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    • 专利摘要:
    The present invention relates to a process for producing octane gasoline and co-producing aromatic bases from a naphtha (1) cup comprising paraffins and naphthenes, the process comprising the following steps: sending the naphtha section to a first catalytic reforming unit (2) so as to convert at least a portion of the paraffins and / or naphthenes to aromatics and produce hydrogen; b) withdrawing from the first catalytic reforming unit (2) a first effluent (3) and a hydrogen stream (4); c) the first effluent (3) is sent to an aromatics separation unit (5) so as to separate a first aromatic section and a raffinate (7) containing paraffins and / or unconverted naphthenes; d) the raffinate (7) is fed to a second catalytic reforming unit (9) so as to convert the unconverted paraffins and / or naphthenes to aromatics and produce hydrogen; e) withdrawing from the second catalytic reforming unit (9) a reformate (11) containing aromatic compounds and a hydrogen stream (10).
    公开号:FR3014894A1
    申请号:FR1362749
    申请日:2013-12-17
    公开日:2015-06-19
    发明作者:Heloise Dreux；Alexandre Pagot；Priscilla Avenier；Julien Gornay；Goff Pierre-Yves Le
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a method for producing high octane gasoline cuts and concomitantly aromatic hydrocarbon cuts which are bases for petrochemistry. In particular, the subject of the invention is a process for coproducing, from a naphtha section, gasolines with a high octane number (RON greater than 95) and aromatic hydrocarbon cuts useful in petrochemistry, for example production of xylene, toluene and benzene. STATE OF THE ART The traditional objective of a catalytic reforming unit is to convert the naphthenic (cycloalkane) and paraffinic hydrocarbon compounds (n-paraffins and iso-paraffins) into aromatic hydrocarbon compounds. The main reactions involved are the dehydrogenation of naphthenes, the dehydrocyclization of paraffins to aromatics and possibly the isomerization of paraffins and naphthenes. Other so-called "parasite" reactions can occur such as hydrocracking and hydrogenolysis of paraffins and naphthenes, hydrodealkylation of alkyl aromatics giving rise to lighter compounds and lighter aromatics, as well as the formation of coke on the surface of the catalyst.
    [0002] The performances that one seeks to optimize for a gasoline application are the liquid reformate yield as well as the octane number of said reformate. While for a petrochemical application, the desired performances are the yield of aromatic hydrocarbons as well as the distribution of the aromatic hydrocarbons produced. The aromatic hydrocarbons are then generally treated in an aromatic complex to maximize the production of one or more products, most often xylenes and benzene. Toluene and heavier aromatics can be upgraded for the basic gasoline constitution or for the production of xylenes. Conventional feedstocks of a catalytic reforming unit are rich in paraffinic and naphthenic compounds and relatively low in aromatic compounds. These are typically naphthas from crude distillation or natural gas condensates that are treated by catalytic reforming. In addition to these conventional feedstocks, there are other available fillers in a refinery that contain varying amounts of aromatics, namely heavy catalytic cracked (FCC) naphthas, coking, hydrocracking, or gasoline. steam cracking. These charges, which are more or less rich in aromatic compounds, can be used to feed a catalytic reforming unit for the production of gasoline bases or aromatic bases.
    [0003] A catalytic reforming unit generally comprises four reactors in series which comprise either a fixed bed or a moving bed of reforming catalyst. When the reforming unit is composed of moving bed catalyst reactors it further includes a continuous regenerator of the catalyst in which is carried out the removal in the form of CO2 coke deposited on the catalyst by slow combustion and controlled. This so-called continuous regenerative unit comprises complex catalyst circulation devices which can thus alternatively ensure its function in the reactors and then undergo a regeneration treatment with return to the reactors. It is known in the state of the art the document FR 2925065 which discloses a method for obtaining a gasoline high octane and simultaneously aromatic bases from a naphtha cut. The proposed scheme consists in sending a naphtha feed into an aromatic separation unit which produces a so-called "extracted" cut containing the majority of aromatics, and a "raffinate" cut containing the majority of the non-aromatic compounds. At least a portion of the raffinate is fed to a catalytic reforming unit from which a hydrogen stream and a high octane gasoline cut are produced. The high-octane gasoline cut is either sent entirely to the gasoline pool or a part is processed in a so-called aromatic complex unit and the other part used in the gasoline pool. Furthermore, it is envisaged in this process to send all or part of the extract in a so-called aromatic complex unit for producing aromatic bases and the other part of the extract is sent to the gasoline pool. The scheme described in this document therefore separates the aromatics from the naphtha feed which generally has a low aromatic content prior to the catalytic reforming step and then processes the paraffinic and naphthenic compounds in the reforming step together.
    [0004] An object of the invention is to provide a flexible process that allows to direct the effluents towards the production of gasoline bases or to the production of aromatic bases according to the needs of the refiner and for which the conversion conditions are optimized and which , for a given processing capacity, produces more aromatics compounds so gasoline high octane and / or aromatic bases for petrochemistry than the schemes according to the prior art. SUMMARY OF THE INVENTION For this purpose, there is provided a process for the production of gasoline with an octane number greater than 95 and of co-production of aromatic bases, from a naphtha section comprising paraffins and naphthenes, the process comprising the following steps: a) the naphtha section is sent to a first catalytic reforming unit in which the naphtha section is brought into contact with a reforming catalyst so as to convert at least part of the paraffins and / or naphthenes into aromatic compounds and produce hydrogen; b) withdrawing from the first catalytic reforming unit a first effluent and a flow of hydrogen; c) the first effluent is sent to an aromatics separation unit so as to separate a first aromatic cut and a raffinate containing paraffins and / or unconverted naphthenes; d) feeding the raffinate to a second catalytic reforming unit in which the raffinate is contacted with a reforming catalyst so as to convert unconverted paraffins and / or naphthenes to aromatics and produce hydrogen; e) a hydrogen stream and a reformate rich in aromatic compounds are withdrawn from the second catalytic reforming unit.
