JP2017136588A - Hydrotreating catalyst for hydrocarbon oil, method for producing the same and hydrotreating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrotreating catalyst for a hydrocarbon oil which can regenerate a catalyst having excellent desulfurization activity and high performance while maintaining high industrial productivity.SOLUTION: There is provided a hydrotreating catalyst for a hydrocarbon oil which is obtained by depositing, for example, 15 to 28 pts.mass of molybdenum and/or tungsten in terms of oxides and 2 to 7 pts.mass of cobalt and/or nickel in terms of oxides on a γ-alumina carrier, based on 100 pts.mass of the catalyst, wherein the content of carbon derived from an organic acid is 2.0 pts.mass or less on an elemental basis. The catalyst has a specific surface area of 200 to 320 m/g and an average pore diameter of 50 to 110 Å as measured by a mercury penetration method. The ignition loss of the catalyst is 5.0% or less and the adsorption amount of nitric oxide on the sulfurized catalyst is 8.0 ml/g or more.SELECTED DRAWING: None

Description

  The present invention relates to a hydrotreating catalyst for removing a sulfur content in a hydrocarbon oil in the presence of hydrogen, a production method thereof, and a hydrotreating method.

  In the hydrogenation treatment, the reaction is allowed to proceed under high temperature and high pressure using a catalyst. However, since the economic efficiency of the process is enhanced by lowering the reaction conditions at low temperature and low pressure, it is desired that the activity of the catalyst is high. There are the following public knowledge about the reduction temperature of molybdenum.

  R. L. According to Cordero, it is described that the reduction temperature of molybdenum under a hydrogen stream of a catalyst in which molybdenum is supported on alumina or silica varies greatly depending on the support species and composition. However, nickel and cobalt, which are cocatalysts, are not added, and it is difficult to say that they are knowledge as practical catalysts. In addition, since there is no mention of the relationship between this property and the desulfurization activity, no optimum catalyst reduction temperature is mentioned.

  J. Escobar et al. Have two reduction peak temperatures attributed to molybdenum under a hydrogen stream of an unburned catalyst in which nickel, molybdenum and phosphorus are supported on an alumina support. The latter are 384 to 403 ° C and 539 to 576 ° C. It was clarified that the peak was larger than the former. However, although the knowledge about the reduction peak temperature of the unfired catalyst is described, the fired product catalyst is not mentioned, and the relationship between the reduction peak temperature and reduction profile of molybdenum on the composite oxide and the desulfurization activity is described. It has not been.

In Patent Document 1, a sulfide catalyst containing a base metal element selected from Group 8 to 10 of the periodic table such as nickel, cobalt, molybdenum, tungsten, etc., from Group 8 to 10 of the periodic table of rhodium, palladium, platinum, etc. It has been reported that by adding selected noble metals, high hydrotreating performance is exhibited by utilizing spillover hydrogen. In addition, it is described that it is desirable that the behavior of the catalyst component that serves as a reaction active point undergoes reduction is closely related to the catalytic activity of the hydrotreatment, and that the reduction peak temperature of the catalyst in a hydrogen stream is 500 ° C. or less. Has been. However, since noble metals are used, the catalyst price is higher than that of base metals, and it is not desirable from the viewpoint of depleting earth resources.
Although the knowledge referring to the reduction temperature of molybdenum as described above has been reported, no proposal has been made on a catalyst that is inexpensive, excellent in desulfurization performance, and easily regenerated.

  In addition to saving energy and improving economic efficiency, there is an increasing number of refineries that recycle and use spent catalysts at each refinery in light of reducing environmental impact. In such a situation, the following is the conventional knowledge about the production method of an alumina carrier aiming at high performance of the catalyst. Patent Document 2 discloses a method for producing an alumina carrier prepared from a boehmite sol using a pH adjuster as a method for producing a heat-resistant alumina carrier for catalytic combustion, and even when used in a high temperature atmosphere of 1000 ° C. or higher. The effect that a high surface area can be stably maintained is described. This finding is expected that the boehmite used is sol-like and thin, pH adjustment is somewhat complicated, and is somewhat unsuitable industrially.

Patent Document 3 discloses a method for producing an alumina catalyst carrier using an alumina hydrate having a pseudoboehmite crystal structure. In the production process of the alumina support, water is added to the hydrated alumina to plasticize it, and the plasticized product is kneaded and adjusted to an arbitrary pseudoboehmite crystal size, whereby an alumina support having a desired pore size can be obtained. It is described that it can be manufactured. In this preparation method, the crystal size is controlled by the reaction temperature and reaction time of the plasticized product, and many skills are required for property management, and in many cases the quality is expected to be unstable.
Patent Document 4 discloses a method for producing an alumina carrier using pseudo boehmite alumina powder, and this production method is a method for producing a highly pure and highly active alumina catalyst carrier by adjusting the particle shape of an alumina raw material. It is grasped that there is. In this manufacturing method, a method of changing the aspect ratio of the particles by changing the mixing ratio of the two kinds of alumina raw material powders is taken, and the adjustment is expected to largely depend on the alumina raw material and its mixed state. Is done.

  In Patent Document 5, a catalyst obtained by supporting an active metal such as cobalt, nickel, molybdenum and tungsten on a γ-alumina carrier and calcining is further impregnated with polyethylene glycol as an organic additive, and the organic additive remains in the catalyst. A method for producing a hydrogenation catalyst characterized by drying under such conditions has been reported. Depending on the method for preparing such a catalyst, the effect of promoting the hydrodesulfurization reaction by allowing the organic additive to remain can be expected. However, on the other hand, the carbonaceous material derived from organic additives is very unstable and not only affects the stability of the performance during use, but also the performance recovery rate of the used catalyst regenerated product is very poor. Need to supplement the burned-out organic additives.

In Patent Document 6, as a method for producing porous alumina, water and at least one monobasic acid or salt thereof are added to one or more kinds of aluminum hydroxide and / or alumina, and a sol-formation reaction is performed in a temperature range of 250 ° C. or less. There is described a production method characterized in that an aqueous alumina gel and / or alumina gel is obtained by performing, and the aqueous alumina gel and / or alumina gel is dried and fired. Patent Document 5 describes a method of adding an oxygen-containing organic substance, an inorganic polybasic acid, or the like as a pore control agent to an alumina preparation solution. However, the additive is used only in one step, and the catalyst performance is greatly increased. There is no mention of the adjustment of the OH groups on the surface of the supporting carrier. In addition, the solation reaction in the aging process is carried out at a temperature exceeding 100 ° C. in a sealed container, and this treatment requires the use of an autoclave (pressure sealed container), so it is economical for industrial preparation. It ’s hard to say.
Patent Document 7 describes a process for aging alumina hydrate fine particles to which a buffer material and a peptizer are added as a method for producing alumina hydrate fine particle powder, but the crystallinity of alumina is touched. Not.

  Patent Document 8 includes a process for forming molded particles containing at least 90% by weight of boehmite as a method for producing a highly active hydrodesulfurization catalyst, and converting it into γ-alumina by heat treatment. It is described that the amount is γ-alumina (alumina other than γ-alumina is less than 10% by weight). However, the crystallinity control factor is only the firing temperature.

