JPS60225645A - Preparation of hydrogenating treatment catalyst - Google Patents

Preparation of hydrogenating treatment catalyst

Info

Publication number
JPS60225645A
JPS60225645A JP59081961A JP8196184A JPS60225645A JP S60225645 A JPS60225645 A JP S60225645A JP 59081961 A JP59081961 A JP 59081961A JP 8196184 A JP8196184 A JP 8196184A JP S60225645 A JPS60225645 A JP S60225645A
Authority
JP
Japan
Prior art keywords
group
silica
catalyst
periodic table
carrier
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
Application number
JP59081961A
Other languages
Japanese (ja)
Other versions
JPH0513706B2 (en
Inventor
Ikuo Akizuki
秋月　郁夫
Hiroshi Kaya
茅　博司
Shohei Okano
岡野　正平
Nobuo Otake
大竹　信雄
Keiji Kumagai
熊谷　啓二
Yoshito Kaneko
金子　吉人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tonen General Sekiyu KK
Original Assignee
Toa Nenryo Kogyyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toa Nenryo Kogyyo KK filed Critical Toa Nenryo Kogyyo KK
Priority to JP59081961A priority Critical patent/JPS60225645A/en
Priority to JP59133072A priority patent/JPS6115739A/en
Priority to CA000479461A priority patent/CA1249570A/en
Priority to DE8585302790T priority patent/DE3583356D1/en
Priority to EP85302790A priority patent/EP0160475B1/en
Priority to FI851626A priority patent/FI851626L/en
Priority to NO851641A priority patent/NO851641L/en
Priority to ES542525A priority patent/ES8608567A1/en
Priority to AU41693/85A priority patent/AU570794B2/en
Priority to KR1019850002793A priority patent/KR850007568A/en
Priority to AR30020085A priority patent/AR241872A1/en
Publication of JPS60225645A publication Critical patent/JPS60225645A/en
Priority to US07/084,467 priority patent/US4837193A/en
Priority to JP4166874A priority patent/JPH0772273B2/en
Publication of JPH0513706B2 publication Critical patent/JPH0513706B2/ja
Granted legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

PURPOSE:To prepare a highly active hydrogenating treatment catalyst, by supporting metals belonging to the Group VIII and the Group VIB of the Periodic Table by a silica-alumina carrier in a well dispersed state. CONSTITUTION:Silica-alumina containing 2-35wt% of silica or silica-alumina- containing substance is used as a carrier and this carrier is immersed in a solution of an ammine complex of a metal belonging to the Group VIII of the Periodic Table such as nickel or cobalt to support 0.5-20wt% of said metal by the carrier as oxide. Subsequently, said carrier is dried in air and baked while the baked carrier is immersed in a solution of a soluble salt of a metal belonging to the Group VIB of the Periodic Table such as molybdenum or tungsten to allow the carrier to support 5-30wt% of said metal as oxide.

Description

【発明の詳細な説明】 本発明は、炭化水素油の水素化処理に使用される水素化
処理用触媒に関するものであり、特にシリカアルミナ又
はシリカアルミナを含有する担体上に周期表第■族及び
第ＶＩ　Ｂ族金属を分散性よく担持させ高活性の水素化
処理用触媒を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrotreating catalyst used for hydrotreating hydrocarbon oils, and in particular, a hydrotreating catalyst used for hydrotreating hydrocarbon oil. The present invention relates to a method for producing a highly active hydrotreating catalyst by supporting a Group VI B metal with good dispersion.

本発明の説明において「水素化処理」とは、炭化水素油
と水素との接触による処理方法を称し、比較的反応条件
の苛酷度の低い水素化精製、比較的苛酷度の高い若干の
分解反応を伴う水素化精製、水添異性化、水素化脱アル
キル化及びその他の水素の存在下における炭化水素油の
反応を包含するものである。例えば、常圧蒸留又は絨圧
蒸留の留出油及び残渣油の水素化脱硫、水素化膜窒素、
及び水素化分解を含み、又灯油留分、軽油留分、ワック
ス、潤滑油留分の水素化精製等を包含するものである。In the description of the present invention, "hydrotreatment" refers to a treatment method by contacting hydrocarbon oil with hydrogen, including hydrorefining with relatively less severe reaction conditions, and some decomposition reactions with relatively more severe reaction conditions. This includes hydrorefining, hydroisomerization, hydrodealkylation and other reactions of hydrocarbon oils in the presence of hydrogen. For example, hydrodesulfurization of distillate oil and residual oil of atmospheric distillation or gaseous pressure distillation, hydrogenated membrane nitrogen,
It also includes hydrorefining of kerosene fractions, gas oil fractions, waxes, lubricating oil fractions, etc.

本発明に従って製造される触媒は、特に灯油留分及び軽
油留分の如き中質留出油、減圧蒸留の重鎖留出油、アス
ファルトを含有する残渣油又はこれらの混合油の水素化
脱硫を実施す゛るのに好適であるため、本ＢＡＭ魯では
特に水素化脱硫に関連して説明する。The catalyst prepared according to the invention is particularly useful for the hydrodesulfurization of medium distillate oils such as kerosene fractions and gas oil fractions, heavy chain distillate oils of vacuum distillation, asphalt-containing residue oils or mixtures thereof. The present BAM will specifically discuss hydrodesulfurization because of its suitability for implementation.

従来、石油精製時の水素化脱硫においては、アルミナ担
体に元素周期表第■族金属及び／又は元素周期表第ｖＩ
Ｂ族金属の群から選択される一種又は二種以上の金属を
担持させて製造される、例えばコバルトモリブデン系又
はニッケルモリブデン系の水素化処理用触媒が広く使用
されている。斯ろ水素化処理用触媒の製造において最も
重要なことは、均一な組成のモリブデン−コバルト又は
モリブデン−ニッケル粒子を担体に多量に（酸化物とし
て約２０１＃量Ｘ）、しかも高度に分散した状態で相持
せしめることである。Conventionally, in hydrodesulfurization during petroleum refining, metals from group Ⅰ of the periodic table and/or metals from group iv of the periodic table are added to an alumina carrier.
For example, cobalt-molybdenum-based or nickel-molybdenum-based hydrogenation catalysts are widely used, which are produced by supporting one or more metals selected from the group B metals. The most important thing in the production of catalysts for hydrotreating is to prepare molybdenum-cobalt or molybdenum-nickel particles of uniform composition in a large amount (approximately 201# amount x as oxide) on a carrier and in a highly dispersed state. It is important to make sure that they are mutually compatible.

水素化処理用触媒の製造法としては、従来（１）共沈法
、（２）混練法及び（３）含浸法が提案され又一般に実
施されている。しかしながら、共沈法は、前記水素化処
理用触媒のように活性金属成分が複数の場合には、これ
ら活性金属成分を均一に、しかも再現性よく製造するこ
とが困難であるという欠点を有している。混線法も又、
前述のように活性金属成分を複数有するような水素化処
理用触媒においては担体及び複数の活性金属成分を互い
に十分に近接させ、且つ均一で完全な混合をなすことが
必要であるが、該混線法ではこのような状態を達成する
ことが極めて困難であるという欠点を有している。上記
三方法に比べ、含浸法は、前述のように活性金属成分を
複数有するような水素化処理用触媒、例えばアルミナな
担体としたコバルトモリブデン系触媒、又はニッケルモ
リブデン系触媒の製造にはより適しているということが
できる。As methods for producing hydrotreating catalysts, (1) a coprecipitation method, (2) a kneading method, and (3) an impregnation method have been proposed and generally practiced. However, the coprecipitation method has the disadvantage that when there are multiple active metal components, such as the above-mentioned hydrotreating catalyst, it is difficult to produce these active metal components uniformly and with good reproducibility. ing. The crosstalk method also
As mentioned above, in a hydrotreating catalyst having multiple active metal components, it is necessary to place the carrier and the multiple active metal components sufficiently close to each other and to achieve uniform and complete mixing. The disadvantage of this method is that it is extremely difficult to achieve this condition. Compared to the above three methods, the impregnation method is more suitable for producing hydrotreating catalysts that have multiple active metal components, such as cobalt-molybdenum-based catalysts with alumina supports, or nickel-molybdenum-based catalysts, as described above. It can be said that

含浸法による水素化処理用触媒の製造において、通常神
体としてはアルミナを使用し、モリブデンを先ずアルミ
ナ担体に相持しく第１ステツプ）、次でコバルト又はニ
ッケルを該活性金属とモリブデンとの相互作用によりモ
リブデン−コバルト又はモリブデン−ニッケルの微粒子
として担体に担持させる（第２ステツプ）方法（２段式
含浸法）が提案されているが、第１ステツプで約１５Ｘ
ものモリブデンを高度に分散した状態でアルミナ担体に
担持せしめることは離しく、最終的に得られる触媒の分
散性も実質的に、該第１ステツプにおけるモリブデンの
分散状態で決ってしまい、従って活性の低下が余儀なく
される。In the production of hydrotreating catalysts by the impregnation method, alumina is usually used as the base material, molybdenum is first added to the alumina support (in the first step), and then cobalt or nickel is added through the interaction between the active metal and molybdenum. A method (two-stage impregnation method) in which molybdenum-cobalt or molybdenum-nickel is supported on a carrier as fine particles (second step) has been proposed;
It is difficult to support molybdenum in a highly dispersed state on an alumina support, and the dispersibility of the final catalyst is also substantially determined by the dispersion state of molybdenum in the first step. A decline is forced.

含浸法における前述のような欠点を解決するべく、第１
ステツプにてコバルトと又はニッケルをアルミナ担体に
担持させ、次でモリブデンを担持させることも考えられ
るが、この場合には、コバルト又はニッケルの如き活性
金属成分はアルミナ担体上ではアルミナ担体と十分な相
互作用を持たず、活性を有さないＣＯ３Ｏ４とｌ−て塊
状に凝集するか又はコバルトアルミネートを形成して不
活性となり、所望の性能を達成することができない。In order to solve the above-mentioned drawbacks of the impregnation method, the first
It is also conceivable to deposit cobalt and/or nickel on the alumina support in a step, followed by the molybdenum, but in this case the active metal components such as cobalt or nickel have sufficient interaction with the alumina support on the alumina support. It has no effect and coagulates with inactive CO3O4, or forms cobalt aluminate and becomes inactive, making it impossible to achieve the desired performance.

又、含浸法によって複数の活性金属を同時にアルミナ担
体に相持させる方法は、担体内に各成分を均一に分布せ
しめることが難しく、好ましいものではない。Further, the method of impregnating a plurality of active metals onto an alumina carrier at the same time is not preferred because it is difficult to uniformly distribute each component within the carrier.

以上のように、水素化処理用触媒のように、活性金属成
分の担持量が高い触媒で肚つ複数成分の活性金属を担持
する場合に、各成分を均一な組成で、且つ高度に分散し
た状態に担持することは、従来の既知の方法では極ぬて
困難である。As described above, when supporting multiple active metal components on a catalyst with a high amount of active metal components supported, such as a catalyst for hydrotreating, it is necessary to maintain a uniform composition of each component and to ensure a high degree of dispersion. This is extremely difficult to achieve using conventionally known methods.

従って、本発明の主たる目的は、元素周期表第■族金属
及び第Ｖｉ　Ｂ族金属より成る水素化処理用触媒の製造
法において、元素周期表第ｖｌＩＩ族金属と担体との結
合力を利用して、両活性金属成分を分散性よく担持する
ことにより、高活性の水素化処理用触媒を得る触媒の製
造法を提供することである。Therefore, the main object of the present invention is to provide a method for producing a hydrotreating catalyst consisting of a metal of Group I of the Periodic Table of Elements and a metal of Group ViB of the Periodic Table of Elements, which utilizes the bonding force between a metal of Group VlII of the Periodic Table of Elements and a support. Another object of the present invention is to provide a method for producing a highly active catalyst for hydrogenation treatment by supporting both active metal components with good dispersion.

本発明の更に他の目的は、シリカアルミナ又はシリカア
ルミナを含有する相体上に、イオン交換法を用いてコバ
ルト又はニッケルを、分散性よく且つ化学的均一性（相
持されたコバルト又はニッケルと担体との結合強さの均
一性）を向上せしめて担持せしめることができ、従って
主活性金属成分であるモリブデンを相体上に分散性及び
均一性よく担持せしめることのできる水素化処理用触媒
の製造法を提供することである。Still another object of the present invention is to apply cobalt or nickel onto silica alumina or a phase containing silica alumina using an ion exchange method with good dispersibility and chemical uniformity (supported cobalt or nickel and carrier). Production of a catalyst for hydrotreating that can support molybdenum, which is the main active metal component, with improved dispersion and uniformity on the phase. It is to provide law.

本発明者等は、従来の諸製造法を改良するべく種々研究
、実験を行なった結果、水素化処理用触媒の活性金属成
分であるコバルト及びニッケルは、担体の酸性点に担持
され、従来のアルミナ担体に代えて、酸性点を有するシ
リカアルミナ担体又はシリカアルミナ含有担体を使用す
ることにより、コバルト又はニッケルを第１ステツプに
て分散性良く且つ安定に担持し得ることを見出した。こ
れは、シリカアルミナの酸性点に化学的結合力によって
コバルト又はニッケルが担持されるからだと考えられ、
特にシリカアルミナ担体又はシリカアルξす含有担体に
コバルト又はニッケルをイオン交換法によって担持させ
ることによってその分散性を飛躍的に向上せしめ得るこ
とを見出した。The present inventors conducted various studies and experiments to improve conventional manufacturing methods, and found that cobalt and nickel, which are active metal components of hydrotreating catalysts, are supported on the acidic sites of the carrier, It has been found that cobalt or nickel can be stably supported with good dispersibility in the first step by using a silica-alumina carrier having acidic points or a silica-alumina-containing carrier instead of an alumina carrier. This is thought to be because cobalt or nickel is supported on the acidic sites of silica alumina by chemical bonding force.
In particular, it has been found that by supporting cobalt or nickel on a silica-alumina carrier or a silica-aluminum-containing carrier by an ion exchange method, its dispersibility can be dramatically improved.

