JPH06228572A - Hydrotreatment of kerosene or gas oil fraction - Google Patents
Hydrotreatment of kerosene or gas oil fractionInfo
- Publication number
- JPH06228572A JPH06228572A JP3730593A JP3730593A JPH06228572A JP H06228572 A JPH06228572 A JP H06228572A JP 3730593 A JP3730593 A JP 3730593A JP 3730593 A JP3730593 A JP 3730593A JP H06228572 A JPH06228572 A JP H06228572A
- Authority
- JP
- Japan
- Prior art keywords
- gas oil
- catalyst
- kerosene
- hydrotreating
- oil
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、灯軽油留分の水素化処
理方法に関し、より詳しく言うと、灯油留分又は軽質軽
油、重質軽油、分解軽油、減圧軽油等の各種の軽油留分
あるいはこれらの混合物から硫黄分を効率よく除去し、
脱硫率が高く、性状のよい有用炭化水素油を生産性よく
製造するための灯軽油留分の水素化処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for hydrotreating a kerosene gas oil fraction, more specifically, a kerosene fraction or various gas oil fractions such as light gas oil, heavy gas oil, cracked gas oil and vacuum gas oil. Or efficiently remove sulfur from these mixtures,
The present invention relates to a method for hydrotreating a kerosene gas oil fraction for producing a useful hydrocarbon oil having a high desulfurization rate and good properties with high productivity.
【０００２】[0002]
【従来の技術】原油の常圧あるいは減圧蒸留工程から得
られる各種の留分やその分解によって得られる分解油に
は、通常、数％にも及ぶ硫黄分が含まれている。こうし
た硫黄分を水素化処理によって十分に除去するための技
術（脱硫技術）は、環境保護（大気汚染防止）の点から
極めて重要である。また、水素化処理により脱硫し、性
状を改善した炭化水素油を燃料や原料油として用いるこ
とによって、燃焼反応や転化反応、特に硫黄分を嫌う触
媒反応［触媒燃焼、排ガス触媒浄化処理（脱硝等）、接
触分解プロセス等］の効率を著しく向上させることもで
きる。2. Description of the Related Art Various fractions obtained from atmospheric distillation or reduced pressure distillation of crude oil and cracked oil obtained by cracking the crude oil usually contain sulfur content of several percent. A technique (desulfurization technique) for sufficiently removing such sulfur content by hydrotreatment is extremely important from the viewpoint of environmental protection (prevention of air pollution). In addition, by using hydrocarbon oil that has been desulfurized by hydrotreating and whose properties have been improved as fuel and feedstock oil, combustion reactions and conversion reactions, especially catalytic reactions that dislike sulfur content [catalyst combustion, exhaust gas catalyst purification treatment (such as denitration, etc. ), Catalytic cracking process, etc.] can be significantly improved.
【０００３】このような点から、水素化処理技術の重要
性はますます高まってきており、近年、特に、灯軽油留
分（すなわち、灯油や軽質軽油、重質軽油、減圧軽油、
分解軽油等の軽油類）の水素化処理において、脱硫活性
が高く、性状の良い生成油を生産性よく得ることができ
る水素化処理用触媒（脱硫触媒）の開発が望まれてい
る。From this point of view, the importance of the hydrotreatment technology is increasing, and in recent years, in particular, kerosene and light oil fractions (that is, kerosene, light gas oil, heavy gas oil, reduced pressure gas oil,
In hydrotreatment of light oils such as cracked gas oil), development of a hydrotreating catalyst (desulfurization catalyst) capable of obtaining a product oil having high desulfurization activity and good properties with high productivity is desired.
【０００４】そのような脱硫触媒としては、耐火性酸化
物（アルミナ、シリカアルミナ、チタニア等）を主体と
する耐火性酸化物系触媒担体に、水素化脱硫活性を有す
る金属成分（特に、Ｎｉ−Ｍｏ、Ｃｏ−Ｍｏ、Ｎｉ−
Ｗ、Ｃｏ−Ｗ等の周期表ＶＩＡ族金属とＶＩＩＩ族金属
の組み合わせ系など）が担持されたものが一般に広く使
用されている。As such a desulfurization catalyst, a refractory oxide catalyst carrier mainly composed of refractory oxides (alumina, silica-alumina, titania, etc.) is used, and a metal component having hydrodesulfurization activity (particularly Ni- Mo, Co-Mo, Ni-
A material carrying a combination system of a Group VIA metal and a Group VIII metal such as W or Co-W) is generally widely used.
【０００５】ところで、一般に、担持金属系触媒の触媒
性能は、担体や担持金属成分の種類が同じ場合でも、調
製法によって異なるのが普通であり、特に活性金属成分
の担持状態（例えば、分散度等）などによって著しく異
なることが知られている。したがって、上記のような構
成の脱硫触媒（水素化処理用触媒）についても、同様
に、調製法の違いによって脱硫活性等の触媒性能が大き
く異なることが期待されるので、その調製法の研究は重
要であり、実際、脱硫活性等の反応成績の改善を図るべ
く各種の触媒調製技術が提案されている。By the way, in general, the catalytic performance of a supported metal-based catalyst is usually different depending on the preparation method even when the type of carrier or supported metal component is the same, and particularly the supported state of the active metal component (for example, dispersity). Etc.) and the like. Therefore, with respect to the desulfurization catalyst (hydrotreating catalyst) having the above-mentioned structure, it is expected that the catalytic performance such as desulfurization activity greatly varies depending on the preparation method. It is important, and in fact, various catalyst preparation techniques have been proposed in order to improve reaction results such as desulfurization activity.
【０００６】例えば、特公平３−１２９３５号公報に
は、周期表ＶＩＡ族金属の塩とＶＩＩＩ族金属の塩を含
有する水溶液にリンゴ酸を添加し、これに更にアンモニ
アを作用させて該溶液のｐＨを調整した後、その溶液を
担体（アルミナ等の耐火性酸化物系触媒担体）に含浸
し、次いで焼成することによって水素化処理用触媒を得
るという方法が提案されている。しかしながら、この方
法では、触媒調製時に有毒で発火性のあるアンモニア蒸
気が発生するので危険性が高く、しかも、得られた触媒
の灯軽油留分の水素化処理に対する反応成績も良好とは
言いがたい。For example, in Japanese Examined Patent Publication No. 12935/1993, malic acid is added to an aqueous solution containing a salt of a Group VIA metal and a salt of a Group VIII metal of the Periodic Table, and ammonia is further added to the solution to form a solution of the solution. A method has been proposed in which, after adjusting the pH, a carrier (a refractory oxide catalyst carrier such as alumina) is impregnated with the solution and then calcined to obtain a hydrotreating catalyst. However, this method is highly dangerous because toxic and flammable ammonia vapor is generated during catalyst preparation, and the reaction results of the obtained catalyst for hydrotreatment of kerosene gas oil fraction are not said to be good. I want to.
【０００７】また、特開平４−１６６２３２号公報に
は、アルミナ等の耐火性酸化物系触媒担体に周期表ＶＩ
Ａ族金属の塩とＶＩＩＩ族金属の塩を担持してなる触媒
前駆体に、多価アルコールを添加してから２００℃以下
の温度で乾燥することによって水素化処理用触媒を得る
という方法が開示されている。しかしながら、この方法
では、活性金属成分を担持後に多価アルコールを添加し
ていることもあって、活性金属成分の担持状態の改善効
果が少なく、また、焼成を低温で行っているので、触媒
中に多価アルコールが残存し、これが触媒の前処理時や
触媒反応時にコーキングを起こすので触媒性能に悪影響
を及ぼす。実際、この方法によって得た触媒では、灯軽
油留分の水素化処理に対する脱硫活性の向上効果は不十
分であるし、反応成績も良好ではない。Further, in Japanese Patent Laid-Open No. 4-166232, a refractory oxide type catalyst carrier such as alumina is described in Periodic Table VI.
Disclosed is a method of obtaining a hydrotreating catalyst by adding a polyhydric alcohol to a catalyst precursor supporting a salt of a group A metal and a salt of a group VIII metal and then drying the catalyst precursor at a temperature of 200 ° C. or lower. Has been done. However, in this method, since the polyhydric alcohol is added after supporting the active metal component, the effect of improving the supported state of the active metal component is small, and the calcination is carried out at a low temperature. Polyhydric alcohol remains in the catalyst, which causes coking during the pretreatment of the catalyst and the catalytic reaction, which adversely affects the catalytic performance. In fact, with the catalyst obtained by this method, the effect of improving the desulfurization activity for the hydrotreatment of kerosene gas oil fraction is insufficient, and the reaction results are not good.
【０００８】これらのほかに、アルミナヒドロゲルにポ
リエチレングリコールを添加して焼成することによって
特定の細孔分布を有するアルミナ担体を調製し、このア
ルミナ担体に前記の如き脱硫活性金属成分を担持するこ
とによって水素化処理触媒を調製するという方法も提案
されている（特開昭５２−１０４４０９号公報、同５４
−１０４４９３号公報）。しかしながら、この触媒調製
法では、アルミナ担体の細孔容積が大きくなりすぎ、担
体の（したがって、触媒の）機械的強度が低くなるなど
の問題が生じる。また、この場合、ポリエチレングリコ
ールは、活性金属成分が添加される前に焼成によって除
去されており、金属成分の担持状態に直接影響を及ぼさ
ないので、金属成分の担持状態の改善効果は不十分であ
る。実際、この方法で得た触媒の灯軽油留分の水素化処
理に対する脱硫活性等の反応成績は良好とは言いがた
い。In addition to these, by adding polyethylene glycol to alumina hydrogel and calcining, an alumina carrier having a specific pore distribution is prepared, and by supporting the desulfurization active metal component as described above on the alumina carrier. A method of preparing a hydrotreating catalyst has also been proposed (Japanese Patent Laid-Open Nos. 52-104409 and 54-54).
-104493). However, this catalyst preparation method has problems that the pore volume of the alumina carrier becomes too large and the mechanical strength of the carrier (and thus the catalyst) becomes low. Further, in this case, polyethylene glycol is removed by calcination before the active metal component is added, and since it does not directly affect the loading state of the metal component, the effect of improving the loading state of the metal component is insufficient. is there. In fact, it is difficult to say that the reaction results such as desulfurization activity for the hydrotreatment of the kerosene gas oil fraction of the catalyst obtained by this method are good.
【０００９】このように、従来から水素化処理触媒の改
善が種々試みられてはいるが、いずれの触媒も灯軽油留
分の水素化処理用触媒としては、活性や性能の点でなお
不十分であるという問題点があった。As described above, various attempts have been made to improve the hydrotreating catalysts, but all of them are still insufficient in terms of activity and performance as hydrotreating catalysts for kerosene and light oil fractions. There was a problem that was.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、触媒
調製法の改善特に活性金属成分の担持方法の改善によっ
て灯軽油留分の水素化処理に十分な活性（特に脱硫活
性）及び性能を示す有効な触媒を開発し、該触媒を用い
ることによって、灯油や軽質軽油、重質軽油、減圧軽
油、分解軽油等の各種の軽油類あるいはこれらの混合物
から硫黄分を効率よく除去し、脱硫度が高く、性状のよ
い有用炭化水素油（脱硫灯油や脱硫軽油等）を生産性よ
く製造するための方法である改善された灯軽油留分の水
素化処理方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to improve the activity of catalyst preparation (especially desulfurization activity) and performance for hydrotreatment of kerosene gas oil by improving the method of supporting active metal components. By developing an effective catalyst shown below and using it, sulfur content can be efficiently removed from various light oils such as kerosene, light gas oil, heavy gas oil, reduced pressure gas oil, cracked gas oil, etc. It is an object of the present invention to provide an improved method for hydrotreating a kerosene gas fraction, which is a method for producing a useful hydrocarbon oil (desulfurized kerosene, desulfurized gas oil, etc.) with high productivity and good productivity.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、前記目的
を達成すべく、灯軽油留分の水素化処理（特に脱硫反
応）に対して効率の良い触媒を得るための触媒調製方法
（特に、活性金属成分の担持方法）について鋭意研究を
重ねた結果、例えばアルミナやシリカアルミナ等の各種
の耐火性酸化物を主体とする耐火性酸化物系担体に脱硫
活性金属成分（周期表ＶＩＡ族金属の化合物及び／又は
ＶＩＩＩ族金属の化合物）担持するに際して、水酸基及
び／又はエーテル結合を有し、分子量が１５０以上で、
酸ではない水溶性有機化合物という特定の有機化合物の
存在下で担持し、次いで適当な条件下で焼成してなる触
媒が各種の灯軽油留分（灯油、あるいは前記各種の軽油
類等）の水素化処理反応（特に脱硫反応）に高い活性及
び良好な性能を示し、脱硫度が高く、性状の良い各種の
有用な炭化水素油（脱硫灯油や脱硫軽油等）を効率よく
生産することができることを見いだし、これらの知見及
び事実に基づいて、本発明を完成するに至った。SUMMARY OF THE INVENTION In order to achieve the above object, the present inventors have proposed a method for preparing a catalyst for obtaining an efficient catalyst for hydrotreatment of kerosene gas oil fraction (particularly desulfurization reaction) ( In particular, as a result of earnest studies on a method for supporting an active metal component), for example, a desulfurization active metal component (Group VIA of the Periodic Table) is applied to a refractory oxide-based carrier mainly composed of various refractory oxides such as alumina and silica-alumina. When carrying a metal compound and / or a Group VIII metal compound), it has a hydroxyl group and / or an ether bond, and has a molecular weight of 150 or more,
A catalyst obtained by supporting in the presence of a specific organic compound, which is a water-soluble organic compound that is not an acid, and then calcining it under appropriate conditions is used as a catalyst for hydrogen of various kerosene fractions (kerosene or the various diesel oils mentioned above). It is possible to efficiently produce various useful hydrocarbon oils (desulfurized kerosene, desulfurized gas oil, etc.) that show high activity and good performance in chemical treatment reaction (particularly desulfurization reaction), have high desulfurization degree, and have good properties. The present invention has been completed, and based on these findings and facts, the present invention has been completed.
【００１２】すなわち、本発明は、耐火性酸化物系触媒
担体に周期表ＶＩＡ族金属の化合物及び／又は周期表Ｖ
ＩＩＩ族金属の化合物を分子量が１５０以上でかつ水酸
基及び／又はエーテル結合を有する水溶性有機化合物
（但し、酸は除く。）の存在下で担持させ４００℃以上
で焼成することによって調製された水素化処理用触媒
に、灯油留分又は軽油留分あるいはこれらの混合物を水
素の存在下で接触して水素化処理することを特徴とする
灯軽油留分の水素化処理方法を提供するものである。That is, according to the present invention, a refractory oxide-based catalyst carrier is provided with a compound of Group VIA metal of the periodic table and / or V of the periodic table.
