US20130030232A1 - Catalyst for production of monocyclic aromatic hydrocarbons and method of producing monocyclic aromatic hydrocarbons - Google Patents
Catalyst for production of monocyclic aromatic hydrocarbons and method of producing monocyclic aromatic hydrocarbons Download PDFInfo
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- US20130030232A1 US20130030232A1 US13/522,867 US201113522867A US2013030232A1 US 20130030232 A1 US20130030232 A1 US 20130030232A1 US 201113522867 A US201113522867 A US 201113522867A US 2013030232 A1 US2013030232 A1 US 2013030232A1
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- aromatic hydrocarbons
- monocyclic aromatic
- zeolite
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- 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
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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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
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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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
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- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Definitions
- the present invention relates to a catalyst for producing monocyclic aromatic hydrocarbons and a method of producing monocyclic aromatic hydrocarbons, which are capable of producing monocyclic aromatic hydrocarbons from oil containing a large amount of polycyclic aromatic hydrocarbons.
- LCO Light cycle oil
- monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 such as benzene, toluene, xylene and ethylbenzene
- Patent Document 1 to Patent Document 3 disclose methods of producing monocyclic aromatic hydrocarbons from polycyclic aromatic hydrocarbons contained in large amounts within LCO and the like by using zeolite catalysts.
- Patent Document 4 discloses a method of producing monocyclic aromatic hydrocarbons from aromatic compounds having a carbon number of 9 or more by using beta-type zeolite, which has a 12-membered ring structure and a large pore size, as a catalyst.
- Patent Document 5 discloses a method of producing monocyclic aromatic hydrocarbons from paraffin-based hydrocarbons having a carbon number of 2 to 12 by using beta-type zeolite as a catalyst.
- Patent Document 1 to Patent Document 3 the yields of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 have not been entirely satisfactory.
- the methods disclosed in Patent Document 4 and Patent Document 5 are not methods of obtaining both monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
- An object of the invention is to provide a catalyst for production of monocyclic aromatic hydrocarbons and a method of producing monocyclic aromatic hydrocarbons, which are capable of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 from feedstock containing polycyclic aromatic hydrocarbons with high yield.
- a catalyst for production of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
- the catalyst contains crystalline aluminosilicate including large-pore zeolite having a 12-membered ring structure, and intermediate-pore zeolite having 10-membered ring structure.
- a method is provided of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8.
- the method includes bringing feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower into contact with the catalyst for production of monocyclic aromatic hydrocarbons according to any one of (1) to (6).
- monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is preferably produced with high yield from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
- the catalyst for production of monocyclic aromatic hydrocarbons according to this embodiment (hereinafter, abbreviated as “catalyst”) is used for producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 (hereinafter, abbreviated as “monocyclic aromatic hydrocarbons”) from feedstock containing polycyclic aromatic hydrocarbons and saturated hydrocarbons, and contains crystalline aluminosilicate.
- the crystalline aluminosilicate contains large-pore zeolite having a 12-membered ring structure, and intermediate-pore zeolite having a 10-membered ring structure.
- zeolites having a framework type of an AFI type, an ATO type, a BEA type, a CON type, an FAU type, a GME type, an LTL type, an MOR type, an MTW type, and an OFF type is preferably exemplified.
- the BEA type, the FAU type, and the MOR type are preferable from an industrially usable aspect, and the BEA type is more preferable because the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is relatively raised.
- the intermediate-pore zeolite having a 10-membered ring structure for example, zeolites having a framework type of an AEL type, an EUO type, an FER type, an HEU type, an MEL type, an MFI type, an NES type, a TON type, and a WEI type is preferably exemplified.
- the MFI type is preferable because the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is relatively raised.
- all of the framework type types of the zeolite which are exemplified in this embodiment, are structure codes based on the definition of the International Zeolite Association.
- the crystalline aluminosilicate may contain small-pore zeolite having a structure of a 10-membered ring or less, and ultra-large-pore zeolite having a structure of a 14-membered ring or more.
- zeolites having a framework type of an ANA type, a CHA type, an ERI type, a GIS type, a KFI type, an LTA type, an NAT type, a PAU type, and a YUG type is preferably exemplified.
- ultra-large-pore zeolite for example, zeolites having a framework type of a CLO type, and a VPI type is preferably exemplified.
- the content of the crystalline aluminosilicate is preferably 60 to 100% by mass on the basis of 100% by mass of the entirety of the catalyst, and more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass.
- the content of the crystalline aluminosilicate is 60% by mass or more, the total yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 is sufficiently raised.
- the content of the crystalline aluminosilicate is preferably 20 to 60% by mass on the basis of 100% by mass of the entirety of the catalyst, and more preferably 30 to 60% by mass, and still more preferably 35 to 60% by mass.
- the content of the crystalline aluminosilicate is 20% by mass or more, the total yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 is sufficiently raised.
- the content of the crystalline aluminosilicate exceeds 60% by mass, the content of a binder that may be mixed with the catalyst becomes small, and thus may be not appropriate as the catalyst for the fluidized bed.
- a mass ratio of the large-pore zeolite to the intermediate-pore zeolite is preferably 2/98 to 50/50, more preferably 5/95 to 50/50, still more preferably 10/90 to 30/70.
- the mass ratio is 2/98 or more, an effect of using the large-pore zeolite is sufficiently exhibited, and thus the yield of the monocyclic aromatic hydrocarbons is sufficiently raised.
- the mass ratio is 50/50 or less, coking of the feedstock is prevented, and thus the yield of the monocyclic aromatic hydrocarbons is sufficiently raised.
- the catalyst may contain gallium and/or zinc as necessary.
- gallium and/or zinc are contained, a generation ratio of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 tends to be increased.
- gallium As a method used to incorporate gallium into the catalyst, a type in which gallium is incorporated in a lattice framework of the crystalline aluminosilicate (crystalline aluminogallosilicate), a type in which gallium is carried by the crystalline aluminosilicate (gallium-supporting crystalline aluminosilicate), and a type including both of these types is exemplified.
- crystalline aluminogallosilicate crystalline aluminogallosilicate
- gallium-supporting crystalline aluminosilicate gallium-supporting crystalline aluminosilicate
- crystalline aluminozincosilicate crystalline aluminozincosilicate
- zinc-supporting crystalline aluminosilicate a type in which zinc is carried by the crystalline aluminosilicate
- a type including both of these types is exemplified.
- the crystalline aluminogallosilicate and the crystalline aluminozincosilicate have a structure in which SiO 4 , AlO 4 , and GaO 4 /ZnO 4 structures have a tetrahedral coordination in a framework.
- the crystalline aluminogallosilicate and the crystalline aluminozincosilicate may be obtained, for example, by gel crystallization through hydrothermal synthesis, by a method in which gallium or zinc is inserted into the lattice framework of the crystalline aluminosilicate, or by a method in which aluminum is inserted into the lattice framework of crystalline gallosilicate or crystalline zincosilicate.
- the gallium-supporting crystalline aluminosilicate may be obtained by supporting gallium on a crystalline aluminosilicate using a conventional method such as an ion-exchange method or impregnation method.
- a conventional method such as an ion-exchange method or impregnation method.
- gallium source used in these methods examples include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
- the zinc-supporting crystalline aluminosilicate may be obtained by supporting zinc on a crystalline aluminosilicate using a known method such as an ion-exchange method or impregnation method.
- a known method such as an ion-exchange method or impregnation method.
- the zinc source used in these methods include zinc salts such as zinc nitrate and zinc chloride, and zinc oxide.
- the lower limit of the content of gallium and/or zinc is preferably 0.01% by mass or more on the basis of 100% by mass of the total mass of the crystalline aluminosilicate, and more preferably 0.05% by mass or more.
- the upper limit thereof is preferably 5.0% by mass or less, and more preferably 1.5% by mass or less.
- the catalyst may contain phosphorus and/or boron as necessary.
- phosphorus and/or boron when phosphorus and/or boron is contained, a decrease with the passage of time in the total yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbon having a carbon number of 3 to 4 may be prevented, and the coke may be prevented from being generated on the surface of the catalyst.
- a method of incorporating phosphorus in the catalyst examples thereof include a method in which phosphorus is made to be supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminozincosilicate by using an ion-exchange method, impregnation method, or the like, a method in which a phosphorus compound is incorporated during synthesis of the zeolite, and a part in the framework of the crystalline aluminosilicate is substituted with phosphorus, a method in which a crystallization promoter containing phosphorus is used during synthesis of the zeolite, and the like.
- a solution which is prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, or another water-soluble phosphate salt in water at an arbitrary concentration, is preferably used.
- a method of incorporating boron in the catalyst examples thereof include a method in which boron is made to be supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminozincosilicate by using an ion-exchange method, impregnation method, or the like, a method in which a boron compound is incorporated during synthesis of the zeolite, and a part in the framework of the crystalline aluminosilicate is substituted with boron, a method in which a crystallization promoter containing boron is used during synthesis of the zeolite, and the like.
- the lower limit of the content of phosphorus and/or boron is preferably 0.1% by mass or more on the basis of 100% by mass of the total mass of the crystalline aluminosilicate, and more preferably 0.2% by mass or more.
- the upper limit thereof is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less.
- the catalyst has a powder form, a granular form, or a pellet form, or the like depending on a reaction format.
- the catalyst in the case of a fluidized bed, the catalyst has the powder form, whereas in the case of a fixed bed, the catalyst has the granular form or the pellet form.
- an oxide inactive to the catalyst is mixed with the catalyst as a binder as necessary, and then the resultant mixture is molded with various types of molding machine.
- the binder containing phosphorus and/or boron can be used.
- the content of phosphorus and/or boron that are contained in the crystalline aluminosilicate (% by mass of phosphorus and/or boron on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) is preferably 0.1 to 5.0% by mass.
- An amount of phosphorus and/or boron that are contained in the crystalline aluminosilicate represents an amount of phosphorus and/or boron that act on the crystalline aluminosilicate.
