JPWO2011043066A1 - Method for producing monocyclic aromatic compound - Google Patents

Method for producing monocyclic aromatic compound Download PDF

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JPWO2011043066A1
JPWO2011043066A1 JP2011535286A JP2011535286A JPWO2011043066A1 JP WO2011043066 A1 JPWO2011043066 A1 JP WO2011043066A1 JP 2011535286 A JP2011535286 A JP 2011535286A JP 2011535286 A JP2011535286 A JP 2011535286A JP WO2011043066 A1 JPWO2011043066 A1 JP WO2011043066A1
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JP5449383B2 (en
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智史 古田
智史 古田
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Eneos Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof

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Abstract

本発明は、高圧水素ガスを使用することなく、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を効率的に製造することが可能な単環芳香族化合物の製造方法に関し、より詳しくは、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を製造する方法であって、多環芳香族化合物を含有する炭化水素油に対して水を添加し、炭化水素油と水との混合物を、少なくともチタンを含有する触媒と接触させることを含むことを特徴とする単環芳香族化合物の製造方法である。The present invention relates to a method for producing a monocyclic aromatic compound that can efficiently produce a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound without using high-pressure hydrogen gas, and more Specifically, a method for producing a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound, wherein water is added to the hydrocarbon oil containing the polycyclic aromatic compound, A method for producing a monocyclic aromatic compound comprising contacting a mixture with water with a catalyst containing at least titanium.

Description

本発明は、単環芳香族化合物を製造する方法に関し、特には、系外から水素を供給することなく、多環芳香族化合物を含有する炭化水素油から単環芳香族化合物を製造する方法に関するものである。   The present invention relates to a method for producing a monocyclic aromatic compound, and particularly relates to a method for producing a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound without supplying hydrogen from outside the system. Is.

従来、石油化学製品の原料等として有用な、ベンゼン、トルエン、キシレン等の芳香環を１つだけ有する単環芳香族化合物を、多環芳香族化合物または多環芳香族化合物を含有する炭化水素油から製造する方法としては、熱分解法や、水素化分解法等が知られている（例えば、特許文献１、特許文献２参照）。   Conventionally, monocyclic aromatic compounds having only one aromatic ring such as benzene, toluene, xylene and the like, which are useful as raw materials for petrochemical products, are polycyclic aromatic compounds or hydrocarbon oils containing polycyclic aromatic compounds. As a method for producing from the above, a thermal decomposition method, a hydrocracking method, and the like are known (see, for example, Patent Document 1 and Patent Document 2).

しかしながら、熱分解法には、芳香環の開裂が殆ど起こらず、単環芳香族化合物の製造効率が悪いという問題があった。また、水素化分解法には、分解反応に大量の高圧水素ガスを使用するため大規模な水素ガス製造設備が必要になり、コストが増大するという問題があった。   However, the thermal decomposition method has a problem that the aromatic ring is hardly cleaved and the production efficiency of the monocyclic aromatic compound is poor. Further, the hydrocracking method has a problem that a large-scale hydrogen gas production facility is required because a large amount of high-pressure hydrogen gas is used for the cracking reaction, which increases costs.

特開２００３−９６４７１号公報JP 2003-96471 A 特開２００８−２９７４５２号公報JP 2008-297452 A

そのため、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を効率的に製造する方法として、高圧水素ガスを使用することなく芳香環を開裂させて単環芳香族化合物を製造することができる方法を開発することが求められていた。   Therefore, as a method for efficiently producing a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound, the monocyclic aromatic compound is produced by cleaving the aromatic ring without using high-pressure hydrogen gas. There was a need to develop a method that could

本発明者は、鋭意研究を重ねた結果、チタンを含有する触媒と、多環芳香族化合物を含有する炭化水素油とを水の存在下で接触させることにより、多環芳香族化合物の芳香環を開裂させて単環芳香族化合物を製造することができることを見出し、本発明を完成させるに至った。   As a result of extensive research, the present inventor made an aromatic ring of a polycyclic aromatic compound by contacting a catalyst containing titanium and a hydrocarbon oil containing a polycyclic aromatic compound in the presence of water. Has been found to be able to produce a monocyclic aromatic compound, and the present invention has been completed.

