JPH0598271A - Hydrocracking of hydrocarbon - Google Patents
Hydrocracking of hydrocarbonInfo
- Publication number
- JPH0598271A JPH0598271A JP3289467A JP28946791A JPH0598271A JP H0598271 A JPH0598271 A JP H0598271A JP 3289467 A JP3289467 A JP 3289467A JP 28946791 A JP28946791 A JP 28946791A JP H0598271 A JPH0598271 A JP H0598271A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- aluminosilicate
- periodic table
- inorganic oxide
- group
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【産業上の利用分野】本発明は、炭化水素類、特には減
圧軽油、重油等の重質炭化水素類を水素化分解する方法
に関する。TECHNICAL FIELD The present invention relates to a method for hydrocracking hydrocarbons, particularly heavy hydrocarbons such as vacuum gas oil and heavy oil.
【０００２】[0002]
【従来の技術】近年、石油精製においては、処理する原
油が重質化する傾向にあり、しかも需要は白油化、軽質
化が進行し、需給のバランスを取るために重質留分の軽
質留分への転化が図られている。2. Description of the Related Art In recent years, in petroleum refining, the crude oil to be processed has tended to become heavier, and the demand for white oil has become lighter and lighter. Conversion to fractions is being attempted.
【０００３】この転化のための技術は多数開発されてい
るが、その中でも、減圧軽油、重油等の重質炭化水素類
の水素化分解は、良質の軽質油が得られ、二次処理等も
必要がないため、最も好ましい方法と考えられている。Many techniques for this conversion have been developed. Among them, the hydrocracking of heavy hydrocarbons such as vacuum gas oil and heavy oil gives high quality light oil, and secondary treatment is also possible. It is considered the most preferred method because it is not necessary.
【０００４】この水素化分解方法は、従来、アルミナ等
のアモルファスな無機酸化物担体或いは結晶性アルミノ
けい酸塩ゼオライト含有担体に活性金属を担持させた触
媒が用いられている。前記アモルファスな無機酸化物担
体からなる触媒を用いる方法は、高沸点留分の分解性に
優れ中間留分収率が高いが、この高分解率を達成するた
めには高温が必要で、この高温のために脱硫活性や脱窒
素活性の劣化が著しく速くなり、触媒寿命が短くなると
いう欠点があった。一方、ゼオライト含有担体は、上記
アモルファスな無機酸化物担体触媒に比べて、１０〜２
０℃低い温度で高分解率を得ることができるが、重質炭
化水素中の重金属、残留炭素、アスファルテン等による
被毒を受けやすく、分解活性の劣化が速いという欠点を
有する。In this hydrocracking method, conventionally, a catalyst in which an active metal is supported on an amorphous inorganic oxide carrier such as alumina or a carrier containing a crystalline aluminosilicate zeolite is used. The method using a catalyst composed of the amorphous inorganic oxide carrier is excellent in decomposability of high-boiling fractions and high in the yield of middle distillates, but high temperature is required to achieve this high decomposition rate. Therefore, the desulfurization activity and the denitrification activity are significantly deteriorated, and the catalyst life is shortened. On the other hand, the zeolite-containing carrier is 10 to 2 compared with the above amorphous inorganic oxide carrier catalyst.
Although it is possible to obtain a high decomposition rate at a temperature as low as 0 ° C., it has a drawback that it is easily poisoned by heavy metals, residual carbon, asphaltene, etc. in heavy hydrocarbons and its decomposition activity deteriorates rapidly.
【０００５】このため、無機酸化物と周期律表第VI族金
属成分及び周期律表第VIII族金属成分からなる前処理触
媒で水素化処理し、しかるのち、所定の結晶性アルミノ
けい酸塩ゼオライトと無機酸化物、周期律表第VI族金属
成分、同第VIII族金属成分、リン、ホウ素等からなる触
媒で水素化分解する方法が提案されている(特開昭６１
−１２６１９６号公報)。しかし、この方法は、分解性
能、灯軽油留分収率などで必ずしも満足のいくものでは
ない。For this reason, a hydrogenation treatment is carried out with a pretreatment catalyst comprising an inorganic oxide, a Group VI metal component of the Periodic Table and a Group VIII metal component of the Periodic Table, and then a predetermined crystalline aluminosilicate zeolite is used. A method has been proposed in which hydrogenolysis is carried out with a catalyst composed of an inorganic oxide, a group VI metal component of the periodic table, a group VIII metal component of the periodic table, phosphorus, boron, and the like (JP-A-61).
-126196 publication). However, this method is not always satisfactory in terms of cracking performance, kerosene gas oil fraction yield, and the like.
【０００６】[0006]
【発明が解決しようとする課題】一般に、結晶性アルミ
ノけい酸塩であるゼオライトとアルミナ等の無機酸化物
マトリックスとからなる担体を、ｐＨ値が３.０以下の
周期律表第VI族金属化合物、第VIII族金属化合物および
リンの水溶液と接触させると、強い酸性条件下であるた
め、ゼオライトの結晶構造は破壊されてしまい、水素化
分解活性は著しく低下する。Generally, a carrier composed of a crystalline aluminosilicate zeolite and an inorganic oxide matrix such as alumina is used as a carrier of a Group VI metal compound having a pH value of 3.0 or less. When brought into contact with an aqueous solution of a Group VIII metal compound and phosphorus, the crystal structure of zeolite is destroyed due to the strongly acidic condition, and the hydrocracking activity is significantly reduced.
【０００７】このため、ゼオライト結晶構造の破壊を避
けるために、ｐＨ値が３より高い水溶液を用いる方法が
提案されている(特開昭５９-２１６６３５号公報)。し
かし、この方法では、無機酸化物マトリックスの等電点
が低い場合、担体上に均質に担持できない。また、ｐＨ
が３より高い水溶液中ではリンと周期律表第VI族金属成
分は一部は重合錯体を形成するが、一部は単核イオンと
して存在する。この単核イオンはゼオライト細孔内に入
り、ゼオライトの結晶構造を一部破壊し、分解活性の低
下を招くことが知られている(例えば、特開昭５９-２１
６６３５号公報、特公昭５９-４００５８号公報参照)。Therefore, in order to avoid the destruction of the zeolite crystal structure, a method of using an aqueous solution having a pH value higher than 3 has been proposed (JP-A-59-216635). However, in this method, when the inorganic oxide matrix has a low isoelectric point, it cannot be supported uniformly on the carrier. Also, the pH
In an aqueous solution having a value of higher than 3, phosphorus and Group VI metal components of the Periodic Table partially form a polymer complex, but some exist as mononuclear ions. It is known that these mononuclear ions enter the pores of the zeolite and partially destroy the crystal structure of the zeolite, leading to a decrease in the decomposition activity (for example, JP-A-59-21).
