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(12) United States Patent (10) Patent No.: US 7.241,931 B2 Pazzuconi Et Al

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(12) United States Patent (10) Patent No.: US 7.241,931 B2 Pazzuconi Et Al US00724.1931B2 (12) United States Patent (10) Patent No.: US 7.241,931 B2 PaZZuconi et al. (45) Date of Patent: Jul. 10, 2007 (54) PROCESS FOR THE PREPARATION OF 3,962,364 A 6/1976 Young 2,6-DIMETHYLNAPHTHALENE 3,972,832 A 8, 1976 Butter et al. 4,002,698 A 1/1977 Kaeding (75) Inventors: Giannino Pazzuconi, Broni (IT): Carlo 4,088,706 A 5/1978 Kaeding 4,402,867 A 9, 1983 Rodewald Perego, Carnate (IT): Giuseppe 4.421,941 A 12/1983 Olson et al. Bellussi, Piacenza (IT) 4,590,321 A 5, 1986 Chu 4,605,804 A 8/1986 Chang et al. (73) Assignees: Enichem S.p.A., San Donato Milanese 5,981,418 A 11/1999 Drake et al. (IT): ENI S.p.A., Rome (IT): 6,048,816 A 4/2000 Brown et al. Enitechnologie S.p.A., San Donato 6,147,270 A 1 1/2000 Pazzuconi et al. Milanese (IT) 6, 187982 B1 2/2001 Becket al. 6,232,517 B1 5, 2001 PaZZuconi et al. (*) Notice: Subject to any disclaimer, the term of this 7,019, 186 B2 3/2006 Pazzuconi et al. patent is extended or adjusted under 35 2003, OO69459 A1 4/2003 Girotti et al. U.S.C. 154(b) by 0 days. FOREIGN PATENT DOCUMENTS (21) Appl. No.: 11/333,201 EP O 296 582 12, 1988 EP O 621 251 10, 1994 (22) Filed: Jan. 18, 2006 EP O 95O 650 10, 1999 EP 1 069 102 1, 2001 (65) Prior Publication Data GB 2 246 T88 2, 1992 WO WO 90,03960 4f1990 US 2006/O122445 A1 Jun. 8, 2006 WO WO 98.41595 9, 1998 Related U.S. Application Data Primary Examiner Thuan Dinh Dang (62) Division of application No. 10/357.379, filed on Feb. (74) Attorney, Agent, or Firm Oblon, Spivak, McClelland, 4, 2003, now Pat. No. 7,019,186, which is a division Maier & Neustadt, P.C. of application No. 09/690,011, filed on Oct. 17, 2000, now abandoned. (57) ABSTRACT (30) Foreign Application Priority Data A highly selective process is described for preparing 2.6- dimethylnaphthalene which comprises reacting a naphtha Oct. 18, 1999 (IT) .............................. MI99A2171 lene hydrocarbon selected from naphthalene, methylnaph (51) Int. Cl. thalenes, dimethylnaphthalenes, trimethylnaphthalenes, C07C 5/22 (2006.01) polymethylnaphthalenes, and/or their mixtures with one or more benzene hydrocarbons selected from benzene, toluene, C07C 5/27 (2006.01) Xylenes, trimethylbenzenes, tetramethylbenzenes, pentam (52) U.S. Cl. ....................................... 585/481: 585/.480 ethylbenzene and/or hexamethylbenzene, under at least par (58) Field of Classification Search ................ 585/481, tially liquid phase conditions and in the presence of a 585/.480 catalytic composition comprising a Zeolite belonging to the See application file for complete search history. MTW structural type and at least one element selected from (56) References Cited P. B and Si. The process is preferably carried out in the presence of a methylating agent. U.S. PATENT DOCUMENTS 3,832,449 A 8, 1974 Rosinski et al. 2 Claims, No Drawings US 7,241,931 B2 1. 2 PROCESS FOR THE PREPARATION OF ticularly preferred. In order to reduce undesired isomeriza 2,6-DIMETHYLNAPHTHALENE tion reactions which cause the formation of 1-alkyl-naph thalene, the Zeolitic catalyst is previously subjected to a A highly selective process is described for preparing precarbonization treatment. An illustration is provided of the 2,6-dimethylnaphthalene which comprises reacting a naph alkylation of 2-methylnaphthalene with methanol, in gas thalene hydrocarbon selected from naphthalene, methyl phase, catalyzed by ZSM-5: the conversion obtained naphthalenes, dimethylnaphthalenes, trimethylnaphtha between 0.5 and 8 hours ranges from 5 to 7%, the yield to lenes, polymethylnaphthalenes, or their mixtures with one or dimethylnaphthalenes ranges from 4 to 5% and the 2.6- more benzene hydrocarbons selected from benzene, toluene, dimethylnaphthalene isomer forms 50% of the dimethyl Xylenes, trimethylbenzenes, tetramethylbenzenes, pentam 10 ethylbenzene and/or hexamethylbenzene, under at least par naphthalene fraction. tially liquid phase conditions and in the presence of a Italian patent application MI98A000809 describes a pro catalytic composition comprising a Zeolite belonging to the cess for preparing 2,6-dimethylnaphthalene by the reaction MTW structural type and at least one element selected from of naphthalene, methylnaphthalenes, dimethylnaphthalenes, P. B and Si. The process is preferably carried out in the 15 trimethylnaphthalenes and/or polymethylnaphthalenes with presence of a methylating agent. one or more benzene hydrocarbons selected from benzene, 2,6-dimethylnaphthalene is an intermediate in the synthe toluene, Xylenes, trimethylbenzenes, tetramethylbenzenes, sis of 2.6-naphthalenedicarboxylic acid, used as monomer in pentamethylbenzene and hexamethylbenzene, carried out the preparation of PEN (polyethylnaphthalate). It is known under at least partially liquid phase conditions and in the that it can be recovered from fractions coming from the presence of a zeolite belonging to the MTW structural type reforming of kerosene (U.S. Pat. No. 4,963.248) or FCC oil and optionally in the presence of a methylating agent. This fractions (European Chemical News, page 30, 28.09. 1992). process allows better results to be obtained in terms of yield, In the former case, the dimethylnaphthalenes must be sepa selectivity, conversion to useful products in the time unit and rated by distillation and the 2.6 isomer is subsequently catalyst life, with respect to what is described in the prior art. isolated by means of selective absorptions and/or crystalli 25 MTW Zeolites in particular, under the conditions described zation. In the latter case there is a further problem due to the presence of nitrogen and Sulfur which poison the catalysts in MI98A000809, prove to be more active than the same used for the separation and/or isomerization phases. There is Zeolites used according to the conditions described in prior also a process (U.S. Pat. No. 4,990,717: U.S. Pat. No. documents, and also with respect to BEA and MFI zeolites 5,118,892; U.S. Pat. Nos. 5,073,670; 5,030,781; 5,012,024) 30 already described in the known art as the best catalysts for for the selective synthesis of 2,6-dimethylnaphthalene by the preparation of 2,6-dimethylnaphthalene. Zeolites of the means of a series of alkenylation, cyclization, dehydroge MTW structural type which can be used in said invention are nation, isomerization processes. Such a high number of for example: ZSM-12, CZH-5, Nu-13, Theta-3 and TPZ-12. passages is obviously extremely costly and in addition each The CZH-5 Zeolite is described in GB 207,9735A; Nu-1 is passage or chemical reaction involves secondary reactions 35 described in EP 59059: Theta-3 is described in EP 162,719 requiring separation to guarantee the purity of the interme and TPZ-12 in U.S. Pat. No. 4,557,919. The MTW structural diates or end-product. type Zeolite preferably used in MI98A000809 is a silico U.S. Pat. No. 5,043,501 describes a synthesis method of aluminate with a molar ratio SiO/Al2O greater than or 2,6-dimethylnaphthalene in two steps. The first comprises equal to 20. This zeolite is described in A. Katovic and G. the alkylation of an alkylaromatic with a Cs olefin in the 40 Giordano, Chem. Ind. (Dekker) (Synthesis of Porous Mate presence of a Zeolitic catalyst, the second step includes rials) 1997 69, 127–137. The aluminum can be totally or dehydrocyclization at 400–500°C. with a catalyst consisting partly substituted by B. Ga, Fe or their mixtures, as of Pt/Ba/K on L. Zeolite, obtaining a product containing described by Toktarev & Ione, in Chon et al., Progress in dimethylnaphthalenes which are then isomerized mainly to Zeolites and Microporous Material, SSSC, vol. 105, 1997. 2.6 isomer. 45 According to a preferred aspect of patent application In Applied Catalysis A, General 146 (1996) 305-316, S. MI98A000809, ZSM-12 zeolite is used, a porous crystalline B. Pu and T. Inui describe the alkylation of methylnaphtha material having, in its calcined and anhydrous form, a molar lene with methanol, catalyzed by Zeolites of the BEA, FAU composition of oxides corresponding to the following for and MTW group, carried out without a solvent and in mula: exclusively gaseous phase. The best results are obtained 50 with beta Zeolite and faujasite. A. S. Loktev and P. S. 1.0+0.4M.O.W.O.20-500YOzH2O Chekriy, in Zeolites and Related Microporous Materials: State of Art 1994, SSSC vol. 84, J. Weitkamp et al. (Eds) wherein M is H" and/or a cation of an alkaline or earthal describe the alkylation of naphthalene or methylnaphthalene kaline metal with a valence n, Wis selected from aluminum, with methanol catalyzed by ZSM-12, carried out in the 55 gallium or their mixtures, Y is selected from silicon and presence of paraflinic Solvents and in gaseous phase. The germanium, Z ranges from 0 to 60. M is preferably selected yields to dimethylnaphthalenes, and 2.6 isomer in particular, from Sodium, potassium, hydrogen or their mixtures. W is are Zero or negligible. Furthermore, significant quantities of preferably aluminum and Y is preferably silicon. W can be heavy by-products are obtained, due to the reaction and/or at least partially substituted by boron, iron or their mixtures. decomposition conditions of the paraflinic solvents used. 60 ZSM-12 Zeolite is described in U.S. Pat. No. 3,832,449, in U.S. Pat. No. 4,795,847 describes a process for the Ernst et al., Zeolites, 1987, Vol. 7, September, and in preparation of 2,6-dialkylnaphthalenes which comprises the Toktarev & Ione, Chon et al., Progress in Zeolites and alkylation in gas phase of naphthalene or 2-alkyl-naphtha Microporous Material, SSSC, Vol.
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