JP2005254141A - Hydrodesulfurization catalyst of petroleum hydrocarbon oil and its hydrodesulfurization method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrodesulfurization catalyst of a petroleum hydrocarbon oil which has high desulfurization activities and is capable of stably performing the long term operation at a reduced deterioration rate. <P>SOLUTION: The hydrodesulfurization catalyst is characterized by containing 20-25 mass% of molybdenum calculated in terms of the oxide and 55 mass% or more of alumina from the weight of the catalyst in the catalyst carrier comprised of alumina as a main component and further containing at least one selected from silica, titania, zirconia and boria. The hydrodesulfurization catalyst is further characterized by satisfying the relation: A/(A+B+C)≤0.3, and 0.25≤B/(B+C)≤0.55, wherein the peak area having the peak top in a range of 232-233.5 eV of the binding energy is designated as A, the peak area having the peak top in a range of 230-231.5 eV is designated as B and the peak area having the peak top in a range of 228-230 eV is designated as C among the peaks attributing to the orbit 3d5/2 of molybdenum obtained by X-ray photoelectron spectroscopy of the sulfurized catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydrodesulfurization catalyst effective for hydrodesulfurization of petroleum hydrocarbon oils and a hydrodesulfurization method using the catalyst.

  In recent years, awareness of environmental problems and air pollution is increasing, and the sulfur content in transportation fuel oil has attracted particular attention. In particular, exhaust gas discharged from diesel vehicles using light oil as fuel contains fine particles called particulates in addition to chemical substances such as SOx and NOx, and there is concern about damage to health. For this reason, it has been proposed to install a particulate removal filter such as DPF or a device having a particulate combustion removal function at the rear stage of the engine as a measure for removing particulates, and application to diesel engine vehicles is being studied. Further, for NOx, a reduction removal catalyst or the like is being developed. However, these devices and catalysts are affected by poisoning, deterioration, and the like due to SOx generated by changing the sulfur content in the fuel oil. In diesel vehicles such as transport trucks, which have a longer mileage than gasoline vehicles, deterioration of these exhaust gas purifiers and catalyst poisoning are more serious problems. In order to solve such problems, it is strongly desired to reduce the sulfur content in light oil as much as possible. At this time, the light oil used as diesel fuel is also mixed with a fraction that is classified into kerosene fraction as the boiling range in order to maintain the product properties optimally. In order to lower the sulfur content, it is necessary to reduce the sulfur content in both the kerosene fraction and the light oil fraction. Furthermore, by using low sulfur, generation of harmful sulfur oxides and the like can be reduced when used as a heating appliance fuel such as a stove. These heating appliances are used indoors in some cases, and the generation of harmful substances may have a great influence directly on the human body.

  Since petroleum hydrocarbon fractions other than residue oil obtained by crude oil distillation or heavy oil cracking reaction contain sulfur content of about 0.1 to 3% by mass, usually after hydrodesulfurization treatment is carried out Used as fuel substrate. The main sulfur compounds present in these petroleum hydrocarbon fractions are thiophene, benzothiophene, dibenzothiophene and their derivatives. However, in the petroleum hydrocarbon oil, the desulfurization depth of each fraction such as kerosene and light oil is When the desulfurization is advanced to the low sulfur region as the temperature advances, the reactivity tends to be poor. That is, the sulfur compounds remaining in the fractions with the progress of hydrodesulfurization are poor in reactivity, and desulfurization is difficult to proceed unless the conditions are more severe. For example, benzothiophenes for kerosene fractions and alkyl-substituted dibenzothiophenes having a plurality of methyl groups represented by 4,6-dimethyldibenzothiophene as substituents for gas oil fractions are particularly poor in reactivity and sulfur content. This is an obstacle to proceeding with desulfurization to a lower sulfur region such as 10 ppm by mass.

  In the desulfurization catalyst, the active metal supported on the carrier is usually converted to sulfide before use and exhibits activity in the state of metal sulfide. Further, it is said that increasing the amount of active metal increases the active sites and improves the desulfurization activity. However, as a result of various studies conducted by the present inventors, it has been found that even if the amount of supported metal is increased, the supported metal is not necessarily sufficiently converted to sulfide, and instead the desulfurization activity may be reduced. It was. Further, it has been found that if the supported metal is not sufficiently sulfided, coke formation is promoted during use, resulting in an increase in the rate of catalyst activity deterioration, a shortened catalyst life, and long-term operation.

