JPS62213843A - Additive for catalytic cracking - Google Patents

Abstract

PURPOSE:To promote catalytic cracking while preventing the deterioration of a catalyst, by preparing an additive, which is used jointly with a catalyst for catalytically cracking metal-containing crude oil, from a magnesium compound containing 0.1-35wt% of a silicon compound as silicon oxide. CONSTITUTION:A magnesium compound containing 0.1-35wt%, pref., 1-30wt% of a silicon compound as silicon oxide is molded into a granular form to obtain an additive. As concrete examples of the aforementioned silicon-containing magnesium compound, there are magnesium oxide, magnesium hydroxide and magnesium chloride etc. The additive obtained is added to a catalyst for catalytic cracking before use but the use amount thereof is usually about 1-80wt% of the catalyst. As the catalytic cracking catalyst, there are silica and alumina, etc., and, as crude oil intended for catalytic cracking, there is oil containing a metal such as nickel.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an additive for catalytic cracking, and more specifically, it is used together with a catalyst when catalytically cracking feedstock oil such as heavy oil containing metal components. This invention relates to an additive that suppresses deterioration of.

[Prior art and problems to be solved by the invention] Generally, when catalytically cracking heavy oil containing heavy metal components and sulfur, various additives are used together with the catalytic cracking catalyst for the purpose of preventing deterioration of the catalyst. is known to be used.

For example, sulfur oxides (
In order to reduce SOX), it is known to impregnate a catalytic cracking catalyst with a group IIA metal (Japanese Patent Publication No. 51-29882). In addition, magnesium is added to the catalytic cracking catalyst in order to immobilize the vanadium content in the feed oil (Japanese Patent Publication No. 59-49275), and furthermore, to prevent deterioration of the catalyst due to metal content such as vanadium and nickel. For this purpose, the addition of particles of magnesium oxide in combination with a thermally stable metal compound (U.S. Pat. No. 446
No. 5779) and the like are known.

However, none of these conventional techniques could sufficiently achieve the intended purpose. Specifically, U.S. Patent No. 4465
The technique disclosed in the specification of No. 779 had a problem in that the magnesium oxide particles added were worn out, resulting in a significant drop in performance.

Therefore, the present inventor solved the problems of the above-mentioned conventional technology, and
We conducted intensive research to develop an additive that can prevent the deterioration of catalytic cracking catalysts, have excellent mechanical strength, and maintain performance over a long period of time.

[Means for solving problems]

As a result, they discovered that a magnesium compound containing a certain proportion of a silicon compound can be an additive with the desired performance, and have completed the present invention.

That is, the present invention provides an additive for catalytic cracking that is used together with a catalyst when catalytically cracking a metal-containing feedstock oil, and is made of a magnesium compound containing 0.1 to 35% by weight of a silicon compound as silicon oxide. It is something to do.

The additive of the present invention contains a silicon compound of 0.1 to 3 as described above.
5% by weight (calculated as silicon oxide S i O!), preferably 1
It is a magnesium compound containing ~30% by weight. Here, the silicon compound is contained in the magnesium compound in various forms, and there is no particular restriction on the type. Specifically, silicon oxide (colloidal silica or anhydrous silica), silicon hydroxide, and silicates (sodium silicate, potassium silicate, etc.).

Examples include silicon tetrachloride and silicate ester. However, since the additives of the present invention are usually produced through a firing process, most of them are often in the form of oxides.

On the other hand, there are various types of magnesium compounds, which are the main components of additives, such as magnesium oxide, magnesium hydroxide, magnesium chloride, magnesium carbonate, magnesium nitrate, and magnesium sulfate. However, it is usually fired into magnesium oxide in the same way as silicon compounds.

The additive of the present invention contains a silicon compound in the above-mentioned magnesium compound, and the content of the silicon compound is 0.01 to 35% by weight, preferably 1 to 30% by weight based on the entire additive. is within the range of If the content of the silicon compound is less than 0.1% by weight, the wear resistance will not be sufficient when the resulting additive is used in the form of particles. Moreover, if the amount exceeds 35% by weight, there will be a disadvantage that the effect of suppressing catalyst deterioration due to the addition of the additive will not be observed.

Note that this additive may be configured as a mixture of a silicon compound and a magnesium compound, or may be configured as a double salt of a recompound, magnesium silicate, or the like. Furthermore, a portion may be a double salt or the like, and the remainder may be a mixture.

