[0001]The present invention, hydrotreating catalyst for removing sulfur content in the hydrocarbon oil in the presence of hydrogen, to a process for their preparation, and hydroprocessing process.　
BACKGROUND
[0002]Hydrotreating is the reaction proceeds under high temperature and pressure with a catalyst, the reaction conditions low, because the growing process economics by the low pressure below, the activity of the catalyst it is desired higher. There is something like the following as findings public regarding reduction temperature of molybdenum.
[0003]
　R. L. Reduction temperature of molybdenum in a stream of hydrogen of the catalyst according to Cordero of molybdenum supported on alumina or silica have been described to vary greatly depending on the carrier type and composition. However, not being added nickel or cobalt as the promoter, it is hard to say that knowledge as practical catalysts. In addition, the relationship between the nature and desulfurization activity because not mentioned, does not refer to reduction temperature optimum catalysts.
[0004]
　J. Escobar et al., Nickel on an alumina carrier, molybdenum, 384 ~ 403 ° C. As the reduction peak temperature attributable to the molybdenum in a stream of hydrogen unfired catalyst supporting phosphorus, there are two 539 ~ 576 ° C., the latter Write peaks revealed that greater than the former. However, although describes knowledge reduction peak temperature of uncalcined catalyst, to is not mentioned fired product catalyst, wherein the relationship between the reduction peak temperature and reduced profile and desulfurization activity of molybdenum on the composite oxide It has not been.
[0005]
　Patent Document 1, nickel, cobalt, molybdenum, a sulfide catalyst comprising a base metal element selected from the Periodic Table Group 8-10 such as tungsten, rhodium, palladium, from the periodic table Group 8-10 metal such as platinum by adding a noble metal selected, it has been reported to exhibit high hydrogenation performance by the use of spillover hydrogen. Further, according to the behavior to undergo reduction of the catalyst component as a reaction active sites, have a close relationship with the catalytic activity of hydrotreating, it is desirable reduction peak temperature of the catalyst in a stream of hydrogen is 500 ° C. or less It is. However, since using a noble metal, undesirable from the aspect of depletion of natural resources with the catalyst cost becomes expensive in comparison with the base metal.　
　Although mentioned findings for reducing the temperature of the molybdenum as described above have been reported, inexpensive excellent desulfurization performance, not readily proposed reproducing capable catalysts.
[0006]
　In addition to improving the energy efficiency and economy, light of environmental load reduction, there is a situation that increasingly use regenerated spent catalyst in refineries. In such a situation, the aim of performance of the catalyst, the conventional wisdom regarding the preparation of the alumina support is the following. In Patent Document 2, as a method for producing the catalytic combustion heat resistance alumina carrier, and pH adjusting agents preparation of alumina carrier prepared from boehmite sols with is disclosed, even when used in a high temperature atmosphere of more than 1000 ° C. effect of stably maintaining a high surface area is described. This finding, boehmite to be used is expected to be thinner and pH adjusted sol is rather unsuitable for somewhat complex industrial.
[0007]
　Patent Document 3, a manufacturing method of an alumina catalyst support with the alumina hydrate having a pseudo boehmite crystal structure is disclosed. In the manufacturing process of the alumina support, the alumina hydrate Water was added to kneading the plasticized product is plasticized, is with adjustable to any pseudoboehmite crystal size, whereby the alumina carrier having a desired pore size is described can be manufactured. This preparation method is for controlling the crystal size depending on the reaction temperature and reaction time of the plasticizing compound, often quality many skills sought to manage the properties is expected to be unstable.　
　In Patent Document 4, which is a manufacturing method of an alumina support using pseudoboehmite alumina powder is disclosed, this process is a process for preparing a high purity and high activity alumina catalyst support by adjusting the particle shape of the alumina raw material It is grasped that there is. In this process, expected by changing the mixing ratio of the two alumina raw material powder has been taken a technique of changing the aspect ratio of the particles, the adjustment to depend largely on its admixture with alumina raw material It is.
[0008]
　In Patent Document 5, .gamma.-alumina carrier cobalt, nickel, molybdenum, impregnated with polyethylene glycol as further organic additives on the catalyst was calcined by supporting an active metal such as tungsten, residual organic additives in the catalyst method for producing a hydrogenation catalyst, characterized by drying to such conditions has been reported. Such Depending such preparation of the catalyst, can be expected to promote the hydrodesulfurization reaction by residual organic additives. However, not only the carbonaceous derived while the organic additive also affects the stability of highly unstable performance during use, performance recovery rate refurbished spent catalyst is very poor, when the reproduction it is necessary to supplement the organic additive was destroyed.
[0009]
　Patent Document 6, as a method for producing a porous alumina, to one or more of aluminum hydroxide and / or alumina, the sol reaction with water and at least one monobasic acid or a temperature range of 250 ° C. or less added salt thereof by performing, to obtain an aqueous alumina gel and / or alumina gel, the aqueous alumina gel and / or alumina gel drying, the production process and firing is described. In Patent Document 5, oxygen-containing organics as pore controlling agent, but a technique that an inorganic polybasic acid, etc. is added to the alumina-containing mixture is described, additives are used in only one step, increase the catalytic performance It does not refer to adjustment of the OH groups of influence support surface. Further, the sol reaction falls ripening process is carried out at temperatures above 100 ° C. in a closed vessel, since the use of this process an autoclave (pressurized sealed container) is essential, in performing the industrially prepared economically it is hard to say that basis.　
　Patent Document 7, a manufacturing method of alumina hydrate fine particles, although the step of aging the alumina hydrate particles were added to the buffer material and deflocculating agents have been described, mention the crystalline alumina not.
[0010]
　Patent Document 8, at least 90% by weight As a method for producing highly active hydrodesulfurization catalyst boehmite to form a molded particles comprising, by heating treatment includes the step of converting the γ-alumina, essentially all and the amount is described as a gamma-alumina (gamma-alumina other than-alumina is less than 10% by weight). However, regulators of crystallinity only firing temperature.　
　Patent Document 9, phosphorus as inorganic composite oxide support - process for preparing a catalyst on a silica-alumina support have been disclosed. Give the phosphorus-containing alumina hydrate aluminum salts anxiety solution containing phosphate ions and the neutralizing agent are mixed to pH 6.5-9.5, obtained by washing the hydrate was the slurry and the silica sol are mixed, shaped, dried, carrier obtained by firing is used. This method of preparation is not described admixture with other elements not adjust the crystallite size of the alumina.　
　Patent Document 10, alumina, silica, titania, zirconia, diameter of oxide selected from zeolites have been described for the catalyst using granules carrier and the carrier of 2 ~ 7 mm. Other This granulate sectional transmission electron microscopy by point to 10,000 times shell-like concentrated layer was observed with magnification is observed, it is a granular hydrotreating catalyst carrier or the average pore diameter There is such that a relatively large 0.99 ~ 300 Å differs from this matter that mentioned as a feature.
[0011]
　Patent Document 11 discloses a carrier composed of alumina from the base Toshikatsu plurality of juxtaposed the aggregate, for a fixed bed reactor of a catalyst containing a total of 0.1 to 50 wt% of the active metal. Phosphorus, boron, and from the group consisting of silicon and halogens are used inorganic composite oxide support containing at least one additive element, a thin plate-like material piled state and needles form aggregates in some a carrier comprising said needles is characterized and surrounding stacking-like material of the thin plate-like material, to be simultaneously uniformly dispersed and between the thin plate material. Point is a carrier comprising agglomerates is significantly different from the present.
[0012]
　Patent Document 12, at least one metal oxide of group IVB of the Periodic Table of the Elements containing substantial amounts, discloses a method for producing and use thereof catalyst support contains silica. Mass ratio of the amount of silica containing the Group IVB metal oxide content and carriers are included between 5 and 70, it is characterized on a carrier mixed with titanium or zirconium in terms of containing silica. Carrier composition on this matter and different.
[0013]
　Patent Document 13 discloses a carrier containing titanium, a manufacturing method thereof, hydrogenation of hydrocarbon oil processing catalyst and the hydrotreating process using the same. Carriers are contained basic oxide is an oxide of titanium and rare earth metals on a refractory inorganic oxide and / or activated carbon, titanium are homogeneously supported on a refractory inorganic oxide and / or activated carbon it is a feature. However, a method of contacting the refractory inorganic oxide support containing titanium aqueous solution impregnation method, the complex industrial over process is often expected to be somewhat unsuitable.　
　Patent Document 14 and Patent Document 15, phosphorus-alumina, there is described a manufacturing method of high performance hydroprocessing catalyst using inorganic composite oxide support prepared by mixing phosphorus and titania. These in order to obtain excellent desulfurization performance and denitrogenation performance point of carbon derived from the organic acid catalysts criteria may include more than 2 wt% is a catalyst that has not been fired as a feature is a major feature. However, it is envisioned catalyst regeneration is difficult, while a high performance.
CITATION
Patent Document
[0014]
Patent Document 1: JP 2002-210362 Patent Publication
Patent Document 2: JP-A 07-256100 JP-
Patent Document 3: JP-A-07-155597 Publication
Patent Document 4: WO97 / 12670 Patent Publication No.
Patent Document 5: JP-A-8- 332385 JP
Patent Document 6: WO2001 / 056,951 discloses
Patent Document 7: JP 2014-133687 JP
Patent Document 8: WO2006 / 034,073 discloses
Patent Document 9: JP 2000-135437 JP
Patent Document 10: JP-11 -319554 JP
Patent Document 11: JP 2000-176288 JP
Patent Document 12: JP 2001-17860 JP
Patent Document 13: JP 2004-074148 JP
Patent Document 14: JP 2009-101362 Patent Publication
JP 15: JP 2013-027847 JP
Non-patent literature
[0015]
Non-Patent Document 1: R. L. Cordero et al, Applied Catalysis, 74 , 125-136 (1991)..
Non-Patent Document 2: J. Escobar et al, Applied Catalysis B:. Environmental, 88, 564-575 (2009).
Summary of the Invention
Problems that the Invention is to Solve
[0016]
　An object of the present invention is to provide an industrially high productivity maintained excellent desulfurization activity while, also hydrogenation of hydrocarbon oils which can reproduce a high-performance catalytic treatment catalysts and production method thereof . Another object is to provide a hydrotreating process of a hydrocarbon oil capable of removing sulfur content in the hydrocarbon oil at a high removal rate.　
Means for Solving the Problems
[0017]
　Hydrotreating catalyst for hydrocarbon oil of the invention,
and it is a, the following a or b a carrier composed mainly of (1) alumina,
a. consisting of 100% γ- alumina
b. Relative to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and the carrier is determined from the half bandwidth of the XRD diffraction spectrum (020) peak of pseudoboehmite alumina as a main component in the precursor and the crystallite diameter is 15 or more 40Å or less
(2) on the support, a first metal component is at least one of molybdenum and tungsten, cobalt and the second metal is at least one of nickel a component, and that but are supported,
(3) the content of the first metal component, the catalyst 100 parts by weight, 15 to 27 mass parts as an oxide equivalent, the second metal component content, relative to the catalyst 100 parts by weight, and from 2 to 7 parts by mass as the oxide
equivalent, (4) for a carrier of said a has a specific surface area of the catalyst is 200 ~ 320 m / G, the carrier of the b has a specific surface area of the catalyst is 180 ~ 320 m 2 and that / g, an average pore diameter of the catalyst as measured by mercury porosimetry is 50 ~ 110 Å, (5) an ignition loss of 5 and it is 2.0 wt% or less, (6) carbon derived from the organic acid, the catalyst 100 parts by weight, and not more than 2.0 parts by weight elemental basis, of (7) sulfide treated catalyst and that adsorbed amount of nitrogen monoxide is 8.0 ml / g or more,

　Characterized by comprising a.