- the catalyst in a case where the catalyst contains a binder or the like, the catalyst is produced by mixing the binder or the like, and gallium and/or zinc supporting crystalline aluminosilicate or crystalline aluminogallosilicate and/or crystalline aluminozincosilicate, and then adding phosphorus and/or boron to the resulting mixture.
- the content of phosphorus and/or boron that are contained in the crystalline aluminosilicate is preferably 0.1 to 5.0% by mass.
- the binder or the like that is mixed with the catalyst an inorganic oxide is used, and as the binder or the like, a material containing phosphorus and/or boron can be used.
- the content of phosphorus and/or boron with respect to the total weight of the catalyst be 0.1 to 10% by mass, and the lower limit thereof be more preferably 0.5% by mass or more.
- the upper limit thereof is more preferably 9% by mass or less, and still more preferably 8% by mass or less.
- the method of producing monocyclic aromatic hydrocarbons according to this embodiment is a method in which feedstock contacts with the above-mentioned catalyst to react with the other.
- the reaction in this embodiment is a method in which acid points of the catalyst and the feedstock are brought into contact with each other, and through various reactions including decomposition, dehydrogenation, cyclization, hydrogen transfer, and the like, the polycyclic aromatic hydrocarbons are cleaved and are converted into monocyclic aromatic hydrocarbons having a carbon number of 6 to 8.
- the acid points are points which are, on a catalyst support, capable of releasing protons or capable of accepting electrons, and which are active points exhibiting acidity.
- the feedstock that is used in this embodiment is oil in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
- BTX Benzene, Toluene, and Xylene
- the yield of the monocyclic aromatic hydrocarbons is low and an amount of deposited coke on the catalyst increases, such that there is a tendency for activity of the catalyst to rapidly decrease.
- the 10 vol % distillation temperature of the feedstock be 150° C. or higher and the 90 vol % distillation temperature of the feedstock be 380° C. or lower.
- vol % distillation temperature and the 90 vol % distillation temperature described here represent values that are measured in accordance with JIS K2254 “Petroleum Products-Distillation Test Method”
- the feedstock in which the 10 vol % distillation temperature is 140° C. or higher and the 90 vol % distillation temperature is 380° C. or lower for example, LCO produced by a fluid catalytic cracking unit, coal liquefaction oil, hydrocracked refined oil from heavy oil, straight-run kerosene, straight-run light oil, coker kerosene, coker light oil, and hydrocracked refined oil from oil sands may be exemplified.
- the content of polycyclic aromatic hydrocarbons (the polycyclic aromatic content) in the feedstock is preferably 50% by volume or less, and more preferably 30% by volume or less.
- polycyclic aromatic content described here represents the total value of the content of bicyclic aromatic hydrocarbons (the bicyclic aromatic content) and the content of tricyclic or higher aromatic hydrocarbons (the tricyclic or higher aromatic content) measured in accordance with JPI-5 S-49 “Petroleum Products—Determination of Hydrocarbon Types—High Performance Liquid Chromatography”.
- Examples of the reaction format used for bringing the feedstock into contact with the catalyst for reaction include a fixed bed, a moving bed and a fluidized bed.
- the fluidized bed is preferable as it enables the coke fraction adhered to the catalyst to be removed in a continuous manner and enables the reaction to proceed in a stable manner.
- a continuous regeneration-type fluidized bed in which the catalyst is circulated between a reactor and a regenerator, and thus a reaction-regeneration cycle is continuously repeated, is more preferable.
- the feedstock when being brought into contact with the catalyst is preferably in a gaseous state.
- the raw material is preferably diluted with a gas as necessary. Furthermore, in a case where unreacted raw material occurs, this may be recycled as necessary.
- reaction temperature is preferably 350 to 700° C.
- the lower limit is more preferably 450° C. or higher.
- the upper limit temperature of 650° C. or lower is preferable as it is not only more advantageous from an energy perspective, but also enables easy regeneration of the catalyst.
- the reaction pressure during contact of the feedstock with the catalyst for reaction is preferably 1.0 MPaG or lower.
- the reaction pressure is 1.0 MPaG or lower, the generation of by-product light gases may be prevented, and the pressure resistance required for a reaction device may be lowered.
- the contact time between the feedstock and the catalyst there are no particular limitations on the contact time between the feedstock and the catalyst as long as a desired reaction actually proceeds, but in terms of the gas transit time across the catalyst, a time of 1 to 300 seconds is preferable.
- the lower limit for this time is more preferably 5 seconds or more, and the upper limit is more preferably 60 seconds or less.
- the contact time is 1 second or more, reliable reaction is achieved, and when the contact time is 300 seconds or less, deposition of carbonaceous matter on the catalyst due to coking or the like is suppressed. Furthermore, the amount of light gas generated by cracking may also be suppressed.
- the polycyclic aromatic hydrocarbons are cleaved and monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 are obtained.
- the yield of monocyclic aromatic hydrocarbons is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. It is not preferable that the yield of monocyclic aromatic hydrocarbons is lower than 25% by mass, because the low concentration of the desired products in a reaction mixture causes low recovery efficiency.
- the solution (B) was added gradually to the solution (A) while the solution (A) was continuously stirred at room temperature.
- the resultant mixture was stirred vigorously for 15 minutes using a mixer, thereby breaking up the gel and forming a uniform fine milky state.
- this mixture was placed in a stainless steel autoclave, and a crystallization operation was performed under conditions including a temperature of 165° C., a reaction time of 72 hours, a stirring rate of 100 rpm, and under self-generated pressure.
- the resultant product was filtered, the solid product was recovered, and the washing and filtering of the solid product was repeated 5 times using approximately 5 liters of deionized water.
- the solid material obtained by the filtering was dried at 120° C., and was then baked under a stream of air at a high temperature of 550° C. for 3 hours.
- a 30% by mass aqueous solution of ammonium nitrate was added to the obtained baked product in a ratio of 5 mL of the aqueous solution per 1 g of the baked product, the resultant mixture was heated at 100° C. while being stirred for 2 hours, and then the mixture was filtered and washed with water. This operation was repeated 4 times, and then the product was dried for 3 hours at 120° C., thereby obtaining an ammonium-type MFI zeolite. Subsequently, the product was baked for 3 hours at 780° C., thereby obtaining a proton-type MFI zeolite.
- BEA-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.
- silicic acid SiO 2 : 89% by mass
- tetraethylammonium hydroxide aqueous solution 40% by mass
- This solution was added to a second solution that was prepared by solving 0.74 g of Al-pellets and 2.69 g of sodium hydroxide in 17.7 g of water.
- reaction mixture having a composition (in terms of molar ratio of oxides) of 2.4 Na 2 O-20.0 (TEA) 2 -Al 2 O 3 -64.0SiO 2 -612H 2 O.
- This reaction mixture was placed in a 0.3 L autoclave, and was heated at 150° C. for 6 days.
- the obtained product was separated from the mother liquid and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, BEA-type zeolite was confirmed from XRD patterns.
- the BEA-type zeolite was baked at 550° C. for 3 hours, whereby proton-type BEA zeolite was obtained.
- FAU-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.
- the FAU-type zeolite was baked at 550° C. for 3 hours, whereby proton-type FAU zeolite was obtained. Then, this FAU-type zeolite was treated under vapor at a temperature of 650° C. to stabilize this zeolite, whereby stabilized proton-type FAU zeolite (USY zeolite) was prepared.
- MOR-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.
- the MOR-type zeolite was baked at 550° C. for 3 hours, whereby proton-type MOR zeolite was obtained. Then, this MOR zeolite was treated under vapor at a temperature of 650° C. to stabilize this zeolite, whereby stabilized proton-type MOR zeolite was prepared.
- a mixture in which 49 g of the proton-type MFI zeolite, and 1 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 1 was obtained.
- Feedstock having properties shown in Table 1 and the catalyst were made to come into contact and react with each other under conditions of a reaction temperature of 550° C. and a reaction pressure of 0 MPaG by using a flow type reaction device in which 10 ml of the Catalyst 1 was filled in a reactor thereof. At this time, nitrogen as a diluting agent was introduced in order for the contact time between the feedstock and the catalyst to be 6.4 seconds. Under this condition, reaction was carried out for 30 minutes, and thereby monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 were prepared.
- composition analysis of the product was performed by an FID gas chromatography instrument that was directly connected to the reaction device and the yield of the monocyclic aromatic hydrocarbon having a carbon number of 6 to 8 was measured. From this measurement, 42% by mass was confirmed. A measurement result is shown in Table 2.
- a mixture in which 45 g of the proton-type MFI zeolite, and 5 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 2 was obtained.
- a mixture in which 35 g of the proton-type MFI zeolite, and 15 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 3 was obtained.
- a mixture in which 25 g of the proton-type MFI zeolite, and 25 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 4 was obtained.
- the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured in the same way as Examples 2 to 4 except that the reaction temperature in Examples 2 to 4 was changed to 500° C. From the measurement, 45% by mass in Example 5, 43% by mass in Example 6, and 37% by mass in Example 7 were confirmed, respectively. A measurement result is shown in Table 2.
- This gallium-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 6 was obtained.
- This zinc-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 7 was obtained.
- Example 9 Catalyst Catalyst 6 Catalyst 7 BEA zeolite/MFI zeolite (mass ratio) 30/70 30/70 Kinds of supporting metal Gallium Zinc Content of gallium or zinc (% by mass) 0.4 0.4 Yield of monocyclic aromatic 44 44 hydrocarbons (% by mass)
- the Catalyst 3 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 3 that was hydrothermally degraded in a pseudo manner.
- the feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 3 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation.
- the pseudo-degraded Catalyst 3 18% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed.
- An evaluation result is shown in Table 4.
- This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 8 was obtained.
- the Catalyst 8 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 8 that was hydrothermally degraded in a pseudo manner.
- the feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 8 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation.
- the pseudo-degraded Catalyst 8 32% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- a mixture in which 35 g of the proton-type MFI zeolite, and 15 g of the stabilized proton-type FAU zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 9 was obtained.
- the Catalyst 9 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 9 that was hydrothermally degraded in a pseudo manner.
- the feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 9 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation.
- the pseudo-degraded Catalyst 9 15% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 10 was obtained.
- the Catalyst 10 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 10 that was hydrothermally degraded in a pseudo manner.
- the feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 10 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation.
- the pseudo-degraded Catalyst 10 32% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- a mixture in which 35 g of the proton-type MFI zeolite, and 15 g of the stabilized proton-type MOR zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 11 was obtained.
- the Catalyst 11 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 11 that was hydrothermally degraded in a pseudo manner.
- the feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 11 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation.
- the pseudo-degraded Catalyst 11 16% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed.
- An evaluation result is shown in Table 4.
- This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 M Pa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 12 was obtained.
- the Catalyst 12 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 12 that was hydrothermally degraded in a pseudo manner.
- the feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 12 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation.
- the pseudo-degraded Catalyst 12 32% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- Example 11 Example 12
- Example 13 Example 14
- Example 15 Catalyst Pseudo- Pseudo- Pseudo- Pseudo- Pseudo- Pseudo- degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded degraded de
- monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 may be produced with high efficiency from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
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Abstract
A catalyst is provided for production of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower. The catalyst contains crystalline aluminosilicate including large-pore zeolite having a 12-membered ring structure, and intermediate-pore zeolite having a 10-membered ring structure.
Description
- The present invention relates to a catalyst for producing monocyclic aromatic hydrocarbons and a method of producing monocyclic aromatic hydrocarbons, which are capable of producing monocyclic aromatic hydrocarbons from oil containing a large amount of polycyclic aromatic hydrocarbons.
- Priority is claimed on Japanese Patent Application No. 2010-010262, filed Jan. 20, 2010, the content of which is incorporated herein by reference.
- Light cycle oil (hereinafter, referred to as “LCO”), which is cracked light oil produced by a fluidized catalytic cracking, contains a large amount of polycyclic aromatic hydrocarbons, and has been used as light oil or heavy oil. However, in recent years, investigations have been conducted to obtain, from LCO, monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 (such as benzene, toluene, xylene and ethylbenzene), which may be used as high-octane gasoline base materials or petrochemical raw materials, and offer significant added value.
- For example, Patent Document 1 to Patent Document 3 disclose methods of producing monocyclic aromatic hydrocarbons from polycyclic aromatic hydrocarbons contained in large amounts within LCO and the like by using zeolite catalysts.
- In addition, as a method of producing monocyclic aromatic hydrocarbons through reaction using zeolite catalysts, Patent Document 4 discloses a method of producing monocyclic aromatic hydrocarbons from aromatic compounds having a carbon number of 9 or more by using beta-type zeolite, which has a 12-membered ring structure and a large pore size, as a catalyst.
- Patent Document 5 discloses a method of producing monocyclic aromatic hydrocarbons from paraffin-based hydrocarbons having a carbon number of 2 to 12 by using beta-type zeolite as a catalyst.
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- [Patent Document 1] Japanese Unexamined Patent Application, First publication No. H3-2128
- [Patent Document 2] Japanese Unexamined Patent Application, First publication No. H3-52993
- [Patent Document 3] Japanese Unexamined Patent Application, First publication No. H3-26791
- [Patent Document 4] Published Japanese Translation No. H4-504577 of the PCT International Publication
- [Patent Document 5] Japanese Unexamined Patent Application, First publication No. H2-184517
- However, in the methods disclosed in Patent Document 1 to Patent Document 3, the yields of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 have not been entirely satisfactory. In addition, the methods disclosed in Patent Document 4 and Patent Document 5 are not methods of obtaining both monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and aliphatic hydrocarbons having a carbon number of 3 to 4 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
- An object of the invention is to provide a catalyst for production of monocyclic aromatic hydrocarbons and a method of producing monocyclic aromatic hydrocarbons, which are capable of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 from feedstock containing polycyclic aromatic hydrocarbons with high yield.
- (1) According to an embodiment of the invention, a catalyst is provided for production of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower. The catalyst contains crystalline aluminosilicate including large-pore zeolite having a 12-membered ring structure, and intermediate-pore zeolite having 10-membered ring structure.
- (2) The catalyst for production of monocyclic aromatic hydrocarbons according to (1), wherein in the crystalline aluminosilicate, a mass ratio of the large-pore zeolite to the intermediate-pore zeolite (large-pore zeolite/intermediate-pore zeolite) is preferably 2/98 to 50/50
- (3) The catalyst for production of monocyclic aromatic hydrocarbons according to (1) or (2), wherein the large-pore zeolite is preferably a zeolite of any type selected from a BEA type, an FAU type, and an MOR type.
- (4) The catalyst for production of monocyclic aromatic hydrocarbons according to any one of (1) to (3), wherein the large-pore zeolite is preferably BEA-type zeolite.
- (5) The catalyst for production of monocyclic aromatic hydrocarbons according to any one of (1) to (4), wherein the intermediate-pore zeolite is preferably MFI-type zeolite.
- (6) The catalyst for production of monocyclic aromatic hydrocarbons according to any one of (1) to (5), wherein the catalyst preferably further contain phosphorus.
- (7) According to another embodiment of the invention, a method is provided of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8. The method includes bringing feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower into contact with the catalyst for production of monocyclic aromatic hydrocarbons according to any one of (1) to (6).
- (8) The method of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 according to (7), wherein as the feedstock, light cycle oil produced by a fluidized catalytic cracking is preferably used.
- (9) The method of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 according to (7) or (8), wherein the feedstock is preferably brought into contact with the catalyst for production of monocyclic aromatic hydrocarbons in a fluidized bed reaction unit.
- According to the catalyst for production of monocyclic aromatic hydrocarbons and the method of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8, monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is preferably produced with high yield from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
- The catalyst for production of monocyclic aromatic hydrocarbons according to this embodiment (hereinafter, abbreviated as “catalyst”) is used for producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 (hereinafter, abbreviated as “monocyclic aromatic hydrocarbons”) from feedstock containing polycyclic aromatic hydrocarbons and saturated hydrocarbons, and contains crystalline aluminosilicate.
- (Crystalline Aluminosilicate)
- In this embodiment, the crystalline aluminosilicate contains large-pore zeolite having a 12-membered ring structure, and intermediate-pore zeolite having a 10-membered ring structure.
- As the large-pore zeolite having a 12-membered ring structure, for example, zeolites having a framework type of an AFI type, an ATO type, a BEA type, a CON type, an FAU type, a GME type, an LTL type, an MOR type, an MTW type, and an OFF type is preferably exemplified. Among these, the BEA type, the FAU type, and the MOR type are preferable from an industrially usable aspect, and the BEA type is more preferable because the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is relatively raised.
- As the intermediate-pore zeolite having a 10-membered ring structure, for example, zeolites having a framework type of an AEL type, an EUO type, an FER type, an HEU type, an MEL type, an MFI type, an NES type, a TON type, and a WEI type is preferably exemplified. Among these, the MFI type is preferable because the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is relatively raised.
- In addition, all of the framework type types of the zeolite, which are exemplified in this embodiment, are structure codes based on the definition of the International Zeolite Association.
- In addition to the large-pore zeolite, the crystalline aluminosilicate may contain small-pore zeolite having a structure of a 10-membered ring or less, and ultra-large-pore zeolite having a structure of a 14-membered ring or more.
- Here, as the small-pore zeolite, for example, zeolites having a framework type of an ANA type, a CHA type, an ERI type, a GIS type, a KFI type, an LTA type, an NAT type, a PAU type, and a YUG type is preferably exemplified.
- As the ultra-large-pore zeolite, for example, zeolites having a framework type of a CLO type, and a VPI type is preferably exemplified.
- In a case where the catalyst is used as a catalyst for a fixed bed, the content of the crystalline aluminosilicate is preferably 60 to 100% by mass on the basis of 100% by mass of the entirety of the catalyst, and more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass. When the content of the crystalline aluminosilicate is 60% by mass or more, the total yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 is sufficiently raised.
- In a case where the catalyst is used as a catalyst for a fluidized bed, the content of the crystalline aluminosilicate is preferably 20 to 60% by mass on the basis of 100% by mass of the entirety of the catalyst, and more preferably 30 to 60% by mass, and still more preferably 35 to 60% by mass. When the content of the crystalline aluminosilicate is 20% by mass or more, the total yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbons having a carbon number of 3 to 4 is sufficiently raised. When the content of the crystalline aluminosilicate exceeds 60% by mass, the content of a binder that may be mixed with the catalyst becomes small, and thus may be not appropriate as the catalyst for the fluidized bed.
- In the crystalline aluminosilicate, a mass ratio of the large-pore zeolite to the intermediate-pore zeolite (large-pore zeolite/intermediate-pore zeolite) is preferably 2/98 to 50/50, more preferably 5/95 to 50/50, still more preferably 10/90 to 30/70. When the mass ratio is 2/98 or more, an effect of using the large-pore zeolite is sufficiently exhibited, and thus the yield of the monocyclic aromatic hydrocarbons is sufficiently raised. When the mass ratio is 50/50 or less, coking of the feedstock is prevented, and thus the yield of the monocyclic aromatic hydrocarbons is sufficiently raised.
- (Other Components)
- The catalyst may contain gallium and/or zinc as necessary. When gallium and/or zinc are contained, a generation ratio of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 tends to be increased.
- As a method used to incorporate gallium into the catalyst, a type in which gallium is incorporated in a lattice framework of the crystalline aluminosilicate (crystalline aluminogallosilicate), a type in which gallium is carried by the crystalline aluminosilicate (gallium-supporting crystalline aluminosilicate), and a type including both of these types is exemplified.
- As a method used to incorporate zinc into the catalyst, a type in which zinc is incorporated in a lattice framework of the crystalline aluminosilicate (crystalline aluminozincosilicate), a type in which zinc is carried by the crystalline aluminosilicate (zinc-supporting crystalline aluminosilicate), and a type including both of these types is exemplified.
