Method for converting aromatic hydrocarbons

Abstract: A method for converting aromatic hydrocarbons comprises contacting a benzene-containing, aromatic hydrocarbon material having a non-aromatic compound content of at most 1 % by weight, with a catalyst. By this method, aromatic hydrocarbons such as C7 and C8 are efficiently increased and the catalyst deactivation is reduced.

Description: The present invention relates to a method for converting aromatic hydrocarbons, more precisely to a method for converting a starting aromatic hydrocarbon material containing benzene with efficiently increasing useful aromatic hydrocarbons such as C7 and C8 aromatic hydrocarbons and with reducing catalyst deactivation. (The wording "C7-, C8 and C9+ hydrocarbons" referred to herein is meant to indicate hydrocarbons having at most 7 carbon atoms, those having 8 carbon atoms and those having at least 9 carbon atoms, respectively, and the same shall apply hereinunder unless otherwise specifically indicated.) Requirements for regulating environmental problems are much more severe these days. Above all, there is a considerably increasing demand for cleaner fuel. Regarding gasoline, in particular, the influence of benzene therein on human health is a serious problem. In the United States, the benzene content of gasoline is regulated. Also in Japan and Europe, it is being regulated, and oil companies are tackling the problem of reducing the benzene content of gasoline. To meet the market needs of high-octane fuel, benzene and alkyl-aromatic hydrocarbons such as toluene and xylene having a high octane value have heretofore been much used in gasoline as important gasoline bases, and their concentration in gasoline is high. In general, gasoline is produced in an oil refining process including catalytic reforming and cracking steps, in which the distillates fractionated in each step contain benzene. In case where benzene is removed from gasoline so as to meet the environmental requirements mentioned above, a relatively large amount of benzene shall be extracted out of gasoline, and effective use of benzene is an emergent problem in the art. For utilizing it, a technique is known in which benzene is mixed with C9+ aromatic hydrocarbons to give toluene and xylene by transalkylation. At present, it is considered that toluene and xylene present no problematic influence on human health, unlike benzene. In addition, since toluene and xylene have a higher octane value than benzene, the transalkylation of the known technique to provide them is preferred for increasing the octane value of gasoline. In general, benzene having been extracted out of gasoline is separated from gasoline by distillation. The benzene fraction contains a large amount of non-aromatic compounds of which the boiling point range is near to that of benzene, especially non-aromatic hydrocarbons such as olefins and naphthenes. In case where a benzene fraction containing such a large amount of non-aromatic compounds is directly transalkylated with C9+ aromatic hydrocarbons in the presence of hydrogen, the aromatic transalkylation is often accompanied by a side reaction of paraffin decomposition. The side reaction of paraffin decomposition is problematic in that its hydrogen consumption is large and the reaction system is much heated owing to the decomposition heat. US-A-5347061 discloses a method of converting benzene in a gasoline distillate, and C9+ hydrocarbons into C7 and C8 alkyl-aromatic hydrocarbons. In this, a benzene-rich C6 hydrocarbon stream derived from distillation of reformed gasoline, and a C9+ hydrocarbon stream are converted into C7 and C8 aromatic hydrocarbons by cracking, transalkylation and alkylation in the presence of an acidic metallosilicate catalyst. However, by this method, the C9+ hydrocarbon is positively subjected to catalytic cracking to give an alkylating agent for benzene alkylation, for which, therefore, the presence of a non-aromatic hydrocarbon is indispensable. JP-A-38497/1997 discloses a method for converting aromatic hydrocarbons, in which a starting material comprising a benzene-containing distillate from a catalytically-reformed product of naphtha, and a trialkylbenzene-containing distillate from a catalytically-cracked product is transalkylated in the presence of a crystalline aluminosilicate catalyst which carries a metal component of Group VIII of the Periodic Table therewith, to give a reaction product essentially comprising monoalkylbenzenes and dialkylbenzenes. They say therein that mordenite having a low morphology selectivity index is poorly practicable for the conversion as considerable deactivation occurs through coking, while TSZ is preferred as its total adsorption capacity and morphology selectivity index are both large. The total adsorption capacity referred to therein is meant to indicate the total of toluene, 1,2,4-trimethylbenzene and 1,2,3-trimethylbenzene adsorbed by the catalyst (in terms of ml/100 g of the catalyst, crystalline aluminosilicate); and the morphology selectivity index is meant to indicate the ratio of toluene adsorption capacity/(1,2,4-trimethylbenzene + 1,2,3-trimethylbenzene) adsorption capacity of the catalyst. JP-A-155198/1997 