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Method Of Producing Monocyclic Aromatic Hydrocarbons

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 5 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.

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Patent Information

Application #
Filing Date
24 July 2012
Publication Number
05/2014
Publication Type
INA
Invention Field
CHEMICAL
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2019-12-23
Renewal Date

Applicants

JX NIPPON OIL & ENERGY CORPORATION
6-3  Otemachi 2-Chome  Chiyoda-ku  Tokyo 100-8162

Inventors

1. SHINICHIRO YANAGAWA
c/o JX Nippon Oil & Energy Corporation  8  Chidori-cho  Naka-ku  Yokohama-shi  Kanagawa 231-0815
2. MASAHIDE KOBAYASHI
c/o JX Nippon Oil & Energy Corporation  8  Chidori-cho  Naka-ku  Yokohama-shi  Kanagawa 231-0815
3. KAZUAKI HAYASAKA
c/o JX Nippon Oil & Energy Corporation  8  Chidori-cho  Naka-ku  Yokohama-shi  Kanagawa 231-0815

Specification

DESCRIPTION 5 CATALYST FOR PRODUCTION OF MONOCYCLIC AROMATIC HYDROCARBONS AND METHOD OF PRODUCING MONOCYCLIC AROMATIC HYDROCARBONS TECHNICAL FIELD '[0001] The present invention relates to a catalyst for producing monocyclic aromatic 10 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 January 20, 2010, the content of which is incorporated herein by reference. 15 BACKGROUND ART - - [0002] Light cycle oil (hereinafter, referred to as "LCO"), which is cracked light oil producedby a fluidized catalytic cracking, contains a large amount of polycyclic 20 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. 25 For example, Patent Document I to Patent Document 3 disclose methods of 2 producing monocyclic aromatic hydrocarbons from polycyclic aromatic hydrocarbons contained in large amounts within LCO and the like by using zeolite catalysts. [0003] In addition, as a method of producing monocyclic aromatic hydrocarbons 5 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 10 hydrocarbons from paraffin-based hydrocarbons having a carbon number of 2 to 12 by using beta-type zeolite as a catalyst. Citation List Patent Document 15 [0004] [Patent Document 1] Japanese Unexamined Patent Application, First publication-No. H3=2128 [Patent Document 2] Japanese Unexamined Patent Application, First publication No. H3-52993 20 [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 25 publication No. H2-184517 3 DISCLOSURE OF INVENTION Technical Problem [0005] 5 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 10 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 15 number of 6 to 8 from feedstock containing polycyclic aromatic hydrocarbons with high yield. Solution to Problem [0006] 20 (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 25 intermediate-pore zeolite having 10-membered ring structure. 4 (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. 5 (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 preferablyBEA-type 10 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 15 according to any one of (1) to (5), wherein the catalyst preferably further contain phosphorus. (7) According to another embodiment-of-the invention, amethod 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 20 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 25 produced by a fluidized catalytic cracking is preferably used. 5 (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. 5 Advantageous Effects of Invention [0007] According to the catalyst for production of monocyclic aromatic hydrocarbons and the method of producing monocyclic aromatic hydrocarbons having a carbon number 10 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. BEST MODE FOR CARRYING OUT THE INVENTION 15 [0008] (Catalyst for Production of Monocyclic Aromatic Hydrocarbon) The catalyst for production of monocyclie aromatic`h rocarbons according this embodiment (hereinafter, abbreviated as "catalyst") is used for producing monocyclic aromatic hydrocarbons having a carbon number of 6 to 8 (hereinafter, 20 abbreviated as "monocyclic aromatic hydrocarbons") from feedstock containing polycyclic aromatic hydrocarbons and saturated hydrocarbons, and contains crystalline aluminosilicate. [0009] (Crystalline Aluminosilicate) 25 In this embodiment, the crystalline aluminosilicate contains large-pore zeolite 6. 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 AFT type, an ATO type, a BEA type, a CON type, 5 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. 10 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 15 raised. In addition, all of the framework type types of the zeolite , which are exemplified in this- embodiment are structure codes based on thezlefinitior ofthu-lnWrnational Zeolite Association. [0010] 20 In addition to the large -pore zeolite, the crystalline aluminosilicate may contain small-pore zeolite having a stricture 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 25 type, a PAU type, and a YUG type is preferably exemplified. 7 As the ultra-large-pore zeolite, for example, zeolites having a framework type of a CLO type, and a VPI type is preferably exemplified. [0011] In a case where the catalyst is used as a catalyst for a fixed bed, the content of 5 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 10 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 15 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 20 fluidized bed. [0012] 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 25 mass ratio is 2/98 or more, an effect of using the large-pore zeolite is sufficiently 8 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. [0013] 5 (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 haying a carbon number of 6 to 8 tends to be increased. [0014] 10 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. 15 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 typeinwhich zinc is carried-bythe crystalline aluminosilicate (zinc-supporting crystalline aluminosilicate), and a type including both of these types is exemplified. 20 The crystalline aluminogallosilicate and the crystalline aluminozincosilicate have a structure in which SiO4 , A1O4, 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 25 lattice framework of the crystalline aluminosilicate, or by a method in which aluminum is 9 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 5 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 10 used in these methods, and examples include zinc salts such as zinc nitrate and zinc chloride, and zinc oxide. [0015] 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 15 100 % by mass of the total mass of the crystalline aluminosilicate, and more prefer