- The crystalline aluminogallosilicate and the crystalline aluminozincosilicate have a structure in which SiO4, AlO4, and GaO4/ZnO4 structures have a tetrahedral coordination in a framework. In addition, the crystalline aluminogallosilicate and the crystalline aluminozincosilicate may be obtained, for example, by gel crystallization through hydrothermal synthesis, by a method in which gallium or zinc is inserted into the lattice framework of the crystalline aluminosilicate, or by a method in which aluminum is inserted into the lattice framework of crystalline gallosilicate or crystalline zincosilicate.
- The gallium-supporting crystalline aluminosilicate may be obtained by supporting gallium on a crystalline aluminosilicate using a conventional method such as an ion-exchange method or impregnation method. There are no particular limitations on the gallium source used in these methods, and examples include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
- The zinc-supporting crystalline aluminosilicate may be obtained by supporting zinc on a crystalline aluminosilicate using a known method such as an ion-exchange method or impregnation method. There are no particular limitations on the zinc source used in these methods, and examples include zinc salts such as zinc nitrate and zinc chloride, and zinc oxide.
- In a case where the catalyst contains gallium and/or zinc, the lower limit of the content of gallium and/or zinc is preferably 0.01% by mass or more on the basis of 100% by mass of the total mass of the crystalline aluminosilicate, and more preferably 0.05% by mass or more. On the other hand, the upper limit thereof is preferably 5.0% by mass or less, and more preferably 1.5% by mass or less. When the content of gallium and/or zinc is 0.01% by mass or more, a generation ratio of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is relatively raised. When the content thereof exceeds 5.0% by mass, a generated amount of coke is increased, and thus the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is lowered. Therefore, this case is not preferable.
- The catalyst may contain phosphorus and/or boron as necessary. When phosphorus and/or boron is contained, a decrease with the passage of time in the total yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 and the aliphatic hydrocarbon having a carbon number of 3 to 4 may be prevented, and the coke may be prevented from being generated on the surface of the catalyst.
- There are no particular limitations on a method of incorporating phosphorus in the catalyst, and examples thereof include a method in which phosphorus is made to be supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminozincosilicate by using an ion-exchange method, impregnation method, or the like, a method in which a phosphorus compound is incorporated during synthesis of the zeolite, and a part in the framework of the crystalline aluminosilicate is substituted with phosphorus, a method in which a crystallization promoter containing phosphorus is used during synthesis of the zeolite, and the like. Although there are no particular limitations on a phosphate ion-containing aqueous solution used at that time, a solution, which is prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, or another water-soluble phosphate salt in water at an arbitrary concentration, is preferably used.
- There are no particular limitations on a method of incorporating boron in the catalyst, and examples thereof include a method in which boron is made to be supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminozincosilicate by using an ion-exchange method, impregnation method, or the like, a method in which a boron compound is incorporated during synthesis of the zeolite, and a part in the framework of the crystalline aluminosilicate is substituted with boron, a method in which a crystallization promoter containing boron is used during synthesis of the zeolite, and the like.
- In a case where the catalyst contains phosphorus and/or boron, the lower limit of the content of phosphorus and/or boron is preferably 0.1% by mass or more on the basis of 100% by mass of the total mass of the crystalline aluminosilicate, and more preferably 0.2% by mass or more. On the other hand, the upper limit thereof is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less. When the content of phosphorus and/or boron is 0.1% by mass or more, a decrease with the passage of time in the yield is further prevented. When the content thereof exceeds 5.0% by mass, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 is lowered, and thus this is not preferable.
- (Form)
- The catalyst has a powder form, a granular form, or a pellet form, or the like depending on a reaction format. For example, in the case of a fluidized bed, the catalyst has the powder form, whereas in the case of a fixed bed, the catalyst has the granular form or the pellet form.
- In the case of obtaining the catalyst having the granular form or the pellet form, an oxide inactive to the catalyst is mixed with the catalyst as a binder as necessary, and then the resultant mixture is molded with various types of molding machine.
- In a case where the catalyst of this embodiment contains a binder or the like, the binder containing phosphorus and/or boron can be used. At this time, in the catalyst, the content of phosphorus and/or boron that are contained in the crystalline aluminosilicate (% by mass of phosphorus and/or boron on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) is preferably 0.1 to 5.0% by mass. An amount of phosphorus and/or boron that are contained in the crystalline aluminosilicate represents an amount of phosphorus and/or boron that act on the crystalline aluminosilicate.
- In addition, in a case where the catalyst contains a binder or the like, the catalyst is produced by mixing the binder or the like, and gallium and/or zinc supporting crystalline aluminosilicate or crystalline aluminogallosilicate and/or crystalline aluminozincosilicate, and then adding phosphorus and/or boron to the resulting mixture. At this time, in the catalyst, the content of phosphorus and/or boron that are contained in the crystalline aluminosilicate (% by mass of phosphorus and/or boron on the basis of 100% by mass of the total mass of the crystalline aluminosilicate) is preferably 0.1 to 5.0% by mass.
- As the binder or the like that is mixed with the catalyst, an inorganic oxide is used, and as the binder or the like, a material containing phosphorus and/or boron can be used. By also considering the amount of phosphorus and/or boron that act on the crystalline aluminosilicate in the case of using the binder or the like that contains phosphorus and/or boron, it is preferable that the content of phosphorus and/or boron with respect to the total weight of the catalyst be 0.1 to 10% by mass, and the lower limit thereof be more preferably 0.5% by mass or more. The upper limit thereof is more preferably 9% by mass or less, and still more preferably 8% by mass or less. When the content of phosphorus and/or boron with respect to the total weight of the catalyst is 0.1% by mass or more, a decrease in the yield, over time, of the monocyclic aromatic hydrocarbon is prevented, and when the content is 10% by mass or less, the yield of the monocyclic aromatic hydrocarbon is raised.
- (Method of Producing Monocyclic Aromatic Hydrocarbons)
- The method of producing monocyclic aromatic hydrocarbons according to this embodiment is a method in which feedstock contacts with the above-mentioned catalyst to react with the other.
- The reaction in this embodiment is a method in which acid points of the catalyst and the feedstock are brought into contact with each other, and through various reactions including decomposition, dehydrogenation, cyclization, hydrogen transfer, and the like, the polycyclic aromatic hydrocarbons are cleaved and are converted into monocyclic aromatic hydrocarbons having a carbon number of 6 to 8.
- Here, the acid points are points which are, on a catalyst support, capable of releasing protons or capable of accepting electrons, and which are active points exhibiting acidity.
- (Feedstock)
- The feedstock that is used in this embodiment is oil in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower. In the oil in which the 10 vol % distillation temperature is lower than 140° C., BTX (Benzene, Toluene, and Xylene) is produced from light oil, and thus this does not match with the gist of this embodiment. In addition, in the case of using oil in which the 90 vol % distillation temperature is higher than 380° C., the yield of the monocyclic aromatic hydrocarbons is low and an amount of deposited coke on the catalyst increases, such that there is a tendency for activity of the catalyst to rapidly decrease.
- It is preferable that the 10 vol % distillation temperature of the feedstock be 150° C. or higher and the 90 vol % distillation temperature of the feedstock be 380° C. or lower.
- In addition, the 10 vol % distillation temperature and the 90 vol % distillation temperature described here represent values that are measured in accordance with JIS K2254 “Petroleum Products-Distillation Test Method”
- As the feedstock in which the 10 vol % distillation temperature is 140° C. or higher and the 90 vol % distillation temperature is 380° C. or lower, for example, LCO produced by a fluid catalytic cracking unit, coal liquefaction oil, hydrocracked refined oil from heavy oil, straight-run kerosene, straight-run light oil, coker kerosene, coker light oil, and hydrocracked refined oil from oil sands may be exemplified.
- In addition, when the feedstock contains a large amount of polycyclic aromatic hydrocarbons, the yield of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 tends to decrease, and therefore the content of polycyclic aromatic hydrocarbons (the polycyclic aromatic content) in the feedstock is preferably 50% by volume or less, and more preferably 30% by volume or less.
- In addition, the polycyclic aromatic content described here represents the total value of the content of bicyclic aromatic hydrocarbons (the bicyclic aromatic content) and the content of tricyclic or higher aromatic hydrocarbons (the tricyclic or higher aromatic content) measured in accordance with JPI-5 S-49 “Petroleum Products—Determination of Hydrocarbon Types—High Performance Liquid Chromatography”.
- (Reaction Format)
- Examples of the reaction format used for bringing the feedstock into contact with the catalyst for reaction include a fixed bed, a moving bed and a fluidized bed. In this embodiment, since a heavy oil fraction is used as the raw material, the fluidized bed is preferable as it enables the coke fraction adhered to the catalyst to be removed in a continuous manner and enables the reaction to proceed in a stable manner. A continuous regeneration-type fluidized bed, in which the catalyst is circulated between a reactor and a regenerator, and thus a reaction-regeneration cycle is continuously repeated, is more preferable. The feedstock when being brought into contact with the catalyst is preferably in a gaseous state. Furthermore, the raw material is preferably diluted with a gas as necessary. Furthermore, in a case where unreacted raw material occurs, this may be recycled as necessary.
- (Reaction Temperature)
- Although there are no particular limitations on the reaction temperature during contact of the feedstock with the catalyst for reaction, a reaction temperature is preferably 350 to 700° C. In terms of achieving satisfactory reaction activity, the lower limit is more preferably 450° C. or higher. On the other hand, the upper limit temperature of 650° C. or lower is preferable as it is not only more advantageous from an energy perspective, but also enables easy regeneration of the catalyst.
- (Reaction Pressure)
- The reaction pressure during contact of the feedstock with the catalyst for reaction is preferably 1.0 MPaG or lower. When the reaction pressure is 1.0 MPaG or lower, the generation of by-product light gases may be prevented, and the pressure resistance required for a reaction device may be lowered.
- (Contact Time)
- There are no particular limitations on the contact time between the feedstock and the catalyst as long as a desired reaction actually proceeds, but in terms of the gas transit time across the catalyst, a time of 1 to 300 seconds is preferable. The lower limit for this time is more preferably 5 seconds or more, and the upper limit is more preferably 60 seconds or less. When the contact time is 1 second or more, reliable reaction is achieved, and when the contact time is 300 seconds or less, deposition of carbonaceous matter on the catalyst due to coking or the like is suppressed. Furthermore, the amount of light gas generated by cracking may also be suppressed.
