JP2009160498A - Method of regenerating hydrogenation catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of regenerating a hydrogenation catalyst which regenerates a used hydrogenation catalyst to such an extent that the catalytic activity of the catalyst is restored close to that of the unused catalyst. <P>SOLUTION: The regenerating method has the first process of baking a used hydrogenation catalyst to remove carbonaceous matter adhering to the catalyst so as to obtain a baked catalyst and the second process of causing an active metal ingredient to be supported in the baked catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for regenerating a spent hydroprocessing catalyst to the same extent as the catalytic activity of an unused hydroprocessing catalyst.

Conventionally, hydrotreating catalysts used for hydrotreating light oils (eg, naphtha, kerosene, light gas oil, heavy gas oil, vacuum gas oil, etc.) with low carbon and metal impurities such as asphaltene and residual coal. A method is known in which the carbonaceous material adhering to the surface is removed by calcination (hereinafter, also simply referred to as “used catalyst”; hereinafter the same).
Moreover, the hydrotreating catalyst used for the hydrotreating of heavy oil (for example, atmospheric residual oil, vacuum residual oil, etc.) is a carbonaceous material such as asphaltene contained in heavy oil and vanadium, iron, The specific surface area decreases due to adhesion or sintering of metal impurities such as nickel, and the activity (for example, desulfurization activity, demetalization activity, etc.) is reduced. A method of removing the attached carbonaceous material and regenerating it has been developed (see, for example, Patent Document 1). Furthermore, there is also known a method for regenerating a hydroprocessing catalyst in which a used catalyst from which carbonaceous matter has been removed by calcination is washed to remove attached metal impurities (for example, see Patent Document 2).

JP 2006-61845 A Japanese Patent No. 3715893

However, the activity of the regenerated catalyst obtained by calcining the used catalyst treated with light oil is about 95% of the activity of an unused (new) hydrotreating catalyst (hereinafter also referred to simply as “unused catalyst”, the same shall apply hereinafter). There was a problem of staying.
Also, in the method of removing the carbonaceous material by calcining the used catalyst treated with heavy oil, the metal impurities adhering to the used catalyst cannot be removed, so that the activity of the regenerated catalyst is 80% of the activity of the unused catalyst. There was a problem of staying around%. The method of washing after calcination can remove attached metal impurities, but there is a problem that active metal components such as molybdenum and nickel supported on the hydrotreating catalyst may also be removed.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for regenerating a hydroprocessing catalyst that regenerates a used hydroprocessing catalyst to the same level as the catalytic activity of an unused hydroprocessing catalyst. And

The method for regenerating a hydrotreating catalyst according to the present invention in accordance with the above object is a first step of obtaining a calcined catalyst by calcining a used hydrotreating catalyst to remove carbonaceous matter adhering to the hydrotreated catalyst. And a second step of supporting the active metal component on the calcined catalyst.
Here, in the first step, first, it is preferable that the used catalyst is treated in, for example, a nitrogen stream at 180 to 220 ° C. to substantially remove the adhering oil and then calcined. In the firing operation, in an air stream (oxygen concentration of about 21% by volume) or in an atmosphere in which the oxygen concentration exceeds 21% by volume (that is, in an air stream having a higher oxygen concentration than air), 350 to 700 ° C., preferably 450 ˜550 ° C. and 60 to 300 minutes, preferably 120 to 240 minutes, and the attached carbonaceous matter can be removed by combustion. Thereby, a calcined catalyst containing 3% by mass or less, preferably 1% by mass or less of carbonaceous matter can be obtained with respect to the calcined catalyst. In addition, many carbonaceous matter has adhered to the used catalyst which processed heavy oil, and it is not necessary to remove this carbonaceous matter completely by a calcination process. About 1% by mass of carbonaceous matter may remain. Moreover, as an active metal component, it is normally used for a hydroprocessing catalyst, For example, molybdenum, nickel, cobalt, palladium, platinum etc. can be used.
In the method for regenerating a hydroprocessing catalyst according to the present invention, in the second step, the calcination catalyst may be impregnated with an active metal component-containing solution, and then dried and / or calcined.
Here, as a method of impregnating the calcination catalyst with the active metal component, a known method such as a reduced pressure impregnation method, a pore filling method, a dipping method, an equilibrium adsorption method or the like can be used.

