WO2012133180A1 - 単環芳香族炭化水素の製造方法 - Google Patents
単環芳香族炭化水素の製造方法 Download PDFInfo
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- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
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- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/68—Aromatisation of hydrocarbon oil fractions
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/40—Characteristics of the process deviating from typical ways of processing
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
Definitions
- the present invention relates to a method for producing monocyclic aromatic hydrocarbons.
- This application claims priority based on Japanese Patent Application No. 2011-067877 filed in Japan on March 25, 2011, the contents of which are incorporated herein by reference.
- LCO light cycle oil
- FCC fluid catalytic cracking
- a method for producing a BTX fraction from a polycyclic aromatic component for example, the following methods are known.
- (1) A method of hydrocracking a hydrocarbon containing a polycyclic aromatic component in one stage (Patent Documents 1 and 2).
- (2) A method in which a hydrocarbon containing a polycyclic aromatic component is hydrogenated in the former stage and then hydrocracked in the latter stage (Patent Documents 3 to 5).
- (3) A method of converting a hydrocarbon containing a polycyclic aromatic component directly into a BTX fraction using a zeolite catalyst (Patent Document 6).
- (4) A method of converting a mixture of a hydrocarbon containing a polycyclic aromatic component and a light hydrocarbon having 2 to 8 carbon atoms into a BTX fraction using a zeolite catalyst (Patent Documents 7 and 8).
- the methods (1) and (2) have a problem in that addition of high-pressure molecular hydrogen is essential, and hydrogen consumption is large. Also, under hydrogenation conditions, many LPG fractions and the like that are not required in the purpose of producing the BTX fraction are by-produced, and not only energy is required for the separation, but also the raw material efficiency is lowered. In the method (3), it cannot be said that the conversion of the polycyclic aromatic component is necessarily sufficient.
- the method (4) is a combination of BTX production technology using light hydrocarbons as a raw material and BTX production technology using hydrocarbons containing polycyclic aromatics as a raw material to improve the heat balance. It does not improve the BTX yield from ring aromatics.
- the present invention provides a method by which a BTX fraction can be produced more efficiently than a conventional method from a fraction containing cracked light oil (LCO) produced by an FCC apparatus.
- LCO cracked light oil
- a feed oil having a 10 vol% distillation temperature of 140 ° C. or higher and a 90 vol% distillation temperature of 380 ° C. or lower is brought into contact with a catalyst for producing monocyclic aromatic hydrocarbons containing crystalline aluminosilicate.
- a method for producing a ring aromatic hydrocarbon comprising: A hydrocarbon oil A having a 10% by volume distillation temperature of 140 ° C. or higher and a 90% by volume distillation temperature of 380 ° C.
- a method for producing a monocyclic aromatic hydrocarbon which is prepared by mixing a hydrocarbon oil B containing more monocyclic naphthenobenzene than the hydrocarbon oil A.
- a feed oil having a 10% by volume distillation temperature of 140 ° C. or more and a 90% by volume distillation temperature of 380 ° C. or less is brought into contact with a catalyst for producing monocyclic aromatic hydrocarbons containing crystalline aluminosilicate.
- a method for producing a ring aromatic hydrocarbon comprising: A hydrocarbon oil A having a 10 volume% distillation temperature of 140 ° C.
- a process for producing a monocyclic aromatic hydrocarbon characterized by being hydrogenated or by mixing the hydrocarbon oil A and a hydrogenated version of the hydrocarbon oil A.
- a feed oil having a 10% by volume distillation temperature of 140 ° C. or higher and a 90% by volume distillation temperature of 380 ° C. or lower is converted to a monocyclic ring containing crystalline aluminosilicate.
- the method for producing a monocyclic aromatic hydrocarbon of the present invention comprises a raw material oil having a 10% by volume distillation temperature of 140 ° C. or higher and a 90% by volume distillation temperature of 380 ° C. or lower containing crystalline aluminosilicate.
- the saturated hydrocarbon contained in the feedstock oil is obtained by bringing the feedstock oil into contact with a catalyst for producing monocyclic aromatic hydrocarbons containing crystalline aluminosilicate.
- a catalyst for producing monocyclic aromatic hydrocarbons containing crystalline aluminosilicate Used as a hydrogen donor, partially hydrogenated polycyclic aromatic hydrocarbons by hydrogen transfer reaction from saturated hydrocarbons, ring-opened to convert to monocyclic aromatic hydrocarbons, obtained in feedstock or in cracking process
- the saturated hydrocarbon can also be converted to a monocyclic aromatic hydrocarbon by cyclization and dehydrogenation. Furthermore, it is possible to obtain monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms by decomposing monocyclic aromatic hydrocarbons having 9 or more carbon atoms.
- This product contains hydrogen, methane, ethane, ethylene, LPG (propane, propylene, butane, butene, etc.), etc., in addition to monocyclic aromatic hydrocarbons and heavy fractions.
- the heavy fraction contains a large amount of bicyclic aromatic hydrocarbons such as naphthalene, methylnaphthalene, and dimethylnaphthalene, and also contains tricyclic or higher aromatic hydrocarbons such as anthracene depending on the feedstock. ing.
- these two-ring aromatic hydrocarbons and three or more ring aromatic hydrocarbons are collectively referred to as polycyclic aromatic hydrocarbons.
- the feedstock oil used in the present invention is an oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower. With an oil having a 10% by volume distillation temperature of less than 140 ° C., a monocyclic aromatic hydrocarbon is produced from a light oil and does not meet the gist of the present invention. In addition, when oil having a 90% by volume distillation temperature exceeding 380 ° C. is used, the yield of monocyclic aromatic hydrocarbons is lowered and coke deposition on the catalyst for producing monocyclic aromatic hydrocarbons The amount tends to increase and cause a sharp decrease in catalyst activity.
- the lower limit of the 10 vol% distillation temperature of the feedstock is 140 ° C or higher, preferably 150 ° C or higher, while the upper limit is preferably 300 ° C or lower.
- the upper limit of the 90 volume% distillation temperature of feedstock oil is 380 degrees C or less, It is preferable that it is 360 degrees C or less, On the other hand, it is preferable that a minimum is 160 degrees C or more.
- the 10 vol% distillation temperature and 90 vol% distillation temperature mentioned here mean values measured in accordance with JIS K2254 “Petroleum products-distillation test method”.
- the content ratio of components other than monocyclic naphthenobenzene (monocyclic aromatic component, polycyclic aromatic component, paraffin component, naphthene component, olefin component) in the feedstock oil used in the present invention is not particularly limited. , It may contain polycyclic aromatic hydrocarbons of two or more rings, saturated hydrocarbons such as paraffin and naphthene, monocyclic aromatic hydrocarbons such as alkylbenzene, etc., as long as the target reaction is not significantly inhibited. Hetero atoms such as oxygen and nitrogen may be contained.
- the content of polycyclic aromatic hydrocarbons in the feedstock is The amount is preferably 1 to 50% by volume, more preferably 2 to 40% by volume with respect to 100% by volume of the feedstock oil.
- the polycyclic aromatic component mentioned here is measured according to JPI-5S-49 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”, or FID gas chromatograph method or two-dimensional gas chromatograph.
- the feed oil according to the present invention has a monocyclic naphthenobenzene content ratio of 10 to 90% by weight, preferably 12 to 90% by weight, more preferably 15 to 90% by weight with respect to 100% by weight of the feed oil.
- the monocyclic naphthenobenzene here refers to a compound in which a monocyclic aromatic ring and a naphthene ring coexist in one molecule, such as a tetralin skeleton. Specific examples include tetralins, indanes, octahydroanthracenes, octahydrophenanthrenes, and the like.
