RECOVERY OF AROMATIC HYDROCARBONS USING LUBRICATING OIL CONDITIONED MEMBRANES

Abstract: Selectively permeable separation of aromatic hydrocarbons from non-aromatic hydrocarbons in a feed stream is accomplished using improved asymmetric membranes. The preferred membranes are fashioned from a polyimide and conditioned with a lubricating oil. Feed streams containing a mixture of aromatic and non-aromatic hydrocarbons are contacted with the dense active layer side of the polyimide membrane under a pressure and temperature sufficient to selectively permeate the desired aromatic hydrocarbon.

Description: RECOVERY OF AROMATIC HYDROCARBONS USING LUBRICATING OIL CONDITIONED MEMBRANES The present invention relates a method of using membranes for the separation of aromatic hydrocarbons from non-aromatic hydrocarbons. Of particular interest, the membranes are useful for the recovery of aromatic hydrocarbons, e.g. toluene, having a high purity from process streams containing aromatic and non-aromatic hydrocarbons in a commercial process for the production of aromatic hydrocarbons. Aromatic hydrocarbons (benzene, toluene, xylenes, naphthalenes etc.) serve as important precursors in the production of petrochemicals such as nylon, polyurethanes, polyesters, resins, plasticizers and intermediates. These petrochemicals are for the most part commodities, where the product conforms to a common specification with limited opportunity for differentiation. A key to profitability in the petrochemical industry is to create and maintain a sustainable cost advantage over competitors. The cash cost of production is a critical factor, of which a significant portion is related to raw materials cost and utilities. While there is in principle no shortage of aromatics feed for production of petrochemicals, the cost of feed can vary significantly depending on the source of the feed. For example, a traditional way to recover high-purity aromatics is distillation, followed by liquid/liquid extraction, followed by further distillation. The liquid/liquid extraction step is expensive, due in part to the costs involved in purchase and recovery of the extraction solvent. A lower-cost alternative is to avoid the extraction step, and recover aromatics via distillation alone. However, distilled feeds contain co-boiling non- aromatics and other impurities that may impact yields and operations of the subsequent conversion process. The separation of aromatics from non-aromatics is useful in upgrading aromatics-containing streams in petroleum refineries, such streams including naphtha streams (such as heavy catalytic naphtha, intermediate catalytic naphtha), light aromatic streams such as BTX, refinery and petrocemical plant streams containing naphthalenes such as the substituted naphthalenes, e.g. methyl naphthalenes and higher alkylnaphthalenes, for example, refinery cycle oil streams such as light cycle oil (LCO), cracker streams and reformate streams, and in chemical operations for the recovery of aromatics such as benzene, toluene, xylenes, naphthalene, etc. The use of membranes to separate aromatics from saturates has long been pursued by the scientific and industrial community. Methods of membrane separation include hyperfiltration, also known as reverse osmosis (RO) in aqueous separations, pervaporation and perstraction. Pervaporation relies on vacuum on the permeate side to evaporate the permeate from the surface of the membrane and maintain the concentration gradient driving force which drives the separation process. In perstraction, the permeate molecules in the feed diffuse into the membrane film, migrate through the film and reemerge on the permeate side under the influence of a concentration gradient. A sweep flow of liquid or gas is used on the permeate side of the membrane to maintain the concentration gradient driving force. In contrast, hyperfiltration does not require the use of external forces on the permeate side of the membrane, but drives the separation through application of a pressure gradient across the membrane. Early work with hyperfiltration or reverse osmosis, using cellulose acetate and polyethylene films showed some aromatics enrichment but at low membrane fluxes (Sourirajan, S., Reverse Osmosis, Academic Press, 1970). Subsequent studies demonstrated that the separation potential of a pervaporation system is much higher than that of RO (Rautenbach, R. and Albrecht, R, Journal of Membrane Science, 25, 1-54, 1985). Membrane separation of aromatics from saturates has been the subject of numerous patents. U.S. Patent No. 3,370,102 discloses a general process for separating a feed into a permeate stream and a retentate stream and utilizes a sweep liquid to remove the permeate from the face of the membrane to thereby maintain the concentration gradient driving force. The process can be used to separate a wide variety of mixtures including various petroleum fractions, naphthas, oils, hydrocarbon mixtures, including the separation of aromatics from kerosene. U.S. Patent No. 2,958,656 discloses the separation of hydrocarbons by type, i.e., aromatic, unsaturated, saturated, by permeating a portion of the mixture through a non-porous cellulose ether membrane and removing permeate from the permeate side of the membrane using a sweep gas or liquid. Feeds include hydrocarbon mixtures, naphtha (including virgin naphtha, naphtha from thermal or catalytic cracking, etc.). U.S. Patent No. 2,930,754 discloses a method for separating hydrocarbons e.g., aromatic and/or olefins from gasoline boiling range mixtures, by the selective permeation of the aromatic through certain cellulose ester non-porous membranes. The permeated hydrocarbons are continuously removed from the permeate zone using a sweep gas or liquid. U.S. Patent No. 4,1 15,465 discloses the use of poiyurethane membranes to selectively separate aromatics from saturates via pervaporation. U.S. Patent No. 4,929,358 discloses the use of poiyurethane membranes for the separation of aromatics from non-aromatics. Permeation is suggested under pervaporation, perstraction, reverse osmosis, or dialysis conditions, however none of the experimental results reported in this patent were obtained under reverse osmosis conditions. Polyimide membranes have been used for the separation of aromatics. U.S. Patent 4,571 ,444 discloses the separation of alkylaromatics from aromatic solvents using a polyimide polymer membrane. The polyimide membrane of choice was an asymmetric polyimide polymer membrane prepared from a fully imidized, highly aromatic polyimide copolymer. Permeation was performed under reverse osmosis conditions. U.S. Patent 