JP4564673B2 - Light hydrocarbon oil hydrotreating catalyst, method for producing the same, and light hydrocarbon oil hydrotreating method using the same - Google Patents

Description

【００４９】
【表２】
水素化脱硫実験条件

【００５０】
【発明の効果】
本発明によれば、周期律表第８〜１０族卑金属元素から選ばれる少なくとも一つの元素の化合物（Ａ）と、周期律表第８〜１０族貴金属元素から選ばれる少なくとも一つの元素の化合物（Ｂ）とを含有する触媒において、前記化合物（Ａ）及び化合物（Ｂ）は還元処理を行ったものであり、化合物（Ａ）に帰属する昇温還元法の還元ピーク温度を５００℃以下としたことにより、水素化反応活性の向上、長寿命化が可能となり、また高価な貴金属の使用量を低くして高性能の軽質炭化水素油の水素化処理触媒が提供される。またこのような高性能の水素化処理触媒はイオン交換金属析出法等の方法で容易に製造することができる。
【図面の簡単な説明】
【図１】触媒を水素還元雰囲気中で一定の速度で昇温した時に得られる昇温還元曲線である。横軸：温度
縦軸：熱伝導度検出器からの信号強度
▲１▼：触媒▲１▼の昇温還元曲線
▲２▼：触媒▲２▼の昇温還元曲線
▲３▼：触媒▲３▼の昇温還元曲線[0001]
BACKGROUND OF THE INVENTION
The present invention mainly comprisesLightTECHNICAL FIELD The present invention relates to a catalyst for hydrotreating a hydrocarbon raw material, a method for producing the catalyst, and a hydrotreating method for light hydrocarbon oil using the catalyst, and particularly enables hydrotreating at a low temperature in the field of petroleum refining. The present invention relates to a highly active hydrotreating catalyst, a method for producing the catalyst, and a method for hydrotreating light hydrocarbon oil using the catalyst.
[0002]
[Prior art]
In the field of oil refining, hydroprocessing is an extremely important technology and is widely used for reforming and refining methods. For example, hydrodesulfurization treatment that removes sulfur compounds in feedstock by reacting them in the presence of hydrogen, hydrodenitrogenation treatment that removes nitrogen compounds, and hydrogen that decomposes and lightens hydrocarbons in feedstock It is used for hydrocracking treatment, hydrogenation treatment for hydrogenating unsaturated hydrocarbons such as aromatic hydrocarbons in feedstock. In the present invention, the hydrogenation treatment refers to all treatments involving hydrogenation. In these hydrotreatments, a catalyst is used to advance the reaction at high temperature and high pressure. However, it is desirable that the activity of the catalyst is high in order to improve the economics of the process by reducing the reaction conditions to low temperature and low pressure. .
[0003]
The hydrotreating catalyst used for hydrotreating is usually a supported catalyst carrying a metal or compound having hydrogenation activity using a porous material having a large surface area such as a metal oxide as a carrier. In general, a catalyst using a noble metal has high hydrogenation activity, but is easily poisoned by substances such as sulfur. On the other hand, sulfide catalysts mainly composed of sulfides of metals such as nickel, cobalt, molybdenum and tungsten are known to be resistant to sulfur poisoning, although their hydrogenation activity is not as high as that of noble metal catalysts. In the hydrotreatment, various catalysts are selected and used depending on the purpose, raw materials, and the like.
[0004]
Thus, many types of catalysts have been used as hydroprocessing catalysts up to now. However, against the background of increasing demands for environmental conservation in recent years, a catalyst that is more active and has high sulfur resistance and a long catalyst life is desired for the purpose of improving economy and reducing the burden on the environment. It is in the current situation.
[0005]
[Problems to be solved by the invention]
As the hydrotreating catalyst, the above-mentioned two kinds of catalysts, that is, a catalyst containing a compound of a periodic table group 6 element or a periodic table group 8-10 base metal element such as molybdenum, tungsten, nickel, cobalt, etc., and rhodium Simply mixing a catalyst containing a group 8-10 noble metal element of the periodic table, such as palladium, platinum, etc., a high-performance hydrogenation catalyst having both features cannot be obtained.
