Silicon scavenger for hydrogenation treatment, manufacturing method thereof, hydrogenation treatment method of hydrocarbon oil

Abstract

To provide a manufacturing method of a silicon scavenger exhibiting excellent desiliconization performance in relatively heavy distillate.SOLUTION: A silicon scavenger for hydrogenation treatment of hydrocarbon oils, which is a silicon scavenger carrying a hydrogenated active metal on an alumina or alumina-phosphorous carrier, characterized in that (1) a specific surface area is 100 m2 / g or more, (2) a total pore volume (PVT) measured by mercury intrusion porosimetry is in the range of 0.80 to 1.50 ml / g, (3) a pore distribution has a maximum value in the range of pore diameter of 10 to 30 nm, (4) a ratio of a pore volume (ΔPV) in the range of ± 2nm of a pore diameter in the maximum value and a ratio (ΔPV / PVme) of the pore volume (PVme) in the range of a pore diameter of 5 to 100 nm is 0.40 or less, (5) the pressure resistance is 10 N / mm or more, (6) phosphorous in terms of P2O5 concentration equivalent based on the total amount of the scavenger is 10.0 mass% or less, and (7) the hydrogenation-active metal is at least one kind of a metal selected from the group 6 metal and at least one kind of a metal selected from the groups 8 to 10 of a periodic table.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a silicon adsorbent for hydrogenation treatment, and more particularly to a silicon adsorbent used in the hydrogenation treatment of heavy hydrocarbon oils such as vacuum diesel fuel and residual oil containing silicon contaminants, a method for producing the same, and a method for hydrogenating hydrocarbon oil using the adsorbent. [Background technology]

[0002] In the pretreatment process for hydrocarbon oils, a hydrogenation catalyst is used to remove metals such as nickel and vanadium, sulfur, nitrogen, and asphaltenes from the feed oil, thereby obtaining a clean product. However, the feed oil used in hydrogenation may contain silicon derived from defoaming agents, and this silicon can cause rapid catalyst deactivation, which can be problematic. To ensure the long-term activity of the hydrogenation catalyst in feed oils containing silicon, it is desirable to install a silicon adsorbent upstream of the hydrogenation catalyst to protect it.

[0003] Several studies have been disclosed regarding the removal of silicon. Non-patent document 1 states that in nickel and molybdenum-alumina support systems, a high amount of surface hydroxyl groups per unit area is important for the silicon trapping ability in diesel oil, i.e., LGO (gas diesel fuel). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Catalyst Today, 2019, vol 329, 1, 53. [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the silicon content in the LGO fraction described in non-patent literature is thought to be a relatively small molecular weight silicon-containing organic compound, and trapping agents with a large amount of hydroxyl groups are not necessarily effective against the silicon content in heavy components such as vacuum diesel and residual oil.

[0006] The silicon content in heavy feedstock oils such as vacuum diesel and residual oil is thought to be relatively large and have a wide molecular weight distribution, and the inventors of this invention considered that the design of the pore structure of the trapping agent is important. Therefore, the object of the present invention is to provide a method for producing a silicon adsorbent that exhibits excellent silicon removal performance in relatively heavy fractions such as vacuum diesel and residual oil. [Means for solving the problem]

[0007] As a result of diligent research, the inventors have discovered that a scoping agent comprising a predetermined alumina or alumina-phosphorus support bearing a hydrogenated metal, having a maximum pore distribution in the range of pore diameter 10 to 30 nm and a broad pore distribution in the range of pore diameter 5 to 100 nm, exhibits excellent silicon scoping ability.

[0008] In other words, the present invention provides a silicon adsorbent and a method for producing the same, as described below. [1] A silicon adsorbent comprising an alumina or alumina-phosphorus support on which a hydrogenated metal is supported, (1) Specific surface area of ​​100m 2 / g or more, (2) The total pore volume (PVT) measured by the mercury intrusion method is in the range of 0.80 to 1.50 ml / g. (3) The pore distribution has a maximum value in the range of pore diameter 10 to 30 nm, (4) The ratio of the pore volume (ΔPV) in the range of ±2 nm of the pore diameter at the maximum value to the pore volume (PVme) in the range of 5 to 100 nm of the pore diameter (ΔPV / PVme) is 0.40 or less. (5) Pressure resistance strength of 10 N / mm or more, (6) Contains phosphorus at a concentration of 10.0% by mass or less based on the total amount of the collecting agent, (7) The hydride-active metal is at least one metal selected from Group 6 and Groups 8-10 of the periodic table. A silicon adsorbent for the hydrogenation treatment of hydrocarbon oils, characterized by the following features.

