JPH025798B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved method for hydrogenating a pitch-like material containing 7% by weight or more of toluene-insoluble matter to reduce the molecular weight of the pitch-like material and solubilizing the toluene-insoluble matter. In recent years, while the demand for oil has increased significantly, the discovery and development of new oil fields has plateaued, resulting in a global energy shortage. In response, research and development regarding new or alternative energy is being actively conducted, and in particular, many processes are being considered for the production of alternative fuels by liquefying coal, which has the largest reserves of fossil energy. In coal liquefaction methods, a multi-stage treatment method is generally adopted, and in the first stage treatment, a primary coal liquefied product is obtained which is a pitch-like substance that is solid at room temperature. This primary coal liquefied product is then subjected to hydrocracking and hydrorefining in the second and subsequent stages of treatment to produce a coal liquefied oil suitable for fuel oil. Primary coal liquefied material contains toluene-insoluble matter and has a high aromatic carbon ratio (fa), making it extremely difficult to hydrotreat. Therefore, various difficulties arise in the conventional hydrotreatment of primary coal liquefaction.
This has significantly hindered the practical application of coal liquefaction processes. For example, primary coal liquefied products are generally hydrotreated in the presence of a catalyst at high temperatures and under pressurized hydrogen in order to reduce the molecular weight and solubilize the toluene-insoluble components contained therein. However, in this case, the most difficult problem to solve is that of the catalyst. Conventionally, this type of catalyst has been made of alumina.
Expensive desulfurization catalysts that support Mo, Co, Ni, etc. are used, but such catalysts not only generate a large amount of coke but also release toluene insolubles and metals contained in the primary coal liquefaction. There is a problem in that the catalytic activity rapidly decreases due to components, coke, etc., and the catalyst must be replaced frequently. Moreover, in the case of the above-mentioned catalyst, the selectivity of hydrocracking for the primary coal liquefied product is poor, and it is difficult to reduce the molecular weight of the primary coal liquefied product and to hydrocracking the toluene-insoluble components contained therein. In addition, hydrogenation to condensed aromatics constituting the primary coal liquefied product and its hydrocracking,
When an aromatic medium oil is used, a problem arises in that the medium oil is also hydrocracked. and,
Such hydrogenation and hydrocracking into aromatic nuclei significantly increases hydrogen consumption and is one of the causes of increased coal liquefaction costs. The present inventors have conducted various studies to solve the above-mentioned problems in the hydrogenation treatment of pitch-like materials containing a large amount of toluene-insoluble materials such as primary liquefied coal, and have surprisingly discovered that alumina, silica, alumina, etc. We have discovered that this objective can be achieved by using a catalyst in which a hydrogenation-active metal component is supported on a non-acidic porous carrier such as magnesium silicate or silica, rather than an acidic porous carrier such as
The present invention has now been completed. That is, according to the present invention, toluene insoluble matter 7
% by weight or more is hydrogenated at elevated temperature and under pressurized hydrogen in the presence of a catalyst in which a hydrogenation-active metal component is supported on a non-acidic porous carrier to remove at least the toluene-insoluble content. A method for hydrotreating pitches is provided, characterized in that a partially solubilized product is obtained. In addition, the pitch-like material as used in the present invention refers to a primary coal liquefied product, for example, a pitch-like material obtained by solvent extraction treatment of coal (deashed coal), a pitch-like material obtained by hydrotreating coal. In addition, it refers to tar pitch, petroleum pitch, pitch-like materials obtained from hydrocracking of petroleum or heat treatment of residual oil, and similar products thereof. Further, the toluene insoluble content has substantially the same meaning as the benzene insoluble content, and was measured according to the method for measuring benzene insoluble content according to JIS standards. The catalyst used in the present invention is formed by supporting a hydrogenation-active metal component on a non-acidic porous carrier. In this case, a non-acidic porous carrier means that when methyl red, which is used as an indicator for measuring the surface acidity of a catalyst carrier, is adsorbed onto the surface of the carrier, the methyl red becomes non-acidic, that is, neutral or basic. This refers to a porous carrier that develops a yellow color. Examples of such non-acidic porous carriers include silica, magnesium silicate,
