The invention relates to a process and apparatus for producing paraxylene including xylene isomerization.
The xylene isomers are important intermediates, which find wide and varied application in chemical syntheses. By way of example, paraxylene (PX) is a feedstock for terephthalic acid which finds use in the manufacture of synthetic fibers; metaxylene (MX) is used in the manufacture of dyes, and orthoxylene (OX) is used as a feedstock for phthalic anhydride, which finds use in the manufacture of plasticizers.
Xylenes are found in various fractions such as coal tar distillate, petroleum reformates and pyrolysis liquids in admixture with other compounds of like boiling points. The aromatic components are readily separated from non-aromatics by methods such as solvent extraction. A fraction consisting essentially of C8 aromatics may then be obtained readily such as by distillation. “C8 aromatics” means aromatic hydrocarbons having 8 carbon atoms, including particularly ethylbenzene and the xylene isomers paraxylene (p-xylene or PX), orthoxylene (o-xylene or OX), and metaxylene (m-xylene or MX).
While difficult to separate, due to their similar chemical structures, physical properties, and identical molecular weights, there are various methods used to separate the C8 isomers. For instance, orthoxylene is separable from other C8 aromatics by fractional distillation, and paraxylene is separable from other C8 aromatics by fractional crystallization or selective adsorption. Present demand is largely for paraxylene and it is desirable to convert metaxylene, the principal xylene present in the feed stream, and also orthoxylene, to paraxylene, to meet the market demand. At ordinary temperatures at which xylenes are processed in a typical petrochemical plant, the thermodynamic equilibrium content is approximately 24 mol % paraxylene, 56 mol % metaxylene, and 20 mol % orthoxylene, based on the total amount of xylenes in the feed.
Fractional crystallization is a method of separating components of a mixture and takes advantage of the differences between the freezing points and solubilities of the components at different temperatures. Due to its relatively higher freezing point, paraxylene can be separated as a solid from a C8 aromatic stream by fractional crystallization while the other components are recovered in a paraxylene-depleted filtrate stream. High paraxylene purity, a key property needed for satisfactory conversion of paraxylene to terephthalic acid and terephthalate esters, can be obtained by this type of fractional crystallization. U.S. Pat. No. 4,120,911 provides a description of this method. Commercially available fractional crystallization processes and apparatus include the crystallization isofining process, the continuous countercurrent crystallization process, direct CO2 crystallizer, and scraped drum crystallizers. Due to high utility usage and the formation of a eutectic between paraxylene and metaxylene, it is usually more advantageous to use a feed with as high an initial paraxylene concentration as possible when using fractional crystallization to recover paraxylene.
An alternative xylene separation method uses molecular sieves, such as zeolites, to selectively adsorb paraxylene from a C8 aromatic feedstream to form a paraxylene-depleted effluent. The adsorbed paraxylene can then be desorbed by various ways such as heating, lowering the paraxylene partial pressure or stripping. (See generally U.S. Pat. Nos. 3,706,812, 3,732,325, and 4,886,929). Two commercially available processes, using molecular sieves to adsorb paraxylene are the PAREX™ and ELUXYL™ processes. In such molecular-sieve based adsorption processes, a higher amount of paraxylene, typically over 90%, compared with that from a fractional crystallization process, typically below 65%, may be recovered from the paraxylene present in a particular feed.
Paraxylene plants that employ both adsorption and crystallization units for paraxylene recovery often suffer from the problem of low energy efficiency and high material loss. This is mainly due to the crystallization unit's relatively low recovery of paraxylene, which produces a filtrate stream that contains a level of paraxylene in the range of 10 to 15 wt %. The liquid filtrate stream is subsequently processed in an energy-intensive vapor-phase isomerization unit to raise the paraxylene concentration to the equilibrium concentration of about 24 wt %.
In
Continuing to refer to the prior art process shown in
Continuing with the system shown in
Another prior art process for paraxylene production that employs both selective adsorption and crystallization for paraxylene recovery is shown in
Continuing to refer to the prior art process shown in
Known technologies integrate vapor phase xylene isomerization and liquid phase xylenes isomerization in paraxylene separation and isomerization loops. For example, U.S. Patent Publication No. 2012/0108868 describes separating paraxylene depleted (C8 aromatics) stream from paraxylene recovery through a parallel configuration of vapor phase xylene isomerization and liquid phase xylenes isomerization. U.S. Pat. No. 7,439,412 teaches using an isomerization unit under liquid phase conditions in order to recover one or more high purity xylene isomers, In an example, the product of the liquid phase isomerization unit is returned to the first fractionation tower in the system. See also U.S. Pat. No. 7,626,065. Similarly, U.S. Pat. No. 8,697,929 is directed to a xylenes isomerization process, including a liquid phase isomerization, for the production of equilibrium or near-equilibrium xylenes.