[0009] [2] In the silicon adsorbent described in [1] above, the phosphorus content in the alumina-phosphorus carrier is 0.5 to 7.0% by mass as P2O5 concentration on a basis of the total amount of carrier. The silicon adsorbent for hydrogenation treatment according to feature 1.

[0010] [3] A silicon adsorbent according to [1] or [2] above, characterized in that the hydrogenated active metal is contained in an amount equivalent to 1 to 25% by mass of the total amount of the adsorbent in terms of oxide concentration.

[0011] [4] A method for hydrogenating hydrocarbon oil using the silicon adsorbent described in [1] to [3] above. [5] A hydrogenation treatment method as described in [4] above, wherein the hydrocarbon oil is vacuum-reduced diesel oil or heavy hydrocarbon oil. [6] A method for producing a silicon adsorbent, wherein after producing an alumina carrier, a hydrogenated metal is supported on the carrier, The first step involves adding an aqueous solution of basic aluminum to an acidic aluminum solution, adjusted to a pH of 2.0-5.0, while stirring, to obtain alumina hydrate, until the pH reaches 7.5-10.0. A second step to obtain alumina hydrate from which by-product salts of the alumina hydrate have been removed, A third step of obtaining an alumina support from the alumina hydrate is A method for producing a silicon adsorbent for hydrogenation treatment, characterized by the presence of [a specific feature]. [7] A method for producing a silicon adsorbent, wherein after producing an alumina-phosphorus carrier, a hydrogenated metal is supported on the carrier, The first step involves adding an aqueous solution of basic aluminum to an acidic aluminum solution, adjusted to a pH of 2.0-5.0, while stirring, to obtain alumina hydrate, until the pH reaches 7.5-10.0. A second step of adding phosphorus to the alumina hydrate from which by-produced salts of the alumina hydrate have been removed to obtain an alumina-phosphorus hydrate; And a third step of obtaining an alumina-phosphorus carrier from the alumina-phosphorus hydrate. A method for producing a silicon scavenger for hydrogenation treatment, characterized by comprising these steps.

Effects of the Invention

[0012] The silicon scavenger of the present invention exhibits excellent silicon scavenging ability. Therefore, in the hydrogenation treatment process, by filling it as a guard above the hydrogenation treatment catalyst, the hydrogenation treatment catalyst is protected, and even when treating heavy feed oils such as vacuum gas oil and residual oil, a system that can withstand long-term operation can be achieved.

Modes for Carrying Out the Invention

[0013] Silicone adsorbent The silicon scavenger according to the present invention (hereinafter also referred to as "this scavenger") is a silicon scavenger in which a hydrogenation active metal is supported on an alumina carrier or an alumina-phosphorus carrier. The carrier used in the present invention is at least one of an alumina carrier and an alumina-phosphorus carrier, and may be alumina alone or contain an oxide of alumina and phosphorus, and may also contain other inorganic oxides such as silica, boria, titania, zirconia, and manganese.

[0014] Hereinafter, preferred embodiments of the silicon scavenger of the present invention will be described in detail. The silicon scavenger of the present invention satisfies the following requirements. (1) The specific surface area is 100 m 2 / g or more <000009!>The specific surface area of this scavenger is 100 m 2 / g or more. When the specific surface area is less than 100 m 2 / g, the silicon scavenging ability tends to decrease. The specific surface area is preferably in the range of 150 to 250 m 2 / g. When the specific surface area is 250 m 2If the value exceeds / g, the specific surface area increases while the pore volume decreases, which may actually reduce the silicon collection capacity. Note that the specific surface area in this invention is the value measured by the BET method.