即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の単環芳香族化合物の製造方法は、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を製造する方法であって、多環芳香族化合物を含有する炭化水素油に対して水を添加し、前記炭化水素油と水との混合物を、少なくともチタンを含有する触媒と接触させることを含むことを特徴とする。このように、炭化水素油と、少なくともチタンを含有する触媒とを水の存在下で接触させれば、反応系に水素を添加することなく、炭化水素油中の多環芳香族化合物の芳香環を開裂させて単環芳香族化合物を製造することができる。ここで、本発明において、単環芳香族化合物とは、芳香環を一つのみ有する化合物を指し、多環芳香族化合物とは、芳香環を二つ以上有する化合物（縮合多環芳香族化合物および非縮合多環芳香族化合物）を指す。また、少なくともチタンを含有する触媒とは、金属チタン（Ｔｉ）のみからなる触媒や、Ｔｉを含有する触媒や、二酸化チタン（ＴｉＯ２）を含有する触媒などのチタン元素を含む触媒を指す。That is, the present invention aims to advantageously solve the above-mentioned problems, and the method for producing a monocyclic aromatic compound of the present invention comprises a monocyclic aromatic from a hydrocarbon oil containing a polycyclic aromatic compound. A method for producing a compound, comprising adding water to a hydrocarbon oil containing a polycyclic aromatic compound, and bringing the mixture of the hydrocarbon oil and water into contact with a catalyst containing at least titanium. It is characterized by including. Thus, if the hydrocarbon oil and the catalyst containing at least titanium are brought into contact in the presence of water, the aromatic ring of the polycyclic aromatic compound in the hydrocarbon oil can be obtained without adding hydrogen to the reaction system. Can be cleaved to produce a monocyclic aromatic compound. Here, in the present invention, the monocyclic aromatic compound refers to a compound having only one aromatic ring, and the polycyclic aromatic compound refers to a compound having two or more aromatic rings (condensed polycyclic aromatic compound and Non-condensed polycyclic aromatic compound). Further, the catalyst containing at least titanium refers to a catalyst containing titanium element such as a catalyst made of only titanium metal (Ti), a catalyst containing Ti, or a catalyst containing titanium dioxide (TiO 2 ).

ここで、本発明の単環芳香族化合物の製造方法は、前記炭化水素油が、多環芳香族化合物を１０質量％以上含有することが好ましい。本発明の製造方法によれば、多環芳香族化合物を１０質量％以上含有する炭化水素油からでも、効率的に単環芳香族化合物を製造することができるからである。なお、炭化水素油中の多環芳香族化合物の量は、例えばガスクロマトグラフなどにより測定することができる。   Here, as for the manufacturing method of the monocyclic aromatic compound of this invention, it is preferable that the said hydrocarbon oil contains 10 mass% or more of polycyclic aromatic compounds. This is because according to the production method of the present invention, a monocyclic aromatic compound can be efficiently produced even from a hydrocarbon oil containing 10% by mass or more of a polycyclic aromatic compound. The amount of the polycyclic aromatic compound in the hydrocarbon oil can be measured by, for example, a gas chromatograph.

また、本発明の単環芳香族化合物の製造方法は、前記炭化水素油が、硫黄分および／または窒素分を含有していてもよい。本発明の製造方法によれば、炭化水素油が硫黄分および／または窒素分を含有していても、炭化水素油と、少なくともチタンを含有する触媒とを水の存在下で接触させれば、反応系に水素を添加することなく、炭化水素油中の硫黄分および／または窒素分を除去することができる。従って、原料として使用する炭化水素油が硫黄分および／または窒素分を含有する場合であっても、前記混合物と前記触媒との接触により生成する単環芳香族化合物を含む生成油からは、硫黄分および／または窒素分の少なくとも一部を除去することができる。ここで、本発明において、硫黄分とは、ＩＣＰ分析やＧＣ−ＳＣＤにより測定可能な硫黄分を指し、窒素分とは、ＩＣＰ分析やＧＣ−ＮＰＤにより測定可能な窒素分を指す。   In the method for producing a monocyclic aromatic compound of the present invention, the hydrocarbon oil may contain a sulfur content and / or a nitrogen content. According to the production method of the present invention, even if the hydrocarbon oil contains sulfur and / or nitrogen, if the hydrocarbon oil and a catalyst containing at least titanium are brought into contact with each other in the presence of water, Sulfur and / or nitrogen in the hydrocarbon oil can be removed without adding hydrogen to the reaction system. Therefore, even if the hydrocarbon oil used as a raw material contains a sulfur content and / or a nitrogen content, the product oil containing a monocyclic aromatic compound produced by the contact of the mixture and the catalyst has a sulfur content. At least a portion of the minute and / or nitrogen can be removed. Here, in the present invention, the sulfur content refers to a sulfur content that can be measured by ICP analysis or GC-SCD, and the nitrogen content refers to a nitrogen content that can be measured by ICP analysis or GC-NPD.

そして、本発明の単環芳香族化合物の製造方法は、前記混合物と前記触媒との接触を、温度３００〜６００℃、圧力０．５〜５０ＭＰａ、液空間速度０．０１〜１０ｈ−１の条件下で行うことが好ましい。このような反応条件とすれば、多環芳香族化合物の芳香環を効率的に開裂させることができるからである。And the manufacturing method of the monocyclic aromatic compound of this invention is the conditions of the temperature of 300-600 degreeC, the pressure of 0.5-50 MPa, and the liquid space velocity of 0.01-10 h < -1 > contact with the said mixture and the said catalyst. It is preferable to carry out below. This is because, under such reaction conditions, the aromatic ring of the polycyclic aromatic compound can be efficiently cleaved.

