JP2008168257A - Hydrogenation catalyst, its manufacturing method, and hydrogenation treatment catalyst, its production method and hydrogenation treatment method of heavy oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenation treatment catalyst which is highly active, shows little deactivation, has a high abrasion strength of a new catalyst and a regenerated catalyst and also is easily regenerated after a heavy oil is treated, to provide its production method and a hydrogenation treatment method which enables the stable use of a deactivated catalyst for a long time even after it is regenerated after the heavy oil is hydrogenation treated using the hydrogenation treatment catalyst. <P>SOLUTION: The hydrogenation treatment catalyst is obtained by supporting NiO of 1-10 mass%, MoO<SB>3</SB>of 5-20 mass%, MgO of 0.3-1.5 mass% and P<SB>2</SB>O<SB>5</SB>of 2-5 mass%, based on the whole amount of the catalyst, on a fire-resistive oxide carrier, wherein a MgO compound is dissolved in an organic acid to be supported so that the compound satisfies, as MgO, 0.2≤MgO/the organic acid(mol ratio)≤0.6. The production method of this catalyst is provided. In the hydrogenation treatment method of the heavy oil, the heavy oil is hydrogenation treated using the hydrogenation treatment catalyst and thereafter the deactivated catalyst is regenerated to be used. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a hydrotreating catalyst, a method for producing the same, and a hydrotreating method for heavy oil. The present invention relates to a catalyst, a method for producing the same, and a method for hydrotreating heavy oil.

In general, it is said that the cause of the decrease in the catalyst performance in the hydrotreatment of light sulfur-containing hydrocarbons such as kerosene oil is the deposition of coke (carbon content) on the catalyst.
On the other hand, in heavy oil hydrotreating, unlike light oil, a large amount of metal impurities such as vanadium and nickel present in the feedstock accumulate on the catalyst during the hydrotreating to cover the active sites. Poisoning reduces catalyst performance.
In addition, in the hydrotreatment of heavy oil with a high boiling point, it is necessary to perform the treatment at a higher temperature than the light oil, so that catalytically active metal components such as molybdenum in the catalyst are aggregated and the catalyst performance is further deteriorated. To do.
Furthermore, since heavy oil contains a lot of hard-to-desulfurize sulfur compounds, it is more easily affected by the accumulation of vanadium and other metals compared to hydrogenation of light oil.

In recent years, due to increasing environmental problems, it is desired to recycle the hydrotreating catalyst in order to reduce catalyst waste.
However, in the case of heavy oil hydrotreating, coke can be removed by calcination, but it is difficult to remove accumulated metals such as vanadium and nickel. In addition, since the wear strength of the catalyst is reduced during regeneration, the catalyst particle gap is clogged when the catalyst is recharged after regeneration, and operation becomes impossible when using the regenerated catalyst. there were.
Recently, a catalyst in which nickel oxide, molybdenum trioxide, magnesium oxide, and phosphorus pentoxide are supported on an alumina carrier has been proposed (see, for example, Patent Documents 1 and 2).
However, even in this method, the problem of reduction in the wear strength of the catalyst during complete regeneration has not been solved, and it has been difficult to regenerate and use the catalyst.

JP 11-319567 A JP 2005-254083 A

  The present invention has been made to solve the above-mentioned problems, and is a hydrotreatment that is highly active and less deteriorated, the wear strength of the new catalyst and the regenerated catalyst is large, and easy to regenerate after heavy oil treatment. Catalyst, method for producing the same, and method for hydrotreating heavy oil that can be stably used for a long period of time after regenerating the catalyst after hydrotreating the heavy oil using the hydrotreating catalyst The purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have found that magnesium oxide becomes 0.2 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.6 with the magnesium compound as magnesium oxide. Thus, the present inventors have found that a catalyst dissolved and supported in an organic acid is effective and completed the present invention.

