Hydrotreating catalyst for heavy hydrocarbon oil, method for producing the same, and hydrotreating method

Abstract

To provide a hydrogenation treatment catalyst of a heavy oil exhibiting a catalytic performance (for example, desulfurization performance, denitrification performance, residual coal removal performance) higher than a conventional hydrogenation treatment catalyst and its manufacturing method.SOLUTION: A catalyst used for hydrogenation of heavy hydrocarbon oil contains an inorganic oxide carrier comprising alumina as a main component and a metal component carried on the inorganic oxide support, has a specific surface area in a predetermined range, and has a reduction peak temperature of lower than 450°C in a temperature reduction measurement of the catalyst above a predetermined temperature, and a hydrogenation catalyst of heavy hydrocarbon oil has a nitrogen monoxide absorption amount after sulfurization of the catalyst, which is within a predetermined range.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a hydrotreating catalyst for efficiently removing sulfur and other components in heavy hydrocarbon oil (hereinafter also referred to as "heavy oil") in the presence of hydrogen, a method for producing the same, and a method for hydrotreating heavy hydrocarbon oil.

Background Art

[0002] In recent years' heavy oil hydrotreating processes, further improvement in catalyst performance has been demanded in order to cope with further heavyweight of feedstock oil and increase in throughput in heavy oil hydrotreating apparatuses. For the above reasons, development of hydrotreating catalysts by various approaches has been promoted.

[0003] For example, Patent Document 1 discloses that a hydrodesulfurization catalyst prepared from an alumina-phosphorus carrier containing phosphorus in an amount of 0.5 to 2.0% based on P2O5 and having two maximum peaks between pore diameters of 6 to 13 nm in the Log differential pore volume distribution measured by mercury intrusion porosimetry exhibits high desulfurization activity in the hydrotreating reaction of atmospheric residue oil.

[0004] Patent Document 2 discloses a method for producing a heavy oil hydrodesulfurization catalyst in which a metal component is supported on a carrier containing alumina and titania prepared using a water-soluble titanium complex with an impregnating solution containing polyethylene glycol. It is also described that a catalyst obtained by supporting an active metal component on a carrier containing alumina and titania prepared according to the disclosed production method exhibits high desulfurization activity and high abrasion resistance.

[0005] Patent Document 3 discloses a hydrotreating catalyst prepared by supporting an active metal component on a silica-alumina-based carrier having a structure in which a silica layer is formed on the alumina surface and containing 2 to 40% by weight of silica based on the total weight of the carrier, the hydrotreating catalyst having a first peak in the pore diameter range of 40 to 200 Å and a second peak in the pore diameter range of 200 to 2000 Å in the pore volume distribution, that is, having a bimodal distribution. It is described that the addition of silica improves the dispersibility of the active component and increases the cracking activity and desulfurization activity by highly dispersing and uniformly distributing Bronsted acid and Lewis acid, and this catalyst is described to be effective in improving the desulfurization activity in the hydrotreating of light oil, improving the desulfurization activity in the hydrocracking of vacuum residue oil, and sediment inhibition ability.

[0006] In the heavy oil hydrotreating process, for example, in the heavy oil for ship fuel use, the upper limit regulation of the sulfur content by the International Maritime Organization has been lowered in 2020, etc., and further improvement of the desulfurization activity has become an important issue. In addition, it is required to cope with an increase in the processing capacity in the heavy oil hydrotreating apparatus.

[0007] As a measure for improving the performance of the hydrotreating catalyst, a method focusing on the reduction temperature of the active metal supported on the carrier under a hydrogen stream is known. Patent Document 4 describes that by adding a noble metal selected from Groups 8 to 10 of the periodic table such as rhodium, palladium, and platinum to a sulfide catalyst containing a base metal element selected from Groups 8 to 10 of the periodic table which are iron, cobalt, and nickel, high hydrotreating performance is exhibited by the utilization of spillover hydrogen. Also, the behavior of the catalyst component serving as the reaction active site undergoing reduction has a close relationship with the catalytic activity of the hydrotreating, and it is described that it is desirable that the reduction peak temperature attributed to iron, cobalt, and nickel of the catalyst under a hydrogen stream is 500 °C or lower.

[0008] Patent Document 5 describes that on an inorganic oxide carrier, at least one of molybdenum and tungsten as an active metal is carried in an amount of 15 to 30 parts by mass, and at least one of cobalt and nickel as a metal component is carried in an amount of 3 to 7 parts by mass. A catalyst with a peak temperature of desorbed water in the range up to 450 °C based on the temperature-programmed reduction method of the catalyst being 412.0 °C or lower is described as showing high desulfurization activity because the sulfidation treatment of molybdenum can proceed sufficiently.

[0009] Non-Patent Document 1 describes the preparation of an alumina-titania mixed carrier with a varying amount of titania added, and further a catalyst with molybdenum carried as an active metal. Since the reduction peak temperature attributed to molybdenum by the temperature-programmed reduction method decreased and the hydrogen consumption also increased due to the addition of titania, it is described that the reduction of molybdenum species is promoted by the addition of titania, and furthermore, a catalyst containing such an active metal with promoted reduction shows high hydrodesulfurization activity.

[0010] Non-Patent Document 2 describes the measurement results of hydrodesulfurization activity and temperature-programmed reduction method depending on the presence or absence of ethylenediaminetetraacetic acid (EDTA) when nickel and molybdenum are carried on a silica-alumina carrier. It is described about the possibility that the reduction of active metal species is promoted by the addition of EDTA, thereby improving the hydrodesulfurization activity.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Non-Patent Literature

[0012]

Non-Patent Literature 1

Non-Patent Literature 2

Summary of the Invention

Problems to be Solved by the Invention

[0013] Existing catalysts have problems such that they are insufficient in activity for use in the hydrotreating of heavy oil, or the amount of metal components to be supported is too large, which is inappropriate and expensive on the catalytic active surface.

[0014] An object of the present invention is to provide a hydrotreating catalyst for heavy oil that exhibits higher catalytic performance (for example, desulfurization performance, denitrification performance, decarbonization performance) than conventional hydrotreating catalysts and a method for producing the same, and to provide a method for hydrotreating heavy oil with higher performance (for example, desulfurization performance, denitrification performance, decarbonization performance) than conventional hydrotreating methods.

Means for Solving the Problems

[0015] As a result of intensive studies to solve the above problems, the present inventors have found that a catalyst showing a reduction peak in a specific temperature range in the temperature-rising reduction measurement of the catalyst exhibits higher sulfur, nitrogen, and decarbonization removal performance than conventional ones in the hydrotreating of heavy oil.

[0016] The present invention relates to, for example, the following [1] to [9]. [1] A hydrotreating catalyst for heavy hydrocarbon oil, comprising an inorganic oxide carrier mainly composed of alumina and containing an added oxide component, and a metal component supported on the inorganic oxide carrier, The metal component contains molybdenum and contains nickel and / or cobalt, the content of molybdenum is 5 to 16% by mass in terms of oxide, and the total content of nickel and cobalt is 1 to 6% by mass in terms of oxide, the specific surface area measured by the nitrogen adsorption method is 150 to 320 m 2 / g, in the temperature-programmed reduction measurement of the catalyst, the value of the reduction peak temperature (°C) below 450 °C is not less than the value A (°C) represented by the following formula, Value A (°C) = 1.0 × (content of molybdenum in the catalyst in terms of MoO3 (% by mass)) + 25 × (ratio of the content of cobalt in terms of CoO to the total content of nickel in terms of NiO and cobalt in terms of CoO in the catalyst (% by mass)) + 339 the nitric oxide adsorption amount after the sulfidation treatment of the catalyst is 4.0 ml / g or more when the molar ratio of the amount of nickel to the total amount of nickel and cobalt in the catalyst (Ni / (Ni + Co)) is 0.5 or more, and 5.0 ml / g or more when the molar ratio is less than 0.5, Hydrotreating catalyst for heavy hydrocarbon oil.

[0017] [2] the inorganic oxide carrier contains 1 to 30% by mass of the additive oxide component, and the additive oxide component includes at least the following (a) to (c): (a) Magnesium or boron, (b) A combination of silicon and at least one element (group) M selected from the group consisting of titanium, zirconium, boron, magnesium, and phosphorus, and the ratio of silicon to the element (group) M is 0.4 to 3.5 as (mass of silica) / (mass of oxide of the element (group) M), (c) A combination of titanium and phosphorus, or a combination of zirconium and phosphorus The hydrotreating catalyst for heavy hydrocarbon oil according to [1], containing an oxide of any one of the additive element (groups).

