JP2010069466A - Hydrogenation catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenation catalyst capable of efficiently and stably carrying out a hydrogenation treatment for a long period of time, even when treating heavy hydrocarbon oil of an inferior property detrimental to carrying out a hydrogenation treatment including hydrogenation desulfurization, metal removal by hydrogenation, and hydrogenation decomposition, or the like. <P>SOLUTION: The dehydrogenation catalyst is characterized in that a coke component in an amount of from 20-40 mass% and a sulfur component in an amount of from 5-10 mass% based on the amount of the whole catalyst are contained therein, and H/C (in mole ratio) of the coke component is from 0.5-0.7. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydroprocessing catalyst, and more particularly to a hydroprocessing catalyst effective as a hydrodesulfurization catalyst for heavy hydrocarbon oils.

Sulfur compounds of heavy hydrocarbon oils such as atmospheric residual oil and vacuum residual oil are present in macromolecules, so hydrotreatment to remove the sulfur content is a severe high temperature It must be handled with conditions. However, when hydrotreating is usually performed under such conditions, the production of cake is promoted on the surface of the hydrotreating catalyst, so that the catalyst is rapidly deteriorated and the operating period (catalyst life) is shortened. There was a drawback. This tendency becomes more prominent as the properties of the heavy hydrocarbon oil to be hydrotreated are inferior (high boiling point, high sulfur content, high residual carbon content, etc.).
In order to solve such problems, conventionally, a method has been employed in which the hydrotreating catalyst is continuously or periodically replaced, or the load per unit catalyst is reduced to reduce the load. However, in these methods, since economical efficiency is lowered, it has been difficult to treat substantially inferior heavy hydrocarbon oil.
Therefore, there has been a demand for the appearance of a hydrotreating catalyst that is not easily deteriorated, that is, has a long catalyst life.

Much research has been conducted on hydrotreating heavy hydrocarbon oils and catalysts capable of performing the hydrotreating stably for a long time. For example, Patent Document 1 discloses a hydrodesulfurization catalyst in which nickel oxide, molybdenum trioxide, magnesium oxide, and phosphorus pentoxide are supported on a refractory oxide carrier at a specific ratio with respect to the catalyst. However, increasing the amount of the basic substance to be added to increase the activity is not preferable because the desulfurization activity may decrease.
Patent Document 2 relates to hydrotreating such as crude oil and vacuum residue, and supports a group 6B metal and a group 8 metal on the periodic table on an alumina-containing support, and the distribution of these metals is determined on the outermost surface of the catalyst particles. Discloses a hydrotreating method using a hydrotreating catalyst supported at a higher concentration in the central part than in the part. This catalyst is intended to reduce the poisoning of the catalyst by optimizing the distribution of the active metal supported on the catalyst carrier. However, the catalyst production method is complicated and industrial production is difficult.
Further, Patent Document 3 discloses a hydrorefining catalyst for heavy hydrocarbon oil containing molybdenum and phosphorus, boron or fluorine, and discloses a catalyst containing no nickel or cobalt in order to suppress catalyst poisoning. However, it is a catalyst with extremely low desulfurization performance and has not been a fundamental solution to the problem.

JP 11-319567 A JP-A-6-184558 JP-A-2-35938

  The present invention enables efficient and long-term stable hydroprocessing such as hydrodesulfurization, hydrodemetallation, and hydrocracking even for heavy hydrocarbon oils that have poor properties when performing hydroprocessing. It aims at providing the hydrotreating catalyst which can be implemented.

