WO2011043066A1 - Méthode de production d'un composé aromatique monocyclique - Google Patents

Méthode de production d'un composé aromatique monocyclique Download PDF

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Publication number
WO2011043066A1
WO2011043066A1 PCT/JP2010/005974 JP2010005974W WO2011043066A1 WO 2011043066 A1 WO2011043066 A1 WO 2011043066A1 JP 2010005974 W JP2010005974 W JP 2010005974W WO 2011043066 A1 WO2011043066 A1 WO 2011043066A1
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WO
WIPO (PCT)
Prior art keywords
aromatic compound
hydrocarbon oil
monocyclic aromatic
catalyst
mass
Prior art date
Application number
PCT/JP2010/005974
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English (en)
Japanese (ja)
Inventor
智史 古田
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Ｊｘ日鉱日石エネルギー株式会社
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Application filed by Ｊｘ日鉱日石エネルギー株式会社 filed Critical Ｊｘ日鉱日石エネルギー株式会社
Priority to JP2011535286A priority Critical patent/JP5449383B2/ja
Priority to CA2774686A priority patent/CA2774686C/fr
Publication of WO2011043066A1 publication Critical patent/WO2011043066A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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

Definitions

  • 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.
  • 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.
  • a thermal decomposition method, a hydrocracking method, and the like are known (see, for example, Patent Document 1 and Patent Document 2).
  • 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.
  • 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.
  • the monocyclic aromatic compound is produced by cleaving the aromatic ring without using high-pressure hydrogen gas.
  • 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.
  • 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.
  • 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.
  • the monocyclic aromatic compound refers to a compound having only one aromatic ring
  • the polycyclic aromatic compound refers to a compound having two or more aromatic rings (condensed polycyclic aromatic compound and Non-condensed polycyclic aromatic compound).
  • 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 ).
  • the hydrocarbon oil preferably contains 10% by mass or more of a polycyclic aromatic compound. 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.
  • the hydrocarbon oil may contain a sulfur content and / or a nitrogen content.
  • the hydrocarbon oil and the 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.
  • the sulfur content refers to a sulfur content that can be measured by ICP analysis or GC-SCD
  • the nitrogen content refers to a nitrogen content that can be measured by ICP analysis or GC-NPD.
  • the contact between the mixture and the catalyst is performed under the 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 . 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • the hydrocarbon oil contains a sulfur content and a nitrogen content
  • 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.
  • 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.
  • examples of the nitrogen content include nitrogen content contained in hydrocarbon oils in the form of quinoline, carbazole and the like and measurable by ICP analysis or GC-NPD.
  • 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.
  • water is used as a hydrogen source when the aromatic ring of the polycyclic aromatic compound is cleaved (ring opening reaction).
  • the amount of water added to the hydrocarbon oil may be an amount sufficient to cleave the aromatic ring of the polycyclic aromatic compound. For example, it is 10 to 3000 per 100 parts by mass of the hydrocarbon oil.
  • the amount may 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.
  • 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.
  • 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 preferred, and the range of 10 to 1000 parts by mass is particularly preferred.
  • the amount of water added to 3000 parts by mass or less 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, and an increase in cost and a decrease in desulfurization / denitrogenation efficiency are avoided. be able to.
  • titanium-containing catalyst 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.
  • the titanium-containing catalyst preferably contains 5 to 100% by mass of Ti as Ti element, more preferably 10 to 80% by mass, and particularly preferably 20 to 60% by mass. 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.
  • 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.
  • 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.
  • 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
  • the space velocity can be 0.01 to 10 h ⁇ 1 , preferably 0.08 to 10 h ⁇ 1 .
  • 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.
  • 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. .
  • liquid space velocity 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 have a sulfur content and / or a nitrogen content. If it is contained, the desulfurization / denitrogenation efficiency may be lowered. 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.
  • the method for producing a monocyclic aromatic compound of the present invention hydrogen necessary for the ring-opening reaction of the polycyclic aromatic compound is supplied from water, so that 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.
  • 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.
  • 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.
  • a titanium-containing catalyst is used as a catalyst, and hydrothermally synthesized zeolite or ⁇ 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 significantly 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.
  • 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
  • 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. Also, 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. For C2-C5 benzene, the yield was determined using the total amount of isomers.
  • 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.
  • the reaction product was analyzed using a gas chromatograph (GC14-B, Shimadzu Corporation GC14-B, column DB-1 60 m), and the conversion rate was calculated from the peak area of quinoline to obtain the nitrogen 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.
  • 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.
  • Example 2 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 .
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte: sur une méthode de production d'un composé aromatique monocyclique permettant de l'obtenir à partir d'un hydrocarbure de pétrole contenant un composé aromatique polycyclique, sans utiliser d'hydrogène à haute pression; et spécifiquement sur une telle méthode selon laquelle on ajoute de l'eau audit hydrocarbure et on met en contact ledit hydrocarbure avec un catalyseur contenant au moins du titane.
PCT/JP2010/005974 2009-10-06 2010-10-05 Méthode de production d'un composé aromatique monocyclique WO2011043066A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2011535286A JP5449383B2 (ja) 2009-10-06 2010-10-05 単環芳香族化合物の製造方法
CA2774686A CA2774686C (fr) 2009-10-06 2010-10-05 Methode de production d'un compose aromatique monocyclique

Applications Claiming Priority (4)

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JP2009-232292 2009-10-06
JP2009232292 2009-10-06
JP2009-232305 2009-10-06
JP2009232305 2009-10-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112424240A (zh) * 2018-09-26 2021-02-26 日本瑞翁株式会社 单体组合物的纯化方法和聚合物的制造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63205142A (ja) * 1987-02-18 1988-08-24 ジュート　ヒェミー　アクチェンゲゼルシャフト 炭化水素を水蒸気リフォーミングするための触媒

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63205142A (ja) * 1987-02-18 1988-08-24 ジュート　ヒェミー　アクチェンゲゼルシャフト 炭化水素を水蒸気リフォーミングするための触媒

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FOSTER ET AL.: "ETUDE EN ENCEINTE DE SIMULATION DE LA PHOTODEGRA DATION DU NAPHTALENE EN PRESENCE DE PARTICULES.", PHYS.-CHEM. BEHAV. ATMOS. POLLUT., vol. 5TH, 1990, pages 289 - 299 *
YUHIKO SAITO ET AL.: "Pt-kei Shokubai o Mochiita Naphthalene/Benzen no Suijoki Kaishitsu Hanno ni Kansuru Kenkyu", SEKIYU· SEKIYU KAGAKU TORONKAI KOEN YOSHI, vol. 39TH, 22 October 2009 (2009-10-22), pages 84 - 85 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112424240A (zh) * 2018-09-26 2021-02-26 日本瑞翁株式会社 单体组合物的纯化方法和聚合物的制造方法

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CA2774686A1 (fr) 2011-04-14
CA2774686C (fr) 2016-12-20
JP5449383B2 (ja) 2014-03-19
JPWO2011043066A1 (ja) 2013-03-04

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