JPS58101193A - Hydrogenating and removing metal from heavy oil with fine particulate catalyst - Google Patents

Abstract

PURPOSE:To remove a metal from a heavy oil with ease, by depositing soluble V and other soluble metals in the heavy oil in a high proportion on a fine particulate catalyst under specific hydrogenating conditions, and separating the fine particulate catalyst by the high gradient magnetic separation method. CONSTITUTION:A raw material heavy oil containing soluble V and other soluble metals is hydrogenated in the presence of a fine particulate catalyst having 0.1- 200mu volume mean diameter at 350-500 deg.C and 10-350kg/cm<2> hydrogen partial pressure to deposit the metallic components on the fine particulate catalyst. The resultant hydrogenated oil containing the used catalyst is then treated in a high gradient magnetic separator to separate the catalyst therefrom.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrodemetallization process for removing soluble metals, particularly vanadium, contained therein from heavy oil.

Heavy hydrocarbons (herein simply referred to as heavy oil) usually contain metals such as vanadium, nickel, and iron in the form of soluble compounds, along with sulfur compounds and nitrogen compounds. . These impurities contained in heavy oil pose a major hindrance to the use of heavy oil as a fuel, and also to its use as a raw material for chemical processing. In particular, when heavy oil is hydrotreated in the presence of a catalyst, soluble metals contained in heavy oil accumulate on the catalyst and significantly reduce the activity of the catalyst.

In order to remove the above-mentioned contaminants from heavy oil, a so-called hydrodesulfurization method is carried out in which heavy oil is hydrotreated in the presence of a catalyst containing a hydrogenation-active metal.

This method is mainly aimed at removing sulfur compounds and nitrogen compounds contained in heavy oil by hydrogenolysis.1. In this case, as described above, a problem arises in that the soluble metals contained in the heavy oil poison the catalyst and rapidly reduce its catalytic activity. Therefore, conventionally, much research has been directed toward the development of catalysts that are less susceptible to such catalyst poisoning and the development of methods for removing soluble metals from heavy oil in advance.

Conventionally, the only way to remove soluble metals from heavy oil in advance is to use ordinary desulfurization catalysts, waste catalysts with almost no denitrification activity, or inexpensive low-activity catalysts such as bauxite and red mud. A method is known in which heavy oil is hydrotreated and soluble metals are deposited on a catalyst and removed. However, in this method, it is necessary to frequently exchange the catalyst, and there are also problems such as significant precipitation of carbonaceous substances when the reaction temperature is raised to increase the demetalization rate.

On the other hand, in the hydrodemetalization treatment of heavy oil as described above, if a slurry catalyst containing fine particles with a volume average particle diameter of 200 μm or less is used, it becomes possible to continuously extract the catalyst from the reaction system. However, in this case, the catalyst slurry from the reaction system and the produced oil extracted from the grass can be easily maintained at a constant level. , significant difficulties are involved in separating the finely divided catalyst. In particular, when ultrafine catalyst particles having a volume average particle diameter of 50 μm or less are used, it is very difficult to separate them from the produced oil, which is extremely disadvantageous from an economic standpoint.

As a result of intensive research to overcome the above-mentioned drawbacks found in conventional hydrodemetalization treatment of heavy oil, the present inventor has discovered that when heavy oil is hydrotreated in the presence of a fine particle catalyst, , it is possible to deposit a high proportion of soluble metals contained in heavy oil on fine particle catalysts, and these fine particles with a large amount of metal deposited can be used to separate produced oil by high gradient magnetic separation method. The present invention was completed based on the unexpected discovery that it can be easily separated from

That is, according to the present invention, raw material heavy oil containing soluble vanadium and other soluble metals has a volume average particle diameter of 0.
Temperature 350-5 in the presence of a fine particle catalyst of 1-200μ
A hydrogenation treatment in which soluble vanadium contained in the heavy oil and other soluble metals are deposited on the fine particle catalyst by hydrogenation treatment under the conditions of 00°C and a hydrogen partial pressure of 10 to 350K9/1yn2. A method is provided for removing the fine particle catalyst having wire mesh components by subjecting hydrotreated product oil containing the fine particle catalyst with deposits of these metal components as a spent catalyst to high gradient magnetic separation treatment.

In the present invention, the reason why the fine particles with accumulated metal content can be separated from the produced oil by the high gradient magnetic separation method is not clear, but it is thought to be due to the vanadium content contained in the heavy oil. In other words, the vanadium content in heavy oil is deposited on fine particles as vanadium sulfide with high magnetic susceptibility under the above-mentioned hydrotreating conditions, but in this case, the particles that form the core of the metal deposit are fine particles. Moreover, since the metal deposition ratio is relatively large, the fine particles as a whole are considered to have sufficient magnetization required for high gradient magnetic separation.

In the present invention, heavy hydrocarbons include sulfur compounds and nitrogen compounds, as well as metals such as vanadium, nickel, and iron, of which at least 10% by volume is heated to 550°C or higher. It has a boiling point and also has a boiling point of 20
Hydrocarbons are defined as having a specific gravity of 0.93 or more at °C, and these include atmospheric distillation residue oil, vacuum distillation residue oil, pitch, tar, deasphalting residue, crude oil,
tar sant humen, soer oil, coal tar, liquefied coal, solvent-refined coal, synthetic crude oil, and bituminous coal with a carbon content of 60 to 90% by weight on an anhydrous and ash-free basis;
This applies to all types of coal, including subbituminous coal and katsu charcoal, which have a high content of residual carbon and asphaltene. The amount of soluble metals contained in the heavy oil is 20 ppm (weight) or more,
In particular, it is 200 ppm or more, but the higher the vanadium content, the more advantageous it is, and 100 ppm as metal vanadium.
Above, those containing 200 ppm or more are particularly preferred. Also, among heavy oils, considering the dispersibility of fine particles in heavy oil, it is preferable to use heavy oils with high viscosity and specific gravity. % or more, particularly vacuum distillation residue oil is particularly preferred.

The fine particles generally applied as a catalyst in the present invention have a volume average particle diameter in the range of 0.1 to 200μ, but are not necessarily limited to this, and in some cases, particles outside the above range may be used. is also available. For example, in the present invention, the smaller the particle size of the catalyst, the more advantageous it is, so if there are no manufacturing problems, catalysts with a particle diameter of 0 or 1μ can be advantageously used. In addition, the particle diameter as used in this specification means a volume average particle diameter.

The fine particles used as a catalyst in the present invention can be arbitrarily selected from almost all kinds of fine solid particles or solid colloids. Usually 200μ or less, preferably 100μ or less, such as 79%, alumina, titania,
In addition to zirconia, alumina silica, silica titania, magne 7a, magne/lamb silicate, calcium silicate, carbon, coke, etc., pulverized ordinary hydrotreating catalysts are used.