- 1-ring naphthenobenzene content ratio was measured based on the two-dimensional gas chromatograph method.
- the content ratio of monocyclic naphthenobenzene in the feedstock is adjusted to 10 to 90% by mass with respect to 100% by mass of the feedstock.
- monocyclic naphthenobenzene can be more efficiently converted to a monocyclic aromatic compound having 6 to 8 carbon atoms when contacted with the catalyst for producing a monocyclic aromatic hydrocarbon used in the present application.
- Naphthenobenzene may produce monocyclic aromatic hydrocarbons through decomposition and ring-opening reactions, while polycyclic aromatic hydrocarbons are produced through dehydrogenation reactions.
- the catalytic activity may be reduced by coking of group hydrocarbons and accumulating on the catalyst.
- the present inventors have used monocyclic aromatic hydrocarbons by using raw material oils containing a large amount of monocyclic naphthenobenzene among naphthenobenzenes and selecting appropriate catalysts and reaction conditions. Has been found to be able to be produced efficiently, and the present invention has been completed.
- naphthenobenzene other than monocyclic naphthenobenzene may be contained in the raw material oil, bicyclic naphthenobenzene represented by dihydrophenanthrene, tetrahydroanthracene and the like is difficult to decompose the aromatic ring portion.
- Examples of the method for adjusting the monocyclic naphthenobenzene content ratio of the raw material oil to 10 to 90% by mass with respect to 100% by mass of the raw material oil include the following methods.
- (I) Method of mixing hydrocarbon oil A and hydrocarbon oil B containing a large amount of monocyclic naphthenobenzene (ii) Method of hydrogenating hydrocarbon oil A
- (iii) Hydrocarbon oil A and hydrocarbon oil Method of mixing with hydrogenated A Hydrocarbon oil A is not particularly limited except that it is an oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower.
- Examples thereof include cracked light oil (LCO) produced by a fluid catalytic cracking (FCC) apparatus, coal liquefied oil, straight-run kerosene, straight-run light oil, coker kerosene, and coker light oil.
- the hydrocarbon oil A has a monocyclic naphthenobenzene content of preferably 0 to 9.9% by mass, more preferably 1 to 9.9% by mass, and still more preferably 100% by mass of the hydrocarbon oil A. 2 to 9.2% by mass.
- the hydrocarbon oil B is a hydrocarbon having a monocyclic naphthenobenzene content higher than 10 mass% with respect to 100 mass% of the hydrocarbon oil B, and at least a monocyclic naphthenobenzene content higher than that of the hydrocarbon oil A.
- the oil is not particularly limited, but is preferably a hydrocarbon oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower. Examples thereof include heavy oil hydrocracked refined oil, oil sand hydrocracked refined oil, and oil shale hydrocracked refined oil.
- the hydrocarbon oil B has a monocyclic naphthenobenzene content of preferably 10 to 90% by mass, more preferably 12 to 90% by mass with respect to 100% by mass of the hydrocarbon oil B.
- the value of (single-ring naphthenobenzene content in hydrocarbon oil B) / (one-ring naphthenobenzene content in hydrocarbon oil A) is preferably 1.1 or more, more preferably 1.5 or more. preferable.
- the hydrocarbon oil A and the hydrocarbon oil B containing a large amount of 1-ring naphthenobenzene may be mixed in advance before being charged into the reactor.
- a and hydrocarbon oil B containing a large amount of 1-ring naphthenobenzene may be directly mixed.
- the amount of 1-ring naphthenobenzene of hydrocarbon oil A just before charging into the reactor and 1-ring naphthenobenzene of hydrocarbon oil B containing a large amount of 1-ring naphthenobenzene That is, the monocyclic naphthenobenzene content of the raw material oil after mixing is 10 to 90% by mass, preferably 12 to 90% by mass, more preferably 100% by mass of the raw material oil after mixing. Is preferably 15 to 90%.
- (Ii) includes a method of hydrogenating hydrocarbon oil A, and the like. Hydrogenation of the hydrocarbon oil A is performed in order to increase the content of monocyclic naphthenobenzene. That is, by hydrogenating the hydrocarbon oil A, the polycyclic aromatic hydrocarbons contained in the hydrocarbon oil A are partially hydrogenated to produce monocyclic naphthenobenzene. Therefore, the polycyclic aromatic hydrocarbon content in the hydrocarbon oil A is preferably 10 to 95% by mass, more preferably 15 to 95% by mass with respect to 100% by mass of the hydrocarbon oil A. More preferably, it is 20 to 95% by mass.
- the monocyclic naphthenobenzene content ratio in the hydrogenated hydrocarbon oil A is preferably 10 to 90% by mass, more preferably 12 to 90% by mass with respect to 100% by mass of the hydrogenated hydrocarbon oil A. It is.
- polycyclic aromatic hydrocarbons are partially hydrogenated to become naphthenobenzene.
- naphthenobenzene is converted to naphthene.
- the naphthene content is not particularly limited, but excessive naphthene production is not preferable because it reduces the content of monocyclic naphthenobenzene and also increases the hydrogen consumption required for hydrogenation. Therefore, the naphthene content is preferably 0.1 to 40% by mass and more preferably 0.1 to 20% by mass with respect to 100% by mass of the hydrocarbon oil A after hydrogenation.
- a method of hydrogenating the hydrocarbon oil A a method of hydrotreating the hydrocarbon oil A under the following conditions can be preferably exemplified.
- a preferred example of the reaction mode is a fixed bed.
- the hydrogenation catalyst a known hydrogenation catalyst (for example, nickel catalyst, palladium catalyst, nickel-molybdenum catalyst, cobalt-molybdenum catalyst, nickel-cobalt-molybdenum catalyst, nickel-tungsten catalyst, etc.) should be used. Can do.
- the hydrogenation reaction temperature varies depending on the hydrogenation catalyst used, but is usually in the range of 100 to 450 ° C., more preferably 200 to 400 ° C., and still more preferably 250 to 380 ° C.
- the hydrogenation reaction pressure varies depending on the hydrogenation catalyst and raw materials used, but is preferably in the range of 0.7 MPa to 10 MPa, more preferably 1 MPa to 8 MPa, and particularly preferably 1 MPa to 6 MPa. . If the hydrogenation reaction pressure is reduced to 10 MPa or less, the production of naphthene can be suppressed and it can be efficiently converted to 1-ring naphthenobenzene, and a hydrogenation reactor with a low withstand pressure can be used. it can.
- the hydrogenation reaction pressure is preferably 0.7 to 13 MPa from the viewpoint of increasing the content of monocyclic naphthenobenzene.
- the hydrogen consumption is preferably 2500 scfb (422 Nm 3 / m 3 ) or less from the viewpoint of efficiently increasing the content of monocyclic naphthenobenzene by suppressing the production of naphthene, and 1500 scfb (253 Nm 3 / m 3 ). Or less, more preferably 1000 scfb (169 Nm 3 / m 3 ) or less.
- the hydrogen consumption is preferably 300 scfb (50 Nm 3 / m 3 ) or more from the viewpoint of increasing the content of monocyclic naphthenobenzene.
- the hydrogen consumption is preferably 300 ⁇ 2500scfb (50 ⁇ 422Nm 3 / m 3), more preferably 300 ⁇ 1500scfb (50 ⁇ 253Nm 3 / m 3).
- the liquid hourly space velocity (LHSV) is preferably be less than 0.1 h -1 or 20h -1, 0.2 h -1 or 10h -1 or less is more preferable.
