JP2000246110A - Hydrogenation catalyst and its production - Google Patents
Hydrogenation catalyst and its productionInfo
- Publication number
- JP2000246110A JP2000246110A JP11053270A JP5327099A JP2000246110A JP 2000246110 A JP2000246110 A JP 2000246110A JP 11053270 A JP11053270 A JP 11053270A JP 5327099 A JP5327099 A JP 5327099A JP 2000246110 A JP2000246110 A JP 2000246110A
- Authority
- JP
- Japan
- Prior art keywords
- sulfide
- catalyst
- mixed
- molybdenum sulfide
- molybdenum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水素化触媒及びそ
の製造方法に関するものである。[0001] The present invention relates to a hydrogenation catalyst and a method for producing the same.
【０００２】[0002]
【従来の技術】石油精製には水素化深度を上げたり、脱
硫や脱窒素を行なうなど、水素化処理技術が多く用いら
れている。そこで使用される触媒は、主にアルミナを担
体にし、酸化モリブデン、酸化コバルトあるいは酸化ニ
ッケルを担持させた触媒である。使用に際しては硫化し
て、活性化の処理を施さなければならない。それらを使
用する反応装置は、固定床型反応器または流動床型反応
器を備えたものである。今日、水素化精製の高度化、さ
らには原油の重質化、石炭の液化などの重質系炭化水素
の水素化処理への要求が益々重要になっている。その処
理に従来の担持触媒を適用させても、触媒被毒が激しく
触媒寿命に問題があり、それに替わる新規な触媒の開発
が要請されている。担持触媒に替わるものとすれば非担
持の粉末触媒になり、原料との混合スラリーを形成さ
せ、反応器として沸騰床型や懸濁気泡型が使われること
になる。2. Description of the Related Art Hydrorefining techniques, such as increasing the depth of hydrogenation and performing desulfurization and denitrification, are widely used in petroleum refining. The catalyst used there is a catalyst mainly comprising alumina as a carrier and carrying molybdenum oxide, cobalt oxide or nickel oxide. In use, it must be sulfurized and subjected to an activation treatment. The reactor using them has a fixed-bed reactor or a fluidized-bed reactor. 2. Description of the Related Art Today, demands for sophistication of hydrorefining, and furthermore, the demand for hydrotreating heavy hydrocarbons such as heavy crude oil and liquefaction of coal are increasing. Even if a conventional supported catalyst is applied to the treatment, catalyst poisoning is severe and there is a problem in catalyst life, and development of a new catalyst to replace the catalyst is required. If the catalyst is replaced with a supported catalyst, it becomes an unsupported powder catalyst, forms a mixed slurry with the raw material, and uses a boiling bed type or a suspended bubble type as a reactor.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、非担持の粉
末からなる高活性の水素化触媒及びその製造方法を提供
することをその課題とする。An object of the present invention is to provide a highly active hydrogenation catalyst comprising unsupported powder and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、硫化モリブテンと硫
化コバルトとの混合粉砕化物からなることを特徴とする
水素化触媒が提供される。また、本発明によれば、硫化
モリブテンと硫化ニッケルとの混合粉砕化物からなるこ
とを特徴とする水素化触媒が提供される。さらに、本発
明によれば、硫化コバルトをあらかじめ粉砕した後、硫
化モリブテンを添加して混合粉砕することを特徴とする
前記水素化触媒の製造方法が提供される。さらにまた、
本発明によれば、硫化ニッケルをあらかじめ粉砕した
後、硫化モリブテンを添加して混合粉砕することを特徴
とする前記水素化触媒の製造方法が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a hydrogenation catalyst comprising a mixed and pulverized product of molybdenum sulfide and cobalt sulfide. Further, according to the present invention, there is provided a hydrogenation catalyst comprising a mixed and pulverized product of molybdenum sulfide and nickel sulfide. Further, according to the present invention, there is provided the method for producing a hydrogenation catalyst, wherein cobalt sulfide is pulverized in advance, and then molybdenum sulfide is added and mixed and pulverized. Furthermore,
According to the present invention, there is provided the method for producing the hydrogenation catalyst, wherein nickel sulfide is pulverized in advance, and then molybdenum sulfide is added and mixed and pulverized.
