JPH0832308B2 - Process for producing hydrodesulfurization catalyst composition for hydrocarbon oil - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a hydrodesulfurization catalyst composition for hydrocarbon oil, and more specifically, zeolite and alumina, etc. which are ion-exchanged with a specific hydrogenation-active metal. The present invention relates to a method for producing a catalyst composition for hydrodesulfurization of hydrocarbon oil, which comprises mixing a certain amount of the above with a certain amount of the remaining amount of a specific hydrogenation active metal.

[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, it is necessary to reduce the sulfur content of the hydrocarbon oil in advance in order to suppress air pollution due to sulfur oxides when the hydrocarbon oil is burned.

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

In recent years, environmental problems such as acid rain and nitrogen oxides have been taken up on a global scale, and it has been desired to remove sulfur components at a level higher than the current technical level.

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

However, in such a method, carbonaceous matter is deposited on the catalyst to reduce the activity of the catalyst. In particular, when the hydrocarbon oil is a light fraction, there are adverse effects on properties such as hue stability and storage stability.

Thus, there is a limit to obtaining deep desulfurization by controlling operating conditions.

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

Conventionally, as a general method for producing a catalyst for hydrodesulfurization, a so-called "impregnation method" 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 , "Coprecipitation method" of precipitating a metal compound by adding an aqueous solution of Group 6B metal salt and an aqueous solution of Group 8 metal salt to an aqueous solution in which alumina or alumina gel is dispersed, alumina or alumina gel, periodic There is a "kneading method" in which a mixed paste of an aqueous solution of a Group 6B metal salt and an aqueous solution of a Group 8 metal salt is heated while kneading to remove water ("Catalyst preparation chemistry", edited by Ken Ozaki, Kodansha Saien). Tick, pp. 250-252).

Alumina is the most commonly used carrier for these.

Also, although not as much as alumina, silica, titania,
Alumina-silica in which boria etc. are combined with alumina,
Alumina-titania, alumina-boria, etc. are also used as the carrier, and further, alumina-zeolite in which alumina and zeolite are combined may be used as the carrier.

At present, a catalyst in which an active metal component is supported on the above carrier is widely used as a catalyst for hydrodesulfurization of hydrocarbon oil.

[Problems to be Solved by the Invention]

By the way, the catalyst produced by the method of supporting the hydrogenation active component on the above alumina-zeolite carrier is such that a relatively high molecular weight reactant is reacted in the alumina portion and a relatively low molecular weight reactant is reacted in the zeolite portion. By doing so, the desulfurization activity of the entire catalyst is improved.

However, when the hydrogenation active metal component is supported on the alumina-zeolite support, most of the active metal component is supported on the alumina portion due to the excellent reactivity between the active metal component and alumina.

As a result, the amount of the hydrogenation active metal component to be supported is limited as compared with the case where only alumina is used alone as a carrier in the whole carrier.

The problem to be solved by the present invention is to develop a production method capable of effectively utilizing the acidity characteristic of zeolite and obtaining a catalyst capable of containing a larger amount of hydrogenation active metal components as a whole catalyst. Especially.

[Means for solving the problem]

The present inventors have conducted extensive studies in order to solve the above problems, and as a result, among the hydrogenation active metal components, a zeolite ion-exchanged with nickel or cobalt metal ion of Group 8 metal of the periodic table in advance. A catalyst prepared by a method in which a mixture of alumina and alumina, etc. is prepared in advance, and the remaining amount of nickel or cobalt metal and Group 6B metal of the periodic table are supported on this mixture is hydrodesulfurization of hydrocarbon oil. It has been found that it is extremely effective for the above, and has completed the present invention.

