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    • 专利摘要:
    The invention relates to a method for deep conversion of a heavy hydrocarbon feedstock comprising the following steps: a) a first boiling bed hydroconversion step, b) a step of separating at least a portion of the hydroconverted liquid effluent from step a), c) a step of hydrocracking at least part of the vacuum gas oil fraction resulting from step b) d) a step of fractionation of at least a portion of the effluent from of step c) e) a step of recycling at least a portion of the unconverted vacuum gas oil fraction from step d) in said first hydroconversion step a).
    公开号:FR3030568A1
    申请号:FR1462715
    申请日:2014-12-18
    公开日:2016-06-24
    发明作者:Frederic Morel；Jacinthe Fecon
    申请人:Axens SA；
    IPC主号:
    专利说明:

    [0001] . The invention relates to the field of the production of diesel fuel from petroleum residues. The sequence of conversion and hydrocracking units in the treatment of petroleum residue feedstocks is known from the state of the art.
    [0002] US Pat. Nos. 5,980,730 and 6,017,441 disclose a process for deep conversion of a heavy petroleum fraction, said process comprising a three-phase bubbling bed hydroconversion stage, atmospheric distillation of the effluent obtained, vacuum distillation of the atmospheric residue obtained. after this distillation, a deasphalting of the vacuum residue obtained and a hydrotreatment of the deasphalted fraction mixed with the distillate obtained during the distillation under vacuum. It is also possible in this process to send at least a fraction of the hydrotreated effluent to a catalytic cracking section, or to recycle a fraction of the effluent from deasphalting or according to another variant a fraction of the asphalt to the first hydroconversion step or to send a heavy liquid fraction resulting from the hydrotreatment step in a fluidized catalytic cracking section US Pat. No. 6,620,311 describes a conversion process making it possible to increase the yield of middle distillates . This process comprises a step of three-phase bubbling bed conversion, sending the effluent obtained in a separation section to produce a distillate head comprising gas, gasoline and gas oil and basically hydrocarbons having a boiling point higher than an atmospheric gas oil. The distillate is then treated in a hydrodesulfurization unit and the bottom fraction treated in a catalytic cracking section in the absence of hydrogen, for example of the fluidized bed cracking type.
    [0003] This type of cracking thus differs from a hydrocracking operated in fixed bed and in the presence of hydrogen. US Pat. No. 7,919,054 describes a heavy petroleum feedstock treatment plant comprising a bubbling bed hydroconversion section, a separation and a hydrotreatment section in a fixed bed and in the presence of hydrogen of the distillate obtained. This hydrotreatment can be a mild hydrocracking (4.5 to 16 MPa) or a more severe hydrocracking (7 to 20 M Pa). The processes proposed in the prior art, however, suffer from a limitation in the production yield of diesel fuel. In fact, these processes produce a relatively large amount of purge of vacuum distillates at the bottom of the column of the vacuum separation units of the hydroconversion effluents. However, these fractions resulting from vacuum separations, because of their poly-condensed structures, are difficult to recover as an oil base, this in comparison with vacuum distillate fractions from direct distillation of petroleum fractions.
    [0004] The applicant proposes a new process having a particular arrangement of conversion units and possibly solvent deasphalting to obtain higher yields of gas oil production than the processes of the prior art, namely a yield of at least 55 The purpose of the invention is therefore to achieve a deep conversion of the petroleum residue charge while maximizing the production of diesel fuel. The present invention relates to a process for deep conversion of a heavy hydrocarbon feedstock comprising the following steps: a) a first hydroconversion stage in a bubbling bed of the feedstock, in the presence of hydrogen, comprising at least one three-phase reactor, containing at least one ebullated bed hydroconversion catalyst, b) a step of separating at least a portion of the hydroconverted liquid effluent from step a) into a fraction comprising a gasoline cut and a cut gas oil, a gas oil fraction under vacuum, and an unconverted residual fraction, C) a step of hydrocracking at least a portion of the vacuum gas oil fraction from step b) in a reactor comprising at least one catalyst of fixed-bed hydrocracking; d) a step of fractionating at least a portion of the effluent from step c) into a gasoline fraction, a gas oil fraction and an unconverted vacuum gas oil fraction; recycling step of at least a portion of the unconverted vacuum gas oil fraction from step d) in said first hydroconversion step a). The filler according to the present invention is advantageously chosen from heavy hydrocarbon feeds of the atmospheric or vacuum residue type obtained for example by direct distillation of petroleum fraction or by vacuum distillation of crude oil, distillate-type feedstocks such as diesel fuel. vacuum or deasphalted oils, coal suspended in a hydrocarbon fraction such as for example gas oil obtained by vacuum distillation (also called vacuum distillation gas oil), crude oil, or distillate from the liquefaction of coal, alone or in mixture. The filler according to the invention may contain vacuum residues such as Arabian Heavy vacuum residues, Ural vacuum residues and the like, vacuum residues from heavy Canadian or Venezuelan type heavy crudes, or a mixture of atmospheric residues. or under vacuum of various origins. DETAILED DESCRIPTION OF THE INVENTION The method according to the invention comprises at least a first hydroconversion step bubbling bed of the load according to the invention. This technology is marketed in particular as the H-Oil IO process.
