JP2001179105A - Catalyst for hydrodesulfurization and isomerization of light hydrocarbon oil and method of producing the same - Google Patents
Catalyst for hydrodesulfurization and isomerization of light hydrocarbon oil and method of producing the sameInfo
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- JP2001179105A JP2001179105A JP36785299A JP36785299A JP2001179105A JP 2001179105 A JP2001179105 A JP 2001179105A JP 36785299 A JP36785299 A JP 36785299A JP 36785299 A JP36785299 A JP 36785299A JP 2001179105 A JP2001179105 A JP 2001179105A
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、有機硫黄化合物を
含有する軽質炭化水素油の水素化脱硫と異性化とを同時
に達成することが可能であって、従来技術にくらべて簡
単な設備で使用でき、経済的な、軽質炭化水素油の水素
化脱硫異性化用の触媒に関し、その触媒の製造方法に及
ぶ。TECHNICAL FIELD The present invention is capable of simultaneously achieving hydrodesulfurization and isomerization of a light hydrocarbon oil containing an organic sulfur compound, and can be used with a simpler facility than the prior art. A possible and economical catalyst for hydrodesulfurization isomerization of light hydrocarbon oils, and extends to a process for producing the catalyst.
【0002】[0002]
【従来の技術】軽質炭化水素油の異性化は、石油精製工
業および石油化学工業で従来から広く行なわれている技
術である。とくに近年、自動車および航空機のエンジン
の高性能化に伴い、燃料として使用されるガソリンには
高いオクタン価が要求され、それに応えるために、異性
化が重要になってきている。これまでも、ガソリンの軽
質基材のひとつとして、軽質炭化水素油であるライトナ
フサを異性化してオクタン価を向上させた、いわゆる異
性化ガソリンが用いられている。2. Description of the Prior Art Isomerization of light hydrocarbon oil is a technique which has been widely used in the petroleum refining industry and petrochemical industry. In particular, in recent years, with higher performance of engines of automobiles and aircraft, gasoline used as fuel has been required to have a high octane number, and isomerization has become important to meet the demand. Until now, as one of the light base materials of gasoline, a so-called isomerized gasoline obtained by isomerizing light naphtha, which is a light hydrocarbon oil, to improve the octane number has been used.
【0003】軽質炭化水素油を異性化する方法について
は、従来から数多くの研究がなされており、異性化反応
に用いる触媒も種々のものが知られているが、その中で
最も有用な異性化触媒として、固体酸触媒を挙げること
ができる。固体酸触媒の製造方法およびそれを用いた異
性化方法は、たとえば、特公平5−29503号公報、
特公平6−29199号公報に開示されている。[0003] Many studies have been made on the method of isomerizing light hydrocarbon oils, and various catalysts used for the isomerization reaction are known. Examples of the catalyst include a solid acid catalyst. A method for producing a solid acid catalyst and an isomerization method using the same are described in, for example, Japanese Patent Publication No. 5-29503,
It is disclosed in Japanese Patent Publication No. 6-29199.
【0004】しかし、原油を蒸留した留分のままである
ライトナフサのような軽質炭化水素油には、有機硫黄化
合物が通常500〜700ppm程度含まれていて、これ
が固体酸触媒の触媒毒となるため、ライトナフサを直接
異性化することは、触媒寿命の点から、工業的実施に適
するプロセスではなかった。現在実施されているプロセ
スでは、まず、ライトナフサをCo−Mo/Al2O3な
どの水素化脱硫触媒で処理して有機硫黄化合物を硫化水
素に変換し、この硫化水素を生成油から分離することに
よって硫黄含有量を数ppm以下に低減させた脱硫ライト
ナフサを取得し、その後、これを異性化原料油として用
いるという、二段階の操作を行なう。つまり、現行の軽
質炭化水素油の異性化プロセスにおいては、水素化脱硫
工程が異性化工程の前段に必要不可欠である。[0004] However, light hydrocarbon oils such as light naphtha, which are still fractions obtained by distilling crude oil, usually contain about 500 to 700 ppm of organic sulfur compounds, which become catalyst poisons for solid acid catalysts. Therefore, direct isomerization of light naphtha was not a process suitable for industrial implementation in terms of catalyst life. In the process currently being performed, first, it converts the light naphtha was treated with hydrodesulfurization catalyst such as Co-Mo / Al 2 O 3 and organic sulfur compounds to hydrogen sulfide, to separate the hydrogen sulfide from the product oil Thus, a two-stage operation of obtaining desulfurized light naphtha whose sulfur content has been reduced to several ppm or less and then using it as an isomerized feedstock oil is performed. That is, in the existing light hydrocarbon oil isomerization process, the hydrodesulfurization step is indispensable before the isomerization step.
【0005】もし、軽質炭化水素油の異性化に使用する
触媒を、水素化脱硫と異性化とを同時に達成することが
できるものに置き換えることができれば、異性化プロセ
スに必要不可欠であった水素化脱硫工程を省略すること
ができ、従来技術にくらべてより簡単な設備で、経済的
に異性化を行なうことが可能になる。具体的には、既存
の軽質炭化水素油の異性化反応塔に耐硫黄性を有する異
性化触媒を充填し、異性化の原料油として有機硫黄化合
物を含有する軽質炭化水素油を供給して、水素化脱硫お
よび異性化反応を同時に行なえるようにすることが望ま
しい。[0005] If the catalyst used for isomerization of light hydrocarbon oils can be replaced with a catalyst capable of simultaneously achieving hydrodesulfurization and isomerization, hydrogenation which is indispensable for the isomerization process is required. The desulfurization step can be omitted, and the isomerization can be carried out economically with simpler equipment than in the prior art. Specifically, an existing light hydrocarbon oil isomerization reaction tower is charged with a sulfur-resistant isomerization catalyst, and a light hydrocarbon oil containing an organic sulfur compound is supplied as a raw material oil for isomerization, It is desirable to be able to perform hydrodesulfurization and isomerization reactions simultaneously.
【0006】発明者らは、このような要望に応えること
を意図して研究した結果、ある種の固体酸触媒が、炭化
水素の異性化活性のみならず有機硫黄化合物に対する脱
硫活性をも有し、耐硫黄性に優れた異性化触媒として役
立つことを見出した。[0006] The inventors of the present invention have conducted studies with the intention of responding to such a demand. As a result, certain solid acid catalysts have not only an isomerization activity for hydrocarbons but also a desulfurization activity for organic sulfur compounds. It was found to be useful as an isomerization catalyst having excellent sulfur resistance.