(See Japanese Patent No. 6635 and Japanese Patent Publication No. 59-40058).
【０００８】本発明者は、かかる問題を解決するために
鋭意検討した結果、Ｙ型ゼオライトを特定の処理をし、
所定の格子定数を有する結晶性アルミノシリケートとし
たものを用いると、初期ｐＨ値が３.０以下の水溶液と
接触させても、結晶構造の崩壊を起こさず、しかもこの
方法で調製した触媒を用いて炭化水素類の水素化分解反
応を行なったところ、極めて高い分解活性と灯軽油留分
収率を得られることを見出した。The present inventor has conducted extensive studies in order to solve such a problem, and as a result, treated the Y-type zeolite with a specific treatment,
If a crystalline aluminosilicate having a predetermined lattice constant is used, even if it is brought into contact with an aqueous solution having an initial pH value of 3.0 or less, the crystal structure does not collapse, and the catalyst prepared by this method is used. When hydrocracking reaction of hydrocarbons was carried out, it was found that extremely high cracking activity and kerosene gas oil fraction yield could be obtained.
【０００９】また、上記触媒で水素化分解する前に、無
機酸化物担体に活性金属を担持した触媒を用いて水素化
処理を行うと、上記触媒の被毒を著しく低減でき、高い
分解活性を長期に渡って維持できることが分かった。If hydrogenation is carried out using a catalyst in which an active metal is supported on an inorganic oxide carrier before hydrocracking with the above catalyst, poisoning of the above catalyst can be remarkably reduced and high decomposition activity can be achieved. It turns out that it can be maintained for a long time.
【００１０】本発明はかかる知見に基づきなされたもの
で、本発明の目的は灯軽油留分の収率が高く、しかも長
期に渡って運転が可能な水素化分解方法を提供するもの
である。The present invention has been made on the basis of such findings, and an object of the present invention is to provide a hydrocracking method which has a high yield of a kerosene gas oil fraction and which can be operated for a long period of time.
【００１１】[0011]
【課題を解決するための手段】本発明は、炭化水素類
を、周期律表第VI族及び周期律表第VIII族に属する金属
の少なくとも１種を無機酸化物担体に担持した第１の触
媒を用いて、３３０〜４００℃の温度で水素化処理し、
次いで、Ｎａ2Ｏの含有量が０.３重量％以下、ＳｉＯ2
／Ａｌ2Ｏ3のモル比が５〜９で、かつ格子定数が２４.
４２乃至２４.３０Åの結晶性アルミノシリケート及び
／又は前記格子定数が２４.４２乃至２４.３０Åの結晶
性アルミノシリケートを遷移金属含有溶液で処理した遷
移金属含有アルミノシリケートと無機酸化物マトリック
スとからなる担体に周期律表第VI族に属する金属の少な
くとも１種とリンとを含むｐＨ３以下の水溶液を含浸、
乾燥させた後、或いは乾燥させることなく、周期律表第
VIII族に属する金属の少なくとも１種を含む水溶液を含
浸、乾燥、焼成して得られた第２の触媒を用いて、３６
０〜４２０℃の温度で水素化分解する方法である。The present invention provides a first catalyst in which at least one metal belonging to Group VI and Group VIII of the Periodic Table of Hydrocarbons is supported on an inorganic oxide carrier. Is hydrotreated at a temperature of 330 to 400 ° C.,
Next, the content of Na 2 O is 0.3 wt% or less, SiO 2
/ Al 2 O 3 molar ratio is 5-9, and the lattice constant is 24.
42 to 24.30Å crystalline aluminosilicate and / or crystalline aluminosilicate having a lattice constant of 24.42 to 24.30Å treated with a transition metal-containing solution, and a transition metal-containing aluminosilicate and an inorganic oxide matrix The carrier is impregnated with an aqueous solution of pH 3 or less containing at least one metal belonging to Group VI of the periodic table and phosphorus.
After drying or without drying,
Using a second catalyst obtained by impregnating with an aqueous solution containing at least one metal belonging to Group VIII, drying and firing, 36
It is a method of hydrocracking at a temperature of 0 to 420 ° C.
【００１２】本発明は、原油、石炭液化油、シェールオ
イル等から得られる炭化水素類、全てを原料とすること
ができるが、特には、これらの蒸圧蒸留残油、減圧蒸留
軽油、減圧蒸留残油等、残留炭素、アスファルテンを含
有するものが好適である。In the present invention, all hydrocarbons obtained from crude oil, coal liquefied oil, shale oil, etc. can be used as raw materials, but in particular, steam distillation residual oil, vacuum distillation gas oil, vacuum distillation of these Those containing residual carbon such as residual oil and asphaltene are preferable.
【００１３】上記本発明の第１の触媒とは、従来公知の
無機酸化物担体、例えば、アルミナ、シリカ、チタニ
ア、ボリア、ジルコニア、マグネシアの１種あるいは２
種以上の耐火性無機酸化物からなる担体に、周期律表第
VI族金属、例えばモリブデンまたはタングステン及び周
期律表第VIII族金属、例えばコバルトまたはニッケルの
いずれか１種または２種以上を８〜２０重量％担持した
もので、特には、アルミナ担体に６〜１５重量％のモリ
ブデン及び２〜５重量％のニッケルまたはコバルトを担
持したものを用いることが好ましい。この触媒は、１５
０m2/g以上の表面積、０.５〜０.８ml/gの細孔容積、８
０〜１５０Åの平均細孔直径を有するものが好ましい。The first catalyst of the present invention is a conventionally known inorganic oxide carrier, for example, one or two of alumina, silica, titania, boria, zirconia and magnesia.
A carrier consisting of one or more refractory inorganic oxides and a periodic table
A Group VI metal such as molybdenum or tungsten and a Group VIII metal of the periodic table, such as cobalt or nickel, supported on 8 to 20% by weight, and particularly on an alumina carrier of 6 to 15%. It is preferable to use one supporting molybdenum by weight and 2 to 5% by weight of nickel or cobalt. This catalyst is 15
Surface area of 0 m 2 / g or more, pore volume of 0.5 to 0.8 ml / g, 8
Those having an average pore diameter of 0 to 150Å are preferred.
