EP1307526B1 - Vefahren zur herstellung von basisölen und von mitteldestillaten aus einem heteroatomhaltigen einsatz - Google Patents

Vefahren zur herstellung von basisölen und von mitteldestillaten aus einem heteroatomhaltigen einsatz 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
separation
removal
catalyst
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French (fr)
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EP1307526A1 (de
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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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    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining 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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment 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
    • 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
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment 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

Definitions

  • 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.
  • VIP viscosity index
  • middle distillates especially gas oils, kerosene
  • 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.
  • 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.
  • 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.
  • 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.
  • This step is carried out an isomerization of n-paraffins on an ICR 404 catalyst.
  • the process also ends with a hydrofinishing step.
  • 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.
  • the catalyst used is based on silicalite or ZSM-5 type zeolite.
  • 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. .
  • 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 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.
  • 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 °
  • 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, 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.
  • conversion units such as FCC, coker or visbreaking
  • RAT atmospheric residues
  • RSV reducts under vacuum
  • hydrocracking residues or 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 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 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.
  • 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.
  • 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.
  • 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. .
  • 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 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).
  • 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.
  • a quantitative estimate of the local silicon contents and other elements can be made.
  • 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%
  • 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%.
  • 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.
  • catalysts also contain phosphorus in addition to boron and / or silicon.
  • 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.
  • 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.
  • a gas separation means for example a gas-liquid separator
  • gases such as hydrogen, hydrogen sulphide (H 2 S), ammonia (NH 3 ) formed, and gaseous hydrocarbons up to 4 carbon atoms.
  • the effluent undergoes a separation of compounds with a boiling point below 150 ° C. (gasoline), generally carried out by stripping and / or atmospheric distillation.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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 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 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.
  • 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.
  • 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 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.
  • 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%.
  • 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. %.
  • 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 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
  • 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 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.
  • 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.
  • 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.
  • 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%.
  • a preferred catalyst is noble metal, chlorine, fluorine and alumina.
  • 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 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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. . 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 .
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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).
  • 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.
  • 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.
  • 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).
  • 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).
  • 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).

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Claims (18)

