JPS608861B2 - Catalyst composition for hydrocracking of heavy hydrocarbon oils - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a catalyst composition for hydrocracking heavy hydrocarbon oils.

Hydrocracking of hydrocarbon oils using catalysts containing zeolite components is widely used industrially and is well known.

In particular, hydrocracking of hydrocarbon oils with a boiling point range of 30,000 to 55,000 or lower, called vacuum gas oil, has already been carried out, such as LPG, gasoline, kerosene, diesel oil, etc. is replaced by useful vertical hydrocarbon oil. However, heavy hydrocarbon oil with a boiling point of 30,000 or higher has a sulfur content, nitrogen content,
Because it contains relatively large amounts of metals, asphaltene, and residual carbon, harsh reaction conditions are required during silting by hydrogenolysis, making it extremely difficult to maintain stable catalyst activity. Have difficulty.

Catalysts for treating virgin hydrocarbon oils include catalysts supporting metal oxides or sulfides of cobalt-molybdenum, nickel-molybdenum, and nickel-cobalt-molybdenum using alumina as a carrier, silica-alumina,
A catalyst in which a metal component is supported on a binary oxide carrier having collective acidity such as silica/magnesia, silica/zirconia, or silica/titania, and zeolite or zeolite belonging to crystalline aluminosilicate, alumina, silica, etc.
Possible catalysts include metal-supported catalysts on composite oxide carriers such as silica/alumina and silica/magnesia.

Also, to avoid coke and metal deposition on the catalyst,
It is desirable that the catalyst be active at as low a temperature as possible.

Among the catalysts that meet this requirement, zeolite-based catalysts are attracting attention, but in order to exhibit sufficient functionality,
There is room for further research. As a result of extensive research into catalysts for hydrocracking heavy hydrocarbon oils, the present inventors have discovered a catalyst composition that is highly active at relatively low temperatures, and have thus arrived at the present invention. That is, the present invention comprises supporting palladium on a carrier composed of three components, substituted Y zeolite, titanium oxide, and alumina, or two components, substituted Y zeolite and titanium oxide, and supports palladium on a carrier composed of three components, substituted Y zeolite, titanium oxide, and alumina, or two components, substituted Y zeolite and titanium oxide. Atomic ratio of titanium to aluminum is 1:2
The gist of the present invention is a catalyst composition for hydrocracking heavy hydrocarbon oil, characterized in that the ratio is within the range of 1 to 0.

The substituted type Y zeolite referred to in the present invention refers to a zeolite belonging to the natural or synthetic faujasite type, in which as many exchangeable cations as possible are exchanged with ammonium ions by an ion exchange method, and the Na type Y zeolite is replaced with ammonium ion. In the case of ion exchange, the ion exchange must be performed to reduce the residual sodium content to at least 0.5% by weight.

Further, ammonium-substituted Y zeolite in which 90% or more of the exchanged ammonium ions are ion-exchanged with one or more rare metals such as cerium and lanthanum can also be used as the substituted Y zeolite in the present invention. Further, titanium oxide in the present invention includes Ti(S04)2, T
Titanium hydroxide derived from titanium hydroxide produced by adding an alkaline aqueous solution such as NrOH to an aqueous titanium salt solution such as IC14 can be used.

Furthermore, alumina derived from alumina gel produced by adding an alkaline aqueous solution such as NH40 to alumina hydrosol or alumina organosol can be used. In the present invention, the method for preparing the carrier composed of substituted Y zeolite, titanium oxide, and alumina as defined above is to knead the three components of substituted Y zeolite, titanium hydroxide, and alumina gel, or to prepare a carrier composed of substituted Y zeolite, titanium oxide, and alumina gel. Add N to a mixed solution of aqueous solution and alumina hydrosol or alumina organosol.
Either method may be employed, including adding an alkaline aqueous solution such as Ben○H and dispersing the substituted Y zeolite in the co-pillarized gel. Further, in the case of a carrier composed of substituted Y zeolite and titanium oxide, it can be prepared in the same manner as the above method except that the alumina component is omitted. After that, methods such as forming into an arbitrary shape, drying and firing, or drying and firing the powder and forming it into pellets of an arbitrary shape are adopted. The mixing ratio of titanium oxide and alumina is based on the total weight of substituted Y zeolite, titanium oxide, and alumina, or the total weight of substituted Y zeolite and titanium oxide, and the proportion of substituted Y zeolite is 3 to 6% by weight. The content is appropriately selected within the range, but if the amount of substituted Y zeolite is too small, the decomposition activity will decrease, and if it is too large, the decomposition selectivity and activity will deteriorate significantly, so it is preferably 10 to 4% by weight.

Furthermore, when expressed as the atomic ratio of titanium to aluminum, the ratio of titanium oxide and alumina is selected to be in the range of 1:2 to 1:0, as is clear from the experimental examples described later, and within these mixing ratios. When using a catalyst carrier selected from the following, it shows high activity at relatively low temperatures in the hydrocracking of heavy hydrocarbon oils. The catalyst composition of the present invention is one in which palladium is even supported on the above-mentioned carrier.

Although the catalyst composition of the present invention can be applied to the hydrocracking of light hydrocarbon oils having a boiling point of 30,000 or less, it is more suitable for use in the hydrocracking of vehicle quality hydrocarbon oils having a boiling point of 30,000 or higher. It is.

As reaction conditions for hydrocracking heavy hydrocarbon oil using the catalyst composition of the present invention, the reaction temperature is usually 30°C.
0~4500C, preferably 360~420oo
selected within the range.