【０００５】[0005]
【発明の実施の形態】本発明で水素化触媒原料として用
いる金属硫化物は、いずれも市販品を用いることができ
る。BEST MODE FOR CARRYING OUT THE INVENTION As the metal sulfide used as a hydrogenation catalyst raw material in the present invention, any commercial product can be used.
【０００６】本発明による硫化モリブテン（ＭｏＳ2）
と硫化コバルト（ＣｏＳ）との混合粉砕化物からなる水
素化触媒は、硫化コバルトをあらかじめ粉砕し、次いで
硫化モリブテンを添加し、混合粉砕することによって製
造される。Molybdenum sulfide (MoS 2 ) according to the present invention
A hydrogenation catalyst comprising a mixed and pulverized product of sulfide and cobalt sulfide (CoS) is produced by previously pulverizing cobalt sulfide, then adding molybdenum sulfide, and mixing and pulverizing.
【０００７】硫化コバルトと硫化モリブテンの使用割合
は特に制約されず、従来のＭｏ−Ｃｏ系触媒の場合と同
様の割合であればよい。一般的には、硫化コバルトと硫
化モリブテンとの合計量に対する硫化コバルトの割合
で、１０〜９０重量％、好ましくは２０〜８０重量％で
ある。また、混合粉砕化物において、その硫化モリブテ
ンの平均粒径は０．１μｍ以下、及びその硫化コバルト
の平均粒径は０．１５μｍ以下にするのがよい。その混
合粉砕化物の平均粒径は０．１５μｍ以下、好ましくは
０．１μｍ以下である。その平均粒径の下限値は０．０
２μｍ程度である。[0007] The proportion of cobalt sulfide and molybdenum sulfide used is not particularly limited, and may be the same as in the case of the conventional Mo-Co catalyst. Generally, the proportion of cobalt sulfide to the total amount of cobalt sulfide and molybdenum sulfide is 10 to 90% by weight, preferably 20 to 80% by weight. In the mixed and pulverized product, the average particle size of the molybdenum sulfide is preferably 0.1 μm or less, and the average particle size of the cobalt sulfide is preferably 0.15 μm or less. The average particle size of the pulverized mixture is 0.15 μm or less, preferably 0.1 μm or less. The lower limit of the average particle size is 0.0
It is about 2 μm.
【０００８】本発明による硫化モリブテン（ＭｏＳ2）
と硫化ニッケル（ＮｉＳ）との混合粉砕化物からなる水
素化触媒は、硫化ニッケルをあらかじめ粉砕し、次いで
硫化モリブテンを添加し、混合粉砕することによって製
造される。[0008] Molybdenum sulfide (MoS 2 ) according to the present invention
A hydrogenation catalyst comprising a mixed and pulverized product of nickel and nickel sulfide (NiS) is produced by pulverizing nickel sulfide in advance, then adding molybdenum sulfide, and mixing and pulverizing.
【０００９】硫化ニッケルと硫化モリブテンの使用割合
は特に制約されず、従来のＭｏ−Ｎｉ系触媒の場合と同
様の割合であればよい。一般的には、硫化ニッケルと硫
化モリブテンとの合計量に対する硫化モリブテンの割合
で、１０〜９０重量％、好ましくは２０〜８０重量％で
ある。また、混合粉砕化物において、その硫化モリブテ
ンの平均粒径は０．１μｍ以下、及びその硫化ニッケル
の平均粒径は０．１５μｍ以下にするのがよい。その混
合粉砕化物の平均粒径は０．１５μｍ以下、好ましくは
０．１μｍ以下である。その平均粒径の下限値は０．０
２μｍ程度である。The proportion of nickel sulfide and molybdenum sulfide used is not particularly limited, and may be the same as in the case of the conventional Mo-Ni catalyst. Generally, the ratio of molybdenum sulfide to the total amount of nickel sulfide and molybdenum sulfide is 10 to 90% by weight, preferably 20 to 80% by weight. In the mixed and pulverized product, the average particle size of the molybdenum sulfide is preferably 0.1 μm or less, and the average particle size of the nickel sulfide is preferably 0.15 μm or less. The average particle size of the pulverized mixture is 0.15 μm or less, preferably 0.1 μm or less. The lower limit of the average particle size is 0.0
It is about 2 μm.
