TY - JOUR
T1 - Critical role of formaldehyde during methanol conversion to hydrocarbons
AU - Liu, Yue
AU - Kirchberger, Felix M.
AU - Müller, Sebastian
AU - Eder, Moritz
AU - Tonigold, Markus
AU - Sanchez-Sanchez, Maricruz
AU - Lercher, Johannes A.
N1 - Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - Formaldehyde is an important intermediate product in the catalytic conversion of methanol to olefins (MTO). Here we show that formaldehyde is present during MTO with an average concentration of ~0.2 C% across the ZSM-5 catalyst bed up to a MeOH conversion of 70%. It condenses with acetic acid or methyl acetate, the carbonylation product of MeOH and DME, into unsaturated carboxylate or carboxylic acid, which decarboxylates into the first olefin. By tracing its reaction pathways of 13 C-labeled formaldehyde, it is shown that formaldehyde reacts with alkenes via Prins reaction into dienes and finally to aromatics. Because its rate is one order of magnitude higher than that of hydrogen transfer between alkenes on ZSM-5, the Prins reaction is concluded to be the major reaction route from formaldehyde to produce dienes and aromatics. In consequence, formaldehyde increases the yield of ethene by enhancing the contribution of aromatic cycle.
AB - Formaldehyde is an important intermediate product in the catalytic conversion of methanol to olefins (MTO). Here we show that formaldehyde is present during MTO with an average concentration of ~0.2 C% across the ZSM-5 catalyst bed up to a MeOH conversion of 70%. It condenses with acetic acid or methyl acetate, the carbonylation product of MeOH and DME, into unsaturated carboxylate or carboxylic acid, which decarboxylates into the first olefin. By tracing its reaction pathways of 13 C-labeled formaldehyde, it is shown that formaldehyde reacts with alkenes via Prins reaction into dienes and finally to aromatics. Because its rate is one order of magnitude higher than that of hydrogen transfer between alkenes on ZSM-5, the Prins reaction is concluded to be the major reaction route from formaldehyde to produce dienes and aromatics. In consequence, formaldehyde increases the yield of ethene by enhancing the contribution of aromatic cycle.
UR - http://www.scopus.com/inward/record.url?scp=85063753902&partnerID=8YFLogxK
U2 - 10.1038/s41467-019-09449-7
DO - 10.1038/s41467-019-09449-7
M3 - Article
C2 - 30931945
AN - SCOPUS:85063753902
SN - 2041-1723
VL - 10
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 1462
ER -