JPS60255145A - Heavy oil reforming catalyst - Google Patents

Abstract

PURPOSE:To provide pour point depressing activity and to improve the durability by depositing nickel, molybdenum, etc. on a carrier consisting of a mixture of iron-contg. zeolite and gamma-alumina to form the titled heavy oil reforming catalyst. CONSTITUTION:A catalyst carrier is formed of a mixture of iron-contg. zeolite consisting of crystalline metallosilicate obtained by substituting a part of Si at the apex of the crystal lattice for Fe and gamma-alumina. In this case, 20-70wt% iron-contg. zeolite is mixed with 30-80wt% gamma-alumina. When the content of the iron-contg. zeolite becomes <=20wt%, the pour point depressing activity is eliminated, and the denitrifying and desulfurizing activity is deteriorated, when the content becomes >=70wt%. A catalyst component consisting of 3-10wt% NiO, 3-10wt% CoO, 10-30wt% MoO3, and 10-30wt% WO3 is deposited on the carrier to obtain the heavy oil reforming catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a reforming catalyst for petroleum-based atmospheric residual oil, vacuum residual oil, or heavy oil such as tar sand and sierre oil.

(Prior Art) In recent years, as part of the development of oil-alternative energy, fossil fuels such as coal, oil shale, and tar sand have been effectively utilized.

Heavy oil obtained by heat-treating these fossil fuels is used for transportation and as a fuel for combustion, but these oils contain higher silicon and sulfur content than petroleum, so if they are burned as is, they cause nitrogen oxidation. This is undesirable as it releases a lot of substances and sulfur oxides into the atmosphere. Furthermore, oil such as sierre oil has a high pour point because it contains a large amount of paraffin fraction, and when transported by pipeline, heating is required and a large amount of energy is required.

Currently, refining of these heavy oils is carried out using a two-stage process that combines pretreatment such as coking and hydrorefining, although this varies depending on the properties of the heavy oil, product demand structure, and required properties. This hydrogenation process decomposes hydrocarbons, reacts nitrogen compounds to ammonia, and sulfur compounds to hydrogen sulfide in the presence of a catalyst, but the key factors are the lifetime and selectivity of the catalyst's activity. ing. As a method of controlling the properties, the pore distribution within the pore volume is generally studied.

Conventional catalysts used in petroleum-based hydrotreating processes are mostly r-alumina carriers, which support all active metal components such as nickel and molybdenum. Since hydrogen treatment promotes gasification at high temperatures, the amount of hydrogen consumed is very high. Furthermore, although denitrification and desulfurization of heavy oil are promoted, it hardly has the function of lowering the pour point.

On the other hand, kerosene fraction is used as a catalyst for lowering pour point.
, silica-alumina-based zeolite (1), which is a strongly acidic substance, is used to perform hydrogenolysis of paraffinic hydrocarbons. However, since silica-alumina-based zeolite is poisoned by the nitrogen content in the oil, the pour point hardly decreases when used in heavy oil containing a large amount of nitrogen.

(Problem to be solved by the invention) Therefore, in order to hydro-reform heavy oil that has a high pour point and contains a large amount of nitrogen, the inventors developed a technology that has both denitrification, desulfurization, and dewaxing activities. We worked diligently to develop catalysts, and as a result, we discovered the present invention.

(Findings of the Invention) The inventors focused on the dewaxing activity of zeolite, and in particular, by using a catalyst in which nickel and molybdenum are supported on a carrier that is a mixture of silica/iron zeolite and γ-ATO, the inventors achieved remarkable results. I found out that it is effective.

Is this touchstone's function only for the conventional γ-jin 403? Compared to the catalyst used as a carrier, the denitrification and desulfurization performance is the same, and the dewaxing performance is greatly promoted.

Silica/iron-based zeolites are more durable than silica/alumina-based zeolites because they are less susceptible to nitrogen poisoning. Furthermore, since active metals can be supported without changing the amount of acid, the hydrogenation ability of nickel and molybdenum remains almost the same.

(Structure of the Invention) That is, the present invention is a heavy oil reforming catalyst characterized in that the entire carrier is a mixture of iron-containing zeolite and T-alumina.

The iron-containing zeolite referred to in the present invention is 81 of the crystal lattice points.
It is a crystalline metallosilicate in which a part of f is substituted with Fe.

The mixing ratio of iron-containing zeolite and r-alumina is iron-containing zeolite:T-alumina: 20-70wt = 30-8
It is in the range of 0 wt. Iron-containing zeolite is 20
When the wt is below 4, the pour point depressing ability is lost, 7 Ow
This is because denitrification and desulfurization activities deteriorate when the amount exceeds t.

The catalyst components that can be supported on a mixture carrier of iron-containing zeolite and γ-alumina include Ni, Co, Mo,
W, loading amount on carrier FiN10: 3-10w
T person, C00;! 1 to 10 chi.

MOO Hatake: 10-30 wt%, won; 10
~30wt person.