That is, the present invention, the first step of mixing 5 to 60 parts by weight of zeolite ion-exchanged cobalt or nickel, and 40 to 95 parts by weight of alumina or alumina-containing material,
Cobalt or nickel and a second step of supporting a Group 6B metal of the periodic table are carried out, and the amount of cobalt or nickel to be ion-exchanged in the first step is 2 to 8% by weight based on the zeolite in terms of oxide. The total amount of nickel is 0.5 to 15% by weight of the catalyst in terms of oxide, and the amount of Group 6B metal of the periodic table is 2 to 30% by weight of the catalyst in terms of oxide. The gist is a method for producing a hydrodesulfurization catalyst composition.

The first step in the method of the present invention is a step of mixing about 5 to 60% by weight of the zeolite ion-exchanged with a specific amount of cobalt or nickel and about 40 to 95% by weight of alumina or an alumina-containing material.

The zeolite may be natural or synthetic, and examples thereof include faujasite X-type zeolite, faujasite Y-type zeolite (hereinafter referred to as “Y zeolite”), chapasite-type zeolite, and mordenite-type zeolite. , So-called ZSM-based zeolite containing an organic cation (as ZSM-based zeolite, ZSM-4, ZSM-5, Z
SM-8, ZSM-11, ZSM-12, ZSM-20, ZSM-21, ZSM-23, ZSM
-34, ZSM-35, ZSM-38, ZSM-43, etc.) and the like, and particularly Y zeolite, stabilized Y zeolite or
ZSM-5 and the like are preferred.

The atomic ratio Si / Al of silicon element to aluminum element in the zeolite is preferably about 1 or more.

Alkali metal ions such as sodium in zeolite lower the catalytic activity when the content is high, so it is usually preferable to set the content to about 0.5% by weight or less with respect to the zeolite.

The above Y zeolite or stabilized Y zeolite is
Known ones can be used.

Y zeolite has basically the same crystal structure as natural faujasite, and when expressed as an oxide, it can be expressed as the following composition formula.

_{0.7~1.1R 2 / m O.Al 2 O 3} · 3~5SiO 2 · 7~9H in ₂ O (wherein, R is Na, K, and other alkali metal ions or alkaline earth metal ion, m is Stabilized Y zeolite is described, for example, in US Pat. No. 3,293,19.
Those described in No. 2 and No. 3,402,996 are preferably used.

Stabilized Y zeolite shows remarkable resistance to deterioration of crystallinity by performing steam treatment at high temperature several times.

Stabilized Y zeolite has an R _{2 / m} O content of about 4% by weight.
Below, preferably about 1% by weight or less, the unit cell size is about
It is 24.5Å.

Stabilized Y zeolite means Y zeolite characterized by an Si / Al atomic ratio of about 3 to 7 or higher.

ZSM-5 is US Pat. Nos. 3,894,106 and 3,894,107.
No. 3,928,483, British Patent No. 1,402,981, Japanese Patent Publication Sho
Those obtained by the synthetic method described in 55-67522 are preferably used.

The ion-exchange type zeolite used in the present invention is the above-mentioned zeolite ion-exchanged with cobalt or nickel metal ions.

Examples of compounds that can be used for ion exchange include nitrates, sulfates, chlorides and acetates of cobalt or nickel.

The amount of cobalt or nickel to be ion-exchanged is about 2 to 8% by weight, preferably about 3 to 7% by weight, based on the zeolite in terms of oxide. If the amount is too small, further hydrogenation activity cannot be expected, and if the amount is too large, overdecomposition occurs or the surface area of the zeolite is reduced, which is not preferable.

The ion exchange can be carried out by a usual method as described below. That is, the zeolite is immersed in an aqueous solution containing a predetermined metal (the concentration of the aqueous solution is about 0.3 to 1.0 N solution), and the reflex temperature of water is about 80 to 100 ° C. while slowly stirring for one day. After this, the step of washing the zeolite part with a large amount of water is repeated several times or more.

Alumina that can be used in the present invention is γ-
Alumina, χ-alumina or η-alumina 1
Species or mixtures thereof are preferred. The alumina-containing material is a composition obtained by mixing a carrier material in addition to alumina, and for example, one or more kinds of silica, magnesia, calcium oxide, zirconia, titania, boria and the like are mixed with alumina. can do.