[0018]
　For example, the carrier may consist of 100 parts by weight of γ- alumina crystallite size determined from the half value width of the XRD diffraction spectrum (020) peak of pseudoboehmite alumina is a precursor is less than 45 Å.
[0019]
　The method of the present invention to produce a hydrotreating catalyst for hydrocarbon oil according to the present invention is as follows.
[0020]
　The carrier, wherein (1) a carrier as described in a a (carrier comprising 100 parts by weight of γ- alumina),
obtained by mixing the aqueous solution of (A) a basic aluminum salt solution and an acidic aluminum salt a first aging step of aging the slurry containing alumina,
dehydrated aged slurry, comprising the steps of washing,
a second ripening stage of aging the slurry containing the object to be cleaned which was then washed,
then kneading the slurry the steps of concentrating,
the steps of molding the concentrate slurry was concentrated,
then molding was dried, including the steps of firing, a step of preparing a γ- alumina support,
(B) of molybdenum and tungsten at least one of a first metal component, were prepared and cobalt and the second metal component is at least one of nickel, and organic acid, an impregnation liquid containing the first gold A step of carrying the component and a second metal component to the γ- alumina carrier,
(C) the obtained in the steps (B), gamma said first metal component and second metal component is supported - obtaining a hydrotreating catalyst by heating the alumina support,
and having a.
[0021]
　Listed specific method of the present invention is not intended to limit the scope of the present invention.
[0022]
　In a second aging step in the step (A), adding a first organic compound to the slurry. Wherein the first organic compound is added in an amount of from 0.5 to 5.0 parts by weight for example based on alumina 100 parts by mass.　
　　Kneading the slurry in the step (A), step concentrated later, prior to the step of molding the concentrate, adding a second organic compound. The second organic compound is added in an amount of from 0.5 to 5.0 parts by weight for example based on alumina 100 parts by mass.　
　The organic compound is, for example organic acids, at least one kind of sugars.　
　Basic aluminum salt solution in the step (A) contains a carboxylic acid salt.　
　In the first ripening stage and a second maturation phase contained in the step (A), the alumina concentration is less than 20%, kneading the slurry in the step (A), in the step of concentration, alumina concentration above 20% it is.　
　The temperature of the heat treatment in the step (A) is at a temperature of 100 ~ 600 ° C..　
　Above described techniques is when the carrier corresponds to the (carrier consisting of 100 parts by weight of γ- alumina) which was a carrier according to a (1).
[0023]
　Next, when the carrier is equivalent to b of the (1), it lists a more detailed structure of a hydrotreating catalyst for hydrocarbon oil of the present invention. In this case the carrier, relative to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and carrier, XRD diffraction spectrum of pseudoboehmite alumina as a main component in the precursor (020) peak crystallite size determined from the half value width of 15 or more 40Å or less.
[0024]
　Inorganic composite oxide support, transmission Fourier transform infrared corresponding to acidic OH groups measured by the outside spectrophotometer 3674 ~ 3678Cm -1 to the absorbance Sa spectral peaks in the wave number range, corresponding to the basic OH groups ~ 3774Cm 3770 -1 wave number range of
the ratio Sb / Sa of the absorbance Sb spectral peaks that are in the range from 0.20 to 0.45.　
Inorganic composite oxide support,
a. The inorganic composite oxide support 100 weight parts, those containing phosphate phosphate conversion 5.0 parts by mass or less,
b. The inorganic composite oxide support 100 weight parts, those containing silicon in terms of silica 3.0 parts by weight or less,
c. The inorganic composite oxide support 100 weight parts, those containing more than 18.0 parts by mass of titanium titania terms,
d. The inorganic composite oxide support 100 weight parts, those containing less 9.0 parts by mass of zirconium oxide zirconia terms,
　at least corresponding one to one of the.　
Inorganic composite oxide support, the diffraction peak area showing the aluminum crystal structure attributed to a boehmite (020) plane measured from XRD diffraction spectrum P1, a diffraction peak area showing the crystal structure of γ- alumina (440) plane When P2, the ratio P2 / (P1 + P2) of P2 to the total value of P1 and P2 is 0.9 or more.
[0025]
　The method for producing a hydrocarbon oil hydroprocessing catalyst of the present invention (when the carrier corresponds to b of the (1)) is,
(D) a step of preparing an inorganic composite oxide support
(E) molybdenum and a first metal component is at least one of tungsten, and cobalt and the second metal component is at least one of nickel, and organic acid, an impregnating solution containing the prepared, the first metal component and the a step of carrying the second metal component in the inorganic composite oxide support,
(F) obtained by the process of the (E), the inorganic mixed oxide of the first metal component and second metal component is supported obtaining a hydrotreating catalyst objects carrier is heated at a temperature of 100 ~ 600 ° C.,
　characterized in that it comprises a.
[0026]
　(1) Specific examples of the step of preparing inorganic composite oxide support,
prepared (D-1) was mixed with an aqueous solution of a basic metal salt solution and an acidic metal salt complex metal hydrate slurry a slurry preparation step of,
the first ripening step of ripening the (D-2) the composite metal hydrate slurry
and washing the (D-3) and then the composite metal hydrate slurry,
(D-4 ) Thereafter, the a second aging step for the aging the composite metal hydrate slurry,
and (D-5) Thereafter, the composite metal hydrate slurry kneading step kneading and concentrated to concentrate,
(D-6 ) wherein the step of composite metal hydrate slurry molding a concentrate obtained by concentration,
and a step of drying, baking and then molded (D-7),
wherein the (D-4) in the second ripening step, adding the first organic compound.　
　Listed further embodiment of a process for preparing an inorganic composite oxide support.　
　Basic aluminum salt solution in the slurry preparation step of the (D-1) contains a carboxylic acid salt. The first organic compound is added in an amount of 0.5-4.0 parts by weight with respect to the inorganic composite oxide 100 parts by weight. In kneading and concentration step of the (D-5), adding a second organic compound. The second organic compound is added in an amount of 0.5-4.0 parts by weight with respect to the inorganic composite oxide 100 parts by weight. The (D-4) Inorganic composite oxides concentration in the slurry in the second aging step of less than 20%, inorganic composite oxides concentration in the slurry in the kneading and concentration step of the (D-5) 20% or more.　
　The organic compound is citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), is at least one selected from diethylenetriaminepentaacetic acid (DTPA), and sugars (monosaccharides, polysaccharides, etc.) .　
The present invention is not limited to the specific examples described in this item.
[0027]
　The hydrotreating a hydrocarbon oil of the present invention, in the presence of a hydrotreating catalyst of the present invention, the hydrogen partial pressure is 3 ~ 8 MPa, the temperature is 260 ~ 420 ° C., a liquid hourly space velocity is 0.3 ~ 5 hr -1 wherein the the condition by performing a hydrotreating a hydrocarbon oil.
Effect of the invention
[0028]
　Hydrotreating catalysts of the present invention, by using a carrier consisting of γ- alumina, high strength, high stability, large surface area obtained and facilitate the control of the crystallinity can be expected high productivity. The hydrotreating catalyst of the present invention, by using a carrier consisting of inorganic composite oxides having enhanced dispersibility of the different elemental metals while mainly of γ- alumina, high surface area, high activity catalyst with a high strength get it can be expected. And since it is a suitable active metal composition, high dispersibility of the active metal can be obtained and attained the adsorption amount of increase of nitric oxide which is an indicator of the active sites of (NO). Since the further control the OH groups of the support surface, high dispersibility of the active metal can be obtained in this respect. Furthermore, ignition loss, since it is properly the carbon content, catalyst regeneration is easy.　
　And by using the hydrotreating catalyst for hydrocarbon oil of the present invention, it can be carried out hydrodesulfurization a hydrocarbon oil having a high desulfurization activity.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029]
[1] Carrier A according to the first embodiment, a transmission type Fourier transform infrared spectrophotometer measurements of K.
FIG. 2 is a graph showing an example of analysis results of the first embodiment the peak temperature of the eliminated water by temperature programmed reduction according to an embodiment.
[3] is an example of a transmission Fourier transform infrared spectrophotometer measurements of carrier according to the second embodiment.
4 is a graph showing an example of the analysis result of the peak temperature of the eliminated water by temperature programmed reduction according to the second embodiment.
DESCRIPTION OF THE INVENTION
[0030]
"First Embodiment"
　Hereinafter, a first embodiment of the present invention will be described in detail.　
About hydrotreating catalyst for hydrocarbon oil]
　first hydrocarbon oil hydroprocessing catalyst according to an embodiment of the present invention (hereinafter in the fields of the first embodiment is also referred to as "catalyst of the present invention") is , and γ- alumina support (hereinafter also referred to as an alumina support), consists of a active metal component, has a predetermined property. Below γ- alumina support described in detail the nature of the active metal component and a catalyst.
[0031]
　<.Gamma.-alumina carrier>　
　.gamma.-alumina carrier which constitutes the hydrotreating catalyst, and an oxide of one to remove impurities content of aluminum whose crystalline state is a state that can be classified as .gamma.-alumina, .gamma.-alumina 100 it is%. The 100% .gamma.-alumina, although impurities or the like contained in the unavoidable from the manufacturing process of the alumina carrier may include means that do not contain otherwise, for example, the content of .gamma.-alumina in alumina carrier 99 and the weight percent (parts by weight) or more, preferably at least 99.5 mass%.
[0032]
　Accordingly, the hydrotreating catalyst, it is possible to keep the industrially high productivity as well as high performance.　
　In order to sufficiently ensure the effective carrying the catalyst activity the active metal component in a highly dispersed state on the carrier is generally a porous carrier is used in, those having the relatively small pores the pore size 500Å It is preferably used. In order to control the mechanical strength and physical properties such as heat resistance of the support or catalyst body may contain a suitable binder components and additives in the formation of the carrier or catalyst body.
[0033]
　Support of the catalyst of the present invention, transmission Fourier transform infrared corresponding to acidic OH groups measured by the outside spectrophotometer 3674 ~ 3678Cm -1 to the absorbance Sa spectral peaks in the wave number range, corresponding to the basic OH groups to ~ 3774Cm 3770 -1 ratio Sb / Sa of the absorbance Sb spectral peaks in the wave number range of in the range of 0.15 to 0.40. Ratio Sb / Sa is more preferably in the range of 0.20 to 0.40. Active metal, the characteristics of the alumina support surface are known to be different dispersibility, high dispersibility of the active metal is observed particularly marked in the carrier surface when the Sb / Sa is in the above range. As a result, this means that a high desulfurization performance can be obtained, it is preferable to prepare the above range. 1, of the present invention the catalyst support (carrier shown in Example A, K) for, 3674 ~ 3678cm corresponding to acidic OH groups -1 3770 ~ 3774Cm corresponding to the wave number range and basic OH groups of -1 of It should show examples of the light absorption spectrum comprising wavenumber range.
[0034]
　Also, when preparing the carrier of the catalyst of the present invention, in order to prepare to γ- alumina via pseudoboehmite crystalline state through the baking process, but the pseudo-boehmite alumina (before firing), which is a precursor it is characteristic crystallite size determined from the half value width of the XRD diffraction spectrum (020) peak is less than 45 Å. Control of the crystallite size of the boehmite is important for influencing the crystal transition difficulty by subsequent firing with optimization of the pore structure of the alumina support. If the crystallite size exceeds 45Å, since the average pore diameter is large and the specific surface area decreases, which is not preferable possibility that the catalyst performance is decreased. Further, in the crystal transition it becomes difficult to proceed during the firing, occur if the boehmite structure remains crystalline form of the alumina support, is not preferable since the generated concern that the stability of the catalyst performance is impaired.