Examples include calcium silicate, magnesia, calcium oxide, barium oxide, rare earth oxides, alkali silicates, and porous glass. For the purpose of the present invention, it is inappropriate to use acidic substances such as alumina, silica/alumina, etc. However, even if such acidic substances are used, as long as the amount of such acidic substances is such that the carrier does not exhibit substantial acidity. , does not preclude the addition of these substances. As the hydrogenation-active metal component supported on the non-acidic porous carrier, those used in general catalysts for hydrogenation of heavy hydrocarbons are used, and selected from transition metals and tin. At least one kind is used. Among these metals,
In particular, Cu, Zn, Y, lanthanad, Sn, V, Cr,
At least one metal selected from Mo, W, Mn, Fe, Co, and Ni is preferable because it has high hydrogenation activity for the raw material heavy hydrocarbon used in the present invention and can be obtained at low cost. It is something.
Furthermore, various conventionally used methods can be used to support these metals on the carrier. The form of the metal component in the catalyst is oxide,
It may be a sulfide or a mixture thereof.
The catalyst used in the present invention generally has a specific surface area of 10 m ² /g or more, preferably 150 m ² /g or more, and a specific surface area of 0.2
It has a pore volume of cc/g or more, preferably 0.5 cc/g or more, and an average pore diameter of 50 to 500 Å, preferably 100 to 300 Å. A preferred catalyst for use in the present invention is one in which a hydrogenation-active metal component is supported on porous magnesium silicate. Here, porous magnesium silicate refers to porous clay minerals such as sepiolite, palygorskite, and attapulgite, and products modified by chemical or physical processing such as crushing, kneading, or acid extraction, or aluminum hydroxide. This term includes all types of sol, alumina-silica sol, titania sol, and products formed by adding small amounts of additives such as other clay minerals. Amphibole asbestos mineral is a magnesium silicate mineral with an extremely small pore volume as it is, but it can be easily made porous by a known method, and is one of the supports that satisfies the purpose of the present invention. be. The most desirable porous magnesium silicates are sepiolite, palygorskite, and attapulgite, considering the performance of the resulting catalyst or the ease of catalyst preparation. All of these are known as fibrous clay minerals in which silicon bonds have a so-called double-chain structure, and sepiolite is also known to have some of the magnesium or rare earth elements replaced by other metals. is mainly composed of magnesia and silica. Further, palygorskite and attapulgite are also porous clay minerals having a double-chain structure similar to sepiolite, and can be used for the purpose of the present invention. Among these, sepiolite is particularly desirable as it has excellent characteristics as a carrier. That is, (1) the resulting catalyst has a large specific surface area and pore volume, is highly active, and is resistant to deterioration due to the accumulation of metals such as iron and titanium; (2) the magnesium content in sepiolite is A portion of the catalyst is easily converted by other metals, the supported metals are extremely well dispersed, and highly active catalysts can be obtained at low cost. As the metal supported on the porous magnesium silicate catalyst, one or more selected from the group consisting of transition metals and tin is used. Among these metals, Cu, Zn, Y, lanthanide, Sn, V, Cr,
1 selected from Mo, W, Mn, Fe, Co, and Ni
A catalyst supporting more than one species is suitable because it has a high hydrocracking activity for coals and can be obtained at a relatively low cost. The type or combination of these supported metals is appropriately selected depending on the type of magnesium silicate, the raw material pit, the properties, the reaction method, conditions, etc. The amount of metal supported is also determined by many factors and varies over a wide range, but usually a total of 0.1% by weight of metal,