In order to use the fine particles used in the present invention as a slurry catalyst, it is preferable to use them in the form of ultrafine catalyst particles having a particle size of 50 μm or less, particularly 10 μm or less. Catalyst slurries containing such ultrafine catalysts can be composted like almost homogeneous liquids, significantly reduce reactor wear compared to catalyst slurries containing coarse-grained catalysts, and further reduce the production When hydrogenation is carried out while passing oil together with a fixed bed made of a conventionally known hydrogenation catalyst, the oil passes through the fixed bed easily without clogging it. Examples of such ultrafine particles include solid colloidal particles of 1μ or less, Japanese Patent Application No. 53-1
Examples include fine colloidal particles disclosed in Japanese Patent No. 09361. Specific examples of preferable ultrafine particle catalysts used in the present invention include β-diketone metal salts of VatVIa+group II metals of the periodic table, penta- or hexacarbonyls of V+Mo+Fe+CoνN1, heteropolyacids of group IV metals of the periodic table, and Mo+Oo+Ni Naphthenate, Cu +
Colloidal particles or fine solid particles obtained by treating metal compounds such as V+Fe +Oo +Ni +Pt phthalo/anine, molybdenum blue, V+MotTi chloride or oxychloride under pressure of hydrogen or/and hydrogen sulfide at high temperature. Yes, and periodic table ■a
There are ultrafine pulverized products of oxides or sulfides of 9.a or group 1 gold maple. Furthermore, the ultrafine particle catalyst used in the present invention may be, for example, a known hydrotreating catalyst, a catalyst in which a hydrogenation-active metal is supported on a ridged carrier, or one derived from a natural product containing a hydrogenation-active metal. According to Inventor Church's completely new knowledge, a substance that had been completely overlooked as a catalyst in the past,
White carbon (including particulate silica or particulate calcium silicate) developed as a substitute for carbon black used as a filler in the rubber and plastic fields, or manufactured using a method similar to that used for white carbon. Even metal oxide fine powders such as alumina, titania, alumina/silica, etc., which are used in the present invention, exhibit excellent performance as the fine particle catalyst of the present invention. White carbon is already widely available on the market and there is no need to explain it, but if necessary, please refer to ``The Science of New Industrial Materials'' (
Please refer to pages 31-58 (edited by Akira Nagai, Kannahara Publishing, 1967).

The fine particles exemplified above include those that contain a hydrogenation-active metal called a so-called catalytic metal, and those that do not substantially contain any cavities, and both of these are suitable. The reason why fine particles that do not contain hydrogenation-active metals exhibit catalytic activity is that approximately 5 to 5,000 ppm of oil-soluble vanadium compounds in hydrocarbons containing residual oil release hydrogen at the beginning of the reaction during the hydrotreating process. It is thought that this is because it precipitates on fine particles that have almost no catalytic activity, and these contribute as a catalytic metal. The inventor discovered that when hydrocarbons containing soluble vanadium were subjected to hydrogenation treatment by adding a small amount of silica, which is made up of ultrafine particles that are said to have almost no hydrogenation activity, the desulfurization rate and demetalization rate increased over time. , the asphaltene decomposition rate gradually improved. On the contrary, it was observed that the amount of carbonaceous material deposited on the catalyst decreased. However, it increases the reaction rate, especially the removal rate of sulfur, nitrogen, soluble metals, etc., and reduces residual carbon and asqualtenes.
In order to obtain a treated oil with a low bromine number and a low unsaturation content, it is desirable to use a catalyst containing a metal having hydrogenation activity. Supporting such metals also reduces the deposition of carbonaceous substances on the catalyst, prevents agglomeration of the catalyst, and
Furthermore, supports commonly used for initial hydrogenation catalysts can be used. As a method for supporting metal hydride on such a fine powder carrier, conventional methods such as impregnation method, spray drying method, and vapor deposition method are employed, and in addition, according to the method described in Japanese Patent Application No. 139883/1983, A method can be adopted in which a fine powder carrier contains a solution formed by dissolving a metal compound such as acetylacetone metal salt, metal phthalo/anine, or metal carbonyl in an organic solvent such as alcohol or ester. Furthermore, a fine particle catalyst containing a hydrogenation-active metal can be obtained by supporting a multimetal on a coarse particle support by a known method and then pulverizing the support in a wet or dry manner. Furthermore, the desired fine catalyst can be obtained by pulverizing a solution or dispersion containing a soluble or sol-like precursor of the carrier and a metal compound by a spray drying method and then calcining it. The catalyst carrier used in the present invention generally has a 0.
It has a pore volume of 2 cc/2 or more, preferably 0.5 cc/2, more preferably 2 cc/''2 or more, and a specific surface area of 1 m27f or more, preferably som27y or more.

In the present invention, the fine particle catalysts include c111 lanthanide, Ti+V+MoνFe+Co, and NI
Containing at least one hydrogenation-active metal selected from among, for example, silica, alumina or glue.
Alumina supports these metals, and titania or lanthanide oxide supports V, Mo, F.
A material on which at least one metal selected from e r Co and N1 is supported is preferably employed. Such a catalyst can be easily separated from produced oil in the form of a slurry by a high gradient magnetic separation method, has little carbon deposit on the catalyst, and has high activity.

In the present invention, as the catalyst fine particles, those already contained in the raw material heavy oil can be used as they are. For example, tar sant bitumen has an iron content of 1~
0.2 fine solids with a particle diameter of 0.1 to 30μ containing 5%
However, when using such a raw material heavy oil, the object of the present invention can be achieved without particularly adding a fine particle catalyst from the outside.

The hydrotreating conditions used in the present invention are such that in order to perform hydrocracking while suppressing excessive carbonaceous deposition on the catalyst,
Usually, the hydrogen partial pressure is 10 to 350 Kg/cm2, preferably 30 to 250 Kg/α2, and the reaction temperature is 350 to 50 Kg/cm2.
The temperature is 0°C, preferably 400-480°C, more preferably the hydrogen pressure is 50-200 Kg/cm2 and the reaction temperature is 430-460°C. Hydrogen partial pressure is 1
Although the hydrogenation reaction occurs even at 0 K9/crn2 or less, the amount of coke deposited on the catalyst increases significantly, which makes it more likely to coagulate, so it is not preferable to perform the treatment under extremely low hydrogen pressure. In addition, the upper limit of hydrogen partial pressure is a condition set for the purpose of minimizing chemical hydrogen consumption, and in reactions using fine particles as catalysts, even under such low hydrogen pressure,
It is characterized by the reaction proceeding at a high reaction rate.

Almost all heavy oil raw materials used for hydrotreating contain sulfur, and some of this is eliminated as hydrogen sulfide, and the reaction is usually carried out in an atmosphere that substantially contains hydrogen sulfide. be exposed. Such an increase in hydrogen sulfide partial pressure contributes to suppressing carbonaceous deposition on catalyst particles.1. This has the effect of improving the metal removal rate.

Therefore, it is extremely important to actively try to increase the hydrogen sulfide partial pressure by adding easily decomposable hydrogen sulfide precursors such as carbon disulfide and mercaptans to the raw material, without relying solely on naturally occurring hydrogen sulfide. Effective. Hydrogen sulfide partial pressure is 0.1-50Kg/crn2 depending on the type of catalyst, reaction conditions, etc.
, preferably arbitrarily selected within the range of 9/crn2 to 0.5 to 15.