JP 2002-210362 A JP 07-256100 A Japanese Patent Application Laid-Open No. 07-155597 WO97 / 12670 Publication JP-A-8-332385 WO2001 / 056951 Publication JP 2014-133687 A WO2006 / 034073

R. L. Cordero et al., Applied Catalysis, 74, 125-136 (1991). J. Escobar et al., Applied Catalysis B: Environmental, 88, 564-575 (2009).

  An object of the present invention is to provide a hydrotreating catalyst for hydrocarbon oil that is excellent in desulfurization activity while maintaining high industrial productivity and can regenerate a high-performance catalyst, and a method for producing the same. . Another object of the present invention is to provide a method for hydrotreating hydrocarbon oil that can remove sulfur in hydrocarbon oil at a high removal rate.

The hydrocarbon oil hydrotreating catalyst of the present invention is:
(1) On the γ-alumina support, a first metal component that is at least one of molybdenum and tungsten and a second metal component that is at least one of cobalt and nickel are supported,
(2) The γ-alumina support is composed of 100% γ-alumina,
(3) The content of the first metal component is 15 to 28 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst, and the content of the second metal component is relative to 100 parts by mass of the catalyst. And 2 to 7 parts by mass in terms of oxide,
(4) The specific surface area of the catalyst is 200 to 320 m ² / g, the average pore diameter of the catalyst measured by mercury porosimetry is 50 to 110 mm,
(5) The ignition loss is 5.0 mass% or less,
(6) Carbon derived from an organic acid is 2.0 parts by mass or less as an element basis with respect to 100 parts by mass of the catalyst,
(7) The adsorption amount of nitric oxide of the sulfurized catalyst is 8.0 ml / g or more,
It is characterized by being.

  For example, the carrier has a crystallite diameter of 45 mm or less determined from the half width of the XRD diffraction spectrum (020) peak of pseudoboehmite of alumina as a precursor.

The method of the present invention for producing a hydrocarbon oil hydrotreating catalyst according to the present invention is as follows.
(1) a first aging step of aging a slurry containing alumina obtained by mixing an aqueous solution of a basic aluminum salt and an aqueous solution of an acidic aluminum salt;
Cleaning the aged slurry after dehydration,
A second aging step of aging the slurry containing the washed object;
Then, kneading and concentrating the slurry,
Forming a concentrated concentrate of the slurry;
A step of drying and firing the molded product, and preparing a γ-alumina carrier;
(2) preparing an impregnating solution containing a first metal component which is at least one of molybdenum and tungsten, a second metal component which is at least one of cobalt and nickel, and an organic acid, Supporting the metal component and the second metal component on the γ-alumina support,
(3) a step of heat-treating the γ-alumina carrier on which the first metal component and the second metal component are obtained obtained in the step (2) to obtain a hydrotreating catalyst;
It is characterized by having.

Although the specific method of this invention is enumerated, it does not limit the scope of the present invention.
In the second aging step in the step (1), a first organic compound is added to the slurry. The first organic compound is added in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina, for example.
After the step of kneading and concentrating the slurry in the step (1), the second organic compound is added before the step of forming the concentrate. The second organic compound is added in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina, for example.
The organic compound is, for example, at least one of organic acids and saccharides.
The basic aluminum salt aqueous solution in the step (1) contains a carboxylate.
In the first aging stage and the second aging stage included in the step (1), the alumina concentration is less than 20%, and in the step of kneading and concentrating the slurry in the step (1), the alumina concentration is 20% or more. It is.
The temperature of the heat treatment in the step (3) is a temperature of 100 to 600 ° C.
The hydrocarbon oil hydrotreating method of the present invention is a hydrogen partial pressure of 3 to 8 MPa, a temperature of 260 to 420 ° C., and a liquid space velocity of 0.3 to 5 hr in the presence of the hydrotreating catalyst of the present invention. ^-Hydrocarbon oil is hydrotreated under the conditions of ^-1 .

Since the hydrotreating catalyst of the present invention uses a carrier made of γ-alumina, high strength, high stability, a large surface area can be obtained, crystallinity can be easily controlled, and high productivity is expected. . And since it is a suitable active metal composition, the high dispersibility of an active metal is obtained, and the increase in the adsorption amount of nitric oxide (NO) used as the parameter | index of an active site amount can be aimed at. Further, since the OH group on the surface of the carrier is controlled, high dispersibility of the active metal can be obtained from this point. Furthermore, the catalyst regeneration is easy because the ignition loss and carbon content are appropriate.
And the hydrodesulfurization method of hydrocarbon oil with high desulfurization activity can be implemented by using the hydrotreating catalyst for hydrocarbon oil of the present invention.

It is a transmission-type Fourier-transform infrared spectrophotometer measurement result of the carriers A and K. It is a graph which shows an example of the analysis result of the peak temperature of the desorption water by a temperature rising reduction method.

Hereinafter, preferred embodiments of the present invention will be described in detail.
[Hydroprocessing catalyst for hydrocarbon oil]
The hydrocarbon oil hydrotreating catalyst of the present invention comprises a γ-alumina carrier (hereinafter also referred to as an alumina carrier) and an active metal component, and has predetermined properties. The properties of the γ-alumina support, the active metal component and the catalyst are described in detail below.

<Γ-alumina support>
The γ-alumina support constituting the hydrotreating catalyst is an aluminum oxide excluding impurities, and its crystal state can be classified as γ-alumina, and is 100% γ-alumina. The term “100% γ-alumina” means that impurities contained inevitable from the production process of the alumina carrier can be contained, but not contained otherwise. For example, the content of γ-alumina in the alumina carrier is 99%. It is at least 9 mass%, preferably at least 99.5 mass%. Therefore, as a hydrotreating catalyst, not only high performance but also high industrial productivity can be maintained.
In order to effectively support the active metal component in a highly dispersed state on the support and to ensure sufficient catalytic activity, a porous support is usually used and has a relatively small pore having a pore diameter of 500 mm or less. Are preferably used. In addition, in order to control physical properties such as mechanical strength and heat resistance of the support or catalyst body, an appropriate binder component or additive can be contained in the formation of the support or catalyst body.

The support of the catalyst of the present invention corresponds to a basic OH group with respect to absorbance Sa of a spectral peak in a wave number range of 3673 to 3678 cm ⁻¹ corresponding to an acidic OH group measured by a transmission type Fourier transform infrared spectrophotometer. The ratio Sb / Sa of the absorbance Sb of the spectral peak in the wave number range of 3770 to 3774 cm ⁻¹ is in the range of 0.15 to 0.40. The ratio Sb / Sa is more preferably in the range of 0.20 to 0.40. The active metal is known to have different dispersibility depending on the characteristics of the alumina support surface. When Sb / Sa is in the above range, the high dispersibility of the active metal on the support surface is particularly noticeable. As a result, since high desulfurization performance is obtained, it is preferable to prepare in the said range. 1, of the present invention a catalyst for the carrier (carrier A, K shown in the examples), of 3770～3774Cm ^-1 corresponding to the wave number range and basic OH groups 3674～3678Cm ^-1 corresponding to acidic OH group An example of a light absorption spectrum including a wave number range will be shown.

