EP1278812A1 - Procede flexible de production de bases huiles avec une zeolithe zsm-48 - Google Patents
Procede flexible de production de bases huiles avec une zeolithe zsm-48Info
- Publication number
- EP1278812A1 EP1278812A1 EP01928020A EP01928020A EP1278812A1 EP 1278812 A1 EP1278812 A1 EP 1278812A1 EP 01928020 A EP01928020 A EP 01928020A EP 01928020 A EP01928020 A EP 01928020A EP 1278812 A1 EP1278812 A1 EP 1278812A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocracking
- catalyst
- hydrogen
- group
- residue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Definitions
- the present invention relates to an improved process for manufacturing very high quality base oils, ie having a high viscosity index (VI), a low aromatic content, good UV stability and a low pour point. , from petroleum fractions having a boiling point above 340 ° C, with possibly simultaneously the production of very high quality middle distillates (gas oils, kerosene), that is to say having a low aromatic content and a low pour point.
- the process according to the invention uses catalytic dewaxing a catalyst based on ZSM-48.
- lubricants are most often obtained by a succession of refining steps allowing the improvement of the properties of an oil cut.
- a treatment of heavy petroleum fractions with high contents of linear or slightly branched paraffins is necessary in order to obtain good quality base oils and this with the best possible yields, by an operation which aims at eliminating linear or very paraffins. poorly connected, fillers which will then be used as base oils.
- This operation can be carried out by extraction with solvents such as toluene / methyl-ethyl ketone or methyl-isobutyl ketone mixtures, this is called methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) dewaxing.
- solvents such as toluene / methyl-ethyl ketone or methyl-isobutyl ketone mixtures, this is called methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK) dewaxing.
- MEK methyl ethyl ketone
- MIBK methyl isobutyl ketone
- Zeolite catalysts such as ZSM-5, ZS -11, ZSM-12, ZSM22, ZSM-23, ZSM-35 and ZSM-38 have been described for use in these methods.
- the Applicant has focused its research efforts on the development of an improved process for manufacturing very high quality lubricating oils.
- the present invention therefore relates to a series of processes for the joint production of very high quality base oils and very high quality middle distillates (gas oils).
- the oils obtained have a high viscosity index VI), a low aromatic content, low volatility, good UV stability and a low pour point, from petroleum fractions having a boiling point above 340 ° C. .
- the invention relates to a process for the production of high quality oils and possibly high quality middle distillates from a hydrocarbon feedstock of which at least 20% by volume boils above 340 ° C., process comprising successively the following stages:
- the dewaxed effluent is directly subjected to a hydrofinishing treatment carried out at a temperature of 180-400 ° C, which is lower than the temperature of the catalytic dewaxing by at least 20 ° C and at most 200 ° C, under a total pressure of 1-25Mpa, with an hourly volume velocity of 0.05-1 OOh "1 , in the presence of 50-2000 liter of hydrogen / liter of charge, and in the presence of an amorphous catalyst for the hydrogenation of aromatics, comprising at least one metal chosen from the group of metals from group VIII and metals from group VI B,
- the effluent 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 oil fraction at a boiling point above 340 ° C, and which has a pour point of less than -10 ° C, a weight content of aromatic compounds of less than 2%, and an IV of more than 95, a viscosity at 100 ° C of at least 3cSt (i.e. 3mm 2 / s) and so as to optionally separate at least one middle distillate fraction having a pour point of less than or equal to -20 ° C., an aromatic content of at most 2% by weight and a polyaromatic content of at most 1% by weight.
- a distillation step comprising an atmospheric distillation and a vacuum distillation so as to separate at least one oil fraction at a boiling point above 340 ° C, and which has a pour point of less than -10 ° C, a weight content of aromatic compounds of less than 2%, and an IV of more
- the hydrocarbon feedstock from which the oils and possibly the high quality middle distillates are obtained contains at least 20% boiling volume above 340 ° C.
- the feed can be for example LCO (light cycle oil), vacuum distillates from the direct distillation of crude oil or from conversion units such as FCC, coker or visbreaking, or from extraction units aromatics, or from desulfurization or hydroconversion of RAT (atmospheric residues) and / or RSV (vacuum residues), or the filler can be a deasphalted oil, or any mixture of the charges mentioned above.
