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    • 专利摘要:
    The present invention discloses a process for producing high purity paraxylene from a xylenes section which may contain ethylbenzene and C9 compounds, said process using two series-operated simulated moving bed separation units and two isomerization.
    公开号:FR3023840A1
    申请号:FR1456940
    申请日:2014-07-18
    公开日:2016-01-22
    发明作者:Heloise Dreux；Philibert Leflaive；Le Cocq Damien Leinekugel
    申请人:IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The production of paraxylene has been steadily increasing for thirty years. The uses of paraxylene are the production of terephthalic acid and polyethylene terephthalate resins, to provide synthetic textiles, bottles, and more generally plastics. To meet the ever increasing demand for paraxylene, petrochemists have the choice between practicing capacity increases on existing units (called debottlenecking in the rest of the text), or building new units. The present invention makes it possible to respond to these two cases, and more particularly to debottlenecking of existing units, since the modifications involved are relatively modest. In the remainder of the text we speak of a simulated moving bed separation unit (abbreviated as SMB), or a separation unit (SMB). A separation unit (SMB) may contain one or more adsorbers. EXAMINATION OF THE PRIOR ART The production of high purity paraxylene by adsorptive separation is well known in the prior art. In an industrial manner, this operation is carried out within a sequence of processes known as "C8-aromatic loop". This "C8-aromatic loop" includes a step of removing heavy compounds (i.e., more than 9 carbon atoms, denoted C9 +) in a distillation column called "xylenes column". The overhead stream of this column, which contains the C8-aromatic isomers, is then fed into the paraxylene separation process which is generally a simulated moving bed adsorption separation process. The extract, which contains paraxylene, is then distilled by means of an extract column and then a toluene column to obtain high purity paraxylene.
    [0002] The raffinate, rich in metaxylene, orthoxylene and ethylbenzene, after a step of removal of the solvent by distillation, is treated in a catalytic isomerization unit which gives a mixture of C8 aromatics, in which the proportion of xylenes (ortho- , meta-, para-xylenes) is practically at thermodynamic equilibrium, and the amount of ethylbenzene diminished. This mixture is again sent to the "xylenes column" with the fresh load. The prior art proposes numerous variants of this basic scheme employing one or more separation units (by adsorption, crystallization, distillation or membrane) and / or one or more isomerization units in the gas phase (converting the ethylbenzene by isomerization to xylenes or by dealkylation to benzene), or in liquid phase (not converting ethylbenzene). In particular, the patent FR2862638 describes a process for producing paraxylene from a hydrocarbon feedstock, in an adsorption column working in simulated moving bed at least five zones and delivering an extract, a raffinate-2 and a intermediate raffinate. The raffinate-2 is sent to an isomerization preferably operating in the liquid phase and at low temperature. The intermediate raffinate with an enriched ethylbenzene content is isomerized in the vapor phase.
    [0003] Alternatively, US Pat. No. 8,227,334 discloses a process for producing paraxylene comprising: (a) separating a feed containing C8 hydrocarbons to produce a C8 hydrocarbon rich stream, (b) separating a first portion C8 rich hydrocarbon stream to produce a first paraxylene rich stream and a first paraxylene poor raffinate; (c) isomerization of at least a portion of the raffinate to obtain an isomerate; (d) separation of a second part of the C8 hydrocarbon rich stream to produce a second paraxylene rich stream and a second paraxylene poor raffinate, (e) at least partially liquid phase isomerization of at least a portion of the second raffinate to produce an isomerate, ( f) recovering at least a portion of at least one of the two paraxylene rich streams to make paraxylene at high purity via adsorption separation, (g) sending at least one of not part of the first isomerate and at least a portion of the second isomerate to the separation unit (a).
    [0004] It should be noted that, when the paraxylene separation unit is an adsorption separation process, the C9 + content must be very low in the feed (typically less than a few hundred ppm wt) in order to avoid accumulation. of these compounds in the solvent recycle loop. Industrially and in the above patents, there is thus systematically a treatment of at least a portion of the feed supplying the distillation adsorption separation unit (s) with a very severe specification on the C9 content. -aros. However, this separation is very expensive in energy. There is therefore a need to optimize the sequence of processes within the C8-aromatic loop in order to limit the operating costs, especially those related to the separation of C9-aromatics. Such a problem also arises during remodeling of existing units in order to increase the amount of paraxylene produced. This operation is called debottlenecking, a term that will be used in the rest of the text. It is then a question of limiting as much as possible the investment costs related to the modifications to be made to the C8-aromatic loop, as well as the operating costs of operating the process sequence after remodeling. The present invention utilizes two LMS adsorption separations, and two isomerizations, combined with fresh charge injection on only one of two adsorption separation. It makes it possible to limit or eliminate the treatment of the charge upstream of one of the separation units, contrary to the solutions proposed by the prior art. The use of two LMS adsorption separation units makes it possible to process more charge than the sequence proposed in patent FR2862638, which makes it possible to maximize the use of high-performance new-generation adsorbents and to meet current paraxylene production needs of more than 1 million tonnes per year at a single site.
    [0005] Mutualization of the columns downstream of the two adsorption separation units also makes it possible not to multiply the distillation columns and thus to minimize the investment. This also allows optimal use of existing distillation columns in the case of remodeling an existing 24-bed separation unit into two 12-bed separation units. Finally, the mixture of the two intermediate (ethylbenzene enriched) refineries from the two adsorptive separation units allows the optimization of the EB conversion in gas phase isomerization. In the remainder of the text we speak of a separation unit to designate the simulated moving bed separation units, of adsorbers to designate groups of adsorbent beds, a unit that can contain one or more adsorbers. We are talking about isomerization unit and distillation columns to designate the other equipment of the process. SUMMARY DESCRIPTION OF THE FIGURES FIG. 1 represents the scheme of the process according to the present invention with the two simulated moving bed separation units noted SMB-1 and SMB-2 and the two ISOM-1 and ISOM-isomerization units. 2. FIG. 2 represents a variant of the method according to the invention which leads to the use of columns with internal walls known as "divided wall columns" in the English terminology. FIG. 3 is a schematic of the process according to the prior art which is used for Example 1. SUMMARY DESCRIPTION OF THE INVENTION The present invention can be defined as a process for the production of high purity paraxylene from a xylenes section containing ethylbenzene and C9 + compounds, using two simulated moving bed separation units (SMB-1 and SMB-2) operating in series, and two isomerization units (ISOM-1 and ISOM -2).