  As a result of intensive studies to develop the above-mentioned preferred catalyst, the present inventor has found that a catalyst supporting a specific amount of coke and having a specific property can meet the above purpose. The present invention has been completed based on such findings. That is, the present invention

[1] It contains 20 to 40% by mass of coke and 5 to 10% by mass of sulfur based on the total amount of catalyst, and H / C (molar ratio) of coke is 0.5 to 0.7. Hydroprocessing catalyst,
[2] The hydrotreating catalyst according to [1] above, wherein Sp2 in X-ray electroluminescence analysis (XPS) has a peak of 160.0 to 163.0 eV,
[3] The hydrotreating catalyst according to the above [1] or [2], which is a catalyst in which a coke fraction is supported on a hydrotreating catalyst not containing a coke fraction,
[4] The hydrotreating catalyst not containing the coke component is a refractory oxide carrier, based on the total amount of the catalyst, 1 to 10% by mass of nickel oxide and / or cobalt oxide, and 5 to 30% by mass of molybdenum trioxide. And the hydrotreating catalyst according to any one of [1] to [3], which is a catalyst supporting 3 to 10% by mass of phosphorus pentoxide,
[5] (1-a) A hydrotreating catalyst containing no coke is subjected to a preliminary sulfidation treatment, and then hydrotreating hydrocarbon oil using the catalyst, or (1-b) a coke is A first step which is a step of supporting a coke component by immersing a hydroprocessing catalyst not contained in a hydrocarbon containing sulfur having a boiling point of 400 to 600 ° C., and (2) a catalyst obtained in the above step. The method for producing a hydrotreating catalyst according to any one of [1] to [4], comprising a second step of heat treatment at 400 to 600 ° C. in an inert gas atmosphere,
[6] The method for producing a hydrotreating catalyst according to [5], further comprising performing a third step of exposing to air at 300 to 400 ° C.
[7] The hydrotreating catalyst according to any one of [1] to [4], or the hydrotreating catalyst obtained by the method for producing a hydrotreating catalyst according to [5] or [6] A hydrodesulfurization process for hydrocarbon oil, characterized in that hydrodesulfurization is performed by contacting a heavy hydrocarbon oil;
Is to provide.

  According to the present invention, hydroprocessing such as hydrodesulfurization, hydrodemetallation, hydrocracking and the like can be carried out efficiently and for a long time even for heavy hydrocarbon oils having inferior properties when performing hydroprocessing. A hydrotreating catalyst that can be stably carried out can be provided.

The catalyst of the present invention needs to contain 20 to 40% by mass of coke and 5 to 10% by mass of sulfur based on the total amount of the catalyst. If the coke content is less than 20% by mass or the sulfur content is less than 5% by mass, the required stabilization of the activity cannot be obtained. On the other hand, if the coke content exceeds 40% by mass or the sulfur content exceeds 10% by mass, the catalyst The pores may be clogged and the activity itself may decrease, leading to a situation where efficient catalyst performance is not exhibited. A preferable coke content is 25 to 35% by mass, and a preferable sulfur content is 7 to 9% by mass.
The coke content and sulfur content are values measured by carbon sulfur simultaneous analysis (infrared absorption method).

The hydrotreating catalyst of the present invention further requires that the coke H / C (molar ratio) is 0.5 to 0.7. If the H / C (molar ratio) of the coke does not satisfy this range, it may not be possible to satisfy the desired activity stabilization effect and the activity reduction suppression effect due to clogging of the catalyst pores. The coke H / C (molar ratio) is preferably 0.55 to 0.65.
In addition, H / C (molar ratio) is a value measured by the CHN simultaneous analysis method.

The coke content further has an X-ray electroluminescence analysis (XPS) Sp2 of 160. It preferably has a peak of ˜163.0 eV. If it has such a peak, the probability of the activity stabilization effect and the activity reduction inhibitory effect by clogging of catalyst pores can be increased.
XPS was performed by the following method.

[Measurement method of XPS]
(Preprocessing)
The catalyst was pulverized in an agate mortar to obtain an XPS measurement sample.
(Measurement condition)
Measurements were made at an output of 150 W using an aluminum X-ray source. Further, Al2p was set to 74.8 eV as a reference binding energy.

The hydrotreating catalyst of the present invention is usually a catalyst in which coke is supported on a hydrotreating catalyst that does not contain coke.
The “hydrotreating catalyst not containing coke” is not particularly limited, and includes all catalysts classified as hydrotreating catalysts, with heavy hydrocarbon oil hydrodesulfurization treating catalysts being particularly preferred.