  The present invention relates to a hydrodesulfurization catalyst for petroleum hydrocarbon oils having high desulfurization activity, low deterioration rate, and capable of stable long-term operation, and a hydrodesulfurization method for hydrocarbon oils using the catalyst. It is intended to provide.

  As a result of diligent research, the inventors of the present invention have found that when molybdenum is supported as an active metal on a catalyst, the properties of molybdenum on the sulfided catalyst have a certain relationship between peaks in a specific range in X-ray photoelectron spectroscopy. The inventors have found that the object of the present invention can be effectively achieved, and have completed the present invention.

That is, the present invention is a hydrodesulfurization catalyst in which at least nickel and / or cobalt and molybdenum are supported as active metals on a catalyst carrier mainly composed of alumina, and molybdenum is converted into an oxide in terms of oxide with respect to the catalyst weight. ~ 25% by mass, containing 55% by mass or more of alumina with respect to the catalyst weight, and further comprising at least one selected from silica, titania, zirconia and boria as a component other than alumina in the catalyst carrier, and Among the peaks derived from the molybdenum 3d5 / 2 orbit obtained by X-ray photoelectron spectroscopy of the sulfided catalyst, the area of the peak having a peak top in the range of the binding energy 232 to 233.5 eV is A, 230 to 231.5 eV Peak area with peak top in the range of B, peak in the range of 228-230eV When the area of the peak having a peak is C, these have the relationship of A / (A + B + C) ≦ 0.3 and 0.25 ≦ B / (B + C) ≦ 0.55 The present invention relates to a hydrodesulfurization catalyst for petroleum hydrocarbon oil.
The present invention also relates to a hydrodesulfurization method for petroleum hydrocarbon oil, characterized in that petroleum hydrocarbon oil is hydrodesulfurized using the hydrodesulfurization catalyst.

The present invention is described in detail below.
The hydrodesulfurization catalyst in the present invention is a catalyst in which at least nickel and / or cobalt and molybdenum are supported as active metals on a catalyst carrier made of an inorganic porous carrier mainly composed of alumina.
The alumina content needs to be 55% by mass or more, preferably 65% by mass with respect to the catalyst weight. Alumina is a porous material suitable for providing a pore volume suitable for diffusion of sulfur-containing hydrocarbon molecules contained in petroleum hydrocarbons having a boiling point of 150 to 550 ° C. such as kerosene, light oil or vacuum gas oil fraction. When it is a support | carrier and alumina content is less than 55 mass%, it becomes difficult to obtain sufficient support | carrier pore volume.

The carrier component other than alumina is at least one selected from silica, titania, zirconia and boria, and preferably at least two.
The carrier component in the hydrodesulfurization catalyst of the present invention is preferably a combination of silica-alumina, titania-alumina, boria-alumina, silica-titania-alumina, silica-zirconia-alumina, silica-boria-alumina, and more preferably. Is silica-titania-alumina, silica-zirconia-alumina, silica-boria-alumina, more preferably silica-titania-alumina, silica-boria-alumina.
The total content of the carrier constituents other than alumina is preferably 1 to 9% by mass, more preferably 3 to 9% by mass, and further preferably 4 to 8% by mass with respect to the carrier weight. preferable. When the total content is 1% by mass or less, a predetermined X-ray photoelectron spectroscopy spectrum does not appear and sufficient desulfurization activity and stability cannot be exhibited. Further, when the total content exceeds 9% by mass, the acidity of the carrier increases, decomposition of the gas oil fraction occurs, and the rate of activity deterioration increases due to the decrease in yield and the decrease in activity due to coke formation accompanying the decomposition. There is a fear.
In the present invention, in addition to these components, phosphorus may be included as a carrier constituent component. When phosphorus is included as a carrier, the content is preferably 1 to 5% by mass, more preferably 2 to 3.5% by mass in terms of oxide with respect to the weight of the carrier.

  The method for preparing the support component alumina is not particularly limited. For example, it can be obtained via an alumina intermediate obtained from a method of neutralizing an aluminum salt such as aluminum sulfate and an aluminate, or a method of hydrolyzing aluminum amalgam or aluminum alcoholate. Moreover, you may use a commercially available alumina intermediate body and boehmite powder.