Alumina gel is a gel produced by neutralizing aluminum salts such as aluminum sulfate and aluminum nitrate with a base such as ammonium, or an aluminate such as sodium aluminate with an acidic aluminum salt or acid. Can be prepared by washing and aging with heating.

 One aspect of the method for preparing the alumina gel is as follows.

Acidic aluminum aqueous solution (preferably its concentration is about 0.
(In the range of 3 to 2 moles) and an alkali aluminate solution to which an alkali hydroxide solution or the like is added to produce a hydrogel or hydrosol at a pH of about 6.0 to 11.0, preferably about 8.0 to 10.5, or ammonia water, nitric acid. Alternatively, add acetic acid as appropriate to adjust the pH, and add the suspension to about 50 to 90 ° C
Heat to and hold for at least 2 hours. The precipitate is then filtered off and washed with ammonium acetate and water to remove impurity ions.

Next, the above cobalt or nickel ion exchange type zeolite is used in a dry ratio of about 5 to 60 parts by weight, preferably about 10 to 50 parts by weight.
Parts by weight, particularly preferably about 15 to 40 parts by weight and, for example, about 40 to 95 parts by weight, preferably about 50 to about 50 parts by weight of the alumina gel or the alumina-containing material gel prepared as described above in terms of oxide.
90 parts by weight, particularly preferably about 60 to 85 parts by weight, are mixed.

If there are too few zeolite parts and too many alumina parts,
If a sufficient effect cannot be obtained and conversely the amount of zeolite is too large and the amount of alumina is too small, coking occurs due to overdecomposition, coke is accumulated, and desulfurization active sites disappear.

Mixing is performed by a physical method, the obtained mixed gel is adjusted in water content, then molded by an extrusion molding machine, dried, and calcined at about 400 to 700 ° C. for about 1 to 5 hours to obtain a mixture.

The second step of the present invention is a step of supporting the remaining amount of cobalt or nickel and the specific amount of the Group 6B metal of the periodic table on the mixture obtained in the first step.

The method for supporting the cobalt or nickel and the hydrogenation active component of the Group 6B metal of the periodic table can also be carried out by a usual method as described below.

For example, a mixture of the cobalt or nickel ion-exchange type zeolite obtained in the first step and alumina or an alumina-containing material is dipped in a solution containing the hydrogenation active component, or the mixture and this solution are mixed. Kneading
Containing the mixture and the hydrogenation active component, such as dropping this solution onto the mixture or adding a precipitant for the hydrogenation active component while the mixture is immersed in the solution to deposit the hydrogenation active component on the mixture. The hydrogenation-active component can be supported on the mixture by contacting with the solution.

Either the cobalt or nickel and the Group 6B metal of the periodic table may be loaded first, or they may be loaded simultaneously.

Cobalt or nickel compounds that can be used as a solution include cobalt or nickel nitrates, sulfates, fluorides, chlorides, bromides, acetates, carbonates, phosphates and the like.

Furthermore, examples of the Group 6B metal of the periodic table that can be used as a solution include, as molybdenum compounds, ammonium paramolybdate, molybdate acid, ammonium molybdate, ammonium phosphomolybdate, phosphomolybdic acid, and the like.

In addition to these compounds, compounds known to those skilled in the art as those available in this type of field can be used.

After carrying out the treatment for supporting the active ingredient in the mixture as described above, it is preferable to carry out drying, firing and the like by a usual method.

Drying is usually at room temperature to about 150 ° C, especially about 100 to 120
It is preferable to hold at about 5 hours or more, particularly about 12 to 24 hours, and firing is usually about 350 to 600 ° C, especially about 400 to 550.
It is preferable to hold at about 3 hours or more, particularly about 12 to 24 hours.

