Catalyst for hydrotreating heavy hydrocarbon oil, method for producing same, and method for hydrotreating heavy hydrocarbon oil

Abstract

To provide a catalyst for hydrotreating heavy hydrocarbon oil, which exhibits excellent demetallization performance, desulfurization performance, and deasphaltenization performance and has high strength.SOLUTION: Provided is a hydrotreatment catalyst for hydrotreating heavy hydrocarbon oil, including an alumina-phosphorus oxide carrier and a hydrogenation active metal component supported by the carrier, wherein the phosphorous content in the carrier is 0.4-2.0 mass% in terms of P2O5; the carrier has a maximal value for differential pore volume distribution in a range of 18-22 nm in pore diameter as measured by a mercury intrusion method; in the carrier, the ratio (ΔPV / PVT) of the volume (ΔPV) of pores having a pore diameter in a range outside ±2 nm of the pore diameter at the maximal value with respect to the total pore volume (PVT) as measured by the mercury intrusion method is 0.50 or less; and the crystalline form of the alumina portion in the alumina-phosphorus oxide carrier is γ-alumina.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a catalyst for hydrotreating heavy hydrocarbon oils, a method for producing the same, and a method for hydrotreating heavy hydrocarbon oils, more particularly to a catalyst used in the hydrotreating of heavy hydrocarbon oils such as residual oils containing asphaltene, vanadium, nickel, or other metal contaminants, a method for producing the same, and a hydrotreating method using the catalyst. [Background technology]

[0002] In the pretreatment process for heavy hydrocarbon oil, high demetallization and desulfurization performance as well as deasphalting performance are required. Asphaltenes are abundant in heavy hydrocarbon oils, have large molecular weights, and contain large amounts of metals, hydrotreating is necessary for advanced demetallization. Furthermore, if the asphaltenes in the feedstock oil cannot be sufficiently hydrotreated in the hydrotreating process for heavy hydrocarbon oils, the resulting oil will contain a large amount of dry sludge. Since a base oil containing a large amount of dry sludge has poor storage stability and can cause various problems, it is important to hydrotreat the asphaltenes in the feedstock oil to a high degree.

[0003] To hydrotreat asphaltenes with large molecular weights, catalysts with larger pores and bimodal catalysts with two peaks in the differential pore volume distribution have been developed. In recent years, in response to the increasing heaviness of feedstock oils, further performance improvements are required to reduce the burden on R-FCC processing after the hydrotreating process.

[0004] For example, Patent Document 1 discloses a catalyst that has high demetallization and desulfurization performance by using a bimodal catalyst having mesopores in the range of 7 to 20 nm and macropores in the range of 300 to 800 nm.

[0005] For example, Patent Document 2 discloses a catalyst having high demetallization and desulfurization performance by using a catalyst having mesopores in the range of 10 to 30 nm. For example, Patent Document 3 discloses that a catalyst containing 1 to 15% zinc based on the carrier and having an average pore diameter of 18 to 35 nm exhibits the effect of improving the storage stability of the produced oil while maintaining high desulfurization activity and demetallization performance. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-181562 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-091010 [Patent Document 3] International Publication No. 2015 / 046316 Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional catalysts for hydrotreating heavy hydrocarbon oils have room for further improvement in terms of deasphalting performance and the like. In view of the above problems in the prior art, an object of the present invention is to provide a catalyst for hydrotreating heavy hydrocarbon oils, which exhibits excellent demetallization performance, desulfurization performance, and deasphaltene removal performance, and also has high strength, and a method for producing the same. [Means for solving the problem]

[0008] As a result of extensive research, the present inventors have found that the above problems can be solved by using a carrier having a predetermined pore distribution, composition and crystal morphology, and have thus completed the present invention. The present invention relates to, for example, the following [1] to [9].

[0009] [1] A catalyst for hydrotreating heavy hydrocarbon oils, comprising: The catalyst comprises an alumina-phosphorus oxide support and a hydrogenation active metal component supported on the support, The phosphorus content in the carrier is 0.4 to 2.0 mass% in terms of P2O5, the carrier has a maximum value of a differential pore volume distribution in a pore diameter range of 18 to 22 nm as measured by mercury intrusion porosimetry, In the support, the total pore volume (PV) measured by mercury intrusion porosimetry is determined by dividing the volume (ΔPV) of pores having pore diameters in a range outside the range of the pore diameter at the maximum value ±2 nm. T ) (ΔPV / PV T ) is 0.50 or less, The crystalline form of the alumina in the alumina-phosphate support is γ-alumina. Hydrotreating catalyst.

[0010] [2] The hydrotreating catalyst according to [1] above, wherein the differential pore volume distribution of the support is unimodal.

[0011] [3] Total pore volume (PV) measured by water pore filling method H2O ) is 0.65 to 1.00 ml / g.

