TW201720522A - Method for producing propylene or aromatic hydrocarbon - Google Patents

Abstract

A method for producing propylene or an aromatic hydrocarbon, wherein the production method includes a conversion reaction step in which a hydrocarbon raw material including a sulfur compound as an impurity and containing at least one C4-12 olefin is brought into contact with a zeolite-containing catalyst in a production reactor, and a catalyst regeneration step for burning off the carbonaceous substance adhered to the zeolite-containing catalyst; in the catalyst regeneration step, the temperature of the equipment and line through which the regeneration gas flows is maintained at or above the dew point temperature of the sulfuric acid contained in the regeneration gas flowing through the equipment and line.

Description

Method for producing propylene or aromatic hydrocarbon

The present invention relates to a process for producing propylene or an aromatic hydrocarbon from a hydrocarbon feedstock containing olefins having 4 to 12 carbon atoms.

A zeolite-containing molded body catalyst (hereinafter also referred to as "zeolite-containing catalyst" or "zeolite catalyst") obtained by molding a zeolite and a molding agent is widely used as a propylene or aromatic derived from a hydrocarbon raw material. Catalyst for the contact conversion reaction of hydrocarbons. For example, Patent Document 1 discloses a method of producing propylene using a zeolite catalyst having a high SiO ₂ /Al ₂ O ₃ molar ratio. Here, the zeolite catalyst used for the reaction and after a certain period of time is degraded by the adhesion of the carbonaceous substance (hereinafter also referred to as "coking"), and therefore the carbon material (hereinafter also referred to as " The coke ") is removed to regenerate the catalyst, and activation of the activity is sought. As a method of removing the coke attached to the catalyst, for example, a method of burning and removing the coke using an oxygen-containing gas can be mentioned. Further, in the case where the hydrocarbon raw material is derived from a fossil fuel, it is known to contain a sulfur compound as an impurity. For example, Patent Document 2 discloses a method of producing an olefin-containing hydrocarbon raw material containing a sulfur-containing hydrocarbon to produce a olefin having a lower molecular weight than that of the raw material and hydrogen sulfide, and describing the mixture after the reaction (hereinafter, also referred to as " The reaction mixture") contains olefins and hydrogen sulfide. [Prior Art Document] [Patent Document 1] [Patent Document 1] European Patent No. 109,060 [Patent Document 2] European Patent No. 1,840,189

[Problems to be Solved by the Invention] In the method of obtaining a propylene or an aromatic hydrocarbon from a hydrocarbon raw material using a zeolite-containing catalyst as described in Patent Documents 1 and 2, the reaction time may be generated earlier than usual. Decrease in selectivity or deterioration in coking. It is an object of the present invention to provide a method and apparatus for producing propylene or an aromatic hydrocarbon from a hydrocarbon feedstock by a conversion reaction step using a zeolite-containing catalyst, which method and apparatus can inhibit the catalyst accompanying the passage of reaction time The production of propylene or aromatic hydrocarbons is reduced while the performance is lowered. [Technical means for solving the problem] There are a plurality of reasons for the decrease in the selectivity of the target product of the catalyst or the deterioration of the coking, and the inventors have found that one of the causes is that foreign matter such as rust enters the reactor and adheres thereto. catalyst. Further, it is presumed that the source of the rust or the like may be in the piping and/or the machine of the regeneration system, and further research has been carried out. As a result, it is found that one part of the sulfur is adsorbed to the catalyst during the reaction, and the catalyst is released as a sulfur oxide when the catalyst is regenerated, if it is regenerated. The temperature of the gas is below the dew point of the sulfuric acid, causing corrosion of the piping and/or machine. It is known that sulfur derived from a sulfur compound contained in a hydrocarbon raw material mainly becomes hydrogen sulfide in a reaction in a reducing environment. However, the inventors of the present invention conducted research and found that not all of the sulfur derived from the sulfur compound is converted into hydrogen sulfide or the like, and the component in the mixture after the reaction is released to the outside of the reaction device, but a part thereof is adsorbed. Remains in the state of the catalyst containing zeolite. Further, a new problem has been discovered in which, when regeneration using a catalyst containing an oxygen-containing gas, sulfur adsorbed to the catalyst is released as sulfur oxide into the regeneration gas, thereby being stored in a piping system or apparatus through which the regeneration gas flows. It is the cause of corrosion of the manufacturing equipment. Further, it has been found that foreign matter such as rust or corroded metal sheets generated by the corrosion is mixed into a reaction system, particularly a reactor or a catalyst, and is deposited, so that the selectivity of the target product is lowered, acceleration of coking deterioration is accelerated, and The cause of the production of propylene or aromatic hydrocarbons is hindered by the deterioration of the amount of coke, the generation of the differential pressure in the reactor, the bias of the material gas, and the fluctuation of the reaction effect caused by the bias. In addition, when the hydrocarbon raw material contains 20% by mass or more of the olefin component having 4 to 12 carbon atoms, the deterioration rate of the catalyst due to coking is increased, so that the frequency of regeneration must be further increased, and the corrosion of the above-mentioned manufacturing apparatus becomes easier. get on. The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, reached the conclusion that the temperature of the pipeline and the machine through which the regeneration gas flows in the catalyst regeneration step of the zeolite-containing catalyst used in the contact conversion reaction described above The present invention can be completed based on the knowledge by maintaining the dew point temperature of sulfuric acid above the regeneration condition of the regeneration step, thereby protecting the manufacturing apparatus from acid corrosion caused by sulfur oxides. Further, at this time, the dew point temperature of the sulfuric acid contained in the regeneration gas can be obtained by measuring the sulfuric acid concentration and the water pressure in the regeneration gas. Further, the dew point temperature (dew point estimation temperature) of the sulfuric acid contained in the regeneration gas can be estimated by a method based on the sulfur deposition rate or the sulfur accumulation amount on the zeolite-containing catalyst. Further, as described below, the sulfur accumulation rate and the sulfur accumulation amount on the catalyst can be estimated by knowing the amount of the acid of the zeolite-containing catalyst in advance, and the sulfuric acid contained in the regeneration gas can be estimated in the same manner as described above. Dew point temperature. Further, the "dew point temperature" in the present embodiment means both the measured dew point temperature and the dew point estimated temperature estimated based on the sulfur deposition rate or the like. That is, the present invention is as follows. [1] A production method for producing propylene or an aromatic hydrocarbon, and comprising the steps of: a conversion reaction step of causing a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms; The catalyst is contacted with the zeolite-containing catalyst; and the catalyst regeneration step is performed by burning and removing the carbonaceous material attached to the zeolite-containing catalyst; and in the catalyst regeneration step, the regeneration gas is circulated The temperature of the pipeline and the machine is maintained at a temperature above the dew point of the sulfuric acid contained in the regeneration gas flowing through the pipeline and the machine. [2] A production method which is a method for producing propylene, and comprising the steps of: a conversion reaction step of producing a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms in a reactor Contacting with a zeolite-containing catalyst; a catalyst regeneration step of burning and removing the carbonaceous material attached to the zeolite-containing catalyst; and a separation step of separating the reaction mixture obtained in the above conversion reaction step into a main a light fraction containing hydrogen and a hydrocarbon having 1 to 3 carbon atoms and a heavy fraction mainly containing at least one hydrocarbon having 4 or more carbon atoms; and a recycling step of recycling part or all of the above heavy fraction to the above The reactor is used to produce the hydrocarbon raw material; and in the catalyst regeneration step, the temperature of the pipeline and the machine through which the regeneration gas flows is maintained as the dew point of the sulfuric acid contained in the regeneration gas flowing through the pipeline and the machine. Above temperature. [3] The production method according to [1] or [2] above, wherein the regeneration gas is recycled. [4] The production method according to any one of the above [1] to [3] wherein the production reactor is two or more insulated fixed-bed reactors, and the conversion reaction step is performed in the reactor The above catalyst regeneration step. [5] The production method according to any one of the above [1] to [4] wherein the hydrocarbon raw material contains 20% by mass or more of the olefin having 4 to 12 carbon atoms. [6] The production method according to any one of the above [1] to [5] wherein the catalyst regeneration step is carried out at a frequency of one or more times a month. [7] The method according to any one of the above [1] to [6] wherein the zeolite-containing catalyst contains a zeolite having an intermediate pore diameter of 5 to 6.5 Å. [8] The production method according to any one of [1] to [7] wherein the zeolite-containing catalyst contains a Group IB metal. [9] The method according to any one of the above [1] to [8] wherein the zeolite-containing catalyst contains a porous refractory inorganic oxide. [10] The production method according to any one of [1] to [9] wherein the zeolite-containing catalyst is heat-treated at a temperature of 500 ° C or higher in the presence of water vapor before being contacted with the hydrocarbon feedstock. . [11] The production method according to any one of [1] to [10] wherein the catalyst regeneration step is started at a temperature lower than the temperature of the conversion reaction step. [12] The production method according to any one of the above [1] to [11], further comprising a drying step of cooling the regeneration gas used in the catalyst regeneration step to remove water in the regeneration gas Vapor. [13] The production method according to any one of the above [1] to [12], comprising the step of calculating a correlation between an acid amount of the zeolite-containing catalyst and a catalyst accumulation ratio of sulfur or a catalyst accumulation amount. The sulfuric acid concentration is determined from the sulfuric acid concentration to determine the dew point of the sulfuric acid contained in the regeneration gas. [14] A device for producing propylene or an aromatic hydrocarbon, which is a device for producing propylene or an aromatic hydrocarbon, and having at least one production reactor having a conversion reaction step of performing a process of bringing a hydrocarbon feedstock into contact with a catalyst. And a function of a catalyst regeneration step of combusting and removing the carbonaceous material adhering to the catalyst by the conversion reaction step by contacting the oxygen-containing gas with the catalyst, the production reactor having the first piping system And feeding the hydrocarbon raw material into the above-mentioned manufacturing reactor and sending the reaction mixture from the manufacturing reactor; and a second piping system that feeds the oxygen-containing gas into the manufacturing reactor and the regeneration gas The second piping system includes a dryer that removes water vapor in the regeneration gas. [15] The apparatus for producing propylene or an aromatic hydrocarbon according to [14] above, wherein the second piping system further includes a temperature measuring device that measures a temperature of the regeneration gas. [Effects of the Invention] According to the production method of the present invention, when the propylene or aromatic hydrocarbon is produced from the olefin-based hydrocarbon raw material, corrosion of the production apparatus occurs, and the influence of the foreign matter mixed by the corrosion can be avoided, thereby stably and stably The olefin-based hydrocarbon feedstock produces propylene or an aromatic hydrocarbon.