[0018] [3] The heavy hydrocarbon oil hydrotreating catalyst of [1] or [2] wherein the inorganic oxide carrier has an average pore diameter (PD) measured by mercury intrusion porosimetry of 9.0 to 15.0 nm, the total pore volume in the range of pore diameters of 20 nm or more is 10% or less of the total pore volume, the total pore volume in the range of average pore diameter ± 2 nm is 50% or more of the total pore volume, and the pore volume (PV) measured by the pore filling method of water is 0.5 to 1.1 ml / g.

[0019] [4] A method for producing the heavy hydrocarbon oil hydrotreating catalyst of [1], comprising: (1) preparing a slurry having a pH of 7 to 10 containing a precursor of the inorganic oxide carrier, and then molding the precursor; (2) firing the molded precursor at 400 to 800 °C to obtain the inorganic oxide carrier; (3) preparing an impregnating solution containing a raw material of the metal component, an acid, and water, impregnating the impregnating solution into the inorganic oxide carrier, and supporting the raw material of the metal component on the inorganic oxide carrier; and (4) firing the inorganic oxide carrier supporting the raw material of the metal component at a temperature of 400 to 800 °C to obtain the hydrotreating catalyst. comprising: Step (1) includes an operation (1-1) of preparing a slurry of the precursor containing alumina hydrate by adding an aqueous solution (b) containing a basic aluminum salt to an aqueous solution (a) having a pH of 2 to 5 containing an acidic aluminum salt, and an operation (1-2) of mixing the alumina hydrate and / or its raw material with the raw material of the added oxide component. A method for producing a heavy hydrocarbon oil hydrotreating catalyst.

[0020] [5] In the operation (1-2), (i) mixing an aqueous solution of an acidic aluminum salt with the raw material of the added oxide component to prepare the aqueous solution (a), or (ii) mixing an aqueous solution of a basic aluminum salt with the raw material of the added oxide component to prepare the aqueous solution (b). (iii) Mixing the aqueous solution (a), the aqueous solution (b), and the raw material of the additive oxide component to prepare a slurry containing the precursor, or (iv) Mixing the slurry containing the alumina hydrate and the raw material of the additive oxide component to prepare a slurry containing the precursor. The method for producing a hydrotreating catalyst for heavy hydrocarbon oil according to [4] above.

[0021] [6] A method for hydrotreating heavy hydrocarbon oil, comprising a step of hydrotreating the heavy hydrocarbon oil in the presence of the hydrotreating catalyst according to any one of [1] to [3] above.

[0022] [7] The heavy hydrocarbon oil has a density of 0.90 to 1.05 g / cm 3 and contains 80% by mass or more of components having a sulfur content of 1 to 6% by mass and a boiling point of 360°C or higher. The method for hydrotreating heavy hydrocarbon oil according to [6] above.

[0023] [8] The step of hydrotreating the heavy hydrocarbon oil is carried out under the conditions of a hydrogen partial pressure of 5.0 to 20 MPa, a reaction temperature of 350 to 420°C, and a liquid hourly space velocity of 0.1 to 0.5 hr -1 The method for hydrotreating heavy hydrocarbon oil according to [6] or [7] above.

[0024] [9] The method for hydrotreating heavy hydrocarbon oil according to any one of [6] to [8] above, which is carried out as a pretreatment for fluidized bed catalytic cracking of heavy hydrocarbon oil.

[0025] In the development of hydrotreating catalysts utilizing conventional temperature-programmed reduction measurements, it was considered important for improving catalyst performance to lower the reduction peak temperature of the metal component, that is, to promote the reduction of the metal component on the carrier, by adding a second component to the carrier or adding an organic substance to the impregnation solution. In contrast, the technical idea of the present invention lies in the consideration that a catalyst with suppressed reduction of the metal component is suitable for heavy oil hydrotreating.

[0026] Furthermore, as a result of intensive studies based on the above concept, it has been found that the catalyst according to the present invention, which exhibits properties such as characteristic reduction peak temperature and nitric oxide adsorption amount, actually shows high performance in the hydrotreating of heavy oil. Furthermore, it has been found that such a catalyst can be obtained by using a specific composite oxide carrier instead of alumina or alumina-phosphorus carrier widely used in conventional hydrotreating catalysts, and the present inventors have completed the present invention.

Advantages of the Invention

[0027] When the hydrotreating of heavy oil is carried out using the hydrotreating catalyst of the present invention, a product oil with sulfur content, nitrogen content, and residual carbon content lower than those achievable with conventional heavy oil hydrotreating catalysts can be obtained. Furthermore, such a product oil becomes a suitable feedstock for a fluidized bed catalytic cracking reactor of heavy oil, and can reduce the yield of low-value-added heavy residual oil components in the catalytic cracking reactor, which is industrially important.

[0028] Furthermore, the hydrotreating catalyst of the present invention does not require a noble metal as a metal component, so it is inexpensive and can be industrially used for the hydrotreating of heavy oil. In addition, when manufacturing the catalyst of the present invention, since there is no need for a major change or modification from the manufacturing process of conventional catalysts in its manufacturing process, according to the manufacturing method of the present invention, a hydrotreating catalyst for heavy oil with improved performance while maintaining high productivity can be manufactured using the same equipment as conventional catalysts.

[0029] Although the reason why the catalyst of the present invention with suppressed reduction of the metal component is suitable for heavy oil hydrotreating has not been fully elucidated, the present inventors consider the following mechanism. It should be noted that the present invention is not limited to the hypothesis of the mechanism described below.

[0030] In the hydrotreating of hydrocarbon oils in which there are various feedstocks such as naphtha, kerosene, gas oil, and vacuum gas oil, the hydrotreating of heavy oils is operated under particularly severe conditions, and it is considered that coke formation and metal component aggregation due to high-temperature operation are likely to progress. Setting the reduction peak temperature of the catalyst to a predetermined temperature or higher, that is, making it difficult for the reduction of metal components to proceed, improves the stability of the metal component species on the carrier, and thus has the effect of suppressing coke poisoning of the metal by the metal component and suppressing the aggregation of the metal component species. It is thought that the function of the active sites is maintained over a longer period as a result.

Brief Description of the Drawings

[0031] [Figure 1] Figure 1 shows the results of measuring the reduction temperature of the metal component by the temperature-raising reduction method of the catalyst (7) of Example 1.

Modes for Carrying Out the Invention

[0032] Hereinafter, embodiments of the present invention will be described. The present invention provides a hydrotreating catalyst for heavy oils, a method for producing the same, and a method for hydrotreating heavy oils. The catalyst produced according to the present invention (hereinafter also referred to as "the present catalyst") can be filled and used in any region of the demetallization section, desulfurization section, and transition section between them in a heavy oil hydrotreating apparatus, but it can be preferably used particularly in the desulfurization section.

[0033] In the demetallization section of a heavy oil hydrotreating apparatus, demetallization by a demetallization catalyst is mainly carried out in the presence of hydrogen gas, and metal components in the feedstock oil are removed. On the other hand, in the desulfurization section, a hydrogenation reaction mainly by a desulfurization catalyst is carried out in the presence of hydrogen gas, and sulfur content, nitrogen content, residual carbon content, etc. are removed.

[0034] [Hydrogenation catalyst] The hydrotreating catalyst according to the present invention is a catalyst used for the hydrotreating of heavy hydrocarbon oils, It contains an inorganic oxide carrier mainly composed of alumina and a metal component supported on the inorganic oxide carrier, has a specific surface area within a predetermined range, the reduction peak temperature below 450 °C in the temperature-rising reduction measurement of the catalyst is equal to or higher than a predetermined temperature, the amount of nitric oxide adsorbed after the sulfidation treatment of the catalyst is within a predetermined range and is characterized by this.

[0035] <Inorganic oxide carrier> The inorganic oxide carrier used in the catalyst according to the present invention is a carrier mainly composed of alumina and containing an added oxide component.

[0036] The inorganic oxide carrier preferably contains aluminum in an amount of 70 to 99% by mass, more preferably 75 to 98% by mass, and even more preferably 80 to 97% by mass based on the oxide (Al2O3). Since the inorganic oxide carrier is mainly composed of alumina within the above composition range, it has a high specific surface area, pore diameters suitable for treating heavy oil, high pressure resistance and abrasion resistance, and high productivity such as being suitable for extrusion molding. Therefore, it is suitable as a carrier for a hydrotreating catalyst.