[0012] [4] The hydrotreating catalyst according to any one of [1] to [3] above, which contains 1.0 to 5.0 mass % of phosphorus calculated as P2O5.

[0013] [5] The hydrotreating catalyst according to any one of [1] to [4] above, wherein the hydrogenation active metal component contains at least one metal selected from the group consisting of metals in Group 6 and Group 8 of the periodic table.

[0014] [6] The hydrotreating catalyst according to any one of [1] to [5] above, wherein the content of the hydrogenation active metal component is 1 to 25 mass % calculated as the amount of metal oxide contained in the hydrogenation active metal component.

[0015] [7] A method for producing a catalyst for hydrotreating heavy hydrocarbon oil, comprising: a first step of adding a basic aluminum salt aqueous solution to an acidic aluminum salt aqueous solution adjusted to a pH of 2.0 to 6.0 to obtain a slurry containing alumina hydrate and having a pH of 9.7 to 10.5; a second step of washing the alumina hydrate and adding water and a phosphorus component to the washed alumina hydrate to obtain an alumina-phosphate hydrate; a third step of calcining the alumina-phosphate hydrate at 400 to 800°C to obtain an alumina-phosphate support; a fourth step of supporting a hydrogenation active metal component on the alumina-phosphorus oxide support to obtain a hydrotreating catalyst; A method for producing a hydrotreating catalyst comprising:

[0016] [8] The method for producing a hydrotreating catalyst according to [7] above, wherein the amount of the phosphorus component added in the second step is such that the phosphorus content in the support obtained in the third step is 0.4 to 2.0 mass% in terms of P2O5.

[0017] [9] A method for hydrotreating heavy hydrocarbon oil, comprising a step of hydrotreating heavy hydrocarbon oil in the presence of the hydrotreating catalyst according to any one of the above [1] to [6]. [Effects of the Invention]

[0018] The heavy hydrocarbon oil hydrotreating catalyst of the present invention has excellent demetallization performance, desulfurization performance, and deasphaltene generation performance, and also has high strength. Therefore, it is particularly effective in the hydrotreating of heavy hydrocarbon oil. Furthermore, the production method of the present invention makes it possible to produce a heavy hydrocarbon oil hydrotreating catalyst having such properties. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 2 is an integral pore distribution diagram of the catalyst A produced in Example 1. [Figure 2] FIG. 2 is a differential pore distribution diagram of the catalyst A produced in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0020] [Heavy hydrocarbon oil hydrotreating catalyst] The heavy hydrocarbon oil hydrotreating catalyst according to the present invention (hereinafter simply referred to as the "hydrotreating catalyst" or "catalyst") is a catalyst in which a hydrogenation active metal is supported on a carrier, satisfies the following requirements (1) to (4), and is used for hydrotreating heavy hydrocarbon oil.

[0021] Requirement (1): The support is an alumina-phosphate support. The support is an alumina-phosphate support. Alumina-phosphate is presumed to be a composite oxide of aluminum and phosphorus. The alumina-phosphate support may contain only alumina and phosphate, or may also contain inorganic oxides such as silica, boria, titania, and zirconia. From the viewpoints of maintaining support strength and reducing production costs, the support contains aluminum in an amount equivalent to preferably 65 mass % or more, more preferably 75 mass % or more of alumina based on the total amount of the support.

[0022] The carrier contains 0.4 to 2.0 mass% of phosphorus, preferably 0.5 to 1.4 mass% of phosphorus, calculated as P2O5, based on the total amount of the carrier. A phosphorus content of less than 0.4 mass% is undesirable because it reduces the catalyst strength (wear resistance). A phosphorus content of more than 2.0 mass% is undesirable because it reduces the pore diameter of the catalyst, specifically the pore diameter at the maximum value described below.

[0023] Requirement (2): The support has a maximum value of the differential pore volume distribution in the pore diameter range of 18 to 22 nm. The carrier has a maximum value of the differential pore volume distribution in the pore diameter range of 18 to 22 nm in the pore distribution measured by mercury intrusion porosimetry. If the maximum value is in the pore diameter range of less than 18 nm, the demetalization performance of the catalyst will be significantly reduced, while if the maximum value is in the pore diameter range of more than 22 nm, the desulfurization performance of the catalyst will tend to be reduced, which is undesirable.

[0024] The details of the measurement method are as follows. Approximately 3 g of the measurement sample is placed in a porcelain crucible and heated at 500°C for 1 hour, then placed in a desiccator and cooled to room temperature to obtain a measurement sample, after which the pore size distribution is measured by mercury intrusion porosimetry (mercury contact angle: 150 degrees, surface tension: 480 dyn / cm).

[0025] Requirement (3): The total pore volume (PV) of the volume (ΔPV) of pores having a pore diameter in the range of ±2 nm of the pore diameter at the maximum value T ) (ΔPV / PV T ) is less than or equal to 0.50.

