JP2000143245A - Production of tungsten - chromium - zinc multiple sulfide optionally containing nickel and hydrogenation catalyst consisting of the same multiple sulfide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production process for various metal sulfides each used as a hydrogenation catalyst having capability of effecting hydrogenation/ring-opening of an aromatic ring and also to provide a hydrogenation catalyst consisting of such a metal sulfide. SOLUTION: This production process for tungsten - chromium - zinc multiple sulfide comprises: adding an ammonium thiotangustate aqueous solution to zinc hydroxychromate hydrate in an amount sufficient to provide a W/(Zn+Cr) atomic ratio of 0.003-0.05; mixing and agitating them, to evaporate water in the resulting mixture and to obtain a solid material; and then, subjecting the solid material to reductive decomposition. The production process for this nickel - tungsten - chromium - zinc multiple sulfide hydrogenation catalyst comprises: adding an ammonium thiotangustate aqueous solution to zinc hydroxychromate hydrate in an amount sufficient to provide a W/(Zn+Cr) atomic ratio of 0.003-0.05 to obtain a mixture; further adding a nickel salt aqueous solution to the mixture in an amount sufficient to provide an Ni/W atomic ratio of <=1.0 thereafter, mixing and agitating them, to evaporate water in the resulting mixture and to obtain a solid material; and then, subjecting the solid material to reductive decomposition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a tungsten-chromium-zinc composite sulfide which may contain nickel and a hydrogenation catalyst.

[0002]

2. Description of the Related Art Aromatic hydrocarbons are major components of fossil fuel oils such as gasoline and kerosene oil, and in recent years, from the viewpoint of environmental protection on a global scale, reduction of aromatic components in fuel oils has been required. Is coming. To meet this demand, a hydrogenation ring-opening reaction is required alongside the hydrogenation of aromatic fractions in fuel oil, but there is no hydrogenation-opening process currently in industrial operation. . The ring opening reaction is a reaction accelerated by the acid site of the catalyst.As a strong acid catalyst, a catalyst in which a metal having high hydrogenation activity is supported on a solid acid carrier such as zeolite or silica / alumina is used. In this case, secondary decomposition of the ring-opened product occurs, and it is difficult to establish a process. On the other hand, petroleum refining catalysts such as nickel-molybdenum / alumina also have a hydrogenation ring-opening ability and are effective for ring opening of methylnaphthalene, acenaphthene, fluorene and the like. A reaction temperature is required, and secondary decomposition of the ring-opening product also proceeds.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing various metal sulfides and a hydrogenation catalyst as a hydrogenation catalyst having the ability to open the aromatic ring by hydrogenation.

[0004]