[0037] The added oxide component is an oxide of an added element (group) other than aluminum, and examples thereof preferably include oxides of any one of the following added element (groups) (a), (b), or (c). (a) Magnesium or boron, (b) A combination of silicon and at least one element (group) M selected from the group consisting of titanium, zirconium, boron, magnesium, and phosphorus, where the ratio of silicon to element (group) M is 0.4 to 3.5 as (mass of silica) / (mass of oxide of element (group) M), and (c) A combination of titanium and phosphorus, or a combination of zirconium and phosphorus The inorganic oxide carrier preferably contains the added element (group) in an amount of 1 to 30% by mass, more preferably 2 to 25% by mass, and even more preferably 3 to 20% by mass based on the oxide.

[0038] In addition, the fact that the inorganic oxide carrier contains alumina and the additive oxide component usually means that the inorganic oxide contains a composite oxide of aluminum and the additive element(s).

[0039] The inorganic oxide carrier preferably satisfies the following requirements (i) and (ii), and more preferably further satisfies the following requirement (iii). Requirement (i): The average pore diameter (PD) measured by the mercury intrusion method is 9.0 to 15.0 nm, preferably 9.0 to 14.0 nm.

[0040] Requirement (ii): The total pore volume in the range of the average pore diameter ± 2 nm occupies 50% or more, preferably 55% or more of the total pore volume. Requirement (iii): The total pore volume in the range where the pore diameter is 20 nm or more is 10% or less of the total pore volume.

[0041] In addition, the inorganic oxide carrier preferably satisfies the following requirement (iv). Requirement (iv): The pore volume (PV) measured by the water porosimetry method is 0.5 to 1.1 ml / g, preferably 0.6 to 1.0 ml / g.

[0042] Details of the measurement methods for each physical property are as described in the column of the examples described later. A catalyst containing an inorganic oxide carrier having such component and composition characteristics has both high diffusibility of heavy oil with a relatively large molecular size and a high specific surface area important for maintaining the dispersibility of the metal component in the solid catalyst, and is considered to have excellent catalyst performance.

[0043] <Metal component> The catalyst according to the present invention contains a metal component supported on the inorganic oxide carrier. The metal component contains molybdenum and contains nickel and / or cobalt.

[0044] The content of molybdenum in the catalyst according to the present invention is 5 to 16% by mass, preferably 6 to 15% by mass, in terms of oxide (MoO3). The total content of nickel and cobalt in the catalyst according to the present invention is 1.0 to 6.0% by mass, preferably 1.5 to 5.0% by mass, in terms of oxides (NiO, CoO).

[0045] <Specific surface area> The specific surface area of the catalyst according to the present invention, measured by the nitrogen adsorption method (the details of the measurement method are as described in the examples section below), is 150 to 320 m 2 / g.

[0046] When the specific surface area is less than 150 m 2 / g, the metal components may not be sufficiently dispersed on the inorganic oxide carrier and aggregates of the metal components may be formed, which is not preferable. Also, when the specific surface area of the catalyst exceeds 320 m 2 / g, the pore diameter becomes small, and in the reaction using heavy oil with a large molecular size as the feedstock oil, the diffusibility of the heavy oil molecules decreases, which is not preferable.

[0047] <Reduction peak temperature> The inventors of the present invention have worked on the development of a novel heavy oil hydrotreating catalyst based on the temperature-programmed reduction measurement of the catalyst. Compared with the catalyst prepared using the alumina carrier conventionally used by those skilled in the art, it has been found that a catalyst showing a reduction peak temperature higher than a certain level exhibits high performance for the hydrotreating of heavy oil. Furthermore, it has been found that the reduction peak temperature has a correlation with the amount of molybdenum in the catalyst and the ratio of the amount of cobalt to the total amount of nickel and cobalt, and the following conditions have been proposed.

[0048] That is, a catalyst in which the value (°C) of the reduction peak temperature below 450 °C in the temperature-programmed reduction measurement of the catalyst according to the present invention is equal to or higher than the value A calculated by the following formula (1), preferably equal to or higher than the value A' calculated by the following formula (1'), and more preferably equal to or higher than the value A" calculated by the following formula (1") exhibits high catalytic activity in the hydrotreating of heavy oil.

[0049] Value A (°C) = 1.0 × B + 25 × C + 339 …(1) Value A’ (°C) = 1.0 × B + 25 × C + 340 …(1’) Value A” (°C) = 1.0 × B + 25 × C + 342 …(1”) (In formulas (1), (1’), and (1”), B is the content of molybdenum in the catalyst in terms of MoO3 (mass %), C is the ratio of the content of cobalt in terms of CoO to the total content of nickel in terms of NiO and cobalt in terms of CoO in the catalyst (mass %).) Note that the details of the temperature-rising reduction measurement and the reduction peak temperature are as described in the Examples section below.

[0050] The fact that the value of the reduction peak temperature of the catalyst is equal to or higher than value A, preferably equal to or higher than value A’, and more preferably equal to or higher than value A” indicates that the metal components on the catalyst are more difficult to reduce than the catalysts prepared using conventional carriers containing alumina and additive oxide components. The catalyst of the present invention having such a reduction peak temperature is suitable for use as a heavy oil desulfurization catalyst because the structure and function of the active sites are easily maintained, and as a result, the hydrogenation treatment activity is increased.

[0051] Formulas (1), (1’), and (1”) are obtained from the finding that the reduction peak temperature increases as the amount of MoO3 in the catalyst increases, and also increases as the ratio of the amount of CoO to the total amount of NiO and CoO in the catalyst increases, and from the comparative evaluation of the reduction peak temperature and the hydrogenation treatment performance of the catalyst according to the present invention and the catalysts produced in the comparative examples.

[0052] As one example of a method for producing a catalyst having such a reduction peak temperature, the method for producing a hydrogenation treatment catalyst described below is exemplified, but it is not limited thereto. The upper limit value of the reduction peak temperature may be, for example, about (value A + 10) °C.

[0053] <Nitric oxide adsorption amount> The dispersibility of the metal components of the hydrogenation catalyst can be evaluated by measuring the amount of nitric oxide adsorbed by the sulfided catalyst. Details of the sulfiding treatment method and the measurement method are as described in the Examples section below. Depending on the molar ratio of nickel to nickel and cobalt, the structure of the supported metal components is different, and generally, when the molar ratio of nickel is high, the amount of nitric oxide adsorbed is considered to be low.

[0054] The amount of nitric oxide adsorbed after sulfiding treatment of the catalyst according to the present invention is 4.0 ml / g or more when the molar ratio of the amount of nickel to the total amount of nickel and cobalt in the catalyst (Ni / (Ni + Co)) is 0.5 or more, and 5.0 ml / g or more when the mass ratio is less than 0.5. A lower amount of nitric oxide adsorption than the above range means low dispersibility of the metal components on the catalyst and a small number of active sites, which is not preferable.

[0055] The upper limit value of the amount of nitric oxide adsorbed may be about 9.0 ml / g, for example. The amount of nitric oxide adsorbed can be increased or decreased, for example, by changing the calcination temperature of the carrier or the catalyst, adding an arbitrary chelating agent to the impregnating solution containing the active metal, etc. in the method for producing the hydrogenation catalyst described below.

[0056] The properties and shape of the inorganic oxide carrier are appropriately selected according to various conditions such as the type and composition of the metal components to be supported and the use of the catalyst. In order to effectively support the metal components on the carrier in a highly dispersed state and sufficiently ensure the catalytic activity, a carrier having pores and being porous is usually preferably used. Further, in order to control physical properties such as the mechanical strength and heat resistance of the carrier or the catalyst body, an appropriate binder component or additive may be contained when forming the carrier or the catalyst.

[0057] The carrier may further contain additives other than the added oxide component, and examples thereof include minerals such as aluminosilicates (for example, zeolite, talc, kaolinite, montmorillonite).

[0058] Furthermore, although the method for preparing the carrier is not particularly limited, a catalyst with improved hydrocracking activity, crushing strength, etc. can be produced by adding the additive to the carrier precursor obtained by the following preparation method.