更に又、上記の如くに第１ステツプにてコバルト又はニ
ッケルが担持されたシリカアルミナ担体又はシリカアル
ミナ含有担体に第２ステツプとしてモリブデンを担持せ
しめることができ、このときモリブデンはコバルト又は
ニッケルとの結合力によってコバルト又はニッケルの囲
りに担持され、モリフテンーコバルト又はモリブデン−
ニッケルの微粒子が均一に且つ高分散状態で担持される
ことが分った。Furthermore, molybdenum can be supported in the second step on the silica-alumina carrier or silica-alumina-containing support on which cobalt or nickel was supported in the first step as described above, and in this case, molybdenum is bonded with cobalt or nickel. Molyftene-cobalt or molybdenum-
It was found that nickel fine particles were supported uniformly and in a highly dispersed state.

上述のように、本発明者等は、担体としてシリカアルミ
ナ又はシリカアルミナ含有物を使用した場合コバルト及
びニッケルはプロモータ（助触媒）であり、同時にモリ
ブデンのアンカーとして機能し、活性金属成分であるモ
リブデンの分散性、安定性を向上させる効果を有するこ
とを見出した。As mentioned above, the inventors have found that when silica alumina or silica alumina-containing material is used as a support, cobalt and nickel act as promoters (co-catalysts) and at the same time act as anchors for molybdenum, and molybdenum is an active metal component. It has been found that it has the effect of improving the dispersibility and stability of.

本発明は斯る新しい知見に基づきなされたものである。The present invention has been made based on this new knowledge.

要約すると、本発明は担体としてシリカアルミす又はシ
リカアルミナ含有物を使用し、該担体トに、先ず元素周
期表第■族金属の群から選択される一種又は二種以上の
金属を担持させ、次で元素周期表第Ｖ［Ｂ族金属の群か
ら選択される一種又は二種以上の金属を担持させること
を特徴とする水素化処理用触媒の製造法である。特に本
発明によると、第Ｖｉｌｌ　ｔＭ金金属担持量を少なく
して良好な触媒活性を得るという特徴を有する。To summarize, the present invention uses silica-alumina or silica-alumina-containing material as a support, and first supports one or more metals selected from the group of metals of group Ⅰ of the periodic table of elements, The following is a method for producing a catalyst for hydrotreating, characterized in that one or more metals selected from the group V [B metals of the periodic table of elements] are supported. In particular, the present invention is characterized in that good catalytic activity is obtained by reducing the amount of gold metal supported on the VilltM.

本発明による水素化処理用触媒の製造法においては、ア
ルミナ担体の代わりに酸性点を有するシリカアルミナ担
体又はシリカアルミナ含有担体が使用される。相体とし
てシリカアルミナ又はシリカアルミナ含有物を使用する
ことによって第１ステツプにて元素周期表第■族金属を
担持させても、該活性金属成分がシリカアルミナの酸性
点に結合することによって分散性良く且つ安定に担持さ
れる。このように、第１ステツプにて第■族金属を相体
の酸性点上に分散性よく相持することにより、主活性金
属である元素周期表第ＶＩ　Ｂ族金属を第１１Ｎ族金属
の外側、つまり第Ｖ族金属層の上に担持することかでき
、水素住処’Ｊ！４！Ｊ−４１触媒としては棲めて好適
である。In the method for producing a hydrotreating catalyst according to the present invention, a silica-alumina carrier or a silica-alumina-containing carrier having acidic sites is used instead of an alumina carrier. Even if silica alumina or a silica alumina-containing material is used as a phase to support a metal from group Ⅰ of the periodic table in the first step, the active metal component binds to the acidic sites of the silica alumina, resulting in improved dispersibility. It is well and stably supported. In this way, in the first step, by adhering the group Ⅰ metal on the acidic points of the phase with good dispersion, the main active metal, the group VI B metal of the periodic table, is placed outside the group 11N metal. In other words, it can be supported on the Group V metal layer, making it a hydrogen home! 4! It is suitable as a J-41 catalyst.

一方、水素化処理、特に水素化脱硫及び水素化膜窒素に
おいて触媒は所望の固体酸性度を保持させることが重要
であり、又担体中のシリカ含有量によって酸性制御が可
能で））ることか知られている。本発明においても、シ
リカアルミナ担体又はシリカアルミナ含有担体のシリカ
含有量が過大となった場合には、水素化脱硫反応又は水
素化脱窒率反応において過度の分解反応に伴う水素消費
量の増大又はコークの生成等といった好ましくない反応
を併発せしめることとなる。On the other hand, in hydrotreating, especially in hydrodesulfurization and hydrogenation membrane nitrogen, it is important that the catalyst maintains the desired solid acidity, and acidity can be controlled by controlling the silica content in the carrier. Are known. In the present invention, when the silica content of the silica-alumina carrier or the silica-alumina-containing carrier becomes excessively high, hydrogen consumption may increase due to excessive decomposition reaction in the hydrodesulfurization reaction or hydrodenitrification rate reaction. Unfavorable reactions such as the formation of coke may also occur.

従って、本発明においてシリカアルミナ担体又はシリカ
アルミナ含有担体中のシリカの含有量は２〜３５重量％
好ましくは５〜３０重量％、より好ましくは７〜１２ｔ
ｉｉｌ”％の範囲となすべきである。Therefore, in the present invention, the silica content in the silica-alumina carrier or silica-alumina-containing carrier is 2 to 35% by weight.
Preferably 5-30% by weight, more preferably 7-12t
iii”%.

又、シリカアルミナ担体の表面積及び細孔分布は特に規
定されるものではないが、触媒担体として好ましい表面
積、例えば５０　ｍ２７１７以上、特に２００ｍ２／ｇ
以上が好適である。斯るシリカアルミナ担体の製造法と
しては、アルミナ及びシリカのゲルを各々あらかじめ製
造しておき両者を混合する方法、シリカゲルをアルミニ
ウム化合物の溶液に浸漬した後に、塩基性物質を適当量
添加し、アルミナゲルをシリカゲル上に沈着させる方法
、又は水溶性アルミニウム化合物と水溶性珪素化合物と
の均一混合溶液に塩基性物質を添加し、両者を共沈させ
る方法等を採用することができる。Furthermore, the surface area and pore distribution of the silica alumina carrier are not particularly defined, but the surface area is preferably 50 m2/g or more, particularly 200 m2/g as a catalyst carrier.
The above is preferable. Methods for producing such a silica-alumina carrier include a method in which alumina and silica gels are each prepared in advance and then mixed together, and a method in which silica gel is immersed in a solution of an aluminum compound, and then an appropriate amount of a basic substance is added to form alumina gel. A method of depositing a gel on silica gel, a method of adding a basic substance to a homogeneous mixed solution of a water-soluble aluminum compound and a water-soluble silicon compound, and co-precipitating both can be adopted.

担体−Ｆに第１スデツプにて担持させる水素化活性金属
成分は、元素周期表第Ｘｎｌ　族金属の群から選択され
る一種又は二種以上の金属である。即ち、第四（族の鉄
、コバルト、ニッケル、パラジウム、白金、オスミウム
、イリジウム、ルテニウム及びロジウム等から一種又は
二種以上を選択して使用する。好ましくは、コバルト及
びニッケルが単独で又は両者を組合せて使用されるであ
ろう。The hydrogenation active metal component supported on the carrier-F in the first step is one or more metals selected from the group of metals of group Xnl of the periodic table of elements. In other words, one or more of iron, cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium, rhodium, etc. of the fourth group are selected and used. Preferably, cobalt and nickel are used alone or in combination. May be used in combination.

第２ステツプにて相体に担持させる水素化活性金属成分
は、元素周期表第ｖｔ　Ｂ族金属の群から選択される一
種又は二種以上の金属である。即ち、第ＶＴＢ族のクロ
ム、モリブデン及びタングステンから一種又は二種以上
選択して使用される。好ましくはモリブデン及びタング
ステンが単独で又は両者を組合せて使用されるであろう
。又所望に応じ、第三の金属を添加することも可能であ
ろう。The hydrogenation-active metal component supported on the phase in the second step is one or more metals selected from the group Vt B group metals of the Periodic Table of the Elements. That is, one or more selected from chromium, molybdenum, and tungsten of the VTB group are used. Preferably molybdenum and tungsten will be used alone or in combination. It would also be possible to add a third metal if desired.

上記第１族及び第ＶＩ　Ｂ族の水素化活性金属成分は、
酸化物及び／又は硫化物として担持させることが好適で
ある。斯る活性金属成分の担持量は、酸化物として触媒
基準で、第■族金属は０．５〜２０重量％、好ましくは
１〜８重量％、より好ましくは２〜５重量％であり、第
ＶＩ　Ｂ族金属は５〜３０重童％、好ましくは８〜２５
１１量％、より好ましくは１５〜２０重掃％である。第
Ｖｌ族金属を０．５重量％μ下担持させたのでは十分な
触媒が得られず、又２０重重要以上では担体と結合しな
い遊離の金属成分が増加する。第■族金属の遊離成分が
増加すると、次で第Ｖ［Ｂ族金属を担持させる場合に不
活性の複合酸化物が生成し、第Ｖ［Ｂ族金属の分散性を
低下せしめ、触媒活性を低下させる。The above-mentioned Group 1 and Group VIB hydrogenation-active metal components are:
It is preferable to support it as an oxide and/or a sulfide. The supported amount of the active metal component is 0.5 to 20% by weight, preferably 1 to 8% by weight, more preferably 2 to 5% by weight, based on the catalyst as an oxide. Group VI B metal is 5 to 30%, preferably 8 to 25%
It is 11% by weight, more preferably 15-20% by weight. If the group Vl metal is supported at less than 0.5% by weight, a sufficient catalyst cannot be obtained, and if it is supported by 20% by weight or more, the amount of free metal components that are not bonded to the support increases. When the free component of Group Ⅰ metal increases, an inert composite oxide is formed when supporting Group V[B metal, which reduces the dispersibility of Group V[B metal and reduces the catalytic activity. lower.

一方、第Ｖ［Ｂ族金属が５重量％以下では活性が得られ
す、３０重量％以上では分散性が低下すると同時に第ｖ
ｍ族金属の助触媒効果が発揮されない。On the other hand, if the Group V [B metal content is less than 5% by weight, the activity is obtained; if it is more than 30% by weight, the dispersibility decreases and at the same time
The promoter effect of group m metals is not exhibited.

本発明において、第１及びｉ＠２ステップにおける活性
金属成分の担体への相持方法としては、担体を前＝ｒ金
金属可溶性塩の水溶液に浸漬し、金属成分を相体中に導
入する含浸法を採用することができる。含浸操作として
は、担体な常温又は常温以上で含浸溶液に浸漬して所望
成分が十分和体中に含浸１−る条件に保持する。含浸溶
液の量及び温度は、所望量の金属が担持されるように適
宜調整することができる。担持量の如伺により、含浸溶
液に浸漬する担体の蓋を決定する。In the present invention, the active metal component is supported on the carrier in the first and i@2 steps by an impregnation method in which the carrier is immersed in an aqueous solution of a gold metal soluble salt and the metal component is introduced into the phase. can be adopted. In the impregnation operation, the carrier is immersed in an impregnating solution at room temperature or above room temperature and maintained under conditions such that the desired components are sufficiently incorporated into the solution. The amount and temperature of the impregnating solution can be adjusted as appropriate to support the desired amount of metal. The lid of the carrier to be immersed in the impregnating solution is determined depending on the amount of support.

一方、本発明者等は、本発明に従った触媒製造法におけ
る第１ステツプはシリカアルミナ担体又はシリカアルミ
ナ含有相体表面上のプロトンと前記金属イオンの交換を
アンモニウムイオンを介して行なうイオン交換法が極め
て好適であるということを見出した。本発明をイオン交
換法に基づき実施すると、触媒の分散度は通常の含浸法
触媒に比べ著しく向上し、更に化学的均一性も向上する
ことが分った。On the other hand, the present inventors have discovered that the first step in the catalyst production method according to the present invention is an ion exchange method in which protons on the surface of a silica-alumina support or a silica-alumina-containing phase are exchanged with the metal ions via ammonium ions. It has been found that this is extremely suitable. It has been found that when the present invention is carried out based on the ion exchange method, the degree of dispersion of the catalyst is significantly improved compared to that of a conventional impregnation method catalyst, and the chemical uniformity is also improved.

イオン交換法に基づく触媒の製法は、活性金属のアンミ
ン錯塩溶液を調製し、該溶液にシリカアルミナ担体を浸
漬し、該金属を担体に担持させることによって行なわれ
る。アンミン錯塩溶液の量及び濃度は、所望量金属が担
持されるように適宜調整することができる。A method for producing a catalyst based on an ion exchange method is carried out by preparing an ammine complex salt solution of an active metal, immersing a silica alumina carrier in the solution, and supporting the metal on the carrier. The amount and concentration of the ammine complex salt solution can be adjusted as appropriate so that a desired amount of metal is supported.