- LCO light cycle oil
- RAT atmospheric residues
- RSV vacuum residues
- the filler can be a deasphalted oil, or any mixture of the charges mentioned above.
- fillers suitable for the oil objective have an initial boiling point greater than 340 ° C, and better still greater than 370 ° C.
- the feed is first subjected to a hydrotreatment, during which it is brought into contact, in the presence of hydrogen, with at least one catalyst comprising an amorphous support and at least one metal having a hydro-dehydrogenating function ensured for example.
- at least one catalyst comprising an amorphous support and at least one metal having a hydro-dehydrogenating function ensured for example.
- at least one element from group VI B and at least one element from group VIII at a temperature between 330 and 450 ° C, preferably 360-420 ° C, under a pressure between 5 and 25 Mpa, preferably lower at 20 MPa, the space speed being between 0.1 and 6 h "1 , preferably 0.3-3 h " 1 , and the quantity of hydrogen introduced is such that the hydrogen / hydrocarbon volume ratio is between 100 and 2000.
- This first step makes it possible, by pre-cracking the load to be treated, to adjust the properties of the oil base at the outlet of this first step as a function of the quality of the oil base which it is desired to obtain at the outlet of the process. .
- this adjustment can be made by varying the nature and the quality of the catalyst used in the first step and / or the temperature of this first step, so as to raise the viscosity index for the oil base, fraction of a point. boiling above 340 ° C, at the end of this stage.
- the viscosity index obtained, before dewaxing is preferably between 80 and 150, and better still between 90 and 140, or even 90 and 130.
- the support generally is based on (preferably consists essentially) of alumina or of amorphous silica-alumina; it can also contain boron oxide, magnesia, zirconia, titanium oxide or a combination of these oxides.
- the hydro-dehydrogenating function is preferably fulfilled by at least one metal or compound of metal from groups VIII and VI 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 brings two advantages to hydrotreatment catalysts: ease of preparation during in particular the impregnation of nickel and molybdenum solutions, and better hydrogenation activity.
- the preferred catalysts are the Ni o 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 else the NiMo and / or NiW catalysts on silica-alumina, or on silica-alumina-titanium oxide doped or not with at least one element included in the group of atoms formed by phosphorus, boron, fluorine and silicon.
- the total concentration of oxides of metals from groups VI and VIII is between 5 and 40% by weight and preferably between 7 and 30% and the weight ratio expressed as metal oxide between metal (or metals) of group VI on metal (or metals) of group VIII is preferably between 20 and 1.25 and even more preferably between 10 and 2.
- the concentration of phosphorus oxide P2O5 will be less than 15% by weight and preferably 10% by weight.
- the product obtained at the end of this first stage is sent to a second catalyst in a second stage without intermediate separation of ammonia (NH 3 ) and hydrogen sulfide (H 2 S), nor distillation.
- NH 3 ammonia
- H 2 S hydrogen sulfide
- the effluent from the first step (a) is completely introduced onto the catalyst of the second step (b) in the presence of hydrogen where it is hydrocracked in the presence of a bifunctional catalyst comprising a zeolitic acid function and a hydro-dehydrogenating metal function.
- the polyaromatic and polynaphthenoaromatic compounds partially and or completely hydrogenated during the first stage are hydrocracked on the acid sites to lead to the formation of paraffins.
- These paraffins in the presence of a bifunctional catalyst can undergo isomerization then optionally a hydrocracking to lead respectively to the formation of isoparaffins and lighter cracking products.
- the second stage catalyst comprises a zeolite, a support and a hydro-dehydrogenating function.
- the hydro-dehydrogenating function is advantageously obtained by a combination of metals from groups VI B (for example molybdenum and / or tungsten) and / or metals from group VIII preferably non-noble (for example cobalt and / or nickel) of the classification of the elements.
- this catalyst may also contain at least one promoter element deposited on the surface of the catalyst, element included in the group formed by phosphorus, boron and silicon and advantageously phosphorus.
- the total concentration of metals of groups VI B and VIII, expressed as metal oxides relative to the support, is generally between 5 and 40% by weight, preferably between 7 and 30% by weight.
