Effect of different metal sulfate precursors on structural and catalytic performance of zirconia in dehydration of methanol to dimethyl ether
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Abstract: ZrO2 was treated with 10% SO42- from different metal sulfate precursors for methanol dehydration to dimethyl ether. All the samples exhibited tetragonal phase and no diffraction peaks corresponding to metal sulfates or metal oxides were observed. The FT-IR results revealed that there were different interactions between sulfate and ZrO2, and this had a great effect on the surface area of the samples. The catalytic activity was measured over the catalysts in the temperature range of 100-300℃. The results revealed that sulfated zirconia with CuSO4·5H2O and Al2(SO4)3·16H2O showed the best catalytic activity. The maximum yield of DME ≈ 87% was obtained over CuSZ at a reaction temperature of 275℃. Moreover, the catalytic activity of the catalysts was correlated well with their surface acidity that measured by dehydration of isopropanol.
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Key words:
- MSO4/ZrO2 /
- methanol /
- dehydration /
- DME
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Figure 4 N2 adsorption-desorption isotherms of pure ZrO2 and the different sulfated samples
Figure 5 Activity variation of isopropanol dehydration over pure ZrO2 and the different sulfated samples at 200 ℃ reaction temperature
Figure 6 Effect of reaction temperature on the catalytic dehydration of methanol over pure ZrO2 and the different sulfated samples
Table 1 Theoretical and actual weights percent of metal loaded, surface texture and crystallite sizes of pure ZrO2 and the different sulfated samples
Catalyst Theoretical of metal w/% Actual of metala w/% ABET/(m2 ·g-1) Total pore volume v/(cm3·g-1) Average pore diameter d/nm DXRD/nmb Pure ZrO2 0.00 0.00 36.5 0.0324 3.6 11 NaSZ 4.79 4.65 5.80 0.0069 4.8 20 KSZ 8.12 7.99 5.60 0.0061 4.4 15 CaSZ 4.16 4.10 43.8 0.0359 3.3 14 MgSZ 2.53 2.50 15.3 0.0155 4.1 17 CdSZ 11.70 11.74 40.4 0.0272 2.7 18 FeSZ 2.93 3.03 15.3 0.0178 4.6 17 AgSZ 22.4 22.21 4.30 0.0058 5.5 23 ZnSZ 6.80 6.88 25.0 0.0199 3.2 26 CoSZ 2.91 2.80 42.8 0.0266 2.5 16 MnSZ 5.72 5.68 50.5 0.0327 2.6 21 NiSZ 6.11 6.20 40.0 0.0269 2.7 18 NH4SZ 0.00 0.00 12.6 0.0101 3.2 19 AlSZ 1.87 1.80 40.1 0.0270 2.7 18 CuSZ 6.61 6.50 38.7 0.0255 2.6 17 a: measured by atomic absorption technique; b: crystallite size: determined from XRD results 
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