[0015] (2) The total pore volume (PVT) measured by the mercury intrusion method is in the range of 0.80 to 1.50 ml / g. The total pore volume (PVT) of this adsorbent is in the range of 0.80 to 1.50 ml / g. When the total pore volume (PVT) is less than 0.80 ml / g, the silicon adsorption capacity tends to decrease, and when it is greater than 1.50 ml / g, the strength of the adsorbent decreases. The total pore volume (PVT) is preferably in the range of 0.85 to 1.40 ml / g, and more preferably in the range of 0.90 to 1.30 ml / g. In this invention, the total pore volume (PVT) refers to the pore volume of pores with a pore diameter in the range of 3.2 to 10000 nm. In this invention, the pore diameter, pore volume, and pore distribution were measured by the mercury intrusion method, and the pore diameter was calculated using a mercury surface tension of 480 dyne / cm and a contact angle of 150°.

[0016] (3) Points having a maximum value in the pore distribution in the range of pore diameter 10 to 30 nm. The pore distribution of this adsorbent has a maximum value in the pore diameter range of 10 to 30 nm. If this maximum value is in the range of a pore diameter less than 10 nm, the reaction rate of silicon collection does not decrease significantly, but the pore volume is also thought to decrease, which may lead to a decrease in the amount of silicon that can be collected. If this maximum value is in the range of a pore diameter greater than 30 nm, the strength of the adsorbent tends to decrease. The preferred range of pore diameters where this maximum value exists is 12 to 25 nm, and more preferably 15 to 20 nm.

[0017] (4) The ratio of the pore volume (ΔPV) within ±2 nm of the pore diameter at the maximum value to the pore volume (PVme) in the pore diameter range of 5 to 100 nm (ΔPV / PVme) is 0.40 or less. In the pore distribution of this adsorbent, the ratio of the pore volume (ΔPV) within ±2 nm of the pore diameter at the maximum value to the pore volume (PVme) in the pore diameter range of 5 to 100 nm (ΔPV / PVme) is 0.40 or less. If ΔPV / PVme exceeds 0.40, the reactivity with silicon-containing organic compounds having a broad molecular weight distribution decreases, which may reduce the silicon adsorption capacity.

[0018] (5) Pressure resistance strength of 10 N / mm or more The pressure resistance of this adsorbent is 10 N / mm or higher. If the pressure resistance is less than 10 N / mm, the adsorbent is prone to breaking during filling, which can cause flow deviation and pressure loss during the reaction. Therefore, the pressure resistance must be 10 N / mm or higher. Note that pressure resistance is also called crushing strength, and the pressure resistance in this invention is the value measured with a Kiya hardness tester.

[0019] (6) The phosphorus content is 10% by mass or less on a basis of the total catalyst amount, in terms of P2O5 concentration. This collecting agent contains phosphorus at a concentration of 10.0% by mass or less based on the total amount of the collecting agent. If the phosphorus content exceeds 10.0% by mass, the specific surface area of ​​the collecting agent may decrease. It is preferable that the collecting agent contains phosphorus at an amount of 8.0% by mass or less, and more preferably at an amount of 7.5% by mass or less. When the phosphorus content is within the aforementioned range, a catalyst with high catalytic strength and compressive strength, and having a predetermined pore diameter and pore distribution can be obtained.

[0020] (7) The hydride-active metal is at least one metal selected from Group 6 and Groups 8-10 of the periodic table. In this collection agent, the supported hydrogenation-active metal is at least one metal selected from Group 6 and Groups 8-10 of the periodic table.

[0021] From the viewpoint of reactivity, it is preferable to use a combination of the Group 6 metals and Group 8-10 metals of the periodic table as the metals to be supported on the carrier. Molybdenum and tungsten are preferred as Group 6 metals, and nickel and cobalt are preferred as Group 8-10 metals. The amount of the hydrogenated active metal supported is preferably in the range of 1 to 25% by mass as an oxide, more preferably in the range of 3 to 20% by mass, and even more preferably in the range of 3 to 15% by mass, based on the total amount of catalyst. When this metal support is 1% by mass or more, the effects of the present invention can be further exhibited. Furthermore, when this metal support is 25% by mass or less, it is preferable in that the stability of the silicon collection ability can be maintained.

[0022] Furthermore, for metals in Group 6 of the periodic table, the preferred loading amount as an oxide is in the range of 1 to 20 mass%, more preferably in the range of 3 to 15 mass%. For metals in Groups 8 to 10 of the periodic table, the preferred loading amount as an oxide is in the range of 0.1 to 10 mass%, more preferably in the range of 0.3 to 5 mass%.

[0023] The shape of the adsorbent is not particularly limited and may be molded into a predetermined shape, such as granular, pelletized, columnar, or honeycomb-shaped, and its size may be appropriately selected according to the size of the processing equipment.

[0024] Next, preferred embodiments for manufacturing this adsorbent will be described below. The present invention's adsorbent includes a step of supporting a metal after manufacturing a carrier. In the case of alumina carriers, they are manufactured as follows:

[0025] [Method for manufacturing alumina carrier] (1st step) An acidic aluminum aqueous solution is prepared by adding an acidic aluminum salt to an aqueous solution containing 0.1 to 2.0% by mass as Al2O3 and with a pH of 2.0 to 5.0. The aqueous solution is then heated to 50 to 80°C, preferably 60 to 70°C, while being stirred. The acidic aluminum salt used in this invention can be any water-soluble salt, such as aluminum sulfate, aluminum chloride, aluminum acetate, or aluminum nitrate. It is desirable to use an aqueous solution containing 0.5 to 20% by mass, preferably 2 to 10% by mass, in terms of Al2O3.

[0026] Next, while stirring the acidic aluminum aqueous solution, an aqueous solution of basic aluminum is added over 30 to 200 minutes, preferably 60 to 180 minutes, to adjust the pH to 7.5 to 10.0, thereby obtaining alumina hydrate. Examples of basic aluminum salts used in this invention include sodium aluminate and potassium aluminate, and it is desirable to use an aqueous solution containing 2 to 30% by mass, preferably 10 to 25% by mass, in terms of Al2O3.

[0027] (2nd process) Next, the obtained alumina hydrate is washed with pure water at 50-70°C, preferably 55-65°C, to remove impurities such as sodium and sulfate, and a washed cake is obtained. Furthermore, pure water is added to the washed cake to adjust the Al2O3 concentration to 5-18% by mass, preferably 7-15% by mass, to obtain a washed alumina hydrate recovery. The recovery may be in the form of a cake containing water, a paste, or a slurry.

[0028] (3rd step) An alumina support is obtained from the recovered washed alumina hydrate. In the third step, the process is not particularly limited as long as an oxide support can be obtained from the hydrate. For example, the recovered material can be appropriately molded to match the shape of the carrier. Known molding methods such as extrusion molding can be used for molding. An alumina carrier can be obtained by heat-treating the molded product as needed. Heat treatments include drying to adjust the moisture content and firing at 400-800°C for 0.5-10 hours.

[0029] The recovered washed alumina hydrate may be aged beforehand in an aging tank equipped with a reflux condenser. Aging is carried out at 30°C or higher, preferably 80-100°C, for 1-10 hours, preferably 2-5 hours. Alternatively, the recovered washed alumina hydrate may be kneaded to produce a moldable paste. Heating may be used during kneading as needed. Additionally, an auxiliary agent may be added during kneading at an appropriate amount of about 2% by mass relative to the dry weight of the carrier. This makes it possible to change the pore diameter and pore distribution. Examples of auxiliary agents include molding aids, thickeners, and reinforcing agents.

[0030] In the case of alumina-phosphorus carriers, they are manufactured as follows. [Method for producing alumina-phosphorus carrier] (1st step) Alumina hydrate is prepared in the same manner as in the first step for the alumina carrier.

[0031] (2nd process) Next, the obtained alumina hydrate is washed with pure water at 50-70°C, preferably 55-65°C, in the same manner as described above, to remove impurities such as sodium and sulfate, and to obtain a washed cake. Furthermore, pure water is added to the washed cake to adjust the Al2O3 concentration to 5-18% by mass, preferably 7-15% by mass, and then a phosphorus source is added to the alumina hydrate to obtain alumina-phosphorus hydrate. It is preferable that the phosphorus source be added in the carrier in an amount of 10% by mass or less as P2O5 concentration, as described above. Phosphate compounds such as phosphoric acid, phosphorous acid, ammonium phosphate, potassium phosphate, and sodium phosphate can be used as phosphorus sources.

[0032] (3rd step) From the obtained alumina-phosphorus hydrate, an alumina-phosphorus support is obtained in the same manner as in the third step for the alumina support.