Hydrogen prepared by supporting a Group III metal compound in the presence of a water-soluble organic compound having a molecular weight of 150 or more and having a hydroxyl group and / or an ether bond (excluding acids) and calcining at 400 ° C. or higher. Provided is a method for hydrotreating kerosene gas oil fraction, which is characterized in that a kerosene fraction, a gas oil fraction, or a mixture thereof is contacted with a catalyst for gasification treatment in the presence of hydrogen for hydrotreatment. .
【００１３】本発明の方法においては、灯軽油留分の水
素化処理を行うに当たり、前記特定の方法（担持方法）
によって調製した触媒を使用する。In the method of the present invention, the above-mentioned specific method (supporting method) is used for hydrotreating a kerosene gas oil fraction.
The catalyst prepared by is used.
【００１４】該触媒の調製に使用する前記耐火性酸化物
系触媒担体としては、従来の水素化処理用触媒の担体と
して使用あるいは提案されているものなど各種のものが
使用可能であり、具体的には例えば、アルミナ、シリ
カ、マグネシア、チタニア、ジルコニア等の単独酸化物
系担体、あるいは、シリカアルミナ、シリカマグネシ
ア、シリカチタニア、アルミナチタニア、アルミナボリ
ア、シリカアルミナマグネシア等の複合酸化物系担体、
更には、これらのうちの少なくとも１種を成分として含
有する組成物若しくは複合担体を挙げることができる。
これらの中でも、アルミナ、シリカアルミナ等のアルミ
ナ系の担体が特に好適に使用される。As the refractory oxide-based catalyst carrier used for preparing the catalyst, various carriers such as those used or proposed as carriers for conventional hydrotreating catalysts can be used. In, for example, alumina, silica, magnesia, titania, a single oxide-based carrier such as zirconia, or, silica-alumina, silica magnesia, silica titania, alumina titania, alumina boria, composite oxide-based carrier such as silica-alumina magnesia,
Furthermore, a composition or a composite carrier containing at least one of these as a component can be mentioned.
Among these, alumina-based carriers such as alumina and silica-alumina are particularly preferably used.
【００１５】なお、これらの担体は、必要に応じて適
宜、表面積や細孔制御等の適当な前処理を施し、予め特
性を改善したものを用いてもよい。また、これらの担体
は、例えば、微粒子状、粉末状、顆粒状、あるいは、ビ
ーズ状、ペレット状、押出成形物状等の成形品若しくは
造粒品、更には、モノリス状のもの（モノリス体にコー
ティングしたもの等）など種々の形状及びサイズのもの
として使用することができる。If desired, these carriers may be subjected to appropriate pretreatments such as surface area and pore control to improve their properties in advance. Further, these carriers are, for example, fine particles, powders, granules, beads, pellets, extrudates, or other molded or granulated products, and further monolithic ones (in monolithic form It can be used in various shapes and sizes (such as coated ones).
【００１６】前記耐火性酸化物系触媒担体には、水素化
処理反応時に特に脱硫反応に対して十分な活性を示す金
属成分（以下、活性金属成分と呼ぶ。）となる調製原料
金属化合物である周期表ＶＩＡ族金属の化合物及び／又
は周期表ＶＩＩＩ族金属の化合物を担持する（以下、該
調製原料金属化合物を活性金属化合物と呼ぶことがあ
る。）。The refractory oxide-based catalyst carrier is a prepared raw material metal compound which becomes a metal component (hereinafter referred to as an active metal component) which exhibits sufficient activity particularly for desulfurization reaction during the hydrotreating reaction. A compound of Group VIA metal of the periodic table and / or a compound of Group VIII metal of the periodic table is supported (hereinafter, the prepared raw material metal compound may be referred to as an active metal compound).
【００１７】前記周期表ＶＩＡ族金属としては、通常、
モリブデン、タングステンが好適であり、一方、周期表
ＶＩＩＩ族金属としては、通常、コバルト、ニッケル、
鉄等が好適である。The Group VIA metal of the periodic table is usually
Molybdenum and tungsten are preferred, while the Group VIII metals of the Periodic Table are usually cobalt, nickel,
Iron or the like is preferable.
【００１８】特に好適な水素化処理触媒（脱硫触媒）を
与える担持金属の種類あるいは組み合わせとしては、単
独金属担持系の場合には、例えば、ニッケルやモリブデ
ンを挙げることができ、また、複合金属担持系の場合に
は、例えば、コバルト・モリブデン、ニッケル・モリブ
デン、ニッケル・タングステン、ニッケル・モリブデン
・タングステン、コバルト・モリブデン・タングステ
ン、コバルト・ニッケル・モリブデン、コバルト・ニッ
ケル・モリブデン・タングステン等の（コバルト及び／
又はニッケル）と（モリブデン及び／又はタングステ
ン）の組み合わせ系、あるいは、これらに鉄や他の金属
を添加した系、また、鉄・モリブデン系などを例示する
ことができる。In the case of a single metal supporting system, for example, nickel or molybdenum can be cited as the kind or combination of supporting metals which provide a particularly suitable hydrotreating catalyst (desulfurization catalyst). In the case of a system, for example, cobalt molybdenum, nickel molybdenum, nickel tungsten, nickel molybdenum tungsten, cobalt molybdenum tungsten, cobalt nickel nickel molybdenum, cobalt nickel molybdenum tungsten, etc. /
Alternatively, a combination system of nickel) and (molybdenum and / or tungsten), a system in which iron or another metal is added to these, or an iron / molybdenum system can be exemplified.
【００１９】なお、必要に応じて、これらの金属成分の
他に、他の金属成分を担持してもよい。In addition to these metal components, other metal components may be supported as needed.
【００２０】前記担体への担持に際してこれらの金属
は、例えば、酸化物、硝酸塩、硫酸塩、炭酸塩、塩基性
炭酸塩、塩化物等のハロゲン化物、アンモニウム塩ある
いはアンミン錯体等の無機化合物、蓚酸塩、酢酸塩等の
有機酸塩、カルボニル錯体、アセチルアセトナト錯体等
の各種の有機錯体化合物など各種の種類及び形態の化合
物として使用することができるが、コバルト、ニッケル
及び鉄の場合には、通常、硝酸塩、酢酸塩等の水溶性の
塩が好適に使用され、一方、モリブデン、タングステン
の場合には、通常、パラモリブデン酸アンモニウム、メ
タモリブデン酸アンモニウム、パラタングステン酸アン
モニウム、メタタングステン酸アンモニウム等によって
代表されるモリブデン酸塩、タングステン酸塩などが好
適に使用される。When loaded on the carrier, these metals are, for example, oxides, nitrates, sulfates, carbonates, basic carbonates, halides such as chlorides, inorganic compounds such as ammonium salts or ammine complexes, and oxalic acid. Salts, organic acid salts such as acetate, carbonyl complex, various organic complex compounds such as acetylacetonato complex can be used as various types and forms of compounds, in the case of cobalt, nickel and iron, Usually, water-soluble salts such as nitrates and acetates are preferably used, while in the case of molybdenum and tungsten, they are usually ammonium paramolybdate, ammonium metamolybdate, ammonium paratungstate, ammonium metatungstate, etc. Molybdates and tungstates represented by are preferably used.
