JPS617385A - Hydrogenation treatment of coal tar pitch - Google Patents

Abstract

PURPOSE:A coal tar pitch containing a fraction insoluble in toluene is hydrogenated to a light extent in the presence of a catalyst under specific conditions to give a carbon material which is suitable used for needle coke and carbon fiber of high quality. CONSTITUTION:A coal tar pitch containing a fraction insoluble in toluene is hydrogenated in the presence of a catalyst, which is prepared by supporting a metal in group VIB and or VIII or its oxide or sulfide on a carrier of a inorganic refractory, at 250-400 deg.C, preferably 280-350 deg.C and 30-250kg/cm<2>, LHSV 0.1- 10hr<-1> at a hydrogen to liquid ratio of 500-2,000Nl/l to effect a light extent of hydrogenation. EFFECT:Advantageous production of carbon materials of reduced contents of heteroatoms such as N, S, O, Na or Fe.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for hydrogenating -:l-rutarbidge. More specifically, the present invention relates to a method for hydrotreating coal tar pitch to produce lightly hydrogenated coal tar big, which is useful as a carbon material raw material, from coal tar pitch containing a large amount of turquoise insoluble matter. be. More specifically, the nucleus is partially hydrogenated to have a saw structure while retaining the polycyclic condensed structure, and the content of heteroatoms such as nitrogen, sulfur, oxygen, sulfur, iron, etc. is low. In particular, the present invention relates to a method for industrially producing a carbon material raw material having properties suitable for use in high-grade needle coke and carbon fiber.

It is known that by hydrogenating Rutar pitch, L]-Lucour pitch, which is excellent as a raw material for carbon materials such as pitch coke, especially needle coke, and charcoal EH11 navy blue, can be obtained. This hydrogenation is mild.

For example, Japanese Unexamined Patent Publication No. 936/725 'r' discloses that pitch is slightly hydrogenated with tetrahydroquinoline or the like in order to produce carbon fibers. Also, Japanese Patent Publication No. 4.9-11, 602f] describes a method for producing knee 1-lux 1-x using coal tar pitch, in which the pitch is hydrogenated and furthermore, by being subjected to a mild hydrogenation treatment. It has been reported that coal tar pitch can be obtained by obtaining needle coke of excellent quality3.Strh et al. J, the same as (
1.) Nitrogen.

J is thought to modify the pitch by removing and covering heteroatoms such as sulfur and oxygen.

[Problems to be Solved by the Invention] - When hydrogenating rutarbidge, the first prerequisite is that the product be of high quality, but even more so in the case of industrial production, which requires continuous hydrogenation over a long period of time. The key is to obtain 1q of products of a certain quality.

In the treatment of straight-run petroleum-based heavy oil, mild hydrogenation treatment as in the present invention will not cause any problems in long-term continuous production. This is because in the case of straight-run petroleum-based heavy oil, vanadium and nickel are the main causes of deterioration of the catalyst, and mild hydrogenation treatment does not significantly deteriorate the catalyst, resulting in a product of constant quality for a long time. This is because it is possible to obtain

However, the coal tar pitch targeted by the present invention has properties that are similar to those of straight-run petroleum-based heavy oil. In other words, unlike petroleum-based heavy oil, coal tar pitch contains almost no vanadium and nickel, and these do not cause deterioration of the catalyst, but direct-run petroleum-based heavy oil contains almost no vanadium or nickel. It contains a large amount of toluene insoluble matter (hereinafter referred to as TI),
Carbon deposition on the catalyst or in the gaps between the catalysts caused by TI is significant, and the catalyst deteriorates in an extremely short period of time, making long-term continuous catalytic hydrogenation treatment difficult to carry out.

In order to prevent catalyst deterioration, the catalyst life can be extended by removing TI in advance, but as will be described later, TI has a basic stage of l-, polycyclic condensed structure, and is partially hydrogenated. After treatment, carbon material raw materials that can be converted into high-grade properties are removed, so the original purpose of producing high-grade carbon material raw materials cannot be achieved.