It is preferably arbitrarily selected within the range of 0.5 to 10% by weight. These metals are usually used in the form of nitrates, sulfates, chlorides, metal salts, complex salts or other solvent-soluble compounds. Water is usually used as the solvent from the viewpoint of practicality and safety, but nonaqueous solvents such as methanol, acetone, or liquid ammonia can also be used. As a method for supporting metals, any known method such as dipping, spraying, kneading, etc. can be used. Further, in the case of a shaped catalyst, the metals may be supported at a stage before the shaping process, or may be carried out in parts. The present inventors have discovered that metals supported on magnesium silicate supports such as sepiolite by ion exchange are extremely highly and uniformly dispersed, and even when the supported amount is extremely small, high molecular weight condensed aromatic hydrocarbons can be produced. It has been found that it exhibits high activity in the hydrogenolysis reaction of toluene-insoluble matter. In addition to periodic table b, b, and a and iron group metals, metals that can be supported on a carrier by ion exchange method include
Examples include V, Cr, and Sn. These metals are used in the form of aqueous solutions such as metal mineral salts such as chlorides, sulfates, and nitrates, organic acid salts such as silicates and acetates, or ammine complex salts, but optional salts or acids may be added as necessary. Adjust the pH to 1 to 7 before use. When supporting metals by the ion exchange method, the supported metals are exchanged with magnesium etc. that constitute the carrier,
A metal that is required to be supported is simply attached or adsorbed without being replaced by magnesium or the like in the carrier, and the activity per metal weight is lower than that of the substituted metal. Therefore, it is desirable to recover such attached or adsorbed metals by cleaning or the like and reuse them to effectively replace them. When a metal that can be supported by an ion exchange method and a metal that cannot be supported are supported on the same carrier, it is also possible to support the metals in different supported states through a multi-stage process. For example, after the first metal group is supported by an ion exchange method, the second metal group is supported as a basic or neutral solution such as an ammonia or amine aqueous solution. According to studies conducted by the present inventors, among porous magnesium silicate carriers, sepiolite is the most desirable for supporting metals using the above-mentioned ion exchange method. This is because, in addition to the large specific surface area and pore volume of sepiolite, it is more easily ion-exchanged by active metals than porous magnesium silicate such as palygorskite or attapulgite, and the amount of metal supported by ion exchange is higher. It is assumed that this is due to the fact that there are many
Among the metals supported on sepiolite by ion exchange, Fe, Ni, Co, Cu, Zn, V, Cr, Sn
is particularly suitable since a highly active catalyst can be obtained.
After supporting these metals by ion exchange, Mo, W, etc. may be further supported. The raw material pitch used in the present invention has an aromatic carbon ratio (fa) of 0.5 or more, especially in the range of 0.6 to 0.8, and contains 60% by weight or more of components having a boiling point of 450°C or more, especially 70% by weight or more. ~100% by weight, and the toluene insoluble content is 7% by weight or more, especially 20 to 70% by weight.
It has a softening point of 50-400℃ containing % by weight. Such pitch-like materials include various coal-based and/or petroleum-based pitch-like materials as described above. Depending on the type, pitches may contain moisture and ash, but these impurity components make solid-liquid separation of the product difficult after hydrogenation of pitches. It is best to remove it from the pitch-like material by drying or removing ash in advance. In the present invention, the above-mentioned pitch-like material is hydrogenated to lower its molecular weight and to solubilize at least a portion (substantial amount) of the toluene-insoluble matter contained therein. Pitches are generally supplied to the hydrotreating process by being dispersed in a medium oil consisting of an aromatic hydrocarbon oil that is substantially soluble in toluene in order to improve its handling and reactivity. . That is, a pitch-like material is finely pulverized to a viscosity of 100 mesh passes or less or a particle size of 150 μ or less, and dispersed in a medium oil to form a slurry.