    [0005] The process according to the invention makes it possible to produce gasoline cuts rich in aromatic hydrocarbon compounds which can be valorized not only at the gasoline pool but also as bases for a unit of aromatic complex. Thus, depending on the needs of the refiner, the petrol cuts rich in aromatic hydrocarbon compounds are either totally oriented to the gasoline pool when there is a need for gasoline, or are directed in their entirety to the aromatic complex in the case where a demand for aromatic compounds exists in petrochemicals, is allocated to the gasoline and aromatic complex (in any proportion) when there is a need not only for the production of gasoline but also for aromatics for petrochemicals.
    [0006] The process according to the invention is also optimized in terms of capacity and yield of aromatic products through the implementation of a first step and a second catalytic reforming step with an intermediate stage of separation of the aromatics formed in the first stage of reforming. The separation step makes it possible to recover the aromatic compounds produced in the first reforming step and thus avoid a loss of yield due to parasitic reactions of hydrodealkylation and polycondensation which lead to the formation of coke on the catalyst (loss of catalyst activity) especially on the catalyst of the second reforming step. The second catalytic reforming step is then conducted under optimal conditions on the raffinate rich in nonaromatic compounds (paraffinic and naphthenic unconverted in the first reforming stage) more refractory to conversion. According to a preferred embodiment, the first reforming step is carried out under conditions such that the dehydrogenation of the naphthenic compounds which are easier to dehydrogenate and to convert to aromatic compounds is favored than the paraffins for which a dehydrocyclization reaction. The second reforming step is then carried out under more severe conditions in order to promote the dehydrocyclization reaction of the paraffins. The method according to the present invention thus makes it possible to avoid the disadvantages due to the conversion of aromatic-rich feedstocks in the catalytic reforming unit, and to improve the yields towards the desired products. Furthermore, the fact of carrying out two successive reforming steps with an intermediate separation step of the aromatics formed in the first step and thus of treating in the second reforming stage only the raffinate which essentially contains unconverted nonaromatic compounds. optimizes the capacity of the production unit. Indeed, it is not necessary to unnecessarily increase the capacity of the production unit because the aromatic compounds produced in the first step do not need to undergo unnecessarily a second catalytic reforming step. In addition, the presence of an intermediate stage of separation of the compounds between two catalytic reforming stages thus makes it possible to treat different charges in the reforming units and thus to operate these units under optimal operating conditions depending on the load. to maximize the production of aromatic compounds.
    [0007] According to one embodiment, when seeking to promote the production of aromatic bases for petrochemistry, the entire aromatic section is sent to an aromatic complex unit. According to another embodiment in which it is sought to produce aromatic bases for petrochemistry and gasoline, part of the first aromatic cut is sent to one aromatic complex unit and the other part of the first aromatic cut is sent to the gasoline pool. According to an embodiment in which one seeks to produce gasoline, the entire reformate is sent to the gasoline pool. According to an alternative embodiment, a portion of the reformate is sent to one aromatic complex unit and the other portion of the reformate is sent to the essence pool. Advantageously, before being sent to the gasoline pool and / or the aromatic complex unit, the reformate is sent to the aromatic separation unit. In a particular embodiment according to the invention, the naphtha cut is previously treated in a hydrotreatment unit before step a). For example, the hydrotreatment stage is chosen from a hydrodemetallation, hydrodesulphurization, hydrodenitrogenation and / or hydrogenation step of the olefins and diolefins. According to a preferred embodiment, before step a), the naphtha cut is sent to a separation unit configured to separate a C4- hydrocarbon cut and a C5 + hydrocarbon cut and said C5 + cut is sent to the cutter. step a). According to an advantageous embodiment, the raffinate from step c) is sent to a separation unit configured to separate a C6- cut and a C7 + cut or a C7- cut and a C8 + cut, and the c7 + cut is sent. or C8 + in the catalytic reforming step d) and the C6- or C7- cut is treated in an isomerization unit so as to increase its octane number. The first and second catalytic reforming steps a) and d) are conducted in the presence of hydrogen under the following conditions: an average reactor inlet temperature of between 420 and 600 ° C .; A pressure of between 0.3 and 1 MPa; a mass space velocity, expressed by the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 8 h -1; a molar ratio of H 2 / feed of between 0.2 and 8;
    [0008] Preferably, the first catalytic reforming step a) is carried out in the presence of hydrogen at: a mean reactor inlet temperature of between 420 and 500 ° C .; a pressure of between 0.3 and 1 MPa; a mass space velocity, expressed by the ratio of the mass flow rate of the feedstock to the catalyst mass of between 2.5 and 8 h -1. a molar ratio H 2 / charge of between 0.2 and 8. Preferably, the second catalytic reforming stage d) is carried out in the presence of hydrogen at: a mean reactor inlet temperature of between 500 and 600 ° VS ; a pressure of between 0.3 and 1 MPa; a mass space velocity, expressed as the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 2.5 h -1. A molar ratio H 2 / charge of between 0.2 and 8. According to the invention, the naphtha fraction is derived from one or more units: atmospheric distillation, FCC, coking, steam-cracking, hydrocracking, fractionation of natural gas condensates . Preferably, the catalytic reforming catalyst used in steps a) and d) comprises an alumina support and platinum. Very preferably, the catalytic reforming catalyst is promoted with one of the following elements: Re, Sn, In, P, Ge, Ga, Bi, B, Ir, rare earths. Preferably the promoter element is tin. According to a preferred embodiment, the catalytic reforming catalyst of step a) is a catalyst having a chlorine content of less than 0.1% by weight, preferably less than 0.05% by weight relative to the weight of the catalyst. Preferably, the catalytic reforming catalyst of step d) has a chlorine content of between 0.8 and 1.5% by weight, preferably between 0.8 and 1.2% by weight, and preferably more preferably between 0.9 and 1.1% by weight based on the weight of the catalyst.