The ratio of fine particle catalyst to heavy oil is 0.01 to 20% by weight, based on the total heavy oil supplied to the hydrotreating process.
Preferably it is 0.1 to 10% by weight. Particle diameter 0.5
When using an ultrafine particle catalyst of ~1Oμ, the catalyst concentration in the heavy oil subjected to hydrotreating is 0.01-10% by weight, preferably 0.1-1% by weight, especially 0.01-10% by weight. 1-0.5
Preferably, it is expressed as % by weight.

When heavy oil is hydrotreated in the presence of a fine particle catalyst according to the present invention, vanadium content of at least 1.0% by weight, preferably 5.0% by weight or more in terms of metal, is deposited on the fine particle catalyst. Operate as follows.

The produced oil extracted from the heavy oil hydrotreating process together with the fine particle catalyst deposited with metal components is sent to a high gradient magnetic separation process, where spent catalyst particles are separated from the produced oil. Although high gradient magnetic separation methods are well known, their details can be found in, for example, RoR, Qrde
[IEEE Transactionon Ma
genetics J Mag vol. 12, A5.628
~435 P (1976), and “Powder Engineering Society Journal”
See Vol. 18, A1128-46P (1981), etc. Conventionally, solid-liquid separation by high gradient magnetic separation of magnetic catalyst particles containing a considerable amount of ferromagnetic metal acid has been well known. There is no known phenomenon in which the catalyst particles become magnetized and magnetically separable.

High gradient magnetic separation equipment consists of a container filled with ferromagnetic thin wires (matrix) made of iron group metals or their alloys (ferritic stainless steel, etc.) in the magnetic field inside Lunaid. By flowing the liquid into this container, the magnetic particles adhere to the ferromagnetic wire and are separated into solid and liquid. In this high-gradient magnetic separation device, by using extremely small wires with a diameter of about 1 to 50 μm as ferromagnetic wires,
The feature is that the magnetic gradient near the thin wire can be made thicker. Because of this, the magnetic attraction force acting on the magnetic particles in the liquid to be processed is 100 to 100, compared to a normal high-magnetic magnetic separation device.
Becomes 0 times larger. The high gradient magnetic separation processing conditions in the present invention are preferable depending on the desired degree of solid-liquid separation, the properties of the fine particle catalyst in the produced oil, especially the size and composition (vanadium content, etc.), the viscosity of the produced liquid, etc. M) The thickness of the ferromagnetic thin wire forming the IJ lux is usually about 1 to 100 μm, preferably about 5 to 30 μm, and the porosity of the matrix is usually 60 to 98%, preferably 80 to 90%. When filling the matrix, the thickness of the thin wires and the porosity are appropriately selected depending on the properties of the fine particle catalyst to be attached and separated.

In the present invention, when the produced oil containing a fine particle catalyst with deposited metal components is subjected to high gradient magnetic separation treatment, the linear velocity of the produced oil passing through the matrix is usually 0.5 to
/hour, preferably in the range of 1 to 2 om/hour. If the linear velocity of the produced oil is low, solid-liquid separation can be achieved with high efficiency, but a large-scale device is required, and if the linear velocity of the produced oil becomes too high, solid-liquid separation cannot be achieved sufficiently. In the present invention, high gradient magnetic separation can be performed in multiple stages, for example, fine particles with high magnetic susceptibility can be separated in the first stage, fine particles with low magnetic susceptibility can be separated in the second stage, and,
If necessary, the separated particles with high magnetic susceptibility can be recycled and used again as catalyst particles.

In the present invention, the magnetic susceptibility of the fine particle catalyst with accumulated metal content is low due to the small amount of all soluble classes contained in heavy oil, making solid-liquid separation difficult, or when it is desired to further increase the degree of solid-liquid separation. In some cases, as fine particles themselves, at least one kind of magnetic metal selected from O'% lanthanide, TIIVνN1゜CO and Fe is supported on a carrier such as titania or lanthanide oxide. Depending on the M.

By using a catalyst formed by also supporting the above, separation from the produced oil can be made easier.

Furthermore, it is possible to make solid-liquid separation even easier by adding ferromagnetic fine powder to the produced oil and performing a high gradient magnetic separation process. Product oil with extremely low solid content can be obtained at a high linear velocity through which the product oil passes. The ferromagnetic fine powder used in this case (magnetic susceptibility I x 10-'emu/? or more, preferably 5XlO'emu/f or more) has a particle diameter of 0.1 to 200μ, preferably 1 to 50μ. Specific examples include iron powder, ferrite powder, natural magnetite powder, and the like. In the present invention, natural magnetite powder is preferably used because it is inexpensive and available in large quantities. The addition ratio of the ferromagnetic fine powder to the fine particle catalyst in the produced oil is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, per 1 part by weight of the fine particle catalyst.
It is 3 parts by weight. When high-gradient magnetic separation is performed by adding ferromagnetic fine powder to produced oil, the fine particle catalyst is separated from the produced oil together with the ferromagnetic fine powder, but after these are separated from each other, the fine particle catalyst becomes hydrogen. Recycled in the chemical treatment process,
The ferromagnetic powder can also be reused in high gradient magnetic separation processes. Although the fine particle catalyst and the ferromagnetic fine powder may be separated by using the difference in specific gravity or particle size, the difference in magnetic susceptibility can be used to separate the fine particle catalyst and the ferromagnetic fine powder. It is advantageous to magnetize and separate large ferromagnetic fine powders.

In the present invention, when the fine particle catalyst is separated from the produced oil by high gradient magnetic separation, the product obtained from the hydrogen treatment step is subjected to gas-liquid separation treatment to separate hydrogen and light products. In addition to high-gradient magnetic separation treatment, hydrogenated products can be subjected to gas-liquid separation treatment and high-gradient magnetic separation treatment under high pressure.Furthermore, light products can be separated from the produced oil by distillation, etc. After separating the fraction, the resulting heavy residual oil containing fine particle catalyst can also be subjected to high gradient 6d magnetic separation treatment.

In the present invention, at least a part of the fine particle catalyst separated in the high gradient magnetic separation step is optionally
After being subjected to appropriate cleaning and regeneration treatments, it can be recycled to the hydrogenation process. When the separated fine particle catalyst is washed and recycled to the hydrogenation process, the washing liquid may include various hydrocarbons and their substituted substances, oxygen-containing organic compounds, pyridines, quinolines, etc. Various solvents capable of dissolving and removing carbonaceous substances and pinch-like substances deposited on the fine particles are applied. A specific example of a cleaning solution is heat.
Chloroform, carbon tetrachloride, trifle/binary carbon, methyl ethyl ketone, phenol, tetralin, alkylnaphthalene, pyridine, quinone, hydroquinoline, creosote, etc.; Obtained generation? 75 (preferable, especially boiling point 150-60
Preference is given to using hydrocarbon oils at 0°C. These hydrocarbon oils have excellent ability to dissolve pinch-like substances, and even if some of them are supplied to the hydrotreating process together with fine particle catalysts, they will not cause corrosion of the equipment, and will not cause corrosion in the hydrotreating process. Since it does not cause any damage to catalysts and is inexpensive, it can be advantageously applied as a cleaning liquid for fine particle catalysts. Washing of the fine particle catalyst separated from the product oil is advantageously carried out at a high temperature of 20° C. to 450° C., optionally under pressure. In this case, the fine particle catalyst can be washed while adhering to the matrix of the high gradient magnetic separation device.

