Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond

ConspectusIn the recent years methane has become increasingly abundant. However, transportation costs are high and methane recovered as side product is often flared rather than valorized. The chemical utilization of methane is highly challenging and currently mainly based on the cost-intensive production of synthesis gas and its conversion. Alternative routes have been discovered in academia, though high temperatures are mostly required. However, the direct conversion of methane to methanol is an exception. It can already be carried out at comparably low temperatures. It is challenging that methanol is more prone to oxidation than methane, which makes high selectivities at moderate conversions difficult to reach. Decades of research for the direct reaction of methane and oxygen did not yield a satisfactory solution for the direct partial oxidation toward methanol. When changing the oxidant from oxygen to hydrogen peroxide, high selectivities can be reached at rather low conversions, but the cost of hydrogen peroxide is comparably high. However, major advancements in the field were introduced by converting methane to a more stable methanol precursor. Most notable is the conversion of methane to methyl bisulfate in the presence of a platinum catalyst. The reaction is carried out in 102% sulfuric acid using SO3 as the oxidant. This allows for oxidation of the platinum catalyst and prevents the in situ hydrolysis of methyl bisulfate toward the less stable methanol. With a slightly different motif, the stepped conversion of methane to methanol over copper-zeolites was developed a decade ago. The copper-zeolite is first activated in oxygen at 450 °C, and then cooled to 200 °C and reacts with methane in the absence of oxygen, thus protecting a methanol precursor from overoxidation. Subsequently methanol can be extracted with water. Several active copper-zeolites were found, and the active sites were identified and discussed. For a long time, the process was almost unchanged. Lately, we implemented online steam extraction rather than off-line extraction with liquid water, which enables execution of successive cycles. While recently we reported the isothermal conversion by employing higher methane pressures, carrying out the process according to prior art only yielded neglectable amounts of methane. Using a pressure <40 bar methane gave higher yields under isothermal conditions at 200 °C than most yields in prior reports. The yield, both after high temperature activation and under isothermal conditions at 200 °C, increased monotonously with the pressure. With this account we show that the trend can be represented by a Langmuir model. Thus, the pressure dependence is governed by methane adsorption. We show that the isothermal and the high temperature activated processes have different properties and should be treated independently, from both an experimental and a mechanistic point of view.