【0007】[0007]
【発明が解決しようとする課題】本発明の目的は、発明
者らの得た上記の新しい知見を生かし、簡便な設備によ
り経済的に、硫黄を含有する軽質炭化水素油の脱硫と異
性化とを同時に達成することができる触媒と、その好適
な製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to utilize the above-mentioned new knowledge obtained by the present inventors to economically desulfurize and isomerize light sulfur-containing hydrocarbon oils with simple equipment. And a suitable production method thereof.
【0008】[0008]
【課題を解決するための手段】本発明の軽質炭化水素油
の水素化脱硫異性化用の触媒は、ジルコニウムの酸化物
または水酸化物からなる担体に、硫酸根を硫黄分にして
1〜3質量%含有させるとともに、白金を0.5〜10
質量%担持させ、550〜800℃の温度で焼成安定化
させてなり、比表面積が50〜150m2/gであること
を特徴とする。The catalyst for hydrodesulfurization and isomerization of a light hydrocarbon oil according to the present invention is obtained by converting a sulfuric acid group into a sulfuric acid on a carrier comprising zirconium oxide or hydroxide. %, And 0.5 to 10% platinum.
It is characterized by having a specific surface area of 50 to 150 m < 2 > / g.
【0009】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【0010】本発明の触媒は、上記のように、ジルコニ
ウムの酸化物または水酸化物を担体とし、これに硫酸根
を硫黄分にして1〜3質量%含有させるとともに、白金
を0.5〜10質量%、好ましくは0.6〜7質量%、
さらに好ましくは0.7〜5質量%担持させたものであ
る。白金担持量が0.5質量%未満では活性点が少なす
ぎて、異性化と脱硫とを同時に行なうことができず、一
方、10質量%より多いと、白金が超強酸性を有する酸
点を覆うため、かえって活性が低下することがある。[0010] As described above, the catalyst of the present invention uses zirconium oxide or hydroxide as a carrier, and contains 1 to 3% by mass of sulfate as sulfur content, and platinum of 0.5 to 0.5%. 10% by weight, preferably 0.6 to 7% by weight,
More preferably, 0.7 to 5% by mass is supported. When the amount of platinum supported is less than 0.5% by mass, the active sites are too small to simultaneously perform isomerization and desulfurization. On the other hand, when the amount is more than 10% by mass, platinum has an acid site having super-strong acidity. In some cases, the activity is reduced due to the covering.
【0011】担体に与える硫酸根(SO4)の量は、硫
黄(S)分として1〜3質量%、好ましくは1.5〜2
質量%である。硫酸根の量が硫黄分として1質量%に達
しないと、触媒の酸性度が低いため固体超強酸性が弱
く、異性化触媒としての活性が不十分である。3%を超
える多量になると、ジルコニアの表面を硫酸根が過剰に
覆って積み重なり、活性点をつぶしてしまうため、かえ
って活性が低下する。The amount of sulfate (SO 4 ) given to the carrier is 1 to 3% by mass as sulfur (S), preferably 1.5 to 2%.
% By mass. If the amount of the sulfate group does not reach 1% by mass in terms of sulfur content, the acidity of the catalyst is low, so that the solid superacidity is weak and the activity as an isomerization catalyst is insufficient. When the amount is more than 3%, the surface of zirconia is excessively covered with sulfate groups and piled up, thereby crushing the active sites, and consequently the activity is reduced.
【0012】触媒中の硫黄分の測定は、試料を酸素気流
中で燃焼させ、試料中に含まれているSを酸化させてS
O2にし、水分とダストを除去した後、赤外吸収検出
器、たとえばソリッド・ステート型の検出器により、検
出・測定する。この分析方法によれば、試料中の硫黄分
の量を、0.001〜99.99%の濃度範囲で求める
ことができる。[0012] The sulfur content in the catalyst is measured by burning a sample in an oxygen stream and oxidizing S contained in the sample.
After removing the water and dust to O 2 , detection and measurement are performed with an infrared absorption detector, for example, a solid state type detector. According to this analysis method, the amount of sulfur in the sample can be determined in a concentration range of 0.001 to 99.99%.
【0013】X線回折分析によれば、 担体が酸化ジル
コニウム(ZrO2)である場合、その結晶構造には正
方晶と単斜晶とが存在する。触媒担体として有用なもの
は正方晶であり、単斜晶構造の割合が高いと、触媒活性
が低くなってしまう。酸化ジルコニウム中の単斜晶構造
と正方晶構造の存在比は、触媒のX線回折ピークを測定
し、CuKα線による2θ=28.2(単斜晶構造の主
ピーク)のピークと、2θ=30.2(正方晶構造の主
ピーク)のピークとのX線回折ピーク積分強度比をもっ
て定める。このようにして酸化ジルコニウム中の単斜晶
構造と正方晶構造の存在比を算出したときに、その値
が、単斜晶/正方晶=20/80〜0/100の範囲に
あることが好ましい。より好ましい範囲は、10/90
〜0/100である。According to X-ray diffraction analysis, when the carrier is zirconium oxide (ZrO 2 ), its crystal structure includes tetragonal and monoclinic. Those useful as catalyst carriers are tetragonal, and a high proportion of monoclinic structure results in low catalytic activity. The abundance ratio of the monoclinic structure and the tetragonal structure in zirconium oxide was determined by measuring the X-ray diffraction peak of the catalyst, and the peak of 2θ = 28.2 (the main peak of the monoclinic structure) and 2θ = The X-ray diffraction peak integrated intensity ratio with the peak of 30.2 (the main peak of the tetragonal structure) is determined. When the abundance ratio between the monoclinic structure and the tetragonal structure in zirconium oxide is calculated in this manner, the value is preferably in the range of monoclinic / tetragonal = 20/80 to 0/100. . A more preferred range is 10/90
00/100.
【0014】本発明の触媒は、550〜800℃で焼成
安定させた後、BET法により測定した比表面積が、5
0〜150m2/gの範囲にあることが必要である。比表
面積が50m2/g未満では、担持された金属の分散性が
悪く、水素化異性化のための活性点も少数に止まる。そ
の上、ジルコニウム酸化物の結晶構造も、単斜晶と正方
晶の比率が20/80よりも大きくなりがちであって、
好ましくない。一方、比表面積が150m2/gを超える
ものは、焼成によるジルコニウム酸化物の結晶化が進行
せず、その中の酸化ジルコニウム正方晶構造の割合が低
いために、水素化脱硫異性化の活性が低い値に止まる。After the catalyst of the present invention is calcined at 550 to 800 ° C. and has a specific surface area of 5
It must be in the range of 0 to 150 m 2 / g. When the specific surface area is less than 50 m 2 / g, the dispersibility of the supported metal is poor, and the number of active sites for hydroisomerization is small. In addition, the crystal structure of zirconium oxide also tends to have a monoclinic / tetragonal ratio greater than 20/80,
Not preferred. On the other hand, when the specific surface area exceeds 150 m 2 / g, the crystallization of the zirconium oxide does not proceed by firing, and the ratio of the zirconium oxide tetragonal structure therein is low, so that the activity of hydrodesulfurization isomerization is low. It stays low.
