JP2013039549A - Method for producing catalyst for catalytic cracking of hydrocarbon, method for producing aromatic hydrocarbon and/or olefin having four or less carbon atom, and catalyst for catalytic cracking of hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for improving steam resistance of a catalyst for catalytic cracking of hydrocarbons to increase the yields of an aromatic hydrocarbon and/or olefin having ≤4 carbon atoms.SOLUTION: The method for producing the catalyst for catalytic cracking of hydrocarbons comprises: a step (1) of mixing zeolite, a water-soluble aluminum-containing compound and water to obtain a catalyst precursor obtained by supporting aluminum on the zeolite; and a step (2) of mixing the catalyst precursor, a water-soluble phosphorus-containing compound and water to obtain the catalyst for catalytic cracking of hydrocarbons obtained by supporting phosphorus on the catalyst precursor.

Description

  The present invention relates to a method for producing a catalyst for catalytic cracking of hydrocarbons, a method for producing aromatic hydrocarbons and / or olefins having 4 or less carbon atoms using the catalyst for catalytic cracking of hydrocarbons produced by this production method, and hydrocarbons The present invention relates to a catalyst for catalytic cracking.

  Aromatic hydrocarbons such as ethylene, propylene, butene and other olefins having 4 or less carbon atoms (hereinafter, this olefin is appropriately referred to as “light olefin”) and BTX (benzene, toluene, and xylene) It is an important chemical product used as a raw material for chemical products. One of these production methods is a naphtha pyrolysis process. However, this pyrolysis process requires a high temperature of 800 ° C. or more, and consumes a large amount of energy to perform pyrolysis, which is an endothermic reaction. Among light olefins, propylene demand is expected to increase and supply shortage is expected, but this thermal cracking process has a high ethylene selectivity, making it difficult to cope with increased propylene production.

  Therefore, realization of catalytic cracking of naphtha using a catalyst was expected. Catalytic cracking enables a reaction at a relatively low temperature of about 500 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.

  As a catalyst for catalytic cracking of naphtha, various studies have been conducted on solid acid catalysts centered on zeolite. However, there is a problem that the catalyst is caulked by the sequential reaction of the products, and as a result, the catalyst is deactivated. In addition, when zeolite is used as a catalyst, there is a problem that dealumination of the zeolite skeleton occurs due to water vapor generated when coke is burned and removed, or steam coexisting during the reaction, resulting in deactivation of the catalyst. there were. The deactivation of the catalyst due to coking can be regenerated by removing deposits by combustion, but the deactivation of the catalyst due to dealumination is difficult to regenerate and is particularly problematic in long-term operation.

  So far, the following methods have been reported as methods for suppressing such deactivation. For example, in JP-A-11-180902 (Patent Document 1), in catalytic cracking using zeolite, a decrease in activity in a reaction in which steam coexists is suppressed by loading the rare earth element and phosphorus on the zeolite. It is disclosed.

  In JP 2010-42344 A (Patent Document 2), in catalytic cracking using a zeolite carrying an alkaline earth metal, a rare earth element and phosphorus, the zeolite is loaded with components other than phosphorus and phosphorus in separate steps. It is disclosed that when a catalyst is used, a decrease in activity is suppressed as compared with the case where a catalyst in which these are simultaneously supported is used.

  In JP 2010-202613 (Patent Document 3), in the catalytic cracking of paraffin using MCM-68, MCM-68 having a low Si / Al ratio is dealuminated by nitric acid treatment to obtain a Si / Al ratio. It is disclosed that the raised one suppresses the decrease in activity compared to the one not dealuminated.

  In particular, the following methods have been reported as methods for suppressing the decrease in catalyst activity due to steam. For example, in JP 2010-104909 A (Patent Document 4), in catalytic cracking using a zeolite supporting an alkaline earth metal and phosphorus, the zeolite is alkalinized using a water-soluble salt containing an alkaline earth metal and phosphorus. It is disclosed that by supporting an earth metal and phosphorus, a decrease in catalyst activity due to steam treatment and a decrease in catalyst activity in a reaction in which steam coexists are suppressed.

  In Japanese Patent No. 4112943 (Patent Document 5), catalytic cracking is performed using a pentasil-type zeolite containing a rare earth element and further containing manganese, zirconium and / or phosphorus, and the activity of the catalyst is reduced by steam treatment. It is disclosed to suppress a decrease in the activity of a catalyst in a reaction in which the coexistence of the catalyst is present.

