JP2013193027A - Method for producing catalyst for decomposing hydrocarbon oil, and method for decomposing hydrocarbon oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a catalyst for decomposing hydrocarbon oil, which is a catalyst used in decomposing the hydrocarbon oil in the presence of water, containing a composite metal oxide as a catalytically active component and high in mechanical strength and stability in a reaction system, and to provide a method for decomposing the hydrocarbon oil using the catalyst for decomposing the hydrocarbon oil, prepared using the producing method.SOLUTION: A method is provided for producing a catalyst for decomposing hydrocarbon oil, used for decomposing the hydrocarbon oil, wherein the catalyst for decomposing the hydrocarbon oil includes a composite metal oxide. The method for producing the catalyst for decomposing the hydrocarbon oil includes a mixing step of kneading a catalyst raw material powder containing the composite metal oxide, an acidic solution and an organic molding assistant to prepare a mixture with a pH of >1.0 and <6.0, a molding step of molding pellets made of the mixture, and a baking step of baking the pellets to prepare the catalyst for decomposing the hydrocarbon oil. A method for decomposing the hydrocarbon oil includes bringing the hydrocarbon oil into contact with the catalyst for decomposing the hydrocarbon oil in the presence of water to decompose the hydrocarbon oil.

Description

  The present invention relates to a method for producing a hydrocarbon oil cracking catalyst and a hydrocarbon oil cracking method, and in particular, a catalyst used for cracking and lightening hydrocarbon oil without supplying hydrogen from outside the system. The present invention relates to a production method and a method for cracking hydrocarbon oil using a catalyst prepared by using the production method.

  Conventionally, as a method of obtaining light hydrocarbon oil useful as a raw material for petrochemical products, fuel oil, etc. and light hydrocarbon gas useful as fuel gas, etc. by decomposing and lightening heavy hydrocarbon oil Hydrocracking, thermal cracking and fluid catalytic cracking are known.

  Here, the hydrocracking method is a method for lightening a heavy hydrocarbon oil by bringing the heavy hydrocarbon oil into contact with a hydrogenation catalyst in a high-temperature, high-pressure hydrogen atmosphere (for example, patents). Reference 1). The thermal decomposition method is a method for lightening a heavy hydrocarbon oil without using a catalyst by thermally decomposing hydrocarbon molecules under high temperature conditions (see, for example, Patent Document 2). Furthermore, the fluid catalytic cracking method is a method of reducing the weight of heavy hydrocarbon oil by bringing a flowing catalyst and heavy hydrocarbon oil into contact with each other (see, for example, Patent Document 3).

  However, in the hydrocracking method, a large amount of high-pressure hydrogen gas is used for the cracking reaction, so that a large-scale hydrogen gas production facility is required and the cost increases. In addition, in the pyrolysis method, a large amount of coke is generated and the aromatic ring is hardly cleaved, so that the production efficiency of light hydrocarbon oil is poor and the heavy hydrocarbon oil cannot be decomposed sufficiently. was there. Furthermore, the fluid catalytic cracking method has a problem that the operating cost of the apparatus is high.

  Further, in the hydrocracking method, it has been necessary to desulfurize and denitrogenate the heavy hydrocarbon oil in advance in order to prevent deterioration (poisoning) of the hydrogenation catalyst. Furthermore, in the thermal cracking method and fluid catalytic cracking method, there is almost no desulfurization reaction or denitrogenation reaction of hydrocarbon oil, so it is necessary to desulfurize and denitrogenate the heavy hydrocarbon oil in advance as in the hydrocracking method. was there. That is, the hydrocracking method, the thermal cracking method, and the fluid catalytic cracking method have a problem that a pretreatment of heavy hydrocarbon oil is required.

JP 2008-297452 A JP 2009-102471 A JP-A-8-269464

  Accordingly, the present inventor provides a method capable of reducing the weight of hydrocarbon oil efficiently at low cost without desulfurizing and denitrifying the hydrocarbon oil in advance and without using high-pressure hydrogen gas. We conducted intensive research for the purpose of doing this. And this inventor is using hydrocarbon oil cracking catalyst which contains a predetermined mixed metal oxide as a catalyst active ingredient, and does not supply hydrogen from the outside of a reaction system, but does not supply hydrocarbon oil in the presence of water. It was newly found that it can be decomposed and lightened.

  By the way, when hydrocarbon oil is lightened industrially using a catalyst in an oil refining plant or the like, from the viewpoint of proceeding the decomposition reaction (lightening reaction) of hydrocarbon oil in the reaction vessel as desired, the reaction vessel It is necessary that the catalyst filled therein does not break or denature during the catalyst filling or the decomposition reaction. That is, a catalyst used for industrial hydrocarbon oil cracking is required to have high mechanical strength and stability in the reaction system. Therefore, it is necessary to increase the mechanical strength of the catalyst and the stability in the reaction system when industrially using the hydrocarbon oil cracking catalyst containing a composite metal oxide as a catalytic active component. .

  Here, for example, in Japanese Patent Application Laid-Open No. 2001-314770 (Patent Document 4), when a hydrocarbon oil is industrially hydrocracked, a catalytically active component is used as a carrier having high mechanical strength and high stability in the reaction system. Is used. Specifically, in Patent Document 4, a catalyst obtained by supporting a catalytically active component on a zinc-containing alumina support containing zinc is used as a hydrogenation catalyst used when hydrocracking hydrocarbon oil. According to the hydrogenation catalyst described in Patent Document 4, since the mechanical strength of the catalyst and the stability in the reaction system can be increased by using the zinc-containing alumina support, the hydrocracking of hydrocarbon oil. Can proceed as desired.

  However, the hydrocarbon oil cracking catalyst containing a composite metal oxide as a catalytic active component is used in the presence of high-temperature and high-pressure water (steam). Therefore, the catalytically active component of the hydrocarbon oil cracking catalyst cannot be used by being supported on a carrier such as the above-described zinc-containing alumina carrier or silica carrier. This is because the crystal structure of γ-alumina and silica is greatly changed by high-temperature and high-pressure steam (that is, the stability in the reaction system is low). On the other hand, when a hydrocarbon oil cracking catalyst is formed using only a catalytically active component made of a composite metal oxide without using a carrier, sufficient mechanical strength cannot be obtained.

Therefore, it has been required to establish a technique for improving the mechanical strength of the catalyst and the stability in the reaction system for the hydrocarbon oil cracking catalyst containing a composite metal oxide as a catalytic active component.
Therefore, the present invention is a catalyst used when cracking hydrocarbon oil in the presence of water, comprising a composite metal oxide as a catalytically active component, and having mechanical strength and stability in the reaction system. An object of the present invention is to provide a method for producing a hydrocarbon oil cracking catalyst having a high content. It is another object of the present invention to provide a method for cracking hydrocarbon oil using a hydrocarbon oil cracking catalyst prepared by using the production method.

  The present inventor establishes a method for increasing the mechanical strength of a catalyst without degrading the stability of the catalyst in the reaction system for the hydrocarbon oil cracking catalyst containing a composite metal oxide as a catalyst active component. For this purpose, we conducted an extensive study. Then, the present inventor uses a acidic solution such as an aqueous nitric acid solution to once peptize the composite metal oxide particles, and then agglomerate or condense the peptized particles again to obtain a hydrocarbon oil decomposition catalyst. The idea was to increase the mechanical strength of the catalyst without reducing the stability of the catalyst in the reaction system.

However, the present inventor kneaded the composite metal oxide and an acidic solution to once peptize the composite metal oxide particles, and then agglomerate or condense the peptized particles again. An attempt was made to prepare a hydrocarbon oil cracking catalyst with high mechanical strength by molding and firing a mixture with an acidic solution. However, the mixture could not be formed into a desired shape, and the hydrocarbon oil cracking catalyst was Could not be prepared.
Therefore, the present inventors have further studied for the purpose of improving the moldability of the above mixture and preparing a hydrocarbon oil cracking catalyst having high mechanical strength and high stability in the reaction system. And this inventor improves the moldability of a mixture by using organic shaping | molding auxiliary | assistance, and controlling the pH of the mixture containing composite metal oxide, an acidic solution, and a shaping | molding adjuvant. The inventors have found that a hydrocarbon oil cracking catalyst having high mechanical strength and high stability in the reaction system can be produced, and the present invention has been completed.

That is, the present invention aims to advantageously solve the above-mentioned problems, and the method for producing a hydrocarbon oil cracking catalyst according to the present invention comprises a hydrocarbon oil cracking catalyst used for cracking hydrocarbon oil. The hydrocarbon oil cracking catalyst contains a composite metal oxide, and a catalyst raw material powder containing the composite metal oxide, an acidic solution, and an organic forming aid are kneaded. a mixing step for preparing a mixture having a pH of more than 1.0 and less than 6.0, a forming step for forming pellets made of the mixture, and a firing step for preparing hydrocarbon oil cracking catalysts by firing the pellets. It is characterized by including.
In the present invention, “pH of the mixture” can be measured by a glass electrode method.

Here, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, the acidic solution is preferably an aqueous nitric acid solution.
In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the nitric acid concentration in the aqueous nitric acid solution is more preferably 0.75 to 2.75% by mass.

  In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the organic molding aid is preferably cellulose.

  Furthermore, the method for producing a hydrocarbon oil cracking catalyst according to the present invention includes a kneading system of the catalyst raw material powder and the organic molding aid before the end of charging the acidic solution into the kneading system in the mixing step. It is preferable to end the charging into the inside.

Further, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, the composite metal oxide comprises:
(A) a composite metal oxide having a perovskite structure;
(B) a composite metal oxide having a pseudo-brookite structure;
(C) It consists of one kind of element X selected from Group IVA elements, Group IIIA elements, Group VIA elements and Group VIIA elements, Group IVA elements in the 4th to 6th periods, and Group VIII elements in the 4th period One element Y ₁ selected from the group and different from the element X, a group IIIA element, a group VIA element and a group VIIA element, and a group IVA element in the fourth to sixth periods and a group VIII in the fourth period Selected from the group consisting of group elements and containing one element Y ₂ different from the element X and the element Y ₁ , the abundance of the element Y ₁ (y ₁ ) and the abundance of the element Y _{2 (y 2)} ratio of the total abundance of the element X with respect to _{(y 1 + y 2) (} x) and _{(x / (y 1 + y} 2)) is, is 0.5 to 2.0, the element _{Y 1} abundance of elements _{Y 2} with respect to the amount of presence _{(y 1) (y 2} The ratio of _(y 2 / y ₁₎ comprises a composite metal oxide is 0.02 to 0.25,
Preferably, it consists of at least one selected from the group consisting of.
Here, in the present invention, the “element abundance” is determined by analyzing the solution obtained by dissolving the composite metal oxide by ICP emission spectroscopic analysis, and calculating each element in the composite metal oxide from the obtained measurement value. It can obtain | require by calculating the molar concentration in conversion of a metal simple substance. The “element abundance ratio (molar ratio)” can be obtained by calculating the calculated molar concentration ratio of each element (hereinafter, the element abundance ratio calculation method is “melt / It may be referred to as “ICP-AES method”).
In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the composite metal oxide having a perovskite structure is LaAlO ₃ , NiTiO ₃ , CoTiO ₃ , KTiO ₃ , BaTiO ₃ , SrTiO ₃ , and these It is preferably selected from the group consisting of composite metal oxides in which part of the metal elements of the composite metal oxide is substituted with other metal elements.
In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the composite metal oxide having the pseudo-brookite structure is preferably Fe ₂ TiO ₅ .
Furthermore, in the method for producing a hydrocarbon oil cracking catalyst according to the present invention, the element X is zirconium, the element Y ₁ is cerium, and the element Y ₂ is selected from the group consisting of tungsten, iron, and manganese. One type is preferable.

And the method for producing a hydrocarbon oil cracking catalyst of the present invention, the hydrocarbon oil cracking catalyst further comprises a binder comprising an inorganic oxide, and the binder has an Al content of 1% by mass or less, And it is preferable that Si content is 1 mass% or less, and the said catalyst raw material powder contains the said binder.
In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the inorganic oxide is preferably titanium dioxide.
Here, in the present invention, the “Al content” and the “Si content” can be obtained by analyzing a solution obtained by dissolving the binder by ICP emission spectroscopy.

  Further, the present invention aims to advantageously solve the above-mentioned problems, and the hydrocarbon oil cracking method of the present invention comprises a hydrocarbon oil and the above-described hydrocarbon oil cracking in the presence of water. Hydrocarbon oil is decomposed by bringing it into contact with a hydrocarbon oil cracking catalyst produced using any one of the production methods for a catalyst.

  According to the method for producing a hydrocarbon oil cracking catalyst of the present invention, a catalyst used when cracking hydrocarbon oil in the presence of water, comprising a composite metal oxide as a catalytically active component, and a machine It is possible to produce a hydrocarbon oil cracking catalyst having high mechanical strength and high stability in the reaction system. Further, according to the hydrocarbon oil cracking method of the present invention, hydrocarbons can be efficiently produced at low cost without desulfurizing and denitrifying the hydrocarbon oil as a raw material in advance and without using high-pressure hydrogen gas. The oil can be broken down.

