Higher-value chemicals can be produced from methane with small exergy losses by partial oxidation if the chemical conversion proceeds in an internal combustion engine (ICE) as a polygeneration process (Gossler and Deutschmann, 2015). Kinetics models are not sufficiently validated for the very fuel-rich and high-pressure conditions relevant for this process. Therefore, ignition delay times of fuel-rich methane/(additive)/air mixtures were measured in a shock tube at about 30 bar and temperatures between 600 and 1650 K. n-heptane and diethylether were used as additives to increase the reactivity of the fuel so that the polygeneration process can be realized in an ICE at HCCI conditions at lower compression temperatures. At ϕ = 2, measured ignition delay times agree well with simulations using different mechanisms from literature. Synthesis gas (CO, H₂) is the main product at these conditions (Sen et al., 2016). For the production of higher hydrocarbons, the equivalence ratio must be increased. Very fuel-rich mixtures (ϕ = 10) were used because the temperature increase during the reaction of these mixtures is quite low (<450 K), so that post-ignition temperatures stay below the lower limit of soot formation. Only for mixtures with n-heptane as additive, good agreement of measured and simulated ignition delay times is found. The other mixtures show strong deviations with all mechanisms. As a further parameter to improve and validate the mechanisms at ϕ = 10, product distributions after ignition were determined by sampling in the cooling phase with a fast-opening valve and GC/MS analysis. Besides H₂ and H₂O, CO and higher hydrocarbons like C₂H₂, C₂H₄, C₂H₆, and C₆H₆ were detected as main products. About half of the carbon of the consumed methane is converted to CO, the other half to higher hydrocarbons. The product distributions are well predicted by simulations.

如果化学转化是在内燃机（ICE）中作为多联产过程进行的，则通过部分氧化可以从甲烷中产生较高价值的化学药品，但会有少量的火用损失（Gossler and Deutschmann，2015）。对于与该过程相关的非常富燃料和高压条件，动力学模型尚未得到充分验证。因此，点火富燃料甲烷/（添加剂）的延迟时间/在激波管，测定在约600和1650 K之间30巴和温度空气混合物Ñ-庚烷和二乙醚用作添加剂以增加燃料的反应性，从而可以在HCCI条件下的ICE中以较低的压缩温度在ICE中实现多联产过程。在ϕ = 2时，测得的点火延迟时间与文献中使用不同机理的模拟结果非常吻合。在这些条件下，合成气（CO，H ₂ ）是主要产物（Sen等，2016）。为了生产高级烃时，当量比必须增加。使用非常富燃料的混合物（ϕ = 10），因为这些混合物反应期间的温度升高非常低（<450 K），因此点火后温度保持在烟灰形成的下限以下。仅适用于具有n的混合物-庚烷作为添加剂，发现实测和模拟的点火延迟时间吻合良好。其他混合物在所有机理上均表现出强烈的偏差。作为改善和验证ϕ = 10机理的另一个参数，通过在冷却阶段使用快速打开的阀门进行采样并进行GC / MS分析，确定着火后的产物分布。除了H ₂和H ₂ O之外，还包括CO和高级碳氢化合物，例如C ₂ H ₂，C ₂ H ₄，C ₂ H ₆和C ₆ H ₆被检测为主要产品。消耗的甲烷中约有一半的碳转化为CO，另一半转化为高级烃。通过模拟可以很好地预测产品分布。