JP5901061B2 - Method for producing hydrocarbon oil cracking catalyst and hydrocarbon oil cracking method - Google Patents

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 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 has intensively studied to solve the above problems. And this inventor decomposes | disassembles hydrocarbon oil with high mechanical strength and high stability in a reaction system by baking the mixture of the complex metal oxide which is a catalyst active component, and the acidic solution containing zinc. The present invention has been completed by finding that an industrial catalyst can be produced.

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 includes a composite metal oxide, and the composite metal oxide is selected from one element X selected from Group IVA elements and Group IIIA elements. 1 element Y ₁ and one element Y ₂ selected from group VIA elements , and the abundance of element Y ₁ (y ₁ ) and abundance of element Y ₂ (y ₂ ) the total abundance of the element X with respect to (y ₁ + y ₂₎ ratio (x) (x / (y 1 + y 2)) is, is 0.5 to 2.0, the abundance of the elements Y ₁ (y ₁ abundance of elements Y ₂ with respect to) (the ratio of _{y 2) (y 2 / y} 1) is 0.02 to 0.25 complex metal oxide , And the characterized by comprising said composite metal oxide, a mixing step of preparing a mixture of an acidic solution containing zinc, and a firing step of preparing a hydrocarbon oil cracking catalysts by calcining the mixture .

  Here, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, it is preferable that the mixture is prepared by kneading in the mixing step.

In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the acidic solution containing zinc is preferably a zinc nitrate aqueous solution.
In the method for producing a hydrocarbon oil cracking catalyst of the present invention, the zinc nitrate concentration in the aqueous zinc nitrate solution is more preferably 1 to 10% by mass.

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. From the obtained measurement value, each element in the composite metal oxide is analyzed. 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 of manufacturing a hydrocarbon oil cracking catalysts of the present invention, the element X is zirconium, the element Y ₁ is cerium, it is preferable that the element Y ₂ is tungsten.

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 in the said mixing process, the mixture of the said complex metal oxide, the acidic solution containing the said zinc, and the said binder is prepared.
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, the method for producing a hydrocarbon oil cracking catalyst of the present invention is characterized in that a hydrocarbon oil cracking catalyst is formed by firing a mixture of a composite metal oxide and an acidic solution containing zinc. . 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. Then, the composite metal oxide is a complex metal oxide containing a predetermined element X, the Y ₁ and Y _2.
The crystal structure of the composite metal oxide can be evaluated using, for example, X-ray diffraction analysis.

As the complex metal oxide containing the predetermined element X, the predetermined element Y ₁ and the predetermined element Y ₂ ,
(A) one element X selected from group IVA elements;
(B) with one of the elements Y ₁ selected from Group IIIA elements,
One of the elements Y ₂ is selected from (c) VIA group 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 determined by the melting / ICP-AES method,
(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, mention may be made of Zr, Ce as the element Y _1, a composite metal oxide containing W as the element Y ₂ as the element X.

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 is not biased 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.

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 containing zinc. 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 kneading apparatus such as a kneader or a Banbury mixer is mixed with a particulate composite metal oxide and a particulate particulate oxide. A binder made of an inorganic oxide is added and kneading is started (S1). Next, while sequentially adding an acidic solution containing zinc (hereinafter sometimes referred to as “zinc-containing acidic solution”), the composite metal oxide, the binder, and the zinc-containing acidic solution are kneaded (S2), A mixture of the composite metal oxide, the binder, and the zinc-containing acidic solution is obtained (mixing step). Thereafter, the obtained mixture is optionally extruded using an extrusion molding apparatus (S3) and formed into a pellet (molding process). 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 zinc-containing acidic solution is not particularly limited, and an aqueous solution containing zinc and having a pH of 3 to 6 can be used. Specifically, as the zinc-containing acidic solution, for example, a zinc nitrate aqueous solution, a zinc sulfate aqueous solution, or a zinc chloride aqueous solution can be used.

  Further, in the mixing step, the condition for kneading the composite metal oxide, the binder, and the zinc-containing acidic solution is to obtain a mixture in which the composite metal oxide, the binder, and the zinc-containing acidic solution are uniformly dispersed. It can be set as arbitrary conditions.

  Here, in the mixing step, the zinc-containing acidic solution may be added all at once into the kneading apparatus, but is added sequentially as described above, or a part (for example, half of the total input amount) is kneaded. It is preferable to add the remaining amount sequentially after being put in. This is because when the entire amount of the zinc-containing acidic solution is charged all at once into the kneading apparatus, the mixture tends to become lumpy and it is difficult to prepare a mixture in which the composite metal oxide, the binder, and the zinc-containing acidic solution are uniformly dispersed. .

  Moreover, it is preferable that the quantity of the zinc-containing acidic solution mixed with a composite metal oxide and a binder in a mixing process shall be 25-35 mass% of the obtained mixture. This is because if the amount of the zinc-containing 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.