本発明の単環芳香族化合物の製造方法によれば、高圧水素ガスを使用することなく、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を効率的に製造することができる。また、使用する炭化水素油が硫黄分および／または窒素分を含有していても、本発明の単環芳香族化合物の製造方法によれば、高圧水素ガスを使用することなく、生成油から硫黄分および／または窒素分を効率的に除去しつつ、単環芳香族化合物を効率的に製造することができる。   According to the method for producing a monocyclic aromatic compound of the present invention, a monocyclic aromatic compound can be efficiently produced from a hydrocarbon oil containing a polycyclic aromatic compound without using high-pressure hydrogen gas. Moreover, even if the hydrocarbon oil to be used contains a sulfur content and / or a nitrogen content, according to the method for producing a monocyclic aromatic compound of the present invention, sulfur can be produced from the produced oil without using high-pressure hydrogen gas. A monocyclic aromatic compound can be efficiently produced while efficiently removing the component and / or nitrogen component.

以下、本発明の実施の形態を詳細に説明する。ここに、本発明の単環芳香族化合物の製造方法は、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を製造する方法である。そして、本発明の単環芳香族化合物の製造方法では、多環芳香族化合物を含有する炭化水素油に対して水を添加し、得られた炭化水素油と水との混合物を、少なくともチタンを含有する触媒と接触させることで、炭化水素油中の多環芳香族化合物の芳香環を開裂させて単環芳香族化合物を製造する。   Hereinafter, embodiments of the present invention will be described in detail. Here, the method for producing a monocyclic aromatic compound of the present invention is a method for producing a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound. And in the manufacturing method of the monocyclic aromatic compound of this invention, water is added with respect to the hydrocarbon oil containing a polycyclic aromatic compound, The mixture of the obtained hydrocarbon oil and water is made into at least titanium. By making it contact with the catalyst to contain, the aromatic ring of the polycyclic aromatic compound in hydrocarbon oil is cleaved, and a monocyclic aromatic compound is manufactured.

ここで、多環芳香族化合物としては、例えば、１−メチルナフタレン、キノリン、アントラセン、フェナントレンなどの縮合多環芳香族化合物や、ジベンゾチオフェン、ビフェニルなどの非縮合多環芳香族化合物が挙げられる。そして、多環芳香族化合物を含む炭化水素油としては、例えば、石油精製時に得られる、常圧蒸留残油、減圧蒸留残油、減圧軽油（ＶＧＯ）、流動接触分解装置から得られる沸点１８０℃以上の留分（ＬＣＯ、ＤＯ）などが挙げられる。なお、効率的に単環芳香族化合物を製造するという観点からは、多環芳香族化合物は、炭化水素油中に１０質量％以上含まれていることが好ましく、１５質量％以上含まれていることが更に好ましく、２０質量％以上含まれていることが特に好ましい。   Here, examples of the polycyclic aromatic compound include condensed polycyclic aromatic compounds such as 1-methylnaphthalene, quinoline, anthracene, and phenanthrene, and non-condensed polycyclic aromatic compounds such as dibenzothiophene and biphenyl. And as hydrocarbon oil containing a polycyclic aromatic compound, the boiling point 180 degreeC obtained from an atmospheric distillation residue, a vacuum distillation residue, a vacuum gas oil (VGO), a fluid catalytic cracking device obtained at the time of refinement | purification of petroleum, for example Examples thereof include the above fractions (LCO, DO). From the viewpoint of efficiently producing a monocyclic aromatic compound, the polycyclic aromatic compound is preferably contained in the hydrocarbon oil by 10% by mass or more, and is contained by 15% by mass or more. It is more preferable that 20% by mass or more is contained.

また、上記炭化水素油が硫黄分および窒素分を含有している場合、硫黄分としては、例えば、ジベンゾチオフェン、ベンゾチオフェン、スルフィドなどの形で炭化水素油中に含まれている、ＩＣＰ分析やＧＣ−ＳＣＤにより測定可能な硫黄分が挙げられる。なお、硫黄分は、炭化水素油中に０．１質量％以上含まれていてもよく、５．０質量％以下であることが好ましい。一方、窒素分としては、例えば、キノリン、カルバゾールなどの形で炭化水素油中に含まれている、ＩＣＰ分析やＧＣ−ＮＰＤにより測定可能な窒素分が挙げられる。なお、窒素分は、炭化水素油中に０．１質量％以上含まれていてもよく、１．０質量％以下であることが好ましい。   Further, when the hydrocarbon oil contains a sulfur content and a nitrogen content, as the sulfur content, for example, ICP analysis contained in the hydrocarbon oil in the form of dibenzothiophene, benzothiophene, sulfide, etc. The sulfur content measurable by GC-SCD is mentioned. In addition, 0.1 mass% or more of sulfur content may be contained in hydrocarbon oil, and it is preferable that it is 5.0 mass% or less. On the other hand, examples of the nitrogen content include nitrogen content that can be measured by ICP analysis or GC-NPD contained in hydrocarbon oil in the form of quinoline, carbazole, or the like. In addition, 0.1 mass% or more of nitrogen content may be contained in hydrocarbon oil, and it is preferable that it is 1.0 mass% or less.