- In the method of producing the monocyclic aromatic hydrocarbons according to this reaction, by contacting the feedstock with acid points of the catalyst, and through various reactions including decomposition, dehydrogenation, cyclization, hydrogen transfer, and the like, the polycyclic aromatic hydrocarbons are cleaved and monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 are obtained.
- In this embodiment, the yield of monocyclic aromatic hydrocarbons is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. It is not preferable that the yield of monocyclic aromatic hydrocarbons is lower than 25% by mass, because the low concentration of the desired products in a reaction mixture causes low recovery efficiency.
- Hereinafter, the embodiment will be described in detail on the basis of examples and comparative examples, but this embodiment is not limited to these examples.
- (Preparation of Proton-Type MFI Zeolite)
- A solution (A) composed of 1706.1 g of sodium silicate (J Sodium Silicate No. 3, SiO2: 28 to 30% by mass, Na: 9 to 10% by mass, remainder is water; manufactured by Nippon Chemical Industrial Co., Ltd.) and 2227.5 g of water, and a solution (B) composed of 64.2 g of Al2(SO4)3.14 to 18H2O (special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.), 369.2 g of tetrapropylammonium bromide, 152.1 g of H2SO4 (97% by mass), 326.6 g of NaCl, and 2975.7 g of water were prepared independently.
- Subsequently, the solution (B) was added gradually to the solution (A) while the solution (A) was continuously stirred at room temperature. The resultant mixture was stirred vigorously for 15 minutes using a mixer, thereby breaking up the gel and forming a uniform fine milky state.
- Then, this mixture was placed in a stainless steel autoclave, and a crystallization operation was performed under conditions including a temperature of 165° C., a reaction time of 72 hours, a stirring rate of 100 rpm, and under self-generated pressure. After the crystallization operation was completed, the resultant product was filtered, the solid product was recovered, and the washing and filtering of the solid product was repeated 5 times using approximately 5 liters of deionized water. The solid material obtained by the filtering was dried at 120° C., and was then baked under a stream of air at a high temperature of 550° C. for 3 hours.
- From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the resultant baked product, it was confirmed that the product had a MEI structure. Furthermore, from fluorescent X-ray analysis (apparatus model: Rigaku ZSX101e), it was revealed that a SiO2/Al2O3 ratio (molar ratio) was 64.8. In addition, based on these results, the amount of aluminum element incorporated in the lattice framework was calculated as 1.32% by mass.
- A 30% by mass aqueous solution of ammonium nitrate was added to the obtained baked product in a ratio of 5 mL of the aqueous solution per 1 g of the baked product, the resultant mixture was heated at 100° C. while being stirred for 2 hours, and then the mixture was filtered and washed with water. This operation was repeated 4 times, and then the product was dried for 3 hours at 120° C., thereby obtaining an ammonium-type MFI zeolite. Subsequently, the product was baked for 3 hours at 780° C., thereby obtaining a proton-type MFI zeolite.
- (Preparation of BEA-Type Zeolite)
- BEA-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.
- 59.1 g of a silicic acid (SiO2: 89% by mass) was dissolved in 202 g of tetraethylammonium hydroxide aqueous solution (40% by mass) to prepare a first solution. This solution was added to a second solution that was prepared by solving 0.74 g of Al-pellets and 2.69 g of sodium hydroxide in 17.7 g of water.
- The two solutions were mixed, thereby obtaining a reaction mixture having a composition (in terms of molar ratio of oxides) of 2.4 Na2O-20.0 (TEA)2-Al2O3-64.0SiO2-612H2O. This reaction mixture was placed in a 0.3 L autoclave, and was heated at 150° C. for 6 days. The obtained product was separated from the mother liquid and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, BEA-type zeolite was confirmed from XRD patterns.
- Then, after being subjected to ion-exchange using ammonium nitrate aqueous solution (30% by mass), the BEA-type zeolite was baked at 550° C. for 3 hours, whereby proton-type BEA zeolite was obtained.
- (Preparation of FAU-Type Zeolite)
- FAU-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.
- 3 g of sodium aluminate containing 30.0% by mass of Na2O, 44.1% by mass of Al2O3, and 25.9% by mass of H2O, and 16.4 g of sodium hydroxide containing 77.5% by mass of Na2O were dissolved in 131 ml of deionized water. This resultant solution was added to 74.5 g of aqueous colloidal silica sol containing 29.5% by mass of silica, and these two solutions were mixed, thereby obtaining a reaction mixture having a composition (in terms of molar ratio of oxides) of 16.9 Na2O—Al2O3-28.2SiO2-808H2O. This mixture was mixed and stirred until it reached a uniform state, and this reaction mixture was placed in a 0.3 L autoclave, and was heated at 120° C. for 3 hours. The obtained product was separated from the mother liquid and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, FAU-type zeolite (Y-type zeolite) was confirmed from XRD patterns.
- Then, after being subjected to ion-exchange using ammonium nitrate aqueous solution (30% by mass), the FAU-type zeolite was baked at 550° C. for 3 hours, whereby proton-type FAU zeolite was obtained. Then, this FAU-type zeolite was treated under vapor at a temperature of 650° C. to stabilize this zeolite, whereby stabilized proton-type FAU zeolite (USY zeolite) was prepared.
- (Preparation of MOR-Type Zeolite)
- MOR-type zeolite was prepared as described below according to a hydrothermal synthesis method in the related art.
- 2.7 g of sodium aluminate containing 30.0% by mass of Na2O, 44.1% by mass of Al2O3, and 25.9% by mass of H2O, and 6.3 g of sodium hydroxide were dissolved in 200 ml of deionized water. This resultant solution was added to 241 cc of aqueous colloidal silica sol containing 27.8% by mass of silica, thereby obtaining a reaction mixture having a composition (in terms of molar ratio of oxides) of 1.9 Na2O—Al2O3-13SiO2. This mixture was mixed and stirred until it reached a uniform state, and this reaction mixture was placed in a 0.3 L autoclave, and was heated at 150° C. for 8 hours. The obtained product was separated from the mother liquid and the separated product was cleaned with distilled water. From a result of X-ray diffraction analysis (apparatus model: Rigaku RINT-2500V) on the product, MOR-type zeolite was confirmed from XRD patterns.
- Then, after being subjected to ion-exchange using ammonium nitrate aqueous solution (30% by mass), the MOR-type zeolite was baked at 550° C. for 3 hours, whereby proton-type MOR zeolite was obtained. Then, this MOR zeolite was treated under vapor at a temperature of 650° C. to stabilize this zeolite, whereby stabilized proton-type MOR zeolite was prepared.
- A mixture in which 49 g of the proton-type MFI zeolite, and 1 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 1 was obtained.
- Feedstock having properties shown in Table 1 and the catalyst were made to come into contact and react with each other under conditions of a reaction temperature of 550° C. and a reaction pressure of 0 MPaG by using a flow type reaction device in which 10 ml of the Catalyst 1 was filled in a reactor thereof. At this time, nitrogen as a diluting agent was introduced in order for the contact time between the feedstock and the catalyst to be 6.4 seconds. Under this condition, reaction was carried out for 30 minutes, and thereby monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 were prepared. Then, composition analysis of the product was performed by an FID gas chromatography instrument that was directly connected to the reaction device and the yield of the monocyclic aromatic hydrocarbon having a carbon number of 6 to 8 was measured. From this measurement, 42% by mass was confirmed. A measurement result is shown in Table 2.
-
TABLE 1 Analysis Properties of raw material method Density (@15° C.) g/cm3 0.906 JIS K 2249 Kinetic viscosity(@30° C.) mm2/s 3.640 JIS K 2283 Distillation Initial distillation ° C. 175.5 JIS K 2254 properties point 10 vol % distillation ° C. 224.5 temperature 50 vol % distillation ° C. 274.0 temperature 90 vol % distillation ° C. 349.5 temperature End point ° C. 376.0 Compositional Saturated % by volume 35 JPI-5S-49 analysis portion Olefin portion % by volume 8 Total aromatic % by volume 57 portion Monocyclic % by volume 23 aromatic portion Bicyclic % by volume 25 aromatic portion Tricyclic % by volume 9 aromatic portion - A mixture in which 45 g of the proton-type MFI zeolite, and 5 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 2 was obtained.
- In addition, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured by using the Catalyst 2 in place of the Catalyst 1 in Example 1. From the measurement, 45% by mass was confirmed. A measurement result is shown in Table 2.
- A mixture in which 35 g of the proton-type MFI zeolite, and 15 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 3 was obtained.
- In addition, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured by using the Catalyst 3 in place of the Catalyst 1 in Example 1. From the measurement, 43% by mass was confirmed. A measurement result is shown in Table 2.
- A mixture in which 25 g of the proton-type MFI zeolite, and 25 g of the proton-type BEA zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 4 was obtained.
- In addition, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured by using the Catalyst 4 in place of the Catalyst 1 in Example 1. From the measurement, 36% by mass was confirmed. A measurement result is shown in Table 2.
- The yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured in the same way as Examples 2 to 4 except that the reaction temperature in Examples 2 to 4 was changed to 500° C. From the measurement, 45% by mass in Example 5, 43% by mass in Example 6, and 37% by mass in Example 7 were confirmed, respectively. A measurement result is shown in Table 2.
- 50 g of the proton-type BEA zeolite was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 5 was obtained.
- In addition, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured by using the Catalyst 5 in place of the Catalyst 1 in Example 1. From the measurement, 21% by mass was confirmed. A measurement result is shown in Table 2.
-
TABLE 2 Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 1 Catalyst Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4 Catalyst 2 Catalyst 3 Catalyst 4 Catalyst 5 BEA zeolite/MFI 2/98 10/90 30/70 50/50 10/90 30/70 50/50 100/0 zeolite (mass ratio) Reaction 550 500 550 temperature (° C.) Yield of monocyclic 42 45 43 36 45 43 37 21 hydrocarbons (% by mass) - (Results)
- In Examples 1 to 7 using the catalysts 1 to 4 containing both of the BEA-type zeolite and the MFI-type zeolite, the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 were obtained with high yield.