The additive of the present invention is used by being added to a catalyst for catalytic cracking during catalytic cracking. Usually, a composition is prepared by mixing additive particles and catalyst particles, each of which has been grated, and is used in the form of this composition, but it is also used by adding the additive particles and catalyst particles separately to the reaction system of catalytic cracking. You can also. Here, the amount of additive used depends on its type, catalyst type,
Although it varies depending on the properties of the raw material oil to be catalytically cracked, it is usually used in an amount of 1 to 80% by weight, preferably 3 to 60% by weight based on the catalyst.

The catalyst used in this catalytic cracking includes various catalysts that have been widely known as catalysts for catalytic cracking. Specific examples include silica, alumina, silica-alumina, alumina-magnesia, silica-titania, alumina-titania, various clays, various crystalline aluminosilicates, or mixtures thereof.

In addition, raw oils to be subjected to catalytic cracking include nickel, vanadium, w4. This is an oil that contains metals such as iron, and a feedstock oil is selected that more easily deteriorates the catalyst than the metals during catalytic cracking. Specifically, crude oil, atmospheric distillation residue oil, vacuum distillation residue oil, shale oil, and tar sands oil.

Coal liquefied oil, solvent-deasphalted oil, solvent-deasphalted asphalt, distillate oil or residual oil obtained by secondary treatment of these using hydrogen, or distillate oil or residual oil obtained by secondary treatment of these without using hydrogen, Alternatively, distillate oil usually at 200°C or higher obtained from atmospheric distillation or reduced production distillation of these oils, such as light gas oil (LGO) (boiling point range 200-300°C)1
Heavy gas oil (HGO) (boiling point range 300-500℃
) and/or vacuum gas oil (VGO) (boiling point range 300 to 750°C). The concentration of distillate nodules at 200° C. or higher in the mixed oil is 98% or less.

Furthermore, catalytic cracking of metal-containing feedstock oil using the additive of the present invention and the above catalyst can be carried out in various ways and under various conditions.

For example, there are systems such as a fluidized bed type and a moving bed type, and the regeneration tower may be a single-stage regeneration tower or a multi-stage regeneration tower. Further, the conditions include a reaction temperature of 450 to 800°C.

Pressure 0.5-5 ktr/cm”cr, catalyst regeneration temperature 5
The temperature may be selected within the range of 50 to 950°C, catalyst/oil conversion ratio of 2 to 20% 1 t/t, and contact time of 0.2 to 5 seconds.

〔Effect of the invention〕

When a metal-containing feedstock oil is catalytically cracked using the additive of the present invention such as ridges, most of the metal content in the feedstock oil will adhere to the additive without adhering to the catalyst surface.

Because it is absorbed, catalyst deterioration is suppressed, high catalytic activity is maintained over a long period of time, and efficient catalytic cracking reaction proceeds.

In addition, when the additive of the present invention is formed into particles and used together with catalyst particles in a fluidized bed reaction tower, it has extremely high wear resistance compared to conventional magnesium oxide additives, so it can be used for a long period of time. It can be sufficiently tolerated and its effects can be sustained.

Therefore, the additive of the present invention can be widely and effectively utilized in the field of petroleum refining industry.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Sodium silicate aqueous solution 1 containing 52.5 g as silica
To 213 g, 305 g of an aqueous magnesium chloride solution containing 17.5 g of magnesium oxide was added with vigorous stirring, and the pH was finally adjusted using an aqueous sodium hydroxide solution.
was adjusted to 9.5. The resulting slurry was aged at 90°C for 2 hours and then filtered, and the resulting cake was aged at 120°C for 12 hours.
Let dry for an hour. Furthermore, wash with 85℃ water,
It was dried again at 120°C for 12 hours and fired in a Matsufuru furnace at 590°C for 6 hours. The obtained fired product was granulated to a size of 65 to 150 mesh to obtain silica-magnesia additive particles.

Next, nickel naphthenate and vanadium naphthenate were added to the obtained silica-magnesia additive particles by Mitch.
ell method (Ind, Hng, Chem, Pr
od, Res.

Vanadium 1) 300 ppm+, nickel 3700 ppm- according to Dev., 19.209 (1980))
It was carried at a ratio of .