Due to the demand for paraxylene, there is an ongoing need for new processes and modifications to existing processes which significantly reduce energy consumption and prevents material loss.
The invention is directed to a paraxylene production process and an apparatus for performing the process, in which a selective adsorption unit and a crystallization unit are operated in parallel to produce two separate paraxylene-enriched streams and two separate paraxylene-depleted streams. At least a portion of the paraxylene-depleted stream from the crystallization unit is sent to a liquid isomerization unit, rather than a vapor isomerization unit, to save energy and prevent material loss. The remainder of the paraxylene-depleted stream from the crystallization unit and the paraxylene-depleted stream from the selective adsorption unit is sent to vapor phase isomerization.
In embodiments, both the adsorption unit and the crystallization unit are fed from the overhead of the same fractionation unit. In other embodiments, the adsorption unit and the crystallization unit are fed from two separate fractionation units.
In embodiments, at least a portion of the liquid-phase isomerized product containing xylenes at equilibrium or near-equilibrium is then recycled to the crystallization unit. In other embodiments, at least a portion of the liquid-phase isomerized product containing xylenes at equilibrium or near-equilibrium is recycled to the initial fractionation.
It is an object of the invention to significantly reduce energy consumption by increasing the crystallization unit's recovery of paraxylene and utilizing liquid phase isomerization to isomerize at least a portion of the filtrate stream to produce an isomerized product containing xylenes at equilibrium or near-equilibrium.
These and other objects, features, embodiments and advantages will become apparent as reference is made to the following detailed description, preferred embodiments, examples, and appended claims.
In the accompanying drawings, like reference numerals are used to denote like parts.
According to the invention, an adsorption unit and a crystallization unit are operated in parallel to each produce a paraxylene-enriched stream and a paraxylene-depleted stream, followed by vapor phase isomerization of at least a portion of each of the paraxylene-depleted streams. The improvement includes introducing at least a portion of the paraxylene-depleted stream from the crystallization unit to a liquid phase isomerization unit to produce an isomerized product containing xylenes at equilibrium or near-equilibrium, which may be recycled directly to the crystallization unit. Sending at least a portion of the paraxylene-depleted filtrate from the crystallization unit to liquid phase isomerization, rather than vapor phase isomerization, saves energy and prevents material loss by avoiding the vaporization of the filtrate. Additionally, the liquid-phase isomerized product may be recycled to the crystallization unit rather than a fractionation unit, further saving energy and preventing material loss.
The invention may be better understood by reference to specific embodiments illustrated in
The feed stream(s) to the system shown in
In the flow configuration or schematic shown in
In another embodiment shown in
Regarding separation of xylenes in the paraxylene recovery, two preferred methods are fractional crystallization and selective adsorption, the details of which are per se known in the art. See U.S. Pat. No. 7,439,412, and references cited in the Background section. Likewise, the details of vapor phase xylenes isomerization and liquid phase xylenes isomerization are also per se known in the art. In this regard, see for example, U.S. Pat. No. 6,180,550.
An apparatus for the production of paraxylene according to the inventive process comprises at least one fractionation unit fluidly connected to a selective adsorption unit and a crystallization unit. In one preferred embodiment, one fractionation unit is connected to both the adsorption unit and crystallization unit such that the overhead from the fractionation unit is split, with one portion passing to the selective adsorption unit and another portion passing to the crystallization unit. In another preferred embodiment, a first fractionation unit is fluidly connected to provide an overhead to the adsorption unit and a second fractionation unit is fluidly connected to provide an overhead to the crystallization unit.
The adsorption unit and crystallization unit are fluidly connected to a vapor phase isomerization unit. The crystallization unit is also fluidly connected with a liquid phase isomerization unit to allow at least a portion of a paraxylene-depleted filtrate from the crystallization unit to pass to the liquid phase isomerization unit to produce a liquid phase isomerate recycle and the liquid phase isomerate recycle to pass back to the crystallization unit. The liquid phase isomerization unit is also in fluid communication with at least one of the fractionation units.