[0033] [Method for supporting metal on a carrier] The silicon adsorbent of the present invention can be manufactured by conventional means supporting at least one metal selected from Group 6 and Groups 8-10 of the periodic table on the aforementioned alumina or alumina-phosphorus support. As raw materials for such metals, metal compounds such as nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate can be used, and these are supported on the support by well-known methods such as impregnation or immersion. The support after metal support is usually calcined at 400-600°C for 0.5-5 hours to become the silicon adsorbent of the present invention.

[0034] Furthermore, the above-mentioned requirements (1) to (5) for this adsorbent can be controlled by the amount of phosphorus added, but they can also be controlled by adjusting other conditions such as the addition of auxiliary agents during kneading, the baking time and temperature, the amount of water during kneading, and the viscosity of the paste after kneading.

[0035] The silicon adsorbent of the present invention is suitably used as a guard for hydrogenation catalysts of heavy hydrocarbon oils such as residual oil and vacuum diesel containing contaminants such as silicon and arsenic, and existing hydrogenation treatment equipment and operating conditions can be adopted. Furthermore, since this collecting agent is easy to manufacture, it has high productivity and is advantageous in terms of manufacturing costs.

[0036] The present invention relates to a hydrocarbon oil hydrogenation treatment method, in which a known hydrogenation catalyst is packed into a fixed-bed reactor or the like, and the treatment is carried out under high temperature and high pressure conditions in a hydrogen atmosphere, for example, a hydrogen partial pressure of 3 to 8 MPa, a temperature of 300 to 385°C, and a liquid space velocity of 0.3 to 5 h. -1 A silicon adsorbent is used when performing hydrogenation treatment under these conditions.

[0037] A typical fixed-bed reactor is divided into 1 to 6 packed beds. The silicon adsorbent of the present invention may be packed into the upstream packed bed, or a fluidized bed may be provided upstream of the fixed-bed reactor and packed with the silicon adsorbent of the present invention. The hydrocarbon oil hydrogenation method of the present invention can be suitably used for treating hydrocarbon oils that have a relatively large and broad molecular weight distribution, such as vacuum diesel or heavy hydrocarbon oil, and hydrocarbon oils that contain silicon impurities. [Examples]

[0038] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0039] [Measurement method] For each of the examples and comparative examples of the present invention, numerical values ​​regarding the content of components, specific surface area, and properties of the silicon adsorbent were measured, and these measurements were performed as follows.

[0040] <Method for measuring the content of carrier components (alumina, phosphorus, silica, titania, zirconia) and metal components (molybdenum, cobalt, nickel, phosphorus, copper, iron)> Three g of the sample was placed in a 30 ml lidded zirconia ball, which was then heat-treated (200°C, 20 minutes) and calcined (700°C, 5 minutes). After that, two g of Na2O and one g of NaOH were added and melted for 15 minutes. Furthermore, two g of H2SO4 and two g of water were added to dissolve the mixture, and then it was diluted with pure water to a volume of 500 ml to prepare the sample. The content of each component in the obtained sample was measured using an ICP instrument (Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000) on an oxide basis (Al2O3, P2O5, SiO2, TiO2, ZrO2, MoO3, NiO, CoO).

[0041] <Method for measuring specific surface area> Approximately 30 ml of the sample was placed in a porcelain crucible (Type B-2), heated at 300°C for 2 hours, and then cooled to room temperature in a desiccator to obtain the sample for measurement. Next, 1 g of this sample was taken and the specific surface area (m²) of the sample was measured using a fully automated surface area analyzer (MultiSorb 12, manufactured by Yuasa Ionics Co., Ltd.). 2 The concentration (per g) was measured using the BET method.

[0042] <Method for measuring loss on ignition> The sample used for measurement, the adsorbent, was calcined at 570°C for 2 hours, and the mass loss due to calcination was used to calculate the result.

