Processes and apparatuses for production of aromatic products

Processes and apparatuses for producing a C8 aromatic isomer product are provided. The apparatus comprises an isomerization unit to provide an isomerized stream. An isomerate stripper column is in communication with the isomerization unit to provide an isomerate stripper overhead stream comprising C6− hydrocarbons in an isomerate overhead line and an isomerate stripper bottoms stream in an isomerate bottoms line. A dividing wall naphthene splitter column is in communication with the isomerate bottoms line to provide an overhead naphthene splitter stream comprising the C8 naphthenes and C7 aromatic hydrocarbons in a naphthene splitter overhead line and a naphthene splitter sidedraw stream comprising C8 aromatic isomers in a naphthene splitter sidedraw line. An extractive distillation column is in communication with the naphthene splitter overhead line to provide a recycle feedstream comprising the C8 naphthenes in a recycle line and an extract stream comprising the C7 aromatic hydrocarbons in an extract line.

TECHNICAL FIELD

The technical field generally relates to apparatuses and processes for producing a C8aromatic isomer product in an aromatics complex with an integrated scheme for handling naphthenes produced in the process. More particularly, the technical field relates to the apparatus and processes for reducing contaminants to a para-xylene separation unit in an aromatics complex producing para-xylene having an integrated scheme for handling naphthenes produced in the process.

BACKGROUND

Most new aromatics complexes are designed to maximize the yield of benzene and C8aromatic isomer (para-xylene, meta-xylene, ethylbenzene and ortho-xylene). Benzene is a versatile petrochemical building block used in many different products based on its derivation including ethylbenzene, cumene, and cyclohexane. In many instances, the sought C8aromatic isomer is para-xylene as para-xylene is an important building block, which is used almost exclusively for the production of polyester fibers, resins, and films formed via terephthalic acid or dimethyl terephthalate intermediates. Accordingly, an aromatics complex may be configured in many different ways depending on the desired products, available feedstocks, and investment capital available. A wide range of options permits flexibility in varying the product slate balance of benzene and para-xylene to meet downstream processing requirements.

A prior art aromatics complex flow scheme has been disclosed by Meyers in the HANDBOOK OFPETROLEUMREFININGPROCESSES, 2d. Edition in 1997 by McGraw-Hill.

In an aromatics complex, the production of commercial-grade C8aromatic isomers involves multiple separation steps such as fractionation, adsorptive separation and/or crystallization and reaction steps including transalkylation, isomerization, dealkylation etc. In typical aromatic complexes used to produce high purity C8aromatic isomers, the isomer-depleted raffinate stream from the separation process, either simulated moving bed adsorption or crystallization, is sent to an isomerization process in which the remaining xylene isomers are isomerized to produce the desired isomer (near equilibrium concentration) and convert ethylbenzene (EB) to other components which can be separated via fractionation or other means. One type of xylene isomerization process also isomerizes EB to xylenes via a C8naphthene intermediate. In a typical paraxylene complex using simulated moving bed (SMB) adsorption, the C8naphthenes remain in the feed to the SMB unit. This is feasible due to the typical use of para-diethylbenzene as the desorbent in the SMB process. In paraxylene complexes using toluene as the SMB desorbent, the majority of the C8napthenes must be removed from the feed to the SMB unit in order to avoid accumulation of the C8naphthenes in the circulating toluene desorbent. This also holds true for complexes designed to produce meta-xylene which also utilizes toluene as the SMB desorbent. This is necessary because the C8naphthene isomers have boiling points within the range of toluene (at the low end) and xylenes (at the high end). As a result, C8isomers, such as 1,1,3-trimethyl cyclopentane which has a boiling point slightly lower than toluene, will accumulate in the toluene desorbent supply, thus making the material less suitable as a desorbent. In addition, because some of the C8naphthene isomers have boiling points close to toluene and toluene is a byproduct produced in the xylene/EB isomerization process, it is also necessary to remove toluene from the C8naphthene recycle stream to avoid accumulation of toluene in the isomerization feed.

Further, the feed stream separated from C8naphthenes which is passed to the xylene separation unit may contain higher molecular weight hydrocarbons i.e. C9+components as contaminants making the xylene separation process inefficient.

Accordingly, it is desirable to provide improved methods and apparatuses for separating C8naphthenes from an isomerate product stream before being recycled to the xylene separation unit. Further, it is desirable to provide a cost-effective method and apparatus to solve the problem of accumulation of C8naphthenes in the desorbent supply in a xylene separation unit. Also, it is desirable to remove toluene from the C8naphthene recycle stream to avoid accumulation of toluene in the isomerization feed. Moreover, it is desirable to reduce the amount of C9+alkylaromatic hydrocarbons being passed to the xylene separation unit as contaminants in an efficient and cost-effective way. Furthermore, other desirable features and characteristics of the present subject matter will become apparent from the subsequent detailed description of the subject matter and the appended claims, taken in conjunction with the accompanying drawings and this background of the subject matter.