  In preparing the catalyst support of the present invention, a calcination step is performed to prepare γ-alumina via the pseudoboehmite crystal state, but the precursor pseudoboehmite XRD of alumina (before calcination) is used. It is characterized in that the crystallite diameter determined from the half-value width of the diffraction spectrum (020) peak is 45 mm or less. Control of the crystallite size of pseudoboehmite is important because it affects the difficulty of crystal transition by subsequent firing as well as optimization of the pore structure of the alumina support. When the crystallite size exceeds 45 mm, the average pore diameter is large and the specific surface area is small, which is not preferable because the performance of the catalyst may be lowered. In addition, since it is difficult for the crystal transition to proceed during calcination, a boehmite structure may remain in the crystal form of the alumina support, which may cause a concern that the stability of the catalyst performance may be impaired.

<Active metal component>
On the γ-alumina support, for example, molybdenum as a first metal component and cobalt as a second metal component are supported as active metal components.
The first metal component may be tungsten instead of molybdenum, or both molybdenum and tungsten. A preferable range of the content (supported amount) of the first metal component is 15 to 27% by mass in terms of oxide on the catalyst basis (15 to 27 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). A more preferable range is 15 to 20% by mass.

If the content of the first metal component is excessively less than 15% by mass in terms of oxide, the desulfurization activity necessary for the reaction may not be ensured. If it is excessively greater than 27% by mass, the metal component is likely to aggregate. Therefore, the dispersibility may be hindered.
The second metal component may be nickel instead of cobalt, or both cobalt and nickel. The content (supported amount) of the second metal component needs to be 2 to 7% by mass in terms of oxide on the catalyst basis (2 to 7 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). It is. The second metal component acts as a promoter for the first metal component, and when the content is less than 2% by mass in terms of oxide, the first metal component and the second metal component which are active metal components However, when it becomes difficult to maintain an appropriate structure and the content exceeds 7% by mass in terms of oxide, aggregation of the active metal component tends to proceed and the catalyst performance decreases.

  When the active metal component is supported on the alumina support by the impregnation method, an organic acid is usually contained in the impregnation liquid, and thus the organic acid becomes a carbon supply source supported on the alumina support. Examples of the organic acid used for the active metal component include citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA), and more preferably citric acid and malic acid. , Tartaric acid, gluconic acid and the like. In addition to organic acids, for example, when using organic additives such as saccharides (monosaccharides, disaccharides, polysaccharides, etc.), in this specification, the content of carbon derived from organic acids refers to organic acids. And the content of carbon derived from both organic additives.

<Properties of catalyst>
The catalyst of the present invention needs to have a specific surface area (SA) measured by the BET (Brunauer-Emmett-Teller) method in the range of 200 to 320 m ² / g. When the specific surface area (SA) is smaller than 200 m ² / g, the metal components are likely to aggregate and the desulfurization performance may be deteriorated. On the other hand, when it is larger than 320 m ² / g, the average pore diameter and pore volume are decreased, and the desulfurization activity tends to be lowered, which is not preferable.
The average pore diameter must be 50 to 110 mm. The average pore diameter is a value measured by a mercury intrusion method (mercury contact angle: 130 degrees, surface tension: 480 dyn / cm), and represents a pore diameter corresponding to 50% of the total pore volume. The pore volume represents the volume of pores having a pore diameter of 41 mm or more. If the average pore size is less than 50%, the desulfurization performance may be reduced, and if the average pore size is greater than 110%, the catalyst strength may be reduced.

The catalyst of the present invention has an ignition loss (Ig Loss) of 5.0% by mass or less. The ignition loss can be obtained by heating the catalyst at a high temperature as described in the item of the measurement method described later. In order to reduce the ignition loss of the catalyst to 5.0% by mass or less, it is necessary that the γ-alumina carrier is impregnated with the impregnation liquid and then calcined at a temperature of, for example, 300 ° C. or more.
By setting the loss on ignition of the catalyst to 5.0% by mass or less, the desulfurization performance of an unused catalyst (fresh catalyst) whose activity at the time of catalyst regeneration is 100% is assumed to be 80% or more. Can do. When the ignition loss of the catalyst increases. There is a concern that the active metal component agglomerates during the calcination step during catalyst regeneration.

By setting the carbon content in the catalyst to 2.0% by mass or less as the elemental standard on the catalyst basis, the desulfurization performance of an unused catalyst (fresh catalyst) with a novel activity during catalyst regeneration is 100%. 80% or more. If the carbon content is large, there is a concern that the active metal component aggregates due to the firing step during catalyst regeneration.
The catalyst of the present invention has a peak temperature of desorbed water in the range of up to 450 ° C. (temperature at which the peak of the desorption spectrum of water appears) based on the catalyst temperature reduction method is 415 ° C. or lower. A specific example of the temperature reduction method will be described later. Usually, the sulfidation treatment is performed on molybdenum with hydrogen sulfide or the like under a hydrogen stream, and the reaction requires oxygen to be desorbed from molybdenum oxide. Since the desorption peak of water is just the detection of desorption of oxygen from the molybdenum oxide as water, the progress of the sulfidation treatment and the reduction temperature of molybdenum are considered to have a correlation. Therefore, it is considered that the sulfurization treatment of molybdenum can be sufficiently advanced by lowering the peak temperature of the desorbed water.

If the reduction temperature is too high, that is, if the peak temperature of the desorbed water is too high, the water is weakly interacting with the alumina support, so there is a high possibility that active metal aggregates are present. . For this reason, it is presumed that the sulfurization process does not proceed sufficiently. Therefore, it is necessary to lower the reduction temperature and to reduce the interaction between water and the alumina support in order to highly disperse the active metal.
The desorbed water is mainly produced in the molybdenum reduction process, and its peak temperature varies depending on the carrier composition, active metal composition and the like. According to the knowledge of the present inventor, in order to set the desorption peak temperature of water (peak temperature of desorption water) to 415 ° C. or less, on the alumina support, at least one of molybdenum and tungsten (as the active metal component) ( It is necessary that 15 to 28% by mass in terms of oxide) and 2 to 7% by mass in terms of oxide of at least one of cobalt and nickel.
When the amount of the active metal component is less than this range, the catalyst performance is insufficient, which is not preferable. When the amount of the active metal component is more than this range, it is not preferable because an aggregate of the active metal is generated and the dispersibility may be impaired. .