SUMMARY OF THE INVENTION As a result of many years of research, the present inventors have found that an unsupported tungsten disulfide catalyst prepared by reductive decomposition of a sulfur-containing tungsten salt has a high hydrogenation capacity and a high hydrogenation ring opening. And found that the ring-opened product does not easily undergo secondary decomposition. To use hydrogenation ring-opening catalysts in existing industrial processes,
The catalyst must be a supported molded catalyst, and the present inventors have further researched a method of supporting these tungsten sulfide catalysts, and as a result, added an aqueous solution of ammonium thiotungstate to zinc hydroxychromate hydrate. ,
It has been found that by reductive decomposition, the hydrogenation ring-opening ability is remarkably increased as compared with the unsupported tungsten disulfide catalyst, and a catalyst having an increased hydrogenation ability is prepared. The present inventors further added an aqueous solution of ammonium thiotungstate and an aqueous solution of a nickel salt to zinc hydroxychromate hydrate and reductively decomposed the hydrogenated ring-opening of the tungsten-zinc-chromium sulfide catalyst. It has been found that a catalyst having an increased hydrogenation capacity is prepared while maintaining almost the same capacity. Conventional non-supported and tungsten sulfide catalysts supported on alumina, etc., significantly reduce the hydrogenation ring-opening ability of tungsten sulfide by adding nickel,
A catalyst of the type in which the hydrogenation ring-opening ability of tungsten sulfide hardly decreases even when nickel is added as in the present invention has not been reported so far. The present invention has been made based on the above findings. That is, according to the present invention, an aqueous solution of ammonium thiotungstate is added to zinc hydroxychromate hydrate in a W / (Zn + Cr) atomic ratio of 0.003 or more and 0.05 or less, and mixed.
A method for producing a tungsten-chromium-zinc composite sulfide, which comprises evaporating water while stirring to obtain a solid component and reductively decomposing the solid component, is provided. Further, according to the present invention, an aqueous solution of ammonium thiotungstate is added to zinc hydroxychromate hydrate in an atomic ratio of W / (Zn + Cr) in the range of 0.003 or more and 0.05 or less. Aqueous solution with an atomic ratio of Ni / W of 1.0
A method for producing a nickel-tungsten-chromium-zinc composite sulfide catalyst characterized by adding water in the following range, evaporating water while mixing and stirring to obtain a solid component, and reductively decomposing the solid component. . Further, according to the present invention, there is provided a hydrogenation catalyst comprising the above-obtained tungsten-chromium-zinc composite sulfide and / or nickel-tungsten-chromium-zinc composite sulfide.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a tungsten-chromium-zinc composite sulfide (hereinafter abbreviated as ZnCrW / S) and a nickel-tungsten-chromium-zinc composite sulfide (hereinafter ZnCrNiW / S). Abbreviated as S). In order to produce ZnCrW / S, first, a paste-like zinc hydroxychromate hydrate ZnCrO _4. (0.3-3.0) Zn (OH) _2.
nH ₂ O (n: 1 or more, preferably 2 to 5) is prepared. For example, it can be prepared by adding an aqueous solution of chromium trioxide CrO ₃ to zinc oxide ZnO powder and kneading with a kneader. In this case, the Zn / Cr atomic ratio is adjusted to 0.5-4, preferably 1-3. Cr
The concentration of CrO ₃ in the O ₃ aqueous solution is 10% by weight or less, preferably 3 to 7% by weight.

Next, the aqueous solution of ammonium thiotungstate is kneaded with a kneader at room temperature while gradually adding an aqueous solution of ammonium thiotungstate to the paste-like zinc hydroxychromate hydrate, and further heated at 50 to 90 ° C., preferably 50 to 70 ° C. The moisture is evaporated while kneading with a kneader at a temperature to form a molded product, and the temperature is gradually increased to a temperature from room temperature to 300 ° C, preferably from room temperature to 150 ° C, to obtain a molded product. In this case, the addition amount of ammonium thiotungstate is such that the W / (Zn + Cr) atomic ratio is 0.003 to 0.05, preferably 0.005 to 0.5.
03. The concentration of ammonium thiotungstate in the aqueous solution is 2 to 20% by weight, preferably 5 to 15% by weight. The shape of the molded product is not particularly limited, and may be a pellet, a sphere, or the like. The molded product can be pulverized to a powder if necessary.

Next, the molded product or powder obtained as described above is reduced and decomposed. The reaction formula in this case is as follows.

Embedded image The reductive decomposition is carried out in the presence of hydrogen by heating at room temperature to 550 ° C, preferably at room temperature to 460 ° C. In this reductive decomposition, hydrogen sulfide is used in an amount of 0.02 to 0.2 mol, preferably 0.04 to 0.2 mol per mol of hydrogen gas.
It is preferable to add at a ratio of 12 mol.

