EP1346010B2 - Verbessertes flexibles verfahren zur herstellung von grundölen und destillaten durch hydroisomerisierung-konversion an einem schwach dispergierten katalysator und anschliessende katalytische entparaffinierung - Google Patents

Verbessertes flexibles verfahren zur herstellung von grundölen und destillaten durch hydroisomerisierung-konversion an einem schwach dispergierten katalysator und anschliessende katalytische entparaffinierung Download PDF

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EP1346010B2
EP1346010B2 EP01270585A EP01270585A EP1346010B2 EP 1346010 B2 EP1346010 B2 EP 1346010B2 EP 01270585 A EP01270585 A EP 01270585A EP 01270585 A EP01270585 A EP 01270585A EP 1346010 B2 EP1346010 B2 EP 1346010B2
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stage
process according
catalyst
weight
hydrogen
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EP1346010A1 (de
EP1346010B1 (de
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Eric Benazzi
Nathalie Marchal-George
Tivadar Cseri
Pierre Marion
Christophe Gueret
Slavik Kasztelan
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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
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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 relates to an improved process for manufacturing base oils of very high quality, ie having a high viscosity index (VI), a good UV stability and a low pour point, from hydrocarbon feedstocks. (and preferably from hydrocarbon feeds from the Fischer-Tropsch process or from hydrocracking residues), possibly with the simultaneous production of middle distillates (especially gas oils, kerosene) of very high quality, ie say having a low pour point and a high cetane number.
  • VI viscosity index
  • lubricants are most often obtained by a succession of refining steps to improve the properties of a petroleum cut.
  • a treatment of heavy petroleum fractions with high levels of linear paraffins or little branched is necessary in order to obtain base oils of good quality and with the best possible yields, by an operation which aims to eliminate linear paraffins or very poorly connected, loads that will then be used as base oils.
  • Zeolite catalysts such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 have been described for use in these processes. All the catalysts currently used in hydroisomerization are of the bifunctional type associating an acid function with a hydrogenating function.
  • the acid function is provided by supports with large surface areas (generally 150 to 800 m 2 .g -1 ) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), phosphorus aluminas, combinations of oxides of boron and aluminum, amorphous silica-aluminas and silica-aluminas.
  • the hydrogenating function is provided either by one or more metals of group VIII of the periodic table of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by a combination of at least one Group VI metal such as chromium, molybdenum and tungsten and at least one Group VIII metal.
  • FR-A-2,792,946 describes a process for producing oil bases by conversion-hydroisomerization on poorly arranged catalyst.
  • FR-A-2698863 describes the application of zeolites of ZSM-48 type in absorption and catalysis.
  • the equilibrium between the two acid and hydrogenating functions is the fundamental parameter which governs the activity and the selectivity of the catalyst.
  • a weak acidic function and a strong hydrogenating function give catalysts which are not very active and selective towards isomerization whereas a strong acid function and a low hydrogenating function give very active and cracking-selective catalysts.
  • a third possibility is to use a strong acid function and a strong hydrogenating function to obtain a very active catalyst but also very selective towards isomerization. It is therefore possible, by judiciously choosing each of the functions to adjust the activity / selectivity couple of the catalyst.
  • the Applicant therefore proposes, according to the process described in the invention, to jointly produce middle distillates of very good quality, base oils VI and pour point at least equal to those obtained with a hydrorefining process and or hydrocracking.
  • the applicant has focused its research efforts on the development of an improved process for manufacturing high quality lubricating oils and high quality middle distillates from hydrocarbon feedstocks and preferably from hydrocarbon feedstocks from Fischer-Tropsch process or from hydrocracking residues.
  • the present invention therefore relates to a series of processes for the joint production of very high quality base oils and middle distillates (especially gas oils) of very high quality from petroleum fractions.
  • the oils obtained have a high viscosity index (VI), low volatility, good UV stability and a low pour point.
  • Step (a) is therefore optionally preceded by a hydrotreatment step generally carried out at a temperature of 200-450 ° C., under a pressure of 2 to 25 MPa, with a space velocity of 0.1-6 h -1 , in the presence of hydrogen in the hydrogen / hydrocarbon volume ratio of 100-2000 l / l, and in the presence of an amorphous catalyst comprising at least one Group VIII metal and at least one Group VI B metal.
  • step (a) is optionally followed by separation of the light gases from the effluent obtained at the end of step (a).