For this reason, there are major obstacles when hydrogenating Rutar Pi 1 in the presence of a catalyst continuously for a long period of time. 1980-18 /I 21 Q, JP 1982-196
Therefore, we had no choice but to resort to a method of hydrogenating tetrahydroquinoline using an expensive hydrogen-donating solvent without using a catalyst, as disclosed in No. 292. Not only does the use of donor solvents incur high processing costs, but their hydrogenation effect on pitch is weaker than that of catalysts, so there is a strong tendency for heteroatom removal and hydrogenation reform to be insufficient. .

Further, in Japanese Patent Publication No. 49-11602, the only example is an autoclave, and no description is disclosed regarding the life of the catalyst, which becomes a problem when TI-type production is performed.

Therefore, it is necessary to have a high-performance catalyst that maintains high catalytic activity without causing carbon deposition even for pitch containing a large amount of TI, and to prevent the catalyst from degrading. It is extremely important to research and develop a method for hydrotreating pitch under certain treatment conditions, and the inventors of the present invention have focused on this point, made extensive efforts, and finally solved this problem.

Means for Solving the Problems The present inventors have developed an optimal method for lightly hydrogenating coal tar pitch containing a large amount of TI in the presence of a suitable high-performance catalyst and in which the catalyst does not paternate. The Sung Dynasty conducted extensive research on how to treat coal tar bits under hydrogenation conditions, and solved the wood problem using the following method, completing the Ming Dynasty. That is, the present invention
Coal tar pitch containing components 1-1 of Group VIB and ■hl of the periodic table on a refractory inorganic oxide carrier.
- JI consisting of metals, oxides and sulfides of elements belonging to
In the presence of a hydrotreating catalyst supporting at least one type of 3U LJ from Y, the reaction temperature was 250-400°C, the hydrogen pressure was 30-250++/cm2G,
I-,1-Is Vo.

1-10h+Hydrogen to liquid ratio 500-200 ON 1
This method is characterized by mild hydrogenation treatment under conditions of /l. Furthermore, as a method for carrying out mild hydrogenation of -1-lutalbitch for industrial purposes, the above-mentioned method in which the hydrogenation temperature is set at 280-3 B O"C'-Cti and the operation start temperature is set at 280 -350 ``C'' I have provided the above-mentioned method to solve the problem.

Coal tar pitch, which is the object of the present invention, is the residue obtained by carbonizing or liquefying coal.
In particular, in order to use it as a carbon material raw material, toluene insoluble matter (
It refers to a substantially condensed polymeric hydrocarbon substance that is insoluble in toluene as a solvent. ), at least 3% or more, preferably 8% or more]-, and refers to those containing about 60% of -. Specifically, there are soft pitch with a softening point of 70°C or lower, medium pitch with a softening point of about 70° to 85°C, and hard big with a softening point of 85°C or higher.

A soft pitch at about ~70°C is preferred. Such pitch can be obtained by controlling the distillation point of oil during distillation of coal tar, or by adding heavy oil back to pitch having a high softening point.

In general, the quinoline-insoluble content (hereinafter +Q
1 to 5 wt%, toluene insoluble content 5 to 60 wt.
%, 0.2 to 1% by weight, 1 to 2% by weight of nitrogen, and a hydrogen to carbon atomic ratio of 0.5 to 0.7.

In the present invention, coal tar pitch is subjected to mild hydrogenation treatment in the presence of a hydrogenation catalyst, but the hydrogenation treatment may be performed in the coexistence of a hydrogenation solvent, but the hydrogenation catalyst has sufficient hydrogenation effect. It is not suitable for the coexistence of hydrogenated solvents, as there is a small amount of base precipitation.

Here, mild hydrogenation treatment means that the hydrogenation rate defined as the difference in the atomic ratio of hydrogen to carbon of 41 raw materials ≧ 1 pitch and the hydrogenation process is 0.05・-0. , 35.