BRIEF SUMMARY

Various embodiments contemplated herein relate to apparatuses and processes for producing a purified C8aromatic isomer product in an aromatics complex. The exemplary embodiments taught herein include apparatuses and processes for reducing contaminants comprising C9+hydrocarbons to a para-xylene separation unit in an aromatics complex producing para-xylene and having an integrated scheme for handling naphthenes produced in the process.

In accordance with an exemplary embodiment, an apparatus is provided for producing para-xylene, wherein the apparatus comprises an isomerization unit to provide an isomerized stream. An isomerate stripper column is in communication with the isomerization unit to provide an isomerate stripper overhead stream comprising C6−hydrocarbons in an isomerate overhead line and an isomerate stripper bottoms stream in an isomerate bottoms line. A dividing wall naphthene splitter column is in communication with the isomerate bottoms line to provide an overhead naphthene splitter stream comprising the C8naphthenes and C7aromatic hydrocarbons in a naphthene splitter overhead line and a naphthene splitter sidedraw stream comprising C8aromatic isomers in a naphthene splitter sidedraw line. An extractive distillation column is in communication with the naphthene splitter overhead line to provide a recycle feedstream comprising the C8naphthenes in a recycle line and an extract stream comprising the C7aromatic hydrocarbons in an extract line.

In accordance with another exemplary embodiment, an apparatus is provided for producing para-xylene, wherein the apparatus comprises an isomerization unit to provide an isomerized stream. An isomerate stripper column is in communication with the isomerization unit to provide an isomerate stripper overhead stream comprising C6−hydrocarbons in an isomerate overhead line and an isomerate stripper bottoms stream in an isomerate bottoms line. A dividing wall naphthene splitter column is in communication with the isomerate bottoms line to provide an overhead naphthene splitter stream comprising the C8naphthenes and C7aromatic hydrocarbons in a naphthene splitter overhead line and a naphthene splitter sidedraw stream comprising C8aromatic isomers in a naphthene splitter sidedraw line. The dividing wall column having one or more vapor-liquid contacting stages comprising a dividing wall having an upper end and a lower end that divides the naphthene splitter column into a feed section and a product section and the lower end of the dividing wall extends to a last stage of the one or more vapor-liquid contacting stages. An extractive distillation column is in communication with the naphthene splitter overhead line to provide a recycle feedstream comprising the C8naphthenes in a recycle line and an extract stream comprising the C7aromatic hydrocarbons in an extract line.

In accordance with another exemplary embodiment, a process is provided for the production of para-xylene, wherein the process comprises introducing a raffinate product stream comprising C8aromatic isomers to an isomerization unit to provide an isomerized stream, wherein the isomerized stream is produced in the presence of an ethylbenzene (EB) isomerization catalyst. The isomerized stream is passed to an isomerate stripper column to provide an isomerate stripper overhead stream comprising C6−hydrocarbons and an isomerate stripper bottoms stream. The isomerate stripper bottoms stream is passed to a dividing wall naphthene splitter column to provide an overhead naphthene splitter stream comprising the C8naphthenes and C7aromatic hydrocarbons and a naphthene splitter sidedraw stream comprising C8aromatic isomers and less than about 1 wt % of C9+alkylaromatic hydrocarbons. The overhead naphthene splitter stream is passed to an extractive distillation column to provide a recycle feedstream comprising the C8naphthenes and an extract stream comprising the C7aromatic hydrocarbons. Finally, the recycle feedstream is passed to the isomerization unit.

These and other features, aspects, and advantages of the present disclosure will become better understood upon consideration of the following detailed description, drawings and appended claims.

DEFINITIONS

As used herein, the term “stream” can include various hydrocarbon molecules and other substances.

As used herein, the term “stream”, “feed”, “product”, “part” or “portion” can include various hydrocarbon molecules, such as straight-chain and branched alkanes, naphthenes, alkenes, alkadienes, and alkynes, and optionally other substances, such as gases, e.g., hydrogen, or impurities, such as heavy metals, and sulfur and nitrogen compounds. Each of the above may also include aromatic and non-aromatic hydrocarbons.

As used herein, the term “overhead stream” can mean a stream withdrawn at or near a top of a vessel, such as a column.

As used herein, the term “bottoms stream” can mean a stream withdrawn at or near a bottom of a vessel, such as a column.