    [0009] According to the invention, the first and second catalytic reforming units can implement either "fixed bed" reactors according to a so-called "semi-regenerative" mode, or reactors in a moving bed according to a so-called "continuous regeneration" mode. . For a fixed bed system, this comprises for example at least two reactors operating in parallel in which a first reactor is used to regenerate the catalyst and a second reactor is used for the reforming reaction. According to a preferred embodiment according to the invention, the reforming units operate in "continuous regeneration" (Continuous Catalyst Regeneration (CCR) according to the English terminology). Such units are characterized by a continuous in-situ regeneration of a part of the catalyst in a dedicated regenerator and by continuous addition of the regenerated catalyst to the reactors carrying out the conversion reaction. Such a "continuous regeneration" reforming unit therefore comprises at least one reactor and one regenerator. Preferably, the reforming unit comprises two reactors in series used to convert the paraffinic and naphthenic hydrocarbon compounds into aromatic compounds and a catalyst regenerator. According to a preferred embodiment when the catalyst is identical in the two reforming units, the first reforming unit is composed of at least one conversion reactor and the second reforming unit comprises at least one conversion reactor and a regenerator with a circulation of the regenerated catalyst to the first reactor of the first catalytic reforming unit. This embodiment is advantageous because it thus makes it possible to pool the regenerator to regenerate the catalyst used in the first and second reforming units. In the case where different catalysts are employed in each of the first and second reforming units, these are composed of at least one conversion reactor and one regenerator. DETAILED DESCRIPTION OF THE INVENTION Other features and advantages of the invention will be better understood and will become clear from reading the description given below with reference to the drawings in which: FIG. 1 schematizes a first embodiment the process according to the invention; FIG. 2 diagrammatically represents a second embodiment of the method according to the invention; FIG. 3 represents a third embodiment of the method according to the invention. Similar items are generally referred to as identical reference signs. In addition, the dashed lines or blocks designate optional elements. For the sake of understanding the text, hereinafter called "naphtha" is a petroleum fraction of any chemical composition, and preferably having a distillation range of between 50 ° C. and 250 ° C. The distribution in chemical family identified by PONA (P for Paraffins, O for olefins, N for naphthenes and A for aromatics) can be arbitrary. "Petrol" is a petroleum fraction having a distillation range similar to that of naphtha and having an octane number of greater than 95, preferably greater than 98. Xylenes (paraxylene, metaxylene) are generally referred to as "aromatic bases". Orthoxylene), ethylbenzene, toluene and benzene, and optionally heavier aromatics such as styrene monomer, cumene or linear alkylbenzenes. "Reformat" is a high octane gasoline cut produced by catalytic reforming. Finally, the term "raffinate" refers to a petroleum fraction of a distillation range analogous to that of naphtha which essentially contains non-aromatic compounds (typically paraffins and / or naphthenes) and which has an octane number generally lower than that of an aromatic cut resulting from the catalytic reforming. Hydrocarbon feedstock Hereinafter, naphtha, alone or in admixture with other naphthas, is defined as the feedstock which is capable of being processed by the process according to the invention. This filler is a hydrocarbon fraction rich in paraffinic and naphthenic compounds and relatively low in aromatic hydrocarbon compounds. For example, a naphtha feedstock is obtained from the atmospheric distillation of crude oil or a condensate of natural gas. The process according to the invention also applies to heavy naphthas produced by a catalytic cracking (FCC), coking, hydrocracking or steam cracking gasoline unit. These charges, which are more or less rich in aromatic hydrocarbon compounds, can be used to feed a catalytic reforming unit for the production of gasoline bases or aromatic bases. The present invention can be defined as a process for producing gasoline with an octane number of greater than 95, and preferably greater than 98, and of co-production of aromatic bases from one or more naphtha cuts originating from one or more of following units: atmospheric distillation, FCC, Coking, steam cracking, hydrocracking, or from the fractionation of natural gas condensates. Figure 1 shows a diagram of the method according to a first embodiment. The naphtha feed 1 described above is sent to a first catalytic reforming unit 2 which comprises two reactors in series equipped with a catalytic reforming catalyst bed, for example a fixed bed or a moving bed. The first reforming unit operates under operating conditions and in the presence of a catalyst which make it possible to optimize the conversion of the naphthenic (cycloalkane) and / or paraffinic hydrocarbon compounds into aromatic hydrocarbon compounds. In order to limit the formation of coke on the reforming catalyst, the reforming step is carried out in the presence of hydrogen. The catalyst used in this first reforming unit 2 comprises a support and an active metal phase, for example platinum. Preferably the metal and in particular platinum is associated with other elements (promoters) which are chosen from: Re, Sn, In, P, Ge, Ga, Bi, B, Ir, rare earths, or any what combination of these elements. The support is preferably an alumina. This first catalytic reforming unit operates in the following operating ranges: an average reactor inlet temperature of between 420 and 600 ° C .; a pressure of between 0.3 and 1 MPa; - molar ratio H2 / charge between 0.2 and 8 mol / mol; a mass space velocity, expressed as the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 8 h -1.
