JP2013006965A - Production method of aromatic hydrocarbon and/or olefin having at most four carbon atoms, and production apparatus for aromatic hydrocarbon and/or olefin having at most four carbon atoms - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an aromatic hydrocarbon and/or a light olefin, in which deactivation of a catalyst due to coking can be suppressed.SOLUTION: The production method of an aromatic hydrocarbon and/or an olefin having at most 4 carbon atoms is provided. The method comprises: allowing a hydrocarbon to pass through a first catalyst section containing zeolite (A) having an acid amount by 0.001 to 1 mmol/g and a porous structure of a 10-membered ring; then allowing the hydrocarbon to pass through a second catalyst section containing a solid acid catalyst (B) having an acid amount of 90% or less of the acid amount of the zeolite (A); and cracking the hydrocarbon in the second catalyst section at a reaction temperature of lower than 600°C.

Description

  The present invention relates to a method for producing an aromatic hydrocarbon and / or an olefin having 4 or less carbon atoms (hereinafter sometimes referred to as “light olefin”).

  Light olefins such as ethylene, propylene, and butene and aromatic hydrocarbons such as BTX (benzene, toluene, and xylene) are important chemicals that are raw materials for polymers and various chemicals. One of these production methods is a naphtha pyrolysis process, which requires a high temperature of 800 ° C. or more, and consumes a large amount of energy to perform an endothermic pyrolysis. Among light olefins, propylene demand is expected to increase and supply shortage is expected, but thermal cracking has a high ethylene selectivity, making it difficult to cope with increased propylene production.

  Therefore, realization of catalytic cracking of naphtha using a catalyst is expected. Catalytic cracking enables a reaction at a temperature as low as about 600 to 700 ° C., so that it can save energy and generally exhibits higher propylene selectivity than thermal cracking. In addition, the control of the selectivity according to the supply and demand balance of each product and the improvement of the total active ingredient selectivity are expected by controlling the catalyst.

  Various studies have been conducted on solid acid catalysts, mainly zeolite, as catalysts for catalytic cracking of naphtha. However, there is a problem that the catalyst is caulked by the sequential reaction of the product and deactivated. When zeolite is used as a catalyst, dealumination occurs due to dealumination from the zeolite skeleton caused by water vapor generated when coke is burned and removed, or steam coexisting during the reaction.

  Methods for suppressing such deactivation have been reported so far. For example, in Japanese Patent Application Laid-Open No. 2010-42344 (Patent Document 1), in catalytic cracking using zeolite supporting alkaline earth metal, rare earth element, and phosphorus, zeolite is loaded with components other than phosphorus and phosphorus in separate steps. It is described that the use of a catalyst suppresses a decrease in activity as compared with the case of using a simultaneously supported catalyst.

  In JP 2010-104878 (Patent Document 2), in catalytic cracking using a zeolite supporting an alkaline earth metal, a rare earth element and phosphorus, the zeolite is in the order of alkaline earth metal, phosphorus, rare earth element or alkali. It is described that the use of a catalyst supported in the order of earth metal, phosphorus, rare earth, and phosphorus suppresses a decrease in activity as compared with the case of using a catalyst supported simultaneously or in a different order.

  In JP 2010-104909 A (Patent Document 3), in catalytic cracking using a zeolite supporting an alkaline earth metal and phosphorus, the zeolite is supported using a water-soluble salt containing an alkaline earth metal and phosphorus. It is described that the decrease in activity is suppressed.

  In JP 2010-202613 (Patent Document 4), in the catalytic cracking of paraffin using MCM-68, MCM-68 having a low Si / Al ratio is dealuminated by nitric acid treatment to increase the Si / Al ratio. By doing, it is described that an activity fall is suppressed compared with what is not dealuminated.

  These reports are intended to improve performance by using only one type of catalyst for the reaction. In catalytic cracking, the raw material hydrocarbon concentration is high at the beginning of the reaction, and the raw material hydrocarbon concentration is low at the later stage of the reaction. Instead, the product concentration of light olefins, aromatics, light paraffins and the like is high. Therefore, since the reactivity, coking, deactivation behavior, and the like are different between the initial stage and the late stage of the reaction, it is estimated that the suitable catalyst is different in each stage.