4,532,029 discloses the use of an asymmetric polyimide membrane for the separation of aromatics from lower aromatic middle distillate feeds. Permeation of the feeds in the presence of a light polar solvent, e.g., acetonitriie, was required to obtain permeates having a high aromatic content, i.e., greater than 86%. U.S. Patent 4,879,044 discloses a pervaporation process for separation of heavy catalytically cracked naphtha into a highly aromatic gasoline octane blending component and a low aromatic, high cetane distillate; U.S. Patents 4,944,880, 4,946,594, 5,039,418 and 5,093,003 disclose improvements to membrane stability at high temperatures and U.S. Patents 5,095,171 and 5,416,259 disclose improvements to the oxidative stability of membranes. The majority of investigations for aromatic/non-aromatic separations have involved pervaporation or perstraction separation techniques. This is probably due to reports of prior literature that very high operational pressures are required in hyperfiltration to reach an equivalent performance achievable by pervaporation and perstraction processes. Unfortunately, pervaporation and perstraction separation systems are higher cost systems than hyperfiltration systems, due to expenses associated with vacuum, refrigeration and heat transfer systems. Consequently, it is an object of this invention to provide an improved process for the separation of aromatic hydrocarbons from non-aromatic hydrocarbons under hyperfiltration conditions. The separation is particularly useful in improving the feed quality to an aromatic separation or aromatic conversion process by separating non- aromatic compounds from aromatic hydrocarbons in a feed stream containing these components. The separation is carried out by selectively permeating at least a portion of the aromatic hydrocarbons contained in the feed stream through a permselective (slectively permeable) membrane and diverting a primarily non-aromatic retentate out of the feed stream. The present invention is directed to a method of separating aromatic hydrocarbons from non-aromatic hydrocarbons in a feed stream by contacting a liquid feed stream containing a mixture of aromatic and non-aromatic hydrocarbons with a dense active layer side of an asymmetric polyimide membrane to produce a retentate stream which is relatively enriched in the non-aromatic component. In a preferred form, the membrane is treated with a lubricating oil conditioning agent. The present hyperfiltration process can be used for improving the quality of an aromatic hydrocarbon-containing feed stream to an aromatic separation or aromatic conversion process by separating non-aromatic compounds from the aromatic hydrocarbons in the feed stream by selectively permeating at least a portion of the aromatic hydrocarbons contained in the feed stream through the permselective membrane and diverting a primarily non-aromatic retentate out of the feed stream. Conversely, the process can be used to improve the feed quality to a hydrocarbon separation or conversion process which would benefit from a reduction in the concentration level of aromatics in the feed, by selectively permeating aromatics out of the feed stream by means of a permselective membrane. Asymmetric membranes have high selectivity to permeate aromatic hydrocarbons in the presence of non-aromatic hydrocarbons. Membranes used in accordance with the invention exhibit over 30% rejection of the non-aromatic hydrocarbon materials at a commercially adequate flow rate in a temperature range of -20 to 150° C. Using the preferred membranes, permselective separation of aromatic hydrocarbons from non-aromatic hydrocarbons in a feed stream may be accomplished by hyperfiltration with sufficient flux and selectivity to offer improved economics over pervaporation separation conditions. However, this the separation process is not limited to the hyperfiltration mode of operation. Additionally, a method is disclosed which enables lower quality feedstocks to be used in an aromatics conversion process without impacting its performance. This method involves the use of membrane-based separations to selectively remove non- aromatics introduced to the process with the feed. Compared to other processing options such as liquid/liquid extraction, membrane separation has the advantages of having significantly lower capital investment cost and energy requirements, and minimal operational impact on an existing conversion process. Figure 1 (Prior Art) shows a simplified schematic of a representative process without membranes. Figure 2 shows an improved process with the membrane separations unit located upstream of the reactor to process fresh feed. Figure 3 shows an improved process with the membrane separation step treating an unreacted recycle stream. Figure 4 shows an improved process with the membrane separation unit having the ability to process both the fresh feed and recycle feed. Figures 5-7 illustrate an embodiment of the use of the present invention in an aromatics separation process, and a manner of integrating the membrane separation devices of the present invention into a hybrid aromatics separation/conversion process. Figure 5 (Prior Art) illustrates a conventional aromatics separation process utilizing at least one fractionation column to separate mixed boiling point hydrocarbon components. Figure 6 shows a manner of incorporating a membrane separation unit, according to the invention, into the separation process unit of Fig. 5. Figure 7 shows an integrated hybrid aromatics separation/conversion unit, in which a membrane unit according to the present invention is used in combination with both a separation unit, as illustrated in Figs. 5 or 6, and a conversion unit, as illustrated in Figs. 1 -4. The term "aromatic" is used herein to designate a hydrocarbon-based organic compound containing one or more aromatic rings. A compound having an aromatic ring is typified by, for example, benzene. Aromatic compounds having one or more than one aromatic ring include, for example, tetrahydronaphthalene, naphthalene, anthracene, fluorene, biphenyl, pyridine, thiophene, etc. The feed to the process of the present invention is preferred to contain aromatic hydrocarbons having 1 to 2 aromatic rings. The term "non-aromatic" is used herein to designate a hydrocarbon compound having no aromatic nucleus. The term "hydrocarbon" is used to mean an organic compound having a predominately hydrocarbon character. It is contemplated within the scope of this definition that a "hydrocarbon" may contain at least one non-hydrogen or non-carbon atom (e.g. sulfur or oxygen), provided that the atom(s) does not