JP4721759B2 - Method for producing hydrotreating catalyst for light oil - Google Patents

Description

  The present invention relates to a method for producing a hydrotreating catalyst for light oil, and more particularly, shows high hydrotreating and desulfurization activity when used in hydrotreating to reduce aromatic hydrocarbons and sulfur content in light oil. The present invention relates to a method for producing a hydroprocessing catalyst for light oil with little deterioration.

Diesel engines have high economic advantages such as good fuel consumption, high durability, and low CO ₂ emissions, as well as global environmental conservation. On the other hand, air pollution caused by diesel exhaust gas has a major negative impact on urban areas and roads. Giving. In particular, the impact on the health of particulate matter (formed from soot, organic solvent insoluble matter, sulfate, moisture, etc.) is a serious problem.
As one of the methods for reducing the particulate matter from the exhaust gas, it has been recognized worldwide that the quality of light oil is improved. For this reason, the development of a high-performance catalyst that can reduce sulfur content in gas oil and at the same time reduce aromatic hydrocarbons has become an important issue. Proposed.

For example, Patent Document 1 proposes a hydrotreating catalyst for hydrocarbon oil, a method for producing the same, and a method for activating the same, and the γ-alumina support has at least one selected from Group 6 metals in the periodic table. A hydrogenation catalyst is produced by impregnating an organic additive on a catalyst supporting at least one active metal selected from group 9 or group 10 metal of the periodic table and an oxide of phosphorus. In the method, the organic additive is selected from the group consisting of 2 to 3 carbon alcohols having 2 to 10 carbon atoms per molecule or ethers thereof, polyethylene glycols, monosaccharides, disaccharides and polysaccharides. A method for producing a hydrocarbon oil hydrotreating catalyst is characterized in that it is dried under such a condition that the organic additive remains in the catalyst.
However, a conventional hydrotreating catalyst in which an active component such as nickel-molybdenum or nickel-tungsten is supported on a porous inorganic oxide carrier such as alumina has some effect of reducing the sulfur content in the light oil, but in the light oil. This type of catalyst was not suitable as an aromatic hydrogenation catalyst because of its low hydrogenation ability to reduce aromatic hydrocarbons.

On the other hand, a catalyst using a noble metal as an active ingredient has a high aromatic ring hydrogenation activity, but conversely has a drawback that it is susceptible to reaction inhibition such as sulfur poisoning and easily deteriorates. Thus, noble metal hydrogenation catalysts having high resistance to poisoning substances such as sulfur have been proposed.
For example, Patent Document 2 by the present inventors describes a hydrogenation catalyst characterized in that palladium and / or platinum is supported on an ultra-stabilized Y-type zeolite carrier modified with heavy rare earth elements. Patent Document 3 discloses an aromatic hydrocarbon hydrogenation catalyst comprising at least one element selected from heavy rare earth elements and at least one noble metal selected from Group VIII noble metals of the periodic table A composition is described.
However, even with these improved catalysts, the deterioration of the activity over time was observed to the extent that would be a problem when used industrially. In particular, basic nitrogen compounds contained in light oil strongly adsorb to the acid sites on the carrier, neutralize the acid and lower the sulfur resistance of the active metal, and further aggregate the noble metal, thereby increasing the activity of the catalyst. There was a problem that deterioration was promoted.

JP-A-8-332385 JP 2001-29792 A JP 2001-246253 A

  The object of the present invention is to solve the above-mentioned problems and use it for hydrogenation treatment of light oil containing sulfur compounds and nitrogen compounds to have high hydrogenation activity and high desulfurization activity in hydrogenation of aromatic hydrocarbons. It is another object of the present invention to provide a method for producing a gas oil hydrotreating catalyst having high resistance to sulfur compounds and nitrogen compounds and having little deterioration in hydrogenation and desulfurization activities.

As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention impregnated an aqueous solution containing a specific oxygen-containing organic compound in a method for producing a noble metal-based hydrotreating catalyst for light oil, at a relatively low temperature. The catalyst obtained by calcining with NO was found to have little deterioration in hydrogenation and desulfurization activity, and the present invention was completed.

That is, according to the first aspect of the present invention, a porous inorganic oxide carrier is impregnated with an aqueous solution containing at least one oxygen-containing organic compound selected from the group consisting of saccharides and derivatives thereof, dried, and then subjected to periodic table VIII. Impregnating an aqueous solution containing at least one kind of noble metal selected from group noble metals, drying and calcining to obtain a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in the infrared absorption spectrum. The present invention relates to a method for producing a featured gas oil hydrotreating catalyst.
In the second aspect of the present invention, the porous inorganic oxide support includes at least one noble metal selected from Group VIII noble metals in the periodic table, and at least one oxygen-containing organic compound selected from the group consisting of saccharides and derivatives thereof. An oil hydrotreating catalyst characterized in that a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in an infrared absorption spectrum is obtained by impregnating an aqueous solution containing It relates to a manufacturing method.
The third aspect of the present invention is an aqueous solution containing at least one kind of noble metal selected from Group VIII noble metals of the periodic table on a porous inorganic oxide support, and at least one kind of oxygen containing substance selected from the group consisting of saccharides and derivatives thereof. Impregnation by simultaneously introducing an aqueous solution containing an organic compound through different inlets, drying, and firing to obtain a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in the infrared absorption spectrum The present invention relates to a method for producing a gas oil hydrotreating catalyst.
In the fourth aspect of the present invention, the porous inorganic oxide support is impregnated with an aqueous solution containing at least one noble metal selected from Group VIII noble metals in the periodic table, dried, and then selected from the group consisting of saccharides and derivatives thereof. It is characterized in that a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in an infrared absorption spectrum is obtained by impregnating an aqueous solution containing at least one oxygen-containing organic compound, drying and firing. The present invention relates to a method for producing a gas oil hydrotreating catalyst.
In the fifth aspect of the present invention, the porous inorganic oxide carrier is crystalline aluminosilicate zeolite, alumina, silica, titania, zirconia, alumina-silica, alumina-boria, alumina-titania, alumina-silica-boria, silica-titania. An inorganic oxide selected from the group consisting of alumina-silica-titania, alumina-titania-boria, alumina-phosphorus, alumina-phosphorus-boria, alumina-silica-phosphorus, and alumina-titania-phosphorus-boria. The present invention relates to a method for producing a gas oil hydrotreating catalyst according to any one of claims 1 to 4.
The sixth aspect of the present invention is the gas oil hydrotreating catalyst according to any one of claims 1 to 5, wherein the impregnation amount of the noble metal is in a range of 0.1 to 10 wt% as a metal on a catalyst basis. It relates to the manufacturing method.
According to a seventh aspect of the present invention, the noble metal is composed of palladium (Pd) and platinum (Pt), and the Pd / Pt atomic ratio is in the range of 0.1 / 1 to 10/1. 6. A method for producing a gas oil hydrotreating catalyst according to any one of 6 above.
According to an eighth aspect of the present invention, the oxygen-containing organic compound is an oxygen-containing organic compound selected from the group consisting of monosaccharides, disaccharides, polysaccharides, aldonic acids , sugar acids, uronic acids, and lactones. The present invention relates to a method for producing a gas oil hydrotreating catalyst according to any one of claims 1 to 7.
The ninth aspect of the present invention is that the amount of impregnation of the oxygen-containing organic compound is in the range of 1 to 20 wt% with respect to the porous inorganic oxide support. The present invention relates to a method for producing a gas oil hydrotreating catalyst.
The tenth aspect of the present invention is that the amount of residual carbon contained in the hydroprocessing catalyst is in the range of 0.5 to 10 wt% as carbon on a catalyst basis. The present invention relates to a method for producing a gas oil hydrotreating catalyst.