  • the effluent resulting from the conversion-hydroisomerization treatment is subjected to a distillation step (preferably atmospheric) so as to separate the compounds having a boiling point below 340 ° C. (gas, gasoline, kerosene, diesel fuel). ) products having an initial boiling point of at least 340 ° C and which form the residue.
  • a middle distillate fraction having a pour point of at most -20 ° C and a cetane number of at least 50 is generally separated.
  • the catalytic dewaxing step (b) preferably applies to at least the residue from the distillation which contains compounds with a boiling point of at least 340 ° C.
  • the effluent from step (a) is not distilled before carrying out step (b). At most, it undergoes a separation of at least a portion of the light gases (by flash .%) and is then subjected to catalytic dewaxing.
  • the effluent from the dewaxing treatment is subjected to a distillation step advantageously comprising an atmospheric distillation and a vacuum distillation so as to separate at least one oil fraction at a boiling point greater than at least 340 ° C. It most often has a pour point of less than -10 ° C and a VI greater than 95, a viscosity at 100 ° C of at least 3cSt (or 3mm2 / s).
  • This distillation step is essential when there is no distillation between steps (a) and (b).
  • the effluent from the dewaxing treatment is subjected to a hydrofinishing treatment.
  • 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 preferably contains at least 20% by volume of compounds boiling above 340.degree. C., preferably at least 350.degree. at least 380 ° C. This does not mean that the boiling point is 380 ° C or higher, but 380 ° C or higher.
  • the feed contains n-paraffins.
  • the feed is an effluent from a Fischer-Tropsch unit.
  • a wide variety of fillers can be processed by the process.
  • the feedstock may also be, for example, vacuum distillates obtained from the direct distillation of the crude or from conversion units such as FCC, coker or visbreaking, or from aromatic extraction units, or from hydrotreatment or hydroconversion of RAT (atmospheric residues) and / or RSV (vacuum residues), or the charge may be a deasphalted oil, or a hydrocracking residue for example derived from DSV or any mixture of charges previously mentioned.
  • conversion units such as FCC, coker or visbreaking, or from aromatic extraction units
  • RAT atmospheric residues
  • RSV vacuum residues
  • the charge may be a deasphalted oil, or a hydrocracking residue for example derived from DSV or any mixture of charges previously mentioned.
  • the fillers suitable for the objective oils have an initial boiling point of at least 340 ° C and more preferably at least 370 ° C.
  • the feed introduced in step (a) conversion-hydroisomerization must be clean.
  • cleaning load we mean the fillers whose sulfur content is less than 1000 ppm by weight and preferably less than 500 ppm by weight and even more preferably less than 300 ppm by weight or better still, 200 ppm by weight.
  • the nitrogen content is less than 200 ppm by weight and preferably less than 100 ppm by weight and even more preferably less than 50 ppm by weight.
  • the metal content of the filler such as nickel and vanadium is extremely low, that is to say less than 50 ppm weight and more advantageously less than 10 ppm by weight, or better still less than 2 ppm by weight.
  • the feedstock (for example from the Fischer-Tropsch process) must, before entering the hydroisomerisation zone, undergo a hydrotreatment in a hydrotreating zone. Hydrogen is reacted with the feedstock in contact with a hydrotreatment catalyst whose role is to reduce the content of unsaturated and oxygenated hydrocarbon molecules (produced, for example, during Fischer-Tropsch synthesis). The oxygen content is thus reduced to at most 0.2% by weight.
  • the charge to be treated is not specific to the meaning defined above, it is first subjected to a preliminary hydrotreatment step, 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 VIB element and at least one group VIII element, at a temperature of between 200 and 450 ° C., preferably 250-450 ° C advantageously 330-450 ° C or 360-420 ° C, at a pressure of 5 and 25 MPa or better still less than 20 MPa, preferably between 5 and 20 MPa, the space velocity being between 0.1 and 6 h -1 , preferably 0.3-3 h -1 , and the amount of hydrogen introduced is such that the volume ratio hydrogen / hydrocarbon is between 100 and 2000 liters / liter.
  • a preliminary hydrotreatment step 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
  • the support is generally based (preferably essentially consisting of) of alumina or amorphous silica-alumina; it may also contain boron oxide, magnesia, zirconia, titanium oxide or a combination of these oxides.
  • the hydro-dehydrogenating function is preferably filled with at least one metal or group VIII and VIB metal compound preferably chosen from; molybdenum, tungsten, nickel and cobalt.