This is supplied to the hydrogenation process. As a medium oil, it is substantially soluble in toluene and has a boiling point of 200~
Aromatic hydrocarbon oils having a temperature of 550°C and an aromatic carbon ratio (fa) of 0.5 or more are used, such as coal liquefied oil, cracked oil, petroleum residue oil, coal tar, anthracene oil, alkylnaphthalene, and tetralin. Examples include. The mixing ratio of pitches and medium oil can be arbitrarily determined depending on the fluidity of the mixture and the desired hydrolysis rate of pitches, but usually, the weight of pitches per weight on an anhydrous and ash-free basis The ratio is 0.1 to 3 parts by weight. Hydrotreating conditions in the present invention vary depending on the properties of the condensed aromatic hydrocarbon and the desired properties of the produced oil, but generally the hydrogen pressure is 30 to 350 kg/
^cm2 , preferably 100~200Kg/ ^cm2 , processing temperature 350~
500°C, preferably 380-450°C. The feedstock space velocity (LHSV) is between 0.1 and 2.0 Hr ^-1 .
As the reaction method, fixed bed, fluidized bed, moving bed, moving bed, etc. are arbitrarily adopted. According to the present invention, the pitch-like material is reduced in molecular weight, and the toluene-insoluble matter contained therein is solubilized and significantly reduced. Furthermore, according to the present invention, quinoline-insoluble components in the pitch-like material can also be reduced. The products obtained according to the present invention can vary widely depending on the type of raw material pitch and the hydrogenation conditions, for example:
In addition to liquid oil suitable as fuel oil or fuel oil raw material,
It is also possible to obtain a pitch-like material suitable as a carbon material by mild hydrogenation treatment. According to the present invention, as described above, it is possible to hydrogenolyze a pitch-like material while suppressing hydrogenation to aromatics, thereby simultaneously achieving lower molecular weight and hydrogenolysis of toluene-insoluble components. Therefore, unlike the conventional method, the product according to the present invention has a lower increase rate in its hydrogen/carbon ratio (H/C) and a lower aromatic carbon ratio (fa) than in the conventional method. It does not decrease significantly as in the case, but rather shows a tendency to increase at the same level as that of the raw material pitch. For example, from a pitch having an aromatic carbon ratio (fa) of 0.6 to 0.8, it is possible to obtain a hydrotreated product with an aromatic carbon ratio (fa) in the range of 0.7 to 0.9. The products according to the invention can be optionally processed according to conventionally known methods. for example,
After solid-liquid separation of the product, the produced oil is further refined by hydrotreating, the light fraction is separated, and the heavy fraction is recycled to the previous hydrotreating step, the produced oil is hydrorefined. After that, there is a method in which the medium oil is separated and the medium oil is recycled to the first stage hydrotreating step, or a method in which the medium oil is separated from the produced oil and recycled for reuse. The catalyst used in the present invention is different from the conventional acidic porous carrier supporting a hydrogenation-active metal component, as it uses a non-acidic porous carrier supporting a metal component. Although it has various advantages, the effects of the catalyst will be described in more detail below. Although the reason why the above-mentioned unique effect is obtained by using a non-acidic carrier in the present invention has not yet been clearly elucidated, the pitch-like material is extremely rich in aromatic properties and has a basic effect. In order to achieve this, in the case of acidic catalysts, catalyst contamination components such as highly aromatic toluene-insoluble components are adsorbed onto the catalyst and easily polycondensed with the solid acid, resulting in a decrease in catalyst activity. However, in the case of non-acidic carriers,
This is thought to be due to the fact that such inconveniences are significantly suppressed. (1) The catalyst of the present invention has remarkable selectivity for hydrogenolyzing only the condensed aromatic hydrocarbons constituting pitch-like substances into lower molecular weight products while suppressing the hydrogenolysis of the aromatic nucleus itself. It is excellent. Therefore, when hydrotreating pits using the catalyst of the present invention, hydrocracking of the medium oil is avoided and hydrogen consumption is significantly reduced. When using conventional alumina or silica/alumina catalysts, in addition to hydrogenolysis of pitch-like materials,