[0006]
In order to obtain a highly active hydrogenation catalyst, a periodic cycle is selectively provided in the vicinity of a reaction active point comprising a compound of a periodic table group 6 element or a periodic table group 8-10 base metal element as a main active component. It is important that the group 8-10 noble metal element of the table is present, and thereby hydrogen is activated on the group 8-10 noble metal of the periodic table, and the hydrogen is efficiently spilled over to the reaction active point. Can do. This hydrogen spillover increases the hydrogen on the reaction active site, improving the hydrogenation reaction activity, improving the sulfur resistance by promoting the hydrogenation of sulfur compounds that are poisonous substances, and reducing the activity of coke Longer life can be achieved by promoting hydrogenation. Thereby, the catalyst performance can be enhanced while keeping the amount of expensive noble metal used low.
[0007]
[Means for Solving the Problems]
  Therefore, the inventors of the present inventionZhouIt is important that the group 8-10 noble metal element of the periodic table is selectively present in the vicinity of the reaction active point composed of the group 8-10 base metal element compound in the periodical table, and thereby the amount of expensive noble metal used. As a result of intensive research to obtain a high-performance hydrotreating catalyst, focusing on the fact that the catalyst performance can be improved while keeping the catalyst low, the behavior of the catalyst component that becomes the reaction active site when undergoing reduction is hydrogenated. It has been found that only a hydrotreating catalyst that has a close relationship with the catalytic activity of the treatment and has a specific reduction characteristic has a high activity, and has found a method for obtaining a catalyst having such a reduction characteristic. Completed the invention.
[0008]
  That is, the present inventionZhouA compound (A) of at least one element selected from Group 8 to 10 base metal elements of the periodic table and a compound (B) of at least one element selected from Group 8 to 10 noble metal elements of the periodic table ,The compound (A) and the compound (B) are subjected to reduction treatment,And the reduction peak temperature of the temperature rising reduction method belonging to the compound (A) is 500 ° C. or less, a light hydrocarbon oil hydrotreating catalyst, a process for producing the catalyst, and a light hydrocarbon using the same This is a method for hydrotreating oil. A catalyst having such a reduction characteristic can be obtained by contacting the compound (B) with a solution after carrying the reduction treatment by supporting the compound (A) on a carrier.
  In addition, the following is mentioned as reference invention of this invention.
A compound (A) of at least one element selected from Group 6 elements of the periodic table and a compound (B) of at least one element selected from Group 8 to 10 noble metal elements of the periodic table, (A) and the compound (B) have undergone a reduction treatment, and the reduction peak temperature of the temperature-reduction method attributed to the compound (A) is 500 ° C. or less. It is a hydrotreating catalyst.
  Hereinafter, the present invention will be described in detail.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
  Hydrotreating catalyst of the present inventionZhouTwo components of a compound (A) of at least one element selected from group 8 to 10 base metal elements of the periodic table and a compound (B) of at least one element selected from group 8 to 10 noble metal elements of the periodic table Contains as an essential component. The group numbers according to the periodic table are based on the long-period periodic table according to the 1989 IUPAC inorganic chemical nomenclature revised edition. In the present invention, a compound of a certain element includes a simple substance of the element.
[0010]
  The Group 6 element of the periodic table used in the reference invention of the present invention refers to chromium, molybdenum, and tungsten. Among them, molybdenum and tungsten are preferable, and molybdenum is more preferable.
[0011]
A periodic table group 8-10 base metal element refers to iron, cobalt, and nickel, and cobalt and nickel are preferable in it.
[0012]
  As the component (A) of the catalyst, only Group 6 elements of the periodic table are used.Is a reference invention of the present invention, but in the present invention,Although only the group 8-10 base metal elements of the periodic table may be used, both may be used.
[0013]
The form of the compound (A) of these elements is arbitrary, but is preferably a sulfide, an oxide, or a metal, and more preferably a sulfide or a metal. The content of the component (A) in the catalyst is arbitrary, but is preferably 1 to 50% by weight based on the total amount of the catalyst (including the carrier) in terms of weight when an oxide is used. More preferably, it is 2 to 30% by weight. In addition, when this oxide is expressed in chemical formula,_ThreeO_Four, Co_ThreeO_Four, NiO, CrO_Three, MoO_Three, WO_ThreeIt is converted as an anhydride.