Hereinafter, the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail with reference to the drawings as needed. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention. In the drawings, the same elements are denoted by the same reference numerals, and the description thereof will not be repeated. Further, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawing unless otherwise specified. Further, the dimensional ratio of the drawings is not limited to the illustrated ratio. The method for producing propylene or an aromatic hydrocarbon according to the present embodiment includes: a conversion reaction step of causing a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms in a reactor for synthesizing with a zeolite-containing contact a medium contact; and a catalyst regeneration step of burning and removing the carbonaceous material attached to the zeolite-containing catalyst; and in the catalyst regeneration step, maintaining the temperature of the pipeline and the machine through which the regeneration gas flows is The dew point temperature of the sulfuric acid contained in the regeneration gas flowing through the pipeline and the machine is equal to or higher than the dew point. [Propylene Production Reaction] (1) Manufacturing Apparatus A method for producing propylene according to the first aspect of the present embodiment will be described. Fig. 1 is a schematic view showing an example of a manufacturing apparatus for carrying out the method for producing propylene according to the embodiment. The manufacturing apparatus shown in Fig. 1 is connected by piping: a tank 1 for containing a hydrocarbon feedstock; and a reactor 4 for producing a reaction mixture containing propylene by contact conversion of a hydrocarbon feedstock; heat exchangers 2, 3; Performing heat exchange of the above reaction mixture with a hydrocarbon feedstock; a heater 6, which heats the hydrocarbon feedstock to a specific temperature; a heat exchanger (cooler) 10 which cools the reaction mixture; and a compressor 11, which is a reaction mixture Compressing; a heat exchanger (cooler) 12 that cools the compressed reaction mixture; a tank 13 that stores the fraction condensed by the heat exchangers 10, 12; and a distillation column 14 that separates the reaction mixture into hydrogen and carbon a fraction of 3 or less and a fraction having a carbon number of 4 or more; a heat exchanger (cooler) 15 which cools hydrogen and a fraction having a carbon number of 3 or less at the top of the column of the distillation column 14; and a tank 16 which stores the cooled fraction It is refluxed to the top of the column of the distillation column 14. Further, in Fig. 2, the line through which the regeneration gas flows in the catalyst regeneration step is indicated by a thick solid line. Further, with respect to the more front end portion of the pressure holding valve 9 of Fig. 2, since the regeneration gas is only released and not returned to the reactor, the portion is excluded from the line to be circulated. Further, the following members are connected by piping: a reactor 5 which simultaneously performs regeneration of the catalyst while the reactor 4 provides a reaction; a heater 6 which heats the regeneration (combustion) gas to a specific temperature; the heat exchanger 7, which The heat exchange of the regeneration gas is performed; the compressor 8 compresses the regeneration gas; and the pressure maintaining valve 9 flushes the necessary amount of regeneration gas. 3 is a schematic view showing an example of a manufacturing apparatus in which a heat exchanger (dryer) 17 is provided in a line through which a regeneration gas flows, and the regeneration gas is cooled by a heat exchanger (dryer) 17 to remove the regeneration gas. Water vapor in the water. A heat exchanger (dryer) 17 is provided as needed. As shown in FIG. 1, when a plurality of reactors are used to carry out a reforming reaction in a part of the reactor 4, while performing a regeneration operation in the reactor 5 of another portion, from the viewpoint of safety, It is preferable to use a double block bleed isolation reaction system and a regeneration system to prevent the feed hydrocarbons charged into the reactor 4 for performing the conversion reaction from being mixed with the oxygen supplied to the reactor 5 for performing the regeneration operation. Form an explosive mixture. That is, it is preferred to carry out the conversion reaction step and the catalyst regeneration step in the production of the reactor. For example, the catalyst regeneration step may be carried out in the reactor 5 while the conversion reaction step is carried out in the reactor 4 during the first period, and the conversion reaction step is carried out in the reactor 5 while performing the conversion reaction step in the reactor 5 in the second period. Catalyst regeneration step. Further, the catalyst regeneration step may be carried out in the reactor 5 while the conversion reaction step is carried out in the reactor 4 during the first period, and the conversion reaction step is carried out in the reactor 5 while in the second period. The catalyst regeneration step is carried out, and the conversion reaction step is carried out in the reactors 4, 5 during the third period. Further, the reactors 4 and 5 are not limited to two in total, and may be three or more in total. For example, the catalyst regeneration step can be carried out in the reactor 5 while the conversion reaction step is carried out in the reactors 4, 4a (not shown) during the first period, and the conversion is carried out in the reactors 4, 5 during the second period. In the reaction step, a catalyst regeneration step is carried out in the reactor 4a, and a catalyst regeneration step is carried out in the reactor 4 while performing a conversion reaction step in the reactors 4a and 5 in the third period. In the case where the number of reactors is one, the conversion reaction step may be carried out in the reactor during the first period, and the catalyst regeneration step may be carried out in the same reactor during the second period. Thus, the steps carried out in the reactors 4, 5 can be switched between the conversion reaction step and the catalyst regeneration step depending on the period, but the following is the reactor 4 as the reactor for carrying out the conversion reaction step, and the reactor 5 is used as the reactor The reactor in which the catalyst regeneration step is carried out will be described. Reactor 4 is a reactor for carrying out a conversion reaction step by contacting a hydrocarbon feedstock with a zeolite-containing catalyst. In the reactor 4, a hydrocarbon raw material is accommodated through the heat exchangers 2, 3, and the hydrocarbon raw material is subjected to contact conversion by a zeolite-containing catalyst, whereby a reaction mixture containing propylene is obtained. Further, the heat exchanger 2 can heat the hydrocarbon feedstock introduced into the manufacturing apparatus by utilizing the heat of the hydrocarbon fluid in the reactor 4. The reaction mixture containing propylene obtained in the reactor 4 is sent to the distillation column 14 as needed by being compressed by the compressor 11. Preferably, at least a part of the specific fraction separated in the distillation column 14 , specifically, at least a part of the heavy fraction mainly containing a hydrocarbon having 4 or more carbon atoms is contained in the reactor 4 by recycling, and is contacted. Conversion. The aspect of this recycling will be explained below. In the distillation column 14, the propylene-containing reaction mixture obtained from the reactor 4 separates propylene as a light fraction. Examples of the separation of the reaction mixture include a separation step of a light fraction separated into a hydrocarbon mainly containing hydrogen and having 1 to 3 carbon atoms and a heavy fraction mainly containing at least one hydrocarbon having 4 or more carbon atoms, and further The above-mentioned light fraction separates the form of propylene, but is not limited to this aspect. Further, as the reactor 4, any of a fixed bed type, a moving bed type, a fluidized bed type, and a gas stream transfer type can be used. Among them, a heat insulating fixed bed type reactor having a simple structure is preferable. In the case where the reactor 4 is a moving bed type or a fluidized bed type or a gas stream conveying type, the method of isolating the connection between the reaction system including the reactor 4 and the regeneration system including the reactor 5 by the connection of the piping may be a double cutoff. Release, or not to double discharge. The material constituting the reactor 4 and the reactor 5 is preferably a metal material such as carbon steel or stainless steel. (2) Hydrocarbon Raw Material In the method for producing propylene according to the present embodiment, a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms is used as the hydrocarbon raw material used in the reaction. The term "hydrocarbon feedstock" means a hydrocarbon having 1 to 12 carbon atoms, for example, a cycloalkane selected from the group consisting of a normal paraffin having 1 to 12 carbon atoms, an isoalkane, an olefin, a naphthene, and a naphthene having a side chain alkyl group. a raw material for at least one hydrocarbon in the group. In addition, the term "olefin" used in the present specification is used as a term encompassing linear, branched, cyclic olefins and cycloalkanes. When the total amount of all the hydrocarbons contained in the hydrocarbon raw material is 100% by mass, the content of the olefin in the hydrocarbon raw material is preferably 20% by mass or more, more preferably 30% by mass or more, and further preferably It is 40% by mass or more. If the content of the olefin is less than 20% by mass, the yield of propylene tends to decrease. In the present embodiment, a hydrocarbon raw material containing a sulfur compound as an impurity is used. Specifically, when the hydrocarbon raw material is 100% by mass as a whole, a hydrocarbon raw material containing at least one or more ppm by mass of a sulfur compound is used. The hydrocarbon raw material may be a hydrocarbon raw material containing a total of 0.001% by mass or more of one or more sulfur compounds, or may be a hydrocarbon raw material containing 0.01% by mass or more. The total content of the sulfur compounds in the hydrocarbon raw material is preferably 5% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less. When the content of the sulfur compound in the hydrocarbon raw material exceeds 5% by mass, the action of the zeolite catalyst as a catalytic poison increases, and it is difficult to achieve stable operation. The sulfur compound contained in the hydrocarbon raw material is not particularly limited, and examples thereof include mercaptans such as hydrogen sulfide, carbonyl sulfide, carbon disulfide, and methyl mercaptan, and thioethers such as dimethyl sulfide, and dimethyl disulfide. Disulfides such as ethers and thiophenes. In order to suppress the corrosion of the pipeline and the machine in the catalyst regeneration step, the desulfurization operation for reducing the amount of the sulfur compound contained in the hydrocarbon feedstock may be performed before the supply to the conversion reaction step, but at the same time, the amount of the olefin component in the hydrocarbon feedstock is reduced, so that It is preferred not to perform the desulfurization operation. Further, a small amount of an oxygen-containing compound such as a third butanol, methyl tertiary dibutyl ether or methanol or a nitrogen-containing compound may be contained in the hydrocarbon raw material. The hydrocarbon raw material may also contain a diene (diene) compound such as propadiene, butadiene or pentadiene or an acetylene compound such as methyl acetylene. It is known that these diene compounds and acetylene compounds are highly polymerizable and cause deterioration of coking of the catalyst. Therefore, it is preferred to minimize the content of the diene compound and the acetylene compound before the contact conversion reaction by pretreatment such as distillation separation or partial hydrogenation. In the case where the following catalyst is used, when the total amount of the diolefin compound and the acetylene compound is 2.5% by mass or less based on the total amount of the hydrocarbon raw material, the above pretreatment is not necessary, and it can be directly used as a reaction raw material. tendency. When it is desired to produce propylene more stably, the total amount of the diolefin compound and the acetylene compound is preferably 2% by mass or less based on the total amount of the hydrocarbon raw material. Also, the hydrocarbon feedstock can be a mixture with a diluent gas. Examples of the diluent gas include inert gases such as hydrogen, methane, steam, and nitrogen, and it is preferred that dilution by hydrogen is not performed. That is, hydrogen can be used to suppress the deterioration of the coke of the catalyst, but at the same time, hydrogenation reaction such as formation of propylene or the like may be caused, so that the purity of the olefin contained in the mixture after the reaction (also referred to as "reaction mixture") (propylene/(propylene) may be present. + propane), etc.) the possibility of reduction. As the hydrocarbon raw material, for example, the following enumerators can be used. (a) a C4 fraction and a C5 fraction obtained by thermally decomposing a petroleum-based hydrocarbon such as naphtha, and a fraction obtained by partially hydrogenating a diene in the C4 fraction and the C5 fraction to an olefin; (b) a fraction obtained by separating or removing one or all of butadiene and isobutylene from the C4 fraction; (c) a