When the ion exchange amount in the first step and the supported amount in the second step are summed, the amount of cobalt or nickel metal is about 0.5 to 15% by weight, preferably about 1.0 to 12% by weight of the catalyst in terms of oxide.
In the second step, the total amount is about 0.5 to 1 because it is wt%.
The remaining amount is about 0.4 to 10.2 wt% obtained by subtracting the ion exchange amount of about 0.1 to 4.8 wt% (= about 2 to 8 wt% x about 5 to 60 wt parts) in the first step from 5 wt%.

The amount of Group 6B metal in the periodic table is about 2 to 30% by weight, preferably about 7 to 25% by weight, based on the catalyst, in terms of oxide.

If the catalyst obtained by the process according to the invention is used in the form of sulphides, it is presulphurised.

As the sulfurization method, a method is used in which a hydrocarbon oil containing about 1.0% by weight or more of sulfur or a gas phase sulfur compound is passed over the catalyst under 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 distillates and residues of crude oil, vacuum distillate distillates and residues, visbreaking oil, tar sand oil, shale oil, etc. Is mentioned.

Further, the hydrodesulfurization conditions of the hydrocarbon oil by the catalyst obtained by the method of the present invention are as follows: temperature: about 200 to 450 ° C., pressure: about 10 to 200 K
The g / cm ² , LHSV (liquid hourly space velocity) is preferably about 0.1 to 5.0 Hr ^-1 .

[Action]

In the method of the present invention, unlike the conventional method of supporting the hydrogenation active component after preparing the alumina-zeolite carrier, the zeolite is ion-exchanged in advance with a part of the active component of cobalt or nickel metal, and then alumina or A carrier is prepared by mixing with an alumina-containing material, and then the remaining cobalt or nickel and the active ingredient of Group 6B metal of the periodic table are supported.

As a result, a considerable amount of the hydrogenation active component will be carried on the zeolite part, which is inferior in reactivity to the alumina part.

As a result, from the viewpoint of the catalyst as a whole, in a highly dispersed state,
In addition, by supporting an effective amount of hydrogenation active components, it is possible to realize highly desulfurized fuel products that can achieve desulfurization with extremely high efficiency against hydrodesulfurization of hydrocarbon oils and meet global demand. Can be provided.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Example 1 (first preparation of alumina gels in step) was dissolved aluminum nitrate _{Al (NO 3) 3 · 9H} 2 O2.33Kg distilled water 6, 28% aqueous ammonia 2.8Kg and distilled water while stirring the aqueous solution 6 was added to the mixture.

At this time, the pH of the aqueous solution was maintained at 9 or higher. An Al (NO ₃ ) ₃ aqueous solution was slowly added so that the pH would not locally drop, and the resulting suspension was filtered after stirring for 4 hours as it was.

The separated precipitate was retained and aged in a 1N aqueous solution of ammonium carbonate 8 at 50 ° C. for 12 hours, cooled, and again dehydrated by filtration.

Then, it was further washed with 0.2% ammonia water 12 to obtain an alumina gel.

(Preparation of cobalt ion exchange type zeolite in the first step) Stabilized H-type Y zeolite with a Si / Al ratio of 4.5 was added 5 times as much as 1N.
Ion exchange was performed at 80 ° C. for 8 hours with a cobalt nitrate aqueous solution.

Then, filter, wash with water, dry at 100 ° C for 12 hours, and then 550
Calcination was carried out for 3 hours.

At this time, the cobalt content as an oxide was 3.5% by weight based on zeolite.

(Preparation of Mixture of Alumina Gel and Cobalt Ion Exchange Type Zeolite in First Step) 180 g of alumina gel obtained as described above (dry basis)
And 120 g of cobalt ion-exchange type zeolite (dry basis) were suspended in distilled water 5, thoroughly stirred and mixed, and then the suspension was filtered.

The filtration product was extruded into a cylindrical shape with a diameter of 1/20 inch (1.25 mm) to prepare a mixture carrier of cobalt ion exchange type zeolite and alumina.

(Second step) The mixture carrier obtained in the first step was impregnated with an aqueous solution of ammonium molybdate so that the amount of the catalyst was 10% by weight in terms of oxide, and the molybdenum component was supported.