discloses a method for converting C9+ aromatic hydrocarbon compounds in crude oil having a specific boiling point range and not containing benzene, into toluene and C8 aromatic hydrocarbon compounds, in the presence of hydrogen and by the use of a catalyst of a metal selected from metals of Group VIII and Group VIA of the Periodic Table or its compound carried by a carrier which contains zeolite having a maximum micropore diameter of from 0.6 to 1.0 nm and having a ratio of SiO 2 /Al 2 O 3 of at least 50. In this, they say that mordenite is preferred for the specific zeolite to be used, and nickel, palladium and molybdenum are preferred for the metal. JP-A-38505/1997 discloses a method for converting benzene and C9+ aromatic hydrocarbon compounds in crude oil having a specific boiling point range, into toluene and C8 aromatic hydrocarbon compounds, in the presence of hydrogen and by the use of a catalyst of a metal selected from metals of Group VIII and Group VIA of the Periodic Table or its compound carried by a carrier which contains zeolite having a maximum micropore diameter of from 0.6 to 1.0 nm and having a ratio of SiO 2 /Al 2 O 3 of at least 50. JP-A-187658/1997 discloses a method for converting benzene and C9+ aromatic hydrocarbon compounds in crude oil having a specific boiling point range, into toluene and C8 aromatic hydrocarbon compounds, in the presence of hydrogen and by the use of a catalyst of a metal selected from metals of Group VIII and Group VIA of the Periodic Table or its compound carried by a carrier which contains zeolite having a maximum micropore diameter of from 0.6 to 1.0 nm and having a ratio of SiO 2 /Al 2 O 3 of smaller than 50. WO-A-98/12159 discloses a process for converting an aromatic material containing ethyl or propyl-having C9 hydrocarbon compounds in an amount of at least 20 %, into a toluene and xylene-rich product, in which the starting aromatic material is contacted with a catalyst which contains palladium-carrying de-aluminated mordenite having a silica/alumina ratio of from 12 to 30, in the presence of hydrogen to give the product. WO-A-96/24568 discloses a process for converting a material containing C9+ aromatic hydrocarbons, and benzene and/or toluene, into C9- (excluding C9) aromatic hydrocarbons, in which the starting material is contacted with a catalyst which contains zeolite having a control index of from 0.5 to 3 and in which the catalyst has a hydrogenation site but has been so processed that its nucleus hydrogenation capacity is reduced. US-A-5406016 discloses a process for converting benzene and a C10+ alkyl-aromatic compound having at least 2 alkyl groups, into methylbenzenes, in which the starting compounds are processed with a 12-membered cyclic zeolite under specific reaction conditions. In these examples, however, the aromatic compound conversion efficiency is low, and the references noted above say nothing as to how to treat non-aromatic compounds that may be in the starting materials. US-A-3632835 discloses the use of a mordenite zeolite in combination with both platinum and rhenium for isomerization of aliphatic and aromatic hydrocarbons. There is no mention of the treatment of fractions containing benzene. The present invention addresses the problem of converting a benzene-containing, aromatic hydrocarbon material into C7, C8 and other useful aromatic hydrocarbons in the presence of a catalyst, with increasing the content of the useful aromatic hydrocarbons in the converted product. The invention also addresses the problem of converting a benzene-containing, aromatic hydrocarbon material into such useful aromatic hydrocarbons in the presence of a catalyst, while reducing the benzene content of the converted product. The invention also addresses the problems of converting a benzene-containing, aromatic hydrocarbon material into such useful aromatic hydrocarbons in the presence of a catalyst, while reducing catalyst deactivation and of converting a benzene-containing, aromatic hydrocarbon material into such useful aromatic hydrocarbons in the presence of a catalyst and hydrogen, while depressing hydrogen consumption. To solve above problems, or at least minimise the difficulties previously found, the invention provides a method for converting aromatic hydrocarbons, which comprises contacting a starting material of aromatic hydrocarbons containing 5 to 80% by weight of benzene and having a non-aromatic compound content of at most 1 % by weight, with a catalyst containing mordenite and rhenium; and provides a method for converting aromatic hydrocarbons, which comprises removing non-aromatic compounds from a starting material of aromatic hydrocarbons containing benzene and non-aromatic compounds so as to reduce the non-aromatic compound content of the starting material to at most 1 % by weight, followed by contacting the material with a catalyst containing mordenite and rhenium. The catalyst contains from 0.02 to 2% by weight of rhenium, based on the weight of the catalyst. Preferred embodiments of the invention will now be described in more detail. In the process of the invention, a benzene-containing, aromatic hydrocarbon material which has a benzene content of from 5 