The catalyst used in the present invention is at least selected from the group consisting of metals, oxides and sulfides of elements in Group VIB and Group I of the Periodic Table on a refractory non-generic oxide support. This is a hydrogenation catalyst that supports one type of hydrogenation catalyst. Examples of refractory inorganic oxides include, but are not limited to, alumina, silica, poly), phosphor, zirconia,
Chromino 7, Ngnesia, Titania, etc. are fine, and this can be used in combination 1:〕I! 7. Nijirikar alumina, aluminaboria, aluminospheres, silical magnesia, etc. may be used.1. The more desirable oxide is one mainly composed of alumino or silica.
More preferably, alumina subjected to -tJR separation is used (3, supporting metals include molybdenum-nickel, molybdenum-]pal) ~, molybdenum-nickel = 1 pal 1 It is preferable that the total amount of supported metals is 15 to 35w based on the oxide.
t%, and it is preferable that the supported amount ω is increased compared to the case where it is used for the oil system. The catalyst is preferably sulfurized in advance according to a known method before being subjected to the reaction, and the metal on the catalyst is preferably used in the form of sulfide. Also, the catalyst
! l, the average molecular weight of coal tar pitch is 20
Considering that the average pore diameter is about 0 to 400, the average pore diameter is 50.
~250 people, surface area of 50 to 300 m2/g, and pore volume of 0.2 to 1°0CG/Q are most effective.

The catalyst used in the present invention described above can be used for hydrogenation of pitch containing TI, which easily deposits carbon on the catalyst, with little deterioration of the catalyst and stable pitch hydrogenation over a long period of time. It has extremely excellent performance that makes it possible to perform the following tasks.

Next, the hydrogenation catalyst f1 has a reaction thirst of 250 to 400°C, preferably 280 to 380°C, and a reaction H power of 330 to 250k.
O/cm2 -Q, preferably! i n −□ 200
ko/cm2-G, LH8V0. 1
−1(1, l+r−1.

Preferably 0.2 to 2 hr-1, hydrogen vs. H! i ratio is 50
0~200011! /fi, preferably BOO...1
It is appropriate to carry out the hydrogenation at 50 ONλ/l, and the hydrogenation treatment conditions are selected so that the hydrogenation rate is 0.05 to 0.35 k2 within the range shown in Section 42. 400 here
48 degrees Celsius and below, 48 thermal decomposition reactions occur due to the reaction at high temperatures rather than the intended hydrogenation of the light product, and the cracking increases rapidly when the temperature exceeds 400℃. So I don't like it. Carbon deposition on the catalyst also tends to accelerate as the temperature exceeds 400°C, and there is a strong possibility that the catalyst layer will become clogged with coking. Therefore, prevention of catalyst deterioration”1
Therefore, the reaction temperature must be set to exceed 400°C from the viewpoint of operational safety. Also, the reaction temperature was set to 25
If the temperature is below 0°C, the specified hydrogenation treatment cannot be carried out.

Even better in setting the initial reaction temperature: L/<L
Selecting t from 280 to 380°C is effective in preventing catalyst deterioration. That is, at temperatures below 380° C., carbon deposition on the catalyst is extremely slow, and catalyst deterioration is suppressed to a minimum, so that stable operation for a long period of time can be achieved.

By the way, in hydrogenation treatment using a normal fixed bed, LHSV cannot be changed due to production volume, so the deterioration of catalyst activity is compensated for by increasing the reaction temperature and the hydrogenation treatment is carried out at a constant rate for a long time. A comprehensive method is adopted.

However, unless continuous operation is carried out for at least 2,000 hours, there will be a major industrial disadvantage. This is because it requires a great deal of effort and expense to stop a V2 unit that is running smoothly, remove the catalyst, fill it, and start it up again, so the operating method of the equipment is determined to minimize the number of times this occurs. . Even if the highly active and long-life catalyst developed by the present inventors is used, coal tar pitch containing a large amount of TI has a very strong tendency to lose its catalytic activity due to carbon precipitation. Stable operation for this long period of time is not easy.

Therefore, the present inventors performed the above-mentioned reaction tli2 +! u 2
Considering that catalyst deterioration is extremely small if treated at 80...380°C, the operating humidity is set at 280...350°C, preferably 300-320°C, for long-term stable continuous operation for 2000 hours or more. We have now completed a method to achieve this. According to this operation method 11, carbon 4Ii is released into the catalyst at temperatures below 380°C, so it is possible to carry out the 1-ζ water treatment mainly in the region where catalyst deterioration is slow, so it is industrially possible to It is published by Tj.

Hydrogenation treatment can be fixed bed, suspended bed, S++ body fI'
It can also be done using h, but it is easier to operate.
It is industrially most advantageous to use bamboo and C fixed beds in terms of reliability, equipment construction costs, and operating costs.

Coal tar pitch contains Ql (primary Qr) of 1 to 5%, if' ff1%, and as is already known, this is used when making needle coke 'FJ' or carbon fiber etc. This must be removed before or after the hydrogenation process, as it becomes an obstacle during the production of hydrogen. However, the primary Ql in coal tar pitch is mostly solubilized by U even by hydrogenation treatment.
Also, since it has almost no effect of deteriorating the catalyst, even if pitch containing primary QI is hydrogenated, the primary Ql
Hydrogenated bitchma1
~ There is no difference in the properties of the lix, but if you try to hydrotreat bidge using an industrially advantageous fixed bed, the space between the catalyst layers will be blocked by the primary QT, so when using a fixed bed, It is necessary to remove Qr as a pretreatment, and without this pretreatment, GJ operation is impossible due to blockage of the fixed bed. However, in the pretreatment, up to polycyclic condensation m such as TI or I-11 (hexine insoluble matter) is removed, and preferable carbon 1, 1 carbon atoms are removed by partial nuclear hydrogenation.
In order to produce high-grade carbon materials, it is necessary to keep the residual rate of TI at 80% or more, while IJ does not remove as much of the material as possible.

As for the above-mentioned pretreatment method, mechanical methods such as filtration and centrifugation can be used, but for example,
-30150 and ↑! 1-ma Akimi 53-66901'3
As exemplified in , hexane, A-ctane, anti-oil, aliphatic solvents such as naphtha, butanols, and aromatic solvents such as benzene, toluene, methylnaphthalene, 71-nols, etc. Add any mixed solvent to the solvent mixture and precipitate QI into the mixed solvent along with unnecessary components.
The method of separating and removing 0υ is effective, and the most advantageous is the method of separating and removing 0υ.

The light fraction at 270 °C is produced as a by-product during the hydrogenation process of the present invention, and is rich in 2- to 3-ring aromatic groups and Z aromatic-alicyclic groups, and is suitable for the production of carbon resin. The most suitable raw material is 1! V is received. .

EXAMPLES Hereinafter, the present invention will be further explained in detail based on examples.

Example 1 Coal tar soft pitch (softening point 3 E"l 'C: )
Part 3 1. : T, aromatic light oil (boiling point 190~ζ3
00'C) were mixed at 80°C and the precipitated supernatant liquid was distilled to obtain soft pitch (hereinafter simply referred to as pitch) with a softening point of 33.5°C. Although most of Qr was removed by this solvent treatment, there was no significant difference in other properties of A. The survival rate of TI after t5 was 84.3%. Table 1 shows the properties of the pitch after solvent treatment.

Using this pitch, when performing a mild aqueous treatment in the presence of catalyst A shown in Table 2 using a fixed bed isothermal continuous hydrotreater, the reaction pressure was increased to 180 +J/Cm2G,
L-H8V0.4hr-1, hydrogen to liquid ratio 1000N
ffi,-'! The operation was started at a starting temperature of 315°C, and the hydrogenation rate (difference in the hydrogen to carbon atomic ratio between the hydrogenated product and the hydrogenation product) was reduced to 0. J which becomes 2,
When the operation was stopped when the reaction temperature reached 400° C., the total operation time surprisingly reached about 6.0 OOfR.

The operating progress at that time is shown in Figure 1. In this example, since steady operation was performed at a hydrogenation rate of $0.2, the properties of the hydrogenated pitch at any operating time were almost the same. The properties of the filtered and hydrogenated pitch are illustrated in Table 3.The lightly hydrogenated pitch was distilled to remove about 20 wt% of the 1,.]c Kenga fraction and adjust its softening point to 40°C. It was made into hydrogenated pitch.

As shown in Table 3, the hydrogenated pipe 11. i average minute i'M
is approximately 300, which is approximately equal to the average f)r ratio of the raw material J21, and H/C, aromatic t! 1.1. ．． J-
The notene ring number is determined by the pitch of the raw material (τ = 0.69゜0
．． 91.0.50, whereas the hydrogenated pitches are 0.80, 0.7b, and 2.5, respectively, and basically have a polycyclic condensed structure). This shows that pitch with desirable properties as a hydrogenated carbon material raw material was obtained in J, -) after extensive hydrogenation treatment. History t;l;N,S.

Heteroatoms such as O, oligothorium, and iron were largely removed compared to the raw material t1, and the carbon material raw material had extremely favorable properties 4 (in addition to 11).

Comparative Example 1 In the same manner as in Example 1, the pitch used in Example 1 was subjected to a light hydrogenation treatment using a fixed bed isothermal continuous hydrogenation apparatus in the presence of a catalyst of 1z. At that time, the reaction temperature was 42
5℃9 reaction pressure 100 kg/am2G, LH8V5
．． After 0hr-1i', the hydrogenation rate was 0.22 for about 50 hours after the start of operation, which was good if the carbon material raw material was 1!
However, after about 200 hours, the hydrogenation rate was 0.04. This deterioration was extremely large considering the short period of time.After the operation was completed, the catalyst of Example 1 and the catalyst of Example 1 were extracted and compared, and η was found.
It was found that an extremely large amount of carbon was precipitated on the outer surface of the catalyst in Example 1.
A large amount of carbon was observed to be precipitated, about 4 liters compared to the amount of carbon. As described above, when the humidity is 400° C. or higher, an extremely large amount of carbon is deposited on the catalyst, and the catalyst deteriorates slowly, making stable operation over a long period of time impossible.

Comparative Example 2 In the same manner as in Example 1, the pitch used in Example 1 was subjected to mild hydrotreating in the presence of catalyst A using a fixed bed isothermal continuous hydrotreater 'G:'f+' /i -, 1k3.
Operation start temperature 240℃ 9 reaction pressure 20 ('l kg
,' cm9 (2.

LH8VO, Ihr-1, hydrogen to liquid ratio 1 (') 00
Although N ffi /2 was set, almost no hydrogenation reaction occurred.
-y 4i or -λl, = 1゜Example 2 Similar to Example 1, when performing light hydrogenation treatment using a fixed bed '4ff vortex type water accumulation treatment device (2nd, 4th In the presence of catalyst B shown in the table, reaction L1 force 80 k<+,
'cm2G,L)isVO,3hr'', Hydrogen to liquid ratio 1
00ON (1/(l), the operation was started at a starting temperature of 335°C, and the hydrogenation rate was increased to 0.2 while suppressing the deterioration of catalyst activity by gradually increasing the reaction temperature.
When the reaction temperature reached 400°C, the total operating time was about 2,800 hours. The operating progress at that time is shown in Figure 1.

Example 3 Same as Example 1, the pitch is fixed bed 15'! During mild hydrotreating using L'' hydrotreating equipment (tj''-), the reaction Ll force was 100 kg in the presence of catalyst C with the size shown in Table 5.
z'cm2c+, l-1-1svo, 3hr-1,
Hydrogen to liquid ratio 100011! /l, the operation was started at a starting temperature of 325°C, and while compensating for the deterioration of catalyst activity by slightly increasing the reaction temperature, the hydrogenation rate was 0.2.
The operation was continued while maintaining the temperature at all times, and the operation was terminated when the reaction temperature reached 400°C. The total operating time was approximately 3°500°C.
Figure 1 shows the operation progress when the time was reached.