    [0010] In a preferred embodiment, the first catalytic reforming unit is operated under conditions in which the dehydrogenation reaction of the naphthenes present in the naphtha feed is promoted. The dehydrocyclization reactions of paraffins in aromatics being slower than the dehydrogenation of naphthenes, paraffins are practically not converted in this first reforming step. The first reforming step is thus preferably carried out under the following conditions: an average reactor inlet temperature of between 420 and 500 ° C .; a pressure of between 0.3 and 1 MPa; - molar ratio H2 / charge between 0.2 and 8 mol / mol; a mass space velocity, expressed as the ratio of the mass flow rate of the feedstock to the catalyst mass of between 2.5 and 8 h -1. In this preferred embodiment, a reforming catalyst comprising an alumina support, platinum and tin and said catalyst having a chlorine content of less than 0.1% by weight, preferably less than 0.05% by weight relative to the weight of the catalyst. The first catalytic reforming unit 2 produces an effluent 3 containing aromatic compounds derived in particular from the conversion of naphthenes and / or paraffins (preferably naphthenes) and unconverted nonaromatic compounds and thus a flow of hydrogen. 4. The flow of hydrogen 4 is either sent to hydrotreatment units present in the refinery or in the second catalytic reforming unit. In accordance with the invention, the effluent 3 is sent to an aromatics separation unit 5 which produces an aromatic section 6 predominantly containing aromatic compounds and a raffinate 7 containing the majority of unconverted nonaromatic hydrocarbon compounds. The separation of aromatics (compounds generally having between 6 and 11 carbon atoms) can be carried out by processes "known to those skilled in the art" based on an absorption system such as liquid-liquid extraction or extractive distillation. employing one or more solvents, or based on an adsorption system. The process according to the invention is not related to any particular technology concerning the aromatic separation unit. Preferably the separation of the aromatic compounds is carried out according to the liquid-liquid extraction technology. The extraction is carried out by means of a solvent, preferably of the sulfolane type, of chemical formula C4H802S, having a high affinity with the aromatic compounds. The products resulting from the aromatic separation unit are a raffinate 7 rich in non-aromatic compounds, in particular rich in paraffins, and an aromatic section which concentrates the aromatic compounds contained in the effluent 3.
    [0011] For example, the effluent 3 from the first catalytic reforming unit 2 is contacted with the solvent in a first extraction column from which are recovered a solvent rich in aromatic compounds and a raffinate consisting of non-aromatic compounds. The raffinate is subsequently purified in a washing column to remove residual traces of solvent. The solvent rich in aromatic compounds is first freed of the last nonaromatic compounds in a "stripping" column, then sent to a column for recovering aromatic compounds in which the solvent is separated which is recycled after regeneration and the aromatic cut 6 As indicated in FIG. 1, the aromatic section 6 may serve either as a gasoline base and is sent wholly or partly to the gasoline pool 24 (via the stream 13), or to be used as an aromatic base for a unit 8 called "aromatic complex". ". An "aromatic complex" unit refers to a combination of different fractionation units whether by adsorption, distillation, extractive distillation, liquid-liquid extraction, or crystallization, and / or conversion units of either aromatic rearrangement such as methods for transalkylation of aromatics or disproportionation, selective or not, the units of de-alkylation or alkylation of aromatics, or the isomerization units of xylenes with or without de-alkylation of ethylbenzene. The products of an aromatic complex are mainly petrochemical intermediates such as benzene, paraxylene, orthoxylene, methaxylene, xylenes, ethylbenzene, styrene monomer, cumene or linear alkylbenzenes, or the ingredients for constituting the petrol bases such as toluene, or a heavy aromatics section According to the invention, the raffinate 7 from the aromatics separation unit is treated in a second catalytic reforming unit 9 which comprises for example two series mobile bed catalyst reactors and a continuous catalyst regeneration reactor. In operation, the regenerated catalyst in the regeneration reactor is transferred to the first reactor of the first catalytic reforming unit 2. From the second catalytic reforming unit 9, a hydrogen stream 10 and a high-index reformate 11 are produced. octane. This second catalytic reforming step is intended to convert the non-aromatic non-aromatic compounds (paraffins and / or naphthenes) of the raffinate into aromatic compounds. In order to limit the formation of coke on the reforming catalyst, the reforming step is carried out in the presence of hydrogen.
    [0012] The operating conditions used in the second catalytic reforming stage are: an average reactor inlet temperature of between 420 and 600 ° C .; a pressure of between 0.3 and 1 MPa; - H2 / charge ratio between 0.2 and 8 mol / mol; a mass space velocity, expressed as the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 8 h -1. Preferably, the operating conditions used are more severe than those of the first reforming step because this second step aims at converting more refractory paraffinic and / or naphthenic compounds. In particular, conditions are chosen which favor the dehydrocyclization reactions of paraffins in aromatic compounds which are slower reactions than the dehydrogenation of naphthenes. The second reforming step is therefore carried out at a higher temperature and / or with a longer residence time than in the first reforming step, namely: an average reactor inlet temperature of between 500 and 600 ° C. ; a pressure of between 0.3 and 1 MPa; an H2 / charge ratio of between 0.2 and 8 mol / mol; a mass space velocity, expressed by the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 2.5 h -1.
    [0013] The reforming catalyst used in the second reforming step may be identical to that used in the first reforming step. Preferably, a catalyst comprising an alumina support and a platinum-active metal phase is used. Platinum is preferably associated with other elements (promoters) which are chosen from: Re, Sn, In, P, Ge, Ga, Bi, B, Ir, rare earths, or any combination of these elements. . Very preferably, the catalyst has a chlorine content of between 0.8 and 1.5% by weight, preferably between 0.8 and 1.2% by weight, and more preferably between 0.9 and 1 , 1% by weight relative to the weight of the catalyst. According to a preferred embodiment, the catalyst of the second reforming stage comprises an alumina support, platinum and tin and has a chlorine content of between 0.8 and 1.5% by weight, preferably chlorine of between 0.8 and 1.2% by weight, and more preferably between 0.9 and 1.1% by weight relative to the weight of the catalyst.
