Adsorbent for aromatic isomers and separation thereof

Abstract: An adsorbent comprises a zeolite containing Cs and/or Rb, in which the ratio of [the number of moles of Cs and/or Rb in the zeolite] to [the number of moles of Al in the zeolite] is 0.1 or less. This adsorbent permits efficient separation of an isomer from a mixture of aromatic isomers.

Description: The present invention relates to a process for separating aromatic isomers by adsorption separation and to an adsorbent used therefor. As processes for separation of aromatic isomers, particularly halogenated aromatic isomers, rectification, cryogenic separation, and adsorption separation are known so far. The present invention relates to a process for adsorption separation. Separation by rectification suffers the disadvantage of requiring a rectifying column with a large number of plates because halogenated aromatic isomers differ from one another only slightly in boiling point. Cryogenic separation suffers the disadvantage of requiring valuable equipment and high energy costs for cooling. In order to eliminate these disadvantages, processes for adsorption separation have been studied and developed. Japanese Patent Publication No. 5155/1962 discloses the use of an adsorbent prepared by introduction of alkali metal ions or alkaline earth metal ions into zeolite X for separation of halogenated aromatic isomers. EP-A-0125077 discloses a process for adsorptive separation of a specific isomer, for example, 2,6-dichlorotoluene, 3,5-dichlorotoluene or 2-chloro-m-xylene, using a faujasite-type zeolite which may contain a metal cation M selected from sodium, silver and cesium. Japanese Patent Laid-Open No. 105434/1978 discloses a process for separation of specific isomers from a mixture of dichlorobenzene isomers by means of an adsorbent prepared by introduction of Cs or Rb ions into zeolite Y. Japanese Patent Laid-Open Nos. 31627/1982, 35528/1982, and 191933/1982 disclose a process for adsorption separation of chlorotoluene isomers by means of K ion-exchanged zeolite Y as an adsorbent. Japanese Patent Laid-Open Nos. 131923/1983 and 176223/1984 respectively disclose Ag ion- and K ion-exchanged zeolite Y and Na ion- and Cu ion-exchanged zeolite Y to be used as an adsorbent for separation of m-chlorotoluene. These adsorbents permit separation of aromatic isomers but their performance is not satisfactory. The present invention addresses the problems of providing a process for separation of m-disubstituted aromatic isomers containing a halogen substituent by adsorption separation with an adsorbent for selective separation of the meta-isomer from a mixture of halogenated aromatic isomers according to claim 1. The present invention provides a process for separation of at least one species of halogen-substituted aromatic isomer from a mixture of halogen-substituted aromatic isomers with the aid of (1) an adsorbent which is a faujasite-type zeolite containing Cs, wherein the ratio of the number of moles of Cs in the zeolite to the number of moles of Al in the zeolite is 0.1 or more and (2), a desorbent and wherein (a) a separated halogen substituted aromatic isomer is a m-disubstituted aromatic isomer containing a halogen substituent and selected from (i) m-chlorotoluene and (ii) m-dichlorobenzene; (b) the desorbent is composed of m-xylene; (c) the faujasite-type zeolite containing Cs is a faujasite-type Y zeolite; (d) when the separated halogen substituted aromatic isomer is (i) m-chlorotoluene, the faujasite-type Y zeolite containing Cs additionally contains K and/or Ag and the m-chlorotoluene is separated as the raffinite from a mixture of chlorotoluene isomers; and (e) when the separated halogen substituted aromatic isomer is (ii) m-dichlorobenzene, the faujasite-type Y zeolite containing Cs additionally contains K and/or Pb and the m-dichlorobenzene is separated as the raffinite from a mixture of dichlorobenzene isomers. Preferred embodiments of the invention will now be described with reference to the accompanying drawings in which: Fig. 1 is a schematic diagram showing the procedure for adsorption separation by a simulated moving bed, which is one embodiment according to the present invention. Fig. 2 is a diagram showing the change with time of the amount of effluent of each component in Example 5 of the present invention. Fig. 3 is a diagram showing the change with time of the amount of effluent of each component in Comparative Example 8. Fig. 4 is a diagram showing adsorption separation of dichlorobenzene isomers in Comparative Example 11 and Comparative Example 12. The adsorbent used in