In the method for regenerating a hydrotreating catalyst according to the present invention, the active metal component preferably contains one or both of molybdenum (Mo) and nickel (Ni). In this case, based on the mass of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst, the molybdenum as a molybdenum oxide is 0.5 to 3% by mass, preferably 1 to 2% by mass, and / or Alternatively, 0.2 to 3% by mass, preferably 0.5 to 1% by mass of nickel as nickel oxide may be newly supported on the calcined catalyst. When molybdenum is less than 0.5% by mass as molybdenum oxide, the predetermined activity cannot be obtained, and when it exceeds 3% by mass, the rate of increase in activity is low, which is not economical. Further, when nickel is less than 0.2% by mass as nickel oxide, the predetermined activity cannot be obtained, and when it exceeds 3% by mass, the rate of increase in activity is low, which is not economical. Here, molybdenum trioxide, ammonium molybdate, or the like can be suitably used as the molybdenum supply source, and nickel carbonate, nickel nitrate, or the like can be suitably used as the nickel supply source.
In the present invention, the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst is obtained by calcining the calcined catalyst at 600 to 1200 ° C. (for example, 1000 ° C.), for example, high-frequency combustion carbon analysis. This is a catalyst obtained by removing the carbonaceous matter measured by the meter up to the limit of quantification, and the mass of this catalyst is obtained by removing the mass of the carbonaceous matter adhering to the calcined catalyst. Thus, since the mass of the active metal component supported on the calcined catalyst is determined based on the mass of the catalyst from which the carbonaceous matter has been substantially completely removed, regardless of the mass of the carbonaceous material remaining in the calcined catalyst, A predetermined amount of active metal component can be newly supported.

In the method for regenerating a hydroprocessing catalyst according to the present invention, the first step may be performed in an atmosphere having an oxygen concentration exceeding 21% by volume. Here, the oxygen concentration exceeding 21% by volume indicates that the oxygen concentration is higher than that of air as described above.
In the method for regenerating a hydrotreating catalyst according to the present invention, the hydrotreating catalyst may be one used for hydrotreating light oil. Here, examples of the light oil include naphtha, kerosene, light gas oil (Light Gas Oil, LGO), heavy gas oil (Heavy Gas Oil, HGO), and vacuum gas oil (Vacuum Gas Oil, VGO).
In the method for regenerating a hydrotreating catalyst according to the present invention, the hydrotreating catalyst may be used for hydrotreating heavy oil. In this case, a chelating agent is added in the second step. It is preferable to add. The chelating agent may be added to an active metal component-containing solution described later, or a solution containing a chelating agent may be separately prepared and used. Here, as the chelating agent, for example, malic acid, citric acid, tartaric acid, oxalic acid and the like can be used, and 0.1 to 0.1 based on the mass of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst. 10% by mass, preferably 0.3-5% by mass, more preferably 0.4-2% by mass is added. If the chelating agent is less than 0.1% by mass, the effects described later are hardly obtained. At the same time, the stability of the active metal component is lowered, and if it exceeds 10% by mass, the economy becomes worse and the strength of the catalyst becomes weaker. Here, examples of the heavy oil include atmospheric residual oil (Atmospheric Residue, AR), and vacuum residual oil (Vacuum Residue, VR).