[0043] [Example 1] 35.2 kg of pure water was placed in a tank equipped with a circulation line having two chemical addition ports. 13.0 kg of aluminum sulfate aqueous solution (7% by mass as Al2O3) was added while stirring, and the mixture was heated to 70°C and circulated. The pH of the alumina aqueous solution at this time was 2.3. Next, 9.5 kg of sodium aluminate aqueous solution (22% by mass as Al2O3) was added over 180 minutes while stirring and circulating, maintaining a temperature of 70°C, to obtain alumina hydrate. The pH after addition was 9.5. Next, the obtained alumina hydrate was washed with pure water at 60°C to remove impurities such as sodium and sulfate, and a washing cake was obtained. Pure water was added to the washing cake to adjust the Al2O3 concentration to 8% by mass. Then, 256 g of phosphoric acid (62% by mass as P2O5) was added to the alumina hydrate, and the mixture was aged for 3 hours at 95°C in an aging tank equipped with a reflux condenser to obtain alumina-phosphorus hydrate. After maturation, the slurry was dewatered and kneaded in a dual-arm kneader equipped with a steam jacket until it reached a predetermined moisture content. The resulting kneaded material was extruded into 1.7 mm four-leaf clover-shaped columns using an extruder. The resulting alumina molded product was dried at 110°C for 12 hours, and then calcined at 680°C for 3 hours to obtain alumina-phosphorus carrier a. Carrier a contained 5% by mass of phosphorus (based on P2O5 concentration) and 95% by mass of aluminum (based on Al2O3 concentration) (both based on the total amount of carrier).

[0044] 26.6 g of molybdenum oxide and 9.7 g of nickel carbonate were suspended in 400 ml of deionized water. This suspension was heated at 95°C for 5 hours using a suitable reflux apparatus to prevent a decrease in liquid volume. Then, 13.3 g of malic acid was added and dissolved to prepare an impregnation solution. This impregnation solution was spray-impregnated onto 500 g of carrier a, dried at 250°C, and then calcined in an electric furnace at 550°C for 1 hour to obtain adsorbent A (hereinafter simply referred to as "adsorbent A"; the same applies to the following examples). The metal components of adsorbent A were 5% by mass of MoO3 (based on the total amount of catalyst) and 1% by mass of NiO (based on the total amount of catalyst). The properties of adsorbent A are shown in Table 1.

[0045] [Example 2] In Example 1, alumina-phosphorus carrier b was obtained in the same manner as in Example 1, except that 99.4 g of phosphoric acid was added. Carrier b contained 2% by mass of phosphorus (based on P2O5 concentration) and 98% by mass of aluminum (based on Al2O3 concentration) (both based on the total amount of carrier). Using carrier b, adsorbent B was obtained in the same manner as in Example 1. The properties of adsorbent B are shown in Table 1.

[0046] [Example 3] In Example 1, alumina-phosphorus carrier c was obtained in the same manner as in Example 1, except that 150.7 g of phosphoric acid was added. Carrier c contained 3% by mass of phosphorus (based on P2O5 concentration) and 97% by mass of aluminum (based on Al2O3 concentration) (both based on the total amount of carrier). Using carrier c, adsorbent C was obtained in the same manner as in Example 1. The properties of adsorbent C are shown in Table 1.

[0047] [Example 4] In Example 1, an alumina carrier d was obtained in the same manner as in Example 1, except that phosphoric acid was not added and an auxiliary agent was added during heating and kneading in an amount of 2% by mass relative to the carrier solid content. Using carrier d, a collection agent D was obtained in the same manner as in Example 1. The properties of collection agent D are shown in Table 1.

[0048] [Comparative Example 1] In Example 1, an alumina carrier e was obtained in the same manner as in Example 1, except that phosphoric acid was not added. Using carrier e, a scavenging agent E was obtained in the same manner as in Example 1. The properties of scavenging agent E are shown in Table 1.

[0049] [Comparative Example 2] In Example 1, an alumina-phosphorus carrier f was obtained in the same manner as in Example 1, except that 9.8 g of phosphoric acid was added. Carrier e contained 0.2% by mass of phosphorus on a P2O5 basis and 99.8% by mass of aluminum on an Al2O3 basis (both based on the total amount of carrier). Using carrier f, a filtration agent F was obtained in the same manner as in Example 1. The properties of filtration agent F are shown in Table 1.

[0050] [Comparative Example 3] In Example 1, an alumina-phosphorus carrier g was obtained in the same manner as in Example 1, except that 481.8 g of phosphoric acid was added. Carrier g contained 9% by mass of phosphorus (based on P2O5 concentration) and 91% by mass of aluminum (based on Al2O3 concentration) (both based on the total amount of carrier). Using carrier g, a collection agent G was obtained in the same manner as in Example 1. The properties of collection agent G are shown in Table 1.

