Design and operation of integrated pilot-scale dimethyl ether synthesis system via pyrolysis/gasification of corncob

The integrated pilot-scale dimethyl ether (DME) synthesis system from corncob was demonstrated for modernizing utilization of biomass residues. The raw bio-syngas was obtained by the pyrolyzer/gasifier at the yield rate of 40-45 Nm(3)/h. The content of tar in the raw bio-syngas was decreased to less than 20 mg/Nm(3) by high temperature gasification of the pyrolysates under O-2-rich air. More than 70% CO2 in the raw bio-syngas was removed by pressure-swing adsorption unit (PSA). The bio-syngas (H-2/CO approximate to 1) was catalytically converted to DME in the fixed-bed tubular reactor directly over Cu/Zn/Al/HZSM-5 catalysts. CO conversion and space-time yield of DME were in the range of 82.0-73.6% and 124.3-203.8 kg/m(cat)(3)/h, respectively, with a similar DME selectivity when gas hourly space velocity (GHSV, volumetric flow rate of syngas at STP divided by the volume of catalyst) increased from 650 h(-1) to 1500 h(-1) at 260 degrees C and 4.3 MPa. And the selectivity to methanol and C-2(+) products was less than 0.65% under typical synthesis condition. The thermal energy conversion efficiency was ca. 32.0% and about 16.4% carbon in dried corncob was essentially converted to DME with the production cost of ca. (sic) 3737/ton DME. Cu (111) was assumed to be the active phase for DME synthesis, confirmed by X-ray diffraction (XRD) characterization.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.