Specific examples of the hydrodesulfurization treatment catalyst for heavy hydrocarbon oil include, for example, a catalyst in which nickel oxide, molybdenum trioxide and phosphorus pentoxide are supported as active metals on a refractory oxide carrier. Is mentioned. In this case, the supported amount is 1 to 10% by mass of nickel oxide, 5 to 30% by mass of molybdenum trioxide, phosphorus pentoxide from the viewpoint of securing desired performance and avoiding active metal agglomeration and reducing the activity. 3-10 mass% is suitable.
Examples of the refractory oxide carrier include alumina, silica, titania, zirconia, and composite oxide carriers thereof. Alumina is preferred from the viewpoint of metal dispersibility.

The method for producing the hydrotreating catalyst not containing the coke content is not particularly limited. Usually, a refractory oxide carrier is impregnated with an impregnation solution in which a nickel compound, a molybdenum compound and a phosphorus compound are dissolved. In that case, it is preferable to carry out the supporting treatment of the active metal species in the presence of an organic acid compound and ethylene glycol having a molecular weight of 100 or more. A method of firing at a temperature of 400 to 600 ° C. or higher after the supporting treatment is preferable.
As described above, a heavy oil hydrodesulfurization catalyst containing no coke is obtained.
As the active metal supported on the heavy oil desulfurization catalyst not containing coke, nickel oxide, molybdenum trioxide and the like were mentioned, but together with or instead of them, tungsten oxide (preferably supported amount is 5 to 30 mass) %) Or cobalt oxide (preferably supported amount is 1 to 10% by mass). Among them, the one using cobalt oxide together with the nickel oxide or in place of nickel oxide is a preferable example. it can.

In the method for producing a hydrotreating catalyst of the present invention, for example, (1-a) a hydrotreating catalyst containing no coke is subjected to a presulfiding treatment, and then a hydrocarbon oil is hydrotreated using the catalyst. Or (1-b) a first step in which a hydrotreating catalyst containing no coke is immersed in a hydrocarbon containing sulfur at a boiling point of 400 to 600 ° C. to carry the coke, and (2) The method which consists of the 2nd process of heat-processing the catalyst obtained at the said process at 400-600 degreeC by inert gas atmosphere is mentioned.
In this production method, it is more preferable to perform the third step of exposing to air at 300 to 400 ° C.

The pre-sulfiding treatment in the first step (1-a) usually uses hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide or the like as a pre-sulfiding agent, a temperature range of 200 to 400 ° C., and a reaction pressure of 15 to 250 kg. It is preferable to select the range of / cm ² .
The reaction conditions for hydrotreating (hydrodesulfurization) vary depending on the type of the target feedstock, but the reaction temperature is usually 200 to 500 ° C., the reaction pressure is 15 to 250 kg / cm ² , and the LHSV (liquid space velocity) is 0. It is preferable to select in the range of 1 to 45 (1 / hr). In addition, the supply ratio of hydrogen gas to hydrocarbon oil (hydrogen / hydrocarbon oil ratio) is usually preferably selected in the range of 50 to 2,000 Nm ³ / kl.
Moreover, the method of immersing the hydrocarbon which contains a sulfur component with the boiling point of 400-600 degreeC of a 1st process (1-b) should just normally immerse and carry | support hydrocarbon oil directly at 100-200 degreeC. In this case, the sulfur content of the hydrocarbon is preferably 2 to 5% by mass.

  The heat treatment in an inert gas atmosphere in the second step is a heat treatment in an atmosphere of an inert gas such as nitrogen, argon, helium, and a combustion gas free of oxygen. Moreover, it is preferable that heat processing are 400-600 degreeC. Heat treatment at 400 to 600 ° C. is preferable in that dehydrogenative condensation can be performed for the good amount of attached coke. Therefore, the heat treatment is more preferably 450 to 550 ° C. The time for performing the heat treatment is usually selected in the range of 0.5 to 40 hours.