alter the predominant hydrocarbon nature of the organic compound and/or does not react to alter the chemical properties of the membrane within the context of the present invention. A significant distinction of the present process over those of the background art is the relatively high concentration level of aromatics in the fresh feed to the membrane. As a result, a simpler hyperfiltration operation is possible and low temperatures can be used. However, in view of the relatively high aromatics concentration in the feed stream, and since the desired aromatic compounds are permeated through the membranes, it is very advantageous to utilize membranes having a high flux for aromatic compounds, in order to effectively permeate large quantities of aromatics. In contrast, the compositions which are disclosed in the background art have non-aromatics contents well above the less than 10 wt% level particularly preferred for the present process. Processes that can take advantage of this concept include any number of aromatics conversion reactions where non-aromatics contained in the feed adversely impact performance, whether by providing a pathway for undesirable secondary reactions, by affecting catalyst aging, by reducing reaction rate due to feed dilution, by affecting product purity specifications, or by increasing the traffic in downstream recovery. The inventive concept is especially advantageous for processes that limit feed aromatics conversion to achieve a desired product selectivity or purity, and utilize recycle of the unreacted feed. In these applications, non-aromatics can build to substantial levels in the recycle stream, especially if these compounds have low reactivity in the reactor and boil within the boiling range of the recycle stream. Accordingly, it is necessary to establish a purge-off of the recycle stream to control non-aromatics buildup, which if left unchecked, would ultimately reduce unit capacity. Examples of processes which may benefit from membrane separations according to the invention include aromatic isomerization, aromatic disproportionation, aromatic hydrogenation, aromatic alkylation and aromatic dealkylation. In these processes, it is desirable that non-aromatics content in the fresh feed is restricted to low levels. The membranes of the invention can be used to upgrade aromatics-containing streams in petroleum refineries and petrochemical plants, such streams including naphtha streams (such as heavy catalytic naphtha, intermediate catalytic naphtha), light aromatic streams such as BTX, refinery and petrochemical plant streams containing naphthalenes such as the substituted naphthalenes, e.g. methyl naphthalenes and higher alkylnaphthalenes, for example, refinery cycle oil streams such as light cycle oil (LCO), cracker streams and reformate streams, and in chemical operations for the recovery of aromatics such as benzene, toluene, xylenes, naphthalene, etc. The boiling ranges of such streams may vary from C5 upwards, for example, from C 5 to 165°C or higher e.g. 200°C for naphtha streams and up to 400°C for cycle oil streams, depending on the cut point used in the refinery or petrochemical plant although various fractions within these ranges may also be used. A typical full range light cycle oil stream may have a boiling range of 200° to 400°C , with light cut light cycle oils, typically with boiling ranges of 150°-345°C. with more restricted boiling range feeds from 165°-315°C or with higher initial boiling points, for example, in a 195°-315°C light cut LCO. Benefits for selective removal of non-aromatics in the feed to an aromatics conversion process can be captured in many ways. Reducing non-aromatics buildup in the recycle loop (loop traffic) reduces the overall amount of non-aromatics to the reactor, which improves product yield and selectivity and reduces catalyst aging. Reducing loop traffic also enables additional capacity to the reactor. Alternatively, a higher non-aromatics content fresh feed can be used and selective membrane rejection brings the non-aromatics level back down to required levels. This provides increased feedstock flexibility, enabling feed from extracted and purchased sources to be backed out for less expensive, unextracted feeds. In addition, increased flexibility is given to upstream reformer operations (primary source of aromatics feed to petrochemical processes) which typically need to be run at high severities to minimize formation of non-aromatics. Accordingly, the reformer may be run under less severe conditions when the membrane separation process of the present invention is in place. Furthermore, reformate fractionation specifications can be less stringent with a more relaxed non-aromatics content target in the fresh feed. Likewise, a benefit may be obtained in the use of the process of the present invention to enrich the non-aromatic concentration in the retentate stream. The enriched non-aromatic streams can be sent to subsequent processes which would benefit from reduced levels of aromatic compounds in the feedstream; e.g. solvent extraction units in lube processing plants. Additionally, other refinery or petrochemical processes involving separation and/or purification of aromatic compounds, such as distillation, crystallization, extraction, adsorption or filtration processes and apparatuses, may benefit from the use of membrane separations. For example, placing a membrane separation device upstream of a conventional distillation column, such that the membrane separation device effects a preliminary separation of aromatics from non-aromatics, will act to unload the distillation column, increasing its effective capacity and throughput, while also improving the purity of the aromatic compounds separated by the distillation step, due to reduction or elimination of co-boiling non-aromatics from the column feed stream. Also, hybrid processes involving aromatics, such as a hybrid aromatics conversion/separation process, a catalytic distillation process, or other hybrid adsorption, distillation, extraction or reforming processes, may benefit from the use of membranes according to the present invention. When used in a hybrid process with other separation technologies, the invention membrane is not required to make 100% separation of aromatics from non-aromatics, but can instead be used to perform partial separation of aromatics to complement overall separation processes. The membrane of the invention thus offers excellent efficiencies in bulk separation processes which when coupled with other more selective unit operations can offer enhanced performance. Membranes suitable for the