[0026] In the catalyst according to the present invention, the total pore volume (PV) measured by mercury intrusion porosimetry is calculated by dividing the volume (ΔPV) of pores having pore diameters outside the range of ±2 nm of the pore diameter at the maximum value (i.e., the pore diameter at which the differential pore volume distribution is maximized within the pore diameter range of 18 to 22 nm measured by mercury intrusion porosimetry). T ) (ΔPV / PV T ) is 0.50 or less, preferably 0.46 or less, and more preferably 0.45 or less. T If ΔPV / PV exceeds 0.50 excessively, the reactivity between the catalyst and asphaltene molecules decreases, and the demetalization performance and deasphaltene performance decrease, which is undesirable. T The lower limit of is, for example, about 0.41.

[0027] Requirement (4): The crystalline form of the alumina in the alumina-phosphate support is γ-alumina. If the crystalline form of the alumina portion of the alumina-phosphate constituting the support is γ-alumina, the alumina-phosphate support has many surface hydroxyl groups necessary for supporting the active metal components, and the catalyst exhibits high desulfurization activity. On the other hand, if the crystalline form is α-alumina or θ-alumina, the alumina-phosphate support has few surface hydroxyl groups necessary for supporting the active metal components, and high desulfurization activity cannot be expected. However, a small portion of the alumina portion may have a crystalline form other than γ-alumina (for example, α-alumina or θ-alumina) as long as it does not impair the effects of the present invention.

[0028] The catalyst according to the present invention preferably satisfies one or more of the following requirements (5) to (9). Requirement (5): The differential pore volume distribution of the support is unimodal. In the catalyst according to the present invention, the differential pore volume distribution of the support is unimodal.

[0029] Requirement (6): The specific surface area of ​​the catalyst is 100m 2 / g or more. The specific surface area of ​​the catalyst according to the present invention measured by the BET method is 100 m 2 / g or more, preferably 140 to 220m 2 / g. When the specific surface area is equal to or greater than the lower limit, the desulfurization reaction rate is high. When the specific surface area is equal to or less than the upper limit, the demetallization property (demetallization selectivity) and stability of catalytic activity are excellent. The specific surface area can be increased or decreased by changing, for example, the calcination temperature or the calcination atmosphere.

[0030] Requirement (7): The total pore volume (PV) of the catalyst measured by the water pore filling method H2O ) is in the range of 0.65 to 1.00 ml / g. The total pore volume (PV) of the catalyst according to the present invention was measured by the water pore filling method. H2O The total pore volume (PV) is in the range of 0.65 to 1.00 ml / g, preferably 0.68 to 0.95 ml / g, and more preferably 0.70 to 0.90 ml / g. H2O When the total pore volume (PV) is equal to or greater than the lower limit, the demetalization performance lasts for a long time. H2O ) is equal to or less than the upper limit, the catalytic strength is high.

[0031] Requirement (8): The catalyst has a pressure resistance of 10 N / mm or more. The catalyst according to the present invention has a pressure resistance (also referred to as a crushing strength) of 10 N / mm or more as measured by a Kiya hardness tester. When this pressure resistance is equal to or greater than the lower limit, the catalyst is less likely to break when packed, and it is possible to suppress drift or pressure loss during the reaction.

[0032] Requirement (9): The hydrogenation active metal is at least one metal selected from the group consisting of metals in Groups 6 and 8 of the periodic table. In the catalyst according to the present invention, the supported hydrogenation active metal is at least one metal selected from the group consisting of metals in Groups 6 and 8 of the periodic table.

[0033] From the viewpoint of reactivity, it is preferable to use a combination of the metals of Group 6 and Group 8 of the periodic table as the metals to be supported on the carrier. Preferred Group 6 metals are molybdenum and tungsten, and preferred Group 8 metals are nickel and cobalt.

[0034] The amount of the hydrogenation active metal supported (assuming the amount of catalyst as 100% by mass) is preferably 1 to 25% by mass, and more preferably 5 to 16% by mass, calculated as the amount of hexavalent metal oxide, for metals of Group 6 of the periodic table, and is preferably 0.1 to 10% by mass, and more preferably 0.3 to 5% by mass, calculated as the amount of divalent metal oxide, for metals of Group 8 of the periodic table. A supported amount of metal equal to or less than the upper limit mentioned above is preferred in terms of demetalization ability (demetalization selectivity), stability of catalytic activity, and reduction of production costs.

[0035] [Method for producing a catalyst for hydrotreating heavy hydrocarbon oil] The method for producing a catalyst for hydrotreating heavy hydrocarbon oil of the present invention includes the first to fourth steps described below.