In the method for regenerating a hydrotreating catalyst of the present invention, after the used hydrotreating catalyst is baked to remove adhering carbonaceous matter, an active metal component is further supported, so the supported active metal component is removed. Without regenerating to the same extent as the activity of the unused catalyst. Here, the same level as the activity of the unused catalyst means that the relative desulfurization activity of the regenerated catalyst when the activity of the unused catalyst is 100% is 98 to 110% in the hydrotreating catalyst treated with light oil. In the hydroprocessing catalyst which processed the heavy oil, it means about 90 to 110%.
In addition, when the calcination treatment catalyst is impregnated with the active metal component-containing solution and then dried and / or calcined, the active metal component can be easily supported. When the active metal component contains molybdenum and / or nickel, high activity can be obtained. On the basis of the mass of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst, 0.5 to 3% by mass of molybdenum as molybdenum oxide and / or 0 as nickel as nickel oxide. When 2 to 3% by mass is newly supported, the activity can be obtained with a small amount of support.
Furthermore, when firing is performed in an atmosphere where the oxygen concentration exceeds 21% by volume, the carbonaceous matter can be efficiently removed. In addition, when regenerating the hydrotreating catalyst used in the hydrotreating of heavy oil, a chelating agent is added when supporting the active metal component, and the agglomerated deposited metal (particularly vanadium) is redispersed. The catalyst can be efficiently regenerated.

A method for regenerating a hydrotreating catalyst obtained by hydrotreating light oil according to the first embodiment of the present invention will be described.
(First step)
Hydrotreating catalyst (used catalyst) used for hydrotreating light oil such as naphtha, kerosene, light gas oil, heavy gas oil, vacuum gas oil, etc. is used in, for example, a nitrogen stream at 180 to 220 ° C. (oxygen than air). In a low concentration state, that is, nitrogen concentration is 80% by volume or more, preferably 90% by volume or more, more preferably 95% by volume or more. After the removal, in an air stream (oxygen concentration of about 21% by volume), 350 to 700 ° C., preferably 450 to 550 ° C., more preferably more than 500 ° C. and 550 ° C. or less, and 60 to 300 minutes, preferably Calcination is performed for 120 to 240 minutes, and the adhering carbon is burned and removed to obtain a calcination catalyst. Here, calcination is performed so that the carbonaceous matter attached to the calcination catalyst is 3 mass% or less, preferably 1 mass% or less, for example, about 0.1 mass% with respect to the calcination catalyst. It is good to do. Alternatively, oxygen may be added to the air stream to create an atmosphere in which the oxygen concentration during firing exceeds 21% by volume. In the present embodiment, the mass of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst is the mass of the catalyst after calcining the calcined catalyst at 1000 ° C., and the calcined catalyst. The difference between the masses before and after calcining at 1000 ° C. is calculated as the carbonaceous mass adhering to the calcined catalyst (the same applies to the following embodiments). In addition, when a calcination process catalyst is baked at 1000 degreeC, it can be confirmed by the measurement by a high frequency combustion type | mold carbon analyzer, for example whether carbonaceous material is removed completely.

(Second step)
Next, a solution containing an active metal component, for example, one or both of molybdenum (Mo) and nickel (Ni) (active metal component-containing solution. Is impregnated by a known method such as a reduced pressure impregnation method, a pore filling method, an immersion method, an equilibrium adsorption method, etc., and then from room temperature to 300 ° C., preferably from room temperature to 270 ° C., more preferably from room temperature to 250 ° C. Recycled by heating and drying, and further calcining in an air stream at 400 to 700 ° C., preferably 500 to 600 ° C. and 30 to 120 minutes, preferably 45 to 90 minutes, and carrying the active metal component on the calcined catalyst. A catalyst is produced. Here, the amounts of molybdenum (Mo) and nickel (Ni) newly supported on the calcined catalyst are molybdenum oxides based on the mass of the catalyst from which the carbonaceous matter is substantially completely removed from the calcined catalyst. (MoO ₃ ) is 0.5 to 3% by mass, preferably 1 to 2% by mass, and nickel oxide (NiO) is 0.2 to 3% by mass, preferably 0.5 to 1% by mass. Here, molybdenum trioxide, ammonium molybdate, or the like can be used as a supply source of molybdenum, and nickel carbonate, nickel nitrate, or the like can be used as a supply source of nickel. The pore filling method described above is to prepare an active metal-containing solution in an amount corresponding to the total pore volume of the calcined catalyst weighed in advance, and the calcined catalyst degassed under reduced pressure conditions. In this method, the active metal component is impregnated in the pores by being taken into the pores. The total pore volume of the calcined catalyst can be determined by a known method such as a water titration method or a mercury intrusion method.

