU-13, EU-1, ZSM-48.
      (d) hydrofinishing of at least part of the effluent from stage (c), carried out at a temperature of 180-400°C, under a pressure of 1-25MPa, at an hourly volume rate of 0.05-100h-1, in the presence of 50-2000 1 of hydrogen/l of charge, and in the presence of an amorphous catalyst, at least one hydro-dehydrogenating metal and at least one halogen.
      (e) separation of the effluent obtained in stage (d) to obtain at least one oil fraction, said separation including a vacuum distillation.
    2. Process according to Claim 1, in which the hydrorefining catalyst contains at least one element selected from Co and Ni, at least one element selected from Mo and W, and at least one doping element selected from P, B and Si, said elements being deposited on a support.
    3. Process according to either of Claims 1 and 2, in which the hydrorefining catalyst contains as doping elements phosphorus and boron deposited on an alumina-based support.
    4. Process according to either of Claims 1 and 2, in which the hydrorefining catalyst contains as doping elements boron and silicon deposited on an alumina-based support.
    5. Process according to Claim 4 in which the catalyst also contains phosphorus.
    6. Process according to any one of the preceding claims, in which the support of the hydrorefining catalyst is an acid support.
    7. Process according to any one of the preceding claims, in which the hydrorefining catalyst also contains at least one element selected from the group formed by the elements of Group VB, the elements of Group VIIA and the elements of Group VIIB.
    8. Process according to Claim 7, in which the hydrorefining catalyst contains at least one element selected from niobium, fluorine, manganese and rhenium.
    9. Process according to any one of the preceding claims, in which the hydrofinishing catalyst contains at least one metal of Group VIII and/or at least one metal of Group VIB, a support without zeolite and at least one element of Group VIIA.
    10. Process according to Claim 9 in which the catalyst contains platinum, chlorine and fluorine.
    11. Process according to any one of the preceding claims, in which, in the hydrorefining stage, the conversion into products with boiling points below 340°C is equal to 50% by weight maximum.
    12. Process according to any one of the preceding claims, in which stage (b) and/or stage (e) is carried out by gas-liquid separation, then stripping followed by vacuum distillation.
    13. Process according to Claim 12 in which stage (b) and/or stage (e) is carried out by gas-liquid separation, then atmospheric distillation followed by vacuum distillation.
    14. Process according to any one of the preceding claims, in which the charge is selected from the group formed by the vacuum distillates produced by direct distillation of the crude or conversion units, hydrocracking residues, vacuum distillates from desulphuration or hydroconversion of atmospheric residues or vacuum residues or mixtures of these.
    15. Installation for the production of oils and middle distillates comprising:
      - a hydrorefining zone (2) containing a hydrorefining catalyst, and having at least one pipe (1) to introduce the charge to be treated
      - a separation train comprising at least one means of separation of the gases (4) having a pipe (3) carrying the effluent from zone (2), said means having at least one pipe (5) for removal of the gases, at least one means (7) of separation of the compounds with a boiling point below 150°C, said means having at least one pipe (8) for removal of the fraction containing the compounds boiling below 150°C, and at least one pipe (9) for removal of an effluent containing compounds boiling at at least 150°C, said train also comprising at least one vacuum distillation column (10) for treatment of said effluent, said column having at least one pipe (11) for removal of at least one oil fraction,
      - a catalytic dewaxing zone (15) with a catalyst comprising at least one hydro-dehydrogenating element and at least one molecular sieve selected from the group of zeolites formed by Ferrierite, NU-10, EU-13, EU-1, ZSM-48 for treatment of at least one oil fraction, and having at least one pipe (16) for removal of the dewaxed effluent,
      - a hydrofinishing zone (17) for treatment of the dewaxed effluent from the pipe (16), and having at least one pipe (18) for removal of the hydrofinished effluent,
      - a final separation train comprising at least one means of separation of the gases (19) having at least one pipe (18) carrying the hydrofinished effluent, said means having at least one pipe (20) for removal of the gases, at least one means (22) of separation of the compounds with a boiling point below 150°C, said means having at least one pipe (24) for removal of the fraction containing compounds boiling below 150°C, and at least one pipe (25) for removal an effluent containing compounds boiling at at least 150°C, said train also comprising at least one vacuum distillation column (26) for treatment of said effluent, said column having at least one pipe (28) for removal of at least one oil fraction.
    16. Installation according to Claim 15 in which the means of separation of the gases (4) (19) is a gas - liquid separator.
    17. Installation according to either of Claims 15 or 16 in which the means of separation (7) of the compounds with a boiling point below 150°C is a stripper and the stripped effluent removed by the pipe (9) is passed into a vacuum distillation column (10), having at least one pipe (11) for removal of at least one oil fraction and at least one pipe (12) for removal of at least one medium distillate fraction.
    18. Installation according to either of Claims 15 or 16 in which the means of separation (22) of the compounds with a boiling point below 150°C is an atmospheric distillation section, having at least one pipe (23) for removal of at least one medium distillate fraction, at least one pipe (24) for removal of at least one gasoline fraction, and at least one pipe (25) for removal of the residue, said residue being passed into a vacuum distillation column (26) separating at least one oil fraction removed by at least one pipe (28).
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    US20040004021A1 (en) 2004-01-08
    US7250107B2 (en) 2007-07-31
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