[0059] [Method for producing hydrogenation catalyst] The method for producing a hydrotreating catalyst according to the present invention (1) A step of molding a carrier precursor, (2) A step of firing the carrier precursor to obtain an inorganic oxide carrier, (3) A step of supporting a metal component raw material on the inorganic oxide carrier, and (4) A step of firing the inorganic oxide carrier supporting the metal component raw material to obtain a hydrotreating catalyst is characterized by including.

[0060] (Step (1)) Step (1) is a step of preparing a slurry having a pH of 7 to 10 containing a precursor of the inorganic oxide carrier (hereinafter also referred to as "carrier precursor"), and then molding the carrier precursor. An operation (1-1) of preparing the carrier precursor containing alumina hydrate by adding an aqueous solution (b) containing a basic aluminum salt to an aqueous solution (a) containing an acidic aluminum salt, and An operation (1-2) of mixing the alumina hydrate and / or its raw material with the raw material of the additive oxide component (hereinafter also referred to as "additive oxide component raw material") are included.

[0061] Operation (1-2) is carried out together with operation (1-1) or separately from operation (1-1) depending on its specific embodiment. Further, the carrier precursor contains the alumina hydrate and the additive oxide component raw material.

[0062] 《Operation (1-1)》 In operation (1-1), an aqueous solution (b) containing a basic aluminum salt is added to an aqueous solution (a) containing an acidic aluminum salt to prepare a slurry of a carrier precursor containing alumina hydrate.

[0063] The aqueous solution (a) containing an acidic aluminum salt is prepared, for example, by adding an acidic aluminum salt to sprinkling water. This aqueous solution (a) is prepared such that, for example, the aluminum content is, in terms of Al2O3, 0.1 to 2.0% by mass and the pH is 2.0 to 5.0, and while stirring, the liquid temperature is heated to, for example, 50 to 80°C.

[0064] The acidic aluminum salt is a water-soluble salt, examples of which include aluminum sulfate, aluminum chloride, aluminum acetate, and aluminum nitrate. When preparing the aqueous solution (a) by adding an acidic aluminum salt to sprinkling water, the acidic aluminum salt is preferably added in the form of an aqueous solution containing 0.5 to 20% by mass in terms of Al2O3.

[0065] Next, while stirring this aqueous solution (a) containing an acidic aluminum salt, an aqueous solution (b) containing a basic aluminum salt is added thereto over, for example, 30 to 200 minutes so that the pH becomes 7 to 10, thereby obtaining a slurry of a carrier precursor containing alumina hydrate.

[0066] Then, the alumina hydrate is washed with pure water at, for example, 40 to 70°C to remove by-produced salts that are impurities such as sodium and sulfate radicals, thereby obtaining a cake-like alumina hydrate. Examples of the basic aluminum salt include sodium aluminate and potassium aluminate. The aqueous solution of the basic aluminum salt preferably contains aluminum in an amount of 2 to 30% by mass in terms of Al2O3.

[0067] 《Operation (1-2)》 In operation (1-2), the alumina hydrate and / or its raw material and the raw material of the added oxide component are mixed.

[0068] Examples of the mode of mixing the raw material of the alumina hydrate and the raw material of the added oxide component include (i) Mixing an aqueous solution of an acidic aluminum salt with a raw material of the additive oxide component to prepare the aqueous solution (a). (ii) Mixing an aqueous solution of a basic aluminum salt with a raw material of the additive oxide component to prepare the aqueous solution (b). (iii) Mixing the aqueous solution (a), the aqueous solution (b), and a raw material of the additive oxide component to prepare a slurry containing the precursor, and (iv) Mixing a slurry containing the aluminum hydroxide hydrate with a raw material of the additive oxide component to prepare a slurry containing the precursor. Such aspects include.

[0069] Examples of the aspect of (i) include the addition of the raw material of the additive oxide component to the water for spreading when obtaining the aluminum hydroxide hydrate, and the addition of the raw material of the additive oxide component to the aqueous solution of the acidic aluminum salt. Examples of the aspect of (ii) include the addition of the raw material of the additive oxide component to the aqueous solution of the basic aluminum salt.

[0070] Examples of the aspect of (iv) include the addition of the raw material of the additive oxide component to the slurry after obtaining the aluminum hydroxide hydrate, the addition of the raw material of the additive oxide component to the aluminum hydroxide hydrate after washing and desalting, the addition of the raw material of the additive oxide component to the aluminum hydroxide hydrate after high-temperature aging, and the addition of the raw material of the additive oxide component to the aluminum hydroxide hydrate during kneading in a kneader.

[0071] The specific aspects of operation (1-2) are not limited to these, and are appropriately selected according to various conditions such as the type and composition of the components to be added and the use of the catalyst. Examples of the raw material of the additive oxide component include water-soluble salts, oxide powders, sols of oxides or hydroxides, and gels of oxides or hydroxides.

[0072] Examples of the raw material of the additive oxide component containing phosphorus include phosphate compounds that generate phosphate ions or phosphite ions in water, such as ammonium phosphate, potassium phosphate, sodium phosphate, phosphoric acid, and phosphorous acid.

[0073] Examples of the raw material of the additive oxide component containing silicon include sodium silicate, silicon tetrachloride, silica powder, silica sol, and silica gel. Sodium silicate is particularly preferred because it is inexpensive.

[0074] Examples of the raw material of the additive oxide component containing titanium include titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, titanium nitrate, titanium hydroxide gel, metatitanic acid, and titania powder. Titanium sulfate and titanyl sulfate are particularly preferred because they are inexpensive.

[0075] Examples of the raw material of the additive oxide component containing zirconium include zirconium sulfate, zirconium acetate, zirconium nitrate, zirconium oxychloride, zirconium carbonate, and zirconia powder.

[0076] Examples of the raw material of the additive oxide component containing boron include boric acid, ammonium borate, sodium borate, and aluminum borate. Examples of the raw material of the additive oxide component containing magnesium include magnesium oxide, magnesium hydroxide, and magnesium sulfate.

[0077] <Additive> After adding at least one organic additive selected from organic acids or saccharides to the obtained slurry of the carrier precursor as needed, the carrier precursor may be aged. Examples of the organic acids include citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA). Examples of the saccharides include monosaccharides, disaccharides, and polysaccharides.

[0078] 《Shaping of the Carrier Precursor》 The carrier precursor containing the alumina hydrate and the raw material of the additive oxide component is, for example, put into a double-arm kneader with a steam jacket, heated and kneaded to obtain a kneadable mass, and then formed into a desired shape such as a cylinder type, a three-leaf type, or a four-leaf type by extrusion molding or the like.

[0079] (Step (2)) In step (2), the molded product of the carrier precursor obtained in step (1) is fired to produce an inorganic oxide carrier. Before firing, the molded product may be heated and dried at, for example, 70 to 150 °C, preferably 90 to 130 °C. The firing temperature is, for example, 400 to 800 °C, preferably 400 to 600 °C, and the firing time is, for example, 0.5 to 10 hours, preferably 2 to 5 hours. Firing at too low a temperature may cause residual organic additives or a decrease in the average pore diameter, which is not preferable. Also, firing at too high a temperature may cause a decrease in the specific surface area, which is not preferable.

[0080] (Step (3)) In step (3), an impregnating solution containing a raw material of the metal component, an acid, and water is prepared, and the impregnating solution is impregnated into the inorganic oxide carrier to support the raw material of the metal component on the inorganic oxide carrier.

[0081] <Raw material of metal component> The obtained carrier is brought into contact with an impregnating solution containing the raw material of the metal component. Examples of the raw material of the metal component include molybdenum trioxide, ammonium molybdate, cobalt nitrate, cobalt carbonate, nickel nitrate, and nickel carbonate.

[0082] The blending amount of the raw material of each metal component is set so that the amount of molybdenum and the amount of nickel and / or cobalt in the produced hydrogenation catalyst are within the above-mentioned ranges. The amount or composition of the raw material of the metal component is appropriately selected according to the type of the feedstock oil for the hydrogenation treatment or the use of the produced oil.

[0083] When the raw material of the metal component is supported on the inorganic oxide carrier, an impregnating solution in which the raw material of the metal component is dissolved is prepared and supported on the carrier.

[0084] <Impregnating solution> When preparing the impregnating solution, it is preferable to use an inorganic acid or an organic acid to adjust the pH of the impregnating solution to 4 or less to dissolve the raw material of the metal component. Examples of the inorganic acid include phosphoric acids and nitric acid. As the phosphoric acids, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimeta phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, etc. are used. As the organic acid, for example, citric acid, malic acid, tartaric acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) can be used, and in particular, citric acid and malic acid are preferably used.