【0015】本発明の触媒の製造方法には、とくに限定
はなく、硫酸根を与え、白金を担持させる方法も、順序
も任意であるが、好適なのは、次にあげるような製造方
法である。The method for producing the catalyst of the present invention is not particularly limited, and the method of providing a sulfate group and supporting platinum and the order thereof are arbitrary, but the following production methods are preferred.
【0016】第一の製造方法は、水酸化ジルコニウム
を、これに硫酸根を与える処理剤で処理したのち、白金
化合物を含浸させ、550℃〜800℃の温度で焼成す
ることからなる。The first production method comprises treating zirconium hydroxide with a treating agent that gives a sulfate group thereto, impregnating with a platinum compound, and firing at a temperature of 550 ° C. to 800 ° C.
【0017】第二の製造方法は、水酸化ジルコニウム
を、これに硫酸根を与える処理剤で処理し、いったん5
50℃〜800℃の温度で焼成したのち、白金化合物を
含浸させ、ついで300℃〜700℃、好ましくは50
0℃〜600℃の温度において再度焼成することからな
る。In the second production method, zirconium hydroxide is treated with a treating agent that gives a sulfate group to the zirconium hydroxide.
After firing at a temperature of 50 ° C. to 800 ° C., impregnation with a platinum compound is performed, followed by 300 ° C. to 700 ° C., preferably 50 ° C.
Baking again at a temperature of 0 ° C to 600 ° C.
【0018】第三の製造方法は、水酸化ジルコニウム
と、これに硫酸根を与える物質とを混練し、550℃〜
800℃の温度における焼成を行ったのち、白金化合物
を含浸させ、ついで300℃〜700℃、好ましくは5
00℃〜600℃の温度において再度焼成することから
なる。A third production method is to knead zirconium hydroxide and a substance which gives a sulfate group thereto, and
After calcination at a temperature of 800 ° C., impregnation with a platinum compound is performed, and then 300 ° C. to 700 ° C., preferably 5 ° C.
Baking again at a temperature of 00 ° C to 600 ° C.
【0019】第四の製造方法は、水酸化ジルコニウム
と、硫酸根を与える物質および白金化合物とを混練し、
550℃〜800℃の温度で焼成することからなる。In a fourth production method, zirconium hydroxide is kneaded with a substance providing a sulfate group and a platinum compound,
Baking at a temperature of 550 ° C to 800 ° C.
【0020】ジルコニウムの酸化物または水酸化物であ
る担体に硫酸根を与える処理剤としては、0.1〜5N
の硫酸、0.1〜10モル濃度の硫酸アンモニウム水溶
液等が代表的である。これらの処理剤は、担体に対して
1〜10倍の量を使用する。その他、硫化水素や亜硫酸
ガスのような処理剤を用いて、焼成安定化処理の後に硫
酸根を与えることによっても、同様な効果をあげること
ができる。As a treating agent for giving a sulfate group to a carrier which is an oxide or hydroxide of zirconium, 0.1 to 5 N
Of sulfuric acid, and an aqueous solution of ammonium sulfate having a concentration of 0.1 to 10 mol are representative. These treatment agents are used in an amount of 1 to 10 times the amount of the carrier. In addition, a similar effect can be obtained by using a treating agent such as hydrogen sulfide or sulfurous acid gas to give a sulfate group after the firing stabilization treatment.
【0021】硫酸根の与え方は、硫酸処理剤として前述
のような液体や気体の状態にあるものだけでなく、固体
の状態にあるものを担体と混練することによってもよ
く、混練物を焼成安定化することで、同様の効果をあげ
ることができる。混練の手段としては、一般に触媒調製
に用いられている混練機であればどのようなものでも使
用できる。混練に当たっては、適宜の液体、たとえば
水、エタノール、イソプロパノール、アセトン、メチル
エチルケトン、ジエチルケトン、メチルイソブチルケト
ンなどを添加する。担体、硫酸根処理剤、溶媒等の添加
順序はとくに制限がなく、混練温度および時間も、触媒
の性能が影響を受けない範囲内であれば、別段制約され
ない。The sulfate group may be provided by kneading not only the above-mentioned liquid or gaseous state as a sulfuric acid treating agent but also a solid state with a carrier. By stabilizing, a similar effect can be obtained. As a kneading means, any kneading machine generally used for catalyst preparation can be used. In kneading, an appropriate liquid, for example, water, ethanol, isopropanol, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, or the like is added. There are no particular restrictions on the order of addition of the carrier, the sulfate treatment agent, the solvent, and the like, and the kneading temperature and time are not particularly limited as long as the performance of the catalyst is not affected.
【0022】触媒に白金を担持させる方法は、塩化白金
酸、テトラアンミン白金錯体等の白金化合物の水溶液に
担体を浸漬し、引き上げて乾燥する含浸法が代表的であ
る。水溶液の含浸でなく、塩化白金酸、テトラアンミン
白金錯体等を、前記した硫酸根処理剤との混練時に混合
することによっても、白金を担持させることは可能であ
る。A typical method of supporting platinum on a catalyst is an impregnation method in which a carrier is immersed in an aqueous solution of a platinum compound such as chloroplatinic acid or a tetraammineplatinum complex, pulled up and dried. It is also possible to carry platinum by mixing chloroplatinic acid, tetraammineplatinum complex or the like at the time of kneading with the above-mentioned sulfate group treating agent instead of impregnation with an aqueous solution.
【0023】焼成安定化処理は、酸化性の雰囲気下に、
550〜800℃の範囲、好ましくは600〜750℃
の範囲の温度に、0.5〜10時間加熱することによっ
て行なう。焼成温度が550℃未満では、ジルコニウム
化合物中に含まれる水酸化ジルコニウムの割合が多く、
正方晶のジルコニウム酸化物の占める割合が少ないため
固体酸の性質が発現せず、触媒に水素化脱硫異性化の活
性が生じない。一方、高温で加熱すると水酸化物は減る
が、800℃を超えると、単斜晶の酸化ジルコニウムの
占める割合が多くなり、触媒活性にとって好ましくな
い。また硫酸根も脱離して行くため、触媒中の硫黄分の
量が1質量%未満になり、固体酸強度が低下してしま
う。さらに、白金のシンタリングも起こり、水素化脱硫
異性化の活性点が減少する。なお、触媒の焼成安定化処
理を還元雰囲気で行なうと、白金または白金化合物の上
で硫酸根の結合状態が変化したり、還元分解に起因する
と思われる硫酸根の減少によって、触媒活性が低下す
る。The firing stabilization treatment is performed under an oxidizing atmosphere.