    [0006] By series operation of the simulated moving bed separation units (SMB-1 and SMB-2) it is meant that the effluent from the separation unit (SMB-1) is used indirectly as the load of the separation unit (SMB-2), indirectly meaning that separation or isomerization units can be intercalated in the path of the effluent of the separation unit (SMB-1). More specifically, the process according to the present invention consists of the following sequence of steps: - the charge (2) is sent to a distillation column (S-1) from which a mixture (3) is withdrawn at the top (3) comprising most of the metaxylene, paraxylene, ethylbenzene, and at least a portion of the orthoxylene, and from which a stream (4) of C9-C10 hydrocarbons is withdrawn in the bottom and the portion remaining orthoxylene, - separating the head mixture (3) in the separation unit (SMB-1) comprising at least one adsorber containing a plurality of interconnected beds and working in closed loop, said adsorber comprising at least five zones delimited by the injections of the flow (3) and the desorbent (16), and the withdrawals of a first extract (5) containing paraxylene, a first intermediate raffinate (7) containing ethylbenzene, and a first raffinate-2 (8) containing orthoxylene and metaxylene, a separation in the separation unit (SMB-2) of the isomerate (11) from the isomerization unit (ISOM-1), said separation unit (SMB -2) consisting of at least one adsorber containing a plurality of interconnected beds and preferably working in a closed loop, and said separation unit comprising at least five zones delimited by the injections of the flow (11) and the desorbent (17), and the withdrawals of a second extract (12). ) containing paraxylene, a second intermediate raffinate (14) containing ethylbenzene, and a second raffinate-2 (15) containing orthoxylene and metaxylene, - distilling the first extract (5) from of the column (SMB-1) in a column (EXT-1), to recover a first fraction (6) enriched in paraxylene, - the two raffinate-2, stream (8) and (15), are mixed together to form the stream (9) which is distilled in a column (RAF-2) so as to substantially remove all the desorbent and to extract a first distilled fraction (10), the first isomerization unit (ISOM-1) is fed with the stream (10) to obtain the first isomerate (11), the two intermediate raffinates are mixed, and 7) and (14), to form the stream (18) which is distilled in a column (RAFINTER) to substantially remove all the desorbent and to withdraw a second distilled fraction (19), - feeds the stream (19) a second isomerization unit (ISOM-2) to obtain a second isomerate (20) which is recycled to the inlet of the separation column (S-1). The present invention may have several variants, some of which are described below. All these variants are compatible with each other. According to one variant of the process for producing high purity paraxylene according to the invention, the first extract (5) from the separation unit (SMB-1) is distilled in a column (EXT-1) to recover a first fraction (6) enriched in paraxylene, - distilling the second extract (12) in a column (EXT-2), to recover a second fraction (13) enriched in paraxylene. In another variant of the process for producing high purity paraxylene according to the invention, the two extracts (5) and (12) are distilled in a single column of common extract to recover a single fraction enriched in paraxylene. According to a preferred variant of the method of producing high purity paraxylene according to the invention, the isomerization unit (ISOM1) operates in the liquid phase under the following conditions: - Temperature below 300 ° C, preferably between 200 and 260 ° C, 5 - Pressure less than 4 MPa, preferably between 2 and 3 MPa, - Space velocity of less than 10 h -1, preferably of between 2 h -1 and 4 h -1, - Catalyst comprising at least a zeolite having channels whose opening is defined by a ring with 10 or 12 oxygen atoms (10 MR or 12 MR), preferably a catalyst comprising at least one zeolite having channels whose opening is defined by a ring with 10 oxygen atoms (10 MR), and even more preferably, a catalyst comprising a zeolite type ZSM-5. According to another variant of the method of producing high purity paraxylene according to the invention, the isomerization unit (ISOM-2) operates in the gas phase under the following conditions: - temperature above 300 ° C., preferably 360 ° At 480 ° C., a pressure of less than 2.5 MPa and preferably 0.5 to 0.8 MPa, a space velocity of less than 10 h -1, preferably of between 0.5 h -1 and 6 h -1; h-1, - hydrogen to hydrocarbon molar ratio of less than 10, and preferably of between 3 and 6. According to another variant of the process for producing high purity paraxylene according to the invention, the catalyst used for the unit of ISOM-2 isomerization contains an acidic zeolite, for example of structural type MFI, MOR, MAZ, MTW, FAU and / or EUO, and preferably contains a zeolite of structural type EUO, and at least one metal of the group VIII of the Periodic Table of Elements. According to another variant of the method for producing high purity paraxylene according to the invention, the catalyst used for the ISOM-2 isomerization unit comprises at least one zeolite having channels whose opening is defined by a ring with 10 or 12 oxygen atoms (10 MR or 12 MR), and at least one Group VIII metal with a content of between 0.1 and 0.3% by weight, inclusive.
    [0007] According to another variant of the process for producing high purity paraxylene according to the invention, the separation unit (SMB-1) uses the PDEB as desorbent.
    [0008] In a variant of the process according to the present invention, the separation unit (SMB-2) uses toluene as desorbent. In a variant of the process according to the present invention, the separation units (SMB-1) and (SMB-2) contain from 6 to 24 beds, and preferably from 8 to 15 beds, distributed over one or more adsorbers, the number of beds being adjusted so that each bed preferably has a height of between 0.70 m and 1.40 m. In another variant of the process according to the present invention, the distribution of the amount of adsorbent solid in the separation units (SMB-1) and (SMB-2) is as follows: the amount of adsorbent solid in zone 1 is 16% ± 5%, the amount of adsorbent solid in zone 2 is 40% ± 5%, the amount of adsorbent solid in zone 3A is 16% ± 5%, the amount of adsorbent solid in zone 3B is 16% ± 5%, the amount of adsorbent solid in zone 4 is 12% ± 5%. In another variant of the process for producing high purity paraxylene according to the invention, the volume ratio of desorbent on charge is at most 1.7 / 1 and preferably between 1.5 / 1 and 0.4 / 1, inclusive. In another variant of the process for the production of high purity paraxylene according to the present invention, the ratio of the intermediate raffinate and raffinate 2 feed rates is between 0.3 / 1 and 5/1, and preferably between 0 , 4/1 and 1/1 terminals included. In another variant of the process for the production of high purity paraxylene according to the invention, for the separation unit (SMB-2), the desorbent volumetric charge ratio is at most 1.7 / 1 and preferred between 1.5 / 1 and 0.4 / 1 inclusive.
    [0009] In another variant of the process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds according to claim 1, wherein for the separation unit (SMB-2), the ratio of intermediate raffinate and raffinate 2 rates is between 0.3 / 1 and 5/1, and preferably between 0.4 / 1 and 1/1 inclusive. In another variant of the process for producing high purity paraxylene according to the invention, it is possible to proceed to the degoulotage of an existing separation unit consisting of two adsorbers in series, as follows: - the last bed of the first adsorber at the first bed of the first adsorber via a line containing at least one recirculation pump, this first adsorber serving as separation unit (SMB-1) - the last bed of the second adsorber is connected to the first bed of the second adsorber via a line containing at least one recirculation pump, this second adsorber serving as separation unit (SMB-2). In general, the configuration of the two adsorbers may be fixed number of beds in each of the adsorbers, or number of fixed beds in one of the adsorbers and variable in the other, or variable for both adsorbers. Preferably, the two adsorbers have a fixed number of beds in each of the chromatographic zones. Finally, in another variant of the process for producing high purity paraxylene according to the invention, the configuration of the two adsorbers in a simulated moving bed has a fixed number of beds in each of the chromatographic zones of each of the two adsorbers. DETAILED DESCRIPTION OF THE INVENTION The feed (2) is fed to a distillation column (S-1) from which a mixture (3) comprising most of the metaxylene ethylbenzene, and at least a portion of the orthoxylene, and from which a stream (4) of C9-C10 hydrocarbons and the remaining portion of orthoxylene are withdrawn at the bottom.
    [0010] A first separation of the head mixture (3) is carried out in the separating unit (SMB1) consisting of a plurality of interconnected beds and working in a closed loop, said separation unit comprising at least five zones delimited by the flow injections. (3) constituting the first charge of the column and the desorbent (16), and the withdrawals of a first extract (5) containing paraxylene, a first intermediate raffinate (7) containing ethylbenzene, and a first raffinate-2 (8) containing orthoxylene and metaxylene. The five zones of the separation unit (SMB-1) are the following: the zone 1 between the injection of the desorbent (16) and the withdrawal of the extract (5), the zone 2 between the withdrawal of the extract (5) and the injection of the charge (3), - the zone 3A between the injection of the charge (3) and the withdrawal of the intermediate raffinate (7), - the zone 3B between withdrawing the intermediate raffinate (7) and withdrawing the raffinate-2 (8), - the zone 4 between the raffinate-2 (8) and the desorbent (16). A second simulated moving bed separation (SMB-2) of the isomerate (11) from the isomerization (ISOM-1) is carried out, from which all or part of the C9 and C10 heavy compounds have been optionally removed by distillation. (either in a dedicated column or in column S-1). Preferably, the isomerate (11) is sent to the simulated moving bed separation unit (SMB-2) without an intermediate step of removing the C9 + compounds. The separation unit (SMB-2) consists of a plurality of interconnected and closed-loop beds, said separation unit comprising at least five zones delimited by the injections of the stream (11) constituting the second charge of the column and desorbent (17), and withdrawals of a second extract (12) containing paraxylene, a second intermediate raffinate (14) containing ethylbenzene, and a second raffinate-2 (15) containing orthoxylene and metaxylene. The five zones of the SMB-2 column are the following: Zone 1 between the injection of the desorbent (17) and the extraction of the extract (12). The zone 2 between the withdrawal of the extract (12) and the injection of the second charge (11), - the zone 3A between the injection of the second charge (11) and the withdrawal of the second intermediate raffinate (14), - the zone 3B between withdrawing the second intermediate raffinate (14) and withdrawing the second raffinate-2 (15), - Zone 4 between the withdrawal of the second raffinate-2 (15) and the injection of the desorbent (17).
    [0011] A first extract (5) is preferably distilled in a distillation column (EXT-1) to recover a first fraction (6) enriched in paraxylene. A second extract (12) is preferably distilled in a distillation column (EXT2) to recover a second fraction (13) enriched in paraxylene. Both extracts (5) and (12) can also be distilled in a single common extract column to recover a single paraxylene enriched fraction. The two raffinates-2 streams (8) and (15) are preferably mixed to form the stream (9) which is distilled in a distillation column (RAF-2) to remove substantially all the desorbent and to withdraw a first distilled fraction (9) poor in ethylbenzene. The two raffinate-2 streams (8) and (15) can also be distilled in two different columns, and then the two distilled fractions poor in ethylbenzene are mixed. The distilled fraction (s) obtained feeds a first isomerization unit (ISOM-1) to obtain a first isomerate (11) preferentially supplying the separation unit (SMB-2). ), but can be partly recycled at the inlet of the distillation column (S-1). The two intermediate fluxes (7) and (14) are preferably mixed to form the stream (18) and distilled in a column (RAFINTER) to remove substantially all the desorbent and to withdraw a second distillate fraction (19) rich in ethylbenzene .
    [0012] The two intermediate raffinate streams (7) and (14) can also be distilled in two different columns and then the two distilled fractions rich in ethylbenzene are mixed. The distilled fraction (s) obtained feeds a second isomerization unit (ISOM-2) to obtain a second isomerate (20) recycled at the inlet of the separation column (S-1). ). The first isomerization unit (ISOM-1) preferably working in liquid phase, is generally operated under the following conditions: - Temperature below 300 ° C, preferably 200 ° C to 260 ° C - Pressure less than 4 MPa, preferably 2 to 3 MPa - hourly space velocity (VVH) less than 10 h -1 (10 liters per liter per hour), preferably between 2 and 4 h -1. Catalyst comprising at least one zeolite having channels whose opening is defined by a ring with 10 or 12 oxygen atoms (10 MR or 12 MR), preferably a catalyst comprising at least one zeolite having channels whose opening is defined by a ring with 10 oxygen atoms (10 MR), and even more preferably, a catalyst comprising a zeolite type ZSM-5.
    [0013] The second isomerization unit (ISOM-2) operating in the gas phase is generally operated under the following conditions: - Temperature above 300 ° C., preferably 350 ° C. to 480 ° C. - Pressure below 4 MPa, preferably between between 0.5 and 2 MPa - hourly space velocity (VVH) less than 10 h -1 (10 liters per liter per hour), preferably between 0.5 and 6 h -1. Catalyst comprising at least one zeolite having channels whose opening is defined by a ring with 10 or 12 oxygen atoms (10 MR or 12 MR), preferably a catalyst comprising a zeolite of structure type EUO, MTW or MOR, and at least one group VIII metal. H 2 / hydrocarbon molar ratio of less than 10, preferably of between 3 and 6.
    [0014] The catalyst of the gas phase isomerization unit (ISOM-2) may comprise a zeolite of structure type EUO, MTW or MOR, and at least one metal of group VIII of the periodic table of elements in a weight ratio of 0 , 01% to 2% relative to the catalyst. The catalyst of the gas phase isomerization unit (ISOM-2) may in some cases contain an EU-1 zeolite and platinum. The desorbents used in the simulated moving bed separation units (SMB-1 and SMB-2) are generally chosen from paradiethylbenzene, toluene, paradifluorobenzene or mixed diethylbenzenes.
    [0015] The volume ratio of the desorbent on the feedstock in the simulated moving bed separation units (SMB-1 and SMB-2) is between 0.5 and 2.5, and preferably between 0.8 and 2. The units in a simulated moving bed (SMB-1 and SMB-2) are operated at a temperature between 20 ° C and 250 ° C, preferably between 90 ° C and 210 ° C, and more preferably between 140 ° C C and 180 ° C, and under a pressure between the bubble pressure of xylenes at the operating temperature and 2 MPa. The ethylbenzene content of the second distilled fraction from raffinate-2 (stream (8) and (14)) is less than that of the feed and preferably reaches at most 10% by weight. The operation of the process according to the invention, and in particular the composition of the different streams, is specified below with reference to FIG. 1. The fresh feedstock is introduced via line (1) into a distillation column (S- 1). This fresh feed contains mainly C8-aromatic compounds, xylenes and ethylbenzene, in variable proportion depending on the origin of the cut. It may optionally contain impurities in a variable amount depending on the origin of the feed which will essentially be aromatic compounds C9 and C10 and paraffinic and naphthenic compounds. The content of naphthenic or paraffinic impurities is advantageously less than 1% by weight. Preferably, this content is less than 0.3% by weight, and more preferably this content is less than 0.1% by weight.
    [0016] The feed may be from either a reforming unit, a toluene disproportionation unit, a transalkylation unit of toluene and aromatic C9. To the fresh feed is added an isomerate conveyed by a line (20).
    [0017] The bottom effluent (4) of the (S-1) column consists essentially of aromatic C 9 and C 10 compounds, and optionally orthoxylene. Optionally, the mixture (4) of orthoxylene and aromatic hydrocarbons C9-C10 withdrawn at the bottom of the distillation column (S1), can be sent to another distillation column from which the top is extracted. a flow of orthoxylene of high purity (at least 98.5%), and in bottom a stream containing C9-C10 hydrocarbons. The overhead effluent (3) from column (S-1) constitutes the charge of a simulated moving bed separation unit (SMB-1). The simulated moving bed separation unit (SMB-1) is fed on the one hand by the load conveyed by the line (3), and on the other hand by the desorbent conveyed by a line (16). Any type of desorbent can be used. The preferred desorbent is paradiethylbenzene, however other desorbents such as toluene, paradifluorobenzene or mixed diethylbenzenes may also be suitable. The effluents of the unit (SMB-1) are an extract (5), an intermediate raffinate (7) and a raffinate-2 denoted (8), said separation unit comprising at least five zones delimited by the charge injections and desorbent, and raffinate intermediate raffinate-2 and extract 30 withdrawals.
    [0018] The total number of beds of the separation unit (SMB-1) according to the invention is preferably between 6 and 24 beds, and even more preferably between 8 and 15 beds distributed over one or more adsorbers.