to 80% by weight and a non-aromatic compound content of at most 1 % by weight is converted. Preferably, the starting material is prepared from a crude material having a non-aromatic compound content of at least 1 % by weight, by removing non-aromatic compounds therefrom to reduce the non-aromatic compound content of the material to at most 1 % by weight. The converted aromatic hydrocarbons may be used as starting materials for ordinary chemicals. In case where a benzene distillate from gasoline is used as the starting material in the invention, the converted aromatic hydrocarbons may be used as additional gasoline bases for the benzene-poor gasoline. In that manner of one preferred embodiment of the invention, the process is favourable for effectively utilizing benzene extracted from gasoline. Non-aromatic compounds referred to herein are compounds other than aromatic hydrocarbons, specifically including non-aromatic hydrocarbons such as paraffins, olefins, naphthenes, etc. The process of invention is characterized in that the starting material of benzene-containing aromatic hydrocarbons has a non-aromatic compound content of at most 1 % by weight. Aromatic hydrocarbon conversion in the invention specifically indicates at least one of transalkylation, dealkylation and disproportionation. The reaction is effected under the condition under which at least one of transalkylation, dealkylation and disproportionation is effected, generally in the presence of hydrogen. The reaction pressure may be from 0.1 to 100 MPa, preferably from 0.5 to 60 MPa, more preferably from 1 to 50 MPa. If the reaction pressure is too low, the catalyst used will soon deactivate and the reaction speed will lower; but if too high, it is uneconomical in view of the cost of equipment. The reaction temperature may be from 200 to 650°C, preferably from 250 to 500°C. If the reaction temperature is too low, the reaction speed will lower; but if too high, the aromatic hydrocarbons being processed will decompose considerably and the catalyst used will soon deactivate. The hydrogen flow rate may be from 0.1 to 20, preferably from 0.5 to 10 in terms of hydrogen/starting material (mol/mol). If the hydrogen flow rate is too low, the catalyst used will soon deactivate; but if too high, it is uneconomical. The starting material to be processed in the invention contains aromatic·hydrocarbons with benzene. The aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, tetramethylbenzene, ethylxylene, diethylxylene, propyltoluene, and other aromatic hydrocarbons. In case where the starting material is converted into a product containing toluene and/or xylene, the toluene and/or xylene content of the starting material shall be lower than the equilibrium composition of toluene and/or xylene in the starting material. The starting material may be any of those to be obtained in ordinary oil refineries and having a boiling point that falls within a gasoline boiling point range, including, for example, catalytically-reformed oil, etc. If desired, oil fractions obtained in oil refineries may be combined for the starting material. In general, refined oil, especially catalytically-reformed oil can be fractionated into C5-, C6, C7, C8, C9+ and other fractions through distillation, depending on their boiling point ranges. After having been thus fractionated, different fractions may be combined for the starting material to be processed in the invention. As the case may be, refined oil may be directly used as the starting material for the invention, without being fractionated into different fractions. Anyhow, the starting material to be processed in the invention must contain benzene. In general, reformed oil fractions having fewer carbon atoms have a higher non-aromatic compound content. For example, the non-aromatic compound content of the C6 fraction of reformed oil may be higher than 50 %. Preferably, the non-aromatic compounds in the oil fractions are removed from the aromatic compounds therein through distillation or extraction. In the process of the invention, the starting material or aromatic compounds, from which non-aromatic compounds have been removed and which therefore have a non-aromatic compound content of at most 1 % by weight, is converted by contacting it with a catalyst in the invention. The starting material of benzene-containing aromatic compounds to be processed in the invention is characterized in that its non-aromatic compound content is at most 1 % by weight. If the non-aromatic compound content of the starting material is larger than 1 % by weight, the conversion of the starting material into C7, C8 and other useful aromatic hydrocarbons is poor. If so, in addition, the starting material will decompose considerably and will therefore generate much decomposition heat, while consuming much hydrogen, with the result that the decomposed products will seriously deactivate the catalyst used. Preferably, the non-aromatic compound content of the starting material is at most 0.5 % by weight, more preferably at most 0.1 % by weight. Preferably, the crude starting material is distilled or extracted to remove non-aromatic compounds from it. Removing non-aromatic compounds from the