  • This catalyst may advantageously contain phosphorus; in fact, it is known in the prior art that the compound provides two advantages to hydrotreatment catalysts: an ease of preparation, especially when impregnating the nickel and molybdenum solutions, and a better hydrogenation activity.
  • the preferred catalysts are the NiMo and / or NiW catalysts on alumina, also the NiMo and / or NiW catalysts on alumina doped with at least one element included in the group of atoms formed by phosphorus, boron, silicon and fluorine, or alternatively NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-titanium oxide doped or not doped with at least one element included in the group of atoms formed by phosphorus, boron, fluorine and silicon .
  • the total concentration of metal oxides of groups VIB and VIII is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of Group VI on metal (or metals) of group VIII is preferably between 20 and 1.25 and even more preferably between 10 and 2.
  • the concentration of phosphorus oxide P 2 O 5 will be less than 15% by weight and preferably 10% by weight.
  • the product obtained at the end of the hydrotreatment undergoes, if necessary, an intermediate separation of water (H 2 O), H 2 S and NH 3 so as to bring the water contents, in H 2 S and NH 3 to values respectively less than at most 100 ppm, 200 ppm, 50 ppm in the feed introduced in step (a). It is possible at this level to possibly separate the products having a boiling point below 340 ° C so as to treat in step (a) only a residue.
  • a hydrocracking residue is treated, it is then in the presence of a feedstock which has already undergone hydrotreatment and hydrocracking.
  • the own charge can then be processed directly in step (a).
  • the hydrocracking takes place over a zeolitic catalyst, more often based on zeolite Y, and in particular dealuminated Y zeolites.
  • the catalyst also contains at least one non-noble GVIII group metal and at least one Group VIB metal.
  • Step (a) takes place in the presence of hydrogen and in the presence of a bifunctional catalyst comprising at least one noble metal deposited on an amorphous acid support, the noble metal dispersion being less than 20%.
  • the n-paraffins in the presence of a bifunctional catalyst are subjected to isomerization and then optionally hydrocracking to lead respectively to the formation of isoparaffins and lighter cracking products such as gas oils and kerosene.
  • the fraction of the noble metal particles having a size of less than 2 nm represents at most 2% by weight of the noble metal deposited on the catalyst.
  • At least 70% preferably at least 80%, and more preferably at least 90%
  • noble metal particles have a size greater than 4 nm (% number).
  • the support is amorphous, it does not contain molecular sieve; the catalyst does not contain molecular sieves either.
  • the acidic support may be chosen from the group formed by a silica alumina, boron oxide, a zirconia alone or mixed with one another or with a matrix (non-acidic for example).
  • the amorphous acidic support is generally selected from the group formed by a silica-alumina, a halogenated alumina (preferably fluorinated), a silicon-doped alumina (deposited silicon), a titanium oxide alumina mixture, a sulphated zirconia, a tungsten-doped zirconia, and mixtures thereof with one another or with at least one amorphous matrix chosen from group formed by alumina, titanium oxide, silica, boron oxide, magnesia, zirconia, clay for example.
  • Preferred supports are amorphous silica-alumina and silica-alumina-titanium oxide (amorphous).
  • the measurement of acidity is well known to those skilled in the art. It can be done for example by programmed temperature desorption (TPD) with ammonia, by infra-red measurement of absorbed molecules (pyridine, CO ....), catalytic cracking test or hydrocracking model molecule. ...
  • TPD programmed temperature desorption
  • absorbed molecules pyridine, CO ....
  • catalytic cracking test or hydrocracking model molecule.
  • a preferred catalyst according to the invention comprises (preferably consists essentially of) from 0.05 to 10% by weight of at least one Group VIII noble metal deposited on an amorphous silica-alumina support.
  • the preparation and shaping of the silica-alumina and of any support in general is made by usual methods well known to those skilled in the art.
  • the support may undergo calcination, for example a heat treatment at 300-750 ° C. (600 ° C. preferred) for a period of between 0.25 and 10 hours (2 hours). preferred) under 0-30% volume of water vapor (about 7.5% preferred for a silica-alumina).
  • the metal salt is introduced by one of the usual methods used to deposit the metal (preferably platinum) on the surface of a support.
  • One of the preferred methods is dry impregnation which consists of introducing the metal salt into a volume of solution which is equal to the pore volume of the catalyst mass to be impregnated.
