JPH10180097A - Catalyst for hydrogen treatment of hydrocarbon oil and hydrogen treating method of gas oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a catalyst for a hydrogen treatment of a hydrocarbon oil having a high hydrogenation activity to an arom. compd. together with a high resistance to sulfur and also having a high desulfurizing performance and to provide a production method of a gas oil blend base material having low sulfur content and low arom. compd. content by executing a contact reaction of the gas oil containing the arom. compd. by using the catalyst. SOLUTION: In the catalyst, 0.1-8 mass % at least one kind platinum group metal based on the catalyst and expressed in terms of metal or 0.1-2 mass % germanium based on the catalyst and expressed in terms of metal is incorporated together with at least one kind platinum group metal as an active component for hydrogenation in the carrier containing 2-50 mass % silica, 2-20 mass % ziroconia and 30-96 mass % alumina. The gas oil is subjected to the hydrogen treatment by executing the contact reaction of a gas oil fraction containing the arom. compd. at 3-8MPa hydrogen partial pressure, at 200-370 deg.C and at 0.3-5hr<-1> liq. space velocity by using this catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst used in a hydrogenation reaction of a hydrocarbon oil to reduce the aromatic compound content and the sulfur content of the hydrocarbon oil, and to hydrogenate light oil using the catalyst. Regarding the treatment method, more specifically, a catalyst having high hydrogenation activity for aromatic compounds and high sulfur resistance, and also having high desulfurization performance, and using the catalyst, low sulfur content and The present invention relates to a method for producing a gas oil blend base material having a low aromatic compound content.

[0002]

BACKGROUND ART A diesel engine frequently used as an internal combustion engine is obtained by subjecting a straight gas oil fraction having a specific boiling point obtained by atmospheric distillation of crude oil or a hydrogen gas treatment to the straight gas oil fraction. The fuel is a gas oil fraction or a gas oil obtained by blending the gas oil fraction obtained from another source with the gas oil fraction as a main base material.

[0003] Gas oil straight cuts suitable for diesel engines contain only a limited amount of crude oil per unit amount of crude oil, and the available crude oil is becoming heavier every year. The content of the fraction tends to be further reduced. Therefore, in order to secure a necessary amount of the gas oil fraction, heavy oil is decomposed and converted into a gas oil base material.

[0004] On the other hand, demand for light oil is partly due to an increase in demand for light oil accompanying an increase in diesel engine vehicles.
It is increasing, and it is expected that the supply of gas oil will be significantly short in the near future.

[0005] One of the methods to cope with the shortage of the gas oil fraction obtained as a straight fraction from crude oil, in other words, to cope with the increased demand for gas oil, is to produce a blend base material to be blended with the straight gas oil fraction. It is to increase the amount.

[0006] Therefore, a light cracking gas oil (Light Cycle) having a specific boiling point range obtained from a catalytic cracking unit.
Oil (hereinafter abbreviated as LCO) has attracted attention as a feedstock for a new blend base material for light oil. This is because, contrary to the light oil fraction, LCO tends to be excessive due to the above-mentioned heavy crude oil, and it is desirable to divert the LCO to the blend base material in view of the supply and demand balance of the fraction.

[0007] However, since LCO contains a large amount of aromatic components, if LCO is blended as it is with a straight gas oil fraction, the content of aromatic compounds increases,
There is concern that the cetane number of the blended light oil will be reduced and the quality of the light oil will be reduced. In addition, since the content of the aromatic compound is high, there is a concern that when the blended light oil is used as a fuel for a diesel engine, the amount of generated particulates is significantly increased. Particulates are fine particulate air pollutants generated by incomplete combustion of some aromatic compounds, and the emission of large amounts of particulates into the atmosphere poses a serious environmental conservation problem. Will cause. In addition, LCO has a unique coloring, and if it is used as it is as a blend base material for light oil, the quality of the product light oil in terms of hue becomes a problem.

In order to solve such concerns and to use LCO as a good blend substrate, attempts have been made to subject LCO to catalytic hydrogenation to reduce the content of aromatic compounds in LCO. I have.