[0035]
　
　to γ- on an alumina support, as active metal component, for example molybdenum which is a first metal component, the second is for example cobalt metal component is supported.　
　The first metal component may be a tungsten instead of molybdenum, it may be both molybdenum and tungsten. A preferred range of the content of the first metal component (weight bearing) is located at 15-27% by mass in terms of oxide in the catalyst reference (with respect to 100 parts by weight of the catalyst, 15-27 parts by weight in terms of oxide) , more preferred range is 15 to 20 mass%.
[0036]
　When the content of the first metal component is excessively smaller than 15 mass% in terms of oxide, there is a risk that the desulfurization activity required for the reaction can not be secured, if excessively greater than 27 wt%, the metal component is likely to agglomerate becomes, it may inhibit the dispersibility.　
　The second metal component may be a nickel instead of cobalt, it may be both cobalt and nickel. The content of the second metal component (weight bearing) is 2 to 7% by weight as oxide equivalent in catalyst reference (with respect to 100 parts by weight catalyst, 2-7 parts by weight in terms of oxide) must be a it is. The second metal component acts as a cocatalyst for a first metal component, a first metal component and second metal component content is 2% by mass is less than the active metal ingredient as oxide equivalent is difficult to maintain the appropriate structure, the content is more than 7% by mass in terms of oxide, the aggregation of the active metal component tends to progress, the catalytic performance is lowered.
[0037]
　Upon supporting the alumina support by the active metal component impregnation, an organic acid is contained in the normal impregnation solution, Therefore organic acid is a source of carbon that is supported on an alumina carrier. The organic acid used in the active metal component, e.g., citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) is used, more preferably, citric acid, malic acid , tartaric acid, gluconic acid. The example in addition to the organic acid, saccharides (monosaccharides, disaccharides, polysaccharides, etc.) in the case of using an organic additive, such as, in this specification, the content of carbon derived from the organic acid is an organic acid and the content of carbon derived from both organic additives.
[0038]
　 [
　catalyst of the present invention, BET (Brunauer-Emmett-Teller ) measured specific surface area method (SA) is, 200 ~ 320 m 2 is required to be in the range of / g. The specific surface area (SA) is, 200 meters 2 when less than / g, undesirably there is a possibility that the metal component is likely to agglomerate, the desulfurization performance is lowered. On the other hand, 320 m 2 / g larger than the average pore diameter and the pore volume is reduced, since the desulfurization activity tends to decrease, such being undesirable.　
　Also it is necessary that the average pore diameter of 50 ~ 110 Å. The average pore diameter, mercury porosimetry (contact angle of mercury: 130 °, surface tension: 480 dyn / cm) is a value measured by, represents the pore diameter corresponding to 50% of the total pore volume. Incidentally, the pore volume represents the pore volume having a pore diameter greater than the pore diameter of 41 Å. There is a possibility that the average pore diameter is decreased as small as desulfurization performance than 50 Å, the average pore diameter is larger than 110 Å, there is a possibility that the catalyst strength is decreased.
[0039]
　The catalyst of the present invention, ignition loss (Ig Loss) is not more than 5.0 mass%. The ignition loss is obtained by calculating by heating the catalyst as described in the item of measurement method described later at a high temperature. To the loss on ignition of the catalyst with 5.0 wt% or less, .gamma. after alumina support impregnated liquid to was spray impregnated, it is necessary to firing, for example, 300 ° C. or higher.　
　By loss on ignition of the catalyst with 5.0 wt% or less, 80% or more when the activity during catalyst regeneration is defined as 100% desulfurization performance of the new, unused catalyst (fresh catalyst) can. Loss on ignition of the catalyst many become. Active metal component by firing step during catalyst regeneration is a concern that aggregation.
[0040]
　The content of carbon in the catalyst, by 2.0 mass% or less elemental basis in the catalyst basis, the desulfurization performance of the catalyst regeneration time of the active novel fresh catalyst (fresh catalyst) 100% it can be 80% or more upon. When the high content of carbon, the active metal component by firing step during catalyst regeneration is a concern that aggregation.　
　The catalyst of the present invention is based on the temperature programmed reduction of the catalyst, the peak temperature of the eliminated water (temperature desorption peak in the spectrum of water appears) ranging up to 450 ° C. is 415 ° C. or less. It will be described later examples of temperature programmed reduction. Usually, sulfurization treatment is carried out by hydrogen sulfide in a stream of hydrogen to molybdenum, as the reaction, it is necessary to oxygen from the molybdenum oxide is desorbed. Desorption peaks of water, because just those that detect the desorption of the oxygen of water from the molybdenum oxide is considered that there is a correlation reduction temperature of progression and molybdenum sulfide process. Therefore, by temperature reduction peak temperature of eliminated water is considered possible to sufficiently proceed the sulfurization process molybdenum.
[0041]
　Also when the reducing temperature is too high, that is, if the peak temperature of the eliminated water is too high, because water is a weakly interacts with the alumina support, more likely to aggregate the active metal is present . Therefore, it is inferred that the sulfurization step does not proceed sufficiently. Accordingly, the reduction temperature is lowered, reducing the interaction between the water and the alumina support is required in order to highly disperse the active metal.　
　Eliminated water has been generated primarily molybdenum reduction step, the peak temperature, the carrier composition, varies depending on the active metal composition and the like. According to the findings of the present inventors, on the alumina support to desorption peak temperature of the water (peak temperature of eliminated water) to 415 ° C. or less, as the active metal component, at least one of molybdenum and tungsten ( as oxides converted kind), 15-28 wt%, it is necessary to 2-7 wt% at least one of cobalt and nickel (one) as the oxide equivalent.　
　If the active metal component is less than this range is not preferable because the catalytic performance is insufficient, when the active metal component is higher than this range is not preferable because the possibility of aggregates of the active metal is generated impaired dispersibility becomes higher .
[0042]
　The catalyst of the present invention is the adsorption amount of nitric oxide catalyst treated sulfide 8.0 ml / g or more. The adsorption amount, more preferably, is 8.3 ml / g or more. Based on Nitric Oxide adsorption amount, it is possible to measure the reaction active sites of the catalyst.　
　If the amount of adsorption of nitrogen monoxide is less than 8.0 ml / g is outside the scope of the present is not preferable because the effect of improving reduced catalyst performance reaction active sites of the catalyst can not be obtained.　
　Nitric oxide adsorption amount after sulfurization treatment of the catalyst, the physical properties and chemical properties of the carrier will vary depending on the active metal composition and the like. And to carry out the nitric oxide adsorption consists in the need sulfurization treatment, and necessary to lower below a certain temperature in the reduction temperature of the active metal. According to the findings of the present inventors, the adsorption amount of nitrogen monoxide to a 8.0 ml / g or
more, a) a specific surface area (SA) of 180 ~ 320 m in the alumina support 2 in the range of / g ,
b) transmission Fourier transform infrared corresponding to acidic OH groups measured by the outside spectrophotometer 3674 ~ 3678Cm -1 to the absorbance Sa spectral peaks in the wave number range, corresponding to the basic OH groups 3770 ~ 3774Cm - 1 that the ratio Sb / Sa of the absorbance Sb spectral peaks in the wave number range in the range of 0.15 ~ 0.40,
　c) as an active metal components on an alumina support, at least one from among molybdenum and tungsten 15 to 28 wt% as oxide equivalent, that at least one of cobalt and nickel from 2 to 7% by weight as oxide equivalent ,
　It is important to the desorption peak temperature of d) water to 415 ° C. or less.
[0043]
　[Production method of hydrotreating catalyst for hydrocarbon oil]
Next, a method for manufacturing a hydrocarbon oil hydroprocessing catalyst of the present invention.　
　Method for producing a hydrotreating catalyst for hydrocarbon oil according to the present invention,　
　.gamma. a first step of preparing an alumina support,　
　a first metal component is at least one of molybdenum and tungsten, cobalt and nickel a second metal component is at least one, a second step of an organic acid, an impregnating solution containing the prepared, carrying said first metal component and second metal component to the alumina carrier,　
　the second step obtained by, having, a third step of obtaining a hydrotreating catalyst is heat treated in the first metal component and the second temperature of the alumina support metal components are supported 100 ~ 600 ° C..　
　Hereinafter, the respective steps will be described.
[0044]
　 «1-1. Step »obtain alumina slurry
　firstly an aqueous solution of a basic aluminum salt solution and an acidic aluminum salt, pH 6.5 to 9.5 preferably 6.5 to 8.5, more preferably 6.8 to 8.0 mixed and to be obtain the hydrate of an inorganic oxide. In this case, the basic aluminum salt solution, it is desirable to include a carboxylate. And after aging by slurry of the desired approach hydrate of an inorganic oxide (first ripening step), except washed with byproduct salt, to obtain a slurry containing alumina.　
　Carboxylate as used herein, polyacrylic acid, hydroxypropylcellulose, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, citric acid include salts are preferably added in an amount of 0.5-5.0 parts by weight per 100 parts by weight of alumina.
«1-2. The second aging step »alumina
　to the slurry obtained hydrate in the 1-1 step, adding at least one organic compound (first organic compound), in the aging tank with a reflux condenser, 30 ° C. or more, preferably at 80 ~ 100 ° C., for example, 1 to 20 hours, preferably heat aged for 2 to 10 hours (second ripening step). In the first ripening stage and the second ripening stage, it is preferred that the alumina concentration is less than 20%.
«1-3. Kneading and molding and drying steps »
　After heating the alumina concentration taking into aging was steam jacketed twin arm kneader obtained in the 1-2 step was concentrated to 20% or more, at least one organic compound (second organic compound) It was added and after a subsequent further heating kneaded moldable kneaded product is molded into a desired shape by extrusion molding. The timing of the addition of a second organic compound may be a middle of concentrating the ripening thereof.
«1-4. Heat treatment (drying, calcining) step »
　The molded product obtained in Step 1-3, and then for example 70 ~ 0.99 ° C., preferably dried by heating at 90 ~ 130 ° C., preferably further example 400 ~ 800 ° C., preferably is obtained in 400 ~ 600 ° C., for example, 0.5 to 10 hours, preferably by baking 2-5 hours alumina support.　
　The basic aluminum salt used here, sodium aluminate, and potassium aluminate is preferably used. As the acidic aluminum salt, aluminum sulfate, aluminum chloride, etc. aluminum nitrate is preferably used.　
　When mixing the two kinds of aluminum salt aqueous solution, usually 40 ~ 90 ° C., preferably heated and held in 50 ~ 70 ° C., a temperature ± 5 ℃ of the solution, preferably ± 2 ° C., and more preferably It warmed mixed aqueous solution ± 1 ° C., pH 6.5 to 9.5 as preferably of 6.5 to 8.5, more preferably 6.5-8.0, usually 5-20 min, preferably to produce a continuously added precipitated during the 7 to 15 minutes, to obtain a slurry of hydrate.
[0045]
　The time required for addition of the mixed aqueous solution to a basic aluminum salt aqueous solution, because it may in addition to bayerite and undesirable crystals such as gibbsite pseudoboehmite becomes longer is generated, desirably 15 minutes or less, 13 minutes or less is further preferable. Since bayerite and gibbsite, the specific surface area when heated to become bad.　
　Further, as the first organic compound used in the first step and the second organic compound, at least one selected from organic acids or sugars are preferred. As the organic acids, citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), include diethylenetriaminepentaacetic acid (DTPA) it is. As also saccharides, monosaccharides, disaccharides, polysaccharides and the like. Amount at this time is preferably in the range of 0.5-5.0 parts by weight per 100 parts by weight of alumina. Effect is obtained hardly by the addition of the additive amount of organic compound is less than this range, not only the physical properties of the catalyst becomes too small pore structure by too strong effect if it exceeds this range is not optimal range undesirable because the efficiency of the preparation is poor.
[0046]
　OH groups on the surface of the carrier, such as active metal species dispersibility, is an important factor in determining the carrying state. Control of the OH group, together with crystalline carrier alumina precursor can be performed everywhere in the carrier preparation step. However, it is very difficult to adjust the OH group while maintaining the physical properties of the carrier. To meet this, it is preferred to carry out the adjustment of the OH group in a separate step after performing the control of the crystallinity. Therefore, after control the crystallinity in the second aging step, adding an organic compound in the step of kneading and concentrated (second organic compound), it is preferable to adjust the state of the OH group.
[0047]
　
　alumina support, contacting the impregnated solution containing a first metal component and second metal component and a carbon component described above.　
　The raw material of the first metal component, e.g., molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, and tungsten trioxide is preferably used. As the raw material of the second metal component, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate or the like is preferably used.　
　When addition of supporting phosphorus on an alumina carrier, orthophosphoric acid (hereinafter, simply referred to as "phosphate"), ammonium dihydrogen phosphate, ammonium phosphate dibasic, trimetaphosphate, pyrophosphate, etc. tripolyphosphate is used .
[0048]
　Impregnation solution to a pH of 4 or less using an organic acid, it is preferable to dissolve the metal component. stability of the metal components which pH is dissolved in excess of 4 tends to precipitate decreases. The organic acid, such as citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), available diethylenetriaminepentaacetic acid (DTPA), in particular, citric acid, malic acid is preferably used. The organic additives, saccharides (monosaccharides, disaccharides, polysaccharides, etc.) are used. Incidentally organic additive in an organic acid, for example, dextrose (glucose; C 6 H 12 O 6 ), fruit sugar (fructose; C 6 H 12 O 6 ), malt sugar (maltose; C 12 H 22 O 11 ), milk sugar (lactose; C 12 H 22 O 11 C;), sucrose (sucrose 12 H 22 O 11 may be added, etc.).
[0049]
　
　the carrier supporting the metal component obtained by contacting with the impregnation solution in the second step, 100 ~ 600 ℃, preferably 110 ~ 600 ° C., more preferably 400 ~ 600 ℃, 0.5 ~ 10 hours, preferably after heating treatment for 1 to 8 hours, to produce a hydrotreating catalyst of the present invention. Now the firing temperature is excessively lower than 100 ° C., the operability is deteriorated due to residual moisture, also there is a fear that hardly becomes uniform metal-supported state, when excessively exceeds 600 ° C., metals cause flocculation, dispersion undesirable because there is a possibility that maintaining effect can not be expected.　
　Here it is noted one of the advantages of the first to third steps. When performing the second aging step alumina in the first step, a slurry of hydrate, is added an organic compound (first organic compound), and heat digestion. By performing such processing, the crystallite size of the pseudo boehmite alumina which is a precursor can be below 45 Å, it is possible to increase the small and the specific surface area of the average pore diameter of the catalyst. Since the crystal transition proceeds readily at the time of firing the boehmite structure in the crystal form of alumina support is less likely to remain, it is possible to stabilize the catalytic performance.
[0050]
　In the hydrotreating catalyst, which catalyst satisfies a good balance of both high surface area and high strength is desired. To prepare the γ- alumina, although baking process through the pseudo-boehmite crystalline state is effected by controlling the crystalline state of the pseudo-boehmite, improved performance of the catalyst has been expected. According to this embodiment, it is possible to control the crystalline state of the pseudo-boehmite, which contributes to the production of high performance hydroprocessing catalysts.
[0051]
　About hydrotreating process of a hydrocarbon oil]　
　hydrocarbon oils of interest to reduce the desulfurization by hydrotreating catalysts of the present invention, for example, straight-run kerosene or straight run gas oil obtained from atmospheric distillation unit for crude oil, atmospheric distillation to obtain the straight-run heavy oil or residue査油obtained from the device by treatment with vacuum distillation apparatus vacuum gas oil or vacuum heavy gas oil, catalytic cracking obtained by catalytically cracking desulfurized heavy oil kerosene or catalytic cracking gas oil , vacuum heavy gas oil or hydrocracked kerosene or hydrocracking gas oil obtained desulfurized heavy oil by hydrocracking, thermal cracking kerosene or pyrolysis gas oil and the like obtained from the thermal cracking unit such as a coker can be mentioned, boiling point 180 the fraction of ~ 390 ° C. is inclusive fraction 80 vol% or more. Hydrogenation process using the catalyst, under a hydrogen atmosphere filled with a catalyst in a fixed bed reactor, carried out at elevated temperature and pressure conditions.
[0052]
　[Measurement method for]
　As described below, the hydrotreating catalyst in each of Examples and Comparative Examples of the present invention, the content of the component, but measures the figures for specific surface area and properties, make these measurements keep describes a method.　

　a measurement sample 3g taken lid zirconia balls of capacity 30 ml, heat treatment (200 ° C., 20 min) was , calcined (700 ° C., 5 minutes), and then, Na 2 O　2 was melted for 15 minutes by the addition of 2g and NaOH 1 g. Furthermore, H 2　SO 4 After dissolved by adding 25ml of water 200 ml, and a sample was diluted to 500ml with purified water. The obtained sample, ICP apparatus (Shimadzu Corp., ICPS-8100, the analysis software ICPS-8000) using, in terms of oxide relative to the content of each component (Al 2 O 3 , P 2 O 5 , MoO 3 was measured in, NiO, CoO).
[0053]
　
　X-ray diffractometer (Rigaku Co., Ltd.: RINT2100) using a measurement sample and observing samples that compacting non-reflecting plates for measurement, crystalline state was measured by X-ray diffraction. The crystallite size of the carrier alumina precursor is calculated in Scherrer method from being attributed to boehmite (020) plane, the crystal structure of the calcined support was judged by comparison of diffraction peak attributed to boehmite and γ- alumina . Desirably alumina oxide support matter is γ- alumina, specifically, a diffraction peak area showing a boehmite (020) plane and the (120) plane each crystal structure as determined by X-ray diffraction analysis, the diffraction peak area showing the aluminum crystal structure attributed to a γ- alumina (440) plane, should be less than 1/10. That is, assigning a diffraction peak area showing the crystal structure of boehmite (020) plane measured by X-ray diffraction analysis P1, a diffraction peak area showing the crystal structure of the (120) plane P2, .gamma.-alumina (440) plane When a diffraction peak area showing the aluminum crystal structure P3
is, (P1 / P3) × 100 (%) value and (P2 / P3) of the values of × 100 (%), greater the value of it is 10% it is less than.　
　When boehmite structure increases the crystal of the carrier it is not preferable because the catalyst strength may be lowered not only it is difficult to control the carrier physical properties.
[0054]
　Here, boehmite (020) plane and the (120) plane diffraction peak showing the crystal structure, each 2 [Theta] = 14 °, are those 2 [Theta] = 28 °, in measured, aluminum attributed to γ- alumina (440) plane diffraction peaks indicating crystalline structure was measured at 2θ = 67 °.　
　The method of calculating the respective diffraction peak area performs fitting with baseline correction by the least squares method graph obtained by X-ray diffraction analysis by X-ray diffraction apparatus, obtains the height of the maximum peak value to the baseline ( the peak width (half width) at the time of half value of the peak intensity W) obtained peak intensity (1 / 2W), and the product of the half width and the peak intensity and the diffraction peak area. From diffraction peak area was determined and calculated "boehmite diffraction peak area / .gamma.-alumina diffraction peak area".
[0055]
　
　transmission Fourier transform infrared spectrometer (manufactured by JASCO Corporation: FT-IR / 6100) at, maximum peak wave number of acidic OH groups in the following manner, in that the wave number absorbance maximum peak wave number of basic OH groups, and the absorbance was measured at the wave number.　
(Measurement method)
　Sample 20mg and filled in the molding container (inner diameter 20 mm.phi) 4 ton / cm 2 (39227N / cm 2 and pressure compressed), and molded into a thin disk shape. The molded body, the degree of vacuum is 1.0 × 10 -3 Pa or less conditions, after 2 hours at 500 ° C., the absorbance was measured by cooling to room temperature.
[0056]
　Specifically, in TGS detector, resolution 4 cm -1 , the number of integrations is 200 times, the wave number range 3000 ~ 4000 cm -1 were baseline corrected. Absorbance was converted per unit mass. Absorbance per unit mass (g -1 ) = Absorbance / molded mass
　In any samples of Examples 1-13 below, the wave number of the maximum peak position of the absorption spectrum corresponding to the acidic OH group 3674 ~ 3678Cm -1 is in the range of wave numbers of the maximum peak position of the absorption spectrum due to the basic OH groups ~ 3774Cm 3770 -1 is in the range of.
[0057]
　
　The measurement sample was about 30ml collected porcelain crucible (B-2 type), after 2 hours of heat treatment at a temperature of 300 ° C., then cooled to room temperature in a desiccator, to obtain a sample for measurement It was. Next, this sample 1g up, fully automatic surface area measuring device (manufactured by Yuasa Ionics Inc., Multisorb 12 type) with a specific surface area of the sample (m 2 a / g) was measured by the BET method.
[0058]
　
　catalyst is a measurement sample was calcined 2 hours at 570 ° C., is calculated from the weight loss due to firing.　
　
In temperature programmed reduction, manufactured by BEL Japan catalytic analyzer using (BEL CAT-A), a catalyst 0.05g was sieved to 250 ~ 710 .mu.m 1 hour at 120 ° C., was subjected to a pretreatment under a flow of helium gas is switched to hydrogen gas (99.99%), it was heated at 10 ° C. / min from 50 ° C. to 900 ° C.. Desorption spectrum of Pfeiffer Vacuum Inc. quadrupole mass spectrometer of the water during heating: measured by (m / z 18.34), resulting, read desorption peak temperature of the water from the desorption spectrum It was.　
　Figure 2, previously a graph which is an example of analysis results of the peak temperature of the eliminated water by temperature programmed reduction. The horizontal axis of FIG. 1 is the temperature, the vertical axis represents the detection current of the quadrupole mass spectrometer.
[0059]
　
　Measurement of nitric oxide adsorption amount with a fully automated catalyst gas adsorption amount measuring apparatus (manufactured by Riken Okura), the hydrotreating catalyst was treated sulfide, helium gas and nitrogen monoxide a mixed gas of a gas (nitrogen monoxide concentration of 10% by volume) was introduced at the pulse was measured nitric oxide molecular adsorption amount per hydrotreating catalyst 1g. Specifically, the catalyst was ground to 60 mesh or less to about 0.02g weighed, which was filled in a quartz cell, and heating the catalyst to 360 ° C., hydrogen sulfide 5 volume% / hydrogen 95 vol% of gas for 1 hour sulfurization treatment by flow through at 0.2 liters / min flow rate, and held 1 hour thereafter 340 ° C., it was discharged hydrogen sulfide that are physically adsorbed to the outside of the system. Then the nitric oxide molecule in helium gas and a gas mixture of nitrogen monoxide gas is adsorbed at 50 ° C., it was measured nitric oxide molecular adsorption.
[0060]
　EXAMPLES
　Preparation examples of γ- alumina support, and Preparation of the impregnation solution, a preparation example of a hydrotreating catalyst which is an embodiment of the present invention using the alumina carrier and the impregnation solution, the alumina support and impregnation described below for the preparation example of hydrotreating catalyst is a comparative example using a liquid.　
　First describes the preparation example of a carrier.
[0061]
　 tank steam jacketed a) capacity 100L (liters), Al 2 O 3 at a concentration in terms of putting 22 wt% aqueous sodium 9.09kg aluminate, and diluted with ion-exchanged water was 40.00kg. Then, this solution a concentration of 26 wt% aqueous sodium gluconate 230.8g was added and heated with stirring to 60 ° C..　
　Separately, concentration of Al 2 O 3 were prepared translated at 7 wt% aqueous solution of aluminum sulfate was heated to 60 ° C. The aluminum sulfate aqueous solution prepared by diluting the aqueous solution of aluminum sulfate 14.29kg with deionized water 25.71Kg.　
　Next, the while sales the concentration of 5% by mass of sodium aluminate, Sodium gluconate mixed solution, a constant rate of aluminum sulfate solution thereto, was added in 10 minutes, Al 2 O 3 concentration of 3.8 mass as % of the alumina hydrate slurry was prepared. At this time, pH of the slurry was 7.2. Alumina hydrate slurry was then aged for 60 minutes with stirring at 60 ° C..　
b) Then, after dewatering the aged alumina hydrate slurry was washed with concentration of 0.3 wt% aqueous ammonia solution 1.5 L.　
c) concentration cake slurry after washing Al 2 O 3 was slurried diluted with deionized water to a 10 wt% in terms of citric acid was added to 0.60kg of 10% by weight solution as the first organic compound, 15 wt% of the ammonia after the water was added and adjusted to pH 10.2, and aged 10 hours with stirring 95 ° C..　
d) the slurry after completion of aging is dehydrated, concentrated until heated alumina concentration while kneading in a double-arm kneader with a steam jacket is 20% or more, 10 wt% malic acid as the second organic compound solution in addition of 0.30 kg, it was then further heated to kneading concentrated to a predetermined moisture.　
e) Then, the diameter and the resulting kneaded product at screw extruder and molded into 1.6mm cylindrical.　
f) Then, after drying for 12 hours at 110 ° C., to obtain a hydrotreating catalyst carrier A made of fired to γ- alumina 3 hours at 500 ° C..
[0062]
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 0.60kg gluconate in 10% by weight solution as the first organic compound, the malic acid in 10 wt% solution as the second organic compound It was added 0.30 kg, to obtain a carrier B.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 1.20kg gluconate in 10% by weight solution as the first organic compound, the malic acid in 10 wt% solution as the second organic compound It was added 0.30 kg, to obtain a carrier C.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 0.60kg at 10% by weight solution of tartaric acid as the first organic compound, the malic acid in 10 wt% solution as the second organic compound 0 It was added .30Kg, to obtain a carrier D.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 0.60kg at 10% by weight solution of sucrose as the first organic compound, the malic acid in 10 wt% solution as the second organic compound 0 It was added .30Kg, to obtain a carrier E.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 0.60kg malic acid in 10 wt% solution as the first organic compound, the malic acid in 10 wt% solution as the second organic compound It was added 0.30 kg, to obtain a carrier F.　
　　
　In carrier prepared in analogy to the preparation of carrier A, a 1.50kg at 10% by weight solution of sucrose as the first organic compound, malic acid was added 0.30kg at 10% by weight solution as the second organic compound, to obtain a carrier G.
[0063]
　　
　in the carrier prepared in analogy to the preparation of carrier A, a 0.60kg acetic acid in 10 wt% solution as the first organic compound, the malic acid in 10 wt% solution as the second organic compound 0 It was added .30Kg, to obtain a carrier H.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 0.60kg gluconate in 10% by weight solution as the first organic compound, citric acid in 10 wt% solution as the second organic compound It was added 0.30 kg, to obtain a carrier I.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, a 0.45kg gluconate in 10% by weight solution as the first organic compound, citric acid in 10 wt% solution as the second organic compound It was added 0.60 kg, to obtain a carrier J.　
　　
　in carrier be prepared in analogy to the preparation of carrier A, without adding a first organic compound and the second organic compound at all, to obtain a carrier K.　
　　
　in the carrier prepared in analogy to the preparation of carrier A, citric acid was added to 0.60kg of 10% by weight solution as the first organic compound, the second organic compound without adding anything, carrier It was obtained L.　
　　
　in the carrier prepared in analogy to the preparation of carrier A, a 1.80kg at 10% by weight solution of sucrose as the first organic compound, the malic acid in 10 wt% solution as the second organic compound 0 .30kg was added. Other steps in the same manner as the preparation of the support A, to obtain a carrier M.　
　　
　in carrier A was obtained in the same manner as the preparation of the support A, the firing temperature in the drying after an electric furnace at 110 ° C. and 700 ° C., to obtain a carrier N by baking for 3 hours.　
　　
　in carrier A obtained in the same manner as the preparation of the carrier A, the firing temperature in the drying after an electric furnace at 110 ° C. and 350 ° C., to obtain a support O by baking for 3 hours.
[0064]
　　
　in carrier A was obtained in the same manner as the preparation of the support A, the firing temperature in the drying after an electric furnace at 110 ° C. and 430 ° C., to obtain a carrier P by firing for 3 hours.
[0065]
　
　describes adjustment example of the next impregnation liquid.　
　　
　molybdenum trioxide 255g and 101g of cobalt carbonate, was suspended in ion-exchanged water 700 ml, 5 hours liquid volume of the suspension at 95 ° C. is subjected to a suitable recirculation system so as not to reduce after heating, dissolved by adding a phosphate 43g and 121g of citric acid, to prepare an impregnating solution a.
[0066]
　　
　molybdenum trioxide 257g and nickel carbonate 135 g, was suspended in ion-exchanged water 700 ml, 5 hours liquid volume of the suspension at 95 ° C. is subjected to a suitable recirculation system so as not to reduce after heating, dissolved by adding a phosphate 44g and 135g of citric acid, to prepare an impregnating solution b.　
　　
　molybdenum trioxide 255g cobalt carbonate 78g and nickel carbonate 27 g, was suspended in ion-exchanged water 700 ml, as 5 hours liquid volume of the suspension at 95 ° C. is not reduced appropriate reflux after heating by applying apparatus, and dissolved by addition of phosphoric acid 43g and 121g of citric acid, to prepare an impregnating solution c.　
　　
　molybdenum trioxide 201g cobalt carbonate 63 g, was suspended in ion-exchanged water 700 ml, 5 hours liquid volume of the suspension at 95 ° C. is subjected to a suitable recirculation system so as not to reduce after heating, dissolved by adding a phosphate 30g citric acid 75 g, to prepare an impregnating solution d.　
　　
　molybdenum trioxide 462g cobalt carbonate 162 g, was suspended in ion-exchanged water 700 ml, 5 hours liquid volume of the suspension at 95 ° C. is subjected to a suitable recirculation system so as not to reduce after heating, it was dissolved by adding 99g phosphoric acid and 195g of citric acid, to prepare an impregnating solution e.　
　　
　Molybdenum trioxide 157g cobalt carbonate 40 g, was suspended in ion-exchanged water 700 ml, after 5 hours liquid capacity is heated by applying a suitable recirculation system so as not to reduce in the suspension 95 ° C., 39g phosphoric acid and dissolved by addition of citric acid 48 g, to prepare an impregnating solution f.　
　Explaining the embodiments specifically the present invention indicates below, but the present invention is limited to these.
[0067]
　　
　after the impregnation solution a was spray impregnated on the carrier A1000g, dried at 200 ° C., a further 1 hour calcined hydrotreating catalyst (or less at 450 ° C. in an electric furnace , simply referred to as "catalyst". the same applies to the following examples.) was obtained.　
　　
　combinations as shown in Table 1 Type (Preparation) and the later preparation of the kind carriers as described above with (Preparation Example) impregnating solution and others in the same manner as in example 1 to prepare a catalyst of example 2 to example 16.
[0068]
　Next a comparative example will be described.　
　　
　combinations as shown in Table 1 below and the preparation of the kind carriers as previously described (Preparation) and the type of impregnation liquid (Preparation Example) and others in the same manner as in example 1 to prepare a catalyst of Comparative example 1 to Comparative example 7.　
　　
　using an impregnation solution a of Example 1 as impregnating liquid, after being sprayed impregnated on a carrier A1000g prepared in Example 1, without drying and calcining thereafter at 120 ° C. to obtain a hydrotreating catalyst.　
　Above prepared in Example 1 obtained through Example 16 and Comparative Examples 1 to Table 1A the properties of each carrier in 8, shown in Table 1B, it shows the properties of each catalyst shown in Table 2A, 2B. Table 1A, in Table 1B, the specific surface area represents the specific surface area of the catalyst. The Table 2A, in 2B, the supported amount of each element (mass%) is already the value of the catalyst reference as mentioned. Also the value of the catalyst reference also carbon content.　
[0069]
[Table. 1A]

[0070]
[TABLE 1B]

[0071]
[Table. 2A]

[0072]
[Table 2B]

　　
　(Confirmation Test for evaluation)　
　The catalysts of Examples 1 to 16 and Comparative Examples 1-8 were evaluated for the catalyst performance and catalyst regeneration performance.　
　(1) Confirmation test for evaluation of catalyst performance　
　of each catalyst was packed in a fixed bed reactor, the oxygen atoms contained in the catalyst in order to activate desorbed was presulfided. This process is performed by circulating the liquid or gas containing sulfur compounds 200 ° C. ~ 400 ° C. of temperature, in a controlled reaction vessel under a hydrogen pressure atmosphere of normal pressure ~ 100 MPa.　
　Then, a fixed-bed flow in the reactor, straight run gas oil (density of 0.8468g / cm at 15 ° C. 3 feed, sulfur content 1.13 wt%, nitrogen content 0.083 wt%) at a rate of 150ml / Time to perform hydrodesulfurization treatment was carried out hydrorefining. The reaction conditions for the above, a hydrogen partial pressure of 4.5 MPa, the liquid hourly space velocity 1.0 h -1 , the hydrogen oil ratio 250 Nm 3 is / kl. The reaction temperature was varied in the range of 300 ~ 385 ° C. and subjected to sulfur analysis in refined oil at each temperature, sulfur content in refined oil was determined each temperature to be 10 ppm.
[0073]
　(2) Confirmation test for evaluation of catalyst regeneration performance　
　regeneration of the catalyst was carried out using the following procedure. The spent catalyst 100g taken out after the reaction, was placed in a nitrogen atmosphere held at 200 ° C., to remove the oil adhered to the surface. Thereafter, while controlling the temperature of the catalyst to 400 ~ 450 ° C., it was fired in an air atmosphere until the carbon content is below 1 wt%. The catalyst after calcination was cooled and used in the activity tests again.　
　Performance calculation method after regeneration is as follows. Test results of activity test determines the reaction rate constant than Arrhenius plot was calculated playback rate from the fresh catalyst (fresh catalyst). Specifically, after the sulfurization process by flow through the hydrogen sulfide, it was hydrodesulfurized in the described conditions in the above (1). From the change in sulfur concentration in hydrocarbon oil before and after passing through the reactor, it was determined and the reaction rate constant based on Equation 1 below. Then, the reaction rate constants of the unused catalyst (K n0 for), the value of the ratio expressed in percentage of the reaction rate constant (Kn) of the regenerated catalyst ((K n / K n0 ) × 100 [%]) of the relative activity and the.　
　K n = LHSV × 1 / (n-1) × (1 / S n-1 -1 / S 0 n-1 ) ... Equation 1　 　where,
　 K n
: Reaction rate constant　
　n: or desulfurization reaction rate is proportional to what power of the sulfur concentration of the feedstock (in LGO 1.5) S:　
　Sulfur Concentration (%) in treated oil S　
　0 : sulfur concentration in the feedstock (　
%) LHSV: liquid hourly space velocity (hr -1 )　
　the above confirmation test results are shown in Table 3.　