水素化活性金属成分を担持した担体は、含浸溶液から分
離した後、水洗、乾燥及び焼成を行なう。After the carrier supporting the hydrogenation-active metal component is separated from the impregnating solution, it is washed with water, dried, and calcined.

乾燥及び焼成の条件は、前記担体の場合の条件と同一で
よい。重質炭化水素油の水素化脱硫において、触媒は、
使用に先立ち、予備硫化を行なうことが好ましい。その
方法については、後に記載する。The drying and calcination conditions may be the same as those for the carrier. In the hydrodesulfurization of heavy hydrocarbon oils, the catalyst is
It is preferable to carry out presulfurization prior to use. The method will be described later.

本発明によって製造された触媒は、活性劣化が小さく、
苛酷度の低い反応条件、特に、低反応圧においても高い
脱硫率を達成することができる。The catalyst produced according to the present invention shows little activity deterioration and
A high desulfurization rate can be achieved even under less severe reaction conditions, especially at lower reaction pressures.

水素化脱硫を行なうにあたり、触媒は、固定床、流動床
又は移動床のいずれの形式でも使用することができるが
、装置面又は操作上からは固定床反応塔な採用すること
が好ましい。又、二基以上の複数基の反応塔を結合して
水素化脱硫を行ない、高度の脱硫率を達成することもで
きる。更に、本発明触媒は、脱硫・脱窒素反応を主体と
する主反応塔に前置の金属除去を目的とするガード・ド
ラムに充填使用することもできる。In carrying out hydrodesulfurization, the catalyst can be used in any of fixed bed, fluidized bed, or moving bed formats, but from the standpoint of equipment and operation, it is preferable to use a fixed bed reaction column. Furthermore, a high desulfurization rate can be achieved by combining two or more reaction towers to perform hydrodesulfurization. Furthermore, the catalyst of the present invention can also be used by filling a guard drum for the purpose of removing metals before a main reaction tower mainly carrying out desulfurization and denitrification reactions.

触媒は、使用に先立ち予備硫化を行なうことが好ましい
。予備硫化は、反応塔のその場において行なうことがで
きる。すなわち、焼成した触媒な含硫留出油と、温度；
約１５０〜４００℃、圧力（全圧）；約２０〜１００ｋ
ｇ／ｍ２、液空間速度；約ｎ、　３〜２．　ＯＶ／Ｈ／
Ｖ及び約５０〜１．５００ｉｌ／７１の水素含有ガスの
存在下において接触させ、硫化処理の終了後含硫留出油
を原料油に切替え原料油の脱硫に適当な運転条件に設定
し運転を開始する。Preferably, the catalyst is presulfided before use. Presulfurization can be carried out in situ in the reaction column. That is, the calcined catalytic sulfur-containing distillate and the temperature;
Approximately 150-400℃, pressure (total pressure); approximately 20-100k
g/m2, liquid space velocity; approximately n, 3-2. OV/H/
V and about 50 to 1.500 il/71 of a hydrogen-containing gas, and after the sulfurization treatment is completed, the sulfur-containing distillate is switched to feedstock oil, and the operating conditions are set appropriate for desulfurization of the feedstock oil, and operation is started. Start.

硫化処理の方法としては、以上の如き方法の他に、硫化
水素その他の硫黄化合物を直接触媒と接触させるか又は
適当な留出油に添加してこれを触媒と接触させることも
できる。In addition to the methods described above, the sulfurization treatment may be carried out by directly contacting hydrogen sulfide or other sulfur compounds with the catalyst, or by adding it to a suitable distillate and bringing it into contact with the catalyst.

本発明者等は、前述の如き本発明に従った触媒の製造法
を研究し、種々の実験を行なった結果、本発明に係る触
媒の製造法によるとシリカを約２〜３５重量％含有する
アルミナ担体上に、光素周期表筆■族金属の群から選択
される一種又は二種以上の金属及び元素周期表第ＶＩ　
Ｂ族金属ｆ）群から選択される一種又は二種以上の金属
を担持させて成り、 ■　３０〜１００人の範囲の直径を有する細孔の容積が
０〜１５０人の範囲の直径を有する細孔の容積の７０Ｘ
以上 ■　１００〜３００人の範囲の直径を有する細孔の容積
が０〜３００人の範囲の直径を有する細孔の容積の約６
０％以下（上記■及び■の細孔容積は窒素吸着法により
測定） ■　水銀圧入法により測定した１５０〜ｊ５０．Ｏｆ’
ＩＯ人の範囲の直径を有する細孔の容積が約０．００５
〜［Ｌ２５ＩＬ／／ｇ、好ましくは０．１　ｍｌ　／　
９以下■　水銀圧入法により測定した１５０〜２．００
０にの範囲の直径を有する細孔の容積が約００１１１Ｌ
ｌ／ｇ以下 ■　窒素吸着法により測定した０〜３００人の範囲の直
径を有する細孔の容積が約［１３０〜０．７０ｍｅ　／
　９の範囲 ■　比表面積が約２００〜４００ｍ２／ｇの範囲である
炭化水素油の水素化処理用触媒を好適に製造し得ること
を見出した。又、該触媒は全細孔容積；０、４〜０．　
ｑ　ｍｌ　／　９、カサ密度；約Ｑ、　５〜ｔ　Ｏ９／
ｍｌ、側面破壊強度；約０．８〜ｘｓｋｇ／■であった
。The present inventors researched the method for producing the catalyst according to the present invention as described above and conducted various experiments. As a result, the present inventors found that according to the method for producing the catalyst according to the present invention, the catalyst contains about 2 to 35% by weight of silica. On an alumina support, one or more metals selected from the group of group I metals of the periodic table and elements VI of the periodic table.
The pores have a diameter of 30 to 100 pores and have a volume of 0 to 150 pores. 70X of hole volume
More than ■ The volume of pores with a diameter in the range of 100 to 300 μm is approximately 6 of the volume of pores with a diameter in the range of 0 to 300 μm
0% or less (the pore volumes of ■ and ■ above are measured by the nitrogen adsorption method) ■ 150 to j50 as measured by the mercury intrusion method. Of'
The volume of pores with diameters in the range of IO is approximately 0.005
~[L25IL//g, preferably 0.1 ml/
9 or less ■ 150 to 2.00 measured by mercury intrusion method
The volume of pores with diameters ranging from 0 to 00111 L
l/g or less ■ The volume of pores with diameters in the range of 0 to 300 me measured by nitrogen adsorption method is approximately [130 to 0.70 me /
9. Range (1) It has been found that a catalyst for hydrotreating hydrocarbon oil having a specific surface area in the range of about 200 to 400 m2/g can be suitably produced. The catalyst also has a total pore volume of 0.4 to 0.
q ml/9, bulk density; approximately Q, 5~t O9/
ml, side breaking strength: approximately 0.8 to xskg/■.

従来、残渣油の水素化脱硫方法は、石油燃料中の硫黄化
合物が燃焼により亜硫酸ガスとなり大気汚染源の一つと
なるに及んで、亜硫酸ガスの放散量を低下させる目的で
、積極的な開発が行なわれ、多数提案されている。例え
ば、アスファルト及び金属含有化合物を含有する炭化水
素油の水素化脱硫及び水素化膜窒素を行なうためには、
使用する水素化精製用触媒の細孔分布が活性及び活性維
持能に大きく影響を与えることを予想して、原料油中の
アスファルト及び金属含有化合物の浸入を防止するため
に細孔半径８０Å以上の細孔容積を全細孔容積の１０Ｘ
以下に抑えた細孔分布を有する触媒を使用する方法（特
公昭４５−３８１４２号公報）又は前記同残渣油の水素
化脱硫において半径１２０Å以下の細孔の容積が１０λ
間隔で比較的均一に分布した触媒を使用する方法（特公
昭４５−３８１４３号公報）等が知られている。ヌ、約
５０〜１００人の範囲の孔径を有する粒子の細孔容積を
全容積の少なくとも５０％とし、０〜５ＯＵの範囲の孔
径を有する細孔容積を最大２５％とする原油又は接頭原
油の水素化脱硫触媒も開示されている（特開昭４７−１
０”＋５６号公報）。Conventionally, hydrodesulfurization methods for residual oil have been actively developed with the aim of reducing the amount of sulfur dioxide released, as sulfur compounds in petroleum fuel become sulfur dioxide gas when burned, becoming one of the sources of air pollution. Many proposals have been made. For example, in order to perform hydrodesulfurization and hydrogenation membrane nitrogen of hydrocarbon oil containing asphalt and metal-containing compounds,
Anticipating that the pore distribution of the hydrorefining catalyst to be used will greatly affect its activity and ability to maintain activity, we have developed a catalyst with a pore radius of 80 Å or more to prevent asphalt and metal-containing compounds from penetrating into the feed oil. The pore volume is 10X of the total pore volume.
A method using a catalyst having a pore distribution suppressed to below (Japanese Patent Publication No. 45-38142) or hydrodesulfurization of the same residual oil in which the volume of pores with a radius of 120 Å or less is 10λ
A method using catalysts distributed relatively uniformly at intervals (Japanese Patent Publication No. 45-38143) is known. of crude oil or prefixed crude oil having a pore volume of at least 50% of the total volume of particles with pore sizes in the range of about 50 to 100 OU and up to 25% of the pore volume with pore sizes in the range of 0 to 5 OU; A hydrodesulfurization catalyst has also been disclosed (Japanese Unexamined Patent Publication No. 47-1
0” + Publication No. 56).

しかしながら、これらの水素化脱硫方法においては、使
用する触媒の細孔半径３０口λ以−ヒのいわゆるマクロ
ボアーの細孔分布については十分検討されておらず、そ
の触媒性能に与える影響は無視されている。すなわち、
従来開示された技術は、いわゆるミクロボアー重点が置
かれているが、ミクロボアのみでは常圧蒸留残渣油、波
圧蒸留軽油及び減圧蒸留残渣油等の如き多量の硫黄分、
望素分、金属分、アスファルトおよびその他の不純物を
含有する炭化水素油の水素化精製の活性および活性維持
能を向上させることができない。However, in these hydrodesulfurization methods, the pore distribution of so-called macropores, which have a pore radius of 30 λ or more, of the catalyst used has not been sufficiently studied, and its influence on catalyst performance has been ignored. There is. That is,
The conventionally disclosed technology focuses on so-called microbore, but with microbore alone, large amounts of sulfur such as atmospheric distillation residue oil, wave pressure distillation gas oil, vacuum distillation residue oil, etc.
It is not possible to improve the activity and activity maintenance ability of hydrorefining hydrocarbon oil containing desired elements, metals, asphalt, and other impurities.

本発明者等は、触媒のミクロボアー及びマクロボアーの
両領域にわたる細孔分布が脱硫及び脱窒素に多大の影響
を与えることを見出した。即ち、水釧圧入法により測定
した細孔直径１５０〜２、０００人の細孔容積が約０．
０１１１１／／ｇ以下であり、目、つ９素吸着法により
測定した３０〜１００人の範囲の直径を有する細孔の容
積が０〜１５０にの範囲の直径を有する細孔の容積の７
０％以上、好ましくは８０％以上、更に好ましくは９０
％以上であり、更に１００〜３００大の範囲の直径を有
する細孔の容積が０〜３００λの範囲の直径を有する細
孔の容積の３０Ｘ以下、好ましくは２０％以下である触
媒が極めて顕著な脱硫効果を発揮することを見出した。The inventors have discovered that the pore distribution across both the microbore and macrobore regions of the catalyst has a profound effect on desulfurization and denitrification. That is, the pore volume of a person with a pore diameter of 150 to 2,000 as measured by the Suizhou intrusion method is about 0.
01111//g, and the volume of pores with a diameter in the range of 30 to 100, measured by the element adsorption method, is 7 to 150 g.
0% or more, preferably 80% or more, more preferably 90%
% or more, and the volume of pores with a diameter in the range of 100 to 300 λ is extremely significant It was discovered that it exhibits a desulfurization effect.

つまり水素化精製用触媒の存在下における水素との接触
において重質炭化水素油、特に、残渣油に含有されるア
スファルト及びレジン分が触媒の細孔に侵入し、触媒の
活性劣化の原因となることを防止するためには、マクロ
ボアーの細孔容積を低減させることが必要である。In other words, upon contact with hydrogen in the presence of a hydrorefining catalyst, heavy hydrocarbon oil, especially asphalt and resin contained in residual oil, enter the pores of the catalyst, causing deterioration of catalyst activity. In order to prevent this, it is necessary to reduce the pore volume of the macrobore.

又、飽和炭化水素の炭素間開裂に伴う炭化水素油の軽質
化を抑制し、アスファルト及びレジン分による触媒の細
孔の閉塞を防止するためには直径３０λ以下の細孔を低
減することが好ましいわけである。In addition, in order to suppress the lightening of hydrocarbon oil due to intercarbon cleavage of saturated hydrocarbons and to prevent the pores of the catalyst from being blocked by asphalt and resin components, it is preferable to reduce pores with a diameter of 30λ or less. That's why.