[0014]
The group 8-10 noble metal elements in the periodic table refer to ruthenium, rhodium, palladium, osmium, iridium and platinum, among which ruthenium, rhodium, palladium and platinum are preferable. More preferred are rhodium, palladium and platinum, and most preferred is rhodium. Although the form of the compound of these elements is arbitrary, Preferably it is a metal. Moreover, although one kind of periodic table group 8-10 noble metal element may be used as the component (B), it is preferable to use a plurality of group 8 noble metal elements of the periodic table. In particular, it is preferable to use rhodium in combination with palladium and / or platinum. Although content of (B) component in a catalyst is arbitrary, 0.01-5 weight% is preferable with respect to the catalyst whole quantity (a support | carrier is included) in conversion of the weight at the time of setting it as a metal. More preferably, it is 0.05-2 weight%.
[0015]
The content ratio of the component (A) and the component (B) in the catalyst is preferably (B) / (A) of 10% by weight or less, particularly preferably 5% by weight or less as a metal.
[0016]
The hydrotreating catalyst of the present invention may contain components other than both components (A) and (B) as necessary. Preferred examples of the other components include a carrier component and a metal oxide having a non-stoichiometric composition. As the metal oxide having a non-stoichiometric composition, oxides of lanthanum and lanthanide are preferable, and oxides of lanthanum, cerium, and samarium are more preferable.
[0017]
Although it is not essential for the hydrotreating catalyst of the present invention to contain a carrier, it is preferred to contain a carrier because the surface area of the active ingredient can be increased to enable efficient reaction. The carrier is optional, and a commonly used carrier can be used. Examples thereof include porous, large surface area metal oxides such as alumina, silica, titania, magnesia, and zirconia, composite metal oxides such as silica alumina and alumina boria, various clay minerals, and activated carbon.
[0018]
Further, the carrier preferably contains a substance having ion exchange ability. Examples of substances having ion exchange ability include zeolites, various molecular sieves, metalloaluminophosphates typified by silicoaluminophosphate, clay minerals, and the like. Of these, zeolite and clay minerals are preferred. Preferred zeolites include faujasite (X zeolite, Y zeolite, ultrastable Y zeolite), mordenite, β zeolite, pentasil type zeolite (MFI, etc.), ferrierite, L zeolite, A zeolite and the like. More preferred are faujasite, mordenite, β zeolite, MFI, ferrierite, and L zeolite. Preferred clay minerals include smectite having a three-layer structure (montmorillonite (including bentonite, activated clay, acid clay), saponite, hectorite, stevensite, etc.), kaolinite having a two-layer structure, sepiolite, and the like. Among these, synthesized smectite (saponite, hectorite, stevensite) and sepiolite, particularly saponite and stevensite are preferable.
[0019]
Further, the carrier may contain a binder as necessary. Although the kind of binder is arbitrary, the thing excellent in a moldability and high heat resistance after preparation is preferable. Alumina sol, boehmite, silica sol, various clay minerals and the like can be suitably used.
[0020]
When a carrier is used, the loading method of the compound (A) is optional such as impregnation method, coprecipitation method, kneading method, etc., but preferred methods include impregnation method (Incipient wetness method, immersion method, etc.), ion exchange method, gas phase Supporting methods (CVD method etc.) etc. are mentioned. The form of the raw material compound to be loaded varies depending on the loading method, but in the case of the impregnation method and ion exchange method, water-soluble chlorides, nitrates, acetates and the like are preferably used.
[0021]
The loading method of the compound (B) is arbitrary such as impregnation method, coprecipitation method, kneading method, etc., but preferred methods include impregnation method (Incipient wetness method, immersion method, etc.), ion exchange method, vapor phase support method (CVD). And the like, and an ion exchange metal deposition method, which will be defined later, and the like. A particularly preferred supporting method is the ion exchange metal deposition method. The form of the raw material compound to be loaded varies depending on the loading method, but water-soluble chlorides, nitrates, acetates, ammine complexes and the like are preferably used in the impregnation method, ion exchange method, and ion exchange metal deposition method. In addition, a part of the compound (B) may be supported by an ion exchange metal deposition method, and a part of the compound (B) may be supported by another supporting method such as an impregnation method or an ion exchange method.