  In the third step, the method of exposing the catalyst obtained in the second step to air is preferably exposed to air at a temperature of 300 to 400 ° C. The exposure time is usually preferably 1 to 10 minutes.

The hydrotreating catalyst of the present invention preferably satisfies the following conditions.
For example, the specific surface area of the refractory oxide support, preferably ^{5~500m 2 / g, 50~300m 2 /} g is more preferable. When the specific surface area is less than 5 m ² / g, the dispersibility of the supported metal may be lowered, and when it exceeds 500 m ² / g, diffusion of the reactant may be inhibited. Further, the pore volume is preferably ^{0.2~1.5cm 3 / g, 0.3~1.2cm 3 /} g is more preferable. If the pore volume is less than 0.2 cm ³ / g, catalyst pores may be clogged due to the deposition of metal and coke in the raw material oil, and if it exceeds 1.5 cm ³ / g, the catalyst strength will be significantly reduced. May not be practical. The pore diameter is preferably such that the 50% point of the pore volume is in the range of 100 to 300 mm.
These physical properties are sizes suitable for the molecular size of the hydrocarbon fraction that is a reactant, and are suitable sizes that can diffuse to the reaction active sites inside the catalyst pores.
The pore volume and pore distribution were measured by an adsorption / desorption method using nitrogen, and the BJH method [E. P. Barref. L. G. Joyner and P.M. P. Halnda, J .; Amer. Chem. Soc. , 73, 373 (1951)]. Further, the specific surface area is determined by B.V. E. T. T. It was obtained by law.

  The shape of the hydrotreating catalyst of the present invention is not particularly limited, and may be any of a cylinder, a sphere, three to six leaves, a honeycomb, and the like. For example, in a fixed bed flow type reaction apparatus, a catalyst in the form of a cylinder, a three-leaf, or a four-leaf is usually preferably used.

The hydrotreating method of the present invention is a hydrotreating method for hydrocarbon oil, characterized in that hydrotreating is performed by bringing the hydrotreating catalyst into contact with a hydrocarbon oil.
Examples of the hydrocarbon oil used in the hydrotreating include light sulfur-containing hydrocarbon oils such as kerosene, and heavy sulfur-containing hydrocarbon oils such as atmospheric residual oil and vacuum residual oil.
In particular, it can be suitably applied to hydrodesulfurization of inferior heavy hydrocarbon oils. Inferior heavy hydrocarbon oils are obtained from heavy crude oils having an API index of 20 or less, such as atmospheric residual oil and vacuum residual oil, solvent history oil, pyrolysis oil, asphaltene oil, tar sand and viscosity. For the purpose of adjustment, there may be mentioned raw oils once preliminarily hydrotreated, or those diluted with light oils.

Inferior heavy hydrocarbon oils usually have the following properties.
[Properties of inferior heavy hydrocarbon oil]
・ Sulfur content: 0.5 mass% or more ・ Nitrogen content: 200 mass ppm or more ・ Vanadium content: 5 mass ppm or more ・ Residual carbon content: 5 mass% or more

When performing the hydrotreating using the hydrotreating catalyst of the present invention, it is preferable to perform a presulfidation treatment as a stabilization treatment before the hydrotreating reaction. This preliminary sulfidation treatment is performed in a temperature range of 200 to 400 ° C. using hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide or the like as a preliminary sulfiding agent. The reaction conditions for the hydrodesulfurization treatment vary depending on the type of the target feedstock, but the normal reaction temperature is 200 to 500 ° C., the reaction pressure is 15 to 250 kg / cm ² , and the LHSV (liquid space velocity) is 0.1. It selects in the range of -45 (1 / hr). The supply ratio of hydrogen gas to hydrocarbon oil (hydrogen / hydrocarbon oil ratio) is usually selected in the range of 50 to 2,000 Nm ³ / kl.
The reaction format is not particularly limited, but usually, various processes such as a fixed bed, a moving bed, a boiling bed, and a suspension bed are adopted, and a flow system using a fixed bed is preferably adopted from the viewpoint of economy. The

Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.
The physical properties of the catalyst were measured by the following method.
[Method for measuring physical properties of catalyst]
(1) Quantitative determination of molybdenum Measured by inductively coupled plasma emission spectroscopy (ICP).
(2) Measured by quantitative fluorescent X-ray analysis of nickel and phosphorus.
(3) Average pore diameter It measured by the method described in the specification.
(4) Pore volume It measured by the method described in the specification.
(5) Specific surface area It measured by the method described in the specification.