In the present invention, the fine particles separated from the produced oil are treated as they are or after the washing treatment described above, in the presence of the hydrocarbon oil as described above, under a hydrogen pressure of lo to 250 kg/cm2, at a temperature of 300 to 450. After regeneration by treatment with 'C, it can also be recycled to the hydrotreating step. By this hydrogenation treatment, the hardly soluble carbonaceous substances on the fine particle catalyst are hydrogenated and dissolved and removed. moreover,
The fine particle catalyst separated from the produced oil is sometimes deposited on a high gradient magnetic separator (IJ Lux) [
After the carbonaceous material is oxidized and roasted by heating to 300 to 800°C while supplying L oxygen-containing gas and removed, it can be recycled to the hydrogenation process.

In the present invention, by combining the hydrotreating (first hydrotreating) with the subsequent second hydrotreating for the purpose of demetallization using the above-mentioned fine particle catalyst, it is possible to hydrogenate heavy oil, which is extremely advantageous. oxidation treatment method is achieved. In other words, the oil obtained in the first hydrotreating process has been removed from the metal components that would poison the catalyst, and therefore cannot be subjected to conventionally known hydrotreating processes, such as hydrodesulfurization treatment, or for the purpose of lightening. It is possible to advantageously perform hydrocracking treatment and the like. In this case, as the second hydrotreating catalyst, in addition to a fixed bed catalyst, a moving bed catalyst or an ebullated bed catalyst is applied.

When combining the first hydrogenation treatment and the second hydrogenation treatment, the first
The product obtained from the hydrotreating is then subjected to high gradient magnetic separation under high pressure without substantial gas-liquid separation of hydrogen or light products to remove at least part of the fine particle catalyst from the product. After the fraction has been separated and removed, it can be fed to a second hydrogenation treatment. In this case, the pressure in the high gradient magnetic separation step is substantially equal to the pressure in the second hydrogen treatment step, and a fixed bed catalyst is preferably used as the catalyst in the second hydrogen treatment. According to such a combination treatment method, there is no need to pressurize the feedstock oil and hydrogen supplied to the second hydrotreatment step again, which is advantageous. Of course, after gas-liquid separation of hydrogen and light products from the first hydrogenated product, the produced oil is subjected to a high gradient magnetic separation treatment, and the produced oil from which at least a portion of the fine particle catalyst has been removed is subjected to a second hydrogenation treatment. It can also be supplied to Furthermore, the produced oil from the first hydrotreating step is supplied to the second hydrotreating step without substantially separating the fine particle catalyst, and the produced oil obtained in the second hydrotreating step is It is also possible to separate catalyst particles. Furthermore, after subjecting the produced oil containing the fine particle catalyst obtained in the first or second hydrotreating step to high gradient magnetic separation treatment, it is separated into a light oil component and a heavy oil component, and at least a portion of the heavy oil component is removed. It can also be recycled to the first or second hydrotreating step. In any case,
In the present invention, there are various ways of combining the first hydrogenation process and the second hydrogenation process.
And/or regarding the treatment of the fine particle catalyst separated from the product oil obtained in the second hydrotreating step, a part or all of it may be used as it is or after being washed and/or regenerated, and then subjected to the first hydrotreating step. There are various methods such as recycling, or discarding as the case may be.

The composition and physical properties of the catalyst used in the second hydrogenation treatment are appropriately selected depending on the purpose of the treatment, but generally one selected from group 1b+Ilb+ll1a+Va+■a+■a and group II metals of the periodic table. The above is supported on a porous carrier. Porous carriers include alumina, silica, alumina/silica, zeolite, magnesia, magnesia/silica, magnesia/silica/alumina, alumina/boria, aluminum phosphate, titania, silica/ titania,
Synthetic products such as zirconia, natural products such as kaolin, pumice, montmorillonite, attapulgite, sepiolite, natural zeolite, or mixtures thereof are used.

The second hydrotreatment includes hydrorefining and/or denitrification such as desulfurization and denitrification.
or when applied for the purpose of lightening, especially M
Metal component 5~ containing one or more types selected from O and W
15% by weight and 1 to 10% by weight of a metal component selected from Ni and CaO, supported on porous alumina or alumina-silica, with an average pore diameter of 50 to 150 Specific surface area 150m2. It is advantageous to use a hydrotreating catalyst having a pore volume of Q or more and a pore volume of 0.3 to 1.5 CC/f. On the other hand, if you want to further reduce the soluble metals and asphaltene content remaining in the product oil obtained in the first hydrotreating step, VIMoνW
+ Cu + 1.0% by weight or more of at least one metal component selected from Ni and Co, preferably 5 to 10% by weight, supported on porous magnesia silica, silica, seviolite or sepiolite-containing material, Average pore diameter 100~400mm, preferably 150~3009mm
Human, specific surface area 100m2/r or more, preferably 120~
300m27? and pore volume 0.5~l, 5CC/r
It is advantageous to use catalysts having a CC/r, preferably from 0.7 to 1.2 CC/r.

The second hydrogenation treatment conditions are appropriately selected depending on the purpose of the treatment, but generally the following conditions are adopted: temperature of 350 to 420°C and hydrogen pressure of 30 to 200 KLi/.

Next, preferred embodiments of the present invention will be explained with reference to the drawings. 1 to 7 show examples of flowcharts for carrying out the method of the present invention.

FIG. 1 shows the basic flow chart of the present invention, in which feedstock heavy oil containing soluble metals passes through line 50, fine particle catalyst introduced from line 51 and optionally Spent fine particle catalyst recycled through line 33, recycled hydrogen from line 22 and line 5
Together with the hydrogen from 2, it is fed to the hydrotreating reaction column 1. In the hydrotreating reaction tower 1, soluble vanadium in the feedstock oil is deposited in the form of sulfide on the fine particle catalyst together with other soluble metals. In addition, in this reaction tower 1, a lightening reaction and a desulfurization reaction of heavy oil are performed depending on reaction conditions. The reaction product is sent from the reaction column 1 to the gas-liquid separator 2, and the gaseous material separated here is circulated through the line/22 to the reaction column 1 as circulating hydrogen, while the separated liquid product is The produced oil is sent to the high gradient magnetic separation device 3 through the line 21 and subjected to solid-liquid separation. The produced oil obtained from this separator 3 from which fine particles (spent catalyst) with accumulated metal content have been removed or reduced is extracted from line 31, while the spent catalyst is extracted from line 32, and as needed. Accordingly, at least a portion thereof is recycled through line 33 to reactor l. The spent catalyst to be circulated is washed with an appropriate solvent to dissolve and remove pitch-like substances and carbonaceous substances that adhere to the surface, or hydrogenated to solubilize and desorb, as necessary. Alternatively, it can be oxidized and roasted and then circulated through the line 33. In such a heavy oil demetallization treatment method, the concentration of fine particle catalyst in the heavy oil at the inlet of the reaction tower 1 is 0.
01-10] i% by weight, preferably 0.1-5% by weight, while the vanadium content in the spent catalyst extracted from reactor I is at least 1.0% by weight, in terms of metal;
Usually, it is in the range of 5 to 50% by weight.