  There are no particular limitations on the raw materials that are precursors of silica, titania, zirconia, and boria, which are carrier constituents other than alumina, and general solutions containing silicon, titanium, zirconium, and boron can be used. For example, silicic acid, water glass and silica sol for silicon, titanium sulfate, titanium tetrachloride and various alkoxide salts for titanium, zirconium sulfate and various alkoxide salts for zirconium, and boric acid for boron, etc. it can. As phosphorus, phosphoric acid or an alkali salt of phosphoric acid can be used.

  The catalyst carrier used in the present invention can be prepared by calcining these carrier raw materials. For the preparation of the catalyst carrier in the present invention, a method in which a raw material of a carrier constituent component other than alumina is added to an alumina raw material and then calcined is preferably employed. For example, it may be added to an aqueous aluminum solution in advance, and may be an aluminum hydroxide gel containing these components, or may be added to a prepared aluminum hydroxide gel, or commercially available alumina intermediate or boehmite powder with water or acidic Although it may be added to the step of adding and kneading the aqueous solution, a method of coexisting at the stage of preparing the aluminum hydroxide gel is more preferable. Although the mechanism of the effects of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which affects the mode of interaction between the carrier and molybdenum. It is presumed that the sulfide state is controlled by exerting.

The catalyst of the present invention is obtained by supporting nickel and / or cobalt and molybdenum on the catalyst carrier. Nickel and cobalt can be used alone or in combination.
The total supported amount of cobalt and nickel is preferably 1.5 to 7% by mass, more preferably 2 to 5% by mass, and further preferably 2 to 4.5% by mass based on the catalyst weight in terms of oxide. If the total supported amount of cobalt and nickel is less than 1.5% by mass, a sufficient catalytic effect cannot be obtained and the desulfurization activity may be reduced. On the other hand, when the amount is more than 7% by mass, the metal is not effectively dispersed and does not reach a sufficient sulfidation state, which may promote a decrease in desulfurization activity and an activity deterioration.
The supported amount of molybdenum is preferably 20.0 to 25.0 mass%, more preferably 20.5 to 24.0 mass%, and further preferably 21.0 to 23.5 mass% based on the catalyst weight in terms of oxide. % By mass. When the supported amount of molybdenum is less than 20.0% by mass, the number of active sites decreases, and the desulfurization activity decreases. On the other hand, when the amount is more than 25.0% by mass, the metal is not effectively dispersed, does not reach a sufficient sulfurized state, and promotes a decrease in desulfurization activity and activity deterioration.

  The method of incorporating nickel and / or cobalt and molybdenum into the catalyst is not particularly limited, and a known method applied when producing an ordinary desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.

In the present invention, it is preferable to support phosphorus in addition to nickel and / or cobalt and molybdenum as the active metal component. The method for supporting phosphorus is not particularly limited, but phosphoric acid or phosphate may be coexistent in a solution containing nickel and / or cobalt and molybdenum, and nickel and / or cobalt and molybdenum are supported. Then, it may be supported sequentially.
The supported amount of phosphorus to be supported is preferably 1.0 to 5.0% by mass, more preferably 1.2 to 4.5% by mass, and still more preferably based on the catalyst weight in terms of oxide. It is 1.5-4.0 mass%. If the amount is less than 1.0% by mass, the active metal may be aggregated, or when active as a sulfide, the active site may not be sufficiently formed, and the desulfurization activity may be reduced. . On the other hand, if the amount is more than 5.0% by mass, a side reaction such as decomposition may proceed.

  When the catalyst prepared as described above is used in the hydrodesulfurization reaction, a preliminary sulfidation treatment is performed. The conditions for this preliminary sulfidation treatment are not particularly limited. For example, a sulfur component contained in a petroleum hydrocarbon fraction or a sulfurizing agent such as dimethyl disulfide is used, and a petroleum hydrocarbon fraction alone or a fraction to which a sulfurizing agent is added. It is possible to use a method in which the active metal is brought into a sulfide state under a temperature condition of 200 ° C. or higher by passing oil.