Method for producing a gas oil hydrotreating catalysts of the present invention, the porous inorganic oxide support to a saccharide and water solution and the Group VIII of periodic table including at least one oxygen-containing organic compound selected from the group consisting of a derivative thereof A catalyst containing a residual carbon and having a clear absorption at 2200 cm ⁻¹ in an infrared absorption spectrum is obtained by impregnating an aqueous solution containing at least one kind of noble metal selected from noble metals, drying and firing. And

As the porous inorganic oxide carrier in the present invention, a porous inorganic oxide carrier that is usually used for a hydrotreating catalyst such as light oil can be used.
Examples of the porous inorganic oxide carrier include crystalline aluminosilicate zeolite and / or alumina, silica, titania, zirconia, alumina-silica, alumina-boria, alumina-titania, alumina-silica-boria, silica-titania, and alumina. -An inorganic oxide selected from silica-titania, alumina-titania-boria, alumina-phosphorus, alumina-phosphorus-boria, alumina-silica-phosphorus, and alumina-titania-phosphorus-boria is preferable.
As the crystalline aluminosilicate zeolite, pentasil type represented by A-type zeolite, X-type zeolite, Y-type zeolite, L-type zeolite, beta-type zeolite, mordenite, chabazite, erionite, AlPO ₄ , SAPO and ZSM zeolite. Examples include MFI type zeolite such as zeolite.
In particular, an ultrastable Y-type zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 5 or more, preferably 10 to 1000, more preferably 10 to 300, is suitable because it has a suitable solid acid. The crystalline aluminosilicate zeolite is used as a carrier alone or in combination with other inorganic oxides.
As the porous inorganic oxide support, those having a known shape such as a columnar shape, a cylindrical shape, a trilobal shape, and a four-leaf shape can be used. In addition, the porous inorganic oxide support | carrier in this invention is not limited to these.

As the at least one oxygen-containing organic compound selected from the group consisting of saccharides impregnated in the porous inorganic oxide carrier and derivatives thereof, an oxygen-containing organic compound that dissolves in water is used.
Examples of the saccharide and / or derivative thereof include D-glucose (glucose), D-fructose (fructose), monosaccharides such as aldose and ketose including D-galactose, and disaccharides such as sucrose (sucrose) and maltose. , Polysaccharides such as starch, aldonic acids such as gluconic acid and mannonic acid (one carboxyl group, five alcohol groups), sugar acids such as sugar acid, mannosugar acid and mucic acid (two carboxyl groups, 4 alcohol groups), uronic acids such as glucuronic acid and galacturonic acid (1 carboxyl group and 4 alcohol groups), and at least selected from lactones that form a cyclic ester in the molecule such as glucolactone A kind of oxygen-containing organic compound is preferable.

The impregnation amount of the oxygen-containing organic compound is preferably in the range of 1 to 20 wt% with respect to the porous inorganic oxide support.
When the impregnation amount of the oxygen-containing organic compound is less than 1 wt%, the obtained catalyst may not be used for the hydrogenation treatment of light oil to obtain the desired effect of preventing deterioration of the hydrogenation and desulfurization activities. Even if the impregnation amount of the oxygen-containing organic compound is more than 20 wt%, there is no difference in the effect. The impregnation amount of the oxygen-containing organic compound is more preferably in the range of 2 to 15 wt%.

Examples of the Group VIII noble metals in the periodic table include ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. The amount of impregnation of the above-mentioned noble metal is preferably in the range of 0.1 to 10 wt% as a metal on the basis of the catalyst (support and metal component).
When the impregnation amount of the noble metal is less than 0.1 wt%, the desired hydrogenation and desulfurization activity may not be obtained. Costs tend to be high.
The amount of impregnation of the noble metal is more preferably in the range of 0.5 to 5 wt% as a metal.