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.

Also, according to this example of the method for producing a hydrocarbon oil cracking catalyst, pellets made of a mixture containing a zinc-containing acidic solution are calcined, so that the hydrocarbon has high mechanical strength and high stability in the reaction system. An oil cracking catalyst can be prepared.
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.

  Here, the high mechanical strength of the hydrocarbon oil cracking catalyst is such that when pellets made of a mixture containing a zinc-containing acidic solution are fired, zinc in the pellets becomes zinc oxide (ZnO), and the zinc oxide serves as a binder. Inferred to be achieved to function. That is, zinc dispersed in the pellet becomes zinc oxide when the pellet is fired, and the composite metal oxides in the pellet, the binders, or the composite metal oxide and the binder are strongly strengthened through the zinc oxide. It is presumed that a hydrocarbon oil cracking catalyst having high mechanical strength can be obtained because of being bonded.

Moreover, the high stability in the reaction system of the hydrocarbon oil cracking catalyst is because the mechanical strength of the catalyst is increased by utilizing zinc oxide produced when a mixture containing a zinc-containing acidic solution is calcined. Inferred to be achieved. That is, since the hydrocarbon oil cracking catalyst is used in the presence of high-temperature and high-pressure water (steam), if zinc oxide that is stable (not easily modified) even under high-temperature and high-pressure steam is used as the binder, It is presumed that the mechanical strength of the catalyst can be increased while enhancing the stability of the catalyst. Zinc oxide is also suitable as a binder in that it is a compound that has little influence on the properties of the hydrocarbon oil cracking catalyst (for example, the acid properties of the catalyst surface).
Incidentally, when trying to increase the mechanical strength of the catalyst by using an oxide of aluminum (Al), silicon (Si), tin (Sn) (for example, alumina, silica, tin oxide) or the like as a binder, those Since the oxide is denatured under high-temperature and high-pressure steam, the stability of the catalyst in the reaction system is lowered. Therefore, the mixture used in the method for producing a hydrocarbon oil cracking catalyst of the present invention preferably has a total content of Al, Si, and Sn of 1% by mass or less of the mixture, and substantially contains Al, Si, and Sn. More preferably not. The hydrocarbon oil cracking catalyst obtained by 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, and contains Al, Si, Sn. More preferably, it does not contain substantially.

  Here, it is preferable to use a zinc nitrate aqueous solution as the zinc-containing acidic solution described above. This is because zinc nitrate is thermally decomposed into zinc oxide even at a relatively low temperature (for example, 200 to 300 ° C.) as compared with zinc sulfate or the like. In addition, since the aqueous zinc nitrate solution has a pH of about 3 to 6, an apparatus (for example, a kneading apparatus) used for preparing the hydrocarbon oil decomposition catalyst is hardly corroded.

  In addition, it is preferable that the zinc nitrate density | concentration of zinc nitrate aqueous solution is 1-10 mass%, and it is still more preferable that it is 5-10 mass%. As described above, from the viewpoint of obtaining a mixture having a water content and fluidity suitable for molding, the amount of zinc nitrate aqueous solution used is limited by itself. However, if the zinc nitrate concentration is 1% by mass or more, the catalyst machine This is because the mechanical strength can be sufficiently increased. On the other hand, if the zinc nitrate concentration is more than 10% by mass, the production cost of the catalyst increases as the amount of zinc nitrate used increases, which is economically disadvantageous.

  Here, in the above example of the method for producing a hydrocarbon oil cracking catalyst, a composite metal oxide, a binder and a zinc-containing acidic solution are kneaded in the mixing step to prepare a mixture, and then the mixture is extruded to form pellets. Produced. However, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, a mixture of a composite metal oxide, a binder, and a zinc-containing acidic solution may be prepared by impregnating the composite metal oxide and a binder in a zinc-containing acidic solution. Good. Specifically, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, a binder comprising a particulate composite metal oxide and a particulate inorganic oxide is kneaded while adding water as necessary, The obtained kneaded product may be extruded into pellets as necessary, and then impregnated with a zinc-containing acidic solution to prepare a mixture of a composite metal oxide, a binder, and a zinc-containing acidic solution. However, when a mixed metal oxide and binder are impregnated in a zinc-containing acidic solution to prepare a mixture of the composite metal oxide, binder and zinc-containing acidic solution, the hydrocarbon oil decomposition catalyst obtained by firing the mixture is: Most of the surface is covered with zinc oxide, reducing the amount of catalytically active component present on the surface of the catalyst (ie, reducing the catalytic activity). Therefore, from the viewpoint of ensuring sufficiently high catalytic activity, in the method for producing a hydrocarbon oil cracking catalyst of the present invention, it is preferable to prepare a mixture by kneading.