The method for regenerating a hydrotreating catalyst obtained by hydrotreating heavy oil according to the second embodiment of the present invention is greatly different from the first embodiment described above in that a chelating agent is added in the second step. Is different. This will be described in detail below.
(First step)
For example, an oil component deposited by treating a hydrotreating catalyst (used catalyst) used for hydrotreating heavy oil such as normal pressure residue or reduced pressure residue in a nitrogen stream at 180 to 220 ° C. After being almost removed, it is baked in an air stream at 350 to 700 ° C., preferably 450 to 550 ° C. and 60 to 300 minutes, preferably 120 to 240 minutes. A calcination treatment catalyst is obtained by combustion removal so that the amount is 3% by mass or less, preferably 1% by mass or less, for example, about 0.1% by mass with respect to the calcination treatment catalyst. The oxygen concentration during firing may be performed in an atmosphere exceeding 21% by volume.
(Second step)
Next, an impregnating solution containing the active metal component and a chelating agent (for example, malic acid, citric acid, tartaric acid, oxalic acid, etc.) is added to the obtained calcination treatment catalyst under reduced pressure impregnation method, pore filling method, immersion method. Then, after impregnation by a well-known method such as an equilibrium adsorption method, the temperature is dried from room temperature to 300 ° C, preferably from room temperature to 270 ° C, more preferably from room temperature to 250 ° C, and further from 400 to 700 ° C in an air stream. The regenerated catalyst in which a predetermined amount of active metal components (molybdenum and nickel) are supported on the calcined catalyst is produced by calcining, preferably at 500 to 600 ° C. and for 30 to 120 minutes, preferably 45 to 90 minutes. Here, the impregnating liquid contains, for example, 0.1 to 10% by mass, preferably 0.3 to 5% by mass, based on the mass of the catalyst from which the carbonaceous matter is substantially completely removed from the calcined catalyst. The chelating agent is preferably contained in an amount of 0.4 to 2% by mass. At this time, when the chelating agent is less than 0.1% by mass, the active metal component may be precipitated to generate a precipitate. In addition, the supply source and addition amount of the active metal component, that is, molybdenum and nickel are the same as the conditions in the second step of the first embodiment.

[Regeneration of hydrotreating catalyst used for hydrotreating light oil]
Example 1
A new alumina-supported catalyst (unused catalyst) carrying nickel and molybdenum is placed in a light oil hydrotreating apparatus, and light light oils having the properties shown in Table 1 (an example of light oil) are shown in Table 2. Under light oil desulfurization conditions, oil was passed through for 16000 hours to obtain a used hydroprocessing catalyst (used catalyst). Next, this used catalyst is aerated in a nitrogen stream maintained at 200 ° C. to remove oil adhering to the surface, and then calcined for 3 hours in an air stream maintained at 500 ° C. This was removed to obtain a calcination catalyst α. Moreover, after weighing a part of the obtained calcination treatment catalyst α, this was calcinated at 1000 ° C. to produce a catalyst from which the carbonaceous matter was substantially completely removed from the calcination treatment catalyst α. The mass of carbonaceous matter adhering to the calcined catalyst α was determined from the difference in mass from the catalyst α. Here, properties of the calcination catalyst α are shown in Table 3. The catalyst from which the carbonaceous matter was substantially completely removed from the calcined catalyst α was measured with a high-frequency combustion type carbon analyzer, and it was confirmed that the carbonaceous matter was completely removed.