  As a reaction using a plurality of catalysts, for example, in US Patent Publication No. 2010 / 0213101A1 (Patent Document 5), a catalyst in which a group VIII metal is supported on a beta zeolite having a low acid amount is disposed in the previous stage, and a high Si ZSM -5 describes that a catalyst supporting a Group VIII metal is disposed in the subsequent stage. These catalysts are selected for the purpose of improving the selectivity of naphtha reforming at about 800 to about 1100 ° F. (about 427 to about 593 ° C.) and increasing the octane number of the oil produced. .

JP 2010-42344 A JP 2010-104878 A JP 2010-104909 A JP 2010-202613 A US Patent Application Publication No. 2010/0213101

  However, the technique described in Patent Document 5 does not assume that catalyst deactivation due to coking in catalytic cracking is suppressed.

  This invention is made | formed in view of such a condition, The place made into the objective is providing the manufacturing method of the aromatic hydrocarbon and / or light olefin which can suppress the deactivation of the catalyst by coking.

  In order to solve the above problems, a production method according to an aspect of the present invention is a method for producing an aromatic hydrocarbon and / or an olefin having 4 or less carbon atoms. In this production method, the hydrocarbon is passed through the first catalyst part containing zeolite (A) having an acid amount of 0.001 to 1 mmol / g and having a 10-membered ring pore structure, and then the acid amount. Is passed through a second catalyst part containing a solid acid catalyst (B) that is 90% or less of the acid amount of the zeolite (A), and the hydrocarbon is reacted at a temperature of less than 600 ° C. in the second catalyst part. Decomposes at temperature.

  Another embodiment of the present invention is an apparatus for producing aromatic hydrocarbons and / or olefins having 4 or less carbon atoms. This manufacturing apparatus includes a reaction unit having at least a first catalyst unit and a second catalyst unit. The first catalyst part includes zeolite (A) having an acid amount of 0.001 to 1 mmol / g and having a 10-membered ring pore structure, and the second catalyst part is downstream from the first catalyst part. And a solid acid catalyst (B) having an acid amount of 90% or less of the acid amount of the zeolite (A). The second catalyst unit is configured to be able to catalytically decompose the supplied hydrocarbon at a reaction temperature of less than 600 ° C.

  According to the present invention, catalyst deactivation due to coking can be suppressed.

  Hereinafter, embodiments for carrying out the present invention will be described in detail. Moreover, the structure described below is an illustration and does not limit the scope of the present invention at all.

  As a result of diligent research, the present inventors have found that a high conversion rate is maintained for a longer time than when each catalyst is used alone by combining solid acid catalysts having different acid amounts, and the present invention is completed. It came.

  Specifically, the production method according to the present embodiment is a method for producing aromatic hydrocarbons and / or light olefins. In this production method, hydrocarbon is a zeolite having an acid amount of 0.001 to 1 mmol / g and having a 10-membered ring pore structure (hereinafter sometimes referred to as “zeolite (A)”). The solid acid catalyst having an acid amount of 90% or less of the acid amount of the zeolite (A) after passing through the first catalyst portion (hereinafter, sometimes referred to as “solid acid catalyst (B)”). And the hydrocarbon is catalytically cracked at a reaction temperature of less than 600 ° C. in the second catalyst portion.

  Here, the first catalyst part (zeolite (A)) is arranged upstream of the second catalyst part (solid acid catalyst (B)). In other words, the second catalyst part is arranged on the downstream side of the first catalyst part.

  In the production method of the present embodiment, examples of suitable hydrocarbons for the raw material include, for example, alkanes having 2 to 20 carbon atoms, olefins having 2 to 20 carbon atoms, aromatic hydrocarbons having 6 to 20 carbon atoms, and 5 carbon atoms. -20 naphthenes and the like. The hydrocarbon is preferably a hydrocarbon having 5 to 12 carbon atoms, more preferably a saturated hydrocarbon having 5 to 9 carbon atoms and / or an aromatic hydrocarbon having 6 to 9 carbon atoms. Examples of the saturated hydrocarbon having 5 to 9 carbon atoms include pentane, hexane and heptane. Examples of the aromatic hydrocarbon having 6 to 9 carbon atoms include benzene, toluene and xylene. The hydrocarbon is preferably a hydrocarbon containing 80% by weight or more of a hydrocarbon having 5 to 12 carbon atoms, more preferably a saturated hydrocarbon having 5 to 9 carbon atoms and / or 6 carbon atoms. It is a hydrocarbon containing 80 wt% or more of -9 aromatic hydrocarbons.

