JPH03278839A - Preparation of hydrotreating catalyst composition for hydrocarbon oil - Google Patents

Abstract

PURPOSE:To obtain a hydrotreating catalyst for hydrocarbon oil having high desulfurization activity by compounding a base material selected from zinc, cobalt and nickel compounds with alumina as the second component and subsequently supporting the first catalytically active component on the obtained compound. CONSTITUTION:An alumina gel and an aqueous solution of a compound selected from zinc, cobalt and nickel compounds are kneaded and the kneaded mixture is molded, dried and baked to form a metal oxide composite. Thereafter, a hydrogenating active component of a metal of the Group 6B of the Periodic Table such as molybdenum or a metal of the Group 8 such as nickel is supported on the composite. By this method, the active component can be supported with remarkably high dispersibility by the affinity of the hydrogenating active component and the second component. Therefore, a catalyst having high desulfurization activity is formed.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to the production of a catalyst composition used for hydrocarbon oil residues and advanced hydrotreating of hydrocarbon oil residues, particularly hydrodesulfurization treatment. Regarding the method. More specifically, for example, a composite carrier of a metal oxide having a high specific surface area is obtained by kneading and calcining alumina gel and an aqueous solution of a zinc, cobalt or nickel compound, and a step of supporting a hydrogenation active component on this is carried out. The present invention relates to a method for producing a catalyst composition for hydrotreating hydrocarbon oil.

[Conventional technology]

Hydrocarbon oils generally contain sulfur compounds, and when these hydrocarbon oils are used as fuel, the sulfur in the sulfur compounds is converted to sulfur oxides and discharged into the atmosphere.

Therefore, in order to suppress air pollution caused by sulfur oxides as much as possible when these hydrocarbon oils are burned, it is necessary to reduce the sulfur content of the hydrocarbon oils in advance.

This reduction in sulfur content can be achieved by catalytic hydrodesulfurization of hydrocarbon oils.

Nowadays, environmental problems such as acid rain and nitrogen oxides are being taken up on a global scale, and there is a desire to remove sulfur at a level higher than the current level of technology.

In order to further reduce the sulfur content in hydrocarbon oil, it can be achieved to some extent by making the operating conditions of the above-mentioned catalytic hydrodesulfurization process for hydrocarbon oil more severe, such as LH3V, temperature, and pressure.

However, in such a method, carbonaceous matter is deposited on the catalyst, reducing the activity of the catalyst. In particular, when the hydrocarbon oil is a light distillate, there may be adverse effects on properties such as hue stability and storage stability.

Thus, there is a limit to how deep desulfurization can be achieved by controlling operating conditions.

Therefore, the best strategy is to develop catalysts with significantly better desulfurization activity.

By the way, conventionally, as a general method for producing a hydrodesulfurization catalyst, a so-called "impregnation method" is used in which a carrier is impregnated with an aqueous solution of a Group 6B metal salt and a Group 8 metal salt of the periodic table, and then dried and calcined. ", "co-precipitation method" in which a metal compound is precipitated by adding an aqueous solution of a group 6B metal salt of the periodic table and an aqueous solution of a group 8 metal salt to an aqueous solution in which alumina or alumina gel is dispersed; alumina or alumina gel; There is a ``kneading method'' in which water is removed by heating a mixed paste of an aqueous solution of a Group 6B metal salt of the periodic table and an aqueous solution of a Group 8 metal salt (``Catalyst Preparation Chemistry'').

(Reference: Rei Ozaki, ed., Kodansha Inc., pp. 250-252).

Here, alumina is most commonly used as the alumina carrier. The alumina can be produced by mixing aqueous solutions of aluminum sulfate and sodium aluminate, adjusting the pH, aging the mixture, and producing a precipitate of aluminum hydroxide (J, 8, Leimis,
J, pp1. che floor, 8.223 (1958))
.

A method in which aluminum metal is dissolved in an aqueous aluminum chloride solution to produce a basic aluminum chloride hydrogel (Universal Oil Products, Japanese Patent Publication No. 1977-1977), an aluminum sulfate solution is neutralized in a calcium carbonate solution, and a basic aluminum chloride hydrogel is obtained. Method for producing and obtaining a colloidal solution of aluminum (Mizusawa)
Kagaku Kogyo, USP3.183,19
4 (1965)) etc. have been reported.

Also, alumina is less common, but silica.

Alumina-silica in which titania, boria, etc. are combined with alumina Alumina-titania, alumina boria, etc. may also be used as carriers.