- LHSV is 20 h ⁇ 1 or less
- polycyclic aromatic hydrocarbons can be sufficiently hydrogenated at a lower hydrogenation reaction pressure.
- the liquid space velocity (LHSV) is 0.1 h ⁇ 1 or more, an increase in the size of the hydrogenation reactor can be avoided. That is, the liquid hourly space velocity (LHSV) is preferably from 0.1 ⁇ 20h -1, more preferably 0.2 ⁇ 10h -1.
- the hydrocarbon oil A and the hydrogenated hydrocarbon oil A may be mixed in advance before being charged into the reactor, as in the method (i).
- the hydrocarbon oil A and the hydrogenated hydrocarbon oil A may be directly mixed.
- the hydrogenation of the hydrocarbon oil A can be performed in the same manner as in the method (ii).
- the content ratio of monocyclic naphthenobenzene in the raw material oil is 10 to 90% by mass, preferably 12 to 90% by mass, and more preferably 15 to 90% by mass with respect to 100% by mass of the raw material oil.
- the method of (i), (ii), (iii) described above is to prepare the 1-ring naphthenobenzene content ratio of the feed oil to be more than 90% by mass. It is difficult.
- Examples of the monocyclic naphthenobenzene include tetralin, alkyltetralin, indane, alkylindan, octahydrophenanthrene, alkyloctahydrophenanthrene, octahydroanthracene, alkyloctahydroanthracene, etc., tetralin, alkyltetralin, indane, Alkyl indan is particularly preferred. It should be noted that these components are mixed in an actual feed oil, and it is not practical to use them separately, and the total amount of these components is 10 to 90% by mass with respect to 100% by mass of the feed oil. % Should be included. Examples of a method for analyzing the content of monocyclic naphthenobenzene include a method of measuring based on a two-dimensional gas chromatographic method.
- reaction format examples of the reaction mode when the raw material oil is brought into contact with and reacted with the catalyst for producing a monocyclic aromatic hydrocarbon include a fixed bed, a moving bed, and a fluidized bed.
- a fluidized bed that can continuously remove the coke component adhering to the catalyst and can stably perform the reaction is preferable.
- a continuous regenerative fluidized bed in which the catalyst circulates between the reactor and the regenerator and the reaction-regeneration can be continuously repeated is particularly preferable.
- the raw material oil in contact with the catalyst is preferably in a gas phase. Moreover, you may dilute a raw material with gas as needed.
- the catalyst according to the present invention contains crystalline aluminosilicate.
- the crystalline aluminosilicate is preferably a medium pore zeolite and / or a large pore zeolite because the yield of monocyclic aromatic hydrocarbons can be further increased.
- the medium pore zeolite is a zeolite having a 10-membered ring skeleton structure. Examples of the medium pore zeolite include AEL type, EUO type, FER type, HEU type, MEL type, MFI type, NES type, and TON type. And zeolite having a WEI type crystal structure. Among these, the MFI type is preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.
- the large pore zeolite is a zeolite having a 12-membered ring skeleton structure.
- Examples of the large pore zeolite include AFI type, ATO type, BEA type, CON type, FAU type, GME type, LTL type, and MOR type. , Zeolites of MTW type and OFF type crystal structures.
- BEA type, FAU type, and MOR type are preferable in terms of industrial use, and the BEA type is more preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.
- the crystalline aluminosilicate may contain, in addition to the medium pore zeolite and the large pore zeolite, a small pore zeolite having a skeleton structure having a 10-membered ring or less, and a very large pore zeolite having a skeleton structure having a 14-membered ring or more.
- examples of the small pore zeolite include zeolites having crystal structures of ANA type, CHA type, ERI type, GIS type, KFI type, LTA type, NAT type, PAU type, and YUG type.
- Examples of the ultra-large pore zeolite include zeolites having CLO type and VPI type crystal structures.
- the content of crystalline aluminosilicate in the catalyst is 100% by mass of the total catalyst. Is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass. If the content of the crystalline aluminosilicate is 60% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased.
- the content of crystalline aluminosilicate in the catalyst is 100% by mass of the entire catalyst. Is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 35 to 60% by mass.
- the content of the crystalline aluminosilicate is 20% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased.
- the content of the crystalline aluminosilicate exceeds 60% by mass, the content of the binder that can be blended with the catalyst is reduced, which may be unsuitable for fluidized beds.
- the catalyst for producing monocyclic aromatic hydrocarbons preferably contains phosphorus and / or boron. If the catalyst for producing monocyclic aromatic hydrocarbons contains phosphorus and / or boron, it is possible to prevent the yield of monocyclic aromatic hydrocarbons from decreasing with time, and to suppress the formation of coke on the catalyst surface.
- phosphorus is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate by an ion exchange method, an impregnation method, or the like.
- Examples thereof include a method, a method in which a phosphorus compound is contained during zeolite synthesis and a part of the skeleton of the crystalline aluminosilicate is replaced with phosphorus, and a method in which a crystal accelerator containing phosphorus is used during zeolite synthesis.
- the phosphate ion-containing aqueous solution used at that time is not particularly limited, but phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and other water-soluble phosphates are dissolved in water at an arbitrary concentration. What was prepared in this way can be used preferably.
- boron is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate by an ion exchange method, an impregnation method, or the like.
- Examples thereof include a method, a method in which a boron compound is contained at the time of zeolite synthesis and a part of the skeleton of the crystalline aluminosilicate is replaced with boron, and a method in which a crystal accelerator containing boron is used at the time of zeolite synthesis.
- the content of phosphorus and / or boron in the catalyst for monocyclic aromatic hydrocarbon production is preferably 0.1 to 10% by mass relative to the total weight of the catalyst, and the lower limit is 0.5% by mass or more.
- the upper limit is more preferably 9% by mass or less, and particularly preferably 8% by mass or less.
- the catalyst for producing monocyclic aromatic hydrocarbons can contain gallium and / or zinc, if necessary. If gallium and / or zinc is contained, the production rate of monocyclic aromatic hydrocarbons can be increased.
- the gallium-containing form in the monocyclic aromatic hydrocarbon production catalyst is one in which gallium is incorporated into the lattice skeleton of crystalline aluminosilicate (crystalline aluminogallosilicate), and gallium is supported on the crystalline aluminosilicate. And those containing both (gallium-supporting crystalline aluminosilicate).
- the zinc-containing form is one in which zinc is incorporated in the lattice skeleton of crystalline aluminosilicate (crystalline aluminodine silicate), or zinc is supported on crystalline aluminosilicate.
- crystalline aluminosilicate crystalline aluminodine silicate
- Crystalline aluminogallosilicate and crystalline aluminodine silicate have a structure in which SiO 4 , AlO 4 and GaO 4 / ZnO 4 structures are present in the skeleton.
- crystalline aluminogallosilicate and crystalline aluminodine silicate are, for example, gel crystallization by hydrothermal synthesis, a method of inserting gallium or zinc into the lattice skeleton of crystalline aluminosilicate, or crystalline gallosilicate or crystalline It is obtained by inserting aluminum into the lattice skeleton of zincosilicate.
- the gallium-supporting crystalline aluminosilicate is obtained by supporting gallium on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method.
- the gallium source used in this case is not particularly limited, and examples thereof include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
- the zinc-supporting crystalline aluminosilicate is obtained by supporting zinc on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method. Although it does not specifically limit as a zinc source used in that case, Zinc salts, such as zinc nitrate and zinc chloride, zinc oxide, etc. are mentioned.