[0036] [Method of manufacturing alumina-phosphate support] (First step: Step of obtaining alumina hydrate) The first step is a step of adding a basic aluminum salt aqueous solution to an acidic aluminum salt aqueous solution whose pH has been adjusted to 2.0 to 6.0 to obtain a slurry containing alumina hydrate and having a pH of 9.7 to 10.5.

[0037] The acidic aluminum salt may be any water-soluble salt, such as aluminum sulfate, aluminum chloride, aluminum acetate, or aluminum nitrate, with aluminum sulfate being preferred. The aqueous solution of the acidic aluminum salt preferably contains 1 to 15 mass %, more preferably 2 to 10 mass %, of the acidic aluminum salt calculated as Al2O3.

[0038] Next, an aqueous solution of a basic aluminum salt is added to this aqueous solution of an acidic aluminum salt having a pH of 2.0 to 6.0. The basic aluminum salt may be any water-soluble salt, such as sodium aluminate or potassium aluminate.

[0039] This addition is usually carried out while stirring the aqueous acidic aluminum salt solution. The aqueous solution of basic aluminum salt is added usually over a period of 30 to 200 minutes, preferably 60 to 180 minutes.

[0040] The aqueous solution of basic aluminum salt preferably contains 5 to 35 mass %, more preferably 10 to 30 mass %, of basic aluminum salt calculated as Al2O3. The basic aluminum salt aqueous solution is added so as to obtain a slurry containing alumina hydrate with a pH of 9.7 to 10.5. If the pH is less than 9.7, the ΔPV / PV of the obtained carrier will be T When the pH is higher than 10.5, the maximum pore diameter of the carrier tends to decrease. Furthermore, it is desirable to carry out the first step so that the resulting slurry contains 5.0 to 9.0 mass %, preferably 6.0 to 8.0 mass %, of alumina hydrate in terms of Al2O3.

[0041] (Second step: Step of obtaining alumina-phosphate hydrate) The second step is a step of washing the alumina hydrate obtained in the first step, and adding water and a phosphorus component to the washed alumina hydrate to obtain an alumina-phosphate hydrate.

[0042] The alumina hydrate obtained in the first step is washed with pure water usually at 50 to 80°C, preferably 60 to 70°C, to remove impurities such as sodium and sulfate radicals, and a washed cake is obtained. The addition of water and phosphorus to the washed cake, i.e., the alumina hydrate after washing, is usually carried out by adding water (usually pure water) to the washed cake to prepare a slurry with an Al2O3 concentration of 5 to 16 mass%, preferably 7 to 14 mass%, and then adding the phosphorus to the slurry. In this way, a slurry of alumina-phosphate hydrate is obtained.

[0043] The phosphorus component is added so that the resulting carrier contains phosphorus at a P2O5 concentration of preferably 0.4 to 2.0 mass %, more preferably 0.5 to 1.4 mass %. Examples of the phosphorus component include phosphoric acid compounds such as phosphoric acid, phosphorous acid, ammonium phosphate, potassium phosphate, and sodium phosphate, and among these, phosphoric acid is preferred.

[0044] (Third step: Step of obtaining an alumina-phosphate support) The third step is a step of calcining the alumina-phosphate hydrate obtained in the second step at 400 to 800° C. to obtain an alumina-phosphate support.

[0045] In the third step, the alumina-phosphate hydrate slurry obtained in the second step is usually aged, then dehydrated, the dehydrated product is kneaded, the kneaded product is formed into a desired shape, dried, and then calcined to obtain an alumina-phosphate support.

[0046] The maturation is usually carried out in a reflux-equipped maturation tank. The aging is carried out usually at 30° C. or higher, preferably 80 to 100° C., for usually 1 to 20 hours, preferably 2 to 10 hours.

[0047] The aged slurry can be dehydrated and kneaded by a conventional method. For example, the dehydrated product is concentrated and kneaded by steam heating using a steam-jacketed twin-arm kneader until the desired water content is reached.

[0048] The kneaded product can be molded by a conventionally known method such as extrusion molding. The molded product is usually dried at 90 to 130°C for 15 minutes to 14 hours. The molded product is fired at 400 to 800°C, preferably 500 to 700°C, and usually for 0.5 to 10 hours. Examples of the shape of the molded product include a cylinder, a three-leaf leaf, and a four-leaf leaf.

[0049] [Method of supporting metal on support] The fourth step is a step of supporting a hydrogenation active metal component (hereinafter also referred to as "metal component raw material") on the alumina-phosphorus oxide support obtained in the third step to obtain a hydrotreating catalyst.

[0050] In the fourth step, a metal component raw material is usually supported on the alumina-phosphate support obtained in the third step, and then the alumina-phosphate support carrying the metal component raw material is calcined, thereby obtaining a hydrotreating catalyst in which a hydrogenation-active metal component is supported on the alumina-phosphate support.