It is a flowchart which shows the manufacturing process at the time of manufacturing the catalyst for hydrocarbon oil decomposition | disassembly using the manufacturing method of the typical catalyst for hydrocarbon oil decomposition | disassembly according to this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Here, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, a catalyst raw material powder containing a composite metal oxide, an acidic solution, and an organic forming aid are kneaded so as to have a predetermined pH. The resulting mixture is shaped and calcined to form a hydrocarbon oil cracking catalyst. The hydrocarbon oil cracking catalyst produced according to the method for producing a hydrocarbon oil cracking catalyst of the present invention decomposes hydrocarbon oil in the presence of water and carbonizes it without supplying hydrogen from outside the reaction system. Used when lightening hydrogen oil.

<Catalyst for hydrocarbon oil decomposition>
The hydrocarbon oil cracking catalyst produced using the method for producing a hydrocarbon oil cracking catalyst of the present invention is suitable for the reaction of cracking hydrocarbon oil in the presence of water without supplying hydrogen from outside the system. A composite metal oxide is included as a component that exhibits catalytic action (a catalytically active component for hydrocarbon oil cracking reaction). The hydrocarbon oil cracking catalyst produced using the method for producing a hydrocarbon oil cracking catalyst of the present invention may optionally contain a binder made of a predetermined inorganic oxide.

Here, the composite metal oxide is an oxide formed by combining two or more metal oxides. The composite metal oxide is not particularly limited, and (A) a composite metal oxide having a perovskite type structure (apatite type structure), (B) a pseudo brookite type structure (pseudo plate titanium stone type). A composite metal oxide having a structure, sometimes referred to as a “pseudobrookite structure”), (C) a composite metal oxide containing predetermined elements X, Y ₁ and Y ₂ , or a composite metal thereof Mention may be made of mixtures of oxides (A) to (C).
The crystal structure of the composite metal oxide can be evaluated using, for example, X-ray diffraction analysis.

Examples of the composite metal oxide having a perovskite structure include a composite metal oxide represented by the general formula: ABO ₃ and a part of at least one of the A site element and the B site element of the composite metal oxide ABO _3. Examples thereof include composite metal oxides substituted with these elements. Specifically, the composite metal oxide having a perovskite structure has the following general formula (1):
A _1-x A ′ _x B _1-y B ′ _y O _3-δ (1)
[In the formula, A represents one element selected from the group consisting of Group IA element, Group IIA element, Group IIIA element and Group VIII element, and A ′ represents a group composed of Group VA element and Group IIIB element. At least one element selected from B, B represents one element selected from the group consisting of Group IIIB elements and Group IVA elements, and B ′ represents a group consisting of Group VA elements and Group IIIB elements Represents at least one element selected from the above, A, A ′, B, and B ′ are different from each other, x is an atomic ratio of the element A ′, and y is an atomic ratio of the element B ′. Yes, δ indicates the amount of oxygen deficiency. ]
The oxide represented by these can be mentioned. Note that the oxygen deficiency is a number at which the oxide represented by the general formula (1) becomes electrically neutral.
Incidentally, when the composite metal oxide in which a part of the A site element or B site element in the general formula (1) is substituted with other elements A ′ and B ′, the atomic ratio x of the element A ′ is: It is preferably 0.4 or less (0 ≦ x ≦ 0.4), and more preferably x = 0 (that is, only the B site element is replaced without replacing the A site element). The atomic ratio y of the element B ′ is preferably 0.4 or less (0 ≦ y ≦ 0.4), more preferably 0.35 or less (0 ≦ y ≦ 0.35), More preferably, it is 0.25 or less (0 ≦ y ≦ 0.25). This is because it may be difficult to maintain the perovskite structure if the atomic ratios of the elements A ′ and B ′ are excessively increased.
The B site element is preferably one element selected from the group consisting of IIIB group elements when the A site element is a IIIA group element. Further, the B site element is preferably one element selected from the group consisting of an IVA group element when the A site element is an IA group element, an IIA group element or a VIII group element.

More specifically, the composite metal oxide having a perovskite structure includes LaAlO ₃ , NiTiO ₃ , CoTiO ₃ , KTiO ₃ , BaTiO ₃ , SrTiO ₃ , or a metal element of these composite metal oxides (A site). Examples thereof include composite metal oxides in which a part of the element and the B site element is substituted with another metal element.

Further, the composite metal oxide having a pseudo-brookite structure is not particularly limited, and Fe ₂ TiO ₅ can be exemplified.

Further, a predetermined element X, a predetermined element Y _1, as a composite metal oxide containing predetermined element Y ₂ is
(A) one element X selected from group IVA elements;
(B) one element Y ₁ selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Is an element different from the element X),
(C) One element Y ₂ selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Element X and element Y ₁ are different elements).
A composite metal oxide containing these three kinds of metal elements in a predetermined ratio can be given.
Here, as the “predetermined ratio”, the ratio (molar ratio) of the abundance of each element X, Y ₁ , Y _{2 in} the composite metal oxide obtained by the melting / ICP-AES method is
(D) a ratio of abundance x of the element X to the total _(y 1 + _{y 2)} between the abundance _{y 2} abundance _{y 1} and the element _{Y 2} elements _{Y 1} is 0.5 to 2.0 (0 .5 ≦ x / (y ₁ + y ₂ ) ≦ 2.0)
(E) a ratio of abundance _{y 2} elements _{Y 2} relative abundance _{y 1} element _{Y 1} is 0.02 to 0.25 (0.02 ≦ _y 2 / _{y 1} ≦ 0.25),
A ratio can be mentioned.

More specifically, the element X, the element Y ₁ , and the element Y ₂ are not particularly limited, and examples thereof include Ti, Zr, Ce, W, Mn, and Fe. The composite metal oxide in which these elements are element X, element Y ₁ or element Y ₂ is, for example, a composite containing Zr as element X, Ce as element Y ₁ , W, Fe or Mn as element Y _2. Mention may be made of metal oxides.

Incidentally, the element X, the element Y _1, the composite metal oxide containing element Y _2, it is particularly preferable element X is zirconium (Zr). This is because if the element X is Zr, the structure of the composite metal oxide can be maintained even when the hydrocarbon oil cracking catalyst is used under high temperature and high pressure conditions. That is, in the composite metal oxide in which the element X is composed of Zr, the hydrothermally synthesized zeolite, silica, or the hydrogenation catalyst composed of γ-alumina, which is used for hydrocracking of hydrocarbon oil, has a high temperature. The crystal structure of the catalytically active component is not greatly changed by high-pressure steam, and the catalyst cannot be used. Further, the catalytically active component is hardly deteriorated, and it is not necessary to pretreat (desulfurize and denitrogenize) the hydrocarbon oil. From the viewpoint of reliably maintaining the structure of the composite metal oxide, the molar ratio (x / m) of the abundance x of the element X to the abundance m of all the metal elements in the composite metal oxide is 0. It is preferably 55 or more, and more preferably 0.60 or more.

In addition, the composite metal oxide mentioned above can be prepared using known methods, such as a coprecipitation method and a sol-gel method. Specifically, for example, when the coprecipitation method is used, the composite metal oxide can be prepared as follows without any particular limitation.
(I) First, an aqueous solution containing a metal element constituting the composite metal oxide is prepared.
(Ii) Next, a coprecipitation agent such as aqueous ammonia or sodium carbonate solution is added to the prepared aqueous solution so that the pH of the aqueous solution does not deviate toward the alkali side (for example, the pH is in the range of 5 to 8). ) Drop while adjusting to produce a coprecipitate.
(Iii) Finally, the obtained precipitate is filtered and dried, and then the dried precipitate is fired to obtain a composite metal oxide.
Here, the temperature for drying the precipitate in (iii) is preferably 100 ° C. or higher from the viewpoint of efficiently evaporating moisture, and 160 ° C. or lower from the viewpoint of preventing rapid drying. preferable. Moreover, the temperature at which the dried precipitate is calcined depends on the structural stability of the resulting composite metal oxide (that is, suppression of structural change of the composite metal oxide when the hydrocarbon oil is decomposed by using it as a catalytically active component). From a viewpoint, it is preferable that it is 500 degreeC or more, and it is preferable that it is 900 degreeC or less from a viewpoint which suppresses the reduction | decrease in the surface area of the composite metal oxide to produce | generate.
Incidentally, a composite metal oxide prepared by using a coprecipitation method, a sol-gel method or the like is usually generated as secondary particles in which a plurality of primary particles are aggregated.

The binder made of a predetermined inorganic oxide is for improving the moldability of a mixture containing a composite metal oxide and an acidic solution. And as an inorganic oxide used as a binder, inorganic oxides other than the said composite metal oxide, for example, titanium dioxide, can be mentioned, without being specifically limited.
In addition, a binder will be contained in the catalyst for hydrocarbon oil decomposition | disassembly formed by baking a mixture. Therefore, the binder is required to be an inorganic oxide that is stable under the use conditions of the hydrocarbon oil cracking catalyst (under high-temperature and high-pressure steam). Therefore, the binder made of an inorganic oxide needs to have an Al content of 1% by mass or less and an Si content of 1% by mass or less. This is because alumina, which is an oxide of Al, and silica, which is an oxide of Si, are modified under high-temperature and high-pressure steam. Incidentally, it is preferable that a binder does not contain Al and Si substantially.

  The hydrocarbon oil cracking catalyst containing the above-described composite metal oxide and optionally further containing a binder can be produced, for example, as follows according to the method for producing a hydrocarbon oil cracking catalyst of the present invention. it can.

<Method for producing hydrocarbon oil cracking catalyst>
In FIG. 1, the manufacturing process at the time of manufacturing the catalyst for hydrocarbon oil decomposition | disassembly using an example of the manufacturing method of the catalyst for hydrocarbon oil decomposition | disassembly of this invention is shown. Here, in this example of the method for producing a hydrocarbon oil cracking catalyst, a hydrocarbon oil cracking catalyst containing the above-described composite metal oxide and the above-described binder is produced.

Specifically, in this example of the method for producing a hydrocarbon oil cracking catalyst, as shown in FIG. 1, first, a catalyst raw material powder (a composite metal oxide and a binder) is placed in a kneader such as a kneader or a Banbury mixer. Then, an organic molding aid and an acidic solution are added, and kneading is started (S1). In this example of the method for producing a hydrocarbon oil cracking catalyst, at the start of kneading, a part (for example, half amount) of the acidic solution to be used is put into the kneading apparatus.
Next, while sequentially adding the remaining amount of the acidic solution, the catalyst raw material powder, the organic forming aid, and the acidic solution are kneaded (S2), the catalyst raw material powder, the organic forming aid, A mixture with an acidic solution is obtained (mixing step). In the mixing step, an acidic solution is added so that the pH of the mixture is more than 1.0 and less than 6.0.
Thereafter, the obtained mixture is extruded using an extrusion molding apparatus (S3), and pellets made of the mixture are formed (molding step).
Finally, the obtained pellets are dried (S4) and calcined (S5) to prepare a hydrocarbon oil decomposition catalyst (calcining step).
In this example of the method for producing a hydrocarbon oil decomposition catalyst, the mixing step and the forming step may be carried out continuously using an extruder instead of the kneading device and the extrusion device.

Here, the catalyst raw material powder is a powder containing a catalytically active component. In this example of the method for producing a hydrocarbon oil decomposition catalyst, the catalyst raw material powder includes a particulate composite metal oxide and a particulate inorganic oxide. It consists of a binder made of an oxide.
In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the catalyst raw material powder may be composed only of the composite metal oxide.

  The acidic solution is not particularly limited, and an aqueous solution capable of peptizing the particles of the catalyst raw material powder when mixed with the catalyst raw material powder, for example, an aqueous solution of strong acid can be used. Specifically, nitric acid aqueous solution, sulfuric acid aqueous solution, and hydrochloric acid can be used as the acidic solution.

  Further, the organic molding aid is not particularly limited, and can improve the moldability of the mixture. In addition, the pellets are burned and decomposed to remain in the hydrocarbon oil decomposition catalyst. Non-forming aids can be used. Specifically, as the organic forming aid, for example, a fibrous organic substance such as cellulose or carbon fiber can be used. The cellulose is not particularly limited as long as it is crystalline and fibrous cellulose, and cellulose powder, crystalline cellulose, cellulose short fiber, cellulose derivative and the like may be used.

Here, in the mixing step, the conditions for kneading the catalyst raw material powder, the acidic solution, and the organic forming aid are such that the catalyst raw material powder, the acidic solution, and the organic forming aid are uniformly dispersed. As long as the pH of the resulting mixture is more than 1.0 and less than 6.0, any condition can be used. In the mixing step, not only the pH of the mixture after kneading but also the pH of the material to be kneaded during kneading is preferably in the range of more than 1.0 and less than 6.0.
Incidentally, the pH of the mixture obtained in the mixing step can be adjusted by changing the concentration and amount of the acidic solution used. Further, the pH control of the material to be kneaded during kneading is performed, for example, by measuring the pH of the material to be kneaded using a pH measuring device and controlling the addition timing of the acidic solution based on the measured pH value. Can do.

  In the mixing step, the entire amount of the acidic solution may be charged all at once into the kneading apparatus. However, as described above, after a part (for example, half of the total charging amount) is charged into the kneading apparatus, the remaining amount is sequentially increased. It is preferable to add or to add all of the total input amount sequentially. This is because if the entire amount of the acidic solution is charged all at once into the kneading apparatus, the resulting mixture tends to become lumpy, and the pH of the material to be kneaded temporarily falls outside the above pH range.

  Furthermore, the amount of the acidic solution kneaded with the catalyst raw material powder and the organic forming aid in the mixing step is preferably 25 to 35% by mass of the resulting mixture. This is because if the amount of the acidic solution is 25 to 35% by mass of the mixture, a mixture having a water content and fluidity suitable for molding can be obtained.

The conditions for extruding the mixture in the molding step can be any conditions that can form the mixture into pellets of a desired shape. Moreover, the shape of the pellet formed by molding the mixture can be any shape such as a columnar shape.
In addition, in the manufacturing method of the catalyst for hydrocarbon oil decomposition | disassembly of this invention, you may shape | mold a pellet using shaping | molding methods other than extrusion molding.

Furthermore, the pellets obtained in the molding step can be dried, for example, by leaving the pellets in a dryer having a temperature of 110 to 130 ° C. for 5 to 20 hours. The pellets are preferably dried until the moisture content is 10% by mass or less. Incidentally, the moisture content of the pellet can be measured by a loss on drying method using, for example, a moisture meter (manufactured by Shimadzu Corporation, MOC63u, etc.).
Moreover, baking of the dried pellet can be performed by baking a pellet for 0.5 to 5 hours in an air atmosphere, for example in the baking furnace of temperature 500-800 degreeC.

  And according to the manufacturing method of the hydrocarbon oil cracking catalyst of this example, since the pellet made of the mixture containing the composite metal oxide is fired, the composite metal oxide is used as a catalytic active component for the hydrocarbon oil cracking reaction. A hydrocarbon oil cracking catalyst can be prepared.

In addition, according to this example of the method for producing a hydrocarbon oil cracking catalyst, a catalyst raw material powder, an organic molding aid, and an acidic solution are kneaded so as to have a predetermined pH. Therefore, the mixture can be formed into a desired shape. Furthermore, according to this example of the method for producing a hydrocarbon oil cracking catalyst, since a binder made of a predetermined inorganic oxide is used, it is easier to prepare a mixture and form pellets than when no binder is used. Can be done.
Furthermore, in this method for producing a hydrocarbon oil cracking catalyst, a mixture obtained by kneading catalyst raw material powder, an organic molding aid, and an acidic solution so as to have a predetermined pH is molded into pellets. In addition, since the pellets are calcined, a hydrocarbon oil cracking catalyst having high mechanical strength and high stability in the reaction system can be prepared.

Here, the high mechanical strength of the hydrocarbon oil cracking catalyst is such that the catalyst raw material powder and the acidic solution are kneaded so that the pH of the mixture is less than 6.0 in the mixing step, and the resulting mixture is molded and calcined. It is surmised that this is achieved because the catalyst for cracking hydrocarbon oil is prepared. That is, when the catalyst raw material powder and the acidic solution are kneaded so that the pH of the mixture is less than 6.0, the catalyst raw material powder particles (complex metal oxide particles and binder particles) are once peptized, and then once It is inferred that a hydrocarbon oil cracking catalyst having high mechanical strength can be obtained because the peptized particles are agglomerated or condensed again and firmly bonded to each other. Incidentally, when the mixture is kneaded so that the pH of the mixture becomes 6.0 or more, the catalyst for cracking hydrocarbon oil has sufficient mechanical strength because peptization of the particles of the catalyst raw material powder does not proceed sufficiently. Cannot be prepared.
In addition, when the catalyst raw material powder particles are peptized using an acidic solution when preparing the mixture, if the peptized particles reagglomerate or reagglomerate early, the particles are firmly bonded in the mixture. Since the viscosity of the mixture increases, the moldability of the mixture decreases. Therefore, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, an organic forming aid is used when preparing the mixture. Also, when the pH of the mixture is lowered too much, the peptization of particles and reaggregation or reagglomeration proceed too much and the moldability of the mixture is lowered. Therefore, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, the mixture is kneaded so that the pH of the mixture exceeds 1.0.

  Incidentally, from the viewpoint of sufficiently increasing the mechanical strength of the hydrocarbon oil cracking catalyst by sufficiently progressing the peptization of the catalyst raw material powder particles, the acidic solution in the kneading apparatus (in the kneading system) is used in the mixing step. It is preferable to feed the catalyst raw material powder into the kneading apparatus (in the kneading system) before the charging is finished. In addition, from the viewpoint of suppressing deterioration of moldability of the mixture due to early reagglomeration or reaggregation of particles in the mixture, in the mixing process, the acidic solution is charged into the kneading apparatus (in the kneading system). It is preferable to introduce an organic molding aid into the kneading apparatus (in the kneading system) before the process is completed.

  Further, from the viewpoint of sufficiently increasing the mechanical strength of the catalyst for hydrocarbon oil decomposition by sufficiently proceeding the peptization of the particles of the catalyst raw material powder, the pH of the mixture is preferably 5.5 or less, more preferably It is preferable to knead so that it may become 5.0 or less. Further, from the viewpoint of suppressing the peptization and reaggregation or reagglomeration of the particles of the catalyst raw material powder and reducing the moldability of the mixture, the pH of the material to be kneaded during the kneading is always adjusted in the mixing step. Kneading is preferably performed so that the pH of the resulting mixture is 1.5 or higher, more preferably 2.0 or higher.

