JPH08281117A - Hydrogenation refining catalyst and hydrogenation refining of hydrocarbon oil and production of desulfurized gas oil - Google Patents
Hydrogenation refining catalyst and hydrogenation refining of hydrocarbon oil and production of desulfurized gas oilInfo
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- JPH08281117A JPH08281117A JP11533895A JP11533895A JPH08281117A JP H08281117 A JPH08281117 A JP H08281117A JP 11533895 A JP11533895 A JP 11533895A JP 11533895 A JP11533895 A JP 11533895A JP H08281117 A JPH08281117 A JP H08281117A
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- catalyst
- silica
- weight
- alumina
- carrier
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高い水素化精製機能、特
には水素化脱硫機能を有する水素化精製触媒およびこの
触媒を用いる水素化精製方法並びに軽油留分中の硫黄濃
度を著しく低減させた脱硫軽油を製造するための方法に
関する。FIELD OF THE INVENTION The present invention significantly reduces the concentration of sulfur in a gas oil fraction, a hydrorefining catalyst having a high hydrorefining function, particularly a hydrodesulfurization function, a hydrorefining method using this catalyst, and a sulfur concentration in a gas oil fraction. It relates to a method for producing desulfurized gas oil.
【０００２】[0002]
【従来の技術】従来、石油留分、石油残渣、石炭液化油
等の炭化水素油の水素化精製、特に脱硫においては、ア
ルミナ担体上に周期律表第VIb族のモリブデンやタング
ステン或いは周期律表第VIII族のコバルト、ニッケルか
ら選択された金属元素を組合せて担持した触媒組成物が
用いられ、特に軽油留分の脱硫においては硫黄分を０.
１重量％程度まで低減させることが行われている。しか
し、最近環境保護の観点からディーゼル軽油中の硫黄分
を０.０５重量％以下まで低減させる、いわゆる深度脱
硫が要請され、高活性の水素化精製触媒の開発が急がれ
ている。2. Description of the Related Art Conventionally, in the hydrorefining of hydrocarbon oils such as petroleum fractions, petroleum residues, and coal liquefied oil, especially desulfurization, molybdenum or tungsten of Group VIb of the periodic table or the periodic table is used on an alumina carrier. A catalyst composition in which a metal element selected from Group VIII cobalt and nickel is supported in combination is used, and particularly in the desulfurization of a gas oil fraction, the sulfur content is reduced to 0.
It is being reduced to about 1% by weight. However, recently, from the viewpoint of environmental protection, so-called deep desulfurization, which reduces the sulfur content in diesel gas oil to 0.05% by weight or less, has been demanded, and development of a highly active hydrorefining catalyst has been urgently required.
【０００３】また、シリカアルミナは、化学合成用とし
て広く知られているが、その強い酸性度のため水素化精
製用の担体として単独で用いられることはほとんどな
く、特に軽油留分の水素化精製に用いると分解が進行し
て脱硫軽油の収率が減少し、好ましいものではなかっ
た。Silica-alumina is widely known for chemical synthesis, but due to its strong acidity, it is rarely used alone as a carrier for hydrorefining, and particularly hydrorefining of light oil fractions. When used for, the decomposition proceeded, and the yield of desulfurized gas oil decreased, which was not preferable.
【０００４】一方、アルミナのみからなる担体を用いた
場合では、水素化精製活性が十分に高くなく、高度に脱
硫された軽油を得るためには、水素化精製を過酷な条件
で行う必要があり、このために分解が促進され、脱硫軽
油の収率が減少するという問題もあった。On the other hand, when a carrier made of only alumina is used, the hydrorefining activity is not sufficiently high, and in order to obtain highly desulfurized gas oil, it is necessary to carry out hydrorefining under severe conditions. However, there is also a problem that the decomposition is accelerated and the yield of desulfurized gas oil is reduced.
【０００５】[0005]
【発明が解決しようとする課題】本発明は上記問題を解
決するもので、本発明の目的は、高い水素化精製活性を
有する水素化精製触媒およびこの触媒を用いる炭化水素
油の水素化精製方法、および特には脱硫軽油の収率をあ
まり低減させないで軽油留分から硫黄分を大幅に低減し
た脱硫軽油を製造する方法を提供することにある。The present invention solves the above problems, and an object of the present invention is to provide a hydrorefining catalyst having a high hydrorefining activity and a method for hydrorefining hydrocarbon oils using this catalyst. And, in particular, to provide a method for producing desulfurized gas oil in which the sulfur content is significantly reduced from a gas oil fraction without significantly reducing the desulfurized gas oil yield.
【０００６】[0006]
【課題を解決するための手段】本発明は、アルミナにシ
リカを３０重量％以上含むシリカアルミナをシリカとし
て１〜８重量％含有させた担体上に、周期律表第VIb族
金属元素から選択された少なくとも１種を当該触媒中に
５〜２０重量％、周期律表第VIII族金属元素から選択さ
れた少なくとも１種を当該触媒中に１〜１０重量％およ
びリンを当該触媒中に０.１〜８重量％担持させたこと
からなる水素化精製触媒、及び炭化水素油を前記水素化
精製触媒の存在下に水素化精製することからなる炭化水
素油の水素化精製方法、並びに軽油留分を前記水素化精
製触媒の存在下に、水素化脱硫を行うことからなる脱硫
軽油の製造方法である。Means for Solving the Problems The present invention is selected from Group VIb metal elements of the periodic table on a carrier containing 1 to 8% by weight of silica, which is silica containing 30% by weight or more of silica in alumina. 5 to 20% by weight of the catalyst, 1 to 10% by weight of at least one selected from Group VIII metal elements of the periodic table, and 0.1% of phosphorus in the catalyst. A hydrorefining catalyst which is carried by ˜8% by weight, and a method for hydrorefining a hydrocarbon oil, which comprises hydrorefining a hydrocarbon oil in the presence of the hydrorefining catalyst, and a gas oil fraction. A method for producing desulfurized gas oil, which comprises performing hydrodesulfurization in the presence of the hydrorefining catalyst.
【０００７】上記本発明で用いるシリカアルミナは、シ
リカを３０重量％以上含有するものであれば、何れでも
支障なく用いることができ、一般に、化学反応用の触媒
あるいは触媒の担体として市販されているシリカアルミ
ナを用いると簡便で、好ましい。また、共沈法等により
シリカを３０重量％以上含むように調製したシリカアル
ミナも使用できる。しかし、シリカ含有量が３０重量％
未満のシリカアルミナを用いると、たとえ担体中にシリ
カとして１〜８重量％含有させても水素化精製活性を著
しく高くすることができず、通常の比較的温和な水素化
精製反応条件のもとでは、直留軽油からの脱硫軽油の硫
黄分を０.０５重量％以下とすることが困難になる。こ
のシリカアルミナ中のシリカは、３０重量％以上含有す
るものであるが、シリカ量が８０重量％以下のシリカア
ルミナを用いることが特に好ましい。また、このシリカ
アルミナはＸ線回折分析(XRD)の測定において結晶性ア
ルミノシリケートを示す特徴的なピークを有さない、非
結晶あるいは結晶性の非常に低いものを用いることが、
特に好ましい。The silica-alumina used in the present invention can be used without any problem as long as it contains 30% by weight or more of silica, and is generally commercially available as a catalyst for a chemical reaction or a catalyst carrier. The use of silica-alumina is simple and preferable. Further, silica-alumina prepared by a coprecipitation method or the like so as to contain silica in an amount of 30% by weight or more can also be used. However, if the silica content is 30% by weight
If less than 1% by weight of silica-alumina is used, the hydrorefining activity cannot be remarkably increased even if 1 to 8% by weight of silica is contained in the carrier. Then, it becomes difficult to reduce the sulfur content of desulfurized gas oil from straight-run gas oil to 0.05% by weight or less. Silica in the silica-alumina is contained in an amount of 30% by weight or more, but it is particularly preferable to use silica-alumina having a silica amount of 80% by weight or less. Further, as this silica-alumina, an amorphous or very low-crystallinity having no characteristic peak indicating crystalline aluminosilicate in the measurement of X-ray diffraction analysis (XRD) is used.
Particularly preferred.
【０００８】本発明の触媒には、上記シリカアルミナ
を、シリカとして１〜８重量％となるようにアルミナに
混合して担体とする。この場合、シリカアルミナ中のシ
リカの量にもよるが、通常、アルミナ８０〜９８重量部
に対してシリカアルミナ２〜２０重量部を混合して担体
を調製すると良い。この担体の調製は、常法、例えば、
上記シリカアルミナの所定量とアルミナのヒドロゲルの
所定量を十分に混合した後、成形し、常温〜１５０℃、
好ましくは、１００〜１３０℃で０.５時間以上乾燥し
た後、３５０〜８００℃、好ましくは、４５０〜６００
℃で０.５時間以上焼成することにより担体が得られ
る。なお、担体中のシリカ含量が１重量％以下、あるい
は８重量％以上とすると十分に高い水素化精製活性能が
得られない。In the catalyst of the present invention, the above silica-alumina is mixed with alumina so as to be 1 to 8% by weight as silica to form a carrier. In this case, although depending on the amount of silica in the silica-alumina, it is usually preferable to prepare a carrier by mixing 2 to 20 parts by weight of silica-alumina with 80 to 98 parts by weight of alumina. This carrier is prepared by a conventional method, for example,
After sufficiently mixing a predetermined amount of the silica-alumina and a predetermined amount of the hydrogel of alumina, molding is performed, and the temperature is from room temperature to 150 ° C.
Preferably, after drying at 100 to 130 ° C. for 0.5 hours or more, 350 to 800 ° C., preferably 450 to 600
A carrier is obtained by calcining at 0.5 ° C. for 0.5 hour or more. If the silica content in the carrier is 1 wt% or less, or 8 wt% or more, a sufficiently high hydrorefining activity cannot be obtained.
【０００９】本発明の触媒は、上記担体にクロム、モリ
ブデン、タングステン等の周期律表第VIb族金属元素の
少なくとも一種、特に好ましくはモリブデンと、鉄、ニ
ッケル、コバルト等の第VIII族金属元素の少なくとも一
種、特に好ましくはニッケルまたはコバルトのいづれ
か、あるいはこの両元素と、さらにリンとを担持させた
ものである。The catalyst of the present invention comprises, on the carrier, at least one metal element of Group VIb of the periodic table such as chromium, molybdenum and tungsten, particularly preferably molybdenum and a metal of Group VIII metal such as iron, nickel and cobalt. At least one of them, particularly preferably nickel or cobalt, or both of them, and phosphorus are further supported.
【００１０】これらの元素の担持は、一般に行われてい
る方法、すなわち上記担体に上記金属元素およびリンの
化合物を含有する水溶液を含浸させることにより行うこ
とができ、次いで常温乃至１５０℃、好ましくは、１０
０〜１３０℃で０.５時間以上乾燥した後、３５０〜８
００℃、好ましくは、４５０〜６００℃で０.５時間以
上焼成することにより触媒として調製することができ
る。The loading of these elements can be carried out by a generally used method, that is, by impregnating the carrier with an aqueous solution containing the metal element and a compound of phosphorus, and then at room temperature to 150 ° C., preferably. 10,
After drying at 0 ~ 130 ℃ for 0.5 hours or more, 350 ~ 8
It can be prepared as a catalyst by calcining at 00 ° C, preferably 450 to 600 ° C for 0.5 hour or more.
【００１１】尚、この場合、第VIb族金属元素は、パラ
モリブデン酸アンモニウム、パラモリブデン酸、モリブ
デン酸アンモニウム、リンモリブデン酸、タングステン
酸アンモニウム、タングステン酸、無水タングステン
酸、リンタングステン酸などの化合物を水溶液として用
いるとよい。また、第VIII族金属元素は、ニッケルある
いはコバルトの硝酸塩、硫酸塩、塩化物、フッ化物、臭
化物、酢酸塩、炭酸塩、リン酸塩などの水溶液が用いら
れる。さらにリンとしては、リン酸、亜リン酸、次亜リ
ン酸、リンモリブデン酸、リンタングステン酸などの酸
及びそれらの塩などが用いられる。これらの担持量は、
脱硫及び脱窒素等の水素化精製活性の観点から、最終触
媒に対し、第VIb族金属元素は、その合計量として金属
元素換算で約５〜２０重量％、第VIII族金属元素は、そ
の合計量として金属元素換算で１〜１０重量％、リンは
リン元素換算で０.１〜８重量％とする。In this case, the Group VIb metal element is a compound such as ammonium paramolybdate, paramolybdic acid, ammonium molybdate, phosphomolybdic acid, ammonium tungstate, tungstic acid, tungstic anhydride, or phosphotungstic acid. It may be used as an aqueous solution. As the Group VIII metal element, an aqueous solution of nickel or cobalt nitrate, sulfate, chloride, fluoride, bromide, acetate, carbonate, phosphate or the like is used. Further, as phosphorus, acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, phosphomolybdic acid, phosphotungstic acid and salts thereof are used. The carrying amount of these is
From the viewpoint of hydrorefining activity such as desulfurization and denitrification, the total amount of the Group VIb metal elements is about 5 to 20% by weight in terms of the total amount of metal elements, and the total amount of the Group VIII metal elements is the total amount of the final catalyst. The amounts are 1 to 10% by weight in terms of metal element, and phosphorus is 0.1 to 8% by weight in terms of phosphorus element.
【００１２】上記方法で調製された触媒は、炭化水素
油、例えば、原油、タールサンド、シェールオイルある
いは石炭液化油等を常圧蒸留または減圧蒸留することに
より得られる各種の留分や残渣油、あるいはこれらの分
解、異性化、改質、溶剤抽出等の処理を行った鉱油等の
水素化精製に適用されるが、特には、直留軽油、分解軽
油、減圧軽油などの水素化脱硫に好適である。The catalyst prepared by the above-mentioned method is a hydrocarbon oil such as crude oil, tar sand, shale oil or coal liquefied oil, which is obtained by atmospheric distillation or vacuum distillation, and various fractions and residual oils, Alternatively, it is applied to hydrorefining of mineral oil, which has been subjected to treatments such as cracking, isomerization, reforming, solvent extraction, etc., and is particularly suitable for hydrodesulfurization of straight-run gas oil, cracked gas oil, vacuum gas oil, etc. Is.
【００１３】上述の方法で調製した触媒を用いて炭化水
素油を水素化精製する場合、この反応の条件は、温度２
５０〜４５０℃、水素分圧約２０〜２００kg/cm2、液空
間速度約０.１〜２０hr-1、水素対炭化水素油の比、約
５０〜４０００l/lの範囲で選定することが好ましい。
また、特に軽油留分を水素化脱硫して脱硫軽油を製造す
る場合は、特に過酷な条件とする必要はなく、軽油留分
に用いられている通常の脱硫条件、あるいはこれよりマ
イルドな条件、すなわち、２８０〜４００℃の温度、２
０〜６０kg/cm2の水素圧力、１〜１５hr-1の液空間速
度、５０〜１０００l/lの水素/油の比等の条件下に行う
ことができる。When a hydrocarbon oil is hydrorefined using the catalyst prepared by the above-mentioned method, the conditions for this reaction are temperature 2
It is preferable to select at 50 to 450 ° C., hydrogen partial pressure of about 20 to 200 kg / cm 2 , liquid hourly space velocity of about 0.1 to 20 hr −1 , hydrogen to hydrocarbon oil ratio of about 50 to 4000 l / l.
Further, in particular, when producing desulfurized gas oil by hydrodesulfurizing a gas oil fraction, it is not necessary to use particularly severe conditions, the usual desulfurization conditions used for gas oil fractions, or milder conditions than this, That is, a temperature of 280 to 400 ° C., 2
It can be carried out under conditions such as a hydrogen pressure of 0 to 60 kg / cm 2 , a liquid hourly space velocity of 1 to 15 hr −1 , and a hydrogen / oil ratio of 50 to 1000 l / l.
【００１４】尚、この触媒は、一般に、炭化水素類を処
理するに先立ち、硫化水素、二硫化炭素といった硫黄化
合物を含有した炭化水素類で予備硫化したのち、用いる
とよい。In general, this catalyst is preferably used after being pre-sulfided with hydrocarbons containing a sulfur compound such as hydrogen sulfide and carbon disulfide prior to treating the hydrocarbons.
【００１５】[0015]
（触媒の調製） （１）触媒Ａ アルミナ水和物(含水量２５重量％)１.８kgに、４重量
％濃度の硝酸水溶液１lとイオン交換水２５０mlを添加
し、ニーダーで３０分間混練したのち、市販のシリカ含
量４０重量％の非晶質シリカ・アルミナ２５０g(担体中
のシリカアルミナの含量が１２重量％、シリカとして５
重量％)を添加し、混練物が成形可能になるようにイオ
ン交換水を適時添加しながら６０分間混練した。(Preparation of catalyst) (1) Catalyst A To 1.8 kg of alumina hydrate (water content: 25% by weight), 1 l of a 4% by weight nitric acid aqueous solution and 250 ml of deionized water were added, and the mixture was kneaded with a kneader for 30 minutes. 250 g of commercially available amorphous silica-alumina with a silica content of 40% by weight (content of silica-alumina in the carrier is 12% by weight, silica
(Wt%) was added, and ion-exchanged water was added at appropriate times so that the kneaded product could be molded, and the mixture was kneaded for 60 minutes.
【００１６】この混練物を押出し成形機で、径１/２０
インチの三ッ葉状ペレットに成形した。成形されたペレ
ットは１３０℃で乾燥し、さらに６００℃で１時間焼成
して担体を得た。This kneaded product was extruded with a machine having a diameter of 1/20.
Molded into inch trilobal pellets. The formed pellets were dried at 130 ° C and further calcined at 600 ° C for 1 hour to obtain a carrier.
【００１７】上記担体にモリブデン酸アンモニウム、硝
酸コバルト及びリン酸の混合水溶液を含浸させたのち、
１３０℃で乾燥し、更に５５０℃で３０分間焼成して触
媒Ａを得た。含浸に際しては、最終的に触媒上に、モリ
ブデン、コバルト、リンを金属重量でそれぞれ１０重量
％、３重量％、２重量％担持されるように含浸液を調製
した。After impregnating the above carrier with a mixed aqueous solution of ammonium molybdate, cobalt nitrate and phosphoric acid,
It was dried at 130 ° C. and further calcined at 550 ° C. for 30 minutes to obtain catalyst A. At the time of impregnation, an impregnation liquid was prepared so that molybdenum, cobalt, and phosphorus were finally loaded on the catalyst in an amount of 10% by weight, 3% by weight, and 2% by weight, respectively.
【００１８】（２）触媒Ｂ 上記触媒Ａの担体調製の混練工程において、１.９kgの
アルミナ水和物及び１８３gのシリカアルミナを用い、
担体中のシリカの含量が３重量％になるように調整した
以外は、上記触媒Ａと同様の方法により触媒Ｂを調製し
た。(2) Catalyst B In the kneading step of preparing the carrier of the above catalyst A, 1.9 kg of alumina hydrate and 183 g of silica-alumina were used,
A catalyst B was prepared in the same manner as the catalyst A except that the content of silica in the carrier was adjusted to 3% by weight.
【００１９】（３）触媒Ｃ 上記触媒Ａの担体調製の混練工程において、１.７kgの
アルミナ水和物及び３３３gのシリカアルミナを用い、
担体中のシリカの含量が６重量％になるように調整した
以外は、上記触媒Ａと同様の方法により触媒Ｃを調製し
た。(3) Catalyst C In the kneading step for preparing the carrier of the above catalyst A, 1.7 kg of alumina hydrate and 333 g of silica-alumina were used,
Catalyst C was prepared in the same manner as catalyst A above, except that the silica content in the carrier was adjusted to 6% by weight.
【００２０】（４）触媒Ｄ 上記触媒Ａの担体調製の混練工程において、１.９kgの
アルミナ水和物及び市販のシリカ含量が６０重量％のシ
リカアルミナ１３２gを用い、担体中のシリカ含量が６
重量％になるように調整した以外は、上記触媒Ａと同様
の方法により触媒Ｄを調製した。(4) Catalyst D In the kneading step for preparing the carrier of the above catalyst A, 1.9 kg of alumina hydrate and 132 g of commercially available silica alumina having a silica content of 60% by weight were used, and the silica content in the carrier was 6%.
A catalyst D was prepared in the same manner as the catalyst A except that the amount was adjusted to be wt%.
【００２１】（５）触媒Ｅ アルミナ単独の担体を得るため、上記触媒Ａの担体調製
の混練工程において、シリカアルミナを使用せずにアル
ミナを２kg用いたこと以外は、上記触媒Ａと同様の方法
により触媒Ｅを調製した。(5) Catalyst E A method similar to that of the above catalyst A except that 2 kg of alumina was used without using silica alumina in the kneading step of the preparation of the catalyst A carrier in order to obtain a carrier of alumina alone. To prepare catalyst E.
【００２２】（６）触媒Ｆ 上記触媒Ａの担体調製の混練工程において、１.５kgの
アルミナ水和物及び５１７gのシリカアルミナを用い、
担体中のシリカ含量が１０重量％になるように調整した
以外は、上記触媒Ａと同様の方法により触媒Ｆを調製し
た。(6) Catalyst F In the kneading step for preparing the carrier of the above catalyst A, 1.5 kg of alumina hydrate and 517 g of silica-alumina were used,
A catalyst F was prepared in the same manner as the catalyst A except that the silica content in the carrier was adjusted to 10% by weight.
【００２３】（７）触媒Ｇ 上記触媒Ａの担体調製の混練工程において、シリカ含量
２０重量％の市販のシリカアルミナ６００gを用い、担
体中のシリカ含量が５重量％になるように調整した以外
は、上記触媒Ａと同様の方法により触媒Ｇを調製した。(7) Catalyst G In the kneading step for preparing the carrier of the catalyst A, 600 g of commercially available silica alumina having a silica content of 20% by weight was used, except that the silica content in the carrier was adjusted to 5% by weight. A catalyst G was prepared in the same manner as the catalyst A.
【００２４】（８）触媒Ｈ 上記触媒Ａの担体調製の混練工程において、シリカアル
ミナの代わりに市販のシリカゲル７０gを用い、これに
２.０kgのアルミナ水和物を用いて、シリカ含量が５重
量％になるように調整した以外は、上記触媒Ａと同様の
方法により触媒Ｈを調製した。(8) Catalyst H In the kneading step for preparing the carrier of the above catalyst A, 70 g of commercially available silica gel was used in place of silica-alumina, 2.0 kg of alumina hydrate was used, and the silica content was 5% by weight. A catalyst H was prepared in the same manner as the catalyst A except that the content was adjusted so that the content of the catalyst H was 0.1%.
【００２５】（水素化脱硫・脱窒素の活性評価試験）触
媒Ａ〜Ｄ（実施例）及び触媒Ｅ〜Ｈ（比較例）につい
て、原料油の炭化水素油として直留軽油(密度15℃：０.
８５１９、硫黄分：１.４４wt%、窒素分：９２wtppm)を
用いて、水素化脱硫・脱窒素の活性評価を行なった。評
価試験には固定床反応器を用い、３５０℃の温度、３０
kg/cm2の反応圧力、１００l/lの水素/原料油比、３hr-1
の液空間速度の反応条件下に、水素化精製して、生成油
の原料油に対する収率、残留硫黄分及び残留窒素分を測
定し、これらの値から反応速度定数を求め、触媒Ｅを基
準として触媒の相対活性評価を行なった。この結果を表
１に示した。(Hydrodesulfurization / denitrification activity evaluation test) For catalysts A to D (examples) and catalysts E to H (comparative examples), straight run diesel fuel (density 15 ° C: 0 .
8519, sulfur content: 1.44 wt%, nitrogen content: 92 wtppm) was used to evaluate the activity of hydrodesulfurization and denitrification. A fixed bed reactor was used for the evaluation test at a temperature of 350 ° C. and 30
Reaction pressure of kg / cm 2 , hydrogen / feed oil ratio of 100 l / l, 3 hr -1
Under the reaction conditions of liquid hourly space velocity, hydrorefining, yield of the produced oil with respect to the feedstock, residual sulfur content and residual nitrogen content were measured, and the reaction rate constant was determined from these values, and the catalyst E was used as a reference As a result, the relative activity of the catalyst was evaluated. The results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】これらの結果から、シリカ含量が３０重量
％以上のシリカアルミナを用い、シリカ含量を２〜８重
量％とした担体からなる触媒が、アルミナ単体の担体や
シリカ含量が３０重量％未満のシリカアルミナを用いた
担体及びシリカ含量８重量％以上の担体等からなる触媒
と比較して、脱硫活性及び脱窒素活性が高く、しかも生
成油の収率が全く減少していないことがわかる。From these results, it is found that a catalyst comprising silica alumina having a silica content of 30% by weight or more and having a silica content of 2-8% by weight has a carrier of alumina alone or a silica content of less than 30% by weight. It can be seen that the desulfurization activity and denitrification activity are higher and the yield of the produced oil is not reduced at all, as compared with the catalyst comprising a carrier using silica-alumina and a carrier having a silica content of 8% by weight or more.
【００２８】[0028]
【発明の効果】以上説明したように、本発明の触媒は高
い水素化精製活性を有し、炭化水素油を効率よく水素化
精製することができるとともに、特には脱硫軽油の収率
をあまり低減させないで軽油留分から硫黄分を大幅に低
減させることができ、高度に脱硫された軽油を収率良く
製造できるという格別の効果を奏する。As described above, the catalyst of the present invention has a high hydrorefining activity and is capable of efficiently hydrorefining hydrocarbon oils, and in particular, the yield of desulfurized gas oil is significantly reduced. It is possible to significantly reduce the sulfur content from the gas oil fraction without performing the treatment, and it is possible to produce a highly desulfurized gas oil in a high yield, which is a particular effect.
Claims (3)
シリカアルミナをシリカとして１〜８重量％含有させた
担体上に、周期律表第VIb族金属元素から選択された少
なくとも１種を当該触媒中に５〜２０重量％、周期律表
第VIII族金属元素から選択された少なくとも１種を当該
触媒中に１〜１０重量％およびリンを当該触媒中に０.
１〜８重量％担持させたことを特徴とする水素化精製触
媒。1. At least one selected from Group VIb metal elements of the Periodic Table of the catalyst is supported on a carrier containing 1 to 8% by weight of silica and alumina containing 30% by weight or more of silica. 5 to 20% by weight, at least one selected from Group VIII metal elements of the periodic table in the catalyst in an amount of 1 to 10% by weight, and phosphorus in the catalyst in an amount of 0.
A hydrorefining catalyst, which is carried by 1 to 8% by weight.
製触媒の存在下に水素化精製することを特徴とする炭化
水素油の水素化精製方法。2. A hydrorefining method for a hydrocarbon oil, which comprises hydrorefining a hydrocarbon oil in the presence of the hydrorefining catalyst according to claim 1.
触媒の存在下に水素化脱硫を行うことを特徴とする脱硫
軽油の製造方法。3. A method for producing desulfurized gas oil, which comprises hydrodesulfurizing a gas oil fraction in the presence of the hydrorefining catalyst according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11533895A JP3355059B2 (en) | 1995-04-18 | 1995-04-18 | Hydrorefining catalyst, method for hydrorefining hydrocarbon oil, and method for producing desulfurized gas oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11533895A JP3355059B2 (en) | 1995-04-18 | 1995-04-18 | Hydrorefining catalyst, method for hydrorefining hydrocarbon oil, and method for producing desulfurized gas oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08281117A true JPH08281117A (en) | 1996-10-29 |
| JP3355059B2 JP3355059B2 (en) | 2002-12-09 |
Family
ID=14660076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11533895A Expired - Lifetime JP3355059B2 (en) | 1995-04-18 | 1995-04-18 | Hydrorefining catalyst, method for hydrorefining hydrocarbon oil, and method for producing desulfurized gas oil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3355059B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005120706A1 (en) * | 2004-06-07 | 2005-12-22 | Nippon Oil Corporation | Catalyst for hydrogenation treatment of hydrocarbon oil and method for hydrogenation treatment using said catalyst |
-
1995
- 1995-04-18 JP JP11533895A patent/JP3355059B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005120706A1 (en) * | 2004-06-07 | 2005-12-22 | Nippon Oil Corporation | Catalyst for hydrogenation treatment of hydrocarbon oil and method for hydrogenation treatment using said catalyst |
| US7429550B2 (en) | 2004-06-07 | 2008-09-30 | Nippon Oil Corporation | Hydrogenation catalyst for hydrocarbon oil and process for hydrogenation using the catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3355059B2 (en) | 2002-12-09 |
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