Hydrocarbon molecules may be abbreviated C1, C2, C3, Cnwhere “n” represents the number of carbon atoms in the one or more hydrocarbon molecules or the abbreviation may be used as an adjective for, e.g., non-aromatics or compounds. Similarly, aromatic compounds may be abbreviated A6, A7, A8, Anwhere “n” represents the number of carbon atoms in the one or more aromatic molecules. Furthermore, a superscript “+” or “−” may be used with an abbreviated one or more hydrocarbons notation, e.g., C3+or C3−, which is inclusive of the abbreviated one or more hydrocarbons. As an example, the abbreviation “C3+” means one or more hydrocarbon molecules of three or more carbon atoms.

As used herein, the term “zone” or “unit” can refer to an area including one or more equipment items and/or one or more sub-zones. Equipment items can include, but are not limited to, one or more reactors or reactor vessels, separation vessels, distillation towers, heaters, exchangers, pipes, pumps, compressors, and controllers. Additionally, an equipment item, such as a reactor, dryer, or vessel, can further include one or more zones or sub-zones.

The term “column” means a distillation column or columns for separating one or more components of different volatilities. Unless otherwise indicated, each column includes a condenser on an overhead of the column to condense and reflux a portion of an overhead stream back to the top of the column and a reboiler at a bottom of the column to vaporize and send a portion of a bottoms stream back to the bottom of the column. Feeds to the columns may be preheated. The top or overhead pressure is the pressure of the overhead vapor at the vapor outlet of the column. The bottom temperature is the liquid bottom outlet temperature. Overhead lines and bottoms lines refer to the net lines from the column downstream of any reflux or reboil to the column unless otherwise shown. Stripping columns omit a reboiler at a bottom of the column and instead provide heating requirements and separation impetus from a fluidized inert media such as steam.

As used herein, the term “rich” can mean an amount of at least generally 50%, and preferably 70%, by mole, of a compound or class of compounds in a stream.

As depicted, process flow lines in the FIGURES can be referred to interchangeably as, e.g., lines, pipes, feeds, gases, products, discharges, parts, portions, or streams.

The term “communication” means that material flow is operatively permitted between enumerated components.

The term “downstream communication” means that at least a portion of material flowing to the subject in downstream communication may operatively flow from the object with which it communicates.

The term “upstream communication” means that at least a portion of the material flowing from the subject in upstream communication may operatively flow to the object with which it communicates.

The term “direct communication” means that flow from the upstream component enters the downstream component without undergoing a compositional change due to physical fractionation or chemical conversion.

The term “predominantly” means a majority, suitably at least 50 mol % and preferably at least 60 mol %.

The term “passing” means that the material passes from a conduit or vessel to an object.

The term “majority” means, suitably at least 40 wt % and preferably at least 50 wt %

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and is not intended to limit the various embodiments or the application and uses thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding background or the following detailed description. Moreover, the reaction conditions including selection of temperature, pressure, LHSV and catalyst in the various units in the aromatics complex described below are conventional which are known to one of ordinary skill in the art, unless wherever mentioned.

An exemplary embodiment of the process and apparatus for reducing contaminants comprising C9+hydrocarbons to a para-xylene separation unit in an aromatics complex producing C8aromatic isomer product with an integrated scheme for handling naphthenes produced in the process is addressed with reference to a process and apparatus100as shown inFIG. 1. The process and apparatus100includes a reformate splitter column104, an aromatics rerun column114, a xylene separation unit124, an extract column130, a xylene column138, a raffinate column144, an isomerization unit152, an isomerate stripper column156, a dividing wall naphthene splitter column164, an extractive distillation column172, an aromatics extraction unit180, a benzene-toluene (BT) column188, a transalkylation unit200, a transalkylation stripper204, a stabilizer212and a heavy aromatics column218.

In accordance with an exemplary embodiment as shown inFIG. 1, a reformate stream in line102comprising aromatic hydrocarbons may be passed to the reformate splitter column104. A reformate overhead stream in line106comprising C7−aromatic hydrocarbons and a reformate bottoms stream in line108comprising C7+aromatic hydrocarbons may be withdrawn from the reformate splitter column104. In accordance with an instant embodiment as shown, an overhead stream from the reformate splitter column106may be condensed and separated in a receiver with a portion of the condensed liquid being refluxed back to the reformate splitter column104to obtain the reformate overhead stream from a net portion in line106. Further, as illustrated, the reformate splitter column104may include a reboiler at a bottom of the column to vaporize and send a portion of the reformate bottoms stream back to the bottom of the column. The reformate bottoms stream in line108may be passed to the aromatics rerun column114for separation. In accordance with an exemplary embodiment as shown inFIG. 1, the reformate bottoms stream in line108may be passed through a clay treater110to treat residual olefin contaminants and provide a treated reformate bottoms stream in line112prior to being passed to the aromatics rerun column114. The aromatics rerun column114may further receive a naphthene splitter bottoms stream in line170comprising C8+aromatic hydrocarbons and a benzene toluene (hereinafter “BT”) column bottoms stream in line198comprising xylenes. Further, the aromatics rerun column114may receive C8+aromatic hydrocarbons in a bottoms stream in line142from the xylene column138discussed later. A net overhead rerun column stream in line116comprising C8aromatic isomers and a net bottoms rerun column stream in line120rich in C9and heavier alkylaromatic hydrocarbons may be withdrawn from the aromatics rerun column114.