【００１４】また、特には上記無機酸化物に、リン及び
／またはホウ素を０.０１〜３重量％含有或いは担持さ
せたものが、重質炭化水素油の水素添加処理能力に優
れ、第２触媒の劣化抑制に効果的であり、好ましい。In particular, the above-mentioned inorganic oxide containing or supporting phosphorus and / or boron in an amount of from 0.01 to 3% by weight is excellent in the hydrogenation treatment capacity of heavy hydrocarbon oils, and is the second catalyst. It is effective and effective in suppressing deterioration, and is preferable.
【００１５】一方、本発明の第２の触媒は、Ｎａ2Ｏの
含有量が０.３重量％以下で、ＳｉＯ2／Ａｌ2Ｏ3のモル
比が５〜９で、かつ格子定数が２４.４２乃至２４.３０
Åの結晶性アルミノシリケートを用いて調製されるもの
である。On the other hand, the second catalyst of the present invention has a Na 2 O content of 0.3% by weight or less, a SiO 2 / Al 2 O 3 molar ratio of 5 to 9, and a lattice constant of 24. .42 to 24.30
It is prepared using Å crystalline aluminosilicate.
【００１６】この場合、Ｎａ2Ｏが０.３重量％以上であ
るとｐＨ３以下の水溶液と接触したときに結晶構造の崩
壊が生じ、分解活性が低下し、灯軽油留分の収率が減少
する。また、ＳｉＯ2／Ａｌ2Ｏ3のモル比が５以下であ
れば骨格が十分に安定化されておらず、前記のＮａ2Ｏ
の場合と同様に酸により結晶崩壊を生じ、さらに９以上
では酸性点の減少により分解活性が低下する。さらに格
子定数が２４.４２Å以上でも、前記と同様酸との接触
により結晶構造の崩壊が生じ、格子定数が２４.３０Å
以下では結晶性が悪く、酸量も少ないことから同様に分
解活性が低下し、灯軽油留分の収率が減少する。尚、格
子定数とはＸ線回折法により得られた面間隔ｄの値よ
り、次式数１で算出されるものである。In this case, when the content of Na 2 O is 0.3% by weight or more, the crystal structure is disintegrated when it comes into contact with an aqueous solution having a pH of 3 or less, the decomposition activity is lowered, and the yield of the kerosene gas oil fraction is reduced. To do. Further, if the SiO 2 / Al 2 O 3 molar ratio is 5 or less, the skeleton is not sufficiently stabilized, and the Na 2 O
In the same manner as in the case of 1, the acid causes crystal collapse, and when it is 9 or more, the decomposition activity decreases due to the decrease of the acid point. Further, even if the lattice constant is 24.42 Å or more, the crystal structure collapses due to contact with an acid as described above, and the lattice constant is 24.30 Å
In the following, the crystallinity is poor and the amount of acid is small, so that the cracking activity is similarly reduced and the yield of kerosene gas oil fraction is reduced. The lattice constant is calculated by the following equation 1 from the value of the interplanar spacing d obtained by the X-ray diffraction method.
【数１】 [Equation 1]
【００１７】このような特性を有する結晶性アルミノシ
リケートは、Ｙ型ゼオライトから調製することができ
る。このＹ型ゼオライトとしては、アルミニウムとケイ
素の比率が１：２.２〜１：３.０のもので、フォージャ
サイト構造を有するものであれば、製法の如何にかかわ
らず、いずれをも支障なく用いることができる。このＹ
型ゼオライトを、先ず、脱アルカリ処理し、ついで水蒸
気処理及び／又は酸処理することにより、上記特性の結
晶性アルミノシリケートを得ることができる。The crystalline aluminosilicate having such characteristics can be prepared from Y-type zeolite. As this Y-type zeolite, if the ratio of aluminum to silicon is 1: 2.2 to 1: 3.0, and it has a faujasite structure, it does not matter which method is used. Can be used without. This Y
The crystalline aluminosilicate having the above characteristics can be obtained by first subjecting the type zeolite to dealkalization, and then steam treatment and / or acid treatment.
【００１８】尚、上記脱アルカリ処理は、例えば、Ｙ型
ゼオライトをアンモニア含有溶液等に浸漬処理して、Ｎ
ａ+のようなアルカリ金属を、アンモニウムイオン等に
よりイオン交換しこれを焼成する、この一連の処理を数
回くりかえすことにより行うことにより、Ｎａ2Ｏを０.
３重量％以下とすることができる。The dealkalizing treatment may be carried out, for example, by dipping the Y-type zeolite in an ammonia-containing solution, etc.
The alkali metal such as a + is ion-exchanged with ammonium ion or the like and baked, and this series of treatments is repeated several times, whereby Na 2 O is reduced to 0.
It can be 3% by weight or less.
【００１９】また、水蒸気処理は上記脱アルカリしたゼ
オライトを、好ましくは５００〜８００℃の温度の水蒸
気と接触させる方法により行うことができる。さらに酸
処理はｐＨ３以下の硝酸水溶液等に浸漬することにより
行うとよい。この水蒸気処理と酸処理はどちらか一方で
も良いが、両処理を併用することにより部分的な脱アル
ミニウムを行ない、ＳｉＯ2／Ａｌ2Ｏ3のモル比が５〜
９のものが得られ、これを乾燥、焼成により、上記格子
定数を有する結晶性アルミノシリケートを調製すること
ができる。The steam treatment can be carried out by a method of bringing the dealkalized zeolite into contact with steam at a temperature of preferably 500 to 800 ° C. Further, the acid treatment may be performed by immersing in an aqueous nitric acid solution having a pH of 3 or less. Either one of the steam treatment and the acid treatment may be used, but by using both treatments together, partial dealumination is performed, and the molar ratio of SiO 2 / Al 2 O 3 is 5 to 5.
No. 9 is obtained, which is dried and calcined to prepare a crystalline aluminosilicate having the above-mentioned lattice constant.