  JP-A-11-192431 (Patent Document 6) discloses a catalyst containing clay, an inorganic oxide, a Y-type zeolite, and a pentasil zeolite, wherein the pentasil zeolite is phosphorus and aluminum, phosphorus and magnesium, or phosphorus. It is disclosed that catalytic cracking is performed using a catalyst containing calcium and calcium to suppress a decrease in the activity of the catalyst due to steam treatment. For modification of pentasil zeolite used as a catalyst, an aqueous solution containing phosphorus and aluminum, phosphorus and magnesium, or phosphorus and calcium is used, and two components are simultaneously supported on the zeolite.

Japanese Patent Laid-Open No. 11-180902 JP 2010-42344 A JP 2010-202613 A JP 2010-104909 A Japanese Patent No. 4112943 Japanese Patent Laid-Open No. 11-192431

  However, in Patent Document 4 described above, the activity of the catalyst is still lowered by the steam treatment, and there is room for improvement in order to improve the steam resistance of the catalyst. Moreover, in patent document 5, although the comparison with the catalyst which performed the steam process is performed, it is not described how much the activity fall is suppressed compared with the steam process before. Moreover, in patent document 6, hydrocarbon heavier than naphtha is used as a raw material, and it is not described whether it has sufficient steam resistance in the catalytic cracking of naphtha. In addition, although the comparison with the catalyst which performed the steam treatment is done, there is no comparison about the catalyst which changed treatment time before the treatment, the catalytic activity is maintained when the catalyst is exposed to the steam for a long time. It is not described whether or not.

  The present invention has been made in view of such a situation, and the object of the present invention is to improve the steam resistance of a catalyst for catalytic catalytic cracking of hydrocarbons so that aromatic hydrocarbons and / or olefins having 4 or less carbon atoms can be used. It is to provide a technique for increasing the yield.

In order to solve the above problems, an embodiment of the present invention is a method for producing a catalyst for catalytic hydrocarbon cracking. This manufacturing method includes the following step (1) and the following step (2).
Step (1): A step of mixing a zeolite, a water-soluble aluminum-containing compound and water to obtain a catalyst precursor obtained by supporting aluminum on the zeolite Step (2): A catalyst precursor and a water-soluble phosphorus-containing compound Step of obtaining a catalyst for catalytic cracking of hydrocarbon by mixing water with catalyst precursor and supporting phosphorus

  Another aspect of the present invention is a method for producing an aromatic hydrocarbon and / or an olefin having 4 or less carbon atoms. This production method includes catalytically cracking hydrocarbons using the hydrocarbon catalytic cracking catalyst produced by the production method of the above aspect.

Another embodiment of the present invention is a catalyst for hydrocarbon catalytic cracking. This hydrocarbon catalytic cracking catalyst has a zeolite carrying aluminum and phosphorus, and when steam-treated at 700 ° C., the conversion rate of hydrocarbon before steam treatment is a ₁ , and the hydrocarbon conversion after steam treatment is When the rate is b ₁ and the degree of decrease in the conversion rate is b ₁ / a ₁ , 60.0% ≦ a ₁ ≦ 99.9% and (b ₁ / a ₁ ) ≧ 0.94 are satisfied And

  ADVANTAGE OF THE INVENTION According to this invention, the steam resistance of the catalyst for hydrocarbon catalytic cracking can be improved, and the yield of an aromatic hydrocarbon and / or a C4 or less olefin can be improved.

  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. All features and combinations thereof described in the embodiments are not necessarily essential to the invention.

  As a result of diligent research, the present inventors have improved the steam resistance of the catalyst by supporting aluminum and phosphorus on the zeolite, and the decrease in activity is small even when exposed to steam for a long period of time, and the high activity is maintained. It has been found that a catalyst for catalytic cracking of hydrocarbons can be obtained, and the present invention has been completed.

Specifically, the hydrocarbon catalytic cracking catalyst according to the present embodiment has a zeolite carrying aluminum and phosphorus. The zeolite is preferably a zeolite having an 8-, 10- or 12-membered ring pore structure, and at least one selected from MFI, MEL, MWW, TON, BEA, MSE, MOR, MTW, and FAU type zeolite. Of these, at least one selected from MFI, MEL, MWW, and TON-type zeolite, which is a zeolite having a 10-membered ring pore structure, is more preferable. The MFI type having high stability is most preferable. ZSM-5, which will be described later, is one type of MFI type zeolite. The Si / Al ₂ ratio of the zeolite is preferably 5 to 2000, more preferably 10 to 400, still more preferably 25 to 100, and most preferably 20 to 50.