また、本発明の製造方法では、水は、多環芳香族化合物の芳香環を開裂（開環反応）させる際の水素源として用いられるものである。そして、炭化水素油に添加する水の量は、多環芳香族化合物の芳香環を開裂させるのに十分な量であれば良いが、例えば、炭化水素油１００質量部に対して、１０〜３０００質量部、好ましくは、１０〜２０００質量部、更に好ましくは１０〜１０００質量部とすることができる。炭化水素油１００質量部に対する水の添加量が１０質量部未満の場合、開環反応の速度が低下すると共に芳香環の開裂が充分に進行しない恐れがあるからである。一方、水の添加量を３０００質量部超とすると、単環芳香族化合物の製造（開環反応）に寄与しない水の量が増大することとなり、コストが増加したり、単環芳香族化合物の製造効率が低下したりするからである。   Moreover, in the manufacturing method of this invention, water is used as a hydrogen source at the time of cleaving the aromatic ring of a polycyclic aromatic compound (ring-opening reaction). And the quantity of the water added to hydrocarbon oil should just be sufficient quantity to cleave the aromatic ring of a polycyclic aromatic compound, for example, 10-3000 with respect to 100 mass parts of hydrocarbon oil. The amount can be 10 parts by mass, preferably 10 to 2000 parts by mass, and more preferably 10 to 1000 parts by mass. This is because when the amount of water added to 100 parts by mass of the hydrocarbon oil is less than 10 parts by mass, the rate of the ring-opening reaction is lowered and the cleavage of the aromatic ring may not proceed sufficiently. On the other hand, if the amount of water added exceeds 3000 parts by mass, the amount of water that does not contribute to the production of the monocyclic aromatic compound (ring-opening reaction) will increase, resulting in an increase in cost or the amount of monocyclic aromatic compound. This is because the production efficiency is lowered.

また、上記炭化水素油が硫黄分および／または窒素分を含有している場合、水は、炭化水素油中の硫黄分および窒素分を水素化反応により硫化水素やアンモニアとして除去する際の水素源としての役割も果たす。ここで、硫黄分および／または窒素分を効率的に除去する観点から、炭化水素油に添加する水の量は、炭化水素油１００質量部に対して、１０〜３０００質量部の範囲が好ましく、１０〜２０００質量部の範囲が更に好ましく、１０〜１０００質量部の範囲が特に好ましい。炭化水素油１００質量部に対する水の添加量を１０質量部以上とすることで、十分な脱硫速度および／または脱窒素速度で硫黄分および／または窒素分を除去することができる。また、水の添加量を３０００質量部以下とすることで、水素化反応（脱硫および脱窒素）に寄与しない水の量を抑制して、コストの増加や、脱硫・脱窒素効率の低下を避けることができる。   Further, when the hydrocarbon oil contains sulfur and / or nitrogen, water is a hydrogen source for removing sulfur and nitrogen in the hydrocarbon oil as hydrogen sulfide or ammonia by a hydrogenation reaction. Also plays a role as. Here, from the viewpoint of efficiently removing sulfur and / or nitrogen, the amount of water added to the hydrocarbon oil is preferably in the range of 10 to 3000 parts by mass with respect to 100 parts by mass of the hydrocarbon oil. The range of 10 to 2000 parts by mass is more preferable, and the range of 10 to 1000 parts by mass is particularly preferable. By setting the amount of water added to 10 parts by mass or more with respect to 100 parts by mass of the hydrocarbon oil, sulfur and / or nitrogen can be removed at a sufficient desulfurization rate and / or denitrification rate. In addition, by controlling the amount of water added to 3000 parts by mass or less, the amount of water that does not contribute to the hydrogenation reaction (desulfurization and denitrogenation) is suppressed to avoid an increase in cost and a decrease in desulfurization / denitrogenation efficiency be able to.

