Process and plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene

Abstract

The present invention relates to a method for preparing a purified benzene composition from a crude hydrocarbon stream containing at least 10% by volume of benzene, comprising the following steps: a) subjecting the crude hydrocarbon stream recycled in step d) and a further benzene-containing stream to a solvent-based extraction to produce a benzene-enriched aromatic stream and a benzene-depleted non-aromatic stream; b) subjecting the benzene-enriched aromatic stream obtained in step a) to hydrodesulfurization to obtain a desulfurized aromatic stream; c) subjecting the desulfurized aromatic stream obtained in step b) to distillation to produce a purified benzene stream and a further benzene-containing stream having a benzene concentration between less than 100% by weight and the azeotropic benzene concentration; and d) at least partially recycling the further benzene-containing stream obtained in step c) to step a).

Description

[Technical Field]

[0001] The present invention relates to a process and plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene. [Background technology]

[0002] Benzene is an important starting material for the synthesis of several chemical compounds, such as ethylbenzene, cumene, cyclohexene, and nitrobenzene. These compounds, in turn, are starting materials for the synthesis of other compounds, such as styrene, which is an important precursor to polymers such as polystyrene, styrene-butadiene rubber, polyamides, and epoxy resins; cleaning actives such as alkylbenzene sulfonic acids; solvents; insecticides; colorants; and more. For this reason, benzene is actually one of the most produced chemicals in the world.

[0003] Several methods are known for producing benzene, including catalytic reforming, steam cracking, toluene hydrodealkylation (HAD), toluene disproportionation (TDP), coke oven light oil (COLO) extraction, LPG Cyclar, and gas-to-aromatics. However, the primary production routes are steam cracking and catalytic reforming. In both of these routes, solvent-based extraction units are used to extract petrochemical-grade benzene from pyrolysis gasoline (also known as pyrolysis gasoline) coming from the steam cracker or reformate resulting from catalytic reforming. Refiners are increasingly extracting aromatics, such as benzene, from fluid catalytic cracking (FCC) gasoline. This trend stems from the predicted growth of petrochemicals, in contrast to declining or stagnant refinery fuel demand. Traditionally, for gasoline benzene management, benzene contained in FCC gasoline has been considered the benzene heart cut from the naphtha splitter on the FCC gasoline. The benzene-rich cut is then sent to either a dedicated benzene saturation unit or a light naphtha isomerization or catalytic reforming unit. Both of these approaches have two major drawbacks. First, the benzene-rich heart cut has a significant amount of high-octane olefins that saturate when sent to a naphtha hydrotreater upstream of a naphtha isomerization or catalytic reforming unit. Alternatively, if sent to a dedicated benzene saturation unit, octane loss also occurs. This octane loss then needs to be compensated for by refinery octane-producing units such as isomerization, reforming, or alkylation. Furthermore, the presence of benzene is an undesirable characteristic of light naphtha isomerization feed. Second, the value of benzene as a petrochemical product in routes such as isomerization or benzene saturation is lost.

[0004] Therefore, due to the aforementioned shortcomings in existing benzene management approaches and the predicted trend toward increased use of petrochemicals in refinery fuels, refiners are now interested in options for extracting aromatics, such as benzene, from FCC gasoline while avoiding octane losses due to saturation of high-octane olefins. However, this is not simple or straightforward. FCC gasoline, in contrast to reformate or pygas, is a challenging feedstock for solvent extraction due to the high presence of naphthenes, cyclic olefins, and olefins. These compounds are difficult to separate from aromatics due to their polarity, close boiling points, and azeotrope formation behavior. When a benzene-rich or C6-C8 FCC naphtha cut is fed to a solvent-based extractive distillation configuration, it results in the following streams: first, an olefin-rich raffinate, which can be sent directly to the gasoline pool for blending since most of the sulfur has been extracted; and second, a benzene- or aromatics (benzene, toluene, and mixed xylenes)-rich extract containing sulfur species.

[0005] For extracted aromatics such as benzene to meet petrochemical-grade specifications, total sulfur specifications of less than 1 ppmw (parts per million by weight) and total nitrogen specifications of less than 1 ppmw are required. For aromatics such as toluene and mixed xylenes, sulfur specifications are less stringent, typically less than 10 ppmw, depending on downstream applications. As explained above, the extraction of aromatics from FCC gasoline also involves the removal of sulfur species such as mercaptans, disulfides, and thiophenes, in the order thiophenes > disulfides > mercaptans. To meet the required sulfur and nitrogen specifications, a hydrodesulfurization (HDS) unit block is deployed downstream of the extracted aromatics. Along with the appropriate design and solvent selection of the upstream extractive distillation unit, several important design considerations must be taken into account when designing this HDS unit, including the appropriate selection of catalysts and operating conditions such as pressure and temperature. This need arises for the following reasons: First, aromatic saturation, such as benzene saturating to cyclohexane (ring loss), must be minimized; otherwise, the purity of downstream benzene products will be irreversibly affected because no other method exists in the system to recover benzene purity. When benzene ring loss higher than the design value—typically limited to less than 0.1 wt%—is encountered in actual operation, re-extraction or solution by diluting with a large reformate or pygas-extracted benzene pool or sending to a downstream reformer unit are the only options available to refiners. Both of these approaches represent economic losses for refiners because they imply additional capital and equipment investment (in the case of re-extraction), affect the refinery's overall benzene purity (in the case of solution by dilution), or absorb additional capacity that could otherwise be used to boost more benzene production by boosting additional processing capacity of heavy naphtha reformer feedstock (in the case of the reformer route). Second, HDS catalysts have an operating envelope from the start of run (SOR) to the end of run (EOR) over their cycle length. During SOR conditions, ring loss may fall below the design value. However, as the catalyst ages, the inlet temperature to the reactor increases to compensate for the loss of catalytic activity.Increased temperature can again cause higher-than-design ring losses, which impacts benzene purity. Third, today's refiners are processing heavier, more difficult feedstocks in residual fluid catalytic cracking (RFCC) or fluid catalytic cracking (FCC) units. This can result in higher-than-expected sulfur content at the inlet of the HDS reactor, again causing ring losses above design values. Fourth, olefin content should be minimized at the inlet of the HDS reactor. This is primarily achieved through appropriate solvent selection and design of the upstream extraction unit. While meeting sulfur specifications such as less than 1 ppmw, olefin saturation occurs throughout the HDS, generating an exotherm. This exotherm can again result in higher-than-expected ring losses. Finally, the presence of trace amounts of C6-cyclic olefins (such as cyclohexene or methylcyclopentene) in the extracted aromatics can again raise concerns about benzene purity. C6-cyclic olefins are largely removed in the upstream extraction section. However, because these compounds are difficult to separate from aromatics in solvent-based extractive distillation systems, some slippage into the extract can occur. These cyclic olefins undergo saturation to C6-naphthenes (cyclohexane or methylcyclopentane) over the HDS while meeting the required sulfur specifications. Therefore, benzene purity can be affected due to slippage of C6 cyclic olefins into the extract from the upstream extractive distillation unit block. Summary of the Invention