  1. Verfahren zur Herstellung von Ölen und Mitteldestillaten aus einem Beschickungsgut, das mehr als 200 ppm nach Gewicht an Stickstoff und mehr als 500 ppm nach Gewicht an Schwefel enthält und das zu mindestens 20 Volumen% oberhalb von 340 °C siedet, wobei das Beschickungsgut aus der Gruppe gewählt ist, die von den Vakuumdestillaten aus der direkten Destillation von Rohöl oder umgewandelten Einheiten, den Rückständen des Hydrocrackens, den Vakuumdestillaten aus der Entschwefelung oder hydrierenden Umwandlung von Rückständen einer Normaldruckbehandlung oder Rückständen einer Vakuumbehandlung, den entasphaltierten Ölen oder Mischungen daraus gebildet wird, wobei das Verfahren die folgenden Schritte aufweist:
    (a) hydrierende Raffination des Beschickungsgutes, durchgeführt bei einer Temperatur von 330 ° bis 450 °C, unter einem Druck von 5 bis 25 MPa, mit einer Raumgeschwindigkeit von 0,1 bis 10 h-1, in Gegenwart von Wasserstoff in einem Wasserstoff/Kohlenwasserstoff-Volumenverhältnis von 100 bis 2000, in Gegenwart eines amorphen Katalysators, der einen Träger und mindestens ein unedles Metall der Gruppe VIII, mindestens ein Metall der Gruppe VIB und mindestens ein Dotierelement, das aus der Gruppe gewählt ist, welche von Phosphor, Bor und Silicium gebildet wird, umfasst, wobei die Umwandlung zu mindestens 60 Gew.-% erfolgt,
    (b) ausgehend von dem Stoffstrom, der in Schritt (a) erhalten wird, Abtrennung mindestens der Gase und der Verbindungen mit einem Siedepunkt von weniger als 150°C, möglicherweise eine Vakuumdestillation beinhaltend,
    (c) Katalytische Entparaffinierung mindestens eines Teils des Stoffstroms, der aus Schritt (b) stammt und die Verbindungen mit einem Siedepunkt von mehr als 340 °C enthält, durchgeführt bei einer Temperatur von 200 bis 500 °C, unter einem Gesamtdruck von 1 bis 25 MPa, mit einer stündlichen Volumengeschwindigkeit von 0,05 bis 50 h-1, mit 50 bis 2000 I Wasserstoff / I Beschickungsgut und in Gegenwart eines Katalysators, der mindestens ein hydrierendes/deshydrierendes Element und mindestens ein Molekularsieb, das aus der Gruppe der Zeolithe gewählt ist, welche von Ferrierit, NU-10, EU-13, EU-1, ZSM-48 gebildet wird, umfasst,
    (d) Hydrofinishing mindestens eines Teils des Stoffstroms aus Schritt (c), durchgeführt bei einer Temperatur von 180 bis 400 °C, unter einem Druck von 1 bis 25 MPa, mit einer stündlichen Volumengeschwindigkeit von 0,5 bis 100 h-1, in Gegenwart von 50 bis 2000 l Wasserstoff / l Beschickungsgut und in Gegenwart eines amorphen Katalysators, mindestens ein hydrierendes/deshydrierendes Element und mindestens ein Halogen; und
    (e) Abtrennung des Stoffstroms, der in Schritt (d) erhalten wurde, um mindestens eine Ölfraktion zu erhalten, wobei die Abtrennung eine Vakuumdestillation beinhaltet.
  2. Verfahren nach Anspruch 1, wobei der Katalysator für die hydrierende Raffination mindestens ein Element, das aus Co und Ni gewählt ist, mindestens ein Element, das aus Mo und W gewählt ist, und mindestens ein Dotierelement, das aus P, B und Si gewählt ist, enthält, wobei die Elemente auf einen Träger aufgebracht sind.
  3. Verfahren nach einem der Ansprüche 1 und 2, wobei der Katalysator für die hydrierende Raffination als Dotierelemente Phosphor und Bor, aufgebracht auf einen Träger auf Basis von Aluminiumoxid, enthält.
  4. Verfahren nach einem der Ansprüche 1 und 2, wobei der Katalysator für die hydrierende Raffination als Dotierelemente Bor und Silicium, aufgebracht auf einen Träger auf Basis von Aluminiumoxid, enthält.
  5. Verfahren nach Anspruch 4, wobei der Katalysator weiterhin Phosphor enthält.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei es sich bei dem Träger des Katalysators für die hydrierende Raffination um einen sauer reagierenden Träger handelt.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei der Katalysator für die hydrierende Raffination weiterhin mindestens ein Element enthält, das aus der Gruppe gewählt ist, die von den Elementen der Gruppe VB, den Elementen der Gruppe VIIA und den Elementen der Gruppe VIIIB gebildet wird.
  8. Verfahren nach Anspruch 7, wobei der Katalysator für die hydrierende Raffination mindestens ein Element enthält, das aus Niob, Fluor, Mangan und Rhenium gewählt ist.
  9. Verfahren nach einem der vorhergehenden Ansprüche, wobei der Hydrofinishing-Katalysator mindestens ein Metall der Gruppe VIII und/oder mindestens ein Metall der Gruppe IVB, einen zeolithfreien Träger und mindestens ein Element der Gruppe VIIA enthält.
  10. Verfahren nach Anspruch 9, wobei der Katalysator Platin, Chlor und Fluor enthält.
  11. Verfahren nach einem der vorhergehenden Ansprüche, wobei im Schritt der hydrierenden Raffination die Umwandlung zu Stoffen mit Siedepunkten von weniger als 340 °C zu höchstens 50 Gewichts% erfolgt.
  12. Verfahren nach einem der vorhergehenden Ansprüche, wobei der Schritt (b) und/oder der Schritt (e) durchgeführt wird, indem eine Gas-Flüssigkeits-Trennung, dann ein Strippvorgang und danach eine Vakuumdestillation erfolgen.