    [0014] Thus, according to a preferred embodiment, a catalyst having an activity directed towards the dehydrogenation of platinum / tin naphthenes on alumina having a chlorine content of less than 0.1% by weight is used in the first reforming unit, preferably less than 0.05% by weight relative to the weight of the catalyst and, in the second reforming unit, a catalyst having a high activity in dehydrocyclization of platinum / tin paraffins on alumina and having a chlorine content of between 0.8 and 1.5% by weight, preferably a chlorine content of between 0.8 and 1.2% by weight, and more preferably between 0.9 and 1.1% by weight relative to the weight of the catalyst.
    [0015] Referring to Figure 1, the reformat 11 which is a high octane gasoline cut is sent in full to the gasoline pool 24 when the refiner is in a gasoline production campaign. Alternatively, the entire reformate 11 is sent via line 12 to the aromatic complex 8 when the refiner wishes to produce aromatic bases for petrochemistry. In an intermediate situation, a part of the reformate 11 is sent to the gasoline pool 24 and the other part 12 is used as a charge for an aromatic complex. According to a preferred embodiment indicated in FIG. 1, the reformate 11 before being sent to the gasoline pool or in the aromatic complex is advantageously recycled to the aromatic separation unit 5, via the line 14, so as to recover the paraffinic and / or naphthenic hydrocarbon compounds not converted in the raffinate 7 and thus increasing the yield of aromatics. As for the aromatic compounds produced in the second reforming stage, they are recovered in the aromatic section 6. Depending on the needs of the refiner, the aromatic section 6 is either transferred in its entirety to the gasoline pool via line 13, or sent in full. to the aromatic complex, is distributed both to the gasoline pool and the aromatic complex. It therefore appears that the process according to the invention has a lot of flexibility because the refiner has all the possibilities of sharing between the production of high octane gasoline and the production of aromatic bases, including the two extreme cases that are the unique production of gasoline and the unique production of aromatic bases. As shown in FIG. 1, optionally, before being sent to step a), the naphtha feed 1 is processed in a hydrotreatment unit 15 to bring said feed into conformity with the specifications in terms of content. sulfur, nitrogen and / or olefinic and diolefinic compounds. FIG. 2 represents another diagram of the process according to the invention which differs from that of FIG. 1 in that the raffinate 7 from the aromatics separation unit 5 is sent to a separation unit 16 per point cutting. The characteristics and advantages mentioned in the description with reference to FIG. 1 can be transposed to the embodiment of FIG. 2. As indicated in FIG. 2, the separation unit 16 for each cutting point, for example a distillation column, is produced. a light cut C6- (a cut comprising hydrocarbons having a carbon number of less than or equal to 6) and a heavy cut c7 + (a cut comprising hydrocarbons having a carbon number greater than or equal to 7) or alternatively a light cut C7 (a section comprising hydrocarbons having a carbon number of less than or equal to 7) and a C8 + heavy cut (a section comprising hydrocarbons having a carbon number greater than or equal to 8). The light cut 18 from the separation unit 16 is sent to an isomerization unit 19 from which a high octane gasoline (isomerate) cut is produced which is sent to the gasoline pool via the line 20. L The isomerization unit allows the conversion of n-paraffins (linear paraffins) of low octane number to iso-paraffins (branched paraffins) of higher octane numbers. The isomerization reactions are slightly exothermic, working at low temperatures between 110 and 250 ° C, at pressures between 2 and 8 MPa and at a time volume velocity (VVH = volume flow charge (m3 / h) / catalyst volume (m 3)) of between 1 and 3 h -1. Thus light paraffins of the C6- or C7- light cut from separation unit 16 are not converted into the second catalytic reforming unit but are isomerized in a dedicated unit. One of the advantages of this embodiment is to increase the index of the C6- or C7- light cut via an isomerization reaction that consumes less energy than a reforming reaction. Indeed, light paraffins are molecules difficult to convert into aromatic compounds and therefore this conversion requires high temperatures which is then accompanied by unwanted reactions of hydrodealkylation and polycondensation which lead to losses of aromatic yield.
    [0016] As shown in FIG. 2, only the heavy cut 17 is sent to the second catalytic reforming unit 9, from which a hydrogen stream 10 and a reformate 11 with a high octane number are produced. The operating conditions and the reforming catalyst of the second reforming step are similar to those described with reference to FIG. 1. The reformate 11 is sent either wholly as a gasoline base to the aromatic complex or sent in full to the gasoline pool. Alternatively, the reformate 11 is sent in part to the aromatic complex and the gasoline pool depending on the production constraints of the refiner. Advantageously, the reformate 11 before being sent to the gasoline pool or in the aromatic complex is recycled via line 14 to the separation unit 5 so as to transfer the aromatic compounds produced in the second reforming step into the aromatic section. 6 and recover the unconverted paraffinic and / or naphthenic hydrocarbon compounds in reformate 7 which are new treated in the second reforming unit 9 (increase in yield of aromatics). The aromatic section 6 is then sent either wholly to the gasoline pool 24, or wholly to the aromatic complex 8, or distributed to both the gasoline pool 24 and the aromatic complex 8. FIG. 3 represents a third embodiment of the process according to the invention based on the scheme of FIG. 2. The third embodiment comprises a step of separating the light hydrocarbon compounds contained in the naphtha feed which is carried out before the catalytic reforming steps described above. This separation step, also called stabilization, consists in separating, by means of a distillation column 21 (also called "splitter"), a C4-hydrocarbon cut at the top of the column and a C5 + hydrocarbon cut (or naphtha). stabilized) at the bottom of the column. As indicated in FIG. 3, the naphtha feedstock 1 is optionally hydrotreated in the hydrotreatment unit 15 before being sent to the separation column 21. With reference to FIG. 3, the C4- cut which contains hydrocarbons having a carbon number of less than or equal to 4 is withdrawn at the top of column 21 by line 23 and the C5 + cut which contains hydrocarbons having a carbon number greater than or equal to 5 is recovered in the bottom of column 21 through line 