How Many Molecules Can Fit in a Zeolite Pore? Implications for the Hydrocarbon Pool Mechanism of the Methanol-to-Hydrocarbons Process

The methanol-to-hydrocarbons (MTH) process is a very advantageous way to upgrade methanol to more valuable commodity chemicals such as light alkenes and gasoline. There is general agreement that, at steady state, the process operates via a dual cycle “hydrocarbon pool” mechanism. This mechanism defines a minimum number of reactants, intermediates, and products that must be present for the reaction to occur. In this paper, we calculate (by three independent methods) the volume required for a range of compounds that must be present in a working catalyst. These are compared to the available volume in a range of zeolites that have been used, or tested, for MTH. We show that this straightforward comparison provides a means to rationalize the product slate and the deactivation pathways in zeotype materials used for the MTH reaction.

Stabilizing the framework of SAPO-34 zeolite toward long-term methanol-to-olefins conversion

As a commercial MTO catalyst, SAPO-34 zeolite exhibits excellent recyclability probably due to its intrinsic good hydrothermal stability. However, the structural dynamic changes of SAPO-34 catalyst induced by hydrocarbon pool (HP) species and the water formed during the MTO conversion as well as its long-term stability after continuous regenerations are rarely investigated and poorly understood. Herein, the dynamic changes of SAPO-34 framework during the MTO conversion were identified by 1D 27Al, 31P MAS NMR, and 2D 31P-27Al HETCOR NMR spectroscopy. The breakage of T-O-T bonds in SAPO-34 catalyst during long-term continuous regenerations in the MTO conversion could be efficiently suppressed by pre-coking. The combination of catalyst pre-coking and water co-feeding is established to be an efficient strategy to promote the catalytic efficiency and long-term stability of SAPO-34 catalysts in the commercial MTO processes, also sheds light on the development of other high stable zeolite catalyst in the commercial catalysis.

Transformation of Dilute Ethylene at High Temperature on Micro- and Nano-Sized H-ZSM-5 Zeolites

Ethylene dehydroaromatisation (EDA) was investigated at 700 °C under 1 bar of ethylene (5 mol% in N2) over a micro-(M) and a nano-sized (N) H-ZSM-5. On the M zeolite an induction period followed by deactivation was observed, which could be related to the presence of long diffusion path lengths in this sample, leading to mass transfer resistance. During the induction step, the aromatics yield increases, despite a significant loss of the acid site concentration as a result of coking. This induction period corresponds to the formation of an active hydrocarbon pool (HCP) composed of units of 2 to 5 aromatic rings with a molecular weight ranging from 130 to 220 g mol−1 (light coke). A kinetic study revealed that the developing HCP species is two times more active than Brønsted acid sites in the fresh zeolite. Diffusion limitations yet impact the product desorption by promoting coke growth and, therefore the deactivation of the HCP and hence of the catalyst. From MA-LDI/LDI-TOF MS (Matrix Assisted Laser Desorption Ionization—Time of Flight Mass Spectroscopy) characterisation was deduced that even after complete catalyst deactivation, the as-deposited coke continues growing at the external surface of the zeolite by condensation reactions, thus leading to heavy coke composed of more than 100 carbon atoms and a molar mass exceeding 1300 g mol−1. Unlike the micro-sized zeolite, the nano-scaled zeolite features a short diffusion path length and promotes fast formation of the active HCP. As a result, higher activity and selectivity into benzene were observed, whilst catalyst deactivation was significantly mitigated.