少なくともチタンを含有する触媒（以下、「チタン含有触媒」と称することがある）としては、金属チタン（Ｔｉ）のみからなる触媒や、Ｔｉを含有する触媒や、二酸化チタン（ＴｉＯ２）を含有する触媒などのチタン元素を含む触媒を用いることができる。具体的には、例えば金属チタンのみからなる触媒や、チタン合金からなる触媒や、メッキや蒸着などの手法で表面をチタンでコーティングした触媒や、共沈法により製造した、ＴｉＯ２と、Ａｌ２Ｏ３やＦｅ２Ｏ３などの周期律表の第３〜第４周期の金属（但し、アルカリ金属、アルカリ土類金属を除く）の酸化物との複合酸化物からなる触媒を用いることができる。なお、触媒に使用するＴｉＯ２の結晶構造は、任意の結晶構造とすることができる。また、上記チタン含有触媒は、Ｔｉ元素として、Ｔｉを５〜１００質量％含むことが好ましく、１０〜８０質量％含むことが更に好ましく、２０〜６０質量％含むことが特に好ましい。Ｔｉ元素として、Ｔｉを５質量％以上含む触媒を使用することで、炭化水素油中の多環芳香族化合物の芳香環をより効率的に開裂させて単環芳香族化合物をより効率的に製造することが可能となる。また、炭化水素油が硫黄分および／または窒素分を含む場合は、Ｔｉ元素として、Ｔｉを５質量％以上含む触媒を使用することで、生成油から硫黄分および／または窒素分をより効率的に除去しつつ、単環芳香族化合物をより効率的に製造することが可能となる。As a catalyst containing at least titanium (hereinafter sometimes referred to as “titanium-containing catalyst”), a catalyst made of only metal titanium (Ti), a catalyst containing Ti, or titanium dioxide (TiO 2 ) is contained. A catalyst containing a titanium element such as a catalyst can be used. Specifically, for example, a catalyst made of only titanium metal, a catalyst made of a titanium alloy, a catalyst whose surface is coated with titanium by a technique such as plating or vapor deposition, TiO 2 and Al 2 manufactured by a coprecipitation method. A catalyst composed of a complex oxide with oxides of metals in the third to fourth periods (excluding alkali metals and alkaline earth metals) of the periodic table such as O 3 and Fe 2 O 3 can be used. . The crystal structure of TiO 2 used for the catalyst can be any crystal structure. Moreover, it is preferable that the said titanium containing catalyst contains 5-100 mass% of Ti as a Ti element, It is more preferable that 10-80 mass% is included, It is especially preferable that 20-60 mass% is included. By using a catalyst containing 5% by mass or more of Ti as the Ti element, the aromatic ring of the polycyclic aromatic compound in the hydrocarbon oil is more efficiently cleaved to produce the monocyclic aromatic compound more efficiently. It becomes possible to do. In addition, when the hydrocarbon oil contains sulfur and / or nitrogen, a catalyst containing 5% by mass or more of Ti is used as the Ti element, so that sulfur and / or nitrogen can be more efficiently produced from the produced oil. It is possible to produce the monocyclic aromatic compound more efficiently while removing them.

そして、本発明の単環芳香族化合物の製造方法では、例えば、反応器内に充填したチタン含有触媒に対し、多環芳香族化合物を含む炭化水素油と水との混合物を接触させて、単環芳香族化合物を製造する。ここで、反応器内で触媒と混合物とを接触させる条件は、例えば、温度：３００〜６００℃、好ましくは４００〜５５０℃、圧力：０．５〜５０ＭＰａ、好ましくは１．０〜４０ＭＰａ、液空間速度：０．０１〜１０ｈ−１、好ましくは０．０８〜１０ｈ−１とすることができる。温度が３００℃未満の場合、反応に必要な活性化エネルギーが得られず開環反応や水素化反応（脱硫および脱窒素）が充分に進行しない恐れがあり、６００℃超の場合、不要なガス（メタン、エタン等）が大量に発生し、単環芳香族化合物の収率が低下して、経済的に不利になる恐れがあるからである。また、圧力が０．５ＭＰａ未満の場合、炭化水素油と水とを反応器へスムーズに流入させることが困難になることがあり、５０ＭＰａ超の場合、反応器の製造コストが高くなるからである。更に、液空間速度が０．０１ｈ−１未満の場合、不要なガスの発生が支配的となり、単環芳香族化合物の収率が低下したり、炭化水素油が硫黄分および／または窒素分を含む場合は、脱硫・脱窒素効率が低下する恐れがあり、１０ｈ−１超の場合、反応時間が短すぎて開環反応や水素化反応（脱硫および脱窒素）が充分に進行しない恐れがあるからである。In the method for producing a monocyclic aromatic compound according to the present invention, for example, a titanium-containing catalyst charged in a reactor is brought into contact with a mixture of a hydrocarbon oil containing a polycyclic aromatic compound and water, and a single catalyst is obtained. A ring aromatic compound is produced. Here, the conditions for bringing the catalyst into contact with the mixture in the reactor are, for example, temperature: 300 to 600 ° C., preferably 400 to 550 ° C., pressure: 0.5 to 50 MPa, preferably 1.0 to 40 MPa, liquid Space velocity: 0.01 to 10 h −1 , preferably 0.08 to 10 h −1 . If the temperature is lower than 300 ° C, the activation energy required for the reaction cannot be obtained and the ring-opening reaction or hydrogenation reaction (desulfurization and denitrogenation) may not proceed sufficiently. This is because a large amount of (methane, ethane, etc.) is generated and the yield of the monocyclic aromatic compound is lowered, which may be disadvantageous economically. Further, when the pressure is less than 0.5 MPa, it may be difficult to smoothly flow hydrocarbon oil and water into the reactor, and when it exceeds 50 MPa, the production cost of the reactor increases. . Furthermore, when the liquid space velocity is less than 0.01 h −1 , generation of unnecessary gas becomes dominant, the yield of monocyclic aromatic compounds decreases, and hydrocarbon oils contain sulfur and / or nitrogen. If it is included, the desulfurization / denitrogenation efficiency may decrease, and if it exceeds 10 h −1 , the reaction time is too short and the ring-opening reaction or hydrogenation reaction (desulfurization and denitrogenation) may not proceed sufficiently. Because.