[0022]
The loading order of both components (A) and (B) is arbitrary, and either may be loaded first or simultaneously, but compound (A) is loaded first, and compound (B) is loaded later. It is preferable to carry it.
[0023]
  The catalyst after supporting each component is preferably subjected to oxidation treatment and reduction treatment. There is no particular limitation on the oxidation treatment, and any method can be adopted. However, oxidation treatment with oxygen is preferable, and specifically, heating in air or a gas containing oxygen is preferable. The temperature is preferably 200 to 700 ° C, more preferably 300 to 650 ° C. There is no particular limitation on the reduction treatment, and any method can be adopted. However, reduction treatment with hydrogen is preferable, and specifically, heating is performed in hydrogen or a gas containing hydrogen. The reduction temperature is preferably 200 to 700 ° C, more preferably 300 to 650 ° C. Further, sulfurization treatment may be performed after the reduction treatment or instead of the reduction treatment. There is no particular limitation on the sulfidation treatment, and any method can be adopted. However, reduction treatment with hydrogen sulfide is preferable, and specifically, heating is performed in hydrogen sulfide or a gas containing hydrogen sulfide. It is preferable to use a mixed gas of hydrogen sulfide and hydrogen. The sulfiding temperature is preferably 200 to 700 ° C, more preferably 300 to 650 ° C.However, the compound (A) and the compound (B) of the present invention are those subjected to reduction treatment.
[0024]
As described above, the main point of the present invention is that the noble metal of the component (B) is selectively present in the vicinity of the reaction active point of the catalyst comprising the component (A), and hydrogen is activated on the noble metal to the reaction active point. By effectively spilling over hydrogen, hydrogen on the reaction active point is increased to improve the hydrogenation reaction activity, sulfur resistance, and extend the life. The hydrotreating catalyst is characterized by the fact that the reduction peak temperature of the temperature-reduction method attributed to the component compound (A) contained is 500 ° C. or lower.
[0025]
This temperature reduction method is an effective means for evaluating the reduction behavior of the catalyst, and it is possible to know the ease of reduction of the catalyst. And by this technique, there is a correlation between the easiness of reduction of the component compound (A) and the reaction activity in the hydrotreatment, and in the case of the catalyst of the present invention, the reduction peak temperature of the temperature rising reduction method is 500 ° C. or less. It has been found that the catalyst is highly active. Here, the reduction peak temperature of the temperature rising reduction method is obtained with the temperature on the horizontal axis and the signal intensity from the thermal conductivity detector on the vertical axis when the catalyst is heated at a constant rate in a hydrogen reduction atmosphere. It is a peak temperature in a temperature reduction curve. A specific method for measuring the reduction peak temperature by the temperature rising reduction method is as follows.
[0026]
(1) Fill a quartz tube having an inner diameter of 5 mm ± 0.5 mm with 0.15 g ± 0.01 g of catalyst dried at 120 ° C. ± 10 ° C. in air for 8 hours or more. The catalyst is retained with coats wool. A thermocouple is installed near the catalyst part and the temperature of the catalyst part is measured.
[0027]
(2) Pre-treat at 400 ° C. ± 10 ° C. for 2 hours or more in a dry air stream (flow rate 20 ml / min ± 2 ml / min).
[0028]
(3) The dry air stream is switched to a hydrogen / argon mixed gas stream (hydrogen 50 to 70 vol% / argon 50 to 30 vol%, flow rate 20 ml / min ± 2 ml / min).
[0029]
(4) In a mixed gas stream (flow rate 20 ml / min ± 2 ml / min), the temperature is raised to 1000 ° C. at a constant temperature rise rate by controlling the temperature rise rate at 10 ° C./min±0.5° C./min. The composition change of the mixed gas accompanying hydrogen consumption is continuously detected by a thermal conductivity detector, and the signal is recorded using a recorder to obtain a chart. A correlation between the composition change of the gas mixture accompanying the consumption of hydrogen and the temperature is obtained from the set temperature rise rate.
[0030]
An example of the chart of the temperature rising reduction curve obtained is shown in FIG. The vertical axis in FIG. 1 represents the signal intensity from the thermal conductivity detector, which is a value corresponding to hydrogen consumption in the temperature-programmed reduction method. Further, the horizontal axis of FIG. 1 shows the passage of time, and since the temperature is increased at a constant speed, it is a value corresponding to the catalyst portion temperature at that time. In the present invention, the catalyst part temperature when the signal intensity (corresponding to hydrogen consumption) gives the highest peak is defined as the reduction peak temperature.