    [0019] The number of beds will be adjusted so that each bed preferably has a height between 0.70 m and 1.40 m. The distribution of the amount of adsorbent solid in each zone is as follows: the amount of adsorbent solid in zone 1 is 16% ± 5%, the amount of adsorbent solid in zone 2 is 40% ± 5%, the amount of adsorbent solid in zone 3A is 16% ± 5%, the amount of adsorbent solid in zone 3B is 16% ± 5%, the amount of adsorbent solid in zone 4 is 12% ± 5%, According to a preferred feature of the invention, the desorbent and the feedstock can be injected into the separation unit (SMB-1) in a desorbent charge-to-charge ratio of at most 1.7 / 1, and preferably included between 1.5 / 1 and 0.4 / 1 inclusive. According to a preferred characteristic of the invention, the ratio of the intermediate raffinate and raffinate 2 feed rates is between 0.3 / 1 and 5/1 inclusive, and preferably between 0.4 / 1 and 1/1. terminals included. The extract (5) consists essentially of toluene, paraxylene and desorbent. The intermediate raffinate (7) consists essentially of toluene, metaxylene and orthoxylene, ethylbenzene, paraxylene for the unrecovered portion in the extract, and desorbent. Raffinate-2 (8) consists essentially of metaxylene and orthoxylene and desorbent. 11 is substantially free of paraxylene and depleted of ethylbenzene. The extract (5) is sent to a distillation column (EXT-1).
    [0020] The desorbent which is returned to the separation unit (SMB-1) is withdrawn from the distillation column (EXT-1) via line (16), and a mixture of paraxylene and toluene via line (6).
    [0021] Raffinate-2 (8) is sent to a distillation column (RAF-2). Distillable column (RAF-2) is withdrawn from the desorbent which is returned to the line (16), and a mixture of metaxylene and orthoxylene through a line (9), which is sent to the unit d isomerization (ISOM-1).
    [0022] The isomerization unit (ISOM-1), preferably in the liquid phase, preferably works under the following conditions: - temperature below 300 ° C., preferably between 200 and 260 ° C., pressure below 4 MPa, preferably between 2 and 3 MPa, - space velocity of less than 10 h -1, preferably of between 2 h -1 and 4 h -1. All catalysts capable of isomerizing hydrocarbons with 8 carbon atoms are suitable for the isomerization unit (ISOM-2) of the present invention. Preferably, a ZSM-5 type zeolite containing catalyst will be used. The isomerization unit effluent (ISOM-1) is returned via line (11), either to the distillation column (S-1). ), or directly at the inlet of the separation unit (SMB-2) in the case where the content of compounds other than C8-aromatics is very low, typically of the order of 1% by weight. The content of C9 is typically less than 1000 ppm by weight. Any type of desorbent can be used. The preferred desorbent is paradiethylbenzene, however other desorbents such as toluene, paradifluorobenzene or mixed diethylbenzenes may also be suitable. The effluents of the separation unit (SMB-2) are an extract (12), an intermediate raffinate (14) and a raffinate-2 (15), said separation unit comprising at least five zones delimited by the injections of feedstock and desorbent, and raffinate intermediate, raffinate-2 and extract withdrawals. The total number of beds of the separation unit (SMB2) according to the invention is preferably between 6 and 24 beds, and even more preferably between 8 and 15 beds distributed over one or more adsorbers.
    [0023] The number of beds will be adjusted so that each bed preferably has a height between 0.70 m and 1.40 m. The distribution of the amount of adsorbent solid in each zone is as follows: the amount of adsorbent solid in zone 1 is 16% ± 5%, the amount of adsorbent solid in zone 2 is 40% ± 5%, the amount of solid adsorbent in zone 3A is 16% ± 5%, the amount of solid adsorbent in zone 3B is 16% ± 5%, the amount of adsorbent solid in zone 4 is 12% ± 5%, According to another preferred characteristic of the invention, the desorbent and the feedstock can be injected into the separation unit (SMB-2) in a desorption charge volumetric ratio of at most 1.7 / 1, and preferably between 1.5 / 1 and 0.4 / 1, inclusive.
    [0024] According to a preferred characteristic of the invention, the ratio of the intermediate raffinate and raffinate 2 feed rates is between 0.3 / 1 and 5/1 inclusive, and preferably between 0.4 / 1 and 1/1 terminals included. The configuration (average number of beds per zone) of the two simulated moving bed units (SMB25 1 and SMB-2) can be: - with fixed number of beds in each of the chromatographic zones ("simulated moving bed" mode as defined in patent FR 2 976 501), with variable number of beds for an adsorber ("VARICOL" mode as defined in patent FR 2 976 501) and fixed for the other, 30 - with variable number of beds for both adsorber. The extract (12) consists essentially of toluene, paraxylene and desorbent.
    [0025] The intermediate raffinate (14) consists essentially of toluene, metaxylene and orthoxylene, ethylbenzene, paraxylene for the unrecovered portion in the extract, and desorbent.
    [0026] Raffinate-2 (15) consists essentially of metaxylene and orthoxylene and desorbent. It is substantially free of paraxylene and depleted of ethylbenzene. The extract (12) is sent to a distillation column (EXT-2).
    [0027] The desorbent which is returned to zone 1 of the column (SMB-2) is withdrawn from the distillation column (EXT-2) via line (17) and a mixture of paraxylene and toluene via line (13). The intermediate raffinate is sent via a line (14) with the intermediate raffinate (7) to the distillation column (RAFINTER). The desorbent which is reintroduced via the line (17) into the separation unit (SMB-2) and a mixture of xylenes and ethylbenzene are withdrawn from the distillation column (RAFINTER) by a line (19). The effluents from the line (19) are sent to the isomerization unit (ISOM-2) operating at high temperature in the vapor phase.
    [0028] The isomerization unit (ISOM-2) is operated preferably under the following conditions: - temperature above 300 ° C., preferably from 360 ° C. to 480 ° C., - pressure below 2.5 MPa, and preferably 0.5 to 0.8 MPa, - space velocity of less than 10 h -1, preferably of between 0.5 h -1 and 6 h -1, - molar ratio of hydrogen to hydrocarbon of less than 10, and preferably of less than 10 from 3 to 6. All catalysts capable of isomerizing hydrocarbons with 8 carbon atoms, whether zeolite or not, are suitable for the isomerization unit (ISOM-2) of the present invention. Preferably, a catalyst containing an acidic zeolite, for example of structural type MFI, MOR, MAZ, FAU and / or EUO, is used. Even more preferably, a catalyst containing a zeolite of structure type EUO and at least one metal of group VIII of the periodic table of elements is used.
    [0029] Preferably, the catalyst of the isomerization unit (ISOM-2) contains from 1 to 70% by weight of a zeolite of structural type EUO (EU-1 for example) comprising silicon and at least one selected element T preferably, aluminum and boron, the Si / T ratio of which is between 5 and 100. Said zeolite is in hydrogen form, at least in part, and the sodium content is such that the atomic ratio Na / T is less than at 0.1. Optionally, the catalyst of the isomerization unit may contain between 0.01 and 2% by weight of tin or indium, and sulfur with 0.5 to 2 atoms per atom of Group VIII metal.
    [0030] The isomerization unit effluent (ISOM-2) is sent to a separator train that allows the recovery of part of the hydrogen that is recycled to the isomerization unit (ISOM-2). The part of non-recycled hydrogen is compensated by a supplement of fresh hydrogen. At the end of the separation train, an isomer is recovered consisting of the heavier fractions which is returned to the distillation column (S-1) via the line (20).
    [0031] The process according to the invention is particularly well suited to modifying an existing unit in order to increase the quantity of paraxylene produced, an operation called debottlenecking.
