JPH03281595A - Hydrodesulfurization catalyst composition for hydrocarbon oil, its production and hydrodesulfurization process using the catalyst - Google Patents

Abstract

PURPOSE:To obtain the subject composition having remarkably prolonged catalytic life by supporting a hydrogenation active component of a metal of group VIB and a metal of group VIII on an alumina(-containing) carrier and supporting a hydrogenation-active component of a noble metal element of group VIII on the supported layer. CONSTITUTION:The objective composition is produced by supporting (A) 2-30wt.% (based on catalyst) of one or more kinds of metals of group VIB in the form of oxides and (B) 0.5-20wt.% of one or more kinds of metals of group VIII in the form of oxides on an alumina(-containing) carrier, drying and calcining the product and supporting (C) 0.05-8.0wt.% of one or more kinds of noble metal elements of group VIII in the form of metal. The use of the catalyst enables industrially profitable hydrodesulfurization process in high desulfurization ratio and the effect to prolong the catalytic life is especially remarkable in the case of using a petroleum distillate raw material.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a catalyst composition used for hydrodesulfurization treatment of hydrocarbon oil residues and hydrocarbon oil residues, and in particular, a catalyst composition that has a significantly improved catalyst life. The present invention relates to the above catalyst composition, a method for producing the same, and a hydrodesulfurization method for hydrocarbon oil using the same. More specifically, a hydrodesulfurization catalyst composition for hydrocarbon oil with a long catalyst life, which is made by first supporting a hydrogenation active component such as molybdenum or nickel on a carrier such as alumina, and further supporting a noble metal after calcination, and its composition. This article relates to a manufacturing method and a hydrodesulfurization method using the same.

[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 hydrodesulfurization treatment 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 the hydrocarbon oil, the operating conditions for the hydrodesulfurization treatment of the hydrocarbon oil, such as L
This can be achieved to some extent by making the HSV, temperature, and pressure more severe.

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.

Conventionally, common methods for producing hydrodesulfurization catalysts include the 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. Co-precipitation method involves 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. There is a ``kneading method 1'' in which water is removed by heating a mixed paste of an aqueous solution of a Group 6B metal salt and an aqueous solution of a Group 8 metal salt in Table 6. (See pages 1 to 252) Currently, catalysts produced by the method described above are widely used as hydrodesulfurization catalysts for hydrocarbon oils.

By the way, the desulfurization activity level of conventionally used catalysts is
For example, in the case of hydrodesulfurization of light oil, the sulfur content is 1. 4% by weight of light oil at a liquid hourly velocity of 5. When hydrodesulfurization was performed under the conditions of OHr temperature 360℃ and pressure 30Kg/cm,
The sulfur content of the produced oil is reduced to about 0.13% by weight.

In the case of hydrodesulfurization of vacuum gas oil (VCO), VCO with a sulfur content of 2.7% by weight is used at a liquid hourly space velocity of 1. 4 hours
-', when hydrodesulfurization is carried out under the conditions of humidity temperature 00°C and pressure 40Kg/cm2, the sulfur content of the produced oil is 0.1
The amount decreases to about 3% by weight.

Furthermore, in the case of hydrodesulfurization of atmospheric residual oil, the sulfur content is 3.
3% by weight of atmospheric residual oil at a liquid hourly space velocity of 0. When hydrodesulfurization was carried out under the conditions of 4Hr-', humidity temperature 10°C, pressure 110Kg/cm20, the sulfur content of the produced oil was 0.3% by weight.
It decreases to a certain degree.

[Problems to be Solved by the Invention] However, a major problem with the conventionally used catalysts as described above is that the desulfurization activity is difficult to maintain at a constant level, and as the desulfurization reaction progresses, the desulfurization activity decreases. However, their lifespan is extremely short.

Needless to say, industrially, these catalysts are used continuously for at least one year, and in most cases, for several years.

Therefore, while the above initial activity level is important for industrially used catalysts, it is also important to
It is even more important that it remains stable for several years.

Therefore, the problem to be solved by the present invention is to create a catalyst with a longer lifespan without impairing the desulfurization activity of conventional catalysts, and to maintain the catalyst life at a certain level even under harsh reaction conditions. The purpose of the present invention is to develop a catalyst composition that can be used, a method for producing the same, and a method for hydrodesulfurization of hydrocarbon oil using the same.

[Means to solve the problem]

In order to solve the above problems, the present inventors have conducted intensive research and found that metals from group 6B of the periodic table, which are normally used in this type of industrial hydrodesulfurization treatment, and periodic A metal with a hydrogenation function of iron group metal of Group 8 of the Periodic Table is supported, and then based on this material, further hydrogenation of iron group metal of Group 8 of the Periodic Table of
By going through the process of supporting precious metals of the group,
The present invention was completed based on the discovery that hydrogenation activity can be improved and that this improvement in hydrogenation activity makes it possible to significantly improve catalyst life.

That is, the present invention provides: (1) an alumina or alumina-containing material carrier containing (A) at least one metal selected from group 6B metals of the periodic table; and (B) an iron group metal of group 8 of the periodic table. (C) at least one selected from the group 8 noble metal elements of the periodic table;
2 to 30% by weight of at least one metal selected from the group 6B metals of the periodic table as an oxide based on the catalyst; The amount of at least one metal selected from the iron group metals of group 8 in the table is 0.5 to 20% by weight of the catalyst as an oxide, and the amount of at least one metal selected from the above noble metal elements of group 8 of the periodic table is 0.5 to 20% by weight based on the catalyst. A hydrodesulfurization catalyst composition for hydrocarbon oil, characterized in that the amount of at least one metal contained in the catalyst is 0.05 to 8.0% by weight based on the catalyst, and (2)
) alumina or alumina-containing material carrier, periodic table 6B
At least one metal selected from group metals and at least one selected from iron group metals from group 8 of the periodic table are supported, and after drying and firing, a noble metal element from group 8 of the periodic table is supported. A method for producing a hydrodesulfurization catalyst composition for hydrocarbon oil, characterized in that it supports at least one selected from the following: and (3) hydrodesulfurization of hydrocarbon oil using the catalyst described in (1) above. The gist of this paper is a method for hydrodesulfurization of hydrocarbon oil, which is characterized by the following.

The catalyst composition of the present invention can be obtained by the production method of the present invention described below.

In the first step in the production method of the present invention, at least one metal selected from group 6B metals of the periodic table and iron group metals of group 8 of the periodic table is added to the alumina or alumina-containing carrier. This is a step of supporting at least one hydrogenation active component.

The alumina that can be used in the present invention is any one of T-alumina, χ-alumina, and η-alumina.
Species or mixtures thereof are preferred.

Furthermore, an alumina-containing material is a composition obtained by blending a carrier material in addition to alumina, such as silica,
magnesia, calcium oxide, zirconia, titania,
One or more types of boria etc. can be blended with alumina.

This alumina support is produced, for example, by neutralizing an aluminum salt such as aluminum sulfate or aluminum nitrate with a base such as ammonia, or by neutralizing an aluminate such as sodium aluminate with an acidic aluminum salt or an acid. The gel can be prepared by processing using conventional processing methods such as washing, heating, molding, drying, baking, etc.

One embodiment of the method for preparing the alumina carrier is as follows.

Acidic aluminum aqueous solution (preferably a concentration of about 0°3-2
molar range) and alkali aluminate solution to form a hydrogel or hydrosil at a pH of about 6.0 to 11°0, preferably about 8.0 to 10.5, or ammonia While adjusting the pH by adding water, nitric acid or acetic acid as appropriate, this suspension was heated to about 50%
Heat to ~90°C and hold for 2 hours. Then, the precipitate is separated and washed with ammonium acetate and water to remove impurity ions. Then, usual methods such as drying and calcination are adopted. and finish it into a carrier.

Drying is carried out by heating from room temperature to about 200°C in the presence or absence of oxygen, and baking is carried out by heating to about 200 to 800°C in the presence of oxygen.

At least one metal selected from Group 6B of the periodic table to be supported on the carrier thus obtained in the first step is preferably chromium or molybdenum ditungsten. Further, at least one metal selected from iron group metals of Group 8 of the periodic table is preferably cobalt or nickel. Particularly preferred are molybdenum-cobalt, molybdenum-nickel, and molybdenum-cobalt-nickel.

Combinations such as tungsten and nickel.

These hydrogenation active metal components are preferably supported as oxides or sulfides.

The method of supporting the hydrogenation-active metal component on the alumina or alumina-containing material carrier can also be carried out by a conventional method.

For example, the carrier may be immersed in a solution containing a hydrogenation-active ingredient, the carrier and this solution may be kneaded, the solution may be dropped onto the carrier, or the carrier may be immersed in a solution to activate hydrogenation. The hydrogenation active ingredient can be supported on the carrier by a method of bringing the carrier into contact with a solution containing the hydrogenation active ingredient, such as adding a precipitant for the component and depositing the hydrogenation active ingredient on the carrier.

When molybdenum or tungsten and nickel or cobalt are used together, either one may be supported first or they may be supported simultaneously.

After supporting, drying, baking, etc. are performed. Drying is usually carried out at room temperature to about 150°C, especially about 100 to 120°C, preferably for about 5 hours or more, especially about 12 to 24 hours.
Firing is usually performed at about 350 to 600°C, especially about 400 to 600°C.
Preferably, the temperature is maintained at 550°C for about 3 hours or more, especially about 12 to 24 hours.

The substance obtained in the first step above is about 2 to 30% by weight, preferably about 5 to 20% by weight as an oxide based on the catalyst.
At least one metal selected from group 6B metals of the periodic table of
Seed metal, and about 0.5 to 20% heavy weight or about 3
Contains ~10% by weight of at least one metal selected from iron group metals of group 8 metals of the periodic table.

Next, in the second step in the production method of the present invention, the material obtained in the first step is further added with noble metals of group 8 of the periodic table, namely platinum, palladium, rhodium, and osmium.
At least one selected from iridium and ruthenium
This is a step in which a seed hydrogenation active component is supported by an impregnation method or the like.

The starting material is not particularly limited. That is, it may be a salt of the above-mentioned noble metal or a metal complex. Of course, the salts containing the above-mentioned noble metals can be used regardless of whether they are cations or anions.

Specifically, chloroplatinic acid, palladium chloride, rhodium chloride, etc. can be used.

The total content of these noble metals is about 0.05 to 8.0% by weight of metal, preferably about 0.05% by weight, based on the final catalyst.
It is 1 to 5.0% by weight. Too much of these precious metals not only reduces the dispersibility of the precious metals and becomes uneconomical, but also
Desulfurization active sites decrease, which is not preferable.

The method for supporting these noble metals on the substance obtained in the first step can also be carried out by a conventional method.

For example, the substance obtained in the first step can be supported by immersing the substance obtained in the first step in an aqueous solution of a noble metal compound, or by dropping this solution onto the substance obtained in the first step.

After supporting, drying, baking, etc. are preferably performed. Drying is usually done at room temperature to about 150" C1, especially about 100 to 120"
℃ for about 5 hours or more, especially about 12 to 24 hours, and the calcination is usually carried out at about 350 to 600 degrees Celsius.
It is particularly preferred to hold the temperature at about 400-550''C for about 3 hours or more, especially about 3-6 hours.

When the catalyst obtained by the production 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 a hydrocarbon oil or a gaseous sulfur compound containing about 1.0% by weight or more of sulfur is passed over the catalyst at high temperature and high pressure.

When reduced with hydrogen after sulfidation, the effect of extending the lifespan becomes even more remarkable.

Hydrocarbon oils that can be applied to the hydrodesulfurization method of the present invention using the catalyst of the present invention include atmospheric distillation distillates and residues of crude oil, vacuum distillation distillates and residues, visbreaking oils, tars, etc. Sand oil.

Examples include shale oil.

Further, the conditions for the hydrodesulfurization method of the present invention are a temperature of about 200 to 450°C, a pressure of about 10 to 200 Kg/cm'',
LH3V (liquid hourly velocity) is preferably about 0.1 to 5.0 Hr-'.

[Effect]

Generally, one of the causes of catalyst activity deterioration is that when the carbon-sulfur bonds and carbon-carbon bonds of hydrocarbons in the oil to be treated are broken, the cutting does not proceed effectively, resulting in excessive condensation. It is said that this is because carbonaceous substances are deposited on the surface of the catalyst as a result of cyclization and cyclization.

In contrast, in the present invention, as described above, at least one metal of group 6B of the periodic table, such as molybdenum or nickel, and a metal of group 8 of the periodic table, such as alumina or an alumina-containing carrier,
Although the reason for this is not clear, by preparing in advance a material on which at least one kind of noble metal of group 8 of the periodic table is supported, and making this material support at least one kind of noble metal of group 8 of the periodic table. , effectively advances the cutting of carbon-sulfur bonds and carbon-carbon bonds of hydrocarbons in the oil to be treated, and suppresses the precipitation of carbonaceous substances.

As a result, the present invention can significantly extend the life of the catalyst even when used under severe conditions.

The hydrodesulfurization method of the present invention using this catalyst can achieve industrially profitable treatment at a high desulfurization rate.

In addition, in the present invention, as described above, in the first step, a group 6B metal of the periodic table, such as molybdenum or nickel, and an iron group metal of group 8 of the periodic table are supported, and in the second step, a metal of group 6B of the periodic table, such as The above effect can only be obtained when a noble metal from group 8 is supported, and the order of the support may be reversed, or when metals from group 6B of the periodic table or iron group from group 8 are supported. Even if one metal and a noble metal from group 8 of the periodic table are supported at the same time, the above-mentioned effect does not occur, although the reason is not clear.

〔Example〕

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

"Catalyst Production Example 1; Example 1 (First Step) In 50! of ion-exchanged water, 29.8Kg of sodium aluminate solution (containing about 23% as A 1 z O3) and 38.0Kg of sodium aluminate solution were added. Aluminum sulfate solution (AI!
, 203 (containing about 7.9%) was slowly added dropwise. At this time, the pH of the solution was maintained between 8 and 9.

Finally, add the remaining sodium aluminate solution,
The pH of the solution was finally set 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.

Ion-exchanged water was again added to the alumina powder obtained by spray-drying this alumina cake to adjust the humidity.

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.

5 kg of the thus prepared alumina carrier was collected, and a group 6B metal of the periodic table and an iron group metal of group 8 of the periodic table were supported thereon in the following manner.

That is, first, 1252 g of ammonium rosemolybdate was added and dissolved in a 2900 rr + 42 ammonia aqueous solution, and further, 785 g of nickel nitrate was added thereto to prepare a solution free of precipitates.

This solution was then carefully dropped onto the above alumina support.

After dropping all the solutions, let stand for 3 hours, then 120
Dry at °C for 12 hours. Finally, it was baked at 500°C for 12 hours.

(Second Step) 2 kg of the material obtained in the first step was collected, and a noble metal of Group 8 of the periodic table was supported in the following manner.

That is, first, 5000mj of diluted hydrochloric acid aqueous solution! was prepared, and 410 g of chloroplatinic acid was dissolved therein.

Next, the substance obtained in the first step was soaked in this aqueous solution and left for 3 hours.

After that, the pickled food was taken out and heated to 120°C for 12 hours.
Catalyst A
I got it.

This catalyst A contained 5% by weight of nickel oxide, 17% by weight of molybdenum oxide, and 0.6% by weight of platinum.

Example 2 2 kg of the material obtained in the first step of Example 1 was collected, and a noble metal of group 8 of the periodic table was supported on it in the following manner.

That is, first, 5000 rne of water was prepared, and 325 g of palladium chloride was dissolved therein.

Next, the substance obtained in the first step was soaked in this aqueous solution and left for 3 hours.

After that, take out the soaked food and boil it at 120"C for 12 hours.
Catalyst B was obtained by drying for hours and finally calcining at 450''C for 3 hours.

This catalyst B contained 5% by weight of nickel oxide, 17% by weight of molybdenum oxide, and 3.3% by weight of palladium.

Example 3 2 kg of the material obtained in the first step of Example 1 was collected, and a noble metal of Group 8 of the periodic table was supported on it in the following manner.

That is, first, 5000 mj2 of water was prepared, and 293 g of rhodium chloride was dissolved therein.

Next, the substance obtained in the first step was soaked in this aqueous solution and left for 3 hours.

After that, the pickled food was taken out and heated to 120°C for 12 hours.
The catalyst was dried for hours and finally calcined at 450°C for 3 hours to obtain catalyst C.

This catalyst C contains 5% by weight of nickel oxide, 17% by weight of molybdenum oxide, and 1.5% by weight of rhodium. It contained 9% by weight.

Comparative Example 1 The substance obtained in the first step of Example 1 was used as a catalyst as it was.

This catalyst contained 5% by weight of nickel oxide and 17% by weight of molybdenum oxide.

Comparative Example 2 In the method of supporting Group 6B metals and Iron group metals of Group 8 of the periodic table in the first step of Example I, 1252 g of ammonium rosemolybdate and 7
Catalyst E was prepared in the same manner as in Example 1, except that 85 g of nickel nitrate and 108 g of palladium chloride were dissolved and the second step of Example I was omitted.

This catalyst E contained 5% by weight of nickel oxide, 17% by weight of molybdenum oxide, and 1.5% by weight of palladium. It contained 0% by weight.

Hydrodesulfurization treatment example 1 of hydrocarbon oil; Example 1 above
The hydrodesulfurization treatment method of the present invention was carried out using catalysts A-E obtained in ~3 and Comparative Example 1.2, and the relative activity of hydrodesulfurization was evaluated for each catalyst A-E under the following conditions. In addition, the catalyst life under the following conditions was evaluated.

of Arabian Light light gas oil (AL-1, Go).

The relative hydrodesulfurization activity for vacuum gas oil (AL-VGO) or Arabian heavy atmospheric residual oil (AH-AR) was measured using a fixed bed reaction tube with an inner diameter of 10 mmφ for 10 days (
Condition 11 Condition 2), Condition 3) on the 20th day, Condition 4) on the 25th day (at the beginning of the reaction, the sulfur content of the product is low, but it increases and stabilizes as the days pass, so on the 10th day and 20th day, 25
It was marked as the day. ) The initial relative desulfurization activity obtained from the residual sulfur content (wt%) of the reaction product was determined.