[0006] In light of the above, it is an object of the present invention to provide a method and plant for preparing a purified benzene composition from a benzene-containing crude hydrocarbon stream (such as, in particular, the C6-cut or C6-C8-cut of FCC gasoline or COLO), comprising a solvent-based extraction step and a hydrodesulfurization step, which reliably ensures a high purity benzene product even in the case of higher than expected benzene ring losses during the hydrodesulfurization step due to factors such as those explained above, and the high purity of the benzene is not affected even in the case of slippage of C6-cyclic olefins or C7-isoolefins from the upstream extraction section.

[0007] According to the invention, the object is a process for preparing a purified benzene composition from a crude hydrocarbon stream containing at least 10% by volume of benzene, comprising: a) subjecting the recycled crude hydrocarbon stream of step d) and a further benzene-containing stream to a solvent-based extraction to produce a benzene-enriched aromatic stream and a benzene-depleted non-aromatic stream; b) subjecting the benzene-enriched aromatic stream obtained in step a) to hydrodesulfurization to obtain a desulfurized aromatic stream; c) subjecting the desulfurized aromatic stream obtained in step b) to distillation to produce a purified benzene stream and a further benzene-containing stream having a benzene concentration between less than 100 wt.% and the azeotropic benzene concentration; d) at least partially recycling the further benzene-containing stream obtained in step c) to step a); The method is satisfied by a method including:

[0008] The term "another benzene-containing stream having a benzene concentration between less than 100% by weight and the azeotropic benzene concentration" means, according to the present invention, a stream having a benzene concentration between less than 100% by weight and the final azeotropic benzene concentration indicated by the vapor-liquid equilibrium of the compounds contained in the further benzene-containing stream, the further benzene-containing stream comprising benzene and at least one of cyclohexane, methylcyclopentane, 2,3-dimethylpentane, and 2,4-dimethylpentane. In other words, when the further benzene-containing stream contains only benzene and cyclohexane, the azeotropic benzene concentration is the concentration of benzene in the azeotrope formed from these two components, i.e., the azeotrope of benzene and cyclohexane. When the further benzene-containing stream contains benzene, cyclohexane, and methylcyclopentane, the azeotropic benzene concentration is the concentration of benzene in the azeotropic mixture formed from these three components, i.e., the concentration of benzene in the azeotropic mixture of benzene, cyclohexane, and methylcyclopentane. All subsequent references to a "benzene- and cyclohexane-containing stream" actually mean a further benzene-containing stream having a benzene concentration between less than 100 wt.% and the azeotropic benzene concentration, the further benzene-containing stream comprising benzene and at least one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane, and 2,4 dimethylpentane. Thus, the further benzene-containing stream is benzene and at least one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane, and 2,4 dimethylpentane-containing streams.

[0009] By performing the distillation in step c) so that the desulfurized aromatics stream obtained in the hydrodesulfurization in step b) is separated into a purified benzene stream and a further benzene-containing stream containing, in addition to benzene, at least one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane, and 2,4 dimethylpentane at the above-mentioned benzene concentrations, and by at least partially, preferably completely, recycling the further benzene-containing stream to the solvent-based extraction in step a), no benzene is lost in the further benzene-containing stream, or only a small amount is lost, if any. More specifically, even if a negligible amount of benzene is lost in the further benzene-containing stream during the solvent-based extraction into the raffinate (or the benzene-depleted non-aromatic stream, respectively), substantially all of the benzene is extracted into the benzene-rich aromatics stream by the solvent. By subjecting the benzene-rich aromatics stream after the solvent-based extraction to hydrodesulfurization to obtain a desulfurized aromatics stream, which is then subjected to distillation, the purity of the final benzene product remains unchanged, even if the ring loss is higher than expected during the hydrodesulfurization step (e.g., 0.4 wt. % actual-life operation, compared to a design value of 0.1 wt. %). Furthermore, even if C6-cyclic olefins and / or C7-iso-olefins should slip into the benzene-rich aromatic stream from the solvent-based extraction step, the saturated forms of these compounds (i.e., C6-naphthenes or C7-isoparaffins) are formed during the hydrodesulfurization step and also form azeotropes with benzene, so these compounds are reliably separated from benzene as well. Another important feature of the process of the present invention is that in the distillation of step c), it is not necessary to produce additional benzene and at least one of a cyclohexane-, methylcyclopentane-, 2,3-dimethylpentane-, and 2,4-dimethylpentane-containing stream having a final azeotropic composition. Instead, only additional benzene and at least one of a cyclohexane-, methylcyclopentane-, 2,3-dimethylpentane-, and 2,4-dimethylpentane-containing stream, which tends with respect to its benzene concentration relative to the azeotropic composition, is sufficient for this purpose.In other words, in the case of a higher ring loss, for example, 0.4 wt.%, the distillation unit downstream of the hydrodesulfurization can be designed to produce an additional benzene-containing stream having a benzene concentration of about 95 wt.% instead of 52 wt.% (which is the benzene concentration in the azeotropic mixture of benzene and cyclohexane), which corresponds to about 5% of the total benzene in the stream coming from downstream of the hydrodesulfurization step. Therefore, the impact of recycling the additional benzene-containing stream on the overall capital and equipment investment of the plant is minimal, and the plant referred to herein as a combination of a solvent-based extraction unit, a hydrodesulfurization unit, and an (azeotropic) distillation unit is particularly advantageous when a C6 cut or a C6-C8 cut of FCC gasoline or COLO is used as the feedstock for the process. Furthermore, these advantageous effects are also obtained in the case of very long operating times, including the operating temperature window from catalyst start-up to shutdown, in the case of heavier-than-expected feedstocks fed to the FCC, RFCC, or COLO, or in the case of slippage of C6-cycloolefins and / or C7-isoolefins into the benzene-rich aromatic stream obtained in the solvent-based extraction step. More specifically, the resulting purified benzene stream typically has a benzene purity of greater than 99.8% and a content of sulfur- and nitrogen-containing compounds of less than 1 ppmw. The resulting benzene product is petrochemical grade eligible and does not require further processing such as re-extraction or dilution with larger pigas or reformate benzene pools.