Further, in the catalyst for catalytic catalytic cracking according to the present embodiment, the hydrocarbon conversion rate before the steam treatment when the steam treatment is performed at 700 ° C. is a ₁ , and the hydrocarbon conversion rate after the steam treatment is b _1. When the degree of conversion reduction is b ₁ / a ₁ , 60.0% ≦ a ₁ ≦ 99.9% and (b ₁ / a ₁ ) ≧ 0.94 are satisfied. Further, the catalyst for catalytic cracking of hydrocarbon is 60.0% ≦ a ₁ ≦ 99.9% and (b ₁ / a ₁ ) ≧ 0.00 when steam-treated at 30 ° C. steam for 50 hours at 700 ° C. 94, preferably 50 vol% steam, steaming at 700 ° C. for 65 hours, satisfying 60.0% ≦ a ₁ ≦ 99.9% and (b ₁ / a ₁ ) ≧ 0.94 It is more preferable. Further, the degree of decrease in the conversion rate (b ₁ / a ₁ ) is more preferably 0.95 or more, further preferably 0.96 or more, and still more preferably 0.97 or more. The degree of conversion reduction (b ₁ / a ₁ ) was a two-digit value.

Thus, the hydrocarbon catalytic cracking catalyst according to the present embodiment has a zeolite carrying aluminum and phosphorus, and the degree of conversion reduction (b ₁ / a ₁ ) when steam-treated at 700 ° C. The condition of (b ₁ / a ₁ ) ≧ 0.94 is satisfied. Thereby, since the activity fall of the catalyst after a steam process is suppressed in the catalytic cracking of a hydrocarbon, the yield of an aromatic hydrocarbon and / or a C4 or less olefin can be raised.

Further, the hydrocarbon catalytic cracking catalyst according to the present embodiment, when steam-treated at 700 ° C., the total selectivity of benzene, toluene and xylene before the steam treatment (hereinafter referred to as BTX selectivity as appropriate). the _{a 2,} when the selectivity of BTX after steaming _{b 2,} a decrease of the selectivity of BTX by steaming was _b 2 / _{a 2,} satisfying the _{(b 2 / a 2) ≧} 0.52 Is preferred. Further, the catalyst for catalytic cracking of hydrocarbon preferably satisfies (b ₂ / a ₂ ) ≧ 0.52 when steam-treated at 30 vol% steam, 50 hours, 700 ° C., and more preferably 50 vol% steam, 65 hours. When the steam treatment is performed at 700 ° C., it is more preferable that (b ₂ / a ₂ ) ≧ 0.52 is satisfied. Further, the degree of decrease in the selectivity of BTX (b ₂ / a ₂ ) is more preferably 0.74 or more, further preferably 0.84 or more, and even more preferably 0.94 or more. preferable. The degree of reduction in the selectivity of BTX (b ₂ / a ₂ ) was a value with two significant digits.

Then, the manufacturing method of the catalyst for hydrocarbon catalytic cracking which concerns on this Embodiment is demonstrated. This manufacturing method includes the following step (1) and the following step (2).
Step (1): A step of mixing a zeolite, a water-soluble aluminum-containing compound and water to obtain a catalyst precursor obtained by supporting aluminum on the zeolite Step (2): A catalyst precursor and a water-soluble phosphorus-containing compound Step of obtaining a catalyst for catalytic cracking of hydrocarbon by mixing water with catalyst precursor and supporting phosphorus

  In the production method according to the present embodiment, in step (1), the zeolite, the water-soluble aluminum-containing compound and water are mixed, and the zeolite and the water-soluble aluminum-containing compound are brought into contact with each other. Aluminum is supported. In the subsequent step (2), the catalyst precursor obtained by supporting aluminum on zeolite, a water-soluble phosphorus-containing compound, and water are mixed to bring the catalyst precursor and the water-soluble phosphorus-containing compound into contact with each other. Thus, phosphorus is supported on the catalyst precursor. Thereby, the catalyst for hydrocarbon catalytic cracking is obtained.

  At least one of the contact by mixing the zeolite and the aluminum-containing compound in the step (1) and the contact by mixing the catalyst precursor and the phosphorus-containing compound in the step (2) is preferably performed by an impregnation method. Examples of the impregnation method include an evaporation to dryness method, an incipient wetness method, and an equilibrium adsorption method. For example, in the evaporation to dryness method, first, a zeolite serving as a carrier is immersed in a solution of an aluminum-containing compound, and is heated and dried under normal pressure or reduced pressure to allow the zeolite to carry aluminum. Thereafter, firing is usually performed to obtain a catalyst precursor. Subsequently, the obtained catalyst precursor is immersed in a solution of a phosphorus-containing compound and dried by heating under normal pressure or reduced pressure to allow the catalyst precursor to carry phosphorus. Thereafter, the catalyst is usually obtained by calcination. In any step, the firing temperature is preferably 200 ° C. or higher, and more preferably 400 to 700 ° C. The firing atmosphere is usually air, but may be an inert gas such as nitrogen. Moreover, you may bake in these mixed atmosphere.