  Further, in the above method for producing a hydrocarbon oil cracking catalyst, a hydrocarbon oil containing the composite metal oxide and the binder is prepared by kneading the composite metal oxide, the binder, and the zinc-containing acidic solution in the mixing step. A cracking catalyst was produced. However, in the method for producing a hydrocarbon oil cracking catalyst according to the present invention, when producing a hydrocarbon oil cracking catalyst containing only a composite metal oxide, in the mixing step, the composite metal oxide and the zinc-containing acidic solution are used. May be mixed to prepare a mixture.

<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. It is surmised that the composite metal oxide containing the product, particularly the predetermined elements X, Y ₁ and Y ₂ has a high supply rate of lattice oxygen and a 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

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, with respect to 100 parts by mass of the hydrocarbon oil It is desirable to add 5 to 2000 parts by mass of water, 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)
Zinc nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare an aqueous zinc nitrate solution having the concentrations shown in Table 1. The element X is zirconium, an element Y ₁ is cerium complex metal oxide element Y ₂ is tungsten (Daiichi Kigenso Kagaku Kogyo Co., Ltd., Z-2001) and dioxide as a binder Titanium (Taika Co., Ltd., IP212) and a zinc nitrate aqueous solution having the concentrations shown in Table 1 were kneaded to prepare a mixture. Specifically, 450 g of composite metal oxide, 150 g of titanium dioxide, and 300 g of an aqueous zinc nitrate solution were kneaded with a Banbury mixer to obtain a mixture. In addition, half the amount (150 g) of the zinc nitrate aqueous solution was put into the Banbury mixer at the start of kneading, and the remaining 150 g was 450 g of the composite metal oxide, 150 g of titanium dioxide, and 150 g of the zinc nitrate aqueous solution for 30 minutes. After kneading, it was added sequentially over 5 minutes.
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 zinc nitrate solution used was changed to the concentration 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.

Example 4
A kneaded product of the composite metal oxide and titanium dioxide was obtained in the same manner as in Example 1 except that the same amount (300 g) of pure water was used instead of the zinc nitrate aqueous solution. And the obtained kneaded material was extrusion-molded to prepare pellets (columnar shape, diameter 2 mm), and the obtained pellets were immersed in an aqueous zinc nitrate solution having the concentrations shown in Table 1.
Next, the pellet immersed in the zinc nitrate aqueous solution was 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.

(Comparative Example 1)
A hydrocarbon oil decomposition catalyst was produced in the same manner as in Example 1 except that the same amount (300 g) of pure water was used instead of the zinc nitrate aqueous solution, and no zinc nitrate aqueous solution was used.
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.

<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 4 have higher mechanical strength than the hydrocarbon oil cracking catalyst of Comparative Example 1. It can also be seen that the hydrocarbon oil cracking catalysts of Examples 1 to 3 have higher catalytic activity than the hydrocarbon oil cracking catalyst of Example 4.
Incidentally, carbonization was conducted in the same manner as in Example 1 using a hydrocarbon oil cracking catalyst formed by mixing γ-alumina and 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 catalyst for cracking hydrocarbon oils having a high value. 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 (7)

A method for producing a hydrocarbon oil cracking catalyst used for cracking hydrocarbon oil,
The hydrocarbon oil cracking catalyst includes a composite metal oxide,
The composite metal oxide is one and element X selected from Group IVA elements, and one element Y ₁ is selected from the Group IIIA elements, and one element Y ₂ is selected from Group VIA element containing ratio (x / (y abundance of elements Y ₁ (y ₁₎ and abundance of the elements Y ₂ (y ₂₎ the sum of the (y ₁ + y ₂₎ presence of the element X with respect to (x) ₁ + y ₂₎₎ is, is 0.5 to 2.0, the ratio of the abundance of the elements Y ₁ (y ₁₎ the presence of the element Y ₂ with respect to _{(y 2) (y 2 /} y 1) is A composite metal oxide of 0.02 or more and 0.25 or less,
A mixing step of preparing a mixture of the composite metal oxide and an acidic solution containing zinc;
Calcination step of calcining the mixture to prepare a hydrocarbon oil cracking catalyst;
The manufacturing method of the catalyst for hydrocarbon oil decomposition | disassembly characterized by including this.   2. The method for producing a hydrocarbon oil cracking catalyst according to claim 1, wherein in the mixing step, a mixture is prepared by kneading.   The method for producing a hydrocarbon oil cracking catalyst according to claim 1 or 2, wherein the acidic solution containing zinc is an aqueous zinc nitrate solution.   The method for producing a hydrocarbon oil cracking catalyst according to claim 3, wherein the zinc nitrate aqueous solution has a zinc nitrate concentration of 1 to 10% by mass. 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.
In the said mixing process, the mixture of the said complex metal oxide, the acidic solution containing the said zinc, and the said binder is prepared, The hydrocarbon oil decomposition | disassembly in any one of Claims 1-4 characterized by the above-mentioned. A method for producing a catalyst. 6. The method for producing a hydrocarbon oil cracking catalyst according to claim 5 , 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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