In the present invention, the noble metal is preferably composed of palladium (Pd) and platinum (Pt), and the Pd / Pt atomic ratio is preferably in the range of 0.1 / 1 to 10/1. By using a combination of palladium and platinum, a high hydrogenation function is maintained and resistance to sulfur compounds is increased.
This is presumably because palladium has a high affinity for sulfur and thus protects platinum from poisoning.
The combination of palladium and platinum is preferably in the range of 0.1 / 1 to 10/1 in terms of Pd / Pt atomic ratio. If the Pd / Pt atomic ratio is less than 0.1 / 1 or greater than 10/1, the resistance to sulfur compounds may decrease, and a high hydrogenation function may not be maintained.

Furthermore, it is desirable to support at least one element selected from heavy rare earth elements on the aforementioned porous inorganic oxide carrier in addition to the aforementioned noble metal.
The heavy rare earth element means four elements of ytterbium (Yb), gadolinium (Gd), terbium (Tb), and dysprosium (Dy).
By supporting heavy rare earth elements in addition to the above-mentioned noble metals, the effects of sulfur poisoning resistance and nitrogen poisoning resistance of noble metals are increased. The supported amount of the heavy rare earth element is preferably in the range of 0.5 to 40 wt% (catalyst basis), more preferably 2.5 to 20 wt% as a metal. When the loading amount of the heavy rare earth element is less than 0.5 wt%, the increase in the effect is small, and even if the loading amount is more than 40 wt%, the effect does not change so much and the manufacturing cost tends to increase. As a method for supporting heavy rare earth elements, known methods such as an impregnation method and a kneading method are employed.

For the impregnation of the aqueous solution containing the oxygen-containing organic compound and / or the aqueous solution containing the noble metal described above into the porous inorganic oxide carrier described above, a well-known impregnation method is employed.
Examples of the impregnation method include an adsorption method, an equilibrium adsorption method, a pore filling method, an incipient wetness method, an evaporation to dryness method, and a spray method.
The porous inorganic oxide carrier is impregnated with the aqueous solution containing the oxygen-containing organic compound and / or the aqueous solution containing the noble metal described above by the above-described well-known impregnation method. Then, after drying, it may be impregnated with an aqueous solution containing the aforementioned noble metal, or impregnated with an aqueous solution containing the aforementioned noble metal, dried and then impregnated with an aqueous solution containing the aforementioned oxygen-containing organic compound. good. Further, it may be impregnated with an aqueous solution containing the aforementioned noble metal and the aforementioned oxygen-containing organic compound. Further, the aqueous solution containing the above-mentioned noble metal and the aqueous solution containing the above-mentioned oxygen-containing organic compound may be impregnated by simultaneously spraying them from different inlets.

In the production method of the present invention, the porous inorganic oxide carrier is impregnated with the aqueous solution containing the oxygen-containing organic compound and / or the aqueous solution containing the noble metal described above by the impregnation method, and then dried and dried. Remove.
Drying in the present invention is performed for a time during which water is removed by 10 wt% or more, preferably 50 to 100 wt%, in a temperature range in which the impregnated oxygen-containing organic compound does not decompose and burn.
Specifically, the drying conditions for 0.1 to 20 hours are exemplified in the temperature range of 60 to 200 ° C.
In particular, drying by microwave irradiation is preferable. As the microwave, the 2.45 GHz frequency of a microwave oven used at home is particularly suitable.
The dried catalyst is calcined in the presence of oxygen, preferably in a stream of oxygen at a relatively low temperature to stabilize the active component. Specifically, firing conditions for 0.1 to 20 hours and the like are exemplified in a temperature range of 200 to 400 ° C.
The hydrotreating catalyst obtained as a result of this calcination desirably contains residual carbon in the range of 0.5 to 10 wt% as carbon on a catalyst basis. When the amount of residual carbon is less than 0.5 wt%, the obtained catalyst may not be used for the hydrogenation treatment of light oil to obtain the desired effect of preventing deterioration of hydrogenation and desulfurization activity. There is no difference in effect even if the amount of residual carbon is more than 10 wt%.