[0085] (Step (4)) In step (4), the inorganic oxide carrier supporting the raw material of the metal component is calcined to produce the hydrogenation treatment catalyst according to the present invention.

[0086] The calcination temperature is, for example, 400 to 800 °C, preferably 400 to 700 °C, more preferably 450 to 650 °C, and the calcination time is, for example, 0.5 to 10 hours, preferably 1 to 8 hours. Calcination at too high a temperature causes a decrease in catalyst activity due to aggregation of the metal component, which is not preferable.

[0087] The hydrogenation treatment catalyst according to the present invention described above can be produced by the method for producing a hydrogenation treatment catalyst according to the present invention.

[0088] [Hydrogenation method] The method for hydrogenating a heavy hydrocarbon oil (heavy oil) according to the present invention is characterized by including a step of hydrogenating a heavy hydrocarbon oil (heavy oil) in the presence of the hydrogenation treatment catalyst according to the present invention.

[0089] The heavy oil to be treated with the catalyst according to the present invention is mainly composed of the distillation residue of crude oil, has a wider molecular weight distribution than the light gas oil fraction, and its properties vary greatly depending on the origin of the crude oil. Representative heavy oils from the Middle East and Central and South America have a high sulfur content and asphaltene content, and those with a high asphaltene content contain a large amount of residual carbon and impurity metals such as vanadium and nickel. Heavy oil becomes a raw material for low-sulfur heavy oil or a feedstock for a fluid catalytic cracking unit (RFCC) through hydrorefining treatment in a heavy oil hydrotreating unit.

[0090] There is no particular limitation on the heavy oil, and examples thereof include high-density petroleum fractions such as atmospheric distillation residue oil (AR) and vacuum distillation residue oil (VR) of crude oil, catalytic cracking residue oil, bis-breaking oil, and bitumen. These heavy oils usually contain 1% by mass or more of asphaltene, and asphaltene extracted from these heavy oils can also be used as a raw material oil. In the present invention, these may be used alone or in combination of two or more as the raw material oil. In addition, coker oil, synthetic crude oil, naphtha cut crude oil, heavy light oil, vacuum gas oil, LCO, GTL (Gas To Liquid) oil, wax, etc. can be mixed with atmospheric distillation residue oil, etc. and subjected to hydrotreating as heavy oil.

[0091] As the raw material heavy oil, preferably, those having a density of 0.90 to 1.05 g / cm 3 , a sulfur content (sulfur concentration) of 1 to 6% by mass, and a distillation property in which components having a boiling point of 360 °C or higher account for 80% by mass or more are used. The nitrogen content (nitrogen concentration) of the raw material heavy oil is preferably more than 2000 mass ppm and 10000 mass ppm or less.

[0092] The hydrotreating using the catalyst of the present invention is carried out, for example, by stacking and filling the catalyst in a fixed bed reactor in the flow direction so as to form a demetallization section, a transition section, and a desulfurization section, and passing heavy oil under high temperature and high pressure conditions in a hydrogen atmosphere.

[0093] The obtained treated oil is subjected to catalytic cracking treatment in a fluid catalytic cracking unit if necessary. The catalytic cracking treatment by the above fluid catalytic cracking unit is not particularly limited and may be performed by known methods and conditions. For example, an amorphous catalyst such as silica-alumina or silica-magnesia, or a zeolite catalyst such as faujasite-type crystalline aluminosilicate is used, and the reaction temperature is about 450 to 650 °C, preferably 480 to 580 °C, the regeneration temperature is about 550 to 760 °C, and the reaction pressure is about 0.1 to 5 MPa, preferably 0.2 to 2 MPa, and may be appropriately selected within this range. The product oil subjected to catalytic cracking treatment in the fluid catalytic cracking unit, which is the final step, can be used as a raw material for fuels and petrochemical products.

Examples

[0094] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples at all.

[0095] <Method for measuring the contents of carrier components (such as aluminum, phosphorus, titanium, zirconium, boron, silicon, magnesium, etc.) and metal components (such as molybdenum, cobalt, nickel, etc.)> After pulverizing about 10 g of the measurement sample in a mortar, about 0.5 g was collected, heat-treated (200 °C, 20 minutes), calcined (700 °C, 5 minutes), then 2 g of Na2O2 and 1 g of NaOH were added and melted for 15 minutes. Further, 25 ml of H2SO4 and 200 ml of water were added and dissolved, and then diluted with pure water to 500 ml to obtain a sample. For the obtained sample, the contents of each component other than aluminum were measured on an oxide conversion basis using an ICP emission spectrometer (manufactured by Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000). The content of aluminum (in terms of Al2O3) was taken as the value obtained by subtracting the contents of other components from the amount of the measurement sample.

[0096] <Method for measuring the surface area of the catalyst (specific surface area N2) determined by the BET single-point method of nitrogen adsorption and desorption measurement> Approximately 30 mL of the measurement sample was collected in a magnetic crucible (type B-2), heat-treated at a temperature of 500 °C for 1 hour, placed in a desiccator, and cooled to room temperature to obtain a measurement sample. Next, 1 g of this sample was taken and the specific surface area (m 2 / g) of the sample was measured by the BET method using a fully automatic surface area measurement device (MultiSorb 12 type, manufactured by Yuasa Ionics).

[0097] <Method for Measuring the Average Pore Diameter of the Carrier> Approximately 3 g of the measurement sample was collected in a magnetic crucible, heat-treated at a temperature of 500 °C for 1 hour, placed in a desiccator, and cooled to room temperature to obtain a measurement sample. After that, it was measured by the mercury intrusion method (Porometer GT-60 manufactured by Quantachrome, contact angle of mercury: 150 degrees, surface tension: 480 dyn / cm). The average pore diameter was defined as the pore diameter corresponding to 50% of the pore volume.

[0098] <Method for Measuring the Pore Volume of the Carrier> Approximately 30 g of the measurement sample was collected in a magnetic crucible, heat-treated at a temperature of 500 °C for 1 hour, placed in a desiccator, and cooled to room temperature to obtain a measurement sample. After that, the pore volume was measured by the water porosimetry method.

[0099] <Method for Measuring the Nitric Oxide Adsorption Amount of the Sulfurized Catalyst> The measurement of the nitric oxide adsorption amount was carried out using a fully automatic catalyst gas adsorption amount measurement device (manufactured by Okura Riken). A mixed gas of helium gas and nitric oxide gas (nitric oxide concentration 10% by volume) was introduced in pulses into the sulfurized hydrogenation catalyst, and the nitric oxide molecule adsorption amount per 1 g of the hydrogenation catalyst was measured. Specifically, approximately 0.2 g of the catalyst pulverized to 60 mesh or less was weighed and filled into a quartz cell. The catalyst was heated to 360 °C, and a gas of 5% by volume hydrogen sulfide / 95% by volume hydrogen was passed at a flow rate of 0.2 L / min for 1 hour for sulfidation treatment. Then, it was held at 340 °C for 1 hour to discharge the physically adsorbed hydrogen sulfide outside the system. After that, nitric oxide molecules were adsorbed at 50 °C with a mixed gas of helium gas and nitric oxide gas, and the nitric oxide molecule adsorption amount was measured by a TCD (thermal conductivity detector).

[0100] <Measurement method of temperature-programmed reduction method> In the temperature-programmed reduction method, using a fully automatic catalyst gas adsorption amount measuring device (manufactured by Okura Riken Co., Ltd.), 0.05 g of the catalyst sized to 250 to 710 μm was pretreated at 400 °C for 1 hour under the flow of argon gas and then cooled to 50 °C. Then, the argon gas was switched to a hydrogen / argon mixed gas with a hydrogen concentration of 65% and a supply rate set to 24 ml / min, and the temperature was raised from 50 °C to 600 °C at a rate of 3 °C / min. The flowing gas during the temperature increase was measured with a TCD (thermal conductivity detector) to obtain a hydrogen gas consumption spectrum, and the reduction peak temperature of the metal component was read from the hydrogen gas consumption spectrum.

[0101] Figure 1 shows a graph which is an example of the analysis result by the temperature-programmed reduction method. The horizontal axis is the catalyst sample temperature, and the vertical axis is the relative value of the hydrogen gas consumption. In the present invention, the "reduction peak temperature" is the catalyst sample temperature at the point when the hydrogen consumption is the highest in the temperature range of less than 450 °C, as can also be read in the example shown in Figure 1.