That is, the present invention
1. To the refractory oxide carrier, 1 to 10% by mass of nickel oxide, 5 to 20% by mass of molybdenum trioxide, 0.3 to 1.5% by mass of magnesium oxide and 2 to 2 of phosphorus pentoxide, based on the total amount of the catalyst. A catalyst supported by 5% by mass, in which the magnesium oxide is supported by being dissolved in an organic acid such that the magnesium compound is magnesium oxide and 0.2 ≦ magnesium oxide / organic acid ≦ 0.6. A hydrotreating catalyst characterized by being,
2. Any one or two kinds of organic acids selected from citric acid, malic acid, tartaric acid, tartronic acid, glyceric acid, hydroxybutyric acid, succinic acid, tartaric acid, succinic acid, malonic acid, formic acid, acetic acid, propionic acid The hydroprocessing catalyst according to the above 1, which is a mixed acid as described above,
3. 3. The method for producing a hydrotreating catalyst according to 1 or 2 above, wherein a nickel compound, a molybdenum compound, a magnesium compound, a phosphorus compound and an organic acid are converted into a refractory oxide carrier in the presence of polyethylene glycol having a molecular weight of 200 or more. A method for producing a hydrotreating catalyst,
4). 4. The hydrogenation treatment according to 3 above, wherein a nickel compound, a molybdenum compound, a magnesium compound, a phosphorus compound, and an organic acid are supported on a refractory oxide carrier in the presence of polyethylene glycol having a molecular weight of 200 or more, and then fired at 400 ° C. or higher. Production method of catalyst,
5. Hydrogen of heavy oil, characterized by using one or more catalysts selected from the hydrotreating catalyst according to 1 or 2 and the hydrotreating catalyst obtained by the production method according to 3 or 4 above. Processing method,
6). Hydrotreating heavy oil using one or more catalysts selected from the hydrotreating catalyst according to 1 or 2 and the hydrotreating catalyst obtained by the production method according to 3 or 4 above. Then, the carbonaceous substance accumulated from the deteriorated catalyst is removed by calcination, and a heavy oil hydrotreating method used again for heavy oil hydrotreating is provided.

  According to the present invention, a catalyst in which 0.3 to 1.5% by mass of magnesium oxide is supported on a refractory oxide carrier on the basis of the total amount of the catalyst, the magnesium oxide having a magnesium compound as magnesium oxide, 0 .2 ≦ Magnesium oxide / Organic acid ≦ 0.6 The catalyst supported by dissolving in organic acid is highly active and has improved wear strength. It will be very easy.

The hydrotreating catalyst of the present invention is a refractory oxide carrier, based on the total amount of the catalyst, 1 to 10% by mass of nickel oxide, 5 to 20% by mass of molybdenum trioxide, and 0.3 to 1.5% of magnesium oxide. A catalyst carrying 2% by mass and 2% by mass of phosphorus pentoxide, wherein the magnesium oxide is 0.2 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.6 when the magnesium compound is magnesium oxide. Thus, it is dissolved and supported in an organic acid.
The hydrotreating catalyst of the present invention is a catalyst for hydrotreating heavy oil such as residual oil containing metal components such as vanadium and nickel as impurities, hydrodesulfurization, hydrodenitrogenation, hydrocracking, hydrogen Although it can be used for hydrotreating reactions such as hydrodearomatics, it can be used particularly effectively for hydrodesulfurization reactions.
The hydrotreating catalyst of the present invention is produced by firing a nickel compound, a molybdenum compound, a magnesium compound, a phosphorus compound and an organic acid on a refractory oxide carrier in the presence of polyethylene glycol having a molecular weight of 200 or more and then firing. can do.
Specifically, an organic acid is used to carry magnesium oxide, nickel oxide, morbuden trioxide and phosphorus pentoxide on a refractory oxide carrier.
Here, the refractory oxide support usually contains alumina, but may contain inorganic oxides such as silica, titania, zirconia, etc. as other components, or a composite oxide support thereof. It may be.
In particular, an alumina support is preferable.
From the viewpoint of dispersibility of metal oxides such as nickel oxide and molybdenum trioxide, an alumina carrier is preferable.

In the hydrotreating catalyst of the present invention, the content of magnesium oxide is 0.3 to 1.5% by mass, preferably 0.3 to 1.0% by mass, more preferably 0.4 to 4%, based on the total amount of the catalyst. It is 0.9 mass%, More preferably, it is 0.5-0.8 mass%.
When the magnesium oxide content is 0.3% by mass or more, sufficient wear strength is obtained, and when it is 1.5% by mass or less, the magnesium oxide reacts with a supported metal such as molybdenum or nickel to perform composite oxidation. No activity is formed and activity is increased.
Examples of the magnesium compound used for supporting magnesium oxide include magnesium oxide, basic magnesium carbonate, magnesium chloride, magnesium nitrate, and magnesium sulfate.