Hereinafter, the characteristics of the catalyst of the present invention will be explained in detail with reference to Examples.

[Example-1] The method for preparing catalyst 1 is described below.

6462 Fe04-6 H2O and 294f MaOB
, i 55 B'r dissolved in distilled water (H 0'). Next, a mixture of colloidal silica 1530f (solid content 20 wt%) and distilled water 600f is added to the above solution while stirring (preparation ratio Sio, /Fe!03 =
40').

Further, 290 t' of tetra-n-propylambromide (TPABr) ft was added, and the mixture was placed in an autoclave and sealed. Zeolite was hydrothermally synthesized while keeping the autoclave at 160° C. and stirring. After 3 days, the autoclave was opened and the contents were heated. The recovered crystalline material was washed with a large amount of water and dried at 120°C. The iX-ray diffraction pattern of this dry substance was identified as ZEIM-5.
It was confirmed that it is a type of crystalline substance. Furthermore, this zeolite li was calcined at 500°C for 3'hr.

Zeorai)? For ion exchange to H type, 5N NH
The zeolite was immersed in 1 t of an aqueous solution of 4O, and stirred at 60° C. for 5 hours. After performing the above ion exchange several times, the zeolite was washed and filtered, dried at 120°C for 10 hours, and calcined at 500°C for 3 hours.

Next, the zeolite prepared above) 36ft alumina sol 5
bot (solid content 10 it%) and mixed. An equal amount of ammonium hydroxide is added to this mixture to obtain a mixed gel. The obtained gel is dried at 120° C. for 18 hours and calcined at 500 t for 3 hours to obtain a carrier for catalyst 1.

The above catalyst carrier 30tf, distilled water 20dK5,8?
(7) Impregnation using a solution containing 1.640 f of N1 (NO3). Furthermore, 7.39 (
Impregnated using a solution dissolved in NH4)6M07024.4 Ego'. After impregnating, it was dried at 120C for 10 hours and fired at 500C for 3 hours.

Catalyst 1 prepared in this manner is a catalyst in which active metals NiO and Mo01 are supported at 5 wt% and 1/iwt%, respectively, on a mixed carrier of zeolite and alumina.

Using this Catalyst 1, a hydrogenation reaction was carried out on the feedstock oil (Sierre oil) shown in Table 1 below under the hydrogenation conditions shown in Table 2.

The results are also shown in Table 1.

Table 1 Table 2 [Example 2] The preparation method of catalyst 2 was the same as that of catalyst 1 prepared in Example 1 except that the amount of FeCl2.6H20 charged during hydrothermal synthesis of zeolite 11 was 32.3f. This is the same method as .

The charging composition ratio of slo/1reos of this zeolite is 80.

Using these two catalysts, a hydrogenation reaction was carried out under the same hydrogenation conditions as in Example 1 with the raw material oil, and as a result, the hydrogenated oil shown in Table 3 was obtained.

Table 3 [Example 3] Catalyst 3 was also prepared in the same manner as Catalyst 1 prepared in Example 1. The characteristics of catalyst 3 are that the amount of Fθa4・isH,0 charged amount of zeolite that forms the catalyst carrier is 1142f;
The point is that the SiO,/Fe, Os charging composition ratio was set to 160.

Using 3 tons of this catalyst, a hydrogenation reaction was carried out under the same hydrogenation conditions as in Example 1 with the raw material oil, and as a result, the hydrogenated oil shown in Table 4 was obtained.

Table 4 As shown above, when the hydrogenated oil treated with the three types of catalysts is used as a total fuel oil, S and 11, which cause pollution problems, are almost completely removed. Furthermore, the pour point is -5℃ or less, which is 55℃ compared to raw oil.
Less reduced, pipeline transportation of oil has become significantly easier.

[Comparative example]

Normally used γ-A403 with n1o (5%) and M
Hydrogenation tests of sierre oil with a conventional catalyst supported on OO, (16%) 1 were carried out. Its performance is shown in Table 5. However, the hydrogenation reaction conditions depend on Table-2.

Table 5 From the comparison between Table 1.3.4 and Table 5, the three types of catalysts of the present invention are:
It can be seen that the catalyst exhibits the same performance as conventional catalysts in terms of denitrification and desulfurization activities, and also has a dewaxing activity that lowers the pour point of heavy oil.

In addition, a durability test was conducted for Catalyst 1 for 1000 hours under the same conditions as shown in Table 2, by continuously supplying the raw material oil. As a result, it was confirmed that there was almost no change from the initial stage in the deodorization activity, desulfurization activity, and pour point depressing activity.

Examples of the above? , 2.3 and the comparative examples, it is clear that the catalyst of the present invention is a durable reforming catalyst that has pour point lowering activity compared to conventional reforming catalysts for heavy oil.

Among the sub-agents: 1) Akira Sub-agent Ryo Hagi Hara -

Claims (1)

[Claims] A heavy oil reforming catalyst characterized in that the entire carrier is a mixture of iron-containing zeolite and γ-alumina.