The flow 7 shown in FIG. 2 is basically similar to that shown in FIG. 1, but in this FIG. Oil separation device 4
where the light oil is separated through line 41, while a portion of the heavy oil separated from the light oil is circulated through line 43 and the remainder is sent to the high gradient magnetic separator. sent to. In this case, the light separator 4 is
Any device capable of separating heavy and light oils may be used, such as a distillation device or a solvent deasphalter. Further, in FIG. 2, if necessary, an appropriate amount of ferromagnetic fine powder can be added from line 45 to increase the separation efficiency in the high gradient magnetic separation apparatus 3. The light oil from the line 41 and/or the heavy residual oil from the line 31 can be further desulfurized, denitrified, or hydrocracked by known fixed bed hydrotreating, if necessary.

FIG. 3 shows a flow sheet suitable for processing heavy oils containing high amounts of ash (usually 0.2-5% by weight).

Examples of such heavy oils include tar sant bitumen, coal liquefied oil, solvent extracted coal, and the like.

The flow note shown in Figure 3 is suitable for lightening heavy oil with a high ash content.
weight%) and a large amount of soluble vanadium (usually 100~
It is suitable for the hydrorefining of tar sand bitumen containing 700 ppm).

In FIG. 3, a feedstock such as tar sand bitumen from line 50 is fed to hydrotreating reactor 1 along with hydrogen from line 22 and optionally ash recycled from line 33.

In the hydrotreating reaction tower 1, soluble sodium in the feedstock oil is deposited in the form of sulfide on the ash contained in the feedstock oil and acts as a hydrotreating catalyst, achieving lightening of the feedstock oil. The hydrotreated product is sent from the reactor 1 to the gas-liquid separator 2, where it is separated into gas and liquid, and then the liquid product is sent through line 22 to the high gradient magnetic separator 3. Separated into solid and liquid.

The ash separated here, if necessary, a part of it is recycled through line 33 and the remainder is recovered from line 32. The product oil (supernatant liquid) from which the ash content has been separated is sent through line 31 together with hydrogen from line 62 to the fixed bed second hydrotreating reaction tower 5 for hydrotreating.

The catalyst packed in the fixed bed is selected depending on the purpose of the treatment, and when obtaining a product oil with few soluble metals and asphaltenes, a large catalyst such as sepiolite (magne/umsolicate-containing material) supporting hydrogen-rich active metals is used. When a catalyst with a pore size is selected, and the main purpose is desulfurization or denitrification, an alumina or alumina/7-liquid catalyst having an average pore diameter of 50 to 150 particles and carrying a hydrogenation active metal is selected.

The second hydrotreated product is withdrawn through line 51;
Gas and liquid are separated in the gas-liquid separator 6, the gaseous material is circulated through line 61 as circulating hydrogen gas, and the liquid product is recovered through line 61 as hydrotreated oil.

In addition, in FIG. 3, by operating the high gradient magnetic separator 3 at substantially the same pressure as the inlet pressure of the second hydrotreating reaction column 50, the pressure of the product oil extracted through the line 31 increases. It can be sent to the second hydrogenation reaction tower 5 as it is without being subjected to any process.

The flow sheet in Figure 4 is similar to that in Figure 3, but
In FIG. 4, the product from the first hydrotreating reaction tower 1 through which the slurry catalyst flows is not separated into gas and liquid, but is sent to the high gradient magnetic separation device 3 together with hydrogen in a pressurized state. was obtained from this high gradient magnetic separation device 3. The produced oil is sent to the fixed bed second hydrotreating reaction tower 5 through a line 31 while being pressurized together with hydrogen. In the case of such a flow sheet, the hydrogen circulation compressor and raw material supply pump in the deep reaction tower 5 can be substantially omitted.

The flow sheet shown in Figure 5 is similar to Figure 4, but
In FIG. 5, ultrafine particles (usually particle diameters of 50 μm or less, especially 10 μm or less) are used as the fine particle catalyst, and the product from the first hydrotreating reaction column 1 is subjected to solid-liquid separation. instead, it is directly sent to the second hydrotreating reaction tower 5. Incidentally, gradient magnetic separation is performed on the produced oil from the reaction tower 5.

The supernatant liquid from the high gradient magnetic separation device 3 is sent to the light oil separation device 4 by the life 31;
At least a portion of the residual oil separated in can also be recycled to the first hydrotreating reaction tower 1 via line 43, if necessary. By circulating this residual oil, it is possible to increase the yield of light oil and reduce the yield of residual oil.

In the float 7 shown in FIG. 6, a hot separator 8 is disposed between the first hydrogenation reaction tower 1 and the second hydrogenation reaction tower 5, and the first hydrogenation reaction tower tower 1
The product from is subjected to light oil separation at high temperature and pressure in the presence of hydrogen blown through line 52. The separated light oil component passes through the life 81 together with hydrogen and is supplied to the fixed bed hydrotreating apparatus 5. hot separator 6
The heavy oil separated is sent to the high gradient magnetic separator 3 through a line 82 where it is separated into solid and liquid. This separation device 3
The product oil from the i1. After being recycled or recycled as required, it is circulated through line 33 and, if necessary, a portion thereof is recovered through line 32.

Distillate oil is extracted from the gas-liquid separator 2 through a line 22.

In the flow sheet shown in FIG. 7, the residual oil sent from the light oil separator 4 through the line 42 contains ferromagnetic fine powder such as magnetite circulated from the line 73 and new ferromagnetic powder from the line 45. Fine powder is added and the mixture is sent to the high gradient magnetic separator 3. From this high gradient magnetic separator 3, produced oil is withdrawn through line 31, and a mixture of spent catalyst and ferromagnetic fine powder is withdrawn through line 3.
2 and sent to a strong magnetic separator 7. The ferromagnetic fine powder magnetized and separated here is circulated through line 73, while the spent catalyst is extracted from line 71, and if necessary, a part of it is passed through line 72 to the first hydrogen. It is recycled to the chemical treatment reaction tower 1.

Next, the present invention will be explained in more detail with reference to Examples.

Example-1 Powdered Ni+M is a super heavy oil with the following properties.

After hydrocracking using a supported alumina catalyst, the used powdered catalyst was separated from the resulting oil into solid and liquid to obtain a cracked oil with extremely low ash and soluble metals.

Raw material oil sulfur 5.18% vanadium
1130ppm nickel 1
061) pmn-hebutane insoluble content: 11.5% Conradone residual carbon: 15.9% 350°C "Residue content: 86.5% Ni+Mo-supported alumina powder catalyst was obtained roughly as follows. First, aluminum sulfate aqueous solution was mixed with ammonia aqueous solution. The aluminum hydroxide gel was thoroughly washed with warm water.The alumina content of the aluminum hydroxide gel thus obtained was approximately 15%.Next, paramolybdenum was added to the gel. An ammonia aqueous solution containing acid ammonium and nickel sulfate was added and mixed thoroughly, and the mixture was dried at 120°C for 3 hours, and then dried at 50°C for 1 hour.
Baked for an hour. The properties of the obtained catalyst were as follows.