As a method for producing this alumina-silica carrier, a method has been reported such as a method in which a silica hydrogel obtained from a sodium silicate solution and an alumina gel obtained from an aluminum nitrate solution are mixed (Japanese Patent Publication No. 55-44795).

Further, an alumina-titania-alumina-boria support can also be produced by a similar method.

A catalyst in which a metal active component is supported on a carrier produced by such a method is widely used as a hydrodesulfurization catalyst for hydrocarbon oil.

[Problem to be solved by the invention]

However, with the above-mentioned conventional manufacturing techniques, it is not possible to obtain a catalyst having a higher activity than the current level, as environmental issues are being taken up on a global scale these days.

By the way, in order to increase the desulfurization activity of a catalyst for hydrodesulfurization of hydrocarbon oil, it is necessary to use a carrier having a high specific surface area and to highly disperse active metals therein.

For this purpose, the properties of the carrier portion on which the active metal is supported are extremely important, and it is necessary to manufacture a carrier that can further improve the dispersibility of the active metal than the carrier obtained by the prior art described above.

Therefore, the problem to be solved by the present invention is to develop a catalyst composition for hydrotreating hydrocarbon oil rivers, which can support a large amount of hydrodesulfurization active metal in a highly dispersed manner and, as a result, can increase desulfurization activity. The goal is to develop manufacturing methods.

[Means to solve the problem]

In order to solve the above problems, the inventors of the present invention conducted extensive research, and as a result, first of all, zinc and cobalt were added to alumina, which are normally used in this type of catalyst carrier.

By blending one or more base materials selected from nickel compounds as the second component of the carrier using a specific method, and then supporting the catalytically active component on this, the catalytically active component is The present inventors have discovered that a high degree of dispersion is possible, and have completed the present invention.

That is, the present invention involves kneading (A) alumina gel and (B) an aqueous solution of at least one of zinc, cobalt, or nickel compounds, molding, drying, and firing to obtain a metal oxide composite; Thereafter, the hydrocarbon oil hydrotreating catalyst is characterized in that at least one hydrogenation active component selected from group 6B metals of the periodic table and at least one hydrogenation active component selected from group 8 metals is supported. The gist is a method for producing the composition.

Alumina gel, which is a precursor of alumina and is the first component of the carrier used in the method of the present invention, can be obtained by neutralizing an aluminum salt such as aluminum sulfate with a base such as ammonium, or by neutralizing an alumina gel such as sodium aluminate with a base such as ammonium. It can be obtained by neutralizing the salt with an acidic aluminum salt or an acid, and thoroughly washing the resulting gel with aqueous ammonia or the like.

On the other hand, zinc and cobalt are the second components of the carrier.

Alternatively, the nickel oxide precursor may be an industrially available aqueous solution or hydroxide of nitrate, sulfate, chloride, etc., and the raw material is not specified.

The amount of this second component is about 0. 5-0.8% by weight, preferably about 1.0-5
．． It is 0% by weight.

In the method of the present invention, the alumina gel obtained as described above and an aqueous solution or hydroxide of at least one of zinc, cobalt or nickel compounds are placed in a kneader and thoroughly kneaded. do.

The mixing conditions are not particularly limited, but preferably kneading at about 40 to 80°C for about 3 to 6 hours is suitable.

During the kneading stage, the moisture content is adjusted to the extent that extrusion molding is possible.

After kneading, the catalyst is molded using an extrusion molding machine to the required catalyst diameter, dried, and heated at about 350 to 600°C, preferably about 400 to 550°C, for about 3 hours or more, preferably about 12 to 24°C. A carrier is obtained by firing for a period of time.

The carrier is generally prepared by methods well known in the art, such as extruding a precursor of the desired carrier through a die having openings of the desired size and shape, and then cutting the precursor to the desired length. As a result, shaped particles are obtained.

As the active component supported on the above-mentioned carrier, various metals commonly used as catalysts for hydrodesulfurization can be used. At least one metal selected from Group 6B and Group 8 metals of the periodic table is mainly used, particularly molybdenum and tungsten.

Cobalt nickel is preferred.

The method for supporting Group 6B and Group 8 metals on the above-mentioned carrier can also be carried out by a conventional method.

For example, the carrier may be immersed in a solution containing these hydrogenation-active metal components, the carrier may be mixed with this solution, the solution may be dropped onto the carrier, or hydrogenation may be carried out while the carrier is immersed in the solution. A method of supporting a hydrogenation-active metal component on a carrier by bringing the support into contact with a solution containing the hydrogenation-active metal component, such as adding a precipitant for the active metal component and depositing the hydrogenation-active metal component on the support. can be adopted.

Furthermore, the order of carrying Group 6B and Group 8 of the periodic table may be either first or at the same time.

Examples of molybdenum compounds that can be used as solutions of Group 6B metals of the periodic table include ammonium paramolybdate, molybdic acid, ammonium molybdate, and ammonium phosphomolybdate.

Examples of nickel compounds that can be used as solutions for Group 8 metals in the periodic table include phosphomolybdic acid, etc.
Nickel nitrates, sulfates, fluorides, chlorides, bromides, acetates, carbonates, phosphates, etc. Besides this,
Compounds of metals from Groups 6B and 8 of the Periodic Table known to those skilled in the art as being available in this field may be used.

After carrying out the treatment of supporting the active ingredient on the carrier as described above, it is preferable to carry out drying, calcination, etc. by a conventional method.

Drying is usually done at room temperature to about 150" C1, especially about 100"
It is preferable to hold the temperature at ~120°C for about 5 hours or more, especially about 12 to 24 hours, and the firing is usually carried out at about 350 to 60 °C.
Preferably, the temperature is maintained at 0°C, especially about 400-550''C, for about 3 hours or more, especially about 12-24 hours.

The catalyst obtained by the method of the present invention is usually about 7 to 25% by weight, preferably about 10% by weight, calculated as oxide, based on the catalyst.
It contains ~20% by weight Group 6B metal and about 3-6% by weight, preferably about 3-5% by weight Group 8 metal. It is considered that most of these hydrogenation-active metal components become oxides and some become simple elements in the above-mentioned fired catalyst.

When the catalyst obtained by the method of the present invention is used in the form of a sulfide, the catalyst is presulfurized.

As the sulfiding method, a method is employed in which hydrocarbon oil or gas phase sulfide containing about 1.0% by weight or more of sulfur is passed over the catalyst at high temperature and high pressure.

Hydrocarbon oils to which the catalyst obtained by the method of the present invention can be applied include atmospheric distillate oils and residues of crude oil, vacuum distillate oils and residues, visbreaking oils, tar sand oils, shale oils, etc. can be mentioned.

In particular, the catalyst obtained by the method of the present invention is suitable for hydrogenation of medium distillate oils such as kerosene fractions and gas oil fractions, heavy distillate oils from vacuum distillation, asphalt-containing residual oils, or mixtures thereof. It is suitable for carrying out chemical treatment.

Further, the conditions for hydrogenating hydrocarbon oil using the catalyst obtained by the method of the present invention are a temperature of about 200 to 450°C and a pressure of about 10°C.
~200Kg/cm2. LH3V (liquid hourly velocity) approximately 0.
It is preferable to set it as 1-5,0 Hr-'.

[Effect]

In the method of the present invention, unlike conventional methods such as impregnating and supporting an active ingredient on an alumina carrier or co-precipitating the active ingredient, the method of the present invention uses a part of the active ingredients such as zinc, cobalt, and nickel as the second component of the carrier in advance. The mixture is sufficiently kneaded to be uniformly mixed with alumina, which is the main component of the carrier, and fired.

Next, the sixth component is added to the carrier containing the second component in a uniform state.
An active component for hydrotreating consisting of Group B and Group 8 metals is supported.

Then, the Group 6B and Group 8 metals are supported on the above-mentioned carrier with a high degree of dispersion. Although the reason for this is not necessarily clear, it is presumed that it is due to the affinity of the second component with the Group 6B and Group 8 metals.

The catalyst according to the present invention, which supports active ingredients in a highly dispersed state, realizes extremely highly efficient hydrogenation of hydrocarbon oils and meets global demands. A responsive highly desulfurized fuel product can be provided.

In addition, "hydrotreatment" in the present invention refers to treatment by contacting hydrocarbon oil with hydrogen, and includes hydrorefining with relatively low severity of reaction conditions, and some decomposition reactions with relatively high severity of reaction conditions. This includes hydrorefining, hydroisomerization, hydrodealkylation, and other reactions of hydrocarbon oils in the presence of hydrogen.

Examples include hydrodesulfurization of distillates and residual oils of atmospheric distillation or vacuum distillation, hydrogenated membrane nitrogen, hydrocracking, and hydrorefining of kerosene fractions, gas oil fractions, waxes, and lubricating oil fractions. etc.

〔Example〕

Hereinafter, the present invention will be explained in more detail using Examples and Comparative Examples.

Example 1 (Preparation process of alumina gel and second component) In 50f of ion-exchanged water, 29.8Kg of sodium aluminate solution (containing about 23% as A j2203) and 38.
0 kg of aluminum sulfate solution (containing about 7.9% as Affi20:l) was slowly added dropwise. At this time,
The pH of the solution was maintained between 8 and 9. Finally, the remaining sodium aluminate solution was added to bring the final pH of the solution to 11.

Pass the alumina slurry produced by the above operations,
The separated precipitate (alumina gel) is first washed repeatedly with water to which the pH has been adjusted to 9 by adding ammonia, and then repeatedly washed again with water to which the pH has been adjusted to 6 by adding nitric acid. I got it.

On the other hand, 3.5! The second component was prepared by dissolving 950 g of zinc nitrate in ion-exchanged water.

(Kneading Step) The above alumina gel and zinc nitrate aqueous solution were placed in a kneader and kneaded for 3 hours.

Thereafter, the inside of this kneader was heated to 70° C., and the humidity was adjusted so that the moisture content was sufficient for extrusion molding.

This was extruded and molded using an extrusion molding machine to match the required catalyst diameter.

This extruded product was dried at 120°C for a day and night, and then baked at 550°C for 12 hours.

The specific surface area of the carrier obtained by the above operation is 303 m”/
It was g.

(Active ingredient supporting step) First, 2800 ml of ammonia aqueous solution was prepared, and 1252 g of ammonium rosemolybdate was added and dissolved therein. Further, 785 g of nickel nitrate was added thereto. There was no precipitate in this solution.

The solution thus prepared was carefully dropped onto 5 kg of the catalyst carrier prepared in the above-mentioned kneading process.

After dropping all the solutions, let stand for 3 hours, then 120
Dry at °C for 12 hours. Finally, catalyst A was obtained by calcining at 500°C for 12 hours. Catalyst A contained 5% by weight of nickel oxide, 17% by weight of molybdenum oxide, and 3% by weight of zinc oxide.

Example 2 (Process for preparing alumina gel and second component) Alumina gel was prepared in the same manner as for catalyst A in Example 1.

On the other hand, 3.51! The second component was prepared by dissolving 317 g of cobalt nitrate in ion-exchanged water.

(Kneading Step) The above alumina gel and cobalt nitrate aqueous solution were placed in a kneader and kneaded for 3 hours.

Thereafter, the inside of this kneader was heated to 70° C., and the humidity was adjusted so that the moisture content was sufficient for extrusion molding.

This was extruded and molded using an extrusion molding machine to match the required catalyst diameter.

This extruded product was dried at 120°C for a day and night, and then baked at 550°C for 12 hours.

The specific surface area of the carrier obtained by the above operation is 291 m27
It was g.

(Active component supporting step) Catalyst B was obtained by supporting an active component in the same manner as catalyst A in Example 1. This catalyst B contained 5% by weight of nickel oxide, 17% by weight of molybdenum oxide, It contained 1% by weight of cobalt oxide.

Example 3 (Process for preparing alumina gel and second component) Alumina gel was prepared in the same manner as for catalyst A in Example 1.

On the other hand, 3.5I! The second component was prepared by dissolving 317 g of nickel nitrate in ion-exchanged water.

(Kneading Step) The above alumina gel and nickel nitrate aqueous solution were placed in a kneader and kneaded for 3 hours.

Thereafter, the inside of this kneader was heated to 70° C., and the humidity was adjusted so that the moisture content was sufficient for extrusion molding.

This was extruded and molded using an extrusion molding machine to match the required catalyst diameter.

This extruded product was dried at 120"C overnight,
Then, it was baked at 550°C for 12 hours.

The specific surface area of the carrier obtained by the above operation is 295 m27
It was g.

(Active component supporting step) An active component was supported in the same manner as catalyst A in Example 1 to obtain catalyst C. This catalyst C contained 6% by weight of nickel oxide and 17% by weight of molybdenum oxide. It was

Comparative Example 1 Alumina gel was prepared in the same manner as for Catalyst A in Example 1.

This alumina gel and 3.5 g of ion-exchanged water were put into a kneader and kneaded for 3 hours.

Thereafter, the inside of this kneader was heated to 70° C., and the humidity was adjusted so that the moisture content was sufficient for extrusion molding.

This was extruded and molded using an extrusion molding machine to match the required catalyst diameter.

This extruded product was dried at 120°C for a day and night, and then baked at 550°C for 12 hours.

An active ingredient was supported on the carrier obtained by the above operation in the same manner as the catalyst of Example 1 to obtain a catalyst.

This catalyst contained 5% by weight of nickel oxide and 7% by weight of molybdenum oxide.

Comparative Example 2 1 kg of the catalyst of Comparative Example 1 was collected, and 72 kg of zinc nitrate was added to it.
．． A solution of 1 g dissolved in 550 rnl of ion-exchanged water was carefully added dropwise.

After dropping all the solutions, let stand for 3 hours, then 120
Dry at °C for 12 hours.

Finally, catalyst E was obtained by calcining at 500''C for 12 hours.

This catalyst E contained 5% by weight of nickel oxide, 16% by weight of molybdenum oxide, and 3% by weight of zinc oxide.

Catalyst A obtained in Examples 1 to 3 and Comparative Example 1.2 above
-E was evaluated in a hydrodesulfurization relative activity evaluation test under the following conditions.

Arabian light gas oil (AL-LGO), J pressure gas oil (A
L-VCO) or Arabian Heavy Atmospheric Residual Oil (AH
-AR) with an inner diameter of 10 mmφ
10 days (conditions 1) and 2 days using fixed bed reaction tubes.
Day 0 (condition 2).

Day 25 (Condition 3) (At the beginning of the reaction, the sulfur content of the product is low, but it increases and stabilizes as the days pass, so
Day 0 and Day 25 were designated as days. ) The initial relative desulfurization activity obtained from the residual sulfur content (wt%) of the reaction product was determined.

The properties and reaction conditions of the feedstock oil are shown in Table 1, and the results are shown in Table 2 (light gas oil), Table 3 (vacuum gas oil), and Table 4 (atmospheric residual oil).

Table 2 Note 1) The desulfurization reaction rate constant of No. 4 (Catalyst D) is 10
Relative value expressed as 0. Values in parentheses indicate produced oil sulfur concentration (wt%)
).

As is clear from Table 2, all of the catalysts A to C produced in Examples 1 to 3 had better desulfurization activity for light gas oil than catalysts E and E produced in Comparative Examples 1 and 2. It can be seen that the results are excellent.

Table Note 2) The desulfurization reaction rate constant of No. 9 (Catalyst D) was set to 100.
Relative value expressed in . Values in parentheses are produced oil sulfur concentration (wt%)
.

Generally, it is believed that the heavier the feedstock oil is, the smaller the difference in initial relative desulfurization activity values due to differences in catalyst components, etc. However, as is clear from Table 3, there is a difference in initial relative desulfurization activity values between catalysts A-C manufactured in Examples 1 to 3 of the present invention and catalyst DE manufactured in Comparative Example 1.2. It can be seen that Catalysts A to C produced in the present invention all showed superior results in the desulfurization activity of vacuum gas oil compared to Catalysts A and E produced in Comparative Examples.

Table 4 Note 3) The desulfurization reaction rate constant of No. 12 (Catalyst D) was set to 10
Relative value expressed as 0. Values in parentheses indicate produced oil sulfur concentration (wt%)
).

As is clear from Table 4, Catalyst A manufactured in Example 1 shows superior results in the desulfurization activity of atmospheric residual oil compared to the catalyst manufactured in Comparative Example 1. I understand.

〔Effect of the invention〕

In the method of the present invention, some of the active ingredients zinc, cobalt, and nickel are used as the second component of the carrier, and a so-called composite carrier prepared by uniformly kneading them into alumina, which is the main component of the carrier, is used for hydrogenation treatment. Because it goes through a step of supporting the active ingredient, the affinity between the active ingredient for hydrotreating and the above-mentioned second component allows the catalyst to support the active ingredient with dramatically higher dispersibility than catalysts using conventional methods. can be obtained.

Therefore, the catalyst obtained by the method of the present invention exhibits significantly higher desulfurization activity for both petroleum fractions and residual bone stock oils than catalysts produced by conventional methods. It has a remarkable effect on raw materials.

Patent distributor Cosmo Research Institute Co., Ltd. Cosmo Oil Co., Ltd.

Claims (1)

[Claims] (A) alumina gel and (B) an aqueous solution of at least one of zinc, cobalt, or nickel compounds are kneaded, molded, dried, and fired to obtain a metal oxide composite, and then,
A hydrotreating catalyst composition for hydrocarbon oil, characterized in that it supports at least one hydrogenation active component selected from group 6B metals of the periodic table and at least one hydrogenation active component selected from group 8 metals. How things are manufactured.