JP5881218B2 - Hydrocarbon oil cracking catalyst and hydrocarbon oil cracking method - Google Patents

Description

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

  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).

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

  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.

  Therefore, the present invention provides a hydrocarbon oil cracking that can efficiently lighten a hydrocarbon oil at low cost without desulfurizing and denitrifying the hydrocarbon oil in advance and without using high-pressure hydrogen gas. It is an object to provide a catalyst for hydrocarbons and a method for cracking hydrocarbon oil.

  The present inventors have intensively studied to solve the above problems, and by using a catalyst containing a specific element in a specific ratio, a hydrocarbon oil can be used in the presence of water without using hydrogen gas. The present invention has been completed.

That is, the present invention aims to advantageously solve the above-mentioned problems, and the hydrocarbon oil cracking catalyst of the present invention is used when cracking hydrocarbon oil in the presence of water. One element X selected from group elements and one element Y ₁ selected from group IIIA elements
If, VIA group elements, contain one of the elements Y ₂ that will be selected from the group consisting of VIII group elements of group VIIA elements, and the fourth period, the abundance of the elements Y ₁ (y ₁₎ and the element Y ₂ the amount of presence (y ₂₎ the sum of the (y ₁ + y ₂₎ presence of the element X with respect to the ratio of (x) (x / (y 1 + y 2)) is, is 0.5 to 2.0, abundance of elements Y ₁ is the presence of the element Y ₂ with respect to (y ₁₎ the ratio of _{(y 2) (y 2 /} y 1), characterized in that 0.02 to 0.25.
In the present invention, the “element abundance” refers to a solution obtained by dissolving the catalyst by ICP emission spectroscopic analysis, and from the obtained measurement value, the molar amount of each element in the catalyst in terms of simple metal. It can be obtained by calculating the concentration. 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”).

Here, the hydrocarbon oil cracking catalyst of the present invention is preferably composed of a complex oxide containing the element X, the element Y _1, and the element Y ₂ .

In the hydrocarbon oil cracking catalyst of the present invention, the element X is preferably zirconium.
In the hydrocarbon oil cracking catalyst of the present invention, it is more preferable that the element Y ₁ is cerium and the element Y ₂ is one selected from the group consisting of tungsten, manganese and iron.

  Further, the present invention aims to advantageously solve the above-described problems, and the hydrocarbon oil cracking method of the present invention comprises a hydrocarbon oil and the above-mentioned hydrocarbon oil cracking in the presence of water. Hydrocarbon oil is decomposed by contacting with any of the catalysts.

  According to the hydrocarbon oil cracking catalyst and hydrocarbon oil cracking method of the present invention, the hydrocarbon oil can be efficiently produced at low cost without desulfurizing and denitrifying the hydrocarbon oil in advance and without using high-pressure hydrogen gas. The hydrocarbon oil can be lightened.

  Hereinafter, embodiments of the present invention will be described in detail. Here, the hydrocarbon oil cracking catalyst of the present invention is used when cracking and lightening hydrocarbon oil. In the hydrocarbon oil cracking method of the present invention, the hydrocarbon oil is brought into contact with the hydrocarbon oil cracking catalyst in the presence of water without supplying hydrogen from outside the reaction system. Decomposes to produce light hydrocarbon oil.

  Here, the hydrocarbon oil to be decomposed (lightened) using the hydrocarbon oil cracking catalyst of the present invention is not particularly limited, and is an atmospheric distillation residue or a vacuum distillation residue obtained during petroleum refining. Of heavy hydrocarbon oils. Specifically, as hydrocarbon oil lightened using a hydrocarbon oil cracking catalyst, hydrocarbon oil having a 50 vol% distillation temperature (T50) in atmospheric distillation of 150 ° C. or higher and 550 ° C. or lower, or T50 Can be exemplified by hydrocarbon oils having a temperature of 200 ° C. or more and 550 ° C. or less, and hydrocarbon oils having a T50 of 250 ° C. or more and 550 ° C. or less.