In FIG. 1, the reduction peak temperature is 373 ° C. for (1) and 512 ° C. for (2).
[0031]
In the catalyst containing a group 8-10 noble metal element in the periodic table, a peak due to the reduction of the group 8-10 noble metal element in the periodic table appears depending on the conditions such as the content thereof. ), (B) In the catalyst composed of two components, the peak due to the reduction of the noble metal elements of Groups 8 to 10 of the periodic table may be maximized. However, since the peak resulting from the reduction of the Group 8-10 noble metal element in the periodic table appears below 300 ° C., the peak appearing below 300 ° C. in the present invention is attributed to the reduction of the Group 8-10 noble metal element in the periodic table. It is regarded as a peak, and the reduction peak temperature of the temperature reduction method attributed to the compound (A) in the present invention is defined as a temperature that gives the maximum peak among peaks at 300 ° C. or higher.
[0032]
The hydrotreating catalyst of the present invention is characterized in that the reduction peak temperature of the temperature reduction method attributed to the component compound (A) measured by the above measurement method is 500 ° C. or less, preferably It is 450 ° C. or lower, more preferably 400 ° C. or lower, particularly preferably 390 ° C. or lower, and most preferably 380 ° C. or lower.
[0033]
In order to obtain such a catalyst, the hydrotreating catalyst of the present invention is preferably prepared by an ion exchange metal deposition method as defined herein. This method consists of the following steps.
(1) The compound (A) is supported on a carrier.
(2) Perform reduction treatment.
(3) The compound (B) solution is brought into contact.
[0034]
In the step (1), the supporting method is arbitrary, and the above-described supporting method can be adopted. In addition to the compound (A), other components may be supported. Further, a part of the compound (B) which is the other catalyst component may be supported simultaneously.
[0035]
  In the step (2), the method for the reduction treatment is arbitrary, and various reducing agents can be used in addition to hydrogen, but a preferred reduction treatment is a reduction treatment with hydrogen. Although the reduction treatment temperature in this step varies depending on the type of the compound (A), it is preferably 200 to 700 ° C., more preferably 300 to 650 ° C. in the group 8-10 base metal of the periodic table.Used in the reference invention of the present inventionIn Group 6 element of the periodic table, 300 to 900 ° C is preferable, and 500 to 800 ° C is more preferable. In the step (2), it is important that part or all of the compound (A) supported in the step (1) is reduced to a metal state.
[0036]
In the step (3), the solution of the compound (B) is brought into contact with the reduced catalyst obtained in the step (2). The contact method is arbitrary, but there are a method in which the catalyst after the reduction treatment obtained in the step (2) is immersed in a solution, and a method in which the solution is poured into the catalyst after the reduction treatment obtained in the step (2). Preferred examples can be given. In the method of immersing the reduced catalyst obtained in the step (2) in the solution, the immersion time is preferably 1 minute to 1 day, particularly 2 minutes to 5 hours. The temperature for contact is preferably 0 to 100 ° C, particularly preferably 10 to 80 ° C. Although the kind of solution to be used is arbitrary, it is preferable that the main solvent is water. The form of the compound (B) to be contacted is arbitrary, but when the main solvent is water, a water-soluble chloride, nitrate, acetate, ammine complex or the like is preferably used. The concentration at this time is preferably 0.05 to 10% by weight, particularly preferably 0.1 to 5% by weight. Furthermore, it is desirable that the operation in this step be performed in an inert gas. As the inert gas, nitrogen, argon, helium and the like are preferable. In this step, the compound of the component (A) reduced to the metal state and the compound (B) react, and a noble metal element in Groups 8 to 10 of the periodic table is deposited on the metal as a metal. This is why this method is called an ion exchange metal deposition method.
[0037]
Furthermore, it is preferable to perform a reduction process after this. By this treatment, the active point is stabilized. Further, sulfurization treatment may be performed after the reduction treatment or instead of the reduction treatment.