[0010] As described above, in step c), the desulfurized aromatic stream obtained in step b) is subjected to distillation to produce a purified benzene stream and a further benzene-containing stream having a benzene concentration between less than 100 wt% and the azeotropic benzene concentration. Preferably, the distillation in step b) is carried out to produce a purified benzene stream and a further benzene-containing stream having a benzene concentration between less than 99 wt%, more preferably less than 98 wt%, more preferably less than 97 wt%, and even more preferably less than 96 wt% and the azeotropic benzene concentration, for example, a benzene concentration of 90 to 96 wt%. Alternatively, it is preferred that the distillation in step b) is carried out to produce a purified benzene stream and a further benzene-containing stream having a benzene concentration of less than 90 wt%, more preferably less than 80 wt%, more preferably at most 70 wt%, such as a benzene concentration of 70 to 90 wt%.

[0011] As noted above, a particular advantage of the present invention is that the process for preparing a purified benzene composition from a crude hydrocarbon stream containing at least 10% by volume of benzene is particularly suitable for processing crude hydrocarbon streams having a comparable low benzene content, such as FCC or RFCC naphtha or COLO, especially from either the C6-cut or the C6-C8-cut thereof. However, good results are also obtained when the crude hydrocarbon stream contains higher amounts of benzene, for example, preferably 100% by weight, at least 20% by volume, more preferably at least 30% by volume, and even more preferably at least 50% by volume of benzene.

[0012] For example, the process according to the invention makes it possible to obtain highly purified benzene in high yields from a crude hydrocarbon stream which contains, in addition to aromatics, 100% by weight: i) 20-60% by volume, preferably 30-50% by volume, of paraffins; ii) 10-50% by volume, preferably 20-30% by volume, of olefins; and iii) 5-40% by volume, preferably 10-25% by volume, of naphthenes.

[0013] Particularly good results are obtained when the crude hydrocarbon stream fed to the process according to the invention is a C6 cut or a C6-C8 cut from fluid catalytic cracking naphtha or a C6 cut or a C6-C8 cut from coke oven gas oil.

[0014] According to the present invention, the crude hydrocarbon stream and the further benzene-containing stream recycled in step d) are subjected to a solvent-based extraction to produce a benzene-enriched aromatic stream and a benzene-depleted non-aromatic stream. This means that, according to the present invention, the crude hydrocarbon stream and the further benzene-containing stream recycled in step d) are fed separately from each other to a solvent-based extraction unit, such as a solvent-based extractive distillation unit, or the crude hydrocarbon stream and the further benzene-containing stream recycled in step d) are mixed together in a combined feed stream before being fed to the solvent-based extraction unit, where the solvent-based extraction is carried out.

[0015] Thus, according to a particularly preferred embodiment of the present invention, in step a), the crude hydrocarbon stream is mixed with a further benzene-containing stream that is recycled in step d) to obtain a feed stream that is subjected to solvent-based extraction. The crude hydrocarbon stream can be mixed with the recycled further benzene-containing stream by using a mixer, such as a static mixer and / or a dynamic mixer, or without any specific mixing equipment, by simply combining the line for the crude hydrocarbon stream and the line for the recycled further benzene-containing stream into one line.

[0016] According to an alternative embodiment of the present invention, the crude hydrocarbon stream recycled in step d) and the further benzene-containing stream are fed separately from each other to a solvent-based extraction unit, such as an extractive distillation column. For example, the hydrocarbon stream may be fed to the bottom end of an extractive distillation column and the further benzene-containing stream recycled in step d) is fed to the extractive distillation column above it, or vice versa.

[0017] The present invention is not particularly limited with respect to the type of solvent-based extraction carried out in step a). Thus, in principle, the solvent-based extraction can be carried out in an extraction column without packing, with packing such as structured packing and / or random packing, or with trays to optimize the contact area between the solvent and the crude hydrocarbon stream on the one hand, and the recycled additional benzene-containing stream on the other hand. Preferably, the solvent-based extraction is carried out in an extraction column containing trays.

[0018] Particularly good results are obtained if the crude hydrocarbon stream recycled in step d) and the additional benzene-containing stream are subjected to extractive distillation in step a). In the extractive distillation, a benzene-depleted non-aromatic stream is obtained at the top of the distillation column, while a stream containing aromatics and solvent is obtained at the bottom of the distillation column. The stream containing aromatics and solvent can then be led to a second distillation column, where the aromatics (mainly benzene when a C6-cut is used, or a mixture of benzene, toluene, and mixed xylenes when a C6-C8-cut is used together with sulfur species contained in the hydrocarbon feed stream) are separated from the solvent, so that the solvent is obtained at the bottom of the second distillation column, usually called a solvent recovery column, while a benzene-enriched aromatic stream is obtained at the top of the distillation column. The solvent recovery column preferably contains packing in one part and trays in another part.

[0019] To completely separate aromatics from non-aromatics in step a) during solvent-based extraction, a further development of the inventive concept proposes using a solvent with a relatively high polarity and a relatively high boiling point in step a). Such a solvent has a high solubility for benzene and other aromatic compounds, allowing for good separation of benzene and other aromatic compounds from non-aromatic compounds in the solvent-based extraction, but also exhibits high removal behavior for species such as cyclohexane (possibly due to ring loss from the solvent-based extraction or cyclohexene slippage and saturation during hydrodesulfurization), methylcyclopentane (possibly due to methylcyclopentene slippage from the solvent-based extraction and saturation during hydrodesulfurization), and 2,3 dimethylpentane and 2,4 dimethylpentane (possibly due to C7-isoolefin slippage from the solvent-based extraction and saturation during hydrodesulfurization). Furthermore, it is advantageous for the solvent to exhibit high olefin (including cyclic olefin) rejection behavior so that the downstream inlet of the hydrodesulfurization reactor has a minimal olefin content. This is advantageous because the presence of olefins in the hydrodesulfurization reactor can lead to heat generation due to saturation. The exotherm may cause higher than designed benzene ring loss.

[0020] Particularly good results are obtained when the solvent used in step a) is selected from the group consisting of sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, 3-ethylsulfolane, N-methylpyrrolidone, 2-pyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-formylmorpholine, dimethylsulfone, diethylsulfone, methylethylsulfone, dipropylsulfone, dibutylsulfone, tetraethylene glycol, triethylene glycol, dimethylene glycol, ethylene glycol, ethylene carbonate, propylene carbonate, and any combination of two or more thereof.