Example 1
(Preparation of hydrotreating catalyst A0 containing no coke)
165.0 parts by mass of molybdenum trioxide and 39.3 parts by mass of basic nickel carbonate in an equivalent amount of NiO were added to 500 parts by mass of ion-exchanged water. During the addition, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour. Next, 50.8 parts by mass of phosphoric acid in an amount equivalent to P ₂ O _{5 was} added, and dissolution was confirmed. Next, 60 parts by mass of triethylene glycol (molecular weight 150) was added. Next, this impregnating solution was adjusted to an amount suitable for the water absorption amount of the carrier, and the four-leaf type alumina carrier having physical properties of an average pore diameter of 140 mm, a pore volume of 0.60 ml / g, and a specific surface area of 200 m ² / g. It was supported on 1,000 parts by mass by a normal pressure impregnation method. This support was dried at 120 ° C. for 3 hours and calcined in air at 450 ° C. for 5 hours to obtain a metal-supported catalyst A0.
The metal-supported catalyst A0 thus obtained contained 2.9% by mass as NiO, 13.4% by mass as MoO ₃ , and 3.6% by mass as P ₂ O ₅ per dry mass.
(Preparation of coke supported catalyst)
Next, 100 cc of this metal-supported catalyst A0 was charged into a reaction tube of a small high-pressure fixed bed reactor. Using light gas oil whose sulfur concentration was adjusted to 2.5 mass% by adding dimethyl disulfide (DMDS) as a sulfiding agent, this was performed under conditions of LHSV 1h ⁻¹ at 250 kg in a hydrogen stream at 130 kg / cm ² . Presulfided for 21 hours. Next, the normal pressure residual oil (raw oil A) shown in Table 1 was passed for 5 days at a reaction pressure of 130 kg / cm ² , a liquid space velocity of 0.5 h ⁻¹ , a hydrogen / oil ratio of 740 Nm ³ / kl, and 350 ° C. Coke-supported catalyst A1 was obtained. This coke-supported catalyst A1 was extracted from the reaction tube, heat-treated in nitrogen at 450 ° C. for 1 hour, and allowed to cool in air to obtain coke-supported catalyst A2. Table 2 shows the physical properties of this catalyst.
(Catalyst performance evaluation)
A reaction tube of a small high-pressure fixed bed reactor was filled with 100 cc of the coke-supported catalyst A2. This was lightly sulfidized with LDSV 1h ⁻¹ for 21 hours at 250 ° C. in a hydrogen gas stream at 130 kg / cm ^{2 in} a hydrogen gas stream by adding DMDS as a sulfiding agent to adjust the sulfur concentration to 2.5 mass%. Subsequently, the normal pressure residual oil (raw oil A) shown in Table 1 was passed at a reaction pressure of 130 kg / cm ² , a liquid space velocity of 0.5 h ⁻¹ , and a hydrogen / oil ratio of 740 Nm ³ / kl to produce a sulfur content of the product oil. Was processed for 1500 hours while adjusting the temperature to be 0.5% by mass. Table 3 shows changes in the target achievement temperature.