Example 4 When performing mild hydrotreating using the same pitch used in Example 1 using a fixed bed hydrotreater, in the presence of catalyst Δ, reaction pressure 80 kg/Cm2G, LH8V
Operation was started at a temperature of 355° C. at a hydrogen-to-liquid ratio of 1000 fl/m for 0.8 hr-1. Although the catalyst gradually deteriorated, continuous operation was attempted by gradually increasing the reaction temperature so that the hydrogenation rate was always 0.20°.

However, at about 2.100 hours the reaction temperature was 4.
When the temperature reached 00°C, the operation was terminated. The operating progress at this time is shown in Figure 1.

Table 1, pitch removal - softening point (℃) 33.5 specific gravity
(20℃) 1.227 specific gravity (8
0℃＞1.172 viscosity (80℃
)(C,P,) 525 viscosity (140℃)
(C, r', > 20 Conradson residual coal rate (wt
%) 33. /IQl (wt%)
0. OT, I (wt%) 8.6 C (wt%) 91, 35H (
wt%) 5.45N (
wt%) 1,2 S (wt%) 0.550
(wt%) 1.6ON
a (Wtl)+1111)
4.3Fe (Wtppm>
P.

H,/C (atomic ratio) 0.69 Average molecular weight 295 Aromaticity
0.91 Number of side chain carbons
1.7 Number of aromatic rings
4.9 Number of naphthene rings 0.5 Table 2, catalyst △ Chemical composition Δ1203' 74.3wt%P20s
2.3wt%MO0319,8wt
%NiO3,6wt% Physical surface area 160m2/(1 pore volume
0.50cc/g average pore diameter
1258 Table 3, Hydrogenation treatment conditions for hydrogenated pitch Reaction temperature ('C) 32!
reaction pressure<KO/cm2G) I
F'30LH3V (hrl)
0. /1 specific gravity 25℃)
119 viscosity (140℃)
(C,P,) /15 viscosity (200℃)
(C, P,) E3] Radson residual coal rate (wt%)
2C3,2Ql (wt%)0.
0 TI (W1%)
2. F2O (wt%)
92.11H (wt%)
C3,12N (wt%)
' (1,9S (wt%)
0.1:INa
(Wtl)11m)
3. OFe (wtppm)
1, 3Q (wt%)
0. ε)OH/C (atomic ratio) 0. F'IO average molecular weight 281 Aromaticity 0.75 Number of side chain carbons 1.7 Number of aromatic rings: 1.01 Table of Contents, Catalyst B Chemical Composition AI 203 71.4 wt% B203
4.6wt%MOO3,1'8,
Qwt% Nio 6. owt% physical surface area 161 m2/(1 pore volume
0.462cc/(] Average pore diameter
115 people Table 5, Catalyst C Chemical composition △1203 70. :Y1%.

P205 5.8W1%MOO320
,2w1% NiO3,0wt% Physical properties Surface area 190 m', /! 1 pore volume 0, 4, 'l l': f;,
, +'(+Average pore diameter
- Rutar pitch h eye high grade coal cumulative 1 month: [The old one has been industrially produced continuously without any trouble for 1 month! ? Is Rukoto.

That is, by employing the hydrotreating method of the present invention, the hydrogenation process can be carried out for more than 2,000 hours. 1. Operation that satisfies business performance becomes possible. This effect (31) was completely unexpected based on the concept that it was impossible to maintain long-term operation in the hydroprocessing of l1 oil containing a large amount of toluene-insoluble matter. be.

[Brief explanation of the drawing]