22. The C5 + cut thus constitutes the naphtha feed which is then treated in the first catalytic reforming unit 2. The effluent 3 produced by the first catalytic reforming unit 2 is sent to a separation unit aromatics 5 which produces an aromatic cut 6 containing the majority of the aromatic compounds produced in the first catalytic reforming unit 2 and a so-called "raffinate" cut 7 containing predominantly nonaromatic hydrocarbon compounds not converted in the first reforming step. The aromatic section 6 can then be wholly sent to an "aromatic complex" unit 8 or to the gasoline pool 24 via line 13. Alternatively, part of the aromatic section 6 is sent to the "aromatic complex" 8 and the other part is sent to the gasoline pool 24 via line 13. The raffinate 7 from the aromatic separation unit 5 is sent to a distillation column 16 which produces a C7- light cut and a C8 + heavy cut. Light cut 18 is processed in an isomerization unit 19 which produces a high octane gasoline cut, which is sent to the gasoline pool. As for the heavy cut 17, it is used as a feedstock in the second catalytic reforming unit 9, from which a hydrogen stream 10 and a reformate 11 which is a gasoline cut with a high octane number are produced. As mentioned before, the reformate 11 is advantageously sent in full to the gasoline pool when the refiner is in a gasoline production campaign. Alternatively, the entire reformate 11 is sent via line 12 to the aromatic complex 8 when the refiner wishes to produce aromatic bases for petrochemistry. In an intermediate situation, part of the reformate 11 is sent to the gasoline pool and the other part 12 is used as a feedstock for an aromatic complex. Advantageously, before being sent to the gasoline pool or to the aromatic complex, the reformate 11 is sent to the aromatic separation unit 5 via the line 14 in order to eliminate any traces of unconverted paraffins and so recovering the aromatic compounds produced in the second reforming step in the aromatic section 6. This third embodiment is advantageous because it easily integrates into a refinery scheme between the gasoline stabilization column and the fuel cell. isomerization of the light essences that are already existing. According to another embodiment not shown, the naphtha feedstock is first stabilized so as to separate a C4- hydrocarbon cut and a C5 + hydrocarbon cut. The C5 + hydrocarbon fraction is then treated according to the scheme of the process of FIG.
    [0017] Examples Example 1 The following example compares two process schemes: a scheme according to the invention (in accordance with FIG. 1) called A and a scheme not in accordance with the invention B in which there is no aromatic separation unit. In both cases, the naphtha feed has the following composition: Composition Paraffins 64.3 feedstock (wt.%) Olefins 0 Naphthenes 22.3 Aromatics 13.3 Flow (t / h) In the non-compliant process B, the naphtha feed is sent in a catalytic reforming unit composed of four reactors. A hydrogen stream and a high octane reformate withdrawn from the 4th reactor are produced The composition of the reformate obtained is described in Table 1 below.
    [0018] In the process according to the invention A, the naphtha feed is sent to a first catalytic reforming unit 2 composed of two reactors. The effluent 3 of this first catalytic reforming unit 2 is sent to an aromatic separation unit 5 which produces an aromatic section 6 and a so-called "raffinate" section 7 containing the majority of the nonaromatic hydrocarbon compounds. The raffinate 7 is treated in a second catalytic reforming unit 9 composed of two reactors, from which a hydrogen stream 10 and a reformate 11 with a high octane number are produced. The aromatic section 6 and the reformate 11 are mixed, the composition of the mixture is given in Table 1 below.
    [0019] In this example 1, the catalytic reforming units are operated under the same conditions: average reactor inlet temperature = 520 ° C. space mass velocity: 2 h -1 (it should be noted that for process A according to US Pat. the spatial mass velocity is recalculated for the second reforming unit which does not process the same flow rate in order to keep a constant amount of catalyst between the case A and the non-compliant case B). - relative pressure = 0.5 MPa - a molar ratio H2 / load = 2 - cycle time = 3 days. The catalyst used in the examples is a platinum / tin catalyst on chlorinated alumina.
    [0020] The aromatic separation step involves liquid-liquid extraction with sulfolane. Table 1 below gives the composition of the mixture (reformate + aromatic section) obtained with Scheme A according to the invention and the composition of the reformate obtained with Scheme B not according to the invention: Reform of Scheme B Mixture ( aromatic section + reformate) of scheme A according to the invention Gains not according to the invention RON 101.80 102.62 0.82 Yield C5 + 87.13 88.78 1.64 (%) Yield H2 3.48 3 , 73 0.24 (%) Yield 65.49 68.27 2.77 aromatics (%) Yield Cl - 9.38 7.50 -1.89 C4 (%) Coke formed on the catalyst of the 4lth 7.28 , 75 -5.53 reactor (% by weight) Table 1 The scheme according to the invention with respect to the non-compliant scheme allows a gain of 0.8 points on the RON, of 1.6% on the yield of C5 + compounds, 0.24% on the production of hydrogen and 2.8% on the production of aromatics.
    [0021] There is also less cracking so a light compound production lower by 1.9% and a decrease of 5.5% by weight of coke on the catalyst of the 41st reactor. The fact of separating the aromatics from the effluent leaving the second reactor of the first catalytic reforming unit before sending said effluent to the third reactor (which corresponds to the first reactor of the second catalytic reforming unit) makes it possible to to limit not only the "parasitic" reactions of hydro-dealkylation which generate a loss in aromatic yield but also to limit the polycondensation reactions which are responsible for the deposition of coke on the catalyst and thus its deactivation. The very low coke content of the catalyst at the outlet of the 41st reactor in the invention therefore makes it possible to increase the catalyst cycle time before it is replaced. Example 2 The following Example 2 compares two process schemes: a scheme C according to the invention according to Figure 2 and non-conforming scheme B in which there is no aromatic separation unit. In both cases, the naphtha feed has the following composition: Composition Paraffins 64.3 feedstock (% wt) Olefins 0 Naphthenes 22.3 Aromatic 13.3 Flow (t / h) 20 In Scheme B not in accordance with the invention , the naphtha feedstock is sent to a catalytic reforming unit composed of four reactors from which a stream of hydrogen and reformate is produced. The composition of the reformate obtained at the outlet of the 4th reactor is given in Table 2 below.