the present invention is a faujasite Y type zeolite containing Cs, the zeolite having a ratio of the number of moles of Cs in the zeolite to the number of moles of Al in the zeolite of 0.1 or more. The term "zeolite" usually refers to a porous crystalline aluminosilicate. Zeolites used in the present invention are crystalline metallosilicates of the faujasite Y type but in which aluminium may be substituted by iron or gallium. Any faujasite Y type metallosilicate is acceptable Such zeolites are capable of ion exchange and trivalent or divalent metal silicates are desirable. Such zeolites also have a pore inlet diameter larger than a ring of 12 oxygen atoms and have a multidimensional pore structure and are thus particularly desirable. An aluminosilicate may be represented by the following formula 0.9 ± 0.2 M 2/n O : Al 2 O 3 : xSiO 2 : yH 2 O where, M denotes a cation and n denotes its valence. In the case of a faujasite, x is usually in the range of from 2 to 6. Faujasite is classified as zeolite X if x is 2 to 3 and as zeolite Y if x is 3 to 6. Zeolite Y, used in a process of the invention, may become ultrastable zeolite (USY) upon dealuminization to have the value of x of 6 or more. In the case of separation of m-chlorotoluene from a mixture of chlorotoluene isomers using zeolite Y, m-chlorotoluene is a non-adsorptive component (or raffinite). Incidentally, the value of y varies depending on the degree of hydration. The cation M in a zeolite of the faujasite-type usually includes sodium. This cation may be replaced by any other one by ion exchange. Cation exchange may be accomplished usually by bringing the zeolite into contact with an aqueous solution of a compound containing the desired cation. Examples of such a compound include chlorides, nitrates, sulfates, carbonates, and hydroxides. The amount of ion exchange varies depending on the kind of cation; it may be established as desired according to the amount of cation in the aqueous solution and the number of ion exchange treatments. Ion exchange should be followed by thorough rinsing for removal of those ions (such as sodium ions, chlorine ions and nitrate ions) which have been exchanged and dissolved in the aqueous solution. The adsorbent used in the present invention contains Cs as essential cation. This cation may not be at ion exchange sites so long as they are contained in the zeolite. However, it should preferably be at ion exchange sites. The content of Cs should be such that the number of moles of Cs in the zeolite to the number of moles of Al in the zeolite is 0.1 or more, preferably 0.3 or more, particularly 0.5 or more. Such a specific content is necessary for efficient separation of halogenated aromatic isomers. The upper limit of ion exchange is usually equal to the number of moles of Al in zeolite. In other words, it is 1.0. However, in the case of the adsorbent used in the present invention, the upper limit of ion exchange would be 0.7 because not all Cs ion exchange with ions in zeolite X or Y because of its large ionic radius. The content of Cs may be determined in any manner, such as atomic absorption spectrometry, fluorescent X-ray analysis, and energy dispersion X-ray analysis, which is capable of specifying the ratio of elements. To be more specific, elements contained in zeolite are traced and determined and the content of Cs is estimated. In the case of molded zeolite containing a binder, the content of Cs and/or Rb may be calculated by subtracting the content of aluminum in the binder, if the amount of the binder is known, or it may be replaced by the content of Cs in metals excluding Si and Al, if the amount of the binder is unclear. The kind of the metals that can coexist with Cs without adverse effect varies depending on the halogenated aromatic isomers to be separated. For example, the presence of K and/or Ag is if m-chlorotoluene is to be separated as raffinate from a mixture of chlorotoluene isomers, or the presence of Pb and/or K, in addition to Cs, is necessary if m-dichlorobenzene is to be separated as raffinate from a mixture of dichlorobenzene isomers. Adsorbents are usually used in the form of granules obtained by coagulating zeolite. Granulation may be accomplished with the aid of a binder such as alumina and clay. Granulation may be accomplished by mixing zeolite together with a binder, extruding the mixture through an extruder, and shaping the extrudate into spheres by using a Marumerizer. The particle size is usually larger than 0.1 mm. Particles smaller than 0.1 mm may lead to an increase in pressure loss. The upper limit of the particle size