    [0032] In the case of debottlenecking of an existing aromatic loop, the invention consists in significantly increasing the fresh feed rate and the flow of paraxylene produced while continuing to use the main equipment of the loop, namely: 1) the xylenes distillation column (S-1) 2) the simulated moving bed xylenes separation unit typically operating in 24 beds 3) the isomerization unit (ISOM-2) fed by the raffinate withdrawn from the column of an ethylbenzene converting separation using, for example, an EUO structural type zeolite catalyst comprising a reactor, a recycle compressor, a stabilization column and a column for recovering the C8 and C9 naphthenes so as to recycle them to the charge, 4) the raffinate column (RAFINTER) 5) the extract column (EXT-1) To carry out this debottlenecking according to the invention, a simulated moving bed is transformed into 24 beds containing they are adsorbers of 12 beds in series in a two-adsorber process of twelve beds each connected in parallel. To do this: - The twelfth bed of the first adsorber is connected to the first bed of said first adsorber via a line containing at least one recirculation pump, - the twelfth bed of the second adsorber is connected to the first bed of said second adsorber via a line containing at least less a recirculation pump. The system for controlling and regulating the charge and desorbent injection rates and the extraction rates of the extract and the raffinate of the 24-bed adsorption stage is adapted so as to be able to independently manage the flow rates. injection and withdrawal in each of the two adsorbers of the remodeled method according to the invention. For injection devices, this operation can be carried out either by doubling the pump system + measuring member to regulate the flow injected into each of the adsorbers, or, in order to minimize costs, by using the pump and the pump. pre-existing measuring unit that will manage all of the two streams to be injected and adding a flow measurement and regulation system feeding one of the two adsorbers. When the supply or draw-off of fluids on all the trays of the existing 24-bed process is ensured by a plurality of on-off valves, there are no additional modifications to be made to the supply networks. and racking. When the supply or withdrawal of fluids on all the trays of the existing process in 24 beds is ensured by the use of a multi-way rotary valve, these functions will preferably be ensured by the use of two multi-way rotary valves 15 (possibly recycling the pre-existing valve to one of the two tracks after adaptation). In the case of an existing 24-bed unit consisting of two-twelve beds in series, the main stream flows from the bottom of the first adsorber to the head of the second adsorber, and from the bottom of the second adsorber to the head of the first adsorber.
    [0033] The flows from the bottoms of the two adsorbers are then redirected to flow to the head of the adsorber from which they are derived by performing the valve and pipe modifications. The bottom flow of the first adsorber is recycled to the head of said adsorber and the bottom flow of the second adsorber is recycled to the head of said adsorber.
    [0034] The configuration (average number of beds per zone) of the two adsorbers can be according to one of the 3 variants set out above, ie: A number of fixed beds in each of the chromatographic zones for the two adsorbers, with variable number of beds for one adsorber and fixed for the other, - with variable number of beds for both adsorbers. In order to separate the raffinate-2 from the desorbent, a new distillation column (RAF-2) will also have to be put in place. The top of the distillation column (RAF-2) will be isomerized in the isomerization unit preferably in the liquid phase (ISOM-1) as described above. A second isomerization unit in the liquid phase (ISOM-1) is added, the effluent of which feeds the simulated moving bed (SMB-2) preferably without passing through the separation column (S-1) to avoid adding a second xylenes separation column. On the other hand, it is necessary to add an extract column (EXT-2) fed by the extract (12) of the separation unit (SMB-2). FIG. 2 shows a variant of the process scheme according to the invention which differs from that of FIG. 1 in that the separation unit (SMB-1) uses the PDEB as desorbent and the separation unit (SMB -2) toluene. The raffinate-intermediate streams (stream (7) and (14)) are mixed before the entry of the distillation column (RAFINTER). To remove the toluene at the top of the distillation column (RAFINTER), the PDEB at the bottom and the intermediate-raffinate 30 with these desorbents removed on the side, a column with longitudinal division called column with internal walls (" dividing wall column "in the English terminology).
    [0035] An internal wall distillation column separates 3 high purity compounds via a single column. It is optionally the same for the distillation column (RAF-2) which is fed by raffinate flux-2 (streams (8) and (14)). In the case where the distillation column is not of the internal wall type, only the paradiethylbenzene is left at the bottom of the column to be recycled, the toluene being sent to the isomerization with the C8-aromatic cut. The fact of using two different desorbents in the two separation units (SMB-1 and SMB-2) has the advantage of avoiding the accumulation of aromatic impurities such as benzene and C9 and C10 heavy aromatics. . Using two different desorbents in the two separation units (SMB-1 and SMB-2) also makes it possible to achieve thermal integration between the distillation columns (EXT-1 and EXT-2). Indeed, the distillation column head (EXT-1) can potentially reboil all or part of the distillation column (EXT-2). EXAMPLES Example 1 According to the Prior Art: This example illustrates the prior art and describes an aromatic complex consisting of two C8-aromatic loops in parallel, typical of industrial complexes where the amount of paraxylene produced is greater than the acceptable capacity by a single C8-aromatic loop, as schematized in FIG. 3 and comprising: two xylenes column (S-10 and S-20) making it possible to extract the aromatics at C9 and C10 (streams 104 and 113) and sending to the adsorption units (SMB-10 and SMB-20) a stream (103) and a stream (112) consisting essentially of C8 aromatics, - a first simulated moving bed adsorption unit (SMB-10) at 4 zones from which an extract (105) and a single raffinate (107) are withdrawn, a first isomerization unit (ISOM-10) fed by a portion (108) of the raffinate (107) after removal of the desorbent ( 109) by means of the distillation column (RAF-10), - a first column of ext paraxylene (EXT-10) from which the desorbent which is recycled to the adsorption (SMB-1) is withdrawn via the stream (109) and at the top a paraxylene-rich cut (106), - a second unit 4-zone simulated moving bed adsorption (SMB-20) from which an extract (114) and a single raffinate (116) are withdrawn; a second isomerisation unit (ISOM-20) fed by a portion ( 117) of the raffinate (116) after removal of the desorbent (118) by means of the distillation column (RAF-20), - a second column of paraxylene extract (EXT-20) from which the desorbent which adsorption (SMB-2) is recycled via stream (118) and at the top is a paraxylene-rich cut (115). The material balance of the process is described in Table 1 below. Only the C8-aromatic and C9 + compounds are described neglecting the other compounds and the formation of C9 + in the isomerization units. As a unit of flow, 1,000 tonnes per year (kt / year) are used. PX EB MOX C9 + Total Fresh Charge 101 23.6 15.6 67.7 13.8 120.6 Charge S-10 102 50.0 22.9 148.5 6.9 228.3 Charge SMB-103 50.0 22.9 148.5 0 221.4 10 Bottom S-10 104 0 0 0 6.9 6.9 Head EXT-10 106 50.0 0 0 0 50.0 Input ISOM-10 108 0 22.9 148, 5 0 171.4 ISOM-110 output 38.2 15.1 114.7 0 168.0 10 Charge S-20 111 50.0 22.9 148.5 6.9 228.3 Charge SMB-112 50.0 22.9 148.5 0 221.4 20 Bottom 5-20 113 0 0 0 6.9 6.9 Head EXT-20 115 50.0 0 0 0 50.0 Input ISOM-20 117 0 22.9 148, 171.4 ISOM output 119 38.2 15.1 114.7 0 168.0 TABLE 1 The feed (101) which feeds the aromatic loop (mixture of the heavy reformate and the bottom of the toluene column) a flow rate of 120.6 kt / year. This load is divided into two equal streams of 60.3 kt / year. A first part of the charge (101) is added 168 kt / year of isomerate (110) recycled from the isomerization unit (ISOM-10) in order to isomerize the ethylbenzene. The resulting stream (102) is distilled in the xylenes column (S-10). 