- the weight ratio (expressed as metal oxides) of metals of group VIII to metals of group VI B is preferably between
- This type of catalyst can advantageously contain phosphorus, the content of which, expressed as phosphorus oxide P2O5 relative to the support, will generally be less than 15% by weight, preferably less than 10% by weight.
- the boron and silicon contents are less than 15% by weight and preferably less than 10% by weight (expressed as oxide).
- the amorphous or poorly crystallized support is chosen from the group formed by alumina, silica, silica alumina, alumina-boron oxide, magnesia, silica-magnesia, zirconia, titanium oxide, clay, alone or in mixtures.
- the zeolite is advantageously ⁇ selected from the group consisting of Y zeolite (type structura) FAU, faujasite) and Beta zeolite (structural type BEA) according to the nomenclature developed in "Atlas of zeolite structure types", WM Meier, DH Olson and Ch. Baerlocher, 4 t revised Edition 1996, Elsevier.
- the zeolite content by weight is between 2 and 80% and preferably between 3 and 50% relative to the final catalyst, and advantageously between 3-25%.
- the zeolite can optionally be doped with metallic elements such as, for example, the metals of the rare earth family, in particular lanthanum and cerium, or noble or non-noble metals of group III, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
- metallic elements such as, for example, the metals of the rare earth family, in particular lanthanum and cerium, or noble or non-noble metals of group III, such as platinum, palladium, ruthenium, rhodium, iridium, iron and other metals such as manganese, zinc, magnesium.
- a particularly advantageous acidic zeolite HY is characterized by different specifications: a Si ⁇ 2 / Al2 ⁇ 3 molar ratio of between approximately 6 and 70 and preferably between approximately 12 and 50: a sodium content of less than 0.15% by weight determined on the calcined zeolite at 1100 ° C; a crystalline parameter has elementary mesh ranging between 24.58 x 10 " 10 m and 24.24 x 10 m and so
- a capacity C ⁇ a of recovery in sodium ions expressed in grams of ⁇ a per 100 grams of modified zeolite, neutralized then calcined, greater than about 0.85; a specific surface area determined by the BET method greater than approximately 400 m 2 / g and preferably greater than 550 m 2 / g, a water vapor adsorption capacity at 25 ° C. for a partial pressure of 2.6 torrs (i.e. 34.6 MPa), greater than about 6%, a porous distribution, determined by physisorption of nitrogen, comprising between 5 and 45% and preferably between 5 and 40% of the total pore volume of the zeolite contained in
- a preferred catalyst essentially contains at least one group VI metal, and / or at least one non-noble group VIII metal, zeolite Y and alumina.
- An even more preferred catalyst essentially contains nickel, molybdenum, a Y zeolite as defined above and alumina.
- the pressure will be maintained between 5 and 25 MPa, advantageously between 5 and 20 MPa and preferably 7 to 15 MPa, the space speed will be between 0.1 h ' ⁇ and 5 h " 1 and preferably between 0.5 and 4 .0h ⁇ 1.
- the temperature is adjusted in the second step (b), so as to obtain the viscosity and the V.l. desired. It is between 340 and 430 ° C, and in general it is advantageously between 370 and 420 ° C.
- These two stages (a) and (b) can be carried out on the two types of catalysts in (two or more) different reactors, or and preferably on at least two catalytic beds installed in the same reactor.
- step c From the effluent leaving the hydrocracker, the hydrogen is separated, the effluent is then subjected directly to atmospheric distillation (step c) so as to separate the gases (such as ammonia and hydrogen sulfide ( H 2 S) formed, as well as the other light gases which would be present, possibly hydrogen ). At least one liquid fraction containing products with a boiling point above 340 ° C. is obtained.
- gases such as ammonia and hydrogen sulfide ( H 2 S) formed, as well as the other light gases which would be present, possibly hydrogen .
- This fraction has a VI, before dewaxing, between 95 and 165 and preferably at least 110.
- this fraction (residue) will then be treated in the step of catalytic dewaxing, that is to say without undergoing vacuum distillation.
- the residue undergoes, before being catalytically dewaxed, an extraction of the aromatic compounds (constituting a step (c 1 ).
- This extraction is carried out by any known means, the most used solvents are furfurol and N-methylpyrrolidone.