The high stability in the reaction system of the hydrocarbon oil cracking catalyst ensures that the catalyst raw material powder particles once while ensuring the moldability of the mixture by using an organic molding aid and controlling the pH of the mixture. It is surmised that this is achieved by increasing the mechanical strength of the catalyst by reaggregating or reaggregating after peptization.
That is, when an oxide of aluminum (Al), silicon (Si), tin (Sn) (for example, alumina, silica, tin oxide) or the like is used as a binder to increase the mechanical strength of the catalyst, the oxidation of the catalyst Since the product is denatured under high-temperature and high-pressure steam, the stability of the catalyst in the reaction system is lowered. However, if the mechanical strength of the catalyst is increased by peptization and reagglomeration or reaggregation of the catalyst raw material powder without using aluminum, silicon or tin oxide, etc., it is easy to modify under high temperature and high pressure steam. The amount of components can be reduced or zero to increase the stability of the catalyst in the reaction system. If the moldability of the mixture is secured by using organic molding aids that burn and decompose during firing and controlling the pH of the mixture, the amount of easily denatured components under high-temperature and high-pressure steam is reduced or zero. The stability of the catalyst in the reaction system can be improved.
Incidentally, from the viewpoint of increasing the stability of the catalyst in the reaction system by reducing or eliminating the amount of components easily denatured under high temperature and high pressure steam, the mixture used in the method for producing a hydrocarbon oil cracking catalyst of the present invention The total content of Al, Si, and Sn is preferably 1% by mass or less of the mixture, and more preferably substantially free of Al, Si, and Sn. The hydrocarbon oil cracking catalyst formed by molding and firing the mixture preferably has a total content of Al, Si, and Sn of 2% by mass or less of the hydrocarbon oil cracking catalyst, Al, Si, More preferably, Sn is not substantially contained.

  Here, a nitric acid aqueous solution is preferably used as the acidic solution described above. This is because if the aqueous nitric acid solution is used, it is possible to prevent the firing furnace from being corroded by the exhaust gas generated when the pellets are fired, as compared with the case where hydrochloric acid is used. Moreover, since sulfuric acid is a non-volatile liquid, when sulfuric acid aqueous solution is used, there exists a possibility that a sulfuric acid may remain in the hydrocarbon oil decomposition | disassembly catalyst obtained by baking a pellet.

  The nitric acid concentration of the aqueous nitric acid solution is preferably 0.75 to 2.75% by mass, and more preferably 1.0 to 2.0% by mass. As described above, from the viewpoint of obtaining a mixture having a water content and fluidity suitable for molding, the amount of nitric acid aqueous solution used is restricted by itself. If the nitric acid concentration is 0.75% by mass or more, the catalyst raw material powder This is because the mechanical strength of the catalyst can be sufficiently increased by sufficiently proceeding the peptization of the particles. Further, if the nitric acid concentration exceeds 2.75% by mass, the peptization and reaggregation or reaggregation of the particles of the catalyst raw material powder proceed too rapidly, and the moldability of the mixture may be lowered.

  Moreover, it is preferable to use cellulose as the organic molding aid described above.

  In addition, it is preferable that the quantity of the shaping | molding adjuvant in a mixture shall be 1-5 mass% of the quantity of the catalyst raw material powder in a mixture. This is because if the amount of the organic molding aid is less than 1% by mass of the amount of the catalyst raw material powder, the moldability of the mixture may not be sufficiently ensured. In addition, when the amount of the organic forming aid exceeds 5% by mass of the amount of the catalyst raw material powder, when the pellet made of the mixture is baked to produce the hydrocarbon oil decomposition catalyst, the combustion decomposition of the forming aid is performed. This is because a large number of voids are generated in the hydrocarbon oil cracking catalyst, and the mechanical strength of the catalyst may not be sufficiently increased.

<Decomposition method of hydrocarbon oil>
The hydrocarbon oil cracking catalyst prepared as described above is used to produce light hydrocarbon oil by industrially decomposing (lightening) hydrocarbon oil according to the hydrocarbon oil cracking method of the present invention. Can be used.

  Here, the hydrocarbon oil used as a raw material when producing a light hydrocarbon oil using the hydrocarbon oil cracking method of the present invention is not particularly limited, and is an atmospheric distillation residue obtained during petroleum refining. And heavy hydrocarbon oils such as vacuum distillation residue. Specifically, as the hydrocarbon oil used as a raw material for the light hydrocarbon oil, a hydrocarbon oil having a 50 vol% distillation temperature (T50) in atmospheric distillation of 150 ° C. or higher and 550 ° C. or lower, or T50 of 200 ° C. or higher. Examples thereof include hydrocarbon oils having a temperature of 550 ° C. or lower and hydrocarbon oils having a T50 of 250 ° C. or higher and 550 ° C. or lower.

And the hydrocarbon oil cracking method of the present invention comprises a reactor for cracking a hydrocarbon oil as a raw material into a light hydrocarbon oil, and a raw material supply means for feeding the hydrocarbon oil as a raw material into the reactor. It can be carried out using a light hydrocarbon oil production apparatus comprising water supply means for supplying water into the reactor.
Specifically, hydrocarbon oil cracking (lightening) using the hydrocarbon oil cracking method of the present invention supplies hydrocarbon oil and water into the reactor filled with the hydrocarbon oil cracking catalyst described above. And it can carry out by making hydrocarbon oil and the catalyst for hydrocarbon oil decomposition | disassembly contact in presence of water.

Here, the reason why the hydrocarbon oil can be decomposed by bringing the hydrocarbon oil decomposition catalyst and the hydrocarbon oil into contact with each other in the presence of water is not clear. In particular, a composite metal oxide having a perovskite structure, a composite metal oxide having a pseudo-brookite structure, or a composite metal oxide containing predetermined elements X, Y ₁ and Y ₂ has a lattice oxygen supply rate. This is presumably because of its high ability to decompose water and release oxygen and hydrogen. That is, when these composite metal oxides decompose heavy hydrocarbon compounds using water as a hydrogen source, a part of the hydrocarbon compounds and water react as shown in the following reaction formula to generate hydrogen. This is presumed to be because the generation of hydrogen as a source can be promoted.
_{C n H m + 2nH 2 O} → nCO 2 + (2n + (m / 2)) H 2