6.9 kt / year of a mixture of aromatic C9 and C10 (104) and 221.4 kt / year of an aromatic C8 cut (103) are withdrawn at the bottom of the column (5-10). The paraxylene content is 22.6%, the ethylbenzene content is 10.3%, the orthoxylene and metaxylene content is 67.1%. This section is sent to a four-zone simulated moving bed adsorption unit (SMB-10) and four main streams: the feed (103), the desorbent (109), the extract (105) and the raffinate ( 107). This unit is composed of 12 beds containing a zeolite X exchanged with barium. The temperature is 175 ° C. The configuration is: 2 beds in zone 1, 5 beds in zone 2, 3 beds in zone 3 and 2 beds in zone 4. The solvent used is paradiethylbenzene. The extract (105) at the outlet of the adsorption unit (SMB-10) is sent to a distillation column (EXT-10) from which the recycled desorbent is drawn down to the adsorption unit ( SMB-10), and at the top 50 kt / year of a mixture (106), essentially consisting of toluene and paraxylene. The raffinate is sent to a distillation column (RAF-10) from which the recycled desorbent is drawn down to the adsorption unit (SMB-10) and at the top 171.4 kt / year of a mixture. (108). This stream is sent to an isomerization unit (ISOM-10). The isomerization unit (ISOM-10) works in the gas phase under the following conditions: Temperature: 385 ° C. Catalyst: contains platinum and zeolite EU-1 Spatial velocity: 3.5 h -1 H 2 / hydrocarbons ratio : 4.4: 1 Pressure: 0.9 MPa The ethylbenzene content of the mixture introduced into the isomerization unit (ISOM-10) is 13.4%. 2% loss by cracking is observed in this isomerization, ie a flow rate of 3.4 kt / year. Ethylbenzene is partially isomerized, with 9% remaining in the exit stream (110). This isomerate (110) has a flow rate of 168 kt / yr, is recycled to the inlet of the S-10 column where it is mixed with a portion of the fresh feed (101) which has a flow rate of 60.3 kt / year. A first part of the charge (101) is added 168 kt / year of isomerate (119) recycled from the isomerization unit (ISOM-20) in order to isomerize the ethylbenzene. The resulting stream (111) is distilled in the xylene column (S-20). 6.9 kt / year of a mixture of aromatic C9 and C10 (stream 113) are withdrawn at the bottom of the column (S-20) and 221.4 kt / year of aromatic C8 cut (stream 112) at the top of which the Paraxylene content is 22.6%, and the ethylbenzene content is 10.4%. This section is sent to a four-zone simulated moving bed adsorption unit (SMB-20) and four main streams: the feed (stream 112), the desorbent (stream 118), the extract (stream 114) and the raffinate (stream 116). This unit is composed of 12 beds containing a zeolite X exchanged with barium. The temperature is 175 ° C. The configuration is: 2 beds in zone 25 1, 5 beds in zone 2, 3 beds in zone 3 and 2 beds in zone 4. The solvent used is paradiethylbenzene. The extract (114) at the outlet of the adsorption unit (SMB-20) is sent to a distillation column (EXT-20) from which the recycled desorbent is drawn down to the adsorption unit 30 ( SMB-20), and at the top 50 kt / year of a mixture (115) consisting essentially of toluene and paraxylene.
    [0036] The raffinate is sent to a distillation column (RAF-20) from which the recycled desorbent is drawn down to the adsorption unit (SMB-20) and at the top 171.4 kt / year of a mixture ( 117).
    [0037] This stream is sent to an isomerization unit (ISOM-20). The obtained isomerate (119) is recycled to the inlet of the S-20 column where it is mixed with a portion of the fresh feed (101). The isomerization unit (ISOM-20) works in the gas phase under the following conditions: Temperature: 385 ° C Catalyst: contains platinum and zeolite EU-1 Space velocity: 3.5 h-1 H2 / hydrocarbons ratio: 4.4: 1 Pressure: 0.9 MPa The ethylbenzene content of the mixture introduced into the isomerization unit (ISOM-20) is 13.4%. 2% loss by cracking is observed in this isomerization, ie a flow rate of 3.4 kt / year. The ethylbenzene is isomerized in part. There is 9% left in the output stream (119). This isomerate (119) has a flow rate of 168 kt / year. It is recycled to the inlet of the S-20 column where it is mixed with a part of the fresh feed (101) which has a flow rate of 60.3 kt / year. EXAMPLE 2 According to the Invention This example illustrates the process according to the invention and describes the aromatic loop schematized in FIG. 1 and comprising: a column of xylenes (S-1) making it possible to extract the aromatics at C9 and C10 (4) and to send to the adsorption unit (SMB-1) a stream (3) consisting essentially of C8 aromatics, - a first simulated moving bed adsorption unit (SMB-1) to 5 zones from which an extract (5), an intermediate raffinate (7) and a raffinate-2 (8) are withdrawn, - a first column of paraxylene extract (EXT-1) from which the desorbent which the adsorption units (SMB-1 and SMB-2) are recycled via the streams (16) and (17) and at the top a paraxylene rich section (stream 6), - a second adsorption unit in a moving bed simulated (SMB-2) with 5 zones from which an extract (12), an intermediate raffinate (14) and a raffinate-2 (15) are withdrawn, - a second column of paraxylene extract (EXT-2) of which one n The desorbent is recycled to the adsorption units (SMB-1 and SMB-2) via the streams (16) and (17) and at the top of a paraxylene rich section (stream 13). isomerization unit (ISOM-1) fed by a portion (10) of the raffinate-2 (9) consisting of the mixture of the streams (8) and (15) after removal of the desorbent by means of the distillation column (RAF- 2), - a second isomerization unit (ISOM-2) fed by a portion (19) of the intermediate raffinate (18) constituted by mixing the streams (7) and (14) after removal of the desorbent by means of the distillation column (RAFINTER). The material balance of the process is described in Table 2 below. Only the C8-aromatic and C9 + compounds are described, the other compounds and the formation of C9 + are neglected in the isomerization units. As a unit of flow, 1,000 tonnes per year (kt / year) are used. 25 30 PX EB MOX C9 + Total Fresh load 1 22.6 15.2 64.7 13.2 115.8 Load S-1 2 51.1 26.5 150.4 13.2 241.2 Load SMB-1 3 51.1 26.5 150.4 0 228.0 Bottom S-1 4 0 0 0 13.2 13.2 Head EXT-1 6 51.1 0 0 0 51.1 RAFF INTER 7 0 15.9 50, 4 0 66.3 RAFF-2 8 0 10.6 100.0 0 110.6 Input ISOM LIQ 10 0 17.7 195.6 0 213.3 Output ISOM LIQ 11 48.9 17.7 146.7 0 213 , 3 Head EXT-2 13 48.9 0 0 0 48.9 RAFF-INTER 14 0 10.6 51.0 0 61.7 RAFF-2 15 0 7.1 95.7 0 102.8 Input ISOM GAS 19 0 26.5 101.5 0 128.0 ISOM output GAS 20 28.5 11.3 85.6 0 125.4 TABLE 2 The fresh feed (1) that feeds the aromatic loop has a flow rate of 115.8 kt / year.
    [0038] This feedstock is supplemented with 125.4 kt / yr of isomerate (20) recycled from the isomerization unit (ISOM-2) isomerizing ethylbenzene. The resulting stream (2) is distilled in the xylene column (S-1).