Since a large amount of hydrogenation and hydrogenolysis to aromatic nuclei occurs, and further hydrogenation of the medium oil occurs, the amount of hydrogen consumed becomes enormous. (2) According to the catalyst of the present invention, it is possible to rapidly and selectively react heavy components of asphaltenes or higher (quinoline insoluble components, toluene insoluble components, n-peptane insoluble components), so that the heavy components can be reacted quickly and selectively. It is possible to obtain a pitch-like material suitable as a selectively hydrocracked carbon material raw material. Conventional catalysts, such as Co--Mo--Al ₂ O ₃ , do not have such selectivity and therefore cannot provide products suitable as carbon material raw materials. (3) The catalyst of the present invention has the advantage that the amount of coke generated is small and troubles such as clogging of the catalyst layer are less likely to occur. According to experiments conducted by the present inventors, in the case of conventional alumina or alumina-silica catalysts suitable for hydrotreating petroleum-based hydrocarbons, when hydrotreating pit-like materials, the formation of pits is significant and the reaction It was observed that the vessel was easily contaminated by coke and that the catalyst activity decreased in a short period of time. Therefore, for example, in the case of a fixed bed catalyst bed, the catalyst bed becomes clogged due to the accumulation of coke, making it impossible to continue operation. (4) The catalyst of the present invention has an excellent ability to hydrogenate quinoline-insoluble components in pitch-like materials, and maintains hydrogenation activity for a long period of time. Using ordinary alumina or silica/alumina as a carrier, Pt,
Conventional expensive hydrotreating catalysts supporting metal components such as Pd, Mo, Co, and Ni have poor ability to hydrogenate quinoline-insoluble components, and as a result, catalyst pores are blocked by quinoline-insoluble components. , the hydrogenation activity decreased significantly. Therefore, the cost of replacing the catalyst increases and is not economical. Next, as a preferred embodiment of the present invention, an example in which the present invention is applied to the hydrogenation treatment of primary liquefied coal will be described in detail with reference to the drawings. In the drawing, coal powder is introduced from line 1 into a mixing tank 21, where it is mixed with medium oil circulated from line 7. here,
The thoroughly mixed and prepared coal slurry is supplied to the hydrogenation pyrolysis tower 22 via line 2. Here, the hydrogen production device 26 is passed through the line 12.
Hydrogen is simultaneously supplied from The raw coal slurry pyrolyzed in the hydrogenation pyrolysis tower 22 is sent to the solid-liquid separation step 23 via the line 3. As this solid-liquid separation, for example, sedimentation separation is used, but it is not limited thereto. The solid content separated here passes through line 11 to hydrogen production step 2.
6. On the other hand, the liquid is supplied through line 4 to the catalytic reaction column 22 according to the present invention. Here, hydrogen is supplied through line 13 from the lower part of the reaction tower, and a hydrogenation reaction is carried out. Of the products, gas is taken out of the system through line 6, or generated hydrocarbon oil is taken out through line 5,
It is sent to a distillation column 25 and divided into fractions based on differences in boiling point. The medium oil is supplied to the mixing tank via line 7 and is used for preparing raw material slurry.
Naphtha and heavy oil are taken out through lines 8 and 9, respectively, and are used for various purposes. From the hydrogen production device 26, ash is transferred to the line 14.
taken from. Next, the present invention will be explained in more detail with reference to Examples. Note that the percentages and ppm shown below are based on weight unless otherwise specified. Example 1 The aromatic carbon ratio, whose properties are shown in Table 1 below, is 0.75.
The solvent-extracted coal was hydrogenolyzed using a catalyst whose properties are shown in Table 2. The catalyst was prepared using sepiolite as a raw material by the method disclosed in JP-A-52-95598 and JP-A-52-113901. The particle size used was 1/16 inch. This sepiolite calcined at 500°C is colored yellow when an ethanol solution of methyl red is adsorbed. (PKa=
4.8)