[0102] <Analysis method of hydrocarbon oil> The sulfur concentration was measured in accordance with JIS K 2541-7. The nitrogen concentration was measured in accordance with JIS K 2609. The metal (nickel and vanadium) concentration was measured in accordance with Petroleum Institute JPI-5S-62. The residue carbon content was measured in accordance with JIS K 2270-2:2009. The density was measured in accordance with JIS K 2249-1. The distillation properties were measured in accordance with ASTM D2892.

[0103] <Production Example 1: Preparation of carrier D> 60.4 kg of pure water was poured into a tank equipped with a circulation line having two chemical solution addition ports, and while stirring, 19.2 kg of an aluminum sulfate aqueous solution (concentration of 7% by mass as Al2O3), which is an acidic aluminum salt aqueous solution, was added. The obtained diluted aqueous solution was heated to 60 °C and circulated. The pH of the aqueous solution was 2.3. While stirring the diluted aqueous solution, 5.00 kg of a titanyl sulfate aqueous solution (concentration of 5% by mass as TiO2) and 1.04 kg of a sodium silicate aqueous solution (water glass, concentration of 24% by mass as SiO2) were sequentially added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (D1).

[0104] Next, 14.3 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and added to the above acidic aluminum salt aqueous solution (D1) over 60 minutes to form a slurry. Then, the pH of the slurry was adjusted to 9.5. Unless otherwise specified, including in other production examples and comparative production examples, the pH adjustment was performed by adding a 15% by mass aqueous ammonia solution or a 10% by mass sulfuric acid aqueous solution. The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 8% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, and further dehydrated to obtain a cake-like alumina-based composite oxide hydrate (D).

[0105] The cake-like alumina-based composite oxide hydrate (D) was concentrated and kneaded in a double-arm kneader equipped with a steam jacket while kneading until it reached a predetermined moisture content (about 40 to 70% including other production examples and comparative production examples). The obtained kneaded product was extruded and formed into a 1.7-mm four-leaf columnar shape using an extrusion molding machine. The obtained molded product was dried at 110°C for 12 hours and then fired at 500°C for 3 hours to obtain a carrier D. The chemical composition of carrier D is shown in Table 1.

[0106] <Production Example 2: Preparation of Carrier E> 64.1 kg of pure water was charged into a tank equipped with a circulation line having two chemical solution inlets, and 19.2 kg of an aqueous aluminum sulfate solution, which is an acidic aluminum salt aqueous solution (concentration: 7% by mass as Al2O3), was added while stirring. The obtained diluted aqueous solution was heated to 60°C and circulated. The pH of the diluted aqueous solution was 2.3. While stirring the diluted aqueous solution, 1.65 kg of an aqueous zirconium sulfate solution (concentration: 18.2% by mass as ZrO2) and 0.83 kg of an aqueous sodium silicate solution (concentration: 24% by mass as SiO2) were sequentially added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (E1).

[0107] Next, 14.3 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and added to the above acidic aluminum salt aqueous solution (E1) over 60 minutes to form a slurry. Subsequently, the pH of the slurry was adjusted to 9.5. The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 8% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, followed by further dehydration to obtain a cake-like alumina-based composite oxide hydrate (E).

[0108] A carrier E was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina-based composite oxide hydrate (E). The chemical composition of the carrier E is shown in Table 1.

[0109] <Production Example 3: Preparation of Carrier F> 63.8 kg of pure water was charged into a tank equipped with a circulation line having two chemical solution inlets, and 20.5 kg of an aqueous aluminum sulfate solution, which is an acidic aluminum salt aqueous solution (concentration: 7% by mass as Al2O3), was added while stirring. The obtained diluted aqueous solution was heated to 60°C and circulated. The pH of the diluted aqueous solution was 2.3. While stirring the diluted aqueous solution, 0.08 kg of phosphoric acid (concentration: 61.6% by mass as P2O5) and 0.63 kg of an aqueous sodium silicate solution (concentration: 24% by mass as sodium silicate and SiO2) were sequentially added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (F1).

[0110] Next, 15.3 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and added to the above acidic aluminum salt aqueous solution (F1) over 60 minutes to form a slurry. Subsequently, the pH of the slurry was adjusted to 9.5. The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 10% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, followed by further dehydration to obtain a cake-like alumina-based composite oxide hydrate (F).

[0111] A carrier F was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina-based composite oxide hydrate (F). The chemical composition of the carrier F is shown in Table 1.

[0112] <Production Example 4: Preparation of Carrier G> 59.6 kg of pure water was charged into a tank equipped with a circulation line having two chemical solution inlets, and 20.3 kg of an aqueous aluminum sulfate solution, which is an acidic aluminum salt aqueous solution (concentration: 7% by mass as Al2O3), was added while stirring. The obtained diluted aqueous solution was heated to 60°C and circulated. The pH of the diluted aqueous solution was 2.3. While stirring the diluted aqueous solution, 5.0 kg of an aqueous magnesium sulfate solution (concentration: 5% by mass as MgO) was added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (G1).

[0113] Next, 15.2 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and added to the above acidic aluminum salt aqueous solution (G1) over 60 minutes to form a slurry. Subsequently, the pH of the slurry was adjusted to 9.5. The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 7% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, followed by further dehydration to obtain a cake-like alumina-based composite oxide hydrate (G).

[0114] A carrier G was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina-based composite oxide hydrate (G). The chemical composition of the carrier G is shown in Table 1.

[0115] <Production Example 5: Preparation of Carrier H> 60.9 kg of pure water was charged into a tank equipped with a circulation line having two chemical solution inlets, and 20.7 kg of an aqueous aluminum sulfate solution, which is an acidic aluminum salt aqueous solution (concentration: 7% by mass as Al2O3), was added while stirring. The obtained acidic aluminum salt aqueous solution (H1) was heated to 60°C and circulated. The pH of the diluted aqueous solution was 2.3. While stirring the diluted aqueous solution, 266 g of boric acid was added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (H1).

[0116] Next, 15.5 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration of 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and then added to the above acidic aluminum salt aqueous solution (H1) over 60 minutes to form a slurry. Subsequently, the pH of the slurry was adjusted to 9.5. The resulting alumina hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 10% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, followed by further dehydration to obtain a cake-like alumina hydrate (H).

[0117] A carrier H was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina-based composite oxide hydrate (H). The chemical composition of the carrier H is shown in Table 1.

[0118] <Production Example 6: Preparation of Carrier I> 60.2 kg of pure water was charged into a tank equipped with a circulation line having two chemical solution inlets, and 19.8 kg of an aqueous aluminum sulfate solution, which is an acidic aluminum salt aqueous solution (concentration of 7% by mass as Al2O3), was added while stirring. The resulting diluted aqueous solution was heated to 60°C and circulated. The pH of the diluted aqueous solution was 2.3. While stirring the diluted aqueous solution, 5.00 kg of an aqueous titanyl sulfate solution (concentration of 5% by mass as TiO2) and 162 g of phosphoric acid (P2O5 concentration of 61.6% by mass) were sequentially added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (I1).

[0119] Next, 14.8 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and then added to the above acidic aluminum salt aqueous solution (I1) over 60 minutes to form a slurry. Subsequently, the pH of the slurry was adjusted to 9.5. The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 8% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, followed by dehydration to obtain a cake-like alumina-based composite oxide hydrate (I).

[0120] A carrier I was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina-based composite oxide hydrate (I). The chemical composition of the carrier I is shown in Table 1.

[0121] <Production Example 7: Preparation of Carrier J> 63.4 kg of pure water was charged into a tank equipped with a circulation line having two chemical solution inlets, and 20.5 kg of an aqueous aluminum sulfate solution, which is an acidic aluminum salt aqueous solution (concentration: 7% by mass as Al2O3), was added while stirring. The obtained diluted aqueous solution was heated to 60°C and circulated. The pH of the diluted aqueous solution was 2.3. While stirring the diluted aqueous solution, 0.08 kg of phosphoric acid (concentration: 61.6% by mass as P2O5) was added to the diluted aqueous solution to obtain an acidic aluminum salt aqueous solution (J1).

[0122] Next, 15.3 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was stirred and circulated while maintaining the temperature at 60°C, and added to the above acidic aluminum salt aqueous solution (J1) over 60 minutes. Then, 0.75 kg of a silica sol (Cataloid SN manufactured by Nippon Shokubai Catalysts & Chemicals Co., Ltd., SiO2 concentration: 20% by mass) was added to form a slurry. Subsequently, the pH of the slurry was adjusted to 9.5. The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare a solution with an Al2O3 concentration of 10% by mass, and then aged at 95°C for 3 hours in an aging tank equipped with a reflux device, followed by further dehydration to obtain a cake-like alumina-based composite oxide hydrate (J).

[0123] A carrier J was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina-based composite oxide hydrate (J). The chemical composition of the carrier J is shown in Table 1.

[0124] <Comparative Production Example 1: Preparation of Carrier A> 31 kg of pure water was charged into a tank equipped with a steam jacket, and 9.1 kg of an aqueous sodium aluminate solution, which is an aqueous basic aluminum salt solution (concentration: 22% by mass as Al2O3), was added while stirring. The obtained aqueous basic aluminum salt solution (A1) was heated to 60°C. The pH of the aqueous basic aluminum salt solution (A1) was 13.

[0125] Next, 40 kg of an aqueous aluminum sulfate solution (concentration of 2.5% by mass as Al2O3), which is an acidic aluminum salt aqueous solution, was added to the above basic aluminum salt aqueous solution (A1) at a constant rate using a roller pump until the pH of the resulting aqueous solution reached 7.2 (addition time: 10 minutes). The obtained alumina hydrate was washed with pure water at 60 °C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. The washed cake-like slurry was diluted with ion-exchanged water so that the Al2O3 concentration was 10% by mass, and then the pH was adjusted to 10.5 with 15% aqueous ammonia. After aging this in an aging tank equipped with a reflux condenser at 95 °C for 10 hours, it was further dehydrated to obtain a cake-like alumina hydrate (A).

[0126] A carrier A was obtained in the same manner as in Production Example 1, except that the alumina-based composite oxide hydrate (D) was changed to the alumina hydrate (A). The chemical composition of the carrier A is shown in Table 1.

[0127] <Comparative Production Example 2: Preparation of Carrier B> 62.7 kg of pure water was charged into a tank equipped with a circulation line having two chemical liquid inlets, and 21.3 kg of an aqueous aluminum sulfate solution (concentration of 7% by mass as Al2O3), which is an acidic aluminum salt aqueous solution, was added while stirring. The obtained acidic aluminum salt aqueous solution (B1) was heated to 60 °C and circulated. The pH of the acidic aluminum salt aqueous solution (B1) was 2.3.

[0128] Next, 15.9 kg of an aqueous sodium aluminate solution (concentration of 22% by mass as Al2O3), which is a basic aluminum salt aqueous solution, was added to the above acidic aluminum salt aqueous solution (B1) over 60 minutes while stirring and circulating and maintaining the temperature at 60 °C to obtain an alumina hydrate (B). After the addition of the aqueous sodium aluminate solution, the pH of the slurry was adjusted to 9.5. The obtained alumina hydrate was washed with pure water at 60 °C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. Pure water was added to the washed cake to prepare it so that the Al2O3 concentration was 10% by mass, and then it was aged in an aging tank equipped with a reflux condenser at 95 °C for 3 hours and further dehydrated to obtain a cake-like alumina hydrate (B).

[0129] A carrier B was obtained in the same manner as in Comparative Production Example 1 except that the alumina hydrate (A) was changed to an alumina hydrate (B). The chemical composition of the carrier B is shown in Table 1.

[0130] <Comparative Production Example 3: Preparation of Carrier C> 31 kg of pure water was charged into a tank equipped with a steam jacket, and while stirring, 8.2 kg of an aqueous sodium aluminate solution (concentration of 22% by mass as Al2O3), which is an aqueous solution of a basic aluminum salt, was added. The resulting diluted aqueous solution was heated to 60°C. The pH of the diluted aqueous solution was 13. While stirring the diluted aqueous solution, 3.00 kg of an aqueous titanyl sulfate solution (concentration of 5% by mass as TiO2) and 0.63 kg of an aqueous sodium silicate solution (concentration of 24% by mass as SiO2) were sequentially added to the diluted aqueous solution. Then, 36.0 kg of an aqueous aluminum sulfate solution (concentration of 2.5% by mass as Al2O3), which is an aqueous solution of an acidic aluminum salt, was added at a constant rate using a roller pump until the pH of the resulting aqueous solution reached 7.2 (addition time: 10 minutes).

[0131] The obtained alumina-based composite oxide hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate ions, and a washed cake was obtained. The washed cake-like slurry was diluted with ion-exchanged water so that the Al2O3 concentration was 10% by mass, and then the pH was adjusted to 10.5 with 15% aqueous ammonia. This was aged at 95°C for 10 hours in an aging tank equipped with a reflux condenser, and then further dehydrated to obtain a cake-like alumina-based composite oxide hydrate (C).

[0132] A carrier C was obtained in the same manner as in Comparative Production Example 1 except that the alumina hydrate (A) was changed to an alumina-based composite oxide hydrate (C). The chemical composition of the carrier C is shown in Table 1.

[0133] <Preparation of Impregnating Solution> (Preparation of impregnation solution a) 73.2 g of molybdenum trioxide and 33.3 g of nickel carbonate were suspended in 350 ml of ion-exchanged water. This suspension was heated at 90 °C for 5 hours using an appropriate reflux apparatus so that the liquid volume did not decrease. Then, 29.7 g of phosphoric acid and 27.4 g of citric acid were added and dissolved to prepare impregnation solution a.

[0134] (Preparation of impregnation solution b) Impregnation solution b was prepared in the same manner as the preparation method of impregnation solution a, except that nickel carbonate was changed to 33.3 g of cobalt carbonate.

[0135] (Preparation of impregnation solution c) Impregnation solution c was prepared in the same manner as the preparation method of impregnation solution a, except that nickel carbonate was changed to 19.9 g of cobalt carbonate and 11.1 g of nickel carbonate.

[0136] (Preparation of impregnation solution d) Impregnation solution d was prepared in the same manner as the preparation method of impregnation solution a, except that nickel carbonate was changed to 10.0 g of cobalt carbonate and 22.2 g of nickel carbonate.

[0137] (Preparation of impregnation solution e) 45.5 g of molybdenum trioxide and 20.7 g of nickel carbonate were suspended in 350 ml of ion-exchanged water. This suspension was heated at 90 °C for 5 hours using an appropriate reflux apparatus so that the liquid volume did not decrease. Then, 18.5 g of phosphoric acid and 17.1 g of citric acid were added and dissolved to prepare impregnation solution e.

[0138] (Preparation of impregnation solution f) 96.9 g of molybdenum trioxide and 44.6 g of nickel carbonate were suspended in 350 ml of ion-exchanged water. This suspension was heated at 90 °C for 5 hours using an appropriate reflux apparatus so that the liquid volume did not decrease. Then, 39.9 g of phosphoric acid and 36.8 g of citric acid were added and dissolved to prepare impregnation solution f.

[0139] <Comparative Example 1: Preparation of Hydrodesulfurization Catalyst (1)> An impregnation liquid a was prepared by adding an appropriate amount of pure water to 500 g of carrier A so that the volume was the same as the total pore volume of the carrier. After spray impregnation, it was dried at 250 °C and then calcined in an electric furnace at 550 °C for 1 hour to obtain a desulfurization catalyst (1) (hereinafter, also simply referred to as "catalyst (1)". The same applies to the following examples.).

[0140] <Comparative Examples 2 - 6 and Examples 1 - 12: Preparation of Hydrodesulfurization Catalysts (2) - (18)> Catalysts (2) - (18) were prepared in the same manner as in Comparative Example 1, except that the carriers and impregnation liquids prepared as described above were combined as shown in Tables 1 - 3.

[0141] <Performance Evaluation of Catalysts> A commercially available demetallization catalyst, transition catalyst, desulfurization catalyst, and the catalyst of the example or comparative example were filled into a fixed - bed flow - type reactor (catalyst filling volume 350 ml) in the following order. 35 ml of a commercially available demetallization catalyst CDS - RS110 (manufactured by JGC Catalysts & Chemicals Ltd.) 35 ml of a commercially available demetallization catalyst CDS - RS210 (manufactured by JGC Catalysts & Chemicals Ltd), 70 ml of a commercially available transition catalyst CDS - RS420 (manufactured by JGC Catalysts & Chemicals Ltd), 105 ml of a commercially available desulfurization catalyst CDS - R38C (manufactured by JGC Catalysts & Chemicals Ltd), 105 ml of the catalyst of the example or comparative example.