[0051] The metal component raw materials are supported on the alumina-phosphate support by a well-known method such as an impregnation method or a dipping method, for example, by preparing an impregnation solution containing the metal component raw materials, an acid, and water, and impregnating the alumina-phosphate support with this impregnation solution.

[0052] Examples of the metal component raw material include metal compounds such as nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate.

[0053] The blending amounts of the respective metal component raw materials are set so that the amount of hydrogenation active metal component in the produced hydrotreating catalyst falls within the above-mentioned ranges. The impregnation solution is prepared, for example, by suspending the metal component raw material in water and adding an acid to dissolve it.

[0054] Acids include inorganic acids and organic acids. Examples of inorganic acids include phosphoric acids and nitric acid, and examples of phosphoric acids include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid.

[0055] Examples of organic acids include citric acid, malic acid, tartaric acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA). Among these, phosphoric acid and citric acid are preferred.

[0056] The impregnation of the alumina-phosphate support with the impregnation liquid is carried out, for example, by spraying the impregnation liquid onto the alumina-phosphate support. The alumina-phosphorus oxide support carrying the metal component raw material (hereinafter also referred to as "raw material-supported support") is preferably dried and then calcined to obtain a hydrotreating catalyst in which the hydrogenation-active metal component is supported on the alumina-phosphorus oxide support.

[0057] The raw material-supporting carrier is usually dried at 200 to 300° C. for 0.5 to 2.0 hours. The raw material-supporting carrier is usually calcined at 400 to 600° C. for 0.5 to 5 hours.

[0058] The method for producing a hydrotreating catalyst according to the present invention can produce the hydrotreating catalyst according to the present invention described above. According to the production method of the present invention, a slurry of alumina hydrate is obtained in the first step so that the pH is 9.7 to 10.5, and in the second step, phosphorus is added to the carrier so that the P2O5 concentration is 0.4 to 2.0 mass% based on the total amount of the carrier. This results in a carrier having a maximum value of the differential pore volume distribution in the pore diameter range of 18 to 22 nm, and a ΔPV / PV T It is possible to obtain a catalyst containing a support with a low value of . In addition, adding phosphorus to the support can improve the strength and desulfurization activity of the catalyst. If the amount of phosphorus is not within the above range, the strength and desulfurization activity of the catalyst may decrease.

[0059] Furthermore, by adding a basic aluminum salt aqueous solution to an acidic aluminum salt aqueous solution, alumina hydrate particles with a large crystallite size are prepared. The phosphorus component added to these alumina hydrate particles after removing by-product salts is thought to function as an inorganic crosslinking agent for the alumina hydrate. After adding the phosphorus component, the alumina-phosphate support is sequentially subjected to aging, kneading, molding, drying, calcination, etc., to obtain an alumina-phosphate oxide support having a pore diameter in the range of 18 to 22 nm.

[0060] Furthermore, it is desirable to set the SO4 concentration in the alumina-phosphate support to 1 mass % or less. A support manufactured so that the SO4 concentration is 1 mass % or less has a pore size that is not too small and has high strength.

[0061] The hydrotreating catalyst composition of the present invention is suitable for use in the hydrotreating, particularly demetallizing, of heavy hydrocarbon oils such as residual oils containing metal contaminants such as vanadium and nickel, and existing hydrotreating equipment and operating conditions therefor can be used. Furthermore, the production of the present composition is simple, resulting in high productivity and an advantage in terms of production costs. [Example]

[0062] The present invention will be specifically explained below with reference to examples, but the present invention is not limited thereto.

[0063] [Measurement method] <Method for measuring the content of carrier components (aluminum, phosphorus) and metal components (molybdenum, nickel)> Approximately 10 g of the sample was ground in a mortar, and approximately 0.5 g of the sample was taken. It was then heated (200°C for 20 minutes) and calcined (700°C for 5 minutes). After that, 2 g of Na2O2 and 1 g of NaOH were added and melted for 15 minutes. 25 ml of H2SO4 and 200 ml of water were added to dissolve the solution, and the solution was diluted to 500 ml with pure water to prepare the sample. The resulting sample was analyzed using an ICP emission spectrometer (Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000) to measure the content of each element except aluminum, calculated on an oxide basis. The aluminum content (Al2O3 equivalent) was calculated by subtracting the content of other elements from the sample volume.

[0064] <Method for measuring sulfate ion content> The content of sulfate ions in the carrier was measured by a combustion method using a sulfur analyzer (CS844, manufactured by LECO Co., Ltd.) using a measurement sample that had been crushed in advance.

[0065] <Method for measuring the differential pore volume distribution of the support> Approximately 3 g of the measurement sample was placed in a porcelain crucible, heated at 500°C for 1 hour, and then cooled to room temperature in a desiccator to obtain a measurement sample. The differential pore volume distribution was then measured by mercury intrusion porosimetry (Quantachrome Poremaster GT-60, mercury contact angle: 150°, surface tension: 480 dyn / cm).