- Conversely, in Comparative Example 1 using the Catalyst 5 composed of only the BEA-type zeolite, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was low.
- 30 g of a mixture in which 35 g of the proton-type MFI zeolite and 15 g of the proton-type BEA zeolite were mixed was impregnated with 30 g of gallium nitrate aqueous solution in order for 0.4% by mass (on the basis of 100% by mass of the total mass of the mixture of the proton-type MFI zeolite and the proton-type BEA zeolite) of gallium to be supported, and then the resultant mixture was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby gallium-supporting crystalline aluminosilicate was obtained. This gallium-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 6 was obtained.
- In addition, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured by using the Catalyst 6 in place of the catalyst 1 in Example 1. From the measurement, 44% by mass was confirmed. A measurement result is shown in Table 3.
- 30 g of a mixture in which 35 g of the proton-type MFI zeolite and 15 g of the proton-type BEA zeolite were mixed was impregnated with 30 g of zinc nitrate aqueous solution in order for 0.4% by mass (on the basis of 100% by mass of the total mass of the mixture of the proton-type MFI zeolite and the proton-type BEA zeolite) of zinc to be supported, and then the resultant mixture was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby zinc-supporting crystalline aluminosilicate was obtained. This zinc-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 7 was obtained.
- In addition, the yield of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was measured by using the Catalyst 7 in place of the Catalyst 1 in Example 1. From the measurement, 44% by mass was confirmed. A measurement result is shown in Table 3.
-
TABLE 3 Example 8 Example 9 Catalyst Catalyst 6 Catalyst 7 BEA zeolite/MFI zeolite (mass ratio) 30/70 30/70 Kinds of supporting metal Gallium Zinc Content of gallium or zinc (% by mass) 0.4 0.4 Yield of monocyclic aromatic 44 44 hydrocarbons (% by mass) - (Result)
- In Examples 8 and 9 using the catalysts 6 and 7 in which gallium or zinc was supported on the zeolite in which the BEA-type zeolite and the MFI-type zeolite were mixed, the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 were obtained with high yield.
- The Catalyst 3 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 3 that was hydrothermally degraded in a pseudo manner.
- The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 3 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded Catalyst 3, 18% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- 30 g of a mixture in which 35 g of the proton-type MFI zeolite and 15 g of the proton-type BEA zeolite were mixed was impregnated with 30 g of diammonium hydrogen phosphate aqueous solution in order for 2.0% by mass (on the basis of 100% by mass of the total mass of the mixture of the proton-type WI zeolite and the proton-type BEA zeolite) of phosphorus to be supported, and then the resultant mixture was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby phosphorus-supporting crystalline aluminosilicate was obtained. This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 8 was obtained.
- Then, the Catalyst 8 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 8 that was hydrothermally degraded in a pseudo manner.
- The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 8 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded Catalyst 8, 32% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- A mixture in which 35 g of the proton-type MFI zeolite, and 15 g of the stabilized proton-type FAU zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 9 was obtained.
- Then, the Catalyst 9 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 9 that was hydrothermally degraded in a pseudo manner.
- The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 9 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded Catalyst 9, 15% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- 30 g of a mixture in which 35 g of the proton-type MFI zeolite and 15 g of the stabilized proton-type FAU zeolite were mixed was impregnated with 30 g of diammonium hydrogen phosphate aqueous solution in order for 2.0% by mass (on the basis of 100% by mass of the total mass of the mixture of the proton-type MFI zeolite and the stabilized proton-type FAU zeolite) of phosphorus to be supported, and then the resultant mixture was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby phosphorus-supporting crystalline aluminosilicate was obtained. This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 10 was obtained.
- Then, the Catalyst 10 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 10 that was hydrothermally degraded in a pseudo manner.
- The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 10 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded Catalyst 10, 32% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- A mixture in which 35 g of the proton-type MFI zeolite, and 15 g of the stabilized proton-type MOR zeolite were mixed was tablet-molded while applying a pressure of 39.2 MPa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 11 was obtained.
- Then, the Catalyst 11 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 11 that was hydrothermally degraded in a pseudo manner.
- The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 11 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded Catalyst 11, 16% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- 30 g of a mixture in which 35 g of the proton-type MFI zeolite and 15 g of the stabilized proton-type MOR zeolite were mixed was impregnated with 30 g of phosphoric acid aqueous solution in order for 2.0% by mass (on the basis of 100% by mass of the total mass of the mixture of the proton-type MFI zeolite and the stabilized proton-type MOR zeolite) of phosphorus to be supported, and then the resultant mixture was dried at 120° C. Then, the resultant dried product was baked under a stream of air at a high temperature of 780° C. for 3 hours, whereby phosphorus-supporting crystalline aluminosilicate was obtained. This phosphorus-supporting crystalline aluminosilicate was tablet-molded while applying a pressure of 39.2 M Pa (400 kgf), and then the resultant tablets were coarsely crushed to have a uniform size of 20 to 28 mesh, whereby a granulated Catalyst 12 was obtained.
- Then, the Catalyst 12 was subjected to a hydrothermal treatment under an environment of a treatment temperature of 650° C., a treatment time of 6 hours, and 100% by mass of vapor to obtain a pseudo-degraded Catalyst 12 that was hydrothermally degraded in a pseudo manner.
- The feedstock was subjected to reaction similarly to Example 1 except that the pseudo-degraded Catalyst 12 was used in place of the Catalyst 1, and composition analysis of the obtained product was performed to evaluate the catalyst activity after the hydrothermal degradation. In the case of using the pseudo-degraded Catalyst 12, 32% by mass of the monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 was confirmed. An evaluation result is shown in Table 4.
- (Result)
- Even when the FAU-type zeolite or the MOR-type zeolite was used as the large-pore zeolite, substantially the same effect as the case of using the BEA-type zeolite was obtained.
- Furthermore, when phosphorus was incorporated in the catalyst, monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 were obtained with high yield even after the pseudo-degradation.
-
TABLE 4 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Catalyst Pseudo- Pseudo- Pseudo- Pseudo- Pseudo- Pseudo- degraded degraded degraded degraded degraded degraded catalyst 3 catalyst 8 catalyst 9 catalyst 10 catalyst 11 catalyst 12 Kinds of large-pore BEA BEA FAU FAU MOR MOR zeolite Kinds of intermediate- MFI MFI MFI MFI MFI MFI pore zeolite Large-pore zeolite/ 30/70 30/70 30/70 30/70 30/70 30/70 intermediate-pore zeolite (mass ratio) Content of phosphorus 0 2 0 2 0 2 (% by mass) on the basis of 100% by mass of total mass of crystalline alumino- silicate Yield of monocyclic 18 32 15 32 16 32 aromatic hydrocarbons (% by mass) - According to the catalyst for production of monocyclic aromatic hydrocarbons of the invention, monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 may be produced with high efficiency from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower.
Claims (9)
1. A catalyst for production of monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 from feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower, the catalyst comprising:
crystalline aluminosilicate including large-pore zeolite having a 12-membered ring structure, and intermediate-pore zeolite having a 10-membered ring structure.
2. The catalyst for production of monocyclic aromatic hydrocarbons according to claim 1 ,
wherein in the crystalline aluminosilicate, a mass ratio of the large-pore zeolite to the intermediate-pore zeolite (large-pore zeolite/intermediate-pore zeolite) is 2/98 to 50/50.
3. The catalyst for production of monocyclic aromatic hydrocarbons according to claim 1 ,
wherein the large-pore zeolite is a zeolite of any type selected from a BEA type, an FAU type, and an MOR type.
4. The catalyst for production of monocyclic aromatic hydrocarbons according to claim 1 ,
wherein the large-pore zeolite is BEA-type zeolite.
5. The catalyst for production of monocyclic aromatic hydrocarbons according to claim 1 ,
wherein the intermediate-pore zeolite is MFI-type zeolite.
6. The catalyst for production of monocyclic aromatic hydrocarbons according to claim 1 , further comprising:
phosphorus.
7. A method of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8, the method comprising:
bringing feedstock in which a 10 vol % distillation temperature is 140° C. or higher and a 90 vol % distillation temperature is 380° C. or lower into contact with the catalyst for production of monocyclic aromatic hydrocarbons according to claim 1 .
8. The method of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 according to claim 7 ,
wherein as the feedstock, light cycle oil produced by a fluidized catalytic cracking unit is used.
9. The method of producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 according to claim 7 ,
wherein the feedstock is brought into contact with the catalyst for production of monocyclic aromatic hydrocarbons in a fluidized bed reaction unit.
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Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110270004A1 (en) | 2009-06-30 | 2011-11-03 | Shinichiro Yanagawa | Catalyst for producing monocyclic aromatic hydrocarbons, and method for producing monocyclic aromatic hydrocarbons |
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JP5949069B2 (en) * | 2012-04-03 | 2016-07-06 | 株式会社明電舎 | Process for producing lower hydrocarbon aromatization catalyst |
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US10118165B2 (en) * | 2015-02-04 | 2018-11-06 | Exxonmobil Chemical Patents Inc. | Catalyst compositions and use in heavy aromatics conversion processes |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4309280A (en) * | 1980-07-18 | 1982-01-05 | Mobil Oil Corporation | Promotion of cracking catalyst octane yield performance |
US5905051A (en) * | 1997-06-04 | 1999-05-18 | Wu; An-Hsiang | Hydrotreating catalyst composition and processes therefor and therewith |
US20060207917A1 (en) * | 2004-09-08 | 2006-09-21 | Laszlo Domokos | Hydrocracking catalyst composition |
US20080093263A1 (en) * | 2004-11-05 | 2008-04-24 | Wu Cheng Cheng | Catalyst for Light Olefins and Lpg in Fludized Catalytic Units |
US20090112034A1 (en) * | 2007-10-31 | 2009-04-30 | Doron Levin | Heavy Aromatics Processing Catalyst and Process of Using the Same |
US20100145127A1 (en) * | 2007-04-04 | 2010-06-10 | Zaiku Xie | Catalytic composition for producing olefins by catalytic cracking |
Family Cites Families (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2727854A (en) | 1953-03-20 | 1955-12-20 | Standard Oil Co | Recovery of naphthalene |
US2769753A (en) | 1953-06-03 | 1956-11-06 | Pure Oil Co | Combination process for catalytic hydrodesulfurization and reforming of high sulfur hydrocarbon mixtures |
US3258503A (en) | 1961-08-18 | 1966-06-28 | Phillips Petroleum Co | Production of benzene |
US3755141A (en) | 1971-02-11 | 1973-08-28 | Texaco Inc | Catalytic cracking |
US3806443A (en) | 1972-05-26 | 1974-04-23 | Mobil Oil Corp | Selective hydrocracking before and after reforming |
US3847793A (en) * | 1972-12-19 | 1974-11-12 | Mobil Oil | Conversion of hydrocarbons with a dual cracking component catalyst comprising zsm-5 type material |
US3926778A (en) | 1972-12-19 | 1975-12-16 | Mobil Oil Corp | Method and system for controlling the activity of a crystalline zeolite cracking catalyst |
US4053388A (en) | 1976-12-06 | 1977-10-11 | Moore-Mccormack Energy, Inc. | Process for preparing aromatics from naphtha |
US4762813A (en) | 1979-10-15 | 1988-08-09 | Union Oil Company Of California | Hydrocarbon conversion catalyst |
US4585545A (en) | 1984-12-07 | 1986-04-29 | Ashland Oil, Inc. | Process for the production of aromatic fuel |
CN86101990B (en) | 1986-03-27 | 1988-06-01 | 中国石油化工总公司石油化工科学研究院 | Process for preparing layered column type of clayey molecular sieve |
JPH02184517A (en) | 1989-01-06 | 1990-07-19 | Mobil Oil Corp | Gallosilicate zeolite beta, making thereof and use thereof as catalyst |
US5002915A (en) | 1989-05-30 | 1991-03-26 | Mobil Oil Corp. | Process for catalyst regeneration with flue gas |
JPH032128A (en) | 1989-05-30 | 1991-01-08 | Idemitsu Kosan Co Ltd | Production of monocyclic aromatic-containing hydrocarbon |
JPH0326791A (en) | 1989-06-23 | 1991-02-05 | Idemitsu Kosan Co Ltd | Production of hydrocarbon |
JPH0352993A (en) | 1989-07-21 | 1991-03-07 | Idemitsu Kosan Co Ltd | Production of hydrocarbon rich in btx |
GB8926555D0 (en) | 1989-11-24 | 1990-01-17 | Shell Int Research | Process for upgrading a sulphur-containing feedstock |
ATE156471T1 (en) | 1989-12-13 | 1997-08-15 | Mobil Oil Corp | METHOD FOR CATALYTIC CONVERSION OF A C9+ AROMATIC CHARGE |
AU652222B2 (en) | 1991-03-12 | 1994-08-18 | Mobil Oil Corporation | Preparation of cracking catalysts, and cracking process using them |
US5183557A (en) | 1991-07-24 | 1993-02-02 | Mobil Oil Corporation | Hydrocracking process using ultra-large pore size catalysts |
CA2103230C (en) | 1992-11-30 | 2004-05-11 | Paul E. Eberly, Jr. | Fluid catalytic cracking process for producing light olefins |
BR9400475A (en) * | 1994-02-09 | 1995-09-19 | Petroleo Brasileiro Sa | Preparation process of modified zeolite and modified zeolite |
US5582711A (en) | 1994-08-17 | 1996-12-10 | Exxon Research And Engineering Company | Integrated staged catalytic cracking and hydroprocessing process |
JPH08277396A (en) | 1995-04-05 | 1996-10-22 | Kao Corp | Burning of heavy oil |
JP3608095B2 (en) | 1996-03-29 | 2005-01-05 | 新日本石油株式会社 | Method for producing heavy oil base |
JP3685225B2 (en) | 1996-07-26 | 2005-08-17 | 山陽石油化学株式会社 | Production of aromatic hydrocarbons |
KR20010012397A (en) | 1997-05-12 | 2001-02-15 | 존 엠. 피쉬 주니어 | Improved catalyst composition useful for conversion of non-aromatic hydrocarbons to aromatics and light olefins |
US5990032A (en) | 1997-09-30 | 1999-11-23 | Phillips Petroleum Company | Hydrocarbon conversion catalyst composition and processes therefor and therewith |
CN1056595C (en) | 1997-10-20 | 2000-09-20 | 中国石油化工总公司 | Process for direct-conversion preparation olefines from multiple fed hydrocarbon |
US5981418A (en) | 1998-04-08 | 1999-11-09 | Phillips Petroleum Company | Zeolite based catalyst containing zinc, boron and phosphorus and method of making such zeolite based catalyst |
AU760751B2 (en) | 1998-11-12 | 2003-05-22 | Mobil Oil Corporation | Diesel fuel |
US6241876B1 (en) | 1998-12-30 | 2001-06-05 | Mobil Oil Corporation | Selective ring opening process for producing diesel fuel with increased cetane number |
US6210563B1 (en) | 1998-12-30 | 2001-04-03 | Mobil Oil Corporation | Process for producing diesel fuel with increased cetane number |
JP4409677B2 (en) | 1999-09-28 | 2010-02-03 | 出光興産株式会社 | Fuel oil composition |
US6900365B2 (en) | 1999-11-15 | 2005-05-31 | Chevron Phillips Chemical Company Lp | Process for converting heavy hydrocarbon feeds to high octane gasoline, BTX and other valuable aromatics |
JP2002146364A (en) | 2000-11-06 | 2002-05-22 | Nippon Mitsubishi Oil Corp | Method for producing heavy oil base |
DE10135490A1 (en) | 2001-07-20 | 2003-01-30 | Basf Ag | Process for the hydrogenation of aromatic compounds with hydrogen containing residual gas |
US20040140246A1 (en) | 2001-08-31 | 2004-07-22 | Lomas David A. | Process for upgrading fcc product with additional reactor |
JP2003096474A (en) | 2001-09-27 | 2003-04-03 | Idemitsu Kosan Co Ltd | Fuel oil composition |
US6709572B2 (en) | 2002-03-05 | 2004-03-23 | Exxonmobil Research And Engineering Company | Catalytic cracking process |
US7553791B2 (en) * | 2002-11-14 | 2009-06-30 | Exxonmobil Chemical Patents Inc. | Heavy aromatics conversion catalyst composition and processes therefor and therewith |
WO2004045766A1 (en) | 2002-11-18 | 2004-06-03 | Ict Co., Ltd. | Exhaust gas purifying catalyst and method for purifying exhaust gas |
FI119588B (en) | 2003-11-27 | 2009-01-15 | Neste Oil Oyj | Precious metal catalyst for hydrocarbon conversion, process of production thereof and process for production of diesel fuel |
ES2913654T3 (en) | 2004-03-08 | 2022-06-03 | China Petroleum & Chem Corp | FCC procedure with two reaction zones |
EP1762299B1 (en) | 2004-03-31 | 2018-05-30 | China Petroleum & Chemical Corporation | A catalyst containing zeolite for hydrocarbon converting and preparation thereof, and a hydrocarbon oil converting method using said catalyst |
EP1586376B1 (en) * | 2004-04-14 | 2009-07-01 | Institut Français du Pétrole | Catalyst comprising a 10MR zeolite and a 12MR zeolite and its use in the transalkylation of alkylaromatic hydrocarbons |
BRPI0510476A (en) * | 2004-05-26 | 2007-11-06 | Shell Int Research | process for preparing a diesel |
JP2006028493A (en) | 2004-06-16 | 2006-02-02 | Idemitsu Kosan Co Ltd | Fuel oil composition for premix compression self-ignition engine |
TWI277648B (en) * | 2004-07-29 | 2007-04-01 | China Petrochemical Technology | A cracking catalyst for hydrocarbons and its preparation |
CN1322924C (en) * | 2004-07-29 | 2007-06-27 | 中国石油化工股份有限公司 | Cracking catalyst for hydrocarbon and preparation method |
CN100389177C (en) * | 2005-01-31 | 2008-05-21 | 中国石油化工股份有限公司 | Heavy-oil catalytic-cracking catalyst and preparing method |
JP4630028B2 (en) | 2004-09-15 | 2011-02-09 | 石油コンビナート高度統合運営技術研究組合 | Fuel composition |
JP4482470B2 (en) | 2004-10-12 | 2010-06-16 | コスモ石油株式会社 | Method for producing light oil composition |
FI1741768T4 (en) | 2005-07-04 | 2023-04-25 | Process for the manufacture of diesel range hydrocarbons | |
