JPH0475061B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst for hydrotreating heavy hydrocarbon oil, and more particularly to a catalyst suitable for hydrotreating to remove impurities such as asphaltene, metals, sulfur, and the like. The purpose of the present invention is to remove undesirable impurities such as asphaltenes, metals, and sulfur contained in heavy hydrocarbon oil by contact treatment in the presence of hydrogen, and to improve the usefulness of converting it into high value-added petroleum products. The goal is to provide a catalyst that can The heavy hydrocarbon oil referred to here is oil sand oil,
The target oil is residual oil obtained by distilling tar sand oil or heavy hydrocarbon oil under normal pressure or reduced pressure. These contain undesirable impurities such as asphaltenes that are insoluble in solvents such as pentane or heptane, organometallic compounds containing vanadium, nickel, etc., sulfur compounds, and nitrogen compounds. As an industrial method for hydrotreating heavy hydrocarbon oil to obtain high-quality petroleum products,
Hydrogenation treatment is generally carried out using a catalyst supporting active metals such as Mo, Co, and Ni, using a reactor such as a fixed bed or an ebullated bed. However, the biggest problem with these methods is that asphaltene and heavy metals contained in the raw materials significantly inhibit desulfurization and various hydrogenation reactions, and
The purpose is to shorten catalyst life by promoting coke formation on the catalyst and clogging of catalyst pores. Therefore, if these impurities can be removed, subsequent hydrodesulfurization or hydrocracking is considered to be relatively easy by applying existing technology. The present inventors believe that the composition of the carrier constituting the catalyst and the pore structure of the catalyst are largely involved in the removal of asphaltene and heavy metals from heavy hydrocarbon oil, and we believe that the removal of asphaltene and heavy metals from heavy hydrocarbon oil is largely affected by the composition of the carrier that makes up the catalyst and the pore structure of the catalyst. A series of catalysts supporting active metals were studied in relation to their pore structure. As a result, the zeolite was selected from the group consisting of molybdenum, tungsten, cobalt, nickel, iron, and chromium on a carrier in which one or more of the group consisting of clinoptilolite, mordenite, and A-type zeolite was composited with alumina. Catalysts that support one or more active metals have significantly improved catalytic activity compared to catalysts supported only by alumina, and have a pore structure with a pore diameter of 120 to 200 Å.
It has been found that a catalyst having a pore volume in the range of 60% or less and a pore diameter of 200 Å or more accounting for at least 30% shows better results. Conventionally, alumina is often used as a carrier for this type of hydrotreating catalyst, and there are few cases in which zeolite alone or a composite of alumina or the like and zeolite is used. In other words, the pore diameter of zeolite is within the range of 3 to 15 Å, and the size of molecules that participate in the reaction is limited within this pore diameter range, so asphaltene and organometallic compounds contained in heavy hydrocarbon oil This is because it is assumed that such macromolecules are difficult to diffuse into the active sites within the pores of zeolite, and the reaction hardly progresses. By the way, in Japanese Patent Application Laid-open No. 57-102235,
A method for hydrogenating and reforming heavy hydrocarbon oil has been proposed that uses a catalyst in which a metal component is supported on a porous carrier in which Y-type zeolite is mixed and composited with alumina or silica-alumina. This method was proposed because it is particularly excellent in improving the yield of middle distillates. The present invention differs from the above method in that it employs specific zeolites such as clinoptilolite, mordenite, and A-type zeolite, which have smaller pore diameters than Y-type zeolite. It has become clear that this type of zeolite exhibits superior effects on the activities of deasphaltenization and demetallization