JOURNAL OF THE CHINESE CERAMIC SOCIETY MCM-41. Modified MCM-41 as Catalyst for Synthesis of Geranyl Propionate

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1 JOURNAL OF THE CHINESE CERAMIC SOCIETY Vol. 40 No. 4 April 2012 MCM-41 ( ) H 2 SO 4 MCM (mobile crystalline material)-41 SO 2 4 SO 2 4 /MCM-41 X NH 3 N 2 SO 2 4 /MCM-41 H 2 SO 4 MCM-41 SO 2 4 /MCM mol/l MCM-41 1 h h SO 2 4 /MCM % 85.20% H 2 SO 4 MCM-41 O A (2012) :18:00 DOI CNKI: /TQ Modified MCM-41 as Catalyst for Synthesis of Geranyl Propionate TANG Xiaohong (Department of Chemistry, Henan Institute of Education, Zhengzhou , China) Abstract: SO 4 2 /mobile crystalline material (MCM-41) was prepared via the modification of MCM-41 with H 2 SO 4. Its structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), NH 3 -temperature programmed desorption (NH 3 -TPD) and N 2 adsorption-desorption, respectively. The geranyl propionate (GP) was synthesized. Using SO 4 2 /MCM-41 as a catalyst. The effects of amount and regeneration of the catalyst on the reaction results were investigated. H 2 SO 4, MCM-41 and SO 4 2 /MCM-41 were used as a catalyst for the synthesis of GP, respectively, and their catalytic properties were compared. The results show that the mesoporous molecular sieves SO 4 2 /MCM-41with a long-range order and a good crystallinity can be obtained by dipping the mesoporous molecular sieves MCM-41 with H 2 SO 4 of 0.50 mol/l for 1.0 h and calcining at 450 for 3.0 h. The conversion could be 88.82% and the selectivity of GP was 85.20% when the modified MCM-41 was used as a catalyst for the esterification of geraniol. The modification effect with H 2 SO 4 on the structure of MCM-41 mesoporous molecular sieves was not obvious, but could improve its acidity. Key words: mesoporous molecular sieves; modification; catalyst; geranyl propionate MCM-41 [1 6] 2 8 nm 700 m 2 /g MCM-41 MCM-41 [7] [8] MCM-41 [9] MCM (1977 ) Received date: Revised date: First author: TANG Xiaohong (1977 ), female, Master, lecturer. txhyxw@126.com

2 40 4 MCM Iliopoulou [10] H 2 SO 4 MCM-41 SO 2 4 SO 2 4 /MCM-41 H 2 SO 4 MCM-41 SO 2 4 /MCM SO 2 4 /MCM-41 [11] MCM-41 ( mol/l) MCM-41 (1 g MCM ml H 2 SO 4 ) ( h) h ( ) 3.0 h SO 2 4 /MCM (GP) 1.0: h 1.3 D/max-3B X X (XRD) Nicolet NEXUS 470 Fourier (FTIR) NH 3 -TPD NH 3 (NH 3 temperature-programmed desorption NH 3 -TPD) ASAP2010 GC-900C 1 XRD Fig. 1 XRD spectra of ssamples Preparing condition of SO 2 4 /MCM-41: Dipping H 2 SO 4 concentration: 0.50 mol/l; dipping time: 1 h; calcination temperature: 450, the same below. XRD 2θ = 2.2 2θ = 3.9 2θ = SO 2 4 /MCM-41 2θ = 2.4 2θ = 4.2 2θ = [12] SO 2 4 /MCM-41 [13] FTIR 2 MCM-41 SO 2 4 / MCM-41 FTIR cm 1 Si O Si 800 cm 1 Si O Si 450 cm 1 Si O Si MCM-41 SO 2 4 /MCM-41 FTIR 3 SO 2 4 /MCM-41 FTIR cm 1 1 S=O [14] XRD MCM-41 SO 2 4 /MCM-41 2 FTIR Fig. 2 FTIR spectra of samples

3 592 SO h NH 3 -TPD 3 NH 3 -TPD 3 MCM NH mmol/g [15] SO 2 4 /MCM NH mmol/g SO 2 4 / MCM-41 MCM-41 1 Table 1 Pore structure of samples Sample BJH mostprobable BET surface area/ BJH pore volume/ pore diameter/nm (m 2 g 1 ) (cm 3 g 1 ) MCM SO 2 4 /MCM SO 2 4 /MCM MCM-41 2 MCM mol/l [14] 0.50 mol/l 2 Table 2 Reaction results of catalysts to geranyl propionate (GP) in different H 2 SO 4 concentrations 3 NH 3 -TPD Fig. 3 NH 3 -TPD spectra of samples MCM-41 SO 2 4 /MCM SO 2 4 / MCM-41 MCM- 41 SO 2 4 MCM- 41 FTIR Concentration of H 2 SO 4 /(mol L 1 ) Conversion/% Selectivity/% Reaction conditions: 30.8 g of geraniol; Mole ratio of geraniol to propionic acid is 1:1.5; 120 ; 8 h, the same below. Catalysts: 1 g (dipping time: 1 h; calcination temperature: 450 ) mol/l h 3 Table 3 Reaction results of catalysts dipped for different time 4 Fig. 4 Nitrogen desorption isotherms of samples p/p 0 is relative pressure. Time/h Conversion/% Selectivity/% Catalysts: 1 g (dipping H 2 SO 4 concentration: 0.50 mol/l; calcination temperature: 450 ).

4 40 4 MCM h % 80.97% MCM-41 ( 2) SO 2 4 MCM-41 ( ) 4 Table 4 Reaction results with catalysts calcinated at different temperatures Temperature/ Conversion/% Selectivity/% Catalysts: 1 g (dipping time: 1 h; dipping H 2 SO 4 concentration: 0.50 mol/l) % 88.37% 1 g 5 Table 5 Reaction performances with different amounts of catalysts Mass of SO 4 2 /MCM-41/g Conversion/% Selectivity/% Catalysts: g (dipping H 2 SO 4 concentration: 0.50 mol/l; dipping time: 1 h; calcination temperature: 450 ) h SO 4 MCM-41 ( ) Table 6 Conversion of geraniol with catalysts at different calcination temperatures Sample Calcinations temperature/ Regeneration before 88.45% 88.82% 81.49% 71.96% Regeneration after 39.71% 53.21% 80.07% 67.15% Catalysts: 1 g (dipping time: 1 h; dipping H 2 SO 4 concentration: 0.50 mol/l) H 2 SO 4 MCM-41 SO 2 4 /MCM-41 2 H 2 SO 4 SO 2 4 /MCM-41 MCM-41 7 H 2 SO 4 SO 2 4 /MCM-41 SO 2 4 /MCM-41 MCM-41 Table 7 7 Catalytic performances of different catalysts Catalyst Conversion/% Selectivity/% MCM H 2 SO SO 2 4 /MCM Catalysts: 1 g. 3 1) 0.50 mol/l MCM-41 1 h h SO 2 4 /MCM-41

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