EA013998B1 (en) | 2005-07-04 | 2010-08-30 | Несте Ойл Ойй | Process for the manufacture of diesel range hydrocarbons |
JP2007154151A (en) * | 2005-11-11 | 2007-06-21 | Toray Ind Inc | Method for producing 6-8c aromatic hydrocarbon |
KR101234448B1 (en) | 2005-11-14 | 2013-02-18 | 에스케이이노베이션 주식회사 | Process for The Preparation of Aromatic Hydrocarbons and Liquefied Petroleum Gas from Hydrocarbon Mixture |
CA2539231C (en) | 2006-03-10 | 2013-08-13 | Baojian Shen | Catalyst composition for treating heavy feedstocks |
CN101134913B (en) * | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
JP5435856B2 (en) * | 2006-11-07 | 2014-03-05 | Jx日鉱日石エネルギー株式会社 | Catalytic decomposition method |
JP5054488B2 (en) | 2006-11-13 | 2012-10-24 | Jx日鉱日石エネルギー株式会社 | Method for producing light oil composition |
JP2008214369A (en) | 2007-02-28 | 2008-09-18 | Showa Shell Sekiyu Kk | Fuel composition for diesel engine |
JP5178033B2 (en) | 2007-03-28 | 2013-04-10 | Jx日鉱日石エネルギー株式会社 | Method for producing C heavy oil composition |
JP5154817B2 (en) | 2007-03-30 | 2013-02-27 | Jx日鉱日石エネルギー株式会社 | Gas oil base and gas oil composition |
JP5396008B2 (en) * | 2007-05-31 | 2014-01-22 | Jx日鉱日石エネルギー株式会社 | Method for producing alkylbenzenes |
ITMI20071610A1 (en) | 2007-08-03 | 2009-02-04 | Eni Spa | INTEGRATED PROCESS OF CATALYTIC FLUID CRACKING TO OBTAIN HYDROCARBURIC MIXTURES WITH HIGH QUALITY AS FUEL |
CN101376823B (en) | 2007-08-31 | 2012-07-18 | 中国石油化工股份有限公司 | Benzin naphtha catalytic reforming method |
JP5213401B2 (en) * | 2007-09-20 | 2013-06-19 | Jx日鉱日石エネルギー株式会社 | Fluid catalytic cracking method for heavy petroleum |
JP5507043B2 (en) | 2007-09-27 | 2014-05-28 | 出光興産株式会社 | Fuel oil composition |
CN101821360B (en) | 2007-09-28 | 2013-05-22 | 日本石油天然气·金属矿物资源机构 | Method for producing synthetic naphtha |
JP2009167257A (en) | 2008-01-11 | 2009-07-30 | Japan Energy Corp | Gas oil composition |
JP5072034B2 (en) | 2008-03-25 | 2012-11-14 | Jx日鉱日石エネルギー株式会社 | Method for producing C heavy oil composition |
JP2009235247A (en) | 2008-03-27 | 2009-10-15 | Toray Ind Inc | Method for producing aromatic hydrocarbon having six to eight carbon atoms |
JP2009235248A (en) * | 2008-03-27 | 2009-10-15 | Toray Ind Inc | Method for producing aromatic hydrocarbon having six to eight carbon atoms |
CN101570698B (en) | 2008-04-29 | 2013-09-04 | 中国石油化工股份有限公司 | Method for catalyzing and transforming naphtha |
JP5176151B2 (en) * | 2008-05-19 | 2013-04-03 | コスモ石油株式会社 | Method for producing high octane gasoline base material |
JP2010001462A (en) | 2008-05-19 | 2010-01-07 | Cosmo Oil Co Ltd | Method for treating petroleum-based hydrocarbon |
FR2933987B1 (en) | 2008-07-18 | 2010-08-27 | Inst Francais Du Petrole | HYDROGENATION PROCESS OF BENZENE |
JP5317605B2 (en) | 2008-09-22 | 2013-10-16 | Jx日鉱日石エネルギー株式会社 | Light oil composition |
KR101503069B1 (en) | 2008-10-17 | 2015-03-17 | 에스케이이노베이션 주식회사 | Production of valuable aromatics and olefins from FCC light cycle oil |
US9243192B2 (en) | 2009-03-27 | 2016-01-26 | Jx Nippon Oil & Energy Corporation | Method for producing aromatic hydrocarbons |
EP2412786A4 (en) | 2009-03-27 | 2012-10-17 | Chiyoda Corp | Method for producing aromatic hydrocarbon |
US20110270004A1 (en) | 2009-06-30 | 2011-11-03 | Shinichiro Yanagawa | Catalyst for producing monocyclic aromatic hydrocarbons, and method for producing monocyclic aromatic hydrocarbons |
EP2438988A4 (en) | 2009-07-29 | 2013-08-21 | Jx Nippon Oil & Energy Corp | Catalyst for production of monocyclic aromatic hydrocarbon, and process for production of monocyclic aromatic hydrocarbon |
WO2011090124A1 (en) | 2010-01-20 | 2011-07-28 | Jx日鉱日石エネルギー株式会社 | Catalyst for production of hydrocarbons and process for production of hydrocarbons |
US20130030232A1 (en) | 2010-01-20 | 2013-01-31 | Jx Nippon Oil & Energy Corporation | Catalyst for production of monocyclic aromatic hydrocarbons and method of producing monocyclic aromatic hydrocarbons |
JP5491912B2 (en) | 2010-03-12 | 2014-05-14 | Jx日鉱日石エネルギー株式会社 | Method for producing kerosene oil base and alkylbenzenes |
KR101830451B1 (en) | 2010-03-26 | 2018-02-20 | 제이엑스티지 에네루기 가부시키가이샤 | Method for producing monocyclic aromatic hydrocarbon |
JP5485088B2 (en) | 2010-09-14 | 2014-05-07 | Jx日鉱日石エネルギー株式会社 | Process for producing aromatic hydrocarbons |
JP5535845B2 (en) | 2010-09-14 | 2014-07-02 | Jx日鉱日石エネルギー株式会社 | Process for producing aromatic hydrocarbons |
JP2012139640A (en) | 2010-12-28 | 2012-07-26 | Jx Nippon Oil & Energy Corp | Catalyst for producing monocyclic aromatic hydrocarbon and method of producing the monocyclic aromatic hydrocarbon |
KR101896733B1 (en) | 2011-03-25 | 2018-10-04 | 제이엑스티지 에네루기 가부시키가이샤 | Method for producing single-ring aromatic hydrocarbons |
JP5868012B2 (en) | 2011-03-25 | 2016-02-24 | Jx日鉱日石エネルギー株式会社 | Monocyclic aromatic hydrocarbon production method |
JP5690624B2 (en) * | 2011-03-25 | 2015-03-25 | Jx日鉱日石エネルギー株式会社 | Monocyclic aromatic hydrocarbon production method |
JP5683342B2 (en) | 2011-03-25 | 2015-03-11 | Jx日鉱日石エネルギー株式会社 | Monocyclic aromatic hydrocarbon production method |
BR112013029915A2 (en) | 2011-05-24 | 2016-12-20 | Chiyoda Corp | method for the production of monocyclic aromatic hydrocarbons |
JP5744622B2 (en) | 2011-05-24 | 2015-07-08 | Jx日鉱日石エネルギー株式会社 | Monocyclic aromatic hydrocarbon production method |
JP5671412B2 (en) * | 2011-05-26 | 2015-02-18 | Jx日鉱日石エネルギー株式会社 | Light oil composition and method for producing the same |
WO2012169651A1 (en) | 2011-06-10 | 2012-12-13 | Sumitomo Chemical Company, Limited | Method for producing aromatic hydrocarbon and/or olefin having 4 or less carbon atoms and apparatus for producing aromatic hydrocarbon and/or olefin having 4 or less carbon atoms |
-
2011
- 2011-01-20 US US13/522,867 patent/US20130030232A1/en not_active Abandoned
- 2011-01-20 BR BR112012018012A patent/BR112012018012A2/en not_active Application Discontinuation
- 2011-01-20 EP EP11734727.8A patent/EP2527036A4/en not_active Withdrawn
- 2011-01-20 CN CN201180014489.2A patent/CN102811814B/en active Active
- 2011-01-20 JP JP2011505307A patent/JP5919587B2/en active Active
- 2011-01-20 WO PCT/JP2011/050995 patent/WO2011090121A1/en active Application Filing
- 2011-01-20 KR KR1020127021322A patent/KR101790368B1/en active IP Right Grant
-
2015
- 2015-07-16 US US14/801,089 patent/US10087376B2/en active Active
-
2016
- 2016-02-03 JP JP2016019280A patent/JP6147376B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4309280A (en) * | 1980-07-18 | 1982-01-05 | Mobil Oil Corporation | Promotion of cracking catalyst octane yield performance |
US5905051A (en) * | 1997-06-04 | 1999-05-18 | Wu; An-Hsiang | Hydrotreating catalyst composition and processes therefor and therewith |
US20060207917A1 (en) * | 2004-09-08 | 2006-09-21 | Laszlo Domokos | Hydrocracking catalyst composition |
US20080093263A1 (en) * | 2004-11-05 | 2008-04-24 | Wu Cheng Cheng | Catalyst for Light Olefins and Lpg in Fludized Catalytic Units |
US20100145127A1 (en) * | 2007-04-04 | 2010-06-10 | Zaiku Xie | Catalytic composition for producing olefins by catalytic cracking |
US20090112034A1 (en) * | 2007-10-31 | 2009-04-30 | Doron Levin | Heavy Aromatics Processing Catalyst and Process of Using the Same |
Cited By (4)
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US11091411B2 (en) * | 2016-10-26 | 2021-08-17 | S-Oil Corporation | Hydrocracking catalyst for preparing light aromatic hydrocarbon, method for preparing same and method for preparing light aromatic hydrocarbon by using same |
US11060400B1 (en) | 2020-05-20 | 2021-07-13 | Halliburton Energy Services, Inc. | Methods to activate downhole tools |
US11255189B2 (en) | 2020-05-20 | 2022-02-22 | Halliburton Energy Services, Inc. | Methods to characterize subterranean fluid composition and adjust operating conditions using MEMS technology |
CN114656313A (en) * | 2022-04-11 | 2022-06-24 | 南方海洋科学与工程广东省实验室(广州) | Method for preparing monocyclic aromatic hydrocarbon by converting natural gas hydrate and PET plastic |
Also Published As
Publication number | Publication date |
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EP2527036A4 (en) | 2014-03-05 |
BR112012018012A2 (en) | 2016-05-03 |
US10087376B2 (en) | 2018-10-02 |
WO2011090121A1 (en) | 2011-07-28 |
EP2527036A1 (en) | 2012-11-28 |
US20150322352A1 (en) | 2015-11-12 |
CN102811814B (en) | 2014-10-15 |
KR101790368B1 (en) | 2017-10-25 |
JPWO2011090121A1 (en) | 2013-05-23 |
JP2016128167A (en) | 2016-07-14 |
JP5919587B2 (en) | 2016-05-18 |
JP6147376B2 (en) | 2017-06-14 |
KR20120123423A (en) | 2012-11-08 |
CN102811814A (en) | 2012-12-05 |
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