in the hydrogenation treatment of heavy hydrocarbon oils, leading to the present invention. That is, in the present invention, a forming aid is added to a mixture of alumina hydrate and the above-mentioned specific zeolite, the mixture is kneaded and formed, and the above-mentioned active metal is supported on an inorganic porous carrier obtained by drying and calcining the mixture. The present invention provides a catalyst for hydrotreating heavy hydrocarbon oil. The starting raw material for the alumina of the present invention may be any of gypsite, boehmite, boehmite gel, and bayerite, but the raw material suitable for the present catalyst is boehmite gel. Boehmite gel means an alumina hydrate having an X-ray boehmite structure (however, each diffraction line is extremely broad compared to the boehmite structure). Zeolite is mixed into the gel. There are various types of zeolite, such as Y-type zeolite, type zeolite, mordenite and clinoptilolite are used. The zeolite used here may be either synthetic or naturally occurring, and it itself contains alkali or alkaline earth metals such as sodium, potassium, and calcium, and these metals are usually removed. This provides active sites for hydrocarbon oil decomposition, so removal operations such as immersion in acidic solutions and washing are added.
In the catalyst of the present invention, it is not necessary to remove these metals, and even if they exist, they do not pose a problem. The content of zeolite is appropriately selected within the range of 5 to 50% by weight on a dry weight basis based on the total amount of alumina and zeolite. Asphaltene, demetalization activity decreases. Preferably zeolite 15~
It is in the range of 40% by weight. The mixture of alumina hydrate and zeolite is further mixed with forming aids such as polyethylene glycol, polypropylene glycol, nitric acid aqueous solution, and aqueous ammonia, and is homogenized by kneading with a kneader. In addition, drying the carrier gel in a water-containing state,
When baking, baking shrinkage generally occurs due to the action of the surface tension of water, creating small pores, but if an organic forming aid such as polyethylene glycol or polypropylene glycol is added to this, the surface tension decreases and baking shrinkage occurs. This is less likely to occur, and pores with large pore diameters and pore volumes are produced. The degree is affected by the amount added, and in the present invention, it can also be adjusted by changing the amount added.
Next, this is extruded, dried and fired to obtain an inorganic porous carrier. The catalyst of the present invention has at least one metal component selected from molybdenum, tungsten, vanadium, cobalt, nickel, iron, and chromium supported on the inorganic porous carrier, and is used as a catalyst for hydrogenation treatment. A usual method is adopted as this supporting method. For example, a so-called impregnation method is employed in which the carrier is brought into contact with an aqueous solution containing a metal compound in a volume corresponding to the pore volume of the carrier. After impregnation, the catalyst of the present invention is obtained by drying and firing. The amount of active metal supported is appropriately selected so that the active metal is contained in the catalyst in an amount of 0.5 to 15% by weight on a dry weight basis. The catalyst according to the present invention not only supports an active metal on a carrier made of alumina and a specific zeolite, but also has physical properties such as a pore volume in the range of 0.4 to 1.2 ml/g as described above. It is within;
Further, it is characterized in that the volume of pores with a pore diameter of 200 Å or less occupies 60% or less, and the volume of pores with a pore diameter of 200 Å or more occupies at least 30%. If the pore volume is small, not only will the desired activity not be obtained, but the activity will be significantly degraded, and if it is too large, the mechanical strength will be poor in practical terms, so it is preferably 0.5~
It is 1.0ml/g. Pores with a pore diameter in the range of 120 to 200 Å are necessary to promote desulfurization activity, and if there are too many, the deasphaltene and metal removal activities will be poor, so the pore volume in this range needs to be kept at less than 60%. There is. Furthermore, pores with a pore diameter of 200 Å or more are necessary to facilitate the diffusion of impurity molecules such as asphaltenes in heavy hydrocarbon oil and heavy metal compounds into the catalyst pores. It has become clear that by increasing the proportion of the catalyst to at least 30%, the activity can be significantly improved and the life of the catalyst can be extended. As a reaction method for hydrotreating heavy hydrocarbon oil using the catalyst according to the present invention, any of conventional flow-through reactors such as a fixed bed, a moving bed, and an ebullated bed may be employed. In addition, as the hydrogenation treatment conditions at this time, the reaction temperature is usually 330 to 450°C, preferably 360 to 420°C, and the reaction pressure is 50 to 200 Kg/cm ²
G, preferably 100 to 160 Kg/cm ² G. Also,
The liquid hourly space velocity (LHSV) when feeding heavy hydrocarbon oil as a raw material to the reactor is usually 0.1 to 10 h ^-1 , preferably 0.2 to 2 h ^-1 , and the hydrogen to oil ratio is usually 300 to 2 h -1.
Within the range of 2000Nm ³ /Kl, preferably 800~
Selected in the range of 1500Nm ³ /Kl. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples unless the gist of the invention is exceeded. Catalyst production example Example 1 Catalyst A - 185 g of commercially available boehmite alumina and 80 g of natural clinoptilolite as zeolite
Add 80g of polypropylene glycol
g, add 220 ml of 30% nitric acid aqueous solution. This mixture is kneaded using a kneader for about 1 hour, during which time 150 ml of a 2.4% ammonia aqueous solution is added. Next, the kneaded product was molded into a cylindrical shape using an extruder having a die with a 1.5 mm diameter hole, and the molded product was dried at 110°C for 15 to 20 hours and placed in an air stream.
Bake at 700℃ for 3 hours. Molybdenum and nickel were supported on the fired carrier by a two-stage impregnation method. Metal support is 13.4% by weight of molybdenum as MoO ₃ and 3.8% by weight of nickel as NiO.
Ammonium paramolybdate was used as the source of molybdenum, and nickel nitrate was used as the source of nickel. That is,
After the carrier was immersed in an ammonium aqueous solution of ammonium paramolybdate for 5 hours, the liquid adhering to the surface was removed, dried at 110°C for 20 hours, and then calcined at 600°C for 3 hours. Next, add 5 to an aqueous solution of nickel nitrate.
After soaking for an hour, remove the liquid on the surface and heat it at 110℃ for 20 hours.
It was dried for hours and then calcined at 600°C for 3 hours to become a catalyst. Catalyst B - A catalyst was prepared in the same manner as Catalyst A except that H-type mordenite was used as the zeolite. Catalyst B' - A catalyst was prepared in the same manner as Catalyst A except that Na-type mordenite was used as the zeolite. Catalyst C - A catalyst was prepared in the same manner as Catalyst A except that Type A zeolite was used as the zeolite. Catalyst D (comparative catalyst) - A catalyst was prepared in the same manner as Catalyst A except that type X zeolite was used as the zeolite. Catalyst E (comparative catalyst) - A catalyst was prepared in the same manner as Catalyst A except that H-type Y zeolite was used as the zeolite. Catalyst F (comparative catalyst) - A catalyst was prepared using basically the same method as Catalyst A, but no zeolite was added to the carrier and only boehmite alumina was used. Evaluation Test Examples Examples 2 to 4, Comparative Examples 1 to 3 Catalysts A to F prepared in Example 1 were used as feedstock oil, specific gravity (15/4°C) 1.028, n-
Heptane insoluble matter (asphaltene) 13.7wt%,
Sulfur content 5.19wt%, vanadium 257ppm, nickel
Using atmospheric residual oil (boiling point 330℃ or higher) of oil sand oil showing properties of 102ppm, a reaction temperature of 390℃ and a reaction pressure of 150Kg/
cm ² G, liquid space velocity 0.7h ^-1 , hydrogen to oil ratio 1200N
Catalyst evaluation tests were conducted under reaction conditions of m ³ /Kl. Table 1 shows the properties of the produced oil after 230 hours of oil passing and the pore structure of the catalyst used.