[0051] [Comparative Example 4] In Example 1, an alumina-phosphorus carrier h was obtained in the same manner as in Example 1, except that the addition time of the sodium aluminate aqueous solution was 10 minutes. Carrier h contained 5% by mass of phosphorus (based on P2O5 concentration) and 95% by mass of aluminum (based on Al2O3 concentration) (both based on the total amount of carrier). Using carrier h, a filtration agent H was obtained in the same manner as in Example 1. The properties of filtration agent H are shown in Table 1.

[0052] [Catalytic Activity Evaluation Test] For silicon adsorbents A to D of Examples 1 to 4 and silicon adsorbents E to H of Comparative Examples 1 to 4, pre-sulfurization was performed using a fixed-bed microreactor in a stacked configuration with the hydrogen desulfurization catalyst CDS-VP2. Then, oil was continuously passed through the reactor for 90 days under the conditions described below. After cooling, the oil flow was stopped, the silicon adsorbents were removed, washed with kerosene, dried at 100°C for 24 hours, and the silicon adsorption capacity was investigated by analyzing the silicon content in terms of SiO2.

[0053] Reaction conditions; Filling amount of silicon collector (upper stage, reactor inlet side): 5 g Filling amount of hydrodesulfurization catalyst (lower stage, reactor outlet side): 25 g Reaction pressure: 6.0 MPa Reaction oil flow rate: 30 mL / h Hydrogen / oil ratio (H2 / HC): 300 Nm 3 / kl Reaction temperature: 370 °C In addition, atmospheric residue oil with the following properties was used as the feed oil. Properties of feed oil; Density (15 °C): 0.9161 g / cm 3 Sulfur content: 2.125 mass % Silicon content: 1.5 mass ppm

[0054] [Table 1]

[0055] [Evaluation results] From the results in Table 1, since the silicon collectors A to D in Examples 1 to 4 in the present invention have a predetermined configuration, the value of the SiO2 equivalent concentration is particularly higher than that of the silicon collectors E to H in Comparative Examples 1 to 4, and it can be seen that the silicon collection ability is high. However, even if the value of ΔPV / PVme is simply within a predetermined range, the collector G of Comparative Example 3 that does not satisfy other configurations of the present invention cannot exhibit the effects of the present invention described above, and it can be seen that the silicon collection ability is low.

Claims

1. A silicon collector having a hydrogenation active metal supported on at least one of an alumina carrier and an alumina-phosphorus carrier, Specific surface area is 100m 2 / g or more, The total pore volume (PVT) measured by mercury intrusion porosimetry is in the range of 0.80 to 1.50 ml / g; The pore distribution has a maximum value in the pore diameter range of 10 to 30 nm, the ratio (ΔPV / PVme) of the proportion of the pore volume (ΔPV) in the range of ±2 nm of the pore diameter at the maximum value to the proportion of the pore volume (PVme) in the range of pore diameters of 5 to 100 nm is 0.40 or less; The compressive strength is 10 N / mm or more, The phosphorus content is P 2 O 5 The concentration is 10.0% by mass or less, A silicon collector in which the hydrogenation active metal is at least one metal selected from the group consisting of metals in Group 6 and metals in Groups 8 to 10 of the periodic table.

2. A method for hydrotreating hydrocarbon oils using the silicon collector of claim 1.

3. A first step of obtaining an alumina hydrate by adding an aqueous solution of basic aluminum to an aqueous solution of acidic aluminum, the pH of which has been adjusted to 2.0 to 5.0, while stirring the aqueous solution so that the pH of the aqueous solution is 7.5 to 10.0; a second step of obtaining an alumina hydrate by removing a by-product salt of the alumina hydrate; a third step of adding phosphorus to the alumina hydrate to obtain an alumina-phosphorus hydrate; a fourth step of aging the alumina-phosphorus hydrate at 80 to 100° C. for 1 to 10 hours; a fifth step of obtaining an alumina-phosphorus support from the aged alumina-phosphorus hydrate; A sixth step of supporting a hydrogenation active metal on the alumina-phosphorus support, A method for producing a silicon collector, comprising the step of adding phosphorus to the alumina hydrate in such a manner that the alumina-phosphorus carrier contains phosphorus in an amount of 10 mass % or less calculated as P 2 O 5 in the third step.