Non-limiting aspects and/or embodiments of the present disclosure:
A process for producing paraxylene in which a first C8 aromatics stream is passed through a selective adsorption unit to produce a first paraxylene-enriched stream and a paraxylene-depleted raffinate stream and a second C8 aromatics stream is passed through a crystallization unit to produce a second paraxylene-enriched stream and a paraxylene-depleted filtrate stream wherein at least a portion of the paraxylene-depleted raffinate stream and at least a portion of the paraxylene-depleted filtrate stream is passed through a vapor phase isomerization unit to produce a first isomerized stream, the improvement comprising introducing a second portion of the paraxylene-depleted filtrate stream to a liquid phase isomerization unit to produce a second isomerized product containing xylenes at equilibrium or near-equilibrium.
The process of Embodiment 1, wherein the first and second C8 aromatic streams are split from the overhead of a single fractionation unit.
The process of Embodiment 1, wherein the first C8 aromatics stream is the overhead of a first fractionation unit and second C8 aromatics stream is the overhead of a second fractionation unit.
The process of any one of Embodiments 1-3, wherein the second isomerized product is recycled to the crystallization unit.
The process of Embodiment 2, wherein a portion of the second isomerized product is recycled to the single fractionation unit.
The process of Embodiment 3, wherein a portion of the second isomerized product is recycled to at least one of the fractionation units.
The process of any one of Embodiments 1-6, wherein the first isomerization product passes to a detoluenization fractionation unit to produce an isomerate recycle stream.
The process of Embodiment 7, wherein at least a portion of the isomerate recycle stream is sent to a single fractionation unit to provide an overhead which split into the first and second C8 aromatics streams.
The process of Embodiment 7, wherein a first portion of the isomerate recycle stream is sent to a first fractionation unit to provide overhead which is the first C8 aromatics stream, and a second portion of the isomerate recycle stream is sent to a second fractionation unit to provide an overhead which is the second C8 aromatics stream.
A process for producing paraxylene comprising: (a) passing a first C8 aromatic stream to a selective adsorption unit to produce a paraxylene-enriched stream and a paraxylene-depleted raffinate stream; (b) isomerizing the paraxylene-depleted raffinate stream in a vapor phase isomerization unit; (c) passing a second C8 aromatic stream to a crystallization unit to produce a paraxylene-enriched stream and a paraxylene-depleted filtrate stream; (d) isomerizing a first portion of the paraxylene-depleted filtrate stream in a liquid phase isomerization unit to produce an isomerized product; (e) recycling the isomerized product to the crystallization unit; and (f) passing a second portion of the paraxylene-depleted filtrate stream to the vapor phase isomerization unit.
The process of Embodiment 10, wherein the first and second C8 aromatics streams in steps (a) and (c) are split from the overhead of a single fractionation unit.
The process of Embodiment 10 or Embodiment 11, wherein the first and second C8 aromatics streams in steps (a) and (c) are the overheads of two separate fractionation units.
The process of Embodiment 11, wherein a portion of the isomerized product is recycled to the single fractionation unit.
The process of Embodiment 12, wherein a portion of the isomerized product is recycled to at least one of the two separate fractionation units.
An apparatus for the production of paraxylene comprising an adsorption unit and a crystallization unit fluidly connected to a vapor phase isomerization unit, wherein the crystallization unit produces a paraxylene-depleted filtrate, the improvement comprising a liquid phase isomerization unit fluidly connected with the crystallization unit, whereby at least a portion of the paraxylene-depleted filtrate is passed to in the liquid phase isomerization unit to produce a liquid phase isomerate recycle.
The apparatus of Embodiment 15, wherein the liquid phase isomerization unit is fluidly connected to the crystallization unit so as to provide the liquid phase isomerate recycle to the crystallization unit.
The apparatus of Embodiment 15 or Embodiment 16, including at least a first fractionation unit fluidly connected to provide an overhead to the adsorption unit and at least a second fractionation unit fluidly connected to provide an overhead to the crystallization unit, wherein the liquid phase isomerization unit is fluidly connected so as to provide the liquid phase isomerate recycle to at least one of the fractionation units.
The apparatus of Embodiment 15 or Embodiment 16, including a fractionation unit fluidly connected to provide a portion of an overhead to the adsorption unit and the crystallization unit, wherein the liquid phase isomerization unit is fluidly connected so as to provide the liquid phase isomerate recycle to the fractionation unit.
While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessary illustrated herein. All references cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with the invention and for all jurisdictions in which such incorporation is permitted.
This application claims the priority of U.S. Provisional Application No. 61/866,288, filed Aug. 15, 2013, the disclosure of which is incorporated herein by reference in its entirety.
Number | Date | Country | |
---|---|---|---|
61866288 | Aug 2013 | US |