Catalyst properties Metal composition Ni0 2.1% Mob 35.7% Specific surface area (BET method) 420 m2/1 Pore volume (mercury intrusion method) 1.7 cc/f Next, a small amount of light oil was added to this catalyst, and a ball mill was used. The mixture was pulverized for about 24 hours. The particle diameter of the finely ground catalyst is approximately 5-30μ
It was about. The catalyst paste thus obtained was added to the above-mentioned extra-heavy oil so that the catalyst content was 0.5% and subjected to hydrocracking. The hydrogenolysis experiment was conducted using a high-pressure flow reactor under the following reaction conditions.

Reaction conditions: Hydrogen pressure: 140 Kg/cm2 Reaction temperature: 440°C Liquid hourly space velocity: 1.0 h 2
Ribbon-shaped Su, S 4 with a width of 0 to 30μ and a width of about 1.
Solid-liquid separation was performed using a high gradient magnetic separator equipped with a stainless steel tube tightly packed with 30 wool. The conditions for high gradient magnetic separation in this experiment were as follows.

Separation conditions Magnetic field strength 9000 Gauss Liquid linear velocity 5.0 m/Hr Temperature
80° C. In this experiment, the magnetized solid content (spent catalyst) was recovered by sufficiently washing with toluene while magnetized in the matrix, turning off the power to the magnet, and flowing toluene. The spent catalyst suspended in toluene and collected was centrifuged to separate it from the toluene, and mixed with the untreated feedstock again to repeat the hydrocracking.

In the repeated use of the spent catalyst, the oxidized roasting residue (ash content) of the used catalyst was determined in advance, and the catalyst addition rate in terms of ash content to the raw oil was adjusted to approximately 0.5%.

The hydrocracked oil subjected to high gradient magnetic separation was filtered under pressure and washed with toluene to determine the toluene-insoluble solid content.

The filtrate was used as a sample for various analyses.

FIG. 8 shows the relationship between the number of times the powder catalyst is used repeatedly and the amount of toluene-insoluble solids in the hydrocracked oil subjected to high gradient magnetic separation. From this, it can be seen that as the number of times the spent catalyst is repeatedly used increases, the amount of residual solid content (in terms of ash content) in the hydrocracked oil tends to decrease. It can be seen from this that the used fine powder catalyst used in the hydrotreatment of heavy oil containing a large amount of soluble metals can be easily separated into solid and liquid by the high gradient magnetic separation method.

The properties of the cracked oil containing no toluene-insoluble solids obtained in this experiment were almost constant regardless of the number of times the catalyst was used repeatedly, and were as follows. Vanadium in the spent catalyst in the first round was 9.2% and nickel was 1.
．． It was 2%.

Properties of cracked oil Sulfur 2.4-2.8% Vanadium 94-105 ppm Nickel 18-20 ppm N-heptane insolubles 4.5-3.7% Conradson residual carbon 8.9-11.1% 350°C Residue minutes 5
8-53% Comparative Example Using the catalyst used in Example-1, vacuum gas oil containing only 2.8% sulfur and no soluble metals was
After hydrogenation treatment under almost the same reaction conditions as in Example-1,
The spent catalyst was collected by centrifugation. Next, the catalyst thus recovered was uniformly dispersed in the cracked oil containing no solids obtained by filtering the cracked oil of the first catalyst repetition in Example-1, and the solid content concentration ( The ash content (calculated as ash content) was adjusted so that the number of repetitions of the catalyst in Example-1 was approximately the same (0.5%) as that of the first time. The thus obtained cracked oil containing essentially no vanadium and containing only 1.4% nickel as a magnetic metal in which the spent catalyst was dispersed was subjected to high gradient magnetic separation in exactly the same manner as in Example-1. The solid content concentration in the treated oil was approximately 0.3% in terms of ash content, and it was found that the solid content was significantly higher than in Example-1.

From the above results, the high solid content separation efficiency in the high gradient magnetic separation process according to the method of the present invention is due not only to the precipitation of ferromagnetic metal compounds such as nickel on the spent catalyst, but also to the precipitation of a large amount of vanadium. It is assumed that this is due to the Therefore, it will be understood that the method of the present invention is particularly suitable for recovering and separating spent catalyst from oil produced by hydrotreating heavy oil containing a large amount of vanadium or nickel as soluble metals using a fine catalyst.

Examples 2 to 4 In Example 1, in place of the Ni+Mo supported alumina powder catalyst, various fine powder catalysts with different types of supported metals and carriers shown in Table 1 were used to produce almost the same amount of the same feedstock oil. Hydrocracking was carried out under the reaction conditions, and the resulting oil was subjected to high gradient magnetic separation in the same manner as in Example 1 to separate the spent catalyst powder. Table 2 shows the residual solid content (ash content equivalent) in the obtained treated oil and the properties of the produced oil (aQ).

From Table 2, according to the method of the present invention, even when it is well known that the magnetic susceptibility of sulfides such as Cu and MO is extremely small, it is possible to use a catalyst supported on a non-magnetic carrier. It will be understood that when heavy oil is hydrotreated, the spent catalyst can be easily separated and recovered from the treated oil.

Based on the above results, when using various powder catalysts to hydrotreat heavy oil containing many soluble metals, this method can be used to remove these spent catalysts from the produced oil, regardless of the properties and composition of the powder catalyst. It is recognized that these spent catalysts can be separated and recovered and recycled in the hydrotreating process if necessary.

Table 1 Catalyst properties Table 2 Residual solid content in treated oil and properties of produced oil *) Almost no difference was observed due to the difference in catalyst.

Example 5 In removing the solid content (ash) of the hydrocracked oil containing the spent catalyst shown in Example 3 by high gradient magnetic separation, a small amount of The same operation was repeated after adding the ferromagnetic fine powder. Magnetite powder (200 mesh passes) containing about 70% iron is used as ferromagnetic fine powder, and about 0.5% of the produced oil containing spent catalyst is used.
added. When this was subjected to high gradient magnetic separation under the same conditions as in Example 3, the solid content in the treated oil was 0.011 as ash content.
It had decreased to %. From this, in the method of the present invention, heavy oil containing a large amount of soluble metals is hydrocracked using an ultrafine catalyst with an extremely small particle size, and then a small amount of ferromagnetic fine powder is added to the cracked oil to perform Hatake gradient magnetic separation. It will be appreciated that this results in a treated oil that is substantially free of spent catalyst.

Example 6 Tar sant bitumen having the properties shown below was hydrogenated by almost the same method as the process shown in FIG.

However, in this experiment, the produced oil from the noncatalytic hydrotreating reaction tower 1 was subjected to high gradient magnetic separation and then distilled under atmospheric pressure, and only the residue was treated in the fixed bed hydrotreating apparatus 5. Furthermore, due to experimental considerations, the vanadium- and iron-rich solids separated in the high-gradient magnetic separator 3 were not circulated to the reaction column 1.