fraction obtained by separating a part or all of isoprene and cyclopentadiene from the above C5 fraction; (d) C4 fraction and gasoline fraction obtained by fluidized medium cracking (FCC) of petroleum-based hydrocarbons such as vacuum gas oil; (e) C4 fraction separated from coke and gasoline fraction The above hydrocarbon raw materials may be used alone or Mix two or more types. (3) Catalyst Containing Zeolite In the method for producing propylene according to the present embodiment, a catalyst containing zeolite is used as a catalyst for the contact conversion reaction. The hydrocarbon raw material is brought into contact with a catalyst containing zeolite in the reactor 4 to carry out a contact conversion reaction of a hydrocarbon raw material containing at least one olefin having 4 to 12 carbon atoms contained in the hydrocarbon raw material, thereby obtaining a reaction mixture containing propylene. Thereafter, propylene is separated from the obtained reaction mixture in the distillation column 14. In the present embodiment, "zeolite" means a crystalline porous aluminosilicate or a metal silicate, and also contains a phosphate-based porous crystal having the same or similar structure. In addition, the metal citrate refers to a zeolite in which a part or all of the aluminum atoms constituting the skeleton of the crystalline porous aluminosilicate are substituted with an element such as Ga, Fe, B, Cr or Ti. Specifically, examples of the zeolite having a small pore diameter (structure of oxygen 8 or less ring or less) include chabazite (a code which is classified according to the zeolite structure according to the International Zeolite Association and is expressed as "CHA"). ; the following is the same classification), hairy zeolite (ERI), type A (LTA). Examples of the zeolite having an intermediate pore diameter (oxygen 10 member ring structure) include ferrierite (FER), MCM-22 (MWW), ZSM-11 (MEL), ZSM-5 (MFI), and AlPO4-11 (AEL). ). Further, examples of the zeolite having a large pore diameter (oxygen 12-membered ring structure) include L-form (LTL), X-form (FAU), Y-form (FAU), faujasite (FAU), and beta-form (BEA). Mordenite (MOR), ZSM-12 (MTW), AlPO4-5 (AFI). Further, examples of the zeolite having a large pore diameter (structure of oxygen 14 or more rings) include UTD-1 (DON), CIT-5 (CFI), and VPI-5 (VFI). Among the above, as the zeolite in the zeolite-containing catalyst, an intermediate pore diameter zeolite having a pore diameter of 5 to 6.5 Å is preferable. The intermediate pore diameter zeolite is not particularly limited. For example, in addition to the above, it may be a ZSM-8, ZSM-12, ZSM-18, ZSM-23, ZSM-35, ZSM having a structure similar to ZSM-5. A so-called pentasil-type zeolite such as -39. Among them, a zeolite classified into an MFI structure according to a skeleton structure type recommended by the IUPAC (International Union of Pure and Applied Chemistry) is preferable, and ZSM-5 is particularly preferable. Further, a zeolite similar to ZSM-5 and ZSM-11 described in "Stud. Surf. Sci. Catal." 33, P. 167-215 (1987, Netherlands) by PA Jacobs and JA Martens can also be used. SiO of zeolite contained in zeolite-containing catalyst ₂ /Al ₂ O ₃ The molar amount is preferably 200 or more and 3,000 or less, more preferably 500 or more and 2,000 or less. If SiO ₂ /Al ₂ O ₃ When the molar ratio is 200 or more, the deterioration of coking of the zeolite-containing catalyst caused by the coke generated by the conversion reaction tends to be suppressed. When the deterioration of the coke of the zeolite-containing catalyst is suppressed, for example, the switching frequency to the regeneration system can be changed when the reactor of the reaction system is switched between the reactor of the reaction system and the reactor of the regeneration system in a fixed-bed double-tower swing mode. It is less, so that the regeneration (permanent) of the catalyst can be prevented from deteriorating. Here, the term "regeneration (permanent) deterioration means that when the catalyst is regenerated, the water vapor generated by the combustion of the coke promotes the detachment of the aluminum of the zeolite crystal lattice at a high temperature to cause structural damage, and thus irreversible deterioration occurs. In this respect, by using the above zeolite-containing catalyst, the progress of regeneration (permanent) deterioration can be suppressed at the same time. Further, the method of the present embodiment contains 2.5% by mass of the hydrocarbon raw material after the hydrocarbon raw material of (d) or (e) or the partial hydrogenation of (a) and the separation and removal of (b) and (c). The following diolefin compounds can also be used. However, in the case where the hydrocarbon raw material contains a diene compound, the deterioration of coking is generally more remarkable as compared with the case where the diene compound is not contained, and the switching frequency of the reaction and regeneration must be further accelerated. In this case, if SiO is used ₂ /Al ₂ O ₃ When the zeolite having a molar ratio of 200 or more is used, the deterioration of the coke caused by the formation of coke is suppressed, and it is not necessary to preliminarily reduce the diene compound in the raw material by the pretreatment, so that it is advantageous in the case of industrial implementation. The tendency. On the other hand, if SiO ₂ /Al ₂ O ₃ When the molar ratio is 3,000 or less, there is a tendency to industrially produce a stable quality zeolite. Furthermore, zeolite SiO ₂ /Al ₂ O ₃ The molar ratio can be adjusted by the conventional methods previously known. Also, zeolite SiO ₂ /Al ₂ O ₃ The molar ratio can be determined by a known method, and can be obtained, for example, by completely dissolving the zeolite in an aqueous alkaline solution or a hydrofluoric acid aqueous solution, and using the plasma emission spectrometry or the like to obtain the resulting solution. Analyze. As the zeolite-containing catalyst, a metal aluminosilicate which is a part of the zeolite skeleton in which an aluminum atom is substituted by an element such as Ga, Fe, B, Cr or the like, or all of the aluminum atoms constituting the zeolite skeleton may be used as described above. Substituted metal citrate. In this case, the content of the above-mentioned elements contained in the metal aluminosilicate or the metal silicate is converted into the number of moles of alumina, and SiO is calculated. ₂ /Al ₂ O ₃ Moerby. As the zeolite containing a zeolite, a zeolite which is substantially free of protons can be used in addition to the proton type and the ammonium type. A zeolite which is substantially free of protons is less likely to cause deterioration of coking than a proton type, and thus it is not necessary to repeat the regeneration operation frequently. As a result, propylene can be produced stably and efficiently for a long period of time. The phrase "substantially free of protons" means that the amount of protons (acid amount) in the zeolite determined by liquid phase ion exchange/filtration titration is 0.02 mmol or less per 1 g of zeolite. It is preferably a zeolite having a proton amount of 0.01 mmol or less per 1 g of the zeolite. In addition, the above-mentioned "proton amount (acid amount) in the zeolite determined by liquid phase ion exchange/filtration titration method" is different from the following "the amount of acid in the zeolite determined from the amount of pyridine detachment" . Here, the liquid phase ion exchange/filtration titration method is referred to as Intrazeolite Chemistry, "ACS Symp. Ser.", 218, P369-382 (1983, USA), Japanese Chemical Society, [3], P.521- The method described in 527 (1989) and the like. The measurement of the proton amount of the zeolite using this method can be carried out as follows. After the ion-exchange treatment of the zeolite-containing catalyst calcined in the air using an aqueous NaCl solution, the catalyst was recovered by filtration, and a filtrate was obtained. The recovered catalyst was washed with pure water, and the entire amount of the obtained washing liquid was recovered, and mixed with the above filtrate to obtain a mixed solution. The amount of proton in the obtained mixed solution was determined by neutralization titration, and the value per unit mass of the zeolite contained in the zeolite-containing catalyst was defined as the proton amount of the zeolite. Further, it is known that an ammonium ion type and a polyvalent metal cation type zeolite (for example, a rare earth metal cation type zeolite) generate a proton by heat treatment. Therefore, it is necessary to carry out the calcination treatment of the zeolite-containing catalyst before the proton amount is measured by the above method. As the zeolite containing a catalyst containing zeolite which is substantially free of protons, a metal containing Group IB of the periodic table (hereinafter also referred to as "Group IB metal"), that is, a group selected from copper, silver, and gold may be used. a zeolite of at least one metal. As the Group IB metal, copper or silver is preferred, and silver is more preferred. Furthermore, in the present specification, the term "periodic table" means CRC Handbook of Chemistry and Physics, 75th edition [(David R. Lide et al., CRC Press Inc. (1994-1995)], 1-15 In the above-mentioned "group IB-containing metal", the IB group metal is contained in the state of the corresponding cation, and the group IB metal is contained in the zeolite in addition to the cation. In addition, it may be contained in the state of the oxide, for example, in the form of an oxide. Examples of the method of including the Group IB metal in the zeolite include a method such as an ion exchange method, an impregnation method, and a kneading method, and preferably an ion exchange method. A method of treating a zeolite containing no Group IB metal. When the zeolite contains a Group IB metal by an ion exchange method, a salt of a Group IB metal is preferably used. Examples of the salt of the Group IB metal include, for example, a salt of a Group IB metal. : silver nitrate, silver acetate, silver sulfate, copper chloride, copper sulfate, copper nitrate, gold chloride. The amount of Group IB metal contained in the zeolite-containing catalyst in the form of Group IB metal cations relative to zeolite-containing The mass of the medium is preferably from 0.005 to 5% by mass, more preferably from 0.01 to 3% by mass. Even if the content of the Group IB metal is more than 5% by mass, the performance of the catalyst containing zeolite is generally difficult to be improved. The content of the Group IB metal can be determined, for example, by X-ray fluorescence analysis or the like. Regarding the zeolite contained in the zeolite-containing catalyst, the remaining ion exchange sites exchanged with the Group IB metal cation can be selected from the base selected from the base. The cation of at least one of the metal and the alkaline earth metal is ion-exchanged. The zeolite contained in the zeolite-containing catalyst is preferably ion-exchanged by a cation selected from at least one metal of an alkali metal, more preferably selected. The cation of at least one of the metals of the group consisting of free sodium and potassium is ion-exchanged. That is, the zeolite-containing catalyst used in the propylene production method of the present embodiment contains zeolite, and may be selected from the group consisting of alkali metals and alkaline earth metals. a zeolite of at least one of the group consisting of at least one metal selected from the group consisting of a group IB metal, and at least one metal selected from the group consisting of alkali metals and alkaline earth metals. The method may be the same as the method of containing a Group IB metal in the zeolite. The content of at least one metal selected from the group consisting of alkali metals and alkaline earth metals varies depending on the kind of the metal, for example, in the case of sodium, relative to The mass of the zeolite-containing catalyst is preferably from 0.01 to 0.4% by mass, and in the case of potassium, the mass of the zeolite-containing catalyst is preferably from 0.01 to 0.8% by mass. In the case, the order or the number of times the method of containing at least one metal selected from the group consisting of alkali metals and alkaline earth metals in the zeolite and the method of containing the group IB metal is not particularly limited, and in any case, as described above Preferably, the metal-containing zeolite is substantially free of protons. For example, in the case of preparing a silver/sodium cation exchange type as a zeolite-containing catalyst, if a base component is present in the zeolite-containing catalyst, a part of the silver is present. It is not possible to carry it in the form of silver cations, and therefore it is preferred that the zeolite is previously converted into a proton type during molding. Specifically, it is preferred to exchange a zeolite-containing molded body catalyst molded as a proton-type zeolite into a sodium type (aprotic type) (preferably using an aqueous solution of sodium nitrate), and then exchange and introduce silver cations (preferably A method using an aqueous solution of silver nitrate). In the catalyst containing zeolite, it may be desirable to suppress coking deterioration or increase propylene yield, and further contains a component selected from the group consisting of V, Cr, Mo, W, Mn, Pt, Pd, Fe, Ni, Zn, Ga, etc. At least one metal of the group consisting of metals of Groups III, Vb, VIb, VIIb, and VIII. As a catalyst containing zeolite, a porous refractory inorganic oxide such as alumina, ceria, cerium oxide/aluminum oxide, zirconium oxide, titanium oxide, diatomaceous earth or clay is usually used as