And the hydrocarbon oil cracking catalyst of the present invention comprises:
(1) one element X selected from group IVA elements of the periodic table;
(2) one element Y ₁ selected from group IIIA elements in the periodic table;
(3) of the periodic table, VIA group elements, and one element Y ₂ is selected from the group consisting of VIII group elements of group VIIA elements, and the fourth period,
These three metal elements are contained in a predetermined ratio.
Here, the element selected from the element group described in the above (1) to (3) as the metal element to be included in the catalyst is adopted because the compound, particularly the oxide, containing the element selected from the element group is used. This is because it is stable in a high-temperature and high-pressure steam atmosphere and has high resistance to poisoning by sulfur compounds and nitrogen compounds. The reason why the three metal elements are contained in a predetermined ratio is that the decomposition reaction of the hydrocarbon oil can be promoted by containing the three metal elements in the predetermined ratio.

Further, in the hydrocarbon oil cracking catalyst of the present invention, the ratio (molar ratio) of each element X, Y ₁ , Y _{2 in} the catalyst determined by melting / ICP-AES method satisfies the following relationship. It is characterized by that.
(4) 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)
(5) a ratio of abundance y ₂ abundance y ₁ element Y ₂ with respect to the element Y ₁ is 0.02 to 0.25 (0.02 ≦ y ₂ / y ₁ ≦ 0.25)

Here, the abundance x of the element X in the catalyst, when less than 0.5 times the sum of the abundance y ₂ abundance y ₁ and the element Y ₂ elements Y ₁ (y ₁ + y _2), carbide The decomposition reaction of hydrogen oil cannot be accelerated sufficiently. Similarly, when the abundance x of the element X exceeds 2.0 times the total of the abundance of the element Y _{1 and} the abundance of the element Y ₂ (y ₁ + y ₂ ), the hydrocarbon oil decomposition reaction is similarly performed. Cannot be promoted sufficiently. Therefore, in the hydrocarbon oil cracking catalyst of the present invention, it is necessary to satisfy 0.5 ≦ x / (y ₁ + y ₂ ) ≦ 2.0. Note that x / (y ₁ + y ₂ ) is preferably 0.7 ≦ x / (y ₁ + y ₂ ) ≦ 1.5, and 0.8 ≦ x / (y ₁ + y ₂ ) ≦ 1.0. More preferably.

Moreover, the abundance y ₂ elements Y _2, when the 0.25-fold of the abundance y ₁ of the elements Y _1, activity of the catalyst decreases. Furthermore, sufficient abundance y ₂ elements Y _2, when less than 0.02 times the abundance y ₁ of the elements Y _1, the effect of improving the catalytic activity obtained by moistened an element Y ₂ in the catalyst Not. Therefore, in the catalyst for cracking hydrocarbon oil of the present invention, it is necessary to satisfy 0.02 ≦ y ₂ / y ₁ ≦ 0.25. Note that y ₂ / y ₁ is preferably 0.04 ≦ y ₂ / y ₁ ≦ 0.25, and more preferably 0.06 ≦ y ₂ / y ₁ ≦ 0.24.

In the hydrocarbon oil cracking catalysts of the present invention, with respect to abundance m of all the metal elements in the catalyst, and the abundance x of the element X, the abundance y ₁ of the elements Y _1, the presence of the element Y ₂ the ratio of the sum of the _{y 2 (x + y 1 +} y 2) is preferably a 0.70 _{(0.70 ≦ (x + y 1} + y 2) / m), 0.80 or more (0.80 ≦ (x + y More preferably, it is ₁ + y ₂ ) / m). This is because if the ratio of the element X, the element Y ₁ and the element Y _{2 in} the metal element contained in the catalyst is small, the catalytic activity cannot be sufficiently improved and the decomposition efficiency of the hydrocarbon oil is lowered. .

Here, an example of the hydrocarbon oil cracking catalyst of the present invention will be described in detail below. An example of the hydrocarbon oil cracking catalyst of the present invention includes the oxides containing the elements X, Y ₁ and Y ₂ of the above (1) to (3), more specifically, the elements X, Y ₁ and Y ₂ . It consists of a complex oxide.

That is, the hydrocarbon oil cracking catalyst of this example is a composite produced by combining three types of oxides, an oxide containing element X, an oxide containing element Y _1, and an oxide containing Y _2. Made of oxide. In this composite oxide, the ratio (molar ratio) of the abundances of the respective elements X, Y ₁ and Y ₂ satisfies the relationships (4) and (5).

