The alkylation of biphenyl over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Sugi, Yoshihiro; Maekawa, Hiroyoshi; Hasegawa, Yukio; Itō, Akira; Asai, Ryota; Yamamoto, Daisuke; Komura, Kenichi; Kubota, Yoshihiro; Kim, Jong-Ho; Seo, Gon

doi:10.1016/j.cattod.2007.10.060

Cited by 17 publications

(18 citation statements)

References 28 publications

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“…A more precise fitting of the transition state with the zeolites, however, was required for the recognition of 2,6-DTBN, even with bulky alkylating agents. Similar results of shape-selective catalysis were observed in alkylation of BP over the zeolites examined in this paper: 21,32,33 the selectivities for 4,4¢-dialkylbiphenyl …”

Section: Steric Interaction Of Reagents With Zeolitessupporting

confidence: 86%

“…Dealuminated H-mordenite (MOR) enhanced shape-selective formation of the smallest 2,6-diisopropylnaphthalene (2,6-DIPN) and 4,4¢-diisopropylbiphenyl (4,4¢-DIPB) in the isopropylation of NP [7][8][9][10][11][12][13][14][15][16][17][18] and BP, [19][20][21][22][23][24] respectively. On the other hand, large-pore zeolites, such as Y zeolite (FAU) and zeolite b (BEA), resulted in only low selectivities in isopropylation of NP 11,[16][17][18]25,[27][28][29][30] and BP, [27][28][29][30]31,33 and the selectivities increased in alkylation of NP 25,[34][35][36][37] and BP 32,[38][39][40] even over these zeolites by the use of bulky alkylating agents. It is interesting how zeolite channels influence catalysis, particularly steric interaction of the transition state, in the alkylation of NP and BP.…”

Section: Introductionmentioning

confidence: 98%

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Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Sugi

2010

J Chinese Chemical Soc

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Steric interaction of reagents with zeolites was studied in isopropylation, sec-butylation, and tertbutylation of naphthalene (NP) over several large-pore zeolites to elucidate the mechanism of selective catalysis. Selectivities for dialkylnaphthalene (DAN) isomers were influenced by the type of zeolite and bulkiness of alkylating agent. Selective formation of b,b-and 2,6-diisopropylnaphthalene (DIPN) occurred only over H-mordenite (MOR) in the isopropylation of NP using propene; bulky transition states of a,a-and a,b-DIPN are excluded because of steric restriction by the channels, resulting in selective formation of b,b-and 2,6-DIPN. However, low selectivities for b,b-and 2,6-DIPN were observed over the zeolites, SSZ-24 (AFI), SSZ-55 (ATS), and SSZ-42 (IFR) with 12-membered-ring (12-MR) pore entrances of one-dimensional channels, CIT-5 (CFI), UTD-1 (DON), and SSZ-53 (SFH) with 14-membered-ring (14-MR) pore entrances of one-dimensional channels, and Y-zeolite (FAU), zeolite b (BEA), and CIT-1 (CON) with 12-MR pore entrances of three-dimensional channels, because their channels are too large for the exclusion of bulky isomers. Catalysis over these zeolites occurs under kinetic and/or thermodynamic control, resulting in predominant formation of a,a-and a,b-DIPN at lower temperatures and an increase of the stable isomer b,b-DIPN at higher temperatures.The selectivities for b,b-and 2,6-DAN were enhanced with the increase in bulkiness of alkylating agents: 1-butene for sec-butylation and 2-methylpropene for tert-butylation. In particular, b,b-di-tertbutylnaphthalene (DTBN) was selectively formed in the tert-butylation. The selectivities for b,b-and 2,6-DAN were enhanced even in large channels: the transition states of the least bulky isomers only fit the channels because other bulky isomers are excluded by steric restriction of the channels. However, tert-butylation over FAU, BEA, and CON had selectivities for 2,6-DTBN of around 50-60%, although selectivities for b,b-DTBN were almost 100% selectivity; these zeolites can hardly recognize the differences between 2,6-and 2,7-DTBN. The results indicate that the fitting of the least bulky isomers to zeolite channels, leading to the exclusion of other bulky isomers, is essential for highly shape-selective catalysis.

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Section: Steric Interaction Of Reagents With Zeolitessupporting

confidence: 86%

Section: Introductionmentioning

confidence: 98%

Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Sugi

2010

J Chinese Chemical Soc

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“…These results support the assertion that FAU channels are too large for the selective formation of 4,4'-DIPB. Figure 8 shows the effects of reaction temperature on the isopropylation of BP over BEA 17) . The princi- pal isomers were 2,x'-DIPB isomers at approximately 50% selectivities at lower temperatures, whereas the selectivities for 4,4'-DIPB were almost constant (26-30%) in the range of 150 to 300ºC.…”

Section: Isopropylation Of Bp Over Fau and Beamentioning

confidence: 99%

“…Figure 7 shows the effect of reaction temperature on the isopropylation of BP over FAU 17) . The isopropylation over FAU is not shape-selective for the formation of IPBP and DIPB, and highly dependent on reaction temperature.…”

Section: Isopropylation Of Bp Over Fau and Beamentioning

confidence: 99%

Alkylation of Biphenyl and Naphthalene over Zeolites: Characteristics of Shape-selective Catalysis in Zeolite Channels

Sugi

2010

J. Jpn. Petrol. Inst.

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“…Among them, mordenite (MOR) supports highly selective formation of the least bulky 4,4 0 -diisopropylbiphenyl (4,4 0 -DIPB) in the isopropylation of BP [5][6][7][8][9][10]. However, large pore zeolites with three-dimensional channels of 12-MR pore entrances, such as Y zeolite (FAU) and zeolite b (BEA) afford non-selective products with the low selectivities for 4,4 0 -DIPB [13,14]. The bulky alkylating agents, such as 1-butene and 2-methylpropene, enhanced the selectivities for 4,4 0 -dialkylbiphenyl (4,4 0 -DAB): 4,4 0 -disec-butylbiphenyl (4,4 0 -DSBB) in the sec-butylation and 4,4 0 -di-tert-butylbiphenyl (4,4 0 -DTBB) in the tert-butylation, respectively, with the increase in the interaction with the channels even over large pore zeolites [11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Alkylation of Biphenyl over Zeolites: Shape-Selective Catalysis in Zeolite Channels

Sugi

Vinu

2015

Catal Surv Asia

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Steric interaction of reactants, products, and transition state intermediates with zeolites with 12-and 14-membered ring pore entrances is discussed in the alkylation of biphenyl (BP) by propene, 1-butene, and 2-methylpropene as alkylating agents. The selectivities for the least bulky 4,4 0 -dialkylbiphenyl (4,4 0 -DAB) depended on the types of zeolite and alkylating agent. The zeolites are classified as two types: Category I: mordenite (MOR), SSZ-24 (AFI), SSZ-31 (STO), CIT-5 (CFI), MCM-68 (MSE), and ZSM-12 (MTW) with straight (or slightly corrugated) channels with 12-MR or 14-MR pore entrances. Category II: SSZ-42 (IFR), SSZ-55 (ATS), SSZ-60 (SSY), Y (FAU), b (BEA), CIT-1 (CON), UTD-1 (DON), and SSZ-53 (SFH) with large channels. Category I zeolites have shape-selective natures in their channels in the isopropylation. Among them, MOR supported the highest selectivities around 85 % for 4,4 0 -diisopropylbipneyl (4,4 0 -DIPB) at moderate temperatures as 250 o C. The selectivities of 4,4 0 -DIPB are: MOR [ AFI, MSE [ MTW, CFI, STO: the differences are due to the recognition of 4,4 0 -and 3,4 0 -DIPB by the channels. Category II zeolites allow the accommodation and the formation of bulky DIPB isomers in their channels, resulting in non-shape selective catalysis under kinetic and/or thermodynamic controls. Bulky alkylating agents, 1-butene and 2-methylpropene, enhance selective formation of the least bulky 4,4 0 -DAB: 4,4 0 -di-sec-butylbiphenyl (4,4 0 -DSSB) and 4,4 0 -di-tert-butylbiphenyl (4,4 0 -DTBB), respectively, even over Category II zeolites. The bulky moieties enhance the exclusion of bulky isomers by their interaction with zeolite channels. The selectivities for 4,4 0 -DSSB were increased remarkably to higher than 80 % for Category I zeolites and to 70 % for ATS in Category II zeolites in the sec-butylation. However, kinetic and thermodynamic controls still worked with the formation of bulky isomers over Category II zeolites: IFR, FAU, BEA, CON, DON, and SFH in the secbutylation. The high selectivities for 4,4 0 -DTTB higher than 80 % were observed for the zeolites, except FAU in the tertbutylation. These results indicate that the selectivities for 4,4 0 -DAB are controlled primarily by space and shape of zeolite channels for active sites, and not always by the size of pore entrances.

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The alkylation of biphenyl over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Cited by 17 publications

References 28 publications

Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Shape‐Selective Alkylation of Naphthalene over Zeolites: Steric Interaction of Reagents with Zeolites

Alkylation of Biphenyl and Naphthalene over Zeolites: Characteristics of Shape-selective Catalysis in Zeolite Channels

Alkylation of Biphenyl over Zeolites: Shape-Selective Catalysis in Zeolite Channels

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