a binder or a thinning agent for molding. (Matrix) was mixed with the above zeolite to obtain a mixture, and the mixture was molded to obtain a molded body, and the obtained molded body was used as a molded body catalyst containing zeolite. In the case of using a matrix or a binder, the content is preferably from 10 to 90% by mass, more preferably from 20 to 50% by mass, based on the total mass of the zeolite and the matrix or the binder. The zeolite-containing catalyst can further improve the resistance to deterioration of coking, and is heat-treated at a temperature of 500 ° C or higher in the presence of water vapor before being contacted with the hydrocarbon raw material. The heat treatment is preferably carried out at a temperature of 500 ° C or more and 900 ° C or less, and a partial pressure of water vapor of 0.01 atm or more. (4) Conversion reaction step The production method of propylene according to the present embodiment includes a conversion reaction step of producing a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms in the reactor. Zeolite-containing catalyst contact. In the conversion reaction step, the zeolite-containing catalyst is filled into a reactor to carry out a contact conversion reaction of a hydrocarbon raw material containing at least one olefin having 4 to 12 carbon atoms. The reaction temperature in the conversion reaction step is preferably from 400 to 600 ° C, more preferably from 500 to 580 ° C. The partial pressure of the hydrocarbon feedstock is preferably lower, usually from 0.01 to 1 MPa, preferably from 0.05 to 0.3 MPa. The hourly weight space velocity WHSV of the hydrocarbon feedstock relative to the mass of the zeolite-containing catalyst is preferably from 1 to 100 hr. ^-1 More preferably 2 to 20 hr ^-1 The scope. The contact time of the hydrocarbon raw material with the zeolite-containing catalyst is preferably 5 seconds or shorter, more preferably 1 second or shorter. When the conditions of the conversion reaction step are in the above range, the olefin having 4 to 12 carbon atoms in the raw material hydrocarbon is converted into propylene at a high selectivity, and the alkane coexisting in the raw material hydrocarbon does not substantially react. Therefore, the conversion reaction of the olefin in the hydrocarbon feedstock is selectively promoted, and the conversion reaction of the alkane is suppressed, and as a result, the by-products of methane, ethane, propane, etc., which are caused by the conversion reaction of the alkane, are suppressed, and the propylene self-reaction The separation and purification of the mixture tends to be easy. The conversion reaction of the alkane is a large endothermic reaction, and the conversion reaction of the olefin varies depending on the reaction conditions, and is a micro endothermic reaction or an exothermic reaction. Therefore, when the olefin in the hydrocarbon feedstock is selectively reacted under the above conditions, it is not necessary to supply the heat of reaction, so that a thermally insulated fixed bed reactor having a simple structure can also be used, which is also an advantage. The method for controlling the formation of the aromatic hydrocarbon component having 6 to 8 carbon atoms in the conversion reaction step is not particularly limited, and a method for reducing the conversion ratio of the olefin in the hydrocarbon raw material is usually employed. The conversion ratio of the olefin herein means the olefin conversion ratio based on the butene represented by the following formula. Olefin conversion rate (%) = {(concentration of olefin having a carbon number of 4 or more in the hydrocarbon feedstock at the reactor inlet - concentration of butene in the hydrocarbon component of the reactor outlet) / carbon number of 4 or more in the hydrocarbon feedstock at the reactor inlet The olefin concentration} × 100 olefin conversion rate is preferably from 30 to 80% by mass, more preferably from 40 to 75% by mass. When the olefin conversion ratio is 30% by mass or more, the desired propylene yield tends to be obtained, and when it is 80% by mass or less, the formation of by-produced aromatic hydrocarbons tends to be suppressed. The method for reducing the conversion of the olefin is not particularly limited, and examples thereof include increasing the hourly weight space velocity of the hydrocarbon raw material, lowering the reaction temperature, or increasing the SiO of the zeolite in the zeolite-containing catalyst. ₂ /Al ₂ O ₃ Moerby and other methods. Further, the zeolite containing at least one metal selected from the group consisting of metals belonging to Group IB of the periodic table and substantially free of protons suppresses the aromaticity of 6 to 8 carbon atoms as compared with the commonly used H-type zeolite. Since the formation of a hydrocarbon is carried out, the conversion of olefin can be further increased, and as a result, there is a tendency for the yield of propylene to increase. (5) Separation step In the method for producing propylene according to the present embodiment, a separation step of separating the reaction mixture obtained in the above conversion reaction step into a light mainly containing hydrogen and a hydrocarbon having 1 to 3 carbon atoms may be included. The fraction is a heavy fraction mainly containing at least one hydrocarbon having 4 or more carbon atoms. The propylene can be further separated from the above light fraction. The separation step can be carried out by various known methods such as combining bifurcation, extraction, and the like. (6) Recycling Step The propylene production method of the present embodiment may further include a recycling step of recycling part or all of the above heavy fraction to a production reactor for use as a hydrocarbon feedstock. As described above, in addition to propylene, an olefin having 4 or more carbon atoms and an aromatic hydrocarbon are present in the reaction mixture. Therefore, in order to increase the propylene yield per unit mass of the hydrocarbon feedstock containing at least one olefin having 4 to 12 carbon atoms as a raw material of the conversion reaction step, the heavy mass mainly containing a hydrocarbon having 4 or more carbon atoms can be separated from the reaction mixture. Part or all of the fraction is recycled to the reactor and reacted again to achieve efficient use of the hydrocarbon feedstock. In the recycling step, the heavy fraction is not refined and used directly as a recycle feedstock, whereby a simpler recycle process can be constructed. Further, by increasing the recycling ratio of the recycling step, there is a tendency to increase the production ratio of propylene. Moreover, in the case of increasing the recycling ratio, it can be an effective method for increasing the purity of propylene. The recycle ratio of the heavy fraction (the ratio of the amount returned to the total amount of the heavy fraction in the reactor 4 of the conversion reaction step) may also be set to 100% by mass (total amount), preferably 10 to 95% by mass. % is more preferably 15 to 90% by mass. If the recycling ratio is less than 10% by mass, there is a tendency that the contribution to the increase in propylene production is small. On the other hand, when the recycling ratio exceeds 95% by mass, the alkane component contained in the raw material hydrocarbon or the aromatic hydrocarbon component having 6 to 8 carbon atoms formed in the reactor becomes large, and there is a reactor for the reactor. The tendency of the load to become too large. However, if the amount of the alkane and the aromatic hydrocarbon in the heavy fraction is within the allowable range of accumulation, the entire amount may be recycled at once. The ratio of the hydrocarbon component having 9 or more carbon atoms in the heavy fraction is preferably 20% by mass or less, more preferably 15% by mass or less. When the ratio of the hydrocarbon component having a carbon number of 9 or more is 20% by mass or less, the ratio of the aromatic hydrocarbon component in the hydrocarbon component having 9 or more carbon atoms is small, and the tendency to obtain propylene more efficiently is obtained. In the case of carrying out the recycling step, the amount of the aromatic hydrocarbon component having a carbon number of 6 to 8 (mass %) generated in the reactor is divided by the partial pressure of hydrocarbon [MPa] from the viewpoint of efficiently obtaining propylene. The calculated value is preferably 13 or less, more preferably 10 or less. When the calculated value is 13 or less, there is a tendency that it is difficult to cause a decrease in activity due to coking, and it is relatively easy to change the ratio of the olefin component in the component having 9 or more carbon atoms of the aromatic hydrocarbon component. The component is recycled to increase the propylene production. When the above calculated value exceeds 13, it is easy to cause a decrease in catalytic activity due to coking under the reaction conditions in which an aromatic hydrocarbon component is easily formed. Further, by increasing the aromatic hydrocarbon component having 6 to 8 carbon atoms formed in the reactor, not only the yield of propylene is lowered, but also the aromatic hydrocarbon component having 6 to 8 carbon atoms and the carbon number of 9 or more in the recycled raw material. The ratio of the aromatic hydrocarbon component also becomes high. As a result, it is easy to cause accumulation in the reaction system and promote coking. Further, it is considered that the amount of sulfur accumulated in the zeolite-containing catalyst is higher than that in the case where the heavy fraction is recycled, but in the regeneration step described below, the regeneration gas is distributed. Keep pipelines and machines above a certain temperature to prevent corrosion caused by the acid in the manufacturing equipment. (7) Example of the case where the C4 fraction is used as a hydrocarbon raw material. Next, a method for producing propylene in the following case will be described in more detail with reference to Fig. 1, that is, a C4 fraction obtained from a steam cracking product of a petroleum-based hydrocarbon, from C4 The fraction obtained by extracting and separating butadiene from a fraction (mainly containing a hydrocarbon having a carbon number of 4 such as butane, isobutane, butylene or isobutylene, and a fraction having a diolefin compound of 2.5% by mass or less) is used as a hydrocarbon raw material, and is heavy. A portion of the fraction is recycled to the manufacturing reactor. Reactor 4 is a reactor for carrying out a conversion reaction step by contacting a hydrocarbon feedstock with a zeolite-containing catalyst. In the reactor 4, a hydrocarbon raw material is accommodated through the heat exchangers 2, 3, and the hydrocarbon raw material is subjected to contact conversion by a zeolite-containing catalyst, whereby a reaction mixture containing propylene is obtained. The reaction mixture (hydrogen and a mixture of hydrocarbons having a carbon number of 1 or more) obtained in the reactor 4 is subjected to heat recovery by the heat exchanger 10 after passing through the heat exchangers 2 and 3, and then pressurized by the compressor 11 to be further exchanged by heat. The device 12 is supplied to the distillation column 14. In the distillation column 14, the reaction mixture is separated into a light fraction mainly containing hydrogen and a hydrocarbon having 1 to 3 carbon atoms and a heavy fraction mainly containing at least one hydrocarbon having 4 or more carbon atoms. The apparatus (C3 separator) used for the separation is not limited to the distillation column, and for example, a sudden evaporation drum (gas-liquid separator) or the like can be used. The propylene is recovered from the obtained light fraction. In another aspect, at least a portion of the above heavy fraction can be recycled to the reactor for use as part of the propylene production feed. The butane contained in the raw material hydrocarbon in the heavy fraction is concentrated by the recycle of the heavy fraction, so that if the entire amount of the heavy fraction is recycled, butane is accumulated in the reactor. Accordingly, it is preferred to control the stacking of butane in the reactor by limiting the amount of heavy fraction recycled to the propylene production reactor to a portion of the resulting heavy fraction. When the initial hydrocarbon feedstock contains moisture or contains an oxygenate as an impurity, the reaction mixture also contains water. Most of the water in the reaction mixture is separated to the bottom of the column of the distillation column 14 (heavy fraction), but the water azeotroped with the propylene in the light fraction is sent to the top of the column and concentrated in the tank 16. Therefore, an extraction line can also be provided at the bottom of the tank 16 to remove water therefrom. In the case where a distillation column is used as the apparatus used for the separation, as the refrigerant of the cooler 15, propylene or ethylene can be used. For the separated light fraction mainly containing hydrogen and a hydrocarbon having 1 to 3 carbon atoms, another distillation column or a flash evaporation drum (gas-liquid separator), preferably a distillation column, may be used, and the separation is mainly composed of hydrogen and carbon number. The fraction of the hydrocarbon of 1 to 2 and the fraction of the hydrocarbon mainly containing 3 carbon atoms can also be carried out in the following manner. In other words, it is a purification system for an ethylene plant which can be purified and separated by hydrogen, methane, ethylene, propylene, C4 fraction, pyrolysis gasoline (hydrocarbon having 5 or more carbon atoms) obtained by thermally decomposing petroleum hydrocarbons