550-800 ° C, preferably 600-750 ° C
By heating to a temperature in the range of 0.5 to 10 hours. When the firing temperature is lower than 550 ° C., the ratio of zirconium hydroxide contained in the zirconium compound is large,
Since the proportion of the tetragonal zirconium oxide is small, the properties of the solid acid are not exhibited, and the catalyst does not have hydrodesulfurization isomerization activity. On the other hand, when heated at a high temperature, the amount of hydroxide decreases, but when the temperature exceeds 800 ° C., the proportion of monoclinic zirconium oxide increases, which is not preferable for the catalytic activity. In addition, since the sulfate is also eliminated, the amount of sulfur in the catalyst becomes less than 1% by mass, and the solid acid strength decreases. Furthermore, sintering of platinum also occurs, and the active sites of hydrodesulfurization isomerization decrease. If the catalyst is stabilized in a calcination stabilizing treatment in a reducing atmosphere, the activity of the sulfate groups on the platinum or platinum compound changes, and the catalytic activity decreases due to the reduction of the sulfate groups, which is considered to be caused by reductive decomposition. .
【0024】焼成安定化処理は、白金を担持する前に行
っても、後に行ってもよい。白金を担持する前に焼成安
定化した場合でも、焼成安定化は、結晶状態が正方晶構
造の酸化ジルコニウムが得られる温度で行なう。好まし
い焼成温度の範囲は550〜800℃であり、さらに好
ましい範囲は600〜750℃である。好ましい焼成時
間は、0.5〜10時間である。焼成安定化後に、白金
を含有させ、さらに300〜700℃、好ましくは50
0℃〜600℃で焼成し、触媒の活性化を行なってもよ
い。The firing stabilization treatment may be performed before or after carrying platinum. Even when firing is stabilized before supporting platinum, the firing is stabilized at a temperature at which zirconium oxide having a tetragonal crystal structure can be obtained. A preferable range of the firing temperature is 550 to 800 ° C, and a more preferable range is 600 to 750 ° C. The preferred firing time is 0.5 to 10 hours. After the sintering is stabilized, platinum is contained, and the temperature is further increased to 300 to 700 ° C, preferably 50 to 700 ° C.
The catalyst may be activated by firing at 0 ° C. to 600 ° C.
【0025】本発明の触媒は、上記の安定化処理によっ
て使用可能になるが、触媒活性の安定化のためには、脱
硫異性化反応への使用に先立って、前処理を施すことが
好ましい。前処理は、触媒を100〜500℃の温度に
1〜5時間維持して乾燥し、ついで100〜400℃の
温度で還元処理することからなる。The catalyst of the present invention can be used by the above stabilization treatment. However, in order to stabilize the catalytic activity, it is preferable to carry out a pretreatment before use in the desulfurization isomerization reaction. The pretreatment consists of drying the catalyst at a temperature of 100-500 ° C. for 1-5 hours, followed by a reduction treatment at a temperature of 100-400 ° C.
【0026】得られた本発明の触媒は、必要に応じてア
ルミナ、シリカアルミナ、シリカ、ボリア、チタニア、
活性炭等を混合して使用することもできる。The obtained catalyst of the present invention may contain, if necessary, alumina, silica alumina, silica, boria, titania,
Activated carbon and the like can be mixed and used.
【0027】また触媒の形状はとくに限定されず、通常
この種の触媒に用いられている種々の形状、たとえば打
錠成型、押出成型により得られる円柱状、四葉型等を採
用することができる。The shape of the catalyst is not particularly limited, and various shapes usually used for this type of catalyst, for example, a columnar shape obtained by tableting and extrusion, a four-leaf type, and the like can be adopted.
【0028】本発明の触媒を用いて、脱硫と同時に異性
化させる原料油としては、原油の常圧蒸留装置から留出
したライトナフサ、同じく原油の常圧蒸留装置から留出
したホールナフサから分離したライトナフサ、またはラ
イトナフサにマーロックス処理を施したマーロックスナ
フサなどの、有機硫黄を含有する軽質炭化水素油が好適
である。とくに好適な原料油は、ASTM蒸留温度が2
5〜130℃、好ましくは25〜110℃のライトナフ
サである。有機硫黄の含有量についていえば、700質
量ppm以下、好ましくは10〜500質量ppm、さらに好
ましくは10〜200質量ppm程度のライトナフサが好
適に使用できる。硫黄分が数ppmまたはそれ以下の軽質
炭化水素油を原料として使用できることは、いうまでも
ない。As the feedstock to be isomerized simultaneously with desulfurization using the catalyst of the present invention, light naphtha distilled from an atmospheric distillation unit for crude oil and hole naphtha distilled from an atmospheric distillation unit for crude oil are also used. Light hydrocarbon oil containing organic sulfur, such as light naphtha, or marlox naphtha obtained by applying marlox treatment to light naphtha, is suitable. Particularly preferred feedstocks have an ASTM distillation temperature of 2
Light naphtha at 5 to 130 ° C, preferably 25 to 110 ° C. Speaking of the content of organic sulfur, light naphtha of 700 ppm by mass or less, preferably 10 to 500 ppm by mass, more preferably about 10 to 200 ppm by mass can be suitably used. It goes without saying that a light hydrocarbon oil having a sulfur content of several ppm or less can be used as a raw material.
【0029】ライトナフサに含まれている有機硫黄化合
物の代表例を挙げれば、チオール化合物(R−SH)と
して2−プロパンチオール(CH3)2CH−SH、エタン
チオールC2H5−SH、スルフィド化合物(R−S−
R)としてメチルエチルスルフィドCH3−S−C
2H5、ジスルフィド化合物(R−SS−R)としてエチ
ルイソプロピルジスルフィドC2H5−SS−CH(C
H3)2などである。本発明の触媒を用いれば、これらの
硫黄化合物を、原料油の異性化と同時に水素化分解して
脱硫を行なうことができる。Typical examples of the organic sulfur compounds contained in light naphtha include 2-propanethiol (CH 3 ) 2 CH-SH, ethanethiol C 2 H 5 -SH as thiol compounds (R-SH). The sulfide compound (RS-
R) as methyl ethyl sulfide CH 3 -SC
2 H 5 , ethyl isopropyl disulfide C 2 H 5 -SS-CH (C
H 3 ) 2 and the like. By using the catalyst of the present invention, desulfurization can be carried out by hydrocracking these sulfur compounds simultaneously with isomerization of the feedstock oil.