In the catalyst of the present invention, the adsorption amount of nitric oxide of the sulfurized catalyst is 8.0 ml / g or more. The adsorption amount is more preferably 8.3 ml / g or more. Based on the amount of adsorbed nitric oxide molecules, the reaction active point of the catalyst can be measured.
When the adsorption amount of nitric oxide is less than 8.0 ml / g, which is outside the range of the present case, the reaction activity point of the catalyst is small and the effect of improving the catalyst performance cannot be obtained.
The amount of nitrogen monoxide adsorbed after sulfiding the catalyst varies depending on the physical and chemical characteristics of the support, the active metal composition, and the like. In order to perform adsorption of nitric oxide, a sulfidation treatment is required, and thus the reduction temperature of the active metal must be lowered to a certain temperature or lower. According to the knowledge of the present inventor, in order to make the adsorption amount of nitric oxide more than 8.0 ml / g,
a) The specific surface area (SA) of the alumina support is in the range of 180 to 320 m ² / g,
b) to the absorbance Sa spectral peaks in the wave number range of 3674～3678Cm ^-1 corresponding to acidic OH groups measured by transmission Fourier transform infrared spectrophotometer, corresponds to the basic OH groups 3770～3774Cm ^-1 The ratio Sb / Sa of absorbance Sb of spectral peaks in the wave number range of 0.15 to 0.40,
c) As an active metal component on the alumina support, at least one of molybdenum and tungsten is 15 to 28% by mass in terms of oxide, and at least one of cobalt and nickel is 2 to 7% by mass in terms of oxide. There is,
d) It is important that the water desorption peak temperature is 415 ° C. or lower.

[Method for producing hydrotreating catalyst for hydrocarbon oil]
Next, the manufacturing method of the hydroprocessing catalyst of the hydrocarbon oil of this invention is demonstrated.
The method for producing a hydrocarbon oil hydrotreating catalyst according to the present invention comprises:
a first step of preparing a γ-alumina support;
An impregnating solution comprising a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid is prepared, and the first metal component And a second step of supporting the second metal component on the alumina support,
A third step of obtaining a hydrotreating catalyst by heat-treating the alumina carrier carrying the first metal component and the second metal component obtained at the second step at a temperature of 100 to 600 ° C .; Have.
Hereinafter, each step will be described.

<First step>
<< 1-1. Step of obtaining alumina slurry >>
First, a basic aluminum salt aqueous solution and an acidic aluminum salt aqueous solution are mixed so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, and more preferably 6.8 to 8.0. Thus, a hydrate of inorganic oxide is obtained. At this time, the basic aluminum salt aqueous solution preferably contains a carboxylate. Then, after aging the slurry of inorganic oxide hydrate by a desired method (first aging step), washing is performed to remove the by-product salt, and a slurry containing alumina is obtained.
The carboxylate used here is polyacrylic acid, hydroxypropyl cellulose, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, citric acid, etc. It is preferable to add in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina.
<< 1-2. Second aging process for alumina >>
At least one organic compound (first organic compound) is added to the hydrate slurry obtained in the step 1-1, and the temperature is 30 ° C. or higher, preferably 80 to 100 in an aging tank equipped with a reflux. Heat aging is carried out at a temperature of, for example, 1 to 20 hours, preferably 2 to 10 hours (second aging step). In the first aging stage and the second aging stage, the alumina concentration is preferably less than 20%.
<< 1-3. Kneading, molding and drying process >>
The aged product obtained in the step 1-2 is placed in a double-arm kneader with a steam jacket, heated and concentrated until the alumina concentration becomes 20% or more, and then at least one organic compound (second organic compound). After that, the mixture is further heated and kneaded to obtain a moldable kneaded product, and then molded into a desired shape by extrusion molding or the like. In addition, the timing of the addition of the second organic compound may be during the concentration of the aged product.
<< 1-4. Heat treatment (drying and firing) process >>
The molded product obtained in step 1-3 is then heat-dried at, for example, 70 to 150 ° C., preferably 90 to 130 ° C., preferably 400 to 800 ° C., preferably 400 to 600 ° C., for example 0. Calcination for 5 to 10 hours, preferably 2 to 5 hours to obtain an alumina support.
As the basic aluminum salt used here, sodium aluminate, potassium aluminate and the like are preferably used. As the acidic aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate, or the like is preferably used.
When mixing the two kinds of aluminum salt aqueous solutions, the temperature is usually kept at 40 to 90 ° C., preferably 50 to 70 ° C., and the temperature of this solution is ± 5 ° C., preferably ± 2 ° C., more preferably The mixed aqueous solution heated to ± 1 ° C. is usually 5 to 20 so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 8.0. Minutes, preferably 7-15 minutes, to form a precipitate to obtain a hydrate slurry.

Here, the time required for the addition of the mixed aqueous solution to the basic aluminum salt aqueous solution is preferably 15 minutes or less because undesirable crystals such as bayerite and gibbsite may be generated in addition to pseudoboehmite when it is long. 13 minutes or less is more desirable. Bayerite and gibbsite are not preferred because their specific surface area decreases when heat-treated.
Moreover, as a 1st organic compound and a 2nd organic compound used at the said 1st process, at least 1 sort (s) chosen from organic acids or saccharides is preferable. Examples of organic acids include citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA). Examples of the saccharide include monosaccharides, disaccharides and polysaccharides. The addition amount at this time is desirably in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina. If the addition amount is less than this range, it is difficult to obtain the effect due to the addition of the organic compound, and if it exceeds this range, the pore structure becomes too small due to the effect that is too strong, and the physical properties of the catalyst are not in the optimum range. This is not preferable because the efficiency of the preparation is deteriorated.

  The OH group on the surface of the carrier is an important factor that affects the loading state, such as the dispersibility of the active metal species. The control of the OH group can be performed at any point in the carrier preparation step together with the crystallinity of the carrier alumina precursor. However, it is very difficult to adjust the OH group while maintaining the physical properties of the carrier. In order to satisfy this, it is preferable to adjust the OH group in another step after controlling the crystallinity. Therefore, it is preferable to adjust the state of the OH group by adding an organic compound (second organic compound) in the kneading and concentration step after controlling the crystallinity in the second aging step.

<Second step>
The impregnating liquid containing the first metal component, the second metal component, and the carbon component described above is brought into contact with the alumina support.
As the raw material for the first metal component, for example, molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, tungsten trioxide and the like are preferably used. Moreover, as a raw material of a 2nd metal component, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, etc. are used suitably.
When phosphorus is supported on an alumina carrier, orthophosphoric acid (hereinafter also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, etc. are used. .

The impregnating solution is preferably made to have a pH of 4 or less using an organic acid to dissolve the metal component. When pH exceeds 4, it exists in the tendency for the stability of the metal component which melt | dissolves to fall and to precipitate. As the organic acid, for example, citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) can be used, and citric acid and malic acid are particularly preferably used. As the organic additive, saccharides (monosaccharide, disaccharide, polysaccharide, etc.) are used. Organic additives such as glucose (glucose; C ₆ H ₁₂ O ₆ ), fructose (fructose; C ₆ H ₁₂ O ₆ ), maltose (maltose; C ₁₂ H ₂₂ O ₁₁ ), lactose (lactose; C ₁₂ H ₂₂ O ₁₁ ), sucrose (sucrose; C ₁₂ H ₂₂ O ₁₁ ) and the like may be added.