[0066] <Method for measuring the pore volume of the carrier> Approximately 30 g of the measurement sample was placed in a porcelain crucible, heated at 500°C for 1 hour, and then placed in a desiccator and cooled to room temperature to obtain a measurement sample, after which the pore volume was measured by the water pore filling method.

[0067] <Method for measuring pressure resistance of carrier> The pressure resistance of the carrier was measured using a Kiya hardness tester.

[0068] <How to confirm the crystal morphology of alumina> The measurement sample was crushed in a mortar and then pressed onto a non-reflective measurement plate to be used as an observation sample, and the crystal morphology was confirmed using an X-ray diffractometer (Rigaku Denki Co., Ltd.: RINT2100).

[0069] [Example 1] (Manufacture of carrier) A tank equipped with a circulation line and two chemical addition ports was charged with 68.4 kg of pure water, and 42.6 kg of an aluminum sulfate aqueous solution (with a concentration of 7% by mass as Al2O3) was added with stirring, and the water was heated to 60°C and circulated. At this time, the pH of the aluminum sulfate aqueous solution was 2.3.

[0070] Next, 31.9 kg of a sodium aluminate aqueous solution (concentration of 22% by mass as Al2O3) was added to the aluminum sulfate aqueous solution over 90 minutes while stirring and circulating, while maintaining the temperature at 60°C, to obtain a slurry a of alumina hydrate (concentration of 7.0% by mass as Al2O3). The pH of the obtained slurry a was 10.0.

[0071] Next, the obtained alumina hydrate was filtered and washed with pure water at 60°C to remove impurities such as sodium and sulfate, thereby obtaining a washed cake. Pure water was added to the washed cake to prepare a slurry so that the Al2O3 concentration was 10 mass%, and then 164 g of phosphoric acid (concentration of 62 mass% as P2O5) was added to the slurry, which was then aged at 95°C for 3 hours in an aging tank equipped with a reflux condenser.

[0072] After aging, the slurry was dehydrated, and the resulting dehydrated product was concentrated and kneaded to the specified moisture content while being kneaded in a twin-arm kneader equipped with a steam jacket. The resulting kneaded product was extruded into 1.7 mm four-leaf clover pillars using an extrusion molding machine. The resulting molded product was dried at 110°C for 12 hours and then calcined at 600°C for 3 hours to obtain alumina-phosphate support a. The carrier a contained 1 mass % of phosphorus in terms of P2O5 and 99 mass % of aluminum in terms of Al2O3 (the total amount of the carrier is taken as 100 mass %).

[0073] (Catalyst Production) 59.4 g of molybdenum oxide and 22.7 g of nickel carbonate were suspended in 400 ml of ion-exchanged water, and the suspension was heated at 95°C for 5 hours using a suitable reflux device to prevent the volume of the suspension from decreasing. 36.7 g of phosphoric acid was then added and dissolved to prepare an impregnation solution. 500 g of carrier a was sprayed and impregnated with this impregnation solution, and carrier a was then dried at 250°C and further calcined in an electric furnace at 550°C for 1 hour to obtain hydrotreating catalyst A (hereinafter simply referred to as "catalyst A"; the same applies to the following examples).

[0074] Catalyst A contained 10 mass% molybdenum in terms of MoO3 and 2.1 mass% nickel in terms of NiO (the total amount of the catalyst is taken as 100 mass%). The properties of catalyst A are shown in Table 1. Figures 1(A) and (B) show the integral and differential pore distribution diagrams of hydrotreating catalyst A, respectively.

[0075] [Example 2] Alumina-phosphorus oxide carrier b was obtained in the same manner as in "Production of carrier" in Example 1, except that the amount of phosphoric acid added was changed to 131 g. Carrier b contained 0.8 mass % of phosphorus in terms of P2O5 and 99.2 mass % of aluminum in terms of Al2O3.

[0076] Next, catalyst B was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier b. The properties of catalyst B are shown in Table 1.

[0077] [Example 3] Alumina-phosphorus oxide carrier c was obtained in the same manner as in "Production of carrier" in Example 1, except that the amount of phosphoric acid added was changed to 197.2 g. Carrier c contained 1.2 mass% of phosphorus in terms of P2O5 and 98.8 mass% of aluminum in terms of Al2O3.

[0078] Next, catalyst C was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier c. The properties of catalyst C are shown in Table 1.

[0079] [Example 4] Hydrotreating catalyst D was obtained in the same manner as in "Catalyst production" of Example 1, except that the amounts of molybdenum oxide, nickel carbonate, and phosphoric acid added were changed to 73.1 g, 32.1 g, and 32.9 g, respectively. Catalyst D contained 12 mass % of MoO3 and 3.2 mass % of NiO. The properties of Catalyst D are shown in Table 1.