  13. Verfahren nach Anspruch 12, wobei der Schritt (b) und/oder der Schritt (e) durchgeführt wird, indem eine Gas-Flüssigkeits-Trennung, dann eine Normaldruckdestillation und danach eine Vakuumdestillation erfolgen.
  14. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Beschickungsgut aus der Gruppe gewählt ist, die von den Vakuumdestillaten aus der direkten Destillation von Rohöl oder umgewandelten Einheiten, den Rückständen des Hydrocrackens, den Vakuumdestillaten aus der Entschwefelung oder hydrierenden Umwandlung von Rückständen einer Normaldruckbehandlung oder Rückständen einer Vakuumbehandlung oder Mischungen daraus gebildet wird.
  15. Anlage zur Herstellung von Ölen und Mitteldestillate, aufweisend
    - einen Bereich für die hydrierende Raffination (2), der einen Katalysator für die hydrierende Raffination enthält und mindestens eine Leitung (1) zum Heranführen des zu behandelnden Beschickungsgutes hat,
    - eine Trennvorrichtung, die mindestens ein Mittel zur Gasabtrennung (4), welches mit einer Leitung (3) versehen ist, die den Stoffstrom aus dem Bereich (2) heranführt, wobei das Mittel mit mindestens einer Leitung (5) zur Abführen der Gase versehen ist, mindestens ein Mittel (7) zur Abtrennung der Verbindungen mit einem Siedepunkt von weniger als 150 °C, wobei das Mittel mit mindestens einer Leitung (8) zum Ableiten der Fraktion, welche die Verbindungen enthält, die unterhalb von 150 °C sieden, und mit mindestens einer Leitung (9) zum Abführen eines Stoffstroms, welcher die Verbindungen enthält, die bei mindestens 150 °C sieden, versehen ist, aufweist, wobei die Vorrichtung weiterhin mindestens eine Vakuumdestillationskolonne (10) zur Behandlung des Stoffstroms aufweist, wobei die Kolonne mit mindestens einer Leitung (11) zum Ableiten mindestens einer Ölfraktion versehen ist,
    - einen Bereich für die katalytische Entparaffinierung (15) mit einem Katalysator, der mindestens ein hydrierendes/deshydrierendes Element und mindestens ein Molekularsieb, das aus der Gruppe der Zeolithe gewählt ist, welche von Ferrierit, NU-10, EU-13, EU-1, ZSM-48 gebildet wird, umfasst, um mindestens eine Ölfraktion zu behandeln, wobei der Bereich mit mindestens einer Leitung (16) zum Abführen des entparaffinierten Stoffstroms versehen ist,
    - einen Hydrofinishing-Bereich (17) zur Behandlung des entparaffinierten Stoffstroms der Leitung (16), wobei der Bereich mit mindestens einer Leitung (18) zum Abführen des Stoffstroms, der ein Hydrofinishing erfahren hat, versehen ist,
    - eine Vorrichtung zur abschließenden Trennung, die mindestens ein Mittel zur Gasabtrennung (19), welches mit einer Leitung (18) versehen ist, die den Stoffstrom heranführt, welcher ein Hydrofinishing erfahren hat, wobei das Mittel mit mindestens einer Leitung (20) zur Abführen der Gase versehen ist, mindestens ein Mittel (22) zur Abtrennung der Verbindungen mit einem Siedepunkt von weniger als 150 °C, wobei das Mittel von mindestens einer Leitung (24) zum Ableiten der Fraktion, welche die Verbindungen enthält, die unterhalb von 150 °C sieden, und von mindestens einer Leitung (25) zum Abführen eines Stoffstroms, welcher die Verbindungen enthält, die bei mindestens 150 °C sieden, ist, aufweist, wobei die Vorrichtung weiterhin mindestens eine Vakuumdestillationskolonne (26) zur Behandlung des Stoffstroms aufweist, wobei die Kolonne mit mindestens einer Leitung (28) zum Ableiten mindestens einer Ölfraktion versehen ist.
  16. Anlage nach Anspruch 15, wobei es sich bei dem Mittel zur Gasabtrennung (4) (19) um einen Gas-Flüssigkeits-Abscheider handelt.
  17. Anlage nach einem der Ansprüche 15 und 16, wobei das Mittel (7) zur Abtrennung der Verbindungen mit einem Siedepunkt von weniger als 150 °C eine Strippvorrichtung ist, und dass der Stoffstrom, der den Strippvorgang erfahren hat und durch die Leitung (9) abgeführt wird, in eine Vakuumdestillationskolonne (10) eingeleitet wird, die mit mindestens einer Leitung (11) zum Abführen mindestens einer Ölfraktion und mindestens einer Leitung (12) zum Ableiten mindestens einer Mitteldestillatsfraktion versehen ist.
  18. Anlage nach einem der Ansprüche 15 und 16, wobei es sich bei dem Mittel (22) zur Abtrennung der Verbindungen mit einem Siedepunkt von weniger als 150 °C um eine Normaldruckdestillation handelt, die mit mindestens einer Leitung (23) zum Ableiten mindestens einer Mitteldestillatsfraktion und mit mindestens einer Leitung (24) zum Abführen mindestens einer Benzinfraktion und mit mindestens einer Leitung (25) zum Ableiten des Rückstands versehen ist, wobei dieser in eine Vakuumdestillationkolonne (26) eingeleitet wird, welche mindestens eine Ölfraktion abtrennt, die durch mindestens eine Leitung (28) abgeführt wird.
EP01958156A 2000-07-26 2001-07-23 Vefahren zur herstellung von basisölen und von mitteldestillaten aus einem heteroatomhaltigen einsatz Expired - Lifetime EP1307526B1 (de)

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