In the hydrotreating catalyst of the present invention, magnesium oxide is supported by being dissolved in an organic acid such that the magnesium compound is magnesium oxide and 0.2 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.6. .
In this case, it is preferable that the pH of the solution be adjusted to 1.0 or more and 3 or less using the organic acid, more preferably pH 1.2 to 2.8, still more preferably pH 1.5 to 2.5.
Organic acids that dissolve magnesium compounds such as magnesium oxide and basic magnesium carbonate include citric acid, malic acid, tartaric acid, tartronic acid, glyceric acid, hydroxybutyric acid, succinic acid, tartaric acid, succinic acid, malonic acid, formic acid, acetic acid. And propionic acid, and malic acid or citric acid is preferable.
The amount of the organic acid used to dissolve the magnesium compound is 0.2 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.6, where the magnesium compound is magnesium oxide.
Preferably, 0.25 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.4.
When the molar ratio is less than 0.2, a sufficient bond between the refractory oxide support and magnesium oxide is not generated, and the protective effect against metals such as vanadium is not effectively exhibited, and the magnesium compound is supported. In the subsequent firing, the strength of the refractory oxide carrier is reduced by the combustion heat of the organic acid.
On the other hand, when the molar ratio exceeds 0.6, the magnesium compound is not sufficiently dissolved in the organic acid, so that it cannot be uniformly applied on the refractory oxide carrier.
In the method for producing a hydrotreating catalyst of the present invention, in particular, when the accumulated carbonaceous matter is removed from the deteriorated catalyst by firing while suppressing destruction of the catalyst structure due to poisonous substances such as vanadium, and repeatedly regenerated and used. As described above, it is preferable that the magnesium compound is magnesium oxide, the magnesium oxide / organic acid is dissolved at a specific molar ratio, and is supported on a refractory oxide carrier molded together with a nickel compound, a molybdenum compound, and a phosphorus compound. .

In the hydrotreating catalyst of the present invention, the shape of the refractory oxide support is not particularly limited, and a shape suitable for a desired reaction mode such as a columnar shape, a spherical shape, a three to six leaf shape, and a honeycomb can be freely selected. .
In particular, in the fixed bed direct hydrodesulfurization reactor, a cylindrical shape, a three-leaf shape, and a four-leaf shape are preferably used.
The refractory oxide carrier having a specific surface area of usually 5 to 500 m ² / g, preferably 50 to 300 m ² / g is used.
When the specific surface area is 5 m ² / g or more, the dispersibility of the supported metal oxide is secured, and when the specific surface area is 500 m ² / g or less, the diffusion of the reaction product is not hindered.
The pore volume of the refractory oxide carrier is usually 0.2 to 1.5 cm ³ / g, preferably 0.3 to 1.2 cm ³ / g.
When the pore volume is 0.2 cm ³ / g or more, the catalyst pores are not immediately clogged due to accumulation of metal impurities such as vanadium in the feedstock and coke deposition, and 1.5 cm ³ / g or less. It is preferable that sufficient catalyst strength that can withstand practical use is secured.
The pore diameter of the refractory oxide carrier usually has an average pore diameter of 10 to 30 nm, preferably 11 to 20 nm, more preferably 12 to 15 nm.
The pore diameter is a pore diameter suitable for the molecular size of the petroleum fraction that is a reactant, and is a pore diameter that allows the reactant to sufficiently diffuse to the reaction active point inside the catalyst pore.
With respect to the above physical property values, 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)].
The specific surface area is B. E. T.A. It can be determined by law.

In the hydrotreating catalyst of the present invention, the content of nickel oxide is 1 to 10% by mass, preferably 2 to 8% by mass, based on the total amount of the catalyst.
The content of molybdenum trioxide is 5 to 20% by mass, preferably 6 to 18% by mass, based on the total amount of the catalyst.
Furthermore, the content of phosphorus pentoxide is 2 to 5% by mass, preferably 2.5 to 4.5% by mass, based on the total amount of the catalyst.
When the content of nickel oxide is 1% by mass or more, sufficient activity is exhibited, and when it is 10% by mass or less, there is no aggregation of nickel sulfide, which is an active species, and high activity is achieved.
Further, when the content of molybdenum trioxide is 5% by mass or more, sufficient activity is exhibited, and when it is 20% by mass or less, there is no aggregation of molybdenum sulfide as an active species and high activity is obtained.
Further, when the phosphorus pentoxide is 2% by mass or more, the spinel suppressing effect is sufficiently exhibited, and when it is 5% by mass or less, the aggregate of nickel-molybdenum-phosphorus is not generated and the activity becomes high. .
Here, the spinel suppressing effect means that when the refractory oxide support contains alumina, nickel forms spinel with alumina, and the catalyst is prevented from being deactivated, thereby improving the catalytic activity.