[0080] [Comparative Example 1] An alumina carrier e was obtained in the same manner as in "Production of carrier" in Example 1, except that phosphoric acid was not added.

[0081] Next, catalyst E was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier e. The properties of catalyst E are shown in Table 1.

[0082] Comparative Example 2 Alumina-phosphorus oxide carrier f was obtained in the same manner as in "Production of carrier" in Example 1, except that the amount of phosphoric acid added was changed to 416.4 g. Carrier f contained 2.5 mass% of phosphorus in terms of P2O5 and 97.5 mass% of aluminum in terms of Al2O3.

[0083] Next, catalyst F was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier f. The properties of catalyst F are shown in Table 1.

[0084] Comparative Example 3 Alumina-phosphorus oxide carrier g was obtained in the same manner as in "Production of carrier" in Example 1, except that the amount of phosphoric acid added was changed to 502.2 g. Carrier g contained 3.0 mass% of phosphorus in terms of P2O5 and 97.0 mass% of aluminum in terms of Al2O3.

[0085] Next, catalyst G was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier g. The properties of catalyst G are shown in Table 1.

[0086] Comparative Example 4 Alumina-phosphorus oxide carrier h was obtained in the same manner as in "Production of carrier" in Example 1, except that the neutralization balance between the aluminum sulfate aqueous solution and the sodium aluminate aqueous solution in Example 1 was changed to a pH of 9.3 after addition when obtaining alumina hydrate. Carrier h contained 1 mass % phosphorus in terms of P2O5 and 99 mass % aluminum in terms of Al2O3.

[0087] Next, catalyst H was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier h. The properties of catalyst H are shown in Table 1.

[0088] Comparative Example 5 A tank equipped with a circulation line and two chemical addition ports was charged with 68.4 kg of pure water, and 31.9 kg of a sodium aluminate aqueous solution (with an Al2O3 concentration of 22% by mass) was added with stirring, and the solution was heated to 60°C and circulated. The pH of the sodium aluminate aqueous solution at this time was 13.4.

[0089] Next, 42.6 kg of an aqueous aluminum sulfate solution (concentration of 7% by mass as Al2O3) was added to the aqueous sodium aluminate solution over 90 minutes while stirring and circulating the solution and maintaining the temperature at 60°C, to obtain an alumina hydrate slurry I. The pH of the obtained slurry I was 10.0.

[0090] An alumina-phosphate support i was obtained in the same manner as in "Production of support" in Example 1, except that slurry a was changed to slurry i. The carrier i contained 1.0 mass % of phosphorus in terms of P2O5 and 99.0 mass % of aluminum in terms of Al2O3.

[0091] Next, catalyst I was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was replaced with carrier i. The properties of catalyst I are shown in Table 1.

[0092] Comparative Example 6 In Comparative Example 6, an alumina-phosphate oxide support j was obtained in the same manner as in "Production of support" in Comparative Example 5, except that the alumina support was calcined at a temperature of 1,050°C and the alumina form was θ-alumina. Support j contained 1 mass% phosphorus in terms of P2O5 and 99 mass% aluminum in terms of Al2O3.

[0093] Next, catalyst J was obtained in the same manner as in "Catalyst production" in Example 1, except that carrier a was changed to carrier j. The properties of catalyst J are shown in Table 1.

[0094] [Catalytic activity evaluation test] For catalysts A to D of Examples 1 to 4 and catalysts E to J of Comparative Examples 1 to 6, the hydrodemetalization activity, desulfurization activity, and deasphaltene activity were examined using a fixed-bed microreactor under the conditions shown below.

[0095] A commercially available demetallization catalyst, an example catalyst or a comparative example catalyst, and a commercially available desulfurization catalyst were packed in a fixed-bed flow reactor (catalyst packed volume: 350 ml) in the following order: 35 ml of commercially available demetalization catalyst CDS-RS110 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) 70 ml of commercially available demetalization catalyst CDS-RS210 (manufactured by JGC Catalysts and Chemicals Co., Ltd.) 105 ml of the example catalyst or the comparative example catalyst, 140 ml of commercially available desulfurization catalyst CDS-R38C (manufactured by JGC Catalysts and Chemicals Co., Ltd.) Reaction conditions; Catalyst filling amount: 350ml Reaction pressure: 13.5 MPa Liquid hourly space velocity (LHSV): 1.0hr -l Hydrogen / oil ratio (H2 / HC): 800Nm 3 / kl Reaction temperature: 370℃

[0096] The feedstock used was atmospheric residue with the following properties: Raw oil properties; Density (15℃): 0.974g / cm 3 Asphaltene content: 4.2 mass% Sulfur content: 4.020% by mass Metal (Ni+V) content: 86 mass ppm The hydrodesulfurization activity, desulfurization activity, and deasphalting activity were expressed as the demetalization rate, desulfurization rate, and deasphalting rate, and the values ​​are shown in Table 1.