アルミナシリカの如き固体酸は、炭化水素油の脱硫反応
及び脱窃素反応に適する触媒成分であることはすでに公
知であるが、水素化精製においては、前述の如く所望の
固体酸性度を保持させることが肝要であり、この目的の
ためにはシリカ含有量により酸性制御をなし得る。本発
明者らは、担体中シリカ含有量による酸性制御に基づく
分解活性の調整と共に触媒の細孔構造を特定することに
より、炭化水素油の水素化反応の接触能及び選択性を調
整できることを閣めていもこの種の選択性は、炭化水素
油の脱硫及び脱窒素において水素消費量を節約し、かつ
、分解反応に伴なう炭素分の生成による触媒活性の低下
を防止する効果を有するものであり、極めて重要な役割
を演する。It is already known that a solid acid such as alumina silica is a catalyst component suitable for the desulfurization reaction and demineralization reaction of hydrocarbon oil, but in hydrorefining, it is necessary to maintain the desired solid acidity as described above. This is important, and for this purpose the acidity can be controlled by the silica content. The present inventors have demonstrated that it is possible to adjust the contact ability and selectivity of the hydrogenation reaction of hydrocarbon oil by adjusting the cracking activity based on acidic control by controlling the silica content in the carrier and by specifying the pore structure of the catalyst. Most importantly, this type of selectivity has the effect of saving hydrogen consumption in desulfurization and denitrification of hydrocarbon oils, and preventing a decrease in catalyst activity due to the production of carbon components accompanying the decomposition reaction. and plays an extremely important role.

従って、水素化脱硫反応又は水素化脱窒素反応において
は、前述の如く、過度の分解反応に伴う水素消費量の増
大又はコークの生成等を制御するためにはアルミナ含有
担体中のシリカの含有量を約２〜３５重ｔＸ、好ましく
は約５〜５０重量％の範囲となすべきである。Therefore, in the hydrodesulfurization reaction or hydrodenitrogenation reaction, as mentioned above, in order to control the increase in hydrogen consumption or the formation of coke due to excessive decomposition reaction, the silica content in the alumina-containing carrier must be controlled. should be in the range of about 2 to 35 weight tX, preferably about 5 to 50 weight percent.

上記水素化処理用触媒は、窒素吸着法により測定した直
径３０〜１００人の範囲に細孔が集中しているが、細孔
は、全体としてかなり広範囲に分布したものである。Although the pores of the above-mentioned hydrotreating catalyst are concentrated in a range of 30 to 100 diameters as measured by the nitrogen adsorption method, the pores are distributed over a fairly wide range as a whole.

本発明により開示する触媒のこのような細孔分布が炭化
水素油の水素化脱硫において活性及び活性維持能に顕著
な効果を賦与する理由については十分解明されていない
が、細孔分布を比較的広範囲となしたことにより、原料
油中のアスファルト、レジン分及び金属含有化合物が、
触媒表面に付着した際、細孔径の極めて小さい細孔は閉
塞され、触媒の活性点は完全に隔離されるのに対し、細
孔径を特定範囲で大きくしておくと、金属含有化合物す
なわち、アスファルト又はレジンが同様に触媒表面に付
着はするが、細孔を完全に閉塞せず、次に触媒上に到達
する炭化水素分子及び硫黄分子を活性点に接近させ得る
ことができ、従って、高性能を発揮するものと推定する
ことができる。The reason why such a pore distribution of the catalyst disclosed by the present invention imparts a remarkable effect on the activity and activity maintenance ability in hydrodesulfurization of hydrocarbon oil is not fully elucidated. As a result of wide-ranging, asphalt, resin content and metal-containing compounds in raw oil are
When attached to the catalyst surface, the pores with extremely small pore diameters are blocked and the active sites of the catalyst are completely isolated. However, if the pore diameter is increased within a certain range, metal-containing compounds, that is, asphalt Alternatively, the resin may similarly adhere to the catalyst surface, but not completely block the pores, allowing hydrocarbon molecules and sulfur molecules that then reach the catalyst to approach the active sites, thus achieving high performance. It can be assumed that the

本発明の触媒に使用する相体は、シリカを約２〜６５重
量％含有するアルミナ又はアルミナ含有物質である。ア
ルミナ含有物質としてはアルミナに他の担体物質を配合
させて得られる組成物であり、例えば、マグネシア、酸
化カルシウム、ジルコニア、チタニア、ボリア、ハフニ
ア及び結晶性ゼオライト等の一種又は二種以上をアルミ
ナに配合することができる。前記シリカは、前述の如く
、触媒の固体酸性度の制御には好適であるため、担体中
約２〜３５重量％、好ましくは約５〜３０重量％の範囲
で使用する。更に好ましいシリカ含有域は約７〜１２重
量％の範囲にあることである。The phase used in the catalyst of the present invention is an alumina or alumina-containing material containing about 2 to 65 weight percent silica. The alumina-containing material is a composition obtained by blending alumina with another carrier material, for example, one or more of magnesia, calcium oxide, zirconia, titania, boria, hafnia, crystalline zeolite, etc. is added to alumina. Can be blended. As mentioned above, the silica is suitable for controlling the solid acidity of the catalyst, and therefore is used in an amount of about 2 to 35% by weight, preferably about 5 to 30% by weight in the carrier. A more preferred silica content range is about 7 to 12% by weight.

シリカは、触媒に強酸点を賦与し、触媒の分解活性を増
大させるが、一方、例えば、マグネシアは、アルミナ−
シリカ等が有する強酸点を減少させ、同時に弱酸点を増
加させて触媒の選択性を向上させる作用を有する。前記
マグネシア、酸化カルシウム、ジルコニア、チタニア、
ボリア、ハフニア及び結晶性ゼオライト等の耐火性無機
酸化物の配合量は、アルミナ−シリカに対して約１〜１
０重量％の範囲が適当である。Silica provides strong acid sites to the catalyst and increases the decomposition activity of the catalyst, whereas magnesia, for example,
It has the effect of reducing the strong acid sites possessed by silica and the like, and at the same time increasing the weak acid sites, thereby improving the selectivity of the catalyst. The magnesia, calcium oxide, zirconia, titania,
The amount of refractory inorganic oxides such as boria, hafnia, and crystalline zeolite is approximately 1 to 1
A range of 0% by weight is suitable.

アルミナとしては、γ−アルミナ、χ−アルミナ又はη
−アルミナのいずれか又はそれらの混合体が好適である
。シリカアルミナ担体又はシリカアルミナ含有担体の製
造法は前述の通りであるが、ただ、ここに述べる水素化
処理用触媒の製造に当っては水素化処理用触媒として必
要な細孔分布及び特性値のものを得るようにアルミナ及
びシリカの水和物の沈殿および熟成における温度、時間
等の製造条件の調整を行なう。As alumina, γ-alumina, χ-alumina or η
- Alumina or mixtures thereof are suitable. The method for producing the silica-alumina support or the silica-alumina-containing support is as described above. The manufacturing conditions such as temperature and time for precipitation and aging of alumina and silica hydrates are adjusted to obtain the desired product.

触媒の製造に使用する原料物質として水溶性化合物、例
えば、水溶性酸性アルミニウム化合物又は水溶性アルカ
リ性アルミニウム化合物、具体的には、アルミニウムの
硫酸塩、塩化物、硝酸塩、アルカリ金属アルミニウム及
びアルミニウムアルコキシドその他の無機塩又は有機塩
を使用することができる。水溶性ケイ素化合物としては
、アルカリ金属ケイ酸塩（Ｎａ＊０：ＳｌＯ！＝１：２
〜１；４が好ましい。）、テシラアルフキシシラン、オ
ルソケイ酸エステル等のケイ素含有化合物が適当である
。これらのアルミニウム及びケイ素の化合物は、水溶液
として使用するととができ、水溶液の濃度は、特に限定
するものではなく、適宜決定して差し支えがないが、ア
ルミニウム化合物溶液の濃度は、約１１５〜２モルの範
囲で採用することができる。アルミナ−シリカ担体又は
その他の担体物質を含有する触媒の好ましい製造法は、
アルミナとシリカとの共沈法であるが、沈着法及びゲル
混合法等も採用することができる。Water-soluble compounds, such as water-soluble acidic aluminum compounds or water-soluble alkaline aluminum compounds, specifically, aluminum sulfates, chlorides, nitrates, alkali metal aluminum, aluminum alkoxides, and other raw materials used in the production of catalysts. Inorganic or organic salts can be used. As a water-soluble silicon compound, an alkali metal silicate (Na*0:SlO!=1:2
~1;4 is preferred. ), tesilaalfoxysilane, orthosilicate esters and the like are suitable. These aluminum and silicon compounds can be used as an aqueous solution, and the concentration of the aqueous solution is not particularly limited and may be determined as appropriate, but the concentration of the aluminum compound solution is about 115 to 2 mol. It can be adopted within the range of A preferred method for preparing a catalyst containing an alumina-silica support or other support material is:
Although this is a coprecipitation method of alumina and silica, a deposition method, a gel mixing method, etc. can also be adopted.

上記水素化処理用触媒に好適なアルミナシリカ担体の製
造法の一態様を例示すれば、次の如くである。An example of an embodiment of the method for producing an alumina-silica carrier suitable for the above hydrotreating catalyst is as follows.

酸性アルミニウム水溶液（好ましくは 約１１５〜２モルの範囲）に水酸化アルカリ溶液を添加
し、ｐＨ４０〜１１Ｇの範囲で約５０〜９８℃に加熱し
た後ケイ酸アルカリの水溶液を加え、ｐＨを約４０〜１
ｔＯ１好ましくけ約８０〜１０５の範囲でヒドロゲル又
はヒドロシルを生成させ、又はアンモニア水、硝酸又は
酢酸等を適宜添加し、ｐＨを調整しながらこの懸濁液を
約５０〜９８℃の温度に加熱して少なくとも２時間保持
する。この場合、オキシカルボン酸又はその塩、例えば
酒石酸、クエン酸その他の水酸基多価カルボン酸及びア
ルカリ金属塩を添加すると更に良好な触媒担体が得られ
る。又、アミノジカル酸及びその塩、例えばグルタミン
酸、アスパラギン酸及びその他のアミン基含有多価カル
ボン酸及びアルカリ金属塩を使用することができる。こ
れらの化合物はアルミニウム化合物１モルに対し０．０
００２〜０．１モルの範囲で添加することができる。こ
の処理が終了した後、沈殿を炉別し、酢酸アンモニウム
及び水で洗浄して不純物イオンを除去し、乾燥及び焼成
等の常法を採用して担体に仕上げる。An alkali hydroxide solution is added to an acidic aluminum aqueous solution (preferably in the range of about 115 to 2 mol), heated to about 50 to 98°C to a pH of 40 to 11G, and then an alkali silicate aqueous solution is added to adjust the pH to about 40. ~1
Hydrogel or hydrosil is produced at tO1 preferably in the range of about 80 to 105, or aqueous ammonia, nitric acid or acetic acid is added as appropriate, and the suspension is heated to a temperature of about 50 to 98°C while adjusting the pH. Hold for at least 2 hours. In this case, an even better catalyst support can be obtained by adding oxycarboxylic acid or a salt thereof, such as tartaric acid, citric acid, other hydroxyl polyhydric carboxylic acids, and alkali metal salts. It is also possible to use aminodical acids and their salts, such as glutamic acid, aspartic acid and other amine group-containing polycarboxylic acids and alkali metal salts. These compounds are 0.0 per mole of aluminum compound
It can be added in a range of 0.002 to 0.1 mol. After this treatment is completed, the precipitate is separated in a furnace, washed with ammonium acetate and water to remove impurity ions, and finished into a carrier by conventional methods such as drying and calcination.

乾燥は、酸素の存在下又は非存在下において、常温−約
２００℃に加熱し、焼成は、酸素の存在下において、約
２００〜８００℃の範囲に加熱することにより行なう。Drying is carried out by heating from room temperature to about 200°C in the presence or absence of oxygen, and baking is carried out by heating to about 200 to 800°C in the presence of oxygen.

担体上に担持させる水素化活性金属成分は前述の通りで
ある。特に、炭化水素油の水素化脱硫のためには、特に
、第ＶＩＢ族金属と第■族金属との組合せ、例えば、モ
リブデン−コバルト、モリブデン−ニッケル、タングス
テン−ニッケル、モリブデン−コバルト−ニッケル又は
タングステン−コバルト−ニッケル等の組合せを好まし
く使用することができる。これらの活性金属成分に第３
の金属、つまり元素周期表第■族金属、例えばマンガン
、及び第■族金属、例えば、錫、ゲルマニウム等を添加
して使用することもできる。これら第３の金属は、第１
ステツプの前に担体の前処理として、又は第２ステツプ
の後に後処理として添加することができる。The hydrogenation-active metal component supported on the carrier is as described above. In particular, for the hydrodesulphurization of hydrocarbon oils, combinations of group VIB metals and group Combinations such as -cobalt-nickel can be preferably used. These active metal components contain a tertiary
It is also possible to add metals such as metals from group 1 of the periodic table, such as manganese, and metals from group 1, such as tin and germanium. These third metals
It can be added as a pre-treatment of the carrier before the step or as a post-treatment after the second step.

これら水素化活性金属成分は、酸化物及び／又は硫化物
として担持させることが好適である。These hydrogenation active metal components are preferably supported as oxides and/or sulfides.

水素化活性金属成分は、前述したように第１及び第２ス
テツプに分けて担体に担持される。The hydrogenation active metal component is supported on the carrier in the first and second steps as described above.

触媒の形状は、円筒状、粒状又は錠剤状その他如何なる
ものでもよく、このような形状は、押出成形、造粒成形
等の成形法により得られる。成形物の直径は０．５〜３
．　Ｏｆｆの範囲が好ましい。The shape of the catalyst may be cylindrical, granular, tablet, or any other shape, and such a shape can be obtained by a molding method such as extrusion molding or granulation molding. The diameter of the molded product is 0.5-3
．． A range of Off is preferable.

水素化活性金属成分を含浸した担体は、含浸溶液を分離
した彼、水洗、乾燥及び焼成を行なう。The carrier impregnated with the hydrogenation-active metal component is separated from the impregnating solution, washed with water, dried and calcined.