    [0005] First hydroconversion stage The conditions of the first hydroconversion stage of the feedstock in the presence of hydrogen are usually conventional bubbling bed hydroconversion conditions of a liquid hydrocarbon fraction or coal suspended in a hydrocarbon liquid phase. It is usually carried out under an absolute pressure generally between 5 and 35 MPa, preferably between 10 and 25 MPa, at a temperature of 260 to 600 ° C and often 350 to 550 ° C. The hourly space velocity (VVH) and the hydrogen partial pressure are important factors that are chosen according to the characteristics of the charge to be treated and the desired conversion. Most often the VVH is in a range of from 0.05 h -1 to 10 h -1 and preferably 0.1 h -1 to 5 h -1.
    [0006] According to the invention, the weighted average temperature of the catalytic bed of the first hydroconversion stage is advantageously between 260 ° C. and 600 ° C., preferably between 300 ° C. and 600 ° C., more preferably between 350 ° C. ° C and 550 ° C. The amount of hydrogen mixed with the feed is usually 50 to 5000 normal cubic meters (Nm3) per cubic meter (m3) of liquid feed. Advantageously, the hydrogen is used in a volume ratio with the feedstock of between 100 and 1000 m 3 / m 3, preferably between 300 and 800 m 3 / m 3, and more preferably between 300 and 600 m 3 / m 3. It is possible to use a granular hydroconversion catalyst of residues in bubbling beds comprising on an amorphous support at least one metal compound having a hydrodehydrogenating function. This catalyst may be a catalyst comprising Group VIII metals, for example nickel and / or cobalt, most often in combination with at least one Group VIB metal, for example molybdenum and / or tungsten. For example, a catalyst comprising from 0.5 to 10% by weight of nickel and preferably from 1 to 5% by weight of nickel (expressed as nickel oxide NiO) and from 1 to 30% by weight of molybdenum of preferably from 5 to 20% by weight of molybdenum (expressed as molybdenum oxide MoO 3) on an amorphous mineral support. This support is for example chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals. This support may also contain other compounds and for example oxides chosen from the group formed by boron oxide, zirconia, titanium oxide and phosphoric anhydride. Most often an alumina support is used and very often a support of alumina doped with phosphorus and possibly boron. The concentration of phosphoric anhydride P2O5 is usually less than 20% by weight and most often less than 10% by weight. This P205 concentration is usually at least 0.001% by weight. The concentration of boron trioxide B 2 O 3 is usually from 0 to 10% by weight. The alumina used is usually a gamma or rho alumina. This catalyst is most often in the form of extruded. In all cases, the attrition resistance of the catalyst must be high given the specific constraints of the bubbling beds. The total content of metal oxides of groups VI and VIII is often from 5 to 40% by weight and in general from 7 to 30% by weight and the weight ratio expressed as metal oxide between metal (or metals) of Group VI on metal (or metals) and Group VIII (Group VI oxide / Group VIII oxide by weight) is generally 20 to 1 and most often 10 to 2. The used catalyst is partly replaced by fresh catalyst by racking down the reactor and introduction to the top of the fresh or new catalyst reactor at regular time interval, that is to say for example by puff or almost continuously. For example, fresh catalyst can be introduced every day. The replacement rate of the spent catalyst with fresh catalyst can be, for example, from 0.01 kilogram to 10 kilograms per cubic meter of charge. This withdrawal and replacement are performed using devices for the continuous operation of this hydroconversion step. The unit usually comprises a recirculation pump for maintaining the bubbling bed catalyst by continuously recycling at least a portion of the liquid withdrawn at the top of the reactor and reinjected at the bottom of the reactor. It is also possible to send the spent catalyst withdrawn from the reactor into a regeneration zone in which the carbon and the sulfur contained therein are eliminated and then to return this regenerated catalyst to the hydroconversion stage a). The spent catalyst can also be sent to a rejuvenation zone to partially extract the metals and coke from the feed and deposited on the catalyst. The hydroconverted liquid effluent from the first boiling bed hydroconversion step (step a)) is advantageously subjected to a separation step b) making it possible to produce at least one fraction comprising a gasoline cut and a gas oil cut, a diesel fraction under vacuum and a residual fraction not converted. According to the invention, the boiling point of the gasoline fraction (or fraction) is advantageously between 20 and 130 ° C, preferably between 20 and 180 ° C; the boiling point of the fraction (or cut) gas oil is advantageously between 130 and 380 ° C, preferably between 180 and 350 ° C; the boiling point of the gas oil fraction under vacuum is advantageously between 350 and 550 ° C, preferably between 380 and 500 ° C; the boiling point of the unconverted residual fraction is preferably at least 500 ° C or even 550 ° C.
    [0007] This separation step is carried out by any means known to those skilled in the art, in particular by atmospheric fractionation followed by vacuum fractionation. Hydrocracking step According to the invention, the fraction of gas oil vacuum (VGO according to the English terminology) separated in step b) is treated in at least one hydrocracking stage comprising at least one hydrocracking reactor. . In the context of the present invention, the term "hydrocracking" includes cracking processes comprising at least one charge conversion step using at least one catalyst in the presence of hydrogen.