[0009] However, when the LCO is hydrogenated by the conventional method, the following problems occur. (1) Sulfur compounds contained in LCO in a relatively large amount and hydrogen sulfide generated by hydrotreating them inhibit the hydrogenation reaction of aromatic compounds and poison active sites on the catalyst. And cause deterioration of activity. (2) LCO has a high content of a high boiling point hardly desulfurizable sulfur compound (eg, 4,6-dimethyldibenzothiophene), although the total sulfur compound content is smaller than that of a straight-run gas oil fraction. Even if LCO is desulfurized, it requires deep desulfurization under severe conditions, which is not economically feasible. (3) Although the total sulfur content is lower than that of straight-run gas oil, LC
In O, the non-desulfurizable sulfur compound exists in a high composition ratio with respect to all the sulfur compounds. For this reason, depending on the properties of the feed oil and the standards required for the product oil, it is necessary to further reduce the sulfur content in the product oil to a predetermined level. There is a need for efficient and effective hydrogenation (desulfurization) performance that can be removed by hydrogenation.

[0010] Accordingly, there is a need for a hydrotreating catalyst for LCO, which is necessary for hydrotreating LCO to reduce aromatic compounds and for using LCO as a good blend base material for a gas oil fraction. The condition is to have both high hydrogenation activity for aromatic compounds and high sulfur resistance, and also have high desulfurization performance capable of hydrogenating and removing hardly desulfurizable sulfur compounds.

Conventional catalysts which have been tried as LCO hydrotreating catalysts are roughly classified into two types, one of which is a hydrotreating catalyst mainly used for hydrotreating light oil. The other one is a group VIA metal-group VIII metal catalyst of the periodic table, for example, a desulfurization catalyst such as a CoMo or NiW catalyst using an alumina carrier.

However, the above hydrotreating catalyst contains a metal species having poor sulfur resistance, such as nickel, palladium, and platinum, as an active component of the catalyst. It works effectively only in a low sulfur atmosphere of less than ppm. For this reason, it is technically difficult to use the above hydrotreating catalyst for hydrotreating LCO having a higher sulfur compound content.

The above desulfurization catalyst is a typical hydrodesulfurization catalyst used in a petroleum refining process, and is originally a catalyst intended for hydrodesulfurization. However, the hydrogenation performance of aromatic compounds is not sufficient. For this reason, the above desulfurization catalyst is
In order to hydrogenate aromatic compounds and convert them to naphthenes, which are used as catalysts for CO hydrotreating, depending on other conditions such as the properties of the feedstock and the reaction temperature under a high hydrogen partial pressure of about 10 MPa. It is necessary to carry out the hydrotreating under the above high hydrogen partial pressure, which increases the equipment cost and the operating cost. Instead of increasing the hydrogen partial pressure, the reaction rate can be increased by increasing the reaction temperature to promote the conversion of the aromatic compound.However, increasing the reaction temperature is not suitable for the exothermic hydrogenation reaction. Not only is it disadvantageous in terms of reaction equilibrium, but also side reactions such as a decomposition reaction and a polycondensation reaction remarkably proceed, so that the yield of a hydrogenated product is reduced, which is not economical. In addition, since the reaction is a high temperature reaction, the problem of the hue of the produced oil is not improved, and further, there is a problem that the equipment cost and the operating cost of the device are increased.

As described above, conventional catalysts have both high hydrogenation activity for aromatic compounds and high sulfur resistance, and have excellent desulfurization performance even for hardly desulfurizable sulfur compounds. Therefore, it was not suitable for the treatment used in the hydrogenation reaction of LCO to reduce the aromatic compound content of LCO.

[0015]

Accordingly, an object of the present invention is, firstly, to provide a catalyst suitable for reducing the aromatic compound content by hydrotreating a hydrocarbon oil, particularly a gas oil fraction. The second is to provide a method for hydrotreating a gas oil fraction using the catalyst.

[0016]

SUMMARY OF THE INVENTION The present inventors have conducted various studies to solve the above-mentioned problems. As a result, first, (a) in order to reduce aromatic compounds by nuclear hydrogenation, a platinum group metal-based catalyst was used. Is promising. However, as mentioned above,
Since the platinum group metal-based catalyst has low sulfur resistance, studies for increasing the sulfur group were further repeated. As a result, (b) if the acid property of the catalyst has a predetermined value, the platinum group metal has a high dispersion. As described in (e) below, not only the sulfur resistance is remarkably improved, but also the hydrogenation action of the aromatic compound is remarkably improved, and (c) platinum as an active metal. Surprisingly, the acid property of the catalyst using a group metal can be easily adjusted to a suitable value by using a carrier composed of an inorganic oxide containing silica-zirconia-alumina as a main component, (d Also, surprisingly, if germanium is supported together with the platinum group metal, the platinum group metal is supported with high dispersibility, and sintering of the platinum group metal is suppressed. Significant improvement in nuclear hydrogenation of compounds (E) According to the above-mentioned catalyst, under the conditions of a high hydrogen / oil ratio which can be carried out at a relatively low cost, and a hydrogen partial pressure and a reaction temperature which are almost similar to those of the conventional hydrotreating. In addition, the activity degradation due to sulfur compounds and the like is suppressed, and a higher hydrogenation activity for aromatic compounds is obtained as compared with conventional desulfurization catalysts such as NiW-based or CoMo-based and platinum-based hydrogenation catalysts. Obtained knowledge.