<Third step>
The carrier carrying the metal component obtained by contacting with the impregnation liquid in the second step is 100 to 600 ° C., preferably 110 to 600 ° C., more preferably 400 to 600 ° C., preferably 0.5 to 10 hours, preferably After the heat treatment for 1 to 8 hours, the hydrotreating catalyst of the present invention is produced. Here, if the firing temperature is excessively lower than 100 ° C., the operability due to residual moisture may be deteriorated, and the metal supporting state may be difficult to be uniform. If it exceeds 600 ° C., the metal causes aggregation and dispersion. Since there is a possibility that the maintenance effect cannot be expected, it is not preferable.
Here, one of the advantages in the first to third steps will be described. When performing the 2nd ageing | curing | ripening process of the alumina in a 1st process, the organic compound (1st organic compound) is added to the slurry of a hydrate, and it heat-ages. By performing such treatment, the crystallite diameter of pseudoboehmite of alumina as a precursor can be reduced to 45 mm or less, the average pore diameter of the catalyst can be reduced, and the specific surface area can be increased. In addition, since the crystal transition at the time of firing easily proceeds, the boehmite structure is less likely to remain in the crystal form of the alumina support, and the catalyst performance can be stabilized.

  As a hydrotreating catalyst, a catalyst that satisfies both a high surface area and a high strength in a balanced manner is desired. In order to prepare γ-alumina, a calcination step is performed via a pseudo boehmite crystal state, and it has been expected that the performance of the catalyst is improved by controlling the crystal state of the pseudo boehmite. According to this embodiment, the crystal state of pseudo boehmite can be controlled, which contributes to the production of a high-performance hydroprocessing catalyst.

[Hydrocarbon hydrotreating method]
The hydrocarbon oil to be desulfurized by the hydrotreating catalyst of the present invention is, for example, straight-run kerosene or straight-run light oil obtained from a crude oil atmospheric distillation device, straight-run heavy oil obtained from an atmospheric distillation device Hydrogenation of reduced pressure light oil or reduced pressure heavy light oil obtained by treating oil and residual oil with a vacuum distillation apparatus, catalytic cracked kerosene or contact cracked light oil obtained by catalytic cracking of desulfurized heavy oil, reduced pressure heavy light oil or desulfurized heavy oil Examples include hydrocracked kerosene or hydrocracked light oil obtained by cracking, pyrolyzed kerosene or pyrolyzed light oil obtained from a thermal cracking apparatus such as a coker, and a fraction having a boiling point of 180 to 390 ° C. is 80% by volume or more. This is the fraction that contains it. The hydrogenation treatment using the catalyst is carried out under a high-temperature and high-pressure condition in a hydrogen atmosphere by filling the fixed bed reactor with the catalyst.

[Measurement method]
As will be described later, for the hydrotreating catalyst in each of the examples and comparative examples of the present invention, numerical values relating to the content, specific surface area, and properties of the components are measured, but a method for performing these measurements is described. deep.
<Measurement method of content of carrier component (alumina) and metal component (molybdenum, cobalt, nickel, phosphorus)>
3 g of a measurement sample was collected in a zirconia ball with a lid having a capacity of 30 ml, heated (200 ° C., 20 minutes), fired (700 ° C., 5 minutes), then added with ₂ g of Na ₂ O ₂ and 1 g of NaOH for 15 minutes. Melted. Further, 25 ml of H ₂ SO ₄ and 200 ml of water were added and dissolved, and then diluted to 500 ml with pure water to prepare a sample. The obtained sample, ICP apparatus (Shimadzu Corp., ICPS-8100, the analysis software ICPS-8000) using, in terms of oxide relative to the content of each component _{(Al 2 O 3, P 2} O 5 , MoO ₃ , NiO, CoO).

<Alumina crystal state identification and crystallite size measurement method>
An X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd .: RINT2100) was used, and the measurement sample was a compacted non-reflective plate for measurement. The crystallite size of the support alumina precursor was calculated by the Scherrer method from the (020) plane attributed to boehmite, and the crystal structure of the baked support was judged by comparing diffraction peaks attributed to boehmite and γ-alumina. . The alumina oxide support of the present case is preferably γ-alumina, specifically, the diffraction peak areas indicating the crystal structures of the boehmite (020) plane and (120) plane measured by X-ray diffraction analysis, It is necessary to be less than 1/10 of the diffraction peak area showing the aluminum crystal structure attributed to the γ-alumina (440) plane. That is, the diffraction peak area showing the crystal structure of the boehmite (020) plane measured by X-ray diffraction analysis is P1, the diffraction peak area showing the crystal structure of the (120) plane is P2, and the γ-alumina (440) plane is assigned. When the diffraction peak area showing the aluminum crystal structure is P3,
Of the values of (P1 / P3) × 100 (%) and (P2 / P3) × 100 (%), the larger value is less than 10%.
If the boehmite structure is increased in the crystal of the support, it is not preferable because the physical properties of the support are difficult to control and the catalyst strength may be reduced.

Here, the diffraction peaks indicating the boehmite (020) plane and (120) plane crystal structures were measured at 2θ = 14 ° and 2θ = 28 °, respectively, and aluminum attributed to the γ-alumina (440) plane. The diffraction peak showing the crystal structure is measured at 2θ = 67 °.
Each diffraction peak area is calculated by fitting a graph obtained by X-ray diffraction analysis with an X-ray diffractometer using the least square method and correcting the baseline to obtain the height from the maximum peak value to the baseline ( Peak intensity W) A peak width (half-value width) at a half value (1/2 W) of the obtained peak intensity was determined, and the product of this half-value width and peak intensity was defined as a diffraction peak area. From each calculated diffraction peak area, “boehmite diffraction peak area / γ-alumina diffraction peak area” was calculated.

<Measurement method of carrier surface OH group>
Using a transmission type Fourier transform infrared spectrometer (manufactured by JASCO Corporation: FT-IR / 6100), the maximum peak wave number of the acidic OH group, the absorbance at that wave number, the maximum peak of the basic OH group Wave number and absorbance at the wave number were measured.
(Measurement method)
20 mg of a sample was filled in a molding container (inner diameter 20 mmφ) and compressed with 4 ton / cm ² (39227 N / cm ² ), and molded into a thin disk shape. This molded body was held at 500 ° C. for 2 hours under a condition where the degree of vacuum was 1.0 × 10 ⁻³ Pa or less, and then cooled to room temperature, and the absorbance was measured.

Specifically, in TGS detector, resolution ^{4 cm -1,} the number of integrations and 200 times were baseline corrected wavenumber range 3000~4000cm ^-1. Absorbance was converted per unit mass. Absorbance per unit mass (g ⁻¹ ) = Absorbance / Molded body mass In any sample of each of Examples 1 to 13 described later, the wave number of the maximum peak position of the absorption spectrum corresponding to the acidic OH group is 3673 to in the range of 3678cm ^-1, wave number of the maximum peak position of the absorption spectrum due to the basic OH groups is in the range of 3770~3774cm ^-1.

<Method for measuring specific surface area>
About 30 ml of a measurement sample was collected in a magnetic crucible (type B-2), heated at 300 ° C. for 2 hours, then placed in a desiccator and cooled to room temperature to obtain a measurement sample. Next, 1 g of this sample was taken, and the specific surface area (m ² / g) of the sample was measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type).