In accordance with an exemplary embodiment as shown, the net overhead rerun column stream may be recovered from an overhead of the aromatics rerun column114after condensing, flashing and refluxing a portion of the overhead stream from the column. Further, as illustrated, the aromatics rerun column114may include a heater at a bottom of the column to vaporize and send a portion of the bottoms stream back to the bottom of the column. A rerun column sidedraw stream in line118rich in C9and C10alkylaromatics may also be withdrawn from the aromatic rerun column114. In accordance with an exemplary embodiment as shown inFIG. 1, the rerun column sidedraw stream in line118may be passed to the transalkylation unit200.

In accordance with an exemplary embodiment as shown inFIG. 1, the net overhead rerun column stream in line116may be combined with a naphthene splitter sidedraw stream in line168comprising C8aromatic isomers to provide a mixed stream in line122. The mixed stream in line122includes para-xylene, meta-xylene, ortho-xylene and ethylbenzene and may be subsequently passed to the xylene separation unit124to obtain a desired C8aromatic isomer product via a separation process. The xylene separation unit124may be one of a para-xylene separation unit, a meta-xylene separation unit or an ortho-xylene separation unit depending on the C8aromatic product desired and the operating conditions can be tailored accordingly. In accordance with an exemplary embodiment as discussed, the xylene separation unit124is a para-xylene separation unit and will be referred to as the para-xylene separation unit124for the purpose of the discussion of the instant embodiment. In accordance with the instant embodiment as discussed, the separation process operates, preferably via simulated moving adsorption bed (SMB) employing a desorbent, to provide a xylene extract stream in line126which is para-xylene extract stream comprising a mixture of para-xylene and desorbent for the instant embodiment. Examples of desorbent include, and are not limited to toluene and para-diethylbenzene. In accordance with the instant embodiment, toluene is used as the desorbent. The para-xylene extract stream in line126may be passed to the extract column130which separates para-xylene from the desorbent. A para-xylene stream in line134may be withdrawn comprising the desired para-xylenes from the extract column130. Further, a first return desorbent stream in line136is withdrawn which may be subsequently recycled to the para-xylene separation unit124. In an aspect as shown inFIG. 1, a desorbent drag stream in line132may also be withdrawn from the extract column130. In accordance with an exemplary embodiment, the desorbent drag stream in line132may comprise primarily C7−hydrocarbons and may be passed to the BT column190. In accordance with another exemplary embodiment, the desorbent drag stream in line132may be passed to the extractive distillation column172to recover additional C8naphthenes. The para-xylene stream in line134may be passed to the para-xylene column to separate the para-xylene product in line140from the heavier hydrocarbons obtained as a bottoms stream in line142which may be subsequently recycled to the aromatics rerun column114.

A raffinate stream in line128comprising non-equilibrium mixture of C8aromatics raffinate and the desorbent may be also withdrawn from the para-xylene separation unit124. The raffinate stream in line128may be passed to the raffinate column144. In accordance with an exemplary embodiment as shown inFIG. 1, a second toluene-enriched stream in line196from the BT column190may also be introduced to the raffinate column144which may act as a makeup for the toluene being used as the desorbent in the para-xylene separation process as per the instant embodiment. The raffinate column144separates a raffinate product stream in line150for isomerization in isomerization unit152from a second return desorbent stream in line146. In accordance with an exemplary embodiment as shown inFIG. 1, the first desorbent rerun in line136and the second desorbent rerun stream in line146may combine to provide a combined desorbent rerun stream in line148which may be subsequently passed to the para-xylene separation unit124.

The raffinate product stream in line150comprising a non-equilibrium mixture of xylene isomers and ethylbenzene is introduced to the isomerization unit152to provide an isomerized stream in line154. In accordance with an exemplary embodiment as shown inFIG. 1, a recycle feedstream in line174(discussed later) from the extractive distillation column172may be recycled to the isomerization unit152. As shown, the recycle stream in line174may combine with the raffinate product stream in line150to provide a combined stream in line176which may be subsequently passed to the isomerization unit152. The raffinate product stream is isomerized in reactor152, which contains an isomerization catalyst to provide a product approaching equilibrium concentrations of C8aromatic isomers. In accordance with the instant embodiment as discussed for producing para-xylenes, additional para-xylene may be produced by reestablishing an equilibrium or near-equilibrium distribution of xylene isomers. Isomerization catalysts that can be used in the present disclosure include conventional isomerization catalysts such as those disclosed in U.S. Pat. No. 6,740,788, the teachings of which are incorporated herein by reference. In accordance with an exemplary embodiment as discussed, the isomerization catalyst is an ethylbenzene (hereinafter “EB”) isomerization catalyst. An isomerized stream is withdrawn in line154from the isomerization unit152. In the instant aspect as discussed using an ethylbenzene EB isomerization catalyst, the conversion of ethylbenzene to additional xylenes takes place via a C8naphthene intermediate. Also, toluene may be produced as a byproduct in the isomerization process. Accordingly, the isomerized stream154may include C8naphthenes and toluene.