The present invention has been made based on the above findings. [1] Silica 2 to 50% by mass, zirconia 2 to 20%
The carrier containing 30 to 96% by mass of alumina and 30 to 96% by mass of alumina contains at least one platinum group metal as a hydrogenation active component in an amount of 0.1 to 8% by mass in terms of metal on a catalyst basis;
Or a catalyst for hydrotreating a hydrocarbon oil, characterized by containing 0.1 to 2% by mass of germanium, in terms of metal, on a catalyst basis, together with the platinum group metal, and [2] the above catalyst A hydrogen partial pressure of 3-8 MPa in the presence of
The gist of the present invention is a gas oil hydrotreating method characterized by performing a catalytic reaction of a gas oil fraction containing an aromatic compound at a temperature of 200 to 370 ° C. and a liquid hourly space velocity of 0.3 to 5 hr ⁻¹ .

The catalyst of the present invention is suitable for hydrotreating hydrocarbon oils, especially gas oil fractions, for example, catalytic cracking gas oil, straight run gas oil, pyrolysis gas oil, hydrotreated gas oil, desulfurized gas oil, etc. ing. As typical properties of these feedstocks,
Boiling range: 150 to 450 ° C, sulfur content: 2000 mass p
pm or less, preferably 500 ppm by mass or less, and aromatic compounds: in the range of 5 to 90% by volume.

The carrier of the catalyst of the present invention contains silica, zirconia and alumina in a ratio of silica: zirconia: alumina = 2 to 50: 2 to 20:30 to 96 (% by mass) on the basis of the carrier. If the silica is out of this range, it becomes impossible or extremely difficult to adjust the acidity of the catalyst to a suitable value.If the zirconia is out of this range, the basicity unique to zirconia does not appear, and coke precipitation occurs. Actions such as suppression are not well exhibited. Preferably,
Silica content 2-30% by mass, zirconia content 2
To 15% by mass, more preferably the silica content is 2%.
-20% by mass, and the zirconia content is 2-10% by mass. Alumina can use various aluminas such as α-alumina, β-alumina, γ-alumina, δ-alumina, and porous alumina having a high specific surface area is preferred, and γ-alumina is particularly suitable. I have.

Note that zirconia has acid properties in addition to the above-mentioned base. By the way, when one catalyst has both acidic and basic properties, the properties cooperate to promote the reaction (both acid-base catalysis). Chemical Dojinsha, 1988). In the present invention, by using zirconia, together with silica, in combination with alumina, the acidity of the catalyst is increased to promote the hydrogenation reaction,
At this time, due to the basicity of zirconia, the action of suppressing coke precipitation, which causes a decrease in activity, occurs as described above. Then, the acid properties and the basicity are harmonized, and the acid properties of the catalyst are adjusted to suitable values, and the sulfur resistance of the catalyst is improved. These effects are favorably exhibited when the content of alumina, silica, and zirconia is within the above range, and is not favorably exhibited when the content is out of the range.

The specific surface area, pore volume, and average pore diameter of the carrier containing silica, zirconia, and alumina are not particularly limited, but are excellent in sulfur resistance, and are preferably hydrocarbon oils, particularly aromatic oils. In order to obtain a catalyst having an enhanced hydrogenation activity and desulfurization activity for the compound, the specific surface area should be 100 to 6
00 m ² / g, preferably 200 to 400 m ² / g, pore volume 0.4 to 1.2 ml / g, average pore size 50 to
Those in the range of 200 °, preferably 50-150 °, are suitable. In addition, the carrier has an ammonia-TP
It is preferable that the acid amount measured by the method D is 0.6 to 3.5 mmol / g.

The active ingredient to be supported on the carrier is at least one kind of platinum group metal, and may be any one of platinum group metals such as platinum, palladium, rhodium, ruthenium, osmium and iridium. Can be used in combination. These platinum group metals are supported in the form of a compound, and specific examples of the compound include metal chlorides, chlorides, nitrates, sulfates, acetates, phosphates, and organic acid salts. Metal chlorides, chlorides and nitrates. These compounds can be used alone or
More than one species can be used in combination.