【００２０】また、このようにして得られる所定の特性
を有する結晶性アルミノシリケートは、亜鉛、銅、鉄、
コバルト、ニッケル、チタン、バナジウム、ジルコニ
ア、カドミウム、スズ、鉛等の遷移金属の塩を含有する
溶液に浸漬することにより、これらのイオンを導入し、
遷移金属含有アルミノシリケートとすることができる。
この遷移金属含有アルミノシリケートを上記結晶性アル
ミノシリケートに代えて第２の触媒の調製のために用い
ることもできる。この場合、遷移金属としては、特に亜
鉛が好ましい。この遷移金属含有アルミノシリケート
は、上記の結晶性アルミノシリケートと混合して用いて
も良い。Further, the crystalline aluminosilicate having the predetermined characteristics obtained in this way is composed of zinc, copper, iron,
Cobalt, nickel, titanium, vanadium, zirconia, cadmium, tin, by introducing these ions by immersing in a solution containing a salt of a transition metal such as lead,
It can be a transition metal-containing aluminosilicate.
This transition metal-containing aluminosilicate can be used in place of the above crystalline aluminosilicate for the preparation of the second catalyst. In this case, zinc is particularly preferable as the transition metal. This transition metal-containing aluminosilicate may be used as a mixture with the above crystalline aluminosilicate.
【００２１】上記結晶性アルミノシリケート及び／又は
遷移金属含有結晶性アルミノシリケートは、無機酸化物
マトリックスと混合して担体とする。この担体の調製
は、常法によって行うことができる。すなわち、上記の
格子定数を有する結晶性アルミノシリケート及び／又は
遷移金属含有アルミノシリケートと無機酸化物マトリッ
クスのヒドロゲルとを十分に混合し、所定の形状に成形
し、常温乃至１５０℃、好ましくは、１００〜１３０℃
で０.５時間以上乾燥した後、３５０〜８００℃、好ま
しくは、４５０〜６００℃で０.５時間以上焼成するこ
とにより担体を得ることができる。この場合、結晶性ア
ルミノシリケート及び／又は遷移金属含有結晶性アルミ
ノシリケートを５〜９０重量％、特には、２０〜５０重
量％、無機酸化物マトリックスを９５〜１０重量％とす
ることが触媒の活性及び寿命上、好ましい。また、無機
酸化物マトリックスとしては、アルミナ、シリカ−アル
ミナ、チタニア−アルミナ、ジルコニア−アルミナな
ど、多孔質で、非晶質のものが好適に用いられる。これ
らの無機酸化物マトリックスは活性金属の担持物として
働くと共に、上記結晶性アルミノシリケート及び／又は
遷移金属含有結晶性アルミノシリケートのバインダーと
して働き、触媒の強度を向上させる役割がある。このマ
トリックスの表面積は３０m2／g以上とすることが望ま
しい。The crystalline aluminosilicate and / or the transition metal-containing crystalline aluminosilicate are mixed with an inorganic oxide matrix to form a carrier. The carrier can be prepared by a conventional method. That is, a crystalline aluminosilicate and / or a transition metal-containing aluminosilicate having the above-mentioned lattice constant and a hydrogel of an inorganic oxide matrix are thoroughly mixed and molded into a predetermined shape at room temperature to 150 ° C, preferably 100 ~ 130 ° C
The carrier can be obtained by drying it for 0.5 hours or more and then calcining at 350 to 800 ° C., preferably 450 to 600 ° C. for 0.5 hour or more. In this case, it is preferable that the crystalline aluminosilicate and / or the transition metal-containing crystalline aluminosilicate is 5 to 90% by weight, particularly 20 to 50% by weight, and the inorganic oxide matrix is 95 to 10% by weight. Also, it is preferable in terms of life. As the inorganic oxide matrix, porous, amorphous ones such as alumina, silica-alumina, titania-alumina and zirconia-alumina are preferably used. These inorganic oxide matrices function not only as a support for the active metal but also as a binder for the crystalline aluminosilicate and / or the transition metal-containing crystalline aluminosilicate, and have the role of improving the strength of the catalyst. The surface area of this matrix is preferably 30 m 2 / g or more.
【００２２】次に、このようにして得られる担体にリン
と第VI族の金属成分を含有したｐＨ３以下の水溶液を含
浸させる。リンと第VI族の金属成分を含有した水溶液の
ｐＨを３以下とすることにより、第VI族の金属イオンの
大部分が重合錯体として存在する。この重合錯体の形成
により、第VI族の金属イオンが上記結晶性アルミノシリ
ケート及び遷移金属含有アルミノシリケートのゼオライ
ト固有の細孔内に入ることはなくなり、これらの結晶構
造を破壊し、分解活性を低下させることがなくなる。実
際には、かかる水溶液の含浸の際にも、３〜２０％程度
の結晶性の低下が見られるが、この程度では、分解性
能、脱硫性能、脱窒素性能において、大きな性能低下は
認められない。Next, the carrier thus obtained is impregnated with an aqueous solution containing phosphorus and a Group VI metal component and having a pH of 3 or less. By adjusting the pH of the aqueous solution containing phosphorus and the Group VI metal component to 3 or less, most of the Group VI metal ions are present as a polymer complex. The formation of this polymer complex prevents Group VI metal ions from entering the zeolite-specific pores of the crystalline aluminosilicates and transition metal-containing aluminosilicates, destroying their crystal structure and reducing the decomposition activity. There is nothing to do. In reality, even when impregnating with such an aqueous solution, a decrease in crystallinity of about 3 to 20% is observed, but at such an extent, no major decrease in performance is observed in decomposition performance, desulfurization performance, and denitrification performance. ..
【００２３】尚、上記含浸する第VI族金属成分は、パラ
モリブデン酸アンモニウム、モリブデン酸、モリブデン
酸アンモニウム、リンモリブデン酸、タングステン酸ア
ンモニウム、タングステン酸、無水タングステン酸、タ
ングストリン酸などの化合物を水溶液として用いるとよ
い。また、重合錯体形成のためのリンは、リン酸、亜リ
ン酸、次亜リン酸、リンモリブデン酸、リンタングステ
ン酸などの酸及びそれらの塩などの水溶液が用いられ
る。このうち、リンモリブデン酸、リンタングステン酸
を用いると、リンと第VI族の金属成分が同時に低ＰＨで
重合錯イオンとして担体に担持できるため、操作が簡便
となり、特に好ましい。これらの担持量は、最終触媒組
成物に対し、第VI族金属成分は、その合計量として、酸
化物換算で約５〜２５重量％、リンは同様に０.０５〜
５重量％とすることが好ましい。The impregnated Group VI metal component is an aqueous solution of a compound such as ammonium paramolybdate, molybdic acid, ammonium molybdate, phosphomolybdic acid, ammonium tungstate, tungstic acid, tungstic anhydride, and tungstophosphoric acid. It is good to use as. As the phosphorus for forming the polymer complex, an aqueous solution of an acid such as phosphoric acid, phosphorous acid, hypophosphorous acid, phosphomolybdic acid, phosphotungstic acid, or a salt thereof is used. Of these, phosphomolybdic acid and phosphotungstic acid are particularly preferable because the phosphorus and Group VI metal components can be simultaneously carried on the carrier as polymerized complex ions with a low PH, and the operation is simplified. The loading amount of the Group VI metal component is about 5 to 25% by weight in terms of oxide as a total amount thereof with respect to the final catalyst composition, and phosphorus is similarly 0.05 to 5.