  In the present invention, in the spectrum obtained by X-ray photoelectron spectroscopy of the sulfided catalyst, the peak of the molybdenum 3d orbital is divided into two peaks in the range of a binding energy of 228 to 232 eV as molybdenum which is considered to be attributed to tetravalence. Molybdenum, which is believed to be attributed to pentavalent, has two peaks in the range of binding energy 230 to 234 eV, and 3d (3/2), respectively, in the range of binding energy 232 to 237 eV, which is believed to be attributed to hexavalent. As two peaks derived from 3d (5/2), peaks are separated using a Forked function. At this time, the measurement conditions of the X-ray photoelectron spectroscopy are an acceleration voltage of 10 kV and an emission current of 20 mA. Further, as the reference energy, the binding energy 74.2 eV of 2p orbital of Al, which is one of the carrier constituent elements, is used. At this time, a peak derived from the 2p orbital of sulfur is observed in the vicinity of 226 eV.

  Among the obtained peaks, the peak attributed to molybdenum 3d5 / 2 has a peak area having a peak top in the range of binding energy 232 to 233.5 eV and A having a peak top in the range of 230 to 231.5 eV. When the area of the peak is B and the area of the peak having a peak top in the range of 228 to 230 eV is C, these must satisfy the relationship of A / (A + B + C) ≦ 0.3, and A / More preferably, (A + B + C) ≦ 0.25. When the value of A / (A + B + C) is more than 0.3, the progress of sulfidation does not proceed and sufficient activity and stability cannot be exhibited.

At the same time, it is necessary to satisfy the relationship of 0.25 ≦ B / (B + C) ≦ 0.55, more preferably 0.25 ≦ B / (B + C) ≦ 0.50, and 0.35 ≦ More preferably, B / (B + C) ≦ 0.50.
The mechanism of the effect of these strength ratios has not been elucidated, but in the case of a catalyst that satisfies these conditions, the active metal is highly dispersed and the hydrogenation proceeds efficiently to suppress coke formation. It seems that there is. In addition, B / (B + C) is considered to indicate a valence of a transition state between a complete oxide and a sulfide. When this value is less than 0.25, the sulfided active metal is agglomerated instead. And cannot fully demonstrate its activity. On the other hand, when it is larger than 0.55, the sulfurization itself does not proceed sufficiently, and the activity and stability are not sufficient.

In the present invention, the sulfurization catalyst used for X-ray photoelectron spectroscopy measurement was completely converted to sulfides in which supported nickel and / or cobalt and molybdenum correspond to the chemical formulas of Ni ₃ S ₂ , Co ₉ S ₈ , and MoS ₂ , respectively. Assuming that dimethyl disulfide is 20 times equivalent or more as a sulfiding agent, a hydrogen pressure is applied in a range of 5 MPa ± 1.0 MPa in an autoclave, and a sulfiding operation is performed at 300 ° C. for 2 hours.

The surface area required by the BET method using nitrogen of the hydrodesulfurization catalyst of the present invention is not particularly limited, but an excessively high surface area cannot ensure sufficient diffusion in the pores of hydrocarbon molecules, and is not more than 290 m ² / g. Preferably, it is 270 m ² / g or less, more preferably 260 m ² / g or less. Further, the lower limit is preferably 220 m ² / g or more, more preferably 225 m ² / g or more, and further preferably 230 m ² / g or more from the viewpoint of maintaining activity.

  The average pore radius of the catalyst is preferably in the range of 30 to 50 mm, more preferably in the range of 32 to 40 mm. If it is smaller than 30 mm, the reaction molecules are not sufficiently diffused in the pores and the activity becomes low. On the other hand, if it is larger than 50%, the surface area of the catalyst becomes small and sufficient desulfurization activity cannot be exhibited.

In the present invention, hydrodesulfurization treatment of petroleum hydrocarbon oil is performed using the above-described catalyst.
The petroleum hydrocarbon oil in the present invention is an oil refining process such as a normal pressure distillation apparatus, a vacuum distillation apparatus, a thermal distillation, catalytic cracking, or a hydrotreating of crude oil containing a fraction having a boiling point range of 140 to 550 ° C. of 80 vol% Is a fraction produced in Furthermore, a petroleum hydrocarbon fraction containing 70 vol% or more of a boiling point range of 240 to 380 ° C that is a light oil fraction, or a 70% or more fraction of a boiling point range of 140 to 240 ° C that is a kerosene fraction. It is preferably a petroleum hydrocarbon fraction containing, and more preferably a petroleum hydrocarbon fraction containing 70 vol% or more of a fraction having a boiling range of 240 to 380 ° C. which is a light oil fraction.
Petroleum hydrocarbon oils can include fractions obtained by distillation of crude oil as well as fractions obtained by thermal cracking, catalytic cracking reaction, etc., but preferably 50% by volume or more in light oil fractions Straight run diesel oil, more preferably 70% by volume or more. Pyrolysis gas oil and catalytic cracking gas oil contain more olefins and aromatics than straight-run gas oil, and when the proportion of these fractions increases, the reactivity tends to deteriorate and the hue of the product oil tends to deteriorate. . Further, 50% by volume or more in the kerosene fraction is preferably straight-run kerosene for the same reason, more preferably 70% by volume.