The catalyst obtained by the production method of the present invention has little activity deterioration except in the very initial stage. That is, the catalyst has a hydrogenation catalyst ability of an aromatic hydrocarbon having a very long life with little deterioration in activity while having a high hydrogenation function.
Although it is not clear why the catalyst has very little deterioration in activity, the oxygen-containing organic compound remaining in the catalyst protects the active site and suppresses aggregation of noble metals, and poisonous substances such as basic nitrogen compounds It is presumed to have a function to mitigate attacks by.
Moreover, the catalyst baked at 200-400 degreeC which shows the high stability obtained by the manufacturing method of this invention has a clear absorption in 2200cm < ^-1 > in an infrared absorption spectrum. The clear absorption is not observed in the catalyst not impregnated with the above-mentioned oxygen-containing organic compound, and the absorption is not observed in the support containing no noble metal.
The absorption is located in a special absorption region not found in organic compounds of sugars. The absorption is presumed to be due to a partial oxide of carbon adjacent to or bonded to the noble metal.
In addition, when CO adsorbs to the noble metal, absorption is obtained at 2100 cm ⁻¹ and 1950 cm ⁻¹ .

The catalyst obtained by the production method of the present invention can employ ordinary light oil hydrogenation reaction conditions. Specific hydrogenation conditions include a hydrogen partial pressure of 2.9 to 14.7 MPa, preferably 3 9.9 to 7.8 MPa, reaction temperature is 200 to 400 ° C., preferably 250 to 350 ° C., liquid space velocity is 0.1 to 5.0 h ⁻¹ , preferably 2.0 to 4.0 h ^−1, etc. can do.

The hydrogenation catalyst composition of the present invention has high hydrogenation activity and high resistance to sulfur and nitrogen compounds in hydrogenation of aromatic and heteroaromatic hydrocarbons, and various aromatics in which sulfur and nitrogen compounds coexist. It can be used as a hydrogenation catalyst for hydrocarbons and / or heteroaromatic compounds.
The hydrogenation catalyst composition of the present invention can be used as a hydrogenation catalyst for simultaneously reducing the aromatic component and sulfur component in light oil.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereby.

Example 1 (Preparation of catalyst)
10 kg of an aqueous solution of sodium aluminate having a concentration of 5 wt% as alumina was put into a preparation container, and an aqueous solution of aluminum sulfate having a concentration of 2 wt% was added until the pH reached 7 while stirring the aqueous solution to produce pseudoboehmite alumina hydrate. . This slurry was washed and aged, and then kneaded with heating to obtain an alumina kneaded product.
Next, 450 g of the alumina hydrate (dry basis) and 1050 g of ultra-stabilized Y-type zeolite (Tosoh Corporation: HSZ-360HUA SiO ₂ / Al ₂ O ₃ molar ratio = 13.9, H-type zeolite) And the mixture was extruded into a cylindrical shape having a diameter of 1/16 inch. The obtained molded product was dried at 110 ° C. for 16 hours and calcined at 550 ° C. for 3 hours to prepare a porous inorganic oxide support of ultra-stabilized Y-type zeolite (70 wt%) and alumina (30 wt%).
10 g of the porous inorganic oxide carrier (dry basis) was immersed in an aqueous glucose solution in which 0.5 g of glucose (corresponding to 5 wt%) was dissolved in pure water. The impregnated product was then dried at 110 ° C. for 10 hours. The dried product was then mixed with Yb 5 wt% ytterbium acetate tetrahydrate 1.31 g, Pd 0.82 wt% tetraamminepalladium chloride 0.22 g, and Pt 0.38 wt% tetraammineplatinum chloride 0.073 g. Was immersed in a Yb—Pd—Pt mixed metal salt aqueous solution prepared by dissolving in water. Next, this impregnated product was dried by irradiation with microwaves having a frequency of 2.45 GHz for 10 minutes, and calcined in an oxygen stream at 260 ° C. for 3 hours (temperature increase temperature: 0.5 ° C./min) to form catalyst A. Got.