Next, 400.2 g (including 0.2 g of carbonaceous matter) of the calcined catalyst α corresponding to 400 g of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst α is weighed, and the pore volume of the calcined catalyst α After impregnating 224 ml of the impregnating solution a having a volume corresponding to 1 by a reduced pressure impregnation method, the regenerated catalyst A was obtained by calcining in an air stream at 500 ° C. for 60 minutes.
Here, the impregnating liquid a is 2.0 g of molybdenum trioxide (the mass of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst α, that is, 0.5% by mass based on 400 g. The same), and nickel carbonate 1.3 g (as NiO, 0.2% by mass) and malic acid 2.0 g (0.5% by mass, at least 2.5 times the mass of NiO) for dissolving nickel carbonate % Is necessary. The same applies hereinafter) was dissolved in water to make a total volume of 224 ml.

(Examples 2 to 6)
In Examples 2 to 6, 224 ml of impregnating liquids b to f shown below were impregnated by a reduced pressure impregnation method with respect to 400.2 g of the calcined catalyst α, respectively, and then calcined at 500 ° C. for 60 minutes in an air stream. Catalysts B to F were prepared.
The impregnating liquid b contains 4.0 g (1.0% by mass) of molybdenum trioxide, 2.6 g of nickel carbonate (0.4% by mass as NiO), and 4.0 g (1.0% by mass) of malic acid. The total volume was made up to 224 ml by dissolving in water. The impregnating liquid c is composed of 8.0 g (2.0 mass%) of molybdenum trioxide, 6.5 g of nickel carbonate (1.0 mass% as NiO), and 10.0 g (2.5 mass%) of malic acid. The total volume was made up to 224 ml by dissolving in water. As the impregnation liquid d, 12.0 g (3.0 mass%) of molybdenum trioxide, 19.5 g (3.0 mass%) of nickel carbonate, and 30.0 g (7.5 mass%) of malic acid are dissolved in water. The total volume was 224 ml. The impregnating solution e was dissolved in water with 12.0 g (3.0% by mass) of molybdenum trioxide to make a total amount of 224 ml. The impregnating solution f was dissolved in 19.5 g of nickel carbonate (3.0% by mass as NiO) and 30.0 g (7.5% by mass) of malic acid in water to make a total amount of 224 ml.
(Comparative Example 1)
The calcined catalyst α was not impregnated with an active metal component and used as a regenerated catalyst G.

(Test Example 1)
Recycled catalysts A to G and unused catalyst are filled in a fixed bed reactor having an inner diameter of 1 inch capable of high pressure reaction, respectively, and the light diesel oil described above is passed under the diesel oil desulfurization conditions shown in Table 2 for hydrogenation treatment. The hydrodesulfurization activity of the regenerated catalysts A to G was evaluated relative to the activity of the unused catalyst as 100%. The results are shown in Table 4.

  As can be seen from these results, the catalyst used in the hydrotreatment of light oil is calcined to remove the adhering carbonaceous matter, and then the active metal component is supported, whereby the catalyst of the unused hydrotreatment catalyst. It was possible to regenerate to the same extent as the activity.

[Regeneration of hydrotreating catalyst used for hydrotreating heavy oil]
(Examples 7 to 13)
An alumina-supported catalyst (unused catalyst) supporting nickel and molybdenum is placed in a heavy oil hydrotreating apparatus, and Middle Eastern atmospheric pressure residual oil (an example of heavy oil) having the properties shown in Table 5 is shown in Table 6. Under the general direct desulfurization conditions shown in Fig. 4, the oil was passed through for 8000 hours to carry out the hydrogenation treatment to obtain a used hydrotreatment catalyst (used catalyst). Next, this used catalyst is aerated in a nitrogen stream maintained at 200 ° C. to remove oil adhering to the surface, and then calcined for 3 hours in an air stream maintained at 500 ° C. This was removed to obtain a calcined catalyst β. Further, the calcined catalyst β is calcined at 1000 ° C. to prepare a catalyst in which carbonaceous matter is substantially completely removed from the calcined catalyst β, and the calcined catalyst β is determined from the difference in mass between the catalyst and the calcined catalyst β. The mass of carbonaceous matter adhering to was determined. Here, Table 7 shows properties of the calcination catalyst β. In addition, the catalyst from which the carbonaceous matter was substantially completely removed from the calcined catalyst β was measured with a high-frequency combustion type carbon analyzer, and it was confirmed that the carbonaceous matter was completely removed.