  Here, in this example hydrocarbon oil cracking catalyst, the element X is preferably zirconium (Zr) or titanium (Ti), and particularly preferably Zr. This is because if the element X is Zr or Ti, the catalyst can maintain a crystal structure even when the catalyst is used under high temperature and high pressure conditions. That is, in the hydrocarbon oil cracking catalyst in which the element X is made of Zr or Ti, hydrothermally synthesized zeolite, silica, or hydrogenation catalyst made of γ-alumina used for hydrocracking of hydrocarbon oil is used. In this way, the crystal structure of the catalyst is not significantly changed by high-temperature and high-pressure steam so that the catalyst cannot be used. Moreover, it is not necessary to pre-process (desulfurization and denitrogenation) hydrocarbon oil. From the viewpoint of reliably maintaining the structure of the composite oxide, the ratio (x / m) of the abundance x of element X to the abundance m of all metal elements in the catalyst is 0.30 or more. Is preferred.

Further, the hydrocarbon oil cracking catalyst of this example, the element Y ₁ is, yttrium (Y), is preferably one selected from the group consisting of lanthanum (La) and cerium (Ce), the element Y ₂ but, molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), and it is not preferable one selected from the group nickel (Ni). The element Y ₁ is particularly preferably cerium. The element Y ₂ is particularly preferably one selected from the group consisting of tungsten, manganese and iron.

Here, in this hydrocarbon oil cracking catalyst comprising a composite oxide, the abundance of the element X to the sum of abundance y ₂ abundance y ₁ and the element Y ₂ elements _{Y 1 (y 1 + y 2} ) x The ratio (x / (y ₁ + y ₂ )) is preferably 0.5 or more. When x / (y ₁ + y ₂ ) is 0.5 or more, the distance between the oxide of the element X and the oxide of the element Y ₁ or the oxide of the element Y ₂ becomes close, and oxygen transfer in the catalyst This is because (the movement of lattice oxygen) is not hindered, so that the decomposition reaction of the hydrocarbon oil can be promoted. X / (y ₁ + y ₂ ) is preferably 2.0 or less. This is because when x / (y ₁ + y ₂ ) is 2.0 or less, oxygen transfer in the catalyst can be promoted, and the hydrocarbon oil decomposition reaction can be promoted.

The reason why the hydrocarbon oil cracking reaction can be promoted by promoting the oxygen transfer in the catalyst is not clear, but the hydrocarbon oil cracking using the hydrocarbon oil cracking catalyst of the present invention is not clear. The reaction is presumed to proceed by decomposing water and releasing oxygen and hydrogen. That is, if the catalyst's supply rate of lattice oxygen or occluded oxygen is increased and the ability to decompose water and release oxygen and hydrogen is increased, water can be used as a hydrogen source or oxygen source to produce heavy hydrocarbons. This is presumably because, when the compound is decomposed, it is possible to promote generation of hydrogen as a hydrogen source by reacting a part of the hydrocarbon compound with water as shown in the following reaction formula.
C _n H _m + 2nH ₂ O → nCO ₂ + (2n + (m / 2)) H ₂

Moreover, the hydrocarbon oil cracking catalyst comprising the composite oxide, the abundance ratio of y ₂ elements Y ₂ relative abundance y ₁ element Y ₁ (y ₂ / y ₁₎ is, is 0.25 or less It is preferable that y ₂ / y ₁ is 0.02 or more. This is because when y ₂ / y ₁ is less than 0.02, the effect of improving the catalytic activity due to the inclusion of the element Y ₂ may not be sufficiently obtained. Further, when y ₂ / y ₁ exceeds 0.25, the effect of improving the catalytic activity due to the inclusion of the element Y ₂ is reduced, but it is difficult to form a composite oxide. In addition, when y ₂ / y ₁ exceeds 0.25, it is not clear that the effect of improving the catalytic activity is reduced, but it is presumed that it is due to the following reason. That is, when an oxide containing the element Y ₂ is further added to the system containing the oxide containing the element X and the oxide containing the element Y ₁ , the amount of the oxide containing the element Y ₂ is very small. Even in such a case, the Gibbs energy of the system greatly changes, so that the activity of the catalyst can be greatly improved while maintaining the properties of the system containing the oxide containing the element X and the oxide containing the element Y ₁ to some extent. However, if the amount of the oxide containing the element Y ₂ becomes too large, the properties of the system approach that of the oxide containing the element Y _2, and the properties of the oxide containing the element X and the oxide containing the element Y ₁ are lost. End up. Therefore, when y ₂ / y ₁ exceeds 0.25 (the amount of element Y ₂ is increased), it is presumed that the effect of improving the catalytic activity is reduced.