The reaction pressure is appropriately selected within the range of 50 to 200 kg/, but if it is too low, coke formation on the catalyst surface increases, so the range of 130 to 200 kg/ is preferred. In addition, when feeding heavy hydrocarbon oil as a raw material to the reactor, its liquid hourly space velocity (LHSV) is usually 0.1 to 10 h[1, preferably 0.2 to 2 h-1], and the hydrogen to oil ratio is is usually 3
00 to 2000N/W, preferably 8
00 to 1500N (selected within the range of A fixed bed reactor etc. can be used.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples unless the gist of the invention is exceeded.

The catalyst was evaluated using the results of hydrogenolysis using Daqing atmospheric residual oil having the properties shown in Table 1.

Table 1 Catalyst Production Example Experimental Example 1 Ammonium-substituted Y zeolite (sodium content: 94%.
(substituted with 7% ammonium) in a commercially available alumina sol at a ratio of 30% by weight based on the total weight with alumina.

Next, an aqueous ammonia solution of about 100 ml was added to form a gel, and after thoroughly washing with deionized water, it was molded and dried at a temperature of about 120° C. for about 1 hour. This dried product was fired at a temperature of about 55,000 ℃ for about 3 hours. The thus obtained ammonium-substituted Y zeolite/alumina carrier was immersed in an aqueous solution of tetraamminepalladium chloride, and 0.5% by weight of palladium metal was supported on the basis of the rod. After that, about 12,000
The catalyst was dried for about 5 hours at a temperature of about 5000C and then calcined for about 3 hours at a temperature of about 5000C to obtain a catalyst. Experimental Example 2 Approximately 4N ammonia aqueous solution was added to the titanium tetrachloride solution with a slight increase, and the pH was adjusted to approximately 8.5 to obtain titanium hydroxide.

In addition, a commercially available alumina sol was added with an aqueous ammonia solution to form a gel, and thoroughly washed with deionized water to obtain an alumina gel. The above titanium hydroxide and alumina gel were mixed so that the atomic ratio of titanium to aluminum was 1:4, and the ammonium-substituted Y zeolite of Experimental Example 1 was added to 3 mice based on the total weight of titanium oxide and alumina. They were mixed in a proportion of % by weight. The mixture is molded and dried at a temperature of about 12,000°C for about 1 hour, and then dried at a temperature of about 550°C.
It was baked at a temperature of 0.00 for about 3 hours. The ammonium-substituted Y zeolite/titanium oxide/alumina support thus obtained is soaked in an aqueous tetraasomine palladium chloride solution,
Palladium metal was supported in an amount of 0.5% by weight based on the carrier. After that, it was dried at a temperature of about 12,000 degrees Celsius for about 5 hours.
The mixture was further calcined at a temperature of about 50,000 ℃ for about 3 hours to obtain a catalyst. Experimental Example 3 Basically, a catalyst was prepared using the same method as in Experimental Example 2, and the atomic ratio of titanium to aluminum in the neck body excluding the ammonium-substituted zeolite was set to 1:3.

Experimental Example 4 Basically, a catalyst was prepared by employing the same method as in Experimental Example 2, except that the ammonium-substituted zeolite was excluded, and the atomic ratio of titanium to aluminum in the support was set to 1:2.

Experimental Example 5 Basically, a catalyst was prepared using the same method as in Experimental Example 2, and the atomic ratio of titanium to aluminum in the carrier except for the ammonium-substituted zeolite was set to 1:1.

Experimental Example 6 Basically, a catalyst was prepared by employing the same method as in Experimental Example 2, and the atomic ratio of titanium to aluminum in the carrier excluding the ammonium-substituted zeolite was set to 1:0.25.

Experimental Example 7 Basically, a catalyst was prepared using the same method as in Experimental Example except that the ammonium-substituted zeolite was removed.The atomic ratio of titanium to aluminum in the carrier was set to 1:0.

Experimental Example 8 The ammonium-substituted Y zeolite of Experimental Example 1 was soaked in a cerium chloride aqueous solution to prepare a substituted Y-zeolite in which 92% of ammonium was ion-exchanged with cerium. The method was adopted to prepare the catalyst.

Evaluation Test Example The hydrocracking activity of each catalyst of Experimental Examples 1 to 7 was evaluated using the Daqing atmospheric residual oil shown in Table 1 as the feedstock oil, and the results are shown in Table 2 and Figure 1. It was shown to.

In hydrocracking, feedstock oil is heated to a liquid hourly space velocity of 0. The reaction was carried out under the following reaction conditions: the reaction temperature was 39,000, the reaction pressure was 150 k9/g, and the hydrogen to oil ratio was 1,200 N.

From the comparison results in Table 2 and Figure 1, it is clear that the catalyst compositions of the present invention (Examples 4 to 8) have a higher decomposition rate than Experimental Examples 1 to 3, and can produce equivalent kerosene and gas oil fractions. I know that it will happen.

Moreover, from the results of Experimental Examples 4 to 8, it can be seen that excluding zeolite, the case where the atomic ratio of titanium to aluminum in the carrier is 1:2 to 1:0 is optimal.

[Brief explanation of the drawing]

FIG. 1 is a chart showing the results obtained in experimental examples of the present invention. Figure 1

Claims (1)

[Claims] 1 Substituted Y zeolite, titanium oxide and alumina 3
or substituted Y zeolite and titanium oxide, and the atomic ratio of titanium to aluminum in the carrier excluding the zeolite is in the range of 1:2 to 1:0. A catalyst composition for hydrocracking heavy hydrocarbon oil, characterized in that: