JPH05317709A - Hydrogenation desulfurization catalyst and its preparation - Google Patents

Abstract

PURPOSE:To provide a desulfurization catalyst which can hydrogenate and desulfurize a hardly reactive sulfur compd. in a deep desulfurization region of a hydrocarbon. CONSTITUTION:This catalyst is a hydrogenation desulfurization catalyst for a hydrocarbon wherein at least one or two or more metals selected from metals of VIB, VIII and VA groups in the periodic table, or oxides, sulfides and salts thereof and a dysprosium compd. are carried on a fire-resistant carrier. Therefore, this hydrogenation desulfurization catalyst exhibits a remarkably higher desulfurization activity, a remarkably extended catalytic life, less decrease in hue and excellent long-term stability in comparison with the conventional hydrogenation desulfurization catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improved catalyst for the hydrodesulfurization of hydrocarbon cuts containing sulfur compounds, in particular gas oil cuts, as well as a process for their preparation and their use.

[0002]

2. Description of the Related Art In the background of the fact that environmental problems have been widely taken up today, the desulfurization technology has been interested in the regulation for reducing the sulfur content in light oil. In Japan, investigation of sulfur content regulation in diesel fuel products started in 1989. As the first stage, the sulfur content in diesel fuel products was regulated to 0.2% by weight or less from April 1992, and the second stage. As a result, a regulation of 0.05% by weight or less by 1997 is being studied.

In the desulfurization technology using the current gas oil desulfurization equipment and existing catalysts, it is the limit to reduce the sulfur content to about 0.1 to 0.15% by weight even if the reaction conditions are increased. It is said. In the existing equipment, if the liquid space velocity is extremely lowered, the processing capacity will decrease, so not only the scale of the equipment needs to be expanded, but it also promotes side reactions and improves the hue (hue value and stability) in the product gas oil. Spoil. In addition, when the reaction temperature is raised to increase the activity, a side reaction occurs, which also reduces the hue in the product gas oil. Therefore, it has been desired to develop a hydrorefining method and a catalyst that works under reaction conditions of lower severity using the current gas oil desulfurization equipment.

Hydrotreating or hydrodesulfurization is generally about 100 to 600 ° C, preferably 200 to 450 ° C.
Temperature in the range of about 10 to 300 Kg / c
m ² , preferably a pressure in the range of 20-100 Kg / cm ² , usually about 0.1-10 hr ^-1 , preferably 0.5.
Liquid hourly space velocity in the range of ~ 6 hr ^-1 , and usually about 3
0 to 1500 Nm ³ / KL, preferably 50 to 500 N
It is carried out under reaction conditions with a feed rate of hydrogen / feedstock ratio in the range of m ³ / KL. The hydrodesulfurization catalyst is preferably a Group VIB metal (usually molybdenum or tungsten) compound of Periodic Table, VIII of the Periodic Table on a refractory support.
Those carrying a group metal (usually cobalt or nickel) compound are widely used.

Various proposals have been made so far for this type of hydrodesulfurization catalyst, catalyst carrier, and methods for producing and using them.

JP-A-50-64190 discloses that a rare earth element (cerium or lanthanum) is further added to a catalyst composed of an iron group metal and a group VIB metal supported on a refractory carrier and having fine pores of different sizes. It is disclosed that the addition thereof not only increases the degree of desulfurization but also reduces the rate of decrease in desulfurization activity.

In Japanese Laid-Open Patent Publication No. 52-5691,
A method for producing a catalyst has been proposed in which a catalyst made of an iron group metal or a group VI metal on a refractory support is refluxed with an aqueous solution of an alkali or alkaline earth metal, a rare earth metal or a transition metal. There is no teaching what kind of element is specifically used as a metal or a transition metal.

Japanese Examined Patent Publication No. 53-6113 discloses VI.
A Group B metal compound, a Group VIII metal compound, and a refractory inorganic oxide are used for mixing and decoupling to form an extrudable soft mass, which is extruded, and the extruded soft mass is dried and calcined. And calcined extruded product to VIB
A method for producing a hydrodesulfurization catalyst is described, which comprises impregnation with a group metal compound and a group VIII metal compound, followed by drying and calcining in an oxidizing atmosphere.

JP-A-54-127406 discloses an improved catalyst for hydrodemetallizing and hydrodesulfurizing petroleum distillation sections such as hydrocarbon oils, especially residual oils, especially hydrodemetallizing. Catalysts suitable for use in the composition of from about 0.5 to about 7.0% by weight, preferably from about 1.0 to about 6.0.
Alumina is impregnated with wt% rare earth element oxide (RE ₂ O ₃ ), and then pre-fired at a temperature of about 704 ° C. to about 927 ° C. to combine alumina and the rare earth element oxide, and then impregnated. Thus, a hydrodemetallization catalyst containing an iron group metal and a Group VIB metal is disclosed.

JP-A-60-255143 discloses at least one compound of molybdenum or tungsten, one compound of cobalt and / or one compound of nickel, and 0.2 to 1.0 per mol of Mo or W. An aqueous impregnating solution having a pH range of 0.7 to 2.7 is prepared by mixing a stabilizing amount of phosphorus of 2 mol and a suitable soluble amine compound of 2 to 6% by weight with respect to the support. , A method for making a supported hydroconversion catalyst comprising impregnating a suitable catalyst support with this solution and drying and calcining the composite material.

In Japanese Patent Laid-Open No. 61-138537, p.
The amorphous alumina hydrate filter cake adjusted to H 7.5 to 10.5 was dehydrated with a filter press to obtain A
After increasing the l ₂ O ₃ concentration to 28 to 35 wt%, the l ₂ O ₃ was supplied to a self-cleaning type kneader and kneaded for a residence time of 10 seconds or more.
20 to 60 wt% (as metal) of Group IB metal and Group VIII metal are simultaneously added as an aqueous solution of a water-soluble salt and kneaded, and then extruded by an extruder and dried. A method for producing a hydrodesulfurization catalyst is described, which comprises calcining, impregnating the calcined product with an ammoniacal aqueous solution of the rest of the catalyst metal, and then calcining dry.

Japanese Patent Publication No. 2-54142 discloses that aluminum sulfate and sodium aluminate have a pH of 6.0 to 6.0.
8.5, a first aqueous slurry containing amorphous alumina hydrate was prepared by reacting under the condition of a temperature of 50 to 65 ° C. Sodium aluminate was added to this aqueous slurry to obtain an Al ₂ O ₃ concentration. Of 2 wt% or more is prepared, the amorphous alumina hydrate contained in the second aqueous slurry is filtered off, and the obtained filter cake is diluted with dilute aqueous ammonia and then diluted. After washing with nitric acid solution, wash again with diluted ammonia water to adjust the pH of the filter cake to 7.5.
Adjust to 10.5 and dehydrate this filter cake with a filter press to adjust its Al ₂ O ₃ concentration to 28 to 35 wt%.
Of the alumina catalyst carrier, which is obtained by extruding the obtained dough, drying the extruded product, and further calcining the dough. The manufacturing method is described.

[0013]

In order to comply with the second stage regulations of Japan, the sulfur content in gas oil products should be 0.1%.
Since it needs to be reduced to less than or equal to wt%, it is also necessary to hydrodesulfurize the difficult-to-react sulfur compounds (polycyclic aromatic sulfur compounds) in the deep desulfurization region, which were not covered in the conventional desulfurization region.

In order to achieve this by using the existing gas oil desulfurization apparatus and hydrodesulfurization catalyst, if the reaction temperature is raised,
Alternatively, the liquid space velocity may be reduced. However, in the former method, the activity of the catalyst is lowered and the life of the catalyst is shortened, and moreover, the hue (hue value and stability) in the light oil of the product is lowered, so that the commercial value is remarkably reduced. On the other hand, if the latter method is adopted, the capacity of the equipment will be insufficient and the equipment will need to be expanded, but this is almost impossible at present. As described above, the conventional hydrodesulfurization catalyst cannot cope with this deep depth desulfurization. Therefore, it has been desired to develop a desulfurization catalyst having higher activity and longer catalyst life.

Further, in the case of using a conventional catalyst, there is a problem that the degree of coloring is increased if the smell of light oil is reduced, and conversely, if the degree of coloring is reduced, the smell is increased. there were.

[0016]

The present inventor has solved such problems, and has an excellent hydrodesulfurization having a higher activity and a longer catalyst life so that the existing facilities can cope with this deep depth desulfurization. As a result of intensive research to develop a catalyst, by adding a dysprosium compound to a conventional hydrodesulfurization catalyst, it becomes a highly active catalyst that can desulfurize even a difficult-to-react sulfur compound, and also has an odor and a color. Both have been found to improve. The present invention has been completed based on such findings.

That is, one embodiment of the present invention is to provide at least one or more metals or oxides or sulfides selected from the metals of Group VIB, Group VIII and Group VA of the periodic table. The present invention provides a hydrodesulfurization catalyst for hydrocarbons, which comprises a salt, a mixture or a mixture thereof, and a dysprosium compound supported on a refractory carrier.

In this case, molybdenum and / or tungsten is preferable as the Group VIB metal of the periodic table,
Cobalt and / or nickel is preferable as the Group VIII metal of the periodic table, and phosphorus is preferable as the Group VA metal of the periodic table.

The amounts of these metals used are calculated in terms of elements on the basis of the weight of all the catalysts supported on the refractory carrier.
Periodic Table Group VIB metal is 4 to 30% by weight, Periodic Table Group VIII metal is 1 to 10% by weight, Periodic Table Group VA metal is 0 to 10% by weight, Dysprosium is 0.05 to 5% by weight. % Is preferable.

Another aspect of the present invention is the periodic table VIB.
At least one or two or more metals or oxides, sulfides, salts or mixtures or binders thereof selected from the group III, VIII and VA metals and dysprosium compounds on a refractory carrier Using a hydrocarbon hydrodesulfurization catalyst characterized by being supported, hydrogen partial pressure in the range of 10 to 300 Kg / cm ² , liquid hourly space velocity in the range of 0.1 to 10 hr ⁻¹ , Three
Sulfur in a sulfur-containing gas oil feedstock or the like, which comprises treating under a reaction condition of a hydrogen / feedstock ratio supply rate in the range of 0 to 1500 Nm ³ / KL and a temperature in the range of 100 to 600 ° C. It is intended to provide an improved method of hydrorefining a hydrocarbon containing a compound.

Still another aspect of the present invention also provides a method for producing a hydrodesulfurization catalyst for these hydrocarbons. In the hydrodesulfurization catalyst of the present invention, a metal compound of Group VIB of the periodic table, a metal compound of Group VIII of the periodic table, dysprosium and, if necessary, a metal compound of Group VA of the periodic table are supported on a refractory carrier. Manufactured by. As the method for supporting the catalyst component, the impregnation supporting method which has been conventionally used can be applied as it is. Similar effects can be obtained by further impregnating and supporting dysprosium on a conventional catalyst. The addition of dysprosium may be performed in any step of preparing a conventional carrier or catalyst.

In this case, as a method for adding the catalyst component to the carrier, a soft lump (dough) of alumina in the extrusion method is used.
The catalyst can be prepared by mixing the compound by a wet method or a dry method and then extruding.

The type of the refractory carrier used in the present invention is not particularly limited, and any refractory carrier can be used. For example, as disclosed in Japanese Examined Patent Publication No. 2-54142, (a) an aluminum sulfate solution and a sodium aluminate solution are simultaneously added to a container containing ion-exchanged water, and aluminum sulfate and sodium aluminate are added. pH 6.0 to 8.5, temperature 50 to 65 ° C
To prepare a first aqueous slurry containing an amorphous alumina hydrate, and (b) this aqueous slurry in a total amount with the sodium aluminate used in step (a), The aluminum sulfate used in step (a) of 0.
An aqueous sodium aluminate solution corresponding to 95 to 1.05 equivalents is added to prepare a second aqueous slurry having an Al ₂ O ₃ concentration of 7% by weight or more, and (c) an amorphous contained in the second aqueous slurry. Alumina hydrate is filtered off, and the obtained filter cake is washed with diluted ammonia water, then with diluted nitric acid solution, and again with diluted ammonia water to adjust the pH of the filter cake to 7.5-10. 5), (d) this filter cake was dehydrated with a filter press to form Al ₂
After increasing the O ₃ concentration to 28 to 35% by weight, this is supplied to a self-cleaning type kneader to knead for a residence time of 10 seconds or more, and the dough obtained from step (e) (d) is extruded and molded. Thereafter, the extruded product is dried and further calcined, whereby an alumina carrier having desired pore characteristic characteristics and specific surface area can be prepared.

An aqueous solution of a soluble compound as described below, using the above-mentioned alumina carrier or a conventional refractory carrier (alumina alone or an alumina oxide containing silica-alumina and / or zeolite) by a conventional impregnation method. Impregnate.

The impregnation treatment of the catalyst component is preferably carried out with a minimum volume of the impregnation solution suitable for uniform dispersion in the carrier. For example, the amount of the carrier used is preferably 0.5 to 1.0 volume of the carrier per volume of the impregnation solution.

One preferred method is to use a steam jacketed evaporator. The carrier is immersed in the impregnating solution and stirred therein by the rotary movement of the evaporator.

Vaporization of the impregnating solution can be promoted by using water vapor in the evaporator jacket and by continuously purging the evaporator with a dry gas, preferably air or nitrogen gas. The impregnated material thus dried is further calcined in an oxygen atmosphere at a temperature of 200 to 650 ° C. for 1 to 24 hours or more.

A particularly suitable Group VIB metal compound is ammonium molybdate, a particularly suitable Group VIII metal compound is cobalt nitrate, a particularly suitable Group VA metal compound is phosphoric acid, and a particularly suitable dysprosium. The compound is dysprosium nitrate. Other suitable VIs
The group B metal compound includes compounds such as molybdic acid anhydride, molybdic acid, tungstic acid, and ammonium tungstate. Other Group VIII metal compounds that can be used include nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, ferrous cobalt sulfate, ferric nitrate, ferric sulfate, and the like. Examples include pyrophosphoric acid, metaphosphoric acid, phosphorus pentachloride, tetraphosphorus tenoxide and the like. Other suitable dysprosium compounds include dysprosium chloride, dysprosium oxide, dysprosium fluoride,
Examples include dysprosium sulfate, dysprosium carbonate, and dysprosium acetate.

Using the dry extrusion method as disclosed in Japanese Examined Patent Publication No. 53-6113, 4 to 30% by weight of the periodic table of the periodic table, VIB, is calculated based on the weight of all the supported catalysts. Group VI and 1 to 10% by weight of the periodic table VI
In loading a Group II metal, 0 to 10% by weight of the periodic table Group VA metal and 0.05 to 5% by weight of dysprosium on a refractory carrier, (a) first, a refractory inorganic oxide and final loading A soft lump that can be extruded by mixing and deflocculating a fine Group VIB metal compound, a Group VIII metal compound, a Group VA metal compound and a dysprosium compound in an amount of 10 to 100% by weight, respectively. (Dough) is formed, (b) this soft lump is extruded, the extruded soft lump is dried and fired in an oxidizing atmosphere, and (c) the fired extruded body is then a Group VIB metal compound or a Group VIII metal. Also prepared by impregnating and supporting the remaining amount of the compound, Group VA metal compound and dysprosium compound, and then (d) drying and firing the impregnated and supported extruded product in an oxidizing atmosphere. Kill. Further, as a wet extrusion method, a sufficient amount of the periodical law is set so that the content of the group (A) Group VIB metal in the periodic table (a) is 4 to 30% by weight based on the weight of all the supported catalysts. A solution of a salt of a Group VIB metal in the table and (b) a content of the Group VIII metal in the periodic table of 1 to
A solution of a salt of a Group VIII metal of the Periodic Table of the invention, and (c) a sufficient amount of a solution of a Group VA metal of the Periodic Table of 0 to 10% by weight. Periodic Table VA
Also prepared by directly adding to the alumina dough in any order a solution of the salt in the group metal and (d) a solution of the salt of dysprosium in an amount sufficient to provide a content of dysprosium of 0.01 to 5% by weight. it can.

The use of alumina dough prepared by the technique disclosed in Japanese Patent Publication No. 2-54142 is preferable because the use of a peptizer can be avoided and a decrease in effective specific surface area can be prevented.

A particularly suitable Group VIB metal compound for incorporation into alumina dough is ammonium molybdate, a particularly suitable Group VIII metal compound is cobalt nitrate, and a particularly suitable Group VA metal compound is phosphoric acid. ,
A particularly suitable dysprosium compound is dysprosium nitrate. Other suitable Group VIB metal compounds include compounds such as molybdic anhydride, molybdic acid, tungstic acid, ammonium tungstate. Other Group VIII metal compounds that can be used include nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, ferrous cobalt sulfate, ferric nitrate, ferric sulfate, and the like. Examples include pyrophosphoric acid, metaphosphoric acid, phosphorus pentachloride, tetraphosphorus tenoxide and the like. Other suitable dysprosium compounds include dysprosium chloride, dysprosium oxide, dysprosium fluoride, dysprosium sulfate, dysprosium carbonate, dysprosium acetate and the like.

[0032]

EXAMPLES The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

[Comparative Example 1] About 9 minutes of amorphous alumina having a water content of 62.5% by weight was used for 3 minutes with a self-cleaning type kneader.
Amorphous alumina hydrate consisting of pseudo-boehmite gel obtained by kneading at 0 ° C. (Al ₂ O ₃ : 37.5% by weight, ignition loss: 62.5% by weight) About 880 g (Al ₂ O ₃ As 33
0 g) of alumina dough, ammonium molybdate aqueous solution (containing 41 g of ammonium molybdate salt) and cobalt nitrate aqueous solution (containing 38 g of cobalt nitrate hexahydrate) were well-kneaded and mixed by a kneader for about 1 hour.
The soft mass mixture was then extruded through a perforated plate with numerous 1.1 mm holes. The extruded body was heated in air at 350 ° C. for 1 hour and then at 600 ° C. for another 2 hours to be dried and fired. The extruded particles having an average length of about 3.5 mm were 2 wt% Co and 6.5 wt% M.
It contained o. Next, this fired extruded body was impregnated. 27 g ammonium molybdate and 4
Molybdenum and cobalt prepared by mixing an aqueous solution consisting of 5 g of ammonium hydroxide, 20 g of cobalt nitrate hexahydrate and 10 g of distilled water, and diluting the resulting aqueous solution to 120 cc with distilled water. 140 g of a fired extruded body was impregnated with an aqueous ammonium solution containing The extruded body was dipped in the impregnating solution and then evaporated to dryness.
It was further dried and baked at 50 ° C. for 2 hours. After firing, the extrudate contained 4 wt% Co and 14.6 wt% Mo. This extruded body is designated as catalyst R.

[Example 1] About 9 minutes of amorphous alumina having a water content of 62.5% by weight was used for 3 minutes with a self-cleaning type kneader.
Amorphous alumina hydrate consisting of pseudo-boehmite gel obtained by kneading at 0 ° C. (Al ₂ O ₃ : 37.5% by weight, ignition loss: 62.5% by weight) About 880 g (Al ₂ O ₃ As 33
0 g) of alumina dough and ammonium molybdate aqueous solution (containing 41 g of ammonium molybdate salt) and cobalt nitrate / dysprosium nitrate mixed aqueous solution (38 g of cobalt nitrate hexahydrate and 6.5 g of dysprosium nitrate pentahydrate). Wet kneading and mixing were performed well with a time kneader. The soft mass mixture was then extruded through a perforated plate with numerous 1.1 mm holes. The extruded body was heated in air at 350 ° C. for 1 hour and then at 600 ° C. for another 2 hours to be dried and fired. Average length is about 3.5
The extruded particles that had been broken into mm were 0.64% by weight D
It contained y, 2 wt% Co and 6.3 wt% Mo.
Next, this extruded body was impregnated. An aqueous solution of 27 g of ammonium molybdate and 45 g of ammonium hydroxide was mixed with an aqueous solution of 20 g of cobalt nitrate hexahydrate and 10 g of distilled water, and the resulting aqueous solution was diluted to 120 cc with distilled water. With an ammonium aqueous solution containing molybdenum and cobalt prepared by
0 g of the fired extruded body was impregnated. The extruded body was immersed in the impregnating solution, evaporated to dryness, and dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours. After firing, the extrudate is 0.5 wt% D
It contained y, 3.9 wt% Co and 14.3 wt% Mo. This extruded body was designated as catalyst A.

Test Example 1 Using the catalyst A obtained in Example 1 and the catalyst R obtained in Comparative Example 1, the following two types of activity tests were conducted.

Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 70 ° C., and the feed oil VGO had a liquid hourly space velocity of 3.0 hr.
^-1 and hydrogen / feedstock ratio feed rate is 320 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 40 ° C., and the feed oil LGO had a liquid space velocity of 2.0 hr.
^-1 and the feed rate of hydrogen / feedstock ratio is 120 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

The results of these activity tests are shown in Table 1 below. In addition, the numerical value of the catalyst A showing the activation effect is the desulfurization rate of the catalyst R (calculated from the sulfur content before and after hydrodesulfurization of the product) is 1
It is represented by an index when 00 is set.

[0039]Table 1 Desulfurization effect of each catalyst  Catalyst R Catalyst A Particle density (g / cc) 1.25 1.27 Particle diameter (cylinder) (mm) 0.85 0.85 Co wt% 4.0 3.9 Mo wt% 14.6 14.3 Dy % By weight 0 0.5 Activity test-1 100 118 Activity test-2 100 110 As is apparent from Table 1, the catalyst A of the present invention is a conventional catalyst.
18% active in desulfurization activity of activity test-1 compared to R
10% superior in desulfurization activity of Test-2
Was backed up.

Comparative Example 2 200 g of an alumina extruded carrier containing 1.5 wt% Co and 3.5 wt% Mo,
An aqueous solution consisting of 37 g of ammonium molybdate and 70 g of ammonium hydroxide, 30 g of cobalt nitrate hexahydrate and 15 g of distilled water were mixed,
The obtained aqueous solution was impregnated with an aqueous ammonium solution containing molybdenum and cobalt prepared by diluting the aqueous solution to 200 cc with distilled water. The extruded carrier was immersed in the impregnating solution, evaporated to dryness, and dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours to prepare a catalyst. It contained 3.7 wt% Co and 12 wt% Mo. This is referred to as catalyst S.

Example 2 According to the present invention, 200 g of the catalyst of Comparative Example 2 was immersed in an impregnating solution prepared by diluting 2.7 g of dysprosium nitrate pentahydrate with distilled water to 180 cc, and then evaporated to dryness. In air, it was dried and calcined at 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours. After calcination, the extruded catalyst was 0.1 wt% Dy and 3.7 wt% C
and 11.9 wt% Mo. This is catalyst B
And

Test Example 2 Using the catalyst B obtained in Example 2 and the catalyst S obtained in Comparative Example 2, the following two kinds of activity tests were conducted.

Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 70 ° C., and the feed oil VGO had a liquid hourly space velocity of 3.0 hr.
^-1 and hydrogen / feedstock ratio feed rate is 320 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 40 ° C., and the feed oil LGO had a liquid space velocity of 2.0 hr.
^-1 and the feed rate of hydrogen / feedstock ratio is 120 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

The results of these activity tests are shown in Table 2 below. In addition, the value of the catalyst B showing the activation effect is the desulfurization rate of the catalyst S (calculated from the sulfur content before and after hydrodesulfurization of the product) is 1
It is represented by an index when 00 is set.