[Table] As is clear from Table 1, by using alumina with clinoptilolite, mordenite, and A-type zeolite added as a carrier,
It can be seen that the catalysts prepared using these are significantly superior and improved in asphaltene removal and metal removal activities. Catalyst Preparation Example Comparative Example 4 In the preparation of Catalyst G-carrier, a catalyst was prepared basically in the same manner as in Catalyst A of Example 1, except that the amount of polypropylene glycol added was reduced. Evaluation Test Example Comparative Example 5 Hydrogenation treatment was carried out using Catalyst A and Catalyst G, using the same feedstock oil, reaction equipment, and reaction conditions as in Example 2. Table 2 shows the properties of the resulting oil and the pore structure of the catalyst used.

[Table] From Table 2, Catalyst G has 73% of the pore volume with pore diameters of 120 to 200 Å and 22% of the pore volume with pore diameters of 200 Å or more. It can be seen that the asphaltene removal and metal removal activities are inferior to that of catalyst A in which the pore volume occupies 40%.
From this, it can be said that it is important to define the pore structure within a specific range. Example 5 In order to investigate the relationship between the zeolite (clinoptilolite) content in the catalyst and the catalytic activity, a catalyst was prepared basically in the same manner as catalyst A in Example 1, and a zeolite-containing The amount is 0 on a dry basis.
Hydrogenation treatment was carried out using the same feedstock oil, reaction equipment, and reaction conditions as in Example 2, using the same catalysts as in Example 2, using catalysts that were varied in the range of ~50% by weight. Figure 1 shows the results of analyzing the produced oil after passing through the oil for 230 hours to examine the relationship between the zeolite content in the catalyst and the removal rate of asphaltene, panadium, and sulfur. As is clear from this diagram, there is an optimal value for the zeolite content for the catalyst of the present invention, which is 5 to 50% by weight.
It can be seen that it is necessary to make an appropriate selection within the range of . Catalyst Preparation Examples Example 6 Catalyst H - A carrier was prepared using basically the same method as for Catalyst A in Example 1, and molybdenum and cobalt were supported by a two-stage impregnation method. The metals were supported at 13.4% by weight of molybdenum as MoO ₂ and 3.8% by weight of cobalt as CoO, using ammonium paramolybdate and cobalt nitrate as the metal compounds, respectively, and by a method similar to Catalyst A in Example 1. catalyzed. Catalyst I - A carrier was prepared basically in the same manner as for Catalyst A in Example 1, impregnated with an ammonia aqueous solution of tungstic acid, dried, and calcined at 550°C for 3 hours. Next, it was impregnated with an aqueous solution of nickel nitrate, dried, and then fired at 550°C for 3 hours.
I got a catalyst. Tungsten was supported in an amount of 9% by weight as WO ₃ and nickel was supported in an amount of 3.2% by weight as NiO. Catalyst J - A support was prepared using essentially the same method as Catalyst A in Example 1, to which molybdenum (10% by weight as MoO ₃ ) and iron (3% by weight as Fe ₂ O ₃ ) were added. carried it. For molybdenum, ammonium paramolybdate was used, and for iron, a compound of iron nitrate was used, and Catalyst A of Example 1 was used.
It was catalyzed by a method according to . Evaluation Test Examples Examples 7 to 9 Hydrogenation was carried out using Catalyst H, Catalyst I, and Catalyst J, and using the same feedstock oil, reaction equipment, and reaction conditions as in Example 2. Table 3 shows the properties of the resulting oil and the pore structure of the catalyst used.

【table】

【table】

[Table] It can be seen from Table 3 that the same results as catalyst A can be obtained when the type of metal is changed.

[Brief explanation of the drawing]

FIG. 1 is a chart examining the relationship between the zeolite (clinoptilolite) content in the catalyst and the removal rate of asphaltene, vanadium, and sulfur in the feed oil.

Claims (1)

[Claims] 1 50 to 95% by weight of alumina and 5 to 95% of zeolite
In the inorganic porous carrier consisting of 50% by weight, the zeolite is clinoptilolite, mordenite,
and A-type zeolite, and a heavy hydrocarbon characterized in that the carrier supports at least one metal component selected from molybdenum, tungsten, cobalt, nickel, iron, and chromium. Oil hydroprocessing catalyst. 2 The pore volume is in the range of 0.4 to 1.2 ml/g, the pore volume with a pore diameter in the range of 120 to 200 Å accounts for 60% or less, and the pore volume with a pore diameter of 200 Å or more accounts for at least 30%. The catalyst of claim 1 which occupies .