Germanium can be supported together with the platinum group metal compound. Specific examples of germanium compounds include germanium tetrachloride, germanium difluoride, germanium tetrafluoride, germanium diiodide,
Germanium monosulfide, their analogous compounds,
These can be carried alone or in combination of two or more.

Among these active ingredients, the content of the platinum group metal is 0.1 to 8% by mass in terms of metal on a catalyst basis.
Preferably it is 0.2 to 2% by mass. The platinum group metal
If the amount is less than 0.1% by mass, the active sites attributed to the platinum group metal cannot be sufficiently obtained. If the amount exceeds 8% by mass, not only the dispersibility of the active metal deteriorates due to aggregation of the platinum group metal compound, but also, Since the active metal content exceeding the limit of the efficiently dispersed metal is exceeded, the cost is also increased.

When germanium is contained in addition to the platinum group metal, the content of germanium is based on the catalyst,
It is 0.1 to 2% by mass in terms of oxide. Germanium improves the dispersibility of the platinum group metal, suppresses sintering of the platinum group metal, and suppresses coke deposition and sulfur deposition on the platinum group metal. Germanium,
If the amount is less than 0.1% by mass, it is insufficient to exert these effects. If the amount exceeds 2% by mass, not only the platinum group metal but also the reactive active sites present on the carrier are covered, No improvement in catalyst activity is observed.

The catalyst of the present invention may contain a halogen in addition to the above-mentioned components in order to make the acidity of the catalyst a suitable value. The content of the halogen is 0.05 to 3% by mass, preferably 0.1 to 1% by mass in terms of an element on a catalyst basis.

The catalyst of the present invention comprising the above components has an acid content of 0.4 to 3 mm as measured by the ammonia-TPD method.
ol / g is preferred. Where ammonia-
TPD (Temperature Program)
The d Desorption method refers to the sample (ie,
A predetermined amount of a carrier or a catalyst is filled in an adsorption tube, and as a pretreatment, the temperature is raised to a predetermined temperature in an inert gas flow for a predetermined time, kept at the same temperature in the same gas flow for a predetermined time, and cooled to room temperature for a predetermined time. After lowering the temperature and performing ammonia adsorption for a predetermined time at room temperature and normal pressure, in a state where the above inert gas is flown, perform deaeration for a predetermined time at a predetermined temperature under a predetermined reduced pressure. A method in which an ammonia desorption spectrum is observed in the above-mentioned inert gas stream at a predetermined heating rate, and the amount of acid is specified by the amount of ammonia obtained from this spectrum.

When the acid amount is less than 0.4 mmol / g, high dispersibility of the platinum group metal cannot be secured, and it becomes difficult to reduce the electron density of the platinum group metal. The effect of improving nuclear hydrogenation and the effect of improving sulfur resistance cannot be sufficiently obtained. When the amount is more than 3 mmol / g, undesired side reactions such as overcracking of a feed oil fraction are caused. Incidentally, in the catalyst of the present invention, the acid amount is 0.4
When the content of each component is within the above-mentioned predetermined range of the present invention, the object of the present invention (nuclear hydrogenation of an aromatic compound or sulfur-desulfurizing sulfur compound) Reduction, etc.) can be achieved more effectively.

The catalyst of the present invention can be prepared by the following method. First, the silica-zirconia-alumina carrier is manufactured by (i) a method in which silica, zirconia, and alumina gels are each manufactured in advance and then mixing them; (ii) a method in which silica gel and zirconia gel are mixed with an aluminum compound solution. A method of adding an appropriate amount of a basic substance after immersion in a silica gel or a zirconia gel; (iii) adding an appropriate amount of a basic substance after immersing the alumina gel or silica gel in a solution of a water-soluble zirconium compound (Iv) immersing the alumina gel or zirconia gel in a solution of a water-soluble silicon compound and then adding an appropriate amount of a basic substance; How to deposit,
(V) a method of immersing silica gel in a solution of a water-soluble aluminum compound and a water-soluble zirconium compound and then adding an appropriate amount of a basic substance, and depositing an alumina gel and a zirconia gel on the silica gel; A method of depositing an alumina gel or silica gel on a zirconia gel by adding an appropriate amount of a basic substance after immersion in a solution of a compound and a water-soluble silicon compound, (v
ii) a method of immersing the alumina gel in a solution of a water-soluble silicon compound and a water-soluble zirconium compound and then adding an appropriate amount of a basic substance, depositing silica gel and zirconia gel on the alumina gel, (viii) water-soluble aluminum compound, water-soluble A method of adding a basic substance to a homogeneous mixed solution of a water-soluble silicon compound and a water-soluble zirconium compound to coprecipitate both can be adopted.