such as naphtha. The light fraction mainly containing hydrogen and a hydrocarbon having 1 to 3 carbon atoms separated in the distillation column 14 is separated into hydrogen, methane (hydrocarbon of carbon number 1), ethylene and ethane (hydrocarbon of carbon number 2), Propylene and propane (hydrocarbons of carbon number 3). Propylene can be separated from propane as 99.9% or more of polymer grade propylene, or as chemical grade propylene containing several percent of propane. In the case where the light fraction separated in the distillation column 14 is introduced into the purification system of the ethylene plant, it is preferred to connect the light fraction line to the vicinity of the alkali compound washing column. Since there is a possibility that the light fraction contains a sulfur compound in the raw material, it is preferred to remove the sulfur compound in the cleaning column. The propylene or ethylene which can be used as the refrigerant of the refrigerator 15 can be propylene or ethylene obtained in the ethylene equipment refining system. Further, as the compressor 11, various types of compressors can be used, and in the case of using a screw compressor, a small amount of lubricating oil may be mixed into the condensate of the reaction mixture. In this case, the mixed lubricating oil is recirculated from the bottom of the distillation column 14 to the tank 1 and remains as a vaporized residue at the bottom of the heat exchanger 2, so that an extraction line may be provided at the bottom of the heat exchanger 2, from which Remove the oil. Further, the evaporation residue in the recycled heavy fraction can be similarly removed from the bottom of the heat exchanger 2. The light fraction is separated into a fraction mainly containing hydrogen and a hydrocarbon having 1 to 2 carbon atoms (hereinafter also referred to as "C2-fraction") and a fraction mainly containing a hydrocarbon having 3 carbon atoms (hereinafter also referred to as "C3 fraction"). Ethylene is recovered from the C2-fraction. In the case of the selective manufacture of propylene, at least a portion of the C2-fraction can be recycled to the reactor, with ethylene in the C2-fraction being used as part of the feedstock. The C2-fraction contains hydrogen, methane, and ethane in addition to ethylene. Therefore, when the entire amount of the C2-fraction is recycled, hydrogen, methane, and ethane are deposited. Therefore, it is preferred to control the accumulation of hydrogen, methane, and ethane by limiting the amount of the C2-fraction recycled to the reactor to a portion of the resulting C2-fraction. On the other hand, propylene is recovered from the C3 fraction, but when it is suitable to set the reaction conditions and separation conditions, it can be directly used as a chemical grade propylene. Further, the heavy fraction may be separated into a fraction mainly containing a hydrocarbon having 4 carbon atoms (hereinafter also referred to as "C4 fraction") and a fraction mainly containing at least one hydrocarbon having 5 or more carbon atoms (hereinafter also referred to as "C5+ fraction". "). The timing of separating the C4 fraction from a fraction mainly containing at least one hydrocarbon having 4 or more carbon atoms (hereinafter also referred to as "C4+ fraction") may be followed by recycling the C4+ fraction. As the apparatus (C4 separator) used for the separation, for example, a distillation column, a flash evaporation drum (gas-liquid separator), or the like can be used, and a distillation column is preferably used. A portion of the resulting C4 cut and/or C5+ fraction can be recycled to the conversion reactor for use as part of the feed hydrocarbon. A preferred embodiment of the recycle reaction system in the case of using the C4+ fraction as the hydrocarbon feedstock is to separate the reaction mixture (hydrogen and a mixture of hydrocarbons having a carbon number of 1 or more) into a C2 fraction and mainly contain at least one carbon number of 3 or more. The hydrocarbon fraction (hereinafter also referred to as "C3+ fraction"). As the apparatus (C2 separator) used for the separation, for example, a distillation column, a flash evaporation drum (gas-liquid separator), or the like can be used, and a distillation column is preferably used. Ethylene is recovered from the obtained C2 fraction, but in the case of selectively producing propylene, as described above, it is preferred to recycle at least a portion of the C2-fraction to the propylene production reactor, and use ethylene in the C2-fraction as a raw material. portion. On the other hand, the above C3+ fraction is separated into a C3 fraction and a C4+ fraction. As the apparatus (C3 separator) used for the separation, for example, a distillation column, a flash evaporation drum (gas-liquid separator), or the like can be used, and a distillation column is preferably used. The propylene is recovered from the C3 fraction, but when it is suitable to set the reaction conditions and the separation conditions, it can be directly used as a chemical grade propylene. [Aromatic Hydrocarbon Production Reaction] A method for producing an aromatic hydrocarbon as a second aspect of the present embodiment will be described. (1) Manufacturing apparatus In the second aspect, the same apparatus as the manufacturing apparatus of the first aspect described above can be used, but in the production of aromatic hydrocarbons, the conversion ratio of olefin as a raw material is approximately 100%, and thus The separation step or the recycling step and the apparatus used therein are omitted. (2) Hydrocarbon raw material As the hydrocarbon raw material used in the reaction, a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms is used in the same manner as in the first aspect. The definition of "hydrocarbon feedstock", the preferred content of sulfur compound, and the preferred embodiment of the hydrocarbon feedstock that can be used are the same as in the first aspect. When the total amount of the hydrocarbons contained in the hydrocarbon raw material is 100% by mass, the content of the olefin in the hydrocarbon raw material is preferably 20% by mass or more, and more preferably 30% by mass or more. When the content of the olefin is less than 20% by mass, in order to maintain the amount of formation of the aromatic hydrocarbon, it is necessary to promote the conversion reaction of the alkane. In this case, the heat absorption amount accompanying the alkane conversion reaction becomes large, so that the reaction temperature is maintained. The effect of increased heat supply from the outside. Further, the fraction having 4 or more carbon atoms formed in the first aspect can also be used as a raw material, whereby the olefin-based hydrocarbon raw material can be effectively utilized. (3) Catalyst containing zeolite In the second aspect, the intermediate pore diameter zeolite for the catalyst containing zeolite is the same as the intermediate pore diameter zeolite detailed in the first aspect, except for the aspects described below. A metal aluminosilicate or metal citrate can be used. Zeolite SiO ₂ /Al ₂ O ₃ The molar amount is preferably 20 or more and 200 or less, more preferably 25 or more and 150 or less. If SiO ₂ /Al ₂ O ₃ When the molar ratio is 20 or more, the stability against high-temperature steam tends to be high. In other words, there is a tendency that the resistance to the so-called regenerative deterioration is high, and when the production method of the present embodiment is industrially carried out, it is difficult to cause regenerative deterioration due to repetition of reaction/regeneration. Also, if SiO ₂ /Al ₂ O ₃ When the molar ratio is 200 or less, the decomposition activity tends to be high, and the aromatic hydrocarbon yield tends to be high. As the zeolite containing a zeolite-containing catalyst, the zeolite described in Japanese Patent No. 3,905,948 can be used. Such a zeolite has a high crystallinity and a stable structure, so that it is highly resistant to regeneration deterioration, and a proton type can be used. In order to further improve the coking deterioration resistance, a zeolite having a large effective surface area and finer particles may be used. However, the crystal structure of such a zeolite often becomes unstable, hydrothermal stability is low, and regeneration (permanent) deterioration is liable to occur. Therefore, in the case of using such a zeolite, it is preferred that the first aspect of the propylene production reaction is substantially free of protons and contains a metal selected from Group IB of the periodic table, namely copper, silver, gold. An IB metal type zeolite of at least one metal of the group. The amount of the Group IB metal contained in the zeolite-containing catalyst as the Group IB metal cation is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass based on the mass of the zeolite-containing catalyst. Even if the content of the Group IB metal is more than 10% by mass, the performance of the catalyst containing zeolite is generally difficult to increase. The zeolite-containing catalyst may contain at least one metal selected from the group consisting of alkali metals and alkaline earth metals, depending on the kind of the metal, for example, in the case of sodium, relative to the mass of the catalyst containing zeolite. It is preferably 0.01 to 2.0% by mass, and in the case of potassium, the mass of the catalyst containing zeolite is preferably in the range of 0.01 to 3.0% by mass. The primary particle diameter of the zeolite is preferably 0.02 to 3 μm. The primary particle diameter when the zeolite is used in a proton type is more preferably 0.3 to 3 μm. When the zeolite is used in the IB metal type, since the hydrothermal stability is improved as compared with the proton type, a zeolite having a primary particle diameter of less than 0.3 μm can also be used. The shape of the primary particles of the zeolite has various shapes, and the primary particle diameter herein means the average diameter of the widest part of each particle. The primary particles may be present separately or may be agglomerated twice. When the primary particle diameter of the zeolite is 0.02 μm or more, there is a tendency to suppress the amount of carbonaceous material deposited on the catalyst during the conversion reaction, and to suppress the generation of the carbonaceous material by combustion with an oxygen-containing inert gas. Permanent activity degradation caused by dealumination in a high temperature environment where moisture is present. In addition, when the primary particle diameter of the zeolite is 3 μm or less, there is a tendency to temporarily reduce the activity of the carbonaceous material deposited on the catalyst during the conversion reaction. The primary particle size of the zeolite of the present embodiment means SiO ₂ /Al ₂ O ₃ Similarly to the molar ratio, the particle diameter of the primary particles in the case of the substantially fresh zeolite was observed by a scanning electron microscope. When the zeolite-containing catalyst is supplied to the conversion reaction, the ratio of the surface acid point to the total acid point in the case of the proton type is preferably from 0.03 to 0.15, more preferably from 0.05 to 0.1. By setting the ratio of the surface acid point to the total acid point to 0.03 or more, there is a tendency to suppress a temporary decrease in the activity due to the carbonaceous substance deposited on the catalyst at the time of the conversion reaction. In addition, when the ratio is 0.15 or less, there is a tendency to suppress the amount of carbonaceous material deposited on the catalyst during the conversion reaction, and to suppress the presence of moisture when the carbonaceous material is burned and removed by the oxygen-containing inert gas. The permanent activity caused by dealumination in a high temperature environment is deteriorated. Here, a method for determining the ratio of the surface acid point to the total acid point will be described below. The zeolite-containing shaped body catalyst preferably contains at least one selected from the group consisting of elements belonging to Groups IB, IIB, IIIB, and VIII of the periodic table, from the viewpoint of obtaining higher dehydrogenation energy. An element. Among them, a metal containing copper, zinc, gallium, indium, nickel, palladium, platinum, and/or the like (oxide, composite oxide, etc.) is preferable, and a compound containing zinc and/or zinc is more preferable. As a method of causing a zeolite-containing molded body catalyst to contain a metal belonging to Group IB, Group IIB, Group IIIB, Group VIII of the periodic table and/or such a compound, a usual ion exchange method or impregnation support can be used. Loading method. The amount of the metal and/or the compound of the element belonging to Groups IB, IIB, IIIB, and VIII of the periodic table contained in the zeolite-containing molded body catalyst is in terms of an element, and is relative to the catalyst as a whole. 