On the other hand, nickel naphthenate and vanadium naphthenate were added to commercially available metal-resistant fluid catalytic cracking (FCC) catalyst particles according to the method of Mitchell (vanadium 1).
It was supported at a ratio of 300 ppo + nickel and 3700 pp haze.

Next, these two types of particles (silica-magnesia additive particles supporting vanadium and nickel and catalyst particles) are mixed in a ratio of 10-t% additive particles and 90-t% catalyst particles to form a catalyst. A composition was air-sintered at 850°C for 4 hours, and then at 710°C for 4 hours.

Pseudo-equilibrium was performed by 100% steam treatment.

The vanadium content in the catalyst composition after this pseudo-equilibration was examined by fluorescent X-ray analysis. The results are shown in Table 1.

Subsequently, this catalyst composition was used, and vacuum gas oil (ASTM MAT standard stock oil) was used as the raw material oil, and the reaction temperature was 482° C. and the pressure was x normal pressure.

Weight hourly space velocity (WH3V) 16hr-', catalyst composition/
The cracking activity of the catalyst composition was evaluated by the ASTM D-3907 MAT (micro activity test) method in which the catalytic cracking reaction was allowed to proceed under conditions of an oil ratio of 39 and an oil passage time of 75 seconds.

4.0 g of the catalyst composition was used for the decomposition activity evaluation.

In addition, JISK1467 is used to evaluate the wear resistance of additive particles.
The particle intensity measurement method was used. These results are shown in Table 1.

Example 2 In Example 1, by changing the mixing ratio of the sodium silicate aqueous solution and the magnesium chloride aqueous solution, MgO/(Si
A silica-magnesia cake of Oz+Mg0)-25 w't% was obtained. An amount of this cake corresponding to a dry weight of 25 g of silica-magnesia was taken and kneaded with Eiwa magnesium oxide corresponding to a dry weight of 50 g. Then filter, dry, wash, and dry.

Firing was carried out in the same manner as in Example 1, and granules were granulated to 65 to 150 mesh to form silica-magnesia additive particles (MgO/
(SiOz+MgO)-75wt%) was obtained. Various tests were conducted in the same manner as in Example 1 except that these additive particles were used. The results are shown in Table 1.

Comparative Example 1 Various tests were conducted in the same manner as in Example 1, except that no additive particles were used. The results are shown in Table 1.

Comparative Example 2.3 Various tests were conducted in the same manner as in Example 1, except that the composition of the additive particles was changed. The results are shown in Table 1.

Comparative Example 4 Except for using sepiolite, a natural mineral containing magnesium, as the additive particles in Example 1,
Various tests were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5 Various tests were conducted in the same manner as in Example 1, except that chrysotile, which is a natural mineral containing magnesium, was used as the additive particles. The results are shown in Table 1.

Comparative Example 6 Various tests were conducted in the same manner as in Example 1 except that the composition of the additive particles was changed. The results are shown in Table 1.

Example 3 FCC catalyst particles 90 treated with steam at 788°C for 4 hours
Overlapping part and silica-magnesia additive particles 10 of Example 1
In the same manner as in Example 1, 2600 ppm of vanadium and 850 ppn+ of nickel were supported on each part by weight. Thereafter, it is mixed to form a catalyst composition, and 78
Pseudo-equilibration was performed at 8°C for 2 hours.

Next, using this catalyst composition, 50% of residual oil containing 4 ppm of nickel and 6 ppm of vanadium was hydrodesulfurized.
-1% and 50-t% of desulfurized vacuum gas oil is supplied to a circulating flow bench equipment, and the reaction temperature is 503-506%.
°C, regeneration temperature 630-670 °C.

Pressure 2-3 kg/cul Q, catalyst composition/oilification7. The reaction was carried out under conditions of a raw oil supply rate of 1000 mj2/hr. The results are shown in Table 2.

Comparative Example 7 In Example 3, the same scraping as in Example 3 was performed except that the silica-magnesia additive particles were not used. The results are shown in Table 2.

Table 2

Claims (2)

[Claims] (1) An additive used together with a catalyst when catalytically cracking metal-containing feedstock oil, which contains silicon compounds as silicon oxide.
．． An additive for catalytic cracking consisting of a magnesium compound containing 1 to 35% by weight. (2) Magnesium compound absorbs silicon oxide by 0.1 to 35
The additive according to claim 1, which is magnesium oxide containing % by weight.