aromatics/non-aromatics separation of the process include, but are not limited to, isotropic or anisotropic materials constructed from cellulose, poiyurethane, polyurea, polyimide, polyamide, polyester, polysulfone, polycarbonate, polyolefin, and copolymers thereof. These can be either asymmetric or composite structures. A sample of polymeric membranes and the corresponding patent reference is given below: Membrane Type US Patent cellulose and cellulose derivatives 2958656, 3299157 poiyurethane 4115465 polyurea 312376 (EP) polyurea/urethane 4879044 polyurethane-imide 4929358 polyimide 4959151 polyester-polyimide 4990275, 5241039, 5643442 polycarbonate 5019666 polsulfone 5159130 polyester-amide 5290452 fluorinated polyolefin 5396019; all of which are incorporated herein by reference. The membrane can also be prepared from inorganic materials including molecular sieves. A membrane with high productivity or flux is as critical to the present invention as having high permselectivity to aromatics. An asymmetric membrane is defined for purposes of this invention as an entity composed of a dense ultra-thin top "skin" layer over a thicker porous substructure of the same or different material. Typically, the asymmetric membrane is supported on a suitable porous backing or support material. Polyimide membranes useful in the practice of the present invention can be produced from a number of polyimide polymer sources. The identity of such polymers are presented in numerous patents. See, for example, U.S. Patent No. 4,307, 135, U.S. Patent No. 3,708,458, U.S. Patent No. 3,789,079, U.S. Patent No. 3,546, 175, U.S. Patent No. 3, 179,632, U.S. Patent No. 3, 179,633, U.S. Patent No. 3,925,21 1 , U.S. Patent No. 4,113,628, U.S. Patent No. 3,816,303, U.S. Patent No. 4,240,914, U.S. Patent No. 3,822,202, U.S. Patent No. 3,853,754 and British Patent No. 1 ,434,629, all of which are incorporated herein by reference. A preferred polyimide polymer useful to prepare the membranes of the invention is available as Matrimid 5218 from Ciba Geigy. The structure of the polyimide, Matrimid, is shown below. The polyimide is also known as the polymer with 1 (or 3)-(4-aminophenyl)-2,3-dihydro-1 ,3,3 (or 1 ,1 ,3)-trimethyl-1 H-inden-5-amine and 5,5'-carbonylbis-1 ,3-isobenzofurandione repeating groups (CAS Number 62929-02-6). A common name for Matrimid is the polymer with 5(6)-amino-1 -(4'-aminophenyl)-1 , 3,3-trimethylindane and benzophenone tetracarboxylic dianhydride repeating groups: Matrimid 5218 Most preferably, the membranes of the invention are prepared from a polyimide polymer described in U.S. Patent No. 3,708,458, assigned to Upjohn. Another polyimide polymer useful in preparing preferred membranes of the present invention is available from HP Polymers, Inc., Lewisvilie, TX as Lenzing P84, which is a copolymer derived from the co-condensation of benzophenone 3,3',4,4'-tetracarboxylic acid dianhydride (BTDA) and a mixture of di(4-aminophenyl) methane and toluene diamine or the corresponding diisocyanates, 4,4'-methyienebis(phenyl isocyanate) and toluene diisocyanate. The obtained copolyimide has imide linkages and may be represented by the following repeating structural formulae: AND Lenzing P84 in which the copolymer comprises from 10 to 90% I and 90 to 10% II, preferably 20% I and 80% II. Another polyimide useful to prepare a membrane in accordance with the invention is a polymer, available from HP Polymers, Inc., Lewisvilie, TX as Lenzing P84 HT. The polymer is the co-condensation product of 1 H,3H-Benzo[1 ,2-c:4,5- c']difuran-1 ,3,5,7-tetrone with 5,5'-carbonylbis[1 ,3-isobenzofurandione], 1 ,3- diisocyanato-2-methylbenzene and 2,4-diisocyanato-1-methylbenzene. The repeating groups in the structure of the polyimide are shown below. AND Lenzing P84 HT The polyimide membranes can be made by dissolving the desired polyimide polymer in a solvent to give a viscous, polymer dope solution, spreading the solution upon a porous support to form a film, partially evaporating the solvent, and quenching the film in water. This precipitates the polymer and forms an asymmetric membrane by the phase inversion process. The polyimide polymer dope solution is prepared by dissolving the polyimide polymer in one or a mixture of the following water-miscible solvents: N-methyl-2- pyrrolidone, hereinafter referred to as NMP, tetrahydrofuran, hereinafter referred to as THF, N,N-dimethylformarnide, hereinafter referred to as DMF, dioxane, γ- butyrolactone, water, alcohols, ketones, and formamide. The weight percent of the polyimide polymer in solution may range from 12% to 30% in the broadest sense, although a 18% to 28% range is preferable and a 20% to 26% range will produce the best results. Additives such as viscosity enhancers may be present in amounts up to 10% by weight of the the polyimide polymer dope solution and these include polyvinyl pyrrolidones, polyethylene glycols and urethanes. Additionally additives such as void suppressors may be used in amounts up to 5% of the weight of the polyimide polymer dope solution, and in this case maleic acid produces the desired results. Once the polyimide polymer is dissolved in the solvent system described, it is cast onto a suitable porous support or substrate. The support can take the form of an inert porous material which does not hinder the passage of permeate through the membrane and does not react with the membrane material, the casting solution, the gelation bath solvent, or the aromatic materials being separated. Typical of such inert supports are metal mesh, sintered metal, porous ceramic, sintered glass, paper, porous nondissolved plastic and woven or non-woven material. Preferably, the support material is a non-woven polyester, polyethylene, or polypropylene material. Following the casting operation, a portion of the solvent may be evaporated under conditions sufficient to produce a dense, ultra-think, top "skin" layer on the polyimide membrane. Typical evaporation conditions adequate for this purpose include air blown over the membrane surface at 15° to 25°C for a duration of less than 30 seconds. The dense ultra-think top "skin" layer of the asymmetric polyimide membranes is characterized by pore sizes below 50A in diameter, is highly resistant to the greater than 3550 kPa (500 psi) operating pressures and has high operating efficiency and stability in the presence of solvent streams having a high aromatic content. The coagulating or quenching medium may consist of water, alcohol, ketones or mixtures thereof, as well as additives such as surfactants, e.g., Triton X-100® available from Aldrich Chemical Company, Milwaukee, Wisconsin (octylphenoxy- polyethoxyethanol). The conditions for effecting coagulation are conventional. The asymmetric polyimide membranes can be washed and dried according to the following techniques. Typically a water-soluble organic compound such as low molecular weight alcohols and ketones including but not limited to methanol, ethanol, isopropanol, acetone, methylethyl ketone or mixtures thereof and blends with water can be used for removing the residual casting solvent (e.g., NMP) from the membrane. Alternatively the membrane may be washed with water. Removal of the residual casting solvent may require successive wash blends in a sequential solvent exchange process. Both membrane efficiency and flow rate can be enhanced by the proper solvent exchange process. The membranes may be conditioned by treating (contacting) the membrane with a conditioning agent dissolved in a solvent to impregnate the membrane with the conditioning agent, a lubricating oil. Lubricating oils include, for example, synthetic oils (e.g. polyolefinic oils, polyalphaolefinic oils, polyisobutylene oils, synthetic wax isomerate oils, ester oils, alkyl aromatic oils and silicone oils) and mineral oils, including solvent refined oils, hydroprocessed mineral oils and petroleum wax isomerate oils. The lubicating oil may be a light neutral oil having a boiling temperature of 400-450°C to a heavy lubricating oil having a boiling temperature from 450-500°C. It is also within the scope of the invention to use other natural lubricating oils such as, for example, vegetable fats and oils. However, use of such fats and oils may be less desirable, due to the possibility of introducing unwanted contaminants into the process streams. Suitable solvents for dissolving the conditioning agent includes alcohols, ketones, aromatics, hydrocarbons, or mixtures thereof. The use of a conditioning agent allows the membrane to maintain a high flux while exhibiting a high selectivity to permeate aromatics in the presence of non- aromatics. The conditioning agent also allows the membrane to be wetted with hydrocarbon solvents, to maintain a suitable pore structure in a dry state for permeation of aromatics, and to produce a flat sheet membrane with improved flexibility and handling characteristics. Following treatment with the conditioning agent, the membrane is typically dried in air at ambient conditions to remove residual solvent. Preferably the membrane is dried in a forced air drying oven designed to capture solvent emissions. Heat treatment can also be used to increase membrane rejection of non- aromatic hydrocarbons. After the conditioning step, the membrane may be heated to 150°C to 320°C, preferably abort 200°C for 1 minute to 2 hours. At 200°C, the heating time is typically 5 minutes. It is preferred that the membrane be air dried before heating. Once the membranes are formed they may be processed into spiral wound modules, into hollow fiber configurations, into flat sheets or into plate and frame configurations. The membrane process of the present invention can be operated in any of hyperfiltration, pervaporation or perstraction modes of operation. The feed stream containing the aromatic hydrocarbons and non-aromatic hydrocarbons to be separated will be contacted with the dense active layer side of the polyimide membrane under pressure and at a temperature sufficient to effect the desired separation. Contacting will typically be at -20°C to 150°C, preferably 20° to 80°C. The pressure employed will be at least greater than that sufficient to overcome the osmotic pressure difference between the feed stream and the permeate stream. Preferably there will be at least a net driving force of 700 to 7000 kPa ( 100 to 1000 psi) across the membrane, more preferably a net driving force of 2800 to 7000 kPa ( 400 to 1000 psi), most preferably 4150 to 5520 kPa ( 600 to 800 psi). Preferably, no additional heating or cooling of the stream is made to minimize energy requirements. The feed stream to be treated has at least 10 wt% aromatics and preferably contains at least 50 wt% of aromatic hydrocarbons. In a preferred embodiment, the membrane is contacted with a feed stream containing an aromatic hydrocarbon content of above 70 wt%, more preferably 80 wt%, and most preferably 90 wt% or higher. In a preferred embodiment, non-aromatics levels in the fresh feed to the membrane are below 10 wt%, and a minimum of 25% reduction, and preferably greater than 50% reduction in the non-aromatics content of the permeate is achieved. Membranes are uniquely qualified for such separations since 2-phase formation to reject non-aromatics in a conventional aromatics extraction process may not occur at high aromatics feed concentrations (i.e., using typical extraction solvents such as sulfolane and glycol-based solvents). A number of configurations can be applied to selectively remove non-aromatics in the feed to an aromatics conversion or separation process. Some of these alternatives are depicted in Figures 1 -4, using for illustration purposes a toluene disproportionation process feeding unextracted toluene containing non-aromatic components. Figure 1 (Prior Art) shows a simplified schematic of the process without membranes. A distilled toluene feed stream 100 joins with a recycle stream 120, both of which are passed through a charge heater 500, to supply a toluene feedstock to disproportionation reactor 200. Products exiting reactor 200 through line 1 19 are piped to one or more fractionation columns 300 for separation of benzene 122 and recovery of the desired products, mixed xylenes, through line 121. An unreacted toluene recycle stream 120 is taken off of the fractionation column(s) and is provided with a non-selective purge-off 150, required to control non-aromatics buildup in reactor 200. This non-selective purge-off represents a loss in potential product yield, since some toluene will inevitably be lost. Figure 2 shows a process modified according to the present invention with a membrane separation unit 400 located upstream of reactor 200 to process fresh feed 100. Removing non-aromatics with a purge 1 10 from the retentate (material not passing through membrane) side of the membrane unit 400, ahead of the reactor 200 reduces the impact of non-aromatics on the reactor and recycle purge requirements. A toluene-enriched stream 100a emerges from the permeate side of the membrane unit 400. Figure 3 shows a process modified with the membrane separation unit 400 treating the unreacted toluene recycle stream 120. The non-aromatics purge-off 160 of retentate from the membrane unit will be more concentrated in non-aromatics than the purge in the Prior