0.1 to 25% by mass, preferably 2 to 20% by mass, more preferably 5 to 20% by mass. The zeolite-containing catalyst can usually be a porous refractory inorganic oxide such as alumina, ceria, cerium oxide/aluminum oxide, zirconia, titanium oxide, diatomaceous earth or clay as a binder or a molding diluent. Matrix). Among them, alumina or cerium oxide is preferred, and alumina is more preferred. The mixture obtained by mixing the binder or the matrix with the above zeolite can be molded, and the obtained molded body can be used as a molded body catalyst containing zeolite. In the case of using a matrix or a binder, the content is preferably from 5 to 50% by mass, more preferably from 10 to 50% by mass, based on the total mass of the zeolite and the matrix or the binder. The zeolite-containing catalyst used in the method for producing an aromatic hydrocarbon of the present embodiment is preferably used for the purpose of improving the resistance to coking deterioration, preferably in the presence of water vapor before contact with the hydrocarbon raw material. The heat treatment is carried out at a temperature of 500 ° C or higher. The heat treatment is preferably carried out at a temperature of 500 ° C or more and 900 ° C or less, and a partial pressure of water vapor of 0.01 atm or more. In the case of containing a mixture of zinc and a compound thereof and alumina, the heat treatment can stabilize the zinc component in the catalyst to zinc aluminate, thereby greatly suppressing the scattering loss of zinc in the reaction environment. . This effect is extremely advantageous when industrially manufacturing aromatic hydrocarbons. Further, the zinc aluminate in the present specification means an X-ray diffraction pattern having the same pattern as that shown in JCPDS 5-0669 NBS Circ., 539, Vol. II, 38 (1953). (4) Conversion reaction step In the second aspect, the conditions of the conversion reaction are the same as those of the conversion reaction detailed in the first aspect except for the aspects described below. The reaction conditions of the method for producing an aromatic hydrocarbon according to the present embodiment vary depending on the ratio of the amount of the olefin to the alkane in the light hydrocarbon raw material, particularly the raw material, and are preferably from 300 to 650 ° C, more preferably from 400 to 600 ° C. At a partial pressure of hydrocarbon of atmospheric pressure to 30 atmospheres, the hourly weight space velocity WHSV of the mass of the hydrocarbon feedstock relative to the mass of the catalyst containing zeolite is preferably 0.1 to 50 hr. ^-1 . Also, the hydrocarbon feedstock can be a mixture with a diluent gas. As the diluent gas, hydrogen, methane, steam, nitrogen, carbon dioxide, carbon monoxide or the like can be used. The content of the diluent gas in the hydrocarbon raw material is preferably 20% by volume or less, more preferably 10% by volume or less. As the reactor for producing an aromatic hydrocarbon, any of a reactor of a fixed bed type, a moving bed type, a fluidized bed type or a gas stream type can be used. Among them, a heat-insulated fixed bed reactor having a simple structure is preferable. [Ceramic Regeneration Step] In the method for producing propylene or an aromatic hydrocarbon according to the present embodiment, a catalyst regeneration step of burning and removing a carbonaceous substance adhering to the zeolite-containing catalyst is carried out. Hereinafter, the catalyst regeneration step will be described. The catalyst regeneration step is common to the first aspect and the second aspect. If the zeolite-containing catalyst is used for the conversion reaction for a long period of time, it will cause deterioration of coking. In this case, the coke on the catalyst is usually burned at a temperature of 400 to 700 ° C in air or a mixed gas containing oxygen and an inert gas (hereinafter also referred to as "regeneration gas"). The catalyst regeneration of the deterioration of the coke (hereinafter, this process is also referred to as "regeneration process"). The catalyst regeneration step is preferably started at a temperature lower than the above-described conversion reaction step. Specifically, in the regeneration treatment, it is preferred to prevent the burning of the carbonaceous material adhering to the catalyst, and further prevent the combustion of the carbonaceous material adhering to the catalyst while temporarily stopping the supply of the raw material. The temperature of the catalyst layer rises sharply, and the temperature of the catalyst layer is slightly lowered. It is preferred to measure the temperature of the catalyst layer and the O in the outlet gas after starting the circulation of the regeneration gas. ₂ , CO, CO ₂ At the concentration, the regeneration temperature and oxygen concentration are slowly increased. The temperature of the catalyst layer before the regeneration treatment is preferably from 400 to 450 °C. Further, it is preferred to start the regeneration treatment at an oxygen concentration of about 0.2 to 2% by volume. The regeneration gas can also be recycled using the compressor 8 of Fig. 1. At this time, in order to prevent the accumulation of water vapor, carbon monoxide, and carbon dioxide generated by the combustion of the carbonaceous material adhering to the catalyst, the self-pressure maintaining valve 9 is suitable for flushing the regeneration gas. Further, the temperature of the catalyst layer is slightly lowered, and the regeneration process is started in a state where the oxygen concentration is low. During the regeneration treatment, the oxygen concentration is monitored, and nitrogen, air, or oxygen is supplied to fix the oxygen concentration. When most of the carbonaceous material adhering to the catalyst is burned, the temperature of the catalyst layer is lowered, so that the temperature of the catalyst layer rises to the vicinity of the conversion reaction temperature. Thereafter, if a large amount of exothermic heat is not found, the oxygen concentration is increased, and the regeneration treatment is performed so as to remove the residual carbonaceous material as much as possible. In the regeneration treatment, the sulfur component attached to the catalyst containing zeolite is SO _X The form moves to the regeneration gas. If the water vapor produced by the combustion of carbon and SO _X Associative, it becomes an acid gas and may become a factor causing acid corrosion of the device. In the production method of the present embodiment, the temperature of the line and the machine through which the regeneration gas flows is adjusted to be equal to or higher than the dew point temperature of the sulfuric acid contained in the regeneration gas. However, if the temperature of the pipeline and the machine through which the regeneration gas flows is excessively increased, the regeneration gas cannot enter the compressor 8 due to the restriction of the apparatus. On the contrary, if the load of the heater 6 is increased, the temperature is preferably set to be the same. Within the scope. Further, in the production method of the present embodiment, when the raw material contains 20% by mass or more of the olefin, the coke formation rate is increased. Therefore, the catalyst regeneration step is carried out once or more per month, preferably once a day for 20 days or more, and more preferably once or more for 10 days. The dew point temperature of the sulfuric acid contained in the regeneration gas can be obtained by taking the sulfuric acid concentration C on the horizontal axis in FIG. _H2SO4 , select the water pressure P _H2O Find by reading the vertical axis. Sulfuric acid concentration C _H2SO4 The sample can be obtained by sampling the regeneration gas and cooling it at 5 ° C, and then measuring the amount of water to be condensed, and titrating the condensed water with a base. Further, it can also be measured using a detection tube for sulfuric acid gas, ion chromatography, or the like. Moisture pressure P _H2O It can also be obtained by directly measuring the regeneration gas by a moisture meter, a dew point meter or the like. Further, by measuring the sulfur deposition rate and the deposition amount of the zeolite-containing catalyst used in the conversion reaction step, it is estimated that the release of sulfur accumulated in the catalyst is generated according to Formula 1 or 1' shown below. The maximum concentration of sulfuric acid in the regeneration gas, used as the sulfuric acid concentration C _H2SO4 . Sulfuric acid concentration: C _H2SO4 [mol%]=W×Sr×Sc×T _React /T _Regene /Q/32×22.4/1,000...Form 1 Sulfuric acid concentration: C _H2SO4 [mol%]=Sw/T _Regene /Q/32×22.4×100...Form 1' Moisture pressure: P _H2O [mmHg]=C _H2O ×10 ^-2 ×(P+0.1)×7,500... Formula 2 (In the formulas 1, 1' and 2, the raw material supply amount W [T/hr], the sulfur concentration in the raw material Sr [wtppm], and the sulfur catalyst accumulation ratio Sc [ Wt%], reaction time T _React [hr], regeneration time T _Regene [hr], the amount of regenerated gas Q [Nm ³ /hr], sulfur-containing zeolite catalyst accumulation amount Sw [kg], regeneration pressure P [MPaG], H in regeneration gas ₂ O concentration C _H2O [mol%]) Further, Fig. 4 is the same as the one described in the revised version of the sulfuric acid manual [Supply of Sulfuric Acid Association (1977)], page 237. Further, by reducing the dew point by recovering the water vapor and the sulfuric acid component by the following heat exchanger (dryer), the minimum management temperature of the pipeline and the machine can be reduced. In other words, when the sulfuric acid aqueous solution is recovered from the regeneration gas by the dryer, the management temperature of the regeneration line after the dryer can be set to the dew point temperature of the sulfuric acid determined by measuring the water pressure and the sulfuric acid concentration at the outlet of the dryer. By maintaining the temperature of the line and the machine through which the regeneration gas flows to be equal to or higher than the dew point temperature of the sulfuric acid contained in the regeneration gas, acid corrosion of the manufacturing apparatus caused by the sulfur oxide can be reduced. Regarding the holding temperature of the pipeline and the machine through which the regeneration gas flows, in consideration of the measurement error or the followability to the rapid temperature change, the dew point temperature is preferably +10 ° C or higher, more preferably the dew point temperature + 20 ° C or higher, and further preferably the dew point. Temperature +30 ° C or more. By setting the temperature of the line through which the regeneration gas flows and the temperature of the machine to the above-described holding temperature, corrosion of the regeneration line and the machine can be suppressed, and as a result, the foreign matter such as rust is less mixed into the reactor. The temperature of the pipeline and the machine through which the regeneration gas flows can be measured by a temperature measuring resistor, a thermocouple, an infrared radiation thermometer, a non-contact thermometer, a test indicator thermometer, or the like. In addition, the temperature of the pipeline and the machine through which the regeneration gas of the present embodiment flows refers to the surface temperature of the pipeline and the machine in contact with the gas, and when the construction is carried out by a heat insulating material or the like, the surface of the pipeline or the machine is made of a thermocouple or the like. The contact was measured. The method of adjusting the temperature of the line and the machine through which the regeneration gas flows is not particularly limited, and examples thereof include heating using a heat exchanger, a heater, a steam tracing, and the like. Further, it is preferable that the pipeline or the machine through which the regeneration gas flows is insulated by the heat insulating material. However, any part of the pipeline and the machine through which the regeneration gas flows may be partially heated or kept warm as long as it is maintained at a dew point of sulfuric acid or higher. Further, it may further include a drying step of cooling the regeneration gas used in the catalyst regeneration step to remove water vapor in the regeneration gas. The method of reducing the dew point of the sulfuric acid contained in the regeneration gas by cooling the regeneration gas and partially or completely condensing the water vapor in the gas and the sulfuric acid component attached thereto. Therefore, a heat exchanger (dryer) 17 for condensing and separating water vapor or the like in the gas can be disposed on the line through which the regeneration gas flows. In this case, the temperature of the apparatus for condensing and separating the water vapor in the gas is preferably a temperature effective for condensing and separating the water vapor, for example, as a lower limit of about 1 ° C or higher, preferably about 5 ° C. The above is managed as the upper limit of about 230 ° C or less, preferably about 160 ° C or less, more preferably about 120 ° C or less. The heat exchanger (dryer) 17 is disposed at a position where the pressure-retaining valve 9 of Fig. 1 is suitable for flushing the regeneration gas until the regeneration gas is introduced into the heater 6, preferably near the compressor 8. Fig. 3 is a schematic view showing a device which is an example of a case where a heat exchanger (dryer) 17 is provided. Further, the material of the heat exchanger (dryer) 17 is preferably SO _X The tolerance is higher than that of the equipment on the pipeline through which the other regeneration gas flows. Further, the heat exchanger (dryer) 17 for performing the above drying step is not included in the machine through which the regeneration gas having a temperature maintained at a dew point of sulfuric acid or more is distributed. Further, in the heat exchanger 17, some or all of the water vapor and the sulfuric acid component accompanying the water vapor are removed, so that the dew point temperature of the sulfuric acid is lowered. In this case, the line and the machine after the heat exchanger 17 are of course more than the dew point temperature of the sulfuric acid of the regeneration gas, and it is not necessary to maintain the same temperature as the previous line of the heat exchanger 17. However, when recycling the regeneration gas, it is necessary to perform heating without increasing the load on the heater 6. Further, as shown in