- the content of gallium and / or zinc in the catalyst for monocyclic aromatic hydrocarbon production is based on 100% by mass of the entire catalyst.
- the content is preferably 0.01 to 3.0% by mass, and more preferably 0.05 to 1.5% by mass. If the gallium and / or zinc content is 0.01% by mass or more, the production ratio of monocyclic aromatic hydrocarbons can be increased, and if it is 3.0% by mass or less, naphthenobenzene dehydrogenation can be performed. This makes it possible to produce monocyclic aromatic hydrocarbons from the raw material oil more efficiently.
- the catalyst for monocyclic aromatic hydrocarbon production is, for example, in the form of powder, granules, pellets, etc., depending on the reaction mode.
- a fluidized bed it is in the form of powder, and in the case of a fixed bed, it is in the form of particles or pellets.
- the average particle size of the catalyst used in the fluidized bed is preferably 30 to 180 ⁇ m, more preferably 50 to 100 ⁇ m.
- the bulk density of the catalyst used in the fluidized bed is preferably 0.4 to 1.8 g / cc, more preferably 0.5 to 1.0 g / cc.
- the average particle size represents a particle size of 50% by mass in the particle size distribution obtained by classification by sieving, and the bulk density is a value measured by the method of JIS standard R9301-2-3.
- an inert oxide may be blended into the catalyst as a binder and then molded using various molding machines.
- the catalyst for monocyclic aromatic hydrocarbon production contains an inorganic oxide such as a binder, one containing phosphorus as the binder may be used.
- reaction temperature when the raw material oil is brought into contact with and reacted with the catalyst for producing monocyclic aromatic hydrocarbons is not particularly limited, but is preferably 400 to 650 ° C. If the minimum of reaction temperature is 400 degreeC or more, raw material oil can be made to react easily, More preferably, it is 450 degreeC or more. Moreover, if the upper limit of reaction temperature is 650 degrees C or less, the yield of monocyclic aromatic hydrocarbon can be made high enough, More preferably, it is 600 degrees C or less.
- reaction pressure About the reaction pressure at the time of making a raw material oil contact and react with the catalyst for monocyclic aromatic hydrocarbon production, it is preferable to set it as 1.5 MPaG or less, and it is more preferable to set it as 1.0 MPaG or less. If the reaction pressure is 1.5 MPaG or less, the by-product of light gas can be suppressed and the pressure resistance of the reactor can be lowered.
- the lower limit of the reaction pressure is not particularly limited, but normal pressure or higher is preferable from the viewpoint of cost and the like.
- the contact time between the feedstock and the catalyst for producing monocyclic aromatic hydrocarbons is not particularly limited as long as the desired reaction substantially proceeds.
- the gas passage time on the catalyst is preferably 1 to 300 seconds. More preferably, the lower limit is 5 seconds or more and the upper limit is 150 seconds or less. If the contact time is 1 second or longer, the reaction can be performed reliably, and if the contact time is 300 seconds or shorter, accumulation of carbonaceous matter in the catalyst due to coking or the like can be suppressed. Or the generation amount of the light gas by decomposition
- the solution (B-1) was gradually added to the solution (A) while stirring the solution (A) at room temperature.
- the resulting mixture was vigorously stirred with a mixer for 15 minutes to break up the gel into a milky homogeneous fine state.
- this mixture was put into a stainless steel autoclave, and crystallization operation was performed under self-pressure under the conditions of temperature: 165 ° C., time: 72 hr, and stirring speed: 100 rpm.
- the product was filtered to recover the solid product, and washing and filtration were repeated 5 times using about 5 liters of deionized water.
- the solid substance obtained by filtration was dried at 120 ° C., and further calcined at 550 ° C. for 3 hours under air flow.
- the obtained fired product was confirmed to have an MFI structure. Further, by MASNMR analysis, SiO 2 / Al 2 O 3 ratio (molar ratio) was 64.8. Moreover, the aluminum element contained in the lattice skeleton calculated from this result was 1.32% by mass.
- a 30 mass% ammonium nitrate aqueous solution was added at a rate of 5 mL per 1 g of the obtained fired product, heated and stirred at 100 ° C for 2 hours, filtered, and washed with water. This operation was repeated 4 times, followed by drying at 120 ° C. for 3 hours to obtain an ammonium type crystalline aluminosilicate. Thereafter, firing was performed at 780 ° C. for 3 hours to obtain a proton-type crystalline aluminosilicate.
- gallium-supporting crystalline aluminosilicate was mixed with 30 g of diammonium hydrogenphosphate aqueous solution so that 0.7% by mass of phosphorus (the value with the total mass of the crystalline aluminosilicate being 100% by mass) was supported. Impregnation and drying at 120 ° C. Thereafter, it was calcined at 780 ° C. for 3 hours under air flow to obtain a catalyst containing crystalline aluminosilicate, gallium and phosphorus.
- the powdery catalyst (henceforth a "powder catalyst") whose average particle diameter is 84 micrometers and whose bulk density is 0.74 g / cc.
- Example 1 using a mixture of hydrocarbon oil A and hydrocarbon oil B: (Raw oil)
- hydrocarbon oil A a cracked light oil (LCO1) produced by a fluid catalytic cracking apparatus in which the content ratio of 1-ring naphthenobenzene was not adjusted was prepared.
- the composition of LCO1 is as follows: Saturated content (total amount of paraffin and naphthene) and unsaturated content (olefin content) (saturated content + olefin content): 23 mass, bicyclic naphthene content: 1 mass%, 1 ring Naphthenobenzene content: 9% by mass, 1-ring alkylbenzene content: 21% by mass, 2-ring aromatic content: 39% by mass, 3% or more aromatic content: 9% by mass.
- Table 1 shows the properties of LCO1.
- hydrocarbon oil B a light oil fraction (MHC-GO) obtained from a mild hydrocracking apparatus containing a large amount of monocyclic naphthenobenzene was prepared.
- the composition of MHC-GO is as follows: the total amount of saturated content (total amount of paraffin and naphthene) and unsaturated content (olefin content) (saturated content + olefin content): 45 mass, bicyclic naphthene content: 14 mass%, 1-ring naphthenobenzene content: 25 mass%, 1-ring alkylbenzene content: 17 mass%, 2-ring aromatic content: 13 mass%, aromatic content of 3 or more rings: 0 mass%.
- Table 1 shows the properties of MHC-GO. LCO1 and MHC-GO were mixed in an equal amount to obtain a feedstock 1 in which the content of monocyclic naphthenobenzene was adjusted to 17% by mass.
- the properties of the feedstock 1 are shown in Table 2.
- the compositional analysis shown in Tables 1 and 2 was analyzed by the method of a two-dimensional gas chromatograph (ZO2006, KT2006 GC ⁇ GC system), and the subsequent compositional analysis of hydrocarbon oil and raw material oil was performed in the same manner. It was.
- Example 2 using a mixture of hydrocarbon oil A and hydrocarbon oil B: (material) The raw material oil 1 of Example 1 was used as a raw material oil.
- Example 3 using a mixture of hydrocarbon oil A and hydrocarbon oil B: (material)
- hydrocarbon oil A a cracked light oil (LCO2) produced by a fluid catalytic cracking apparatus in which the content ratio of monocyclic naphthenobenzene was not adjusted was prepared.
- LCO2 cracked light oil
- the composition of LCO2 is the total amount of saturated content (total amount of paraffin and naphthene) and unsaturated content (olefin content) (saturated content + olefin content): 28 mass, bicyclic naphthene content: 0 mass%, 1 ring Naphthenobenzene content: 3 mass%, 1-ring alkylbenzene content: 4 mass%, 2-ring aromatic content: 52 mass%, aromatic content of 3 or more rings: 14 mass%.