As one specific example, a basic aluminum compound (eg, sodium aluminate) and a basic silicon compound (water) are added to an aqueous solution of an acidic aluminum compound (eg, aluminum sulfate) and an acidic zirconium compound (eg, zirconium sulfate). Glass) was added and mixed, and then alkali hydroxide was added to adjust the pH and silica-
A suspension of zirconia-alumina hydrogel is formed. Next, the precipitate is filtered off with a filter and washed with ammonium carbonate and water to remove impurity ions. Then, it is dried using a spray drier or the like. The gel thus obtained is molded by an extrusion molding machine, dried, and calcined at about 400 to 700 ° C. for about 1 to 10 hours to obtain a carrier.

Next, the active component is supported on the carrier prepared as described above by a known method to prepare the catalyst of the present invention. As a first loading method, an acid, water, a solution prepared by dissolving the active ingredient in a solvent such as alcohols,
An impregnation method in which the carrier prepared as described above is impregnated once or more times to carry the active ingredient on the carrier is exemplified. As the solvent at this time, for example, an acidic solvent such as hydrochloric acid, nitric acid, and sulfuric acid can be used. After the impregnation, drying and baking are performed. If the number of times of the impregnation is plural, drying and baking may be performed for each impregnation.

When the germanium compound is impregnated in addition to the platinum group metal compound, the order of impregnation is not particularly limited, and the germanium compound may be impregnated before or after the platinum group metal compound is impregnated. You may impregnate simultaneously. It is preferable to impregnate simultaneously from the viewpoint of the properties of the product catalyst such as acidity and pore properties, or the operability.

As another method, a part or all of the active ingredient is mixed with a carrier material before being molded as a carrier,
A kneading method of integrally molding, a coprecipitation method, and the like can be given.

The specific surface area, pore volume and average pore diameter of the catalyst of the present invention prepared by the above-mentioned catalyst preparation method are not limited as long as the function as a catalyst is exhibited. In order to increase the hydrogenation activity and desulfurization activity for hydrocarbon oils as in the case of the above-mentioned carriers, those having the following values are suitable.

[0035] The specific surface area is preferably ^{100~600m 2 / g, 200~400m 2 /} g is more preferable. The pore volume is preferably 0.4 to 1.2 ml / g,
0.9 ml / g is more preferred. Average pore size is 50 ~
200 ° is preferable, and 50 to 150 ° is more preferable.
If the average pore diameter is less than 50 °, the reactants are difficult to diffuse into the pores, and the hydrogenation reaction of the aromatic compound and the hardly desulfurizable sulfur compound does not proceed efficiently. 200Å
If it is larger, the diffusivity in the pores is good, but the surface area in the pores decreases, so that the effective specific surface area of the catalyst decreases and the activity decreases.

In order to increase the effective number of pores satisfying the above pore conditions, the pore diameter distribution of the catalyst (that is, the ratio of pores having a pore diameter of an average pore diameter ± 15 °) is 70%.
Or more, more preferably 80% or more.

The method for hydrotreating light oil of the present invention using the above-mentioned catalyst is carried out at a hydrogen partial pressure of 3 to 8 MPa, 200 to 37 MPa.
At a temperature of 0 ° C. and a liquid hourly space velocity of 0.3 to 5 hr ⁻¹ , the catalyst is brought into contact with a light oil fraction containing an aromatic compound, and the aromatic compound is subjected to nuclear hydrogenation to produce an aromatic compound. This is a method for reducing the content of sulfur and the content of sulfur compounds such as non-desulfurization. The typical properties of the gas oil fraction containing the aromatic compound are the same as those described above as examples of the properties of the feedstock oil to which the catalyst of the present invention can be applied.

In order to carry out the hydrotreating method of the present invention on a commercial scale, a fixed bed, a moving bed or a fluidized bed type catalyst layer of the catalyst of the present invention is formed in a reactor, and the catalyst is formed in the reactor. The feedstock may be introduced and the hydrogenation reaction may be performed under the above conditions.
Most commonly, a fixed bed catalyst bed is formed in a reactor,
Feeding the feedstock to the top of the reactor, passing it through the fixed bed from top to bottom, and allowing the product to flow out of the bottom of the reactor,
Conversely, feedstock is introduced into the lower part of the reactor, passes through the fixed bed from bottom to top, and the product flows out from the upper part of the reactor.