    [0039] 13.2 kt / year of a mixture of aromatic C9 and C10 (4) are withdrawn at the bottom of the column (S-1) and, at the top, 228 kt / year of aromatic C8 cut (3) whose content in paraxylene is about 22.4%, the ethylbenzene content about 11.6%, the orthoxylene and metaxylene content about 65.9%.
    [0040] This section is sent to a five-zone simulated moving bed adsorption unit (SMB1) and five main streams: the feed (3), the desorbent (16), the extract (5), the intermediate raffinate (7) and raffinate-2 (8). This unit is composed of 12 beds containing a zeolite X exchanged with barium. The temperature is 175 ° C. The configuration is: 2 beds in zone 1, beds in zone 2, 2 beds in zone 3A, 2 beds in zone 3B and a bed in zone 4. The solvent used is paradiethylbenzene. The extract (5) at the outlet of the adsorption unit (SMB-1) is sent to a distillation column (EXT-1) from which the recycled desorbent is drawn down to the adsorption unit ( SMB-1), and at the top 51.1 kt / year of a mixture (6) consisting essentially of toluene and paraxylene. The isomerate (11) from the isomerization unit (ISOM-1) feeds a second simulated five-zone moving bed adsorption unit (SMB-2) and five main streams: the charge (11), the desorbent (17), the extract (12), the intermediate raffinate (14) and the raffinate-2 (15). This unit is composed of 12 beds containing a zeolite X exchanged with barium. The temperature is 175 ° C.
    [0041] The configuration is: 2 beds in zone 1, 5 beds in zone 2, 2 beds in zone 3A, 2 beds in zone 3B and a bed in zone 4. The solvent used is paradiethylbenzene. The extract (12) at the outlet of the adsorption unit (SMB-2) is sent to a distillation column (EXT-2) from which the recycled desorbent is drawn down to the adsorption unit (SMB). -2), and at the top 48.9 kt / year of a mixture (13) essentially consisting of toluene and paraxylene. The raffinat-2 noted (8) and (15) are mixed and sent to a distillation column (RAF-2) which is drawn bottom desorbent recycled to the adsorption units (SMB-1 and SMB2), and at the top 213.3 kt / year of a mixture (10).
    [0042] This stream is sent to an isomerization unit (ISOM-1). The isomerization unit (ISOM-1) works in the liquid phase under the following conditions: Temperature: 240 ° C. Catalyst: contains zeolite ZSM-5 Space velocity: 3 h-1 Pressure: 1.9 MPa Content: The ethylbenzene mixture introduced into the isomerization unit (ISOM-1) is about 8.3%. Ethylbenzene is not converted, so its quantity is the same in the output stream (11). This isomer (11) has a flow rate of 213.3 kt / yr, it is recycled to the inlet of the adsorption unit (SMB-2) without passing through the column (S-1). Intermediate raffinates (7) and (14) are mixed and sent to a distillation column (RAFINTER) from which the recycled desorbent is drawn down to the adsorption units (SMB-1 and SMB-2), and at the top 128 kt / year of a mixture (19).
    [0043] This stream is sent to an isomerization unit (ISOM-2). The isomerization unit (ISOM-2) works in the gas phase under the following conditions: Temperature: 385 ° C Catalyst: contains platinum and zeolite EU-1 Space velocity: 3.5 h-1 Pressure: 0, 9 MPa The ethylbenzene content of the mixture introduced into the isomerization unit (ISOM-2) is 20.7%. 2% loss by cracking is observed in this isomerization, ie a flow rate of 2.6 kt / year. Ethylbenzene is partially isomerized, with 9% remaining in the exit stream (20). This isomerate (20) has a flow rate of 125.4 kt / year, it is recycled to the inlet of the S-1 column where it is mixed with the fresh feed (1) which has a flow rate of 115.8 kt / year.
    [0044] The invention has several advantages over the prior art. First, isomerization in the liquid phase is less energy consuming than isomerization in the gas phase. Indeed, she works at a lower temperature. It also works without recycle hydrogen, so without recycle compressor. Finally, it produces much less by-products, especially C9 aromatics, which makes it possible to short-circuit the C9 (S-1) aromatic removal column, inducing a very large drop in the energy required for this process. separation.
    权利要求:
    Claims (17)
    [0001]
    CLAIMS 1) A process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds, using two simulated moving bed separation units (SMB-1 and SMB-2), and two isomerization units (ISOM-1 and ISOM-2) consisting of the following series of steps: - the charge (2) is sent to a distillation column (S-1) from which the top is withdrawn a mixture (3) comprising most of the metaxylene, paraxylene, ethylbenzene, and at least a portion of the orthoxylene, and from which a hydrocarbon stream (4) is withdrawn in the bottom; C9-C10 and the remaining portion of orthoxylene, - separation of the overhead mixture (3) in the separation unit (SMB-1) comprising at least one adsorber containing a plurality of interconnected beds and working in a loop closed, said adsorber comprising at least five zones delimited by the injections of the flow (3) and the d sorbent (16), and withdrawals of a first extract (5) containing paraxylene, a first intermediate raffinate (7) containing ethylbenzene, and a first raffinate-2 (8) containing the orthoxylene and metaxylene, a simulated moving bed separation of the isomerate (11) from the isomerization unit (ISOM-1) is carried out in the separation unit (SMB-2) consisting of at least one adsorber containing a plurality of interconnected beds and preferably working in a closed loop, and said adsorber comprising at least five zones delimited by the injections of the flow (11) and the desorbent (17), and the withdrawals of a second extract ( 12) containing paraxylene, a second intermediate raffinate (14) containing ethylbenzene, and a second raffinate-2 (15) containing orthoxylene and metaxylene, the first extract is distilled (5). ) from the separation unit (SMB-1) in a distillation column (EXT-1), to recover a first fraction (6) enriched in paraxylene, the two raffinates-2, stream (8) and (15) are mixed, to form the stream (9) which is distilled in a column (RAF-2) of in order to remove substantially all the desorbent, and to extract a first distilled fraction (10), - is supplied by the stream (10) a first isomerization unit (ISOM-1) to obtain the first isomer (11), - mixing the two intermediate raffinates, stream (7) and (14), to form the stream (18) which is distilled in a column (RAFINTER) to substantially remove all the desorbent and to withdraw a second distilled fraction (19), - a second isomerization unit (ISOM-2) is fed through the stream (19) to obtain a second isomerate (20) which is recycled to the inlet of the distillation column (S-1). 15
    [0002]
    2) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the isomerization unit (ISOM1) operates in liquid phase at the following conditions : - Temperature below 300 ° C, preferably between 200 and 260 ° C, - Pressure less than 4 MPa, preferably between 2 and 3 MPa, 20 - space velocity of less than 10 h -1, preferably between 2 h -1 and 4 h -1, Catalyst comprising at least one zeolite having channels whose opening is defined by a ring with 10 or 12 oxygen atoms (10 MR or 12 MR), preferably a catalyst comprising at least minus a zeolite having channels whose opening is defined by a ring of 10 oxygen atoms (10 MR), and even more preferably a catalyst comprising a zeolite of ZSM-5 type.
    [0003]
    3) A method for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the isomerization unit (ISOM-2) operates in the gas phase under the following conditions: - temperature above 300 ° C, preferably 360 ° C to 480 ° C, - pressure less than 2.5 MPa and preferably 0.5 to 0.8 MPa, - space velocity less than 10 h -1, preferably between 0.5 h -1 and 6 h -1, molar ratio hydrogen on hydrocarbon less than 10, and preferably between 3 and 6.
    [0004]
    4) A method for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 3, wherein the catalyst used for the isomerization unit (ISOM-2) contains an acid zeolite, for example of structural type MFI, MOR, MAZ, MTW, FAU and / or EUO, and preferably contains a zeolite of structural type EUO, and at least one metal of group VIII of the periodic table of elements .