  The hydrodesulfurization catalyst of the present invention is suitable for desulfurization from sulfur molecules having a structure such as thiophenes, benzothiophenes, dibenzothiophenes, and in particular, 80% by volume of a gas oil fraction having a boiling point of 240 to 380 ° C. Although it is suitable for the petroleum-based hydrocarbon oils contained above, it can also be used favorably for petroleum-based hydrocarbon oils containing 80% by volume or more of the fraction having a boiling range of 140 to 240 ° C. as the kerosene fraction. In addition, about the value of the distillation property shown here, it is a value measured based on the method as described in JISK2254 "petroleum product-evaporation test method". As the properties of the raw material oil of such a fraction, generally, the aromatic content is 20 to 30% by volume, the sulfur content (sulfur content) is 0.5 to 2% by mass, and the nitrogen content is 50 to 500% by mass. Contains ppm.

  In the present invention, such a gas oil fraction is preferably hydrodesulfurized using the catalyst of the present invention, so that the sulfur concentration can be reduced to 10 ppm by mass or less. Preferably, the sulfur content can be reduced to 5 mass ppm or less and the nitrogen content can be reduced to 1.5 mass ppm or less. As described above, the smaller the sulfur content, the more advantageous in the exhaust gas treatment of diesel engines, and it is said that the performance of the exhaust gas treatment device is drastically improved. If the sulfur concentration exceeds 10 ppm by mass, there is a possibility that the effect of reducing the sulfur content of the fuel oil in such exhaust gas purification cannot be exhibited sufficiently.

  The kerosene fraction is used by mixing a predetermined amount with the diesel oil fraction in order to adjust the properties as diesel fuel such as fluidity in cold regions. For this reason, in the present invention, preferably, such a kerosene fraction is hydrodesulfurized using the catalyst of the present invention to reduce the sulfur concentration to 10 mass ppm or less, thereby reducing the above-mentioned sulfur in diesel engine exhaust gas treatment. The effect can be demonstrated. Furthermore, when used as a heating appliance fuel such as a stove, it can be expected that generation of harmful sulfur oxides and the like will be significantly reduced by using kerosene having a sulfur concentration of 10 mass ppm or less.

  The sulfur content in this specification refers to the sulfur content based on the total amount of petroleum hydrocarbon oil measured according to the method described in JIS K 2541 “Sulfur Content Test Method” or ASTM-D5453. Mean mass content.

  Further, when the petroleum hydrocarbon oil as the feedstock contains 80% by volume or more of a light oil fraction having a boiling point of 240 to 380 ° C., hydrodesulfurization treatment is performed using the catalyst of the present invention. The hue of the product oil can be 1.0 or less in ASTM color. When it exceeds 1.0, the hue as a light oil becomes a hue close to yellow or brown, and there is a concern that the commercial value is lowered. It has been pointed out that the coloration in the hydrodesulfurization treatment is related to the desulfurization reaction temperature, but according to the present invention, such a high reaction temperature and other severe operating conditions are not employed. Diesel oil that is stable and colorless and has high commercial value can be produced.

  Even in the kerosene fraction, when the reaction temperature or severe operating conditions are employed to promote desulfurization, the hue is colored yellow, and there is a concern that the commercial value will be reduced in the same manner as light oil. According to the present invention, kerosene having a high commercial value can be produced stably, and even when it is mixed as a diesel fuel with a light oil fraction, the concern that the commercial value as a diesel fuel is reduced can be eliminated.

  In the present invention, the ASTM color means a hue measured according to the method described in JIS K2580 “Color Test Method”.