    [0008] The hydrocracking may be carried out according to one-step diagrams comprising in the first place advanced hydrorefining which is intended to carry out extensive hydrodenitrogenation and desulfurization of the feedstock before the effluent is wholly sent to the hydrocracking catalyst. itself, especially in the case where it comprises a zeolite. It also includes two-step hydrocracking which comprises a first step which aims, as in the "one-step" process, to perform the hydrorefining of the feed, but also to achieve a conversion of the feedstock. order in general from 30 to 60 percent. In the second step of a two-stage hydrocracking process, generally only the fraction of the unconverted feedstock in the first step is processed. Conventional hydrorefining catalysts generally contain at least one amorphous support and at least one hydro-dehydrogenating element (generally at least one non-noble group VIB and VIII, and most often at least one group VIB element and at least one a non-noble group VIII element). The matrices that can be used in the hydrorefining catalyst alone or as a mixture are, for example, alumina, halogenated alumina, silica, silica-alumina, clays (selected for example from natural clays such as kaolin or bentonite), magnesia, titanium oxide, boron oxide, zirconia, aluminum phosphates, titanium phosphates, phosphates zirconium, coal, aluminates. It is preferred to use matrices containing alumina, in all the forms known to those skilled in the art, and even more preferably aluminas, for example gamma-alumina. The operating conditions of the hydrocracking step are adjusted so as to maximize the production of diesel fraction while ensuring good operability of the hydrocracking unit. The operating conditions used in the reaction zone (s) are generally an average catalyst bed temperature (WABT) of between 300 and 550 ° C, preferably between 350 and 500 ° C.
    [0009] The pressure is generally between 5 and 35 MPa, preferably between 6 and 25 MPa. The liquid space velocity (charge rate / volume of catalyst) is generally between 0.1 and 10 h -1, preferably between 0.2 and 5 h -1. An amount of hydrogen is introduced such that the volume ratio in m3 of hydrogen per m3 of hydrocarbon at the inlet of the hydrocracking step is between 300 and 2000 m3 / m3, most often between 500 and 1800 m3 / m3, preferably between 600 and 1500 m3 / m3. This reaction zone generally comprises at least one reactor comprising at least one fixed-bed hydrocracking catalyst. The fixed bed of hydrocracking catalyst may be optionally preceded by at least one fixed bed of a hydrorefining catalyst (hydrodesulfurization, hydrodenitrogenation for example). The hydrocracking catalysts used in the hydrocracking processes are generally of the bifunctional type associating an acid function with a hydrogenating function. The acid function can be provided by supports having a large surface area (generally 150 to 800 m 2 g -1) and having surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), combinations of boron oxides and aluminum, amorphous silica-aluminas known as amorphous hydrocracking catalysts and zeolites. The hydrogenating function may be provided either by one or more metals of Group VIII of the Periodic Table of Elements, or by a combination of at least one Group VIB metal of the Periodic Table and at least one Group VIII metal. The hydrocracking catalyst may also comprise at least one crystalline acid function such as a zeolite Y, or an amorphous acid function such as a silica-alumina, at least one matrix and a hydrodehydrogenating function.
    [0010] Optionally, it may also comprise at least one element chosen from boron, phosphorus and silicon, at least one element of group VIIA (chlorine, fluorine for example), at least one element of group VIIB (manganese for example), with least one element of the group VB (niobium for example).
    [0011] Deasphalting step According to the variants, the process according to the invention can implement a deasphalting step. The deasphalting step may be carried out on the unconverted residual fraction resulting from the separation step b).
    [0012] One of the objectives of the deasphalting step is, on the one hand, to maximize the amount of deasphalted oil and, on the other hand, to maintain, or even to minimize, the asphaltene content. This asphaltene content is generally determined in terms of the content of asphaltenes insoluble in heptane, that is to say measured according to a method described in the AFNOR standard (NF-T 60115) of January 2002.
    [0013] According to the invention, the asphaltene content of the deasphalted effluent (also called DeAsphalted Oil or DAO according to the English terminology, or deasphalted hydrocarbon fraction or deasphalted oil) is less than 3000 ppm by weight. Preferably, the asphaltene content of the deasphalted effluent is less than 1000 ppm by weight, more preferably less than 500 ppm by weight. Below an asphaltene content of 500 ppm by weight, the method of the AFNOR standard (NF-T 60115) is no longer sufficient to measure this content. The Applicant has developed an analytical method, covering the quantitative analysis of asphaltenes direct distillation products and heavy products from deasphalting residues. This method can be used for asphaltene concentrations of less than 3000 ppm by weight and greater than 50 ppm by weight. The method in question consists in comparing the absorbance at 750 nm of a sample in toluene solution with that of a sample in solution in heptane after filtration. The difference between the two measured values is correlated with the concentration of insoluble asphaltenes in heptane using a calibration equation. This method complements the AFNOR method (NF-T 60115) and the IP143 standard method which are used for higher concentrations.