It is preferably 5% by weight.
【００２４】このようにして、担体にリンと第VI族の金
属成分を含浸させた後、常温乃至１５０℃、好ましく
は、１００〜１３０℃で０.５時間以上乾燥させるか、
或いは乾燥させることなくそのまま、第VIII族の金属成
分を含有した水溶液を含浸させ、常温乃至１５０℃、好
ましくは、１００〜１３０℃で０.５時間以上乾燥させ
た後、３５０〜８００℃、好ましくは、４５０〜６００
℃で０.５時間以上焼成することにより、本発明の第２
の触媒を調製することができる。Thus, the carrier is impregnated with phosphorus and the metal component of Group VI and then dried at room temperature to 150 ° C., preferably 100 to 130 ° C. for 0.5 hour or more, or
Alternatively, without being dried, it is directly impregnated with an aqueous solution containing a Group VIII metal component, dried at room temperature to 150 ° C., preferably 100 to 130 ° C. for 0.5 hour or more, and then 350 to 800 ° C., preferably Is 450-600
By firing at 0.5 ° C. for 0.5 hour or longer, the second
Can be prepared.
【００２５】この場合、第VIII族成分の含浸には、ニッ
ケルあるいはコバルトの硝酸塩、硫酸塩、塩化物、フッ
化物、臭化物、酢酸塩、炭酸塩、リン酸塩などの水溶液
が用いられる。この第VIII族金属成分はその合計量とし
て酸化物換算で約０.５〜７重量％とすることが好まし
い。In this case, for impregnation of the Group VIII component, an aqueous solution of nickel or cobalt nitrate, sulfate, chloride, fluoride, bromide, acetate, carbonate, phosphate or the like is used. It is preferable that the total amount of the Group VIII metal component is about 0.5 to 7% by weight in terms of oxide.
【００２６】上記第１の触媒を用いて炭化水素類を水素
化処理する場合、この反応の条件は、温度約３３０〜４
００℃、好ましくは３５０〜３８０℃、水素分圧約２０
〜２００kg／cm2、液空間速度約０.２〜２.０ｈｒ-1、
水素対炭化水素類の比、約２００〜２０００Ｎｌ／ｌの
範囲で選定することが好ましい。一般に、この触媒は、
炭化水素類を処理するに先立ち、硫化水素、二硫化炭素
といった硫黄化合物を含有した炭化水素類で、予備硫化
したのち、用いるとよい。In the case of hydrotreating hydrocarbons using the above-mentioned first catalyst, the condition of this reaction is that the temperature is about 330-4.
00 ° C., preferably 350-380 ° C., hydrogen partial pressure about 20
~ 200 kg / cm 2 , liquid space velocity of about 0.2 to 2.0 hr -1 ,
It is preferable to select a ratio of hydrogen to hydrocarbons in the range of about 200 to 2000 Nl / l. Generally, this catalyst is
Prior to treating the hydrocarbons, it is preferable to pre-sulfide the hydrocarbons containing a sulfur compound such as hydrogen sulfide or carbon disulfide before use.
【００２７】引き続き、上記の水素化処理油を第２の触
媒を用いて水素化分解するが、上記水素化処理油は、そ
のまま水素化分解しても良いが、軽質分を分離した後の
重質分のみを水素化分解してもよい。この反応の条件
は、温度約３６０〜４２０℃、水素分圧約２０〜２００
kg／cm2、液空間速度約０.２〜２.０ｈｒ-1、水素対炭
化水素類の比、約２００〜２０００Ｎｌ／ｌの範囲で選
定することが好ましい。また、この触媒も、炭化水素類
を処理するに先立ち、硫化水素、二硫化炭素といった硫
黄化合物を含有した炭化水素類で、予備硫化したのち、
用いるとよい。Subsequently, the above-mentioned hydrotreated oil is hydrocracked by using a second catalyst. The hydrotreated oil may be hydrocracked as it is, but after the light fraction is separated, it is subjected to heavy cracking. Only the mass may be hydrocracked. The conditions for this reaction are a temperature of about 360 to 420 ° C. and a hydrogen partial pressure of about 20 to 200.
It is preferable to select in the range of kg / cm 2 , liquid hourly space velocity of about 0.2 to 2.0 hr −1 and hydrogen to hydrocarbons ratio of about 200 to 2000 Nl / l. Also, this catalyst is also pre-sulfidized with hydrocarbons containing a sulfur compound such as hydrogen sulfide and carbon disulfide before treating the hydrocarbons,
Good to use.
【００２８】[0028]
【実施例】第２の触媒製造例(触媒Ａ) （ａ）ナトリウム型Ｙ型結晶性アルミノシリケート（Si
O2/Al2O3比２.９、Na2O含量１２.３重量％、格子定数２
４.６０Å）２００ｇを１Ｍの硝酸アンモニウム水溶液
２ｌを用いて、５０℃の温度で、イオン交換し、ろ過、
洗浄し、さらに１３０℃の温度で、３時間乾燥したの
ち、４５０℃の温度で、３時間焼成した。この操作を９
回繰返した結果、Ｎａ2Ｏ含量が０.５重量％に減少し、
SiO2/Al2O3比が５.８、格子定数が２４.５５Åになった
（以下これを「ＳＹ」と称する）。これを７００℃の水
蒸気と３時間接触させ、ｐＨ値約１.５に調製した５０
℃の硝酸水溶液２ｌに２時間浸し、ろ過、洗浄し、１３
０℃で、３時間乾燥した後、４５０℃で、３時間焼成し
た（以下これを「ＵＳＹ」と称する）。このようにして
得られたＵＳＹは、格子定数が、２４.３８Åの値を持
ち、４００m2/gの表面積を有していた。[Example] Second catalyst production example (Catalyst A) (a) Sodium-type Y-type crystalline aluminosilicate (Si
O 2 / Al 2 O 3 ratio 2.9, Na 2 O content 12.3% by weight, lattice constant 2
4.60 Å) 200 g of 2 M of 1 M ammonium nitrate aqueous solution was used for ion exchange at 50 ° C., filtration,
It was washed, further dried at a temperature of 130 ° C. for 3 hours, and then baked at a temperature of 450 ° C. for 3 hours. Do this operation 9
As a result of repeating the process twice, the Na 2 O content was reduced to 0.5% by weight,
The SiO 2 / Al 2 O 3 ratio was 5.8 and the lattice constant was 24.55Å (hereinafter referred to as “SY”). This was brought into contact with steam at 700 ° C for 3 hours to adjust the pH value to about 1.5.