<Measurement method of ignition loss>
The catalyst as the measurement sample was calcined at 570 ° C. for 2 hours, and calculated from the amount of mass reduction due to the calcining.
<Measurement method of peak temperature of desorbed water by temperature reduction method>
In the temperature-programmed reduction method, 0.05 g of the catalyst sized to 250 to 710 μm is pretreated at 120 ° C. for 1 hour under the flow of helium gas using a Nippon Bell catalyst analyzer (BEL CAT-A). After the application, the gas was switched to hydrogen gas (99.99%) and the temperature was raised from 50 ° C. to 900 ° C. at 10 ° C./min. The desorption spectrum of water at elevated temperature was measured with a quadrupole mass spectrometer (m / z: 18.34) manufactured by Pfeiffer Vacuum, and the desorption peak temperature of water was read from the obtained desorption spectrum. It was.
FIG. 2 shows a graph as an example of the analysis result of the peak temperature of desorbed water by the temperature reduction method. In FIG. 1, the horizontal axis represents temperature, and the vertical axis represents the detection current of the quadrupole mass spectrometer.

<Measurement method of nitrogen monoxide adsorption amount>
Nitrogen monoxide adsorption is measured using a fully-automatic catalytic gas adsorption measuring device (manufactured by Okura Riken), and a mixed gas of helium gas and nitrogen monoxide gas (nitrogen monoxide concentration of 10) Volume%) was introduced in pulses, and the amount of adsorbed nitric oxide molecules per gram of the hydrotreating catalyst was measured. Specifically, about 0.02 g of the catalyst pulverized to 60 mesh or less was weighed, filled in a quartz cell, and the catalyst was heated to 360 ° C. to obtain 5 vol% hydrogen sulfide / 95 vol% hydrogen. Was conducted at a flow rate of 0.2 liter / min for 1 hour, and then kept at 340 ° C. for 1 hour to discharge the physically adsorbed hydrogen sulfide out of the system. Thereafter, nitric oxide molecules were adsorbed at 50 ° C. with a mixed gas of helium gas and nitric oxide gas, and the amount of adsorbed nitric oxide molecules was measured.

[Example]
Preparation examples of γ-alumina support, preparation examples of impregnation liquid, preparation examples of hydrotreating catalyst which is an embodiment of the present invention using each alumina support and impregnation liquid, and each alumina support and impregnation liquid were used. A preparation example of a hydrotreating catalyst which is a comparative example will be described below.
First, preparation examples of the carrier will be described.

<Preparation of carrier A>
a) A tank with a steam jacket having a capacity of 100 L (liter) was charged with 9.09 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al ₂ O ₃ concentration, and diluted with ion-exchanged water to 40.00 kg. Then, 230.8 g of a 26 mass% sodium gluconate aqueous solution was added to this solution, and the mixture was heated to 60 ° C. with stirring.
Separately, an aluminum sulfate aqueous solution was prepared by heating an aluminum sulfate aqueous solution obtained by diluting 14.29 kg of an aluminum sulfate aqueous solution having a concentration of 7% by mass in terms of Al ₂ O ₃ with 25.71 kg of ion exchange water to 60 ° C.
Next, while expanding the sodium aluminate / sodium gluconate mixed solution having a concentration of 5% by mass, an aqueous aluminum sulfate solution was added thereto at a constant rate for 10 minutes to obtain Al ₂ O ₃ having a concentration of 3.8% by mass. % Alumina hydrate slurry was prepared. At this time, the pH of the slurry was 7.2. The alumina hydrate slurry was then aged at 60 ° C. for 60 minutes with stirring.
b) Next, the aged alumina hydrate slurry was dehydrated and then washed with 1.5 L of an aqueous ammonia solution having a concentration of 0.3% by mass.
c) After the cake-like slurry after washing is diluted with ion-exchanged water so that the concentration becomes 10% by mass in terms of Al ₂ O ₃ , citric acid is added as a first organic compound in a 10% by mass solution. 0.60 kg was added, and then ammonia water having a concentration of 15% by mass was added to adjust the pH to 10.2, followed by aging at 95 ° C. for 10 hours while stirring.
d) The slurry after ripening is dehydrated, heated while being kneaded in a double-arm kneader with a steam jacket, and concentrated until the alumina concentration becomes 20% or higher, and then a 10% by weight solution of malic acid as the second organic compound Then, 0.30 kg was added, and the mixture was further heated and concentrated and kneaded to a predetermined moisture content.
e) Thereafter, the obtained kneaded product was molded into a cylindrical shape having a diameter of 1.6 mm by a screw type extruder.
f) Next, after drying at 110 ° C. for 12 hours, it was calcined at 500 ° C. for 3 hours to obtain a hydrotreating catalyst support A comprising γ-alumina.

<Preparation of carrier B>
In a carrier prepared in the same manner as the carrier A, 0.60 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added. A carrier B was obtained.
<Preparation of carrier C>
In a carrier prepared in the same manner as the carrier A, 1.20 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added. Carrier C was obtained.
<Preparation of carrier D>
In a carrier prepared in the same manner as the carrier A, 0.60 kg of tartaric acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier D was obtained.
<Preparation of carrier E>
In a carrier prepared in the same manner as the carrier A, 0.60 kg of sucrose as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier E was obtained.
<Preparation of carrier F>
In a carrier prepared in the same manner as the carrier A, 0.60 kg of malic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added. A carrier F was obtained.
<Preparation of carrier G>
In a carrier prepared in the same manner as the carrier A, 1.50 kg of sucrose as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier G was obtained.

<Preparation of carrier H>
In the carrier prepared in the same manner as the carrier A, 0.60 kg of acetic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier H was obtained.
<Preparation of carrier I>
In a carrier prepared in the same manner as the carrier A, 0.60 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.30 kg of citric acid as a second organic compound in a 10% by mass solution are added. Carrier I was obtained.
<Preparation of carrier J>
In a carrier prepared in the same manner as the carrier A, 0.45 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.60 kg of citric acid as a second organic compound in a 10% by mass solution are added. A carrier J was obtained.
<Preparation of carrier K>
In the carrier prepared in the same manner as the carrier A, the first organic compound and the second organic compound were not added at all, and the carrier K was obtained.
<Preparation of carrier L>
In a carrier prepared in the same manner as in the preparation of Carrier A, 0.60 kg of citric acid as a first organic compound was added in a 10% by mass solution, and nothing was added to the second organic compound to obtain Carrier L.
<Preparation of carrier M>
In the carrier prepared in the same manner as the carrier A, 1.80 kg of sucrose as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution were added. Other steps were carried out in the same manner as in the preparation of Carrier A to obtain Carrier M.
<Preparation of carrier N>
The carrier A obtained in the same manner as the preparation of the carrier A was dried at 110 ° C. and then fired in an electric furnace at 700 ° C. for 3 hours to obtain a carrier N.
<Preparation of carrier O>
The carrier A obtained in the same manner as the preparation of the carrier A was dried at 110 ° C. and then fired in an electric furnace at 350 ° C. for 3 hours to obtain a carrier O.
<Preparation of carrier P>
The carrier A obtained in the same manner as the preparation of the carrier A was dried at 110 ° C. and then fired in an electric furnace at 430 ° C. for 3 hours to obtain a carrier P.

<Preparation of impregnation liquid>
Next, an example of adjusting the impregnating liquid will be described.
<Preparation of impregnation liquid a>
255 g of molybdenum trioxide and 101 g of cobalt carbonate were suspended in 700 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours with an appropriate refluxing apparatus so that the liquid volume did not decrease. And 121 g of citric acid were added and dissolved to prepare impregnating solution a.

<Preparation of impregnation liquid b>
257 g of molybdenum trioxide and 135 g of nickel carbonate were suspended in 700 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours by applying an appropriate refluxing apparatus so as not to reduce the liquid volume. And 135 g of citric acid were added and dissolved to prepare an impregnating solution b.
<Preparation of impregnation liquid c>
After 255 g of molybdenum trioxide, 78 g of cobalt carbonate, and 27 g of nickel carbonate are suspended in 700 ml of ion-exchanged water, this suspension is heated at 95 ° C. for 5 hours with an appropriate refluxing apparatus so that the liquid volume does not decrease. Then, 43 g of phosphoric acid and 121 g of citric acid were added and dissolved to prepare an impregnating solution c.
<Preparation of impregnation liquid d>
After suspending 201 g of molybdenum trioxide and 63 g of cobalt carbonate in 700 ml of ion-exchanged water and heating the suspension at 95 ° C. for 5 hours with an appropriate refluxing apparatus, 30 g of phosphoric acid is heated. And 75 g of citric acid were added and dissolved to prepare an impregnating solution d.
<Preparation of impregnation liquid e>
After suspending 462 g of molybdenum trioxide and 162 g of cobalt carbonate in 700 ml of ion-exchanged water and heating this suspension at 95 ° C. for 5 hours with an appropriate refluxing apparatus, 99 g of phosphoric acid was heated. And 195 g of citric acid were added and dissolved to prepare an impregnating solution e.
<Preparation of impregnation liquid f>
After suspending 157 g of molybdenum trioxide and 40 g of cobalt carbonate in 700 ml of ion-exchanged water and heating the suspension at 95 ° C. for 5 hours with an appropriate refluxing apparatus, 39 g of phosphoric acid was heated. And 48 g of citric acid were added and dissolved to prepare impregnating solution f.
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Example 1: Preparation of hydrotreating catalyst>
After impregnating the carrier A with 1000 g of the impregnating liquid a, drying at 200 ° C., followed by further calcining in an electric furnace at 450 ° C. for 1 hour, the hydrotreating catalyst (hereinafter also simply referred to as “catalyst”. Examples below) The same applies to.
<Example 2 to Example 16: Preparation of hydrotreating catalyst>
The types of the prepared carrier (preparation example) and the impregnating liquid (preparation example) prepared as described above are combined as shown in Table 1 below, and the others are the same as in example 1, and examples 2 to The catalyst of Example 16 was prepared.

Next, a comparative example will be described.
<Comparative Examples 1 to 7: Preparation of hydrotreating catalyst>
The type of the carrier prepared as described above (preparation example) and the type of impregnation liquid (preparation example) are combined as shown in Table 1 below, and the others are the same as in Example 1, and Comparative Examples 1 to 1 are compared. The catalyst of Example 7 was prepared.
<Comparative Example 8: Preparation of hydrotreating catalyst>
The impregnating liquid a of Example 1 was used as the impregnating liquid, spray impregnated on 1000 g of carrier A prepared in Example 1, and then dried at 120 ° C. to obtain a hydrotreating catalyst without firing.
Tables 1A and 1B show the properties of the carriers in Examples 1 to 16 and Comparative Examples 1 to 8 obtained as described above, and Tables 2A and 2B show the properties of the catalysts. In Table 1A and Table 1B, the specific surface area represents the specific surface area of the catalyst. In Tables 2A and 2B, the supported amount (% by mass) of each element is a catalyst standard value as described above. The amount of carbon is also a catalyst standard value.

<Evaluation of catalyst>
(Confirmation test for evaluation)
For each of the catalysts of Examples 1 to 16 and Comparative Examples 1 to 8, the catalyst performance and the catalyst regeneration performance were evaluated.
(1) Confirmation test for evaluation of catalyst performance
Each catalyst was charged into a fixed bed reactor and pre-sulfided to desorb and activate oxygen atoms contained in the catalyst. This treatment is performed by circulating a liquid or gas containing a sulfur compound in a controlled reaction vessel at a temperature of 200 ° C. to 400 ° C. and a hydrogen pressure atmosphere of normal pressure to 100 MPa.
Next, straight-run gas oil (density 0.8468 g / cm ^{3 at} 15 ° C., sulfur content 1.13% by mass, nitrogen content 0.083% by mass) is supplied at a rate of 150 ml / hour into the fixed bed flow type reactor. Then, hydrodesulfurization treatment was performed and hydrorefining was performed. The reaction conditions at that time are a hydrogen partial pressure of 4.5 MPa, a liquid space velocity of 1.0 h ⁻¹ , and a hydrogen oil ratio of 250 Nm ³ / kl. And reaction temperature was changed in the range of 300-385 degreeC, the sulfur analysis in refined oil in each temperature was performed, and the temperature in which the sulfur content in refined oil became 10 ppm was calculated | required, respectively.

(2) Confirmation test for evaluation of catalyst regeneration performance
The regeneration of the catalyst was performed using the following method. 100 g of the used catalyst extracted after the reaction was placed in a nitrogen atmosphere maintained at 200 ° C. to remove oil adhering to the surface. Thereafter, while controlling the temperature of the catalyst at 400 to 450 ° C., firing was performed in an air atmosphere until the amount of carbon became 1% by weight or less. The calcined catalyst was cooled and used again for the activity test.
The performance calculation method after reproduction is as follows. As the test result in the activity test, the reaction rate constant was obtained from the Arrhenius plot, and the regeneration rate from the fresh catalyst (unused catalyst) was calculated. Specifically, hydrogen sulfide was passed under the conditions described in (1) above after hydrogen sulfide was passed therethrough. From the change in the sulfur concentration in the hydrocarbon oil before and after passing through the reactor, the reaction rate constant was determined based on the following formula 1. The ratio of the reaction rate constant (Kn) of the regenerated catalyst to the reaction rate constant (K _n0 ) of the unused catalyst expressed as a percentage ((K _n / K _n0 ) × 100 [%]) is expressed as relative activity. It was.
K _n = LHSV × 1 / (n−1) × (1 / S ⁿ⁻¹ −1 / S ₀ ⁿ⁻¹ ) Equation 1
here,
K _n : Reaction rate constant
n: The desulfurization reaction rate is proportional to the power of the sulfur concentration of the feedstock (1.5 for LGO)
S: Sulfur concentration in treated oil (%)
S ₀ : Sulfur concentration (%) in the feedstock
LHSV: Liquid space velocity (hr ⁻¹ )
The results of the above confirmation test are shown in Table 3.

(Catalyst properties and evaluation results of confirmation tests)
Examples 1 to 16 all have appropriate values regarding the properties of the catalyst. On the other hand, in Comparative Examples 1 and 4, the ratio of the OH group of the carrier exceeds the upper limit of 0.40, the catalyst surface area is lower than the lower limit of 200 m ² / g, and the catalyst The average pore diameter is not within the preferred range. Also in Comparative Example 2, although the ratio of the OH group of the support exceeds the upper limit of 0.40 and the average pore diameter is within the range of the appropriate value, the catalyst surface area is 200 m ² which is the lower limit of the appropriate value. / G.
Further, in Comparative Example 1, the crystal size of the support alumina precursor simultaneously exceeds 45% which is the upper limit of the appropriate value. In Comparative Example 3, although the catalyst surface area is high, the average pore diameter is below the lower limit of the appropriate value, so that it is not appropriate for loading of the active metal species, and the nitrogen monoxide adsorption amount is the lower limit of the appropriate value. Comparative Example 5 is not preferable because the crystal form of the carrier alumina includes a state other than γ. In Comparative Examples 6 and 7, the amount of supported active metal is not within the optimum range. In Comparative Example 8, the loss on ignition greatly exceeds 5% by weight, which is the upper limit of the appropriate value, and the amount of carbon contained also exceeds 2% by weight, which is the upper limit of the appropriate value.
In Examples 1 to 16, the temperature at which the sulfur content in the refined oil is 10 ppm, which is an indicator of catalyst performance, is 360 ° C. or less, and the above relative activity, which is an indicator of catalyst regeneration performance, is 80% or more. It is. In contrast, Comparative Examples 5 and 8 have inferior catalyst regeneration performance, Comparative Examples 1 to 7 have inferior catalyst performance, and Comparative Example 5 has inferior catalyst performance and catalyst regeneration performance.

  The hydrodesulfurization catalyst of the present invention is extremely useful industrially because it can highly hydrodesulfurize hydrocarbon oils.

Claims (15)

(1) On the γ-alumina support, a first metal component that is at least one of molybdenum and tungsten and a second metal component that is at least one of cobalt and nickel are supported,
(2) The γ-alumina support is composed of 100% γ-alumina,
(3) The content of the first metal component is 15 to 28 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst, and the content of the second metal component is relative to 100 parts by mass of the catalyst. And 2 to 7 parts by mass in terms of oxide,
(4) The specific surface area of the catalyst is 200 to 320 m ² / g, the average pore diameter of the catalyst measured by mercury porosimetry is 50 to 110 mm,
(5) The ignition loss is 5.0 mass% or less,
(6) Carbon derived from an organic acid is 2.0 parts by mass or less as an element basis with respect to 100 parts by mass of the catalyst,
(7) The adsorption amount of nitric oxide of the sulfurized catalyst is 8.0 ml / g or more,
A hydrotreating catalyst for hydrocarbon oils, characterized in that   The carbonization according to claim 1, wherein the peak temperature of desorbed water in the range up to 450 ° C (the temperature at which the peak of the desorption spectrum of water appears) is 415 ° C or less, based on the temperature reduction method of the catalyst. Hydrogen oil hydrotreating catalyst. The carrier is 3770-3774 cm corresponding to basic OH groups with respect to absorbance Sa of spectral peaks in the wave number range of 3673-3678 cm ⁻¹ corresponding to acidic OH groups measured by transmission Fourier transform infrared spectrophotometer. The hydrocarbon oil hydrotreating catalyst according to claim 1 or 2, wherein the ratio Sb / Sa of absorbance Sb of spectral peaks in the wave number range of ^{-1 is in} the range of 0.15 to 0.40. The carrier has a diffraction peak area P1 indicating the crystal structure of the boehmite (020) plane measured by X-ray diffraction analysis, a diffraction peak area P2 indicating the crystal structure of the (120) plane, and a γ-alumina (440) plane. When the diffraction peak area indicating the aluminum crystal structure belonging to is P3,
4. The value of (P1 / P3) × 100 (%) and the value of (P2 / P3) × 100 (%), wherein the larger value is less than 10%. A hydrotreating catalyst for hydrocarbon oils according to claim 1.   5. The carrier according to claim 1, wherein the support has a crystallite diameter of 45 mm or less determined from a half-value width of an XRD diffraction spectrum (020) peak of pseudoboehmite of alumina as a precursor. The hydrocarbon oil hydrotreating catalyst as described. A method for producing a hydrocarbon oil hydrotreating catalyst according to any one of claims 1 to 5,
(1) a first aging step of aging a slurry containing alumina obtained by mixing an aqueous solution of a basic aluminum salt and an aqueous solution of an acidic aluminum salt;
Cleaning the aged slurry after dehydration,
A second aging step of aging the slurry containing the washed object;
Then, kneading and concentrating the slurry,
Forming a concentrated concentrate of the slurry;
A step of drying and firing the molded product, and preparing a γ-alumina carrier;
(2) preparing an impregnating solution containing a first metal component which is at least one of molybdenum and tungsten, a second metal component which is at least one of cobalt and nickel, and an organic acid, Supporting the metal component and the second metal component on the γ-alumina support,
(3) a step of heat-treating the γ-alumina carrier on which the first metal component and the second metal component are obtained obtained in the step (2) to obtain a hydrotreating catalyst;
A process for producing a hydrotreating catalyst for hydrocarbon oils, comprising:   The method for producing a hydrocarbon oil hydrotreating catalyst according to claim 6, wherein a first organic compound is added to the slurry in the second aging stage in the step (1).   8. The method for producing a hydrocarbon oil hydrotreating catalyst according to claim 7, wherein the first organic compound is added in an amount of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina.   The second organic compound is added after the step of kneading and concentrating the slurry in the step (1) and before the step of forming the concentrate. The manufacturing method of the hydrotreating catalyst of the hydrocarbon oil of description.   The method for producing a hydrocarbon oil hydrotreating catalyst according to claim 9, wherein the second organic compound is added in an amount of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina.   The method for producing a hydrotreating catalyst for hydrocarbon oil according to any one of claims 7 to 10, wherein the organic compound is at least one of organic acids and saccharides.   The method for producing a hydrocarbon oil hydrotreating catalyst according to any one of claims 6 to 11, wherein the basic aluminum salt aqueous solution in the step (1) contains a carboxylate. In the first aging stage and the second aging stage included in the step (1), the alumina concentration is less than 20%,
13. The hydrocarbon oil hydrotreating catalyst according to claim 6, wherein in the step of kneading and concentrating the slurry in the step (1), the alumina concentration is 20% or more. Manufacturing method.   The method for producing a hydroprocessing catalyst for hydrocarbon oil according to any one of claims 6 to 13, wherein the temperature of the heat treatment in the step (3) is a temperature of 100 to 600 ° C. In the presence of the hydrotreating catalyst according to any one of claims 1 to 5, the hydrogen partial pressure is 3 to 8 MPa, the temperature is 260 to 420 ° C, and the liquid space velocity is 0.3 to 5 hr ^-1 . A hydrotreating method for hydrocarbon oil, comprising hydrotreating a hydrocarbon oil.

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