Example 2 (Preparation of catalyst)
Fructose obtained by dissolving 10 g (dry basis) of the ultra-stabilized Y-type zeolite and alumina porous inorganic oxide carrier obtained in Example 1 and 0.5 g (corresponding to 5 wt%) of D-fructose (fructose) in pure water. It was immersed in an aqueous solution. The impregnated product was then dried at 110 ° C. for 10 hours.
The dried product was then mixed with Yb 5 wt% ytterbium acetate tetrahydrate 1.31 g, Pd 0.82 wt% tetraamminepalladium chloride 0.22 g, and Pt 0.38 wt% tetraammineplatinum chloride 0.073 g. Was immersed in a Yb—Pd—Pt mixed metal salt aqueous solution prepared by dissolving in water.
Next, the impregnated product was dried by irradiation with microwaves having a frequency of 2.45 GHz for 10 minutes, and calcined in an oxygen stream at 260 ° C. for 3 hours (temperature increase temperature: 0.5 ° C./min) to obtain catalyst B. Got.

Example 3 (Preparation of catalyst)
A sucrose aqueous solution in which 0.5 g (corresponding to 5 wt%) of saccharose (sucrose) was dissolved in pure water of 10 g (dry basis) of a porous inorganic oxide carrier of ultra-stabilized Y-type zeolite and alumina obtained in Example 1 Soaked in. The impregnated product was then dried at 110 ° C. for 10 hours. The dried product was then mixed with Yb 5 wt% ytterbium acetate tetrahydrate 1.31 g, Pd 0.82 wt% tetraamminepalladium chloride 0.22 g, and Pt 0.38 wt% tetraammineplatinum chloride 0.073 g. Was immersed in a Yb—Pd—Pt mixed metal salt aqueous solution prepared by dissolving in water.
Next, the impregnated product was dried by irradiation with microwaves having a frequency of 2.45 GHz for 10 minutes, and calcined in an oxygen stream at 260 ° C. for 3 hours (temperature increase temperature: 0.5 ° C./min) to obtain catalyst C. Got.

Example 4 (Preparation of catalyst)
10 g (dry basis) of a porous inorganic oxide carrier of ultra-stabilized Y-type zeolite and alumina obtained in Example 1, 0.5 g of saccharose (sucrose) and 5 wt% ytterbium acetate tetrahydrate as Yb Saccharose-Yb-Pd-Pt mixed metal salt prepared by dissolving 31 g, 0.22 g of tetraamminepalladium chloride as Pd and 0.073 g of tetraammineplatinum chloride as Pt in 0.38 wt% in pure water It was immersed in an aqueous solution.
Next, the impregnated product was dried by irradiation with microwaves having a frequency of 2.45 GHz for 10 minutes, and calcined in an oxygen stream at 260 ° C. for 3 hours (temperature increase temperature: 0.5 ° C./min) to obtain catalyst D. Got.

Example 5 (Preparation of catalyst)
10 g (dry basis) of the ultra-stabilized Y-zeolite and alumina porous inorganic oxide support obtained in Example 1 were used as Yb, 5 wt% ytterbium acetate tetrahydrate 1.31 g, and Pd 0.82 wt%. It is immersed in a Yb-Pd-Pt mixed metal salt aqueous solution prepared by dissolving 0.23 g of tetraamminepalladium chloride and 0.073 g of tetraammineplatinum chloride as Pt in pure water, and setting a frequency of 2.45 GHz. It was dried by irradiation with microwaves for 10 minutes.
Next, this dried product was immersed in an aqueous saccharose solution in which 0.5 g (corresponding to 5 wt%) of saccharose (sucrose) was dissolved in pure water.
Next, the impregnated product was dried by irradiation with microwaves having a frequency of 2.45 GHz for 10 minutes, and calcined in an oxygen stream at 260 ° C. for 3 hours (temperature increase temperature: 0.5 ° C./min) to obtain catalyst E. Got.

Comparative Example 1 (Preparation of catalyst)
10 g of the porous inorganic oxide support of ultra-stabilized Y-type zeolite and alumina obtained in Example 1 was used. Yb was 5 wt% ytterbium acetate tetrahydrate 1.31 g and Pd was 0.82 wt% tetraamminepalladium chloride. 0.22 g, 0.038 g of tetraammineplatinum chloride as Pt was dissolved in pure water and immersed in a Yb—Pd—Pt mixed metal salt aqueous solution.
Next, the impregnated product was dried by irradiation with microwaves having a frequency of 2.45 GHz for 10 minutes, and calcined in an oxygen stream at 260 ° C. for 3 hours (temperature increase temperature: 0.5 ° C./min) to obtain catalyst F. Got.

Example 6 (Analysis of catalyst)
The amount of carbon in the dry catalyst was measured for the catalysts A to F prepared in Examples 1 to 5 and Comparative Example 1 by a combustion method. The results are shown in Table 1.
Moreover, about the catalysts C and F prepared in Example 3 and Comparative Example 1, the infrared absorption spectrum was measured with the diffuse reflection method with the Fourier-transform infrared absorption spectrum measuring apparatus.
First, prior to measurement, each sample was pulverized and set in a sample holder. Then, it was dried at 110 ° C. for 2 hours in a He stream as a pretreatment. The result of this infrared absorption spectrum is shown in FIG.
As can be seen from FIG. 1, the catalyst C of Example 3 has a clear absorption at 2200 cm ⁻¹ compared to the catalyst F of Comparative Example 1.

Example 7 (Evaluation of catalyst)
The hydrodesulfurization activity and hydrogenation activity of aromatic hydrocarbon oils containing sulfur and nitrogen compounds were evaluated using the catalysts A to F prepared in Examples 1 to 5 and Comparative Example 1.
First, prior to the reaction, each molded catalyst was pulverized and aligned to 22 to 48 mesh. Further, reduction treatment was performed as a pretreatment for the reaction.
That is, the catalyst was filled in a reaction tube, and reduced in a hydrogen stream (normal pressure, 0.2 L / min) at 300 ° C. for 3 hours (temperature increase rate: 0.5 ° C./min).
In the reaction test, a model compound was used for feed in a high-pressure fixed bed flow type reactor (up flow mode). The model compound was tetralin / n-hexadecane = about 30 wt% / about 70 wt% mixed liquid with 4,6-dimethyldibenzothiophene (4,6-DMDBT) sulfur concentration equivalent to 300 ppm and n-butylamine nitrogen concentration equivalent to 20 ppm. I used something.
The reaction was carried out under the conditions of a catalyst amount of 0.25 g, a hydrogen partial pressure of 3.9 MPa, a reaction temperature of 280 ° C., a space velocity (WHSV) of 16 h ⁻¹ , and an H ₂ / Oil ratio of 500 Nl / l.
Liquid products were collected periodically and analyzed by gas chromatogram with FID detector. In addition, an analysis apparatus using a fluorescent ultraviolet method was used for sulfur analysis.
The hydrogenation activity was evaluated by the conversion rate of tetralin (to decalin or the like), and the desulfurization activity was evaluated by the degree of decrease in the sulfur concentration in the product liquid.
The results are shown in FIG. 2 (hydrogenation activity) and FIG. 3 (hydrodesulfurization activity).
The reaction conditions are more severe than the hydrogenation reaction conditions in the actual apparatus for the accelerated life test.
As can be seen from FIGS. 2 and 3, the catalysts A to E obtained by the production method of the present invention exhibit higher hydrogenation activity and hydrodesulfurization activity than the catalyst F of the comparative example, and the activity of the catalyst It can be seen that the deterioration is small.
When a catalyst carrying Ni—Mo, Ni—W or the like was used after sulfidation treatment, only 5% or less of the activity was confirmed for both the hydrogenation activity and hydrodesulfurization activity under these reaction conditions.

