JP4545328B2 - Method for producing hydrotreating catalyst for hydrocarbon oil and hydrotreating method for hydrocarbon oil - Google Patents

Description

【００５１】
〔直留軽油の水素化処理反応〕
上記の実施例及び比較例で調製した触媒を用い、以下の要領にて、下記性状の直留軽油の水素化処理を行った。
先ず、触媒を高圧流通式反応装置に充填して固定床式触媒層を形成し、下記の条件で前処理した。
次に、反応温度に加熱した原料油と水素含有ガスとの混合流体を、反応装置の上部より導入して、下記の条件で水素化反応を進行させ、生成油とガスの混合流体を、反応装置の下部より流出させ、気液分離器で生成油を分離した。
【００５２】
触媒の前処理条件：
圧力 ；常圧
雰囲気；硫化水素（５％）／水素ガス流通下
温度 ；１５０℃にて０．５ｈｒ維持、次いで３５０℃にて１ｈｒ維持のステップ昇温
【００５３】
【表２】
水素化反応条件：
反応温度 ；３６０、３６５℃
圧力（水素分圧) ；４．９Ｍｐａ
液空間速度 ；１．０ｈｒ^−１
水素／オイル比 ；２５０ｍ^３（ｎｏｒｍａｌ）／ｋＬ
【００５４】
【表３】
原料油の性状：
油種 ；中東系直留軽油
比重（１５／４℃）；０．８５６７
蒸留性状 ；初留点が２０３．０℃、５０％点が３１５．５℃、９０％点が３７１．０℃、終点が３８９．０℃
硫黄成分 ；１．３６４質量％
窒素成分 ；１５０ｐｐｍ
動粘度（＠３０℃）；６．６０８ｃＳｔ
流動点 ；５．０℃
くもり点 ；６．０℃
セタン指数 ；５７．１
セイボルトカラー ；−１０
ＡＳＴＭ色 ；０．５
アニリン点 ；７４．３℃
【００５５】
反応結果については、以下の方法で解析した。
３６０℃、３６５℃で反応装置を運転し、６日経過した時点で生成油を採取し、その性状を分析した。
〔１〕脱硫率（ＨＤＳ）（％）
原料中の硫黄分を脱硫反応によって硫化水素に転換することにより、原料油から消失した硫黄分の割合を脱硫率と定義し、原料油及び生成油の硫黄分析値から以下の式により算出した。
〔２〕脱硫反応速度定数（Ｋｓ）：
生成油の硫黄分（Ｓｐ）の減少量に対して、１．３次の反応次数を得る反応速度式の定数を脱硫反応速度定数（Ｋｓ）とする。
なお、反応速度定数が高い程、触媒活性が優れていることを示している。これらの結果は、表４の通りであった。
【００５６】
【数１】
脱硫率（％）＝〔（Ｓｆ−Ｓｐ）／Ｓｆ〕×１００
脱硫反応速度定数＝〔１／（Ｓｐ）^{１．３−１}−１／（Ｓｆ）^{１．３−１}〕×（ＬＨＳＶ）
式中、Ｓｆ：原料油中の硫黄分（質量％）
Ｓｐ：反応生成油中の硫黄分（質量％）
ＬＨＳＶ：液空間速度（ｈｒ^−１）
比活性（％）＝
各脱硫反応速度定数／比較触媒ａの脱硫反応速度定数×１００
【００５７】
【表４】

【００５８】
表４から判るように、本発明の製造法による触媒を用いれば、超深度脱硫領域を容易にクリアーできることがわかる。
【００５９】
以上の結果から明らかなように、本発明により製造した触媒は、従来の軽油水素化処理の場合とほぼ同じ水素分圧や反応温度等の条件下で、超深度脱硫領域での軽油の脱硫反応に対して、極めて優れた活性を有することが判る。
【００６０】
【発明の効果】
以上詳述したように、本発明によれば、次のような効果を奏することができる。
（１）高い脱硫活性を有するため、軽油中の硫黄分の含有率を大幅に低減させることができる。
（２）反応条件を従来の水素化処理の際の反応条件とほぼ同じとすることができるため、従来の装置を大幅改造することなく転用できる。
（３）硫黄含有量の少ない軽油基材を、容易に供給することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a hydrotreating catalyst for hydrocarbon oils, and a hydrotreating method for hydrocarbon oils using the catalyst produced by the production method, and in particular, when hydrotreating light oil, Method for producing catalyst having excellent activity capable of significantly reducing sulfur content in light oil as compared with conventional use of this type of catalyst, and hydrotreating method using catalyst produced by this production method And about.
[0002]
[Technical background]
In recent years, quality control values for diesel oil have been stricter globally in order to improve the air environment. In some Nordic countries, the quality regulations for diesel oil have already been reduced to 50 ppm for sulfur and 5% for aromatics. The tightening of regulations is starting, and such tightening of regulations is expected to become even stricter in the future. In Japan as well, regulations for light oil are expected to be tightened to 50 ppm or less in the near future.
The sulfur content in diesel oil may adversely 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 a countermeasure for exhaust gas. It is the first target for stricter regulations.
[0003]
For the above reasons, there is a demand for further reduction of sulfur in light oil, and further improvement of conventional deep desulfurization technology and ultra-deep desulfurization technology is required.
In the ultra-deep desulfurization of light oil, how to efficiently remove heavy non-desulfurization sulfur compounds of 4,6-dimethyldibenzothiophene (4,6-DMDBT) or more is an issue.
The reason why these substances are not easily desulfurized is thought to be because steric hindrance occurs when they contact the active site of the catalyst because the position of the alkyl substituent is in the vicinity of the sulfur atom.
Therefore, in order to efficiently perform the desulfurization reaction in the ultra-deep desulfurization region, a catalyst that efficiently proceeds the desulfurization reaction of these substances having steric hindrance to the desulfurization active site is designed and these catalysts are used. In other words, how to design a desulfurization process using these catalysts is an important issue.
[0004]
Moreover, in the global economic situation including Japan in recent years, there is an urgent need to design a catalyst or process that can carry out the above ultra-deep desulfurization at a lower cost.
[0005]
Under such circumstances, development of an ultra-deep desulfurization technology that significantly removes sulfur content in light oil is being emphasized.
As a technique for reducing the sulfur content in light oil, usually, the operating conditions of hydrodesulfurization, for example, the reaction temperature, the liquid space velocity, and the like are harsh.
However, when the reaction temperature is raised, carbonaceous matter is deposited on the catalyst and the activity of the catalyst is rapidly reduced.If the liquid space velocity is lowered, the desulfurization ability is improved, but the purification treatment capacity is lowered. Need to expand the scale of
Moreover, such severe operating conditions also have an adverse effect on properties such as hue and storage stability.
Therefore, the best way to achieve ultra-deep desulfurization of light oil without harsh operating conditions is to develop a catalyst with significantly superior desulfurization activity.
[0006]
The conventional desulfurization level (product oil sulfur content 0.2 to 0.05 mass%) can be easily achieved with the current desulfurization catalyst / desulfurization technology. 0.005% by mass or less) becomes abruptly difficult due to substances that cause steric hindrance such as 4,6-DMDBT.
[0007]
Therefore, in order to efficiently perform the desulfurization reaction in the deep desulfurization region, the desulfurization reaction of the substance having steric hindrance to these desulfurization active points is efficiently advanced.
1) increase the number of active points of the catalyst,
2) Increase desulfurization activity per active metal amount,
Therefore, it is necessary to prepare a fine chemical catalyst.
[0008]
Currently, industrially used desulfurization catalysts are CoO—MoO ₃ / A1 ₂ O ₃ catalyst and NiO—MoO ₃ / A1 ₂ O ₃ catalyst. Under the hydrotreating conditions of light oil, the CoO-MoO ₃ / A1 ₂ O ₃ catalyst exhibits a higher desulfurization activity than the NiO-MoO ₃ / A1 ₂ O ₃ catalyst, and is therefore often used as a desulfurization catalyst for light oil. Yes.
[0009]
OBJECT OF THE INVENTION
In view of the above points, an object of the present invention is to provide a method for producing a hydrotreating catalyst that can desulfurize hydrocarbon oil, particularly straight-run gas oil, to a sulfur content of 50 ppm or less.
Furthermore, the objective of this invention is providing the method of hydrotreating hydrocarbon oil, especially a light oil fraction with high efficiency using the catalyst manufactured by the said manufacturing method .
[0010]
SUMMARY OF THE INVENTION
That is, the method for producing the hydrotreating catalyst of the present invention includes any of alumina greater than 80% by mass and 99.5% by mass or less, and zeolite of 0.5% by mass or more and less than 20% by mass , boria, silica, zirconia. A first solution containing a Group 6 metal salt of the periodic table on a composite oxide support having at least one of the above, so that the Group 6 metal becomes 10 to 30% by mass in terms of catalyst and oxide. impregnating carried on, after the drying and baking, the periodic table group 8 metal salts, a second solution comprising a ethylene glycol, catalysts criteria, in terms of oxide, a group said 8 metal is 1 to 15 It is characterized in that it is impregnated and supported so as to be in mass% and dried .
According to this production method, highly active desulfurization active sites (Co—Mo—S phase, Ni—Mo—S phase, etc.) can be precisely controlled. As a result, the desulfurization reaction proceeds efficiently and the reaction conditions are severe. Therefore, it is possible to obtain a high-performance desulfurization catalyst that can easily achieve an ultra-deep desulfurization reaction.
Further, the hydrotreating method of the present invention comprises a sulfur content in the presence of the catalyst produced by the above production method , at a hydrogen partial pressure of 3 to 8 MPa, 300 to 420 ° C., a liquid space velocity of 0.3 to 5 hr ^−1. It is characterized by carrying out a catalytic reaction of a gas oil fraction containing.
[0011]
As the target oil of the present invention, for example, light oil fractions such as straight-run gas oil, catalytic cracking gas oil, pyrolysis gas oil, hydrotreated gas oil, desulfurized gas oil, and vacuum distilled gas oil (VGO) are suitable.
Typical examples of properties of these feedstock oils include those having a boiling range of 150 to 450 ° C. and a sulfur content of 5% by mass or less.
[0012]
Various aluminas such as α-alumina, β-alumina, γ-alumina, and δ-alumina can be used as the alumina in the composite oxide support of the catalyst of the present invention, but the alumina is porous and has a high specific surface area. Of these, γ-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, ⁻ , Fe ₂ O ₃ , Na ₂ O <0.1% by mass in terms of components.
[0013]
The component to be combined with alumina is at least one of zeolite, boria, silica, and zirconia.
Among these, zeolite has an average particle size of about 2.5 to 6 μm, preferably about 3 to 5 μm, more preferably about 3 to 4 μm as measured by an electron micrograph.
Further, the ratio of the zeolite having a particle diameter of 6 μm or less to the whole zeolite particles is about 70 to 98%, preferably about 75 to 98%, more preferably about 80 to 98%.
Such characteristics of zeolite are essential for precise control of the pore diameter in order to facilitate the diffusion of the difficult-to-desulfurize substance into the pores. For example, the average particle size is too large or the large particle size is large. In the process of preparing a composite oxide support, the shrinkage rate of alumina and zeolite during heating and firing differs due to differences in the amount of adsorbed water and crystallinity between the alumina and zeolite during the preparation of the composite oxide support. A relatively large meso or macropore is formed as a hole.
These large pores not only reduce the surface area, but also easily disperse the metal components that become catalyst poisons when processing residual oil, resulting in desulfurization, denitrification and decomposition. Reduce activity.
[0014]
In the present invention, as the zeolite, faujasite X type zeolite, faujasite Y type zeolite, β zeolite, mordenite type zeolite, ZSM type 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-5, TS-1, TS-2 etc. Y-type zeolite, stabilized Y zeolite, and β zeolite are particularly preferable.
Further, the zeolite is preferably a proton type.
As the above boria, silica, and zirconia, those generally used as a carrier component of this type of catalyst can be used.
[0015]
Said zeolite, a boria, a silica, and a zirconia can be used individually or in combination of 2 types or more, respectively.
The compounding amount of these components is about 0.5% by mass or more and less than 20% by mass with respect to more than about 80% by mass of alumina and 99.5% by mass or less in the composite oxide support, preferably about 85 to 85% by mass of alumina. It is about 0.5-10 mass% with respect to 99.5 mass%, More preferably, it is about 0.5-10 mass% with respect to about 90-99.5 mass% of alumina.
If these components are too little or too much, the control of the pore diameter of the composite oxide support will be insufficient, and if it is too little, the Bronsted acid point and Lewis acid point of the composite oxide support will not be sufficiently imparted. If the amount is too large, Mo cannot be highly dispersed.
[0016]
The specific surface area, pore volume, and average pore diameter of the composite oxide support are not particularly limited, but in order to obtain a catalyst having high hydrodesulfurization activity for light oil, the specific surface area is about 240 to 500 m ² / g, Preferably about 300-450 m ² / g, pore volume is about 0.55-0.9 ml / g, preferably about 0.65-0.8 ml / g, average pore diameter is about 60-120 mm, preferably about 65-90 mm is suitable.
[0017]
When the specific surface area is less than about 240 m ² / g, the dispersibility of the active metal is deteriorated, so that the catalyst has a low desulfurization activity.
When the specific surface area is larger than about 500 m ² / g, the pore diameter becomes extremely small, so that the catalyst diameter also becomes small. 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.
[0018]
When the pore volume is less than about 0.55 ml / g, a small amount of solvent enters the pore volume when the catalyst is prepared by the usual 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 surface area of the support is reduced, which is the main cause of desulfurization performance deterioration.
When the pore volume is larger than about 0.9 ml / g, the specific surface area becomes extremely small, the dispersibility of the active metal is deteriorated, and the catalyst has a low desulfurization activity.
[0019]
When the average pore size is less than about 60 mm, the pore size of the catalyst supporting the active metal is also small. When the pore diameter of the catalyst is small, the diffusion of the sulfur compound into the catalyst pores becomes insufficient, and the desulfurization activity decreases.
When the average pore diameter is larger than about 120 mm, the specific surface area becomes small. When the specific surface area is small, the dispersibility of the active metal is deteriorated and the catalyst has a low desulfurization activity.
[0020]
Examples of the Group 6 metal of the periodic table supported on the composite oxide carrier include molybdenum and tungsten, and preferably molybdenum.
Examples of Group 6 metal salts of the periodic table include molybdenum trioxide, molybdophosphoric acid, ammonium molybdate, molybdic acid, and the like.
Examples of the Group 8 metal of the periodic table include cobalt and nickel.
Examples of Group 8 metal salts of the periodic table include carbonates, acetates, nitrates, sulfates and chlorides, with carbonates and acetates being preferred, and carbonates being more preferred.
[0021]
The solvent for dissolving each of the above supported components is not particularly limited in the first solution and the second solution, and various solvents can be used, for example, water, alcohols, ketones, Aromatics etc. are mentioned, Preferably they are water, acetone, benzene, toluene, xylene, tetrahydrofuran, dioxane, etc., Especially preferably, it is water.
[0022]
In the first solution, phosphorus can be added when the group 6 metal compound of the periodic table has insufficient solubility in a solvent.
Examples of the phosphorus source include various phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, and orthophosphoric acid is particularly preferable.
[0023]
In the first solution, the content of the Group 6 metal in the periodic table dissolved in the solvent is about 10 to 30% by mass, preferably about 16 to 28% by mass in terms of catalyst and oxide. It is.
If the Group 6 metal of the periodic table is less than about 10% by mass, it is not sufficient to develop the effect due to the Group 6 metal of the Periodic Table, and if it exceeds about 30% by mass, the Group 6 of the Periodic Table is used. Not only the metal dispersibility is deteriorated due to the metal aggregation, but also the catalytic activity is not improved due to exceeding the limit of the active metal content to be efficiently dispersed, or the catalyst surface area is greatly reduced.
[0024]
In the present invention, in the second solution, it is important to use an organic compound having at least one of a hydroxyl group, an ether bond, a carboxyl group, and an amino group together with the Group 8 metal compound of the periodic table. It is.
These organic compounds include citric acid, malic acid, tartaric acid, malonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriamine, diammoniumethylenediaminetetraacetic acid, tris (2-aminoethyl) amine, triethylenetetramine, ethylene glycol, propylene Glycol, diethylene glycol, trimethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, glycerin, trimethylolethane, trimethylolpropane, molecular weight 200-1000 polyethylene glycol, polyp Propylene glycol, methoxy acetic acid, ethylene carbonate.
The amount of the organic compound used is not particularly limited, but in general, [organic compound] / [Group 6 metal of the periodic table + Group 8 metal of the periodic table] is about 0.02 to 2 in terms of molar ratio. It is suitable to be.
[0025]
In the second solution, the content of the Group 8 metal in the periodic table dissolved in the solvent is about 1 to 15% by mass, preferably about 3 to 8% by mass in terms of catalyst and oxide. It is.
When the group 8 metal of the periodic table is less than about 1% by mass, the active sites belonging to the group 8 metal of the periodic table cannot be obtained sufficiently, and when it exceeds about 15% by mass, the group 8 metal compound of the periodic table The agglomeration of the active metal not only deteriorates the dispersibility of the active metal, but is also an inert precursor such as Co ₃ O ₄ species, NiO species, etc. (Co ₉ S ₈ species, Ni ₃ S ₂ after catalyst sulfidation and during hydrotreatment) The present invention produces Co spinel species, Ni spinel species, and the like incorporated in the lattice of the carrier, so that the catalytic ability is not improved and the catalytic ability is decreased.
[0026]
In the above-described contents of the periodic table group 8 metal and the periodic table group 6 metal, the optimum mass ratio of the active group periodic group 8 metal to the periodic table group 6 metal is the oxide equivalent. The value of [Group 8 metal of the periodic table] / [Group 8 metal of the periodic table + Group 6 metal of the periodic table] is about 0.1 to 0.25.
When the mass ratio of the Group 8 metal of the periodic table to the Group 6 metal of the periodic table is less than about 0.1 in the above value, a Co—Mo—S phase, a Ni—Mo—S phase, etc. that are considered as active sites for desulfurization Cannot be produced sufficiently and the desulfurization activity is not improved. If it is greater than about 0.25, useless Co species and Ni species (Co ₉ S ₈ species, Ni ₃ S ₂ species, Co spinel species and Ni spinel species incorporated into the lattice of the support) that are not involved in the activity are present. And the catalytic activity is reduced.
[0027]
If the amount of the solvent used is too small for both the first solution and the second solution, the support cannot be sufficiently impregnated. If the amount is too large, the dissolved active metal will not be impregnated on the support. Since it adheres to the edge of the container and the desired carrying amount cannot be obtained, it is usually about 50 to 150 g with respect to about 100 g of the carrier in each of the first solution and the second solution, Preferably it is about 50-90g.
[0028]
In the present invention, the above components are dissolved in the solvent to prepare first and second solutions for impregnation. The temperature at this time is about 0 ° C. for both the first and second solutions. If the temperature is within this range, the above components can be dissolved well in the solvent.
[0029]
The first solution and the second solution for impregnation thus prepared are impregnated into the above-mentioned carrier. At this time, first, the first solution is impregnated and dried or calcined or not calcined. Then, the second solution is impregnated and dried. By this operation, each component in the solution is supported on the carrier.
The impregnation conditions may be various conditions for both the first solution and the second solution. Usually, the temperature is more than about 0 ° C. and less than about 100 ° C., preferably about 10 to about 50 ° C., More preferably, about 15 to 30 ° C. is suitable, and the impregnation time is about 15 minutes to 5 hours, preferably about 20 minutes to 4 hours, more preferably about 30 minutes to 3.5 hours. If the temperature of both the first solution and the second solution is too high, drying occurs during the impregnation and the degree of dispersion is biased. Both the first and second solutions are preferably stirred during the impregnation.
[0030]
Drying after the first solution impregnation can be performed by various drying methods such as air drying, hot air drying, heat drying, freeze drying and the like.
Moreover, when firing after drying, it can be performed by a firing method using various apparatuses such as a rotary kiln, electric furnace, muffle furnace, alundum bath, electric tubular furnace, etc., but usually in a rotary kiln or electric furnace. It is preferable to carry out in an air flow or in a muffle furnace.
[0031]
The firing temperature may be appropriately selected and determined according to these firing methods. However, when firing in an air furnace or in a muffle furnace, the firing temperature is about 200 to 800 ° C., preferably about 300 to 700 ° C. More preferably, about 450 to 650 ° C is suitable. If the calcination temperature is too low, the active metal is not sufficiently supported, and poisonous substances remain. If it is too high, sintering will occur. The baking time is about 2 to 10 hours, preferably about 3 to 5 hours.
[0032]
After the impregnation of the second solution, the moisture is removed to some extent (so that the LOI << Loss on ignition >> is about 50% or less) at room temperature to about 80 ° C, in a nitrogen stream, in an air stream or in a vacuum, and then dried Dry in an air stream at about 80 to 200 ° C. for about 10 minutes to 30 hours.
[0033]
The catalyst obtained by the production method according to the present invention as described above preferably has the following values for the specific surface area, pore volume and average pore diameter in order to increase the hydrodesulfurization activity for light oil.
The specific surface area is about 220 to 300 m ² / g, preferably about 230 to 270 m ² / g as measured by a nitrogen adsorption method (BET method). If it is less than about 220 m ² / g, the dispersibility of the active metal is deteriorated, resulting in a catalyst with low desulfurization activity. If it is more than about 300 m ² / g, the pore diameter becomes extremely small, so the pore diameter of the catalyst also becomes small. In the hydrotreatment, the sulfur compound is not sufficiently diffused into the catalyst pores, and the desulfurization activity is reduced.
[0034]
The pore volume is about 0.4 to 0.6 m1 / g, preferably about 0.45 to 0.55 m1 / g, measured by mercury porosimetry. If it is less than about 0.4 m1 / g, the diffusion of sulfur compounds in the catalyst pores will be insufficient during the hydrotreatment, resulting in insufficient desulfurization activity. The specific surface area becomes extremely small, the dispersibility of the active metal is lowered, and the catalyst has a low desulfurization activity.
[0035]
The average pore diameter is about 65 to 95 mm, preferably about 70 to 90 mm in terms of pore distribution measured by mercury porosimetry. If it is less than about 65 mm, the reactants are difficult to diffuse into the pores, so the desulfurization reaction does not proceed efficiently. If it is greater than about 95 mm, the diffusibility in the pores is good, but the surface area in the pores decreases Therefore, the effective specific surface area of the catalyst is reduced and the activity is lowered.
In order to increase the effective number of pores satisfying the above-mentioned pore conditions, the pore size distribution of the catalyst, that is, the proportion of pores having an average pore size of about ± 15 mm is preferably about 75% or more, preferably Is about 80% or more.
Moreover, the pore distribution is preferably monomodal. If the pore size distribution of the catalyst is not sharp, pores that do not participate in activity increase and desulfurization activity decreases.
[0036]
The catalyst shape is not particularly limited, and various shapes usually used for this type of catalyst, for example, a cylindrical shape, a trilobal type, a four-leaf type, and the like can be adopted. The size of the catalyst is usually preferably about 1 to 2 mm in diameter and about 2 to 5 mm in length.
The mechanical strength of the catalyst is preferably about 21 bs / mm or more in terms of side surface breaking strength (SCS << Side crash strength >>). If the SCS is smaller than this, the catalyst charged in the reactor is destroyed, a differential pressure is generated in the reactor, and the hydrotreating operation cannot be continued.
The close-packed bulk density (CBD) of the catalyst is preferably about 0.6 to 1.2.
[0037]
The distribution state of the active metal in the catalyst is preferably a uniform type in which the active metal is uniformly distributed in the catalyst.
[0038]
The hydrotreating method of the present invention comprises a gas oil fraction containing the above catalyst and a sulfur compound under conditions of a hydrogen partial pressure of about 3 to 8 MPa, about 300 to 420 ° C., and a liquid space velocity of about 0.3 to 5 hr ^−1. Is desulfurized by bringing the sulfur compounds into contact with each other to reduce sulfur compounds including hardly desulfurizable sulfur compounds in the gas oil fraction.
The sulfur content of the product oil obtained by the method of the present invention is 50 ppm or less, and the sulfur content can be reduced as compared with the prior art.
[0039]
In order to carry out the hydrotreating method of the present invention on a commercial scale, a fixed bed, moving bed or fluidized bed type catalyst layer of the catalyst of the present invention is formed in the reactor, and the feedstock is introduced into the reactor. The hydrogenation reaction may be performed under the above conditions.
Most commonly, a fixed bed catalyst layer is formed in the reactor, feedstock is introduced into the top of the reactor, the fixed bed is passed from bottom to top, and the product is drained from the top of the reactor. Is.
[0040]
The hydrotreating method of the present invention may be a single-stage hydrotreating method performed by filling the catalyst of the present invention into a single reactor, or multistage continuous hydrogen performed by filling several reactors. It may be a processing method.
[0041]
Note that the catalyst of the present invention is activated by sulfiding in a reactor before use (that is, prior to performing the hydrotreatment method of the present invention).
This sulfidation treatment is conducted at about 200 to 400 ° C., preferably about 250 to 350 ° C. under a hydrogen atmosphere at normal pressure or higher, and a petroleum distillate containing sulfur compounds, dimethyl disulfide or disulfide. It is performed using a material added with a sulfurizing agent such as carbon or hydrogen sulfide.
[0042]
【Example】
Example 1
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 (silica / alumina mass ratio = 1/99, fine, 1/16 inch diameter). Pore volume 0.70 m1 / g, specific surface area 359 m ² / g, average pore diameter 70 mm).
A solution for impregnation was prepared by dissolving 9.81 g of ammonium paramolybdate in 19.6 g of ion-exchanged water.
In an eggplant-shaped flask, 30.0 g of the above silica-alumina composite carrier was added, and the entire amount of the above impregnation solution was added thereto with a pipette and immersed at about 25 ° C. for 3 hours.
Then, it air-dried in nitrogen stream, dried at 120 degreeC in the muffle furnace for about 1 hour, and baked at 500 degreeC for 4 hours.
On the other hand, a solution for impregnation was prepared by dissolving 7.77 g of cobalt nitrate hexahydrate and 2.49 g of ethylene glycol in 19.9 g of ion-exchanged water.
The fired product was put into an eggplant-shaped flask, and the whole amount of the impregnation solution was added thereto with a pipette and immersed at about 25 ° C. for 3 hours.
Thereafter, it was air-dried in a nitrogen stream and dried in a muffle furnace at 100 ° C. for about 24 hours to obtain Catalyst A.