[0021] According to a further particularly preferred embodiment of the present invention, the solvent used in step a) comprises sulfolane in combination with, as co-solvent, 3-methylsulfolane, N-formylmorpholine, 2-pyrrolidone, dipropylsulfone, tetraethylene glycol, water, heavy sulfur residues from FCC gasoline or mixtures thereof.

[0022] The present invention is not particularly limited with respect to the type of hydrodesulfurization carried out in step b) of the process according to the present invention. Therefore, hydrodesulfurization can be carried out in a conventional manner known in the prior art. In particular, good results are obtained when, in step b), the benzene-rich aromatic stream is subjected to a catalyst, together with hydrogen, selected from the group consisting of alloys and compounds containing cobalt and molybdenum or nickel and molybdenum, at a temperature of 200 to 500°C. More preferably, the temperature is 245°C (SOR) to 300°C (EOR), the pressure during hydrodesulfurization is 25 bara, and the hydrogen partial pressure is preferably in the range of 5 to 7 bara. The hydrodesulfurization unit preferably also removes nitrogen species contained in the benzene-rich aromatic stream to ensure that the resulting desulfurized aromatic stream meets the total nitrogen specification.

[0023] In a further development of the inventive concept, it is suggested that the desulfurized aromatic stream in step c) be subjected to one or more distillation steps, at least one of which is carried out using a distillation column having 5 to 100 theoretical stages. However, in order to ensure separation of the desulfurized aromatic stream in step c) into a purified benzene stream and a further benzene-containing stream, it is more preferred that the desulfurized aromatic stream in step c) be subjected to at least one distillation step having more theoretical stages than is usual in the prior art. In particular, good results are obtained when the desulfurized aromatic stream is subjected to one or more distillation steps in step c), and at least one of the distillation steps is carried out using a distillation column having 5 to 100, preferably 10 to 80, theoretical stages. Best results are obtained when at least one distillation step in step c) is carried out using a distillation column having 15 to 60, more preferably 20 to 60, and most preferably 30 to 60 theoretical stages.

[0024] Typically, a distillation column has a reboiler at its bottom and a condenser at its top. If an upper dividing wall column is used, the top section may be equipped with two condensers, one on each side of the top section.

[0025] As described above, the desulfurized aromatics stream is separated in step c) into a purified benzene stream and a further benzene-containing stream. Depending on the composition of the crude hydrocarbon stream, in addition to benzene, the further benzene-containing stream may contain only one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane and 2,4 dimethylpentane, or two of cyclohexane, methylcyclopentane, 2,3 dimethylpentane and 2,4 dimethylpentane, or three of cyclohexane, methylcyclopentane, 2,3 dimethylpentane and 2,4 dimethylpentane, or all of cyclohexane, methylcyclopentane, 2,3 dimethylpentane and 2,4 dimethylpentane.

[0026] Preferably, the distillation in step c) is carried out at a pressure of 0.01 to 1.0 MPa, more preferably 0.05 to 0.5 MPa, even more preferably 0.13 to 0.17 MPa, most preferably 0.10 to 0.20 MPa, for example about 0.15 MPa.

[0027] Furthermore, the distillation in step c) is preferably carried out at a temperature of 80 to 180°C, more preferably 90 to 160°C, even more preferably 90 to 140°C, and most preferably 90 to 100°C.

[0028] According to a further particularly preferred embodiment of the present invention, the desulfurized aromatic stream is subjected to one or more distillation steps in step c), with at least one distillation step being carried out using a divided-wall column, i.e., a column with walls extending perpendicular to the vertical direction. Particularly good results are obtained when at least one distillation step is carried out using an upper divided-wall column. Compared to a conventional three-cut column to achieve the same overall results throughout the plant, an upper divided-wall column offers the advantages of a smaller height and lower energy consumption for the same number of total theoretical stages. It should be noted that while the comparison is made in terms of the total number of theoretical stages, stages on both sides of the wall must be counted along with the stage below the wall. This embodiment is particularly preferred when using a C6 cut or a C6-C8 cut from fluid catalytic cracking naphtha or a C6 cut or a C6-C8 cut from coke oven gas oil as the crude hydrocarbon stream.

[0029] According to a first variant of this embodiment, in step c), a distillation step is carried out, in which the wall of the upper dividing wall column extends downward from the top of the upper dividing wall column by more than 20-70%, preferably more than 20-50%, of the height of the upper dividing wall column. In this embodiment, an off-gas stream containing hydrogen, hydrogen sulfide, and low molecular weight hydrocarbons such as methane, ethane, propane, and butane is obtained on the left side of the dividing wall column top, while a further benzene-containing stream is obtained on the right side of the dividing wall column top, and a purified benzene stream is obtained on the bottom of the dividing wall column. This embodiment is particularly suitable when a C6 cut from fluid catalytic cracking naphtha or a C6 cut from coke oven gas oil is used as the crude hydrocarbon stream.

[0030] This first variant is also particularly suitable when using a C6-C8 cut from fluid catalytic cracking naphtha or a C6-C8 cut from coke oven gas oil as the crude hydrocarbon stream. In this case, a purified benzene stream (i.e., a non-C6 stream) is not obtained at the bottom of the dividing wall distillation column, but a purified C6-C8 aromatics stream is obtained. This C6-C8 aromatics stream can then be easily processed, for example, in a conventional distillation column, to separate the C6-C8 aromatics stream into a purified benzene stream and one or more other aromatics streams.

[0031] According to an alternative embodiment of the present invention, which is particularly suitable when using a C6-C8 cut from fluid catalytic cracking naphtha or coke oven gas oil as the crude hydrocarbon stream, the desulfurized aromatics stream obtained in step b) is subjected to two distillation steps in step c). In this embodiment, the desulfurized aromatics stream obtained in step b) is preferably subjected to a first distillation step in a first distillation column to obtain an off-gas stream containing low molecular weight hydrocarbons, i.e., hydrogen, hydrogen sulfide, C1-C4 hydrocarbons, such as methane, ethane, propane, and butane, at the top of the first distillation column, and a liquid with remaining compounds stream is obtained at the bottom of the first distillation column. Preferably, this liquid stream is subjected to a second distillation step in a second distillation column to obtain a purified benzene stream as a side stream of the second distillation column, and a further benzene-containing stream is obtained at the top of the second distillation column and a C1-C4 hydrocarbon with C2-C4-C6 hydrocarbons stream is obtained at the bottom of the second distillation column. 7+ flow is obtained.

[0032] In a further preferred embodiment of the present invention, the desulfurized aromatics stream is subjected to two distillation steps in step c), where the desulfurized aromatics stream is subjected to a first distillation step in a first distillation column to obtain an off-gas stream containing hydrogen, hydrogen sulfide, and low-molecular-weight hydrocarbons such as methane, ethane, propane, and butane at the top of the first distillation column, and a liquid with the remaining compounds is obtained at the bottom of the first distillation column. Preferably, this liquid stream is subjected to a second distillation step in a second divided wall column to obtain a purified benzene stream as a first sidestream of the second distillation column, a toluene-rich stream as a second sidestream of the second distillation column, a further benzene-containing stream at the top of the second distillation column, and a xylene-enriched stream at the bottom of the second distillation column. Preferably, the second divided wall column is a central divided wall column, which is a column having walls extending vertically in a vertical direction. Preferably, the wall extends from a point located 10 to 30% of the distance from the bottom to the top of the second distillation column to a point located 70 to 90% of the distance from the bottom to the top of the second distillation column.

[0033] Preferably, the ratio of the further benzene-containing stream to the purified benzene stream obtained in step c) is from 1 to 50% by volume, preferably from 2 to 30% by volume, more preferably from 2 to 20% by volume, even more preferably from 3 to 10% by volume, and most preferably from 5 to 10% by volume.

[0034] According to the present invention, in step d), the further benzene-containing stream obtained in step c) is at least partially recycled to step a), i.e., the solvent-based extraction. More preferably, in step d), at least 50% by volume, even more preferably at least 80% by volume, even more preferably at least 90% by volume, and most preferably all, of the further benzene-containing stream obtained in step c) is recycled to step a), i.e., the solvent-based extraction.

[0035] Another aspect of the invention relates to a plant for purifying a crude hydrocarbon stream containing at least 10% by volume of benzene, comprising: i) a solvent-based extraction unit having at least one inlet line and an outlet line for a benzene-enriched aromatic stream; ii) a hydrodesulfurization unit having an inlet line connected to the outlet line of the solvent-based extraction unit and having an outlet line for a desulfurized aromatic stream; iii) a distillation unit having an inlet line connected to the outlet line of the hydrodesulfurization unit, an outlet line for a purified benzene stream, and an outlet line for a further benzene-containing stream; iv) a recycle line connecting the outlet line for the further benzene-containing stream of the distillation unit with one of the at least one inlet lines of the solvent-based extraction unit; Includes.

[0036] Preferably, the plant further comprises a mixing unit for mixing the crude hydrocarbon stream with a further benzene-containing stream recycled via the recycle line, the mixing unit having an inlet line for the crude hydrocarbon stream, an inlet line for the further benzene-containing stream and an outlet line for the mixture of the crude hydrocarbon stream and the further benzene-containing stream, which is also referred to herein as the feed stream.

[0037] In a further development of the inventive idea, it is proposed that the distillation unit comprises only one distillation column having 5 to 100, preferably 10 to 80, more preferably 15 to 60, even more preferably 20 to 60, most preferably 30 to 60 theoretical stages.

[0038] According to a further preferred embodiment of the present invention, the distillation column of the plant is preferably an upper dividing wall column.

[0039] Particularly good results are obtained when the wall of the upper dividing wall column extends vertically downward from the top of the upper dividing wall column over 20 to 70%, preferably over 20 to 50%, of the height of the upper dividing wall column, which is the distance from the bottom to the top of the distillation column.

[0040] In an alternative embodiment of the present invention, it is preferred that the distillation unit comprises two distillation columns, one of which has from 5 to 100, preferably from 10 to 80, more preferably from 15 to 60, even more preferably from 20 to 60, and most preferably from 30 to 60 theoretical stages.

[0041] Preferably, the first of the two distillation columns has an inlet line connected to the outlet line of the hydrodesulfurization unit, has 5 to 30, preferably 15 to 20, theoretical stages and has an outlet line for a liquid stream at its bottom, and the second of the two distillation columns has an inlet line connected to the outlet line for the liquid stream of the first distillation column, has an outlet line for a purified benzene stream and has an outlet line for a further benzene-containing stream.

[0042] It is particularly preferred that the second distillation column is a central dividing wall column, and good results are obtained when the wall of the central dividing wall column extends, as viewed from the bottom to the top of the second distillation column, from a point 10-30% of the distance from the bottom to the top of the second distillation column to a point 70-90% of the distance from the bottom to the top of the second distillation column.

[0043] Specific embodiments according to the invention will now be described, by way of example only, with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0044] [Figure 1a] 1 is a schematic diagram of a plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene according to the prior art. [Figure 1b] FIG. 1b is a more detailed schematic diagram of a solvent-based extraction unit that is part of the plant shown in FIG. 1a. [Figure 2] 1 is a schematic diagram of a plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene, according to a first embodiment of the present invention. [Figure 3] FIG. 2 is a schematic diagram of a plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene, according to a second embodiment of the present invention. [Figure 4] FIG. 1 is a schematic diagram of a plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene, according to a third embodiment of the present invention. [Figure 5] FIG. 1 is a schematic diagram of a plant for preparing a purified benzene composition from a crude hydrocarbon stream containing benzene, according to a fourth embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0045] 1a and 1b, a prior art plant 10 includes a solvent-based extraction unit 12, a hydrodesulfurization unit 14, and a distillation unit 16. The solvent-based extraction unit 12 includes an inlet line 18 for feeding a crude hydrocarbon stream to the solvent-based extraction unit 12, an outlet line 20 for a benzene-rich aromatic stream, and an outlet line 22 for a benzene-depleted non-aromatic stream. The outlet line 20 for the benzene-rich aromatic stream is also an inlet line for the hydrodesulfurization unit 14, which further includes an inlet line 23 for hydrogen and an outlet line 24 for the desulfurized aromatic stream. The outlet line 24 for the desulfurized aromatic stream is an inlet line for the distillation unit 16, which further includes an outlet line 26 for a purified benzene stream and an outlet line 28 for off-gas. The distillation unit 16 includes a distillation column 16′ having 16 theoretical stages.

[0046] The solvent-based extraction unit 12 is shown in more detail in FIG. 1b and includes a first distillation column 30 and a second distillation column 32. An inlet line 18 for supplying a crude hydrocarbon stream is connected to the middle of the first distillation column 30. Furthermore, a solvent (recycle) line 34 leads to the top of the first distillation column 30. During distillation, a benzene-depleted non-aromatic stream is produced as an overhead stream and withdrawn from the first distillation column 30 via outlet line 22. At the bottom of the first distillation column 30, a mixture of solvent and a benzene-rich aromatic stream is obtained, which is withdrawn from the first distillation column 30 via line 36 and then fed to the second distillation column 32, where the solvent is separated from the benzene-rich aromatic stream. The regenerated solvent is returned from the bottom of second distillation column 32 to the top of first distillation column 30 via solvent (recycle) line 34, while a benzene-rich aromatics stream is withdrawn from the top of second distillation column 32 via line 20 and fed to hydrodesulfurization unit 14.

[0047] During operation of plant 10, the benzene-rich aromatics stream is supplied via line 20, and hydrogen is supplied via inlet line 23 to hydrodesulfurization unit 14, where sulfur-containing impurities are desulfurized to non-sulfur compounds and hydrogen sulfide. The hydrodesulfurization unit also removes nitrogen species contained in the benzene-rich aromatics stream to ensure that the resulting desulfurized aromatics stream meets the total nitrogen specification. The resulting desulfurized aromatics stream is supplied via line 24 to distillation column 16'. An off-gas stream obtained during distillation as an overhead product and containing low-molecular-weight hydrocarbons such as C1-C5 hydrocarbons, particularly methane, ethane, propane, butane, hydrogen (remaining after hydrodesulfurization), and hydrogen sulfide (produced during hydrodesulfurization), is withdrawn from distillation column 16' via outlet line 28, while a purified benzene stream obtained as a bottom product is withdrawn from distillation column 16' via outlet line 26.

[0048] In contrast, the process carried out in the plant 10 according to the present invention, as shown in Figures 2 to 5, comprises the steps of subjecting the desulfurized aromatics stream obtained in the hydrodesulfurization unit 14 to distillation to produce a purified benzene stream and a further benzene-containing stream, and at least partially, preferably completely, recycling the further benzene-containing stream thus obtained to the solvent-based extraction unit 12. To this end, the plant 10 according to the present invention, as shown in Figures 2 to 5, comprises a recycle line 38 for the further benzene-containing stream obtained in the distillation unit 16, and a recycle line 34 connects the distillation unit 16 with the solvent-based extraction unit 12. Furthermore, the distillation unit 16 comprises, for this purpose, at least one distillation column having an appropriate number of theoretical stages so that the desulfurized aromatics stream obtained in the hydrodesulfurization unit 14 is separated into a purified benzene stream and a further benzene-containing stream during distillation. Preferably, the number of theoretical stages of this distillation column is 5 to 100, more preferably 10 to 80, even more preferably 15 to 60, even more preferably 20 to 60, and most preferably 30 to 60.

[0049] By carrying out the distillation in step c) so that the desulfurized aromatic stream obtained by the hydrodesulfurization in step b) is separated into a purified benzene stream and a further benzene-containing stream, at least one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane, and 2,4 dimethylpentane contained as an impurity in the further benzene-containing stream is reliably and almost completely separated from the purified benzene stream, thereby obtaining a benzene stream having a very high purity of, for example, at least 99.8% by volume. Since the further benzene-containing stream is at least partially, preferably completely, recycled to the solvent-based extraction in step a), the benzene contained in the further benzene-containing stream is not lost, or if lost, is only in a very small amount. This is due to the fact that the further benzene-containing stream is decomposed into a benzene-rich aromatic stream and a benzene-depleted non-aromatic stream in the solvent-based extraction step a), i.e., the benzene and other aromatics contained in the further benzene-containing stream are separated from at least one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane, and 2,4 dimethylpentane contained as impurities or other impurities in the form of olefins, paraffins, naphthenes, and other non-aromatic compounds. The benzene-rich aromatic stream after the solvent-based extraction is subjected to hydrodesulfurization to obtain a desulfurized aromatic stream, which is then subjected to distillation to produce a purified benzene stream and a further benzene-containing stream, thereby actually recovering the recycled benzene via the further benzene-containing stream from distillation to the solvent-based extraction. Overall, the process according to the present invention makes it possible to reliably and efficiently prepare a purified benzene composition from a benzene-containing crude hydrocarbon stream, having a high benzene concentration, e.g., at least 99.8% by volume, a desired maximum and minimum amount of sulfur compound impurities, e.g., qualified as total sulfur, of up to 1 ppmw, and a total nitrogen content of less than 1 ppmw. In particular, these advantageous effects are also obtained when a C6 cut or a C6-C8 cut of FCC gasoline or a C6 cut or a C6-C8 cut of COLO is used as the feedstock for the process.Furthermore, these beneficial effects are obtained even in the case of very long run times, including the operating temperature window from catalyst start-up to end-of-run, in the case of heavier than expected feedstocks fed to the FCC, RFCC or COLO, or in the case of slippage of C6-cyclic olefins and / or C7-isoolefins into the aromatic stream obtained in the solvent-based extraction process.

[0050] In the embodiment shown in Figure 2, the distillation unit 16 preferably comprises one distillation column 16' having 5 to 100 theoretical stages, and the distillation is preferably carried out at a pressure of 0.1 to 0.2 MPa, for example 0.15 MPa, and a temperature of 90 to 100°C, for example 95°C. This embodiment is particularly suitable when a C6 cut from fluid catalytic cracking naphtha or coke oven gas oil is used as the feedstock.

[0051] The embodiment shown in FIG. 3 differs from the embodiment shown in FIG. 2 in that the distillation unit 16 comprises a divided wall column 17, more specifically, an upper divided wall column 17. Preferably, the wall of the upper divided wall column 17 extends vertically downward from the top of the upper divided wall column 17 over 20 to 70%, preferably 20 to 50%, of the height of the upper divided wall column. In this embodiment, an off-gas stream containing low molecular weight hydrocarbons such as methane, ethane, propane, butane, hydrogen, and hydrogen sulfide is obtained to the left of the top of the divided wall column 17, while a further benzene-containing stream is obtained to the right of the top of the divided wall column 17, and a purified benzene stream is obtained at the bottom of the divided wall column 17. Preferably, the upper divided wall column 17 has 5 to 100 theoretical stages, and the distillation is preferably carried out at a pressure of 0.1 to 0.2 MPa, e.g., 0.15 MPa, and a temperature of 90 to 100°C, e.g., 95°C. The use of the divided wall column 17 has the advantage that the divided wall column 17 requires less height to achieve the same separation results compared to a non-divided wall column, and requires less energy to operate than a conventional distillation column without a dividing wall. This embodiment is particularly suitable when the crude hydrocarbon stream is a C6 cut from fluid catalytic cracking naphtha or a C6 cut from coke oven gas oil.

[0052] 3 is also particularly suitable when using a C6-C8 cut from fluid catalytic cracking naphtha or a C6-C8 cut from coke oven gas oil as the crude hydrocarbon stream. In this case, a purified benzene stream (i.e., a non-C6 stream) is not obtained at the bottom of the dividing wall distillation column 17, but rather a purified C6-C8 aromatics stream. This C6-C8 aromatics stream can then be readily processed, for example, in a conventional distillation column, to separate the C6-C8 aromatics stream into a purified benzene stream and one or more other aromatics streams.

[0053] In the embodiment shown in FIG. 4, the distillation unit 16 includes two distillation columns 40 and 42. The first distillation column 40 preferably has 5 to 30 theoretical stages, and the second distillation column 42 preferably has 5 to 100 theoretical stages. The distillation in the first distillation column 40 is preferably carried out at a pressure of 0.1 MPa to 0.2 MPa, e.g., 0.15 MPa, and a temperature of 90°C to 100°C, e.g., 95°C, while the distillation in the second distillation column 42 is preferably carried out at a pressure of 0.2 MPa to 0.3 MPa, e.g., 0.25 MPa, and a temperature of 90°C to 140°C. During the distillation carried out in the first distillation column 40, an off-gas stream containing low molecular weight hydrocarbons, i.e., C1 to C4 hydrocarbons such as methane, ethane, propane, and butane, hydrogen, and hydrogen sulfide, is obtained at the top of the first distillation column and is withdrawn via outlet line 28, while a liquid containing the remaining compounds is obtained at the bottom of the first distillation column 40. This liquid stream is fed via liquid line 43 to second distillation column 42 and is distilled in second distillation column 42 to produce a purified benzene stream which is withdrawn as a side stream from second distillation column 42 via outlet line 26, a further benzene-containing stream which is recycled to solvent-based extraction unit 12 via recycle line 38 at the top of second distillation column 42, and a C 2 benzene-containing stream which is withdrawn at the bottom of second distillation column 42 via outlet line 44. 7+ This embodiment is particularly suitable when using a C6-C8 cut from fluid catalytic cracking naphtha or coke oven gas oil as the crude hydrocarbon stream.

[0054] The embodiment shown in FIG. 5 differs from the embodiment shown in FIG. 4 in that the distillation unit 16 includes a divided wall column, more specifically, a middle divided wall column, as the second distillation column 42. Preferably, the wall of the middle divided wall column 42 extends from a point located 10-30% of the distance from the bottom to the top of the second distillation column to a point located 70-90% of the distance from the bottom to the top of the second distillation column. The first distillation column 40 preferably has 5-30 theoretical stages, and the second distillation column 42 preferably has 5-100 theoretical stages. The distillation in the first distillation column 40 is preferably carried out at a pressure of 0.1 MPa to 0.2 MPa, e.g., 0.15 MPa, and a temperature of 90°C to 100°C, e.g., 95°C, while the distillation in the second distillation column 42 is preferably carried out at a pressure of 0.2 MPa to 0.3 MPa, e.g., 0.25 MPa, and a temperature of 90°C to 160°C. During the distillation carried out in the first distillation column 40, an off-gas stream containing low molecular weight hydrocarbons, i.e., C1-C4 hydrocarbons such as methane, ethane, propane, and butane, hydrogen, and hydrogen sulfide, is obtained at the top of the first distillation column and withdrawn via outlet line 28, while a liquid containing the remaining compounds is obtained at the bottom of the first distillation column 40. This liquid stream is fed via liquid line 43 to the second distillation column 42 and distilled in the second distillation column 42 to obtain a purified benzene stream withdrawn via outlet line 26 as a first sidestream of the second distillation column 42, a toluene-rich fraction withdrawn via outlet line 46 as a second sidestream of the second distillation column 42, a further benzene-containing stream at the top of the second distillation column 42 which is recycled via recycle line 38 to the solvent-based extraction unit 12, and a mixed xylene-rich stream withdrawn via outlet line 48 at the bottom of the second distillation column 42. This embodiment is particularly suitable when the crude hydrocarbon stream is a C6-C8 cut from fluid catalytic cracking naphtha or coke oven gas oil.

[0055] The invention will now be described with reference to illustrative but non-limiting examples. [Example]

[0056] Example The software ASPEN HYSYS was used to simulate the process as implemented in the plant shown in Figure 3, using the C6 cut of fluid catalytic cracking naphtha as the crude hydrocarbon stream. A ring loss of 0.4 wt% was assumed, exceeding the design value of 0.1 wt%. Furthermore, a benzene recovery of greater than 99% was assumed during the solvent-based extraction step, with a benzene purity of greater than 99.9 wt% being set as the target.

[0057] The composition of the desulfurized aromatic stream, the composition of the further benzene-containing stream, as well as the temperature conditions, pressure conditions and other parameters during distillation in upper dividing wall distillation column 17 are shown in the table below.

[0058] Comparative Example Each process carried out in the plant shown in Figure 1 is simulated using the same C6 cut fluid catalytic cracking naphtha as the crude hydrocarbon stream.

[0059] The composition of the desulfurized aromatic stream as well as the temperature, pressure and other parameters during distillation in distillation column 16' are shown in the table below. TIFF0007743503000001.tif98170

[0060] Note that in the examples the feed is higher because it contains an additional recycled benzene-containing stream. TIFF0007743503000002.tif105170TIFF0007743503000003.tif101170 [Explanation of symbols]

[0061] 10 Plant 12 Solvent-based extraction unit 14 Hydrodesulfurization Unit 16 Distillation Unit 16' distillation column 17 (Upper) Dividing Wall Distillation Column 18 Inlet line for crude hydrocarbon stream 20 Line for benzene-rich aromatic stream 22 Exit line for benzene-depleted non-aromatic stream 23 Hydrogen inlet line 24 Line for desulfurized aromatic stream 26 Exit line for purified benzene stream 28 Exit line for off-gas 30 First distillation column of solvent-based extraction unit 32 Second distillation column of solvent-based extraction unit 34 Solvent (recycle) line 34 36 Line for the mixture of solvent and benzene-rich aromatic stream 38 Recycle line for further benzene-containing stream 40 First distillation column of distillation unit 42 Second distillation column of distillation unit 43 Liquid Line 44 C 7+ Flow Exit Line 46 Toluene-rich fraction outlet line 48 Mixed xylene outlet line

Claims

1. 1. A process for preparing a purified benzene composition from a crude hydrocarbon stream containing at least 10% by volume of benzene, comprising: a) subjecting the crude hydrocarbon stream and the further benzene-containing stream recycled in step d) to a solvent-based extraction to produce a benzene-enriched aromatic stream and a benzene-depleted non-aromatic stream; b) subjecting the benzene-enriched aromatic stream obtained in step a) to hydrodesulfurization so as to obtain a desulfurized aromatic stream; c) subjecting the desulfurized aromatics stream obtained in step b) to distillation to produce a purified benzene stream and a further benzene-containing stream, the further benzene-containing stream comprising benzene and at least one of cyclohexane, methylcyclopentane, 2,3 dimethylpentane and 2,4 dimethylpentane and having a benzene concentration between less than 100 wt.% and the azeotropic benzene concentration, the azeotropic benzene concentration being the concentration of benzene in the azeotropic mixture formed from the compounds contained in the further benzene-containing stream as dictated by the vapor-liquid equilibrium of these compounds; d) at least partially recycling the further benzene-containing stream obtained in step c) to step a); A method comprising:

2. 10. The process of claim 1, wherein the crude hydrocarbon stream contains at least 20% by volume of benzene, on a 100% by weight basis.

3. 3. The process of claim 1 or 2, wherein the crude hydrocarbon stream contains, on a 100 wt.% basis, i) 20 to 60 vol.% paraffins, ii) 10 to 50 vol.% olefins, and iii) 5 to 40 vol.% naphthenes.

4. 1. The crude hydrocarbon stream is a C 2 O 4 O 5 O 6 O 6 O 7 O 8 O 9 O 10 O 11 O 12 O 13 O 14 O 15 O 16 O 17 O 18 O 19 O 20 O 21 O 22 O 23 O 24 O 25 O 26 O 27 O 28 O 29 O 30 O 31 O 32 O ６ -Cut or C ６ ~C ８ -C from cut or coke oven gas oil ６ -Cut or C ６ ~C ８ The method according to any one of claims 1 to 3, wherein the cutting is carried out.

5. 5. The process according to any one of claims 1 to 4, wherein in step a) the crude hydrocarbon stream is mixed with the further benzene-containing stream recycled in step d) to obtain a feed stream which is subjected to solvent-based extraction.

6. 5. The method according to claim 1, wherein the crude hydrocarbon stream recycled in step d) and the further benzene-containing stream are fed separately from each other to the solvent-based extraction.

7. 7. The process according to any one of claims 1 to 6, wherein the recycled crude hydrocarbon stream and the further benzene-containing stream in step d) are subjected to extractive distillation in step a).

8. 8. The method of any one of claims 1 to 7, wherein the solvent used in step a) is selected from the group consisting of sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, 3-ethylsulfolane, N-methylpyrrolidone, 2-pyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-formylmorpholine, dimethyl sulfone, diethyl sulfone, methyl ethyl sulfone, dipropyl sulfone, dibutyl sulfone, tetraethylene glycol, triethylene glycol, dimethylene glycol, ethylene glycol, ethylene carbonate, propylene carbonate, and any combination of two or more thereof.

9. 9. The process according to any one of claims 1 to 8, wherein the desulfurized aromatic stream is subjected to one or more distillation steps in step c), at least one of the distillation steps being carried out using an upper dividing wall column (17).

10. The desulfurized aromatics stream is subjected to two distillation steps in step c), where the desulfurized aromatics stream is separated into C １ ~C ７ The off-gas stream containing hydrocarbons, hydrogen and hydrogen sulfide is subjected to a first distillation step in a first distillation column (40) so as to obtain a liquid stream containing residual compounds at the bottom of the first distillation column (40), which liquid stream is passed through a second distillation column (42) to obtain a purified benzene stream as a side stream, a further benzene-containing stream at the top of the second distillation column (42) and a C 2 -containing stream at the bottom of the second distillation column (42). ７＋ 10. The process according to any one of claims 1 to 9, wherein the distillation product is subjected to a second distillation step in a second distillation column (42) to obtain a stream:

11. The desulfurized aromatics stream is subjected to two distillation steps in step c), where the desulfurized aromatics stream is separated at the top of the first distillation column (40) from C １ ~C ７ 10. The process according to any one of claims 1 to 9, wherein the off-gas stream containing hydrocarbons, hydrogen and hydrogen sulfide is subjected to a first distillation step in a first column (40) to obtain a liquid stream containing residual compounds at the bottom of the first distillation column (40), and the liquid stream is subjected to a second distillation step in a second intermediate dividing wall column (42) to obtain a purified benzene stream as a first substream, a toluene-enriched stream as a second substream, a further benzene-containing stream at the top of the second distillation column (42), and a xylene-enriched stream at the bottom of the second distillation column (42).

12. 1. A plant (10) for purifying a crude hydrocarbon stream containing at least 10% by volume of benzene, comprising: i) a solvent-based extraction unit (12) for producing a benzene-enriched aromatics stream from a crude hydrocarbon stream, the solvent-based extraction unit (12) having at least one inlet line (18) and an outlet line (20); ii) a hydrodesulfurization unit (14) for obtaining a desulfurized aromatic stream from the benzene-rich aromatic stream, the hydrodesulfurization unit (14) having an inlet line (20) connected to the outlet line (20) of the solvent-based extraction unit (12) and having an outlet line (24) for the desulfurized aromatic stream; iii) a distillation unit (16) for producing a purified benzene stream and a further benzene-containing stream from the desulfurized aromatic stream, the distillation unit (16) having an inlet line (24) connected to the outlet line (24) of the hydrodesulfurization unit (14), an outlet line (26) for the purified benzene stream, and an outlet line for the further benzene-containing stream; iv) a recycle line (38) for the recycle of a further benzene-containing stream, the recycle line (38) connecting the outlet line for the further benzene-containing stream of the distillation unit (16) with one of the at least one inlet lines (18) of the solvent-based extraction unit (12); A plant (10) comprising:

13. 13. The plant (10) of claim 12, wherein the distillation unit (16) comprises only one distillation column (16') having between 5 and 100 theoretical stages.

14. 14. The plant (10) of claim 13, wherein the distillation column (16') is an upper dividing wall column (17).

15. 13. The plant (10) of claim 12, wherein the distillation unit (16) comprises two distillation columns (40, 42), one of the two distillation columns (42) having 5 to 100 theoretical stages, a first of the two distillation columns (40) having an inlet line connected to the outlet line (24) of the hydrodesulfurization unit (14) and an outlet line for a liquid stream at its bottom, and a second of the two distillation columns (42) having an inlet line connected to the outlet line for the liquid stream of the first distillation column (40), an outlet line (26) for a purified benzene stream, and an outlet line for a further benzene-containing stream (38).

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