Properties of raw oil Sulfur 4.43% Vanadium
143ppm nickel
78p9m iron 4
10ppm n-hebutane insoluble content 9.3% Conradson residual carbon 13.0% ash content
0.78% toluene insoluble content (>, /μ)
As the 0.97% 350°C + 80% high gradient magnetic separation device, one that could obtain a higher magnetic field strength than the one shown in Example-1 and had a larger processing capacity was used. Further, the high gradient magnetic separator and the atmospheric distillation apparatus were operated in a batch manner to treat the produced oil from the hydrotreater 1.

The operating conditions of the high gradient magnetic separation device are shown below.

Operating conditions Magnetic field strength: 20 + 000 Gauss Processing oil liquid linear velocity: 4 m/) (r Processing temperature: Room temperature Matrix: Ferritic stainless wool Fixed bed hydrotreating catalyst: A highly active desulfurization catalyst having the following properties: Using.

Catalyst properties Particle size: 0.8% Specific surface area: 213m2/7 Pore volume (mercury intrusion method> 35λ): 0.600CC/7 Average pore diameter: 113 people Main chemical composition: Mob, 14.8% Coo
3.8%NiQ
1.7% Al20379.7% The reaction conditions for noncatalytic hydrogenation and fixed bed hydrogenation are shown below.

Reaction conditions Hydrogen pressure Kq/cm2160 160 Temperature °C430 400 Liquid space velocity 1/Hr 1,0 0
,90 hydrogen/feedstock oil 1/-131+ 000
1 t 000 In this experiment, it was observed that the ash content in the non-catalytic hydrotreated oil subjected to high gradient magnetic separation treatment was reduced to 0.12%. In addition, vanadium is concentrated in the separated solid content, and in the non-catalytic hydrogenation process, the solid content in the raw material essentially acts as a fine catalyst, and the soluble vanadium in the raw material is separated and precipitated on top of it. It was approved to do so. The solid content in the raw materials (〉7/μ) is shown below.
and the composition of the solids separated in the high gradient magnetic separation process.

Solid content composition Solid content in raw material High gradient magnetic separation Solid content V ++Q, 1 (%)
1.3 (%) Ni O8j 0.
2Fe 2.7 3.2Si
14 17AI 10
90 11 1
9 Next, the properties of the product obtained by further filtration of the hydrotreated oil subjected to high gradient magnetic separation are shown below.

Produced oily sulfur 3.0% Vanadium 53 ppm Nickel 46 Iron 321/n-hebutane insoluble matter 4.1% Conradone residual carbon 9.7/1 350°C Residue 671/ The catalyst-hydrogenated oil was distilled at normal pressure, and the residue was subjected to fixed-bed hydrogenation at 350°C. The properties of the treated oil obtained 500 hours after the start of the reaction are shown below. Figure 9 shows the reaction tube inlet. In Fig. 9, curves 1 and 3 show the results obtained by the method of the present invention, and curves 2 and 3 show the results obtained by the method of the present invention. The results obtained by the method disclosed in Publication No. 8290 (using the same raw material and directly desulfurizing it) are shown.

Properties of treated oil Sulfur 0.94% Vanadium
9.2 ppm Nickel 1
3. Iron 4.7 n-hebutane insoluble matter 1.5% Conradson residual carbon 5
．． 4 〃 350℃ Residue content 92// In the case of fixed-bed hydrodesulfurization of tar sand and bitumen without deashing, the ash content in the raw material accumulates at the inlet of the catalyst bed, resulting in rapid blockage. Although this is known (for example, see JP-A No. 56-28290), as can be seen from FIG. 9, in this experiment, no signs of catalyst bed clogging were observed even after 1000 hours of reaction time. Moreover, it can be seen that the decrease in activity is extremely small. This is considered to be because in the method of the present invention, most of the toluene-insoluble solids were removed together with soluble metals in the noncatalytic hydrogenation step and the high gradient magnetic separation step. From the above results, it is clear that the method of the present invention is suitable for hydrotreating heavy oils that contain all soluble substances such as vanadium, nickel, and iron as well as a relatively large amount of solids, which makes ordinary fixed bed hydrotreating virtually impossible. It will be recognized that this method is also extremely suitable.

Example-17 The same super-heavy oil as in Example-1 was hydrotreated using an ultra-fine catalyst having the following properties as a fine-powder catalyst according to the process shown in FIG. However, in this experiment, the produced oil from the fixed bed hydrotreating unit 5 was separated by atmospheric distillation, and the entire amount of the residue was circulated to the slurry catalytic reaction tower 1, thereby converting all the feedstock oil into light fractions with a boiling point of 320°C or lower. Chemically decomposed.

Catalyst properties (metal composition) Mob, 5.9% Coo 1.3% A I2036.2% S'02 86.6% (Physical properties) Specific surface area 110m2/7 Pore volume approximately 6cc/Particle diameter 0.1 ~10μ High gradient magnetic separation of the produced oil from reaction column 1 was carried out using the same apparatus and under the same conditions as in Example-1. Therefore, in the process diagram shown in FIG. 3, the high gradient magnetic separation apparatus was operated in a batch manner. The magnetized and separated spent catalyst was thoroughly washed with quinoline at about 150° C. to dissolve and remove the pitch deposited on the catalyst. Next, the residual quinoline is replaced with a small amount of light oil, and the spent catalyst, which reduces pitch-like carbonaceous matter, is desorbed and recovered in light oil, and this is again separated from the feedstock oil and the produced oil from the hydrotreating unit 5. and fed to reactor 1. A portion of the used slurry catalyst was extracted to the outside of the system so that the ash-based catalyst concentration at the inlet of the reactor 1 was approximately 1.0%. The solid content in the treated oil at the outlet of the high gradient magnetic separation process in steady state was approximately 0.03 to 0.6%.

The treated oil subjected to high gradient magnetic separation was hydrotreated using the same desulfurization catalyst used in Example-6, and then
Separation was carried out by atmospheric distillation, and light components below 320°C were separated as products. The remaining aroma was circulated to the port reactor 1.

The reaction conditions in reactors 1 and 5 approximately 200 hours after the start of the reaction are shown below.

Reaction conditions Reactor 1 Reactor 5 Hydrogen pressure K9/crn2140 140 parts ℃
435 380 Liquid space velocity 1/Hr O,941,52 Slurry-catalyst concentration wt% 1,2 (o, o3.~
0.06) Recycling ratio*) -1,66...,,1
．． -0'*) Total feedstock oil/new feedstock oil The yields of each product obtained in this experiment were as follows.