[0046]Table 2 Desulfurization effect of each catalyst  Catalyst S Catalyst B Particle density (g / cc) 1.20 1.21 Particle size (cylinder) (mm) 1.40 1.40 Co wt% 3.7 3.7 Mo wt% 12.0 11.9 Dy % By weight 0 0.1 Activity test-1 100 120 Activity test-2 100 112 As is apparent from Table 2, the catalyst B of the present invention is a conventional catalyst.
20% more active than desulfurization in activity test-1
12% superior in desulfurization activity of Test-2
Was backed up.

Comparative Example 3 1.45 wt% Co and 3.2
200 g of alumina extruded carrier containing wt% Mo
An aqueous solution of 36 g of ammonium molybdate, 20 g of monoethanolamine and 100 G of distilled water, 27 g of 85% phosphoric acid solution and 28 g of cobalt nitrate.
Mix the hexahydrate and an aqueous solution consisting of 15 g of distilled water,
The obtained aqueous solution was impregnated with an aqueous ammonium solution containing molybdenum and cobalt prepared by diluting the aqueous solution to 200 cc with distilled water. The extruded carrier was immersed in the impregnating solution, evaporated to dryness, and dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours to prepare a catalyst. It contained 3.4 wt% Co, 11.2 wt% Mo and 3.0 wt% P. This is designated as catalyst T.

Example 3 According to the present invention, 200 g of the catalyst of Comparative Example 3 was immersed in an impregnation solution prepared by diluting 2.7 g of dysprosium nitrate pentahydrate with distilled water to 180 cc, and then evaporated to dryness. In air, it was dried and calcined at 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours. After calcination, the extruded catalyst was 0.1 wt% Dy and 3.4 wt% C
O, 11.1% by weight Mo and 3.0% by weight P. This is designated as catalyst C.

Test Example 3 Using the catalyst C obtained in Example 3 and the catalyst T obtained in Comparative Example 3, the following two kinds of activity tests were conducted.

Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 70 ° C., and the feed oil VGO had a liquid hourly space velocity of 3.0 hr.
^-1 and hydrogen / feedstock ratio feed rate is 320 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 40 ° C., and the feed oil LGO had a liquid space velocity of 2.0 hr.
^-1 and the feed rate of hydrogen / feedstock ratio is 120 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

The results of these activity tests are shown in Table 3 below. In addition, the value of the catalyst C representing the activation effect is 1% of the desulfurization rate of the catalyst T (calculated from the sulfur content before and after hydrodesulfurization of the product).
It is represented by an index when 00 is set.

[0053]Table 3 Desulfurization effect of each catalyst  Catalyst T Catalyst C Particle density (g / cc) 1.26 1.26 Particle size (cylinder) (mm) 1.40 1.40 Co wt% 3.4 3.4 Mo wt% 11.2 11.1 P Wt% 3.0 3.0 Dy wt% 0 0.1 Activity test-1 100 126 Activity test-2 100 114 As is apparent from Table 3, the catalyst C of the present invention is a conventional catalyst.
26% more active in desulfurization activity in activity test-1 than T
14% superior in desulfurization activity of Test-2
Was backed up.

[Comparative Example 4] 200 g of an alumina extruded carrier containing 1.5 wt% Ni and 3.5 wt% Mo,
An aqueous solution of 37 g of ammonium molybdate and 70 g of ammonium hydroxide was mixed with an aqueous solution of 30 g of nickel nitrate hexahydrate and 15 g of distilled water, and the resulting aqueous solution was diluted to 200 cc with distilled water. Impregnation treatment was carried out with the ammonium aqueous solution containing molybdenum and nickel prepared in the above. The extruded carrier is dipped in the impregnating solution and then evaporated to dryness, and then heated to 350 ° C. in air for 1 hour
Then, the catalyst was prepared by drying and calcining at 550 ° C. for another 2 hours. It contained 3.7 wt% Ni and 12 wt% Mo. This is designated as catalyst U.

Example 4 According to the present invention, 200 g of the catalyst of Comparative Example 4 was immersed in an impregnating solution prepared by diluting 2.7 g of dysprosium nitrate pentahydrate with distilled water to 180 cc, and then evaporated to dryness. In air, it was dried and calcined at 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours. After firing, the extruded catalyst was 0.1 wt% Dy and 3.7 wt% N
i and 11.9 wt% Mo. This is catalyst D
And

[Test Example 4] Using the catalyst D obtained in Example 4 and the catalyst U obtained in Comparative Example 4, the following two types of activity tests were conducted.

Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 70 ° C., and the feed oil VGO had a liquid hourly space velocity of 3.0 hr.
^-1 and hydrogen / feedstock ratio feed rate is 320 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was placed as a fixed bed in a vertical tubular reaction tube kept at 40 ° C., and the feed oil LGO had a liquid space velocity of 2.0 hr.
^-1 and the feed rate of hydrogen / feedstock ratio is 120 Nm ³ /
It was hydrotreated on the catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a high pressure gas-liquid separator at 121 ° C,
The liquid phase was further processed on a stripping column. The liquid phase (produced oil) collected over 8 hours was analyzed for sulfur content.