As hydrodesulfurization reaction conditions in the present invention, LHSV is preferably 0.3~3.0h ^-1, more preferably at 0.35~2.5h ^-1, more preferably 0.4～2.0H ^-1 is there. When LHSV is lower than 0.3 h ⁻¹ , the volume of the reaction tower for obtaining a certain oil flow rate becomes extremely large, and therefore a huge capital investment such as installation of a reaction tower may be required. On the other hand, when LHSV is greater than 3.0 h ⁻¹ , the contact time between the catalyst and the oil is shortened, so that the desulfurization reaction does not proceed sufficiently, and the effects of desulfurization and dearomatization may not be exhibited.

  The hydrogen partial pressure is preferably 3 to 7 MPa, more preferably 3.5 to 7 MPa, and still more preferably 4 to 6.5 MPa. If the hydrogen partial pressure is lower than 3 MPa, the effect of desulfurization and dearomatization cannot be exhibited. If the hydrogen partial pressure is higher than 7 MPa, there is a possibility that a large capital investment such as a review of the compressor and equipment strength may be required. It is not preferable.

  The reaction temperature is preferably 290 to 380 ° C. When the reaction temperature is lower than 290 ° C., a sufficient desulfurization reaction rate may not be obtained, which is not preferable. On the other hand, when the temperature is higher than 380 ° C., the hue of the product oil may be deteriorated or the yield of the target fraction may be reduced due to decomposition.

  The hydrogen / oil ratio is preferably 50 to 500 NL / L. The hydrogen / oil ratio indicates the ratio of the hydrogen gas flow rate to the feed oil flow rate. The higher the hydrogen / oil ratio is, the more hydrogen supply into the system becomes, and the faster the substances that poison the catalytic active sites such as hydrogen sulfide. Since it can be removed out of the system, the reactivity tends to be improved. However, when it exceeds 500 NL / L, the reactivity is improved, but the effect is gradually reduced. Moreover, there is a risk that a large capital investment such as a compressor may be required. On the other hand, when it is less than 50 NL / L, the reactivity may be lowered.

  Although the reaction mode of the reaction tower in hydrodesulfurization is not particularly limited, it can usually be selected from processes such as a fixed bed and a moving bed, but a fixed bed is preferred. Moreover, about the distribution | circulation method of raw material oil, any form of a down flow and an up flow can be employ | adopted.

  The ultra-low sulfur / low aromatic light oil produced when hydrodesulfurization treatment is performed on the gas oil fraction using the catalyst of the present invention may be used alone as diesel light oil. It can also be used as diesel light oil as a light oil composition in which components such as other base materials are mixed with light oil. Moreover, the kerosene fraction produced | generated when a hydrodesulfurization process is performed about a kerosene fraction can be used as one of light oil base materials.

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

(Example 1)
Water glass No. 3 was added to 200 g of a sodium aluminate aqueous solution having a concentration of 5% by mass, and the mixture was placed in a container kept at 65 ° C. A solution obtained by adding a zirconium sulfate aqueous solution to 200 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was prepared in another container kept at 65 ° C. and dropped into the aqueous solution containing sodium aluminate described above. The end point was when the pH of the mixed solution reached 7.0, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry. The cake-like slurry was transferred to a container equipped with a reflux condenser, 60 ml of distilled water and 1 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 24 hours. The slurry was put into a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. 60 g of the obtained shaped carrier was put into an eggplant-shaped flask, and an impregnating solution containing molybdenum trioxide, cobalt nitrate (II) hexahydrate, phosphoric acid (concentration 85%) and malic acid was removed from the flask while degassing with a rotary evaporator. Injected into. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst 1. The physical properties of the prepared catalyst are summarized in Table 1.

(Example 2)
Water glass No. 3 was added to 200 g of a sodium aluminate aqueous solution having a concentration of 5 mass%, and the mixture was placed in a container kept at 65 ° C. A solution obtained by adding a titanium sulfate aqueous solution to 200 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was prepared in another container kept at 65 ° C., and dropped into the aqueous solution containing sodium aluminate described above. The end point was when the pH of the mixed solution reached 7.0, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry. The cake-like slurry was transferred to a container equipped with a reflux condenser, 60 ml of distilled water and 1 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 24 hours. The slurry was put into a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. 60 g of the obtained shaped carrier was put into an eggplant-shaped flask, and an impregnation solution containing molybdenum trioxide, nickel nitrate hexahydrate, phosphoric acid (concentration 85%) and malic acid was poured into the flask while degassing with a rotary evaporator. did. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst 2. The physical properties of the prepared catalyst are summarized in Table 1.