なお、本発明の単環芳香族化合物の製造方法では、多環芳香族化合物の開環反応に必要な水素を水から供給するため、水素を系外から添加する必要はない。また、炭化水素油が硫黄分および／または窒素分を含む場合であっても、脱硫および脱窒素（水素化反応）に必要な水素源として水が利用されるため、水素を系外から添加する必要はない。従って、本発明の単環芳香族化合物の製造方法においては、系外からの水素添加量と炭化水素油供給量とのモル比（水素添加量／炭化水素油供給量）は、０．１以下、好ましくは０とすることができる。よって、本発明の単環芳香族化合物の製造方法によれば、高圧水素ガスを使用することなく、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を効率的に製造することができ、また、原料の炭化水素油が硫黄分および／または窒素分を含む場合であっても、目的生成物の単環芳香族化合物を含む生成油から硫黄分および／または窒素分を効率的に除去することができる。   In addition, in the manufacturing method of the monocyclic aromatic compound of this invention, since hydrogen required for the ring-opening reaction of a polycyclic aromatic compound is supplied from water, it is not necessary to add hydrogen from outside the system. Even if the hydrocarbon oil contains sulfur and / or nitrogen, water is added from outside the system because water is used as a hydrogen source necessary for desulfurization and denitrogenation (hydrogenation reaction). There is no need. Therefore, in the method for producing a monocyclic aromatic compound of the present invention, the molar ratio (hydrogenation amount / hydrocarbon oil supply amount) between the hydrogenation amount from outside the system and the hydrocarbon oil supply amount is 0.1 or less , Preferably 0. Therefore, according to the method for producing a monocyclic aromatic compound of the present invention, it is possible to efficiently produce a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound without using high-pressure hydrogen gas. In addition, even when the raw hydrocarbon oil contains sulfur and / or nitrogen, the sulfur and / or nitrogen can be efficiently removed from the product oil containing the monocyclic aromatic compound of the target product. Can be removed.

ここで、本発明の単環芳香族化合物の製造方法では、触媒としてチタン含有触媒を使用しており、炭化水素油の水素化分解反応で使用されるような、水熱合成されたゼオライトやγ−アルミナを触媒として使用していないので、水の存在下で開環反応を行っても、高温高圧の水蒸気により触媒の結晶構造が大きく変化して触媒が使用不能となることがない。また、触媒の劣化が起こりにくく、炭化水素油を前処理する必要がない。   Here, in the method for producing a monocyclic aromatic compound of the present invention, a titanium-containing catalyst is used as a catalyst, and hydrothermally synthesized zeolite or γ used in a hydrocracking reaction of hydrocarbon oil. -Since alumina is not used as a catalyst, even if the ring-opening reaction is performed in the presence of water, the crystal structure of the catalyst is not greatly changed by high-temperature and high-pressure steam, so that the catalyst cannot be used. Further, the catalyst is hardly deteriorated and it is not necessary to pretreat the hydrocarbon oil.

以下、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to the following Example at all.

（実施例１）
超合金（インコネル６２５）製の反応器（内容積１０ｍｌ）中に、チタン含有触媒として球状チタン（純度９９．８％、粒径２ｍｍ、アユミ製作所製）２４．５ｇを充填した。そして、チタン含有触媒を充填した反応器内に水を導入した後、温度：４６８℃、圧力：２８ＭＰａまで加熱および加圧した。その後、水素を添加することなく、表１に示す組成の炭化水素油と、水とをそれぞれ流量０．１ｍｌ／分（炭化水素油０．８５質量部に対して水１質量部の割合）で反応器内に流通させた（液空間速度０．６ｈ−１）。
そして、通油開始から４時間経過した後に反応生成物を採取し、下記の方法で炭化水素油中の各化合物の転化率等を算出した。結果を表２に示す。Example 1
A superalloy (Inconel 625) reactor (internal volume 10 ml) was charged with 24.5 g of spherical titanium (purity 99.8%, particle size 2 mm, manufactured by Ayumi Seisakusho) as a titanium-containing catalyst. And after introduce | transducing water in the reactor filled with the titanium containing catalyst, it heated and pressurized to temperature: 468 degreeC and pressure: 28MPa. Then, without adding hydrogen, each of the hydrocarbon oil having the composition shown in Table 1 and water at a flow rate of 0.1 ml / min (a ratio of 1 part by mass of water to 0.85 parts by mass of hydrocarbon oil). It was made to distribute | circulate in the reactor (liquid space velocity 0.6h < -1 >).
And after 4 hours passed from the start of oil passing, the reaction product was collected, and the conversion rate of each compound in the hydrocarbon oil was calculated by the following method. The results are shown in Table 2.