  • the catalyst Prior to the reduction operation and to obtain the size distribution of the metal particles, the catalyst is calcined in humidified air at 300-750 ° C (550 ° C preferred) for 0.25-10 hours (preferred 2 hours).
  • the partial pressure of H2O during the calcination is for example 0.05 bar to 0.50 bar (0.15 bar preferred).
  • Other known methods of treatment making it possible to obtain the dispersion of less than 20% are suitable within the scope of the invention.
  • step (a) the conversion is most often accompanied by a hydroisomerization of paraffins.
  • the process has the advantage of flexibility: depending on the degree of conversion, production is more directed to oils or middle distillates.
  • the conversion usually varies between 5-90%.
  • the metal contained in the catalyst is reduced.
  • One of the preferred methods for conducting the metal reduction is the hydrogen treatment at a temperature of from 150 ° C to 650 ° C and a total pressure of from 0.1 to 25 MPa.
  • a reduction consists of a stage at 150 ° C. for 2 hours then a rise in temperature up to 450 ° C. at the rate of 1 ° C./min and then a plateau of 2 hours at 450 ° C. throughout this reduction step, the hydrogen flow rate is 1000 1 hydrogen / l catalyst. Note also that any ex-situ reduction method is suitable.
  • the pressure will be maintained between 2 and 25 MPa (most often at least 5 MPa) and preferably 2 (or 3) to 20 MPa and preferably 2 to 18 MPa, the space velocity will be between 0.1 h - 1 and 10 h -1 and preferably between 0.2 and 10 h -1 is preferably between 0.1 or 0.5 h -1 and 5,0h -1, and a hydrogen rate between 100 and 2000 liters of hydrogen per liter of filler and preferably between 150 and 1500 liters of hydrogen per liter of filler.
  • the temperature used in this step is between 200 and 500 ° C. and preferably from 250 ° C. to 450 ° C., advantageously from 300 to 450 ° C., and even more advantageously above 340 ° C., for example between 320 ° to 450 ° C. .
  • the hydrotreatment and hydroisomerization-conversion steps can be carried out on the two types of catalysts in (two or more) different reactors, and / or on at least two catalytic beds installed in the same reactor.
  • step (a) has the effect of increasing the viscosity index (VI). More generally, it is found that the increase in VI is at least 2 points, the VI being measured on a solvent-dewaxed charge (residue) and on the product from step (a) also dewaxed with the solvent, aiming a pour point temperature of between -15 and -20 ° C. An increase of VI of at least 5 points is usually obtained, and often more than 5 points, or even 10 points or more than 10 points.
  • pour point depression which can range from a few degrees to 10-15 ° C or more (25 ° C for example).
  • the magnitude of the decrease varies according to the conversion and therefore the operating conditions and the load.
  • the effluent from the hydroisomerization-conversion step (a) may be completely treated in the dewaxing step (b). Alternatively, it may undergo separation of at least a portion (and preferably at least a major part) of light gases which include hydrogen and optionally also hydrocarbon compounds up to 4 carbon atoms. Hydrogen can be separated beforehand.
  • the embodiment (except variant), with passage in step (b) of the entire effluent of step (a), is economically interesting, since a single distillation unit is used at the end of the process . In addition, at the final distillation (after catalytic dewaxing or subsequent treatments) a cold cold gas oil is obtained.
  • the effluent from step (a) is distilled so as to separate the light gases and also separate at least one residue containing the compounds with a boiling point greater than at least 340 ° C. vs. It is preferably an atmospheric distillation.
  • this fraction (residue) will then be treated in the catalytic dewaxing step, that is to say without undergoing distillation under vacuum. But in another variant, it is possible to use vacuum distillation.
  • the fraction (s) with initial boiling point of at least 150 ° C and final up to the residue ie generally say up to 340 ° C, 350 ° C or preferably below 370 ° C or 380 ° C.
  • the effluent from step (a) can undergo, before or after distillation, other treatments such as for example an extraction of at least a portion of the aromatic compounds.
  • the catalyst according to the invention comprises the ZBM-30 sieve.
  • the weight content of molecular sieves in the hydrodewaxing catalyst is between 1 and 90%, preferably between 5 and 90% and even more preferably between 10 and 85%.