【table】

[Table] The raw material slurry was prepared by pulverizing solvent-extracted charcoal and then mixing it with α-methylnaphthalene as a medium oil.The weight ratio of α-methylnaphthalene and solvent-extracted charcoal was 87.5:12.5. It was hot. This raw material slurry was passed through a 200 mesh sieve and used. A flow reactor was used for the reaction. The reaction conditions are shown in Table 3. The reaction temperature was increased approximately every 120 hours.

[Table] Next, Table 4 shows the yield and properties of the produced oil (residual oil). Furthermore, from the ¹³ C-NMR spectrum of the produced oil, it was confirmed that the aromatic carbon ratio (fa) of this product was large (approximately 0.66 to 0.68). Also,
As a result of examining gas chromatography after the liquefaction reaction of α-methylnaphthalene used as a medium oil, it was found that no hydrogenation had occurred in this α-methylnaphthalene. FIG. 2 shows temperature changes in the reaction conversion rate (% by weight) of preasphaltene (quinoline soluble, toluene insoluble) and asphaltene contained in the raw material. Curve 1 shows the results for preasphaltenes and curve 2 for asphaltenes.

[Table] Table 5 shows the ratio QI/Ash of quinoline insoluble content (QI) and ash content (Ash) contained in the produced oil (residual oil) in relation to the reaction temperature. Since the QI/Ash ratio decreases with the reaction temperature, it is recognized that the quinoline-insoluble hydrocarbon content does not simply adhere to the catalyst layer and decrease, but that at least a portion of it is solubilized and decreases. .

[Table] Table 4 shows that in this experiment, part of the ash and quinoline insoluble components were precipitated and separated in the catalyst layer, but this was because the liquid linear velocity in the catalyst layer was small in this experiment. This is presumably due to the fact that the sedimentation rate (or particle size) of ash and quinoline-insoluble matter was large. Therefore, when a reactor with a sufficiently large catalyst layer height is used, it is considered that solid content such as ash in the raw material is contained in the product as it is. Table 6 shows the physical properties of the catalyst after the hydrogenation treatment and the analysis of carbon and hydrogen deposited on the catalyst (weight % of carbon and hydrogen based on the weight of the catalyst). From the results in Table 6, it can be seen that there is little change in the catalyst properties even after 450 hours of reaction.

[Table] Example 2 Under the same reaction conditions as Example 1, hydrogen pressure was increased to 104
Kg/cm ² , the liquefaction reaction was carried out in the same manner at a reaction temperature of 399°C. Table 7 shows the conversion rate of each fraction. In this case, the toluene insoluble content in the produced oil was 15.0% by weight.

[Table] Example 3 A liquefaction reaction was carried out under the same reaction conditions as in Example 1, with an LHSV of 0.2 and a reaction temperature of 399°C. Table 8 shows the conversion rate of each fraction. In this case, the toluene insoluble content in the produced oil was 4.4% by weight.

[Table] Examples 4 and 5 After heating coal powder and vacuum residual oil at 400-420°C, the ash content was separated by sedimentation, resulting in coal pitch having the following properties, with a boiling point of 150-250°C. Added creosote oil at a weight ratio of 1:1,
Hydrogenation treatment was carried out using a Mo, Ni supported silica catalyst and a W, Ni supported basic magnesia silica catalyst.

[Table] Mo, Ni-supported silica catalyst was made by extruding commercially available silica fine powder by adding water and calcining it at 400℃ for 2 hours. It was obtained by immersing it in an ammoniacal mixed aqueous solution and then baking it at 500°C for 1 hour. The W,Ni-supported basic magnesia silica catalyst is prepared by mixing basic magnesia fine powder and hydrophobic fine silica powder at a weight ratio of 20:80, adding isopropanol to the mixture, thoroughly kneading it, extruding it, and heating it to 400°C. The mixture was baked for 2 hours. Next, this was impregnated with an aqueous solution of nickel nitrate according to a conventional method, and then fired at 500°C for 1 hour, and then impregnated with an aqueous solution of ammonium paratungstate.
It was obtained by firing at ℃ for 1 hour. The main properties of each catalyst are shown below.

[Table] Hydrogenation of pitts was carried out using a flow reactor as in Example 1 under the reaction conditions of hydrogen pressure 140 Kg/cm ² , reaction temperature 400°C, and liquid hourly space velocity 0.5 Hr ^-1 . When the produced oil was analyzed 10 to 20 hours after the start of the reaction, the following results were obtained. These results show that catalysts in which metals are supported on porous silica, which is a non-acidic carrier, and porous magnesia silica, which exhibits strong basicity, show high activity in hydrogen decomposition of toluene-insoluble substances with a high proportion of aromatic carbon. It will be understood that this compound exhibits high activity in removing soluble metals derived from the manufacturing process of pitches.