- the naphthenoaromatic compounds are thus extracted, and the raffinate obtained has a higher viscosity index than that of the residue entering the extraction step. By this operation, an further increases the VI of the product obtained at the end of the hydrofinishing step.
- the cutting point is lowered, and instead of cutting at 340 ° C. as previously, it is possible for example to include gas oils and possibly kerosene in the fraction containing compounds boiling above 340 ° C. For example, a fraction with an initial boiling point of at least 150 ° C. is obtained.
- the residue can be extracted from the aromatic compounds before being catalytically dewaxed.
- This extraction is carried out by any known means, furfurol being most often used. The usual operating conditions are used.
- the raffinate obtained has a viscosity index higher than the index of the incoming residue.
- the VI of the product obtained at the end of the hydrofinishing is thus further increased.
- the fraction thus obtained which contains said compounds will be treated directly in catalytic dewaxing, the other fractions (150 ° C.) being or not being treated separately in catalytic dewaxing, in this embodiment.
- middle distillates are called the fraction (s) with an initial boiling point of at least 150 ° C. and a final going before the residue, that is to say generally say up to 340 ° C, or preferably 370 ° C.
- An advantage of this conversion process (hydrotreating and hydrocracking) described is that it generally makes it possible to manufacture bases of lubricating oils having a viscosity higher than that obtained by an amorphous catalyst with the same conversion.
- the viscosity at 100 ° C of the fraction of boiling point greater than 340 ° C not converted, and preferably higher than 370 ° C is a decreasing function of the level of conversion obtained.
- this ratio is strictly less than 1, preferably between 0.95 and 0.4.
- HDPC Catalytic hydrodewaxing
- the fraction containing the compounds boiling above 340 ° C., as defined above, resulting from the second stage and from atmospheric distillation (c) is then subjected, at least partly, and preferably entirely, at a catalytic dewaxing step in the presence of hydrogen and a hydrodewaxing catalyst comprising an acid function and a metal hydro-dehydrogenating function and at least one matrix.
- the acid function is provided by at least one zeolite chosen from the group formed by the zeolites ZSm-48, EU-2, EU-11 and ZBM-30.
- zeolites allows in particular the production of products with low pour point and high viscosity index with good yields in the context of the process according to the invention.
- the content by weight of molecular sieve 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 example and without limitation, alumina gels, aluminas, magnesia, amorphous silica-aluminas, and mixtures thereof. Techniques such as extrusion, pelletizing or coating, can be used to carry out the shaping operation.
- the catalyst also includes a hydro-dehydrogenating function provided, for example, by at least one element of group VIII and preferably at least one element included in the assembly formed by platinum and palladium.
- the content by weight of non-noble metal from 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 metal from group VIB (Mo and W preferred). If it is at least one noble metal from 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 can also contain from 0 to 20%, preferably from 0 to 10% by weight (expressed as oxides) phosphorus.
- the combination of Group VI B metal (s) and / or Group VIII metal (s) with phosphorus is particularly advantageous.
- the hydrocracking residue (that is to say the fraction with an initial boiling point greater than 340 ° C.) which obtained in step (c) of the process according to the invention and which is to be treated in this step ( d) hydrodewaxing, has the following characteristics: it has an initial boiling point greater than 340 ° C and preferably greater than 370 ° C, a pour point of at least 15 ° C, a content of nitrogen less than 10 ppm by weight a sulfur content less than 50 ppm by weight or better than 10 ppm by weight, a viscosity index of 35 to 165 (before dewaxing), preferably at least equal to 110 and even more preferably less than 150, an aromatic content less than 10% by weight, a viscosity at 100 ° C greater than or equal to 3 cSt (mm s).
- the reaction temperature is between 200 and 500 ° C and preferably between 250 and 470 ° C, advantageously 270-430 ° C;
- the pressure is between 0.1 and 25 MPa (10 6 Pa) and preferably between 1.0 and 20 MPa;
- the hourly volume speed (vvh expressed in volume of charge injected per unit volume of catalyst and per hour) is between approximately 0.05 and approximately 50 and preferably between approximately 0.1 and approximately 20 h '1 and so even more 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 rate of hydrogen used and expressed in liters of hydrogen per liter of charge is between 50 and approximately 2000 liters of hydrogen per liter of charge and preferably between 100 and 1500 liters of hydrogen per liter of charge.