In order to produce ZnCrNiW / S, first, a paste-like zinc hydroxychromate hydrate ZnCrO _4. (0.3-3.0) Zn
(OH) ₂ .nH ₂ O (n: 1 or more, preferably 2 to 5) is prepared. Next, an aqueous solution of ammonium thiotungstate is kneaded with a kneader at room temperature while slowly adding an aqueous solution of ammonium thiotungstate to the paste-like zinc hydroxychromate hydrate in the same manner as described above. The mixture is kneaded with a kneader at room temperature while being gradually added, and is further kneaded with a kneader under heating at 50 to 90 ° C., preferably 50 to 70 ° C. to evaporate water, molded, and formed at room temperature to 300 ° C., preferably room temperature to The product is gradually heated to 150 ° C. and dried to obtain a molded product. In this case, the addition amount of the nickel salt is such that the atomic ratio of Ni / W is 1.
0 or less, preferably 0.8 or less. The lower limit of the atomic ratio is usually about 0.1. The concentration of nickel in the aqueous solution is 0.1 to 10% by weight, preferably 0.3 to 3% by weight. The shape of the molded product is not particularly limited, and may be a pellet, a sphere, or the like.

Next, the molded product or powder obtained as described above is reduced and decomposed. The reaction formula in this case is as follows.

Embedded image The reductive decomposition is carried out in the presence of hydrogen under heating at room temperature to 550 ° C, preferably at room temperature to 460 ° C. In this reductive decomposition, hydrogen sulfide is used in an amount of 0.02 to 0.2 mol, preferably 0.04 to 0.2 mol per mol of hydrogen gas.
It is preferable to add at a ratio of 12 mol.

[0010]

As described above, the ZnCrW /
S and ZnCrNiW / S are handled in various forms such as powders and molded products, and exhibit excellent functions as hydrogenation catalysts, but are particularly excellent in the function of hydrogenating and opening aromatic rings. The ZnCrW / S and ZnCrN according to the present invention
iW / S is advantageously used as a hydrogenation catalyst when the aromatic components in fuel oils such as gasoline and kerosene light oil are hydrogenated to reduce them.

[0011]

Next, the present invention will be described in more detail with reference to examples.

Example 1 Unsupported tungsten sulfide catalyst (WS ₂ ), alumina supported tungsten sulfide catalyst (WS ₂ / Al ₂ O ₃ ), unsupported nickel sulfide-tungsten catalyst (NiS-WS ₂ ), alumina supported nickel sulfide Tungsten catalyst (NiS-
WS ₂ / Al ₂ O ₃ ), the hydrogenation ability of the tungsten-chromium-zinc composite sulfide catalyst (ZnCrW / S) of the present invention and the nickel-tungsten-chromium-zinc composite sulfide catalyst (ZnCrNiW / S) of the present invention And hydrogenation ring opening ability were compared. The method for preparing each catalyst and the method for measuring the activity of the catalyst are as follows. [Symbol of catalyst used and preparation method thereof] WS ₂ : ammonium thiotungstate (NH ₄ ) ₂ W
It was charged with S ₄ 5 g inside diameter 38mm, quartz glass reaction tube length 400 mm. The reaction tube was inserted into a horizontal electric furnace, and while a 10% hydrogen sulfide-hydrogen mixed gas was flown at normal pressure, the temperature was gradually increased from room temperature, and then reductively decomposed at a final temperature of 400 ° C. to prepare a tungsten sulfide catalyst. . WS ₂ / Al ₂ O ₃ : An aqueous solution of 42.1 g of ammonium thiotungstate was gradually added to 70 g of alumina powder,
Water was evaporated under heating of 70 ° C. while kneading with a kneader, and pulverized after molding and drying (100 ° C.), sieved 20-30 mesh particle fraction was reductive decomposition in the same manner as WS _2. However, the final temperature of sulfurization was 450 ° C. The composition of the catalyst is in terms of _{WS 2 / Al 2 O 3 30/70} ( weight ratio). NiS-WS ₂ : ammonium thiotungstate 67
g of the aqueous solution of nickel ammonium sulfate NiSO ₄ (N
An aqueous solution of 30.3 g of H ₄ ) ₂ SO ₄ .6H ₂ O was added, and 6
The mixture was kneaded with a kneader while evaporating water at a temperature of 0 ° C., dried at 100 ° C., and reductively decomposed in the same manner as in WS ₂ . The composition of the catalyst is such that the atomic ratio of Ni / W is 2/5. _{NiS-WS 2 / Al 2 O} 3: gradual addition of an aqueous solution of thio ammonium tungstate 21.1g of alumina powder 82g kneaded in a kneader, then nickel nitrate _{Ni (NO 3) 2 · 6H} 2 O in 9.6g of Add aqueous solution and add 7
The mixture is kneaded with a kneader while evaporating water at a temperature of 0 ° C., molded, dried (100 ° C.), pulverized, sieved to 20-30 mesh particles, and reduced in the same manner as WS ₂ / Al ₂ O _3. Decomposed. The composition of the catalyst was NiS / WS ₂ / Al ₂ O
It is 3/15/82 (weight ratio) when converted to ₃ .