    [0014] The solvent used in the deasphalting step is advantageously a paraffinic solvent, a petrol cut or condensates containing paraffins. Preferably, the solvent used comprises at least 50% by weight of hydrocarbon compounds having between 3 and 7 carbon atoms, more preferably between 4 and 7 carbon atoms, more preferably 4 or 5 carbon atoms. Depending on the solvent used, the deasphalted oil yield and the quality of this oil may vary. By way of example, when passing from a solvent containing 3 carbon atoms to a solvent containing 7 carbon atoms, the oil yield increases but, in return, the levels of impurities (asphaltenes, metals, Conradson carbon, sulfur, nitrogen ...) also increase. Moreover, for a given solvent, the choice of operating conditions, in particular the temperature and the quantity of solvent injected, has an impact on the deasphalted oil yield and on the quality of this oil. Those skilled in the art can choose the optimum conditions for achieving an asphaltene content of less than 3000 ppm. The deasphalting step may be carried out by any means known to those skilled in the art. This step is generally carried out in a settling mixer or in an extraction column. Preferably, the deasphalting step is carried out in an extraction column. According to a preferred embodiment, a mixture comprising the hydrocarbon feedstock and a first fraction of a solvent feed is introduced into the extraction column, the volume ratio between the solvent feed fraction and the feedstock. hydrocarbons being called the rate of solvent injected with the charge. This step is intended to thoroughly mix the feed with the solvent entering the extraction column. In the settling zone at the bottom of the extractor, it is possible to introduce a second fraction of the solvent charge, the volume ratio between the second solvent loading fraction and the hydrocarbon feed being called the solvent content injected at the bottom of the solvent. extractor. The volume of the hydrocarbon feedstock n considered in the settling zone is generally that introduced into the extraction column. The sum of the two volume ratios between each of the solvent feed fractions and the hydrocarbon feed is referred to as the overall solvent level. The decantation of the asphalt consists of the countercurrent washing of the asphalt emulsion in the solvent + oil mixture with pure solvent. It is generally favored by an increase in the solvent content (it is in fact to replace the solvent + oil environment with a pure solvent environment) and an increase in temperature. The overall solvent content relative to the treated feedstock is preferably between 2.5 / 1 and 20/1, more preferably between 3/1 and 12/1, more preferably between 4 / 1 and 10/1. This overall solvent content is decomposed into a level of solvent injected with the feedstock at the top of the extractor, preferably between 0.5 and 5/1, preferably between 1/1 and 5/1, and a level of solvent injected extractor bottom preferably between 2/1 and 15/1, more preferably between 3/1 and 10/1. Furthermore, according to a preferred embodiment, a temperature gradient is established between the head and the bottom of the column to create an internal reflux, which improves the separation between the oily medium and the resins. Indeed, the solvent + oil mixture heated at the top of the extractor makes it possible to precipitate a fraction comprising resin which goes down into the extractor. The upward countercurrent of the mixture makes it possible to dissolve at a lower temperature the fractions comprising the resin which are the lightest. In the deasphalting step, the typical temperature at the top of the extractor varies according to the chosen solvent and is generally between 60 and 220 ° C., preferably between 70 and 210 ° C., and the temperature at the bottom of the extractor is preferably between 50 and 190 ° C and more preferably between 60 and 180 ° C.
    [0015] The pressure inside the extractor is generally adjusted so that all the products remain in the liquid state. This pressure is preferably between 4 and 5 MPa. Second hydroconversion stage The invention may also comprise a second hydroconversion stage. This second hydroconversion stage can be implemented according to the invention in a fixed bed according to the invention or in a bubbling bed. This second hydroconversion stage is generally carried out on a deasphalted hydrocarbon fraction obtained from the deasphalting step when this step is carried out in the process of the invention. The conditions of the second hydroconversion stage of the feedstock in the presence of hydrogen are usually an absolute pressure generally of between 5 and 35 MPa, preferably of between 10 and 25 MPa, a temperature of 260 to 600 ° C. and often of 350 to 550 ° C. The hourly space velocity (VVH) and the hydrogen partial pressure are important factors that are chosen according to the characteristics of the product to be treated and the desired conversion. Most often the VVH is in a range from 0.1 h -1 to 10 h -1 and preferably 0.15 h -1 to 5 h -1. According to the invention, the weighted average temperature of the catalytic bed of the second hydroconversion stage is advantageously between 260 ° C. and 600 ° C., preferably between 300 ° C. and 600 ° C., more preferably between 350 ° C. C and 550 ° C. The amount of hydrogen mixed with the feedstock is usually 50 to 5000 normal cubic meters (Nm3) per cubic meter (m3) of feedstock. Advantageously, the hydrogen is used in a volume ratio with the feed of between 300 and 2000 m3 / m3, preferably between 500 and 1800 m3 / m3, and more preferably between 600 and 1500 m3 / m3.