【００１０】[0010]
【発明の効果】本発明の触媒は、非担持の粉末触媒とし
て使用され、原料との混合スラリー状で、沸騰床型や懸
濁気泡型反応器に供給される。本発明の触媒は、非担持
触媒で活性金属濃度が高いことから、その触媒活性は非
常に高いものとなる。従って、本発明の触媒を用いる場
合、触媒の使用量は少なくてすみ、反応装置への負荷が
軽減される他、触媒コストも軽減される。本発明の水素
化触媒は、重質油や軽油等の石油の水素化精製用触媒と
して有利に適用される他、芳香族炭化水素の水素化用触
媒、石炭液化における水素化用触媒などとして有利に適
用される。The catalyst of the present invention is used as an unsupported powder catalyst, and is supplied to an ebullating-bed or suspended-bubble reactor in the form of a slurry mixed with raw materials. Since the catalyst of the present invention is a non-supported catalyst and has a high active metal concentration, its catalytic activity is very high. Therefore, when the catalyst of the present invention is used, the amount of the catalyst used is small, the load on the reactor is reduced, and the catalyst cost is also reduced. INDUSTRIAL APPLICABILITY The hydrogenation catalyst of the present invention is advantageously applied as a catalyst for hydrorefining petroleum such as heavy oil and light oil, and is also advantageously used as a catalyst for hydrogenation of aromatic hydrocarbons and a catalyst for hydrogenation in coal liquefaction. Applied to
【００１１】[0011]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００１２】実施例１ 金属硫化物を混合粉砕するための装置としては、粉砕媒
体攪拌ミルを用いた。その装置は、１００ｍｌの内容積
を有し、ＳＵＳの攪拌軸にジルコニア製の攪拌羽根（直
径６ｍｍ、長さ３７ｍｍ）を３本備えたものである。粉
砕媒体としては、ジルコニアビーズ（直径１ｍｍ）２０
０ｇを用いた。市販の硫化コバルト（平均粒径約５．５
μｍ）２ｇを粉砕装置に充填し、５０時間かけて粉砕処
理した後、市販の硫化モリブデン（平均粒径２．６μ
ｍ）４ｇを充填し、さらに粉砕処理した。得られた混合
粉砕物［Ａ］の平均粒径は０．０８μｍであった。この
混合粉砕物［Ａ］における硫化コバルトの含有量〔Ｃｏ
Ｓ／（ＭｏＳ2＋ＣｏＳ）〕は３５重量％であった。Example 1 As a device for mixing and pulverizing metal sulfides, a pulverizing medium stirring mill was used. The apparatus has an inner volume of 100 ml and is provided with three zirconia stirring blades (diameter 6 mm, length 37 mm) on a SUS stirring shaft. As a grinding medium, zirconia beads (diameter 1 mm) 20
0 g was used. Commercially available cobalt sulfide (average particle size of about 5.5
μm) was charged into a pulverizer and pulverized for 50 hours, and then commercially available molybdenum sulfide (average particle size 2.6 μm)
m) 4 g was charged and further pulverized. The average particle diameter of the obtained mixed and crushed product [A] was 0.08 μm. The content of cobalt sulfide [Co
S / (MoS 2 + CoS)] was 35% by weight.
【００１３】実施例２ 実施例１において、硫化コバルトと硫化モリブデンの重
量比を変化させた以外は同様にして混合粉砕物［Ａ−
２］を得た。この混合粉砕物［Ａ−２］における硫化コ
バルトの含有量は５０重量％であった。Example 2 The same procedure as in Example 1 was carried out except that the weight ratio of cobalt sulfide to molybdenum sulfide was changed.
2] was obtained. The content of cobalt sulfide in this mixed ground product [A-2] was 50% by weight.
【００１４】実施例３ 実施例１において、硫化コバルトと硫化モリブデンの重
量比を変化させた以外は同様にして混合粉砕物［Ａ−
３］を得た。この混合粉砕物［Ａ−３］における硫化コ
バルトの含有量は６５重量％であった。Example 3 The same procedure as in Example 1 was carried out except that the weight ratio of cobalt sulfide to molybdenum sulfide was changed.
3] was obtained. The content of cobalt sulfide in this ground mixture [A-3] was 65% by weight.