The results of these activity tests are shown in Table 4 below. In addition, the value of the catalyst D showing the activity effect is 1 of the desulfurization rate of the catalyst U (calculated from the sulfur content before and after the hydrodesulfurization of the product).
It is represented by an index when 00 is set.

[0060]Table 4 Desulfurization effect of each catalyst  Catalyst U Catalyst D Particle density (g / cc) 1.20 1.21 Particle size (cylinder) (mm) 1.40 1.40 Ni wt% 3.7 3.7 Mo wt% 12.0 11.9 Dy % By weight 0 0.1 Activity test-1 100 134 Activity test-2 100 120 As is apparent from Table 4, the catalyst D of the present invention is the conventional catalyst.
Compared to U, 34% in desulfurization activity of activity test-1, activity
20% superior in desulfurization activity of Test-2
Was backed up.

[Test Example 5] -Measurement of catalyst life-Using catalyst C obtained in Example 3 and catalyst T obtained in Comparative Example 3 above, an absolute pressure of 300 psig and a hydrogen / feedstock ratio were supplied. The life of the catalyst was examined under the conditions of a velocity of 400 SCFB and an LHSV (liquid hourly space velocity) of 2.0 hr ⁻¹ . The results are shown in Figure 1. The graph of FIG. 1 shows the change over time in the reaction temperature required when each catalyst is used as a hydrodesulfurization catalyst. Usually, when the reaction temperature exceeds 360 ° C., it becomes unsuitable as a hydrodesulfurization catalyst, and therefore the period up to this temperature is considered to be the life of the catalyst. According to FIG. 1, the life of the conventional catalyst T is about 4.5 months, whereas the life of the catalyst C of the present invention is about 1 year and 3 months, which is significantly long.

[Test Example 6] -Hue Stability-The feedstock oil LGO containing 1.55% by weight of sulfur was hydrodesulfurized using the catalyst C obtained in Example 3 above to contain sulfur. 0.09% and 0.05% by weight
Got light oil. As a control, the catalyst T obtained in Comparative Example 3 was used for the same hydrodesulfurization treatment to obtain gas oils having sulfur contents of 0.09% by weight and 0.05% by weight. Hue value when using each catalyst (Seybolt hue)
2 and FIG. 3 show changes with time. FIG. 2 is a graph showing changes in hue value (Seybolt hue) with time when the catalyst C of the present invention is used, and FIG. 3 is a graph showing changes in hue value (Seybolt hue) with time when the conventional catalyst T is used. Is. According to these graphs, the gas oil hydrodesulfurized using the catalyst of the present invention shows a gradual change in hue regardless of the sulfur content, and after 35 days, almost no change in hue was observed. I can't. On the other hand, when the conventional catalyst was used, the hue was rapidly decreased at any sulfur content, which also confirms the superiority of the catalyst of the present invention.

[0063]

EFFECTS OF THE INVENTION The hydrodesulfurization catalyst of the present invention has a significantly higher desulfurization activity than the conventional hydrodesulfurization catalyst, the catalyst life is remarkably extended, the deterioration of the hue is small, and the long-term stability is excellent. It has a remarkable effect. Therefore, the hydrodesulfurization catalyst of the present invention can sufficiently comply with the second stage regulation of sulfur content and aromatic content in light oil, and greatly contributes to the solution of environmental problems caused by these components. I can say.

[Brief description of drawings]

FIG. 1 is a graph showing a change with time in reaction temperature of a hydrodesulfurization catalyst of the present invention and a conventional hydrodesulfurization catalyst.

FIG. 2 is a graph showing changes in hue value (Seybolt hue) with time when the catalyst of the present invention is used.

FIG. 3 is a graph showing changes in hue value (Seybolt hue) with time when a conventional catalyst is used.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10G 45/08 Z 2115-4H 45/12 Z 2115-4H

Claims (15)