乾燥及び焼成の条件は、前記担体の場合の条件と同一で
よ・い。重質炭化水素油の水素化脱硫において、触媒は
、使用に先立ち、前述したように予備硫化を行なうこと
が好ましい。The drying and firing conditions may be the same as those for the carrier. In hydrodesulfurization of heavy hydrocarbon oil, the catalyst is preferably presulfurized as described above before use.

金属成分の担持量としては、酸化物として前記第Ｖｌ族
金属については触媒基準で約１〜２０重量％の範囲、第
ＶＩＢ族金属は、約５〜６０重量％の範囲でよい。The supported amount of the metal component may be in the range of about 1 to 20% by weight for the Group Vl metal as an oxide, based on the catalyst, and in the range of about 5 to 60% by weight for the Group VIB metal.

このようにして、製造される触媒は、前述の如く、シリ
カを約２〜３５重量％含有するアルミナ又はアルミナ含
有担体上に少なくとも一種の水素化活性金属成分を担持
させて成り、。The catalyst thus produced comprises at least one hydrogenation-active metal component supported on an alumina or alumina-containing support containing about 2 to 35% by weight of silica, as described above.

■　３０〜１００Ａの範囲の直径を有する細孔の容積が
０〜１５０大の範囲の直径を有する細孔の容積の７０Ｘ
以上 ■　１００〜３００人の範囲の直径を有する細孔の容積
が０〜３００λの範囲の直径を有する細孔の容積の約３
０％以下（上記■及び■の細孔容積は窒素吸着法により
測定）′ ■　水銀圧入法により測定した１５０〜１５０，０００
人の範囲の直径を有する細孔の容積が約０００５〜０２
５１ｔｌ／Ｉ、好ましくはｏ、　１　ｍｅ　７９以下■
　水銀圧入法により測定した１５０〜２．０００　’大
の範囲の直径を有する細孔の容積が約００１１１ＬＩ／
９以下 ■　窒素吸着法により測定した０〜３００大の範囲の直
径を有する細孔の容積が約０６０〜０，７゜ｌｎｌ／ｉ
の範囲 及び ■　比表面積が約２００〜４００１ｒＬ２／ｇ　の範囲
であることを特徴とするものであり全細孔容積；［ｌＬ
４〜１１９　ｒａｔ　／　９　、カサ密度；約０５〜１
．ｏｇ７ｍ１．側面破壊強度；約０．８〜５５ｋｇ／ｖ
ｍであって、炭化水素油の良好な水素化精製用触媒を実
現する。■ The volume of pores with a diameter in the range of 30 to 100A is 70X of the volume of pores with a diameter in the range of 0 to 150A.
The volume of pores with a diameter in the range of 100 to 300 λ is approximately 3 of the volume of pores with a diameter in the range of 0 to 300 λ
0% or less (pore volumes of ■ and ■ above are measured by nitrogen adsorption method)' ■ 150 to 150,000 measured by mercury intrusion method
The volume of pores with diameters in the human range is approximately 0.005-0.02
51 tl/I, preferably o, 1 me 79 or less ■
The volume of pores with diameters ranging from 150 to 2.000' as measured by mercury porosimetry is approximately 00111 LI/
9 or less■ The volume of pores with a diameter in the range of 0 to 300 as measured by nitrogen adsorption method is approximately 060 to 0.7゜lnl/i
and (1) a specific surface area of approximately 200 to 4001 rL2/g, and a total pore volume; [1L
4-119 rat/9, bulk density; approximately 05-1
．． og7m1. Side breaking strength: approx. 0.8 to 55 kg/v
m, to realize a catalyst for good hydrorefining of hydrocarbon oil.

触媒の細孔容積の測定法として使用した窒素吸着法及び
水釧圧入法は、Ｐ、Ｈ，エメット他著「キャタリシス」
第１巻、第１２３頁（ラインホールド・パブリジング・
カンパニー発行）（１９５９年）Ｐ、　１１．　Ｅｒｒ
ｍｅｔｔ、　５ｔａｌ、　”　Ｃａｔａｌｙｓｉｓ”　
、　１　、１２５（１９５９）　（Ｒ，ｅｉｎｈｏｌｄ
　Ｐｕｂｌｉｓｈｉｎｇ　Ｃｏ、　）、及び触媒工学講
座、第４巻、第６９頁〜第７８頁（地人書館発行）（昭
和６９年）にｉｆ！駅の方法による。The nitrogen adsorption method and water injection method used to measure the pore volume of catalysts are described in "Catalysis" by P. H. Emmett et al.
Volume 1, page 123 (Reinhold Publishing)
Company Publishing) (1959) P, 11. Err
mett, 5tal, “Catalysis”
, 1, 125 (1959) (R, einhold
Publishing Co, ) and Catalyst Engineering Course, Volume 4, pp. 69-78 (Published by Chijinshokan) (1988) if! Depends on the station method.

水鋏圧入法においては触媒に対する水銀の接触角を１４
０°、表面張力を４８０ダイン／鋼とし、すべての細孔
は円筒形であると仮定した。In the water scissor injection method, the contact angle of mercury to the catalyst is set to 14
0°, surface tension of 480 dynes/steel, and all pores were assumed to be cylindrical.

窒素吸着法に対しては多分子層吸着に基づく補正の方法
が種々提案されており、その中でもＢＪＨ法（Ｅ、Ｐ、
Ｂａｒｒｅｆｆ、　Ｌ、Ｇ、Ｊｏｙｎｅｒ　ａｎｄ　Ｐ
、Ｐ、　Ｈａｌｎｄａ、　Ｊ、　Ａｍｅｒ、、　Ｃｈｅ
ｍ、　Ｓｏｃ、、　７３．３７５（１９５１））及びＣ
Ｉ法［ＲｏＷ、Ｃｒａｎｓｔｏｎ　ａｎｄ　Ｆ、Ａ、Ｉ
ｎｋｌｅｙ。Various correction methods based on multimolecular layer adsorption have been proposed for the nitrogen adsorption method, among which the BJH method (E, P,
Barreff, L.G., Joyner and P.
, P. Halnda, J. Amer, Che.
m, Soc, 73.375 (1951)) and C.
I method [RoW, Cranston and F, A, I
nkley.

”　Ａｄｖａｎｃｅｓ　ｉｎ　Ｃａｔａｌｙｓｉｓ、　
”　ＩＸ　、　１４　Ｓ　（１９５７）（Ｎｅｗ　Ｙｏ
ｒｋ　Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ　）　）が一般に
用いられている。”Advances in Catalysis,
"IX, 14 S (1957) (New Yo
rk Academic Press )) is commonly used.

本発明における細孔容積に係るデータは吸着等温線の吸
着側を使用し、ＤＨ法［Ｄ、Ｄｏｌｌｉｍｏｒｅａｎｄ
　Ｇ、ＲｏＨｅａｌ、　Ｊ、Ａｐｐｌ、、　Ｃｈｅｍ、
１４．１０９（１９６４））によって計算したものであ
る。The data regarding the pore volume in the present invention is obtained using the adsorption side of the adsorption isotherm, using the DH method [D, Dollimore and
G, RoHeal, J, Appl,, Chem.
14.109 (1964)).

本発明に従って製造した触媒の使用による炭化水素油の
水素化脱硫の方法について述べる。A method for hydrodesulfurization of hydrocarbon oil using a catalyst prepared according to the present invention is described.

重質炭化水素油として減圧蒸留軽油、重質分解油等を使
用することができる。減圧蒸留軽油は、常圧蒸留残渣油
を減圧蒸留して得られる約２５０℃〜５６０℃の範囲の
沸点を有する留分な含有する留出油であり、硫黄分、窒
素分及び金属分を相当量含有するものである。例えば、
中東原油減圧蒸留軽油の一例を挙げるならば、約２〜４
重量％の硫黄分、約０．０５〜０．２重量％の窒素分を
含有する。又、残留炭素分を０．４０５重量％含有する
。As the heavy hydrocarbon oil, vacuum distilled light oil, heavy cracked oil, etc. can be used. Vacuum distilled gas oil is a distillate oil that is obtained by vacuum distillation of atmospheric distillation residue oil and contains fractions with a boiling point in the range of about 250°C to 560°C, and has a considerable amount of sulfur, nitrogen, and metals. It contains a certain amount. for example,
An example of vacuum distilled light oil from Middle Eastern crude oil is approximately 2 to 4
It contains about 0.05-0.2% nitrogen by weight. It also contains 0.405% by weight of residual carbon.

重質分解油は、残渣油を熱分解して得られる約２００℃
以上の沸点を有する分解油であり、例えば、残渣油のコ
ーキングおよびビスブレーキング等から得られる軽油を
使用することができる。Heavy cracked oil is obtained by thermally decomposing residual oil at approximately 200°C.
It is a cracked oil having a boiling point above, and for example, light oil obtained from coking and visbreaking of residual oil can be used.

又、炭化水素油としては、硫黄分、窒素分、アスファル
ト及び金属含有化合物を含有し、実質的に約４８０℃以
上に沸点を有するもので、原油の常圧又は減圧蒸留残渣
油を含有する。例えば、常圧において約４８０℃以上の
沸点を有する炭化水素成分が約３０〜１００重量％の範
囲の残渣油は、通常、約２〜４重量写の硫黄分、約２〜
４重量％の窒素分、約１０〜１．０００　ｐｐｍの金属
及び約１重量％の残留炭素分（コンラドソン）を含有す
る。Further, the hydrocarbon oil contains sulfur, nitrogen, asphalt, and metal-containing compounds, has a boiling point substantially above about 480°C, and contains residual oil from normal pressure or vacuum distillation of crude oil. For example, a residual oil containing about 30 to 100% by weight of hydrocarbon components having a boiling point of about 480° C. or higher at normal pressure typically has a sulfur content of about 2 to 4 parts by weight and about 2 to
Contains 4% by weight nitrogen, about 10-1.000 ppm metals and about 1% residual carbon (Conradson).

前記水素化精製法の原料油としては、前記の如き常圧蒸
留残渣油、減圧蒸留残渣油、減圧蒸留軽油重質分解油若
しくは常圧蒸留軽油又はこれらの混合油を使用すること
ができる。As the raw material oil for the hydrorefining method, the above-mentioned atmospheric distillation residue oil, vacuum distillation residue oil, vacuum distillation gas oil heavy cracked oil, atmospheric distillation gas oil, or a mixture thereof can be used.

反応条件は、原料油の種類、脱硫率又は脱悩累率等の如
何により適宜選択することができる。すなわち、反応温
度；約３５０〜４５０℃、反応圧力；約３０〜２００ｋ
ｇ／（：ｒｎ２、水素含有ガスレイト；約５０〜１５ｏ
ＯＡ！／Ｊ、及び液空間速度；約０．２〜２．ＯＶ／Ｈ
／Ｖを採用する。水素含有ガス中の水素濃度は、約６０
〜１００％の範囲でよい。The reaction conditions can be appropriately selected depending on the type of raw oil, the desulfurization rate, the dehydration rate, etc. That is, reaction temperature: about 350-450°C, reaction pressure: about 30-200k
g/(:rn2, hydrogen-containing gas rate; approx. 50-15o
OA! /J, and liquid space velocity; approximately 0.2 to 2. OV/H
/V is adopted. The hydrogen concentration in hydrogen-containing gas is approximately 60
It may be in the range of ~100%.

本発明に従って製造される触媒は、活性劣化が小さく、
苛酷度の低い反応条件、特に、低反応圧においても高い
脱硫率を達成することができる。The catalyst produced according to the present invention shows little activity deterioration and
A high desulfurization rate can be achieved even under less severe reaction conditions, especially at lower reaction pressures.

水素化脱硫を行なうにあたり、触媒は、前述したように
固定床、流動床又は移動床のいずれの形式でも使用する
ことができるが、装置面又は操作上からは固定床を採用
することが好ましい。又、二基以上の複数基の反応塔を
結合して水素化脱硫を行ない、高度の脱硫率を達成する
ごともできる。In carrying out hydrodesulfurization, the catalyst can be used in any of the fixed bed, fluidized bed, and moving bed formats as described above, but it is preferable to use the fixed bed from the standpoint of equipment and operation. It is also possible to perform hydrodesulfurization by combining two or more reaction towers to achieve a high desulfurization rate.

更に、本発明触媒は、脱硫・脱窒素反応を主体とする主
反応塔に前置の金属除去を目的とするカード・ドラムに
充填使用することもできる。Furthermore, the catalyst of the present invention can also be used to fill a card drum for the purpose of removing metals before a main reaction tower mainly for desulfurization and denitrification reactions.

次に、本発明の実施例について説明する。Next, examples of the present invention will be described.

実施例１．２．３ 硝酸コバル）１５．９．９を蒸留水７０ｍ１に溶解し、
更にこれにアンモニア５ｏｒｎｌを加え、コバルトアン
ミン錯塩溶液を得た。この溶液にシリカアルミナ担体（
シリカ含有ｉ１０％）５０ｇを１６時間浸漬し、コバル
トを酸化コバルトとして５重量％担持した。風乾後′５
００℃で焼成したものを触媒Ａ（実施例１）、５００℃
で焼成したものを触媒Ｂ（実施例２）、６００℃で焼成
したものを触媒Ｃ（実施例３）とする。Example 1.2.3 Cobal nitrate) 15.9.9 was dissolved in 70 ml of distilled water,
Further, 5 ornl of ammonia was added to this to obtain a cobalt ammine complex salt solution. Add silica alumina carrier (
50 g of silica-containing i10%) was immersed for 16 hours to support 5% by weight of cobalt as cobalt oxide. After air drying '5
Catalyst A (Example 1) calcined at 00°C, 500°C
The catalyst calcined at 600° C. is designated catalyst B (Example 2), and the catalyst calcined at 600° C. is designated catalyst C (Example 3).