【0030】触媒活性をより長期にわたり維持するため
には、用いるライトナフサ中の芳香族、不飽和炭化水素
および高級炭化水素の量は少ない方がよい。ベンゼン量
は5vol.%以下、できれば3vol.%以下、ナフテン量は
12vol.%以下、できれば9vol.%以下、C7化合物は
15vol.%以下、できれば10vol.%以下とする。In order to maintain the catalytic activity for a longer period of time, the amount of aromatic, unsaturated hydrocarbon and higher hydrocarbon in light naphtha used should be smaller. The benzene content is 5 vol.% Or less, preferably 3 vol.% Or less, the naphthene content is 12 vol.% Or less, preferably 9 vol.% Or less, and the C 7 compound is 15 vol.% Or less, preferably 10 vol.% Or less.
【0031】脱硫異性化の反応条件は、 反応温度:140〜400℃、好ましくは160〜30
0℃、さらに好ましくは180℃〜220℃ 反応圧力:1.0〜4.5MPa、好ましくは1.4〜
3.5MPa LHSV:1.0〜10h-1、好ましくは1.0〜5h
-1 H2/Oil比:1〜3mol/mol、 好ましくは1.5〜2.
5mol/mol である。反応温度が140℃より低いと触媒の寿命が短
くなり、一方、400℃を超えると、活性点である硫酸
根が水素還元され硫化水素として脱離するため活性が低
下する。そのほかの条件すなわち反応圧力、LHSV、
H2/Oil比は、従来行なわれている軽質炭化水素油の異
性化反応の条件とほぼ同様である。The reaction conditions for the desulfurization isomerization are as follows: reaction temperature: 140 to 400 ° C., preferably 160 to 30 ° C.
0 ° C, more preferably 180 ° C to 220 ° C Reaction pressure: 1.0 to 4.5MPa, preferably 1.4 to
3.5 MPa LHSV: 1.0 to 10 h -1 , preferably 1.0 to 5 h
-1 H 2 / Oil ratio: 1~3mol / mol, preferably 1.5 to 2.
It is 5 mol / mol. When the reaction temperature is lower than 140 ° C., the life of the catalyst is shortened. On the other hand, when the reaction temperature is higher than 400 ° C., the activity is reduced because the sulfate group, which is the active site, is reduced by hydrogen and eliminated as hydrogen sulfide. Other conditions, ie reaction pressure, LHSV,
The H 2 / Oil ratio is almost the same as the condition of a conventional light hydrocarbon oil isomerization reaction.
【0032】本発明の触媒は、水素化脱硫異性化触媒と
して、従来の異性化触媒と置き換えて使用することがで
きる。すなわち、軽質炭化水素油中の有機硫黄化合物を
水素化脱硫して硫化水素に変換し、硫黄分を数ppm以下
にすると同時に直接異性化することができ、オクタン価
を向上させた生成油を得ることができる。The catalyst of the present invention can be used as a hydrodesulfurization isomerization catalyst in place of a conventional isomerization catalyst. That is, an organic sulfur compound in a light hydrocarbon oil is hydrodesulfurized and converted into hydrogen sulfide, and the sulfur content can be reduced to several ppm or less and at the same time can be directly isomerized to obtain a product oil having an improved octane number. Can be.
【0033】以下、実施例により本発明をさらに詳細に
説明するが、本発明はこれらの実施例に限定されるもの
ではなく、本発明の趣旨を逸脱しない限り、種々の変更
態様が含まれる。Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples, and includes various modifications without departing from the spirit of the present invention.
【0034】[0034]
【実施例1〜5および比較例1】 触媒A〜Fの製造 下記の触媒A〜Fを製造した。触媒A〜C(実施例)お
よび触媒F(比較例)の製造に当たっては含浸法を採用
し、まず実施例1の(1)および(2)のようにして硫
酸根含有水酸化ジルコニウムを用意し、これに塩化白金
酸の水溶液を含浸させ、乾燥し焼成する手順を踏んだ。
触媒DおよびE(実施例)の製造に当たっては混練法を
採用し、実施例1の(1)のようにして水酸化ジルコニ
ウムを調製して使用した。Examples 1 to 5 and Comparative Example 1 Production of Catalysts A to F The following catalysts A to F were produced. In the production of Catalysts A to C (Example) and Catalyst F (Comparative Example), an impregnation method was adopted. First, zirconium hydroxide containing a sulfate group was prepared as in (1) and (2) of Example 1. This was impregnated with an aqueous solution of chloroplatinic acid, dried and fired.
In producing catalysts D and E (Examples), a kneading method was employed, and zirconium hydroxide was prepared and used as in (1) of Example 1.
【0035】実施例1:触媒A (1)Zr(OH)4の調製 市販のオキシ塩化ジルコニウムZrOCl2・8H2Oの
1000gを4Lの蒸留水に溶かし、攪拌しながら、そ
こへ25%アンモニア水NH3aq.を滴下して、水酸化
ジルコニウムZr(OH)4を沈殿させた。水溶液のpH
が9.0になるように調製し、沈殿した水酸化ジルコニ
ウムを濾過して分離した。濾過後、蒸留水でよく洗浄
し、110℃で一昼夜乾燥させ、水酸化ジルコニウム4
90gを得た。 (2)SO4/Zr(OH)4の調製 上記のようにしてオキシ塩化ジルコニウムから調製した
水酸化ジルコニウムの400gを1N−硫酸4000g
に入れ、30分間攪拌した。攪拌後、濾過して固体分を
110℃で一昼夜乾燥し、硫酸根を含有する水酸化ジル
コニウムSO4/Zr(OH)4452gを得た。 (3)Pt/SO4/ZrO2の調製 塩化白金酸H2PtCl6・xH2Oの0.47gを溶か
した水溶液に、(2)で得られた硫酸根を含有する水酸
化ジルコニウム19gを入れ、Pt塩を含浸させた。1
10℃で一昼夜乾燥した後、マッフル炉に入れて600
℃で3時間焼成し、Pt担持硫酸根含有ジルコニアPt
/SO4/ZrO213.5gを得た。[0035] Example 1: Dissolve 1000g of catalyst A (1) Zr (OH) 4 Preparation commercial zirconium oxychloride ZrOCl 2 · 8H 2 O in distilled water 4L, while stirring, 25% aqueous ammonia thereto NH 3 aq. Was added dropwise to precipitate zirconium hydroxide Zr (OH) 4 . PH of aqueous solution
Was adjusted to 9.0, and the precipitated zirconium hydroxide was separated by filtration. After filtration, wash well with distilled water, dry at 110 ° C. for 24 hours, and add zirconium hydroxide 4
90 g were obtained. (2) Preparation of SO 4 / Zr (OH) 4 400 g of zirconium hydroxide prepared from zirconium oxychloride as described above was mixed with 4000 g of 1N sulfuric acid.
And stirred for 30 minutes. After stirring, the mixture was filtered and the solid was dried at 110 ° C. for 24 hours to obtain 452 g of sulfated zirconium hydroxide SO 4 / Zr (OH) 4 . (3) Preparation of Pt / SO 4 / ZrO 2 In an aqueous solution in which 0.47 g of chloroplatinic acid H 2 PtCl 6 .xH 2 O was dissolved, 19 g of the sulfate-containing zirconium hydroxide obtained in (2) was added. And impregnated with Pt salt. 1
After drying at 10 ° C all day and night, place in a muffle furnace for 600
Calcination for 3 hours at ℃, Pt-supported sulfate-containing zirconia Pt
/ SO 4 / ZrO 2 13.5 g was obtained.
【0036】実施例2:触媒B 塩化白金酸H2PtCl6・xH2Oの2.65gを溶か
した水溶液に、実施例1(1)および(2)に記載した
調製法により調製した硫酸根含有水酸化ジルコニウム2
0gを入れ、Pt塩を含浸させた。以下、実施例1と同
様に乾燥および焼成を行なって、Pt担持硫酸根含有ジ
ルコニアPt/SO4/ZrO214gを得た。Example 2: Catalyst B Sulfate prepared by the preparation method described in Examples 1 (1) and (2) in an aqueous solution in which 2.65 g of chloroplatinic acid H 2 PtCl 6 .xH 2 O is dissolved. Containing zirconium hydroxide 2
0 g was charged and impregnated with Pt salt. Thereafter, drying and firing were carried out in the same manner as in Example 1 to obtain 14 g of Pt-supported sulfate-containing zirconia Pt / SO 4 / ZrO 2 .
【0037】実施例3:触媒C 実施例1(1)および(2)に記載した調製法により調
製した硫酸根含有水酸化ジルコニウム20gを、マッフ
ル炉に入れて600℃に3時間加熱することにより焼成
安定化させ、硫酸根含有ジルコニア15gを得た。塩化
白金酸H2PtCl6・xH2Oの0.36gを溶かした
水溶液に、この硫酸根含有ジルコニア15gを入れ、P
tを含浸させた。110℃で一昼夜乾燥した後、マッフ
ル炉で550℃において2時間焼成し、Pt担持硫酸根
含有ジルコニアPt/SO4/ZrO213gを得た。Example 3: Catalyst C 20 g of sulfate-containing zirconium hydroxide prepared by the preparation method described in Examples 1 (1) and (2) was heated in a muffle furnace at 600 ° C. for 3 hours. The sintering was stabilized to obtain 15 g of sulfate group-containing zirconia. 15 g of this sulfate-containing zirconia was added to an aqueous solution in which 0.36 g of chloroplatinic acid H 2 PtCl 6 .xH 2 O was dissolved.
t impregnated. After drying at 110 ° C. for 24 hours, it was baked in a muffle furnace at 550 ° C. for 2 hours to obtain 13 g of Pt / SO 4 / ZrO 2 containing Pt-supported sulfate group.
【0038】実施例4:触媒D 実施例1(1)で示した調製法により調製した水酸化ジ
ルコニウム22gに市販の硫酸アンモニウム3.1gを
加え、攪拌羽根のついた混練機で、水を加えながら1時
間混練した。得られた硫酸根含有水酸化ジルコニウムを
110℃で一昼夜乾燥した後、マッフル炉に入れ600
℃に3時間加熱して焼成安定化させ、硫酸根含有ジルコ
ニア16gを得た。塩化白金酸H2PtCl6・xH2O
の3.30gを溶かした水溶液に、この硫酸根含有ジル
コニア16gを入れてPtを含浸させた。110℃で一
昼夜乾燥した後、マッフル炉で550℃において2時間
焼成し、Pt担持硫酸根含有ジルコニアPt/SO4/
ZrO214gを得た。Example 4: Catalyst D 3.1 g of commercially available ammonium sulfate was added to 22 g of zirconium hydroxide prepared by the preparation method shown in Example 1 (1), and water was added thereto using a kneader equipped with stirring blades. Kneaded for 1 hour. The obtained sulfate-containing zirconium hydroxide was dried at 110 ° C. for 24 hours, and then placed in a muffle furnace for 600 hours.
C. for 3 hours to stabilize the calcination, thereby obtaining 16 g of sulfate group-containing zirconia. Chloroplatinic acid H 2 PtCl 6 .xH 2 O
Then, 16 g of this sulfate-containing zirconia was added to an aqueous solution in which 3.30 g of the above was dissolved to impregnate Pt. After drying at 110 ° C. for one day and night, it was calcined in a muffle furnace at 550 ° C. for 2 hours, and zirconia containing Pt-supported sulfate group Pt / SO 4 /
14 g of ZrO 2 were obtained.
【0039】実施例5:触媒E 実施例1(1)に記載した調製法により調製した水酸化
ジルコニウム35gに市販の硫酸アンモニウム5.0g
を加え、さらに塩化白金酸H2PtCl6・xH 2Oの
0.93gを加え、攪拌羽根のついた混練機で、水を加
えながら1時間混練した。得られた硫酸根含有水酸化ジ
ルコニウムを110℃で一昼夜乾燥した後、マッフル炉
に入れ600℃で3時間焼成し、Pt担持硫酸根含有ジ
ルコニアPt/SO4/ZrO225gを得た。Example 5: Catalyst E Hydroxide prepared by the preparation method described in Example 1 (1)
To 35 g of zirconium, 5.0 g of commercially available ammonium sulfate
And further add chloroplatinic acid HTwoPtCl6・ XH TwoO's
0.93 g was added, and water was added using a kneader equipped with stirring blades.
While kneading for 1 hour. The obtained sulfated hydroxyl-containing diamine
After drying the ruconium at 110 ° C all day and night, the muffle furnace
And baked at 600 ° C for 3 hours.
Luconia Pt / SOFour/ ZrOTwo25 g were obtained.
【0040】比較例1:触媒F 塩化白金酸六水和物H2PtCl6・xH2Oの1.5g
を溶かした水溶液に、実施例1(1)および(2)に記
載した調製法により調製した硫酸根含有水酸化ジルコニ
ウム168gを入れ、Pt塩を含浸させた。以下は実施
例1と同様に乾燥および焼成を行なって、Pt担持硫酸
根含有ジルコニアPt/SO4/ZrO2119gを得
た。Comparative Example 1: Catalyst F 1.5 g of chloroplatinic acid hexahydrate H 2 PtCl 6 .xH 2 O
Was dissolved in 168 g of sulfate-containing zirconium hydroxide prepared by the preparation method described in Examples 1 (1) and (2), and impregnated with a Pt salt. Thereafter, drying and firing were carried out in the same manner as in Example 1 to obtain 119 g of Pt-supported sulfate-containing zirconia Pt / SO 4 / ZrO 2 .