[0097] The demetalization rate was calculated using the following formula. Metal-free rate = (metal concentration in feedstock oil - metal concentration in hydrotreated product oil) / metal concentration in feed oil x 100

[0098] The desulfurization rate was calculated using the following formula: Desulfurization rate = (sulfur concentration in feedstock oil - sulfur concentration in hydrotreated product oil) / sulfur concentration in feed oil x 100

[0099] The deasphalting rate was calculated using the following formula. Deasphalting rate = (Asphaltene concentration in feedstock oil - Asphaltene concentration in hydrotreated product oil) / Asphaltene concentration in feedstock oil x 100

[0100] [Table 1]

[0101] [Evaluation results] The results in Table 1 show that, since catalysts A to D of the present invention have a predetermined configuration, they have particularly higher demetallization rates and deasphaltene rates than catalysts E to I of comparative examples 1 to 5, and also have higher desulfurization activity.

[0102] Catalyst E of Comparative Example 1 has a pore size distribution with a predetermined structure, but is prepared from a carrier that does not contain phosphorus at a predetermined concentration, and therefore has low pressure resistance and lower catalytic activity than the example catalysts.

[0103] Catalyst F of Comparative Example 2 was prepared from a support containing more phosphorus than the specified range, and its pore size distribution did not have the configuration specified in the present invention, resulting in low demetallization and deasphalting rates.

[0104] Catalyst G in Comparative Example 3 was prepared from a support containing even more phosphorus than Catalyst F. The pore size distribution clearly did not satisfy the predetermined requirements of the present invention, resulting in low demetallization and deasphalting rates.

[0105] Catalyst H of Comparative Example 4 has a phosphorus content within the range specified in the present invention, but the pore size distribution does not satisfy the requirements of the present invention, and the desired catalytic performance is not obtained. This shows that the specified pore size distribution of the present invention is essential for improving catalytic performance.

[0106] Although the amount of phosphorus in Catalyst I of Comparative Example 5 is within the range specified in the present invention, the carrier preparation starts with the step of adding a basic aluminum salt solution to the bed water, which is not in accordance with the production method of the present invention. It is clear that the pore size distribution does not meet the specified requirements of the present invention, and the desired catalytic performance is not obtained.

[0107] Catalyst J of Comparative Example 6 was obtained by calcining the molded product to obtain a carrier in the same manner as in the production method of Catalyst I of Comparative Example 5, except that the calcination temperature was 1050°C. Although the pore size distribution satisfies the range specified in the present invention, the alumina crystal morphology differs from that specified in the present invention. Catalyst J has clearly low pressure resistance and a lower desulfurization rate than the example catalysts.

Claims

1. A catalyst for hydrotreating heavy hydrocarbon oils, comprising: The catalyst comprises an alumina-phosphorus oxide support and a hydrogenation active metal component supported on the support, The phosphorus content in the carrier is P 2 O 5 The converted amount is 0.4 to 2.0 mass %, the carrier has a maximum value of a differential pore volume distribution in a pore diameter range of 18 to 22 nm as measured by mercury intrusion porosimetry, In the support, the total pore volume (PV) measured by mercury intrusion porosimetry of the volume (ΔPV) of pores having pore diameters in a range outside the range of the pore diameter at the maximum value ±2 nm T ) ratio (ΔPV / PV T ) is 0.50 or less, The crystalline form of the alumina in the alumina-phosphorus oxide support is γ-alumina. Hydrotreating catalyst.

2. 2. The hydrotreating catalyst of claim 1, wherein the differential pore volume distribution of the support is unimodal.

3. Total pore volume (PV) measured by the water pore filling method H2O 3. The hydrotreating catalyst according to claim 1, wherein the solubility of the catalyst is 0.70 to 0.90 ml / g.

4. P Rin 2 O 5 The hydrotreating catalyst according to any one of claims 1 to 3, containing 1.0 to 5.0 mass% of hydroxybenzoates in terms of converted amount.

5. 5. The hydrotreating catalyst according to claim 1, wherein the hydrogenation-active metal component comprises at least one metal selected from the group consisting of metals in Groups 6 and 8 of the periodic table.

6. 6. The hydrotreating catalyst according to claim 1, wherein the content of the hydrogenation active metal component is 1 to 25 mass % in terms of the amount of metal oxide contained in the hydrogenation active metal component.

7. A method for hydrotreating heavy hydrocarbon oil, comprising a step of hydrotreating heavy hydrocarbon oil in the presence of the hydrotreating catalyst according to any one of claims 1 to 6.

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