    [0016] It is possible to use a conventional granular hydroconversion catalyst comprising on an amorphous support at least one metal compound having a hydrodehydrogenating function. This catalyst may be a catalyst comprising Group VIII metals, for example nickel and / or cobalt, most often in combination with at least one Group VIB metal, for example molybdenum and / or tungsten. For example, a catalyst comprising from 0.5 to 10% by weight of nickel and preferably from 1 to 5% by weight of nickel (expressed as nickel oxide NiO) and from 1 to 30% by weight of molybdenum of preferably from 5 to 20% by weight of molybdenum (expressed as molybdenum oxide MoO 3) on an amorphous mineral support. This support is for example chosen from the group formed by alumina, silica, silica-aluminas, magnesia, clays and mixtures of at least two of these minerals. This support may also contain other compounds and for example oxides chosen from the group formed by boron oxide, zirconia, titanium oxide and phosphoric anhydride. Most often an alumina support is used and very often a support of alumina doped with phosphorus and possibly boron. The P 2 O 5 phosphoric anhydride concentration is usually less than 20% by weight and most often less than about 10% by weight. This P205 concentration is usually at least 0.001% by weight. The concentration of boron trioxide B 2 O 3 is usually from 0 to 10% by weight. The alumina used is usually a gamma or rho alumina. This catalyst is most often in the form of extruded. The total content of metal oxides of groups VI and VIII is often from 5 to 40% by weight and in general from 7 to 30% by weight and the weight ratio expressed as metal oxide between metal (or metals) of Group VI on metal (or metals) of group VIII is generally from 20 to 1 and most often from 10 to 2. The used catalyst is partly replaced by fresh catalyst by withdrawal at the bottom of the reactor and introduction at the top of the fresh catalyst reactor or nine at regular time interval, that is to say for example by puff or almost continuously. For example, fresh catalyst can be introduced every day. The replacement rate of the spent catalyst with fresh catalyst can be, for example, from 0.01 kilogram to 10 kilograms per cubic meter of charge. This withdrawal and replacement are performed using devices for the continuous operation of this hydroconversion step. The unit usually comprises a recirculation pump for maintaining the bubbling bed catalyst by continuously recycling at least a portion of the liquid withdrawn at the top of the reactor and reinjected at the bottom of the reactor. It is also possible to send the spent catalyst withdrawn from the reactor into a regeneration zone in which the carbon and the sulfur contained therein are eliminated and then to return this regenerated catalyst to the second hydroconversion stage. It is also possible to send the spent catalyst resulting from this stage as a catalyst additive to the upstream vacuum hydroconversion unit in a bubbling bed. The effluent from the second hydroconversion stage is advantageously subjected to a separation step f) making it possible to produce at least one fraction comprising a gasoline cut and a gas oil cut, a vacuum gas oil fraction, and an unconverted residual fraction.
    [0017] This separation step f) is carried out by any means known to those skilled in the art, for example a distillation. First variant of the process according to the invention In a first variant of the process according to the invention called "implementation 1D", the feedstock of the process according to the invention is treated in a first hydroconversion stage (stage a), for example of the H-Oil type and the effluent obtained is separated (step b) into at least one fraction comprising a gasoline cut (also called naphtha) and a gas oil fraction, a vacuum gas oil fraction and an unconverted residual fraction. The vacuum gas oil fraction thus obtained is sent to the hydrocracking step c), optionally with a straight run gas oil fraction (straight run according to the English terminology). According to this first variant of the process of the invention, the effluent resulting from the hydrocracking step is fractionated in the fractionation stage e) in several fractions including a gasoline fraction, a gas oil fraction and a non-vacuum gas oil fraction. converted. The fractionation step is carried out by any means known to those skilled in the art, for example a distillation. All or part of the unconverted vacuum gas oil fraction resulting from the fractionation step e) is recycled to the first hydroconversion stage.
    [0018] Thus, with reference to FIG. 1, the charge A consisting of a vacuum residue (SR VR) is sent via line 1 to a hydroconversion section 20 (denoted HOi1Rc in FIG. 1) making it possible to produce after separation. (Not shown) a fraction (4) comprising a petrol cut (N) and a gas oil cut (GO), a fraction (5) gas oil under vacuum (VGO) and a residual fraction (3) unconverted (VR).
    [0019] The vacuum gas oil fraction (VGO) is then sent through line 5 to a hydrocracking section 30. This fraction can be sent to section 30 (HCK) mixed with a fraction B of vacuum distillate gas oil (SR VGO ). The effluent from the hydrocracking section is then separated in the fractionation zone 40 (denoted FRAC in FIG. 1) into a gasoline fraction (12, N), a gas oil fraction (13, GO) and a gas oil fraction under empty (14, VGO). To maximize the yield of diesel fraction, at least a portion of the VGO is returned via line 9 in the first hydroconversion section 20. This VGO is partly cracked in the hydroconversion section and the unconverted VGO is at its tower partially converted in the hydrocracking section. Thus, compared with the diagram of the prior art shown in FIG. 0 and whose legend is identical to that of FIG. 1, the VGO yield (14) of the process can go from 5% by weight to less than 1% by weight. in favor of an additional co-production in high added value diesel fraction (13). Second variant of the process according to the invention A second variant of the process according to the invention called "2D implementation" implements a step of deasphalting. This variant differs from the variant 1D in that at least a portion of the unconverted residual fraction from step b) can be sent to a deasphalting step in which it is treated in an extraction section. using a solvent under conditions to obtain a deasphalted hydrocarbon fraction and residual asphalt (pitch according to the English terminology).
    [0020] This operation makes it possible to extract a large part of the asphaltenes and to reduce the metal content of the unconverted residual fraction. During this deasphalting step, the latter elements are concentrated in an effluent called asphalt or residual asphalt. The deasphalted effluent, often called deasphalted oil (DeAsphalted Oil according to the English terminology), also called DAO, has a reduced content of asphaltenes and metals. According to this variant of the process called "2D implementation", the deasphalted hydrocarbon fraction resulting from the deasphalting stage is sent to the hydrocracking step c), in a mixture with the vacuum gas oil fraction resulting from stage b ) and optionally with a gas oil fraction under a direct distillation vacuum. The hydrocracking effluent is then fractionated in the fractionation zone in several fractions including a gasoline fraction, a gas oil fraction and an unconverted vacuum gas oil fraction. At least a portion of the vacuum gas oil fraction from the fractionation stage e) is recycled at the inlet of the deasphalting stage, and / or at the inlet of the first hydroconversion stage. Thus, referring to FIG. 2, the vacuum charge A (SR VR) is sent via line 1 to a hydroconversion section 20 (denoted H-OilRc in FIG. 2) making it possible to produce after separation ( not shown) a fraction (4) comprising a gasoline cut (N) and a gas oil cut (GO), a fraction (5) gas oil under vacuum (VGO) and a residual fraction (3) unconverted (VR). The vacuum gas oil fraction is sent via the pipe 5 into the hydrocracking section 30. The unconverted residual fraction (VR) is sent via line 3 to a deasphalting unit 50 (SDA) for extracting a deasphalted oil ( DAO) and a residual asphalt (pitch). The deasphalted oil fraction (DAO) is then sent through line 15 to a hydrocracking section (HCK) 30. The effluent from the hydrocracking section is then separated in the fractionation zone 40 into a gasoline fraction (12, N), a gas oil fraction (13, GO) and a vacuum gas oil fraction (14, VGO). To maximize the yield of diesel fraction, at least a portion of the VGO is returned via lines 9 and 2 in the deasphalting unit 50 (SDA). Part of this VGO can be sent to the first hydroconversion section 30 via line 10. Third variant of the method according to the invention The third variant of the process according to the invention called "3D implementation" is distinguished from the second variant in that the deasphalted hydrocarbon fraction obtained from the deasphalting stage is sent to a second hydroconversion stage in the presence of hydrogen under conditions which make it possible to produce, preferably after a separation stage f) a fraction comprising a section gasoline and a diesel cut, a vacuum gas oil fraction (VGO) and an unconverted residual fraction. This second hydroconversion stage may be carried out under fixed bed hydrocracking conditions according to the invention or under bubbling bed hydrocracking conditions. According to this variant, the vacuum gas oil fraction resulting from the separation step f) is sent to the hydrocracking stage c), in a mixture with the vacuum gas oil fraction resulting from stage b) and optionally with a diesel fraction under direct distillation vacuum. According to this variant of the process, the hydrocracking effluent is fractionated in the fractionation zone (step e)) into several fractions including a gasoline fraction, a gas oil fraction and an unconverted vacuum gas oil fraction. According to this variant of the invention called "3D implementation", at least a portion of the vacuum gas oil fraction from the fractionation step e) is recycled to the inlet of the deasphalting step, and / or to the inlet of the first hydroconversion stage. Thus, referring to FIG. 3, the vacuum residue charge A (SR VR) is sent via line 1 to a hydroconversion section 20 (denoted H-OilRc in FIG. 3) making it possible to produce after separation ( not shown) a fraction (4) comprising a gasoline cut (N) and a gas oil cut (GO), a fraction (5) gas oil under vacuum (VGO) and a residual fraction (3) unconverted (VR). The vacuum gas oil fraction is sent through the line 5 to the hydrocracking section (HCK) 30. The unconverted residual fraction (VR) is sent via line 3 to a deasphalting unit 50 (SDA) for extracting a deasphalted oil (DAO) and residual asphalt (pitch). The deasphalted oil fraction (DAO) is then sent to a hydroconversion section 60 (denoted H-OilDc in FIG. 3) making it possible to produce a fraction (18) comprising a petrol cut (N) and a diesel cut (GO) and a fraction (17) gas oil under vacuum (VGO) and a residual fraction (19) unconverted (VR). The fraction (17) vacuum gas oil from section 60 is then sent via line 5 to the hydrocracking section 30. The effluent of the hydrocracking section is then separated in the fractionation zone 40 into a gasoline fraction. (12, N), a gas oil fraction (13, GO) and a vacuum gas oil fraction (14, VGO). To maximize the yield of diesel fraction, at least a portion of the VGO is returned via lines 9 and 2 in the deasphalting unit 50 (SDA). Part of this VGO can be sent to the first hydroconversion section 30 via line 10.
    [0021] EXAMPLES The filler used in these examples has the composition detailed in Table 1. It is a vacuum residue of the "Arabian Heavy" type, that is to say a vacuum residue obtained by distillation of a crude oil from the Arabian Peninsula.
    [0022] Table 1: Composition of the load used ("Arabian Heavy" vacuum residue) Property Unit Value Density - 1,040 Viscosity at 100 ° C cSt 5200 Conradson carbon% weight 23,5 Asphaltenes in C7% weight 13,8 Nickel ppm 52 Vanadium ppm 140 Nitrogen ppm 5300 Sulfur% Weight 5.4 Cut 565 ° C * * Weight 16.45 * Cup containing products with a boiling point below 565 ° C.
    [0023] This charge is implemented in the various process variants illustrated by the implementation diagrams 0, 1D, 2D, 3D (represented respectively in FIGS. 0, 1, 2 and 3) without the addition of gas oil under vacuum ( SR VGO) at the entry of the hydrocracking step (HCK). Furthermore, as regards the 2D and 3D implementation diagrams, the VGO recycle from the fractionation is only sent to the deasphalting unit (SDA), while it is sent to the first hydroconversion unit H -0iIRC in the case of the 1D scheme. The operating conditions of the conversion sections H-OIRC, H-OilDC, first and second hydroconversion units, HCK (hydrocracking unit) as well as the solvent deasphalting unit (SDA) are summarized in Table 2.
    [0024] The H-Oil hydroconversion units are operated with bubbling bed reactors and the hydrocracking unit with a fixed bed reactor. The deasphalting unit is operated with an extraction column.