- One of the characteristics of the method according to the invention is that;
- the variation in VI during the catalytic hydrodewaxing stage is preferably greater than or equal to 0, for the same pour point, or
- the effluent at the outlet of the catalytic hydrodewaxing stage is, in its entirety and without intermediate distillation, sent to a hydrofinishing catalyst in the presence of hydrogen so as to carry out a thorough hydrogenation of the aromatic compounds which harm stability. oils and distillates.
- the acidity of the catalyst must be low enough not to lead to the formation of cracking product with a boiling point below 340 ° C. so as not to degrade the final yields, in particular of oils.
- the catalyst used in this step comprises at least one metal from group VIII and / or at least one element from group VIB of the periodic table.
- metals are deposited and dispersed on a support of amorphous or crystalline oxide type, such as, for example, aluminas, silicas, silica-aluminas.
- the hydrofinishing catalyst (HDF) can also contain at least one element from group VII A of the periodic table.
- these catalysts contain fluorine and / or chlorine.
- the contents by weight 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 even 0.01 to 10%, preferably 0.01 to 5%.
- catalysts which can be used in this HDF step Mention may be made, among the catalysts which can be used in this HDF step, and which lead to excellent performance, and in particular for obtaining medicinal oils, catalysts containing at least one noble metal from group VIII (platinum for example) and at least one halogen (chlorine and / or fluorine), the combination of chlorine and fluorine being preferred.
- group VIII platinum for example
- halogen chlorine and / or fluorine
- the reaction temperature is between 180 and 400 ° C and preferably between 210 and 350 ° C, preferably 230-320 ° C; the pressure is between 0.1 and 25 MPa (10 6 Pa) and preferably between 1.0 and 20 MPa; the hourly space velocity (vvh expressed in volume of charge injected per unit volume of catalyst and per hour) is between approximately 0.05 and approximately 100 and preferably between approximately 0.1 and approximately 30 h -1 .
- the rate of hydrogen used and expressed in liters of hydrogen per liter of charge is between 50 and approximately 2000 liters of hydrogen per liter of charge and preferably between 100 and 1500 liters of hydrogen per liter of charge.
- the difference T H DP C -TH D F is generally between 20 and 200, and preferably between 30 and 100 ° C.
- the effluent leaving the HDF stage is sent to the distillation train, which integrates atmospheric distillation and vacuum distillation, which aims to separate the conversion products from boiling point below 340 ° C and preferably less than 370 ° C, (and including in particular those formed during the catalytic hydrodewaxing stage (HDPC)), of the fraction which constitutes the oil base and whose initial boiling point is greater than 340 ° C and preferably higher than 370 ° C.
- the distillation train which integrates atmospheric distillation and vacuum distillation, which aims to separate the conversion products from boiling point below 340 ° C and preferably less than 370 ° C, (and including in particular those formed during the catalytic hydrodewaxing stage (HDPC)), of the fraction which constitutes the oil base and whose initial boiling point is greater than 340 ° C and preferably higher than 370 ° C.
- this vacuum distillation section allows the different grades of oils to be separated.
- the base oils obtained according to this process have a pour point of less than -10 ° C, a weight content of aromatic compounds of less than 2%, a VI of more than 95, preferably more than 110 and even more preferably more at 120, a viscosity of at least 3.0 cSt at 100 ° C, an ASTM color less than 1 and UV stability such that the increase in ASTM color is between 0 and 4 and preferably between 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 lubricating oils exposed to a source of UV light.
- the test chamber consists of a metal enclosure provided with a turntable which receives the oil samples. A vial producing the same ultraviolet rays as those of sunlight and placed at the top of the test chamber is directed downwards on the samples. Among the samples is included a standard oil with known UN characteristics.
- Another advantage of the process according to the invention is that it is possible to achieve very low aromatic contents, less than 2% by weight, preferably 1% by weight and better still less than 0.05% by weight) and even go as far as the production of white oils of medicinal quality having aromatic contents lower than 0.01% by weight.
- These oils have UV absorbance values at 275, 295 and 300 nanometers respectively less than 0.8, 0.4 and 0.3 (ASTM D2008 method) and a Saybolt color between 0 and 30.