starting material may be effected either before or after the starting material is fractionated into different fractions through distillation, but indispensably before it is subjected to the reaction for conversion. The non-aromatic compounds thus separated from the starting material may be used as gasoline bases either directly or after having been isomerized to increase their octane value. The benzene content of the aromatic hydrocarbon material to be processed in the invention is from 5 to 80 % by weight, preferably from 10 to 70 % by weight, more preferably from 15 to 60 % by weight, in order that benzene in the material could be efficiently converted into other aromatic hydrocarbons. More preferably, the starting material for the invention contains C9+ alkyl-aromatic hydrocarbons, even more preferably C9 and C10 alkyl-aromatic hydrocarbons. C9 alkyl-aromatic hydrocarbons include trimethylbenzene, ethyltoluene and propylbenzene; and C10 alkyl-aromatic hydrocarbons include tetramethylbenzene, ethylxylene, diethylxylene, propyltoluene and butylbenzene. Of those, preferred are trimethylbenzene and tetramethylbenzene. The C9+ alkyl-aromatic hydrocarbon content of the starting material is not specifically defined, but is preferably from 5 to 90 % by weight for efficient transalkylation of the alkyl-aromatic hydrocarbons with benzene. More preferably, it is from 7 to 85 % by weight, even more preferably from 10 to 80 % by weight. More specifically, in a process embodying the invention, the aromatic hydrocarbon material containing benzene and C9+ aromatic hydrocarbons and having a non-aromatic compound content of at most 1 % by weight is preferably transalkylated to give the intended product. As the case may be, the product may be further transalkylated. The transalkylation includes, for example, formation of toluene and xylene from benzene and trimethylbenzene; formation of toluene, xylene and trimethylbenzene from benzene and tetramethylbenzene; formation of toluene from benzene andxylene; formation of xylene from toluene and trimethylbenzene; formation of xylene and trimethylbenzene from toluene and tetramethylbenzene; and formation of ethylbenzene from benzene and diethylbenzene. Without being limited to these, it may include any other different types of transalkylation. By the conversion, the content of benzene and of C9+ aromatic hydrocarbons in the starting material all decrease, while that of C7 and of C8 aromatic hydrocarbons in the product increase. C7 and/or C8 aromatic hydrocarbons extracted out of the product may be used for producing industrial by useful compounds. The remaining fraction of the product can be recycled. In a process embodying the invention, the transalkylation may be accompanied by disproportionation, dealkylation or alkylation. The mordenite/rhenium catalyst to be used in the invention is for converting aromatic compounds. Specifically, the reaction may be transalkylation. However, as the case may be, the reaction may induce disproportionation, dealkylation or alkylation. Preferably, the catalyst is employed: for selectively dealkylating and transalkylating ethyl and propyl groups, but having no influence on methyl groups. The mordenite zeolite for use in the invention may be ion-exchanged with suitable metal ions, or hydrogen ions. Preferred are hydrogen-exchanged zeolites. In the catalyst, a binder is optionally used. The binder may be, for example, inorganic oxides such as alumina, silica-alumina, titania, magnesia, etc.; clays such as montmorillonite, kaolin, sepiolite, acid clay, etc. Either singly or in combination, any of these may be used herein as the binder. Of these, preferred is alumina. The amount of the binder for use herein is preferably from 20 to 60 % by weight of the catalyst. Preferably, the catalyst has a hydrogenation-active site therein to ensure improved activity and prolonged life. Any such catalyst having hydrogenation activity is employable herein. The zeolite for the catalyst may have hydrogenation activity by itself, but is in any event, combined with rhenium. Preferably, the catalyst carries any of rhenium and its compounds. The rhenium may be introduced into the catalyst by, for example, ion exchange, impregnation, adsorption from the gaseous phase, introduction during zeolite synthesis adsorption of metal vapor, and any known method. The amount of the metal to be introduced into the catalyst is not specifically defined, and may be suitably determined depending on the reaction condition, etc. It is from 0.02 to 2 % by weight of the catalyst. Specific embodiments of the invention will now be described in still more detail with reference to the following Examples. Example 1: 105 g of powdery, sodium-type synthetic mordenite, 45 g of α-alumina, 12 g of alumina sol (having an alumina content of 10 % by weigh), 10.5 g of alumina gel (having an alumina content of 70 % by weight), and a suitable amount of ion-exchanged water were mixed and kneaded for about 2 hours, then shaped into noodles having a size of 1.2 mm (outer diameter) × 1.0 mm (length), and dried at 120°C for 16 hours. 50 g of the noodles (dried at 120°C) were calcined at 400°C in air for 5 hours, and then processed with 100 g of an aqueous 10 wt.