    [0025] Table 2: Operating conditions of the units Parameter H-011 RC H-011 DC HCK SDA VVH Liquid h-1 0.25 0.3 0.25 - Pressure MPa 18 17 18 4.5 WABT SOR * cc 420 445 385 - Temperature extractor 120 at the extractor head 90 at the bottom of the extractor H2 / Charge m3 / m3 400 300 1000 Solvent / feed inlet m3 / m3 m3 / m3 - - - 2/1 extractor 4/1 extractor bottom Catalysts HOC 458TM HRK 1448TM - HTS 458TM HYK 732TM Composition NiMo / A1203 NiMo / A1203 NiMo / A1203 NiMo / zeolite Y catalyst * Weighted average temperature in the catalytic bed at the beginning of the cycle The catalysts used are catalysts marketed by the Axens company. The solvent used in the SDA unit is a mixture of butanes comprising 60% nC4 and 40% iC4.
    [0026] The yields of products obtained are shown in Table 3 as the percentage by weight of each product obtained relative to the initial weight of the vacuum residue feedstock (SR VR) introduced into the process. Table 3: Product yields according to the process scheme used% wt. SR VR * Figure 0 Variant 1D Variant 2D Variant 3D (Art (Invention) (Invention) (Invention) Anterior) LN 8 8 9 9 HN 9 10 12 12 GO 47 50 55 57 VGO 5 <1 4 <1 VR + pitch ( P itch) 22 22 10 11 Total liquids 91 91 90 90 * LN: Light Naphtha (light Naphtha), HN: Heavy Naphtha (Heavy Naphtha), GO: Diesel, VGO: Vacuum Diesel (Vacuum Gasoil), VR: Residue under vacuum (Vacuum Residu), SR straight distillation (Straight Run). According to the Anglo-Saxon terminology Table 4 indicates the properties of the different products obtained by means of the various process schemes. It appears that the diesel yield (GO) increases by 6.5%, 17% and 21% respectively for the 1D, 2D and 3D implementation schemes compared to the scheme according to the prior art (scheme 0) for a constant liquid yield (90 or 91%). The 2D implementation scheme makes it possible to co-produce a little vacuum gas oil (VGO). The 3D implementation scheme is the most efficient in terms of fuel efficiency with a negligible co-production of VGO.
    [0027] Table 4: Properties of products from hydrocracking LN HN GO cc points 30-80 80-150 150-370 cut Density - 0.685 0.755 0.825 Sulfur ppm <1 <1 <10 P / N / A *% wt 63 / 36/1 31/66/3 Cetane - - - 47 * Paraffins / Naphthenes / Aromatics Table 4 shows that the diesel fuel from the hydrocracking stage is Euro V except for cetane. The cetane deficiency (cetane engine measured according to the ASTM D613 standard) can be filled either by additivation or by mixing with other Gasoil cuts of higher cetane number. The naphthas from the hydrocracking step can be recovered as such, for example in catalytic reforming units to produce gasoline.
    [0028] Distillates from H-Oil hydroconversion units (naphtha, and GO in 1D, 2D or 3D implementation schemes) require hydrotreatment steps in order to obtain products with commercial specifications. Vacuum residues (VR from H-OiIRC unit, VR from H-OilDC unit and asphalt from deasphalting) are mainly recovered as heavy fuel oil after viscosity adjustment by mixing with distillates available from site.
    权利要求:
    Claims (11)
    [0001]
    CLAIMS1) Process for deep conversion of a heavy hydrocarbon feedstock comprising the following steps: a) a first hydroconversion step in a bubbling bed of the feedstock, in the presence of hydrogen, comprising at least one triphasic reactor containing at least one catalyst e) a step of separating at least a portion of the hydroconverted liquid effluent from step a) into a fraction comprising a gasoline blow and a gas oil cut, a vacuum gas oil fraction. , and an unconverted residual fraction, C) a step of hydrocracking at least part of the vacuum gas oil fraction resulting from step b) in a reactor comprising at least one fixed bed hydrocracking catalyst, d) a step of fractionating at least a portion of the effluent from step c) into a gasoline fraction, a gas oil fraction and an unconverted vacuum gas oil fraction; e) a step of recycling at least one p part of the unconverted vacuum gas oil fraction from step d) in said first hydroconversion stage a).
    [0002]
    2) A process according to claim 1 wherein at least a portion of the unconverted residual fraction from step b) is sent to a deasphalting section in which it is treated in an extraction step with the aid of a solvent under conditions to obtain a deasphalted hydrocarbon cut and residual asphalt.
    [0003]
    3) A process according to claim 2 wherein at least a portion of the deasphalted hydrocarbon fraction is fed to the hydrocracking step c) in admixture with the vacuum gas oil fraction separated in step b) and optionally with a fraction vacuum distillation diesel fuel.
    [0004]
    4) Process according to claim 2 wherein the deasphalted hydrocarbon fraction is sent in a second hydroconversion stage, in the presence of hydrogen and at least one ebullated bed hydroconversion catalyst.
    [0005]
    5) Process according to claim 4 wherein the effluent from the second hydroconversion stage is subjected to a separation step f) for producing at least a fraction comprising a gasoline cut and a gas oil cut, a diesel fraction under empty, and an unconverted residual fraction. 10
    [0006]
    6) Process according to claim 5 wherein the vacuum gas oil fraction from the separation step f) is sent in the hydrocracking step c), in mixture with the vacuum gas oil fraction from step b ) and optionally with a gas oil fraction under a direct distillation vacuum.