Figure 2011043066
Figure 2011043066

（転化率等の算出）
ガスクロマトグラフ（島津製作所製ＧＣ１４−Ｂ、カラムＤＢ−１ ６０ｍ）を用いて反応生成物を分析し、反応生成物中に残っている各化合物のピーク面積から転化率を算出した。
また、採取した反応生成物の液の質量に対する、反応生成物中のベンゼンおよびＣ１〜Ｃ５ベンゼン（ベンゼン環に結合する炭化水素基の炭素数の合計が１〜５のベンゼン誘導体）の質量の比率をガスクロマトグラフで求め、ベンゼンおよびＣ１〜Ｃ５ベンゼンの収率とした。なお、Ｃ２〜Ｃ５ベンゼンについては、異性体の合計量を用いて収率を求めた。(Calculation of conversion rate, etc.)
The reaction product was analyzed using a gas chromatograph (GC14-B manufactured by Shimadzu Corporation, column DB-1 60m), and the conversion rate was calculated from the peak areas of the respective compounds remaining in the reaction product.
Further, the ratio of the mass of benzene and C1 to C5 benzene (the benzene derivative in which the total number of carbon atoms of the hydrocarbon groups bonded to the benzene ring is 1 to 5) to the mass of the collected reaction product liquid. Was determined by gas chromatography and used as the yields of benzene and C1-C5 benzene. In addition, about C2-C5 benzene, the yield was calculated | required using the total amount of an isomer.

（除去率の算出）
ＩＣＰ分析法を用いて反応生成物を分析し、反応生成物中に残っている硫黄分の定量を行い、硫黄分除去率を算出した。
また、ガスクロマトグラフ（島津製作所製ＧＣ１４−Ｂ、カラムＤＢ−１ ６０ｍ）を用いて反応生成物を分析し、キノリンのピーク面積から転化率を算出し、窒素分除去率とした。この際に、ガスクロマトグラフで、キノリンの脱窒素反応生成物であるＣ３ベンゼンが定量的に得られていることも確認した。(Calculation of removal rate)
The reaction product was analyzed using ICP analysis, the sulfur content remaining in the reaction product was quantified, and the sulfur removal rate was calculated.
Moreover, the reaction product was analyzed using the gas chromatograph (Shimadzu GC14-B, column DB-1 60m), the conversion rate was computed from the peak area of quinoline, and it was set as the nitrogen content removal rate. At this time, it was also confirmed by gas chromatography that C3 benzene, which is a denitrogenation reaction product of quinoline, was obtained quantitatively.

（実施例２）
チタン含有触媒として、共沈法で作製したＴｉＯ２／Ａｌ２Ｏ３複合酸化物（石原産業（株）製、ＴｉＯ２：８８質量％、Ａｌ２Ｏ３：１２質量％、Ｔｉ元素：４２質量％）を用いた以外は実施例１と同様にして水と炭化水素油とを反応器内に流通させた。
そして、実施例１と同様にして炭化水素油中の各化合物の転化率等を算出した。結果を表２に示す。
また、得られた生成物を分析して、物質収支を計算し、表３に示す結果を得た。(Example 2)
As a titanium-containing catalyst, a TiO 2 / Al 2 O 3 composite oxide produced by a coprecipitation method (manufactured by Ishihara Sangyo Co., Ltd., TiO 2 : 88 mass%, Al 2 O 3 : 12 mass%, Ti element: 42 mass) %) Was used in the same manner as in Example 1 except that water and hydrocarbon oil were circulated in the reactor.
Then, the conversion rate of each compound in the hydrocarbon oil was calculated in the same manner as in Example 1. The results are shown in Table 2.
Moreover, the obtained product was analyzed, the mass balance was calculated, and the result shown in Table 3 was obtained.

（比較例１）
チタン含有触媒を充填することなく、水および炭化水素油の反応器内での滞留時間が実施例１，２と同一になるように水および炭化水素油をそれぞれ０．２３ｍｌ／分の流量で流通させた以外は、実施例１と同様にして水と炭化水素油とを反応器内に流通させた。
そして、実施例１と同様にして炭化水素油中の各化合物の転化率等を算出した。結果を表２に示す。(Comparative Example 1)
Water and hydrocarbon oil are circulated at a flow rate of 0.23 ml / min so that the residence time of water and hydrocarbon oil in the reactor is the same as in Examples 1 and 2 without filling the titanium-containing catalyst. Except that, water and hydrocarbon oil were circulated in the reactor in the same manner as in Example 1.
Then, the conversion rate of each compound in the hydrocarbon oil was calculated in the same manner as in Example 1. The results are shown in Table 2.

（比較例２）
触媒として、ＣｅＯ２−Ｆｅ２Ｏ３／ＺｒＯ２複合酸化物（第一稀元素化学工業製、ＣｅＯ２：５９質量％、Ｆｅ２Ｏ３：２０質量％、ＺｒＯ２：２１質量％）を用いた以外は実施例１と同様にして水と炭化水素油とを反応器内に流通させた。
そして、実施例１と同様にして炭化水素油中の各化合物の転化率等を算出した。結果を表２に示す。(Comparative Example 2)
As the catalyst, CeO 2 —Fe 2 O 3 / ZrO 2 composite oxide (manufactured by Daiichi Rare Element Chemical Industry, CeO 2 : 59 mass%, Fe 2 O 3 : 20 mass%, ZrO 2 : 21 mass%) is used. Except that, water and hydrocarbon oil were passed through the reactor in the same manner as in Example 1.
Then, the conversion rate of each compound in the hydrocarbon oil was calculated in the same manner as in Example 1. The results are shown in Table 2.