[0038]
By this ion exchange metal deposition method, the group 8-10 noble metal element in the periodic table can be selectively present in the vicinity of the active point, and as a result, the amount of expensive noble metal used can be reduced. As a preferred example, when rhodium is supported, the amount of rhodium can be 0.01 to 2% by weight. More preferably, it is 0.02 to 1 weight%. In order to reinforce the effect of rhodium, it is desirable to coexist palladium and / or platinum. The supported amount of palladium and platinum is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total amount of the catalyst.
[0039]
The feedstock that is hydrotreated with the catalyst of the present invention is a light hydrocarbon oil. The light hydrocarbon oil referred to in the present invention is a 90 vol% distillation temperature measured by the atmospheric pressure distillation test method of JIS K2254 petroleum product-distillation test method (revised in 1990) of Japanese Industrial Standard. Refers to hydrocarbon oil. Examples of these light hydrocarbon oils are distillate fractions that are distilled when crude oil is distilled with an atmospheric distillation device (topper), including naphtha, kerosene, light oil and some heavy light oils. It is. In addition, when 90 volume% distillation temperature cannot be measured by the atmospheric pressure distillation test method of the test method because the heavy hydrocarbon oil is heavy, it was measured by the vacuum method distillation test method of the test method. The 90 vol% distillation temperature is determined based on the atmospheric pressure conversion distillation temperature obtained from the results.
[0040]
The catalyst of the present invention is widely used in various hydrotreatments of light hydrocarbon oils such as hydrodesulfurization treatment, hydrodenitrogenation treatment, hydrocracking treatment, hydrogenation treatment of aromatic hydrocarbons and unsaturated hydrocarbons. Applicable to.
[0041]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to the range of an Example.
[0042]
(Catalyst preparation 1)
First, cobalt and palladium were supported on a synthetic porous saponite (Smecton SA, Kunimine Industries Co., Ltd.) by the following ion exchange method. 10 g of porous saponite dried at 120 ° C. is mixed at a rate of 1 liter of a mixed aqueous solution of 0.2 mol / liter cobalt nitrate and 0.005 mol / liter palladium (II) nitrate, and 1 at a temperature of 80 ° C. or higher. Stir for 5 hours. Thereafter, the mixture was filtered and washed with 2 liters of distilled water and 100 ml of ethanol for 10 g of the sample. After drying at 120 ° C., firing was performed at 400 ° C. in air for 4 hours. The obtained supported catalyst was reduced at 600 ° C. for 30 minutes in a mixed gas stream of 65 volume% hydrogen / 35 volume% argon. Then, it was made to contact with 0.002 mol / liter rhodium chloride aqueous solution for 10 minutes at room temperature in the inert gas (ion exchange metal deposition method). After drying at 120 ° C. for 8 hours, it was calcined in air at 400 ° C. for 4 hours, and reduced at 600 ° C. for 30 minutes in a 65% hydrogen / 35% argon mixed gas stream. The resulting catalyst was designated as catalyst (1).
[0043]
(Catalyst preparation 2)
First, cobalt and palladium were supported on the synthetic porous saponite by the following ion exchange method. 10 g of porous saponite dried at 120 ° C. is mixed at a rate of 1 liter of a mixed aqueous solution of 0.2 mol / liter cobalt nitrate and 0.005 mol / liter palladium (II) nitrate, and 1 at a temperature of 80 ° C. or higher. Stir for 5 hours. Thereafter, the mixture was filtered and washed with 2 liters of distilled water and 100 ml of ethanol for 10 g of the sample. After drying at 120 ° C., firing was performed at 400 ° C. in air for 4 hours. The obtained supported catalyst was impregnated with an aqueous rhodium chloride solution by an incipient wetness method so that the supported amount of rhodium was 0.1% by weight. After drying at 120 ° C. for 8 hours, it was calcined in air at 400 ° C. for 4 hours, and reduced at 600 ° C. for 30 minutes in a 65% hydrogen / 35% argon mixed gas stream. The resulting catalyst was designated as catalyst (2).
Table 1 shows the metal loadings of catalysts (1) and (2) produced in catalyst preparations 1 and 2.
