JP5228221B2 - Method for producing hydrocarbon oil hydrotreating catalyst - Google Patents

Description

The present invention, hydrogenation of hydrocarbon oil processing catalyst (hereinafter, simply referred to as "hydrotreating catalyst") relates to the production how the. More specifically, when hydrotreating hydrocarbon oils, it has superior desulfurization activity that can reduce sulfur compounds in hydrocarbon oils more than conventional hydrotreating catalysts of this type, and improves heat resistance. It relates to the production how you can get hydrotreating catalyst of long life hydrocarbon oil by.

  In recent years, quality control values for petroleum products (hydrocarbon oils) tend to be stricter worldwide in order to improve the air environment. For example, sulfur compounds in light oil may affect the durability of post-treatment devices such as oxidation catalysts, nitrogen oxide (NOx) reduction catalysts, and continuously regenerating diesel exhaust particulate removal filters that are expected as countermeasures for exhaust gases. Therefore, there is a demand for reduction of sulfur compounds in light oil.

  Under such circumstances, development of ultra-deep desulfurization technology that greatly reduces sulfur compounds in hydrocarbon oils is regarded as important. As a technique for reducing sulfur compounds in hydrocarbon oils, it is usually considered that the operating conditions for hydrodesulfurization, for example, reaction temperature, liquid space velocity, etc., are severe. However, when the reaction temperature is increased, carbonaceous matter is deposited on the catalyst, catalyst deterioration occurs, and the catalyst activity rapidly decreases. Further, when the liquid space velocity is lowered, the desulfurization ability is improved, but the purification treatment ability is lowered, so that the equipment scale needs to be expanded.

  Thus, a good way to achieve ultra-deep desulfurization of hydrocarbon oils without harsh operating conditions is to develop a hydrotreating catalyst with excellent desulfurization activity. Furthermore, when the developed hydrotreating catalyst having excellent desulfurization activity is used for hydrotreating hydrocarbon oils, the used hydrotreating catalyst is reduced in its superior desulfurization activity. Is to develop a method for regenerating spent hydroprocessing catalyst that can be regenerated so that it fully recovers.

  In recent years, many studies on active metal types, active metal impregnation methods, catalyst support improvements, catalyst pore structure control, activation methods, etc. have been conducted in various fields. As a method for producing the catalyst, for example, the above metal and phosphorus are supported on a catalyst carrier using a solution containing at least one of Group 6 metal and Group 8 metal of the periodic table, an organic acid, and phosphorus. After that, it is fired at 200 to 400 ° C., and then impregnated with an organic acid or polyhydric alcohol in an amount of 0.1 to 2.0 times the amount of the supported metal to redisperse the supported active metal And a method for producing a hydrotreating catalyst that is dried at 200 ° C. or lower or calcined at 400 ° C. or higher has been proposed (see Patent Document 1).

  In addition, as a regeneration method for restoring the activity of a spent hydrotreating catalyst having a reduced desulfurization activity used for hydrotreating hydrocarbon oil, for example, spent hydrogenation at an upper limit temperature of 500 ° C. A method for regenerating a spent hydrotreating catalyst, wherein the catalyst is regenerated by contacting the treated catalyst with an oxygen-containing gas, and then dried by contacting the catalyst with an organic additive to retain the organic additive in the catalyst. Has been proposed (see Patent Document 2).

JP-A-7-136523 Special table 2003-503194 gazette

However, the above-described conventional hydroprocessing catalyst production method does not provide a highly active hydroprocessing catalyst that is still satisfactory, and the above-described conventional spent hydroprocessing catalyst regeneration method does not regenerate. Since the process becomes complicated, the equipment needs to be expanded. Therefore, it is difficult to restore the activity of the spent hydrotreating catalyst with low cost, simple and inexpensive.
An object of the present invention, comprising: providing the light of the conventional situations, more excellent in desulfurization activity as satisfactory, long life due to improved heat resistance hydrotreating catalyst for hydrocarbon oil, one excellent layer desulfurization activity, Ru near to provide a process for preparing a catalyst capable of producing a hydrotreating catalyst lifetime hydrocarbon oils.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found a catalyst containing a certain amount of a periodic table group 6 metal, a periodic table group 8 metal, and phosphorus in an inorganic oxide support. , when prepared according to certain procedures, more excellent in desulfurization activity, it has found that you can obtain a hydrotreating catalyst lifetime hydrocarbon oils, and have completed the present invention.

That is, the present invention is, in order to achieve the above object, to provide a manufacturing how hydrotreating catalyst of the following hydrocarbon oil.
(1) At least one selected from 10 to 40% by mass of Group 6 metal of periodic table and at least one selected from Group 6 metal of periodic table on the basis of catalyst and oxide conversion, at least selected from Group 8 metal of Periodic Table A step of containing one kind in an amount of 1 to 15 mass% and phosphorus in an amount of 0.5 to 8 mass%,
A step of firing the inorganic oxide after the above step at 400 to 550 ° C .;
An organic acid is supported on the fired product using the organic acid solution so that the molar ratio of [organic acid ] / [group 8 metal of the periodic table] is 0.2 to 1.2. Process,
And manufacturing how hydrotreating catalyst for hydrocarbon oil, which comprises the step of the fired product after carrying dried at 200 ° C. or less.

According to the production method of the present invention, more excellent in desulfurization activity, it can be produced hydrotreating catalyst lifetime hydrocarbon oils, provide a hydrotreating catalyst superior hydrocarbon oil to one layer desulfurization activity can do. Further, by using the water hydrogenation treatment catalyst produced by the method of the present invention, without requiring severe operating conditions, it is possible to highly desulfurize sulfur compounds in hydrocarbon oil.

<Method for producing catalyst>
First, the manufacturing method of the catalyst of this invention is demonstrated in detail.

In the present invention, various inorganic oxides can be used as the inorganic oxide carrier, but an inorganic oxide whose main component is alumina is preferable.
As the alumina used for the carrier, various aluminas such as α-alumina, γ-alumina, δ-alumina, and alumina hydrate can be used, and porous and high specific surface area alumina is preferable. Alumina is suitable. The purity of alumina is about 98% by mass or more, preferably about 99% by mass or more. Examples of the impurities in alumina include SO ₄ ²⁻ , Cl ⁻ , Fe ₂ O ₃ , Na ₂ O and the like. These impurities are desirably as small as possible, and the total amount of impurities is 2% by mass or less, preferably 1 It is preferable that SO ₄ ^{2 −} <1.5% by mass, Cl ⁻ , Fe ₂ O ₃ , and Na ₂ O <0.1% by mass for each component.

  It is preferable to add another oxide component to the alumina used for the carrier, and the other oxide component is preferably one or more selected from zeolite, boria, silica and zirconia. By compounding these, it is advantageous to laminate molybdenum disulfide that forms desulfurization active sites. Among these, the zeolite preferably has an average particle diameter of 2.5 to 6 μm, more preferably 3 to 4 μm, as measured by a coal counter method (1 mass% NaCl aqueous solution, aperture 30 μm, ultrasonic treatment 3 minutes). It is. In addition, it is desirable that the zeolite has a particle size of 6 μm or less with respect to all the zeolite particles, about 70 to 98%, preferably about 75 to 98%, more preferably about 80 to 98%.

  Zeolite having such characteristics is preferable for precisely controlling the pore diameter of the support. By precisely controlling the pore diameter of the carrier, diffusion of the hardly desulfurizable substance into the pores is facilitated. If the average particle size of zeolite and the proportion of particles having a particle size of 6 μm or less occupy the above range, the amount of adsorbed water and crystallinity of alumina hydrate (alumina precursor) and zeolite in the process of preparing the inorganic oxide support From the difference, when the inorganic oxide support is calcined to increase the strength, the shrinkage rate of the alumina hydrate and the zeolite is different, and the tendency to generate relatively large meso or macropores as the pores of the inorganic oxide support can be suppressed. Further, if there are few large pores, the decrease in specific surface area can be suppressed, and in the case of processing residual oil, the internal diffusion of the metal component that becomes a catalyst poison can be suppressed. Decrease in degradation activity can be suppressed.

In the present invention, preferred zeolites added to alumina include faujasite X zeolite, faujasite Y zeolite, β zeolite, mordenite zeolite, ZSM zeolite (ZSM-4, 5, 8, 11, 12, 20, 21, 23, 34, 35, 38, 46, etc.), MCM-41, MCM-22, MCM-48, SSZ-33, UTD-1, CIT-5, VPI-6, TS-1, TS-2 or the like can be used, and Y type zeolite, stabilized Y zeolite, β zeolite, and ZSM type zeolite are particularly preferable. Further, the zeolite is preferably a proton type.
As the above-mentioned boria, silica, and zirconia, those generally used as this kind of catalyst support component can be used.
Moreover, said zeolite, a boria, a silica, and a zirconia can be used individually or in combination of 2 or more types, respectively.

The addition amount of these other oxide components is generally from more than 65% by mass to 99.4% by mass or less of alumina in the inorganic oxide support, whereas from 0.5% by mass of other oxide components. Less than 25% by mass, preferably 70 to 99% by mass of alumina, while other oxide components are 0.5 to 20% by mass, and more preferably 80 to 98.5% of alumina. The other oxide component is 0.5 to 15% by mass with respect to mass%.
If the amount of addition of these other oxide components is in the above range, the pore diameter can be suitably controlled, and the Bronsted acid point and Lewis acid point can be sufficiently imparted. Group metals, especially molybdenum, can be highly dispersed.

  In the present invention, it is preferable that phosphorus atoms are uniformly dispersed in the catalyst pellet, for example, in order to improve the desulfurization activity. If necessary, a phosphorus oxide can be contained in the inorganic oxide support. The method of incorporating the phosphorus oxide into the inorganic oxide support is not particularly limited and can be performed by an equilibrium adsorption method, a coprecipitation method, a kneading method, or the like, but a catalyst having a high desulfurization activity can be obtained. It is preferable to use a kneading method in which a raw material of phosphorous oxide is kneaded in alumina hydrate as a raw material of the carrier. A normal alumina carrier can be manufactured by a general process such as aging, washing, dehydration drying, molding, drying, and firing of alumina hydrate. Can be done. Specifically, the alumina hydrate heated to 15 to 90 ° C. is kneaded and stirred while adjusting the phosphorus compound aqueous solution heated to 15 to 90 ° C. to have a pH of 4 to 10. The phosphorus-containing alumina hydrate thus obtained is precipitated and, if desired, aged and then washed. The obtained washed product is aged as necessary and then molded into a desired shape. This is dried and fired to obtain a phosphorus-containing alumina support.

As described above, the amount of the phosphorus oxide in the case where the inorganic oxide carrier is previously incorporated with the phosphorous oxide is such that the total amount of the phosphoric oxide supported later on the inorganic oxide carrier described later is based on the catalyst. It is preferable to set it as the range of 0.5-8 mass%. Moreover, it is preferable that the quantity of the phosphorus oxide in a phosphorus containing inorganic oxide support | carrier is made into the range of 0.1-6 mass% on a catalyst basis. If the content of the phosphorus oxide is in the above range, the desulfurization activity improvement effect can be expected, and for example, the place on the alumina surface where the active metal molybdenum disulfide to be described later should be arranged is narrowed. Sintering (aggregation) of molybdenum disulfide does not occur, the area of the edge of the molybdenum disulfide crystal does not decrease, the absolute number of CoMoS phases and NiMoS phases that are desulfurization active points does not decrease, and the catalyst has high desulfurization activity Can be held.
Moreover, various compounds can be used as a raw material for the phosphorus oxide to be contained in the inorganic oxide carrier. For example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid can be mentioned, among which orthophosphoric acid is preferable.

  The inorganic oxide carrier used in the present invention is preferably prepared by baking at 400 to 700 ° C. for 0.5 to 10 hours. When firing at less than 400 ° C. for less than 0.5 hours, sufficient mechanical strength cannot be obtained, and this effect is saturated even when firing for a long time exceeding 10 hours at a high temperature exceeding 700 ° C. In addition, the characteristics such as the specific surface area, pore volume, and average pore diameter of the inorganic oxide support are lowered by baking.

The specific surface area of the inorganic oxide support, pore volume, average pore diameter, in order to obtain a catalyst of high hydrodesulfurization activity for hydrocarbon oil, a specific surface area 230~500m ² / g, preferably 270~500m ² / g, pore volume of 0.5 to 1 ml / g, preferably 0.55 to 0.9 ml / g and an average pore diameter of 40 to 180 mm. The reason is as follows.

Since it is considered that the group 6 metal and the group 8 metal of the periodic table of the active metal in the impregnating solution form a complex, if the specific surface area of the inorganic oxide support is 230 m ² / g or more, In the impregnation, it is difficult to highly disperse the metal due to the bulk of the complex. As a result, even if the resulting catalyst is subjected to sulfiding treatment, precise control of the formation of CoMoS phase, NiMoS phase, etc., which are desulfurization active sites It is estimated that it can be avoided. Moreover, if the specific surface area is 500 m ² / g or less, the pore diameter does not become extremely small, so the pore diameter of the catalyst does not become small, which is preferable. When the pore diameter is small, the diffusion of the sulfur compound into the catalyst pores becomes insufficient, and the desulfurization activity decreases.

  A pore volume of 0.5 ml / g or more is preferable because a small amount of solvent does not enter the pore volume when a catalyst is prepared by a normal impregnation method. When the amount of the solvent is small, the solubility of the active metal compound is deteriorated, the dispersibility of the metal is lowered, and a low activity catalyst is obtained. In order to increase the solubility of the active metal compound, there is a method in which a large amount of acid such as nitric acid is added. However, if too much is added, the support has a low surface area, which is a major cause of desulfurization performance degradation. A pore volume of 1 ml / g or less is preferable because the specific surface area is not reduced, the dispersibility of the active metal is improved, and the catalyst has a high desulfurization activity.

  An average pore diameter of 40 mm or more is preferable because the pore diameter of the catalyst supporting the active metal is not reduced. When the pore diameter of the catalyst is small, the diffusion of sulfur compounds into the catalyst pores becomes insufficient, and the desulfurization activity is lowered. An average pore diameter of 180 mm or less is preferable because the specific surface area of the catalyst is not reduced. When the specific surface area of the catalyst is small, the dispersibility of the active metal is deteriorated and the catalyst has a low desulfurization activity. In order to increase the effective number of pores satisfying the condition of the above average pore diameter, the pore distribution of the catalyst, that is, the proportion of pores having an average pore diameter of ± 15 mm is 20 to 90. %, Preferably 35 to 85%. If it is 90% or less, the compound to be desulfurized is not limited to a specific sulfur compound, and can be uniformly desulfurized, which is preferable. On the other hand, if it is 20% or more, pores that do not contribute to desulfurization of hydrocarbon oil do not increase, and as a result, desulfurization activity does not decrease significantly, which is preferable.

  In the present invention, first, at least one selected from Group 6 metal of the periodic table (hereinafter referred to as “Group 6 metal”) is added to the inorganic oxide support as described above in terms of catalyst and oxide. 40% by mass, at least one selected from Group 8 metal of the periodic table (hereinafter referred to as “Group 8 metal”) is supported in an amount of 1 to 15% by mass and phosphorus to 0.5 to 8% by mass. In the present invention, “Group 6 metal of the periodic table” means a Group 6A metal in the long periodic table, and “Group 8 metal of the periodic table” means in the long periodic table. It means a Group 8 metal (“Chemical Dictionary”, 1st edition, 3rd edition, Tokyo Chemical Co., Ltd., April 1, 1994, p. 1079-1081).

  The group 6 metal to be supported is preferably molybdenum or tungsten, and more preferably molybdenum. The amount of the Group 6 metal supported is 10 to 40% by mass, preferably 10 to 30% by mass in terms of catalyst and oxide. If it is 10 mass% or more, it is sufficient for expressing the effects attributable to the Group 6 metal, and it is preferable. Moreover, if it is 40 mass% or less, the group 6 metal compound does not aggregate in the impregnation (support) step of the group 6 metal, the dispersibility of the group 6 metal is improved, and the group 6 metal that is dispersed efficiently The catalyst activity is improved because it does not exceed the supported amount limit and the surface area of the catalyst is not significantly reduced.

The group 8 metal to be supported is preferably cobalt or nickel. The supported amount of the group 8 metal is 1 to 15% by mass, preferably 3 to 8% by mass in terms of catalyst and oxide. If it is 1 mass% or more, the active point which belongs to a group 8 metal is fully obtained, and it is preferable. Further, if it is 15% by mass or less, the group 8 metal compound is not aggregated in the step of containing (supporting) the group 8 metal, the dispersibility of the group 8 metal is improved, and inactive cobalt and nickel species Co ₈ S species such as Co ₉ S, which is a group 8 metal species such as Ni ₃ S ₂ species, CoO species, NiO species, etc., Co spinel species incorporated into the support lattice, Ni spinel species, etc. are generated. Therefore, it is preferable that the catalytic ability is improved. When cobalt and nickel are used as the group 8 metal, the molar ratio of [Co] / [Ni + Co] is in the range of 0.6 to 1, more preferably in the range of 0.7 to 1. It is desirable to do. When this ratio is 0.6 or more, a coke precursor is not formed on Ni, and the catalytic active sites are not covered with coke, and as a result, the activity does not decrease.

In the above-described contents of the Group 8 metal and the Group 6 metal, the optimum mass ratio of the Group 8 metal to the Group 6 metal is preferably [group 8 metal] / [group 8 metal + group 6 metal] in terms of oxide. The value is 0.1 to 0.25. If this value is 0.1 or more, the generation of CoMoS phase, NiMoS phase and the like, which are considered as active points for desulfurization, is not suppressed, and the degree of improvement of desulfurization activity is increased, which is preferable. If it is 0.25 or less, the production of the above-described inert cobalt, nickel species (Co ₉ S ₈ species, Ni ₃ S ₂ species, etc.) is suppressed, and the catalytic activity is improved, which is preferable.

  In the present invention, the loading of the supporting component of the group 6 metal, the group 8 metal, and phosphorus on the inorganic oxide support is generally performed by preparing an impregnation solution containing a raw material compound containing these supporting components, It is carried out by an impregnation method in which the support is impregnated so that the supported amount of the supported component of the catalyst falls within the predetermined range.

  Examples of the raw material compound containing a Group 6 metal used for supporting the Group 6 metal include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdic acid, and the like, preferably molybdenum trioxide and molybdophosphoric acid. The amount of these compounds added to the impregnation solution is such that the amount of the group 6 metal supported on the obtained catalyst falls within the above-mentioned predetermined range.

  Examples of the raw material compound containing a group 8 metal used for supporting the group 8 metal include cobalt carbonate, nickel carbonate, cobalt nitrate hexahydrate, nickel nitrate hexahydrate and the like. Of these, cobalt carbonate and nickel carbonate are preferred. The amount of these compounds added to the impregnation solution is such that the supported amount of the Group 8 metal in the obtained catalyst falls within the predetermined range.

  Examples of the raw material compound containing phosphorus used to carry phosphorus include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and the like, among which orthophosphoric acid is preferable. The amount of these compounds added to the impregnation solution is such that the amount of phosphorus supported on the obtained catalyst is in the range of 0.5 to 8% by mass, preferably 1 to 8% by mass in terms of the above-mentioned predetermined catalyst standard and oxide. The amount to be. If the supported amount of phosphorus on the catalyst is 0.5% by mass or more, phosphorus that forms heteropolyacid on the catalyst surface and that does not form heteropolyacid disperses on the alumina surface. In addition, a multilayer molybdenum disulfide gas crystal is formed, and it is presumed that the desulfurization active sites can be sufficiently arranged. In addition, if it is 8% by mass or less, the group 6 metal sufficiently forms a heteropolyacid on the catalyst surface, and phosphorus that does not form the heteropolyacid has a high quality desulfurization active site dispersed in the alumina surface in the presulfurization step. Since it does not coat, it is preferable because it does not cause a decrease in activity.

  In the present invention, as described above, an inorganic oxide carrier containing a phosphorus oxide can also be used as a carrier. However, when an inorganic oxide carrier containing a phosphorus oxide is used as a carrier, an inorganic oxide carrier is used. It is preferable that the total phosphorus content and the amount of phosphorus supported thereon are in the range of 0.5 to 8% by mass in terms of the predetermined catalyst standard and oxide.

Preparation of the impregnation solution containing the raw material compounds of the respective supporting components can be performed by a conventional method. The solvent used for dissolving the starting compound of each supported component is generally water. If the amount of the solvent used is too small, the support cannot be sufficiently immersed, and if it is too large, a part of the dissolved active metal cannot be supported on the support and adheres to the edge of the impregnation solution container. Therefore, since a desired carrying amount cannot be obtained, 50 to 90 g is preferable with respect to 100 g of the carrier. The temperature at which the impregnation solution is prepared may exceed 0 ° C. and not more than 100 ° C. Within this range, the raw material compounds of the respective supported components can be dissolved well in the solvent.
In addition, when the above-mentioned Group 6 metal and Group 8 metal raw material compounds are not sufficiently dissolved in the impregnation solution, an acid [nitric acid, organic acid (citric acid, malic acid, tartaric acid, etc.)] is used together with these compounds. An organic acid is preferably used.

  In addition, impregnation of the impregnation solution into the inorganic oxide support can be performed by a conventional method. Various conditions can be adopted as the impregnation conditions. Usually, the impregnation temperature is preferably more than 0 ° C. and less than 100 ° C. The impregnation time is 15 minutes to 3 hours, preferably 20 minutes to 2 hours, and more preferably 30 minutes to 1 hour. If the temperature is too high, drying occurs during the impregnation operation, and the degree of dispersion of the supported components is biased. Moreover, it is preferable to stir during the impregnation.

  The inorganic oxide carrier impregnated with the impregnating solution generally has a moisture content of [LOI (Loss on ignition) of 50% or less to some extent at room temperature to about 80 ° C. in a nitrogen stream, air stream, or vacuum. Remove] and dry.

  In the present invention, as described above, the inorganic oxide carrier on which the supporting component of the group 6 metal, the group 8 metal, and phosphorus are generally supported by the impregnation method is generally dried, and then 400 to 550 ° C., preferably 450 to Bake at 500 ° C. Although the firing time depends on the firing temperature, it is generally 2 to 10 hours, preferably 3 to 5 hours. When the firing temperature is less than 400 ° C., the interaction between the group 6 metal, the group 8 metal and phosphorus and the inorganic oxide carrier is small, and it is assumed that the group 6 metal and the group 8 metal are sintered during the hydrotreating operation. , Which is considered to cause a decrease in desulfurization activity, which is not preferable. Further, at a high temperature exceeding 550 ° C., the group 6 metal, the group 8 metal, and phosphorus are sintered at the time of firing, so that desired catalyst performance cannot be exhibited. Although depending on the firing temperature, generally, when the firing time is 2 hours or longer, it is possible to optimize the interaction between the Group 6 metal, the Group 8 metal and phosphorus and the inorganic oxide carrier. Moreover, if it is 10 hours or less, the required amount of catalyst can be produced without expanding the scale. Although details are unknown, it is considered that the heat resistance of the catalyst can be improved by performing the above-mentioned calcination step, and as a result, a long-life catalyst can be obtained. That is, unless the calcination step is performed, the heat resistance of the final composition of the catalyst cannot be imparted. Therefore, it is presumed that the catalyst is greatly deteriorated due to a change in the reaction temperature of the actual machine and cannot be operated for a long time.

The carbon content of the organic substance supported on the fired product is 2 to 10% by mass, preferably 2 to 6% by mass, and more preferably 2 to 4% by mass based on the catalyst.
When the carbon content is 2% by mass or more, the group 8 metal sufficiently forms a complex compound with an organic substance on the catalyst surface. In this case, the group 6 metal not complexed in the preliminary sulfidation step is the group 8 metal. By sulfiding prior to sulfiding, desulfurization active points (CoMoS phase, NiMoS phase, etc.) are sufficiently formed, so Co ₉ S ₈ species which are metal species of group 8 metals such as inert cobalt and nickel species Ni ₃ S ₂ species and the like, and Co spinel species, Ni spinel species and the like incorporated in the lattice of the support are presumed not to be formed, which is preferable.
When the content is 10% by mass or less, the group 8 metal can sufficiently form a complex compound with an organic substance on the catalyst surface, while the group 6 metal does not form a complex compound with the organic substance. This is preferable because no carbon remains on the catalyst surface.
When a group 6 metal is complexed with an organic substance, during activation (sulfurization), sulfurization of the group 6 metal occurs simultaneously with sulfurization of the group 8 metal, and desulfurization active sites (CoMoS phase, NiMoS phase, etc.) are efficiently produced. It is presumed that Co ₉ S ₈ species, Ni ₃ S ₂ species, etc., which are metal species of Group 8 metals such as inactive cobalt and nickel species, are formed.
Further, excessive carbon covers the desulfurization active site in the sulfidation stage as a poisonous substance for the catalyst, causing a decrease in activity.

  The organic substance to be carried on the fired product is preferably an organic acid or a polyhydric alcohol, more preferably a carboxylic acid, more preferably a polyvalent carboxylic acid, and most preferably an aliphatic polyvalent carboxylic acid. It is done. Examples of the carboxylic acid include citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, salicylic acid, malonic acid, and the like. An acid is preferably used. These organic acids are preferably compounds that do not substantially contain sulfur. These organic acids can be used singly or in combination of two or more as required, and organic substances such as polyhydric alcohols can be used in combination. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, trimethylol ethane, trimethylol propane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, and tetraethylene glycols. Of these, diethylene glycol is preferably used. These polyhydric alcohols can be used alone or in combination of two or more as required.

  In the present invention, an organic substance is supported on the fired product obtained by firing the inorganic oxide carrier on which the supporting component is supported as described above, and then dried at 200 ° C. or lower, preferably 80 to 200 ° C. . The organic substance is supported on the fired product by using an organic solution, and the organic substance is supported in a molar ratio of [organic substance] / [Group 8 metal of the periodic table], preferably 0.2 to 1.2. It is carried out so as to be 0.6 to 1.0, most preferably 0.6 to 0.8. If this molar ratio is 0.2 or more, the group 8 metal sufficiently forms an organic compound and a complex compound on the catalyst surface, and in the preliminary sulfidation step, sufficient desulfurization active sites belonging to the group 8 metal are obtained. preferable. Moreover, if it is 1.2 or less, a group 8 metal can fully form a complex compound with an organic substance on the catalyst surface, and on the other hand, it can suppress that an excess organic substance forms a complex compound with a group 6 metal. Therefore, it is preferable.

  The organic material is supported on the fired product by impregnating the fired product with an organic solution such as an organic acid. The organic impregnation solution can be prepared by a conventional method. The solvent used for dissolving the organic substance is generally water. The temperature at which the impregnation solution is prepared is preferably more than 0 ° C and not more than 100 ° C.

  Further, impregnation of the baked product with an organic impregnation solution can also be performed by a conventional method. Various conditions can be adopted as the impregnation conditions. Usually, the impregnation temperature is preferably more than 0 ° C. and less than 100 ° C., and the impregnation time is suitably 15 minutes to 3 hours. When the impregnation temperature is within the above range, drying occurs during the impregnation, and the dispersibility of the organic matter does not decrease. Moreover, if the impregnation time is within the above range, the organic matter becomes uniform in the fired product.

  The above-mentioned baked product impregnated with an organic impregnation solution and supporting the organic material generally has a certain amount of moisture [LOI of 50% or less at room temperature to about 80 ° C. in a nitrogen stream, an air stream, or in a vacuum. After that, drying is performed in an air stream, a nitrogen stream, or a vacuum at 200 ° C. or lower, preferably 80 to 200 ° C., more preferably 100 to 150 ° C., and 5 hours to 20 hours. In the above baked product carrying an organic substance, it is considered that the carried organic substance is complexed with the active metal previously carried. However, when drying is performed at a temperature of 200 ° C. or lower, the organic substance is carried on the tip. The organic substance complexed with the active metal does not desorb from the surface of the catalyst, and as a result, precise control of the formation of the CoMoS phase and NiMoS phase, which are considered to be the above active sites, is facilitated when the resulting catalyst is subjected to sulfurization treatment. Therefore, it is preferable. However, when drying is performed in a vacuum, it is preferable to perform the drying so that the above temperature range is obtained in terms of pressure of 760 mmHg.

The hydrotreating catalyst obtained as described above according to the present invention has an excellent desulfurization activity, and highly desulfurizes sulfur compounds in hydrocarbon oils without requiring severe operating conditions. Can do. The hydrotreating catalyst obtained by the present invention generally has a specific surface area of 100 to 450 m ² / g, preferably 150 to 300 m ² / g, and a pore volume of 0.3 to 0.9 ml / g, preferably The average pore diameter is 0.3 to 0.6 ml / g and the average pore diameter is 40 to 200 mm, preferably 65 to 140 mm.

  Catalysts obtained by the present invention include, for example, straight-run naphtha, catalytic reforming naphtha, catalytic cracking naphtha, catalytic cracking gasoline, straight-run kerosene, straight-run light oil, catalytic cracking light oil, pyrolysis light oil, hydrotreated light oil, desulfurization treatment It can be suitably used for hydrogenation treatment of fractions such as light oil and vacuum distilled light oil (VGO). As a typical property example of the hydrocarbon oil that can be suitably used for the hydrotreating of the catalyst obtained by the present invention, those having a boiling range of 30 to 560 ° C. and a sulfur compound concentration of 5% by mass or less can be mentioned.

Moreover, the hydrogenation treatment of the hydrocarbon oil as described above with the catalyst obtained by the present invention generally involves a hydrogen partial pressure of 0.7 to 8 MPa, a temperature of 220 to 420 ° C., a liquid space velocity of 0.3 to 10 hr ⁻¹ , It can carry out suitably under the conditions of a hydrogen / oil ratio of 20 to 1000 m ³ (normal) / kl.

<Playback method>
Next, the method for regenerating the catalyst of the present invention will be described in detail.
In the present invention, the hydrotreating catalyst carrying a periodic table group 6 metal, a periodic table group 8 metal, and phosphorus is manufactured by various manufacturing methods regardless of the manufacturing origin or use origin. In addition, it is possible to regenerate various used hydroprocessing catalysts used for hydroprocessing various hydrocarbon oils. The used catalyst to be regenerated in the present invention is a catalyst in which an inorganic oxide carrier carries a group 6 metal in the periodic table, a group 8 metal in the periodic table, and components other than phosphorus, for example, organic substances or organic-derived carbon. It may be. Preferably, it is a catalyst in which an organic substance or carbon derived from an organic substance is supported on an inorganic oxide support containing zeolite in addition to a Group 6 metal, a Group 8 metal, and phosphorus in the periodic table. More preferred is a catalyst in which an organic acid or carbon derived from an organic acid is supported on an inorganic oxide support containing zeolite in addition to a Group 6 metal, a Group 8 metal and phosphorus in the periodic table. More preferably, it is a catalyst in which citric acid or carbon derived from citric acid is supported on an inorganic oxide support containing zeolite in addition to a Group 6 metal, a Group 8 metal and phosphorus in the periodic table. Further, in the present invention, for example, the used catalyst can be suitably regenerated after the catalyst obtained by the production method of the present invention is used for the hydrotreating of hydrocarbon oil such as light oil.

  In the present invention, the spent catalyst is first subjected to oil removal treatment. In general, nitrogen, water vapor, carbon dioxide, air, or the like can be used for this oil removal treatment. For example, when volatile components such as oil are removed from heated catalyst at 300 to 400 ° C. by heated air, the oxygen concentration in heated air varies depending on many processing conditions, but generally 21 vol% Hereinafter, it is preferably 20% by volume or less.

  In the present invention, the spent catalyst subjected to the oil removal treatment as described above is calcined at 400 to 550 ° C, preferably 450 to 500 ° C. The firing time is generally 15 minutes to 10 hours, preferably 30 minutes to 9 hours, although depending on the firing temperature. When the calcination temperature is less than 400 ° C., the carbon cannot be sufficiently removed by depositing on the catalyst, so that the activity cannot be sufficiently recovered. Moreover, since the group 6 metal and the group 8 metal are sintered at a high temperature exceeding 550 ° C., the activity cannot be sufficiently recovered. Although it depends on the calcination temperature, generally, if the calcination time is 15 minutes or longer, it is possible to remove carbon deposited on the catalyst, and if it is 10 hours or less, the equipment scale is expanded. Therefore, the necessary amount of catalyst regeneration can be performed.

The carbon content of the organic substance supported on the burned product of the used catalyst is 2 to 10% by mass, preferably 2 to 6% by mass, and more preferably 2 to 4% by mass based on the catalyst.
When the carbon content is 2% by mass or more, the group 8 metal sufficiently forms a complex compound with an organic substance on the catalyst surface. In this case, the group 6 metal not complexed in the preliminary sulfidation step is the group 8 metal. By sulfiding prior to sulfiding, desulfurization active sites (CoMoS phase, NiMoS phase, etc.) are sufficiently formed, so that Co ₉ S ₈ species which are metal species of group 8 metals such as inert cobalt and nickel species Ni ₃ S ₂ species and the like, and Co spinel species, Ni spinel species and the like incorporated in the support lattice are presumed not to be formed, which is preferable.
When the content is 10% by mass or less, the group 8 metal can sufficiently form a complex compound with an organic substance on the catalyst surface, while the group 6 metal does not form a complex compound with the organic substance. This is preferable because no carbon remains on the catalyst surface.
When a group 6 metal is complexed with an organic substance, during activation (sulfurization), sulfurization of the group 6 metal occurs simultaneously with sulfurization of the group 8 metal, and desulfurization active sites (CoMoS phase, NiMoS phase, etc.) are efficiently produced. It is presumed that Co ₉ S ₈ species, Ni ₃ S ₂ species, etc., which are metal species of Group 8 metals such as inactive cobalt and nickel species, are formed.
Further, excessive carbon covers the desulfurization active site in the sulfidation stage as a poisonous substance for the catalyst, causing a decrease in activity.

As the organic matter to be carried on the burned product of the above-mentioned used catalyst, the same organic matter as the organic matter to be carried on the burned product of the inorganic oxide carrier on which the supporting component such as Group 6 metal is loaded in the catalyst production method of the present invention is used. Can be used. In the case of a catalyst containing an organic substance or a carbon component derived from the organic substance during the production of the catalyst, it is preferable to add the same organic substance as the organic substance used in the production of the catalyst. More preferably, the same and the same amount of organic substance is added.
That is, the organic substance to be supported on the burned product of the used catalyst preferably includes an organic acid and a polyhydric alcohol, more preferably a carboxylic acid, more preferably a polyvalent carboxylic acid, most preferably an aliphatic. A polyvalent carboxylic acid is mentioned. Examples of the carboxylic acid include citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, salicylic acid, malonic acid, and the like. An acid is preferably used. These organic acids are preferably compounds that do not substantially contain sulfur. These organic acids can be used singly or in combination of two or more as required, and organic substances such as polyhydric alcohols can be used in combination. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, trimethylol ethane, trimethylol propane, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol, and tetraethylene glycols. Of these, diethylene glycol is preferably used. These polyhydric alcohols can be used alone or in combination of two or more as required.

  In the present invention, an organic substance is supported on the calcined product obtained by calcining the used catalyst subjected to the oil removal treatment as described above, and then dried at 200 ° C. or lower, preferably 80 to 200 ° C. The organic catalyst is supported on the fired product of the used catalyst by using an organic solution, and the organic compound is supported in a molar ratio of [organic substance] / [group 8 metal of the periodic table] of 0.2 to 1. 2, preferably 0.6 to 1.0, most preferably 0.6 to 0.8. If this molar ratio is 0.2 or more, the group 8 metal sufficiently forms an organic compound and a complex compound on the catalyst surface, and in the preliminary sulfidation step, sufficient desulfurization active sites belonging to the group 8 metal are obtained. preferable. Moreover, if it is 1.2 or less, a group 8 metal can fully form a complex compound with an organic substance on the catalyst surface, and on the other hand, it can suppress that an excess organic substance forms a complex compound with a group 6 metal. Therefore, it is preferable.

  The organic matter is supported on the calcined product of the used catalyst by impregnating the calcined product of the used catalyst with a solution of an organic material such as an organic acid. The organic impregnation solution can be prepared by a conventional method. The solvent used for dissolving the organic substance is generally water.

  Moreover, the impregnation of the impregnated solution of the organic matter into the calcined product of the above-mentioned used catalyst can be performed by a conventional method. Various conditions can be adopted as the impregnation conditions. Usually, the impregnation temperature is preferably more than 0 ° C. and less than 100 ° C., and the impregnation time is suitably from 15 minutes to 3 hours. When the impregnation temperature is within the above range, drying occurs during the impregnation, and the dispersibility of the organic matter does not decrease. Moreover, if the impregnation time is within the above range, the organic matter becomes uniform in the fired product.

  The fired product of the used catalyst impregnated with the organic impregnation solution and supported with the organic material is an inorganic oxide in which a supporting component such as a group 6 metal supporting the organic material is supported in the method for producing a catalyst of the present invention. As in the case of the fired product carrier, in general, moisture is removed to some extent (so that the LOI is 50% or less) in a nitrogen stream, air stream, or vacuum, and thereafter In an air stream, a nitrogen stream, or in a vacuum, drying is performed at 200 ° C. or less, preferably 80 to 200 ° C. for 5 to 20 hours. In the burned product of the above-mentioned used catalyst carrying an organic substance, it is considered that the carried organic substance is complexed with an active metal carried on the used catalyst, but when drying is performed at a temperature of 200 ° C. or less, The organic substance complexed with the active metal supported on the used catalyst does not desorb from the surface of the catalyst, and as a result, the CoMoS phase and NiMoS phase which are considered to be the above active sites when the resulting catalyst is subjected to sulfurization treatment. This is preferable because precise control of the formation of the film becomes easy. However, when drying is performed in a vacuum, it is preferable to perform the drying so that the above temperature range is obtained in terms of pressure of 760 mmHg.

  The hydrotreating catalyst regenerated as described above according to the present invention has sufficiently recovered its desulfurization activity, and highly desulfurizes sulfur compounds in hydrocarbon oils without requiring severe operating conditions. Can do.

  The catalyst regenerated by the present invention is, for example, straight-run naphtha, catalytic reformed naphtha, catalytic cracked naphtha, catalytic cracked gasoline, straight-run kerosene, straight-run light oil, as with the catalyst produced by the production method of the present invention. , Catalytic cracking gas oil, pyrolysis gas oil, hydrotreated gas oil, desulfurized gas oil, vacuum distilled gas oil (VGO), etc. Typical examples of the properties of hydrocarbon oils that can be suitably used for the hydrotreating of the catalyst regenerated by the present invention include those having a boiling range of 30 to 560 ° C. and a sulfur compound concentration of 5% by mass or less. .

Moreover, the hydrogenation treatment of the hydrocarbon oil as described above with the catalyst regenerated according to the present invention generally involves a hydrogen partial pressure of 0.7 to 20 MPa, a temperature of 220 to 420 ° C., and a liquid space velocity of 0.3 to 10 hr ^−1. The hydrogen / oil ratio is preferably 20 to 1000 m ³ (normal) / kl.

  Hereinafter, although an example and a comparative example are given and the present invention is explained, the present invention is not limited to the following examples at all.

Example 1 (Production Example)
A SHY zeolite powder having an SiO ₂ / Al ₂ O ₃ molar ratio of 6 (average particle size 3.5 μm, particle size 6 μm or less is 87% of all zeolite particles) and alumina hydrate are kneaded and extruded, and then 600 A zeolite-alumina composite support of a columnar shaped product having a diameter of 1.5 mm that was fired at 2 ° C. (zeolite / alumina mass ratio: 5/95, pore volume 0.79 ml / g, specific surface area 311 m ² / g, average fine A hole diameter of 93 mm) was obtained.
4.6 g of cobalt carbonate, 2.2 g of phosphoric acid, and 17.4 g of molybdophosphoric acid were dissolved in 25.6 g of ion-exchanged water and stirred to obtain an impregnation solution.
The above impregnation solution is impregnated with 30 g of the zeolite-alumina composite inorganic oxide support in an eggplant type flask at room temperature for 1 hour, dried (air-dried), and then fired at 500 ° C. for 4 hours in a muffle furnace. To obtain a fired product. The calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 1, and dried in a muffle furnace at 120 ° C. for 16 hours to obtain Catalyst A. The chemical composition of the catalyst A obtained is shown in Table 1, and the physical properties are shown in Table 2.

Reference Example 1 (Production Example)
In Example 1, catalyst B was obtained in the same manner as in Example 1 except that the calcined product was impregnated with diethylene glycol in the amount shown in Table 1 instead of citric acid as an organic substance. The chemical composition of the obtained catalyst B is shown in Table 1, and the physical properties are shown in Table 2.

Comparative Example 1 (Production Example)
In Example 1, catalyst a was obtained in the same manner as in Example 1 except that the fired product was not impregnated with citric acid. The chemical composition of the obtained catalyst a is shown in Table 1, and the physical properties are shown in Table 2.

<< Hydrogenation of vacuum gas oil >>
The hydrodesulfurization activity of the catalysts obtained in Example 1 ( Production Example) , Reference Example 1 (Production Example), and Comparative Example 1 (Production Example) is as follows. And evaluated.
That is, first, the catalyst was charged into a high-pressure flow reactor to form a fixed bed type catalyst bed, and pretreated under the following conditions.
Next, a mixed liquid of the raw material oil and the hydrogen-containing gas heated to the reaction temperature is introduced from the upper part of the reaction apparatus, and the desulfurization reaction proceeds under the following conditions. The product oil was separated from the bottom and separated with a gas-liquid separator.

《Catalyst pretreatment conditions》
Hydrogen partial pressure: 4.9 MPa
Temperature: Step temperature rise of holding at 290 ° C. for 15 hours and then maintaining at 320 ° C. for 15 hours.
The heating rate is 25 ° C / h

<Reaction conditions>
Reaction temperature: 360 ° C
Hydrogen partial pressure: 4.9 MPa
Liquid space velocity: 0.66 h ⁻¹
Hydrogen / oil ratio: 500 Nm ³ / kl

<Raw material properties>
Oil type: Arabian light vacuum gas oil Specific gravity (15 ° C / 4 ° C): 0.9313 g / cm ³
Distillation properties: initial boiling point 368 ° C, 50% point 456 ° C, 90% point 510 ° C, end point 549 ° C
Sulfur content: 2.9% by mass
Pour point: 32.5 ° C

<< Method for analyzing raw oil properties >>
Analysis of specific gravity: density test method JIS K 2249
Analysis of distillation properties: Distillation test analysis method JIS K 2254
Analysis of sulfur content: Sulfur content test method JIS K2541
Pour point analysis: pour point test method JIS K 2269

The desulfurization activity of each catalyst was analyzed by the following method.
The reactor is operated under the above reaction conditions, and when 20 days have passed, the product oil is collected, and the desulfurization reaction rate constant (ks) is obtained from the sulfur content of the product oil, the sulfur content of the feedstock oil, and the liquid space velocity. It was. The method for obtaining this ks value is shown below.
The constant of the reaction rate equation for obtaining a reaction order of 1.5 with respect to the reduction amount of the sulfur content (Sp) of the produced oil is defined as a desulfurization reaction rate constant (ks). The higher the reaction rate constant, the better the desulfurization activity.
Desulfurization reaction rate constant = 1 / (1.5-1) × [1 / (Sp) ^(1.5-1) −1 / (Sf) ^(1.5-1) ] × (LHSV)
In formula, Sf: Sulfur content in feedstock (mass%)
Sp: Sulfur content (mass%) in reaction product oil
LHSV: Liquid space velocity (h ^-1 )
Desulfurization relative activity (%) = desulfurization reaction rate constant / desulfurization reaction rate constant of catalyst a of Comparative Example 1 × 100
Table 3 shows the desulfurization relative activities when the sulfur content of the product oil, the desulfurization reaction rate constant, and the reaction rate constant of the catalyst a are set to 100 as the evaluation results of the catalysts A, B, and a.

Reference example 2 (reproduction example)
According to Example 1 of International Publication No. WO2004 / 054712, Catalyst A was produced as follows.
That is, 10.27 g of cobaltous citrate and 2.24 g of phosphoric acid (85% aqueous solution) were added to 22.3 g of ion-exchanged water, heated to 80 ° C. and stirred for 10 minutes. Next, 17.61 g of molybdophosphoric acid was added and dissolved, and stirred at the same temperature for 15 minutes to prepare a solution for impregnation.
Into an eggplant-shaped flask, 30.0 g of the same inorganic oxide support of zeolite-alumina composite as prepared in Example 1 was added, and the entire amount of the above impregnation solution was added thereto with a pipette. Soaked for 3 hours. Thereafter, it was air-dried in a nitrogen stream, and dried in a muffle furnace, in an air stream, at atmospheric pressure, and 120 ° C. for about 16 hours to obtain catalyst i.

  This catalyst (a) was subjected to hydrotreating of hydrocarbon oil and used until its activity dropped to an unacceptable level. Thereafter, the hydrocarbon oil remaining in the spent catalyst was removed by treatment in an air atmosphere at 300 ° C. for 3 hours. The carbon-based impurities precipitated on the used catalyst from which the residual hydrocarbon oil has been removed are removed by calcination at 450 ° C. for 4 hours. The regenerated catalyst C was obtained by impregnating with citric acid and drying in a muffle furnace at 120 ° C. for 16 hours. The chemical composition of the obtained regenerated catalyst C is shown in Table 4, and the physical properties are shown in Table 5.

Reference example 3 (reproduction example)
In Reference Example 2 , regenerated catalyst D was obtained in the same manner as Reference Example 2 , except that it was impregnated with diethylene glycol in the amount shown in Table 4 instead of citric acid. The chemical composition of the obtained regenerated catalyst D is shown in Table 4, and the physical properties are shown in Table 5.

Reference example 4 (reproduction example)
In Reference Example 2 , a regenerated catalyst b was obtained in the same manner as in Reference Example 2 except that the calcined product was not impregnated with citric acid. The chemical composition of the obtained regenerated catalyst b is shown in Table 4, and the physical properties are shown in Table 5.

<< Hydrogenation of vacuum gas oil >>
The hydrodesulfurization activity of the catalyst A and each of the regenerated catalysts obtained in Reference Examples 2 to 4 (Regeneration Examples) was used for evaluation of the catalyst obtained in Example 1 above (Production Example) as a raw material oil. Evaluation was performed in the same manner as the evaluation of the catalyst obtained in Example 1 and the like (Production Example) using a vacuum gas oil having the same properties as those described above. As a result of the evaluation, Table 6 shows the desulfurization relative activity when the sulfur content of the product oil of each catalyst, the desulfurization reaction rate constant, and the reaction rate constant of the catalyst a before use are set to 100.

Example 2 (Production Example)
4.54 g of cobalt carbonate, 2.24 g of phosphoric acid (85% aqueous solution) and 17.70 g of molybdophosphoric acid were dissolved in 25.5 g of ion-exchanged water and stirred to obtain an impregnation solution.
The impregnation solution was impregnated with 30.0 g of an inorganic oxide support of the same zeolite-alumina composite prepared in Example 1 in an eggplant-shaped flask at room temperature for 1 hour, dried (air-dried), Firing was performed by firing at 500 ° C. for 4 hours in a muffle furnace. The calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 7, and dried in a muffle furnace at 120 ° C. for 16 hours to obtain Catalyst E. The chemical composition of the obtained catalyst E is shown in Table 7, and the physical properties are shown in Table 8.

Example 3 (Production Example)
SH2 zeolite powder with an SiO ₂ / Al ₂ O ₃ molar ratio of 6 (average particle size 3.5 μm, particle size 6 μm or less is 87% of all zeolite particles), alumina hydrate and orthophosphoric acid are kneaded and extruded Thereafter, it was calcined at 600 ° C. for 2 hours, and a phosphor-zeolite-alumina composite carrier having a columnar shaped product having a diameter of 1/16 inch (phosphorus oxide / zeolite / alumina mass ratio: 4.4 / 5 / 90.5, A pore volume of 0.66 ml / g, a specific surface area of 374 m ² / g, and an average pore diameter of 61 mm were obtained.
In 23.1 g of ion-exchanged water, 4.47 g of cobalt carbonate and 16.53 g of molybdophosphoric acid were dissolved and stirred to obtain an impregnation solution.
The above impregnation solution was impregnated with 30.0 g of the above-mentioned phosphor oxide-zeolite-alumina composite inorganic oxide support at room temperature for 1 hour in an eggplant-shaped flask, dried (air-dried), and then subjected to 500 ° C. in a muffle furnace. Was fired for 4 hours to obtain a fired product. The calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 7, and dried in a muffle furnace at 120 ° C. for 16 hours to obtain Catalyst F. The chemical composition of the obtained catalyst F is shown in Table 7, and the physical properties are shown in Table 8.

Example 4 (Production Example)
Silica, alumina hydrate and orthophosphoric acid are kneaded, extruded and then fired at 600 ° C. for 2 hours to form a columnar molded product of phosphoric acid-silica-alumina composite support (phosphoric oxide / silica). / Alumina mass ratio: 4.4 / 5 / 90.5, pore volume 0.78 ml / g, specific surface area 324 m ² / g, average pore diameter 98 mm).
In 27.3 g of ion-exchanged water, 4.31 g of cobalt carbonate and 16.48 g of molybdophosphoric acid were dissolved and stirred to obtain an impregnation solution.
The above impregnation solution was impregnated with 30.0 g of the above-described phosphor oxide-silica-alumina composite inorganic oxide support at room temperature for 1 hour in an eggplant-shaped flask, dried (air-dried), and then subjected to 500 ° C. in a muffle furnace. Was fired for 4 hours to obtain a fired product. The calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 7, and dried in a muffle furnace at 120 ° C. for 16 hours to obtain catalyst G. The chemical composition of the obtained catalyst G is shown in Table 7, and the physical properties are shown in Table 8.

Example 5 (Production Example)
Alumina hydrate was kneaded, extruded and then calcined at 600 ° C. for 2 hours to give a columnar molded γ-alumina carrier having a diameter of 1/16 inch (pore volume 0.85 ml / g, specific surface area 249 m ² / g). An average pore diameter of 100 mm) was obtained.
In 29.4 g of ion-exchanged water, 4.60 g of cobalt carbonate, 2.16 g of phosphoric acid (85% aqueous solution) and 17.42 g of molybdophosphoric acid were dissolved and stirred to obtain an impregnation solution.
The above impregnation solution is impregnated in 30.0 g of the above-mentioned inorganic oxide carrier of γ-alumina at room temperature for 1 hour in an eggplant-shaped flask, dried (air-dried), and then fired at 500 ° C. for 4 hours in a muffle furnace. To obtain a fired product. The calcined product was impregnated with citric acid as an organic material in the amount shown in Table 7, and dried in a muffle furnace at 120 ° C. for 16 hours to obtain Catalyst H. The chemical composition of the obtained catalyst H is shown in Table 7, and the physical properties are shown in Table 8.

Example 6 (Production Example)
Silica and alumina hydrate are kneaded, extruded and then fired at 600 ° C. for 2 hours to form a columnar shaped silica-alumina composite carrier having a diameter of 1/16 inch (silica / alumina mass ratio: 1/99, fine Pore volume 0.70 ml / g, specific surface area 359 m ² / g, average pore diameter 70 mm).
4.69 g of cobalt carbonate, 2.32 g of phosphoric acid (85% aqueous solution) and 17.41 g of molybdophosphoric acid were dissolved in 24.2 g of ion-exchanged water and stirred to obtain an impregnation solution.
The impregnating solution was impregnated with 30.0 g of the inorganic oxide carrier of the silica-alumina composite in an eggplant type flask at room temperature for 1 hour, dried (air dried), and then in a muffle furnace at 500 ° C. for 4 hours. Firing was performed to obtain a fired product. The calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 7, and dried in a muffle furnace at 120 ° C. for 16 hours to obtain Catalyst I. The chemical composition of the obtained catalyst I is shown in Table 7, and the physical properties are shown in Table 8.

Reference Example 5 (Production Example)
In Example 2 , catalyst J was obtained in the same manner as in Example 2 , except that the amount of diethylene glycol described in Table 7 was impregnated instead of citric acid as the organic substance. The chemical composition of the obtained catalyst J is shown in Table 7, and the physical properties are shown in Table 8.

Comparative Example 2 (Production Example)
In Example 2 , catalyst c was obtained in the same manner as in Example 2 except that the fired product was not impregnated with citric acid. The chemical composition of the obtained catalyst c is shown in Table 7, and the physical properties are shown in Table 8.

Comparative Example 3 (Production Example)
In Example 2 , catalyst d was obtained in the same manner as in Example 2 , except that the calcined product was impregnated with phosphoric acid in the amount shown in Table 7 instead of citric acid as an organic substance. The chemical composition of the obtained catalyst d is shown in Table 7, and the physical properties are shown in Table 8.

Comparative Example 4 (Production Example)
In Example 2 , catalyst e was obtained in the same manner as in Example 2 , except that the calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 7. The chemical composition of the obtained catalyst e is shown in Table 7, and the physical properties are shown in Table 8.

Comparative Example 5 (Production Example)
In Example 2 , catalyst f was obtained in the same manner as in Example 2 except that the calcined product was impregnated with citric acid as an organic substance in the amount shown in Table 7. The chemical composition of the obtained catalyst f is shown in Table 7, and the physical properties are shown in Table 8.

《Hydroprocessing of straight run diesel oil》
The hydrodesulfurization activity of each catalyst obtained in the above Examples 2 to 6 (Production Examples) , Reference Example 5 (Production Examples) and Comparative Examples 2 to 5 (Production Examples) is used as a raw material oil, and a straight-run gas oil having the following properties: Was evaluated as follows.
That is, first, the catalyst was charged into a high-pressure flow reactor to form a fixed bed type catalyst bed, and pretreated under the following conditions.
Next, a mixed liquid of the raw material oil and the hydrogen-containing gas heated to the reaction temperature is introduced from the upper part of the reaction apparatus, and the desulfurization reaction proceeds under the following conditions. The product oil was separated from the bottom and separated with a gas-liquid separator.

《Catalyst pretreatment conditions》
Sulfurization of catalyst: Liquid sulfidation with raw material oil was performed.
Pressure (hydrogen partial pressure): 4.9 MPa
Atmosphere: Hydrogen and raw material oil (liquid space velocity 1.5 hr ⁻¹ , hydrogen / oil ratio 200 m ³ (normal) / kl)
Temperature: Introduce hydrogen and raw oil at room temperature of about 22 ° C, heat up at 20 ° C / hr, maintain at 300 ° C for 24 hr, then heat up to reaction temperature of 340 ° C at 20 ° C / hr

<< Hydrogenation reaction conditions >>
Reaction temperature: 340 ° C
Pressure (hydrogen partial pressure): 4.9 MPa
Liquid space velocity: 1.0 hr ⁻¹
Hydrogen / oil ratio: 200 m ³ (normal) / kl

<Raw material properties>
Oil type: Middle East straight-run gas oil density (15/4 ° C): 0.8588
Distillation properties: initial boiling point 230.0 ° C, 50% point 310.0 ° C, 90% point 355.0 ° C, end point 374.5 ° C
Sulfur component: 1.41% by mass
Nitrogen component: 210 mass ppm
Kinematic viscosity (30 ° C.): 6.191 cSt

The desulfurization activity of each catalyst was analyzed by the following method.
The reaction apparatus is operated under the above reaction conditions, and after 6 days, the product oil is collected, and the desulfurization reaction rate constant (ks) is obtained from the sulfur content of the product oil, the sulfur content of the raw material oil, and the liquid space velocity. It was. The method for obtaining this ks value is shown below.
The constant of the reaction rate equation that obtains the reaction order of 1.2 with respect to the reduction amount of the sulfur content (Sp) of the product oil is defined as the desulfurization reaction rate constant (ks). The higher the reaction rate constant, the better the desulfurization activity.
Desulfurization reaction rate constant = 1 / (1.2-1) × [1 / (Sp) (1.2-1) −1 / (Sf) (1.2-1)] × (LHSV)
In the formula, Sf: sulfur content of feedstock oil (mass%)
Sp: Sulfur content (mass%) in reaction product oil
LHSV: Liquid space velocity (h-1)
Desulfurization relative activity (%) = desulfurization reaction rate constant / desulfurization reaction rate constant of catalyst c of Comparative Example 2 × 100
Table 9 shows the desulfurization relative activities when the sulfur content of the product oil, the desulfurization reaction rate constant, and the reaction rate constant of the catalyst c are set to 100 as the evaluation results of the catalysts E to J and cf.

Reference example 6 (reproduction example)
The same regenerated catalyst C as in Reference Example 2 was used.

Reference example 7 (reproduction example)
9.38 g of cobaltous citrate and 16.35 g of molybdophosphoric acid were added to 20.2 g of ion-exchanged water, heated to 80 ° C. and stirred for 10 minutes to obtain an impregnation solution.
Into the eggplant-shaped flask, 30.0 g of the inorganic oxide carrier of the same phosphorus oxide-zeolite-alumina composite as prepared in Example 3 was added, and the total amount of the above impregnating solution was added thereto. Was added with a pipette and soaked at about 25 ° C. for 3 hours. After that, it was air-dried in a nitrogen stream, and dried in a muffle furnace in an air stream / atmospheric pressure / 120 ° C. for about 16 hours.
Thereafter, the catalyst was used and treated in the same manner as in Reference Example 2 to obtain a regenerated catalyst K. The chemical composition of the obtained regenerated catalyst K is shown in Table 10, and the physical properties are shown in Table 11.

Reference example 8 (reproduction example)
9.43 g of cobaltous citrate and 17.07 g of molybdophosphoric acid were added to 24.3 g of ion-exchanged water, heated to 80 ° C. and stirred for 10 minutes to obtain an impregnation solution.
Into the eggplant-shaped flask, 30.0 g of the same phosphor oxide-silica-alumina composite inorganic oxide carrier as prepared in Example 4 was added, and the total amount of the impregnation solution was added thereto. Was added with a pipette and soaked at about 25 ° C. for 3 hours. After that, it was air-dried in a nitrogen stream, and dried in a muffle furnace in an air stream / atmospheric pressure / 120 ° C. for about 16 hours.
Thereafter, the regenerated catalyst L was obtained by using and treating in the same manner as in Reference Example 2 . The chemical composition of the obtained regenerated catalyst L is shown in Table 10, and the physical properties are shown in Table 11.

Reference example 9 (reproduction example)
To 26.5 g of ion-exchanged water, 9.44 g of cobaltous citrate and 1.90 g of phosphoric acid (85% aqueous solution) were added, heated to 80 ° C. and stirred for 10 minutes. Next, 17.29 g of molybdophosphoric acid was added and dissolved, and stirred at the same temperature for 15 minutes to prepare a solution for impregnation.
Into the eggplant-shaped flask, 30.0 g of the same inorganic oxide support of γ-alumina as prepared in Example 5 was added, and the whole amount of the above impregnation solution was added thereto with a pipette. Immersion was performed at about 25 ° C. for 3 hours. After that, it was air-dried in a nitrogen stream, and dried in a muffle furnace in an air stream / atmospheric pressure / 120 ° C. for about 16 hours.
Then, it used and processed like the reference example 2, and the reproduction | regeneration catalyst M was obtained. The chemical composition of the obtained regenerated catalyst M is shown in Table 10, and the physical properties are shown in Table 11.

Reference example 10 (reproduction example)
The same regenerated catalyst D as in Reference Example 3 was used.

Reference example 11 (reproduction example)
The same regenerated catalyst b as in Reference Example 4 was used.

Reference example 12 (reproduction example)
In Reference Example 2 , regenerated catalyst g was obtained in the same manner as in Reference Example 2 , except that instead of citric acid, the amount of phosphoric acid described in Table 10 was impregnated. The chemical composition of the obtained regenerated catalyst g is shown in Table 10, and the physical properties are shown in Table 11.

《Hydroprocessing of straight run diesel oil》
Direct distillation having the same properties as those used in the evaluation of the catalyst obtained in Example 2 above (Production Example) using the hydrodesulfurization activity of the catalyst obtained in Reference Examples 6 to 12 (Regeneration Example) as a raw material oil Evaluation was performed in the same manner as the evaluation of the catalyst obtained in Example 2 above (Production Example) using light oil. Table 12 shows the desulfurization relative activity when the sulfur content of the product oil of each catalyst, the desulfurization reaction rate constant, and the reaction rate constant of the catalyst b are set to 100 as the evaluation results.

<Forced deterioration test>
Example 7
A forced deterioration test was conducted using the same catalyst E as in Example 2 . In the same manner as the evaluation of the catalyst obtained in Example 2 etc. (Production Example), the hydrogenation treatment of straight-run gas oil was evaluated, the reaction temperature was increased to 380 ° C., and the catalyst was forcibly deteriorated over 4 days. Again, the reaction temperature was returned to 340 ° C. and the hydrodesulfurization activity was evaluated.

Example 8
A forced deterioration test was conducted in the same manner as in Example 7 using the same catalyst F as in Example 3 .

Comparative Example 6
A forced deterioration test was conducted in the same manner as in Example 7 using the same catalyst c as in Comparative Example 2 .

As an evaluation result, Table 13 shows the desulfurization relative activity when the sulfur content of the product oil after forced deterioration of the catalysts E, F, and c, the desulfurization reaction rate constant, and the reaction rate constant of the catalyst c are set to 100.
By performing the forced deterioration test, the heat resistance and catalyst life of the catalyst can be evaluated. If the catalysts E and F according to the production method of the present invention are used, the catalyst has a high desulfurization activity even after being subjected to a heat history, so that it is determined that the catalyst is heat resistant and has a long life. it can.

  As is clear from the above results, the catalyst produced according to the present invention provides an excellent desulfurization activity and a catalyst capable of long-term operation. Moreover, the catalyst regenerated by the present invention exhibits excellent desulfurization activity.

Claims (1)

10-40 mass% of at least one selected from Periodic Table Group 6 metal and at least one selected from Periodic Table Group 8 metal on the basis of catalyst and oxide conversion on the inorganic oxide support 1-15 mass%, the process of containing phosphorus so that it may become 0.5-8 mass%,
A step of firing the inorganic oxide after the above step at 400 to 550 ° C .;
An organic acid is supported on the fired product using the organic acid solution so that the molar ratio of [organic acid ] / [group 8 metal of the periodic table] is 0.2 to 1.2. Process,
And a process for drying the supported calcined product at 200 ° C. or lower, and a method for producing a hydrocarbon oil hydrotreating catalyst.