[0142] The filled catalysts were pre - sulfided to desorb and activate the oxygen atoms contained in the catalysts. This treatment was carried out by a conventional method, that is, by flowing a liquid or gas containing a sulfur compound in a controlled reaction vessel under a hydrogen pressure atmosphere at a temperature of 200 - 400 °C and a hydrogen pressure of normal pressure - 100 MPa.

[0143] Heavy oil (density at 15 °C: 0.9741 g / cm 3, sulfur content: 4.06% by mass, metal (Ni + V) content: 85.1 ppm by mass, nitrogen content: 2075 ppm by mass, asphaltene content: 4.2% by mass, residual carbon content: 10.7% by mass) were introduced and hydrotreated. The reaction conditions at that time were a hydrogen partial pressure of 13.5 MPa, a liquid hourly space velocity of 0.3 h -1 , and a hydrogen-oil ratio of 800 Nm 3 / kl. Then, the reaction temperature was varied in the range of 360 to 380 °C, and the sulfur content, nitrogen content, and residual carbon content in the finally obtained product oil were analyzed.

[0144] In the activity test, the reaction rate constant was determined from the Arrhenius plot. Taking the reaction rate constant of the evaluation result with catalyst (1) filled in the desulfurization catalyst section at a reaction temperature of 370 °C as 100%, the desulfurization activity, denitrification activity, and decarbonization activity (relative activity) at 370 °C when other catalysts were filled in the desulfurization catalyst section were calculated. The reaction rate constant was determined based on the following formula (1).

[0145] K n = LHSV × 1 / (n - 1) × (1 / P n-1 - 1 / F n-1 ) …(1) Here, K n : Reaction rate constant n: The power to which the desulfurization reaction rate, denitrification reaction rate, or decarbonization reaction rate is proportional to the sulfur, nitrogen, or residual carbon concentration of the feedstock oil, respectively (n = 2.0 for the desulfurization reaction, n = 1.0 for the denitrification reaction, and n = 1.0 for the decarbonization reaction) P: Sulfur concentration (mass %), nitrogen concentration (mass %), or residual carbon content concentration (mass %) in the treated oil F: Sulfur concentration (mass %), nitrogen concentration (mass %), or residual carbon content concentration (mass %) in the feedstock oil LHSV: Liquid hourly space velocity (hr -1 ) is.

[0146] The results are shown in Tables 1 to 3. The catalyst (1) of the comparative example is a comparative example using a carrier composed only of alumina. Although it shows a reduction peak temperature lower than value A and has the same pore characteristics as the catalyst of the present invention, its catalytic activity was not excellent.

[0147] The catalyst (2) contains molybdenum and cobalt as metal components and is a comparative example using a carrier consisting only of alumina. Compared with the catalyst (14) of the example showing a reduction peak temperature higher than value A with the same amount of metal components, the catalytic activity was inferior.

[0148] The catalyst (3) of the comparative example has a carrier component of alumina alone, shows a reduction peak temperature lower than value A, has pore characteristics different from those of the catalyst of the present invention, and the catalytic activity was not excellent.

[0149] The catalyst (4) of the comparative example has a carrier composed of an alumina-titania-silica composite oxide, has pore characteristics similar to those of the present invention, shows a reduction peak temperature lower than value A, and the catalytic activity was not excellent.

[0150] Catalysts (9) and (13) have almost the same chemical composition, but catalyst (9) was prepared using sodium silicate and catalyst (13) was prepared using silica sol, so it is considered that the state of existence of the silica component is different. However, both catalysts (9) and (13) show a reduction peak temperature higher than value A, and other physical properties are also within the range disclosed in the present invention, showing excellent catalytic activity.

[0151] The catalysts of all other examples showed high desulfurization, denitrification, and decarbonization activities. In Tables 2 and 3, the catalytic activities when the amount of active metal is varied are compared. The catalyst (5) is a comparative example with a small amount of metal components, but the carrier component is alumina alone and the reduction peak temperature was lower than value A. On the other hand, the catalyst (17) of the example having the same amount of metal components as catalyst (5) but using a composite oxide carrier as the carrier and having a reduction peak temperature higher than value A showed better catalytic performance than catalyst (5).

[0152] Also, from the comparison of catalysts (6) and (18), it can be seen that even when the amount of metal components is large, when the reduction peak temperature is higher than value A, excellent catalytic activity is shown.

[0153]

Table 1-1

[0154]

Table 1-2

[0155]

Table 2

[0156]

Table 3

Claims

1. A hydrotreating catalyst for heavy hydrocarbon oil, comprising an inorganic oxide carrier having alumina as a main component and containing an added oxide component, and a metal component supported on the inorganic oxide carrier, wherein the metal component contains molybdenum and contains nickel and / or cobalt, the content of molybdenum is 5 to 16% by mass in terms of oxide, and the total content of nickel and cobalt is 1 to 6% by mass in terms of oxide, The specific surface area measured by the nitrogen adsorption method is 150 to 320 m 2 / g, and the value of the reduction peak temperature (°C) below 450°C in the temperature-programmed reduction measurement of the catalyst is not less than the value A (°C) represented by the following formula, Value A (°C) = 1.0 × (content of molybdenum in the catalyst in terms of MoO 3 content (mass %)) + 25 × (ratio of the content of cobalt in terms of CoO (mass %) to the total content of nickel in terms of NiO and cobalt in terms of CoO in the catalyst (mass %)) + 339 the amount of nitric oxide adsorbed after the sulfidation treatment of the catalyst is 4.0 to 9.0 ml / g when the molar ratio (Ni / (Ni + Co)) of the amount of nickel to the total amount of nickel and cobalt in the catalyst is 0.5 or more, and is 5.0 to 9.0 ml / g when the molar ratio is less than 0.5, the added oxide component contains an oxide of at least one of the following additive element(s) (group) (b) and (c): (b) A combination of silicon and at least one element (group) M selected from the group consisting of titanium, zirconium, and phosphorus, wherein the ratio of the silicon to the element (group) M is 0.4 to 3.5 as (mass of silica) / (mass of oxide of the element (group) M), (c) A combination of titanium and phosphorus, or a combination of zirconium and phosphorus

2. A hydrotreating catalyst for heavy hydrocarbon oil, comprising an inorganic oxide carrier having alumina as a main component and containing an added oxide component, and a metal component supported on the inorganic oxide carrier, wherein the metal component contains molybdenum and contains nickel and / or cobalt, the content of molybdenum is 5 to 16% by mass in terms of oxide, and the total content of nickel and cobalt is 1 to 6% by mass in terms of oxide, the specific surface area measured by the nitrogen adsorption method is 150 to 320 m 2 / g, the value of the reduction peak temperature (°C) below 450°C in the temperature-programmed reduction measurement of the catalyst is not less than the value A (°C) represented by the following formula, Value A (°C) = 1.0 × (content of molybdenum in the catalyst in terms of MoO 3 (mass%)) + 25 × (ratio of the content of cobalt in terms of CoO to the total content of nickel in terms of NiO and cobalt in terms of CoO in the catalyst (mass%)) + 339 The amount of nitric oxide adsorbed after the sulfidation treatment of the catalyst is 4.0 ml / g to 6.5 ml / g when the molar ratio of the amount of nickel to the total amount of nickel and cobalt in the catalyst (Ni / (Ni + Co)) is 0.5 or more, and is 5.0 ml / g to 6.5 ml / g when the molar ratio is less than 0.

5. A hydrotreating catalyst for heavy hydrocarbon oil.

3. The hydrotreating catalyst for heavy hydrocarbon oil according to claim 1, wherein the inorganic oxide carrier contains 1 to 30% by mass of the added oxide component.

4. The inorganic oxide carrier has an average pore diameter (PD) measured by the mercury intrusion method of 9.0 to 15.0 nm, the total pore volume in the range of the average pore diameter ± 2 nm is 50% or more of the total pore volume, and the total pore volume in the range of a pore diameter of 20 nm or more is 10% or less of the total pore volume, and the pore volume (PV) measured by the water pore filling method is 0.5 to 1.1 ml / g. The hydrotreating catalyst for heavy hydrocarbon oil according to claim 1 or 2.

5. A method for hydrotreating heavy hydrocarbon oil, comprising a step of hydrotreating the heavy hydrocarbon oil in the presence of the hydrotreating catalyst according to claim 1 or 2.

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