  • the matrices used to carry out the shaping of the catalyst are, by way of examples and in a nonlimiting manner, alumina gels, aluminas, magnesia, amorphous silica-aluminas, and mixtures thereof. Techniques such as extrusion, pelletizing or coating may be used to perform the shaping operation.
  • the catalyst also comprises a hydro-dehydrogenating function ensured, for example, by at least one group VIII element and preferably at least one noble 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 about of 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.
  • the hydrodewaxing catalyst according to the invention may also contain from 0 to 20%, preferably from 0 to 10% by weight (expressed as oxides) of phosphorus.
  • the combination of Group VIB metal (s) and / or Group VIII metal (s) with phosphorus is particularly advantageous.
  • a residue obtained at the end in step (a) and distillation and which is interesting to treat in this step (b) of hydrodewaxing, has the following characteristics: it has an initial boiling point greater than 340 ° C and preferably greater than 370 ° C, a pour point of at least 15 ° C, a viscosity index of 35 to 165 (before dewaxing), preferably at least 110 and even more preferred less than 150, a viscosity at 100 ° C greater than or equal to 3 cSt (mm 2 / s), an aromatic content of less than 10 wt%, a nitrogen content of less than 10 ppm wt, a lower sulfur content at 50 ppm wt or better at 10 ppm wt.
  • 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 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 hydrodewaxing step (b) is sent to the distillation train, which preferably incorporates atmospheric distillation and vacuum distillation, the purpose of which is to separate the conversion products from the boiling below 340 ° C and preferably below 370 ° C, (and including in particular those formed during the catalytic hydrodewaxing step), and to separate the fraction which constitutes the oil base and whose initial point of boiling is greater than at least 340 ° C and preferably greater than or equal to 370 ° C.
  • this vacuum distillation section makes it possible to separate the different grades of oils.
  • the effluent leaving the catalytic hydrodewaxing stage (b) is, at least in part and preferably, in its entirety, sent on a hydrofinishing catalyst (hydrofinishing).
  • hydrofinishing catalyst presence of hydrogen so as to carry out a thorough hydrogenation of aromatic compounds which adversely affect the stability of oils and distillates.
  • the acidity of the catalyst must be low enough not to lead to the formation of cracking product boiling point below 340 ° C so as not to degrade the final yields including oils.
  • the catalyst used in this step comprises at least one Group VIII metal and / or at least one Group VIB element of the Periodic Table.
  • amorphous or crystalline oxide type support such as, for example, aluminas, silicas, silica-aluminas.
  • the hydrofinishing catalyst (HDF) may also contain at least one element of group VII A of the periodic table of elements.
  • these catalysts contain fluorine and / or chlorine.
  • the weight contents of metals are between 10 and 30% in the case of non-noble metals and less than 2%, preferably between 0.1 and 1.5%, and even more preferably between 0.1. and 1.0% in the case of noble metals.
  • the total amount of halogen is between 0.02 and 30 wt.%, Advantageously 0.01 to 15 wt.%, Or even 0.01 to 10 wt.%, Preferably 0.01 to 5 wt.
  • 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 hydrofiniton step (HDF) 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 at the outlet of HDF is sent into the distillation train.
  • the base oils obtained according to this process have a pour point of less than -10 ° C, a VI greater than 95, preferably greater than 110 and even more preferably greater than 120, a viscosity of at least 3, At 100 ° C., an ASTM color of less than 1 and a UV stability such that the ASTM color increase is between 0 and 4 and preferably between 0.5 and 2.5.
  • Another advantage of the process according to the invention is that it is possible to achieve very low aromatics contents, less than 2% by weight, preferably 1% by weight and better still less than 0.05% by weight, and even of go to the production of medicinal grade white oils with aromatic contents of less than 0.01% by weight.
  • These oils have UV absorbance values at 275, 295 and 300 nanometers respectively less than 0.8, 0.4 and 0.3 (ASTM D2008 method) and a Saybolt color between 0 and 30.
  • ASTM D2008 method ASTM D2008 method
  • the process according to the invention also makes it possible to obtain medicinal white oils.
  • White medicinal oils are mineral oils obtained by advanced petroleum refining, their quality is subject to various regulations that aim to ensure their safety for pharmaceutical applications, they are devoid of toxicity and are characterized by their density and viscosity.