- the method according to the invention also makes it possible to obtain medicinal white oils.
- White medical oils are mineral oils obtained by a refined refining of petroleum, their quality is subject to various regulations which aim to guarantee their harmlessness for pharmaceutical applications, they are devoid of toxicity and are characterized by their density and viscosity.
- Medicinal white oils mainly contain saturated hydrocarbons, they are chemically inert and their aromatic hydrocarbon content is low. Particular attention is paid to aromatic compounds and in particular to 6 polycyclic aromatic hydrocarbons (PAH for the Anglo-Saxon abbreviation of polycyclic aromatic hydrocarbons) which are toxic and present at concentrations of one part per billion by weight of aromatic compounds in white oil.
- PAH polycyclic aromatic hydrocarbons
- the total aromatics content can be checked 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 to say that the white oils have aromatic contents of less than 0.01% by weight). These measurements are carried out with concentrations of 1 g of oil per liter, in a 1 cm tank.
- the white oils sold are differentiated by their viscosity but also by their crude origin which can be paraffinic or naphthenic, these two parameters will induce differences both in the physico-chemical properties of the white oils considered but also in their chemical composition .
- This last test consists in specifically extracting polycyclic aromatic hydrocarbons using a polar solvent, often DMSO, and in controlling their content in the extract by measuring UV absorption in the 260-350 nm range.
- the middle distillates obtained have improved pour points (less than or equal to -20 ° C.), low aromatic contents (at most 2% by weight), polyaromatic contents (di and more) less than 1% by weight and for gas oils, a cetane number greater than 50, and even greater than 52.
- Another advantage of the process according to the invention is that the total pressure can be the same in all the reactors, hence the possibility of working in series and using a single unit and therefore generate cost savings.
- FIGS. 1 and 2 The process is illustrated in FIGS. 1 and 2, FIG. 1 representing the treatment of the entire liquid fraction in hydrodewaxing and FIG. 2 that of a hydrocracking residue.
- the charge enters via line (1) into a hydrotreatment zone (2) (which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts) into which enters hydrogen (for example via line (3)) and where the hydrotreatment step (a) is carried out.
- a hydrotreatment zone (2) which may be composed of one or more reactors, and comprise one or more catalytic beds of one or more catalysts
- the hydrotreated charge is transferred via line (4) into the hydrocracking zone (5) (which can be composed of one or more reactors, and include one or more catalytic beds of one or more catalysts) where is carried out, in the presence of hydrogen hydrocracking step (b).
- the hydrocracking zone (5) which can be composed of one or more reactors, and include one or more catalytic beds of one or more catalysts
- the effluent from zone (5) is sent via a line (6) into a flask (7) for separation of the hydrogen which is extracted via a line (8), the effluent is then distilled at atmospheric pressure in the column (9) from which the gaseous fraction is extracted at the head by the pipe (10). Step (c) of the process is thus carried out.
- a liquid fraction containing the compounds with a boiling point above 340 ° C. is obtained at the bottom of the column. This fraction is evacuated via line (11) to the catalytic dewaxing zone (12).
- the catalytic dewaxing zone (12) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) also receives hydrogen via a line (13) to carry out step (d) of the process.
- the effluent leaving this zone via a pipe (14) is sent directly to the hydrofinishing zone (15) (comprising one or more reactors, one or more catalytic beds of one or more catalysts) from which it emerges by a line (16). Hydrogen can be added if necessary in the zone (15) where step (e) of the process is carried out.
- the effluent obtained is separated in a distillation train (step f of the process) comprising, in addition to the flask (17) for separating the hydrogen by a line (18), an atmospheric distillation column (19) and a vacuum column (20) which treats the atmospheric distillation residue transferred by the line (21), residue at initial boiling point above 340 ° C. it is obtained as products at the end of the distillations, an oil fraction (line 22) and lower boiling fractions, such as gas oil (line 23), kerosene (line 24) gasoline (line 25); the light gases being eliminated by the pipe (26) from the atmospheric column and the gases being eliminated by the column (27) in vacuum distillation.
- a distillation train step f of the process
- step f of the process comprising, in addition to the flask (17) for separating the hydrogen by a line (18), an atmospheric distillation column (19) and a vacuum column (20) which treats the atmospheric distillation residue transferred by the line (21), residue at initial boiling point above 340 ° C. it is obtained as products at the end
- the residue leaving via the pipe (11) and which has an initial boiling point greater than 340 ° C is sent, at least in part, to an additional hydrocracking zone (32), different from zone (5) (comprising one or more reactors, one or more catalytic beds of one or more catalysts).
- This other hydrocracking zone can contain the same catalyst as zone (5) or another catalyst.
- the resulting effluent is recycled to the atmospheric distillation stage.
- the residue leaving the column (9) via the pipe (11) is sent to the other hydrocracking zone (32), from which an effluent emerges in a pipe (33) which is recycled in the column (9) .
- a pipe (34) connected to the pipe (11) the residue is sent, which is sent to the dewaxing zone (12).
- FIG. 3 also shows the production in the same reactor (31) of the hydrotreating and (5) hydrocracking zones (2), but separate zones are quite possible in combination with the additional zone (32) d hydrocracking.
- the conversion assembly of FIG. 3 can thus replace the conversion assembly of FIG. 2, the steps hydrodewaxing, hydrofinishing, and the distillation train being unchanged. All the additional possibilities (recycling H2 ..) can be transposed.
- the residue leaving the pipe (1 1) is sent to the aromatic compound extraction unit (35) provided with a line (36) for the entry of the solvent, a line (37) for the outlet of the solvent and a line (38) through which the raffinate leaves which is sent to the catalytic dewaxing zone (12).
- FIG. 4 This variant (corresponding to step (c 1 ) of the method) is shown in FIG. 4.
- the upstream and downstream treatments are those of the method as for example illustrated in FIGS. 2 or 3.
- the invention also relates to an installation for the production of high quality oils and possibly high quality middle distillates, comprising: 0 at least one hydrotreatment zone (2) containing at least one hydrotreatment catalyst and provided at least one line (1) for the introduction of the charge and at least one line (3) for the introduction of hydrogen, 0 at least one hydrocracking zone (5) containing at least one hydrocracking catalyst, for treating the hydrotreated effluent from the zone (2), the hydrocracked effluent leaving the zone (5) via a line (6), at least one atmospheric distillation column (9) to treat the hydrocracked effluent, and provided with at least one line (10) for the outlet of the gaseous fraction, at least one line (1 1) for the outlet of a liquid fraction (residue) containing the point compounds boiling above 340 ° C, at least one line (28, 29 or 30) for the outlet of at least one distillate, 0 at least one aromatic compound extraction unit (35) to treat the residue provided with at least one line (35) for supplying the solvent, at least one line (3
- At least one distillation zone comprising at least one atmospheric distillation column (19) and at least one vacuum distillation column (20), the column (19) being provided with at least one pipe (26) for the outlet light gases, at least one pipe (23, 24, or 25) for the outlet of at least one distillate, and at least one line (21) for recovering a residue, the column (20) comprising at least one line (22) for the exit of the oil fraction and at least one line (27) for the exit of the other compounds.
- an installation in which the zones (2) and (3) are located in the same reactor provided with at least one line (1) for the entry of the load, at least one line (3) for the inlet of hydrogen, and at least one line (6) for the outlet of the hydrocracked effluent, said installation further comprising at least one additional hydrocracking zone (32 ) provided with at least one line (11) for the admission of the residue from the atmospheric distillation column (9), and at least one line (33) for the outlet of the thus hydrocracked effluent, said line (33 ) opening into the pipe (6) to recycle said effluent, and in addition the installation comprises at least one pipe (34) located on the pipe (11) for transferring the residue to the extraction unit (35).
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0005214 | 2000-04-21 | ||
FR0005214A FR2808028B1 (fr) | 2000-04-21 | 2000-04-21 | Procede flexible de production de bases huiles avec une zeolithe zsm-48 |
PCT/FR2001/001221 WO2001081508A1 (fr) | 2000-04-21 | 2001-04-20 | Procede flexible de production de bases huiles avec une zeolithe zsm-48 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1278812A1 true EP1278812A1 (fr) | 2003-01-29 |
EP1278812B1 EP1278812B1 (fr) | 2006-07-12 |
Family
ID=8849537
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP01928020A Expired - Lifetime EP1278812B1 (fr) | 2000-04-21 | 2001-04-20 | Procede flexible de production de bases huiles avec une zeolithe zsm-48 |
Country Status (8)
Country | Link |
---|---|
US (1) | US6884339B2 (fr) |
EP (1) | EP1278812B1 (fr) |
JP (1) | JP2003531276A (fr) |
KR (1) | KR100771963B1 (fr) |
DE (1) | DE60121435T2 (fr) |
ES (1) | ES2267757T3 (fr) |
FR (1) | FR2808028B1 (fr) |
WO (1) | WO2001081508A1 (fr) |
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FR2852864B1 (fr) * | 2003-03-24 | 2005-05-06 | Inst Francais Du Petrole | Catalyseur comprenant au moins une zeolithe choisie parmi zbm-30, zsm-48, eu-2 et eu-11 et au moins une zeolithe y et procede d'hydroconversion de charges hydrocarbonees utilisant un tel catalyseur |
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 |
FR2857020B1 (fr) * | 2003-07-03 | 2007-08-17 | Inst Francais Du Petrole | Procede d'amelioration du point d'ecoulement de charges hydrocarbonees issues du procede fischer-tropsch, utilisant un catalyseur a base d'un melange de zeolithes |
WO2005073349A1 (fr) * | 2004-01-16 | 2005-08-11 | Syntroleum Corporation | Procede pour produire des combustibles et des lubrifiants synthetiques |
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KR101399207B1 (ko) * | 2007-08-22 | 2014-05-26 | 에스케이루브리컨츠 주식회사 | 미전환유를 이용한 고급 윤활기유 공급원료의 제조방법 |
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EP2734605B1 (fr) | 2011-07-20 | 2017-10-25 | ExxonMobil Research and Engineering Company | Production d'huiles de base d'huile lubrifiante |
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US9719034B2 (en) | 2013-12-23 | 2017-08-01 | Exxonmobil Research And Engineering Company | Co-production of lubricants and distillate fuels |
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CN109563418B (zh) | 2016-08-03 | 2022-03-18 | 埃克森美孚研究工程公司 | 用于生产高性能基础油料的萃余油加氢转化 |
US20180355264A1 (en) * | 2017-06-07 | 2018-12-13 | Exxonmobil Research And Engineering Company | Production of diesel and base stocks from crude oil |
WO2019217044A1 (fr) * | 2018-05-07 | 2019-11-14 | Exxonmobil Research And Engineering Company | Processus de fabrication d'huiles de base |
CN112125993B (zh) * | 2019-06-24 | 2022-10-21 | 中国石油化工股份有限公司 | 一种聚乙烯醚液相加氢精制的方法 |
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-
2000
- 2000-04-21 FR FR0005214A patent/FR2808028B1/fr not_active Expired - Lifetime
-
2001
- 2001-04-20 JP JP2001578582A patent/JP2003531276A/ja active Pending
- 2001-04-20 US US10/018,526 patent/US6884339B2/en not_active Expired - Lifetime
- 2001-04-20 EP EP01928020A patent/EP1278812B1/fr not_active Expired - Lifetime
- 2001-04-20 DE DE60121435T patent/DE60121435T2/de not_active Expired - Lifetime
- 2001-04-20 KR KR1020027013763A patent/KR100771963B1/ko active IP Right Grant
- 2001-04-20 ES ES01928020T patent/ES2267757T3/es not_active Expired - Lifetime
- 2001-04-20 WO PCT/FR2001/001221 patent/WO2001081508A1/fr active IP Right Grant
Non-Patent Citations (1)
Title |
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See references of WO0181508A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE60121435D1 (de) | 2006-08-24 |
KR20020086951A (ko) | 2002-11-20 |
ES2267757T3 (es) | 2007-03-16 |
US6884339B2 (en) | 2005-04-26 |
JP2003531276A (ja) | 2003-10-21 |
FR2808028B1 (fr) | 2003-09-05 |
DE60121435T2 (de) | 2006-12-14 |
EP1278812B1 (fr) | 2006-07-12 |
US20020189972A1 (en) | 2002-12-19 |
KR100771963B1 (ko) | 2007-11-01 |
FR2808028A1 (fr) | 2001-10-26 |
WO2001081508A1 (fr) | 2001-11-01 |
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