(Comparative Example 1)
200 g of a sodium aluminate aqueous solution having a concentration of 5% by mass was put in a container kept at 65 ° C. 200 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was prepared in a separate container kept at 65 ° C. and dropped into the aqueous solution containing sodium aluminate described above. The end point was when the pH of the mixed solution reached 7.0, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry. The cake-like slurry was transferred to a container equipped with a reflux condenser, 60 ml of distilled water and 1 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 15 hours. The slurry is put in a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture. In this step, a colloidal silica (particle size: 10 to 20 nm) solution, and then an aqueous zirconium isopropoxide solution are further kneaded while being sequentially dropped, A clay-like kneaded material was obtained. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. 60 g of the obtained shaped carrier was put into an eggplant-shaped flask, and an impregnating solution containing molybdenum trioxide, cobalt nitrate (II) hexahydrate, phosphoric acid (concentration 85%) and malic acid was removed from the flask while degassing with a rotary evaporator. Injected into. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst 3. The physical properties of the prepared catalyst are summarized in Table 1.

(Comparative Example 2)
200 g of a sodium aluminate aqueous solution having a concentration of 5% by mass was put in a container kept at 65 ° C. 200 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was prepared in a separate container kept at 65 ° C. and dropped into the aqueous solution containing sodium aluminate described above. The end point was when the pH of the mixed solution reached 7.0, and the resulting slurry product was filtered through a filter to obtain a cake-like slurry. The cake-like slurry was transferred to a container equipped with a reflux condenser, 60 ml of distilled water and 1 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 80 ° C. for 12 hours. The slurry was put into a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier. 60 g of the obtained shaped carrier was put into an eggplant-shaped flask, and an impregnating solution containing molybdenum trioxide, cobalt nitrate (II) hexahydrate, phosphoric acid (concentration 85%) and malic acid was removed from the flask while degassing with a rotary evaporator. Injected into. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain catalyst 4. The physical properties of the prepared catalyst are summarized in Table 1.

(Example 3)
Catalyst 1 was placed in a 1 g autoclave and 30 times equivalents of dimethyl disulfide were assumed, assuming that the cobalt and molybdenum contained in the catalyst were completely converted to sulfides corresponding to the chemical formulas of Co ₉ S ₈ and MoS ₂ , respectively. In addition to the catalyst, it was pressurized to a hydrogen pressure of 5 MPa and held at 300 ° C. for 2 hours. After completion of sulfiding, the catalyst was recovered in a container under a nitrogen atmosphere and used as it was for X-ray photoelectron spectroscopy. X-ray photoelectron spectroscopy measurement was performed using ESCA3400 manufactured by KRATOS at an acceleration voltage of 10 kV and a current of 10 mA. The peak separation result of the molybdenum 3d orbit in the spectrum obtained by X-ray photoelectron spectroscopy of the sulfurized catalyst 1 is shown in FIG. The peak separation results for catalysts 1 to 4 are summarized in Table 2.

Example 4
The catalyst layer average temperature is 300 using 100 ml of catalyst 1 in a reaction tube having an inner diameter of 25 mm and straight-run gas oil (3% by mass of sulfur) added with dimethyl disulfide so that the sulfur concentration is 3% by mass. The catalyst was presulfided for 4 hours under the conditions of ° C., hydrogen partial pressure 6 MPa, LHSV ¹ h ⁻¹ , and hydrogen / oil ratio 200 NL / L. After preliminary sulfidation, a Middle East straight oil (10% distillation point 240 ° C., 90% distillation point 340 ° C., sulfur content 1.28 mass%, nitrogen content 210 mass ppm) was reacted at 350 ° C., pressure 5 MPa, Hydrodesulfurization was performed by passing oil under conditions of LHSV1h ⁻¹ and a hydrogen / oil ratio of 200 NL / L. In addition, for 40 to 80 days after the start of oil passing, operation was performed while adjusting the reaction temperature so that the sulfur content of the produced oil was 10 ppm by mass, and the activity deterioration rate was measured.
The same procedure was performed for catalyst 2. The reaction test results for each catalyst are summarized in Table 3.

