Scale study of direct synthesis of dimethyl ether from biomass synthesis gas

We investigated the synthesis of dimethyl ether (DME) from biomass synthesis gas using a kind of hybrid catalyst consisting of methanol and HZSM-5 zeolite in a fixed-bed reactor in a 100 ton/year pilot plant. The biomass synthesis gas was produced by oxygen-rich gasification of corn core in a two-stage fixed bed. The results showed that CO conversions reached 82.00% and 73.55%, the selectivities for DME were 73.95% and 69.73%, and the space-time yields were 124.28 kg m- 3 h- 1 and 203.80 kg m- 3 h- 1 when gas hourly space velocities were 650 h- 1 and 1200 h- 1, respectively. Deoxidation and tar removal from biomass synthesis gas was critical to the stable operation of the DME synthesis system. Using single-pass synthesis, the H2/CO ratio improved from 0.98-1.17 to 2.12-2.22. The yield of DME would be increased greatly if the exhaust was reused after removal of the CO2.

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.

A study on the ignition process for the catalytic partial oxidation of methane to synthesis gas by MS-TPSR technique

The ignition processes for the catalytic partial oxidation of methane (POM) to synthesis gas over oxidic nickel catalyst (NiO/Al2O3), reduced nickel catalyst (Ni-0/Al2O3), and Pt-promoted oxidic nickel catalyst (Pt-NiO/Al2O3) were studied by the temperature-programmed surface reaction (TPSR) technique. The complete oxidation of methane usually took place on the NiO catalyst during the CH4/O-2 reaction, even with a pre-reduced nickel catalyst, and Ni-0 is inevitably first oxidized to NiO if the temperature is below the ignition temperature. It is above a certain temperature that Ni-0 is formed again, which leads to the start of the POM. The POM can be initiated at a much lower temperature on a Pt-NiO catalyst because of Pt promotion of the reduction of NiO. The POM in a fluidized bed can be easily initiated due to the addition of Pt.