Art of Fig. 1 . Hence, a smaller purge rate can be used to achieve a given non-aromatics removal rate. Alternatively, purge rate can be left unchanged and the higher non-aromatics removal rate enables a higher non- aromatics content feed to be used. Figure 4 shows a process modified with the separation unit having the ability to process both the fresh toluene feed 100, diverted to the membrane unit 400 through auxiliary line 100b and recycle toluene feed 120 from the fractionator. Figures 5-7 illustrate an embodiment of the use of the present invention in an aromatics separation process (Fig. 6), and a manner of integrating the membrane separation devices of the present invention into a hybrid aromatics separation/conversion process (Fig. 7). Fig. 5 is a diagram of a conventional aromatic (e.g. toluene) separation process, in which an aromatics-containing feedstream 10, such as a product stream from a refinery reformer, is sent into a first distillation column 50. Lighter hydrocarbons such as C 6 " exit the distillation column through line 1 1 , and the remaining heavier hydrocarbons, containing the majority of the toluene, exit distillation column 50 through line 60 and are sent into a second distillation column 70. Distillation column 70 is optimized for separation of toluene, such that Cβ + aromatics exit distillation column 70 through line 61 , while any remaining benzene and light non- aromatics go overhead through line 62 into condenser 71 and accumulator 72 and exit through line 63a. This purge represents a loss in potential product yield since toluene will inevitably be lost. A portion of the condensed overhead vapors in line 63 may also be returned as reflux to the distillation column for further purification. Purified toluene leaves the second distillation column 70 through line 100, where it may be sent into units such as those illustrated in Figs. 1 -4. Fig. 6 illustrates one possible enhancement to the aromatic separation unit of Fig. 5, in which a membrane separation unit 400 is added to the process unit, such that the overhead purge from line 63a enters membrane separation unit 400, where aromatics (toluene) selectively permeate through the permselective membrane and are returned to the distillation column 70 through permeate line 66. Non-aromatics are concentrated and a purge of reduced rate is taken off in line 64. Fig. 7 illustrates an integrated aromatics separation/conversion process unit, in which an aromatics separation unit, such as those illustrated in Figs. 5-6, is incorporated into an aromatics conversion unit, such as those illustrated in Figs. 1 -4. In this instance, a membrane separation unit 400 is incorporated into the system in such a manner to purify aromatics issuing from both line 63a, exiting accumulator 72 and aromatics in recycle stream 120, so as to effectively remove non-aromatics through purge-off 64 and provide purified aromatic feed back into the system through permeate line 66. In all the options shown, a bypass around the membrane unit is incorporated (not shown) to allow control of the amount of feed that is to be processed in the membrane. The optimum location of the membrane unit will depend on the nature of the aromatics conversion process and composition of non-aromatics in the feed. For example, for processes where non-aromatics conversions are sufficiently high such that non-aromatics levels do not accumulate appreciably in the recycle, locating the membrane on the fresh feed stream (Fig. 2) may be more advantageous. Alternately, for processes characterized by a low non-aromatics conversion level such that non- aromatics accumulate readily, locating the membrane on the recycle stream (Fig. 3) may be more beneficial. Maximum flexibility is afforded with a configuration that enables multiple streams to be directed to the membrane unit as shown in Fig. 4, either alternatively or concurrently, or by incorporating several membrane units in various locations throughout the process unit. In general, the stream with the higher non-aromatics content should be processed in the membrane to maximize non- aromatics removal. The Examples below are for illustrative purposes only, and do not limit the invention, or the claims which follow them. ln the cases shown here, the asymmetric polyimide membranes preferentially permeate aromatic over non-aromatic hydrocarbons. The membranes were tested on a small bench unit with four (4) test cells in series under reverse osmosis conditions. The feed solution was continuously flushed over the membrane surfaces, and the permeate and retentate streams were combined and recycled. A typical feed solution consists of a high toluene concentration (80-100%), along with lesser amounts of other aromatic compounds such as benzene and p-xylene and non-aromatic hydrocarbons including branched and unbranched Cβ to Cg isomers. The feed was pressurized, heated to operating temperatures, and pumped over the surface of the membrane. If desired, permeate lines could also be pressurized. Permeate samples were generally collected after overnight operation (18+ hours). Membrane coupons were small disks with 14.2 cm 2 surface area. Flows were determined in ml/min and then converted to liters per square meter per day (LMD). Sample sizes were kept at less than 1 % by weight of material, so that retentate and feed compositions were essentially equal. GC analysis was used to identify concentrations of aromatic and non-aromatic compounds. All concentrations were expresed as weight percent and pressures indicate the differential pressure between the feed and permeate sides of the membrane, unless otherwise indicated. Rejection was calculated from the sum of non-aromatic compounds in both the permeate and retentate streams with the formula: Rejection (%) = (1 - % permeate/% retentate) x 100%. In some cases, specific rejections for a given hydrocarbon were calculated. Example 1 A viscous solution containing 22% Lenzing P84 polyimide (HP Polymers, Inc., Lewisvilie, TX), 67% dioxane, and 1 1 % dimethylformamide (DMF) was prepared and filtered through a 10 micron filter. This solution was cast at 10 ft/min onto a moving web of nonwoven polyester fabric (Hollytex 3329 from Ahlstrom Filtration, Mt. Holly Springs, PA) using a knife blade set at a gap of 7 mil above the fabric. After 15 seconds with an air flow of 1 SCFM the coated fabric was quenched in water at 22°C to form the membrane structure. The membrane was washed with water to remove residual solvents, then solvent exchanged by immersion into methyl ethyl ketone (MEK) for 3 hours, followed by immersion in a solution of 20% light neutral lube