The composite oxide as the hydrocarbon oil cracking catalyst as described above can be prepared by a coprecipitation method, for example, as follows without any particular limitation.
(I) First, a compound containing the element X, a compound containing the element Y _1, and a compound containing the element Y ₂ , for example, X / (Y ₁ + Y ₂ ) is 0.5 to 2.0 (molar ratio). And an aqueous solution containing the elements X, Y ₁ and Y ₂ is prepared by dissolving in ion exchange water in such an amount that Y ₂ / Y ₁ is 0.02 to 0.25 (molar ratio).
(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). ) Add dropwise while adjusting to produce a coprecipitate containing the elements X, Y ₁ , Y ₂ .
(Iii) Finally, the obtained precipitate is filtered and dried, and then the dried precipitate is calcined to obtain a composite oxide.
Here, the temperature at which the precipitate is dried in the above (iii) is preferably 100 ° C. or higher from the viewpoint of efficiently evaporating moisture. Further, the temperature for drying the precipitate is preferably 160 ° C. or less from the viewpoint of preventing rapid drying. The temperature at which the dried precipitate is calcined is determined from the viewpoint of the structural stability of the resulting composite oxide (catalyst) (that is, suppression of structural change of the composite oxide when hydrocarbon oil is decomposed by using it as a catalyst). Is preferably 500 ° C. or higher. Furthermore, it is preferable that the temperature which bakes a precipitate is 900 degrees C or less from a viewpoint of suppressing the reduction | decrease in the surface area of the complex oxide to produce | generate.

  Incidentally, the composite oxide as the hydrocarbon oil cracking catalyst can be prepared by using a known method such as a sol-gel method in addition to the coprecipitation method.

  In the hydrocarbon oil cracking method of the present invention, the hydrocarbon oil is cracked by bringing the hydrocarbon oil into contact with the above-described hydrocarbon oil cracking catalyst in the presence of water. Specifically, in the hydrocarbon oil cracking method of the present invention, for example, a mixture of a hydrocarbon oil and water is circulated in a reactor filled with the catalyst, whereby a catalyst, a hydrocarbon oil, To contact hydrocarbons and decompose hydrocarbon oil.

  Here, the water used for the decomposition of the hydrocarbon oil is to decompose the high molecular weight hydrocarbon compound contained in the hydrocarbon oil into a lower molecular weight hydrocarbon compound, that is, to lighten the hydrocarbon oil. It is used as a hydrogen source or the like when Therefore, the amount of water to be used may be an amount sufficient to lighten the hydrocarbon oil. For example, the amount of water is 5 to 2000 parts by mass, preferably 10 to 10 parts by mass with respect to 100 parts by mass of the hydrocarbon oil. It is desirable to add 1000 parts by mass, 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 lightened. On the other hand, when the amount of water added exceeds 2000 parts by mass, the amount of water that does not contribute to the lightening of the hydrocarbon oil increases, which increases the cost and the decomposition efficiency of the hydrocarbon oil (that is, the light hydrocarbon oil). This is because there is a case where the production efficiency of the product is reduced.

In the hydrocarbon oil cracking method of the present invention, the conditions for bringing the mixture of the hydrocarbon oil and water into contact with the catalyst in the reactor can be appropriately changed.
Specifically, the temperature at which the mixture and the catalyst are brought into contact with each other can be relatively low, for example, 300 to 600 ° C, preferably 350 to 550 ° C, and more preferably 400 to 500 ° C. This is because when the temperature is lower than 300 ° C., the 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.
Moreover, the pressure at the time of making a mixture and a catalyst contact is 0.1-40 Mpa, for example, Preferably it is 0.1-35 Mpa, More preferably, it can be 0.1-30 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.
Additionally, liquid hourly space velocity when flowing the mixture into a reactor filled with a catalyst (LHSV) is, for example 0.01～10H ^-1, preferably 0.05～5H ^-1, more preferably 0.1~2h It can be ^-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. Further, when the liquid space velocity is more than 10 h ⁻¹ , the reaction time is too short, and the hydrocarbon oil decomposition reaction may not sufficiently proceed.

