JP3332163B2 - Method for producing catalyst for hydrorefining treatment and its carrier - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for hydrorefining treatment for desulfurization and denitrification of petroleum, coal liquefied oil, shale oil and the like, especially heavy oil thereof, and a method for producing a carrier thereof. About.

[0002]

2. Description of the Related Art As catalysts for hydrorefining treatment, Group VI metals (Mo, W) and Group VIII metals (Co, N
Those carrying i) are widely used. In order to improve the strength of such a catalyst, a method of supporting titanium on an alumina carrier (Japanese Patent Publication No. 57-40088), and titania on an alumina carrier for the purpose of improving the denitrification activity and the abrasion resistance of the catalyst. (JP-A-54-8)
No. 1187, Japanese Patent Publication No. 54-19491) have been proposed. However, these catalysts have not been satisfactory in terms of desulfurization activity and the like.

The inventor of the present invention has conducted intensive studies in order to solve the above problems. As a result, the alumina in the alumina titania hydrate obtained by coprecipitation of aluminum ions and titanium ions has a substantially pseudo-boehmite structure. It has been found that the desulfurization activity can be increased as long as it has the following.

[0004]

SUMMARY OF THE INVENTION The present invention has been made based on the above findings, and an object of the present invention is to provide a catalyst for hydrorefining treatment having high desulfurization activity using alumina titania and a carrier thereof. .

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for preparing a mixture of an aluminum-containing solution having a concentration of 0.1 to 10% by weight as aluminum ions and a titanium-containing solution having a concentration of 0.1 to 10% by weight as titanium ions. Is mixed and stirred so as to be 6 to 7 to obtain an alumina titania hydrate having an X-ray diffraction peak due to bayerite weaker than an X-ray diffraction peak due to pseudoboehmite, which is calcined to obtain 5 to 40% by weight of titania. A method for producing a catalyst carrier for hydrorefining treatment, characterized by obtaining alumina titania containing the same, and a method for producing a catalyst for hydrotreating wherein the carrier carries a Group VI metal and a Group VIII metal It is.

[0006] The coprecipitation of aluminum ion and titanium ion of the present invention is carried out by mixing an aluminum ion-containing liquid and a titanium-containing liquid and adjusting the pH. In this case, as the aluminum ion-containing liquid, sodium aluminate, aluminum sulfate,
It is preferable to use an aqueous solution of an aluminum compound such as aluminum nitrate or aluminum chloride. This solution has a concentration of 0.1 to 10% by weight as aluminum ions, depending on the solubility of the aluminum compound. Further, as the titanium ion-containing liquid, it is preferable to use an aqueous solution of a titanium compound such as titanium tetrachloride, titanium trichloride, titanium sulfate, and titanium nitrate. This solution has a titanium ion concentration of 0.1 to 10% by weight, depending on the solubility of the titanium compound. The aluminum ion-containing liquid and the titanium-containing liquid are mixed, and if necessary, an acid such as nitric acid, hydrochloric acid, sulfuric acid or the like, or an alkali such as caustic soda or aqueous ammonia can be added for coprecipitation. The mixing ratio of the aluminum ion-containing liquid and the titanium-containing liquid is adjusted such that the content of the hydrate obtained by coprecipitation is 5 to 40% by weight as titania when used as a carrier after drying and firing. I do.

The above-mentioned coprecipitate is dewatered, kneaded and molded as required, and is dried at a temperature of 80 to 150 ° C. for 0.1 to 20 minutes.
After drying for a period of time, a hydrate of alumina titania is obtained. The alumina in the hydrate at this time is substantially pseudo-boehmite, and the content of bayerite needs to be 10% by weight or less. This pseudo-boehmite can be measured by X-ray diffraction analysis of a hydrate of alumina titania, and 2θ
Thus, relatively broad diffraction peaks can be seen at angles of 14.5 °, 28.2 °, 38.4 °, and 49.0 °.
Bayerite is 2θ, 18.8 °, 20.3 °,
Relatively sharp diffraction peaks are observed at angles of 27.8 °, 40.5 ° and 53.1 °. The term "substantially boehmite" as used in the present invention means that the content of bayerite is 10% by weight or less.
In the X-ray diffraction analysis under the measurement conditions of 0 KV, only the pseudo-boehmite peak was observed, and no broad peak of bayerite was present. Under these conditions, the detection limit of bayerite in X-ray diffraction analysis is 10% by weight.

[0008] One method of reducing the content of bayerite to 10% by weight or less in this substantially pseudo-boehmite is to rapidly mix a solution containing aluminum ions, a solution containing titanium ions and an acid or alkali solution required for neutralization, and stir. It is obtained by doing. Although the reason is not known, those prepared by such a method have 10% or less of bayerite, and the activity of the finally obtained catalyst is particularly excellent. When these solutions are mixed, if the solution is heated to 40 to 80 ° C., a low content of bayerite can be obtained.