The isomerized stream in line154may be passed to the isomerate stripper column156to separate an isomerate stripper overhead stream comprising C6−hydrocarbons in an isomerate overhead line160from an isomerate stripper bottoms stream comprising the C8naphthenes and toluene in isomerate bottoms line162, at a first pressure. A vaporous stream in line158comprising lighter ends may also be withdrawn from the isomerate stripper column156and passed to a vent gas compressor and a stabilizer condenser. The isomerate stripper bottoms stream in isomerate bottoms line162may be passed to the dividing wall naphthene splitter column164for further separation. Accordingly, the dividing wall naphthene splitter column164may be in communication with the isomerate bottoms line162. In an aspect, the dividing wall naphthene splitter column164is in direct, downstream communication with the isomerate bottoms line162. Referring now toFIG. 2illustrating the dividing wall naphthene splitter column164according to a representative embodiment of the invention. As illustrated, a vertically elongated dividing wall12, located substantially centrally in the interior of the column164, separates a significant portion of the column interior, along the column height, into a feed section14and a product section16. For simplicity, conventional vapor-liquid contacting devices such as trays or packing materials are not shown, although these contacting devices are present throughout feed and product sections14,16, where they extend across only a portion of the column diameter in these respective sections. Such contacting devices are also generally present in a common upper section18which may be positioned above dividing wall12. Accordingly, the dividing wall naphthene splitter column164includes or more vapor-liquid contacting stages and includes the dividing wall12having an upper end12U and a lower end12L that divides the naphthene splitter column into the feed section14and the product section16. In accordance with an exemplary embodiment as shown inFIG. 2, the lower end12L of the dividing wall12extends to a last stage of the one or more vapor-liquid contacting stages. As shown inFIG. 2, the feed section14of the dividing wall naphthene splitter column may be in communication with the isomerate bottoms line162.

An overhead naphthene splitter stream in line166comprising the C8naphthenes and toluene is separated from the naphthene splitter bottoms stream in line170comprising C8+aromatic hydrocarbons in the dividing wall naphthene splitter column164, at a second pressure. In accordance with an exemplary pressure, the second pressure is greater than the first pressure. Accordingly, in an aspect, the dividing naphthene splitter column164operates at a higher pressure than the isomerate stripper column156. Further, the naphthene splitter sidedraw stream in line168comprising C8aromatic isomers is also withdrawn which may be subsequently passed to the para-xylene separation unit124for further processing as discussed above. In various embodiments, the overhead naphthene splitter stream in line166, the naphthene splitter sidedraw stream in line168and the naphthene splitter bottoms stream in line170may be in downstream communication with the product section16of the dividing wall naphthene splitter column164. In accordance with various embodiments, the overhead naphthene splitter stream in line166comprises a majority of the C8naphthenes present in the isomerized stream and the naphthene splitter sidedraw stream in line168comprises majority of the C8aromatic isomers present in the isomerized stream. Additionally, the naphthene splitter sidedraw stream in line168comprises heavier hydrocarbon compounds such as C9+alkylaromatic hydrocarbons which may slip into the naphthene splitter sidedraw stream as contaminants. In conventional columns, a naphthene splitter sidedraw stream may comprise about 2 wt % of C9+alkylaromatic hydrocarbons. However, applicants have found that using the dividing wall naphthene splitter column as described in the present disclosure, the amount of C9+hydrocarbons slipping into the naphthene splitter sidedraw streams are significantly reduced. In accordance with an exemplary embodiment according to the present disclosure, the naphthene splitter sidedraw stream in line168may comprise less than about 1 wt % of C9+alkylaromatic hydrocarbons. In another aspect, the naphthene splitter sidedraw stream in line168may comprise less than about 0.7 wt % of C9+alkylaromatic hydrocarbons. In yet another aspect, the naphthene splitter sidedraw stream in line168may comprises between about 0.5 wt % to about 1 wt % of C9+alkylaromatic hydrocarbons. Applicants have found that the risk of heavy boiling components slipping into the naphthene splitter sidedraw stream is reduced due to the location of the side draw in the divided wall column as compared to a conventional side draw column. As shown, the feed is on the pre fractionation side i.e. the feed section14of the dividing wall12and the side draw is on the product side i.e. the product section16, thereby inherently mitigating the risk of contamination of the feed to para-xylene unit.

In various embodiments, the para-xylene separation unit124may be in downstream communication with the product section16of the dividing wall naphthene splitter column via the naphthene splitter sidedraw line168. The column is designed and operated such that the liquid flowing downward through the product section of the column is intercepted by a substantially imperforate tray20extending across a midsection of the product section16of the column in an exemplary vapor-liquid contacting stage. The tray20has a liquid collection well22in which a quantity of this descending liquid is collected. The level of the liquid in this well may be monitored by a controller not illustrated. A stream of the collected liquid is withdrawn from the liquid collection well22as the naphthene splitter sidedraw stream in line168. The trap out tray located in a central region of the product section of the dividing wall naphthene splitter column also contains a vapor chimney24to allow the upward passage of vapor through the product section. An overflow weir may also be provided on this trap out tray, with this weir allowing liquid in excess of that required for the generation of the side product stream of line168to overflow the weir and to continue downward to the remainder of the product section.

Further, bottom half of the column shows another exemplary vapor-liquid contacting stage comprising a tray26. In accordance with an exemplary embodiment as shown inFIG. 2, the vapor-liquid contacting stage comprising the tray26is the last vapor-liquid contacting stage of the dividing wall naphthene splitter column164. Accordingly, no stage exists below this stage. Further, as shown, the lower end12L of the dividing wall12extends to tray26of the last vapor-liquid contacting stage. The instant vapor-liquid contacting stage further includes two liquid collection wells28and30in which the descending liquid is collected. A portion of this descending liquid may be withdrawn as the naphthene splitter bottoms stream in line170. Further, one or more reboilers comprising a first reboiler32and a second rebolier34are in communication with the liquid collection wells28and30respectively, to vaporize and send a portion of a bottoms stream back to the bottom of the column. In accordance with an exemplary embodiment, vapor coming from each of the reboiler32and34is controlled using a vapor control mechanism so that the vapor is evenly distributed close to the amount needed for the overall column. Accordingly, constant vapor fractions are provided to each side of the dividing wall naphthene splitter column164.

Another exemplary vapor-liquid contacting stage is shown in the upper half of the column comprising a tray36. The tray36has a liquid collection well38in which a quantity of the descending liquid is collected. The level of the liquid in this well may be monitored by a controller not illustrated. A stream of the collected liquid is withdrawn from the liquid collection well38in line40. As shown inFIG. 2, liquid conduits40a,40bare used to provide liquid flow from liquid collection well38to both feed and product sections14,16on opposite sides of dividing wall12. Both liquid conduits40a,40b, which provide fluid communication to feed and product sections14,16, are shown inFIG. 1as being external to the column and thereby readily controlled using control valves and flow measurement systems (not shown). Material in liquid conduits,40aand/or40b, may be conveyed to feed and product sections14,16using pumps (not shown) or otherwise via gravity in the case of a free draining system. The trays in the dividing wall naphthene splitter column164are high performance trays. The high performance trays can accommodate more vapor and liquid than conventional trays. Suitable high performance trays include, but are not limited to, UOP MD™ trays.

Referring back toFIG. 1, the overhead naphthene splitter stream in line166may be passed to the extractive distillation column172. Accordingly, the extractive distillation column172may be in communication with the naphthene splitter overhead line166. In an aspect, the extractive distillation column172may be in direct, downstream communication with the naphthene splitter overhead line166. In an aspect, the extractive distillation column172is in downstream communication with the naphthene splitter overhead line from the product section16of the dividing wall naphthene splitter column164. Extractive distillation is a technique for separating mixtures of components having nearly equal volatility and having nearly the same boiling point. In extractive distillation, a solvent is introduced into a main extractive-distillation column above the entry point of the hydrocarbon-containing fluid mixture that is to be separated. The solvent affects the volatility of the hydrocarbon-containing fluid component boiling at a higher temperature differently than the hydrocarbon-containing fluid component boiling at a lower temperature sufficiently to facilitate the separation of the various hydrocarbon-containing fluid components by distillation and such solvent exits with the bottoms fraction. The extractive distillation process in extractive distillation column172takes place in the presence of a solvent and separates C8naphthenes in a recycle feedstream in the recycle line174from an extract stream comprising the C7aromatic hydrocarbons and the solvent withdrawn in an extract line178. Suitable solvents include tetrahydrothiophene 1,1-dioxide (or sulfolane), NFM (n-formylmorpholine), NMP (n-methylpyrrolidone), diethylene glycol, triethylene glycol, tetraethylene glycol, methoxy triethylene glycol, and mixtures thereof. Other glycol ethers may also be suitable solvents alone or in combination with those listed above. The recycle feedstream in line174may be passed to the isomerization unit152and processed together with raffinate product stream in line150as discussed above. The extract stream in line178may be sent to a solvent-recovery column for the separation of the solvent from the C7aromatic hydrocarbons. In accordance with an exemplary embodiment as shown inFIG. 1, the extract stream is passed to the aromatics extraction unit180.

Referring back to the reformate splitter column104, the reformate overhead stream in line106comprising C7−aromatic hydrocarbons may be passed to the aromatics extraction unit180. The aromatics extraction unit180can comprise different methods of separating aromatics from a hydrocarbon stream. One industry standard is the Sulfolane™ process, which is an extractive distillation process utilizing sulfolane to facilitate high purity extraction of aromatics. The Sulfolane™ process is well known to those skilled in the art. An aromatics extract stream in line184comprising benzene and toluene and a raffinate stream in line182comprising non-aromatic hydrocarbons may be withdrawn from the aromatics extraction unit180. The aromatics extract stream in line184may be passed to the BT column190to provide benzene and toluene via separation. In accordance with an exemplary embodiment as shown inFIG. 1, the aromatics extract stream in line184may be passed through a clay treater186to treat residual olefin contaminants and provide a treated aromatics extract stream in line188prior to being passed to the BT column190. A transalkylation bottom stream in line208from the transalkylation stripper column204may also be passed to the BT column190. A benzene-enriched stream in line192, a first toluene-enriched stream in line194and the second toluene-enriched stream in line196are withdrawn from the BT column190. Further, the BT column bottoms stream in line198is withdrawn and sent to the aromatics rerun column114for further processing as discussed above. The second toluene-enriched stream in line196may be passed to the raffinate column144as also discussed above. The first toluene-enriched stream in line194may be passed to the transalkylation unit200for production of additional xylenes and benzene.

In accordance with an exemplary embodiment as shown inFIG. 1, in addition to first toluene-enriched stream, the aromatic rerun column sidedraw stream in line118rich in C9and C10alkylaromatics may be passed to the transalkylation unit200along with a heavy aromatics column overhead stream in line220rich in C9and C10alkylaromatics from the heavy aromatics column218. In accordance with an exemplary embodiment as shown inFIG. 1, the aromatic rerun column sidedraw stream in line118and the heavy aromatics column overhead stream in line220combine to provide a mixed alkylaromatic feedstream in line224, which may be subsequently provided to the transalkylation unit200. A make-up hydrogen gas stream (not shown) may also be provided to the transalkylation unit200. In the transalkylation unit200, the incoming feedstreams may be contacted with a transalkylation catalyst under transalkylation conditions. In the transalkylation unit200, the process continues by transalkylating C9and C10alkylaromatics with toluene. A transalkylated stream in line202comprising benzene and xylenes may be withdrawn from the transalkylation unit200.

Transalkylation catalysts that can be used in the present disclosure include conventional transkylation catalysts such as those disclosed in U.S. Pat. No. 6,740,788, the teachings of which are incorporated herein by reference. Conditions employed in the transalkylation unit200normally include a temperature of from about 200° C. to about 540° C. The transalkylation unit200is operated at moderately elevated pressures broadly ranging from about 1 kg/cm′ to about 60 kg/cm2. The transalkylation reaction can be effected over a wide range of space velocities, with higher space velocities affecting a higher ratio of para-xylene at the expense of conversion. Liquid hourly space velocity generally is in the range of from about 0.1 to about 20 hr−1.

The transalkylated stream in line202may be sent to transalkylation stripper204to recover the transalkylation stripper bottoms stream in line208. Light ends may be removed in transalkylation stripper overhead stream in line206and a net overhead stream in line210comprising C6and lighter hydrocarbons may also be withdrawn from the transalkylation stripper204. Subsequently, the transalkylation stripper bottoms stream in line208may be recycled to the BT column190to recover benzene product and unconverted toluene for further processing as previously described. The net overhead stream in line210may be passed to the stabilizer212to provide a stabilizer overhead vaporous stream in line214and a stabilizer bottoms stream in line216. The stabilizer bottoms stream in line216may be passed to the aromatics extraction unit180.

Referring back to the aromatic rerun column114, net bottoms rerun column stream in line120rich in C9and heavier alkylaromatic hydrocarbons is passed to the heavy aromatics column218to separate heavy aromatics comprising C11+alkylaromatic hydrocarbons from C9and C10alkylaromatics recovered as the heavy aromatics column overhead stream in line220. The C11+alkylaromatic hydrocarbons may be withdrawn from the heavy aromatics column218as a bottoms stream in line222. The heavy aromatics column overhead stream in line220rich in C9and C10alkylaromatics may be passed to the transalkylation unit200for production of additional xylenes and benzene as previously described.

SPECIFIC EMBODIMENTS

A first embodiment of the invention is an apparatus for producing para-xylene, wherein the apparatus comprises a) an isomerization unit to provide an isomerized stream; b) an isomerate stripper column in communication with the isomerization unit to provide an isomerate stripper overhead stream comprising C6−hydrocarbons in an isomerate overhead line and an isomerate stripper bottoms stream in an isomerate bottoms line; c) a dividing wall naphthene splitter column in communication with the isomerate bottoms line to provide an overhead naphthene splitter stream comprising the C8naphthenes and C7aromatic hydrocarbons in a naphthene splitter overhead line and a naphthene splitter sidedraw stream comprising C8aromatic isomers in a naphthene splitter sidedraw line; and d) an extractive distillation column in communication with the naphthene splitter overhead line to provide a recycle feedstream comprising the C8naphthenes in a recycle line and an extract stream comprising the C7aromatic hydrocarbons in an extract line. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the dividing wall naphthene splitter column comprises a dividing wall having an upper end and a lower end that divides the naphthene splitter column into a feed section and a product section. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the dividing wall naphthene splitter column comprises one or more vapor-liquid contacting stages. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the lower end of the dividing wall extends to a last stage of the one or more vapor-liquid contacting stages. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the feed section of the dividing wall naphthene splitter column is in downstream communication with the isomerate bottoms line. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising a para-xylene separation unit in downstream communication with the product section of the dividing wall naphthene splitter column via the naphthene splitter sidedraw line. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the para-xylene separation unit being a simulated moving bed adsorption unit using toluene as a desorbent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the extractive distillation column in is downstream communication with the naphthene splitter overhead line from the product section of the dividing wall naphthene splitter column. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph further comprising an aromatics rerun column in downstream communication with a naphthene splitter bottoms line from the product section of the dividing wall naphthene splitter column.

A second embodiment of the invention is an apparatus for producing para-xylene, wherein the apparatus comprises a) an isomerization unit to provide an isomerized stream; b) an isomerate stripper column in communication with the isomerization unit to provide an isomerate stripper overhead stream comprising C6−hydrocarbons in an isomerate overhead line and an isomerate stripper bottoms stream in an isomerate bottoms line; c) a dividing wall naphthene splitter column having one or more vapor-liquid contacting stages comprising a dividing wall having an upper end and a lower end that divides the naphthene splitter column into a feed section and a product section and the lower end of the dividing wall extends to a last stage of the one or more vapor-liquid contacting stages, the dividing wall naphthene splitter being in communication with the isomerate bottoms line to provide an overhead naphthene splitter stream comprising the C8naphthenes and C7aromatic hydrocarbons in a naphthene splitter overhead line and a naphthene splitter sidedraw stream comprising C8aromatic isomers in a naphthene splitter sidedraw line; and d) an extractive distillation column in communication with the naphthene splitter overhead line to provide a recycle feedstream comprising the C8naphthenes in a recycle line and an extract stream comprising the C7aromatic hydrocarbons in an extract line. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the feed section of the dividing wall naphthene splitter column is in communication with the isomerate bottoms line. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a para-xylene separation unit in downstream communication with the product section of the dividing wall naphthene splitter column via the naphthene splitter sidedraw line. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the para-xylene separation unit being a simulated moving bed adsorption unit using toluene as a desorbent. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the extractive distillation column in is downstream communication with the naphthene splitter overhead line from the product section of the dividing wall naphthene splitter column. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising an aromatics rerun column in downstream communication with a naphthene splitter bottoms line from the product s of the dividing wall naphthene splitter column.

A third embodiment of the invention is a process for the production of para-xylene, wherein the process comprises a) introducing a raffinate product stream comprising C8aromatic isomers to an isomerization unit to provide an isomerized stream, wherein the isomerized stream is produced in the presence of an ethylbenzene (EB) isomerization catalyst; b) passing the isomerized stream to an isomerate stripper column to provide an isomerate stripper overhead stream comprising C6−hydrocarbons and an isomerate stripper bottoms stream; c) passing the isomerate stripper bottoms stream to a dividing wall naphthene splitter column to provide a naphthene splitter sidedraw stream comprising C8aromatic isomers and less than about 1 wt % of C9+alkylaromatic hydrocarbons; d) passing the overhead naphthene splitter stream to an extractive distillation column to provide a recycle feedstream comprising the C8naphthenes and an extract stream comprising the C7aromatic hydrocarbons; and e) passing the recycle feedstream to the isomerization unit. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the naphthene splitter sidedraw stream comprises less than about 0.7 wt % of C9+alkylaromatic hydrocarbons. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the dividing wall naphthene splitter column comprises a dividing wall having an upper end and a lower end that divides the naphthene splitter column into a feed section and a product section. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the dividing wall naphthene splitter column comprises one or more vapor-liquid contacting stages. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the lower end of the dividing wall extends to a last stage of the one or more vapor-liquid contacting stages.