Here, the amount of water used for decomposing the hydrocarbon oil may be an amount sufficient for decomposing (lightening) the hydrocarbon oil as a raw material. For example, for 100 parts by mass of the hydrocarbon oil Thus, it is desirable to add water at a ratio of 5 to 2000 parts by mass, preferably 10 to 1000 parts by mass, and more preferably 10 to 500 parts by mass. This is because when the amount of water added to 100 parts by mass of the hydrocarbon oil is less than 5 parts by mass, the hydrogen source may be insufficient and the hydrocarbon oil may not be sufficiently decomposed. On the other hand, if the amount of water added exceeds 2000 parts by mass, the amount of water that does not contribute to the decomposition of the hydrocarbon oil increases, which may increase the cost or decrease the decomposition efficiency of the hydrocarbon oil. Because there is.
Moreover, the temperature in the reactor of a light hydrocarbon oil manufacturing apparatus can be made into comparatively low temperature, for example, 300-600 degreeC, Preferably it is 350-550 degreeC, More preferably, it is 400-500 degreeC. This is because when the temperature is lower than 300 ° C., activation energy necessary for the reaction cannot be obtained, and the hydrocarbon oil may not be sufficiently decomposed. Further, when the temperature is higher than 600 ° C., a large amount of unnecessary gas (methane, ethane, etc.) is generated, and the decomposition efficiency of the hydrocarbon oil may be lowered.
Furthermore, the pressure in the reactor can be, for example, 0.1 to 40 MPa, preferably 0.1 to 35 MPa, and more preferably 0.1 to 30 MPa. This is because when the pressure is less than 0.1 MPa, it may be difficult to smoothly flow the hydrocarbon oil and water into the reactor. Moreover, it is because the manufacturing cost of a reactor may become high when a pressure exceeds 40 Mpa.
Also, the liquid hourly space velocity (LHSV) at the time of flowing the hydrocarbon oil and water to the reactor, for example 0.01～10H ^-1, preferably 0.05～5H ^-1, more preferably 0.1~2h ⁻¹ . This is because when the liquid space velocity is less than 0.01 h ⁻¹ , generation of unnecessary gas becomes dominant and the decomposition efficiency of the hydrocarbon oil may decrease. Moreover, it is because reaction time is too short and decomposition | disassembly of hydrocarbon oil may not fully advance when liquid space velocity is more than 10h- ¹ .

  Here, as described above, according to the hydrocarbon oil cracking method of the present invention, hydrogen necessary for the hydrocarbon oil cracking reaction can be supplied from the water present in the system. Therefore, in the hydrocarbon oil cracking method of the present invention, it is not necessary to add hydrogen from outside the system, but the molar ratio between the amount of hydrogen added from outside the system and the amount of feed of hydrocarbon oil as a raw material (hydrogen addition) Amount / hydrocarbon oil supply amount) can be 0.1 or less, preferably 0. Therefore, according to the hydrocarbon oil decomposition method of the present invention, the hydrocarbon oil can be efficiently decomposed at low cost without using high-pressure hydrogen gas.

The hydrocarbon oil cracking catalyst used in the hydrocarbon oil cracking method of the present invention is unlikely to deteriorate. Therefore, according to the hydrocarbon oil cracking method of the present invention using the catalyst, the raw material hydrocarbon to be cracked There is no need to desulfurize and denitrify the oil beforehand.
The hydrocarbon oil cracking catalyst used in the hydrocarbon oil cracking method of the present invention is manufactured using the hydrocarbon oil cracking catalyst manufacturing method of the present invention. Because of its high stability, it is difficult to be damaged or modified during catalyst filling or decomposition. Therefore, according to the hydrocarbon oil cracking method of the present invention, the hydrocarbon oil cracking reaction (lightening reaction) is carried out in the reaction vessel even when the hydrocarbon oil is industrially cracked (lightening). Proceed as desired.
Incidentally, when the binder is contained in the hydrocarbon oil cracking catalyst, the mass ratio (B / A) of the amount (B) of the binder to the amount (A) of the composite metal oxide in the hydrocarbon oil cracking catalyst is 0. .2 to 1.0. This is because if the amount of the composite metal oxide is small, the hydrocarbon oil may not be sufficiently decomposed. Moreover, it is because the decomposition efficiency of hydrocarbon oil will fall when there is too much quantity of a binder.

  As mentioned above, although embodiment of this invention was described, the manufacturing method of the catalyst for hydrocarbon oil cracking of this invention and the cracking method of hydrocarbon oil are not limited to the said embodiment, Hydrocarbon oil cracking of this invention The method for producing the catalyst for use and the method for cracking the hydrocarbon oil can be appropriately modified.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to the following Example at all.

Example 1
Element X is zirconium, element Y ₁ is cerium, and element Y ₂ is tungsten, a complex metal oxide (manufactured by Daiichi Rare Element Chemical Co., Ltd., Z-2001), and titanium dioxide ( Takeda Co., Ltd., IP212), cellulose as an organic molding aid (manufactured by Nippon Paper Industries Co., Ltd., KC Flock W50GK), and a nitric acid aqueous solution having a concentration shown in Table 1, are shown in Table 1. A pH mixture was prepared. Specifically, 450 g of composite metal oxide, 150 g of titanium dioxide, 18 g of cellulose, and 300 g of nitric acid aqueous solution were kneaded with a Banbury mixer to obtain a mixture. The nitric acid aqueous solution was charged in half (150 g) into the Banbury mixer at the start of kneading, and the remaining 150 g was 450 g of composite metal oxide, 150 g of titanium dioxide, 18 g of cellulose, and 150 g of nitric acid aqueous solution. Were kneaded for 30 minutes and then sequentially added over 30 minutes. The pH of the mixture was measured by a glass electrode method using a pH meter (B-211 manufactured by Horiba, Ltd.).
Next, the obtained mixture was extruded to prepare pellets (columnar shape, diameter 2 mm), and the obtained pellets were dried at a temperature of 130 ° C. for 16 hours. Thereafter, the dried pellets were calcined at a temperature of 600 ° C. in an air atmosphere for 2 hours to produce a hydrocarbon oil decomposition catalyst.
In addition, when the abundance ratio (molar ratio) of Zr, Ce, and W of the used composite metal oxide was confirmed by melting / ICP-AES method, it was Zr: Ce: W = 16: 16: 1.
And about the obtained catalyst for hydrocarbon oil decomposition | disassembly, mechanical strength and catalytic activity were measured with the following method. The results are shown in Table 1.

(Examples 2-3)
A hydrocarbon oil cracking catalyst was produced in the same manner as in Example 1, except that the concentration of the aqueous nitric acid solution used was the concentration shown in Table 1, and the pH of the mixture was the value shown in Table 1.
The resulting hydrocarbon oil cracking catalyst was measured for mechanical strength and catalytic activity in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In the same manner as in Example 1 except that the same amount (300 g) of pure water was used instead of the nitric acid aqueous solution, and the pH of the mixture was changed to the value shown in Table 1, composite metal oxide, titanium dioxide, cellulose, A kneaded product was obtained.
Next, the obtained kneaded material was extrusion-molded to prepare pellets (columnar shape, diameter 2 mm), and the obtained pellets were dried at a temperature of 130 ° C. for 16 hours. Thereafter, the dried pellets were calcined at a temperature of 600 ° C. in an air atmosphere for 2 hours to produce a hydrocarbon oil decomposition catalyst.
The resulting hydrocarbon oil cracking catalyst was measured for mechanical strength and catalytic activity in the same manner as in Example 1. The results are shown in Table 1. The catalyst activity could not be measured because the strength of the catalyst was low and powdered during filling.