[0044]
[Example 1]
(Temperature reduction method measurement)
The temperature reduction method was measured using the catalyst (1). A commercially available apparatus (TP-2000, Okura Riken Co., Ltd.) was used for the measurement. A quartz tube having an inner diameter of 5 mm was filled with 0.15 g of a catalyst dried in air at 120 ° C. for 8 hours, and held with coats wool. A thermocouple was installed near the catalyst part, and the temperature of the catalyst part was measured. After pretreatment in a dry air stream (flow rate 20 ml / min) at 400 ° C. for 2 hours, the dry air stream is converted into a hydrogen / argon mixed gas stream (65% hydrogen / 35% argon, 20 ml / min flow rate). The temperature was increased to 1000 ° C. at a constant temperature increase rate by controlling the temperature increase rate at 10 ° C./min in the mixed gas stream. The composition change of the mixed gas accompanying hydrogen consumption was continuously detected by a thermal conductivity detector, and the signal was recorded using a recorder to obtain a chart. The results are shown in FIG. 1 ((1)).
[0045]
(Hydrodesulphurization experiment)
A hydrodesulfurization experiment was conducted with catalyst (1) using a fixed bed flow reactor. The raw oil used was desulfurized gas oil obtained by desulfurizing the diesel oil fraction of Middle Eastern crude oil. The sulfur content was 452 ppm by weight and the 90 vol% distillation temperature was 360 ° C. Catalyst (1) was charged into the reactor and heated to 180 ° C. in a hydrogen stream, and then feedstock was fed to raise the temperature to the reaction temperature to initiate the reaction. The reaction conditions are shown in Table 2. The product oil 72 hours after the start of the reaction was analyzed to determine the desulfurization rate. The results are shown in Table 1.
[0046]
[Comparative Example 1]
Using the catalyst (2) instead of the catalyst (1), the temperature reduction method was measured in the same manner as in Example 1. The results are shown in FIG. 1 ((2)). Further, a hydrodesulfurization experiment was conducted in the same manner as in Example 1 using the catalyst (2). The results are shown in Table 1.
[0047]
[Comparative Example 2]
Using a commercially available hydrodesulfurization catalyst for light oil (referred to as catalyst (3)) instead of catalyst (1), the temperature reduction method was measured in the same manner as in Example 1. The results are shown in FIG. 1 ((3)). Further, a hydrodesulfurization experiment was conducted in the same manner as in Example 1 using the catalyst (3). The results are shown in Table 1.
[0048]
[Table 1]
Catalyst metal loading

[0049]
[Table 2]
Hydrodesulfurization experimental conditions

[0050]
【The invention's effect】
  According to the present inventionZhouA compound (A) of at least one element selected from Group 8-10 base metal elements of the periodic table and a compound (B) of at least one element selected from Group 8-10 noble metal elements of the periodic table In the catalyst,The compound (A) and the compound (B) are subjected to reduction treatment,By setting the reduction peak temperature of the temperature reduction method attributed to the compound (A) to 500 ° C. or less, the hydrogenation reaction activity can be improved and the life can be extended, and the amount of expensive noble metal used can be reduced and increased. A performance light hydrocarbon oil hydrotreating catalyst is provided. Further, such a high-performance hydrotreating catalyst can be easily produced by a method such as an ion exchange metal deposition method.
[Brief description of the drawings]
FIG. 1 is a temperature reduction curve obtained when a catalyst is heated at a constant rate in a hydrogen reduction atmosphere. Horizontal axis: Temperature
Vertical axis: signal intensity from thermal conductivity detector
(1): Temperature reduction curve of catalyst (1)
(2): Temperature reduction curve of catalyst (2)
(3): Temperature reduction curve of catalyst (3)

Claims (4)

Containing at least one compound of an element with (A), at least one compound of an element selected from periodic table group 8-10 noble metal element and (B) selected from peripheral Kiritsu Table 8-10 base metal element The compound (A) and the compound (B) have been subjected to reduction treatment, and the reduction peak temperature of the temperature rising reduction method belonging to the compound (A) is 500 ° C. or less. Hydrocarbon oil hydrotreating catalyst. The hydrotreating catalyst according to claim 1, wherein at least a part of the compound (B) is a rhodium compound. The method for producing a hydrotreating catalyst according to claim 1 or 2, wherein the support is loaded with the compound (A), subjected to reduction treatment, and then brought into contact with the solution of the compound (B). A method for hydrotreating light hydrocarbon oil, comprising hydrotreating light hydrocarbon oil using the hydrotreating catalyst according to claim 1.

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