ZnCrW / S: 16 of zinc oxide ZnO
2.74 g of chromium trioxide CrO_Three100g of aqueous solution
Knead while gradually adding
A hydrate of zinc hydroxychromate is formed. this
15.1 g of ammonium thiotungstate in the paste
Water solution is gradually added, and water is evaporated under heating at 60 ° C.
Kneading while kneading, molding and drying (140 ° C)
After crushing, sieving 20-30 mesh particles, WS_Two
/ Al_TwoO_ThreeWas subjected to reductive decomposition in the same manner as in The composition of the catalyst is
W: Zn: Cr atomic ratio is 0.043: 2: 1.
You. ZnCrNiW / S: 162.74 g of zinc oxide ZnO
Chromium trioxide CrO _Three100 g of aqueous solution
While kneading with a kneader,
A hydrate of zinc xychromate is formed. To this paste
Aqueous solution of 15.1 g of ammonium thiotungstate
Add slowly and evaporate water under heating at 60 ° C.
And then nickel ammonium sulfate
6.83 g of an aqueous solution was added, and the water was evaporated under heating at 70 ° C.
Kneading again with a kneader while emitting, then forming and drying
After drying (140 ° C), pulverize, and sieve 20-30 mesh particles
Division, WS_Two/ Al_TwoO_ThreeReductive decomposition in the same manner as
Was. The composition of the catalyst is Ni: W: Zn: Cr atomic ratio
0.017: 0.043: 2: 1.

[Reaction sample oil] A commercially available 1-methylnaphthalene was purified by open column chromatography packed with activated alumina, and 150 g thereof was diluted with 550 g of commercially available tetradecane to prepare a sample oil.

[Activity Measurement Method] A stainless steel micro autoclave having an inner volume of 40 ml was charged with 5 ml of sample oil and a catalyst, hydrogen was added at 8 MPa at room temperature, and the reaction was carried out at 330 ° C. for 1 hour. The amount of catalyst used is 1 in terms of tungsten sulfide or the total amount of tungsten sulfide and nickel sulfide.
0 mg, 20 mg, 30 mg and 40 mg. Result: Figure 1 shows the reaction network of 1-methylnaphthalene.
Shown in The products are roughly classified into 1-reactive 5-methyltetralin, methyldecalins, and pentylbenzene. Here, the hydrogenation rate of 1-methylnaphthalene is represented by the total yield of methyltetralins, methyldecalins and pentylbenzene. On the other hand, pentylbenzene is formed by the ring-opening reaction of methyltetralin, and methyldecalins are formed by the hydrogenation reaction of methyltetralin, so the ring-opening reaction is performed based on the total yield of pentylbenzene and methyldecalin. To selectivity. FIG. 2 shows a comparison of the hydrogenation ability of various catalysts in relation to the amount of tungsten and the hydrogenation rate. When the catalysts are arranged in descending order of hydrogenation ability, ZnCrN
_{iW / S, NiS-WS 2} / Al 2 O 3, ZnCrW /
S, NiS-WS ₂ , WS ₂ / Al ₂ O ₃ , WS ₂ ,
It has been shown that ZnCrNiW / S and ZnCrW / S catalysts have better hydrogenation ability than alumina-supported catalyst, which is the most excellent conventional industrial catalyst for hydrorefining.