  Examples of such hydrocarbons include heavy oil, light oil, and naphtha, and naphtha is preferable. The naphtha includes light naphtha, heavy naphtha, and full-range naphtha depending on the boiling point thereof, and any of them may be used, and light naphtha is preferable. Here, light naphtha refers to a naphtha having a relatively low boiling point, and heavy naphtha refers to a naphtha having a relatively high boiling point.

  These raw materials may be recycled and mixed with unreacted raw materials and products of catalytic cracking, or may be used by mixing hydrocarbons produced by other processes. When the raw material is introduced into the reactor, it may be diluted with an inert gas such as nitrogen, but it is preferable not to use an inert gas in consideration of the cost of supplying the inert gas. Although hydrogen may be supplied, it is preferable not to supply hydrogen because the product is hydrogenated and the yield of aromatic hydrocarbons and / or light olefins decreases when the hydrogen concentration increases. Steam may be accompanied for heat supply and coking control.

  In the first catalyst part, the reaction temperature for the catalytic cracking of the hydrocarbon is preferably 500 to 900 ° C, more preferably 550 to 700 ° C, still more preferably 560 to 660 ° C, particularly Preferably, it is 570 degreeC or more and less than 600 degreeC. If the temperature is too low, the reaction will not proceed sufficiently. On the other hand, if the temperature is too high, thermal decomposition proceeds, so methane increases, the yield of aromatic hydrocarbons and / or light olefins decreases, coking increases, and catalyst deactivation is accelerated.

  In the second catalyst part, since the sequential reaction proceeds and coking is easier than in the first catalyst part, the temperature is preferably lower. Therefore, the reaction temperature for the catalytic cracking of hydrocarbons in the second catalyst part is less than 600 ° C, preferably 500 ° C or more and less than 600 ° C, more preferably 550 ° C or more and less than 600 ° C, More preferably, it is 570 degreeC or more and less than 600 degreeC. If the temperature is too low, the reaction will not proceed sufficiently. On the other hand, if the temperature is too high, thermal decomposition proceeds, so methane increases, the yield of aromatic hydrocarbons and / or light olefins decreases, coking increases, and catalyst deactivation is accelerated.

  The zeolite (A) is preferably at least one selected from MFI, MEL, MWW, and TON type zeolite, and among them, the MFI type having particularly high catalytic cracking activity and stability is more preferable. ZSM-5 is a kind of MFI type zeolite.

  Examples of the solid acid catalyst (B) include zeolite, silica alumina, sulfated zirconia, zirconia tungstate, and the like, preferably a zeolite having a pore structure of 8, 10 or 12 membered ring, and 8 or 10 membered. More preferred is a zeolite having a ring pore structure. Hereinafter, although a catalyst layer will be described as an example of one form of the catalyst part, the catalyst part may take various forms without departing from the invention.

  The zeolite having an 8-, 10-, or 12-membered ring pore structure is preferably at least one selected from MFI, MEL, MWW, TON, BEA, MSE, MOR, MTW, and FAU type zeolite, More preferably, it is at least one selected from MFI, MSE, and FAU type zeolite, and among these, the MFI type having particularly high catalytic cracking activity and stability is most preferable. ZSM-5 is a kind of MFI type zeolite.

  As these zeolite (A) and solid acid catalyst (B) (hereinafter sometimes simply referred to as “solid acid catalyst”), those in which all of the catalyst used are not modified may be used. The solid acid catalyst may be one or more selected from alkali metals, alkaline earth metals, rare earth metals, phosphorus, and transition metals of groups 4 to 12 of the periodic table of elements. You may use what was modified with the component.

  The solid acid catalyst may be used in either powder or molded form. When used as a molded catalyst, in addition to the solid acid catalyst, it may contain one or more clay minerals such as kaolin and bentonite and / or one or more inorganic oxides such as silica, alumina and zirconia for the purpose of a binder and the like.

  The acid amount of the solid acid catalyst can be measured by an ammonia temperature programmed desorption method (hereinafter referred to as ammonia TPD method). In addition, about a shaping | molding catalyst, the acid amount obtained by measuring the powder which grind | pulverized the molded object with ammonia TPD is the acid amount of the zeolite (A) used for any catalyst layer (catalyst part) arrange | positioned upstream. Any catalyst in which the amount of acid obtained by measuring the solid acid catalyst before mixing clay mineral, inorganic oxide, etc. with ammonia TPD may be arranged upstream. You may arrange | position a catalyst smaller than the acid amount of the zeolite (A) used for a layer (catalyst part) downstream.

  In the present embodiment, the acid amount of zeolite (A) is 0.001-1 mmol / g, preferably 0.01-0.8 mmol / g, more preferably 0.1-0. 0.5 mmol / g. If the acid amount is too large, the activity is high, but it is easily deactivated by coking. On the other hand, if the acid amount is too small, sufficient activity cannot be obtained.

  In the present embodiment, the acid amount of the solid acid catalyst (B) is 90% or less, preferably 5 to 70%, more preferably 15 to 15% of the acid amount of the zeolite (A). 60%. When using three or more catalyst layers, the acid amount of the solid acid catalyst used in any two catalyst layers should satisfy the above range.

  In the present embodiment, as a method of forming two or more catalyst layers, two or more reactors in which solid acid catalysts having different acid amounts are filled in separate reactors to form catalyst layers are connected in series. You may arrange in. In consideration of the cost of equipment and operation, it is preferable to fill a single reactor with solid acid catalysts having different amounts of acid to form two or more catalyst layers in one reactor.

  When using two or more reactors in which solid acid catalysts having different acid amounts are packed in separate reactors to form a catalyst layer, the type of the reactor may be a fixed bed, a moving bed, or a fluidized bed. Often, different types of reactors may be combined. In consideration of equipment and operating costs, it is preferable that there is no equipment for separating raw materials and product components between the plurality of reactors. Here, the “fixed bed” flow-type reactor is, for example, a reactor of a type in which a granular catalyst is held by some member and can be realized at low cost. As the member for holding the granular catalyst, for example, a combination of quartz wool and quartz sand, a mesh floor, or the like is used. Further, the “fluidized bed” type reactor is a reactor configured such that gas is blown out like a bubble in a powdered catalyst, for example.

  When two or more catalyst layers are formed in one reactor by filling solid acid catalysts having different acid amounts into one reactor, a reactor configured as a fixed bed flow type may be used. preferable. Solid acid catalysts having different acid amounts are packed in series in the reactor, but the stages of the solid acid catalysts having different acid amounts may be in direct contact with each other, in an inert layer, or solid acid catalysts having different acid amounts. Other catalyst layers may be separated from each other by being interposed therebetween. In addition, when using three or more kinds of solid acid catalysts, it is sufficient that at least two of them have a solid acid catalyst having a large acid amount upstream and a solid acid catalyst having a small acid amount downstream, The position of the remaining catalyst is not particularly limited. In addition, it is preferable to divide the solid acid catalyst with a large acid amount in order from the upstream side into a plurality of stages and charge the reactor. The reactor according to the present embodiment is filled with a solid acid catalyst having a relatively high acid amount on the upstream side, and is filled with a solid acid catalyst having a relatively low acid amount on the downstream side.

  As for the weight of the zeolite (A) and the weight of the solid acid catalyst (B), the weight of the solid acid catalyst (B) is preferably 1/100 to 100 times the weight of the zeolite (A). 1/10 to 10 times is more preferable. When three or more catalyst layers are used, it is sufficient that the weight with respect to any solid acid catalyst having a large acid amount falls within the above range. In the case of a molded catalyst, the weight shown here represents the weight of the solid acid catalyst or the entire molded body.

  The catalyst layer to be used may be two or more layers, but it is preferable to use 2 to 5 catalyst layers, and to use 2 to 3 catalyst layers, in consideration of the catalyst production cost and the effect of filling. More preferred.

  Regarding the combination of zeolite (A) and solid acid catalyst (B), solid acid catalysts of different systems such as zeolite and silica alumina may be combined, but from the viewpoint of operability, zeolites having different acid amounts may be combined. Thus, the combination which changed the amount of acids in the same system is more preferable. When using zeolite, zeolites having different structures such as MFI and FAU may be combined. Preferably, at least two kinds are MFI type zeolites having the same crystal structure, and all solid acid catalysts are MFI type zeolites. It is more preferable.

The amount of acid can be controlled by various factors such as raw materials, composition, preparation method, preparation conditions, post-treatment, metal loading, and the method for obtaining solid acid catalysts having different acid amounts is not particularly limited. In the case of zeolite, the amount of acid can be easily controlled, for example, by changing the Si / Al ₂ molar ratio, performing steam treatment, performing acid treatment, performing alkali treatment, or changing the ion exchange rate. Changing the Si / Al ₂ molar ratio is preferred because it does not require post-treatment of the zeolite. In addition, in the case of post-treatment such as steam treatment, acid treatment, and alkali treatment, since zeolites having different acid amounts can be prepared from one zeolite, there is an advantage that the procurement of zeolite can be obtained at a lower cost than when purchasing a plurality of zeolites. is there. Among these post-treatments, the steam treatment is preferable because the waste liquid is only water, unlike the acid treatment and alkali treatment, and the treatment is easy and the amount of catalyst is not reduced.

Both the zeolite (A) and the solid acid catalyst (B) may contain a zeolite represented by the general formula xM ₂ O.yAl ₂ O ₃ .zSiO ₂ .nH ₂ O. The molar ratio z / y of Si and Al ₂ in the zeolite (A) may be different from the molar ratio z / y of Si and Al ₂ in the zeolite (B1) contained in the solid acid catalyst (B). Good. Thus, the amount of acid can be controlled by changing the Si / Al ₂ molar ratio of the zeolite. In general, when the Si / Al ₂ molar ratio is large, the acid amount decreases. The Si / Al ₂ molar ratio can be adjusted by changing the composition of the raw materials, and zeolites having different Si / Al ₂ molar ratios can be easily purchased.

  The steam treatment is a method of treating a zeolite in a gas phase with steam diluted with an inert gas such as steam or nitrogen at a temperature of usually 400 to 900 ° C., preferably 500 to 700 ° C., and aluminum in the zeolite framework is dealuminated. The amount of acid can be reduced. At least one of the zeolite (A) and the zeolite (B1) of the solid acid catalyst (B) may have an acid amount adjusted by treatment with water vapor.

  The acid treatment is a method of treating the zeolite with an acid such as hydrochloric acid, nitric acid, sulfuric acid or the like at 30 to 100 ° C., whereby the aluminum in the zeolite skeleton can be dealuminated to reduce the acid amount.

  Alkali treatment is a method of treating zeolite with an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and accordingly, silicon in the zeolite skeleton can be eluted to increase the acid amount.

  Examples of the present embodiment will be described below, but the present invention is not limited to these.

(1) Measurement of acid amount The acid amount of the catalyst was measured by the ammonia TPD method. The measurement was performed using BELCAT manufactured by Nippon Bell Co., Ltd. The powder sample was filled in a quartz cell, heated to 500 ° C. under He flow, held for 1 h, and then cooled to 100 ° C. Subsequently, 5 vol% NH ₃ / He was supplied at 100 ° C. for 30 minutes to adsorb ammonia, and then purged with He for 15 minutes. Thereafter, the temperature was raised to 700 ° C. at 10 ° C./min and held for 20 minutes, and the desorbed ammonia was quantified. When the zeolite is analyzed, a peak on the low temperature side up to 200 to 300 ° C. and a peak on the high temperature side thereafter appear, but since the peak on the high temperature side is derived from an acid, peak separation is performed between 200 and 300 ° C., The acid amount was calculated from the peak on the high temperature side.

(2) Reaction test n-hexane was used as a hydrocarbon raw material, and catalytic cracking was performed using a fixed bed flow reactor. A catalyst having a particle size of 250 to 500 μm was used. The granular catalyst is held using quartz wool and quartz sand. The catalyst was packed in a Hastelloy C (registered trademark) reaction tube so that the total amount was 0.36 g. The upper and lower sides of the catalyst layer were held with quartz wool, and the upper and lower sides were filled with quartz sand to shorten the residence time of the gas in the reaction tube. When packing a plurality of catalysts in two stages, the upper catalyst layer was filled directly on the lower catalyst layer without filling quartz wool or the like between them. The thermocouple was set so that it might become the center position of a catalyst layer, and the catalyst layer temperature was measured. The gas was supplied from the upper part of the reaction tube and extracted from the lower part. Under a pressure of 0.2 MPa, the reaction tube was heated to a predetermined temperature at 5 ° C./min in a nitrogen stream. Thereafter, the supply of nitrogen was stopped, and n-hexane was supplied at 7.2 g / h while maintaining the pressure at 0.2 MPa. In addition to n-hexane, no dilution gas or water vapor was supplied during the reaction. Immediately after the start of the reaction, the temperature of the catalyst layer rapidly decreases due to the endothermic heat of catalytic cracking. Therefore, the temperature of the electric furnace was adjusted so that the catalyst layer temperature became a predetermined temperature. After the reaction for a predetermined time, the supply of n-hexane was stopped and the system was cooled in a nitrogen stream. The analysis was performed by gas chromatography, and the conversion rate (%) was calculated from the result. The useful components were ethylene, propylene, butenes, and BTX, and their carbon atom conversion selectivity (C-mol%) was calculated. The present embodiment relates to the effect of achieving both high activity and suppression of decrease in activity in a method for producing aromatic hydrocarbons and / or light olefins. Those that showed a high conversion rate later have a great effect.