Soak in 2 l of nitric acid aqueous solution at ℃ for 2 hours, filter, wash,
After drying at 0 ° C. for 3 hours, it was baked at 450 ° C. for 3 hours (hereinafter referred to as “USY”). The thus-obtained USY had a lattice constant of 24.38Å and a surface area of 400 m 2 / g.
【００２９】このＵＳＹ１５０gをアルミナ粉末（コン
デア社製アルミナpural ＳＢ）２００ｇと混合し、イオ
ン交換水約２３０ｇを添加して混練し、直径１mm、長さ
５mmの円柱に押し出し成形し、１３０℃で、３時間乾燥
した後、６００℃で２時間焼成して担体とした。150 g of this USY was mixed with 200 g of alumina powder (alumina pural SB manufactured by Condea), about 230 g of ion-exchanged water was added and kneaded, and the mixture was extruded into a cylinder having a diameter of 1 mm and a length of 5 mm at 130 ° C. After drying for 3 hours, it was baked at 600 ° C. for 2 hours to obtain a carrier.
【００３０】（ｂ）この担体にリンモリブデン酸溶液Ａ
（ｐＨ＝０.８５；黄色溶液）を、細孔容積に見合った
量だけの含浸液を用いて担持を行う湿潤法により含浸さ
せ、１３０℃で、３時間乾燥し、５５０℃の温度で、２
時間焼成して触媒とした（触媒Ａ）。この時、リンモリ
ブデン酸溶液は、最終触媒時に、ＭｏＯ3を８.０重量
％、Ｐを０.２重量％含むように濃度を調整した。(B) Phosphomolybdic acid solution A is added to this carrier.
(PH = 0.85; yellow solution) is impregnated by a wetting method in which an amount of the impregnating liquid commensurate with the pore volume is used for supporting, drying at 130 ° C. for 3 hours, and at a temperature of 550 ° C. Two
It was calcined for a time to obtain a catalyst (catalyst A). At this time, the concentration of the phosphomolybdic acid solution was adjusted so that the final catalyst contained 8.0% by weight of MoO 3 and 0.2% by weight of P.
【００３１】第２の比較触媒製造例(触媒Ｂ) 実施例１において、リンモリブデン酸溶液Ａのかわり
に、リンモリブデン酸溶液Ｂ（ｐＨ＝６；無色溶液；溶
液Ａにアンモニア水を添加して、ｐＨを向上させた）を
用いたことを除いては実施例１と同じ方法により、触媒
Ｂを調製した。 Second Comparative Catalyst Production Example (Catalyst B) In Example 1, instead of phosphomolybdic acid solution A, phosphomolybdic acid solution B (pH = 6; colorless solution; ammonia water was added to solution A). Catalyst B was prepared by the same method as in Example 1, except that the pH was increased.
【００３２】第２の触媒製造例(触媒Ｃ) （ａ）実施例１において得られるＵＳＹ１５０ｇを５０
℃の０.２Ｍ塩化亜鉛溶液１.５ｌと２時間接触させたの
ち、ろ過、洗浄、乾燥、焼成した。（これをＺｎＵＳＹ
と称する。）このようにして得られた遷移金属含有アル
ミナシリケートには、ＺｎＯとして、約２重量％の亜鉛
導入されおり、２４.３８Åの格子定数、３８０m2／gの
表面積を持っている。このＺｎＵＳＹ１５０gを実施例
１の（ａ）に記載した方法と同様の操作で担体とした。 Second catalyst production example (Catalyst C) (a) 50 g of USY 150 g obtained in Example 1
After contacting with 1.5 l of a 0.2 M zinc chloride solution at 0 ° C. for 2 hours, the mixture was filtered, washed, dried and calcined. (This is ZnUSY
Called. The transition metal-containing alumina silicate thus obtained contains about 2% by weight of zinc as ZnO and has a lattice constant of 24.38Å and a surface area of 380 m 2 / g. 150 g of this ZnUSY was used as a carrier by the same operation as in the method described in Example 1 (a).
【００３３】（ｂ）この担体に、モリブデン酸アンモニ
ウム、硝酸ニッケル及びリン酸を、最終触媒時に、Ｍｏ
Ｏ3、ＮｉＯ、Ｐとしてそれぞれ８.０wt％、２.２wt
％、１.０wt％となるように、混合し、これを湿潤法に
より担持した。この時の含浸液のｐＨは約２.８であっ
た。担持後に、実施例１と同様の条件で乾燥、焼成して
触媒Ｃを調製した。(B) Ammonium molybdate, nickel nitrate and phosphoric acid were added to this carrier at the time of final catalyst, and Mo was added.
O 3, NiO, respectively as P 8.0 wt%, 2.2 wt
%, 1.0 wt% and mixed by a wet method. The pH of the impregnating liquid at this time was about 2.8. After the loading, the catalyst C was prepared by drying and firing under the same conditions as in Example 1.
【００３４】第２の比較触媒製造例(触媒Ｄ） 実施例２において、担体として、ＺｎＵＳＹを含まない
アルミナのみの形成体を用いたことを除いて、実施例２
と同じ方法により、触媒Ｄを調製した。 Second Comparative Catalyst Preparation Example (Catalyst D) Example 2 except that in the Example 2 the carrier formed was only alumina without ZnUSY.
Catalyst D was prepared by the same method as described above.
