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This work examines the linear alkylbenzene (LAB) production reaction by alkylation of benzene with 1-dodecene
over a commercial mordenite, containing 30% Al2O3 as a binder, in a fixed bed reactor. The effects of various
steam pretreatments on the properties of mordenite were studied in the LAB reaction and characterized by means
of temperature programming desorption of ammonia. It was found that with steam pretreatment at 10.7 kPa partial
pressure, the mordenite catalyst has a maximum acidity and activity, selectivity of 98% LAB product with 67%
2-phenyl isomer and stability beyond 600 hours operation. In the proposed reaction pathway, the isomer selectivity
and catalytic stability were attributed to the result of product shape selectivity from zeolite pore structures and the
comparative reaction rate of isomerization and alkylation of 1-dodecene, in which alkylation was catalyzed by
strong acid sites. The extent to which external (liquid–solid) and internal (pore diffusion) mass transfer affects the
main reaction was also carefully examined. Furthermore, in benzene enriched feeds, the LAB reaction was found
to be first order with respective to 1-dodecene, with an apparent activation energy of 17 kcal mol21.
prepared by slicing or crushing was also studied. It is clearly Table 2 Dodecene conversion and product selectivity under various
shown in Table 1 that the conversion of the 8–12 mesh crushed temperatures over 12–20 mesh mordenite (pressure: 2.0 MPa; WHSV: 4
hr21; H2/HC: 0.7 mol mol21; time-on-stream: 6 hours)
Table 1 Effects of intraparticle diffusion on dodecene conversion Temperature/K 373 403 473
(pressure: 3.0 MPa; temperature: 433 K; WHSV: 16 hr21; H2/HC: 0.7 mol
mol21; Time-on-stream: 20 hours). Conversion (%) 70.3 98.5 98.6
Product distribution (wt%)
Extrudate 3.2 mm 1.6 mm 1.6 mm Lights <1 <1 37
Propylbenzene <1 <1 12
Sliced Dodecylbenzenes 75 99 51
(high Dodecene dimers 22 <1 <1
Method Crush Crush Crush Sliced Sliced porosity) Heaviers 2 <1 <1
Mesh 20–30 12–20 8–12
Conversion 96% 96% 89% 62% 52% 96% thermodynamic equilibrium is favorable at low temperature,
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Fig. 8 1-Dodecene conversion versus the reaction time using 12–20 mesh
mordenite (temperature: 433–473 K, pressure: 2.0 MPa, WHSV: 1.92 hr21,
H2/HC: 0.70 mol mol21).
kPa).
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