 This was dried at 120 ° C and then calcined at 550 ° C for 5 hours.

After cooling to room temperature, an aqueous cobalt nitrate solution was impregnated into the catalyst so as to be 4% by weight in terms of oxide,
The cobalt component was supported.

This was dried at 120 ° C. and then calcined at 450 ° C. for 5 hours to obtain a catalyst A.

The hydrogenation active components of catalyst A were 10% by weight of molybdenum and 4% by weight of cobalt as oxides, and the balance was zeolite and γ-alumina.

Example 2 (Preparation of alumina gel in the first step) An alumina gel was prepared in the same manner as in Example 1.

(Preparation of nickel ion exchange type zeolite in the first step) A nickel ion exchange type zeolite was prepared in the same manner as in Example 1 except that the nickel nitrate aqueous solution was used instead of the cobalt nitrate aqueous solution.

At this time, the nickel content as an oxide was 3.2% by weight based on the zeolite.

(Preparation of Mixture of Alumina Gel and Nickel Ion Exchange Type Zeolite in First Step) 180 g of alumina gel obtained as described above (dry basis)
A mixture carrier of nickel ion exchange type zeolite and alumina was prepared in the same manner as in Example 1 except that and 120 g of nickel ion exchange type zeolite (dry basis) were used.

(Second Step) A catalyst B was obtained in the same manner as in Example 1 except that the mixture carrier obtained in the first step was used and the nickel nitrate aqueous solution was used instead of the cobalt nitrate aqueous solution.

The hydrogenation active component of catalyst B was 10% by weight of molybdenum and 4% by weight of nickel as oxides, and the balance was zeolite and γ-alumina.

Example 3 (Preparation of alumina gel in the first step) An alumina gel was prepared in the same manner as in Example 1.

(Preparation of cobalt ion-exchange type zeolite in the first step) Stabilized H-type Y zeolite with a Si / Al ratio of 4.5 was added 10 times as much as 1N.
Ion exchange was performed at 80 ° C. for 8 hours with a cobalt nitrate aqueous solution.

Then, filter, wash with water, dry at 100 ° C for 12 hours, and then 550
Calcination was carried out for 3 hours.

At this time, the cobalt content as the oxide was 7.0% by weight based on the zeolite.

(Preparation of Mixture of Alumina Gel and Cobalt Ion Exchange Type Zeolite in First Step) 240 g of alumina gel obtained as described above (dry basis)
A mixture carrier of cobalt ion exchange type zeolite and alumina was prepared in the same manner as in Example 1 except that and 60 g of cobalt ion exchange type zeolite (dry basis) were used.

(Second step) The mixture carrier obtained in the first step is adjusted so that the ammonium molybdate aqueous solution becomes 12% by weight of the catalyst in terms of oxide and the cobalt nitrate aqueous solution becomes 3% by weight of the catalyst in terms of oxide. A catalyst C was obtained in the same manner as in Example 1 except that the catalyst C was impregnated.

The hydrogenation active component of catalyst C was 12% by weight of molybdenum and 3% by weight of cobalt as oxides, and the balance was zeolite and γ-alumina.

Comparative Example 1 180 g of alumina gel (dry basis) obtained in the first step of Example 1 and 120 g of stabilized H-type Y zeolite having a Si / Al ratio of 4.5 (dry basis) were suspended in distilled water 5 and thoroughly After mixing with stirring, the suspension was filtered.

The filtration product was extruded into a cylindrical shape having a diameter of 1/20 inch (1.25 mm) to prepare a mixed carrier of stabilized H-type Y zeolite having an Si / Al ratio of 4.5 and alumina.

This mixture carrier was impregnated with an aqueous solution of ammonium molybdate so that the amount of the catalyst was 10% by weight in terms of oxide, and the molybdenum component was supported.

 This was dried at 120 ° C and then calcined at 550 ° C for 5 hours.