【0041】触媒A〜Fの物性試験結果を、表1にまと
めて示した。 表 1 触媒の物性(その1) 触媒A 触媒B 触媒C 触媒D 触媒の構成 Pt/SO4/ZrO2 Pt/SO4/ZrO2 Pt/SO4/ZrO2 Pt/SO4/ZrO2 焼成条件 600℃×3h 600℃×3h 600℃×3h 600℃×3h 比表面積(m2/g) 121 118 128 132 硫黄分(質量%) 1.72 1.64 2.01 1.73 金属元素分析値(質量%) Pt 0.92 4.50 0.85 7.45 ZrO2結晶構造比 単斜晶/正方晶 3.5/96.5 3.7/96.3 4.1/95.9 4.3/95.7 表 1 触媒の物性(その2) 触媒E 触媒F 触媒の構成 Pt/SO4/ZrO2 Pt/SO4/ZrO2 焼成条件 600℃×3h 600℃×3h 比表面積(m2/g) 119 145 硫黄分(質量%) 1.52 1.64 金属元素分析値(質量%) Pt 0.81 0.35 ZrO2結晶構造比 単斜晶/正方晶 4.5/95.5 4.6/95.4The results of the physical properties tests of Catalysts A to F are summarized in Table 1. Table 1 Physical Properties of Catalyst (Part 1) Catalyst A Catalyst B Catalyst C Catalyst D Structure of Catalyst Pt / SO 4 / ZrO 2 Pt / SO 4 / ZrO 2 Pt / SO 4 / ZrO 2 Pt / SO 4 / ZrO 2 Firing conditions 600 ° C × 3h 600 ° C × 3h 600 ° C × 3h 600 ° C × 3h Specific surface area (m 2 / g) 121 118 128 132 Sulfur content (% by mass) 1.72 1.64 2.01 1.73 Metal element analysis value (% by mass) Pt 0.92 4.50 0.85 7.45 ZrO 2 crystal structure ratio Monoclinic / tetragonal 3.5 / 96.5 3.7 / 96.3 4.1 / 95.9 4.3 / 95.7 Table 1 Physical Properties of Catalyst (Part 2) Catalyst E Catalyst F Catalyst Configuration Pt / SO 4 / ZrO 2 Pt / SO 4 / ZrO 2 firing conditions 600 ℃ × 3h 600 ℃ × 3h Specific surface area (m 2 / g) 119 145 Sulfur content (% by mass) 1.52 1.64 Metal element analysis value (% by mass) Pt 0.81 0.35 ZrO 2 crystal structure ratio Monoclinic Crystal / tetragonal 4.5 / 95.5 4.6 / 95.4
【0042】比表面積の測定には、日本ベル(株)製の
高精度全自動ガス吸着装置「BELSORP28」を使
用した。硫黄分の量は、LECO社の「SC−132」
硫黄分分析計を用いて測定した。For the measurement of the specific surface area, a high-precision fully automatic gas adsorption apparatus "BELSORP28" manufactured by Bell Japan Co., Ltd. was used. The amount of sulfur is "SC-132" manufactured by LECO.
It was measured using a sulfur analyzer.
【0043】[0043]
【触媒使用例】軽質炭化水素油の脱硫異性化反応 触媒充填容量が3mlの固定床流通式反応器を用いて軽質
炭化水素油の脱硫異性化を行ない、触媒A〜Fを評価し
た。反応条件は、次のとおりである: 反応圧力:1.47MPa 反応温度:200℃ LHSV:5h-1 H2/Oil比:2mol/mol 原料:有機硫黄化合物((n−C3H7)2S2)添加n−ペ
ンタン(硫黄分300質量ppm) n−ペンタンの異性化率を表2に示す。[Example of use of catalyst] Desulfurization isomerization reaction of light hydrocarbon oil Light hydrocarbon oil was subjected to desulfurization isomerization using a fixed bed flow reactor having a catalyst filling capacity of 3 ml, and catalysts A to F were evaluated. The reaction conditions are as follows: Reaction pressure: 1.47 MPa Reaction temperature: 200 ° C. LHSV: 5 h −1 H 2 / Oil ratio: 2 mol / mol Raw material: organic sulfur compound ((n-C 3 H 7 ) 2 S 2 ) Added n-pentane (300 ppm by mass of sulfur) Table 2 shows the isomerization ratio of n-pentane.
【0044】ここで、「異性化率」は下記の式で定義さ
れる。 異性化率(%)=(生成油中のi−C5の重量%)/(生成油
中の全C5化合物の重量%の合計)×100Here, the “isomerization ratio” is defined by the following equation. Isomerization rate (%) = (% by weight of iC 5 in product oil) / (total of weight% of all C 5 compounds in product oil) × 100
【0045】 表 2 有機硫黄化合物添加n−ペンタンの異性化 反応温度: 200℃ 反応圧力: 1.47MPa LHSV: 5/h H2/Oil: 2mol/mol 原料: n−C5+(n−C3H7)2S2 (S=300ppm) 触 媒 反応時間(h) C5異性化率(%) 触媒A:Pt/SO4/ZrO2 Pt:0.92質量% 2.8 57 4.7 62 6.5 60 触媒B:Pt/SO4/ZrO2 Pt:4.50質量% 2.1 69 4.9 70 6.9 69 触媒C:Pt/SO4/ZrO2 Pt:0.85質量% 2.9 55 5.2 59 7.0 59 触媒D:Pt/SO4/ZrO2 Pt:7.45質量% 3.1 64 4.9 65 6.9 63 触媒E:Pt/SO4/ZrO2 Pt:0.81質量% 2.9 55 4.8 59 6.9 58 触媒F:Pt/SO4/ZrO2 Pt:0.35質量% 2.1 22 4.2 9 5.3 3Table 2 Isomerization of n-pentane with added organic sulfur compound Reaction temperature: 200 ° C. Reaction pressure: 1.47 MPa LHSV: 5 / h H 2 / Oil: 2 mol / mol Raw material: nC 5 + (nC 3 H 7 ) 2 S 2 (S = 300 ppm ) Catalyst Reaction time (h) C5 isomerization rate (%) Catalyst A: Pt / SO 4 / ZrO 2 Pt: 0.92 mass% 2.8 57 4.7 626 5.560 Catalyst B: Pt / SO 4 / ZrO 2 Pt: 4.50% by mass 2.1 69 4.9 70 6.9 69 Catalyst C: Pt / SO 4 / ZrO 2 Pt: 0.85% by mass 2.9 55 5 .2 59 7.0 59 Catalyst D: Pt / SO 4 / ZrO 2 Pt: 7.45% by mass 3.1 64 4.9 65 6.9 63 Catalyst E: Pt / SO 4 / ZrO 2 Pt: 0.81% by mass 2 9.9 55 4.8 59 6.9 58 Catalyst F: Pt / SO 4 / ZrO 2 Pt: 0.35% by mass 2.1 22 4.2 9 5.3 3
【0046】実施例1〜5に記述した触媒A〜Eを使用
した場合には、出口の硫化水素濃度は約150容積ppm
であり、原料中に含まれる300質量ppmの有機硫黄化
合物のほとんどが水素化され、硫化水素に変換された。
すなわち、触媒A〜Eにおいては、硫酸根により電子不
足状態となり耐硫黄性が増した白金の量が増加したこと
により、n−ペンタンの異性化だけでなく、有機硫黄化
合物の脱硫も同時に行なわれた。When the catalysts A to E described in Examples 1 to 5 were used, the concentration of hydrogen sulfide at the outlet was about 150 ppm by volume.
Most of the 300 mass ppm organic sulfur compound contained in the raw material was hydrogenated and converted to hydrogen sulfide.
That is, in the catalysts A to E, not only isomerization of n-pentane, but also desulfurization of the organic sulfur compound is performed at the same time due to an increase in the amount of platinum whose sulfur resistance has been increased due to the lack of electrons due to the sulfate group. Was.
【0047】一方、比較例の触媒Fを使用した場合は、
異性化率が時間の経過とともに低下し、出口の硫化水素
濃度も約30容積ppmと、原料中の有機硫黄化合物の大
半が硫化水素に変換されなかった。すなわち、触媒Fに
おいては、耐硫黄性を有する白金の量が少ないために、
有機硫黄化合物による被毒を受け、活性が低下した。On the other hand, when the catalyst F of the comparative example was used,
The isomerization rate decreased over time, and the concentration of hydrogen sulfide at the outlet was about 30 ppm by volume, indicating that most of the organic sulfur compounds in the raw material were not converted to hydrogen sulfide. That is, in the catalyst F, since the amount of platinum having sulfur resistance is small,
Poisoned by organic sulfur compounds, the activity decreased.
【0048】[0048]
【発明の効果】本発明の触媒は、軽質炭化水素油の異性
化反応触媒として高い活性を有するだけでなく、耐硫黄
性を有し、異性化反応条件において有機硫黄化合物も水
素化脱硫することができる。このため、有機硫黄化合物
を含有する軽質炭化水素油の異性化に当たって、従来技
術においては不可欠な前処理であった脱硫処理を行なう
必要がなくなった。具体的にいえば、従来の異性化用の
固定床触媒反応装置にこの触媒を充填して、有機硫黄化
合物を含有する軽質炭化水素油を水素とともに流通させ
るだけで、異性化プロセスを完成することができる。従
って本発明によれば、従来のものより簡易な設備を用
い、低減されたランニングコストをもって、軽質炭化水
素油の水素化脱硫異性化を実施することができる。The catalyst of the present invention not only has high activity as a light hydrocarbon oil isomerization reaction catalyst, but also has sulfur resistance and hydrodesulfurizes organic sulfur compounds under isomerization reaction conditions. Can be. For this reason, in the isomerization of the light hydrocarbon oil containing the organic sulfur compound, it is not necessary to perform the desulfurization treatment which is an indispensable pretreatment in the prior art. Specifically, the isomerization process can be completed simply by filling the catalyst into a conventional fixed-bed catalytic reactor for isomerization and allowing the light hydrocarbon oil containing the organic sulfur compound to flow with hydrogen. Can be. Therefore, according to the present invention, hydrodesulfurization isomerization of a light hydrocarbon oil can be carried out at a reduced running cost using equipment simpler than conventional equipment.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 萩原 和彦 埼玉県幸手市権現堂1134−2 コスモ石油 株式会社研究開発センター内 (72)発明者 大塩 敦保 埼玉県幸手市権現堂1134−2 コスモ石油 株式会社研究開発センター内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhiko Hagiwara 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Oil Co., Ltd. (72) Inventor Atsushi Oshio 1134-2 Gongendo, Satte City, Saitama Cosmo Oil R & D Center Co., Ltd.
Claims (5)
らなる担体に、硫酸根を硫黄分にして1〜3質量%含有
させるとともに、白金0.5〜10質量%を担持させ、
550〜800℃の温度で焼成安定化させてなり、比表
面積が50〜150m2/gであることを特徴とする軽質
炭化水素油の水素化脱硫異性化用の触媒。1. A carrier made of a zirconium oxide or hydroxide containing a sulfate group in a sulfur content of 1 to 3% by mass and 0.5 to 10% by mass of platinum.
A catalyst for hydrodesulfurization isomerization of light hydrocarbon oils, which is calcined and stabilized at a temperature of 550 to 800 ° C and has a specific surface area of 50 to 150 m 2 / g.
の触媒の製造方法であって、水酸化ジルコニウムを、こ
れに硫酸根を与える処理剤で処理したのち、白金化合物
を含浸させ、550〜800℃の温度で焼成することか
らなる製造方法。2. The method for producing a catalyst for hydrodesulfurization isomerization according to claim 1, wherein zirconium hydroxide is treated with a treating agent that gives a sulfate group thereto, and then impregnated with a platinum compound. A production method comprising firing at a temperature of 550 to 800 ° C.
の触媒の製造方法であって、水酸化ジルコニウムを、こ
れに硫酸根を与える処理剤で処理したのち、550〜8
00℃の温度における焼成を行ってから、白金化合物を
含浸させ、300〜700℃の温度で焼成することから
なる製造方法。3. The method for producing a catalyst for hydrodesulfurization isomerization according to claim 1, wherein the zirconium hydroxide is treated with a treating agent that gives a sulfate group to the zirconium hydroxide.
A production method comprising performing calcination at a temperature of 00C, then impregnating with a platinum compound, and calcination at a temperature of 300 to 700C.
の触媒の製造方法であって、水酸化ジルコニウムと、こ
れに硫酸根を与える物質とを混練し、550〜800℃
の温度における焼成を行なった後、白金化合物を含浸さ
せ、300〜700℃の温度で焼成することからなる製
造方法。4. The method for producing a catalyst for hydrodesulfurization isomerization according to claim 1, wherein zirconium hydroxide and a substance that gives a sulfate group are kneaded, and the mixture is kneaded at 550 to 800 ° C.
A firing method at a temperature of 300 ° C., followed by impregnation with a platinum compound, and firing at a temperature of 300 to 700 ° C.
の触媒を製造する方法であって、水酸化ジルコニウム
と、これに硫酸根を与える物質および白金化合物とを混
練し、550〜800℃の温度で焼成することからなる
製造方法。5. A method for producing a catalyst for hydrodesulfurization isomerization according to claim 1, wherein zirconium hydroxide, a substance which gives a sulfate group thereto, and a platinum compound are kneaded, and 550-800. A production method comprising firing at a temperature of ° C.
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