The infrared absorption spectrum figure of the catalyst in Example 3 and Comparative Example 1. FIG. The figure which shows the relationship between the oil passing time of a catalyst and hydrogenation activity in each Example. The figure which shows the relationship between the oil passing time of a catalyst and hydrodesulfurization activity in each Example.

Claims (10)

The porous inorganic oxide support is impregnated with an aqueous solution containing at least one oxygen-containing organic compound selected from the group consisting of saccharides and derivatives thereof, dried, and then at least one selected from Group VIII noble metals of the periodic table A gas oil hydrotreating catalyst obtained by impregnating an aqueous solution containing a noble metal, drying, and calcining to obtain a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in an infrared absorption spectrum Manufacturing method. Impregnating a porous inorganic oxide support with an aqueous solution containing at least one noble metal selected from Group VIII noble metals of the periodic table and at least one oxygen-containing organic compound selected from the group consisting of sugars and derivatives thereof; A method for producing a hydrotreating catalyst for light oil, characterized by obtaining a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in an infrared absorption spectrum by drying and calcining. An aqueous solution containing at least one noble metal selected from Group VIII noble metals of the periodic table on a porous inorganic oxide support, and an aqueous solution containing at least one oxygen-containing organic compound selected from the group consisting of saccharides and derivatives thereof It is impregnated by simultaneous introduction from different inlets, dried, and calcined to obtain a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in the infrared absorption spectrum. A method for producing a hydrotreating catalyst. The porous inorganic oxide support is impregnated with an aqueous solution containing at least one noble metal selected from Group VIII noble metals in the periodic table, dried and then at least one oxygen-containing organic selected from the group consisting of saccharides and derivatives thereof A gas oil hydrotreating catalyst obtained by impregnating an aqueous solution containing a compound, drying, and calcining to obtain a catalyst containing residual carbon and having a clear absorption at 2200 cm ⁻¹ in an infrared absorption spectrum Manufacturing method. The porous inorganic oxide carrier is crystalline aluminosilicate zeolite, alumina, silica, titania, zirconia, alumina-silica, alumina-boria, alumina-titania, alumina-silica-boria, silica-titania, alumina-silica-titania, 2. An inorganic oxide selected from the group consisting of alumina-titania-boria, alumina-phosphorus, alumina-phosphorus-boria, alumina-silica-phosphorus, and alumina-titania-phosphorus-boria. The manufacturing method of the hydroprocessing catalyst of the light oil in any one of -4. The method for producing a gas oil hydrotreating catalyst according to any one of claims 1 to 5 , wherein the amount of impregnation of the noble metal is in the range of 0.1 to 10 wt% as a metal on a catalyst basis. The said noble metal consists of palladium (Pd) and platinum (Pt), and Pd / Pt atomic ratio exists in the range of 0.1 / 1-10/1, The one in any one of Claims 1-6 characterized by the above-mentioned. A method for producing a hydrotreating catalyst for light oil. The oxygen-containing organic compound is an oxygen-containing organic compound selected from the group consisting of monosaccharides, disaccharides, polysaccharides, aldonic acids , sugar acids, uronic acids, and lactones. The manufacturing method of the hydroprocessing catalyst of the light oil in any one. The gas oil hydrotreating catalyst according to any one of claims 1 to 8 , wherein the impregnation amount of the oxygen-containing organic compound is in the range of 1 to 20 wt% with respect to the porous inorganic oxide support. Production method. 10. The gas hydrotreating catalyst according to claim 1 , wherein the amount of residual carbon contained in the hydrotreating catalyst is in the range of 0.5 to 10 wt% as carbon on a catalyst basis. Production method.

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