  • White medicinal oils mainly comprise saturated hydrocarbons, they are chemically inert and their content of aromatic hydrocarbons is low. Particular attention is paid to aromatic compounds and in particular to 6 polycyclic aromatic hydrocarbons (PAHs for the abbreviation of polycyclic aromatic hydrocarbons) which are toxic and present at concentrations of one part per billion by weight of aromatic compounds in the form of polycyclic aromatic hydrocarbons. white oil.
  • PAHs polycyclic aromatic hydrocarbons
  • the control of the total aromatic content can be carried out by the ASTM D 2008 method, this UV adsorption test at 275, 292 and 300 nanometers makes it possible to control an absorbance less than 0.8, 0.4 and 0.3 respectively. (That is, the white oils have aromatic contents of less than 0.01% by weight). These measurements are made with concentrations of 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).
  • This last test consists of extracting polycyclic aromatic hydrocarbons specifically using a polar solvent, often DMSO, and controlling their content in the extract by a UV absorption measurement in the range 260-350 nm.
  • the charge enters the line (1) in a hydrotreating zone (2) (which may be composed of one or more reactors, and comprising one or more catalytic beds of one or more catalysts) in which hydrogen enters (For example by the pipe (3)) and where the hydrotreating step is carried out.
  • a hydrotreating zone (2) which may be composed of one or more reactors, and comprising one or more catalytic beds of one or more catalysts
  • hydrogen enters Form example by the pipe (3)
  • the hydrotreated feedstock is transferred via the pipe (4) to the hydroisomerisation zone (7) (which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts) where, in the presence of hydrogen, step (a) hydroisomerization.
  • Hydrogen can be supplied via line (8).
  • the charge to be hydroisomerized is freed from a large part of its water in the flask (5), the water leaving via the pipe (6) and optionally ammonia and hydrogen sulphide H 2 S, in the case where the charge entering through line 1 contains sulfur and nitrogen.
  • the effluent from the zone (7) is sent via a pipe (9) into a flask (10) for separating the hydrogen which is extracted via a pipe (11), the effluent is then distilled at atmospheric pressure in the column (12) from which is extracted at the top by the pipe (13) a light fraction containing compounds with at most 4 carbon atoms and those boiling below.
  • At least one gasoline fraction (14) and at least one middle distillate fraction (kerosene (15) and diesel (16) for example).
  • a fraction containing the compounds with a boiling point greater than at least 340 ° C. is obtained at the bottom of the column. This fraction is evacuated via line (17) to the catalytic dewaxing zone (18).
  • the catalytic dewaxing zone (18) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) also receives hydrogen via a line (19) to carry out step (b) of the process.
  • the effluent obtained leaving the pipe (20) is separated in a distillation train including the balloon (21) to separate the hydrogen by a pipe (22), an atmospheric distillation column (23) and a vacuum column (24) which processes the atmospheric distillation residue transferred via line (25), an initial boiling point residue of greater than 340 ° C.
  • an oil fraction (line 26) and lower boiling fractions such as diesel (line 27), kerosene (line 28) gasoline (line 29) are obtained; the light gases are eliminated through the pipe (30) of the atmospheric column and through the pipe (31) of the vacuum distillation column.
  • the effluent leaving the pipe (20) can advantageously be sent to a hydrofinishing zone (not shown) (comprising one or more reactors, one or more catalytic beds of one or more catalysts). Hydrogen can be added if needed in this area.
  • the outgoing effluent is then transferred into the flask (21) and the described distillation train.
  • step a all of the effluent from the hydroisomerization-conversion zone (7) (step a) passes directly through line (9) into the catalytic dewaxing zone (18) (step b).
  • the effluent from the hydroisomerization-conversion zone (7) undergoes in the flask (32) a separation of at least a portion of the light gases (hydrogen and hydrocarbon compounds at plus 4 carbon atoms) for example by flash.