【００３５】第２の比較触媒製造例(触媒Ｅ) 実施例１のナトリウム型Ｙ型結晶性アルミノシリケート
をイオン交換して得たＮａ2Ｏ含量が０.５重量％、SiO2
/Al2O3比が５.８、格子定数が２４.５５Åの脱アルカリ
処理したアルミノシリケートＳＹを、実施例２のＵＳＹ
の代わりに用いて、実施例２の方法でＭｏＯ3、Ｎｉ
Ｏ、Ｐとしてそれぞれ８.０wt％、２.２wt％、１.０wt
％となるように担持し、触媒Ｅを調製した。 Second Comparative Catalyst Production Example (Catalyst E) Na 2 O content obtained by ion-exchange of the sodium-type Y-type crystalline aluminosilicate of Example 1 was 0.5 wt%, SiO 2
USY of Example 2 was prepared by treating the dealkalized aluminosilicate SY having a ratio of / Al 2 O 3 of 5.8 and a lattice constant of 24.55Å.
In the same manner as in Example 2, except that MoO 3 , Ni
O and P are 8.0 wt%, 2.2 wt% and 1.0 wt, respectively
% So that the catalyst E was prepared.
【００３６】第２比較触媒製造例(触媒Ｆ) ナトリウム型Ｙ型結晶性アルミノシリケートをイオン交
換し、さらに酸処理してＮａ2Ｏ含量が０.０３重量％、
SiO2/Al2O3比が１４.６、格子定数が２４.２９Åのアル
ミノシリケートを実施例２のＵＳＹの代わりに用いて、
実施例２の方法でＭｏＯ3、ＮｉＯ、Ｐとしてそれぞれ
８.０wt％、２.２wt％、１.０wt％となるように担持
し、触媒Ｆを調製した。 Second Comparative Catalyst Production Example (Catalyst F) Sodium-type Y-type crystalline aluminosilicate was ion-exchanged and further acid-treated to give a Na 2 O content of 0.03% by weight,
Using an aluminosilicate having a SiO 2 / Al 2 O 3 ratio of 14.6 and a lattice constant of 24.29Å instead of USY of Example 2,
According to the method of Example 2, MoO 3 , NiO, and P were loaded so as to be 8.0 wt%, 2.2 wt%, and 1.0 wt%, respectively, to prepare a catalyst F.
【００３７】実施例１〜２ 無機酸化物として、ホウ素を６.０重量％含有したアル
ミナ担体に、Ｍｏを金属として１０重量％及びＣｏを金
属として３重量％担持したもので、２００m2/gの表面
積、０.６ml/gの細孔容積、９０Åの平均細孔直径を有
する触媒を第１の触媒とし、水素化Ｈ2圧＝４０kg/c
m2、ＬＨＳＶ＝０.４hr-1、水素／原料油比＝４００、
反応温度＝３６０℃の条件下に、表１の性状を有する減
圧蒸留軽油を用いて水素化処理し、引き続いて、上記触
媒Ａを第２の触媒として、水素化Ｈ2圧＝４０kg/cm2、
ＬＨＳＶ＝０.４hr-1、水素／原料油比＝４００、反応
温度＝４００℃の条件下に、分解反応を行った。反応開
始後１０時間後と８０時間後の分解油を採取し、分解率
(３６０℃以上の留分の減少率で算出）を測定した。こ
の結果を実施例１として表２に示した。第２の触媒とし
て、触媒Ｃを用いて、まったく同様の操作を行った。こ
の結果を実施例２として表２に示した。[0037] As Examples 1-2 inorganic oxides, boron alumina support containing 6.0 wt%, obtained by 3 wt% on the 10 wt% and Co to Mo as the metal as a metal, 200 meters 2 / g The first catalyst is a catalyst having a surface area of 0.5, a pore volume of 0.6 ml / g, and an average pore diameter of 90Å, and the hydrogenation H 2 pressure is 40 kg / c.
m 2 , LHSV = 0.4 hr −1 , hydrogen / feed oil ratio = 400,
Under the condition of reaction temperature = 360 ° C., hydrogenation was carried out using vacuum distilled gas oil having the properties shown in Table 1, and subsequently, hydrogenation H 2 pressure = 40 kg / cm 2 using the above catalyst A as a second catalyst. ,
The decomposition reaction was carried out under the conditions of LHSV = 0.4 hr −1 , hydrogen / feed oil ratio = 400, and reaction temperature = 400 ° C. The cracked oil was collected 10 hours and 80 hours after the start of the reaction, and the decomposition rate
(Calculated by the reduction rate of the fraction at 360 ° C. or higher) was measured. The results are shown in Table 2 as Example 1. Using Catalyst C as the second catalyst, exactly the same operation was performed. The results are shown in Table 2 as Example 2.
【表１】 [Table 1]
【表２】 [Table 2]
【００３８】比較例１〜４ 第１の触媒として実施例１と同じ触媒を用い、第２触媒
として、触媒Ｂ、Ｄ、Ｅ、Ｆをそれぞれ用いて、実施例
１〜２に記載した条件と同じ条件で、水素化処理及び水
素化分解を行った。実施例１と同様に１０時間目と８０
時間目の分解率を測定した結果を表２に示した。 Comparative Examples 1 to 4 Using the same catalyst as in Example 1 as the first catalyst and using catalysts B, D, E, and F as the second catalyst, the conditions described in Examples 1 and 2 were used. Under the same conditions, hydrotreatment and hydrocracking were performed. As in Example 1, after 10 hours and 80
The results of measuring the decomposition rate at the time are shown in Table 2.
【００３９】比較例５〜７ 実施例１の第１の触媒、触媒Ａ、触媒Ｃをそれぞれ単独
で用い、水素化Ｈ2圧＝４０kg/cm2、ＬＨＳＶ＝０.８hr
-1、水素／原料油比＝４００、反応温度＝４００℃の条
件下で、水素化分解を行った。実施例１と同様に１０時
間目と８０時間目の分解率を測定した結果を表２に示し
た。 Comparative Examples 5 to 7 Using the first catalyst of Example 1, catalyst A and catalyst C respectively, hydrogenation H 2 pressure = 40 kg / cm 2 , LHSV = 0.8 hr
The hydrogenolysis was carried out under the conditions of -1 , hydrogen / feed oil ratio = 400, and reaction temperature = 400 ° C. The results of measuring the decomposition rates at 10 hours and 80 hours in the same manner as in Example 1 are shown in Table 2.