The hydrotreating catalyst of the present invention can be produced by supporting the above oxide on a refractory oxide support. Preferred molybdenum and nickel compounds used in the impregnation liquid for supporting treatment include oxides, Sulfates, nitrates, carbonates, basic carbonates, oxalates, acetates, ammonium salts and the like are used.
As the phosphorus compound, phosphorus pentoxide, orthophosphoric acid or the like is used.
In the production of the hydrotreating catalyst of the present invention, when a nickel compound, a molybdenum compound, and a phosphorus compound are supported on a refractory oxide carrier, including a magnesium compound, in the presence of polyethylene glycol having a molecular weight of 200 or more. It is necessary to carry on.
The molecular weight of polyethylene glycol is usually 250 to 10,000, preferably 300 to 6,000.
When the molecular weight is 200 or more, catalytic activity is secured, and when it is 10,000 or less, handling is easy from the viewpoint of solubility and time of the supporting process.
The amount of polyethylene glycol used is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the refractory oxide carrier.
When the amount of polyethylene glycol used is 0.5 parts by mass or more, the following nickel-molybdenum-phosphorus agglomerates are not formed, the catalytic activity increases, and when it is 30 parts by mass or less, loading is easy. Can do.
As described above, when the nickel compound is supported, if the refractory oxide carrier contains alumina, nickel may form a spinel with alumina, and the catalyst may be deactivated. There is an action to suppress the conversion, and the catalytic activity is improved.
If a large amount of phosphorus compound is used without using polyethylene glycol, nickel-molybdenum-phosphorus aggregates are formed, which tends to reduce the catalytic activity. However, when polyethylene glycol is used, As described above, the content of phosphorus oxide can be increased to 2 to 5% by mass, and the catalytic activity can be greatly improved.
There are no particular limitations on the method of supporting the magnesium compound, nickel compound, molybdenum compound, and phosphorus compound, but using a known supporting operation such as atmospheric pressure impregnation method, vacuum impregnation method, coating method, and a combination of these methods, Supported on a conductive oxide carrier.

The refractory oxide carrier impregnated with a magnesium compound or the like is preferably fired at a temperature of 400 ° C. or higher.
In the case of sequentially impregnating a magnesium compound, nickel compound, molybdenum compound, and phosphorus compound, it is possible to sinter at a temperature of 400 ° C. or more for each impregnation, or after impregnation with a plurality of compounds. Finally, it can be fired at a temperature of 400 ° C. or higher.
The firing temperature is more preferably 400 ° C. to 700 ° C. in an air or oxygen atmosphere.
More preferably, it is carried out under such conditions that the residual carbon content in the catalyst with polyethylene glycol is 1.0 mass% or less.
The firing time is about 1 to 48 hours, preferably 2 to 16 hours.

The hydrotreating method of the present invention is applied to hydrodesulfurization treatment of heavy oil in the presence of the catalyst of the present invention.
Heavy oils used in hydroprocessing include atmospheric residual oil, vacuum residual oil, vacuum gas oil, dewaxed vacuum residual oil, asphaltene oil, tar sand oil, residual oil that has been pre-hydrogenated once, etc. Is mentioned.
When hydrotreating using the catalyst of the present invention, it is preferable to perform a presulfidation treatment as a catalyst activation or stabilization treatment before the hydrotreating reaction.
This preliminary sulfidation treatment uses hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide (DMDS) or the like as a preliminary sulfiding agent, and is usually performed in a temperature range of 200 to 400 ° C.

Although the reaction conditions for the hydrotreating of the present invention vary depending on the type of the target feedstock, the reaction temperature is usually selected in the range of 200 to 500 ° C.
The reaction pressure is usually preferably selected in the range of 1.47 to 24.5 MPa (15 to 250 kg / cm ² ).
The reaction format is not particularly limited, but various processes such as a fixed bed, a moving bed, a boiling bed, and a suspended bed are usually employed, and from the viewpoint of economy, a distribution method using a fixed bed is preferable. Adopted.
In the case of such a distribution method, LHSV (liquid space velocity) is preferably selected in the range of 0.1 to 45 (1 / hr).
The supply ratio of hydrogen gas and feedstock (hydrogen / stock feed ratio) is usually preferably selected in the range of 50 to 2,000 Nm ³ / kl.
As described above, hydrodesulfurization treatment of heavy oil can be efficiently performed using the hydrotreating catalyst of the present invention.