Next, a comparison of the ring opening abilities of the above various catalysts is made by comparing an ion chromatogram at m / z = 148 representing pentylbenzene with an ion chromatogram at m / z = 152 representing methyldecalins. 3 is shown. Since pentylbenzene and methyldecalins have different ion chromatographic sensitivities, the selectivity of the ring-opening reaction determined from the yield of these compounds is shown in Table 1. From FIG. 3 and Table 1, the selectivity of the unsupported tungsten sulfide catalyst (WS ₂ ) to the ring opening reaction was 0.29 g, and the unsupported nickel sulfide-tungsten catalyst (NiS-W
The selectivity of S ₂ ) to the ring opening reaction was 0.14, indicating that the addition of nickel significantly reduced the selectivity to the ring opening reaction. The selectivity of the tungsten sulfide catalyst (WS ₂ / Al ₂ O ₃ ) supported on alumina to the ring opening reaction is 0.2.
In Example No. 4, the selectivity to the ring-opening reaction was remarkably reduced to 0.16 due to a slight decrease from the unsupported catalyst and addition of nickel. Compared to these catalysts, ZnCrW / S
The selectivity of the catalyst to the ring opening reaction is 0.46, significantly higher than unsupported and alumina-supported tungsten sulfide catalysts,
The selectivity to the ring-opening reaction of the ZnCrNiW / S catalyst to which nickel was added was 0.22, which was close to the unsupported catalyst and the alumina-supported tungsten sulfide catalyst to which nickel was not added. That is, the catalyst according to the present invention has a hydrogenation ability comparable to that of the conventional catalyst and a ring opening ability much higher than that of the conventional catalyst. This indicates that the catalyst according to the invention has excellent activity as a hydrogenation ring-opening catalyst. The selectivity shown in Table 1 indicates the ratio of the yield of pentylbenzene to the sum of the yield of pentylbenzene and the yield of methyldelican.

[0017]

[Table 1]

Example 2 For the catalyst prepared by the method of the present invention, the relationship between the tungsten content and the hydrogenation ability and hydrogenation ring opening ability was determined by the following equation.
The reaction of methylnaphthalene is shown as an example in FIGS. Abbreviations and preparation methods of each catalyst are as follows. ZnCrW / S-15: In the catalyst prepared by the method of changing the content of tungsten in a manner analogous to ZnCrW / S catalyst of Example 1, the content of tungsten is 15% by weight in terms of WS _2, W: Zn: Cr atomic ratio is 0.1
3: 2: 1. ZnCrW / S-10: In the catalyst prepared by the method of changing the content of tungsten in a manner analogous to ZnCrW / S catalyst of Example 1, the content of tungsten is 10% by weight in terms of WS _2, W: Zn: Cr atomic ratio is 0.08
7: 2: 1. ZnCrW / S-5: the same as the ZnCrW / S catalyst of Example 1. The tungsten content was 5% by weight in terms of WS ₂ , and the W: Zn: Cr atomic ratio was 0.044:
2: 1. ZnCrW / S-2: in a manner analogous to ZnCrW / S catalyst of Example 1, the catalyst prepared by the method of changing the content of the tungsten, the tungsten content is 2% by weight in terms of WS _2, W : The atomic ratio of Zn: Cr is 0.01
7: 2: 1.

[Reaction sample oil] A commercially available 1-methylnaphthalene was purified by open column chromatography packed with activated alumina, and 150 g thereof was diluted with 550 g of commercially available tetradecane to prepare a sample oil.

[Activity Measurement Method] A stainless steel micro-autoclave having an inner volume of 40 ml was charged with 5 ml of sample oil and a catalyst, hydrogen was added at 8 MPa at room temperature, and reacted at 330 ° C. for 1 hour. The amount of the catalyst used is 40% by weight of the entire catalyst.
The content was 0 mg and the content of tungsten sulfide was 20 mg. Results: FIG. 4 shows the relationship between the content of tungsten disulfide and the hydrogenation rate of 1-methylnaphthalene for the above four types of catalysts as a comparison of the activity per total weight of the catalyst. As is clear from FIG. 4, the hydrogenation activity with respect to the catalyst having the same weight was higher with the catalyst having a higher content of tungsten disulfide. FIG. 5 shows the relationship between the content of tungsten disulfide and the hydrogenation rate of 1-methylnaphthalene as a comparison of the activity per the content of tungsten disulfide in the catalyst for the above four types of catalysts. As is clear from FIG. 5, the hydrogenation activity per tungsten disulfide content in the catalyst was maximum when the content of tungsten disulfide was around 5% by weight. FIG. 6 shows the relationship between the content of tungsten disulfide and the selectivity of ring opening for the above four types of catalysts. The ring-opening selectivity was almost constant without depending on the content of tungsten disulfide. If the content of tungsten disulfide in the catalyst is high, the cost per total weight of the catalyst is high, while if the content of tungsten disulfide in the catalyst is low, the use amount of the entire catalyst is increased, so that the cost for equipment and operation is increased. Will be higher. It is considered that the amount of tungsten disulfide supported on the catalyst by the preparation method of the present invention is preferably 2 to 15% by weight.

Example 3 The catalyst prepared by the method of the present invention contains nickel
The ratio of the content to the tungsten content, the hydrogenation capacity of the catalyst and
The relationship between the hydrogenation ring opening ability and the reaction of 1-methylnaphthalene
Examples are shown in FIGS. Abbreviations and preparation methods for each catalyst
It is as follows. ZnCrNiW / S-15: ZnCrNiW of Example 1
To change the nickel content by a method similar to the / S catalyst
The nickel content is NiS_TwoConvert to
Calculated as 1.48% by weight, and the Ni: W atomic ratio was 1: 5.
It is. ZnCrNiW / S-25: ZnCrNiW of Example 1
/ S catalyst. Nickel content is NiS_TwoTo
The conversion is 3.0% by weight, and the atomic ratio of Ni: W is 2: 5.
It is. ZnCrNiW / S-45: ZnCrNiW of Example 1
To change the nickel content by a method similar to the / S catalyst
The nickel content is NiS _TwoConvert to
5.9% by weight, and the Ni: W atomic ratio was 4: 5.
is there. ZnCrNiW / S-85: ZnCrNiW of Example 1
To change the nickel content by a method similar to the / S catalyst
The nickel content is NiS_TwoConvert to
11.9% by weight, and the Ni: W atomic ratio was 8: 5.
It is. ZnCrNiW / S-05: ZnCrW / S of Example 1
Identical to the catalyst and does not contain nickel.

[Reaction sample oil] A commercially available 1-methylnaphthalene was purified by open column chromatography packed with activated alumina, and 150 g thereof was diluted with 550 g of commercially available tetradecane to prepare a sample oil.

[Activity Measurement Method] A stainless steel microautoclave having an inner volume of 40 ml was charged with 5 ml of sample oil and a catalyst, hydrogen was added at 8 MPa at room temperature, and reacted at 330 ° C. for 1 hour. The amount of the catalyst used is 40% by weight of the entire catalyst.
0 mg. Results: FIG. 7 shows the relationship between the ratio of the nickel content and the tungsten content and the hydrogenation ability of the catalysts for the above five types of catalysts. The hydrogenation ability increases with an increase in the nickel content, and reaches a maximum near a Ni: W atomic ratio of about 2: 5.
The reduction in hydrogenation ability became remarkable from around a ratio of 1: 1. FIG.
The relationship between the nickel content ratio and the tungsten content ratio of the above five types of catalysts and the ring opening ability of the catalysts is shown below. Ring opening ability decreased with increasing nickel content. From the relationship between the hydrogenation ability and the ring opening ability, it was shown that the Ni: W ratio is desirably 1: 1 or less as the composition of the catalyst according to the present invention.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between hydrogenation and ring-opening reaction pathways and products in the reaction of 1-methylnaphthalene.