Product yield H285, 0% 01~C, 5,6% C! r-180℃ fraction 22.3% 180-32
0℃l/67.1%

[Brief explanation of drawings]

1 to 7 show examples of flow sheets for carrying out the method of the present invention. FIG. 1 shows a basic flow note, and each of FIGS. 2 to 7 shows various examples of changes to the basic flow note. FIG. 8 is a graph showing the relationship between the residual solid content in the treated oil and the number of times the catalyst is repeatedly used, and FIG. 9 is a graph showing the change over time in relative pressure difference and vanadium removal rate. l...first hydrogenation reaction tower using a fine particle catalyst,
2... Gas-liquid separation device, 3... High gradient magnetic separation device,
4... Light oil fractionator, 5... Second hydrotreating reaction tower, 6... Gas-liquid separation device, 7... Magnetic separator, 8...
・Hot separator. Patent Applicant Chiyoda Corporation Agent Patent Attorney Toshiaki Ikeura Figure 1 2 Figure 7 22 ■ L ---J Figure 8 1 2 3 4 5
Number of times catalyst is used repeatedly

Claims (9)

[Claims] (1) Raw material heavy oil containing soluble vanadium and other soluble metals is mixed with a volume average particle diameter of 0.1 to 200 μm.
Hydrotreating is performed in the presence of a fine particle catalyst at a temperature of 350 to 500°C and a hydrogen partial pressure of 10 to 350 Kg/cm20 to remove soluble vanadium and other soluble metals contained in the heavy oil. A hydrotreating step of depositing on a particle catalyst, and a high gradient magnetic separation treatment of the hydrotreated product oil containing the fine particle catalyst with deposited metal components obtained from the hydrotreating step as a spent catalyst, 1. A method for hydrodemetallization of heavy oil, comprising a high gradient magnetic separation step for separating fine particle catalysts on which metal components are deposited from hydroprocessed oil. (2) The method according to claim 1, wherein the fine particle catalyst contains a hydrogenation-active metal component. (3) The fine particle catalyst has a volume average particle diameter of 0.1 to 50
A method according to claim 1 or claim 2, having μ. (4) The fine particle catalyst has a volume average particle diameter of 0.5 to 10
A method according to claim 1 or claim 2, having μ. (5) At least a part of the used fine particle catalyst on which metal components are deposited obtained from the high gradient magnetic separation process is reused as at least a part of the fine particle catalyst in the hydrotreating process. Any method of Items 1 to 4. (6) The method according to claim 5, wherein the used fine particle catalyst is washed with a solvent and reused. (7) The method according to claim 6, in which the cleaning treatment with a solvent is carried out at a temperature of 200 to 450°C. (8) The method according to claim 6 or 7, in which a hydrocarbon oil with a boiling point of 150 to 600° C. is used as the solvent. (9) The method according to claim 8, wherein the cleaning treatment is carried out at a temperature of 300 to 450°C under hydrogen pressure. Q□ The method according to any one of claims 6 to 9, wherein the used fine particle catalyst is washed with a solvent while being magnetized in a high gradient magnetic separation device. 01) Used fine particle catalyst is reused by being oxidized and roasted while magnetized by a high gradient magnetic device.
Section method. θ odor In the high gradient magnetic separation process, 1000 to 6
Claim 1 using the magnetic field strength of 0000 glass
The method according to any one of Items 1 to 11. Ql high gradient magnetic separation treatment with a volume average particle diameter of 0.
13. The method according to any one of claims 1 to 12, which is carried out in the presence of ferromagnetic fine powder of 1 to 200 microns. 041. The method of claim 13, wherein the ferromagnetic fine powder is magnetite powder. 09 The method according to claim 13 or 14, wherein the ferromagnetic fine powder is used in a proportion of 0.1 to 10 parts by weight per 1 part by weight of the used fine particle catalyst contained in the produced oil. . (To) The method according to any one of claims 1 to 16, wherein the concentration of the fine particle catalyst contained in the total heavy oil supplied to the hydrotreating step is 0.1 to 10% by weight. . (171 The soluble vanadium contained in the raw material heavy oil is 1
00 ppm or more Claims 1 to 16
Either way. (g) The method according to any one of claims 1 to 17, wherein the raw material heavy oil contains 80% by weight or more of heavy components with a boiling point of 350° C. or higher. 0I The method according to any one of claims 1 to 18, wherein the raw material heavy oil is tar sand bitumen containing an ash content of 0.2% by weight or more, and the ash content is used as a fine particle catalyst. 20. The method according to any one of claims 1 to 19, wherein the vanadium content in the used fine particle catalyst is 1.0% by weight or more. 3I Raw material heavy oil containing soluble vanadium and other soluble metals is treated in the presence of a fine particle catalyst with a volume average particle diameter of 001 to 200μ, at a temperature of 350 to 500°C, and a hydrogen partial pressure of 10 to 350 Kg/cm2. a first hydrotreating step in which soluble vanadium contained in the heavy oil and other soluble metals are deposited on the fine particle catalyst; High-gradient magnetic separation that separates the fine particle catalyst with deposits of metal components from the hydroprocessing product oil by subjecting the hydroprocessed oil containing the spent catalyst, which contains fine particle catalysts with deposits of metal components, as a spent catalyst. The hydrotreated oil obtained from the treatment step and the high gradient magnetic separation treatment step, from which the fine particle catalyst on which metal components are deposited has been substantially removed, is passed through a fixed bed packed with a hydrotreated catalyst. A method for hydrodemetallization of heavy oil, characterized by comprising a second hydrotreating step of further hydrotreating. Q2 The hydrotreated product from the first hydrotreating step is sent to a high gradient magnetic separation treatment step without substantially gas-liquid separation treatment, and the inlet pressure is substantially equal to the inlet pressure in the second hydrotreating step. 21. The method of claim 21, wherein the high gradient magnetic separation process is carried out under pressure. @ In the second hydrotreating step, the hydrotreating catalyst filled in the fixed bed has a hydrogenation active metal component supported on a porous carrier, has an average pore diameter of 100 to 400 A, a specific surface area of 1 oorn7y or more, and Claim 21, which is a hydrotreating catalyst having a pore volume of 0.5 CC/P or more
or the method of paragraph 22. 041. The method of claim 23, wherein the porous carrier is selected from magnesia-silica,/silica, sepiolite or sepiolite-containing materials. (c) In the second hydrotreating step, the hydrotreating catalyst filled in the fixed bed is one in which a hydrogenation active metal is supported on porous alumina or silica/alumina, and has an average pore diameter of 50 to 15 pores. The method according to claim 21 or 22, which is a hydrotreating catalyst having a specific surface area of 15 om2/y or more and a pore volume of o, 3 to t, scc/r. (c) Raw material heavy oil containing soluble vanadium and other soluble metals is heated at a temperature of 350 to 500°C and a hydrogen partial pressure of 10 to 350 Ky/cm2 in the presence of a fine particle catalyst with a volume average particle diameter of 0.1 to 200μ. a first hydrotreating step in which soluble vanadium contained in the heavy oil and other soluble metals are deposited on the fine particle catalyst by hydrotreating under the conditions; and the first hydrotreating step. A second hydrotreating step in which the hydrotreated oil containing the fine particle catalyst with deposited metal components obtained from the process as a spent catalyst is further hydrotreated by flowing it through a fixed bed filled with a hydrotreating catalyst; , the hydrotreated oil containing the fine particle catalyst with accumulated metal components obtained from the second hydrotreating step is subjected to a high gradient magnetic separation treatment to produce the fine particle catalyst with accumulated metal components by hydrotreating. 1. A method for hydrodemetallization of heavy oil, comprising a high gradient magnetic separation treatment step for separation from oil.