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.
Example 1
Production of catalyst A1 (supporting magnesium oxide after forming alumina support)
(A) Preparation of Alumina Gel A and Alumina Carrier A A 15% by mass aqueous aluminum sulfate solution was added while heating and stirring an 8% by mass aqueous sodium aluminate solution at 60 ° C. to obtain a precipitate at pH 7.1.
This precipitate was separated and recovered by filtration, and then poured into 0.2 mass% aqueous ammonia maintained at 50 ° C. and washed by stirring.
The washed precipitate was separated and collected by filtration to obtain an alumina gel (hereinafter referred to as alumina gel A).
The above-obtained alumina gel A 833 g (110 g as Al ₂ O ₃ ) was heated to 100 ° C. to evaporate the moisture until the moisture content suitable for molding was reached.
Next, the obtained alumina gel (kneaded product) was molded by extrusion to obtain a four-leaf molded product.
This molded product was dried at 120 ° C. for 3 hours and then calcined in an air stream at 550 ° C. for 3 hours to obtain an alumina carrier A.
(B) Preparation of Catalyst A1 165.0 parts by mass of molybdenum trioxide and 39.3 parts by mass of basic nickel carbonate as nickel oxide (NiO) were dissolved in 500 parts by mass of ion-exchanged water.
Upon dissolution, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour.
Next, 50.8 parts by mass of phosphoric acid as an equivalent amount of phosphorus pentoxide was added, and after dissolution was confirmed, 14.0 parts by mass of basic magnesium carbonate as magnesium oxide was added, and the pH of the aqueous solution was adjusted to 2. Malic acid was added to [magnesium oxide (MgO) / malic acid (molar ratio) = 0.35].
During this time, the temperature of the aqueous solution was kept at about 40 ° C.
Further, an impregnation solution was prepared by adding 60 parts by mass of polyethylene glycol (molecular weight 400).
The impregnating solution obtained as described above was diluted to a volume equivalent to the absorption rate of the alumina carrier A, and then supported on 1,000 parts by mass of the alumina carrier A by the atmospheric pressure impregnation method.
This support was dried at 120 ° C. for 3 hours and calcined in air at 550 ° C. for 5 hours to obtain catalyst A1.
The obtained catalyst A1 contains 2.9% by mass as NiO, 13.4% by mass as MoO ₃ , 1.1% by mass as MgO, and 3.6% by mass as P ₂ O ₅ per dry mass, The average pore diameter was 0.0134 μm, the pore volume was 0.54 ml / g, and the specific surface area was 183 m ² / g.

Example 2
Production of catalyst A2 (supporting magnesium oxide after forming alumina support)
165.0 parts by mass of molybdenum trioxide and basic nickel carbonate as nickel oxide (NiO) were dissolved in 39.3 parts by mass in 500 parts by mass of ion-exchanged water.
Upon dissolution, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour.
Next, 50.8 parts by mass of phosphoric acid as phosphorus pentoxide was added, and after dissolution was confirmed, 14.0 parts by mass of basic magnesium carbonate as magnesium oxide was added, and the pH of the aqueous solution was adjusted to 1.5. Malic acid was added to [magnesium oxide (MgO) / malic acid (molar ratio) = 0.55].
During this time, the temperature of the aqueous solution was kept at about 40 ° C.
Further, an impregnation solution was prepared by adding 60 parts by mass of polyethylene glycol (molecular weight 400).
The impregnating solution obtained as described above was diluted to a volume equivalent to the absorption rate of the alumina carrier A, and then supported on 1,000 parts by mass of the alumina carrier A by the atmospheric pressure impregnation method.
This support was dried at 120 ° C. for 3 hours and calcined in air at 550 ° C. for 5 hours to obtain catalyst A2.
The obtained catalyst A2 contains 2.8% by mass as NiO, 13.2% by mass as MoO ₃ , 1.0% by mass as MgO, and 3.4% by mass as P ₂ O ₅ per dry mass, The average pore diameter was 0.0131 μm, the pore volume was 0.52 ml / g, and the specific surface area was 181 m ² / g.