Hosei Jukuraoka bond case: Hydrodesulfurization treatment was performed under the same conditions as the relative activity evaluation conditions for hydrodesulfurization described above, and the sulfur content of the produced oil increased by 0.2% by weight (Condition 19 Condition 2) ).

The cumulative amount of time required to reach 0.3% by weight (condition 3) and 0.5% by weight (condition 4) was determined and evaluated as relative life.

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).

As is clear from Table 2, in the hydrodesulfurization treatment of light gas oil, the present catalyst A-
Examples 4 to 8 using C maintained the same level of desulfurization as the conventional catalyst produced in Comparative Example 1.2 and Comparative Examples 3 to 5 using E, and also Examples 1 to 8. It can be seen that Examples 4 to 8 using catalysts A to C of the present invention produced in Example 3 have significantly longer catalyst life than Comparative Examples 3 to 5 using conventional catalyst E. .

As is clear from Table 3, in the hydrodesulfurization treatment of vacuum gas oil, the present catalyst A produced in Examples 1 and 3,
Examples 9 and 10 using Comparative Example 1.
Comparative example 6.7 using conventional catalyst E prepared in 2.
In Examples 9 and 1o, which maintained the same level of desulfurization and also used the catalysts A and C of the present invention produced in Examples 1 and 3,
Conventional catalyst.

It can be seen that the catalyst life was significantly extended compared to Comparative Examples 6 and 7 using E.

As is clear from Table 4, in the hydrodesulfurization treatment of atmospheric residual oil, Example 11 using catalyst A of the present invention manufactured in Example 1 was superior to the conventional catalyst manufactured in Comparative Example 1. Example II, which maintained the same level of desulfurization as Comparative Example 8 using catalyst A of the present invention produced in Example 1,
It can be seen that the catalyst life is significantly extended compared to Comparative Example 8 using a conventional catalyst.

〔Effect of the invention〕

As detailed above, according to the catalyst of the present invention obtained by the production method of the present invention, it is possible to effectively proceed with the cleavage of carbon-sulfur bonds and carbon-carbon bonds of hydrocarbons in the oil to be treated. without causing excessive condensation or cyclization, and therefore preventing the precipitation of carbonaceous matter on the catalyst surface.
Catalyst life is significantly extended.

If the catalyst life is extended in this way, even if the catalyst is operated under severe conditions, i.e. increases the throughput or reduces the sulfur content in the product, i.e. deep desulfurization, the catalyst life will be longer than the conventional one. Compared to normal operation, i.e., low-severity operation, the lifespan is not shortened, and the service life can be ensured.

As described above, according to the hydrodesulfurization treatment method of the present invention using the catalyst of the present invention obtained by the production method of the present invention, it is possible to perform hydrodesulfurization treatment that is industrially profitable and at a high desulfurization rate. I can do it.

Moreover, the catalyst of the present invention obtained by the production method of the present invention is
It is effective for both petroleum fractions and residues, and the effect of extending the life of the catalyst is particularly remarkable when petroleum distillate raw materials are used.

Claims (3)

[Claims] (1) The alumina or alumina-containing material carrier contains (A) at least one metal selected from group 6B metals of the periodic table, and (B) at least one metal selected from iron group metals of group 8 of the periodic table. Supporting one kind of hydrogenation active component, furthermore, (C) at least one selected from noble metal elements of Group 8 of the periodic table.
2 to 30% by weight of at least one metal selected from the group 6B metals of the periodic table as an oxide based on the catalyst; The amount of at least one metal selected from the iron group metals of group 8 in the table is 0.5 to 20% by weight of the catalyst as an oxide, and the amount of at least one metal selected from the above noble metal elements of group 8 of the periodic table is 0.5 to 20% by weight based on the catalyst. A hydrodesulfurization catalyst composition for hydrocarbon oil, characterized in that the amount of at least one metal contained in the catalyst is 0.05 to 8.0% by weight based on the catalyst. (2) supporting at least one metal selected from group 6B metals of the periodic table and at least one metal selected from iron group metals of group 8 of the periodic table on alumina or an alumina-containing material carrier; A method for producing a hydrodesulfurization catalyst composition for hydrocarbon oil, which comprises supporting at least one element selected from noble metal elements of group 8 of the periodic table after drying and calcination. (3) A method for hydrodesulfurizing hydrocarbon oil, which comprises hydrodesulfurizing hydrocarbon oil using the catalyst according to claim 1.