    [0005]
    5) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 3, wherein the catalyst used for the isomerization unit (ISOM-2) comprises at least one zeolite having channels whose opening is defined by a ring with 10 or 12 oxygen atoms (10 MR or 12 MR), and at least one group VIII metal with a content of between 0.1 and 0, 3% weight, limits included.
    [0006]
    6) A method for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the separation unit (SMB-1) uses the PDEB desorbent .
    [0007]
    7) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the separation unit (SMB-2) uses toluene as desorbent. 25
    [0008]
    A process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds according to claim 1, wherein the separation units (SMB-1) and (SMB-2) contain from 6 to 24 beds, and preferably from 8 to 15 beds distributed over one or more adsorbers, the number of beds being adjusted so that each bed preferably has a height of between 0.70 m and 1, 40 m.
    [0009]
    9) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the distribution of the amount of adsorbent solid in the separation units (SMB- 1) and (SMB-2) is the following: the amount of adsorbent solid in zone 1 is 16% ± 5%, the amount of adsorbent solid in zone 2 is 40% ± 5%, the amount of solid adsorbent in zone 3A is 16% ± 5%, the amount of solid adsorbent in zone 3B is 16% ± 5%, the amount of adsorbent solid in zone 4 is 12% ± 5%, being defined in the following manner: Zone 1 between the injection of the desorbent and the extraction of the extract, Zone 2 between the extraction of the extract and the injection of the feed, Zone 3A between the injection of the feedstock and the withdrawal of the intermediate raffinate, - Zone 3B between the withdrawal of the intermediate raffinate and the Extraction of raffinate-2, 15 - Zone 4 between the raffinate-2 withdrawal and the injection of the desorbent.
    [0010]
    A process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds according to claim 1, wherein with respect to the separation unit (SMB-1), the Desorbent volumetric ratio on charge is at most 1.7 / 1 and preferably between 1.5 / 1 and 0.4 / 1, inclusive.
    [0011]
    11) A process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds according to claim 1, wherein with respect to the separation unit (SMB-1), the ratio of intermediate raffinate and raffinate 2 rates is between 0.3 / 1 and 5/1, and preferably between 0.4 / 1 and 1/1 inclusive.
    [0012]
    12) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein with respect to the separation unit (SMB-2), the volume ratio desorbent charge is at most 1.7 / 1 and preferably between 1.5 / 1 and 0.4 / 1 inclusive.
    [0013]
    A process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds according to claim 1, wherein with respect to the separation unit (SMB-2), the ratio of intermediate raffinate and raffinate 2 rates is between 0.3 / 1 and 5/1, and preferably between 0.4 / 1 and 1/1 inclusive.
    [0014]
    14) Process for producing high purity paraxylene from a xylenes cut containing ethylbenzene and C9 + compounds according to claim 1, process obtained from the degoulotage of an existing separation unit consisting of two adsorbers in series, as follows: - the last bed of the first adsorber is connected to the first bed of the first adsorber via a line containing at least one recirculation pump, this first adsorber serving as a separation unit (SMB-1) - the last bed of the second adsorber is connected to the first bed of the second adsorber via a line containing at least one recirculation pump, this second adsorber serving as separation unit (SMB-2).
    [0015]
    15) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the configuration of the two separation units (SMB-1) and (SMB) -2) has a fixed number of beds in each of the chromatographic zones of each of the two separation units.
    [0016]
    16) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein: - the first extract (5) from the unit is distilled separation (SMB-1) in a column (EXT-1), to recover a first fraction (6) enriched in paraxylene, - distilling the second extract (12) in a column (EXT-2), to recover a second fraction (13) enriched with paraxylene. 30
    [0017]
    17) A process for producing high purity paraxylene from a xylenes containing ethylbenzene and C9 + compounds according to claim 1, wherein the two extracts (5) and (12) are distilled in a single column. common extract to recover a single fraction enriched in paraxylene.
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    同族专利:
    公开号 | 公开日
    CN106715366A|2017-05-24|
    US20170210682A1|2017-07-27|
    EP3169653B1|2018-08-29|
    FR3023840B1|2016-07-15|
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    KR102343702B1|2021-12-24|
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    引用文献:
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    FR2862638A1|2003-11-26|2005-05-27|Inst Francais Du Petrole|Producing p-xylene from a feed comprising xylenes, ethylbenzene and heavy hydrocarbons comprises a simulated moving bed adsorption step and two isomerization steps|
    US20140155667A1|2012-11-30|2014-06-05|Exxonmobil Chemical Patents Inc.|Process for the Production of Purified Xylene Isomers|WO2018195037A1|2017-04-19|2018-10-25|Uop Llc|Process and apparatus for improved para-xylene yield in an aromatic complex|
    EP3587384A1|2018-06-29|2020-01-01|Axens|Method for producing paraxylene using a step in a simulated moving bed, and a fractionation step via a 3-section column|PL215253B1|2008-06-26|2013-11-29|Uop Llc|Method and apparatus for separating para-xylene from a mixture of aromatic hydrocarbons C8 and C9|
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    EP3664906A4|2017-09-19|2021-03-24|Sulzer Management AG|Use of top dividing wall in isomerization unit|
    CN109665932A|2017-10-17|2019-04-23|中国石化工程建设有限公司|The co-production of ortho-xylene and the charging of paraxylene adsorption separation device|
    FR3104579B1|2019-12-17|2021-12-31|Ifp Energies Now|Device and method for converting aromatic compounds by alkylation of benzene with ethylene|
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    FR3112773A1|2020-07-27|2022-01-28|IFP Energies Nouvelles|Device and method for producing aromatics from biomass pyrolysis gas|
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    2020-04-10| ST| Notification of lapse|Effective date: 20200306 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1456940A|FR3023840B1|2014-07-18|2014-07-18|PROCESS FOR THE PRODUCTION OF HIGH PURITY PARAXYLENE FROM XYLENE CUTTING USING TWO SERIES MOBILE BED SEPARATION UNITS OPERATING IN SERIES AND TWO ISOMERIZING UNITS|FR1456940A| FR3023840B1|2014-07-18|2014-07-18|PROCESS FOR THE PRODUCTION OF HIGH PURITY PARAXYLENE FROM XYLENE CUTTING USING TWO SERIES MOBILE BED SEPARATION UNITS OPERATING IN SERIES AND TWO ISOMERIZING UNITS|
    EP15727015.8A| EP3169653B1|2014-07-18|2015-06-10|Method for the production of high-purity paraxylene from a xylene fraction, using two simulated moving bed separation units operating in series and two isomerisation units|
    CN201580050257.0A| CN106715366B|2014-07-18|2015-06-10|Process for producing high purity para-xylene from xylene fraction using two simulated moving bed separation units and two isomerization units|
    PT15727015T| PT3169653T|2014-07-18|2015-06-10|Method for the production of high-purity paraxylene from a xylene fraction, using two simulated moving bed separation units operating in series and two isomerisation units|
    KR1020177004407A| KR102343702B1|2014-07-18|2015-06-10|Method for the production of high-purity paraxylene from a xylene fraction, using two simulated moving bed separation units operating in series and two isomerisation units|
    PCT/EP2015/062981| WO2016008652A1|2014-07-18|2015-06-10|Method for the production of high-purity paraxylene from a xylene fraction, using two simulated moving bed separation units operating in series and two isomerisation units|
    US15/326,836| US10035739B2|2014-07-18|2015-06-10|Process for the production of high-purity paraxylene from a xylenes cut, using two simulated moving bed separation units operating in series and two isomerization units|
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