The catalyst of the present invention can be used in the case of performing a single-stage hydrogenation treatment by charging it into a single reactor, or it can be used in the case of filling up several reactors and performing multi-stage continuous hydrogenation treatment. It can also be used when performing In particular, when the feedstock is relatively heavy, it is preferable to perform multi-stage hydrotreating.

[0040]

【Example】

[Preparation of Catalyst] The measurement procedure of the catalyst prepared in the following Examples and Comparative Examples and the carrier before preparation by the ammonia-TPD method was as follows. Sample (carrier and catalyst) using ammonia-TPD device manufactured by Bell Japan
0.1 g was charged into an adsorption tube, and the temperature was raised to 500 ° C. in a He gas stream over 50 minutes as a pretreatment, and 500
C. for 1 hour, and cooled to room temperature in 11 minutes and 30 seconds.
After adsorbing ammonia for 15 minutes at room temperature and normal pressure,
e at 100 ° C. under reduced pressure of 150 Torr
For 12 minutes and 30 seconds. With respect to the degassed sample, an ammonia desorption spectrum was observed in a He gas flow at a temperature rising rate of 10 ° C./min, and the total ammonia desorption amount was obtained and defined as an acid amount.

Example 1 In an eggplant type flask, silica-zirconia-alumina having a pore volume of 0.78 ml / g and a surface area of 286 m ² / g (mass ratio of silica / zirconia / alumina = 10/10/8)
0, 1/16 inch diameter columnar molded product, acid amount 0.53m
(mol / g) 19.41 g and 15.14 g there.
0.5205 g of chloroplatinic acid hexahydrate in 1 g of deionized water
Was dissolved using a pipette. About 2
After immersion at 5 ° C. for 2 hours, the mixture was air-dried, the temperature of the immersion mixture was increased to 120 ° C. in a muffle furnace, and the mixture was dried for about 1 hour. Next, the mixture was calcined at 500 ° C. for 4 hours to obtain a catalyst A.

The composition of the catalyst A was Pt (1.14% by mass).
-Cl (0.13% by mass) / SiO ₂(10.40 mass
%)-ZrO₂(9.50% by mass) -Al₂O₃(7
(8.83% by mass). The physical properties of catalyst A
Product 275m²/ G, pore volume 0.67 ml / g, average fineness
The hole diameter was 74 °. The acid amount of catalyst A is 0.48 mmol
/ G.

Example 2 Into an eggplant type flask, 24.87 g of the same silica-zirconia-alumina as used in Example 1 was charged, and 19.40 g of ion-exchanged water was added to chloroplatinic acid hexahydrate. An aqueous solution in which 0.3318 g was dissolved was added using a pipette, and impregnation, drying, and calcining were performed under the same conditions as in Example 1 to obtain Catalyst B.

The composition of the catalyst B was Pt (0.60% by mass).
/ _SiO 2 (10.43 _wt%) - ZrO 2 (8.10
_{Wt%) -} it was Al 2 O 3 (80.87 wt%).
The physical properties of the catalyst B were a surface area of 267 m ² / g, a pore volume of 0.68 ml / g, and an average pore diameter of 75 °. Catalyst B
Was 0.48 mmol / g.

Example 3 Into an eggplant-shaped flask, 24.87 g of the same silica-zirconia-alumina as used in Example 1 was charged, and 32.38 g of a 0.1 N hydrochloric acid aqueous solution was added to 32.38 g of chloroplatinic acid 6 water. 0.5219 g of Japanese product and 0.2380 g of germanium chloride
Example 1 was added using a pipette to add a solution in which
Impregnation, drying and calcination were carried out under the same conditions as in Example 1 to obtain Catalyst C.

The composition of the catalyst C was Pt (0.52% by mass).
-Ge (0.20% by mass) -Cl (0.31% by mass) /
SiO ₂ (10.43 wt%) _- ZrO 2 (8.58 _{wt%) -} was Al 2 O 3 (79.96 wt%). The physical properties of the catalyst C were a surface area of 288 m ² / g, a pore volume of 0.67 ml / g, and an average pore diameter of 66 °. Catalyst C
Was 0.49 mmol / g.

Comparative Example 1 Into an eggplant-shaped flask, 23.23 g of alumina (columnar molded product having a diameter of 1/16 inch) having a pore volume of 0.73 ml / g and a surface area of 380 m2 / g was charged, and 16.96 g was added thereto.
An aqueous solution in which 0.6230 g of chloroplatinic acid hexahydrate was dissolved in the ion-exchanged water of Example 1 was added using a pipette.
Impregnation, drying and calcination were carried out under the same conditions as in Example 1 to obtain Catalyst D.