  • the separated gases are removed via line (33) and the residual effluent is sent via line (34) to the catalytic dewaxing zone (18).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Claims (17)

  1. Verfahren zur Herstellung von Ölen aus einem kohlenwasserstoffhaltigen Einsatzgut, wobei das Verfahren nacheinander die folgenden Schritte umfasst:
    (a) Konversion des Einsatzgutes bei gleichzeitiger Hydroisomerisierung mindestens eines Teils der n-Paraffine des Einsatzgutes, wobei das Einsatzgut einen Schwefelgehalt von weniger als 1000 ppm, bezogen auf das Gewicht, einen Stickstoffgehalt von weniger als 200 ppm, bezogen auf das Gewicht, einen Gehalt an Metallen von weniger als 50 ppm, bezogen auf das Gewicht, einen Sauerstoffgehalt von höchstens 0,2 Gew.-% aufweist, in Gegenwart eines Katalysators, der mindestens ein Edelmetall enthält, das auf einem amorphen, sauren Träger abgelagert ist, wobei die Dispersion an Edelmetall kleiner ais 20 % ist,
    wobei der Schritt (a) bel einer Temperatur von 200 bis 500 °C, unter einem Druck von 2 bis 25 MPa, bei einer Volumengeschwindigkeit von 0,1 bis 10 h-1, in Gegenwart von Wasserstoff in einem Verhältnis, das im Bereich zwischen 100 und 2000 Liter Wasserstoff/Liter Einsatzgut enthalten ist, abläuft,
    (b) katalytische Entparaffinierung mindestens eines Teils des aus dem Schritt (a) resultierenden Abstroms in Gegenwart eines Katalysators, der mindestens ein hydrierend-dehydrierendes Element und das Molekularsieb, ZBM-30, gewählt ist, umfasst,
    wobei der Schritt (b) bei einer Temperatur von 200 bis 500 °C, unter einem Druck von 1 bis 25 MPa, mit einer Volumengeschwindigkeit (pro Stunde) von 0,05 bis 50 h-1 und in Gegenwart von 50 bis 2000 Liter Wasserstoff/Liter Fluid, das in den Schritt (b) eingeht, abläuft.
  2. Verfahren nach Anspruch 1, wobei die Gesamtheit des Abstroms vom Schritt (a) im Schritt (b) behandelt wird.
  3. Verfahren nach einem der Ansprüche 1 oder 2, wobei der Abstrom, der aus dem Schritt (a) resultiert, derart destilliert wird, dass die leichten Gase und mindestens ein Rückstand, der die Verbindungen mit einem Siedepunkt oberhalb von mindestens 340 °C enthält, getrennt werden, wobei der Rückstand dem Schritt(b)unterzogen wird.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei das ausströmende Fluid, das aus dem Schritt (b) resultiert, derart destilliert wird, dass ein Öl abgetrennt wird, welches die Verbindungen mit einem Siedepunkt oberhalb von mindestens 340 °c enthält.
  5. Verfahren nach Anspruch 4, eine atmosphärische Destillation gefolgt von einer Vakuumdestillation des Rückstandes von der atmosphärischen Destillation unfassend.
  6. Verfahren nach einem der vorhergehenden Anspruche, wobei das Einsatzgut, das dem Schritt (a) unterzogen wird, zuvor ein Hydrotreating und dann eventuell ein Abtrennen von Wasser, von Ammoniak und von Schwefelwasserstoff erfahren hat.
  7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass bei dem Katalysator für den Schritt (a) der Anteil der Edelmetallpartikel mit einer Größe von weniger als 2 nm höchstens 2 Gew.-% des auf dem Katalysator abgelagerten Edelmetalls darstellt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass bei dem Katalysator für den Schritt (a) mindestens 70 % der Edelmetallpartikel eine Größe von mehr als 4 nm aufweisen.
  9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Träger aus der Gruppe bestehend aus Tonerde-Kieselerde, Aluminiumhalogenid, Aluminiumoxid, dotiert mit Silicium, einem Gemisch aus Aluminiumoxid/Titanoxid, sulfatiertem Zirconiumdioxid, Zirconiumdioxid, dotiert mit Wolfram, allein oder im Gemisch, gewählt ist.
  10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass der Träger außerdem mindestens eine amorphe Matrix umfasst, die aus der Gruppe bestehend aus Tonerde (Aluminiumoxid), Titanoxid, Kieselerde (Siliciumdioxid), Boroxid, Bittererde (Magnesiumoxid), Zirkonerde (Zirconiumdioxid), Ton gewählt ist.
  11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Tröger aus einem amorphen Tonerde-Kieselerde gebildet ist.
  12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Träger für den Schritt (a) 1 bis 95 Gew.-% Siliciumdioxid enthält und der Katalysator 0,05 bis 10 Gew.-% Edelmetall enthält.
  13. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Edelmetall des Katalysators für den Schritt (a) und das hydrierenddehydrierende Metall des Katalysators für den Schritt (b) aus der Gruppe bestehend aus Platin und Palladium gewählt sind.