- Table 1 shows the properties of LCO2.
- LCO2 and MHC-GO shown in Table 1 were mixed in an equal mass to obtain a feedstock 2 in which the monocyclic naphthenobenzene content ratio was adjusted to 14 mass%.
- the properties of the feedstock 2 are shown in Table 2.
- the composition of the hydrogenated LCO 1 is as follows: the total amount of saturated content (total amount of paraffin and naphthene) and unsaturated content (olefin content) (saturated content + olefin content): 28 mass, bicyclic naphthene content: 6 mass%, 1-ring naphthenobenzene content: 33% by mass, 1-ring alkylbenzene content: 21% by mass, 2-ring aromatic content: 12% by mass, aromatic content of 3 or more rings: 6% by mass.
- Table 1 shows the properties of hydrogenated LCO1.
- the composition of hydrogenated LCO2 is as follows: total amount of saturated component (total amount of paraffin and naphthene) and unsaturated component (olefin component) (saturated component + olefin component): 46 mass, bicyclic naphthene component: 24 mass%, 1-ring naphthenobenzene content: 26 mass%, 1-ring alkylbenzene content: 21 mass%, 2-ring aromatic content: 5 mass%, aromatic content of 3 or more rings: 2 mass%. Properties of the hydrogenated LCO2 are shown in Table 1.
- Example 6 Example 1 using a mixture of hydrocarbon oil and hydrogenated hydrocarbon oil as a feedstock (material) LCO1 and hydrogenated LCO2 shown in Table 1 were mixed in an equal mass to obtain a feedstock 5 in which the monocyclic naphthenobenzene content ratio was adjusted to 18% by mass. Table 2 shows the properties of the raw material oil 5.
- Example 7 Example 2 using a mixture of hydrocarbon oil and hydrogenated hydrocarbon oil as a feedstock: (material) LCO1 and hydrogenated LCO2 shown in Table 1 were mixed at a mass ratio of 70:30 to obtain a raw material oil 6 having a monocyclic naphthenobenzene content ratio adjusted to 14% by mass. Table 2 shows the properties of the raw material oil 6.
- Examples 4 to 7 where the content ratio of the raw material 1-ring naphthenobenzene was adjusted by hydrogenating the hydrocarbon oil the content ratio of the 1-ring naphthenobenzene was adjusted with the hydrogenated hydrocarbon oil. It was confirmed that all of the monocyclic aromatic hydrocarbons having 6 to 8 carbon atoms can be efficiently produced, as compared with Comparative Example 1 that does not.
- the method for producing a monocyclic aromatic hydrocarbon of the present invention is useful for producing a high-value-added monocyclic aromatic hydrocarbon that can be used as a high-octane gasoline base material or a petrochemical raw material.
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Abstract
Description
本願は、2011年3月25日に、日本に出願された特願2011-067877号に基づき優先権を主張し、その内容をここに援用する。
(1)多環芳香族分を含む炭化水素を1段で水素化分解する方法(特許文献1、2)。
(2)多環芳香族分を含む炭化水素を前段で水素化した後、後段で水素化分解する方法(特許文献3~5)。
(3)多環芳香族分を含む炭化水素を、ゼオライト触媒を用いて直接BTX留分に転換する方法(特許文献6)。
(4)多環芳香族分を含む炭化水素と、炭素数2~8の軽質炭化水素との混合物を、ゼオライト触媒を用いてBTX留分に転換する方法(特許文献7、8)。
(3)の方法では、必ずしも多環芳香族分の転換が十分であるとはいえない。
(4)の方法は、軽質炭化水素を原料とするBTXの製造技術と、多環芳香族分を含む炭化水素を原料とするBTXの製造技術とを組み合わせて熱バランスを向上したもので、多環芳香族分からのBTX収率を向上せしめるものではない。
前記原料油の1環ナフテノベンゼン含有比率が10~90質量%となるように、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である炭化水素油Aと、前記炭化水素油Aより1環ナフテノベンゼンを多く含む炭化水素油Bとを混合することによって調整されていることを特徴とする単環芳香族炭化水素の製造方法。
[2]10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である原料油を、結晶性アルミノシリケートを含む単環芳香族炭化水素製造用触媒と接触させて単環芳香族炭化水素を製造する方法であって、
前記原料油の1環ナフテノベンゼン含有比率が10~90質量%となるように、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である炭化水素油Aを水素化するか、あるいは、前記炭化水素油Aと前記炭化水素油Aを水素化したものとを混合することによって調整されていることを特徴とする単環芳香族炭化水素の製造方法。
[3]前記原料油の1環ナフテノベンゼン含有比率が、12~90質量%であることを特徴とする[1]または[2]に記載の単環芳香族炭化水素の製造方法。
[4]前記炭化水素油Aが流動接触分解装置で生成する分解軽油を含むことを特徴とする請求項[1]~[3]のいずれか一項に記載の単環芳香族炭化水素の製造方法。
また、本発明の単環芳香族炭化水素を製造する方法は、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である原料油を、結晶性アルミノシリケートを含む単環芳香族炭化水素製造用触媒と接触させて単環芳香族炭化水素を製造する方法であって、原料油の1環ナフテノベンゼン含有比率が10~90質量%となるように、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である炭化水素油Aを水素化するか、あるいは、炭化水素油Aと炭化水素油Aを水素化したものとを混合することによって調整されている方法である。
本発明で使用される原料油は、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下の油である。10容量%留出温度が140℃未満の油では、軽質のものから単環芳香族炭化水素を製造することになり、本発明の主旨にそぐわなくなる。また、90容量%留出温度が380℃を超える油を用いた場合には、単環芳香族炭化水素の収率が低くなる上に、単環芳香族炭化水素製造用触媒上へのコーク堆積量が増大して、触媒活性の急激な低下を引き起こす傾向にある。
原料油の10容量%留出温度の下限は140℃以上であり、150℃以上であることが好ましく、一方、上限は300℃以下であることが好ましい。また、原料油の90容量%留出温度の上限は380℃以下であり、360℃以下であることが好ましく、一方、下限は160℃以上であることが好ましい。
なお、ここでいう10容量%留出温度、90容量%留出温度とは、JIS K2254「石油製品-蒸留試験方法」に準拠して測定される値を意味する。
なお、ここでいう多環芳香族分とは、JPI-5S-49「石油製品-炭化水素タイプ試験方法-高速液体クロマトグラフ法」に準拠して測定、あるいは、FIDガスクロマトグラフ法または2次元ガスクロマトグラフ法にて分析される2環芳香族炭化水素含有量(2環芳香族分)および、3環以上の芳香族炭化水素含有量(3環以上の芳香族分)の合計値を意味する。以降、多環芳香族炭化水素、2環芳香族炭化水素、3環以上の芳香族炭化水素の含有量が容量%で示されている場合は、JPI-5S-49に準拠して測定されたものであり、質量%で示されている場合は、FIDガスクロマトグラフ法または2次元ガスクロマトグラフ法に基づいて測定されたものである。
なお、1環ナフテノベンゼン含有比率(質量%)は、2次元ガスクロマトグラフ法に基づいて測定されたものである。
ナフテノベンゼンは、分解・開環反応により、単環芳香族炭化水素を製造せしめる可能性がある一方で、脱水素反応により多環芳香族炭化水素が製造され、さらには、それらの多環芳香族炭化水素がコーク化し触媒上に蓄積することで触媒活性を低下させるおそれがあった。そのため、これまではナフテノベンゼンの比率を高めることは、必ずしも単環芳香族炭化水素の収量増加につながるものではなかった。また、単に脱水素能のみを抑制する条件とすると、同時に進行する飽和炭化水素の環化・脱水素が抑制され、単環芳香族炭化水素の収量をあげることができなかった。
なお、原料油中に1環ナフテノベンゼン以外のナフテノベンゼンを含有しても構わないが、ジヒドロフェナントレン、テトラヒドロアントラセン等で代表される2環ナフテノベンゼンは、芳香環部分の分解が困難で単環芳香族炭化水素の収量を向上させないことから、多く含むことは必ずしも好ましくない。ただし、飽和炭化水素との水素移行反応により、単環芳香族炭化水素に移行することも可能であることから、他の多環芳香族炭化水素と同じように含有することができる。
(i)炭化水素油Aと、1環ナフテノベンゼンを多く含む炭化水素油Bとを混合する方法
(ii)炭化水素油Aを水素化する方法
(iii)炭化水素油Aと、炭化水素油Aを水素化したものとを混合する方法
炭化水素油Aとは、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下の油である他は特に制限はないが、例えば、流動接触分解(FCC)装置で生成する分解軽油(LCO)、石炭液化油、直留灯油、直留軽油、コーカー灯油、コーカー軽油などが挙げられる。炭化水素油Aは、1環ナフテノベンゼン含有量が、炭化水素油A100質量%に対し、好ましくは0~9.9質量%であり、より好ましくは1~9.9質量%、さらに好ましくは2~9.2質量%である。
炭化水素油Bとは、炭化水素油B100質量%に対し、1環ナフテノベンゼン含有量が10質量%よりも多く、さらに少なくとも炭化水素油Aよりは1環ナフテノベンゼン含有量が多い炭化水素油であれば、特に制限はないが、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下の炭化水素油であることが好ましい。例えば、重質油水素化分解精製油、オイルサンド水素化分解精製油、オイルシェール水素化分解精製油などが挙げられる。炭化水素油Bは、1環ナフテノベンゼン含有量が、炭化水素油B100質量%に対し、好ましくは10~90質量%であり、より好ましくは12~90質量%である。
また、(炭化水素油B中の1環ナフテノベンゼン含有量)/(炭化水素油A中の1環ナフテノベンゼン含有量)の値は、1.1以上が好ましく、1.5以上がより好ましい。
反応器内で直接混合する場合は、反応器内に投入する直前の炭化水素油Aの1環ナフテノベンゼンの量と、1環ナフテノベンゼンを多く含む炭化水素油Bの1環ナフテノベンゼンの量との合計、すなわち、混合後の原料油の1環ナフテノベンゼン含有量が、混合後の原料油100質量%に対し、10~90質量%、好ましくは12~90質量%、より好ましくは15質量~90%となる量であることが好ましい。
反応形式としては、固定床を好ましく挙げることができる。
水素化触媒としては、公知の水素化触媒(例えば、ニッケル触媒、パラジウム触媒、ニッケル-モリブデン系触媒、コバルト-モリブデン系触媒、ニッケル-コバルト-モリブデン系触媒、ニッケル-タングステン系触媒等)を用いることができる。
水素化反応圧力は、使用する水素化触媒や原料によっても異なるが、0.7MPaから10MPaの範囲とすることが好ましく、1MPaから8MPaとすることがより好ましく、1MPaから6MPaとすることが特に好ましい。水素化反応圧力を10MPa以下にすれば、ナフテンの生成を抑え効率的に1環ナフテノベンゼンに転換することができ、あわせて耐用圧力の低い水素化反応器が使用可能となり、設備費を低減できる。一方、水素化反応圧力は、1環ナフテノベンゼンの含有量を増加させる観点から、0.7~13MPaであることが好ましい。
液空間速度(LHSV)は0.1h-1以上20h-1以下にすることが好ましく、0.2h-1以上10h-1以下がより好ましい。LHSVを20h-1以下とすれば、より低い水素化反応圧力にて多環芳香族炭化水素を十分に水素化することができる。一方、液空間速度(LHSV)を0.1h-1以上とすることで、水素化反応器の大型化を避けることができる。すなわち、液空間速度(LHSV)は、0.1~20h-1が好ましく、0.2~10h-1がより好ましい。
1環ナフテノベンゼンが多い分には制限はないものの、原料油の1環ナフテノベンゼン含有比率を90質量%超に調製することは、前記(i)、(ii)、(iii)の方法では困難である。
なお、実際の原料油には、これらの成分が混合されており、それぞれを分離して用いることは実用的ではなく、これらの成分の総量が、原料油100質量%に対し、10~90質量%含まれていればよい。1環ナフテノベンゼンの含有量を分析する手法としては、例えば、2次元ガスクロマトグラフ法に基づいて測定する方法などが挙げられる。
原料油を単環芳香族炭化水素製造用触媒と接触、反応させる際の反応形式としては、固定床、移動床、流動床等が挙げられる。本発明においては、重質分を原料とするため、触媒に付着したコーク分を連続的に除去可能で、かつ安定的に反応を行うことができる流動床が好ましい。さらに、反応器と再生器との間を触媒が循環し、連続的に反応-再生を繰り返すことができる、連続再生式流動床が特に好ましい。触媒と接触する際の原料油は、気相状態であることが好ましい。また、原料は、必要に応じてガスによって希釈してもよい。
本発明に係る触媒は、結晶性アルミノシリケートを含有する。
結晶性アルミノシリケートは、単環芳香族炭化水素の収率をより高くできることから、中細孔ゼオライトおよび/または大細孔ゼオライトであることが好ましい。
中細孔ゼオライトは、10員環の骨格構造を有するゼオライトであり、中細孔ゼオライトとしては、例えば、AEL型、EUO型、FER型、HEU型、MEL型、MFI型、NES型、TON型、WEI型の結晶構造のゼオライトが挙げられる。これらの中でも、単環芳香族炭化水素の収率をより高くできることから、MFI型が好ましい。
大細孔ゼオライトは、12員環の骨格構造を有するゼオライトであり、大細孔ゼオライトとしては、例えば、AFI型、ATO型、BEA型、CON型、FAU型、GME型、LTL型、MOR型、MTW型、OFF型の結晶構造のゼオライトが挙げられる。これらの中でも、工業的に使用できる点では、BEA型、FAU型、MOR型が好ましく、単環芳香族炭化水素の収率をより高くできることから、BEA型がより好ましい。
ここで、小細孔ゼオライトとしては、例えば、ANA型、CHA型、ERI型、GIS型、KFI型、LTA型、NAT型、PAU型、YUG型の結晶構造のゼオライトが挙げられる。
超大細孔ゼオライトとしては、例えば、CLO型、VPI型の結晶構造のゼオライトが挙げられる。
単環芳香族炭化水素製造用触媒においては、リンおよび/またはホウ素を含有することが好ましい。単環芳香族炭化水素製造用触媒がリンおよび/またはホウ素を含有すれば、単環芳香族炭化水素の収率の経時的な低下を防止でき、また、触媒表面のコーク生成を抑制できる。
単環芳香族炭化水素製造用触媒には、必要に応じて、ガリウムおよび/または亜鉛を含有させることができる。ガリウムおよび/または亜鉛を含有させれば、単環芳香族炭化水素の生成割合をより多くできる。
単環芳香族炭化水素製造用触媒におけるガリウム含有の形態としては、結晶性アルミノシリケートの格子骨格内にガリウムが組み込まれたもの(結晶性アルミノガロシリケート)、結晶性アルミノシリケートにガリウムが担持されたもの(ガリウム担持結晶性アルミノシリケート)、その両方を含んだものが挙げられる。
結晶性アルミノガロシリケート、結晶性アルミノジンコシリケートは、SiO4、AlO4およびGaO4/ZnO4構造が骨格中に存在する構造を有する。また、結晶性アルミノガロシリケート、結晶性アルミノジンコシリケートは、例えば、水熱合成によるゲル結晶化、結晶性アルミノシリケートの格子骨格中にガリウムまたは亜鉛を挿入する方法、または結晶性ガロシリケートまたは結晶性ジンコシリケートの格子骨格中にアルミニウムを挿入する方法により得られる。
亜鉛担持結晶性アルミノシリケートは、結晶性アルミノシリケートに亜鉛をイオン交換法、含浸法等の公知の方法によって担持したものである。その際に用いる亜鉛源としては、特に限定されないものの、硝酸亜鉛、塩化亜鉛等の亜鉛塩、酸化亜鉛等が挙げられる。
単環芳香族炭化水素製造用触媒は、反応形式に応じて、例えば、粉末状、粒状、ペレット状等にされる。例えば、流動床の場合には粉末状にされ、固定床の場合には粒状またはペレット状にされる。流動床で用いる触媒の平均粒子径は30~180μmが好ましく、50~100μmがより好ましい。また、流動床で用いる触媒のかさ密度は0.4~1.8g/ccが好ましく、0.5~1.0g/ccがより好ましい。
粒状またはペレット状の触媒を得る場合には、必要に応じて、バインダーとして触媒に不活性な酸化物を配合した後、各種成形機を用いて成形すればよい。
単環芳香族炭化水素製造用触媒がバインダー等の無機酸化物を含有する場合、バインダーとしてリンを含むものを用いても構わない。
原料油を単環芳香族炭化水素製造用触媒と接触、反応させる際の反応温度については、特に制限されないものの、400~650℃とすることが好ましい。反応温度の下限は400℃以上であれば原料油を容易に反応させることができ、より好ましくは450℃以上である。また、反応温度の上限は650℃以下であれば単環芳香族炭化水素の収率を十分に高くでき、より好ましくは600℃以下である。
原料油を単環芳香族炭化水素製造用触媒と接触、反応させる際の反応圧力については、1.5MPaG以下とすることが好ましく、1.0MPaG以下とすることがより好ましい。反応圧力が1.5MPaG以下であれば、軽質ガスの副生を抑制できる上に、反応装置の耐圧性を低くできる。反応圧力の下限値は特に限定されないが、コストなどの観点から常圧以上が好ましい。
原料油と単環芳香族炭化水素製造用触媒との接触時間については、所望する反応が実質的に進行すれば特に制限はされないものの、例えば、触媒上のガス通過時間で1~300秒が好ましく、さらに下限を5秒以上、上限を150秒以下とすることがより好ましい。
接触時間が1秒以上であれば、確実に反応させることができ、接触時間が300秒以下であれば、コーキング等による触媒への炭素質の蓄積を抑制できる。または分解による軽質ガスの発生量を抑制できる。
結晶性アルミノシリケートを含む単環芳香族炭化水素製造用触媒の調製:
硅酸ナトリウム(Jケイ酸ソーダ3号、SiO2:28~30質量%、Na:9~10質量%、残部水、日本化学工業(株)製)の1706.1gおよび水の2227.5gからなる溶液(A)と、Al2(SO4)3・14~18H2O(試薬特級、和光純薬工業(株)製)の64.2g、テトラプロピルアンモニウムブロマイドの369.2g、H2SO4(97質量%)の152.1g、NaClの326.6gおよび水の2975.7gからなる溶液(B-1)をそれぞれ調製した。
次いで、この混合物をステンレス製のオートクレーブに入れ、温度:165℃、時間:72hr、撹拌速度:100rpmの条件で、自己圧力下に結晶化操作を行った。結晶化操作の終了後、生成物を濾過して固体生成物を回収し、約5リットルの脱イオン水を用いて洗浄と濾過を5回繰り返した。濾別して得られた固形物を120℃で乾燥し、さらに空気流通下、550℃で3時間焼成した。
次いで、得られたガリウム担持結晶性アルミノシリケート30gに、0.7質量%のリン(結晶性アルミノシリケート総質量を100質量%とした値)が担持されるようにリン酸水素二アンモニウム水溶液30gを含浸させ、120℃で乾燥させた。その後、空気流通下、780℃で3時間焼成して、結晶性アルミノシリケートとガリウムとリンとを含有する触媒を得た。
得られたガリウム、リン含有結晶性アルミノシリケートに39.2MPa(400kgf)の圧力をかけて打錠成型し、粗粉砕して20~28メッシュのサイズに揃えて、粒状体の触媒(以下、「粒状化触媒」という。)を得た。
希硫酸に硅酸ナトリウム(Jケイ酸ソーダ3号、SiO2:28~30質量%、Na:9~10質量%、残部水、日本化学工業(株)製)106gと純水の混合溶液を滴下し、シリカゾル水溶液(SiO2濃度10.2%)を調製した。一方、得られたガリウム、リン含有結晶性アルミノシリケート20.4gに蒸留水を加え、ゼオライトスラリーを調製した。上記のゼオライトスラリーとシリカゾル水溶液300gを混合し、調製したスラリーを250℃で噴霧乾燥し、球形触媒を得た。その後、600℃で3時間焼成し、平均粒子径が84μm、かさ密度が0.74g/ccである粉末状の触媒(以下、「粉末状触媒」という。)を得た。
炭化水素油Aと炭化水素油Bとを混合したものを用いた例1:
(原料油)
炭化水素油Aとして、1環ナフテノベンゼン含有比率を調整していない流動接触分解装置で生成する分解軽油(LCO1)を用意した。LCO1の組成は、飽和分(パラフィン分とナフテン分の合計量)と不飽和分(オレフィン分)の合計量(飽和分+オレフィン分):23質量、2環ナフテン分:1質量%、1環ナフテノベンゼン分:9質量%、1環アルキルベンゼン分:21質量%、2環芳香族分:39質量%、3環以上の芳香族分:9質量%であった。LCO1の性状を表1に示す。
炭化水素油Bとして、1環ナフテノベンゼンを多く含む、マイルドハイドロクラッキング装置から得られる軽油留分(MHC-GO)を用意した。MHC-GOの組成は、飽和分(パラフィン分とナフテン分の合計量)と不飽和分(オレフィン分)の合計量(飽和分+オレフィン分):45質量、2環ナフテン分:14質量%、1環ナフテノベンゼン分:25質量%、1環アルキルベンゼン分:17質量%、2環芳香族分:13質量%、3環以上の芳香族分:0質量%であった。MHC-GOの性状を表1に示す。
LCO1とMHC-GOとを等質量混合し、1環ナフテノベンゼン含有比率が17質量%に調整された原料油1を得た。原料油1の性状を表2に示す。
なお、表1、表2に示す組成分析は2次元ガスクロマトグラフ装置(ZOEX社製 KT2006 GC×GCシステム)の方法で分析したもので、以後の炭化水素油および原料油の組成分析も同様に行った。
5.5gの単環芳香族炭化水素製造用触媒を反応器に充填した固定床反応器を用い、反応温度:540℃、反応圧力:0.3MPaGの条件で、原料油1を粒状化触媒と接触、反応させた。原料油1と粒状化触媒に含まれるゼオライト成分との接触時間が12秒となるようにした。
30分反応させた後、装置に直結されたガスクロマトグラフにより生成物の組成分析を行ったところ、炭素数6~8の単環芳香族炭化水素の収率は37質量%、分解ガス(水素、メタン、エタン、エチレン、LPG)の収率は21質量%であった。結果を表3に示す。
炭化水素油Aと炭化水素油Bとを混合したものを用いた例2:
(原料)
原料油として実施例1の原料油1を使用した。
粉末状触媒(400g)を反応器に充填した流動床反応装置を用い、反応温度:540℃、反応圧力:0.3MPaG、原料油1と粉末状触媒に含まれるゼオライト成分との接触時間が12秒となる条件で反応させて単環芳香族炭化水素の製造を行った。その結果、炭素数6~8の単環芳香族炭化水素の生成量が34質量%、分解ガスの生成量が20質量%であった。結果を表3に示す。
炭化水素油Aと炭化水素油Bとを混合したものを用いた例3:
(原料)
炭化水素油Aとして、1環ナフテノベンゼン含有比率を調整していない流動接触分解装置で生成する分解軽油(LCO2)を用意した。LCO2の組成は、飽和分(パラフィン分とナフテン分の合計量)と不飽和分(オレフィン分)の合計量(飽和分+オレフィン分):28質量、2環ナフテン分:0質量%、1環ナフテノベンゼン分:3質量%、1環アルキルベンゼン分:4質量%、2環芳香族分:52質量%、3環以上の芳香族分:14質量%であった。LCO2の性状を表1に示す。
表1に示すLCO2とMHC-GOとを等質量混合し、1環ナフテノベンゼン含有比率が14質量%に調整された原料油2を得た。原料油2の性状を表2に示す。
原料油として、表2に示す原料油2を用いた以外は実施例1と同様の反応を行った。炭素数6~8の単環芳香族炭化水素の収率は34質量%、分解ガスの収率は19質量%であった。結果を表3に示す。
炭化水素油Aを水素化したものを原料油として用いた例1:
(原料)
表1に示すLCO1を市販のニッケル-モリブデン触媒を用い、反応温度350℃、反応圧力3MPa、LHSV=0.5h-1、水素消費量92Nm3/m3の条件で水素化処理し、水素化LCO1を得た。水素化LCO1の組成は、飽和分(パラフィン分とナフテン分の合計量)と不飽和分(オレフィン分)の合計量(飽和分+オレフィン分):28質量、2環ナフテン分:6質量%、1環ナフテノベンゼン分:33質量%、1環アルキルベンゼン分:21質量%、2環芳香族分:12質量%、3環以上の芳香族分:6質量%であった。水素化LCO1の性状を表1に示す。
原料油として、表2に示す原料油3(水素化LCO1を100質量%)を用いた以外は実施例1と同様の反応を行った。炭素数6~8の単環芳香族炭化水素の収率は42質量%、分解ガスの収率は11質量%であった。結果を表3に示す。
炭化水素油Aを水素化したものを原料油として用いた例2:
(原料)
表1に示すLCO1を市販のニッケル-モリブデン触媒を用い、反応温度350℃、反応圧力5MPa、LHSV=0.5h-1、水素消費量194Nm3/m3の条件で水素化処理し、水素化LCO2を得た。水素化LCO2の組成は、飽和分(パラフィン分とナフテン分の合計量)と不飽和分(オレフィン分)の合計量(飽和分+オレフィン分):46質量、2環ナフテン分:24質量%、1環ナフテノベンゼン分:26質量%、1環アルキルベンゼン分:21質量%、2環芳香族分:5質量%、3環以上の芳香族分:2質量%であった。水素化LCO2の性状を表1に示す。
原料油として、表2に示す原料油4(水素化LCO2を100質量%)を用いた以外は実施例1と同様の反応を行った。炭素数6~8の単環芳香族炭化水素の収率は39質量%、分解ガスの収率は20質量%であった。結果を表3に示す。
炭化水素油と水素化した炭化水素油を混合したものを原料油として用いた例1:
(原料)
表1に示すLCO1と水素化LCO2とを等質量混合し、1環ナフテノベンゼン含有比率が18質量%に調整された原料油5を得た。原料油5の性状を表2に示す。
原料油として、表2に示す原料油5を用いた以外は実施例1と同様の反応を行った。炭素数6~8の単環芳香族炭化水素の収率は35質量%、分解ガスの収率は15質量%であった。結果を表3に示す。
炭化水素油と水素化した炭化水素油を混合したものを原料油として用いた例2:
(原料)
表1に示すLCO1と水素化LCO2とを質量比70:30で混合し、1環ナフテノベンゼン含有比率が14質量%に調整された原料油6を得た。原料油6の性状を表2に示す。
原料油として、表2に示す原料油6を用いた以外は実施例1と同様の反応を行った。炭素数6~8の単環芳香族炭化水素の収率は34質量%、分解ガスの収率は13質量%であった。結果を表3に示す。
1環ナフテノベンゼン含有比率を調整していない原料油を用いた例:
(原料)
1環ナフテノベンゼン含有比率を調整していないLCO1を原料油7とした。原料油7の性状を表2に示す。
原料油として、表2に示す原料油7を用いた以外は実施例1と同様の反応を行った。炭素数6~8の単環芳香族炭化水素の収率は32質量%、分解ガスの収率は10質量%であった。結果を表3に示す。
また、炭化水素油を水素化することにより原料の1環ナフテノベンゼンの含有比率を調整した実施例4~実施例7は、水素化した炭化水素油により1環ナフテノベンゼンの含有比率を調整しない比較例1よりも、いずれも炭素数6~8の単環芳香族炭化水素を効率的に製造できることが確認された。
Claims (4)
- 10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下ある原料油を、結晶性アルミノシリケートを含む単環芳香族炭化水素製造用触媒と接触させて単環芳香族炭化水素を製造する方法であって、
前記原料油の1環ナフテノベンゼン含有比率が10~90質量%となるように、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である炭化水素油Aと前記炭化水素油Aより1環ナフテノベンゼンを多く含む炭化水素油Bとを混合することによって調整されていることを特徴とする単環芳香族炭化水素の製造方法。 - 10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である原料油を、結晶性アルミノシリケートを含む単環芳香族炭化水素製造用触媒と接触させて単環芳香族炭化水素を製造する方法であって、
前記原料油の1環ナフテノベンゼン含有比率が10~90質量%となるように、10容量%留出温度が140℃以上かつ90容量%留出温度が380℃以下である炭化水素油Aを水素化するか、あるいは、前記炭化水素油Aと前記炭化水素油Aを水素化したものとを混合することによって調整されていることを特徴とする単環芳香族炭化水素の製造方法。 - 前記原料油の1環ナフテノベンゼン含有比率が、12~90質量%であ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炭化水素の製造方法。
- 前記炭化水素油Aが流動接触分解装置で生成する分解軽油を含むことを特徴とする請求項1~3のいずれか一項に記載の単環芳香族炭化水素の製造方法。
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KR101736197B1 (ko) * | 2015-10-07 | 2017-05-17 | 한국화학연구원 | 다환 방향족 탄화수소로부터 BTEX(벤젠(Benzene), 톨루엔(Toluene), 에틸벤젠(Ethylbenzene), 자일렌(Xylene)) 제조용 Beta 제올라이트 촉매 및 이의 제조방법 |
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US10164177B2 (en) * | 2017-01-18 | 2018-12-25 | Samsung Electronics Co., Ltd. | Method and system for providing a magnetic junction usable in spin transfer torque applications using a post-pattern anneal |
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