【００１５】実施例４ 市販の硫化ニッケル（平均粒径約５μｍ）２ｇを粉砕装
置に充填し、５０時間かけて粉砕処理した後、市販の硫
化モリブデン（平均粒径２．６μｍ）４ｇを充填し、さ
らに粉砕処理した。得られた混合粉砕物［Ｂ］の平均粒
径は０．０６μｍであった。この混合粉砕物［Ｂ］にお
ける硫化モリブデンの含有量〔ＭｏＳ2／（ＭｏＳ2＋Ｎ
ｉＳ）〕は３５重量％であった。Example 4 2 g of commercially available nickel sulfide (average particle size: about 5 μm) was charged into a pulverizer, pulverized for 50 hours, and then charged with 4 g of commercially available molybdenum sulfide (average particle size: 2.6 μm). And further pulverized. The average particle size of the obtained mixed and crushed product [B] was 0.06 μm. Molybdenum sulfide content [MoS 2 / (MoS 2 + N
iS)] was 35% by weight.
【００１６】実施例５ 実施例４において、硫化ニッケルと硫化モリブデンの重
量比を変化させた以外は同様にして混合粉砕物［Ｂ−
２］を得た。この混合粉砕物［Ｂ−２］における硫化モ
リブデンの含有量は５０重量％であった。Example 5 The same procedure as in Example 4 was carried out except that the weight ratio of nickel sulfide to molybdenum sulfide was changed.
2] was obtained. The content of molybdenum sulfide in the mixed and ground product [B-2] was 50% by weight.
【００１７】実施例６ 実施例４において、硫化ニッケルと硫化モリブデンの重
量比を変化させた以外は同様にして混合粉砕物［Ｂ−
３］を得た。この混合粉砕物［Ｂ−３］における硫化モ
ルブデンの含有量は６５重量％であった。Example 6 The same procedure as in Example 4 was carried out except that the weight ratio of nickel sulfide to molybdenum sulfide was changed.
3] was obtained. The content of molybdenum sulfide in this ground mixture [B-3] was 65% by weight.
【００１８】比較例１ 硫化コバルト及び硫化モリブデンをそれぞれ別々に粉砕
した後、両者を均一混合して、その平均粒径が０．０５
μｍの単純混合物［Ｃ］を得た。この単純混合物におけ
る硫化コバルトの含有量〔ＣｏＳ／（ＣｏＳ＋Ｍｏ
Ｓ2）〕は３５重量％であった。COMPARATIVE EXAMPLE 1 Cobalt sulfide and molybdenum sulfide were separately ground, and then both were uniformly mixed to have an average particle diameter of 0.05.
A μm simple mixture [C] was obtained. The content of cobalt sulfide in this simple mixture [CoS / (CoS + Mo
S 2 )] was 35% by weight.
【００１９】比較例２ 比較例１において、硫化コバルトと硫化モリブデンの重
量比を変化させた以外は同様にして単純混合物［Ｃ−
２］を得た。この単純混合物［Ｃ−２］における硫化コ
バルトの含有量は５０重量％であった。Comparative Example 2 The same procedure as in Comparative Example 1 was carried out except that the weight ratio between cobalt sulfide and molybdenum sulfide was changed.
2] was obtained. The content of cobalt sulfide in this simple mixture [C-2] was 50% by weight.
【００２０】比較例３ 比較例１において、硫化コバルトと硫化モリブデンの重
量比を変化させた以外は同様にして単純混合物［Ｃ−
３］を得た。この単純混合物［Ｃ−３］における硫化コ
バルトの含有量は６５重量％であった。Comparative Example 3 In the same manner as in Comparative Example 1, except that the weight ratio between cobalt sulfide and molybdenum sulfide was changed, a simple mixture [C-
3] was obtained. The content of cobalt sulfide in this simple mixture [C-3] was 65% by weight.
【００２１】比較例４ 硫化ニッケル及び硫化モリブデンをそれぞれ別々に粉砕
した後、両者を均一混合して、その平均粒径が０．１２
μｍの単純混合物［Ｄ］を得た。この単純混合物におけ
る硫化モリブデンの含有量〔ＭｏＳ2／（ＮｉＳ＋Ｍｏ
Ｓ2）〕は３５重量％であった。Comparative Example 4 Nickel sulfide and molybdenum sulfide were separately pulverized, and then both were uniformly mixed to have an average particle size of 0.12.