is usually 5 mm. The adsorbent used in this present invention preferably has a smaller particle size for efficient diffusion because it contains large cations such as Cs. The particle size is preferably smaller than 1 mm, more preferably smaller than 0.5 mm. Prior to use, the adsorbent is preferably heated usually at 200 to 600° C to remove water almost completely from zeolite. The adsorbent according to the present invention is used for adsorption separation of a specific isomer from a mixture of halogenated aromatic isomers, and this adsorption separation may be either chromatographic separation or separation by simulated moving bed. The latter is preferable when only one specific isomer is to be separated. The continuous adsorption separation by a simulated moving bed basically consists of the cyclic steps of adsorption, concentration, desorption, and recovery of desorbent which are explained below. (1) Adsorption: In this step, the feed stock containing a mixture of 2-substituted or 3-substituted aromatic isomers according to claim 1 is brought into contact with the adsorbent of the present invention. Selective adsorption takes place according to the adsorptive strength of each component. The strongly adsorbed component is recovered as the extract component together with the desorbent as mentioned later. (2) Concentration: The weakly adsorbed component is further brought into contact with the adsorbent, so that it is purified and recovered as the raffinate together with the desorbent. (3) Desorption: The weakly adsorbed component, which has been highly purified, is recovered as the raffinate. At the same time, the strongly adsorbed component is expelled from the adsorbent by a desorbent and recovered as the extract component together with the desorbent. (4) Recovery of adsorbent: The adsorbent, which has adsorbed substantially only the desorbent, is brought into contact with part of the raffinate flow, so that part of the desorbent contained in the adsorbent is recovered as the recovery flow of the desorbent. Fig. 1 schematically shows the procedure for adsorption separation by a simulated moving bed. There are shown adsorbing chambers 1 to 12 filled with adsorbent, which are serially connected for circulation. There are also shown a desorbent feed line 13, an extract discharge line 14, an isomer mixture feed line 15, a raffinate discharge line 16, a desorbent recovery line 17, and a valve 18. The isomers for adsorption separation according to the present invention are those of aromatic compounds specified in claim 1. The process of the present invention is used for separation of m-chlorotoluene and m-dichlorobenzene isomers. The desorbent employed for the above-mentioned procedure of adsorption separation is composed of m-xylene. Thus, when chlorotoluene isomers are to be separated into m-chlorotoluene or when dichlorobenzene isomers are to be separated into m-dichlorobenzene, an adequate desorbent is that which is entirely m-xylene. As to the conditions for adsorption separation, the temperature is usually in the range of from room temperature to 350°C, preferably from 50 to 250°C. The pressure is usually in the range of from atmospheric pressure to 20 MPa, preferably from atmospheric pressure to 3 MPa. The procedure for adsorption separation according to the present invention may be accomplished in gas phase; however, it is preferably carried out in liquid phase so as to reduce undesirable side reactions of feedstock or desorbent by keeping the operating temperature low. The procedure in accordance with the invention may allow complete isolation of a desired isomer and the term "procedure for adsorption separation" as used herein means not only "separation" but also recovery of specific substances by adsorption separation. EXAMPLES Embodiments of the invention will be described in more detail with reference to the following Examples. In the Examples, the adsorbing characteristics of the adsorbent are expressed by the adsorption selectivity a defined by the equations below. (where o, m, and p each represents the o-isomer, m-isomer, and p-isomer of disubstituted aromatic isomers; and A denotes the adsorption phase and U denotes the liquid phase in equilibrium with the adsorption phase.) These equations suggest that as the value of α becomes larger than 1, m-isomer becomes less prone to adsorption than o-isomer and p-isomer, and that as the value of α becomes smaller than 1, m-isomer becomes more prone to adsorption than o-isomer and p-isomer. For m-isomer to be separated as the raffinate component (unadsorbed component), it is necessary that the values of both α o/m and α p/m should be greater than 1, preferably 1.4 or more from the standpoint of separation efficiency. "number of moles of Cs in zeolite]/[number of moles of Al in zeolite" indicates the content of Cs which are determined by energy dispersion X-ray analysis. Preparation of adsorbents Adsorbent 1 (Comparative) Sodium-type zeolite Y (Na-Y for short hereinafter). 100 pbw of "Zeolum Na-5.1 Y" powder (from Tosoh Corporation) is mixed with 15 pbw (in terms of alumina) of alumina sol as a binder (#200, Al 2 O 3 = 10 wt%, from Nissan Chemical Industries, Ltd.). The resulting mixture is made into granules, 0.15 to 0.5 mm in particle size. The Na-Y zeolite in granular form is dried at 120°C and then calcined at 500°C. The content of Cs is 0. Adsorbent 2 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of cesium nitrate (7.21 g) dissolved in 40 cc of pure water at 80°C for 1 hour. This procedure is repeated twice (in total) using freshly prepared cesium nitrate solution. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0.5. Adsorbent 3 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of silver nitrate (1.26 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated twice (in total) using freshly prepared silver nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of cesium nitrate (7.21 g) dissolved in 40 cc of pure water at 80°C for 1 hour. This procedure is repeated twice (in total) using freshly prepared cesium nitrate solution. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0.5. Adsorbent 4 10 g of adsorbent 1 is immersed in a sdlution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of silver nitrate (1.26 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated twice (in total) using freshly prepared silver nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of cesium nitrate (2.88 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0.3. Adsorbent 5 The same procedure as for adsorbent 4 is repeated except that the amount of cesium nitrate is changed to 1.44 g. The content of Cs is 0.1. Adsorbent 6 (Comparative) The same procedure as for adsorbent 4 is repeated except that the amount of cesium nitrate is changed to 0.72 g. The content of Cs is 0.05. Adsorbent 7 (Comparative) 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of silver nitrate (1.26 g) dissolved in 40 cc of pure water at 80° C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated twice (in total) using freshly prepared silver nitrate solution. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0. Adsorbent 8 (Comparative) 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of silver nitrate (1.26 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated twice (in total) using freshly prepared silver nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of rubidium nitrate (5.45 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated twice (in total) using freshly prepared rubidium nitrate solution. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Rb is 0.4. Adsorbent 9 (Comparative) 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0. Adsorbent 10 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of lead nitrate (2.45 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of cesium nitrate (7.21 g) dissolved in 40 cc of pure water at 80° C for 1 hour. The treated adsorbent is filtered off: This procedure is repeated twice (in total) using freshly prepared cesium nitrate solution. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0.5. Adsorbent 11 (Comparative) 10 g of adsorbent 1 is immersed in a solution of potassium nitrate (4.0 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off. This procedure is repeated eight times (in total) using freshly prepared potassium nitrate solution. The treated adsorbent is filtered off and rinsed thoroughly. The adsorbent is further immersed in a solution of lead nitrate (2.45 g) dissolved in 40 cc of pure water at 80°C for 1 hour. The treated adsorbent is filtered off, rinsed thoroughly, and finally dried. The content of Cs is 0. Adsorption experiments Examples 1 to 4 and Comparative Examples 1 to 3 Adsorbents 2 to 8 were examined for adsorption selectivity in the adsorption of chlorotoluene isomers which employs m-xylene as a desorbent. The procedure is as follows. An autoclave (6 ml internal volume) is filled with 2.6 g of liquid phase mixture and 2.4 g of the adsorbent (calcined at 500° C). The autoclave is allowed to stand at 130° C for 1 hour, with occasional stirring. The liquid phase mixture is composed of n-nonane, desorbent (m-xylene), and chlorotoluene (o:m:p = 39.2 : 40.2 : 20.6) in a ratio of 5:50:50 (by weight). n-nonane is added as an internal standard substance for gas chromatography. It is substantially inactive in this experiment for adsorption. The liquid phase mixture which has been in contact with the adsorbent is analyzed for its composition by gas chromatography. The adsorption selectivity for chlorotoluene isomers is calculated from equation (1). The results are shown in Table 1, in which Comparative Example 3 shows the results for a zeolite Y adsorbent containing Rb, outside the invention. It is apparent from Table 1 that the adsorbent of zeolite Y containing Cs can separate m-chlorotoluene (as the weakly adsorbed component or the raffinate component) from a mixture of chlorotoluene isomers. It is also noted that the adsorption selectivity of α o/m is low if the content of Cs is 0.05 or less. Adsorbent Desorbent α p/m α o/m Example 1 Adsorbent 2 m-xylene 1.80 1.47 Example 2 Adsorbent 3 m-xylene 1.65 1.66 Example 3 Adsorbent 4 m-xylene 1.98 1.48 Example 4 Adsorbent 5 m-xylene 2.03 1.45 Comparative Example 1 Adsorbent 6 m-xylene 2.09 1.33 Comparative Example 2 Adsorbent 7 m-xylene 2.14 1.30 Comparative Example 3 Adsorbent 8 m-xylene 2.01 1.55 Comparative Examples 4 and 5 The same procedure as in Examples 1 and 2 was repeated except that the absorbent was replaced by adsorbents 7 and 9 which were calcined at 500°C and the desorbent was replaced by m-xylene or 3,4-dichlorotoluene. The results are shown in Table 2. Adsorbent Desorbent α p/m α o/m Comparative Example 2 Adsorbent 7 m-xylene 2.14 1.30 Comparative Example 4 Adsorbent 7 3,4-dichlorotoluene 1.31 1.44 Comparative Example 5 Adsorbent 9 m-xylene 2.17 1.18 Comparative Examples 6 and 7 The same procedure as in Examples 1 and 2 was repeated except that the absorbent was replaced by adsorbent 3 which was calcined at 500°C and the desorbent was changed. The results are shown in Table 3. It is apparent from Table 3 that xylene is desirable as the desorbent and m-xylene is particularly desirable as the desorbent to separate m-chlorotoluene as the raffinate component. Adsorbent Desorbent α p/m α o/m Example 2 Adsorbent 3 m-xylene 1.65 1.66 Comparative Example 6 Adsorbent 3 o-xylene 1.55 1.50 Comparative Example 7 Adsorbent 3 3,4-dichlorotoluene 1.40 1.25 Example 5 A stainless steel column, 1 m long and 4.6 mm in inside diameter, is filled with adsorbent 3 which was calcined at 500° C. The filled column is placed in an oil bath at 130° C, and m-xylene as the desorbent is passed through it at a constant flow rate of 1.5 ml/min (at room temperature). Into the column is introduced a mixture of chlorotoluene (CT) (o:m:p = 39.2:40.2:20.6) and n-nonane (n-C9) in a ratio of 100:5 (by weight). The n-nonane is added as a standard for elution time. Its adsorption relative to other components is practically negligible. The eluate from the column outlet is sampled at constant intervals for analysis by gas chromatography. An elution curve as shown in Fig. 2 is obtained. Comparative Example 8 The same procedure as in Example was repeated except that adsorbent 7 which was calcined at 500°C was used and 3,4-dichlorotoluene was used as the desorbent. The elution curve is shown in Fig. 3. Figs. 1 and 2 showing the peaks of respective components indicate that the zeolite Y containing Cs, Ag, and K, when used as an adsorbent in combination with m-xylene as a desorbent, permits efficient separation of m-chlorotoluene as the non-adsorbed component. Example 6 Adsorbent 10 was examined for adsorption selectivity in the adsorption of dichlorobenzene isomers which employs m-xylene as a desorbent. The procedure is as follows. An autoclave (6 ml internal volume) is filled with 2.6 g of liquid phase mixture and 2.5 g of the adsorbent (calcined at 500°C). The autoclave is allowed to stand at 130°C for 1 hour, with occasional stirring. The liquid phase mixture is composed of n-nonane, desorbent, m-xylene, and dichlorobenzene (o:m:p = 39.6 : 40.0 : 20.4) in a ratio of 5:50:50 (by weight). n-nonane is added as an internal standard substance for gas chromatography. It is substantially inactive in this experiment for adsorption. The liquid phase mixture which has been in contact with the adsorbent is analyzed for its composition by gas chromatography. The adsorption selectivity for dichlorobenzene isomers is calculated from equation (1). The results are shown in Table 4. Adsorbent Desorbent α p/m α o/m Example 6 Adsorbent 10 m-xylene 2.14 2.70 Comparative Examples 9 and 10 The same procedure as in Example 7 was repeated except that the absorbent was replaced by adsorbent 