(Comparative Example 3)
100 ml of catalyst 3 was filled in a reaction tube having an inner diameter of 25 mm, presulfided under the conditions shown in Example 4, and then hydrodesulfurized under the same conditions as in Example 4. It carried out similarly about the catalyst 4. The reaction test results for each catalyst are summarized in Table 3.

(Example 5)
50 ml of catalyst 1 was filled in a reaction tube having an inner diameter of 25 mm, and presulfided under the conditions shown in Example 4, followed by Middle East straight-run kerosene (95% distillation point 260 ° C., sulfur content 0.30% by mass, nitrogen content) 10 mass ppm) was subjected to hydrodesulfurization by passing oil under conditions of a reaction temperature of 300 ° C., a pressure of 3.5 MPa, LHSV 2 h ⁻¹ , and a hydrogen / oil ratio of 80 NL / L. Further, for 40 to 80 days after the start of oil passing, LHSV5h- ¹ was set as a forced deterioration test, and the operation was performed while adjusting the reaction temperature so that the sulfur content of the produced oil was 10 ppm by mass, and the activity deterioration rate was measured. The same procedure was performed for catalyst 2. The reaction test results for each catalyst are summarized in Table 4.

(Comparative Example 4)
50 ml of catalyst 3 was filled in a reaction tube having an inner diameter of 25 mm, presulfided under the conditions shown in Example 4, and then hydrodesulfurized under the same conditions as in Example 5. It carried out similarly about the catalyst 4. The reaction test results for each catalyst are summarized in Table 4.

It is a figure which shows the peak separation result of the molybdenum 3d orbit in the spectrum obtained by the X-ray photoelectron spectroscopy of the sulfurized catalyst 1.

Claims (8)

  A hydrodesulfurization catalyst in which at least nickel and / or cobalt and molybdenum are supported as active metals on a catalyst carrier having alumina as a main component, and molybdenum is 20 to 25% by mass in terms of oxide based on the catalyst weight. Of the sulfurized catalyst, and containing at least one selected from silica, titania, zirconia and boria as a component other than alumina in the catalyst support. Of the peaks derived from the molybdenum 3d5 / 2 orbit obtained by line photoelectron spectroscopy, the peak area having a peak top in the range of binding energy 232 to 233.5 eV is A, and the peak top is in the range of 230 to 231.5 eV. The area of the peak having B is the peak having a peak top in the range of 228 to 230 eV. Petroleum hydrocarbons characterized by having a relationship of A / (A + B + C) ≦ 0.3 and 0.25 ≦ B / (B + C) ≦ 0.55 when the product is C Oil hydrodesulfurization catalyst.   2. The hydrodesulfurization catalyst for petroleum hydrocarbon oil according to claim 1, wherein the catalyst carrier contains at least two kinds selected from silica, titania, zirconia and boria in addition to alumina. .   The hydrogen of petroleum hydrocarbon oil according to claim 1 or 2, wherein the total content of the carrier component selected from silica, titania, zirconia and boria is 1 to 9% by mass of the catalyst carrier. Hydrodesulfurization catalyst.   The petroleum hydrocarbon oil according to any one of claims 1 to 3, wherein the catalyst carrier is prepared by adding a raw material of a carrier component other than alumina to an alumina raw material, followed by firing. Hydrodesulfurization catalyst. The average pore radius of the catalyst determined by the BET method using nitrogen is in the range of 30 to 50 mm, and the surface area is in the range of 220 to 290 m ² / g. Hydrodesulfurization catalyst for petroleum hydrocarbon oil.   A hydrodesulfurization method for petroleum hydrocarbon oil, comprising hydrodesulfurizing a petroleum hydrocarbon oil using the hydrodesulfurization catalyst according to any one of claims 1 to 5.   The sulfur content of the product oil obtained by hydrodesulfurizing the kerosene or light oil fraction using the hydrodesulfurization catalyst according to any one of claims 1 to 5 is 10 ppm by mass or less, and the hue is ASTM. The hydrodesulfurization method according to claim 6, which is 1.0 or less in color. The hydrodesulfurization treatment is performed under conditions of LHSV 0.3 to 3.0, hydrogen pressure 3 to 7 MPa, reaction temperature 290 to 380 ° C, and hydrogen oil ratio 50 to 500 NL / L. Or the hydrodesulfurization method according to 7.

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