  In the method for producing a catalyst for catalytic catalytic cracking of the present embodiment, aluminum is supported on zeolite and then phosphorus is supported. Thereby, favorable steam resistance can be provided to the catalyst for hydrocarbon catalytic cracking.

  When an aluminum and phosphorus water-soluble salt is dissolved in order to simultaneously support aluminum and phosphorus on the zeolite, precipitation of insoluble aluminum phosphate easily occurs, and the aluminum phosphate is dispersed as particles on the outer surface of the zeolite. It will be carried. Therefore, the interaction between the supported component and the zeolite is reduced. In addition, when aluminum is supported after phosphorus is supported on zeolite, phosphorus supported on the zeolite is eluted in the aqueous solution of the aluminum-containing compound, resulting in precipitation of insoluble aluminum phosphate. To be carried as particles. Therefore, the interaction between the supported component and the zeolite is reduced. Therefore, when aluminum and phosphorus are supported simultaneously, and when aluminum is supported after phosphorus, sufficient steam resistance cannot be obtained as compared with the case where phosphorus is supported after aluminum.

  In the contact in the step (1), it is preferable to use a water-soluble aluminum-containing compound. When insoluble alumina, boehmite, or the like is used, aluminum adheres as particles only to the outer surface of the zeolite particles. Therefore, the interaction between aluminum and zeolite becomes small. On the other hand, it is considered that by using water-soluble aluminum, the zeolite can be supported on the aluminum in a state where the aluminum is sufficiently in contact with the zeolite. Examples of the water-soluble aluminum-containing compound include aluminum nitrate nonahydrate, aluminum sulfate, aluminum chloride hexahydrate, and aluminum lactate. Of these, aluminum nitrate nonahydrate is preferred. The amount of aluminum supported is 0.1 to 30% by mass, preferably 0.2 to 10% by mass, more preferably 0.5 to 5% by mass, more preferably 0.5% by mass in terms of aluminum atom based on zeolite. Is 1.7 to 4% by mass.

  In the contact in the step (2), it is preferable to use a water-soluble phosphorus-containing compound. As in the case of aluminum, when a water-soluble phosphorus-containing compound is used, phosphorus can be supported on the zeolite in a state where phosphorus is sufficiently in contact with the zeolite as compared with the case where an insoluble phosphorus-containing compound is used. Conceivable. Examples of water-soluble phosphorus-containing compounds include dihydrogen phosphates such as ammonium dihydrogen phosphate, sodium dihydrogen phosphate dihydrate, and potassium dihydrogen phosphate, diammonium hydrogen phosphate, and dihydrogen hydrogen phosphate. Hydrogen phosphates such as potassium, phosphates such as trisodium phosphate and 12 water, phosphonates such as dipotassium phosphonate, hydrogen phosphite such as sodium hydrogen phosphite and 2.5 water, phosphine Examples include calcium phosphite, sodium phosphinate monohydrate, phosphinic acid salts such as ammonium phosphinate, phosphoric acid, phosphinic acid, phosphonic acid and the like. Among these, from the viewpoint that it is difficult for the acid amount of the catalyst to decrease, ammonium salts such as ammonium dihydrogen phosphate and diammonium hydrogen phosphate, phosphoric acid, phosphinic acid or phosphonic acid are preferable, and dihydrogen phosphate or phosphoric acid. Hydrogen salts are more preferred, and among them, at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate is particularly preferred because it is easier to dry than phosphoric acid and phosphinic acid. The amount of phosphorus supported is 0.01 to 10, preferably 0.1 to 2, and more preferably the number of moles relative to the total number of moles of aluminum contained in the zeolite and the supported aluminum. It is 0.2 to 1, more preferably 0.4 to 0.8.

  The catalyst for catalytic catalytic cracking produced by the production method of the present embodiment includes transitions of groups 4 to 12 of the periodic table of alkali metals, alkaline earth metals, rare earth metals, and elements in addition to aluminum and phosphorus. One or more components selected from the group consisting of metals may be included.

  The hydrocarbon catalytic cracking catalyst produced by the production method of the present embodiment may be in the form of a powder or a molded body when used for production of aromatic hydrocarbons and / or light olefins. When a hydrocarbon catalytic cracking catalyst is used as a molded catalyst, this molded catalyst may contain one or more clay minerals such as kaolin and bentonite and / or inorganic oxides such as silica, alumina and zirconia as a binder. Good.