[Table] Comparative Example In Example 1, Table 1 was used instead of the catalyst of the present invention.
Example 1 Using the commercially available desulfurization catalyst whose properties are shown in
The experiment was carried out in almost the same way. As a result, high activity was shown in the initial stage, but after 450 hours, which was the same as in Example 1, the conversion rate of pre-asphaltene was 70%, and the conversion rate of asphaltene was also low.
A significant decrease in activity of 70% was observed. Table 13 shows the product yield and properties of each produced oil obtained in this experiment. The test results show that the hydrogenation activity of the commercial catalyst decreases as the temperature increases.

【table】

【table】

[Table] Furthermore, as a result of examining the ¹³ C-NMR spectrum of the produced oil, it was confirmed that the proportion of aromatic carbon was relatively reduced (approximately 0.55 to 0.60). Also,
As a result of examining the gas chromatogram of the medium oil (α-methylnaphthalene) after the liquefaction reaction, it was confirmed that the hydrogenation reaction of α-methylnaphthalene had progressed considerably. Table 14 shows the QI/Ash ratio in the produced oil. The QI/Ash ratio remains constant despite the rise in temperature, indicating that hydrogenation of QI does not occur.

[Table] Table 15 shows the physical properties of the catalyst after the liquefaction reaction and the results of carbon and hydrogen analysis (% relative to the catalyst) of the deposits on the catalyst.

Table: Compared to the catalyst of the present invention, the commercially available catalyst exhibited significant changes in physical properties after 450 hours of reaction. In addition, the catalyst also retains a large amount of carbonaceous matter, resulting in ash and QI
This, together with the accumulation of water, is a cause of a decrease in hydrogenation activity.

[Brief explanation of drawings]

FIG. 1 shows a flow diagram for an example of an embodiment of the present invention, and FIG. 2 is a graph showing temperature changes in reaction conversion rates of preasphaltene and asphaltene contained in raw materials. 21... Mixing tank, 22... Hydrogenation pyrolysis column, 23... Solid-liquid separation step, 24... Catalytic reaction column, 25... Distillation column,
26...Hydrogen production device.

Claims (1)

[Claims] 1. A pitch-like material containing 7% by weight or more of toluene-insoluble matter is dispersed in a medium oil consisting of an aromatic hydrocarbon oil that is substantially soluble in toluene, and hydrogen is applied to a non-acidic porous carrier. In the presence of a catalyst supporting active metal components, temperature 350-500℃, hydrogen pressure 30-350Kg/cm ²
1. A method for hydrogenating a pitch-like material, the method comprising hydrogenating a pitch-like material under the following conditions to obtain a product in which at least a portion of the toluene-insoluble matter is solubilized. 2. The method according to claim 1, wherein the pitch-like material has a softening point of 50 to 400°C. 3 More than 60% of the pitch-like material has a boiling point of 450℃
Consisting of the above components, and aromatic carbon ratio (fa)
Claim 1 or 2 in which is 0.5 or more
Section method. 4. The method according to any one of claims 1 to 3, wherein the pitch-like material is derived from coal and/or petroleum. 5. The pitch-like material is a pitch-like material obtained by solvent extraction of coal and/or a pitch-like material obtained by hydrotreating coal.
Any method in Section 3. 6 The catalyst has a specific surface area of 10 m ² /g or more and a pore volume of 0.2
cc/g or more and an average pore diameter of 50 to 500 Å. 7. The method according to any one of claims 1 to 6, wherein the non-acidic porous carrier is magnesia silicate. 8. The method of claim 7, wherein the magnesia silicate is sepiolite. 9. The method according to any one of claims 1 to 8, wherein the medium oil is at least one selected from coal liquefied oil, coal tar, anthracene oil, creosote oil, petroleum cracked oil, and alkylnaphthalene. .