[Claims] 1. A metal, an oxide, a sulfide, a salt, or a mixture or a bond of at least one or two or more selected from the metals of Group VIB, Group VIII, and Group VA of the periodic table. And a dysprosium compound supported on a refractory carrier, a hydrodesulfurization catalyst for hydrocarbons. 2. The hydrocarbon hydrodesulfurization catalyst according to claim 1, wherein the Group VIB metal of the periodic table is molybdenum and / or tungsten. 3. The metal of Group VIII of the Periodic Table is cobalt and / or nickel.
Or the hydrocarbon hydrodesulfurization catalyst according to 2. 4. The hydrocarbon hydrodesulfurization catalyst according to claim 1, wherein the metal of Group VA of the periodic table is phosphorus. 5. A Group VIB metal of the periodic table of 1 to 30% by weight in terms of elements based on the weight of all the supported catalysts and 1
10 to 10% by weight of a metal of Group VIII of the periodic table, 0 to 10% by weight of a metal of Group VA of the periodic table and 0.05 to 5% by weight of dysprosium on a refractory carrier. The hydrodesulfurization catalyst for hydrocarbons according to any one of claims 1 to 4. 6. The hydrocarbon hydrodesulfurization catalyst according to claim 1, wherein the refractory carrier is alumina alone or an alumina oxide containing silica-alumina and / or zeolite. .. 7. The content of Group (A) Group VIB metal (a) in the elemental conversion based on the weight of all the supported catalysts is 4 to.
A solution of a salt of a Group VIB metal of the Periodic Table of the invention, and (b) an amount sufficient to provide a content of the Group VIII metal of the Periodic Table of 1 to 10% by weight. After impregnating and supporting a solution of a salt of a Group VIII metal of the Periodic Table on a refractory carrier in any order or at once, it is sufficient that the content of (c) dysprosium is 0.05 to 5% by weight. A method for producing a hydrodesulfurization catalyst for hydrocarbon, further comprising impregnating and supporting a solution of a salt of dysprosium on a refractory carrier in an appropriate amount. 8. The content of Group (A) Group VIB metal (a) in the elemental conversion based on the weight of all the supported catalysts is 4 to.
30% by weight of a solution of a metal of Group VIB of the Periodic Table, (b) a sufficient amount of a Group VIII metal content of the Periodic Table to be 1 to 10% by weight. Periodic table V
A solution of a salt of a Group III metal, (c) a solution of a salt of a Group VA metal of the Periodic Table, and (d) an amount sufficient to bring the content of the Group VA metal of the Periodic Table to 1 to 10% by weight. A hydrocarbon hydrodesulfurization catalyst, characterized in that a sufficient amount of a solution of a salt of dysprosium so that the content of dysprosium is 0.05 to 5% by weight is added to an extruded body in any order. Production method. 9. A group VIB metal of the periodic table of 1 to 30% by weight in terms of elements based on the weight of all supported catalysts and 1
A hydrodesulfurization catalyst comprising -10 wt% metal of Group VIII of the periodic table, 1-10 wt% metal of Group VA of the periodic table and 0.05-5 wt% of dysprosium on a refractory carrier. In the production, (a) first, a refractory inorganic oxide and an amount of 10 to 100% by weight of the final supported amount of each of Group VIB metal compound, Group VIII metal compound, Group VA metal compound and dysprosium of the periodic table. Kneading with the compound to form an extrudable soft mass, (b) extruding the soft mass, and drying the extruded soft mass in an oxidizing atmosphere,
After firing, (c) the VIB is added to the fired extruded body.
A hydrocarbon characterized by impregnating and supporting the remaining amount of a group metal compound, a group VIII metal compound, a group VA metal compound and a dysprosium compound, and then drying and firing the impregnated and supported extruded product in an oxidizing atmosphere. The method for producing a hydrodesulfurization catalyst according to claim 1. 10. The method for producing a hydrocarbon hydrodesulfurization catalyst according to claim 7, wherein the Group VIB metal of the periodic table is molybdenum and / or tungsten. 11. The method for producing a hydrodesulfurization catalyst for hydrocarbons according to claim 7, wherein the Group VIII metal of the periodic table is cobalt and / or nickel. 12. The method for producing a hydrocarbon hydrodesulfurization catalyst according to claim 8, wherein the metal of Group VA of the periodic table is phosphorus. 13. The hydrocarbon hydrodesulfurization catalyst according to claim 7, wherein the refractory carrier is alumina alone or an alumina oxide containing silica-alumina and / or zeolite. Manufacturing method. 14. A Periodic Table Group VIB, Group VIII,
And at least one or more metals selected from the group VA metals or oxides, sulfides, salts or mixtures or combinations thereof, and a dysprosium compound supported on a refractory carrier. In the presence of hydrogen using a hydrodesulfurization catalyst for hydrocarbons
Temperature range of 00 to 600 ° C., 10 to 300 Kg / cm ²
A hydrocarbon fraction containing a sulfur compound under the reaction conditions of a pressure range of 0.1 to 10 hr ^−1, a liquid hourly space velocity range of 0.1 to 10 hr ⁻¹ , and a hydrogen / feed oil feed rate range of ^{30 to} 1500 Nm ³ / KL. A method for hydrodesulfurizing a hydrocarbon fraction, characterized by hydrodesulfurizing. 15. The temperature is in the range of 200 to 450 ° C. and the pressure is in the range of ²⁰ to 100 Kg / cm ² ,
The liquid hourly space velocity is in the range of 0.5 to 6 hr ^-1 , and hydrogen /
The method for hydrodesulfurizing a hydrocarbon fraction according to claim 14, wherein the feed rate of the feedstock ratio is in the range of 50 to 500 Nm ³ / KL.