oil/40% MEK/40% toluene for 3 hours. The membrane was then air dried. The membranes were tested as flat sheet coupons at 50°C and 800 psi with various circulating solutions consisting of a high toluene concentration and additional aromatic and non-aromatic Ce to C 9 hydrocarbons typically found in a toluene process stream in refinery operations. In one of the evaluations, total aromatic content in the feed was 99.37 wt%. The membrane exhibited good rejection (54%) of non-aromatics and a flux of 22.9 GFD. The aromatic content in the permeate was 99.71 wt%. Example 2 A viscous solution containing 24% Lenzing P84 polyimide (HP Polymers, Inc., Lewisvilie, TX), 56% dioxane, and 20% dimethylformamide (DMF) was prepared. This solution was cast at 4 ft/min onto a moving web of nonwoven polyester fabric (Hollytex 3329 from Ahlstrom Filtration, Mt. Holly Springs, PA) using a knife blade set at a gap of 7 mil above the fabric. After 3 seconds with an air flow of 566 l.hr "1 (20 SCFH) the coated fabric was quenched in water at 20°C to form the membrane structure. The membrane was washed with water to remove residual solvents, then solvent exchanged by immersion into methyl ethyl ketone (MEK) for 1 hour, followed by immersion in a 2nd solvent exchange bath of light neutral lube oil in 50/50 MEK/toluene for 1 hour. The membrane was then air dried. A series of Lenzing P84 membranes with differing oil content were prepared by changing levels of oil in the 2nd exchange bath from 0 to 60% oil, while maintaining a 50/50 ratio of MEK/toluene. A feed solution consisting of 88 wt% toluene with six compounds (n-decane (Cιo), 1 -methylnaphthalene (Cn ), n-hexadecane (Cι 6 ), 1 -phenylundecane (C i7 ), pristane (C19), and n-docosane (C 22 ) each at 2 wt% levels was prepared. Coupons of each membrane were tested at 4240 kPa (600 psi) and 50°C . Results are recorded in Table 1 below. Table 1 The membrane having no lube oil present as a conditioning agent had an unacceptably low flux. The membranes conditioned with lube oil exhibited over 40% rejection of non-aromatics with a significant increase in flux over the unconditioned membrane. Example 3 A viscous solution containing 26% Matrimid 5218 polyimide (Ciba Geigy, Hawthorne, NY), 15% acetone, and 59% dimethylformamide (DMF) was prepared and filtered through a 10 micron filter. This solution was cast at 10 ft/min onto a moving web of nonwoven polyester fabric (Hollytex 3329 from Ahlstrom Filtration, Mt. Holly Springs, PA) using a knife blade set at a gap of 0.2mm above the fabric. After 15 seconds with an air flow of 28.3 l.m "1 (1 SCFM) the coated fabric was quenched in water at 22°C to form the membrane structure. The membrane was washed with water to remove residual solvents, then solvent exchanged by immersion into methyl ethyl ketone (MEK) for 3 hours, followed by immersion in a solution of 20% light neutral lube oil/40% MEK/40% toluene for 3 hours. The membrane was then air dried. A feed solution consisting of 94 wt% toluene with three non-aromatic compounds (n-decane, n-hexadecane, and n-docosane) each at 2 wt% levels was prepared. Coupons of each membrane were tested at 600 psi and 50°C. The membrane demonstrated 25% rejection of n-decane, 51 % rejection of n- hexadecane and 68% rejection of n-docosane with a flux of 18.0 GFD. Example 4 A Lenzing P84 membrane was prepared as in Example 2 and with the 2nd solvent exchange bath containing 33% oil. An annealed membrane was prepared by clipping a sample to a glass plate, and heating in an oven at 220°C for set times. The samples were tested with a toluene solution under pressure as in Example 2. Results are recorded in Table 2 below. Table 2 Flux and Rejection for Lenzing P84 Membrane at 600 psi and 50°C Rejection of the non-aromatic components by the membrane increased with heat treatment of the membrane. Example 5 An annealed Lenzing P84 membrane was prepared as in Example 4 by clipping a sample to a glass plate, and heating in an oven at 180°C for 5 minutes. Coupons of this membrane were tested with a toluene stream obtained from a refinery. The non-aromatics in this sample were isomers of C 7 and Cβ including methyl heptanes, ethyl hexanes, dimethyl hexanes, methyl ethyl pentanes, trimethyl pentanes, methyl ethyl cyclopentanes, trimethyl cyclopentanes, and dimethyl cyclohexanes. Results are recorded in Table 3 below. Table 3 Rejection and Flux for Lenzing P84 Membrane at 800 psi and 58°C As shown in Table 3, the membrane exhibited favorable rejection of non- aromatics at favorable process conditions and permeate flow rates. Example 6 A membrane as prepared in Example 1 was tested with a naphtha stream obtained from a refinery. This stream contains mostly Ce to C 1 0 hydrocarbons which are mostly non-aromatic compounds. The major aromatic compound is toluene. Coupon tests at 5617 kPa (800 psi) and 21 °C showed the feed stream at 5.4 wt% toluene and 12.9 wt% total aromatics and the permeate stream at 6.9 wt% toluene and 16.4 wt% total aromatics with a flux of 53 LMD. Again, this membrane enriches aromatic over non-aromatic compounds, although it is less effective with a feed stream at low aromatics content. Example 7 A viscous solution containing 24% Lenzing P84 HT polyimide (HP Polymers, Inc., Lewisvilie, TX), 38% dioxane, and 38% dimethylformamide (DMF) was prepared. This solution was cast at 1.2 m/min onto a moving web of nonwoven polyester fabric (Hollytex 3329) using a knife blade set at a gap of 0.18 mm above the fabric. After 3 seconds with an air flow of 283 l.hr "1 (10 SCFH) the coated fabric was quenched in water at 21 °C to form the membrane structure. The membrane was washed with water to remove residual solvents, then solvent exchanged by immersion into MEK for 1 hour, followed by immersion in a solution of 33% light neutral lube oil/33% MEK/33% toluene for 1 hour. The membrane was then air dried. Coupons were tested with a 230-270°C distillation cut of light cycle oil containing a high percentage of aromatic compounds. The percentage of 1-ring, 2- ring, and 3-ring aromatics and non-aromatic compounds were determined with supercritical fluid chromatography methods. Results from coupon tests at 1000 psi and 57 °C are reported in Table 4. Table 4 Rejection and Flux for Lenzing P84 HT Membrane Example 8 A viscous solution containing 22% Lenzing P84 polyimide, 1 1 % acetone, and 67% N-methyl-2-pyrrolidone (NMP) was prepared. This solution was cast at 1.2 m/min onto a moving web of non-woven polyester fabric (Hollytex 3329) using a knife blade set at a gap of 0.18mm above the fabric. After 3 seconds the coated fabric was quenched in water at 22°C to form the membrane