FIG. 2 is a diagram showing a comparison of the hydrogenation ability of six types of catalysts containing tungsten disulfide. □: WS ₂ catalyst ■: NiS-WS ₂ catalyst ○: WS ₂ / Al ₂ O ₃ catalyst ●: NiS-WS ₂ / Al ₂ O ₃ catalyst △: ZnCrW / S catalyst ▲: ZnCrNiW / S catalyst

FIG. 3 is a diagram showing a comparison of selectivity to a ring-opening reaction by ion chromatograms for six types of catalysts containing tungsten disulfide. m / z = 148 Indicates the amount of pentylbenzene produced. m / z = 152 Indicates the amount of methyldecalins produced.

FIG. 4 shows four types of ZnCr having different tungsten contents.
It is a figure which shows the comparison of the hydrogenation activity of 1-methylnaphthalene per total catalyst weight of a W / S type catalyst.

FIG. 5 shows four types of ZnCr having different tungsten contents.
It is a figure which shows the comparison of the hydrogenation activity of 1-methylnaphthalene per tungsten amount of a W / S type catalyst.

FIG. 6 shows four types of ZnCr having different tungsten contents.
It is a figure which shows the comparison of the selectivity to the ring opening reaction of 1-methylnaphthalene of a W / S type catalyst.

FIG. 7 shows five types of ZnCrNi having different nickel contents.
It is a figure which shows the comparison of the hydrogenation activity of 1-methylnaphthalene per total catalyst weight of a W / S type catalyst.

FIG. 8 shows five types of ZnCrNi having different nickel contents.
It is a figure which shows the comparison of the selectivity to the ring opening reaction of 1-methylnaphthalene of a W / S type catalyst.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C10G 49/04 C10G 49/04 (72) Inventor Yoshikazu Sugimoto 1-1-1, Higashi Tsukuba, Ibaraki Pref. Within the Institute of Engineering, Industrial Technology (72) Inventor Hiromichi Shimada 1-1-1, Higashi, Tsukuba, Ibaraki Pref.Institute of Materials Science and Technology (72) Inventor Fujio Minakami 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Inside the Technical Research Institute (72) Inventor Tetsu Oshima 1-1-1, Higashi, Tsukuba, Ibaraki Pref.Institute of Materials Science and Technology, Institute of Industrial Science (72) Inventor Yasunori Kuriki 1-1-1, Higashi, Tsukuba, Ibaraki Pref. (72) Inventor Morio Yumura 1-1-1 Higashi, Tsukuba, Ibaraki Pref. Within the Technical Research Institute (72) Inventor Nobuyuki Matsubayashi 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Goichi Sato 4-3-9 Toranomon, Minato-ku, Tokyo Inside the Activation Center (72) Inventor Yasuhiro Araki 4-3-9 Toranomon, Minato-ku, Tokyo Inside the Foundation Petroleum Industry Revitalization Center (72) Inventor Kosaku Honam 4-3-9 Toranomon, Minato-ku, Tokyo Foundation 4G048 AA07 AB02 AC08 AE05 AE07 4G069 AA02 AA08 BA01A BA01B BB09A BB09B BC35A BC35B BC58A BC58B BC60A BC60B BC68A BC68B CC02 DA05 EA01Y 4H029 CA00 DA00

Claims (3)

[Claims] 1. An aqueous solution of ammonium thiotungstate is added to zinc hydroxychromate hydrate by W / (Zn + C
r) Tungsten-chromium-zinc, which is added in an atomic ratio of 0.003 or more and 0.05 or less, evaporates water while mixing and stirring to obtain a solid component, and reductively decomposes it. Method for producing composite sulfide. 2. An aqueous solution of ammonium thiotungstate is added to zinc hydroxychromate hydrate by W / (Zn + C
r) An atomic ratio is added in a range of 0.003 or more and 0.05 or less, and an aqueous solution of a nickel salt is further added in a range of an Ni / W atomic ratio of 1.0 or less. A nickel-tungsten-chromium-zinc composite sulfide catalyst, characterized in that a solid component is obtained by evaporating the compound, and the solid component is reductively decomposed. 3. A hydrogenation catalyst comprising the tungsten-chromium-zinc composite sulfide obtained in claim 1 and / or the nickel-tungsten-chromium-zinc composite sulfide obtained in claim 2.