Next, 400.5 g (including 0.5 g of carbonaceous matter) of the calcined catalyst β corresponding to 400 g of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst β is weighed, and the pore volume of the calcined catalyst β After impregnating 240 ml of impregnating liquids a to f (see Example 1) and n each having a volume corresponding to 1 by a reduced pressure impregnation method, the regenerated catalysts H to N were obtained by calcining in an air stream at 500 ° C. for 60 minutes. It was. In addition, the impregnating liquid n was dissolved in water with 12.0 g (3.0% by mass) of molybdenum trioxide and 30.0 g (7.5% by mass) of malic acid in a total amount of 224 ml.
(Comparative Example 2)
The calcined catalyst β was not impregnated with an active metal component and a chelating agent (malic acid) and used as a regenerated catalyst O.

(Test Example 2)
A fixed bed reactor having an inner diameter of 1 inch capable of high-pressure reaction is filled with regenerated catalysts HO and unused catalyst, and the above-mentioned atmospheric residue is passed under the direct desulfurization conditions shown in Table 6 to generate hydrogen. The hydrodesulfurization activity of the regenerated catalysts H to O was evaluated relative to the activity of the unused catalyst as 100%. The results are shown in Table 8.

  As can be seen from these results, the catalyst used for the hydroprocessing of heavy oil is baked to remove the adhering carbonaceous matter, and then the active metal component is supported, so that the catalyst of the unused hydroprocessing catalyst. It was possible to regenerate to the same extent as the activity. Further, when the regenerated catalyst L and the regenerated catalyst N are compared, the effect of malic acid is understood.

The present invention is not limited to the above-described embodiment, and can be changed without changing the gist of the present invention. For example, some or all of the above-described embodiments and modifications are possible. A case where the method for regenerating a hydroprocessing catalyst of the present invention is configured by combining the above is also included in the scope of the present invention.
For example, in the present embodiment, molybdenum trioxide is used as the active metal component, but ammonium molybdate may be used, and nickel nitrate may be used instead of nickel carbonate. In particular, since nickel nitrate dissolves in water, malic acid or the like does not have to be used in the impregnation liquid when used as an active metal component used for regenerating a hydroprocessing catalyst that has been processed with light oil.

Claims (8)

  A first step of calcining a used hydrotreating catalyst, removing carbonaceous matter adhering to the hydrotreating catalyst to obtain a calcined catalyst, and a second step of supporting an active metal component on the calcined catalyst; A method for regenerating a hydrotreating catalyst, comprising:   The method for regenerating a hydroprocessing catalyst according to claim 1, wherein, in the second step, the calcination treatment catalyst is impregnated with an active metal component-containing solution, and then dried and / or calcination.   The method for regenerating a hydroprocessing catalyst according to claim 1 or 2, wherein the active metal component contains one or both of molybdenum and nickel.   On the basis of the mass of the catalyst from which the carbonaceous matter has been substantially completely removed from the calcined catalyst, 0.5 to 3 mass% of the molybdenum as a molybdenum oxide and / or the nickel as a nickel oxide of 0. The method for regenerating a hydroprocessing catalyst according to claim 3, wherein 2 to 3 mass% is newly supported on the calcining catalyst.   The said 1st process is performed in the atmosphere where oxygen concentration exceeds 21 volume%, The regeneration method of the hydroprocessing catalyst of any one of Claims 1-4 characterized by the above-mentioned.   The method for regenerating a hydrotreating catalyst according to any one of claims 1 to 5, wherein the hydrotreating catalyst is used for hydrotreating light oil.   The method for regenerating a hydrotreating catalyst according to any one of claims 1 to 5, wherein the hydrotreating catalyst is used for hydrotreating heavy oil.   8. The method for regenerating a hydroprocessing catalyst according to claim 7, wherein a chelating agent is added in the second step.