[0074]
[Table 3]

　(Evaluation results of properties and confirmation test of the catalyst)
　Examples 1 to 16 are all in the proper values for the properties of the catalyst. In contrast, Comparative Example 1 and 4, the ratio of OH groups of the carrier is above 0.40, which is the upper limit, the catalyst surface area 200m which is the lower limit of the proper value 2 is below the / g, also the catalyst the average pore diameter of not within the preferred range. Comparative Example 2 also, the ratio of the OH groups of the carrier is above 0.40, which is the upper limit, although the average pore diameter is within the scope of sound value, the catalyst surface area, which is the lower limit of the proper value 200 meters 2 / is below the g.　
　In Comparative Example 1 at the same time, the crystal size of the carrier alumina precursor exceeds the, which is the upper limit of the appropriate value 45 Å. Comparative Example 3, since the average pore diameter of the catalyst surface area high is below the lower limit of the proper value, nitric oxide adsorption amount not appropriate is a lower limit of the appropriate values for the active metal species supported. Comparative Example 5 is not preferable since the crystal form of the carrier alumina contains a state other than gamma. Comparative Examples 6 and 7, supported active metal amount is not within the optimal range. Comparative Example 8, the ignition loss are greatly exceed 5% by weight as the upper limit of the appropriate values, even the amount of carbon containing exceeds 2 wt%, which is the upper limit of the appropriate value.　
　The Examples 1 to 16 is indicative of catalyst performance, the temperature at which sulfur is 10ppm in refined oil is at 360 ° C. or less, said relative activity, an indicator of catalyst regeneration performance is 80% or more it is. In Comparative Example 5 and 8 contrast, is poor catalyst regeneration performance, Comparative Examples 1-7 are inferior in catalytic performance, in Comparative Example 5, the catalyst performance is either poor catalyst regeneration performance.　
"The second embodiment"
About hydrotreating catalyst for hydrocarbon oil]
　second hydrocarbon oil hydroprocessing catalyst according to an embodiment of the present invention (hereinafter also referred to as "catalyst of the present invention") is a different element metal γ- alumina mixed with a carrier (hereinafter also referred to as inorganic composite oxide support, or simply carriers), it consists of a active metal component, has a predetermined property. The following inorganic composite oxide support is described in detail the nature of the active metal component and a catalyst.　
　　
　The inorganic composite oxide support that constitutes the hydrotreating catalyst, a carrier for use in known this type of catalyst include those composed of various inorganic substances. Inorganic composite oxide support, an inorganic mixed oxide which remove impurities content mainly containing aluminum and crystalline state of the alumina is a state that can be classified into γ- alumina as the inorganic component of the other constituting the carrier , for example, phosphorus, silica - titania, zirconia, boria, is possible to increase the variety of complex oxide composed of a composite oxide of at least one selected from magnesia possible. In other words, the composite oxide comprises aluminum and phosphorus, silicon, titanium, zirconium, and at least one element selected from boron and magnesium.
[0075]
　Specific examples of the composite oxide, for example, aluminum - silicon, zeolite, aluminum - titanium, aluminum - phosphorus, aluminum - boron, aluminum - magnesium, aluminum - zirconium, aluminum - titanium - phosphorus and the like can be increased, but it is not limited thereto. Nature and shape of the inorganic composite oxide support, depending on various conditions and catalysts applications the type and composition of the metal components to be supported, are appropriately selected.　
　In order to sufficiently ensure the effective carrying the catalyst activity the active metal component in a highly dispersed state on the carrier is generally a porous carrier is used in, those having the relatively small pores the pore size 500Å It is preferably used. In order to control the mechanical strength and physical properties such as heat resistance of the support or catalyst body may contain a suitable binder components and additives in the formation of the carrier or catalyst body.
[0076]
　Support of the catalyst of the present invention, transmission Fourier transform infrared corresponding to acidic OH groups measured by the outside spectrophotometer 3674 ~ 3678Cm -1 to the absorbance Sa spectral peaks in the wave number range, corresponding to the basic OH groups to ~ 3774Cm 3770 -1 ratio Sb / Sa of the absorbance Sb spectral peaks in the wave number range of in the range from 0.20 to 0.45. Ratio Sb / Sa is more preferably in the range of 0.20 to 0.40. Active metal, the characteristics of the support surface are known to be different dispersibility, high dispersibility of the active metal is observed particularly marked in the carrier surface when the Sb / Sa is in the above range. As a result, this means that a high desulfurization performance can be obtained, it is preferable to prepare the above range. 1, the carrier of the present invention the catalyst, acidic OH corresponding to the radical ~ 3678Cm 3674 -1 3770 ~ 3774Cm corresponding to the wave number range and basic OH groups of -1 shows an example of an optical absorption spectrum comprising wavenumber range to keep. Figure 1 shows the optical absorption spectrum of the carrier in the Examples below, (1) to (4) are each carrier L, A2, F, corresponding to the A.
[0077]
　Also when preparing a catalyst support of the present invention, alumina is the subject component undergoes a sintering step to prepare the via γ- alumina pseudoboehmite crystalline state, but is a precursor of alumina (before firing) crystallite size determined from the half value width of the XRD diffraction spectrum (020) peak of the pseudoboehmite is characterized by a 15 ~ 40 Å. Control of the crystallite size of the pseudo-boehmite, followed by crystal transition difficulty by firing with the optimization of the pore structure of the inorganic composite oxide support, also is important for influencing the dispersion of the different elemental metal. If the crystallite size exceeds 40Å, since the average pore diameter is large and the specific surface area decreases, undesirably there is a possibility that the catalyst performance is decreased. Further, in the crystal transition it becomes difficult to proceed during the firing, occur if the boehmite structure remains crystalline form of the alumina support, is not preferable since the generated concern that the stability of the catalyst performance is impaired. In addition, the dispersibility of the different elemental metal inorganic composite oxide carrier is low is not preferable because the effect of the different elemental metals can not be sufficiently exhibited. If the crystallite size is below 15 Å, specific surface area is large and while high dispersibility of the different elemental metal, undesirable for carrying the active metal components to the average pore diameter is small becomes difficult.
[0078]
　Inorganic composite oxide support used in the hydrotreating catalyst for hydrocarbon oil according to the present invention, for example wherein aluminum and phosphorus, silicon, about the content of aluminum in the case of using titanium or a composite oxide comprising zirconium to. The aluminum content in the carrier, aluminum oxide (Al 2 O 3 ) (aluminum oxide (Al relative to 100 parts by weight of carrier 80% in terms of 2 O 3 ) 80 parts by mass or more in terms) are preferred. When the content of aluminum in terms of oxide is less than 80 mass%, there is a tendency that deterioration of the catalyst becomes faster.
[0079]
　The content of phosphorus in the carrier, phosphorus oxide (P 2 O 5 ) converted at 5.0 wt% or less (phosphorus oxide relative to 100 parts by weight of carrier (P 2 O 5 ) converted at 5.0 parts by weight or less) is preferred. In addition to the carrier pore distribution and the phosphorus content is excessively large is broad, the ratio Sb / Sa of the surface OH groups tends to desulfurization performance decreases because below a predetermined range.
[0080]
　Content of silicon in the carrier, silicon oxide (SiO 2 ) in terms of 3.0% by mass or less (silicon oxide with respect to 100 parts by weight of carrier (SiO 2 ) 3.0 parts by weight or less in terms) are preferred . If the content of silicon is excessively large, silica is aggregated carrier pore distribution tends to desulfurization performance decreases since it becomes broad.
[0081]
　The content of titanium in the carrier, titanium oxide (TiO 2 ) 18.0% by weight in terms of the following (titanium oxide with respect to 100 parts by weight of carrier (TiO 2 ) 18.0 parts by mass or less in terms) are preferred . When titanium content of the oxide equivalent is excessively large, the desulfurization performance from becoming br shortage and pore distribution of the carrier pore diameter tends to decrease.
[0082]
　The content of zirconium in the carrier, zirconium oxide (ZrO 2 ) 9.0 wt% in terms of the following (zirconium oxide with respect to 100 parts by weight of carrier (ZrO 2 ) 9.0 parts by weight or less in terms) are preferred . If the zirconium content is excessively large, in addition to the carrier pore distribution is broad, the ratio Sb / Sa of the surface OH groups tends to desulfurization performance decreases for greater than a predetermined range.
[0083]
　
　inorganic composite oxide support, as the active metal component, for example molybdenum which is a first metal component, the second is for example cobalt metal component is supported.　
　The first metal component may be a tungsten instead of molybdenum, it may be both molybdenum and tungsten. Content of the first metal component (weight bearing) is 15-27 wt% as oxide equivalent in catalyst reference (with respect to 100 parts by weight of the catalyst, 15-27 parts by weight in terms of oxide) it must be a it is.
[0084]
　When the content of the first metal component is excessively smaller than 15 mass% in terms of oxide, there is a risk that the desulfurization activity required for the reaction can not be secured, if excessively greater than 27 wt%, the metal component is likely to agglomerate becomes, it may inhibit the dispersibility.　
　The second metal component may be a nickel instead of cobalt, it may be both cobalt and nickel. The content of the second metal component (weight bearing) is 2 to 7% by weight as oxide equivalent in catalyst reference (with respect to 100 parts by weight catalyst, 2-7 parts by weight in terms of oxide) must be a it is. The second metal component acts as a cocatalyst for a first metal component, a first metal component and second metal component content is 2% by mass is less than the active metal ingredient as oxide equivalent is difficult to maintain the appropriate structure, the content is more than 7% by mass in terms of oxide, the aggregation of the active metal component tends to progress, the catalytic performance is lowered.
[0085]
　Upon supporting the active metal component on an inorganic composite oxide support by impregnation, an organic acid is contained in the normal impregnation solution, Therefore organic acid is a source of carbon that is supported on an alumina carrier. The organic acid used in the active metal component, e.g., citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) is used, more preferably, citric acid, malic acid , tartaric acid, gluconic acid. The example in addition to the organic acid, saccharides (monosaccharides, disaccharides, polysaccharides, etc.) in the case of using an organic additive, such as, in this specification, the content of carbon derived from the organic acid is an organic acid and the content of carbon derived from both organic additives.
[0086]
　 [
　catalyst of the present invention, BET (Brunauer-Emmett-Teller ) measured specific surface area method (SA) is, 180 ~ 320 m 2 must lie within the / g, 190 m 2 / g in is preferably more, 200 meters 2 and more preferably as long as / g or more. The specific surface area (SA) is, 180 m 2 when less than / g, the metal component is likely to agglomerate, undesirable because it may decrease the desulfurization performance. On the other hand, 320 m 2 / g larger than the average pore diameter and the pore volume is reduced, since the desulfurization activity tends to decrease, such being undesirable.　
　Also it is necessary that the average pore diameter of 50 ~ 110 Å. The average pore diameter, mercury porosimetry (contact angle of mercury: 130 °, surface tension: 480 dyn / cm) is a value measured by, represents the pore diameter corresponding to 50% of the total pore volume. Incidentally, the pore volume represents the pore volume having a pore diameter greater than the pore diameter of 41 Å. There is a possibility that the average pore diameter is decreased as small as desulfurization performance than 50 Å, the average pore diameter is larger than 110 Å, there is a possibility that the catalyst strength is decreased.
[0087]
　The catalyst of the present invention, ignition loss (Ig Loss) is not more than 5.0 mass%. The ignition loss is obtained by calculating by heating the catalyst as described in the item of measurement method described later at a high temperature. To the loss on ignition of the catalyst with 5.0 wt% or less, after the spray impregnated with impregnation liquid to inorganic composite oxide support, it is necessary to firing, for example, 300 ° C. or higher.　
　By loss on ignition of the catalyst with 5.0 wt% or less, to 85% or more when the activity during catalyst regeneration is defined as 100% desulfurization performance of the new, unused catalyst (fresh catalyst) can. Loss on ignition of the catalyst many become. Active metal component by firing step during catalyst regeneration is a concern that aggregation.　
　The content of carbon derived from the organic acid in the catalyst, desulfurization performance of by 2.0 mass% or less elemental basis in the catalyst basis, the activity at the time of catalyst regeneration is new, unused catalyst (fresh catalyst) the can be 85% or more is taken as 100%. When the high content of carbon, the active metal component by firing step during catalyst regeneration is a concern that aggregation.
[0088]
　The catalyst of the present invention is based on the temperature programmed reduction of the catalyst, the peak temperature of the eliminated water (temperature desorption peak in the spectrum of water appears) ranging up to 450 ° C. is 415 ° C. or less. It will be described later examples of temperature programmed reduction. Usually, sulfurization treatment is carried out by hydrogen sulfide in a stream of hydrogen to molybdenum, as the reaction, it is necessary to oxygen from the molybdenum oxide is desorbed. Desorption peaks of water, because just those that detect the desorption of the oxygen of water from the molybdenum oxide is considered that there is a correlation reduction temperature of progression and molybdenum sulfide process. Therefore, by temperature reduction peak temperature of eliminated water is considered possible to sufficiently proceed the sulfurization process molybdenum.
[0089]
　Also when the reducing temperature is too high, that is, if the peak temperature of the eliminated water is too high, because water is a weakly interacts with composite oxide support, possibly aggregates of the active metal is present higher. Therefore, it is inferred that the sulfurization step does not proceed sufficiently. Accordingly, the reduction temperature is lowered, reducing the interaction between water and the inorganic composite oxide carrier is required to highly disperse the active metal.
[0090]
　Eliminated water has been generated primarily molybdenum reduction step, the peak temperature, the carrier composition, varies depending on the active metal composition and the like. According to the findings of the present inventors, in order to desorption peak temperature of the water (peak temperature of eliminated water) to 415 ° C. or less inorganic composite oxide support, as the active metal component, of molybdenum and tungsten as oxide equivalent at least one (a type), 15-27 wt%, it is necessary to 2-7 wt% at least one of cobalt and nickel (one) as the oxide equivalent.　
　If the active metal component is less than this range is not preferable because the catalytic performance is insufficient, when the active metal component is higher than this range is not preferable because the possibility of aggregates of the active metal is generated impaired dispersibility becomes higher .
[0091]
　The catalyst of the present invention is the adsorption amount of nitric oxide catalyst treated sulfide 8.0 ml / g or more. The adsorption amount, more preferably, is 8.5 ml / g or more. Based on Nitric Oxide adsorption amount, it is possible to measure the reaction active sites of the catalyst.　
　If the amount of adsorption of nitrogen monoxide is less than 8.0 ml / g is outside the scope of the present is not preferable because the effect of improving reduced catalyst performance reaction active sites of the catalyst can not be obtained.　
　Nitric oxide adsorption amount after sulfurization treatment of the catalyst, the physical properties and chemical properties of the carrier will vary depending on the active metal composition and the like. And to carry out the nitric oxide adsorption consists in the need sulfurization treatment, and necessary to lower below a certain temperature in the reduction temperature of the active metal.
[0092]
　本発明者の知見によれば、一酸化窒素の吸着量を８．０ｍｌ／ｇ以上とするためには、
ａ）無機複合酸化物担体の比表面積（ＳＡ）が１８０～３２０ｍ ２／ｇの範囲であること、
ｂ）前記無機複合酸化物担体中のアルミニウムを、無機複合酸化物担体１００質量部に対してアルミナ換算で８０～９８質量部含むこと、
ｃ）担体前駆体の中で主成分となるアルミナの擬ベーマイトのＸＲＤ回折スペクトル（０２０）ピークの半値幅より求めた結晶子径が１５以上４０Å以下であること、
　ｄ）無機複合酸化物担体上に活性金属成分として、モリブデン及びタングステンのうちのを少なくとも一方を酸化物換算として１５～２７質量％、コバルト及びニッケルのうちの少なくとも一方を酸化物換算として２～７質量％であること、が重要である。
また更にｄ）透過型フーリエ変換赤外分光光度計によって測定される酸性ＯＨ基に対応する３６７４～３６７８ｃｍ －１の波数範囲にあるスペクトルピークの吸光度Ｓａに対する、塩基性ＯＨ基に対応する３７７０～３７７４ｃｍ －１の波数範囲にあるスペクトルピークの吸光度Ｓｂの比率Ｓｂ／Ｓａが０．２０～０．４５の範囲であること、水の脱離ピーク温度を４１５℃以下にすることがより好ましい。
[0093]
　[Production method of hydrotreating catalyst for hydrocarbon oil]
Next, a method for manufacturing a hydrocarbon oil hydroprocessing catalyst of the present invention.　
　Method for producing a hydrotreating catalyst for hydrocarbon oil according to the present invention,　
　a first step of preparing an inorganic composite oxide support (preparation),　
　the first metal component is at least one of molybdenum and tungsten, cobalt and the second metal component is at least one of nickel, the organic acid, an impregnating solution containing the prepared, carrying said first metal component and second metal component to the inorganic composite oxide support and 2 steps,　
　obtained by the second step, a third obtaining said first metal component and heat treated to a hydrotreating catalyst at a second temperature of the alumina support metal components are supported 100 ~ 600 ° C. and a step, a.
[0094]
　Hereinafter, the respective steps will be described.　
　 «1-1. Step »obtain inorganic composite oxide slurry
　firstly an aqueous solution of a basic metal salt solution and an acidic metal salt, pH is 6.5-9.5, preferably 6.5-8.5, more preferably 6.8 to It was mixed so that 8.0 to obtain a hydrate of an inorganic composite oxide. In this case, the basic metal salt solution can also include a carboxylic acid salt. And after the slurry of hydrate of an inorganic composite oxides was aged by the desired method (first ripening step), except washed with byproduct salt, to obtain a composite oxide slurry containing alumina as a main component.　
　Carboxylate as used herein, polyacrylic acid, hydroxypropylcellulose, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, citric acid include salts are preferably added in an amount of 0.5-4.0 parts by weight relative to the composite oxide 100 parts by weight.　
　To obtain the hydrate of an inorganic composite oxide containing an element other than aluminum, the pH of the used metal salt, after previous mixing an aqueous solution of an aluminum salt of an acidic aqueous solution or basic aqueous solution, so that the range of the pH and mixing to obtain a hydrate of an inorganic compound oxide.
[0095]
　Further, as the basic aluminum salts, sodium aluminate, and potassium aluminate it is preferably used. As the acidic aluminum salt, aluminum sulfate, aluminum chloride, etc. aluminum nitrate is preferably used, as the phosphate source include phosphite ion, ammonium phosphate, potassium phosphate, sodium phosphate, acid, phosphoric acid compound resulting phosphate ions in water, such as phosphorous acid can be used. As the titanium mineral, titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, is exemplified such as titanium nitrate it is suitably used since in particular titanium sulfate, titanyl sulfate is inexpensive.
[0096]
　Upon mixing the two aqueous metal salt solution, usually 40 ~ 90 ° C., preferably heated and held in 50 ~ 70 ° C., a temperature ± 5 ℃ of the solution, preferably ± 2 ° C., and more preferably It warmed mixed aqueous solution ± 1 ° C., pH 6.5 to 9.5 as preferably of 6.5 to 8.5, more preferably 6.5-8.0, usually 5-20 min, preferably form a precipitate successively added during the 7 to 15 minutes, to obtain a slurry of hydrate.　
　The time required for addition of the mixed aqueous solution to a basic metal salt aqueous solution, because it may in addition to bayerite and undesirable crystals such as gibbsite pseudoboehmite becomes longer is generated, desirably 15 minutes or less, 13 minutes or less is further preferable. Since bayerite and gibbsite, the specific surface area when heated to become bad.
[0097]
　«1-2. The second aging step »inorganic composite oxide
　to a slurry of the resulting hydrate in the 1-1 step, adding at least one organic compound (first organic compound), in the aging tank with a reflux condenser , 30 ° C. or higher, preferably at 80 ~ 100 ° C., for example, 1 to 20 hours, preferably heat aged for 2 to 10 hours (second ripening step). In the first ripening stage and a second maturation phase, inorganic composite oxides concentration is preferably less than 20% (20 wt%).　
　«1-3. Kneading, molding and drying step »
　after said 1-2 The resulting aged product in step is heated kneading placed in a double arm kneader with a steam jacket moldable kneaded product, optionally extrusion molding molding of the shape. In this case, at least one second organic additive is added after the warming inorganic composite oxide concentration was concentrated to a 20% (20 wt%) or more, be further superheated kneaded thereafter good. The timing of the addition of a second organic compound may be a middle of concentrating the ripening thereof.
[0098]
　«1-4. Heat treatment (drying, calcining) step »
　The molded product obtained in Step 1-3, and then for example 70 ~ 0.99 ° C., preferably dried by heating at 90 ~ 130 ° C., preferably further example 400 ~ 800 ° C., preferably is obtained in 400 ~ 600 ° C., for example, 0.5 to 10 hours, preferably by baking 2-5 hours alumina support.　
　Further, as the first organic compound used in the first step and the second organic compound, at least one selected from organic acids or sugars are preferred. As the organic acids, citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), include diethylenetriaminepentaacetic acid (DTPA) it is. As also saccharides, monosaccharides, disaccharides, polysaccharides and the like. For any of the first organic compound and the second organic compound, it is desirable that the addition amount is in the range of 0.5 to 5.0 parts by weight of the inorganic composite oxide 100 parts by weight. Effect is obtained hardly by the addition of the additive amount of organic compound is less than this range, not only the physical properties of the catalyst becomes too small pore structure by too strong effect if it exceeds this range is not optimal range undesirable because the efficiency of the preparation is poor.
[0099]
　OH groups on the surface of the carrier, such as active metal species dispersibility, is an important factor in determining the carrying state. Control of the OH groups, the composition of the inorganic composite oxide support, along with crystalline carrier alumina precursor can be performed everywhere in the carrier preparation step. However, it is very difficult to adjust the OH group while maintaining the physical properties of the carrier. To meet this, it is preferable to appropriately set the composition of the inorganic composite oxide support. Additionally, it is also possible slightly to carry out adjustment of the OH group in a separate step after performing the control of the crystallinity. Therefore, after control the crystallinity in the second aging step, adding an organic compound in the step of kneading and concentrated (second organic compound), it is preferable to adjust the state of the OH group.
[0100]
　
　inorganic composite oxide support is contacted with an impregnation solution containing a first metal component and second metal component and a carbon component described above.　
　The raw material of the first metal component, e.g., molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, and tungsten trioxide is preferably used. As the raw material of the second metal component, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate or the like is preferably used.　
　Upon supporting the phosphorus composite oxide support also orthophosphoric acid (hereinafter, simply referred to as "phosphate"), ammonium dihydrogen phosphate, ammonium phosphate dibasic, trimetaphosphate, pyrophosphate, etc. tripolyphosphate used.　
　Impregnation solution to a pH of 4 or less using an organic acid, it is preferable to dissolve the metal component. stability of the metal components which pH is dissolved in excess of 4 tends to precipitate decreases. The organic acid, such as citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), available diethylenetriaminepentaacetic acid (DTPA), in particular, citric acid, malic acid is preferably used. The organic additives, saccharides (monosaccharides, disaccharides, polysaccharides, etc.) are used. Incidentally organic additive in an organic acid, for example, dextrose (glucose; C 6 H 12 O 6 ), fruit sugar (fructose; C 6 H 12 O 6), Maltose (maltose; C 12 H 22 O 11 ), milk sugar (lactose; C 12 H 22 O 11 C;), sucrose (sucrose 12 H 22 O 11 may be added, etc.).

claims

(1) a carrier composed mainly of alumina, and it is below a or b,
a. consisting of 100% γ- alumina
b. Relative to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and the carrier is determined from the half bandwidth of the XRD diffraction spectrum (020) peak of pseudoboehmite alumina as a main component in the precursor and the crystallite diameter is 15 or more 40Å or less
(2) on the support, a first metal component is at least one of molybdenum and tungsten, cobalt and the second metal is at least one of nickel a component, and that but are supported,
(3) the content of the first metal component, the catalyst 100 parts by weight, 15 to 27 mass parts as an oxide equivalent, the second metal component content, relative to the catalyst 100 parts by weight, and from 2 to 7 parts by mass as the oxide
equivalent, (4) for a carrier of said a has a specific surface area of the catalyst is 200 ~ 320 m / G, the carrier of the b has a specific surface area of the catalyst is 180 ~ 320 m 2 and that / g, an average pore diameter of the catalyst as measured by mercury porosimetry is 50 ~ 110 Å, (5) an ignition loss of 5 and it is 2.0 wt% or less, (6) carbon derived from the organic acid, the catalyst 100 parts by weight, and not more than 2.0 parts by weight elemental basis, of (7) sulfide treated catalyst and that adsorbed amount of nitrogen monoxide is 8.0 ml / g or more,

　Hydrocarbon oil hydroprocessing catalyst comprising the.
[Requested item 2]
　Based on temperature programmed reduction of the catalyst, carbide of claim 1, wherein the eliminated water peak temperature ranging 450 ° C. (temperature at which a peak of desorption spectrum appears in water) is 415 ° C. or less hydrogen oil hydrotreating catalyst.
[Requested item 3]
　The carrier consists of 100% .gamma.-alumina,
the carrier, transmission Fourier transform infrared spectroscopy corresponding to acidic OH groups measured by the photometer 3674 ~ 3678Cm -1 absorbance Sa spectral peaks in the wave number range of for basic OH corresponding to the radical ~ 3774Cm 3770 -1 claim 1, wherein the ratio Sb / Sa of the absorbance Sb spectral peaks in the wave number range is characterized in that in the range of 0.15 to 0.40 a hydrocarbon oil hydroprocessing catalyst.
[Requested item 4]
　　The carrier consists of 100% .gamma.-alumina,
　the carrier, the diffraction peak area showing the crystal structure of boehmite (020) plane measured by X-ray diffraction analysis P1, diffraction showing the crystal structure of the (120) plane the peak area P2, when the diffraction peak area showing the aluminum crystal structure attributed to a γ- alumina (440) plane and
　P3, (P1 / P3) and the value (P2 / P3) of × 100 (%) × 100 ( % of the value of) the larger value of hydrocarbon oil according to claim 1, characterized in that less than 10% hydrotreating catalyst.
[Requested item 5]
　　The carrier consists of 100% .gamma.-alumina,
　the carrier, and wherein the crystallite size determined from the half value width of the XRD diffraction spectrum (020) peak of pseudoboehmite alumina is a precursor is less than 45Å hydrocarbon oil hydroprocessing catalyst according to claim 1 wherein the.
[Requested item 6]
　A method of manufacturing a hydrotreating catalyst for hydrocarbon oil according to claim 1,
　　wherein the carrier consists of 100% .gamma.-alumina,
an aqueous solution of (A) a basic aluminum salt solution and an acidic aluminum salt a first aging step of aging the slurry containing alumina obtained by mixing,
after dehydrating the aged slurry, comprising the steps of cleaning,
followed by a second aging step of aging the slurry containing the washed object to be cleaned and ,
then, kneading the slurry, a step of concentration,
a step of molding the concentrate slurry was concentrated,
dried and then the molded article, including the steps of firing, a step of preparing a γ- alumina support,
(B ) a first metal component is at least one of molybdenum and tungsten, cobalt and impregnating solution containing a second metal component is at least one of nickel, and organic acids, Prepared, and a step of carrying said first metal component and second metal component to the γ- alumina carrier,
(C) the obtained in the steps (B), said first metal component and the second metal component is, obtaining a hydrotreating catalyst by heating the supported γ- alumina carrier
manufacturing method of hydrotreating catalyst for hydrocarbon oil, comprising a.
[Requested item 7]
　In a second aging step in the step (A), producing a hydrocarbon oil hydroprocessing catalyst according to claim 6, wherein the addition of the first organic compound to the slurry.
[Requested item 8]
　Wherein the first organic compound is The process according to claim 7, wherein the hydrotreating catalyst for hydrocarbon oil, which comprises adding 0.5 to 5.0 parts by weight with respect to 100 parts by weight of alumina.
[Requested item 9]
　Kneading the slurry in the step (A), after the step of concentrating said prior to the step of molding the concentrate, hydrogen hydrocarbon oils according to claim 6, characterized in that the addition of the second organic compound method for producing a hydroprocessing catalyst.
[Requested item 10]
　The second organic compound, The method according to claim 9, wherein the hydrocarbon oil hydroprocessing catalyst, characterized by adding in the range of 0.5-5.0 parts by weight per 100 parts by weight of alumina.
[Requested item 11]
　Wherein the first organic compound, organic acids, method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 7, characterized in that at least one kind of sugars.
[Requested item 12]
　The second organic compound, organic acids, method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 9, characterized in that at least one kind of sugars.
[Requested item 13]
　Method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 6 basic aluminum salt solution in the step (A) is characterized in that it comprises a carboxylate.
[Requested item 14]
　In the first ripening stage and a second maturation phase contained in the step (A), the alumina concentration is less than 20%,
kneading the slurry in the step (A), in the step of concentration, alumina concentration above 20% method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 6, characterized in that.
[Requested item 15]
　The temperature of the heat treatment in step (C) is the manufacturing method of the hydrotreating catalyst for hydrocarbon oil according to claim 6, characterized in that the temperature of 100 ~ 600 ° C..
[Requested item 16]
　The carrier, with respect to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and carrier, XRD diffraction spectrum of pseudoboehmite alumina as a main component in the precursor (020) peak crystallite size determined from the half value width is 15 or more 40Å or less,
　the carrier, transmission Fourier transform infrared corresponding to acidic OH groups measured by the outside spectrophotometer 3674 ~ 3678Cm -1 spectrum in the wave number range of to the absorbance Sa peak, 3770 ~ 3774cm corresponding to basic OH groups -1 wave number range of
the ratio Sb / Sa of the absorbance Sb spectral peak is characterized in that in the range of 0.20 to 0.45 claim 1, wherein the hydrocarbon oil hydroprocessing catalyst.
[Requested item 17]
　The carrier, with respect to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and carrier, XRD diffraction spectrum of pseudoboehmite alumina as a main component in the precursor (020) peak crystallite size determined from the half value width is 15 or more 40Å or less,
the carrier,
c. Relative to 100 parts by weight of carrier, those containing phosphate phosphate conversion 5.0 parts by mass or
less, d. Relative to 100 parts by weight of carrier, those containing silicon in terms of silica 3.0 parts by weight or
less, e. Relative to 100 parts by weight of carrier, which contains more than 18.0 parts by mass of titanium titania
terms, f. Relative to 100 parts by weight of carrier, those containing less 9.0 parts by mass of zirconium oxide zirconia terms
　hydrotreating a hydrocarbon oil according to claim 1, characterized in that corresponding to at least one of catalyst.
[Requested item 18]
　The carrier, with respect to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and carrier, XRD diffraction spectrum of pseudoboehmite alumina as a main component in the precursor (020) peak crystallite size determined from the half value width is 15 or more 40Å or less,
the carrier, the diffraction peak area showing the aluminum crystal structure attributed to a boehmite (020) plane measured from XRD diffraction spectrum P1, .gamma.-alumina When a diffraction peak area showing the crystal structure of the (440) plane and P2, according to claim 1, P2 ratio P2 / a with respect to the sum of P1 and P2 (P1 + P2) is equal to or less than 0.9 a hydrocarbon oil hydroprocessing catalyst.
[Requested item 19]
　A method of manufacturing a hydrotreating catalyst for hydrocarbon oil according to claim 1,
　wherein the carrier, relative to 100 parts by weight of carrier, aluminum containing 80-98 parts by weight in terms of alumina, and carrier , crystallite size determined from the half value width of the XRD diffraction spectrum (020) peak of pseudoboehmite alumina as a main component in the precursor is at least 15 40Å or less,
a step of preparing a (D) a carrier
(E ) and molybdenum and the first metal component is at least one of tungsten, and cobalt and the second metal component is at least one of nickel, and organic acid, an impregnating solution containing the prepared, the first metal a step of carrying the component and a second metal component in the inorganic composite oxide support,
(F) the obtained in the step of (E), said first metal component and is supported second metal component Carrier by heating at a temperature of 100 ~ 600 ° C. and a step of obtaining a hydrotreating catalyst
　manufacturing method of hydrotreating catalyst for hydrocarbon oil, which comprises a.
[Requested item 20]
　Preparing a carrier of the (D) is
a slurry preparation step of preparing a composite metal hydrate slurry by mixing a solution of (D-1) a basic metal salt solution and an acidic metal salt,
(D- 2) the a first aging step of aging the composite metal hydrate slurry,
and washing the (D-3) and then the composite metal hydrate slurry,
(D-4) Thereafter, the composite metal hydrate a second aging step for the aged slurry,
(D-5) Thereafter, the composite metal hydrate slurry mixing, kneading and concentration step of concentrating,
the (D-6) the composite metal hydrate slurry a step of molding the concentrate obtained by concentrating,
(D-7) then dried molded body, and a step of firing,
in a second aging step of the (D-4), a first organic hydrogen hydrocarbon oil of claim 19 wherein adding a compound Method for producing a hydroprocessing catalyst.
[Requested item 21]
　Wherein (D-1) according to claim 20 manufacturing method of hydrotreating catalyst for hydrocarbon oil according to the basic aluminum salt solution in the slurry preparation step is characterized in that it comprises a carboxylate.
[Requested item 22]
Wherein the first organic compound, according to claim 20, wherein the addition of 0.5 to 4.0 mass parts of the inorganic composite oxide 100 parts by weight of the hydrocarbon oil hydroprocessing catalyst Production method.
[Requested item 23]
　Wherein the (D-5) kneading and concentration step of the method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 20, characterized by adding the second organic compound.
[Requested item 24]
The second organic compound, according to claim 23, wherein the addition in a range of 0.5-4.0 parts by weight with respect to the inorganic composite oxide 100 parts by weight of the hydrocarbon oil hydroprocessing catalyst Production method.
[Requested item 25]
　The (D-4) Inorganic composite oxides concentration in the slurry in the second aging step of less than 20%, inorganic composite oxides concentration in the slurry in the kneading and concentration step of the (D-5) 20% method for manufacturing a hydrocarbon oil hydroprocessing catalyst according to claim 20, characterized in that at least.
[Requested item 26]
Wherein the first organic compound is citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and sugars (monosaccharides, polysaccharides, etc.) at least one selected from method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 19, characterized in that.
[Requested item 27]
　The second organic compound is citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and sugars (monosaccharides, polysaccharides, etc.) at least one selected from method for producing a hydrotreating catalyst for hydrocarbon oil according to claim 23, characterized in that.
[Requested item 28]
　In the presence of a hydrotreating catalyst according to claim 1, a hydrogen partial pressure of 3 ~ 8 MPa, the temperature is 260 ~ 420 ° C., a liquid hourly space velocity is 0.3 ~ 5 hr -1 hydrotreating hydrocarbon oils at conditions hydrotreating a hydrocarbon oil which is characterized in that a.