A μm simple mixture [D] was obtained. The content of molybdenum sulfide in this simple mixture [MoS 2 / (NiS + Mo
S 2 )] was 35% by weight.
【００２２】比較例５ 比較例４において、硫化ニッケルと硫化モリブデンの重
量比を変化させた以外は同様にして単純混合物［Ｄ−
２］を得た。この単純混合物［Ｄ−２］における硫化モ
リブデンの含有量は５０重量％であった。Comparative Example 5 The same procedure as in Comparative Example 4 was carried out except that the weight ratio between nickel sulfide and molybdenum sulfide was changed.
2] was obtained. The content of molybdenum sulfide in this simple mixture [D-2] was 50% by weight.
【００２３】比較例６ 比較例４において、硫化ニッケルと硫化モリブデンの重
量比を変化させた以外は同様にして単純混合物［Ｄ−
３］を得た。この単純混合物［Ｄ−３］における硫化モ
リブデンの含有量は６５重量％であった。Comparative Example 6 The same procedure as in Comparative Example 4 was carried out except that the weight ratio between nickel sulfide and molybdenum sulfide was changed.
3] was obtained. The content of molybdenum sulfide in this simple mixture [D-3] was 65% by weight.
【００２４】応用例１ 実施例１〜比較例６で得た混合硫化物触媒の水素化活性
を以下のようにして評価した。内容積５０ｍｌのＳＵＳ
３１６製のマイクロオートクレーブに１−メチルナフタ
レン（以下、単に１−ＭＮとも略記する）５ｇと触媒
０．１５ｇから（３ｗｔ％）を充填し、反応温度３５０
℃、水素初期圧（室温）８ＭＰａ、反応時間６０分の条
件で１−ＭＮの水素化実験を行なった。その結果を表１
に示す。Application Example 1 The hydrogenation activity of the mixed sulfide catalysts obtained in Examples 1 to 6 was evaluated as follows. SUS with an inner volume of 50 ml
A 316 micro autoclave was charged with 5 g of 1-methylnaphthalene (hereinafter simply referred to as 1-MN) and 0.15 g of a catalyst (3 wt%), and a reaction temperature of 350 g.
A 1-MN hydrogenation experiment was performed under the conditions of ° C, an initial hydrogen pressure (room temperature) of 8 MPa, and a reaction time of 60 minutes. Table 1 shows the results.
Shown in
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１に示した結果からわかるように、本発
明による金属硫化物の混合粉砕物は、金属硫化物の単純
混合物よりも顕著な水素化活性を有することがわかる。As can be seen from the results shown in Table 1, the mixed and ground metal sulfide according to the present invention has a remarkable hydrogenation activity more than the simple mixture of metal sulfides.
【００２７】応用例２ 応用例１において、触媒の使用量を０．０５ｇ（１ｗｔ
％）にした以外は同様にして実験を行った。その結果を
表２に示す。Application Example 2 In application example 1, the amount of the catalyst used was 0.05 g (1 wt.
%), Except that the experiment was performed. Table 2 shows the results.
【００２８】[0028]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 湯村 守雄 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 大嶋 哲 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 伊ヶ崎 文和 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 Ｆターム(参考） 4G069 AA02 AA08 AA15 BB09A BB09B BC59A BC59B BC67A BC67B BC68A BC68B BD08A BD08B CC02 CC05 DA03 EA01X EA01Y EB18Y FB07 4H029 CA00 DA00 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Morio Yumura 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Tetsu Oshima 1-1-1, Higashi, Tsukuba, Ibaraki, Japan Within the Institute of Engineering Technology (72) Inventor Fumiwa Igasaki 1-1-1, Higashi, Tsukuba, Ibaraki Pref. CC05 DA03 EA01X EA01Y EB18Y FB07 4H029 CA00 DA00
Claims (4)
粉砕化物からなることを特徴とする水素化触媒。1. A hydrogenation catalyst comprising a mixed and pulverized product of molybdenum sulfide and cobalt sulfide.
粉砕化物からなることを特徴とする水素化触媒。2. A hydrogenation catalyst comprising a mixture of pulverized molybdenum sulfide and nickel sulfide.
硫化モリブテンを添加して混合粉砕することを特徴とす
る請求項１の水素化触媒の製造方法。3. After pulverizing cobalt sulfide in advance,
The method for producing a hydrogenation catalyst according to claim 1, wherein molybdenum sulfide is added and mixed and pulverized.