  Here, as described above, according to the hydrocarbon oil cracking method of the present invention, hydrogen or the like necessary for the hydrocarbon oil cracking reaction can be supplied from the water present in the system. Accordingly, 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 hydrocarbon oil to be cracked (hydrogen addition) Amount / hydrocarbon oil supply amount) can be 0.1 or less, preferably 0. Therefore, according to the hydrocarbon oil cracking method of the present invention using the hydrocarbon oil cracking catalyst of the present invention, without using high-pressure hydrogen gas, the hydrocarbon oil is efficiently cracked at low cost, Light hydrocarbons can be obtained.

  Specifically, according to the hydrocarbon oil cracking method of the present invention, for example, condensed polycyclic aromatic compounds such as 1-methylnaphthalene, quinoline, anthracene, phenanthrene, and non-condensed polycycles such as dibenzothiophene and biphenyl. A heavy hydrocarbon oil comprising a mixture of various hydrocarbon compounds such as aromatic compounds is decomposed to obtain a light hydrocarbon oil having a weight average molecular weight of not more than half that of the heavy hydrocarbon oil, preferably not more than 1/3. be able to. That is, a light hydrocarbon oil can be produced by cleaving an aromatic ring of a hydrocarbon compound in a heavy hydrocarbon oil with a very high probability to obtain a monocyclic aromatic compound. In addition, a weight average molecular weight means the polystyrene conversion value measured using gel permeation chromatography (GPC).

  Moreover, according to the hydrocarbon oil cracking method of the present invention using the hydrocarbon oil cracking catalyst of the present invention, it is not necessary to desulfurize and denitrify the raw hydrocarbon oil to be cracked in advance.

  As mentioned above, although embodiment of this invention was described using an example, the catalyst for hydrocarbon oil decomposition | disassembly of this invention and the decomposition | disassembly method of hydrocarbon oil are not limited to the said example, The hydrocarbon oil decomposition | disassembly of this invention The cracking method for the catalyst for use and the hydrocarbon oil can be appropriately changed.

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

Example 1
A catalyst was prepared in which element X was zirconium, element Y ₁ was cerium, and element Y ₂ was iron. Specifically, first, zirconyl nitrate and cerium nitrate were dissolved in ion-exchanged water such that Zr: Ce = 1: 1 (molar ratio) to obtain an aqueous solution. Next, to the obtained aqueous solution, iron nitrate was added and stirred so that Ce: Fe = 1: 0.06 (molar ratio). And ammonia water was dripped with respect to the aqueous solution containing Zr, Ce, and Fe, adjusting so that pH of aqueous solution might not exceed 8, and the precipitation was produced | generated. Finally, the obtained precipitate was aged (still at room temperature for a whole day and night), filtered and dried (130 ° C., 16 hours), and then the dried precipitate was calcined at a temperature of 600 ° C. to obtain Zr, Ce, Fe. A catalyst composed of the composite oxide contained was prepared.
In addition, when the abundance ratio of Zr, Ce, and Fe in the obtained catalyst was confirmed by melting / ICP-AES method, it was Zr: Ce: Fe = 49: 48: 3.
Then, 5.3 g of the prepared catalyst was charged into a superalloy (Inconel 625) reactor (internal volume 10 mL). Next, the inside of the reactor was heated and pressurized to a temperature of 470 ° C. and a pressure of 15 MPa while passing ion exchange water through the reactor filled with the catalyst at a flow rate of 0.1 mL / min. Then, without supplying hydrogen, heavy hydrocarbon oil having properties as shown in Table 1 (oil distilled from the thermal cracking apparatus) and ion-exchanged water were continuously circulated in the reactor ( The flow rate of both ion-exchanged water and heavy hydrocarbon oil is 0.1 mL / min, and LHSV is 0.75 h ⁻¹ ). Then, after 6 hours from the start of oil passing, the effluent (decomposition reaction product) from the reactor was collected for 1 hour, and the decomposition rate of heavy hydrocarbon oil was calculated as follows. The results are shown in Table 2.

Ｃｖ：重質炭化水素油中の沸点３８０℃以上の留分の分解率［質量％］
Ｆ：供給した重質炭化水素油中の沸点３８０℃以上の留分の量［ｇ／ｈ］
Ｒ：分解反応生成物中の沸点３８０℃以上の留分の量［ｇ／ｈ］
Ｃｏｋｅ：触媒上に堆積した炭素質の量［ｇ／ｈ］<Calculation method of decomposition rate>
The decomposition rate Cv of the fraction having a boiling point of 380 ° C. or higher in the supplied heavy hydrocarbon oil was calculated using the following formula. Coke was measured by a combustion ultraviolet fluorescence method.