% ammonium chloride solution at 80 to 85°C for 1 hour. After having been separated from the liquid through filtration, these were washed, withwater. These were further processed with 100 g of an aqueous 5 wt.% tartaric acid solution at 80 to 85°C for 3 hours, separated from the liquid through filtration, and washed with water. Then, these were dipped in 6.5 g of an aqueous 5 wt.% rhenium (VII) oxide solution at room temperature. After having been dried at 120°C for 16 hours, these were calcined in air at 540°C for 8 hours. Thus was prepared an H-type synthetic mordenite catalyst. The catalyst was loaded into a fixed-bed reactor, and a starting material, from which the non-aromatic compounds had been removed through distillation, was contacted with the catalyst in the reactor. Before and after removal of the non-aromatic compounds, the composition of the starting material is given in Table 1; and the composition of the product obtained herein is also given therein. The reaction conditions are as follows: Reaction Conditions: Temperature 400°C Pressure 2.5 Mpa-G Liquid hourly space velocity 2.3 hrs -1 Hydrogen/starting material 4.0 mol/mol The hydrogen consumption throughout the reaction was 0.84 % by weight relative to the starting material; and the catalyst deactivation rate was -0.04 wt.%/100 hrs, calculated from the xylene content of the product. Constituent Ingredients Composition of Crude Material before removal of non-aromatic compound (wt.%) Composition of Starting Material after removal of non-aromatic compounds (wt.%) Composition of Product after 100 hours (wt.%) Non-aromatic Compounds 10.0 0.1 10.7 Benzene 21.3 22.6 8.0 Toluene 1.3 1.4 27.7 C8 Aromatic Compounds 0.3 0.3 33.5 C9 Aromatic Compounds 62.3 70.2 17.6 C10 Aromatic Compounds 4.8 5.4 2.5 Comparative Example 1: The crude material used in Example 1 was, without being subjected to distillation, directly contacted with the catalyst under the same condition as in Example 1. The data obtained are given in Table 2. In this, the hydrogen consumption throughout the reaction was 1.14 % by weight; and the catalyst deactivation rate was -0.08 wt.%/100 hrs. Constituent Ingredients Composition of Starting Material (wt.%) Composition of Product after 100 hours (wt.%) Non-aromatic Compounds 10.0 19.5 Benzene 21.3 7.7 Toluene 1.3 25.8 C8 Aromatic Compounds 0.3 29.7 C9 Aromatic Compounds 62.3 15.1 C10 Aromatic Compounds 4.8 2.2 From the data in Tables 1 and 2, it is understood that, in the process of contacting the benzene-containing aromatic hydrocarbon material, of which the non-aromatic hydrocarbon content is not larger than 1 % by weight, with the catalyst, the aromatic compounds in the material are efficiently converted into useful aromatic hydrocarbons such as toluene and xylene.

Claims: A method for converting aromatic hydrocarbons, which method comprises contacting an aromatic hydrocarbon material containing from 5 to 80% by weight of benzene and having a non-aromatic compound content of at most 1 % by weight, with a catalyst which contains mordenite and rhenium and has a rhenium content, by weight of the catalyst, of from 0.02 to 2% by weight. A method according to claim 1, which includes the preliminary steps of removing non-aromatic compounds from a crude aromatic hydrocarbon material containing benzene and non-aromatic compounds so as to reduce the non-aromatic compound content of the material to at most 1% by weight, and thereafter the material is converted. A method according to claim 1 or claim 2, wherein the aromatic hydrocarbon conversion is for transalkylation. A method according to any preceding claim, wherein hydrogen is present in the reaction system. A method according to any preceding claim, wherein the starting material contains C9+ alkyl-aromatic hydrocarbons. A method according to claim 5, wherein the content of benzene and C9+ aromatic hydrocarbons in the starting material is reduced and the content of C7 and C8 aromatic hydrocarbons in the product is increased. A method according to any one of the preceding claims, wherein the aromatic hydrocarbon material has a non-aromatic compound content of at most 0.5% by weight. A method according to claim 7, wherein the aromatic hydrocarbon material has a non-aromatic compound content of at most 0.1% by weight. A method according to claim 2, which method comprises mixing a benzene-containing fraction obtained by gasoline fractionation, with an aromatic hydrocarbon material that contains C9+ aromatic hydrocarbons, reducing the non-aromatic compound content of the resulting mixture so as to provide an aromatic hydrocarbon material having a non-aromatic compound content of at most 1 % by weight, then contacting the mixture with a catalyst containing mordenite and, by weight of the catalyst, 0.02 to 2% by weight of rhenium to thereby convert the aromatic hydrocarbons therein, and separating the resulting C7 and C8 aromatic hydrocarbons from the reaction mixture.

Inventors: ICHIOKA RYOJI, KITAMURA AKIRA, YAMAKAWA SHINOBU, ICHIOKA, RYOJI, KITAMURA, AKIRA, YAMAKAWA, SHINOBU
Applicants: TORAY INDUSTRIES, TORAY INDUSTRIES, INC.
Application year: 2000
Main classification: C07C6
IPC codes: C07C6, C10G35