[Example 1]
0.18 g of H-ZSM-5 (catalyst A), which is a 10-membered MFI type Si / Al ₂ molar ratio 80 and acid amount 0.424 mmol / g, is packed on the upper side of the catalyst layer. 0.18 g of 10-membered MFI type H-ZSM-5 (catalyst B) having a Si / Al ₂ molar ratio of 500 and an acid amount of 0.091 mmol / g was charged on the lower side of the bottom. The ratio of the acid amount of the lower catalyst to the acid amount of the upper catalyst (catalyst B / catalyst A) was 21%. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

[Comparative Example 1]
Only 0.36 g of catalyst A was charged. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

[Comparative Example 2]
0.36 g of catalyst B alone was charged. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

[Comparative Example 3]
0.18 g of catalyst B was charged on the upper side of the catalyst layer, and 0.18 g of catalyst A was charged on the lower side of the catalyst layer. The ratio of the acid amount of the lower catalyst to the acid amount of the upper catalyst (catalyst A / catalyst B) was 466%. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

[Comparative Example 4]
0.36 g of a mixture of catalyst A and catalyst B that have been sized is mixed at a weight ratio of 1: 1. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

[Comparative Example 5]
The upper stage side of the catalyst layer is filled with 0.18 g of 12-membered BEA type H-beta (catalyst C) having a Si / Al ₂ molar ratio of 41 and an acid amount of 0.502 mmol / g, and the lower stage of the catalyst layer. On the side, 0.18 g of catalyst B was charged. The ratio of the acid amount of the lower catalyst to the acid amount of the upper catalyst (catalyst B / catalyst C) was 18%. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

[Comparative Example 6]
0.18 g of catalyst C is filled on the upper side of the catalyst layer, and 0.18 g of H-beta (catalyst D) having an Si / Al ₂ molar ratio of 200 and an acid amount of 0.092 mmol / g is filled on the lower side of the catalyst layer. Filled. The ratio of the acid amount of the lower catalyst to the acid amount of the upper catalyst (catalyst D / catalyst C) was 18%. About this, the reaction test was done at 580 degreeC. The reaction results are shown in Table 1.

Conversion rate for each reaction time in Example 1 and Comparative Examples 1 to 6, C _2-4 olefins and BTX as useful components, C _2-6 paraffins (except for n-hexane) that can be converted into light olefins, Table 1 shows the selectivity in terms of carbon atoms of methane, which is a by-product that is difficult to convert to light olefins.

  When Example 1 is compared with Comparative Example 1 and Comparative Example 2, the decrease in the conversion rate in Example 1 is smaller than the decrease in the conversion rate in Comparative Example 1 and Comparative Example 2. From this, one of the catalysts was used alone by disposing a zeolite having a large amount of acid and having a 10-membered ring pore structure upstream, and disposing a catalyst having a smaller amount of acid downstream. It became clear that it maintained a high activity for a longer time than the case.

  Further, when Example 1 is compared with Comparative Example 3 and Comparative Example 4 in which the combination of the catalysts used and the amounts of the respective catalysts used are the same as each other, the reduction in the conversion rate in Example 1 is a comparative example. 3 and the lowering of the conversion rate in Comparative Example 4 is smaller. From this, it became clear that the arrangement of the catalyst according to Example 1 maintains the highest activity for the longest time.

  Further, when Example 1 is compared with Comparative Examples 5 and 6, when BEA type zeolite having a 12-membered ring pore structure is arranged upstream (Comparative Example 5 and Comparative Example 6), the initial stage of the reaction Shows a low conversion. On the other hand, when MFI-type zeolite having a 10-membered ring pore structure was disposed upstream (Example 1), it was revealed that high activity was maintained for a long time.

  Further, the present embodiment can be regarded as a manufacturing apparatus. In this case, the aromatic hydrocarbon and / or light olefin production apparatus according to the present embodiment includes a reactor having at least a first catalyst part and a second catalyst part. The first catalyst part includes zeolite (A) having an acid amount of 0.001 to 1 mmol / g and having a 10-membered ring pore structure, and the second catalyst part is downstream from the first catalyst part. And a solid acid catalyst (B) having an acid amount of 90% or less of the acid amount of the zeolite (A). The second catalyst unit is configured to be able to catalytically decompose the supplied hydrocarbon at a reaction temperature of less than 600 ° C.

  Of the main paraffins produced as a by-product in the production method and production apparatus according to the present embodiment, paraffins having 2 to 6 carbon atoms such as ethane and propane other than methane are collected and recycled to the raw material, or another process. Can be converted into useful light olefins. In addition, in catalytic cracking, the selectivity of methane is lower than that of thermal cracking, and the selectivity of other paraffins can be increased. Therefore, it is expected that the yield of the final active ingredient is further improved as compared with the thermal decomposition by the catalytic decomposition in the manufacturing method and the manufacturing apparatus according to the present embodiment.

  The present invention has been described above with reference to the above-described embodiments and examples. However, the present invention is not limited to the above-described embodiments and examples, and the configuration of the embodiments and examples. Those appropriately combined or substituted are also included in the present invention. In addition, based on the knowledge of those skilled in the art, it is possible to appropriately change the combination and processing order in the embodiments and examples, and to add various modifications such as various design changes to the embodiments and examples. Embodiments to which such modifications are added can also be included in the scope of the present invention.

Claims (11)

The hydrocarbon is allowed to pass through the first catalyst part containing zeolite (A) having an acid amount of 0.001 to 1 mmol / g and having a 10-membered ring pore structure. ) Is passed through a second catalyst portion containing a solid acid catalyst (B) that is 90% or less of the acid amount,
And catalytically cracking the hydrocarbon at a reaction temperature of less than 600 ° C. in the second catalyst part,
A process for producing aromatic hydrocarbons and / or olefins having 4 or less carbon atoms. The solid acid catalyst (B) is zeolite (B1),
The zeolite (A) and the zeolite (B1) are both represented by the general formula xM ₂ O.yAl ₂ O ₃ .zSiO ₂ .nH ₂ O,
The manufacturing method according to claim 1, wherein the molar ratio z / y of Si and Al ₂ in the zeolite (A) is different from the molar ratio z / y of Si and Al ₂ in the zeolite (B1).   It is configured so that the selectivity in terms of carbon atom of a product composed of olefin, benzene, toluene and xylene having 4 or less carbon atoms is 40% or more with respect to the total number of carbon atoms contained in the supplied hydrocarbon. The manufacturing method according to claim 1 or 2.   The said hydrocarbon is a manufacturing method of any one of Claims 1-3 containing a C5-C9 saturated hydrocarbon and / or a C6-C9 aromatic hydrocarbon.   The said hydrocarbon contains the naphtha, The manufacturing method of any one of Claims 1-3.   The production method according to any one of claims 1 to 5, wherein the solid acid catalyst (B) is a zeolite having a pore structure of an 8, 10 or 12-membered ring.   The production method according to any one of claims 1 to 6, wherein at least one of the zeolite (A) and the solid acid catalyst (B) is MFI type zeolite.   The production method according to claim 1, wherein the hydrocarbon is catalytically cracked at a reaction temperature of less than 600 ° C. in the first catalyst part. Equipped with a reactor configured as a fixed bed flow-through,
The reactor is divided into a plurality of stages for each catalyst, and the upstream side is filled with the zeolite (A) and the downstream side is filled with the solid acid catalyst (B).
The manufacturing method of any one of Claims 1-8 characterized by the above-mentioned. A reaction unit having at least a first catalyst unit and a second catalyst unit;
The first catalyst part includes a zeolite (A) having an acid amount of 0.001 to 1 mmol / g and having a 10-membered ring pore structure,
The second catalyst part includes a solid acid catalyst (B) that is disposed downstream of the first catalyst part and has an acid amount of 90% or less of the acid amount of the zeolite (A).
The second catalyst part is configured to be able to catalytically crack the supplied hydrocarbon at a reaction temperature of less than 600 ° C.
An apparatus for producing aromatic hydrocarbons and / or olefins having 4 or less carbon atoms.   The production apparatus according to claim 10, wherein the solid acid catalyst (B) is a zeolite having a pore structure of an 8, 10 or 12-membered ring.