比較例１．２ 市販のアルミナ担体を用いて、実施例１と同様の手順で
、コバルトを酸化コバルトとして５重量％担持した。焼
成温度３００　℃のものを触媒Ｄ（比較例１）、６００
℃のものを触媒Ｅ（比較例２）とする。Comparative Example 1.2 Using a commercially available alumina carrier, 5% by weight of cobalt was supported as cobalt oxide in the same manner as in Example 1. Catalyst D (Comparative Example 1) and 600°C were calcined at 300°C.
℃ was designated as Catalyst E (Comparative Example 2).

実施例１．２．３及び比較例１．２で得られた触媒の、
酸化コバルトの担持状態を知るため、昇温還元法による
分析を行なった。手順はジエイ・ダブリュ・ジエンキツ
ス（Ｊ、Ｗ、　Ｊｅｎｋｉｎｓ　）（ＣＨＥＭＴＥＣＨ
Ｖｏｌ　７．３１６−３２０、（１９７７））らの方法
に依った。その結果を第１図〜第５図に示す。Of the catalysts obtained in Example 1.2.3 and Comparative Example 1.2,
In order to understand the supported state of cobalt oxide, analysis was performed using temperature programmed reduction method. The procedure is described by J.W. Jenkins (CHEMTECH).
Vol. 7.316-320, (1977)). The results are shown in FIGS. 1 to 5.

アルミナ担体上において酸化コバルトは、３００℃以下
で還元を受ける状態（担体と結合を有しない酸化コバル
ト微粒子と考えられる）か、又は７００℃において還元
を受けない状態（コバルトアルミネートのようにアルミ
ナと強く結合した酸化コバルトと考えられる）のいずれ
かの状態にある。３００℃焼成の触媒りでは、大部分が
前者であり、６００℃焼成の触媒Ｅでは大部分が後者で
ある。中間の焼成温度においても、両者の比が変化する
のみであり、その他の状態の酸化コバルトは見出されな
い。Cobalt oxide on an alumina carrier is either in a state where it undergoes reduction at temperatures below 300°C (considered to be cobalt oxide fine particles that have no bond with the carrier), or in a state where it does not undergo reduction at 700°C (as in cobalt aluminate, it is not reduced with alumina). considered to be strongly bound cobalt oxide). Most of the catalysts fired at 300°C are the former, and catalysts E fired at 600°C are mostly the latter. Even at intermediate firing temperatures, only the ratio between the two changes, and cobalt oxide in other states is not found.

一方、シリカアルミナ担体上では、アルミナ担体の場合
にみられた２つの状態の酸化コバルトは、むしろ少なく
、５００〜７００℃で還元を受ける酸化コバルト（担体
と中程度に結合した酸化コバルト）が大部分であり、焼
成温度の影響はアルミナ担体の場合に比べ小さい。On the other hand, on the silica-alumina support, the two states of cobalt oxide observed in the case of the alumina support are rather small, and the cobalt oxide that undergoes reduction at 500-700°C (cobalt oxide moderately bound to the support) is large. The effect of firing temperature is smaller than in the case of alumina carriers.

以上の結果は、シリカアルミナ担体と、脱硫触媒用担体
として広く用いられているアルミナとでは、活性金属の
一つである酸化コバルトの相持状態が全く異なっている
ことを示しており、シリカアルミナ担体を用いる場合、
このような特徴を生かした新規な触媒製造法が可能であ
ることを示唆している。The above results show that the state of cobalt oxide, which is one of the active metals, is completely different between the silica-alumina carrier and alumina, which is widely used as a carrier for desulfurization catalysts. When using
This suggests that a new catalyst production method that takes advantage of these characteristics is possible.

実施例４ コバルトアンミン錯塩溶液の代りに、硝酸コノくルト水
溶液を用いて実施例１と同様の手順、同じシリカアルミ
ナ担体を用いて、コバルトを酸化コバルトとして５．　
Ｏｗｔ％担持した。焼成温度５００℃のものを触媒Ｆと
する。Example 4 The same procedure as in Example 1 was carried out using an aqueous nitrate solution instead of the cobalt ammine complex salt solution, and the same silica alumina support was used, and cobalt was replaced with cobalt oxide.5.
Owt% was supported. Catalyst F has a firing temperature of 500°C.

触媒Ｆの昇温還元法による分析結果を第６図に示す。触
媒Ｂに比べ、やや複雑なプロフィルを示し、担持状態が
不均一であることを示している。The analysis results of catalyst F by the temperature program reduction method are shown in FIG. Compared to catalyst B, it showed a slightly more complex profile, indicating that the supported state was non-uniform.

比較例３．４．５．６ シリカを２５％含有するシリカアルミナを担体として用
い、４種のコバルトモリブデン触媒を製造した。Comparative Example 3.4.5.6 Four types of cobalt-molybdenum catalysts were produced using silica alumina containing 25% silica as a support.

触媒Ｇ（比較例３）−モリブデン酸アンモニウム１３２
ｇを５ｏｍｌの３規定アンモニア水に溶解。Catalyst G (Comparative Example 3) - Ammonium Molybdate 132
Dissolve g in 5 oml of 3N ammonia water.

これにシリカアルミナ担体２５９を浸漬し、２時間放置
後、液を捨てて、風乾する。５５０℃で焼成後実施例４
と同様の手順で、コバルトを担持する。風乾後５５０℃
で焼成して、触媒Ｇを得た。The silica-alumina carrier 259 is immersed in this, and after being left for 2 hours, the liquid is discarded and air-dried. Example 4 after firing at 550°C
Cobalt is supported using the same procedure. 550℃ after air drying
Catalyst G was obtained.

触媒Ｈ（比較例４）−触媒Ｇと同様の手順でモリブデン
を担持した後、５５０℃で焼成し、更に、実施例１と同
様の手順でコバルトアンミン＠塩溶液を用いてコバルト
を担持した。風乾後５５０℃で焼成して触媒Ｈを得た。Catalyst H (Comparative Example 4) - Molybdenum was supported in the same manner as in Catalyst G, then calcined at 550°C, and cobalt was further supported in the same manner as in Example 1 using a cobalt ammine@salt solution. After air drying, catalyst H was obtained by calcining at 550°C.

触媒Ｉ（比較例５）−硝酸コパル）１３．９ｇを蒸留水
７０ゴに溶解。この溶液に、アンモニア８０１１７を加
える。これに更にモリブデン酸アンモニウム２６４ｇを
溶解した。この溶液にシリカアルミナ担体ｓａｇを浸漬
し、２時間放置後、液を捨て風乾した後、５５０℃で焼
成して触媒■を得た。Catalyst I (Comparative Example 5) - 13.9 g of copal nitrate was dissolved in 70 g of distilled water. Add ammonia 80117 to this solution. Further, 264 g of ammonium molybdate was dissolved in this. A silica-alumina carrier sag was immersed in this solution, and after being left for 2 hours, the solution was discarded, air-dried, and then calcined at 550° C. to obtain catalyst ①.

触媒Ｊ（比較例６）−リンモリブデン酸２８０ｇをエタ
ノール１５０ｄに溶解。この溶液に硝酸コバル）　２７
．７９を更に溶解した。この溶液にシリカアルぐす担体
５０，９を浸漬し、２時間放置後、−液を捨て、風乾し
た後、５５０℃で焼成して触媒Ｊを得た。Catalyst J (Comparative Example 6) - 280 g of phosphomolybdic acid was dissolved in 150 d of ethanol. Add cobal nitrate to this solution 27
．． 79 was further dissolved. Silica argus carriers 50 and 9 were immersed in this solution, left for 2 hours, the solution was discarded, air-dried, and then calcined at 550°C to obtain catalyst J.

実施例５．６ 触媒Ｋ（実施例５）一実施例１と同様の手順でコバルト
アンミン錯塩浴液を用いて、コバルトを担持した。風乾
後５５０℃で焼成し、更にモリブデン酸アンモニウムの
３規定アンモニア溶液に浸漬して、モリブデンを担持し
、た。風乾後５５０℃で焼成して、触媒Ｋを得た。Example 5.6 Catalyst K (Example 5) Cobalt was supported in the same manner as in Example 1 using a cobalt ammine complex salt bath solution. After air drying, it was calcined at 550°C, and further immersed in a 3N ammonia solution of ammonium molybdate to support molybdenum. After air drying, it was calcined at 550°C to obtain catalyst K.

触媒Ｌ　（実施例６）一実施例４と同様の手順で硝酸コ
バルト水溶液を用いてコバルトを担持した。Catalyst L (Example 6) Cobalt was supported using the same procedure as in Example 4 using an aqueous cobalt nitrate solution.

風乾後５５０℃で焼成し、更に実施例７と同様にして、
モリブデンを担持し、触媒りを得た。After air drying, it was fired at 550°C, and then in the same manner as in Example 7,
A catalyst was obtained by supporting molybdenum.

触媒Ｇ、Ｈ１１，Ｊ、に、Ｌの脱硫活性をチオフェンの
脱硫反応により調べた。The desulfurization activity of catalysts G, H11, J, and L was investigated by desulfurization reaction of thiophene.

フィード組成はチオフェン５．５　ｗｔ％、ピリジン２
、３　ｗｔ％、ｎ−ヘキサン９２．２　ｗｔ５Ｘである
。反応条件は下記の通りである。Feed composition: 5.5 wt% thiophene, 2 wt% pyridine
, 3 wt%, n-hexane 92.2 wt5X. The reaction conditions are as follows.

反応温度　５００℃　反応圧　大気圧 フィード流量　ｔ５Ｗ／Ｈ／Ｗ　水素／フィードモル比
　６．０表１ 以−七の結果、シリカを含有するアルミナ担体において
本発明による触媒に、Ｌが、他の方法によって調製され
た触媒Ｇ、Ｈ，Ｉ、Ｊに比べ大巾に高活性であることが
わかる。Reaction temperature: 500°C Reaction pressure: Atmospheric pressure Feed flow rate: t5W/H/W Hydrogen/feed molar ratio: 6.0 Table 1 As a result, the catalyst according to the present invention in the silica-containing alumina support has a different L content than the other methods. It can be seen that the activity is significantly higher than that of catalysts G, H, I, and J prepared by.

比較例７．８、実施例７〜１３ シリカ含有量の異なる９種類のシリカアルミナ担体を用
いてニッケルモリブデン触媒（Ｍ−Ｕ）を調製した。担
持手順は、ニッケルアンミン錯塩を用いたことを除いて
、実施例５（触媒Ｋ）と同様である。Comparative Example 7.8, Examples 7 to 13 Nickel-molybdenum catalysts (MU) were prepared using nine types of silica-alumina supports having different silica contents. The loading procedure was similar to Example 5 (Catalyst K) except that a nickel ammine complex salt was used.

これらの触媒の性能を中東系話圧留出油の脱硫反応によ
り評価した。反応条件は下記の通りである。The performance of these catalysts was evaluated by desulfurization reaction of Middle Eastern pressure distillate oil. The reaction conditions are as follows.

反応温度（℃）　３２０ 反応圧力（ｋｇ／ｃｒｒＬ２）５０ 触媒充填量（ｍｌ）　１２ フィード流量（Ｖ／Ｈ／Ｖ）　α８ Ｈ２／フイード比（ＳＣＦ’／Ｂ）　２５００上記結果
から、本発明による調製法が、シリカを２　ｗｔ％以上
３５ｗｔ％以下含有するシリカアルミナ担体を使用する
コバルトモリブデン又はニッケルモリブデン触媒の脱硫
および／あるいは脱窒素活性の向上に効果が大きいこと
がわかる。Reaction temperature (℃) 320 Reaction pressure (kg/crrL2) 50 Catalyst loading amount (ml) 12 Feed flow rate (V/H/V) α8 H2/feed ratio (SCF'/B) 2500 From the above results, preparation according to the present invention It can be seen that the method is highly effective in improving the desulfurization and/or denitrification activity of a cobalt-molybdenum or nickel-molybdenum catalyst using a silica-alumina carrier containing 2 wt% or more and 35 wt% or less of silica.

実施例１４ 硝酸コバルト９７９及び硝酸ニッケル１４．９を蒸留水
７０Ｍ１に溶解し、この溶液にシリカを１０重量％含有
するシリカアルミナ担体５０ｆ！を１２時間浸漬［２、
コバルト及びニッケルを酸化物と１゜て各々３５重量％
及び０．５重量％担持した。コバルト及びニッケルを担
持した担体を風乾し、５５０℃で焼成した後、３規定モ
リブデン酸アンモニウム水溶液に浸漬しモリブデンを酸
化モリブデンとして１５重鼠算相持し触媒Ｖを得た。そ
の結果は表３に示される。本発明に従った（７’、（＋
−Ｎ　ｉ　−Ｍｏ　系の触媒も又侵れた脱硫率及び脱窒
素率を７１＜すことが分る。Example 14 Cobalt nitrate 979 and nickel nitrate 14.9 were dissolved in 70M1 of distilled water, and this solution contained 10% by weight of silica to form a silica-alumina carrier 50f! Soak for 12 hours [2,
35% by weight each of cobalt and nickel at 1° with oxide
and 0.5% by weight. The carrier supporting cobalt and nickel was air-dried and calcined at 550°C, and then immersed in a 3N ammonium molybdate aqueous solution to convert molybdenum to molybdenum oxide in a 15-layer co-supported manner to obtain catalyst V. The results are shown in Table 3. According to the present invention (7', (+
It can be seen that the -N i -Mo type catalyst also has an increased desulfurization rate and denitrification rate of 71<.