The hydrate obtained as described above is 40
By calcining at a temperature of 0 to 800 ° C. for 0.1 to 20 hours, a catalyst carrier can be obtained. The titania in the catalyst carrier is 5 to 40% by weight. Below 5% by weight,
No sufficient effect of improving desulfurization activity was found, and 40% by weight
If it becomes above, not only a desulfurization activity but the mechanical strength of a catalyst will fall.

[0010] Such a carrier of the present invention may contain a Group VI metal (M
By supporting o, W) and Group VIII metals (Co, Ni), etc., a catalyst for hydrorefining treatment can be obtained.

[0011]

[Example] (Reference example) 700 g of sodium aluminate was added to 2
Dissolved in 0 l of water to make solution A, 64.6 g of titanium tetrachloride
Was dissolved in 1.3 liters of water, and 16.6 liter of a 1% by weight aqueous hydrochloric acid solution was added thereto to obtain a solution B.

2 liters of water heated to 60 ° C. was placed in a container, and while vigorously stirring, the above solution A and solution B heated to 60 ° C. were added simultaneously for about 10 seconds and stirred for 60 minutes. The pH when stirring was stopped was 10.5. After leaving this hydrogel slurry overnight, it was filtered, and the obtained solid was washed with water until no sodium ion or chloride ion was observed, and concentrated at 130 ° C. This was kneaded in a kneader for 90 minutes, and then extruded with a 1.8 mm hole die. This molded product was dried in a dryer at a temperature of 130 ° C. overnight to obtain an alumina titania hydrate. X-ray diffraction analysis was performed on this hydrate, and the results are shown in Table 1.
Next, this alumina titania hydrate was fired at a temperature of 600 ° C. for 1 hour to obtain a carrier. The composition and pore characteristics of this carrier were measured. The specific surface area, the pore volume, and the median diameter (pore diameter at which the pore volume becomes 50%) of the pore characteristics were measured using a Digisorp 2500 measuring instrument (manufactured by Micromeritics Co., Ltd.) by a nitrogen adsorption method.

An aqueous solution containing 34.0 g of ammonium heptamolybdate and 27.4 g of cobalt nitrate was impregnated and supported on 150 g of the above-mentioned carrier with 10% by weight of molybdenum as a metal and 3% by weight of cobalt as a metal. After drying this support at 130 ° C. overnight, it was calcined at 500 ° C. for 1 hour to obtain a catalyst.

Example A solution A similar to the reference example was prepared. 64.6 g of titanium tetrachloride was dissolved in 1.3 l of water to obtain solution C.

2 liters of water was heated to 60 ° C., and while stirring vigorously, the solution A heated to 60 ° C. was added thereto at about 800 ml / mi.
n, Solution C, which was also heated to 60 ° C., was simultaneously added at a flow rate of about 52 ml / min, and a 3.3% hydrochloric acid aqueous solution was charged therein so that the pH of the titania-alumina hydrogel slurry formed always became 6. Was adjusted. The time required for charging all of the liquids A and C was 24 minutes. Thereafter, the mixture was stirred for 60 minutes. When the stirring was stopped, the pH of the titania-alumina hydrogel slurry was 5.9. After the hydrogel slurry thus obtained was left overnight, the same treatment as in Reference Example was successively performed to obtain a titania-alumina hydrate and further a titania-alumina carrier. Table 1 shows the results of X-ray diffraction measurement of the titania-alumina hydrate, and the composition and pore characteristics of the titania-alumina carrier.

In the titania-alumina carrier, 10% by weight of molybdenum and 3% by weight of cobalt were used in the same manner as in Reference Example.
Supported to prepare a catalyst.

(Comparative Example 1) A liquid A and a liquid C similar to those in the example were prepared.

2 liters of water was heated to 60 ° C., and while stirring vigorously, about 800 ml / m of solution A heated to 60 ° C. was added thereto.
In, a solution C, which was also heated to 60 ° C., was simultaneously added at a flow rate of about 52 ml / min, and a pH of a titania-alumina hydrogel slurry formed by charging a 3.3% hydrochloric acid aqueous solution was further added.
Was always 9.5 to 10.5. The time required for charging all of the liquids A and C was 25 minutes. Thereafter, the mixture was stirred for 60 minutes. When the stirring was stopped, the pH of the titania-alumina hydrogel slurry was 9.8. After leaving the hydrogel slurry thus obtained overnight, the same treatment as in Reference Example was performed sequentially, and titania-alumina hydrate,
Further, a titania-alumina carrier was obtained. This titania-
X-ray diffraction measurement results and titania of alumina hydrate
Table 1 shows the composition and pore characteristics of the alumina carrier.

In the titania-alumina carrier, 10% by weight of molybdenum and 3% by weight of cobalt were used in the same manner as in Reference Example.
Supported to prepare a catalyst.

(Comparative Example 2) A liquid A and a liquid C similar to those in the example were prepared.