Example 2
100 cc of the metal-supported catalyst A1 obtained in Example 1 was put into a container containing 10 L of normal pressure residual oil (raw oil A) shown in Table 1, and slowly stirred at normal pressure at 120 ° C. for 5 hours. Thereafter, the catalyst and the oil were separated by filtration. This catalyst was heat-treated in nitrogen at 550 ° C. for 10 hours and allowed to cool in air to obtain a coke-supported catalyst A3. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Example 3
In Example 1, the same treatment was performed except that the raw material oil C was used in place of the raw material oil A to obtain a coke-supported catalyst A4. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Example 4
In Example 1, the same treatment was carried out except that the feed time of the raw material oil A was 2 days to obtain a coke-supported catalyst A5. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Example 5
In Example 1, the same treatment was performed except that the cooling after the heat treatment was performed in a nitrogen stream to obtain a coke-supported catalyst A6. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.

Comparative Example 1
In Example 1, the same treatment was performed except that the raw material oil B was used in place of the raw material oil A to obtain a coke-supported catalyst A7. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Comparative Example 2
In Example 1, the same treatment was performed except that the raw material oil C was used instead of the raw material oil A, and evaluation was performed using the coke-supported catalyst A8. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Comparative Example 3
In Example 1, the same treatment was performed except that the raw material oil D was used in place of the raw material oil A to obtain a coke-supported catalyst A9. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.

Comparative Example 4
In Example 1, the same treatment was performed except that the raw material oil C was used instead of the raw material oil A and passed for 30 days to obtain a coke-supported catalyst A10. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Comparative Example 5
In Example 1, except that coke responsible lifting catalyst A1 were treated with 700 ° C. in a nitrogen performs the same treatment to obtain coke supported catalyst A11. Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using this catalyst.
Comparative Example 6
Table 3 shows changes in the target achievement temperature when the same evaluation as in Example 1 was performed using the coke-supported catalyst A1 in place of the coke-supported catalyst A2.

  The present invention enables efficient and long-term stable hydroprocessing such as hydrodesulfurization, hydrodemetallation, and hydrocracking even for heavy hydrocarbon oils that have poor properties when performing hydroprocessing. It is a hydrotreating catalyst that can be used and is effectively used for refining hydrocarbon oils that are difficult to hydrotreat.

Claims (7)

The coke content is 20 to 40% by mass and the sulfur content is 5 to 10% by mass based on the total amount of the catalyst, and the H / C (molar ratio) of the coke is 0.5 to 0.7. Hydroprocessing catalyst. Furthermore, Sp2 in a X ray electroluminescence analysis (XPS) has a peak of 160.0-163.0eV, The hydroprocessing catalyst of Claim 1 characterized by the above-mentioned. The hydrotreating catalyst according to claim 1 or 2, wherein the hydrotreating catalyst contains no coke and the coke is supported on the hydrotreating catalyst. The hydrotreating catalyst not containing the coke component is a refractory oxide support, based on the total amount of the catalyst, 1 to 10% by mass of nickel oxide and / or cobalt oxide, 5 to 30% by mass of molybdenum trioxide and pentoxide. The hydrotreating catalyst according to any one of claims 1 to 3, which is a catalyst supporting 3 to 10% by mass of phosphorus. (1-a) a step of presulfiding a hydrotreating catalyst not containing coke, and then hydrotreating hydrocarbon oil using the catalyst, or (1-b) hydrogen not containing coke A first step, which is a step of immersing the catalyst in a hydrocarbon containing sulfur at a boiling point of 400 to 600 ° C. to support a coke component, and (2) the catalyst obtained in the step is treated with an inert gas. It consists of a 2nd process heat-processed at 400-600 degreeC in atmosphere, The manufacturing method of the hydrotreating catalyst in any one of Claims 1-4 characterized by the above-mentioned. Furthermore, the 3rd process exposed to the air at 300-400 degreeC is performed, The manufacturing method of the hydrotreating catalyst of Claim 5 characterized by the above-mentioned. The hydrotreating catalyst according to any one of claims 1 to 4 or the hydrotreating catalyst obtained by the method for producing a hydrotreating catalyst according to claim 5 or 6 and a heavy hydrocarbon oil are brought into contact with each other. A hydrotreating method for hydrocarbon oil, characterized by performing hydrodesulfurization.