【００４０】比較例８ 実施例１の第１の触媒を単独で用い、水素化Ｈ2圧＝４
０kg/cm2、ＬＨＳＶ＝０.８hr-1、水素／原料油比＝４
００、反応温度＝３６０℃の条件下で、水素化分解を行
った。実施例１と同様に１０時間目と８０時間目の分解
率を測定した結果を表２に示した。 Comparative Example 8 Using the first catalyst of Example 1 alone, hydrogenation H 2 pressure = 4
0 kg / cm 2 , LHSV = 0.8 hr −1 , hydrogen / feed oil ratio = 4
00 and reaction temperature = 360 ° C., hydrogenolysis was carried out. The results of measuring the decomposition rates at 10 hours and 80 hours in the same manner as in Example 1 are shown in Table 2.
【００４１】この結果から明らかなように、本発明の触
媒は、比較例の触媒に比べて、分解性能及び分解活性の
寿命の点で優れていることが分かる。As is clear from these results, the catalyst of the present invention is superior to the catalysts of Comparative Examples in terms of decomposition performance and decomposition activity life.
【００４２】本発明は、炭化水素類の水素化分解反応に
おいて、高分解性能を得ることができ、またこの分解活
性を長時間維持でき、触媒寿命の長期化などを図ること
ができ、重質油を効率良く分解することができる。The present invention can obtain high cracking performance in the hydrocracking reaction of hydrocarbons, can maintain this cracking activity for a long time, and can prolong the life of the catalyst. Oil can be decomposed efficiently.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｇ 47/16 2115−4Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C10G 47/16 2115-4H
Claims (3)
律表第VIII族に属する金属の少なくとも１種を無機酸化
物担体に担持した第１の触媒を用いて、３３０〜４００
℃の温度で水素化処理し、次いで、Ｎａ2Ｏの含有量が
０.３重量％以下、ＳｉＯ2／Ａｌ2Ｏ3のモル比が５〜９
で、かつ格子定数が２４.４２乃至２４.３０Åの結晶性
アルミノシリケート及び／又は前記格子定数が２４.４
２乃至２４.３０Åの結晶性アルミノシリケートを遷移
金属含有溶液で処理した遷移金属含有アルミノシリケー
トと無機酸化物マトリックスとからなる担体に周期律表
第VI族に属する金属の少なくとも１種とリンとを含むｐ
Ｈ３以下の水溶液を含浸、乾燥させた後、或いは乾燥さ
せることなく、周期律表第VIII族に属する金属の少なく
とも１種を含む水溶液を含浸、乾燥、焼成して得られた
第２の触媒を用いて、３６０〜４２０℃の温度で水素化
分解することを特徴とする炭化水素類の水素化分解方
法。1. A first catalyst in which at least one metal belonging to Group VI and Group VIII of the Periodic Table of Hydrocarbons is supported on an inorganic oxide support, and a catalyst of 330 to 400 is used.
Hydrogenated at a temperature of ℃, then Na 2 O content of 0.3 wt% or less, SiO 2 / Al 2 O 3 molar ratio of 5-9
And a crystalline aluminosilicate having a lattice constant of 24.42 to 24.30Å and / or the lattice constant of 24.4.
2 to 24.30Å crystalline aluminosilicate treated with a transition metal-containing solution, and a carrier comprising a transition metal-containing aluminosilicate and an inorganic oxide matrix, and at least one metal belonging to Group VI of the periodic table and phosphorus. Including p
A second catalyst obtained by impregnating with an aqueous solution containing at least one metal belonging to Group VIII of the Periodic Table, drying and firing after impregnation with an aqueous solution of H3 or less and drying, or without drying. A method for hydrocracking hydrocarbons, which comprises hydrocracking at a temperature of 360 to 420 ° C.
ホウ素の少なくとも１種を含有させたものであることを
特徴とする炭化水素類の水素化分解方法。2. A method for hydrocracking hydrocarbons, wherein the first catalyst according to claim 1 contains at least one of phosphorus and boron.
属含有アルミノシリケートが亜鉛含有アルミノシリケー
トであることを特徴とする炭化水素類の水素化分解方
法。 【０００１】3. The method for hydrocracking hydrocarbons, wherein the transition metal-containing aluminosilicate in the second catalyst according to claim 1 is a zinc-containing aluminosilicate. [0001]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3289467A JP3057651B2 (en) | 1991-10-09 | 1991-10-09 | Hydrocracking method for hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3289467A JP3057651B2 (en) | 1991-10-09 | 1991-10-09 | Hydrocracking method for hydrocarbons |
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| Publication Number | Publication Date |
|---|---|
| JPH0598271A true JPH0598271A (en) | 1993-04-20 |
| JP3057651B2 JP3057651B2 (en) | 2000-07-04 |
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|---|---|---|---|
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Cited By (2)
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|---|---|---|---|---|
| WO2014027537A1 (en) * | 2012-08-17 | 2014-02-20 | 日揮触媒化成株式会社 | Catalyst for hydrocarbon catalytic cracking |
| WO2014156486A1 (en) * | 2013-03-25 | 2014-10-02 | コスモ石油株式会社 | Hydrogenation desulfurization catalyst for diesel oil and hydrogenation treatment method for diesel oil |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5151372B2 (en) * | 2007-10-01 | 2013-02-27 | セイコーエプソン株式会社 | Liquid ejecting apparatus and method for controlling liquid ejecting apparatus |
-
1991
- 1991-10-09 JP JP3289467A patent/JP3057651B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014027537A1 (en) * | 2012-08-17 | 2014-02-20 | 日揮触媒化成株式会社 | Catalyst for hydrocarbon catalytic cracking |
| AU2013303687B2 (en) * | 2012-08-17 | 2016-10-20 | Jgc Catalysts And Chemicals Ltd. | Catalyst for hydrocarbon catalytic cracking |
| US9731281B2 (en) | 2012-08-17 | 2017-08-15 | Jgc Catalysts And Chemicals Ltd. | Catalyst for hydrocarbon catalytic cracking |
| WO2014156486A1 (en) * | 2013-03-25 | 2014-10-02 | コスモ石油株式会社 | Hydrogenation desulfurization catalyst for diesel oil and hydrogenation treatment method for diesel oil |
| JP5928970B2 (en) * | 2013-03-25 | 2016-06-01 | コスモ石油株式会社 | Gas oil hydrodesulfurization catalyst, hydrodesulfurization catalyst production method, and gas oil hydrotreating method |
| RU2640583C2 (en) * | 2013-03-25 | 2018-01-10 | Космо Ойл Ко., Лтд. | Hydrodesulfurization catalyst for diesel fuel and method of hydrocleaning diesel fuel |
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| Publication number | Publication date |
|---|---|
| JP3057651B2 (en) | 2000-07-04 |
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