Figure 2011043066
Figure 2011043066

Figure 2011043066
Figure 2011043066

表２の反応生成物中のベンゼンおよびＣ１〜Ｃ５ベンゼンの収率より、実施例１および実施例２では、単環芳香族化合物を効果的に製造することができたことが分かる。また、表２の実施例１および２、並びに、比較例１および２より、チタンを含有する触媒を用いれば、系外から水素を添加することなく、炭化水素油中の多環芳香族化合物の芳香環を開裂させて単環芳香族化合物を効率的に製造しつつ、炭化水素油中の硫黄分および窒素分を効率的に除去し得ることが分かる。   From the yields of benzene and C1-C5 benzene in the reaction products of Table 2, it can be seen that in Example 1 and Example 2, monocyclic aromatic compounds could be produced effectively. Further, from Examples 1 and 2 in Table 2 and Comparative Examples 1 and 2, if a catalyst containing titanium is used, the polycyclic aromatic compound in the hydrocarbon oil can be obtained without adding hydrogen from outside the system. It can be seen that the sulfur content and the nitrogen content in the hydrocarbon oil can be efficiently removed while cleaving the aromatic ring to efficiently produce the monocyclic aromatic compound.

また、表３に示す実施例２の物質収支の結果から、水中の水素原子が水素源として利用される一方、水中の酸素原子がＣＯ２の生成に寄与していることが分かる。Moreover, from the result of the mass balance of Example 2 shown in Table 3, it is understood that hydrogen atoms in water are used as a hydrogen source, while oxygen atoms in water contribute to the generation of CO 2 .

本発明によれば、高圧水素ガスを使用することなく、多環芳香族化合物を含む炭化水素油から単環芳香族化合物を効率的に製造することができる。また、本発明によれば、使用する炭化水素油が硫黄分および／または窒素分を含有していても、高圧水素ガスを使用することなく、生成油から硫黄分および／または窒素分を効率的に除去しつつ、単環芳香族化合物を効率的に製造することができる。   According to the present invention, a monocyclic aromatic compound can be efficiently produced from a hydrocarbon oil containing a polycyclic aromatic compound without using high-pressure hydrogen gas. Further, according to the present invention, even if the hydrocarbon oil used contains sulfur and / or nitrogen, the sulfur and / or nitrogen can be efficiently removed from the product oil without using high-pressure hydrogen gas. The monocyclic aromatic compound can be efficiently produced while removing the slag.

Claims (5)

多環芳香族化合物を含む炭化水素油から単環芳香族化合物を製造する方法であって、
多環芳香族化合物を含有する炭化水素油に対して水を添加し、
前記炭化水素油と水との混合物を、少なくともチタンを含有する触媒と接触させる、
ことを含むことを特徴とする、単環芳香族化合物の製造方法。A method for producing a monocyclic aromatic compound from a hydrocarbon oil containing a polycyclic aromatic compound,
Water is added to a hydrocarbon oil containing a polycyclic aromatic compound,
Contacting the mixture of hydrocarbon oil and water with a catalyst containing at least titanium;
The manufacturing method of the monocyclic aromatic compound characterized by the above-mentioned. 前記炭化水素油が、多環芳香族化合物を１０質量％以上含有することを特徴とする、請求項１に記載の単環芳香族化合物の製造方法。   The method for producing a monocyclic aromatic compound according to claim 1, wherein the hydrocarbon oil contains 10% by mass or more of a polycyclic aromatic compound. 前記炭化水素油が、硫黄分および／または窒素分を含有することを特徴とする、請求項１または２に記載の単環芳香族化合物の製造方法。   The method for producing a monocyclic aromatic compound according to claim 1, wherein the hydrocarbon oil contains a sulfur content and / or a nitrogen content. 前記混合物と前記触媒との接触により生成する単環芳香族化合物を含む生成油から、前記硫黄分および／または窒素分の少なくとも一部が除去されていることを特徴とする、請求項３に記載の単環芳香族化合物の製造方法。   The at least part of the said sulfur content and / or nitrogen content is removed from the product oil containing the monocyclic aromatic compound produced | generated by the contact of the said mixture and the said catalyst, The said content is characterized by the above-mentioned. A method for producing a monocyclic aromatic compound. 前記混合物と前記触媒との接触を、温度３００〜６００℃、圧力０．５〜５０ＭＰａ、液空間速度０．０１〜１０ｈ−１の条件下で行うことを特徴とする、請求項１〜４のいずれか一項に記載の単環芳香族化合物の製造方法。The contact between the mixture and the catalyst is performed under conditions of a temperature of 300 to 600 ° C, a pressure of 0.5 to 50 MPa, and a liquid space velocity of 0.01 to 10 h -1 . The manufacturing method of the monocyclic aromatic compound as described in any one.
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