【００２１】これらの活性金属成分の担持量は、得られ
る触媒重量当たりの金属の重量％として計算して、周期
表ＶＩＡ族金属については、通常、０．５〜３０重量％
の範囲に選定するのが好ましく、また、周期表ＶＩＩＩ
族金属については、通常、１〜５０重量％の範囲に選定
するのが好ましい。The amount of these active metal components supported is calculated as the weight% of the metal based on the weight of the catalyst obtained, and is usually 0.5 to 30% by weight for the Group VIA metal in the periodic table.
Of the periodic table VIII.
Regarding the group metal, it is usually preferable to select it in the range of 1 to 50% by weight.
【００２２】本発明の水素化処理方法に使用する前記水
素化処理用触媒は、上記したように適当な耐火性酸化物
系触媒担体に適当な活性金属化合物を担持することによ
り調製するという点においては、従来のこの種の水素化
処理触媒の場合と同様にすることができるのであるが、
本発明の場合には、前記活性金属化合物を前記耐火性酸
化物系触媒担体に担持するに際して、水酸基及び／又は
エーテル結合を有し、分子量が１５０以上で、酸ではな
い水溶性有機化合物（以下、該化合物を水溶性有機化合
物［Ｉ］と呼ぶ。）という特定の有機化合物の存在下で
担持することが重要であり、このようにして担持するこ
とによって調製された水素化処理触媒を用いることによ
って、前記本発明の目的が達成される。The hydrotreating catalyst used in the hydrotreating method of the present invention is prepared by supporting a suitable refractory oxide catalyst carrier with a suitable active metal compound as described above. Can be similar to conventional hydrotreating catalysts of this type,
In the case of the present invention, when the active metal compound is supported on the refractory oxide catalyst carrier, a water-soluble organic compound having a hydroxyl group and / or an ether bond, a molecular weight of 150 or more, and not an acid (hereinafter , The compound is referred to as a water-soluble organic compound [I].) It is important to support the compound in the presence of a specific organic compound, and a hydrotreating catalyst prepared by supporting the compound in this manner is used. By the above, the above-mentioned object of the present invention is achieved.
【００２３】前記水溶性有機化合物［Ｉ］は、水酸基及
び／又はエーテル結合を有し、分子量が１５０以上で、
酸ではない水溶性有機化合物であればどのような種類及
び構造のものでもよく、これらは、１種単独で使用して
もよいし、２種以上を混合物等として併用してもよい。
ここで、酸ではない水溶性有機化合物とは、水に対して
十分な溶解性又は親和性を有する有機化合物であって、
分子全体として通常酸性化合物とはみなされない化合物
（好ましくは、例えばフリーのカルボキシル基やスルホ
ン酸基等の酸性基を持たない化合物）のことを言う。す
なわち、このように、いわゆる酸性化合物ではないもの
であれば、水酸基やエーテル結合の他に、例えばエステ
ル基、アミノ基等の他の官能基を有しているものでもよ
い。なお、分子量については、２００以上のものが好ま
しい。The water-soluble organic compound [I] has a hydroxyl group and / or an ether bond, has a molecular weight of 150 or more,
Any type and structure of water-soluble organic compounds other than acids may be used, and these may be used alone or in combination of two or more.
Here, the water-soluble organic compound which is not an acid is an organic compound having sufficient solubility or affinity for water,
It refers to a compound that is not generally regarded as an acidic compound as a whole molecule (preferably, a compound having no acidic group such as a free carboxyl group or sulfonic acid group). That is, as long as it is not a so-called acidic compound, it may have other functional groups such as an ester group and an amino group in addition to the hydroxyl group and the ether bond. The molecular weight is preferably 200 or more.
【００２４】このような水溶性有機化合物［Ｉ］として
は、多種多様なものがあるが、中でも好ましいものの代
表例を示すと、例えば、ポリエチレングリコール、ポリ
オキシエチレンフェニルエーテル、ポリオキシエチレン
オクチルフェニルエーテル等のエーテル含有水溶性高分
子、ポリビニルアルコール等のアルコール性水酸基含有
水溶性高分子、サッカロース、グルコース等の各種糖
類、メチルセルロース、水溶性デンプン等の水溶性多糖
類若しくはその誘導体などを例示することができる。As the water-soluble organic compound [I], there are various kinds, and typical examples of preferable ones are, for example, polyethylene glycol, polyoxyethylene phenyl ether, polyoxyethylene octyl phenyl ether. Examples include ether-containing water-soluble polymers such as polyvinyl alcohol, water-soluble polymers containing alcoholic hydroxyl groups such as polyvinyl alcohol, saccharides such as sucrose and glucose, water-soluble polysaccharides such as methyl cellulose and water-soluble starch, or derivatives thereof. it can.
【００２５】前記水素化処理用触媒は、前記所定の耐火
性酸化物系触媒担体に、前記所定の活性金属化合物を、
前記水溶性有機化合物［Ｉ］のうちの少なくとも１種の
存在下で担持する限り、他の点については、従来と同様
の手法によって調製することができる。In the hydrotreating catalyst, the predetermined active metal compound is added to the predetermined refractory oxide catalyst carrier.
As long as it is carried in the presence of at least one of the water-soluble organic compounds [I], it can be prepared by a method similar to the conventional method in other respects.
【００２６】この少なくとも水溶性有機化合物［Ｉ］の
存在下で実施する活性金属化合物の担持は、例えば、真
空含浸法、加熱含浸法、浸漬法、混練法など公知の各種
の担持操作手法に従って好適に行うことができる。通常
は、担持に供する前記活性金属化合物を適当な濃度の水
溶液とした状態で水溶性有機化合物［Ｉ］の存在下で担
持する方法が好適に採用される。その際、担持に供する
各成分は、これらを同時に添加混合してもよいし、逐次
的に添加混合するか、水溶性有機化合物［Ｉ］を予め耐
火性酸化物系触媒担体に添加して、次いで、活性金属化
合物の水溶液を添加することが好ましい。The supporting of the active metal compound carried out in the presence of at least the water-soluble organic compound [I] is preferably carried out according to various known supporting operation methods such as vacuum impregnation method, heat impregnation method, dipping method and kneading method. Can be done. Usually, a method of supporting the active metal compound to be supported in the presence of the water-soluble organic compound [I] in the state of an aqueous solution having an appropriate concentration is suitably adopted. At that time, each component to be supported may be added and mixed at the same time, or may be sequentially added and mixed, or the water-soluble organic compound [I] may be added to the refractory oxide-based catalyst carrier in advance, Then, it is preferable to add an aqueous solution of the active metal compound.
【００２７】その際、担持系に共存あるいは添加する水
溶性有機化合物［Ｉ］の割合は、使用する耐火性酸化物
系触媒担体の乾燥重量１００重量部に対して、通常、
０．１〜１００重量部の範囲に選定するのが好適であ
り、特に、１〜５０重量部の範囲に選定するのが好まし
い。この割合が上記の基準で０．１重量部未満であると
水溶性有機化合物［Ｉ］の添加効果が十分に発揮され
ず、一方、１００重量部を超えると、活性金属化合物の
溶解性が悪くなるなどの理由によって、均一に担持する
ことが困難になることがある。In this case, the proportion of the water-soluble organic compound [I] coexisting with or added to the supporting system is usually 100 parts by weight of the dry weight of the refractory oxide catalyst carrier used.
It is preferable to select in the range of 0.1 to 100 parts by weight, and it is particularly preferable to select in the range of 1 to 50 parts by weight. If this ratio is less than 0.1 parts by weight based on the above criteria, the effect of adding the water-soluble organic compound [I] will not be sufficiently exerted, while if it exceeds 100 parts by weight, the solubility of the active metal compound will be poor. For some reason, it may be difficult to support the particles uniformly.
【００２８】なお、前記担持は、水溶性有機化合物
［Ｉ］の他に、必要に応じて他の添加成分の共存下で行
ってもよい。例えば、担持する活性金属化合物の水溶液
の安定性を向上させて、担持をより均一にかつ安定に行
うために、カルボン酸等の適当な有機酸を添加すること
が好適に採用される。この場合、有機酸としては、各種
のものが使用可能であり、具体的には例えば、蓚酸、酒
石酸、コハク酸、マロン酸、リンゴ酸、クエン酸、蟻
酸、酢酸、プロピオン酸などを例示することができる。
これらの有機酸は、必要に応じて、１種又は２種以上添
加してよい。The supporting may be carried out in the coexistence of other additional components, if necessary, in addition to the water-soluble organic compound [I]. For example, in order to improve the stability of the aqueous solution of the active metal compound to be carried and carry out the carrying more uniformly and stably, it is preferable to add an appropriate organic acid such as carboxylic acid. In this case, various organic acids can be used, and specific examples include oxalic acid, tartaric acid, succinic acid, malonic acid, malic acid, citric acid, formic acid, acetic acid, and propionic acid. You can
These organic acids may be added alone or in combination of two or more, if necessary.
【００２９】その際、添加する有機酸の割合は、使用す
る耐火性酸化物系触媒担体の乾燥重量１００重量部に対
して、例えば、０．１〜１００重量部の範囲に選定する
のが好ましく、特に、５〜５０重量部の範囲に選定する
のが好ましい。この割合が上記の基準で０．１重量部未
満であると有機酸の添加効果が十分に発揮されず、一
方、１００重量部を超えると、活性金属化合物の溶解性
が悪くなるなどの理由によって、かえって均一に担持す
ることが困難になることがある。At that time, the proportion of the organic acid to be added is preferably selected in the range of, for example, 0.1 to 100 parts by weight with respect to 100 parts by weight of the dry weight of the refractory oxide catalyst carrier to be used. It is particularly preferable to select the range of 5 to 50 parts by weight. If the ratio is less than 0.1 part by weight based on the above criteria, the effect of adding the organic acid is not sufficiently exerted, while if it exceeds 100 parts by weight, the solubility of the active metal compound deteriorates. On the contrary, it may be difficult to uniformly support the particles.
【００３０】本発明の方法において使用する前記水素化
処理用触媒は、以上のようにして所定の活性金属化合物
を担持した後、適宜、乾燥、焼成することによって得る
ことができる。The hydrotreating catalyst used in the method of the present invention can be obtained by carrying a predetermined active metal compound as described above, and then appropriately drying and calcining.
【００３１】この乾燥温度としては、通常、５０〜１５
０℃、好ましくは、８０〜１３０℃の範囲に選定するの
が好適である。The drying temperature is usually 50 to 15
It is suitable to select in the range of 0 ° C, preferably 80 to 130 ° C.
【００３２】また、焼成は、通常、空気若しくは酸素の
存在下で適当な温度で行うことが好ましく、これによっ
て前記担持後、あるいは担持乾燥後に固体に含有されて
いる水溶性有機化合物［Ｉ］等の有機成分を十分に除去
することが好ましい。これらの有機成分が触媒中に多く
残存すると、それらが触媒反応時あるいは前処理時にコ
ーキングを起こし、触媒活性等の性能に支障をきたすこ
とがある。The calcination is usually preferably carried out in the presence of air or oxygen at an appropriate temperature, whereby the water-soluble organic compound [I] etc. contained in the solid after the supporting or after the supporting is dried. It is preferable to sufficiently remove the organic component of. If a large amount of these organic components remain in the catalyst, they may cause coking during the catalytic reaction or during the pretreatment, which may impair the performance such as catalytic activity.
【００３３】焼成温度は、通常、４００〜６５０℃、好
ましくは、５００〜６００℃の範囲に選定するのが好適
である。なお、前記担持後、乾燥あるいは焼成を行う前
に、必要に応じて、担持物を成形してもよい。The firing temperature is usually 400 to 650 ° C., preferably 500 to 600 ° C. In addition, after carrying, before carrying out drying or firing, the carried product may be molded, if necessary.
【００３４】以上のようにして、脱硫活性に優れ、性能
の良い所望の水素化処理用触媒を好適に得ることができ
る。As described above, a desired hydrotreating catalyst having excellent desulfurization activity and good performance can be suitably obtained.
【００３５】以下、このように、活性金属化合物を水溶
性有機化合物［Ｉ］の存在下で担持することによって調
製した前記水素化処理用触媒を、水素化処理用触媒
［Ａ］と呼ぶ。Hereinafter, the above-mentioned hydrotreating catalyst prepared by supporting the active metal compound in the presence of the water-soluble organic compound [I] is referred to as hydrotreating catalyst [A].
【００３６】本発明の灯軽油留分の水素化処理方法にお
いては、原料油として灯油留分又は軽油留分あるいはこ
れらの混合物を用い、該原料油を水素ガスの存在下で上
記のようにして調製した水素化処理用触媒［Ａ］に接触
させて水素化処理し、これによって該原料油から硫黄分
を効率よく除去し、脱硫度が高く、性状のよい有用炭化
水素油（脱硫灯油や脱硫軽油等）を生産性よく製造す
る。In the method for hydrotreating a kerosene gas oil fraction of the present invention, a kerosene fraction, a gas oil fraction or a mixture thereof is used as a feed oil, and the feed oil is treated in the presence of hydrogen gas as described above. The prepared hydrotreating catalyst [A] is brought into contact with and hydrotreated to effectively remove sulfur from the raw material oil, thereby producing a useful hydrocarbon oil having a high degree of desulfurization and good properties (desulfurization kerosene or desulfurization). Gas oil etc.) with high productivity.
【００３７】前記原料油に用いる灯油留分としては、原
油の常圧蒸留や減圧蒸留によって得られた各種の沸点範
囲にある、軽質軽油留分（ＬＧＯ）、重質軽油留分（Ｈ
ＧＯ）、減圧軽油留分（ＶＧＯ）等の軽油留分や重質油
等の熱分解や接触分解等によって得られた各種の沸点範
囲にある分解軽油留分等の様々な軽油留分を使用するこ
とができる。The kerosene fraction used as the feed oil is a light gas oil fraction (LGO) or a heavy gas oil fraction (HH) in various boiling range obtained by atmospheric distillation or vacuum distillation of crude oil.
Uses various gas oil fractions such as cracked gas oil fractions with various boiling points obtained by thermal cracking or catalytic cracking of gas oil fractions such as GO) and vacuum gas oil fractions (VGO) and heavy oils. can do.
【００３８】これらの灯油留分や軽油留分は、それぞれ
所定の留分を混合せずに単独で使用してもよいし、ある
いは、２種以上の留分を適宜混合して用いてもよい。も
ちろん、必要に応じて、灯油留分と軽油留分の混合留分
を用いてもよいし、軽油留分についても、広い沸点範囲
にある軽油留分を用いてもよい。These kerosene fractions and light oil fractions may be used alone without mixing predetermined fractions, or may be used by appropriately mixing two or more fractions. . Of course, if necessary, a mixed fraction of a kerosene fraction and a gas oil fraction may be used, and as the gas oil fraction, a gas oil fraction having a wide boiling range may be used.
【００３９】また、前記原料油には、本発明の目的を阻
害しない範囲で、前記灯油留分や軽油留分のほかに、他
のより軽質な留分やより重質な留分が含有していてもよ
いし、あるいは、減圧フラッシュ等の中間留分を添加し
てもよい。In addition to the kerosene fraction and the light oil fraction, the feed oil contains other lighter fractions and heavier fractions within a range not impairing the object of the present invention. Or a middle distillate such as a vacuum flash may be added.
【００４０】前記水素化処理に供する原料油における硫
黄含量としては、特に制限はないが、通常、硫黄含量
が、０．５〜２．０重量％の範囲にあるものが好適に使
用される。The sulfur content in the feed oil to be subjected to the hydrotreatment is not particularly limited, but normally, a sulfur content in the range of 0.5 to 2.0% by weight is preferably used.
【００４１】この水素化処理を行うに際して、前記水素
化処理用触媒［Ａ］は、そのまま、反応に用いてもよい
が、必要に応じて、水素等による還元処理や硫化水素等
による予備硫化等の前処理を適宜行ってから反応に供し
てもよい。また、該水素化処理用触媒［Ａ］は、必要に
応じて、例えばアルミナ等の前記耐火性酸化物系触媒担
体やシリコンカーバイトで希釈して用いてもよいし、あ
るいは、適当なガード触媒若しくは担体と共に用いても
よい。In carrying out this hydrotreating, the hydrotreating catalyst [A] may be used as it is for the reaction, but if necessary, reduction treatment with hydrogen or the like, presulfurization with hydrogen sulfide or the like may be carried out. The pretreatment may be appropriately performed before the reaction. If desired, the hydrotreating catalyst [A] may be diluted with the refractory oxide-based catalyst carrier such as alumina or silicon carbide, or used as a suitable guard catalyst. Alternatively, it may be used together with a carrier.
【００４２】この水素化処理に好適に採用される反応条
件は、以下の通りである。The reaction conditions suitably adopted for this hydrotreatment are as follows.
【００４３】すなわち、反応温度は、通常、２００〜４
５０℃程度、好ましくは、２５０〜３８０℃程度の範囲
に選定するのが好適である。反応圧力は水素圧として、
通常、１０〜１００ｋｇ／ｃｍ2 Ｇ程度、好ましくは、
２０〜８０ｋｇ／ｃｍ2 Ｇ程度の範囲に選定するのが好
適である。液空間速度（ＬＨＳＶ）は、通常、０．５〜
１０ｈ-1程度、好ましくは、１〜５ｈ-1程度の範囲に選
定するのが好適である。水素ガスと原料油の供給割合
（Ｈ2／Ｏｉｌ）は、通常、５０〜４００Ｎｌ／ｋｌ程
度、好ましくは、１００〜３００Ｎｌ／ｋｌの範囲に選
定するのが好適である。That is, the reaction temperature is usually 200 to 4
It is suitable to select in the range of about 50 ° C, preferably about 250 to 380 ° C. The reaction pressure is hydrogen pressure,
Usually, about 10 to 100 kg / cm 2 G, preferably
It is preferable to select the range of about 20 to 80 kg / cm 2 G. Liquid hourly space velocity (LHSV) is usually 0.5-
About 10h -1, preferably, suitable to select a range of about 1~5h -1. The supply ratio (H 2 / Oil) of the hydrogen gas and the feedstock oil is usually selected in the range of about 50 to 400 Nl / kl, preferably 100 to 300 Nl / kl.
【００４４】反応型式としては、固定床、流動床、移動
床、沸騰床など各種の型式が適用可能であるが、運転の
容易性、装置の経済性の点から、通常、固定床が最も好
ましい。As the reaction type, various types such as a fixed bed, a fluidized bed, a moving bed, and a boiling bed can be applied, but the fixed bed is usually the most preferable from the viewpoint of easy operation and economical efficiency of the apparatus. .
【００４５】以上のようにして、水素化処理することに
よって、減圧軽油と軽質軽油あるいはこれらと添加した
炭化水素油（重質軽油等）を同時に効率よく水素化処理
（脱硫処理等）することができ、性状に優れた生成油が
得られる。By carrying out the hydrotreating as described above, the reduced pressure gas oil and the light gas oil or the hydrocarbon oil (heavy gas oil etc.) added with these can be efficiently hydrotreated (desulfurization etc.) at the same time. A product oil having excellent properties can be obtained.
【００４６】こうして水素化処理されて得られた脱硫生
成物は、そのままでも燃料や各種の炭化水素類への転化
原料等としても有用であるが、通常、蒸留工程に送ら
れ、所望の種々の留分に分留される。The desulfurized product obtained by the hydrotreatment in this manner is useful as it is as a fuel or a raw material for conversion into various hydrocarbons, etc., but it is usually sent to a distillation step to obtain various desired products. Fractionated into fractions.
【００４７】こうして得られた各種の留分は、硫黄分が
著しく少なく、脱硫減圧軽油についてはその硫黄分を通
常０．３％程度若しくはそれ以下に、脱硫軽質軽油につ
いてはその硫黄分を通常０．０５％程度若しくはそれ以
下にまで容易に低減することができる。The various fractions thus obtained have a remarkably low sulfur content, and for desulfurized vacuum gas oil, the sulfur content is usually about 0.3% or less, and for desulfurized light gas oil, the sulfur content is usually 0%. It can be easily reduced to about 0.05% or less.
【００４８】こうして回収された脱硫減圧軽油は、ＦＣ
Ｃプロセスの原料油あるいはその成分として好適に使用
することができ、これによって、硫黄分の著しく少ない
高品質のガソリンを高い収率で安定に得ることができ
る。The desulfurized vacuum gas oil thus recovered is FC
It can be suitably used as a feedstock of C process or its component, and by this, high-quality gasoline having extremely low sulfur content can be stably obtained in high yield.
【００４９】一方、得られた脱硫軽質軽油等の軽油は、
例えば、ディーゼル油等の燃料など各種の用途に好適に
利用することができる。On the other hand, the obtained light oil such as desulfurized light gas oil is
For example, it can be suitably used for various applications such as fuel such as diesel oil.
【００５０】また、得られたナフサや灯油等の他の留分
も、それぞれ、各種の分野に好適に利用することができ
る。Other fractions such as the obtained naphtha and kerosene can also be suitably used in various fields.
【００５１】[0051]
【実施例】以下に、本発明の実施例及びその比較例を示
し、本発明をより具体的に説明するが、本発明はこれら
の実施例に限定されるものではない。The present invention will be described more specifically below by showing Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.
【００５２】実施例１ パラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・
４Ｈ2Ｏ）］３２．１ｇ、硝酸コバルト［Ｃｏ（ＮＯ3）
3］２７．１ｇ、ポリエチレングリコール４００［ＨＯ
−（ＣＨ2ＣＨ2Ｏ）n−Ｈ：分子量約４００］１０．０
ｇ及びリンゴ酸［ＨＯＣＯＣＨ2ＣＨ（ＯＨ）ＣＯＯ
Ｈ：分子量１３４］１６．０ｇをイオン交換水に溶解
し、全量が８６ｍｌの水溶液（含浸液）を調製した。Example 1 Ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24
4H 2 O)] 32.1 g, cobalt nitrate [Co (NO 3 ).