the following examples, the first or second correlation formula of the acid amount of the catalyst containing zeolite and the catalyst accumulation ratio of sulfur or the catalyst accumulation amount of sulfur may be prepared in advance, depending on the zeolite to be used. The value of the acid amount of the catalyst is used to estimate the catalyst accumulation rate of sulfur and the amount of sulfur catalyst accumulation by the correlation formula. In this case, the catalyst accumulation rate of sulfur and the amount of catalyst accumulation are used in the value obtained by the correlation approximation formula of one or two times to become the acid line of the pipeline and the machine for preventing the circulation of the regeneration gas. An effective method of causing corrosion. The correlation formula under the conditions of the examples of the present specification is shown in the following test examples. Here, the amount of the acid of the zeolite-containing catalyst is represented by the amount of pyridine which is removed at 500 to 900 ° C by the temperature rise-off method, and is expressed as a desorption amount per 1 g of the catalyst containing zeolite. The amount of the acid of the zeolite-containing catalyst can be measured, for example, by the method described below. The SUS column with an inner diameter of 6 mm and a total length of 220 mm was filled with a catalyst of 0.1 to 1 g. If the catalyst is formed into a granular form, it is filled with a length of 1 to 5 mm, and if it is a powder, it is compression-molded to a size of 20 to 30 mesh for filling. As a measuring device for the acid amount, a gas chromatograph GC-14A manufactured by Shimadzu Corporation and a data processing device CR-4A were connected to the SUS column. Nitrogen gas was used as a carrier gas at 60 cc/min, and the inner diameter of the tube made of SUS was 20 mm. The tubular electric furnace with a length of 150 mm is heated to 180 °C. Next, using an auto-sampling microsyringe, a certain amount (1 μcc) of pyridine is continuously injected intermittently from the injection port for a certain period of time (2 to 5 minutes). On the other hand, the carrier gas flowing through the SUS column was analyzed using a FID (flame ionization detector) type detector to obtain a chromatogram in which the periodic pyridine concentration change of the peak occurred periodically. As the number of injections increases, the amount of pyridine adsorbed on the sample approaches saturation, and the amount of non-adsorbed pyridine obtained increases. When the amount of change in the change in the pyridine concentration was 5% or less, it was determined that the amount of pyridine adsorption was saturated. After the saturation adsorption of pyridine on the catalyst was judged under the above conditions, the temperature was raised at a rate of 15 ° C/min using a tubular electric furnace. Here, the gas flow path from the SUS column to the FID type detector is removed from the electric furnace, heated by a heating belt or the like, and the outer side is covered with a heat insulating material, and the heat is 200 °C. The temperature detection of the catalyst portion is performed at a position close to the temperature detecting end provided on the outer side of the catalyst filling portion of the SUS column. The pyridine which was detached from the catalyst during the period when the temperature detecting end reached 900 ° C was detected by an FID type detector, and the amount of detachment was converted using a calibration curve of pyridine. Further, the ratio of the surface acid point to the total acid point was measured in the following manner: pyridine was changed to 4-methylquinoline, and the amount of 4-methylquinoline removed was measured by the same method as above to give 4-methyl The ratio of the amount of quinazoline (μmol/g-cat) to the amount of pyridine (μmol/g-cat) is expressed. The sulfur catalyst accumulation rate can be obtained, for example, by compression-molding the used catalyst, and then performing X-ray analysis using a X-RAY SPECTROMETER RIX 3000 apparatus manufactured by Rigaku Electric Co., Ltd. to determine the quality of sulfur element. %. [Manufacturing Apparatus] The apparatus for producing propylene or an aromatic hydrocarbon according to the present embodiment is an apparatus for producing propylene or an aromatic hydrocarbon, and has at least one production reactor having a switching operation for bringing a hydrocarbon raw material into contact with a catalyst. a reaction step and a function of a catalyst regeneration step of removing a carbonaceous substance adhering to the catalyst by the conversion reaction step by contacting the oxygen-containing gas with the catalyst, wherein the production reactor has: a piping system that feeds the hydrocarbon feedstock into the production reactor and delivers the reaction mixture from the production reactor; and a second piping system that feeds the oxygen-containing gas into the production reactor and The regeneration gas is sent out from the production reactor; and the second piping system includes a dryer that removes water vapor in the regeneration gas. Here, the production reactor may have at least one, and may be manufactured using a plurality of manufacturing reactors. In the case where a production reaction of propylene or an aromatic hydrocarbon is carried out in the reactor 4, and a catalyst regeneration step is carried out in the reactor 5, the first piping system has a hydrocarbon feedstock fed into the production reactor and reacts The function of the mixture from the reactor is as follows: in the tank 1 containing the hydrocarbon raw material in FIG. 1, the reactor 4 containing the propylene reaction mixture is produced by the contact conversion of the hydrocarbon raw material, and the reaction mixture and the hydrocarbon raw material are carried out. Heat exchange heat exchangers 2, 3, a heater (Heater) 6 for heating a hydrocarbon feedstock to a specific temperature, a heat exchanger (cooler) 10 for cooling the reaction mixture, and a compressor 11 for compressing the reaction mixture, a heat exchanger (cooler) 12 cooled by the compressed reaction mixture, storing a tank 13 of a fraction condensed by the heat exchangers 10, 12, and separating the reaction mixture into hydrogen and a fraction having a carbon number of 3 or less and a carbon number of 4 or more The distillation column 14 of the fraction is a heat exchanger (cooler) 15 which cools hydrogen and a fraction having a carbon number of 3 or less at the top of the column of the distillation column 14, stores the cooled fraction and returns it to the tank at the top of the column of the distillation column 14. 16 machine And a connection of such a machine from the bottom of the pipe and the fractionating tower 14 of the connecting pipe tank 1 FIG. The second piping system has a function of feeding an oxygen-containing gas into the production reactor and delivering the regeneration gas from the production reactor, and the reactor 5, the heat exchanger 7, the compressor 8, and the heating in FIG. The valve 6, the pressure maintaining valve 9 and the piping connection to the machines. Further, the second piping system may further include a temperature measuring device that measures the temperature of the regeneration gas. Here, the production reactor, the dryer, the temperature measuring device, and the like in the manufacturing apparatus are the same as those described in the above-described manufacturing method. [Examples] <Test Example 1> Measurement of sulfur deposition rate of catalyst for propylene production reaction 1 ₂ /Al ₂ O ₃ The H-type ZSM-5 zeolite having a ratio of 1068 was mixed with colloidal cerium oxide and Snowtex ST-N manufactured by Nissan Chemical Industries Co., Ltd., and subjected to moisture adjustment, followed by extrusion molding. The obtained molded body was dried at 120 ° C for 6 hours, and then calcined at 550 ° C for 6 hours to obtain a zeolite-containing molded body catalyst (containing SiO ₂ Adhesive 30% by mass, 1.6 mm ). The obtained zeolite-containing molded body catalyst was dispersed in a 1 N nitric acid aqueous solution (10 cc/g-molded catalyst), and subjected to ion exchange treatment at room temperature for 1 hour. Then, filtration, washing with water, and drying to prepare H-exchange type ZSM-5/SiO ₂ Molded body catalyst. The resulting H exchange type ZSM-5/SiO ₂ The molded body catalyst was dispersed in a 1 N aqueous sodium nitrate solution (10 cc/g-zeolite molded body), and subjected to ion exchange treatment three times for one hour at room temperature. Then, filtration, washing with water, and drying to prepare Na exchange type ZSM-5/SiO ₂ Molded body catalyst. This was dispersed in a 0.00045 N silver nitrate aqueous solution (10 cc / g - shaped catalyst), and subjected to ion exchange treatment at room temperature for 2 hours. Then, filtration, washing with water, and drying were carried out to prepare a catalyst A. The amount of Ag of the catalyst A measured by fluorescent X-ray analysis was 0.084% by mass. Fill the catalyst A to the inner diameter of 27.2 mm In the Hessite C reactor, steam treatment was carried out for 5 hours at a temperature of 650 ° C, a steam flow rate of 218 g/hr, and a nitrogen flow rate of 220 NL/hr. The amount of the catalytic acid after the steam treatment was determined by the pyridine temperature rising method, and the result was 21 μmol/g-cat. 60 g of steam treated catalyst A is filled to an inner diameter of 27.2 mm In the Hester alloy C reactor. 30 parts by mass of sulfur-containing raw materials (C3 fraction 6 mass%, C4 olefin 46 mass%, C4 alkane 45 mass%, C5 fraction 3 mass%, and diene 0.04 mass%) were used as a hydrocarbon raw material at a reaction temperature of 550 ° C. The reaction was carried out for 48 hr under the conditions of a raw material supply amount of 435 g/hr and 0.1 MPaG. The catalyst accumulation rate of sulfur after the catalyst A reaction of the catalyst A was 0.5 wt% according to the results of the fluorescent X-ray analysis, and the sulfur accumulation amount per catalyst of the catalyst was 0.05 mg/g-cat. <Test Example 2> Measurement of sulfur deposition rate of catalyst for propylene production reaction 2 Except for using SiO ₂ /Al ₂ O ₃ The same operation as in Test Example 1 was carried out except that the catalyst B containing the amount of Ag was 0.087% by mass was obtained for the H-type ZSM-5 zeolite of 308. The amount of catalyzed acid after steam treatment was determined by the pyridine temperature rising detachment method, and as a result, it was 44 μmol/g-cat, and the catalyst accumulation ratio of the sulfur of the catalyst B after the reaction was 1 wt%, and the catalyst per 1 g was used. The sulfur accumulation was 0.1 mg/g-cat. <Test Example 3> Measurement of the sulfur deposition rate of the catalyst for the aromatic hydrocarbon production reaction The H-type ZSM-5 zeolite was synthesized by the method described in Example 1 of Japanese Patent No. 3,905,948. SiO of the obtained zeolite ₂ /Al ₂ O ₃ The ratio is 42. An alumina sol was prepared by dissolving 1.3 kg of zinc nitrate hexahydrate in 2 kg of the zeolite powder and using zeolite/aluminum = 8/2. It is suitable for mixing and mixing, and is extruded to 1/16 inch x 5-10 mm. The obtained extrusion molding catalyst was dried at 120 ° C for 12 hours and calcined at 500 ° C for 6 hours to obtain a catalyst C. Steam treatment was carried out in the same manner as in Test Example 1 except that the catalyst treatment time was changed to 3 hr. The amount of catalyzed acid after steam treatment was determined by the pyridine temperature rising detachment method and found to be 294 μmol/g-cat. Filling the steam treated catalyst C 100 g to an inner diameter of 27.2 mm In the Hester alloy C reactor. The raw material of Table 1 containing 764 ppm by mass of sulfur was used, and the reaction was carried out for 48 hr under the conditions of a reaction temperature of 515 ° C, a raw material supply amount of 600 g / hr, and a reaction pressure of 0.5 MPaG. The catalyst accumulation rate of sulfur in the catalyst C after the reaction was 5.9%, and the sulfur accumulation per 1 g of the catalyst was 13 mg/g-cat. Moreover, in this test example, the temporal change of the sulfur accumulation amount was traced. The sulfur accumulation amount was 11 mg/g-cat after 3 hours from the start of the feed supply, and reached 13 mg/g-cat after 6 hours. According to the results of Test Examples 1 to 3, when the acid amount of the zeolite-containing catalyst was x (μmol/g-cat), the catalyst deposition rate of sulfur deposited on the zeolite-containing catalyst was set to y ( Wt%), under the conditions of this test example, the relationship between x and y is represented by a correlation of y=0.020x. In addition, it is understood that when the amount of acid of the zeolite-containing catalyst is x (μmol/g-cat), the amount of catalyst deposited on the zeolite-containing catalyst is set to z (mg/g-cat). Then, under the condition of the embodiment, the relationship between x and z is z=0.0002x ² -0.004x of 2 correlations. [Table 1] Composition of raw materials used in Test Example 3 [Example 1] (Production of aromatic hydrocarbon) Using H-type ZSM-5 zeolite (SiO ₂ /Al ₂ O ₃ Ratio = 80), the same method as in Test Example 3 was used, whereby Catalyst D was obtained. The catalyst D was subjected to the same steam treatment as in Test Example 3. The amount of catalyzed acid after steam treatment was determined by the pyridine temperature rising detachment method and found to be 244 μmol/g-cat. Fill the steam treated catalyst D 60 g to an inner diameter of 27.2 mm In the Hester alloy C reactor. The raw material used in the test material of Example 1 was added with ethyl mercaptan and the sulfur content was 210 mass ppm, and the reaction temperature was 515 ° C, the raw material supply amount (W [T / hr]) = 0.00018 T / hr, and the reaction pressure was 0.5. The production of aromatic hydrocarbons was carried out for 48 hours under the conditions of MPaG (sulfur concentration in the raw material (Sr [wtppm]) = 210 wtppm). After the supply of the raw material was stopped at the reaction time (Treact [hr]) = 48 hours, the temperature of the catalyst layer was lowered to 450 ° C while the system was replaced by nitrogen purge. Thereafter, the regeneration pressure (P [MPaG]) = 0.5 MPaG, and the amount of regeneration gas (Q "Nm" ³ /hr")=8.4×10 ^-3 Nm ³ /hr is supplied with 1% by volume of oxygen/99% by volume of nitrogen gas, and combustion removal (regeneration) of coke adhering to the catalyst is started. Measuring CO and CO in the export gas ₂ , O ₂ At the concentration, the regeneration temperature and the oxygen concentration were gradually increased, and finally the regeneration was completed with a regeneration time (Tregene [hr]) = 10 hours, a treatment temperature of 550 ° C, and an oxygen concentration of 5 vol%. According to the amount of water recovered by cooling the regeneration gas at 5 ° C, the average H ₂ O concentration (C _H2O ) is 1.4 mol%, water pressure (P _H2O : equivalent to the steam pressure of Figure 4) is 63 mmHg. The condensed water is titrated with sodium hydroxide, and the concentration of sulfuric acid in the regeneration gas is obtained according to the obtained result (C _H2SO4 ) is 0.6 mol%. As can be seen from Fig. 4, the dew point temperature of sulfuric acid was about 150 °C. Further, a part of the zeolite-containing catalyst after completion of the aromatic hydrocarbon production reaction was subjected to fluorescent X-ray analysis, and as a result, the sulfur adsorption amount (deposited amount) on the catalyst was 9.8 mg/g-cat. The sulfuric acid concentration in the regeneration gas determined according to Formula 1' was 0.49 mol%. If using the above measured water pressure (P _H2O : equivalent to the steam pressure of Fig. 4) 63 mmHg, the dew point estimated temperature of sulfuric acid read from Fig. 4 is about 150 °C. When the acid amount of the catalyst D: 244 μmol/g-cat is applied to the secondary correlation formula obtained from the above test example, the amount of sulfur deposited on the catalyst can be estimated to be 11 mg/g-cat. Based on this value, the sulfuric acid concentration in the regeneration gas obtained according to Formula 1' was 0.55 mol%. The measured water pressure in the above (P _H2O : The steam pressure corresponding to Fig. 4 is 63 mmHg, and the dew point of the sulfuric acid read from Fig. 4 is about 150 °C. This value is in agreement with the value obtained by measuring the water pressure and the sulfuric acid concentration of the regeneration gas and the value of the sulfur accumulation amount of the measured catalyst. The cycle operation of the 48 hour reaction/10 hour regeneration was repeated 10 times under the above conditions. In the regeneration step, the temperature of the line and the machine through which the regeneration gas flows is monitored by a thermocouple and a temperature regulator disposed outside the pipe, and is maintained at 180 °C. After 10 cycles of operation, no acid corrosion of the device SUS304 was observed. [Example 2] A dryer having a material of SUS316L was placed in a line through which the regeneration gas flows (corresponding to the position of 17 in Fig. 3), and the temperature of the line and the machine through which the regeneration gas before the dryer was passed was maintained at 180 °C. The same reaction and regeneration as in Example 1 were carried out except that the water vapor was condensed and separated at 5 ° C in a drier, and the temperature of the line and the machine through which the regeneration gas after the dryer was passed was maintained at 130 ° C. Loop operation. After 10 cycles of operation, no acid corrosion of the machine was observed. [Comparative Example 1] The same reaction/regeneration cycle operation as in Example 1 was carried out except that the temperature of the line and the machine through which the regeneration gas was passed in the regeneration step was maintained at 40 °C. After 10 cycles of operation, it was confirmed that scales containing sulfide were generated on the inner wall of the line. [Example 3] (Manufacture of propylene) The catalyst A 60 g after steam treatment was filled to an inner diameter of 27.2 mm In the Hester alloy reactor. A raw material containing 340 ppm by mass of sulfur (C3 fraction 6 mass%, C4 olefin 46 mass%, C4 alkane 45 mass%, C5 fraction 3 mass%, and diene 0.04 mass%) was used as a hydrocarbon raw material at a reaction temperature of 550 ° C. The feed was supplied under the conditions of 360 g/hr and 0.1 MPaG for 48 hr. The obtained reaction product was cooled to 10 ° C at the outlet of the reactor using a heat exchanger, and then introduced into a gas-liquid separation cylinder to separate a fraction having a C5 or higher. Then, the raw material containing 340 ppm by mass of sulfur was supplied to the reactor at 290 g/hr and the above-mentioned separated C5 or higher fraction was 70 g/h, and a 24 hr propylene production reaction was carried out. Then, the same regeneration operation as in Example 1 was carried out except that the regeneration pressure (P [MPaG]) was set to 0.1 MPaG. The average H obtained by measuring the regeneration gas flushed from the pressure-maintaining valve 9 using a hygrometer ₂ O concentration (C _H2O ) is 0.7 mol% and the water partial pressure is 10 mmHg. Further, the regeneration gas was passed to an aqueous sodium hydroxide solution, and the aqueous sodium hydroxide solution was subjected to ion chromatography (Tosoh IC2010, conductivity detector, column: TSKgel guard column SuperIC-AZ TSKgel Super IC-AZ (4.6 ×150 mm), a solution of the solution: 7.5 mM sodium hydrogencarbonate + 1.1 mM sodium carbonate), and the concentration of the sulfur component in the regeneration gas is measured, and as a result, the concentration of sulfuric acid in the regeneration gas (C) _H2SO4 ) is 0.04 mol%. As can be seen from Fig. 4, the dew point temperature of sulfuric acid was about 80 °C. Further, the catalyst accumulation rate of sulfur after the catalyst production reaction of the catalyst A was 0.5 wt% based on the result of Test Example 1. The sulfuric acid concentration in the regeneration gas obtained according to Formula 1 was 0.037 mol%, and the dew point estimated temperature of sulfuric acid read from Fig. 4 was about 80 °C. Further, the sulfuric acid concentration determined from the amount of the catalyst acid (21 μmol/g-cat) in Formula 1 was 0.031 mol%, and the dew point estimation temperature of sulfuric acid was calculated to be about 80 °C. The 72-hour reaction/10-hour regeneration cycle was repeated five times under the above conditions. In the regeneration step, the temperature of the line and the machine through which the regeneration gas flows is maintained at 130 °C. After 5 cycles of operation, no acid corrosion of the machine was observed. According to the present embodiment, it is known that the dew point estimation temperature of sulfuric acid can be predicted only by measuring the water concentration and the amount of catalyst acid in the regeneration gas, and the dew point of sulfuric acid can be predicted by a simple method without performing gas sampling which may cause complicated operations. Predict the temperature. The present application is based on Japanese Patent Application No. 2015-236785, filed on Dec. [Industrial Applicability] The production method of the present invention can produce a target product safely and stably, and is useful in the field of a method for producing propylene or an aromatic hydrocarbon.

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Fig. 1 is a schematic view showing an example of a manufacturing apparatus for carrying out the method for producing propylene or an aromatic hydrocarbon of the present invention. Fig. 2 is a schematic view showing an example of a manufacturing apparatus of Fig. 1 showing a pipeline through which a regeneration gas flows, in a thick solid line. Fig. 3 is a schematic view showing an example of a manufacturing apparatus in which a heat exchanger (dryer) is provided in a line through which a regeneration gas flows. Figure 4 is a graph showing the relationship between sulfuric acid concentration and vapor pressure and dew point temperature.

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Claims (15)

A manufacturing method for producing propylene or an aromatic hydrocarbon, and comprising the steps of: a conversion reaction step of producing a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one hydrocarbon having 4 to 12 carbon atoms; Contacting with a zeolite-containing catalyst; and a catalyst regeneration step of burning and removing the carbonaceous material attached to the zeolite-containing catalyst; and in the catalyst regeneration step, the pipeline through which the regeneration gas flows and The temperature of the machine is maintained above the dew point temperature of the sulfuric acid contained in the regeneration gas flowing through the pipeline and the machine. A manufacturing method for producing propylene, comprising the steps of: a conversion reaction step of producing a hydrocarbon raw material containing a sulfur compound as an impurity and containing at least one olefin having 4 to 12 carbon atoms in a reactor and a zeolite-containing material Catalyst contact; a catalyst regeneration step of burning and removing the carbonaceous material attached to the zeolite-containing catalyst; and a separation step of separating the reaction mixture obtained in the above conversion reaction step into mainly containing hydrogen and a light fraction of a hydrocarbon having 1 to 3 carbon atoms and a heavy fraction mainly containing at least one hydrocarbon having 4 or more carbon atoms; and a recycling step of recycling part or all of the heavy fraction to the above-mentioned production reactor And used as the hydrocarbon raw material; and in the catalyst regeneration step, the temperature of the pipeline and the machine through which the regeneration gas flows is maintained at a temperature equal to or higher than the dew point temperature of the sulfuric acid contained in the regeneration gas flowing through the pipeline and the machine. The manufacturing method of claim 1 or 2, wherein the regeneration gas is recycled. The production method according to any one of claims 1 to 3, wherein the production reactor is two or more heat insulating fixed bed reactors, and the conversion reaction step and the catalyst regeneration step are carried out in the reactor. The production method according to any one of claims 1 to 4, wherein the hydrocarbon raw material contains 20% by mass or more of a olefin having 4 to 12 carbon atoms. The manufacturing method according to any one of claims 1 to 5, wherein the catalyst regeneration step is carried out at a frequency of one or more times a month. The method of any one of claims 1 to 6, wherein the zeolite-containing catalyst contains a zeolite having an intermediate pore diameter of from 5 to 6.5 Å. The method of any one of claims 1 to 7, wherein the zeolite-containing catalyst contains a Group IB metal. The production method according to any one of claims 1 to 8, wherein the zeolite-containing catalyst contains a porous refractory inorganic oxide. The production method according to any one of claims 1 to 9, wherein the zeolite-containing catalyst is heat-treated at a temperature of 500 ° C or higher in the presence of water vapor before being contacted with the hydrocarbon feedstock. The method of any one of claims 1 to 10, wherein the catalyst regeneration step is started at a temperature lower than the temperature of the conversion reaction step. The manufacturing method according to any one of claims 1 to 11, further comprising a drying step of cooling the regeneration gas used in the catalyst regeneration step to remove water vapor in the regeneration gas. The production method according to any one of claims 1 to 12, comprising the step of calculating a sulfuric acid concentration based on the acid amount of the zeolite-containing catalyst and the catalyst accumulation rate of sulfur or the amount of catalyst accumulated, according to the sulfuric acid The concentration of sulfuric acid contained in the above-mentioned regeneration gas was determined as the concentration. A plant for producing propylene or an aromatic hydrocarbon, which is a device for producing propylene or an aromatic hydrocarbon, and having at least one production reactor having a conversion reaction step of switching a hydrocarbon raw material into contact with a catalyst, and borrowing a function of the catalyst regeneration step of bringing the oxygen-containing gas into contact with the catalyst to burn and remove the carbonaceous material adhering to the catalyst by the conversion reaction step, wherein the production reactor has a first piping system, which will The hydrocarbon feedstock is fed to the production reactor and the reaction mixture is sent out from the production reactor; and a second piping system that feeds the oxygen-containing gas into the production reactor and produces the regeneration gas from the above The reactor is sent out; the second piping system includes a dryer that removes water vapor in the regeneration gas. The apparatus for producing propylene or an aromatic hydrocarbon according to claim 14, wherein the second piping system further includes a temperature measuring device that measures a temperature of the regeneration gas.