実施例１５ モリブデンの代わりにタングステンを使用したこと以外
実施例９と同一の条件及び操作で触媒Ｗを調製した。タ
ングステンの相持にはタングステン酸アンモニウムを蒸
留水に溶解した溶液を使用した。触媒Ｗの結果は表３に
示される。本発明に従ったＮ１−ｗ系の触媒も又優れた
脱硫率及び脱窒素率を示すことが分る。Example 15 Catalyst W was prepared under the same conditions and operations as in Example 9 except that tungsten was used instead of molybdenum. A solution of ammonium tungstate dissolved in distilled water was used to impregnate tungsten. The results for catalyst W are shown in Table 3. It can be seen that the N1-w based catalyst according to the present invention also exhibits excellent desulfurization and denitrification rates.

実施例１６ 純水４．８ノを約７０℃に加熱し、これに水酸化ナトリ
ウム溶液（ＮａｏＨ２３３，６ｇ、純水５８４ｇ）、硫
酸アルミニウム水溶液（硫酸アルミニウム６４４．５ｆ
ｉ、純水９８７ｇ）を加えた後、酒石酸ニアンモニウム
をアルミナ１に対して２ミリモルになるようにそ゛の水
溶液を加え、水酸化ナトリウム溶液または硝酸溶液でｐ
Ｈを８，８〜９２に調節し、約７０℃で約１時間熟成し
た。これに、ケイ酸ナトリウム水溶液（３号水ガラス４
２．５１！、純水１２　ｑ、　４ｇ　）を加え必要に応
じて硝酸溶液を加え、ｐＨを約９とし、温度約７０℃で
３時間熟成した。Example 16 4.8 g of pure water was heated to about 70°C, and a sodium hydroxide solution (233.6 g of NaoH, 584 g of pure water) and an aqueous aluminum sulfate solution (644.5 g of aluminum sulfate) were added to it.
After adding 987 g of pure water), add an aqueous solution of ammonium tartrate to 2 mmol per 1 part alumina, and dilute with sodium hydroxide solution or nitric acid solution.
H was adjusted to 8.8-92, and the mixture was aged at about 70°C for about 1 hour. To this, add sodium silicate aqueous solution (No. 3 water glass 4
2.51! , 12 q, 4 g of pure water) were added, and a nitric acid solution was added as necessary to adjust the pH to about 9, and the mixture was aged at a temperature of about 70° C. for 3 hours.

生じた泥漿をｆ過し、ｆ別したケーキは、１．５−炭酸
アンモニウム溶液で再泥漿化し、ｆ過した後、Ｐ液のナ
トリウム濃度が５　ｐｐｍ以下になるまで炭酸アンモニ
ウム溶液で洗浄した。これを、１００℃で１６時間乾燥
した後、純水及び少量の酢酸を加え、成型可能な含水量
になるまで乾燥しながら混練し、押出し型成型機により
、ｔ５６φの円柱状に成型した。成型されたペレットは
、１００℃で１６時間乾燥し、さらに６００℃で３時間
焼成して担体とした。The resulting slurry was filtered, and the separated cake was re-sludged with a 1.5-ammonium carbonate solution, filtered, and then washed with an ammonium carbonate solution until the sodium concentration of the P solution became 5 ppm or less. After drying this at 100° C. for 16 hours, pure water and a small amount of acetic acid were added, and the mixture was kneaded while drying until the moisture content reached a moldable level, and was molded into a cylindrical shape with a diameter of 56φ using an extrusion molding machine. The molded pellets were dried at 100° C. for 16 hours and further calcined at 600° C. for 3 hours to obtain a carrier.

一方、硝酸ニッケルを蒸留水に溶解し、更にこれにアン
モニアを加えて調製したニッケルアンミン錯塩溶液を使
用した以外は実施例９と同一の方法でニッケル及びモリ
ブデンを担持した。即ち、とのニッケルアンミン錯塩溶
液に前述のシリカアルミナ担体（シリカ含有量１０重量
％）５０ｇを１６時間浸漬し、ニッケルを酸化ニッケル
として４重量％担持した。ニッケルを担持した担体を風
乾し、次いで５５０℃で焼成した後３規定モリブデン酸
アンモニウム水溶液に浸漬してモリブデンを酸化モリブ
デンとして１４重量％担持した。これを風乾後、５５０
℃で焼成し触媒を得た。これを触媒Ｘとする。この触媒
の物理性状を次に示す。On the other hand, nickel and molybdenum were supported in the same manner as in Example 9, except that a nickel ammine complex salt solution prepared by dissolving nickel nitrate in distilled water and adding ammonia thereto was used. That is, 50 g of the aforementioned silica-alumina carrier (silica content: 10% by weight) was immersed in a nickel ammine complex salt solution for 16 hours to support 4% by weight of nickel as nickel oxide. The carrier supporting nickel was air-dried, then calcined at 550°C, and then immersed in a 3N aqueous ammonium molybdate solution to support 14% by weight of molybdenum as molybdenum oxide. After air drying this, 550
A catalyst was obtained by calcining at ℃. This will be referred to as catalyst X. The physical properties of this catalyst are shown below.

４ 物理性状 比表面積（ｍ２／ｇ）２６５ かさ密度Ｃｇ／１７６）　α７２ 側面破壊強度（ｋｇ／ｌｎ）　ｔｆｓ 触媒粒径（最長）（鯨）　ｔｓ 細孔容積（ｍｌ７ｇ＞ ３０Å以下　［Ｌ００２ ３０〜１００人　０．３Ｂ９ １００〜３００人　［１０７２ ０〜１５０人　０．０４２５ ０〜３００ｋ　０．４６３ ６００Ａ以下（窒素ガス吸着法）　０．５２５１５０〜
１５０，０００ｋ（水銀圧入法）０．０２１１５０〜２
，０００人（水銀圧入法）　０００８ＰＶ（３０〜１０
０）／ＰＶ（０〜１５０）Ｘ１００　９１．５ＰＶ（１
ｏｏ〜３００）／ＰＶ（０〜３０のＸ１００　１５．３
実施例７〜１３の触媒Ｎ〜Ｔは市販のシリカアルミナ担
体を使用して調製され、例えばシリカ含有量が１０重量
％である実施例９の触媒Ｐは次のような物理的性状を有
していた。4 Physical properties Specific surface area (m2/g) 265 Bulk density Cg/176) α72 Side fracture strength (kg/ln) tfs Catalyst particle size (longest) (whale) ts Pore volume (ml7g>30Å or less [L002 30~100 People 0.3B9 100-300 people [1072 0-150 people 0.0425 0-300k 0.463 600A or less (nitrogen gas adsorption method) 0.525150~
150,000k (mercury intrusion method) 0.021150~2
,000 people (mercury intrusion method) 0008 PV (30-10
0)/PV(0~150)X100 91.5PV(1
oo~300)/PV(0~30X100 15.3
Catalysts N to T of Examples 7-13 were prepared using commercially available silica-alumina supports, for example catalyst P of Example 9 with a silica content of 10% by weight had the following physical properties: was.

物理性状 比表面積（ｍ２／＆　）　２１９ かさ密度（ｇ／νｖｔｌ）０．８４ 側面破懐強度（ｋｇ／ｓｏ＋　）　１．５触媒粒径（最
長）（Ｉｆｌ＋）１５ 細孔容積（ｍｌ／ｇ’） 細孔直径（λ） ５０人　００５８ ５０〜１００人　［Ｌ１８９ １００〜３００ｋ　０．１１８ ０〜１５０ｋ　［１２８４ ０〜３００ｋ　１１．３６５ ６００に以下　０．５１７ １５０〜１５０，０００人　０．０２６１５０〜２．ｏ
ｏｏＡ　ｏ、ｏ１３ ＰＶ（３０〜１ｏｏ）／ＰＶ（ｏ〜１５０）Ｘ１００　
６６．５Ｐ■（１０ト３００）／Ｐ■（０〜３００）Ｘ
１００　３２．５表３を見ると、特定の細孔分布を有し
た触媒Ｘが他の細孔分布を有した触媒Ｐより優れた脱硫
率及び脱窒素率を有することが分る。Physical properties Specific surface area (m2/& ) 219 Bulk density (g/νvtl) 0.84 Side breaking strength (kg/so+) 1.5 Catalyst particle diameter (longest) (Ifl+) 15 Pore volume (ml/g') ) Pore diameter (λ) 50 people 0058 50-100 people [L189 100-300k 0.118 0-150k [1284 0-300k 11.365 Below 600 0.517 150-150,000 people 0.026150-2 ．． o
ooA o, o13 PV(30~1oo)/PV(o~150)X100
66.5P■(10to300)/P■(0~300)X
100 32.5 Table 3 shows that catalyst X with a specific pore distribution has a better desulfurization rate and denitrification rate than catalyst P with another pore distribution.

実施例１７ 硝酸コバル）　９．５９及び硝酸ニッケル１７．９を蒸
留水７ｏｍｌに溶解し、更に、これにアンモニア８０ｍ
／を加え、コバルト・ニッケル混合アンミン錯塩溶液を
得た。この溶液にシリカ１０重量％を含有するシリカア
ルミナ担体５０ｇを１６時間浸漬し、コバルト及びニッ
ケルを酸化物として各々３４重量％及び０．６重量％を
担持した。風乾、暁成後実施例１４と同様にして、モリ
ブデンを酸化物として１４重量％担持し、触媒Ｙを得た
。Example 17 Cobal nitrate) 9.59 and nickel nitrate 17.9 were dissolved in 7 oml of distilled water, and further, 80 m of ammonia was added to this.
/ was added to obtain a cobalt-nickel mixed ammine complex salt solution. 50 g of a silica-alumina carrier containing 10% by weight of silica was immersed in this solution for 16 hours to support 34% by weight and 0.6% by weight of cobalt and nickel as oxides, respectively. After air drying and aging, 14% by weight of molybdenum was supported as an oxide in the same manner as in Example 14 to obtain catalyst Y.

表３ 実施例１８〜２８ 水素化活性金属の相持量を変え、水素化活性金属の相持
量と触媒活性との関係を調べた。その結果を表４に示す
。表４から、第■族金属の担持量は０．５〜２０重景％
重量ＶＩＢ族金属の相持量は５〜３０重景％重量効であ
ることが分る。Table 3 Examples 18 to 28 The amount of hydrogenation-active metal supported was varied, and the relationship between the amount of hydrogenation-active metal supported and catalytic activity was investigated. The results are shown in Table 4. From Table 4, the amount of Group Ⅰ metals supported is 0.5 to 20%
It can be seen that the amount of weight group VIB metals is 5 to 30% by weight.

実施例２９ 前記触媒Ｙ及び■を使用して中東系原油の常圧軽油留分
を原料油にして以下の反応条件で水素化処理を行なった
ところ良好な結果を得た。Example 29 Good results were obtained when hydrogenation treatment was carried out under the following reaction conditions using the above-mentioned catalysts Y and (2) using the atmospheric gas oil fraction of Middle Eastern crude oil as feedstock oil.

反応条件 反応温度　（Ｔ）　３ｏ。Reaction conditions Reaction temperature (T) 3o.

反応圧力（ｋｇ／ｃｒＩＬ３Ｇ）１゜ 液空間速度（Ｖ／Ｈ／Ｖ）　ｏ、ｓ 水素対原料油の流量比（ＳＣＦ／１３）　ｓｏ。Reaction pressure (kg/crIL3G) 1° Liquid space velocity (V/H/V) o, s Hydrogen to feedstock flow rate ratio (SCF/13) so.