  In order to prevent the catalyst characteristics from being changed by steam after the catalytic cracking reaction of the hydrocarbon is started, the catalyst may be treated with steam in advance and stabilized after preparation of the catalyst and before use in the reaction. The temperature of the treatment with steam is 400 to 900 ° C, preferably 500 to 850 ° C, more preferably 600 to 800 ° C. The partial pressure of steam is 0.001 to 5 MPa, preferably 0.01 to 1 MPa, and more preferably 0.01 to 0.1 MPa. Steam may be diluted with an inert gas such as nitrogen, air, oxygen, carbon monoxide, carbon dioxide, or a mixed gas thereof.

  The method for producing an aromatic hydrocarbon and / or olefin having 4 or less carbon atoms according to the present embodiment uses a hydrocarbon catalytic cracking catalyst produced by the above-described hydrocarbon catalytic cracking catalyst production method. Including catalytic cracking. Examples of the hydrocarbon used in the method for producing an aromatic hydrocarbon and / or an olefin having 4 or less carbon atoms include alkanes having 2 to 20 carbon atoms, olefins having 2 to 20 carbon atoms, and aromatic carbonization having 6 to 20 carbon atoms. Examples thereof include hydrogen and naphthene having 5 to 20 carbon atoms. The hydrocarbon used 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. Moreover, the hydrocarbon-based raw material containing the above-mentioned hydrocarbon that is catalytically cracked by the catalyst for catalytic hydrocarbon cracking preferably contains 80% by mass or more of a hydrocarbon having 5 to 12 carbon atoms, more preferably the number of carbon atoms. It contains 80% by mass or more of 5-9 saturated hydrocarbons and / or aromatic hydrocarbons having 6-9 carbon atoms.

  Examples of such hydrocarbon raw materials include heavy oil, light oil, naphtha and the like, and naphtha is preferable. The naphtha includes light naphtha, heavy naphtha, and full-range naphtha depending on the boiling point thereof, and any of naphtha used as a raw material (reactant) for catalytic cracking may be used, but light naphtha is preferable. The “light naphtha” refers to a naphtha having a relatively low boiling point, and the “heavy naphtha” refers to a naphtha having a relatively high boiling point.

  The raw material for catalytic cracking may be recycled and mixed with the unreacted raw material for catalytic cracking and a part of the product, or may be mixed with hydrocarbons produced by other processes. Moreover, it is preferable to entrain steam for the purpose of suppressing coking, supplying heat, and diluting hydrocarbons. That is, it is preferable to catalytically crack hydrocarbons in the presence of steam. Since the effect of suppressing coking is sufficiently obtained, the deactivation due to dealumination is suppressed, and the supply cost of steam is kept low, the supplied steam has a mass ratio to the supplied hydrocarbon (S / HC ratio: HC is Hydrocarbon) is 0.01 to 10, preferably 0.02 to 1, and more preferably 0.04 to 0.5. 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. In addition, hydrogen may be supplied, but if the hydrogen concentration increases, the product may be hydrogenated, and the yield of aromatic hydrocarbons and / or light olefins may be reduced. Therefore, it is preferable not to supply hydrogen.

  Regarding the reaction temperature for catalytic cracking of hydrocarbons, the higher the temperature, the easier the reaction proceeds, and the equilibrium between the product paraffin (paraffinic hydrocarbon) and olefin (olefinic hydrocarbon) is on the olefin side. Therefore, the yield of aromatic hydrocarbons and / or light olefins is improved. On the other hand, the lower the temperature, the more the coking is reduced and the deactivation of the catalyst can be suppressed. From this point, the reaction temperature of the catalytic cracking of hydrocarbon is 500 to 900 ° C, preferably 550 to 750 ° C, and more preferably 600 to 700 ° C.

  The reaction system between the hydrocarbon catalytic cracking catalyst and the hydrocarbon may be any of a fixed bed (bed), a moving bed, and a fluidized bed, preferably a fixed bed flow. The fixed bed flow type reactor is, for example, a reactor of a type in which a granular catalyst is held by a predetermined 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.

  According to the method for producing a hydrocarbon catalytic cracking catalyst according to the present embodiment described above, a hydrocarbon catalytic cracking catalyst having high steam resistance can be obtained. Thereby, in the production of aromatic hydrocarbons and / or olefins having 4 or less carbon atoms by catalytic cracking of hydrocarbons, catalyst deactivation due to steam can be suppressed, and high catalytic activity can be stably maintained. As a result, the yield of aromatic hydrocarbons and / or olefins having 4 or less carbon atoms can be increased.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. In this example, in order to facilitate analysis and analysis, n-hexane, which is one of the main components of naphtha, was catalytically decomposed instead of naphtha.