Comparative Example 1
Production of catalyst B [magnesium oxide was added to alumina gel to obtain magnesium oxide (MgO) -containing alumina carrier]
14.0 parts by weight of basic magnesium carbonate as magnesium oxide, 21.5 parts by weight of malic acid and 100 parts by weight of ion-exchanged water were added, and the pH of the aqueous solution was adjusted to about 5.0 to obtain a homogeneous solution [magnesium oxide. (MgO) / malic acid (molar ratio) = 2.2].
This water-soluble night was added to the alumina gel A and mixed well, molded, dried at 120 ° C., and then fired at 550 ° C. to obtain an alumina support B containing magnesium oxide (MgO).
On the other hand, 165.0 parts by mass of molybdenum trioxide and basic nickel carbonate as nickel oxide (NiO) were dissolved in 39.3 parts by mass in 500 parts by mass of ion-exchanged water.
Upon dissolution, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour.
Next, 50.8 parts by mass of phosphoric acid as phosphorus pentoxide was added, and dissolution was confirmed. During this time, the temperature of the aqueous solution was kept at about 40 ° C.
Further, an impregnation solution was prepared by adding 60 parts by mass of polyethylene glycol (molecular weight 400).
The impregnating solution obtained as described above was diluted to a volume equivalent to the absorption rate of the magnesium oxide (MgO) -containing alumina carrier B, and then supported on 1,000 parts by mass of the alumina carrier A by atmospheric pressure impregnation. .
This support was dried at 120 ° C. for 3 hours and calcined in air at 550 ° C. for 5 hours to obtain Catalyst B.
The obtained catalyst B contains 3.0% by mass as NiO, 13.4% by mass as MoO ₃ , 1.0% by mass as MgO, and 3.6% by mass as P ₂ O ₅ per dry mass, The average pore diameter was 0.0134 μm, the pore volume was 0.55 ml / g, and the specific surface area was 178 m ² / g.

Comparative Example 2
Production of catalyst C (supporting magnesium oxide after forming alumina support)
165.0 parts by mass of molybdenum trioxide and basic nickel carbonate as nickel oxide (NiO) were dissolved in 39.3 parts by mass in 500 parts by mass of ion-exchanged water.
Upon dissolution, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour.
Next, 50.8 parts by mass of phosphoric acid as phosphorus pentoxide was added, and after dissolution was confirmed, 14.0 parts by mass of basic magnesium carbonate as magnesium oxide was added, and 440 parts by mass of malic acid was added [magnesium oxide ( MgO) / malic acid (molar ratio) = 0.1].
The pH of the aqueous solution was about 0.8.
During this time, the temperature of the aqueous solution was kept at about 40 ° C.
Further, an impregnation solution was prepared by adding 60 parts by mass of polyethylene glycol (molecular weight 400).
The impregnating solution obtained as described above was diluted to a volume equivalent to the absorption rate of the alumina carrier A, and then supported on 1,000 parts by mass of the alumina carrier A by the atmospheric pressure impregnation method.
This support was dried at 120 ° C. for 3 hours and calcined in air at 550 ° C. for 5 hours to obtain Catalyst C.
The obtained catalyst C contains 2.9% by mass as NiO, 13.4% by mass as MoO ₃ , 1.1% by mass as MgO, and 3.6% by mass as P ₂ O ₅ per dry mass, The average pore diameter was 0.0134 μm, the pore volume was 0.54 ml / g, and the specific surface area was 165 m ² / g.

Comparative Example 3
Production of catalyst D (supporting magnesium oxide after forming alumina support)
165.0 parts by mass of molybdenum trioxide and basic nickel carbonate as nickel oxide (NiO) were dissolved in 39.3 parts by mass in 500 parts by mass of ion-exchanged water.
Upon dissolution, the mixture was heated to 80 to 90 ° C. and stirred for 1 hour.
Next, after adding 50.8 parts by mass of phosphoric acid as phosphorus pentoxide and confirming dissolution, 14.0 parts by mass of basic magnesium carbonate as magnesium oxide was added, and 5 parts by mass of malic acid was added [magnesium oxide ( MgO) / malic acid (molar ratio) = 9.4].
The pH of the aqueous solution was 4.3.
During this time, the aqueous solution temperature was kept at about 40 ° C., but there was a slight turbidity.
Further, an impregnation solution was prepared by adding 60 parts by mass of polyethylene glycol (molecular weight 400).
The impregnating solution obtained as described above was diluted to a volume equivalent to the absorption rate of the alumina carrier A, and then supported on 1,000 parts by mass of the alumina carrier A by the atmospheric pressure impregnation method.
This support was dried at 120 ° C. for 3 hours and calcined in air at 550 ° C. for 5 hours to obtain Catalyst D.
The obtained catalyst D contains 2.9% by mass as NiO, 13.1% by mass as MoO ₃ , 1.0% by mass as MgO, and 3.4% by mass as P ₂ O ₅ per dry mass, The average pore diameter was 0.0134 μm, the pore volume was 0.54 ml / g, and the specific surface area was 183 m ² / g.