2 liters of water was poured in, and the mixture was heated to 60 ° C. While stirring vigorously, the solution A heated to 30 ° C was added thereto for about 80 hours.
0 ml / min, solution C was simultaneously added at a flow rate of about 52 ml / min,
Further, a 3.3% hydrochloric acid aqueous solution is charged, and the pH of the resulting titania-alumina hydrogel slurry is always 9.5 to 1
It was set to 0.5. The time required for charging all of the solution A and the solution C was 20 minutes. Thereafter, the mixture was stirred for 60 minutes. When the stirring was stopped, the pH of the titania-alumina hydrogel slurry was 10.2. After leaving the hydrogel slurry thus obtained to stand overnight, the same treatment as in Reference Example was performed to obtain a titania-alumina hydrate and a titania-alumina carrier in this order. Table 1 shows the X-ray diffraction measurement results, the composition, and the pore characteristics.

A 10% Mo-3% Co metal was supported on a titania-alumina carrier in the same manner as in the Reference Example to prepare a catalyst.

Example A liquid A was obtained in the same manner as in the reference example. 145.5 g of titanium tetrachloride was dissolved in 2.9 l of water to obtain solution D.

While heating 2 l of water to 60 ° C. and stirring vigorously, the solution A heated to 60 ° C. was added thereto at about 800 ml / mi.
n, Solution D, which was also heated to 60 ° C., was simultaneously added at a flow rate of about 116 ml / min, and a 3.3% hydrochloric acid aqueous solution was further charged, so that the pH of the resulting titania-alumina hydrogel slurry was always 7 The pH was adjusted to be as follows. The time required for charging all of the solution A and the solution D was 22 minutes.
Thereafter, the mixture was stirred for 60 minutes. The pH of the titania-alumina hydrogel slurry at the end of the stirring was 6.6. After leaving the hydrogel slurry thus obtained to stand overnight,
The same treatment as in the Reference Example was performed to obtain a titania-alumina hydrate and a titania-alumina carrier in this order. Table 1 shows the results of X-ray diffraction measurement, composition and pore characteristics of these titania-aluminas.

In the same manner as in Reference Example, a metal of 10% Mo-3% Co was supported on a titania-alumina carrier to obtain a catalyst.

Comparative Example 3 Liquid A was obtained in the same manner as in Comparative Example 2, and Liquid E was obtained in the same manner as in the Example.

While heating 2 liters of water to 30 ° C. and stirring vigorously, the solution A heated to 30 ° C. was added thereto at about 800 ml / mi.
n, Solution E, which was also heated to 30 ° C., was simultaneously added at a flow rate of about 116 ml / min, and 3.3% hydrochloric acid aqueous solution was further charged. The pH of the resulting titania-alumina hydrogel slurry was constantly 9.5. The pH was adjusted to be 〜１０10.5. The time required to charge all of solution A and solution E is 2
3 minutes. Thereafter, the mixture was stirred for 60 minutes. The pH of the titania-alumina hydrogel slurry when stirring was stopped was 10.1
Met. After leaving the hydrogel slurry thus obtained to stand overnight, the same treatment as in the reference example was carried out, and
-Alumina hydrate and titania-alumina carrier were obtained. Table 1 shows the results of X-ray diffraction measurement, composition and pore characteristics of these titania-aluminas.

A 10% Mo-3% Co metal was carried on a titania-alumina carrier in the same manner as in the Reference Example to prepare a catalyst.

[0029]

[Table 1]

(Catalytic activity test) In the above Examples and Comparative Examples
The hydrodesulfurization activity of the obtained catalyst was measured using a fixed bed flow type high pressure reactor.
Was evaluated using Properties and trials of feedstock oil used in experiments
The test conditions are shown below.Raw material properties  Oil type Vacuum gas oil Sulfur 2.16wt% Nitrogen 570wtppm Specific gravity 0.8974Test condition  Hydrogen pressure 80kg / cm^Two  LHSV 3.0hr^-1  Hydrogen / oil ratio 400l / l Reaction temperature 360 ℃

Table 2 shows the results of measuring the sulfur content in each of the obtained product oils and comparing the desulfurization rates together with the packing density of the catalyst.

[0032]

[Table 2]

The results show that the catalyst prepared from the titania-alumina carrier of the present invention has excellent desulfurization performance.

[0034]

According to the present invention, a catalyst excellent in desulfurization activity can be prepared.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B01J 21/00-38/74 C10G 45/04

Claims (2)

(57) [Claims] 1. An aluminum ion of 0.1 to 10
Are stirred together and the pH of the titanium-containing solution and a mixture of 0.1 to 10 wt% concentration as an aluminum-containing solution and titanium ions wt% concentration so as to 6-7, Ba
X-ray diffraction peak due to earlite due to pseudo-boehmite
Obtaining alumina titania hydrate weaker than the X-ray diffraction peak ,
A method for producing a catalyst carrier for hydrorefining treatment, comprising calcining this to obtain alumina titania containing 5 to 40% by weight of titania. 2. A catalyst for hydrorefining treatment according to claim 1.
Group VI metal and VIII
A method for producing a hydrotreating catalyst carrying a group III metal.