(1) Preparation of catalyst Proton type ZSM-5 (H-ZSM-5) was used as the zeolite, and both aluminum and phosphorus were supported on the zeolite by the impregnation method. Regarding the description of the catalyst, for example, the catalyst of Example 1 is expressed as 3Al4P / ZSM-5 (30). Supporting was performed from the element described on the left (“Al” in Example 1), and the supported amount (% by mass) of the element was indicated on the left side of the element (“3” in Example 1). However, the loading amount of the first component (“Al” in Example 1) (“3” in Example 1) is the loading amount on zeolite, and the second component (“P” in Example 2) is 1 This is the loading amount (“4” in Example 1) with respect to the catalyst in a state where the component eyes are loaded. When two components are supported simultaneously, “-” is inserted between the two components (Examples 5 and 6). The Si / Al ₂ ratio of the zeolite used is shown in parentheses (“(30)” in Example 1).

(2) Measurement of P / Al ratio The molar ratio (P / Al ratio) of supported phosphorus to the total of aluminum in zeolite (aluminum in the framework of the zeolite) and supported aluminum was analyzed by an ICP emission spectrometer. . ICPE-9000 (manufactured by Shimadzu Corporation) was used for measurement of the P / Al ratio. Under heating conditions, the catalyst was dissolved in potassium hydroxide solution and diluted with ion-exchanged water, and then the concentrations of phosphorus and aluminum were measured.

(3) Steam treatment The catalyst was pressure-molded so as not to clog and pulverized. Next, the catalyst was set in a steam treatment apparatus, and the temperature was raised to 700 ° C. at 5 ° C./min in an atmospheric pressure and nitrogen stream. Thereafter, 50 vol% steam / nitrogen was supplied, and steam treatment (steam treatment) was performed for 65 hours. After processing for a predetermined time, it switched to nitrogen and cooled.

(4) Reaction test Using n-hexane as a hydrocarbon raw material, catalytic cracking was performed using a fixed bed flow reactor. As the catalyst, one having a particle size of 250 to 500 μm was used. The catalyst was packed in an Inconel (registered trademark) reaction tube or Hastelloy (registered trademark) reaction tube so that the total amount was 0.83 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. A thermocouple was set at the center position of the catalyst layer, and the catalyst layer temperature was measured. The reaction tube was heated to 650 ° C. at a total pressure of 0.15 MPa and a nitrogen stream at 5 ° C./min.

Thereafter, the nitrogen supply was stopped, and n-hexane was supplied at 16.6 g / h and water 1.7 g / h so that the steam / oil mass ratio (S / O) = 0.1 (WHSV = 20 h ^−1). ). The total pressure is 0.15 MPa, the n-hexane partial pressure is 0.10 MPa, and the H ₂ O partial pressure is 0.05 MPa. Immediately after the start of the reaction, the temperature of the catalyst layer suddenly decreased due to the endothermic reaction of the catalytic cracking reaction. After reacting for a predetermined time, the supply of n-hexane was stopped and the system was cooled in a nitrogen stream.

Analysis was performed by gas chromatography. From the result 1 hour after the start of the reaction, the conversion rate (%) of the hydrocarbon and the selectivity (C-mol%) in terms of carbon atoms of each component converted from the hydrocarbon were calculated. Further, the degree of conversion reduction (b ₁ / a ₁ ) was calculated when the conversion rate of hydrocarbons before steam treatment was a ₁ and the conversion rate of hydrocarbons after steam treatment was b ₁ . Moreover, to calculate the selectivity of BTX before steaming _{a 2,} reduction of the selectivity of BTX by steaming when the selectivity of BTX after steaming and _{b 2} a _{(b 2} / _a 2). Since this embodiment relates to a hydrocarbon catalytic cracking catalyst having high steam resistance and high activity even after being exposed to steam for a long period of time, it is compared with the conversion rate or BTX selectivity before steam treatment. A decrease in the conversion rate or BTX selectivity after the steam treatment is small, and it can be said that the effect obtained by maintaining a high conversion rate or BTX selectivity is great.

[Example 1]
<Catalyst A: Preparation and Evaluation of 3Al4P / ZSM-5 (30)>
After dissolving 6.26 g of aluminum nitrate nonahydrate in 225 ml of ion-exchanged water, 15 g of H-ZSM-5 (30) was added. The obtained slurry (mixed solution) was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was heated to 600 ° C. in the air in a muffle furnace over 4 hours, held for 5 hours, and then fired. 10 g of the obtained solid was added to an aqueous solution in which 1.70 g of diammonium hydrogen phosphate was dissolved in 100 ml of ion exchange water. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain catalyst A. The P / Al ratio of catalyst A was 0.6. Thereafter, the catalyst A was steam-treated. Moreover, the reaction test was implemented about the catalyst A before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

[Example 2]
<Catalyst B: Preparation and Evaluation of 1.5Al3P / ZSM-5 (30)>
After dissolving 3.13 g of aluminum nitrate nonahydrate in 150 ml of ion-exchanged water, 15 g of H-ZSM-5 (30) was added. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was heated to 600 ° C. in the air in a muffle furnace over 4 hours, held for 5 hours, and then fired. 15.6 g of the obtained solid was added to an aqueous solution in which 2.00 g of diammonium hydrogen phosphate was dissolved in 156 ml of ion-exchanged water, and dried under reduced pressure at 40 to 60 ° C. with a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain catalyst B. The P / Al ratio of catalyst B was 0.6. Thereafter, the catalyst B was steamed. Moreover, the reaction test was implemented about the catalyst B before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 1]
<Catalyst C: Preparation and Evaluation of 3Al / ZSM-5 (30)>
After dissolving 6.26 g of aluminum nitrate nonahydrate in 150 ml of ion-exchanged water, 15 g of H-ZSM-5 (30) was added. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was heated to 600 ° C. in the air in a muffle furnace over 4 hours, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain Catalyst C. Thereafter, the catalyst C was steamed. Moreover, the reaction test was implemented about the catalyst C before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 2]
<Catalyst D: Preparation and Evaluation of 2P / ZSM-5 (30)>
After 0.85 g of diammonium hydrogen phosphate was dissolved in 100 ml of ion-exchanged water, 10 g of H-ZSM-5 (30) was added. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain catalyst D. The P / Al ratio of catalyst D was 0.6. Thereafter, the catalyst D was steam-treated. Moreover, the reaction test was implemented about the catalyst D before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 3]
<Catalyst E: Preparation and Evaluation of 10La2P / ZSM-5 (150)>
After 2.47 g of lanthanum acetate hemihydrate was dissolved in 150 ml of ion-exchanged water, 10 g of H-ZSM-5 (150) was added. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. 11.0 g of the obtained solid was added to an aqueous solution in which 0.94 g of diammonium hydrogen phosphate was dissolved in 110 ml of ion-exchanged water, and dried under reduced pressure at 40 ° C. to 60 ° C. with a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain Catalyst E. The P / Al ratio of catalyst E was 0.8. Thereafter, the catalyst E was steamed. Moreover, the reaction test was implemented about the catalyst E before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 4]
<Catalyst F: Preparation and Evaluation of 10La2P / ZSM-5 (30)>
After 2.47 g of lanthanum acetate hemihydrate was dissolved in 150 ml of ion-exchanged water, 10 g of H-ZSM-5 (30) was added. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. 11.4 g of the obtained solid was added to an aqueous solution in which 0.97 g of diammonium hydrogen phosphate was dissolved in 114 ml of ion exchange water, and dried under reduced pressure at 40 ° C. to 60 ° C. with a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain catalyst F. The P / Al ratio of catalyst F was 0.8. Thereafter, the catalyst F was steam-treated. Moreover, the reaction test was implemented about the catalyst F before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 5]
<Catalyst G: Preparation and Evaluation of 3Al-2P / ZSM-5 (30)>
4.17 g of aluminum nitrate nonahydrate and 0.85 g of diammonium hydrogen phosphate were added to 150 ml of ion-exchanged water. Although a precipitate was formed, 10 g of H-ZSM-5 (30) was further added as it was. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was heated to 600 ° C. in the air in a muffle furnace over 4 hours, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain catalyst G. The P / Al ratio of catalyst G was 0.3. Thereafter, the catalyst G was steamed. Moreover, the reaction test was implemented about the catalyst G before and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 6]
<Catalyst H: Preparation and Evaluation of 3Al-4P / ZSM-5 (30)>
4.17 g of aluminum nitrate nonahydrate and 1.71 g of diammonium hydrogen phosphate were added to 150 ml of ion-exchanged water. Although a precipitate was formed, 10 g of H-ZSM-5 (30) was further added as it was. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was heated to 600 ° C. in the air in a muffle furnace over 4 hours, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain catalyst H. The P / Al ratio of catalyst H was 0.5. Thereafter, the catalyst H was subjected to steam treatment. Moreover, the reaction test was implemented about the catalyst H before and after a steam process. The results of the reaction test are shown in Table 1.

[Comparative Example 7]
<Catalyst I: Preparation and Evaluation of 4P3Al / ZSM-5 (30)>
After dissolving 2.56 g of diammonium hydrogen phosphate in 150 ml of ion-exchanged water, 15 g of H-ZSM-5 (30) was added. The obtained slurry was dried under reduced pressure at 40 ° C. to 60 ° C. using a rotary evaporator. The obtained solid was dried in air in a muffle furnace at 120 ° C. for 8 hours, then heated to 600 ° C. over 200 minutes, held for 5 hours, and then fired. 17.0 g of the obtained solid was added to an aqueous solution in which 7.09 g of aluminum nitrate nonahydrate was dissolved in 170 ml of ion-exchanged water, and dried under reduced pressure at 40 ° C. to 60 ° C. with a rotary evaporator. The obtained solid was heated to 600 ° C. in the air in a muffle furnace over 4 hours, held for 5 hours, and then fired. The obtained catalyst was pulverized to obtain Catalyst I. The P / Al ratio of catalyst I was 0.5. Thereafter, the catalyst I was steamed. Moreover, the reaction test was implemented about the catalyst I before a steam process and after a steam process. The results of the reaction test are shown in Table 1.

  As shown in Table 1, the catalyst A of Example 1 and the catalyst B of Example 2 have a small decrease in the conversion rate due to the steam treatment, that is, the degree of decrease in the conversion rate is close to 1 as compared with each comparative example. A high conversion rate was exhibited both before and after treatment. From this, it became clear that Catalyst A and Catalyst B have high steam resistance. In the catalyst C of Comparative Example 1 supporting only aluminum, the conversion rate after the steam treatment was greatly reduced. Compared with the catalyst C, the catalyst D of Comparative Example 2 carrying only phosphorus has a reduced activity due to steam treatment. However, catalyst D had a large reduction in conversion and low steam resistance as compared with catalyst A and catalyst B, which had the same P / Al ratio and also supported aluminum.

  Catalyst A has the same loading amount of aluminum and phosphorus, but Catalyst H of Comparative Example 6 in which aluminum and phosphorus were simultaneously supported, and Catalyst I of Comparative Example 7 in which aluminum was supported after phosphorus was supported, When compared with Catalyst A, Catalyst H and Catalyst I have a high conversion rate before the steam treatment, but the conversion rate after the steam treatment is significantly lower than that of Catalyst A. From this, it was revealed that it is effective to improve the steam resistance by supporting phosphorus after supporting aluminum.

  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 (12)

The manufacturing method of the catalyst for hydrocarbon catalytic cracking characterized by including the following process (1) and the following process (2).
Step (1): Step of obtaining a catalyst precursor obtained by mixing zeolite, a water-soluble aluminum-containing compound and water, and supporting aluminum on the zeolite Step (2): The catalyst precursor and a water-soluble phosphorus-containing compound And a process for obtaining a catalyst for catalytic cracking of hydrocarbon by mixing phosphorus with water on the catalyst precursor In the step (1), a mixed liquid containing the zeolite, the aluminum-containing compound, and the water is dried to form the catalyst precursor,
2. The production method according to claim 1, wherein in the step (2), the hydrocarbon catalytic cracking catalyst is formed by drying a mixed solution containing the catalyst precursor, the phosphorus-containing compound, and the water.   The production method according to claim 1, wherein the phosphorus-containing compound is at least one of dihydrogen phosphate and hydrogen phosphate.   The method according to claim 3, wherein the phosphorus-containing compound is at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.   5. The method according to claim 1, wherein at least one of formation of the catalyst precursor in the step (1) and formation of the hydrocarbon catalytic cracking catalyst in the step (2) is performed by an impregnation method. Production method.   The production method according to any one of claims 1 to 5, wherein the zeolite is MFI type zeolite.   A hydrocarbon is catalytically cracked using the hydrocarbon catalytic cracking catalyst produced by the production method according to any one of claims 1 to 6, wherein the hydrocarbon and / or carbon number is 4 or less. Of producing olefins.   The manufacturing method according to claim 7, wherein the hydrocarbon-based raw material containing hydrocarbon includes naphtha.   The method according to claim 7 or 8, wherein a reaction system between the hydrocarbon catalytic cracking catalyst and the hydrocarbon is a fixed bed flow system.   The method according to any one of claims 7 to 9, wherein the hydrocarbon is catalytically cracked with steam accompanied by the hydrocarbon. In the case of having a zeolite carrying aluminum and phosphorus and steam-treated at 700 ° C., the conversion rate of hydrocarbons before steam treatment is a ₁ , the conversion rate of hydrocarbons after steam treatment is b ₁ , and the conversion rate decreases A hydrocarbon catalytic cracking catalyst characterized by satisfying 60.0% ≦ a ₁ ≦ 99.9% and (b ₁ / a ₁ ) ≧ 0.94 when the degree is b ₁ / a ₁ . In the case of steam treatment at 700 ° C., the total selectivity of benzene, toluene and xylene before steam treatment is a ₂ , the total selectivity after steam treatment is b ₂ , and the degree of decrease in the total selectivity is b when a _{2 / a 2, (b 2} / a 2) a hydrocarbon cracking catalyst of claim 11 satisfying ≧ 0.52.