11 which was calcined at 500°C and the desorbent was replaced by m-xylene and 3,4-dichlorotoluene. The results are shown in Table 5. Adsorbent Desorbent α p/m α o/m Comparative Example 9 Adsorbent 11 m-xylene 1.66 2.37 Comparative Example 10 Adsorbent 11 3,4-dichlorotoluene 1.75 2.00 Example 7 Twelve columns (4.6 mm in diameter and 1 m long) were filled with 160 g of adsorbent 10 which was calcined at 500° C. These twelve columns were used to the simulated moving bed process, four as the desorbing zone, three as the concentrating zone, three as the adsorbing zone, and two as the desorbent recovering zone. They were tested for ability to adsorb and separate a mixture of dichlorobenzene (DCB) isomers. The mixture of dichlorobenzene isomers as the feedstock has the composition of o:m:p = 38:41:21. m-Xylene was used as a desorbent. The procedure was carried out at 120° C. The performance curve is shown in Fig. 4. Comparative Example 11 Twelve columns (4.6 mm in diameter and 1 m long) were filled with 145 g of adsorbent 11 which was calcined at 500° C. These twelve columns were used to the simulated moving bed process, four as the desorbing zone, three as the concentrating zone, three as the adsorbing zone, and two as the desorbent recovering zone. They were tested for ability to adsorb and separate a mixture of dichlorobenzene isomers. The mixture of dichlorobenzene isomers as the feedstock has the composition of o:m:p = 38:41:21. 3,4-Dichlorotoluene was used as a desorbent. The procedure was carried out at 120°C. The performance curve is shown in Fig. 4. In Example 7 and Comparative Example 11, m-isomer is the non-adsorbed component and hence is recovered as the raffinate component. The performance curve Fig. 4 indicates that the performance of separation is good when the concentration of m-isomer is low in the extract and the concentration of m-isomer is high in the raffinate. It has been shown that the adsorbent of the present invention, when used in combination with a specific desorbent, permits efficient separation of m-isomer from a mixture of dichlorobenzene isomers. In a case where, in the zeolite, Al is partially or wholly replaced by another tri-valent metal, the amount of such a metal is taken into account when determining the amount of Cs. Likewise, if it should prove impossible to distinguish between Al present in the zeolite and Al present in the binder of adsorbent, the amount of Cs may be adjusted in dependence upon the number of valences provided by the M 2/n component of a zeolite. Thus, in accordance with the invention, the proportion of Cs and/or Rb in the zeolite is such that either the following respective ratios is at least 0.1: (i) number of moles of Cs in the zeolite: number of moles of Al and/or any other tri-valent metal wholly or partially replacing the Al; and (ii) number of atomic valences provided by the Cs in the zeolite: total number of atomic valences provided by atoms M in the oxide component M 2/n O of a zeolite of the formula a [M 2/n O]. b[Al 2 O 3 ]. x [SiO 2 ]. y[H 2 O] wherein M includes the Cs; each of a, b and x is an integer; and y is zero or an integer]

Claims: A process for separation of at least one species of halogen substituted aromatic isomer from a mixture of halogen-substituted aromatic isomers using (1) an adsorbent which is a faujasite-type zeolite containing Cs wherein the ratio of the number of moles of Cs in the zeolite to the number of moles of Al in the zeolite is 0.1 or more and (2) a desorbent characterized in that (a) a separated halogen substituted aromatic isomer is a m-disubstituted aromatic isomer containing a halogen substituent and selected from (i) m-chlorotoluene and (ii) m-dichlorobenzene; (b) the desorbent is composed of m-xylene; (c) the faujasite-type zeolite containing Cs is a faujasite-type Y zeolite; (d) when the separated halogen substituted aromatic isomer is (i) m-chlorotoluene, the faujasite-type Y zeolite containing Cs additionally contains K and/or Ag and the m-chlorotoluene is separated as the raffinite from a mixture of chlorotoluene isomers; and (e) when the separated halogen substituted aromatic isomer is (ii) m-dichlorobenzene, the faujasite-type Y zeolite containing Cs additionally contains K and/or Pb and the m-dichlorobenzene is separated as the raffinite from a mixture of dichlorobenzene isomers.

Inventors: IWAYAMA KAZUYOSHI, WATANABE MASATOSHI, YOSHIKAWA MASAHITO, IWAYAMA, KAZUYOSHI, WATANABE, MASATOSHI, YOSHIKAWA, MASAHITO
Applicants: TORAY INDUSTRIES, TORAY INDUSTRIES, INC.
Application year: 1999
Main classification: C07C17
IPC codes: B01J20, C07C17