3 ] 27.1 g, polyethylene glycol 400 [HO
- (CH 2 CH 2 O) n -H: molecular weight about 400] 10.0
g and malic acid [HOCOCH 2 CH (OH) COO
H: molecular weight 134] 16.0 g was dissolved in ion-exchanged water to prepare an aqueous solution (impregnation liquid) with a total amount of 86 ml.
【００５３】この含浸液を比表面積２２０ｍ2／ｇの円
柱状アルミナ担体（粒経２ｍｍ）２００ｇに真空含浸法
によって担持した。この担持物を、１２０℃で３時間乾
燥後、空気気流中５５０℃で３．０時間焼成することに
よって所望の触媒を得た。こうして得た触媒は、その乾
燥重量あたり、ＣｏをＣｏＯとして約４重量％、Ｍｏを
ＭｏＯ3として約１５重量％を含んでいる。This impregnating solution was loaded on 200 g of a cylindrical alumina carrier (particle diameter 2 mm) having a specific surface area of 220 m 2 / g by a vacuum impregnation method. The supported material was dried at 120 ° C. for 3 hours and then calcined in an air stream at 550 ° C. for 3.0 hours to obtain a desired catalyst. The catalyst thus obtained contained about 4% by weight of Co as CoO and about 15% by weight of Mo as MoO 3 based on the dry weight thereof.
【００５４】次に、この触媒５０ｃｃを固定床流通式反
応装置の反応管に充填し、前処理として、該触媒層に表
１に示す性状の原料油［中東系軽質軽油（ＬＧＯ）］を
２５０℃で２４時間流通することによって該触媒を予備
硫化した。その後、この予備硫化した触媒層に、反応温
度３１０〜３５０℃（３１０、３３０及び３５０℃の各
温度に順次段階的に昇温）、圧力３０ｋｇ／ｃｍ2Ｇ、
水素ガス／原料油比２００Ｎｌ／ｋｌ、ＬＨＳＶ４．０
ｈ-1の条件で、表１に示す性状の原料油［中東系軽質軽
油（ＬＧＯ）］を水素ガスと共に流通し、該原料油を水
素化処理（水素化脱硫）した。この反応の評価結果を他
の実施例、比較例と共に表２に示す。Next, 50 cc of this catalyst was filled in a reaction tube of a fixed bed flow type reaction apparatus, and as a pretreatment, a feed oil having the properties shown in Table 1 [Middle East light gas oil (LGO)] was added to the catalyst layer in an amount of 250. The catalyst was presulfidized by flowing at 24 ° C. for 24 hours. Thereafter, this pre-sulfided catalyst layer, (sequential stepwise heated to various temperatures 310, 330 and 350 ° C.) the reaction temperature 310? 350 ° C., a pressure 30kg / cm 2 G,
Hydrogen gas / feed oil ratio 200 Nl / kl, LHSV 4.0
Under the condition of h −1 , a stock oil [Middle Eastern light gas oil (LGO)] having the properties shown in Table 1 was circulated together with hydrogen gas, and the stock oil was hydrotreated (hydrodesulfurization). The evaluation results of this reaction are shown in Table 2 together with other examples and comparative examples.
【００５５】[0055]
【表１】 [Table 1]
【００５６】[0056]
【表２】 [Table 2]
【００５７】実施例２ 実施例１において、ポリエチレングリコール４００の代
わりにポリオキシエチレンオクチルフェニルエーテル
［分子量約６５０］２．０ｇを用いた以外は同様にして
触媒を調製した。この触媒について、予備硫化及び水素
化処理反応を実施例１と同様にして行ない、脱硫活性等
の反応成績を評価した。その結果を表２に示す。Example 2 A catalyst was prepared in the same manner as in Example 1 except that 2.0 g of polyoxyethylene octyl phenyl ether [molecular weight of about 650] was used instead of polyethylene glycol 400. Pre-sulfiding and hydrotreating reactions of this catalyst were carried out in the same manner as in Example 1 to evaluate the reaction results such as desulfurization activity. The results are shown in Table 2.
【００５８】実施例３ 実施例１において、比表面積２２０ｍ2／ｇのアルミナ
担体の代わりに比表面積２６３ｍ2／ｇの円柱状アルミ
ナ担体（粒径２．０ｍｍ）２００ｇを用い、金属をＣｏ
Ｏ重量％、ＭｏＯ3２２．５重量％担持させた以外は同
様にして触媒を調整した。この触媒について、予備硫化
及び水素化処理反応を実施例１と同様にして行ない、脱
硫活性等の反応成績を評価した。その結果を表２に示
す。Example 3 In Example 1, 200 g of a cylindrical alumina carrier (particle size 2.0 mm) having a specific surface area of 263 m 2 / g was used in place of the alumina carrier having a specific surface area of 220 m 2 / g, and the metal was Co.
A catalyst was prepared in the same manner except that O weight% and MoO 3 22.5 weight% were supported. Pre-sulfiding and hydrotreating reactions of this catalyst were carried out in the same manner as in Example 1 to evaluate the reaction results such as desulfurization activity. The results are shown in Table 2.
【００５９】比較例１ 実施例１において、ポリエチレングリコール４００を使
用しなかった他は、同様にして触媒を調整した。この触
媒について、予備硫化及び水素化処理反応を実施例１と
同様にして行ない、脱硫活性等の反応成績を評価した。
その結果を表２に示す。Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that polyethylene glycol 400 was not used. Pre-sulfiding and hydrotreating reactions of this catalyst were carried out in the same manner as in Example 1 to evaluate the reaction results such as desulfurization activity.
The results are shown in Table 2.
【００６０】比較例２ 実施例１において、ポリエチレングリコール４００の代
わりにエチレングリコール［分子量６２］１０．０ｇを
用いた以外は同様にして触媒を調整した。この触媒につ
いて、予備硫化及び水素化処理反応を実施例１と同様に
して行ない、脱硫活性等の反応成績を評価した。その結
果を表２に示す。Comparative Example 2 A catalyst was prepared in the same manner as in Example 1 except that 10.0 g of ethylene glycol [molecular weight 62] was used instead of polyethylene glycol 400. Pre-sulfiding and hydrotreating reactions of this catalyst were carried out in the same manner as in Example 1 to evaluate the reaction results such as desulfurization activity. The results are shown in Table 2.
【００６１】比較例３ 実施例３において、ポリエチレングリコール４００を使
用しなかった他は、同様にして触媒を調整した。この触
媒について、予備硫化及び水素化処理反応を実施例１と
同様にして行ない、脱硫活性等の反応成績を評価した。
その結果を表２に示す。Comparative Example 3 A catalyst was prepared in the same manner as in Example 3 except that polyethylene glycol 400 was not used. Pre-sulfiding and hydrotreating reactions of this catalyst were carried out in the same manner as in Example 1 to evaluate the reaction results such as desulfurization activity.
The results are shown in Table 2.
【００６２】上記の実施例１〜３及び比較例１〜３の結
果からも明らかなように、ポリエチレングリコール４０
０やポリオキシエチレンオクチルフェニルエーテル等の
水溶性有機化合物［Ｉ］（分子量１５０以上）を活性金
属化合物の含浸時に共存させて担持、調製した触媒を用
いると、脱硫活性が向上することが判明した。As is clear from the results of Examples 1 to 3 and Comparative Examples 1 to 3, polyethylene glycol 40
It was found that the desulfurization activity is improved by using a catalyst prepared by coexisting and supporting a water-soluble organic compound [I] (molecular weight of 150 or more) such as 0 or polyoxyethylene octyl phenyl ether when impregnating the active metal compound. .
【００６３】また、上記の実施例及び比較例には、含浸
液に有機酸（リンゴ酸）を含有させている場合の結果を
示してあるが、リンゴ酸等の有機酸を用いずに同様にし
て触媒を調整し、それぞれの触媒について、同様にして
脱硫活性等の反応成績を評価したところ、表２の結果と
同様に、水溶性有機酸化合物［Ｉ］の添加効果（脱硫活
性の向上効果）が認められた。すなわち、含浸液に有機
酸を含有させても、させなくても、活性金属化合物の担
持を水溶性有機化合物［Ｉ］の存在化で行なえば、触媒
の脱硫活性が向上することが確認された。Further, the above-mentioned Examples and Comparative Examples show the results when the impregnating liquid contains an organic acid (malic acid), but the same procedure was performed without using an organic acid such as malic acid. When the reaction results such as desulfurization activity were evaluated for each catalyst in the same manner by adjusting the catalyst, the effect of adding the water-soluble organic acid compound [I] (the effect of improving the desulfurization activity) was obtained as in the case of Table 2. ) Was recognized. That is, it was confirmed that the desulfurization activity of the catalyst is improved by carrying the active metal compound in the presence of the water-soluble organic compound [I], whether or not the impregnating liquid contains an organic acid. .
【００６４】なお、担体の種類及び／又は活性金属の種
類や組成を種々変えた場合にも、同様に水溶性有機化合
物［Ｉ］の添加効果（脱硫活性の向上効果）が認められ
た。このことは、担体の種類や金属活性の種類や組成等
を問わず、水溶性有機化合物［Ｉ］の使用が有効である
ことを示している。Even when the type of carrier and / or the type and composition of active metal were variously changed, the effect of adding the water-soluble organic compound [I] (the effect of improving desulfurization activity) was similarly observed. This indicates that the use of the water-soluble organic compound [I] is effective regardless of the type of carrier, the type of metal activity, the composition, and the like.
【００６５】[0065]
【発明の効果】本発明の水素化処理方法によると、灯油
や軽質軽油、重質軽油、減圧軽油、分解軽油等の各種の
軽油類あるいはこれらの混合物から硫黄分を効率よく除
去し、脱硫率が高く、性状のよい有用炭化水素油（脱硫
灯油や脱硫軽油等）を生産性よく製造することができ
る。According to the hydrotreating method of the present invention, the sulfur content is efficiently removed from various light oils such as kerosene, light gas oil, heavy gas oil, reduced pressure gas oil, cracked gas oil and the like, or a mixture thereof, and a desulfurization rate is obtained. It is possible to produce useful hydrocarbon oil having high properties and good properties (desulfurized kerosene, desulfurized gas oil, etc.) with high productivity.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 飯野 明 千葉県袖ケ浦市上泉1280番地 出光興産株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Iino 1280, Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.
Claims (1)
族金属の化合物及び／又は周期表ＶＩＩＩ族金属の化合
物を分子量が１５０以上でかつ水酸基及び／又はエーテ
ル結合を有する水溶性有機化合物（但し、酸は除く。）
の存在下で担持させ４００℃以上で焼成することによっ
て調製された水素化処理用触媒に、灯油留分又は軽油留
分あるいはこれらの混合物を水素の存在下で接触して水
素化処理することを特徴とする灯軽油留分の水素化処理
方法。1. A VIA of the periodic table for a refractory oxide-based catalyst carrier.
A water-soluble organic compound having a molecular weight of 150 or more and a hydroxyl group and / or an ether bond, which is a compound of a group metal and / or a compound of a group VIII metal of the periodic table (however, an acid is excluded).
Of the kerosene fraction or the gas oil fraction, or a mixture thereof, to the hydrotreating catalyst prepared by carrying the catalyst in the presence of the above and calcining at 400 ° C. or higher in the presence of hydrogen for hydrotreating. A method for hydrotreating a kerosene gas oil fraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5037305A JP2854484B2 (en) | 1993-02-03 | 1993-02-03 | Hydroprocessing of kerosene oil fraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5037305A JP2854484B2 (en) | 1993-02-03 | 1993-02-03 | Hydroprocessing of kerosene oil fraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06228572A true JPH06228572A (en) | 1994-08-16 |
| JP2854484B2 JP2854484B2 (en) | 1999-02-03 |
Family
ID=12493992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5037305A Expired - Fee Related JP2854484B2 (en) | 1993-02-03 | 1993-02-03 | Hydroprocessing of kerosene oil fraction |
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| Country | Link |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09164333A (en) * | 1995-10-09 | 1997-06-24 | Idemitsu Kosan Co Ltd | New catalystic composition, its production and hydrotreatment of hydrocarbon oil using catalystic composition |
| JP2000167401A (en) * | 1998-11-26 | 2000-06-20 | Basf Ag | Carried catalyst and its use for hydrogenation |
| JP2001162168A (en) * | 1999-09-29 | 2001-06-19 | Petroleum Energy Center | Hydrogenation catalyst and method for hydrogenation treatment of heavy hydrocarbon oil by using that catalyst |
| JP2003342587A (en) * | 2002-03-20 | 2003-12-03 | Idemitsu Kosan Co Ltd | Method for producing deep-desulfurized light oil |
| EP1145763A4 (en) * | 1999-10-27 | 2004-09-15 | Idemitsu Kosan Co | Hydrotreating catalyst for hydrocarbon oil, carrier for the same and method for hydrotreating of hydrocarbon oil |
| JP2007222751A (en) * | 2006-02-22 | 2007-09-06 | Idemitsu Kosan Co Ltd | Hydrodesulfurization catalyst and hydrodesulfurization method for kerosene fraction |
| CN103785398A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodemetalization catalyst for residuum |
-
1993
- 1993-02-03 JP JP5037305A patent/JP2854484B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09164333A (en) * | 1995-10-09 | 1997-06-24 | Idemitsu Kosan Co Ltd | New catalystic composition, its production and hydrotreatment of hydrocarbon oil using catalystic composition |
| JP2000167401A (en) * | 1998-11-26 | 2000-06-20 | Basf Ag | Carried catalyst and its use for hydrogenation |
| JP2001162168A (en) * | 1999-09-29 | 2001-06-19 | Petroleum Energy Center | Hydrogenation catalyst and method for hydrogenation treatment of heavy hydrocarbon oil by using that catalyst |
| EP1145763A4 (en) * | 1999-10-27 | 2004-09-15 | Idemitsu Kosan Co | Hydrotreating catalyst for hydrocarbon oil, carrier for the same and method for hydrotreating of hydrocarbon oil |
| JP2003342587A (en) * | 2002-03-20 | 2003-12-03 | Idemitsu Kosan Co Ltd | Method for producing deep-desulfurized light oil |
| JP2007222751A (en) * | 2006-02-22 | 2007-09-06 | Idemitsu Kosan Co Ltd | Hydrodesulfurization catalyst and hydrodesulfurization method for kerosene fraction |
| CN103785398A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodemetalization catalyst for residuum |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2854484B2 (en) | 1999-02-03 |
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