    [0022] In Scheme C according to the invention, the naphtha feed is sent to a first catalytic reforming unit 2 composed of two reactors. The effluent 3 from this first unit 2 is sent to an aromatic separation unit 5 which produces an aromatic section 6 and a raffinate 7 containing the majority of the nonaromatic compounds. Raffinate 7 is fed to a cut point separation unit 16 which produces a C7 light cut and a C8 + heavy cut. The light cut 18 is sent to an isomerization unit 19 from which a high octane isomerate is produced. The heavy cut 17 is sent to a second catalytic reforming unit 9 composed of two reactors, from which a hydrogen stream 10 and a reformate 11 with a high octane number are produced. The reformate is mixed with the aromatic section and the isomerate, the composition of said mixture is given in Table 2 below. In this example 2, the catalytic reforming units are operated under the same conditions: average reactor inlet temperature = 520 ° C. space mass velocity: 2 h -1 (It should be noted that for process A according to US Pat. the spatial mass velocity is recalculated for the second reforming unit which does not process the same flow rate in order to keep a constant amount of catalyst between the case A and the non-compliant case B). - relative pressure = 0.5 MPa - a molar ratio H2 / load = 2 - cycle time = 3 days. The catalyst used in the examples is a platinum / tin catalyst on chlorinated alumina. The aromatic separation step involves liquid-liquid extraction with sulfolane.
    [0023] In the case of Scheme C, there is also an isomerization unit of the light cut 07-which is operated under the following conditions and in the presence of a platinum isomerization catalyst on chlorinated alumina and hydrogen: average temperature at the reactor inlet = 120 ° C - space velocity: 1.211-1 - relative pressure = 0.30 MPa - molar ratio H2 / charge = 0.2 Table 2 below gives the composition of the mixture (reformat + aromatic cut + isomerate) obtained with scheme C according to the invention and the composition of the reformate obtained with scheme B not according to the invention: reformate of the mixture (reformat Gains diagram B no + cut according to aromatic + the invention isomerate) Scheme C according to the invention RON 101.8 101.83 0.03 Yield C5 + (%) 87.13 91.15 4.01 Yield H2 (%) 3.48 3.40 -0.09 Yield 65.49 64.31 -1.18 aromatics (%) Yield C1-04 9.38 5.46 -3.93 (%) Coke deposited on the 7.28 1.46 -5.82 catalyst of the 4th Reactor (% wt) Table 2 The scheme according to the invention compared to the prior art allows a gain of 4% on the C5 + yield, a hydrogen yield and a RON quasi-constant and a slight loss of 1.2 % on the production of aromatics. This slight loss is related to the fact that only the C8 + cut of the raffinate is treated in the second reforming step and not the entire raffinate. It is found that there is less cracking so a production of light hydrocarbon compounds lower than 3.9%. Finally, a decrease of 5.8% by weight of coke is observed on the catalyst of the 4th reactor, The fact of separating the aromatics from the effluent leaving the 2nd reactor of the first catalytic reforming unit before its treatment in the third reactor, which corresponds to the first reactor of the second catalytic reforming unit, it is possible to limit the "parasitic" hydro-dealkylation reactions which generate a loss in aromatic yield and to limit the polycondensation reactions which generate the deposition of coke on the catalyst. The fact of carrying out a separation of the nonaromatic raffinate resulting from the separation of the aromatics makes it possible to better adapt the subsequent treatment as a function of the compounds constituting each section. In the present case, the C7- cut is advantageously subjected to an isomerization step rather than to a reforming step. Indeed light paraffins being difficult to reform, it is necessary to implement severe operating conditions that can lead to a significant cracking thus to the formation of light compounds (C1-C4). In this scheme of the process according to the invention the light paraffins are sent to the isomerization where the cracking is limited thanks to the gentle operating conditions, hence the decrease in the amount of light compounds observed in the mixture analyzed. The isomerate thus produced is advantageously used at the gasoline pool.
    权利要求:
    Claims (21)
    [0001]
    REVENDICATIONS1. A process for producing octane gasoline greater than 95 and co-producing aromatic bases from a naphtha cut (1) comprising paraffins and naphthenes, the process comprising the steps of: a) sending the naphtha section in a first catalytic reforming unit (2) in which the naphtha fraction is brought into contact with a reforming catalyst so as to convert at least a portion of the paraffins and / or naphthenes into aromatic compounds and to produce hydrogen ; b) withdrawing from the first catalytic reforming unit (2) a first effluent (3) and a hydrogen stream (4); c) the first effluent (3) is sent to an aromatics separation unit (5) so as to separate a first aromatic section and a raffinate (7) containing paraffins and / or unconverted naphthenes; d) the raffinate (7) is fed to a second catalytic reforming unit (9) in which the raffinate (7) is contacted with a reforming catalyst so as to convert the unconverted paraffins and / or naphthenes to aromatics and produce hydrogen; e) withdrawing from the second catalytic reforming unit (9) a reformate (11) containing aromatic compounds and a hydrogen stream (10).
    [0002]
    The process according to claim 1, wherein the entire aromatic section (6) is sent to an aromatic complex unit (8).
    [0003]
    The process according to claim 1, wherein a part of the aromatic section (6) is sent to one aromatic complex unit (8) and the other part of the aromatic section (6) is sent to the gasoline pool.
    [0004]
    4. Method according to one of the preceding claims, wherein the entire reformate (11) is sent to the gasoline pool (24).
    [0005]
    5. Method according to one of claims 1 to 3, wherein a portion of the reformate (11) is sent in an aromatic complex unit (8) and the other part of the reformate (11) is sent to the gasoline pool (24). ).
    [0006]
    6. Method according to one of the preceding claims, wherein the reformate (11) is processed in the aromatic separation unit (5).
    [0007]
    7. Method according to one of the preceding claims, wherein the naphtha cut is previously treated in a hydrotreating unit (15) before step a).
    [0008]
    8. Method according to one of the preceding claims, wherein the naphtha cut is sent to a separation unit (21) configured to separate a C4 cut and a cut 05 + and said section 05+ is sent to step a ).
    [0009]
    9. Method according to one of the preceding claims, wherein the raffinate (7) from step c) is sent to a separation unit (16) configured to separate a C6- cut and a c7 + cut or a cut 07 and a C8 + cut and the c7 + cut or the C8 + cut is sent to the second catalytic reforming step d) and the C6- cut or the C7- cut is sent to an isomerization unit (19) in order to increase its octane number.
    [0010]
    10. Method according to one of the preceding claims, wherein the first and second catalytic reforming steps a) and d) are performed at: - an average reactor inlet temperature of between 420 and 600 ° C; an average reactor pressure between 0.3 and 1 MPa; a mass space velocity, expressed as the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 8 h -1; an H2 / charge molar ratio of between 0.2 and 8 mol / mol.
    [0011]
    11. Method according to one of the preceding claims, wherein the first catalytic reforming step a) is performed at: - an average reactor inlet temperature between 420 and 500 ° C; an average reactor pressure between 0.3 and 1 MPa; a mass space velocity, expressed by the ratio of the mass flow rate of the feedstock to the catalyst mass of between 2.5 and 8 h -1, and an H 2 / feedstock molar ratio of between 0.2 and 8 mol / mol.
    [0012]
    12. Method according to one of the preceding claims, wherein the second catalytic reforming step d) is performed at: - a mean reactor inlet temperature of between 500 and 600 ° C; an average reactor pressure between 0.3 and 1 MPa; a mass spatial velocity, expressed as the ratio of the mass flow rate of the feedstock to the catalyst mass of between 0.5 and 2.5 h -1; an H2 / charge molar ratio of between 0.2 and 8 mol / mol. 10
    [0013]
    13. Method according to one of the preceding claims, wherein the naphtha cut is derived from one or more units: atmospheric distillation, FCC, coking, steam cracking, hydrocracking, fractionation of natural gas condensates. 15
    [0014]
    14. Method according to one of the preceding claims, wherein the catalytic reforming catalyst used in steps a) and d) comprises an alumina support and platinum. 20
    [0015]
    15. The method of claim 14, wherein the reforming catalyst is promoted with one of the following: Re, Sn, In, P, Ge, Ga, Bi, B, Ir, rare earths.
    [0016]
    16. The process according to one of claims 14 or 15, wherein the catalytic reforming catalyst of step a) has a chlorine content of less than 0.1% by weight, preferably less than 0.05% by weight. relative to the weight of the catalyst.
    [0017]
    17. Method according to one of claims 14 to 16, wherein the catalytic reforming catalyst of step d) has a chlorine content of between 0.8 and 1.5% by weight, preferably between 0.8. and 1.2% by weight, and more preferably between 0.9 and 1.1% by weight based on the weight of the catalyst.
    [0018]
    18. A method according to any one of the preceding claims, wherein the aromatic separation unit (5) comprises a liquid-liquid extraction column employing a solvent having a high affinity for the aromatic compounds. 35
    [0019]
    19. The process according to claim 18, wherein the solvent is of the sulfolane type.
    [0020]
    20. Method according to one of the preceding claims, wherein the first and second catalytic reforming units use an identical catalyst and operate in a continuous regeneration mode and wherein the first catalytic reforming unit comprises at least one reactor and the second catalytic reforming unit comprises at least one reactor and a catalyst regenerator with regenerated catalyst circulation in the reactor of the first catalytic reforming unit.
    [0021]
    The process according to one of claims 1 to 19, wherein the first and second catalytic reforming units use a different catalyst and operate in a continuous regeneration mode and wherein the first catalytic reforming unit comprises at least one reactor and a catalyst regenerator and the second catalytic reforming unit comprises at least one reactor and a catalyst regenerator.
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    同族专利:
    公开号 | 公开日
    CN104711016A|2015-06-17|
    FR3014894B1|2017-02-10|
    KR102366092B1|2022-02-21|
    KR20150070960A|2015-06-25|
    TW201538706A|2015-10-16|
    TWI653328B|2019-03-11|
    CN104711016B|2020-09-08|
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    CN102796553B|2011-05-27|2015-07-29|中国石油化工股份有限公司|A kind of Benzin naphtha catalytic reforming method|CN108018068B|2016-11-04|2020-12-01|中国石油化工股份有限公司|Combined process for preparing aromatic hydrocarbon from methanol and catalytic reforming|
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    CN110699111B|2018-07-09|2021-12-17|中国石油化工股份有限公司|Countercurrent continuous reforming method|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1362749A|FR3014894B1|2013-12-17|2013-12-17|CATALYTIC REFORMING PROCESS|FR1362749A| FR3014894B1|2013-12-17|2013-12-17|CATALYTIC REFORMING PROCESS|
    KR1020140180096A| KR102366092B1|2013-12-17|2014-12-15|Catalytic reforming process|
    TW103143942A| TWI653328B|2013-12-17|2014-12-16|Catalytic reforming process|
    CN201410780040.2A| CN104711016B|2013-12-17|2014-12-17|Catalytic reforming process|
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