    [0007]
    7) Method according to one of claims 2 to 6 wherein at least a portion of the vacuum gas oil fraction from the fractionation step d) is recycled to the inlet of the deasphalting step.
    [0008]
    8) Method according to one of the preceding claims wherein the hydroconversion step a) is carried out under an absolute pressure of between 5 and 35 MPa, at a temperature of 260 to 600 ° C and a space velocity ranging from 0.05 h-1 to 10h-1.
    [0009]
    9) Method according to one of the preceding claims wherein the step c) hydrocracking is operated under an average temperature of the catalyst bed of between 300 and 550 ° C, a pressure of between 5 and 35 MPa, a liquid space velocity between 0.1 and 10h-1. 25
    [0010]
    10) Method according to one of claims 2 to 9 wherein in the deasphalting step, the typical temperature at the extractor head is between 60 to 220 ° C and the bottom temperature of the extractor is between 50 and 190 ° C.
    [0011]
    11) Method according to one of the preceding claims wherein the filler is selected from heavy hydrocarbon feeds of the atmospheric or vacuum residues type obtained for example by direct distillation of petroleum fraction or by vacuum distillation of crude oil, the charges of type distillates such as vacuum gas oils or deasphalted oils, asphalts from solvent deasphalting petroleum residues, coal suspended in a hydrocarbon fraction such as for example gas oil obtained by vacuum distillation of crude oil or distillate from the liquefaction of coal, alone or as a mixture.
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    同族专利:
    公开号 | 公开日
    CA2915286A1|2016-06-18|
    CN105713665B|2019-08-20|
    FR3030568B1|2019-04-05|
    US10501695B2|2019-12-10|
    CN105713665A|2016-06-29|
    US20160177202A1|2016-06-23|
    引用文献:
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    US5980730A|1996-10-02|1999-11-09|Institut Francais Du Petrole|Process for converting a heavy hydrocarbon fraction using an ebullated bed hydrodemetallization catalyst|
    EP1840190A1|2006-03-08|2007-10-03|Ifp|Process and installation for conversion of heavy petroleum fractions in a boiling bed with integrated production of middle distillates with a very low sulfur content|
    WO2012085407A1|2010-12-24|2012-06-28|Total Raffinage Marketing|Method for converting hydrocarbon feedstock comprising a shale oil by hydroconversion in an ebullating bed, fractionation by atmospheric distillation and hydrocracking|WO2019121073A1|2017-12-21|2019-06-27|IFP Energies Nouvelles|Method for converting heavy hydrocarbon feedstocks with recycling of a deasphalted oil|
    WO2019121074A1|2017-12-21|2019-06-27|IFP Energies Nouvelles|Improved method for converting residues incorporating deep hydroconversion steps and a deasphalting step|
    FR3075811A1|2017-12-21|2019-06-28|IFP Energies Nouvelles|PROCESS FOR CONVERTING HYDROCARBON HEAVY LOADS COMPRISING HYDROCONVERSION STEPS IN BEDDRAWER BED AND A RECYCLE OF A DESASPHALTEE OIL|
    FR3075807A1|2017-12-21|2019-06-28|IFP Energies Nouvelles|AN IMPROVED RESIDUAL CONVERSION METHOD INTEGRATING DEEP HYDROCONVERSION STEPS INTO A DRIVEN BED AND A DISASPHALTAGE STEP|US2847353A|1955-12-30|1958-08-12|Texas Co|Treatment of residual asphaltic oils with light hydrocarbons|
    US5372705A|1992-03-02|1994-12-13|Texaco Inc.|Hydroprocessing of heavy hydrocarbonaceous feeds|
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    FR2969650B1|2010-12-24|2014-04-11|Total Raffinage Marketing|HYDROCARBONATE LOADING CONVERSION METHOD COMPRISING SCHIST HYDROCONVERSION OIL IN BOILING BED, ATMOSPHERIC DISTILLATION FRACTIONATION AND LIQUID / LIQUID EXTRACTION OF HEAVY FRACTION|WO2021079272A1|2019-10-22|2021-04-29|Sabic Global Technologies B.V.|Integrated hydrocracking process to produce light olefins, aromatics, and lubricating base oils from crude oil|
    法律状态:
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    2016-06-24| PLSC| Publication of the preliminary search report|Effective date: 20160624 |
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    2019-12-23| PLFP| Fee payment|Year of fee payment: 6 |
    2020-12-29| PLFP| Fee payment|Year of fee payment: 7 |
    2021-12-27| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1462715|2014-12-18|
    FR1462715A|FR3030568B1|2014-12-18|2014-12-18|PROCESS FOR DEEP CONVERSION OF RESIDUES MAXIMIZING GAS OUTPUT|FR1462715A| FR3030568B1|2014-12-18|2014-12-18|PROCESS FOR DEEP CONVERSION OF RESIDUES MAXIMIZING GAS OUTPUT|
    CA2915286A| CA2915286A1|2014-12-18|2015-12-14|Deep conversion process for residue maximising the efficiency of diesel|
    CN201510949673.6A| CN105713665B|2014-12-18|2015-12-18|Conversion residue is improved, the maximized method of gas oil yield is made|
    US14/974,313| US10501695B2|2014-12-18|2015-12-18|Process for the intense conversion of residues, maximizing the gas oil yield|
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