The composition of the catalyst D was Pt (1.11% by mass).
—Cl (0.64% by mass) / Al ₂ O ₃ (98.25% by mass). The physical property of the catalyst D was 291 m in surface area.
² / g, pore volume 0.63 ml / g, average pore diameter 66 °
Met. The acid amount of the catalyst D was 0.39 mmol / g.

Comparative Example 2 47.67 g of the same alumina as that used in Comparative Example 1 was put into an eggplant-shaped flask, and 0.6360 g of chloroplatinic acid hexahydrate was added to 39.57 g of ion-exchanged water. The dissolved aqueous solution was added using a pipette, impregnated, dried and calcined under the same conditions as in Example 1 to obtain Catalyst E.

The composition of the catalyst E was Pt (0.53% by mass).
—Cl (0.46% by mass) / Al ₂ O ₃ (99.01% by mass). The physical properties of the catalyst E were 315 m in surface area.
² / g, pore volume 0.68 ml / g, average pore diameter 66 °
Met. The acid amount of the catalyst E was 0.44 mmol / g.

[Hydrotreatment of Desulfurized Cracking Gas Oil] Examples 4-7, Comparative Examples 3-4 Catalyst A prepared in Examples 1-3 and Comparative Examples 1-2 above
Using E, a hydrotreatment of the desulfurization cracked gas oil having the following properties was performed in the following manner. That is, first, the catalyst was charged into a reactor of a high-pressure flow reactor to form a fixed-bed catalyst layer, which was pretreated under the following pretreatment conditions. Next, a mixed fluid of the feedstock oil heated to the reaction temperature and the hydrogen-containing gas,
The mixture was introduced from the upper part of the reactor, and a hydrogenation reaction was allowed to proceed under the following conditions. A mixed fluid of the generated oil and gas was discharged from the lower part of the reactor, and the generated oil was separated by a gas-liquid separator.

Catalyst pretreatment conditions Pressure (hydrogen partial pressure); 4.9 MPa atmosphere; hydrogen gas flow temperature; 150 ° C. for 1.5 hours, then step temperature rise at 300 ° C. for 2 hours, hydrogenation reaction conditions Reaction temperature: 300 or 350 ° C. Pressure (hydrogen partial pressure): 4.9 MPa Liquid space velocity: 1.5 hr ⁻¹ hydrogen / oil ratio: 560 m ³ / m ³ Properties of feed oil Oil type: Desulfurization cracked gas oil Specific gravity ( 0.9089 Distillation properties: Initial boiling point: 177.0 ° C, 50% point: 276.0 ° C, 90% point: 341.1 ° C, end point: 35
5.5 ° C. Sulfur content; 180 mass ppm Saturated hydrocarbon component; 30.9% by volume Olefin component: 0.0% by volume Single aromatic component: 45.3% by volume Bicyclic aromatic component: 19.8% by volume Ring aromatic component: 4.0% by volume Total aromatic component: 69.1% by volume Saybolt color: -16 or less

The reaction results were analyzed by the following method. The reactor was operated at a reaction temperature of 300 ° C. or 350 ° C., respectively, and after 6 days, each produced oil sample was collected and analyzed for its properties. The dearomatization rate was defined as the rate at which the aromatic component in the feed oil was reduced by the hydrogenation reaction, and was calculated from the analysis value of the aromatic component in the feed oil and product oil by the formula shown in Equation 1. . Further, from the analysis values of the aromatic or sulfur content in the feed oil and product oil and the liquid hourly space velocity, the dearomatic reaction rate constant and the desulfurization reaction rate constant were calculated by the equation shown in Equation 1, and the hydrogenation reaction was performed. Was evaluated for ease of progress. The higher the reaction rate constant, the better the catalytic activity. These results were as shown in Table 1.

[0054]

## EQU1 ## Dearomatization rate (%) = [(A _F -A _P1 ) /
A _F ] × 100 A _F : Aromatic component (% by volume) in feed oil A _P1 : Aromatic component (% by volume) in reaction product oil Dearomatic reaction rate constant = ln (A _F / A _P1 ) × LHS
VLHSV: liquid hourly space velocity (hr ^-1 )

[0055]

[Table 1-1]

[0056]

[Table 1-2]

As can be seen from Table 1, the catalysts A and C of the present invention
Has a lower content of aromatic compounds in the product oil than the comparative catalyst D under the same reaction conditions. This is because the catalyst of the present invention has a high hydrogen / oil ratio of 560 m ³ / m ³ ,
In addition, it shows that it is effective for the hydrogenation reaction of aromatic compounds under substantially the same hydrogen partial pressure and reaction temperature as in the conventional hydrogenation treatment.

Further, as can be seen from Table 1, the product oil treated with the catalysts A and C of the present invention has an extremely low sulfur content as compared with the product oil treated with the catalyst D. This shows that the catalyst of the present invention can produce a product oil containing only a trace amount of sulfur by hydrotreating a feed oil having a sulfur content of about several hundred ppm by mass, and has a sulfur resistance and desulfurization performance. Is high.

[Hydrogenation Reaction of Desulfurized LCO / LGO Mixed Gas Oil] Examples 8-9, Comparative Examples 5-6 The hydrogenation reactions of the desulfurized cracked gas oils of Examples 4-7 and Comparative Examples 3-4 Desulfurization treatment LCO / LGO with the following properties under the same conditions and under the same conditions using the same reactor
Hydrogenation of the mixed gas oil was performed, and the reaction results were analyzed by the same method. The results are shown in Table 2.

Raw oil Oil type; Light oil obtained by desulfurizing a mixed oil of straight-run gas oil and cracked gas oil Specific gravity (15/4 ° C); 0.8440 Viscosity (＠ 30 ° C); 4.026 mm ² / s Distillation properties; Initial boiling point is 172 ° C, 50% point is 2
89 ° C, end point: 381 ° C Sulfur content: 172 mass ppm Saturated hydrocarbon component: 65.7% by volume Olefin component: 0.0% by volume Whole aromatic component: 34.3% by volume Saybolt color: -13.9 or less

The results of the reaction were analyzed in the same manner as in the hydrotreating reaction of the desulfurized cracked gas oils of Examples 4 to 7 and Comparative Examples 3 and 4. The results were as shown in Table 2.

[0062]

[Table 2]

As can be seen from Table 2, the catalyst A of the present invention comprises:
Under the same reaction conditions, the content of the aromatic compound in the product oil is lower than that of Comparative Catalyst D. This is because the catalyst of the present invention has a high hydrogen / oil ratio of 560 m ³ / m ³ and a hydrogen partial pressure and a reaction temperature which are almost the same as those of the conventional hydrotreating. It shows that it is effective for the chemical reaction.

As can be seen from Table 2, the product oil treated with the catalyst B of the present invention has a lower sulfur content than the product oil treated with the comparative catalyst E. This shows that the catalyst of the present invention can produce a product oil containing only a trace amount of sulfur by hydrotreating a feed oil having a sulfur content of about several hundred ppm by mass, and has a sulfur resistance and desulfurization performance. Is high.

[0065]

As described in detail above, according to the present invention,
The following effects can be obtained. (1) Since the monocyclic aromatic compound has a high nuclear hydrogenation activity and also has high sulfur resistance, the content of the aromatic compound in the hydrocarbon oil can be significantly reduced. (2) Under the same conditions as conventional hydrotreating conditions, the hydrotreating of an aromatic compound in a feedstock having a sulfur content of several hundred ppm by mass can be efficiently performed. (3) Even hydrocarbon oils such as LCO containing a large amount of aromatic compounds can efficiently reduce aromatic compounds and sulfur compounds by hydrogenation. (4) A light oil base material capable of suppressing the generation of particulates in exhaust gas and having a low sulfur content can be supplied at low cost. (5) Since the reaction conditions can be made substantially the same as the reaction conditions in the conventional hydrotreating, the conventional apparatus can be diverted without significant modification.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Takashi Fujikawa, Inventor 4-20-2-402, Hanaguri, Soka City, Saitama Prefecture (72) Inventor, Yukio Shibata 4-20-4-403, Hanaguri, Soka City, Saitama Prefecture

Claims (3)

[Claims] 1. Silica 2-50% by mass, zirconia 2-2
On a carrier containing 20% by mass and 30 to 96% by mass of alumina,
A catalyst for hydrotreating hydrocarbon oils, comprising at least one platinum group metal in an amount of 0.1 to 8% by mass in terms of metal on a catalyst basis. 2. The method according to claim 1, wherein germanium is contained as a hydrogenation active component in an amount of 0.1 to 2% by mass in terms of metal on a catalyst basis together with at least one platinum group metal. A catalyst for hydrotreating a hydrocarbon oil according to the above. 3. In the presence of the catalyst according to claim 1, 3
Hydrogenation of gas oil characterized by performing a catalytic reaction of a gas oil fraction containing an aromatic compound at a hydrogen partial pressure of ８8 MPa, a temperature of 200 to 370 ° C., and a liquid hourly space velocity of 0.3 to 5 hr ⁻¹ . Processing method.