(Comparative Examples 2-3)
An attempt was made to produce a hydrocarbon oil cracking catalyst in the same manner as in Example 1, except that the concentration of the aqueous nitric acid solution used was the concentration shown in Table 1, and the pH of the mixture was the value shown in Table 1.
However, in Comparative Example 3, the moldability of the mixture was low, and the mixture was clogged in the extrusion port (die) at the time of extrusion molding, and pellets could not be molded.
The hydrocarbon oil cracking catalyst obtained in Comparative Example 2 was measured for mechanical strength and catalytic activity in the same manner as in Example 1. The results are shown in Table 1.

<Mechanical strength>
About the prepared catalyst for hydrocarbon oil decomposition | disassembly, the catalyst crushing strength (SCS: side crush strength) was measured. Specifically, a columnar hydrocarbon oil cracking catalyst is placed sideways, the outer peripheral surface of the hydrocarbon oil cracking catalyst is pressed with a pin having a diameter of 3 mm, and the load when the hydrocarbon oil cracking catalyst is broken ( The breaking load was measured. Then, the side crush strength (N / mm) was determined by dividing the breaking load by the pin diameter.
<Catalytic activity>
The prepared hydrocarbon oil cracking catalyst was charged into a superalloy (Inconel 625) reactor. Subsequently, the inside of the reactor was heated and pressurized to a temperature of 470 ° C. and a pressure of 15 MPa while passing ion-exchanged water through the reactor filled with the catalyst. Then, without supplying hydrogen, heavy hydrocarbon oil having properties as shown in Table 2 (oil distilled from the thermal cracking apparatus) and ion-exchanged water were continuously circulated in the reactor ( Mass flow rate of ion exchange water / mass flow rate of heavy hydrocarbon oil = 1.0 and LHSV is 0.75 h ⁻¹ ).
And 6 hours after the start of oil passing, the effluent (decomposition reaction product) from the reactor was collected for 1 hour, and a predetermined light hydrocarbon oil (fraction having a boiling point of 180 to 380 ° C.) using the following formula: The yield Y was calculated.
Y = (M / F) × 100%
Y: Yield of fraction (kerosene oil) having a boiling point of 180 to 380 ° C. [mass%]
M: Yield of light hydrocarbon oil [g / hr]
F: Supply amount of heavy hydrocarbon oil [g / hr]

From Table 1, it can be seen that the hydrocarbon oil cracking catalysts of Examples 1 to 3 have higher mechanical strength than the hydrocarbon oil cracking catalysts of Comparative Examples 1 and 2. Moreover, in the comparative example 3, it turns out that the moldability of a mixture is low and a pellet cannot be shape | molded.
In addition, when an attempt was made to produce a hydrocarbon oil decomposition catalyst by preparing a mixture (mixture of composite metal oxide, titanium dioxide, and aqueous nitric acid) without using cellulose, pellets could be formed. There wasn't.
Further, carbonization was conducted in the same manner as in Example 1 using a hydrocarbon oil cracking catalyst formed by mixing γ-alumina and a composite metal oxide (Z-2001, manufactured by Daiichi Rare Element Chemical Co., Ltd.). When hydrogen oil was decomposed, alumina changed to pseudo boehmite, the catalyst could not maintain its shape, and the composite metal oxide flowed out of the reactor.

  According to the present invention, a catalyst used for decomposing a hydrocarbon oil in the presence of water contains a composite metal oxide as a catalytically active component, and has mechanical strength and stability in a reaction system. It is possible to provide a method for producing a hydrocarbon oil cracking catalyst having a high A. Moreover, according to this invention, the method of cracking hydrocarbon oil using the catalyst for hydrocarbon oil cracking prepared using the manufacturing method can be provided.

Claims (9)

A method for producing a hydrocarbon oil cracking catalyst used for cracking hydrocarbon oil,
The hydrocarbon oil cracking catalyst includes a composite metal oxide,
A mixing step of preparing a mixture having a pH of more than 1.0 and less than 6.0 by kneading the catalyst raw material powder containing the composite metal oxide, an acidic solution, and an organic forming aid;
A molding step of molding a pellet made of the mixture;
A calcining step of calcining the pellets to prepare a hydrocarbon oil cracking catalyst;
The manufacturing method of the catalyst for hydrocarbon oil decomposition | disassembly characterized by including this.   The method for producing a hydrocarbon oil cracking catalyst according to claim 1, wherein the acidic solution is an aqueous nitric acid solution.   The method for producing a hydrocarbon oil cracking catalyst according to claim 2, wherein the nitric acid concentration of the aqueous nitric acid solution is 0.75 to 2.75 mass%.   The method for producing a catalyst for cracking hydrocarbon oil according to any one of claims 1 to 3, wherein the organic forming aid is cellulose.   2. In the mixing step, the charging of the catalyst raw material powder and the organic forming aid into the kneading system is terminated before the charging of the acidic solution into the kneading system is completed. The manufacturing method of the catalyst for hydrocarbon oil decomposition | disassembly in any one of -4. The composite metal oxide is
A composite metal oxide having a perovskite structure;
A composite metal oxide having a pseudo-brookite structure;
Selected from the group consisting of one element X selected from Group IVA elements, Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period And one element Y ₁ different from the element X, a group IIIA element, a group VIA element and a group VIIA element, a group IVA element in the fourth to sixth periods, and a group VIII element in the fourth period is selected from the group consisting and wherein contain and one element different from _{Y 2} is the element X and the element _{Y 1,} abundance of elements _{Y 1 (y 1)} and abundance of the elements _{Y 2 (y 2} ) And the ratio (x / (y ₁ + y ₂ )) of the abundance (x) of the element X to the sum (y ₁ + y ₂ ) and the abundance of the element Y ₁ the ratio of the abundance of elements _{Y 2} with respect to _{(y 1) (y 2) y 2} / y ₁₎ comprises a composite metal oxide is 0.02 to 0.25,
The method for producing a hydrocarbon oil cracking catalyst according to any one of claims 1 to 5, comprising at least one selected from the group consisting of: The hydrocarbon oil cracking catalyst further comprises a binder comprising an inorganic oxide;
The binder has an Al content of 1% by mass or less and an Si content of 1% by mass or less.
The method for producing a hydrocarbon oil cracking catalyst according to any one of claims 1 to 6, wherein the catalyst raw material powder contains the binder.   The method for producing a hydrocarbon oil cracking catalyst according to claim 7, wherein the inorganic oxide is titanium dioxide.   Bringing hydrocarbon oil into contact with a hydrocarbon oil cracking catalyst produced using the method for producing a hydrocarbon oil cracking catalyst according to claim 1 in the presence of water, thereby cracking the hydrocarbon oil; A method for cracking hydrocarbon oils.

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