structure. The membrane was washed with water to remove residual solvents, then solvent exchanged by immersion into MEK for 1 hour, followed by immersion in a solution of 40% light neutral lube oil/30% MEK/30% toluene for 1 hour. The membrane was then air dried. A feed solution consisting of 1 1 wt% p-xylene, 15 wt% 1 -methylnaphthalene, and 74 wt% of a light neutral lube distillate obtained from a refinery was prepared. Coupons were tested at 600 psi and 107°C. The lube distillate component can be fractionated by refining processes into extract and raffinate oil. Analysis of the complex mixture as well as pure refinery extract and raffinates was done with GC and UV/visible spectrometry. By monitoring the absorption at 350 nm in methylene chloride, an estimate of the percentage of aromatic-rich extract oil and non-aromatic- rich raffinate oil in the lube distillate is determined. This is reported in Table 5. Table 5 Fractionation of Lube Distillate Oil with Lenzing P84 Membrane As shown in Table 5, the membrane showed good rejection of non-aromatics as indicated by the high aromatics content in the permeate stream. Examples 9-11 In order to confirm the efficacy and viability of using membrane separations in various locations in an aromatics-conversion process, such as depicted in Figs. 2-4 and described above, two samples were obtained from a commercial toluene disproportionation reactor: A "fresh feed" sample, representative of a typical feed stream entering the reactor; and a "recycle feed" sample, which is representative of a portion of the product stream exiting the reactor and recycled to the input side of the reactor. Additionally, a third feed stream was synthesized by mixing the fresh feed with the recycle feed in a 50/50 weight ratio, in order to simulate the feed stream composition which would be present in Fig. 4. Each feed was charged to a Lenzing P84 polyimide membrane coupon, prepared according to Example 1 , at 60°C, under a feed pressure of 5617 kPa (800 psig) at atmospheric (0 psig) permeate pressure for 100 hours on stream. Results are presented in Table 6, below. Table 6 Membrane Separation of Commercial Feed Streams The results also indicate an unexpected result in that processing of the fresh feed and the recycle feed together provides better membrane performance than processing either of the feeds separately. The major difference between these two feeds is that the fresh feed contains more linear and single-branched paraffins (greater than 50% of the non-aromatics are comprised of n-C 8 and methyl-C 7 ), while the recycle feed is more concentrated in multiple-branched paraffins and naphthenes (less than 10% of the non-aromatics are comprised of n-Cβ and me-C 7 ), and is predominantly multiple-branched paraffins. Importantly, the results of the testing demonstrate that the membrane units of the present invention permit relatively high flux for aromatics, the flux being above 400 LMD and preferably above 600 LMD, such high flux rates being necessary for successful scale up to commercial levels. Importantly, according to the present invention, these high rates of flux are attainable with suitable aromatic selectivities to permit commercial operations.

Claims: CLAIMS: 1. A method of separating aromatic hydrocarbons from non-aromatic hydrocarbons in a feed stream, the method comprising contacting a liquid feed stream containing a mixture of aromatic and non-aromatic hydrocarbons with a dense active layer side of an asymmetric polyimide membrane treated with a conditioning agent comprising a lubricating oil 2. The method of Claim 1 , in which the asymmetric membrane is prepared from a polyimide copolymer derived from the co-condensation of benzophenone 3,3', 4,4'-tetracarboxylic acid dianhydride and a mixture of di (4-aminophenyl) methane and toluene diamine or a mixture of 4,4'-methylenebis (phenyl isocyanate) and toluene diisocyanate. 3. The method of Claim 1 , in which the asymmetric membrane is prepared from a fully imidized polymer based on 5(6)-amino-1 -(4'-aminophenyl)-1 ,3,3- trimethylindane and benzophenone tetracarboxylic dianhydride. 4. The method of Claim 1 , in which the asymmetric membrane is prepared from a polyimide copolymer derived from the condensation of 1 H,3H-Benzo[1 ,2-c:4,5- c']difuran-1 ,3,5,7-tetrone with 5,5'-carbonylbis[1 ,3-isobenzofurandione], 1 ,3- diisocyanato-2-methylbenzene and 2,4-diisocyanato-1 -methylbenzene. 5. The method of Claim 1 , in which the lubricating oil is a synthetic oil comprising a silicone oil, a polyolefinic oil, a polyalphaolefinic oil, a polyisobutylene oil, a synthetic wax isomerate oil, an ester oil or an alkyl aromatic oil. 6. The method of Claim 1 , in which the lubricating oil is a mineral oil which is a solvent refined mineral oil, a petroleum wax isomerate oil or a hydroprocessed mineral oil. 7. The method of Claim 1 for improving the feed quality to an aromatic separation or aromatic conversion process comprising separating non-aromatic compounds from aromatic hydrocarbons in an aromatic hydrocarbon-containing feed stream by selectively permeating at least a portion of the aromatic hydrocarbons contained in the feed stream through the membrane and diverting a primarily non- aromatic retentate out of the feed stream. 8. The method of Claim 7, in which the membrane is maintained under hyperfiltration conditions. 9. The method of Claim 10, in which the aromatics conversion reactor is any one of an aromatics isomerization reactor, an aromatics disproportionation reactor, an aromatics hydrogenation reactor, an aromatic alkylation reactor or an aromatics dealkylation reactor. 10. The method of Claim 9, in which the feed stream comprises a recycle feed stream, recycled from the aromatics conversion reactor, alone or containing fresh feed aromatic hydrocarbons. 1 1. The method of Claim 7, in which the aromatic hydrocarbon-containing feed stream is contacted with the membrane at a temperature of -20°C to 150°C. 12. The method of Claim 1 1 , in which the temperature is 20° to 80°C.

Inventors: CHIN ARTHUR A, KNICKERBOCKER BRYAN M, TREWELLA JEFFREY C, WALDRON TERRY R, WHITE LLOYD S, CHIN, ARTHUR, A., KNICKERBOCKER, BRYAN, M., TREWELLA, JEFFREY, C., WALDRON, TERRY, R., WHITE, LLOYD, S.
Applicants: CHIN ARTHUR A, GRACE W R & CO, KNICKERBOCKER BRYAN M, MOBIL OIL CORP, TREWELLA JEFFREY C, WALDRON TERRY R, WHITE LLOYD S, CHIN, ARTHUR, A., KNICKERBOCKER, BRYAN, M., MOBIL OIL CORPORATION, TREWELLA, JEFFREY, C., W. R. GRACE & CO.-CONN., WALDRON, TERRY, R., WHITE, LLOYD, S.
Application year: 1999
Main classification: C07C7
IPC codes: B01D61, B01D67, B01D71, C07C7, C07C15, C10G31, C10G57, C10G67