Cv: Decomposition ratio [mass%] of a fraction having a boiling point of 380 ° C. or higher in heavy hydrocarbon oil
F: Amount [g / h] of a fraction having a boiling point of 380 ° C. or higher in the supplied heavy hydrocarbon oil
R: The amount of the fraction having a boiling point of 380 ° C. or higher in the decomposition reaction product [g / h]
Coke: amount of carbonaceous matter deposited on the catalyst [g / h]

(Example 2)
A catalyst was prepared in which element X was zirconium, element Y ₁ was cerium, and element Y ₂ was tungsten. Specifically, zirconyl nitrate and cerium nitrate were dissolved in ion-exchanged water such that Zr: Ce = 1: 1 (molar ratio) to obtain an aqueous solution containing Zr and Ce. Next, ammonium metatungstate was dissolved in ion-exchanged water to obtain an aqueous solution of ammonium metatungstate having a predetermined concentration. Then, an aqueous ammonium metatungstate solution was added dropwise to the aqueous solution containing Zr, Ce while adjusting the aqueous solution so that the pH of the aqueous solution did not exceed 8, thereby generating a precipitate. Finally, the obtained precipitate was aged (still at room temperature for a whole day and night), filtered and dried (130 ° C., 16 hours), and then the dried precipitate was calcined at a temperature of 600 ° C. to obtain Zr, Ce, W. A catalyst composed of the composite oxide contained was prepared.
And the heavy hydrocarbon oil was decomposed | disassembled like Example 1, and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 2.
In addition, when the abundance ratio of Zr, Ce, and W in the obtained catalyst was confirmed in the same manner as in Example 1, it was Zr: Ce: W = 49: 48: 3.
(Example 3)
A catalyst was prepared in the same manner as in Example 1 except that the element Y ₂ was manganese and manganese nitrate was added instead of iron nitrate so that Ce: Mn = 1: 0.06 (molar ratio). And the heavy hydrocarbon oil was decomposed | disassembled like Example 1, and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 2.
In addition, when the abundance ratio of Zr, Ce, and Mn in the obtained catalyst was confirmed in the same manner as in Example 1, it was Zr: Ce: Mn = 49: 48: 3.
Example 4
A catalyst was prepared in the same manner as in Example 1 except that zirconyl nitrate, cerium nitrate and iron nitrate were added so that Zr: Ce: Fe = 46: 46: 8. And the heavy hydrocarbon oil was decomposed | disassembled like Example 1, and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 2.
When the abundance ratio of Zr, Ce, and Fe in the obtained catalyst was confirmed in the same manner as in Example 1, it was Zr: Ce: Fe = 46: 46: 8.

(Comparative Example 1)
A catalyst containing no element Y ₂ was prepared in the same manner as in Example 1 except that iron nitrate was not added. And the heavy hydrocarbon oil was decomposed | disassembled like Example 1, and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 2.
When the abundance ratio of Zr and Ce in the obtained catalyst was confirmed in the same manner as in Example 1, it was Zr: Ce = 54: 46.
(Comparative Example 2)
A catalyst was prepared in the same manner as in Example 1 except that zirconyl nitrate, cerium nitrate and iron nitrate were added so that Zr: Ce: Fe = 44: 43: 13. And the heavy hydrocarbon oil was decomposed | disassembled like Example 1, and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 2.
In addition, when the abundance ratio of Zr, Ce, and Fe in the obtained catalyst was confirmed in the same manner as in Example 1, it was Zr: Ce: Fe = 44: 43: 13.

(Example 5)
A catalyst was prepared in which element X was titanium, element Y ₁ was cerium, and element Y ₂ was iron. Specifically, first, titanium tetrachloride and cerium nitrate were dissolved in ion-exchanged water so that Ti: Ce = 1: 1 (molar ratio) to obtain an aqueous solution. Next, to the obtained aqueous solution, iron nitrate was added and stirred so that Ce: Fe = 1: 0.25 (molar ratio). And aqueous ammonia was dripped with respect to the aqueous solution containing Ti, Ce, and Fe, adjusting so that the pH of aqueous solution might not exceed 8, and the precipitation was produced | generated. Finally, the obtained precipitate was aged (still at room temperature for a whole day and night), filtered and dried (130 ° C., 16 hours), and then the dried precipitate was baked at a temperature of 600 ° C. to obtain Ti, Ce, Fe. A catalyst composed of the composite oxide contained was prepared.
And the heavy hydrocarbon oil was decomposed | disassembled like Example 1, and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 3.
In addition, when the abundance ratio of Ti, Ce, and Fe in the obtained catalyst was confirmed by a melting / ICP-AES method, it was Ti: Ce: Fe = 44: 45: 11.

(Comparative Example 3)
A catalyst was prepared in the same manner as in Example 5 except that zirconyl nitrate was added instead of cerium nitrate so that Ti: Zr: Fe = 1: 1: 1 (molar ratio). And heavy hydrocarbon oil was decomposed | disassembled like Example 5 and the decomposition rate of heavy hydrocarbon oil was computed. The results are shown in Table 3.
In addition, when the abundance ratio of Ti, Zr, and Fe in the obtained catalyst was confirmed in the same manner as in Example 5, it was Ti: Zr: Fe = 33: 34: 33.

From Tables 2-3, it turns out that the catalyst of Examples 1-5 has a high decomposition rate compared with the catalyst of Comparative Examples 1-3. Moreover, in the catalysts of Examples 1 to 5, it is understood that the hydrocarbon oil can be decomposed and lightened without desulfurizing and denitrifying the hydrocarbon oil in advance. Furthermore, the catalyst of Comparative Example 2 in which y ₂ / y ₁ was set to 0.30, and Comparative Example 3 in which x / (y ₁ + y ₂ ) was set to 0.49 and y ₂ / y ₁ was set to 0.97. It can be seen that the decomposition rate of the catalyst is lower than that of the catalyst of Comparative Example 1.

  In order to evaluate the deterioration resistance of the catalyst, in Example 2 and Comparative Example 2, the decomposition of the heavy hydrocarbon oil was continued for 14 days or more. Then, after 14 days from the start of oil passing, the effluent from the reactor was collected for 2 hours, and the decomposition rate of the heavy hydrocarbon oil was calculated in the same manner as in Example 1. Table 4 shows the decomposition rate of heavy hydrocarbon oil after 6 hours from the start of oil passing and the decomposition rate of heavy hydrocarbon oil after 14 days from the start of oil passing.

  From Table 4, the decomposition rate after 6 hours from the start of oil passage and the decomposition rate after 14 days from the start of oil passage did not change much in Example 2, whereas in Comparative Example 2, the start of oil passage 14 It can be seen that the degradation rate after the passage of days has greatly decreased. Therefore, in Example 2, it turns out that deterioration of a catalyst is suppressed.

  According to the present invention, hydrocarbon oil cracking that can efficiently lighten hydrocarbon oil at low cost without desulfurization and denitrification of hydrocarbon oil in advance and without using high-pressure hydrogen gas. A catalyst can be provided. Moreover, the hydrocarbon oil cracking method using the hydrocarbon oil cracking catalyst can be provided.

Claims (5)

Used in cracking hydrocarbon oils in the presence of water,
One element X selected from group IVA elements;
One element Y ₁ selected from group IIIA elements;
Group VIA elements, VIIA group elements, and the one element Y ₂ that will be selected from the group consisting of VIII group elements of the 4th period,
Containing
Abundance of elements Y ₁ (y ₁₎ and abundance of the elements Y ₂ sum of (y ₂₎ presence of the element X with respect to (y ₁ + y ₂₎ ratio (x) (x / (y 1 + y 2) ) Is 0.5 or more and 2.0 or less,
Abundance of elements Y ₁ is the presence of the element Y ₂ with respect to (y ₁₎ the ratio of _{(y 2) (y 2 /} y 1), characterized in that 0.02 to 0.25, hydrocarbons Oil cracking catalyst. _2. The hydrocarbon oil cracking catalyst according to claim 1, comprising a composite oxide containing the element X, the element Y _1, and the element Y ₂ .   The hydrocarbon oil cracking catalyst according to claim 1 or 2, wherein the element X is zirconium. 4. The hydrocarbon according to claim 1, wherein the element Y ₁ is cerium, and the element Y ₂ is one selected from the group consisting of tungsten, manganese, and iron. Oil cracking catalyst.   A hydrocarbon oil characterized by decomposing a hydrocarbon oil by contacting the hydrocarbon oil with the hydrocarbon oil cracking catalyst according to any one of claims 1 to 4 in the presence of water. Disassembly method.