原料油性状 比重１５／４℃　０．８４３フ イオウ含有量　ｔ０７ 窒素含有ｉｔ　５Ｂ　ｐｐｍRaw oil properties Specific gravity 15/4℃ 0.843f Sulfur content t07 Nitrogen content 5B ppm

【図面の簡単な説明】[Brief explanation of drawings]

第１図〜第３図は、シリカアルミナ担体を使用し、本発
明の方法に従いイオン交換法による＃ｒ１ステップ処理
後の酸化コバルトの相持状態を示すための昇温還元法に
基づく分析結果を示すグラフである。 第４図及び第５図は、アルミナ担体を使用し、イオン交
換法によりコバルトを担持させた触媒の酸化コバルトの
相持状態を示すための昇温還元法に基づく分析結果を示
すグラフである。 第６図は、シリカアルミナ担体を使用し、本発明に従い
含浸法による第１ステツプ処理後の酸化コバルトの相持
状態を示すための昇温還元法に基づく分析結果を示すグ
ラフである。 ４≠々に填冬− （娯盲（饗冬− 〈−脣（嶌へ− く−ト（椹知− 餐≠トに亜永− ４咲“９に嶌知− 手続補正歯 昭和５９年８月例日 特許庁長官　志　賀　学　殿 事件の表示 昭和５９年特許願第　８１９６１、 発明の名称 水素化処理用触媒の製造法 補正をする者 事件との関係　特許出願人 住　所　東京都千代田区−ツ橋−丁目１番１号名　称　
東亜燃料工業株式会社 代理人 住　所　郵便番号　１０５ 東京都港区新橋５丁目１４番２号 鈴エビル　（電話　４５９−８３０９）昭和５９年７月
３１日（発送日） 補正の対象 図面（全図）Figures 1 to 3 show the analysis results based on the temperature programmed reduction method to show the cobalt oxide cobalt state after #r1 step treatment by ion exchange method according to the method of the present invention using a silica alumina support. It is a graph. FIGS. 4 and 5 are graphs showing analysis results based on a temperature programmed reduction method to show the state of cobalt oxide co-supported in a catalyst in which cobalt was supported by an ion exchange method using an alumina carrier. FIG. 6 is a graph showing the results of an analysis based on a temperature-programmed reduction method to show the state of cobalt oxide coexistence after the first step treatment by an impregnation method according to the present invention using a silica-alumina support. 4≠Ni ni Shimachi- (Entertainment Blindness (Entertainment Blindness) 〈-脣(嶌へ-ku-to)(椹ち- supper≠ TO ni Aei- 4 Saki "9 ni Shimachi- Procedural amendment teeth 1988 8 Monthly Patent Office Commissioner Manabu Shiga's case Displayed Patent Application No. 81961 of 1981, Title of Invention Relationship with the Case of Person Amending the Manufacturing Process of a Hydrotreating Catalyst Patent Applicant Address Chiyoda-ku, Tokyo - Tsu Bridge-chome 1-1 name
Toa Fuel Industry Co., Ltd. Agent Address Postal Code 105 Suzue Building, 5-14-2 Shinbashi, Minato-ku, Tokyo (Telephone: 459-8309) July 31, 1980 (shipment date) Drawings subject to amendment (all drawings)

Claims (1)

【特許請求の範囲】 １）担体としてシリカアルミナ又はシリカアルミナ含有
物を使用し、該担体上に先ず元素周期表第■族金属の群
から選択される一種又は二種以上の金属を担持させ、次
で元素周期表第ＶＩＢ族金属の群から選択される一種又
は二種以上の金属を担持させて成る水素化処理用触媒の
製造法。 ２）元素周期表第■族金属はニッケル及びコバルトから
成り、元素周期表第Ｖ［Ｂ族金属はモリブデン及びタン
グステンから成る特許請求の範囲第１項記載の方法。 ３）担体はシリカを２〜３５重ｆＡ、’　Ｘ含有して成
る特許請求の範囲第１項記載の方法。 ４）担体はシリカを５〜５０重ｆ％含有して成る特許請
求の範囲第１項記載の方法。 ５）担体はシリカを７〜１２重景％含有して成る特許請
求の範囲第１項記載の方法。 ６）元素周期表第Ｖ１族金属は酸化物として０５〜２０
重景％含有され、元素周期表第ＶＴ　Ｂ族金属は酸化物
として５〜３０重量％含有するようにした特許請求の範
囲第３項、第４項又は第５項記載の方法。 ７）元素周期表第■族金属は酸化物として１〜８重量％
含有され、元素周期表第Ｗ　Ｂ族金属は酸化物として８
〜２５重量％含有するようにした＠ＦＦ請求の範囲第３
項、第４項又は第５項記載の方法。 ８）元素周期表第■族金属は酸化物として２〜５重量％
含有され、元素周期表第ＶＩＢ族金属は酸化物として１
５〜２０重量％含有するようにした特許請求の範囲第３
項、第４項又は第５項記載の方法。 ９）担体としてシリカアルミナ又はシリカアルミナ含有
物を使用し、該担体を、先ず元素周期表第１１族金属の
群から選択される一種又は二種以上の金属のアンミン錯
塩溶液中に浸漬し、該金属をイオン交換法にて担持させ
、次で風乾及び焼成した後更に元素周期表第ＶＩＢ族金
属の群から選択される一種又は二種以上の金属の可溶性
塩の溶液中に浸漬し、該金属を更に担持させて成る水素
化処理用触媒の製造法。 １０）元素周期表第■族金属はニッケル及びコバルトか
ら成り、元素周期表第ＶＴＢ族金属はモリブデン及びタ
ングステンから成る特許請求の範囲第９項記載の方法。 １１）担体はシリカを２〜３５１量％含有して成る特許
請求の範囲第９項記載の方法。 １２）担体はシリカを５〜３０重量％含有して成る特許
請求の範囲第９項記載の方法。 １３）担体はシリカを７〜１２重惜％含有して成る特許
請求の範囲第９項記載の方法。 １４）元素周期表第ｖＩ族金属は酸化物としてα５〜２
０重量％含有され、元素周期表第ＶＩ　Ｂ族金属は酸化
物として５〜３０重量％含有するようにした特許請求の
範囲第１１項、ｗ、１２項又は第１３項記載の方法。 １５）元素周期表第■族金属は酸化物として１〜８重量
％含有され、元素周期表第ＶＴ　Ｉ３族金属は酸化物と
して８〜２５重１−％含有するようにした特許請求の範
囲第３項、第４項又は第５項記載の方法。 １６）元素周期表第■族金属は酸化物として２〜５重量
％含有され、元素周期表第Ｖ［Ｂ族金属は酸化物として
１５〜２０重量％含有するようにした特許請求の範囲第
１１項、第１２項又は第１６項記載の方法。[Scope of Claims] 1) Using silica-alumina or a silica-alumina-containing material as a carrier, first, one or more metals selected from the group of metals of group Ⅰ of the periodic table of elements are supported on the carrier, A method for producing a hydrotreating catalyst comprising supporting one or more metals selected from the Group VIB metals of the Periodic Table of the Elements. 2) The method according to claim 1, wherein the metals of group 1 of the periodic table of the elements consist of nickel and cobalt, and the metals of group V of the periodic table of the elements consist of molybdenum and tungsten. 3) The method according to claim 1, wherein the carrier contains 2 to 35 times fA,'X of silica. 4) The method according to claim 1, wherein the carrier contains 5 to 50% by weight of silica. 5) The method according to claim 1, wherein the carrier contains 7 to 12 weight percent silica. 6) Group V1 metals of the periodic table of elements are 05 to 20 as oxides.
The method according to claim 3, 4, or 5, wherein the metal of Group VT B of the Periodic Table of the Elements is contained in an amount of 5 to 30% by weight as an oxide. 7) 1 to 8% by weight of Group Ⅰ metals of the Periodic Table of Elements as oxides
The metals of group WB of the periodic table of elements are contained in 8 as oxides.
~25% by weight @FF Claim 3
4. The method according to paragraph 4 or paragraph 5. 8) 2 to 5% by weight of Group Ⅰ metals of the Periodic Table of Elements as oxides
Group VIB metals of the Periodic Table of Elements are contained as oxides of 1
Claim 3 containing 5 to 20% by weight
4. The method according to paragraph 4 or paragraph 5. 9) Using silica alumina or a material containing silica alumina as a carrier, first immerse the carrier in an ammine complex salt solution of one or more metals selected from the group of metals of Group 11 of the Periodic Table of Elements. A metal is supported by an ion exchange method, then air-dried and calcined, and then immersed in a solution of a soluble salt of one or more metals selected from the group VIB metals of the periodic table of elements. A method for producing a catalyst for hydrotreating, which further supports a catalyst. 10) The method according to claim 9, wherein the metals of group 1 of the periodic table of the elements consist of nickel and cobalt, and the metals of group VTB of the periodic table of the elements consist of molybdenum and tungsten. 11) The method according to claim 9, wherein the carrier contains 2 to 351% by weight of silica. 12) The method according to claim 9, wherein the carrier contains 5 to 30% by weight of silica. 13) The method according to claim 9, wherein the carrier contains 7 to 12% silica. 14) Group VI metals of the periodic table of elements have α5~2 as oxides.
14. The method according to claim 11, w, 12 or 13, wherein the metal of group VI B of the periodic table of elements is contained in an amount of 5 to 30 wt% as an oxide. 15) The metal of group Ⅰ of the periodic table of the elements is contained in an amount of 1 to 8% by weight as an oxide, and the metal of group VTI of the periodic table of the elements is contained as an oxide of 8 to 25% by weight. The method described in Section 3, Section 4, or Section 5. 16) The metal of Group I of the Periodic Table of the Elements is contained in an amount of 2 to 5% by weight as an oxide, and the metal of Group V of the Periodic Table of the Elements is contained in an amount of 15 to 20% by weight as an oxide. 12. The method according to paragraph 12 or paragraph 16.
JP59081961A 1984-04-25 1984-04-25 Preparation of hydrogenating treatment catalyst Granted JPS60225645A (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
JP59081961A JPS60225645A (en) 1984-04-25 1984-04-25 Preparation of hydrogenating treatment catalyst
JP59133072A JPS6115739A (en) 1984-04-25 1984-06-29 Hydrogenating-treatment catalyst
CA000479461A CA1249570A (en) 1984-04-25 1985-04-18 Hydrotreating catalyst and process of manufacture
DE8585302790T DE3583356D1 (en) 1984-04-25 1985-04-22 HYDROGEN TREATMENT CATALYST AND METHOD FOR PRODUCING THE SAME.
EP85302790A EP0160475B1 (en) 1984-04-25 1985-04-22 Hydrotreating catalyst and process of manufacture
ES542525A ES8608567A1 (en) 1984-04-25 1985-04-24 Hydrotreating catalyst and process of manufacture.
NO851641A NO851641L (en) 1984-04-25 1985-04-24 HYDRO-TREATMENT CATALYST AND PREPARATION thereof
FI851626A FI851626L (en) 1984-04-25 1985-04-24 VAETEBEHANDLINGSKATALYT OCH DESS FRAMSTAELLNINGSMETOD.
AU41693/85A AU570794B2 (en) 1984-04-25 1985-04-24 Hydrotreating catalyst and process of manufacture
KR1019850002793A KR850007568A (en) 1984-04-25 1985-04-25 Hydroprocessing catalyst and preparation method thereof
AR30020085A AR241872A1 (en) 1984-04-25 1985-04-25 A hydro-treatment catalyst and the procedure for producing it.
US07/084,467 US4837193A (en) 1984-04-25 1987-08-10 Hydrotreating catalyst and process of manufacture
JP4166874A JPH0772273B2 (en) 1984-04-25 1992-06-01 Hydroprocessing method for hydrocarbon oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59081961A JPS60225645A (en) 1984-04-25 1984-04-25 Preparation of hydrogenating treatment catalyst

Publications (2)

Publication Number Publication Date
JPS60225645A true JPS60225645A (en) 1985-11-09
JPH0513706B2 JPH0513706B2 (en) 1993-02-23

Family

ID=13761097

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59081961A Granted JPS60225645A (en) 1984-04-25 1984-04-25 Preparation of hydrogenating treatment catalyst

Country Status (2)

Country Link
JP (1) JPS60225645A (en)
KR (1) KR850007568A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6267874B1 (en) 1997-11-18 2001-07-31 Tonengeneral Sekiyu K.K. Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same
JP2002275212A (en) * 2001-03-21 2002-09-25 Arakawa Chem Ind Co Ltd Method for producing hydrogenated petroleum resin and hydrogenation catalyst used for the production method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6267874B1 (en) 1997-11-18 2001-07-31 Tonengeneral Sekiyu K.K. Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same
JP2002275212A (en) * 2001-03-21 2002-09-25 Arakawa Chem Ind Co Ltd Method for producing hydrogenated petroleum resin and hydrogenation catalyst used for the production method

Also Published As

Publication number Publication date
JPH0513706B2 (en) 1993-02-23
KR850007568A (en) 1985-12-07

Similar Documents

Publication Publication Date Title
US4837193A (en) Hydrotreating catalyst and process of manufacture
US4008149A (en) Process of hydro-refining hydrocarbon oils
JP2547115B2 (en) Hydrotreating catalyst composition for hydrocarbon oil and hydrotreating method using the same
JPS59150541A (en) Hydrotreating catalyst of hydrocarbon oil, production thereof and catalytic hydrotreatment
US4134856A (en) Catalyst for hydro-refining hydrocarbon oils
CN102471700A (en) Hydroprocessing catalyst and method of making the same
WO1998026866A1 (en) Hydrotreating catalyst for heavy hydrocarbon oil, process for producing the catalyst, and hydrotreating method using the same
WO1986003428A1 (en) Catalyst suitable for hydrotreating
US4318801A (en) Supported nickel-molybdenum catalyst, preparation thereof, and hydrodesulfurization of hydrocarbon fractions using same
US5944983A (en) Hydrotreating catalyst and hydrotreating process of hydrocarbon oil by using the same
JPS60225645A (en) Preparation of hydrogenating treatment catalyst
US4399058A (en) Impregnating solution for hydrogenation catalyst manufacture and production thereof
JP5863096B2 (en) Method for producing hydrotreating catalyst
CN107774296B (en) Preparation method of hydrocracking catalyst
JP3802939B2 (en) Catalyst for hydrotreating
JPH06127931A (en) Silica-alumina, its production and catalyst for hydrogenation
JPH07196308A (en) Silica-alumina, its production and catalyst for hydrotreating of light hydrocarbon oil
GB1563593A (en) Catalysts for demtallization tretment of hydrocarbons supported on sepiolite
JPH08224471A (en) Fire resisting inorganic oxide catalyst carrier and hydrogenation catalyst using the same
JP2004277597A (en) Method for hydrogenating hydrocarbon oil by using silica-alumina-based catalyst for hydrogenation
JP4319812B2 (en) Hydroprocessing catalyst and hydrocarbon oil hydroprocessing method
JPS61107946A (en) Hydrotreating catalyst
JPS60220145A (en) Preparation of hydrogen treating catalyst
JPH0576758A (en) Catalyst for hydrogenation treatment
JP3782887B2 (en) Hydrotreating catalyst and hydrotreating method of hydrocarbon oil using the hydrotreating catalyst

Legal Events

Date Code Title Description
EXPY Cancellation because of completion of term