After cooling to room temperature, an aqueous cobalt nitrate solution was impregnated into the catalyst so as to be 4% by weight in terms of oxide,
The cobalt component was supported.

This was dried at 120 ° C and then calcined at 450 ° C for 5 hours to obtain a catalyst D.

The hydrogenation active component of catalyst D was 10% by weight of molybdenum and 4% by weight of cobalt as oxides, and the balance was zeolite and γ-alumina.

Comparative Example 2 180 g of alumina gel (dry basis) obtained in the first step of Example 1 and 120 g of stabilized H-type Y zeolite having a Si / Al ratio of 4.5 (dry basis) were suspended in distilled water 5 and thoroughly After mixing with stirring, the suspension was filtered.

The filtration product was extruded into a cylindrical shape having a diameter of 1/20 inch (1.25 mm) to prepare a mixed carrier of stabilized H-type Y zeolite having an Si / Al ratio of 4.5 and alumina.

This mixture carrier was impregnated with an aqueous solution of ammonium molybdate so that the amount of the catalyst was 10% by weight in terms of oxide, and the molybdenum component was supported.

 This was dried at 120 ° C and then calcined at 550 ° C for 5 hours.

After cooling to room temperature, an aqueous solution of nickel nitrate was impregnated into the catalyst so as to be 4% by weight in terms of oxide,
A nickel component was supported.

This was dried at 120 ° C and then calcined at 450 ° C for 5 hours to obtain a catalyst E.

The hydrogenation active component of catalyst E was 10% by weight of molybdenum and 4% by weight of nickel as oxides, and the balance was zeolite and γ-alumina.

Catalyst A obtained in Examples 1 to 3 and Comparative Examples 1 and 2 above
.About.E were evaluated in a relative activity evaluation test for hydrodesulfurization under the following conditions.

Relative activity evaluation test of hydrodesulfurization: Hydrodesulfurization relative activity against Arabian light gas oil (AL-LGO) or vacuum gas oil (AL-VGO)
20 days (condition 1), 25, using mφ fixed bed reaction tubes
Residual sulfur content (% by weight) for reaction product on day (condition 2) (the sulfur content of the product was small at the beginning of the reaction, but increased and stabilized with the number of days, so it was set on the 20th and 25th days.) The initial relative desulfurization activity obtained from the above was determined.

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

As is clear from Tables 2 and 3, Examples 1 to 3 of the present invention
It can be seen that all of the catalysts A to C produced in 1. exhibited excellent desulfurization activity in both light gas oil and vacuum gas oil as compared with the catalysts D and E manufactured in Comparative Examples 1 and 2.

〔The invention's effect〕

According to the method of the present invention, since the zeolite is ion-exchanged with a part of the hydrogenation active component before mixing the zeolite with alumina or the like, the zeolite part can also contain a considerable amount of the hydrogenation active component. After that, since the remaining amount of the hydrogenation active component is further supported on the mixture of the zeolite and alumina or the like, it is possible to support the effective amount of the hydrogenation active component with improved dispersibility as the whole catalyst.

Such a hydrodesulfurization catalyst obtained by the method of the present invention exhibits high desulfurization activity as compared with a conventional catalyst obtained by supporting a hydrogenation active component on a zeolite-alumina carrier which has not been ion-exchanged in advance. You can

Claims (1)

[Claims] 1. A first step of mixing 5 to 60 parts by weight of zeolite ion-exchanged with cobalt or nickel, 40 to 95 parts by weight of alumina or an alumina-containing material, and cobalt or nickel and 6B of the periodic table. And a second step of supporting a group metal, wherein the amount of cobalt or nickel to be ion-exchanged in the first step is 2 to 8% by weight based on the zeolite in terms of oxide.
The total amount of cobalt or nickel is converted to oxide for the catalyst.
A method for producing a hydrodesulfurization catalyst composition for a hydrocarbon oil, which comprises 0.5 to 15% by weight and the amount of Group 6B metal in the periodic table is 2 to 30% by weight based on the catalyst in terms of oxide.