Examples 3 and 4 and Comparative Examples 4 to 6
<Evaluation of hydrodesulfurization treatment performance (initial activity)>
For the above catalysts A1, A2, B, C and D, using a high pressure fixed bed flow reactor with a catalyst filling amount of 50 ml, and using atmospheric residual oil obtained from heavy crude oil of the Middle East system shown in Table 1 as a raw material, The initial desulfurization performance was evaluated, and the effect of magnesium addition and the influence of the addition method were compared and evaluated.
In addition, since the catalyst of this invention is a desulfurization catalyst, it evaluated by combining with the commercially available demetallation catalyst.

Prior to the reaction, as a pretreatment, dimethyl disulfide (DMDS) as a sulfiding agent is added to the light oil (LGO) to the catalyst, and the pretreatment oil (the sulfur concentration in the pretreatment oil is adjusted to 2.5% by mass). ) Was presulfided by flowing with hydrogen gas at 250 ° C. for 24 hours.
Thereafter, the raw material oil shown in Table 1 was passed through the catalyst together with hydrogen gas, and hydrodesulfurization was performed under the following conditions.
Treatment conditions Hydrogen partial pressure: 13.2 MPa (135 kg / cm ² )
Liquid space velocity: 0.2 (1 / hr)
Hydrogen / oil ratio: 700 Nm ³ / kl

The evaluation results are shown in Table 2.
From Table 2, catalyst A1 (Example 1) having basic magnesium carbonate as magnesium oxide, MgO / malic acid (molar ratio) of 0.35, and catalyst A2 (Example 2) also having 0.55, It can be seen that the initial hydrodesulfurization performance is high.
Further, catalyst B (Comparative Example 1) in which the basic magnesium carbonate is magnesium oxide and MgO / malic acid (molar ratio) is 2.2 in the alumina gel A, and the basic magnesium carbonate is magnesium oxide, and MgO / malic acid. The initial hydrodesulfurization performance of catalyst C (comparative example 2) with a (molar ratio) of 0.1 is as high as that of the catalyst of example 1, but as described later, comparative example 1 and comparative example 2 This catalyst has very poor hydrodesulfurization performance after regeneration.
Furthermore, the initial hydrodesulfurization performance of Catalyst D (Comparative Example 3) with basic magnesium carbonate as magnesium oxide and MgO / malic acid (molar ratio) of 9.4 is the same as that of Example 1 and Example 2. It is clearly inferior to.

Examples 5-6 and Comparative Examples 7-9
<Evaluation of abrasion strength of regenerated catalyst>
(1) Manufacture of deteriorated (used) catalyst For the above catalysts A1, A2, B, C and D, the atmospheric residual oil obtained from the Middle Eastern heavy crude oil shown in Table 1 using a fixed bed reactor. Hydrodesulfurization treatment was performed for 4,000 hours.
The hydrodesulfurization treatment was continued while adjusting the reaction temperature so that the sulfur content of the product oil was constant.
After completion of the reaction, the catalyst in the reactor was washed by passing light oil, dried by circulating nitrogen gas, the catalyst was extracted, and the demetalized catalyst was separated by sieving to obtain a used catalyst. .

(2) Production of regenerated catalyst Using each of the used catalysts obtained above, while supplying 100% nitrogen gas at a rate of 100 ml / min using a rotary calciner (rotation speed: 5 rpm), 300 Treated for 1 hour at ° C.
Then, it baked at 450 degreeC for 3 hours, supplying the mixed gas of 50% nitrogen gas and 50% air at 100 ml / min.
After cooling each obtained catalyst, the lump and powder were removed by sieving to obtain a regenerated catalyst.
(3) The abrasion strength of the regenerated catalyst obtained above was measured.
In addition, abrasion strength was calculated | required by measuring the powdering rate shown below.
(Measurement method of powdering rate)
100 g of the catalyst was enclosed in a cylindrical rotating body having a diameter of 30 cm and rotated at 60 rpm for 30 minutes.
Thereafter, the catalyst was taken out and sieved using a 20-mesh sieve, and the mass of the remaining catalyst was measured.
The reduction amount of the catalyst mass was determined as the powdering rate.
The smaller this value is, the higher the wear strength is.
Table 3 shows the measurement results of the wear strength.
For comparison, the wear strengths of the new catalysts A1, A2, B, C and D were also measured.

  From Table 3, in Examples 5 to 6, the regenerated catalysts A1 and A2 of the used catalysts A1 and A2 are compared with the regenerated catalysts B, C and D of the used catalysts B, C and D in Comparative Examples 7 to 9. It can be seen that the powdering rate is small and the wear strength is excellent.

Examples 7-8 and Comparative Examples 10-11
<Evaluation of hydrodesulfurization performance of regenerated catalyst>
For each of the regenerated catalysts A1, A2, B, and C produced in Examples 5 to 6 and Comparative Examples 7 to 8, 50 ml of each regenerated catalyst was charged into a small high-pressure fixed bed reactor.
The hydrodesulfurization reaction was performed under the same reaction conditions as in the new catalyst (see Examples 3 to 4 and Comparative Examples 4 to 6).
Table 4 shows the properties of the raw material oil used, and Table 5 shows the evaluation results of the hydrodesulfurization performance.

表３及び表５より、本発明の酸化マグネシウムをアルミナ担体Ａに担持した触媒は、触媒摩耗強度が高いのみならず、水素化脱硫性能も高活性であることが分かる。
これは、酸化マグネシウムが、マグネシウム化合物を酸化マグネシウムとして、０．２≦酸化マグネシウム／有機酸（モル比）≦０．６となるように有機酸に溶解して担持されたことにより、酸化マグネシウムの状態が改善され、使用済み触媒に再生時におけるバナジウムの悪影響を抑制していると考えられる。

From Tables 3 and 5, it can be seen that the catalyst in which the magnesium oxide of the present invention is supported on the alumina support A not only has high catalyst abrasion strength but also high hydrodesulfurization performance.
This is because magnesium oxide is supported by being dissolved in an organic acid so that 0.2 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.6 with a magnesium compound as magnesium oxide. The state is improved, and it is considered that the spent catalyst is suppressed from the adverse effect of vanadium during regeneration.

  The hydrotreating catalyst of the present invention is used for hydrotreating heavy oils, and is particularly suitable for use as a regenerated catalyst.

Claims (6)

  To the refractory oxide carrier, 1 to 10% by mass of nickel oxide, 5 to 20% by mass of molybdenum trioxide, 0.3 to 1.5% by mass of magnesium oxide and 2 to 2 of phosphorus pentoxide, based on the total amount of the catalyst. A catalyst supported by 5% by mass, wherein the magnesium oxide is dissolved and supported in an organic acid so that the magnesium compound is magnesium oxide and 0.2 ≦ magnesium oxide / organic acid (molar ratio) ≦ 0.6. A hydrotreating catalyst characterized by being made.   Any one or two kinds of organic acids selected from citric acid, malic acid, tartaric acid, tartronic acid, glyceric acid, hydroxybutyric acid, succinic acid, tartaric acid, succinic acid, malonic acid, formic acid, acetic acid, propionic acid The hydroprocessing catalyst according to claim 1, which is a mixed acid as described above.   A method for producing a hydrotreating catalyst according to claim 1 or 2, wherein a nickel compound, a molybdenum compound, a magnesium compound, a phosphorus compound and an organic acid are added in the presence of polyethylene glycol having a molecular weight of 200 or more in a refractory oxide carrier. A method for producing a hydrotreating catalyst, which is supported on a catalyst.   The hydrogenation according to claim 3, wherein the nickel compound, the molybdenum compound, the magnesium compound, the phosphorus compound, and the organic acid are supported on a refractory oxide carrier in the presence of polyethylene glycol having a molecular weight of 200 or more, and then fired at 400 ° C or higher. A method for producing a treated catalyst.   A heavy oil characterized by using one or more catalysts selected from the hydrotreating catalyst according to claim 1 or 2 and the hydrotreating catalyst obtained by the production method according to claim 3 or 4. Hydrotreating method.   Hydrotreatment of heavy oil using one or more catalysts selected from the hydrotreating catalyst according to claim 1 or 2 and the hydrotreating catalyst obtained by the production method according to claim 3 or 4. After carrying out, the carbonaceous material accumulated from the deteriorated catalyst is removed by calcination, and the heavy oil hydroprocessing method is used again for heavy oil hydroprocessing.