FIG. 1 is a dimensional graph showing the operation progress of Examples and Comparative Examples according to the hydrotreating method of the present invention. Patent Applicant: Chiyoda Corporation, Iron and Steel Chemical Co., Ltd., Chiyoda Kako Construction Co., Ltd. W # Applicant Procedures Amendment 轡 July 26, 1985 Director General of the Patent Office Mr. Michibu Uga 1, Indication of Case 1988 Patent Application No. 127.626 2, Title of the invention: Method for hydrotreating coal tar pitch Voluntary amendment 6, "Claims" and [-Detailed description of the invention] column 7 of the specification subject to the amendment, Contents of the amendment ■Amend the claims as shown in the attached sheet. II. The specification is amended as follows. (1) Correct “hydrogenated refined product” in the 9th true line to “hydrogenated product”. (2) 1 degree on page 11, lines 6 to 8 is appropriate and...select. " is appropriate, and when the reaction temperature is maintained at a slightly high level of 360 to 400'C, the anti-+5 pressure is 30 to 110 ku/
cm2-G, and the hydrogenation treatment strip 1 is selected so that the hydrogenation rate is 0.05 to 0.35 within the above range. ” he corrected. (3) [Cannot be done] in the second line from the bottom of No. 11. Next, 1-Also, set the reaction temperature to 360-400'C and the reaction pressure to 30-110k(]/cm2 ・G
If the hydrogenation rate is set slightly lower, heteroatoms such as nitrogen, sulfur, and oxygen can be selectively removed without increasing the hydrogenation rate too much. ” is inserted. (4) Amend "unnecessary" in line 7 of page 15 to "insoluble." (5) Correct "r33.5°" in the first line of page 16 to "r33.5°C". (6) On page 25, in lines 9 and 10 from the bottom, "Example 5 Soft pitch with the properties shown in Table 6, which was treated in the same manner as in Example 1, was prepared using the catalyst shown in Table 7. The reaction was carried out in the same manner as in Example 1 except that the reaction conditions were changed. Properties C (wt%) 91.711-1 (wt%
>5.25N (wt%)
1.163 (wt%) 0.52
0 (wt%) 1.258/C (+Kyoko ratio> 0.681 Table 7 Catalyst D Nro 3.3wt%MOO317,
2wt% SiO20,6W [% A 1203 78.4wt% From Table 8,
It can be seen that Experiment Nos. 1.2 and 3, in which the hydrogenation treatment was carried out at a relatively high reaction temperature and a relatively low reaction pressure, show a high denitrification rate even if the hydrogenation rate is the same. ”
(1) Containing toluene-insoluble matter]-Lutal pitch on a refractory inorganic oxide support Group VIB and V1 of the periodic table
Reaction temperature 2b in the presence of a hydrotreating catalyst containing at least one selected from the group consisting of metals, oxides and sulfides of elements belonging to Group 11. ~400℃2 reaction pressure 30~250kMC...2・G. LH8V0.1~10hr+, hydrogen to liquid ratio 500~2
．． A method for hydrogenating coal tar pitch, characterized by hydrogenating the light layer under conditions of 00011/C. (2) A method for hydrogenating rutal pitch (as claimed in claim 1) in which the hydrotreated hot stone is heated to 280-380°C. The pressure horn is 3 Cl" 110k (1/cm24 G're6
A method for treating coal tar pitch with hydrogen according to claim 1. (4) The method for hydrotreating coal tar pitch according to claim 1, wherein the starting temperature is 280-350°C. The pitch according to claim 1, wherein the pitch is subjected to a treatment to substantially remove the quinoline-insoluble content and leave 80% by weight or more of the toluene-insoluble content, and then subjected to a hydrogenation treatment. Hydrotreating method.

Claims (4)

[Claims] (1) Coal tar pitch containing toluene-insoluble matter is used as a refractory inorganic oxide carrier with at least one selected from the group consisting of metals, oxides, and sulfides of elements belonging to Groups VIB and VIII of the Periodic Table. In the presence of a hydrotreating catalyst supporting one type, reaction temperature 250-400°C, reaction pressure 30-2
50kg/cm^2・G, LHSV0.1~10hr^
-^1. A method for hydrogenating coal tar pitch, characterized by mild hydrogenation under conditions of a hydrogen-to-liquid ratio of 500 to 2,000 Nl/l. (2) The method for hydrotreating coal tar pitch according to claim 1, wherein the hydrotreating temperature is 280 to 380°C. (3) The method for hydrotreating coal tar pitch according to claim 1, wherein the operation start temperature is 280 to 350°C. (4) The pitch according to claim 1, wherein the pitch is subjected to a treatment to substantially remove the quinoline insoluble content and leave 80% by weight or more of the torque converter insoluble content, and then subjected to a hydrogenation treatment. Hydrotreating method.