Documents

Application Documents

# Name Date
1 6514-DELNP-2012-RELEVANT DOCUMENTS [20-09-2023(online)].pdf 2023-09-20
1 Form-5.doc 2012-07-24
2 6514-DELNP-2012-RELEVANT DOCUMENTS [05-09-2022(online)].pdf 2022-09-05
2 Form-3.doc 2012-07-24
3 Form-1.pdf 2012-07-24
3 6514-DELNP-2012-RELEVANT DOCUMENTS [03-09-2021(online)].pdf 2021-09-03
4 6514-DELNP-2012-RELEVANT DOCUMENTS [27-08-2021(online)].pdf 2021-08-27
4 6514-delnp-2012-GPA-(13-09-2012).pdf 2012-09-13
5 6514-DELNP-2012-RELEVANT DOCUMENTS [29-01-2020(online)].pdf 2020-01-29
5 6514-delnp-2012-Correspondence Others-(13-09-2012).pdf 2012-09-13
6 6514-delnp-2012-Correspondence-others- (18-09-2012).pdf 2012-09-18
6 6514-DELNP-2012-Correspondence-241219.pdf 2019-12-27
7 6514-DELNP-2012-Power of Attorney-241219.pdf 2019-12-27
7 6514-delnp-2012-Correspondence others-(18-12-2012).pdf 2012-12-18
8 6514-DELNP-2012-IntimationOfGrant23-12-2019.pdf 2019-12-23
8 6514-delnp-2012-Form-18-(08-01-2014).pdf 2014-01-08
9 6514-delnp-2012-Correspondence-Others-(08-01-2014).pdf 2014-01-08
9 6514-DELNP-2012-PatentCertificate23-12-2019.pdf 2019-12-23
10 6514-DELNP-2012-FORM-26 [20-12-2019(online)].pdf 2019-12-20
10 Petition under rule 137.pdf 2014-06-16
11 6514-delnp-2012-Correspondence-Others-(18-06-2014).pdf 2014-06-18
11 6514-DELNP-2012-Response to office action (Mandatory) [20-12-2019(online)].pdf 2019-12-20
12 6514-DELNP-2012-ABSTRACT [14-02-2018(online)].pdf 2018-02-14
12 6514-DELNP-2012-FER.pdf 2017-11-14
13 6514-DELNP-2012-CLAIMS [14-02-2018(online)].pdf 2018-02-14
13 6514-DELNP-2012-PETITION UNDER RULE 137 [14-02-2018(online)].pdf 2018-02-14
14 6514-DELNP-2012-COMPLETE SPECIFICATION [14-02-2018(online)].pdf 2018-02-14
14 6514-DELNP-2012-OTHERS [14-02-2018(online)].pdf 2018-02-14
15 6514-DELNP-2012-CORRESPONDENCE [14-02-2018(online)].pdf 2018-02-14
15 6514-DELNP-2012-FER_SER_REPLY [14-02-2018(online)].pdf 2018-02-14
16 6514-DELNP-2012-CORRESPONDENCE [14-02-2018(online)].pdf 2018-02-14
16 6514-DELNP-2012-FER_SER_REPLY [14-02-2018(online)].pdf 2018-02-14
17 6514-DELNP-2012-OTHERS [14-02-2018(online)].pdf 2018-02-14
17 6514-DELNP-2012-COMPLETE SPECIFICATION [14-02-2018(online)].pdf 2018-02-14
18 6514-DELNP-2012-CLAIMS [14-02-2018(online)].pdf 2018-02-14
18 6514-DELNP-2012-PETITION UNDER RULE 137 [14-02-2018(online)].pdf 2018-02-14
19 6514-DELNP-2012-ABSTRACT [14-02-2018(online)].pdf 2018-02-14
19 6514-DELNP-2012-FER.pdf 2017-11-14
20 6514-delnp-2012-Correspondence-Others-(18-06-2014).pdf 2014-06-18
20 6514-DELNP-2012-Response to office action (Mandatory) [20-12-2019(online)].pdf 2019-12-20
21 6514-DELNP-2012-FORM-26 [20-12-2019(online)].pdf 2019-12-20
21 Petition under rule 137.pdf 2014-06-16
22 6514-delnp-2012-Correspondence-Others-(08-01-2014).pdf 2014-01-08
22 6514-DELNP-2012-PatentCertificate23-12-2019.pdf 2019-12-23
23 6514-delnp-2012-Form-18-(08-01-2014).pdf 2014-01-08
23 6514-DELNP-2012-IntimationOfGrant23-12-2019.pdf 2019-12-23
24 6514-delnp-2012-Correspondence others-(18-12-2012).pdf 2012-12-18
24 6514-DELNP-2012-Power of Attorney-241219.pdf 2019-12-27
25 6514-delnp-2012-Correspondence-others- (18-09-2012).pdf 2012-09-18
25 6514-DELNP-2012-Correspondence-241219.pdf 2019-12-27
26 6514-DELNP-2012-RELEVANT DOCUMENTS [29-01-2020(online)].pdf 2020-01-29
26 6514-delnp-2012-Correspondence Others-(13-09-2012).pdf 2012-09-13
27 6514-DELNP-2012-RELEVANT DOCUMENTS [27-08-2021(online)].pdf 2021-08-27
27 6514-delnp-2012-GPA-(13-09-2012).pdf 2012-09-13
28 Form-1.pdf 2012-07-24
28 6514-DELNP-2012-RELEVANT DOCUMENTS [03-09-2021(online)].pdf 2021-09-03
29 6514-DELNP-2012-RELEVANT DOCUMENTS [05-09-2022(online)].pdf 2022-09-05
30 6514-DELNP-2012-RELEVANT DOCUMENTS [20-09-2023(online)].pdf 2023-09-20

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