  14. Verfahren nach einem der vorhergehenden Ansprüche, wobei der Abstrom, der aus dem Schritt (b) resultiert, einem Hydrofining-Schritt unterzogen wird, bevor er destilliert wird.
  15. Verfahren nach einem der vorhergehenden Ansprüche, wobei das behandelte kohlenwasserstoffhaltige Einsatzgut mindestens 20 Vol.-% Verbindungen enthält, die oberhalb von 340 °C sieden.
  16. Verfahren nach einem der vorhergehenden Ansprüche, wobei das behandelte kohlenwasserstoffhaltige Einsatzgut aus der Gruppe bestehend aus Abströmen, die aus der Fischer-Tropsch-Einheit resultieren, Vakuumdestillaten, die aus der direkten Destillation des Rohöls kommen, Vakuumdestillaten, die aus Konversionseinheiten kommen, Vakuumdestillaten, die aus Einheiten zur Extraktion der aromatischen Kohlenwasserstoffe kommen, Vakuumdestillaten, die von der Entschwefelung oder Hydroumwandlung von Rückständen der atmosphärischen Destillation und/oder der Vakuumdestillation kommen, entasphaltierten Ölen, Rückständen des Hydrocrackens oder einem Gemisch aus den Einsatzgütern gewählt ist.
  17. Verfahren nach Anspruch 16, wobei das Einsatzgut ein Rückstand des Hydrocrackens ist.
EP01270585A 2000-12-15 2001-12-13 Verbessertes flexibles verfahren zur herstellung von grundölen und destillaten durch hydroisomerisierung-konversion an einem schwach dispergierten katalysator und anschliessende katalytische entparaffinierung Expired - Lifetime EP1346010B2 (de)

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FR0016368A FR2818285B1 (fr) 2000-12-15 2000-12-15 Procede flexible ameliore de production de bases huiles et de distillats par une conversion-hydroisomerisation sur un catalyseur faiblement disperse suivie d'un deparaffinage catalytique
FR0016368 2000-12-15
PCT/FR2001/003976 WO2002048290A1 (fr) 2000-12-15 2001-12-13 Procede flexible ameliore de production de bases huiles et de distillats par une conversion-hydroisomerisation sur un catalyseur faiblement disperse suivie d'un deparaffinage catalytique

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FR2851569B1 (fr) * 2003-02-21 2007-04-20 Inst Francais Du Petrole Procede d'hydrocraquage en deux etapes utilisant un catalyseur amorphe a base de platine et de palladium
FR2852863B1 (fr) 2003-03-24 2005-05-06 Inst Francais Du Petrole Catalyseur et son utilisation pour l'amelioration du point d'ecoulement de charges hydrocarbonnees
FR2852865B1 (fr) 2003-03-24 2007-02-23 Inst Francais Du Petrole Catalyseur et son utilisation pour l'amelioration du point d'ecoulement de charges hydrocarbonnees
FR2857019B1 (fr) * 2003-07-03 2005-08-19 Inst Francais Du Petrole Procede d'amelioration du point d'ecoulement de charges hydrocarbonees issues du procede fischer-tropsch, utilisant un catalyseur a base de zeolithe zbm-30
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CN100384965C (zh) 2003-07-04 2008-04-30 国际壳牌研究有限公司 制备费-托产品的方法
RU2258733C2 (ru) * 2003-10-06 2005-08-20 ОАО "Всероссийский научно-исследовательский институт по переработке нефти" Способ получения основы смазочных масел
US7402236B2 (en) 2004-07-22 2008-07-22 Chevron Usa Process to make white oil from waxy feed using highly selective and active wax hydroisomerization catalyst
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US20040134834A1 (en) 2004-07-15
US7371315B2 (en) 2008-05-13
WO2002048290A1 (fr) 2002-06-20
FR2818285A1 (fr) 2002-06-21
FR2818285B1 (fr) 2004-12-17
BR0116207A (pt) 2003-12-23
EP1346010A1 (de) 2003-09-24
DE60122210T3 (de) 2010-08-12
EP1346010B1 (de) 2006-08-09
JP4281045B2 (ja) 2009-06-17
DE60122210D1 (de) 2006-09-21
ES2269299T3 (es) 2007-04-01
KR100809507B1 (ko) 2008-03-07
JP2004515637A (ja) 2004-05-27
KR20030060999A (ko) 2003-07-16
DE60122210T2 (de) 2007-06-28

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