[0043]
Example 2
A SHY zeolite powder having an SiO ₂ / A1 ₂ O ₃ molar ratio of 6 (average particle size of 3.5 μm, particle size of 6 μm or less is 87% of all zeolite particles) and alumina hydrate are kneaded, and after extrusion molding, A zeolite-alumina composite carrier of a columnar molded product having a diameter of 1/16 inch and calcined at 600 ° C. for 2 hours (zeolite / alumina mass ratio: 7/93, pore volume 0.69 m1 / g, specific surface area 374 m ² / g, An average pore diameter of 67 mm) was obtained.
A solution for impregnation was prepared by dissolving 11.4 g of molybdophosphoric acid and 1.17 g of phosphoric acid in 22.2 g of ion-exchanged water.
In an eggplant-shaped flask, 30.0 g of the above zeolite-alumina composite carrier was added, and the entire amount of the above impregnation solution was added thereto with a pipette and immersed at about 25 ° C. for 3 hours.
Then, it air-dried in nitrogen stream, dried at 120 degreeC in the muffle furnace for about 1 hour, and baked at 500 degreeC for 4 hours.
On the other hand, an impregnation solution was prepared by dissolving 8.09 g of cobalt nitrate hexahydrate and 2.58 g of ethylene glycol in 18.8 g of ion-exchanged water.
The fired product was put into an eggplant-shaped flask, and the whole amount of the impregnation solution was added thereto with a pipette and immersed at about 25 ° C. for 3 hours.
Then, it air-dried in nitrogen stream, and it was made to dry at 100 degreeC in a muffle furnace for about 24 hours, and the catalyst B was obtained.
[0044]
Example 3
Boria and alumina hydrate are kneaded, extruded, fired at 600 ° C. for 2 hours, and a boria-alumina composite support of a columnar molded product having a diameter of 1/16 inch (boria / alumina mass ratio = 2/98, fine Pore volume 0.71 m1 / g, specific surface area 363 m ² / g, average pore diameter 72 mm).
The same operation as in Example 1 was performed on 30.0 g of this boria-alumina composite carrier, whereby catalyst C was obtained.
[0045]
Example 4
Zirconia and alumina hydrate are kneaded, extruded and then fired at 600 ° C. for 2 hours to form a columnar shaped zirconia-alumina composite carrier (zirconia / alumina mass ratio = 2/98, finer) of 1/16 inch diameter. The pore volume was 0.69 m1 / g, the specific surface area was 348 m ² / g, and the average pore diameter was 70 mm.
The same operation as in Example 1 was performed on 30.0 g of this zirconia-alumina composite carrier, whereby catalyst D was obtained.
[0046]
Example 5
In Example 1, drying and calcination after impregnation with ammonium paramolybdate were carried out in the same manner as in Example 1 except that calcination was omitted, and Catalyst E was obtained.
[0047]
Comparative Example 1
A solution for impregnation was prepared by dissolving 3.31 g of cobalt carbonate, 11.41 g of molybdophosphoric acid and 1.17 g of orthophosphoric acid in 21.6 g of ion-exchanged water.
In an eggplant-shaped flask, 30.0 g of γ-alumina carrier (pore volume 0.69 m1 / g, specific surface area 364 m ² / g, average pore diameter 64 mm) was added, and the total amount of the above impregnation solution was added thereto. It was added with a pipette and soaked at about 25 ° C. for 1 hour.
Then, it air-dried in nitrogen stream, it was made to dry at 120 degreeC in a muffle furnace for about 1 hour, and it baked at 500 degreeC for 4 hours, and the catalyst a was obtained.
[0048]
Table 1 shows the elemental analysis values and physical property values of the catalysts obtained in the above Examples and Comparative Examples.
The method and analytical equipment used for the analysis of the catalyst are shown below.
[0049]
[1] Analysis of physical properties / specific surface area was measured by the BET method by nitrogen adsorption.
As the nitrogen adsorption apparatus, a surface area measuring apparatus (Bell Soap 28) manufactured by Nippon Bell Co., Ltd. was used.
-The pore volume, average pore diameter, and pore distribution were measured by mercury porosimetry.
As the mercury intrusion apparatus, a porosimeter (MICROMERITIC AUTO-PORE 9200: manufactured by Shimadzu Corporation) was used.
[0050]
[Table 1]

[0051]
[Hydrolysis reaction of straight-run gas oil]
Using the catalysts prepared in the above Examples and Comparative Examples, hydrogenation of straight run gas oil having the following properties was performed in the following manner.
First, the catalyst was filled into a high-pressure flow reactor to form a fixed bed catalyst layer, and pretreated under the following conditions.
Next, a mixed fluid of the raw material oil heated to the reaction temperature and the hydrogen-containing gas is introduced from the upper part of the reactor, and the hydrogenation reaction proceeds under the following conditions, and the mixed fluid of the product oil and the gas is reacted. The oil was discharged from the lower part of the apparatus, and the produced oil was separated by a gas-liquid separator.
[0052]
Catalyst pretreatment conditions:
Pressure; normal pressure atmosphere; temperature under hydrogen sulfide (5%) / hydrogen gas flow; step temperature increase of 150 ° C. for 0.5 hr and then 350 ° C. for 1 hr
[Table 2]
Hydrogenation reaction conditions:
Reaction temperature: 360, 365 ° C
Pressure (hydrogen partial pressure); 4.9 Mpa
Liquid space velocity: 1.0 hr ⁻¹
Hydrogen / oil ratio; 250 m ³ (normal) / kL
[0054]
[Table 3]
Raw oil properties:
Oil type: Specific gravity of Middle East straight gas oil (15/4 ° C); 0.8567
Distillation properties: initial boiling point 203.0 ° C, 50% point 315.5 ° C, 90% point 371.0 ° C, end point 389.0 ° C
Sulfur component: 1.364% by mass
Nitrogen component: 150 ppm
Kinematic viscosity (@ 30 ° C); 6.608 cSt
Pour point: 5.0 ° C
Cloudy point: 6.0 ℃
Cetane index; 57.1
Saybolt color -10
ASTM color; 0.5
Aniline point: 74.3 ° C
[0055]
The reaction results were analyzed by the following method.
The reactor was operated at 360 ° C. and 365 ° C., and when 6 days had passed, the product oil was collected and analyzed for its properties.
[1] Desulfurization rate (HDS) (%)
By converting the sulfur content in the raw material into hydrogen sulfide by a desulfurization reaction, the ratio of the sulfur content that disappeared from the raw material oil was defined as the desulfurization rate, and was calculated from the sulfur analysis values of the raw material oil and the product oil by the following formula.
[2] Desulfurization reaction rate constant (Ks):
The desulfurization reaction rate constant (Ks) is defined as a constant in the reaction rate equation that obtains the 1.3th order reaction order with respect to the reduction amount of the sulfur content (Sp) of the product oil.
The higher the reaction rate constant, the better the catalytic activity. These results are shown in Table 4.
[0056]
[Expression 1]
Desulfurization rate (%) = [(Sf−Sp) / Sf] × 100
Desulfurization reaction rate constant = [1 / (Sp) ^1.3-1 -1 / (Sf) ^1.3-1 ] × (LHSV)
In formula, Sf: Sulfur content (mass%) in raw material oil
Sp: Sulfur content (mass%) in reaction product oil
LHSV: Liquid space velocity (hr ⁻¹ )
Specific activity (%) =
Each desulfurization reaction rate constant / desulfurization reaction rate constant of comparative catalyst a × 100
[0057]
[Table 4]

[0058]
As can be seen from Table 4, the ultra-deep desulfurization region can be easily cleared by using the catalyst according to the production method of the present invention.
[0059]
As is clear from the above results, the catalyst produced according to the present invention is a desulfurization reaction of light oil in the ultra-deep desulfurization region under conditions such as hydrogen partial pressure and reaction temperature that are almost the same as those of conventional light oil hydrotreatment. On the other hand, it can be seen that it has extremely excellent activity.
[0060]
【The invention's effect】
As described above in detail, according to the present invention, the following effects can be obtained.
(1) Since it has a high desulfurization activity, the sulfur content in the light oil can be greatly reduced.
(2) Since the reaction conditions can be made substantially the same as those in the conventional hydrotreatment, the conventional apparatus can be diverted without significant modification.
(3) A light oil base material with a low sulfur content can be easily supplied.

Claims (2)

The composite oxide support having at least one of alumina greater than 80% by mass and 99.5% by mass or less and 0.5% by mass or more and less than 20% by mass of zeolite, boria, silica, zirconia, The first solution containing the Group 6 metal salt is impregnated and supported so that the Group 6 metal is 10 to 30 % by mass in terms of catalyst and oxide, dried, calcined, and periodic table. A second solution containing a Group 8 metal salt and ethylene glycol is impregnated and supported so that the Group 8 metal is 1 to 15 % by mass in terms of catalyst and oxide, and dried. A method for producing a hydrodesulfurization catalyst for hydrocarbon oil. In the presence of a catalyst produced by the method for producing a hydrodesulfurization catalyst for hydrocarbon oils according to claim 1 , at a hydrogen partial pressure of 3-8 MPa, 300-420 ° C., and a liquid space velocity of 0.3-5 hr ⁻¹ , A hydrotreating method for hydrocarbon oil, characterized by carrying out a catalytic reaction of a gas oil fraction containing sulfur.