硫化モリブテンを添加して混合粉砕することを特徴とす
る請求項２の水素化触媒の製造方法。4. After pulverizing nickel sulfide in advance,
3. The method for producing a hydrogenation catalyst according to claim 2, wherein molybdenum sulfide is added and mixed and pulverized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05327099A JP3153903B2 (en) | 1999-03-01 | 1999-03-01 | Method for producing hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05327099A JP3153903B2 (en) | 1999-03-01 | 1999-03-01 | Method for producing hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000246110A true JP2000246110A (en) | 2000-09-12 |
| JP3153903B2 JP3153903B2 (en) | 2001-04-09 |
Family
ID=12938069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05327099A Expired - Lifetime JP3153903B2 (en) | 1999-03-01 | 1999-03-01 | Method for producing hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3153903B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824228A (en) * | 2017-03-21 | 2017-06-13 | 合肥工业大学 | A kind of flower-shaped cobalt sulfide photochemical catalyst and preparation method thereof |
| CN109046383A (en) * | 2018-07-31 | 2018-12-21 | 山东大学 | A kind of MoS2/Ni3S2Electrode material and its preparation method and application |
-
1999
- 1999-03-01 JP JP05327099A patent/JP3153903B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824228A (en) * | 2017-03-21 | 2017-06-13 | 合肥工业大学 | A kind of flower-shaped cobalt sulfide photochemical catalyst and preparation method thereof |
| CN106824228B (en) * | 2017-03-21 | 2019-06-18 | 合肥工业大学 | A kind of flower-shaped cobalt sulfide photochemical catalyst and preparation method thereof |
| CN109046383A (en) * | 2018-07-31 | 2018-12-21 | 山东大学 | A kind of MoS2/Ni3S2Electrode material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3153903B2 (en) | 2001-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1799343B1 (en) | Highly active slurry catalyst composition | |
| O’Brien et al. | Activity, selectivity and attrition characteristics of supported iron Fischer–Tropsch catalysts | |
| EA012332B1 (en) | Process for upgrading heavy oil using a highly active slurry catalyst composition | |
| CN100586562C (en) | Method of preparing catalyst support from waste catalyst | |
| JPS63146989A (en) | Hydrogeneration of heavy oil and residual oil | |
| CN102380396A (en) | Bimetal or multi-metal high-dispersion composite coal tar hydrogenation catalyst and preparation method thereof | |
| KR20070057825A (en) | Process for upgrading heavy oil using a highly active slurry catalyst composition | |
| CN105312056B (en) | Catalyst based on natural minerals and the gasification process using the catalyst | |
| CN108348901A (en) | A method of control graphite form | |
| CN105289750B (en) | A kind of oil-soluble hydrogenation catalyst and its preparation method and application | |
| CN103289722B (en) | Recycling method of iron-based waste catalyst for Fischer-Tropsch synthesis and direct coal liquefaction reaction catalyst | |
| WO2015121371A1 (en) | Process for hydrocracking heavy oil and oil residue with a non-metallised carbonaceous additive | |
| JPS5853983A (en) | Coal liquification | |
| JP3153903B2 (en) | Method for producing hydrogenation catalyst | |
| US3594305A (en) | Process for hydrogenation of coal | |
| JPH05501829A (en) | High activity slurry catalyst method | |
| JPH02107335A (en) | Hydrocracking of heavy oil in presence of petroleum coke rulting from operation of heavy oil coke | |
| JPS5879092A (en) | Hydrogenation of heavy hydrocarbon oil | |
| CN108456550B (en) | External circulation type reaction device and kerosene co-refining method | |
| WO2011066257A2 (en) | Hydrogenation of solid carbonaceous materials using mixed catalysts | |
| CA2781305A1 (en) | Hydrogenation of solid carbonaceous materials using mixed catalysts | |
| CN107790195B (en) | Reduction method of iron-based Fischer-Tropsch catalyst | |
| JP4149280B2 (en) | Method for producing coal liquefied highly active catalyst | |
| CN102049310B (en) | Hydrodesulphurization catalyst, preparation method and application thereof in hydrodesulphurization reaction | |
| CN113318772B (en) | Nitrided molten iron catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |