Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Critical role of formaldehyde during methanol conversion to hydrocarbons.

ABSTRACT: 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 ¹³C-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.

SUBMITTER: Liu Y

PROVIDER: S-EPMC6443648 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Critical role of formaldehyde during methanol conversion to hydrocarbons.

Liu Yue Y Kirchberger Felix M FM Müller Sebastian S Eder Moritz M Tonigold Markus M Sanchez-Sanchez Maricruz M Lercher Johannes A JA

Nature communications 20190401 1

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 <sup>13</sup>C- ...[more]

PMID: 30931945

Similar Datasets

Role of formaldehyde in promoting aromatic selectivity during methanol conversion over gallium-modified zeolites

Project description:Gallium-modified HZSM-5 zeolites are known to increase aromatic selectivity in methanol conversion. However, there are still disputes about the exact active sites and the aromatic formation mechanisms over Ga-modified zeolites. In this work, in situ synchrotron radiation photoionization mass spectrometry (SR-PIMS) experiments were carried out to study the behaviors of intermediates and products during methanol conversion over Ga-modified HZSM-5. The increased formaldehyde (HCHO) yield over Ga-modified HZSM-5 was found to play a key role in the increase in aromatic yields. More HCHO was deemed to be generated from the direct dehydrogenation of methanol, and Ga2O3 in Ga-modified HZSM-5 was found to be the active phase. The larger increase in aromatic production over Ga-modified HZSM-5 after reduction‒oxidation treatment was found to be the result of redispersed Ga2O3 with smaller size generating a larger amount of HCHO. This study provides some new insights into the internal driving force for promoting the production of aromatics over Ga-modified HZSM-5. Gallium-modified HZSM-5 zeolites demonstrate increased selectivity towards aromatics during methanol conversion, but the mechanism and the nature of the active sites that lead to this enhanced selectivity are poorly understood. Here, in situ synchrotron radiation photoionization mass spectrometry experiments reveal that increased formaldehyde generation over Ga2O3 species plays a key role in promoting the production of aromatic compounds.

| S-EPMC9814038 | biostudies-literature

Elucidation of radical- and oxygenate-driven paths in zeolite-catalysed conversion of methanol and methyl chloride to hydrocarbons.

Project description:Understanding hydrocarbon generation in the zeolite-catalysed conversions of methanol and methyl chloride requires advanced spectroscopic approaches to distinguish the complex mechanisms governing C-C bond formation, chain growth and the deposition of carbonaceous species. Here operando photoelectron photoion coincidence (PEPICO) spectroscopy enables the isomer-selective identification of pathways to hydrocarbons of up to C14 in size, providing direct experimental evidence of methyl radicals in both reactions and ketene in the methanol-to-hydrocarbons reaction. Both routes converge to C5 molecules that transform into aromatics. Operando PEPICO highlights distinctions in the prevalence of coke precursors, which is supported by electron paramagnetic resonance measurements, providing evidence of differences in the representative molecular structure, density and distribution of accumulated carbonaceous species. Radical-driven pathways in the methyl chloride-to-hydrocarbons reaction(s) accelerate the formation of extended aromatic systems, leading to fast deactivation. By contrast, the generation of alkylated species through oxygenate-driven pathways in the methanol-to-hydrocarbons reaction extends the catalyst lifetime. The findings demonstrate the potential of the presented methods to provide valuable mechanistic insights into complex reaction networks.

| S-EPMC7613158 | biostudies-literature

Hierarchical H-ZSM5 zeolites based on natural kaolinite as a high-performance catalyst for methanol to aromatic hydrocarbons conversion.

Project description:The present work introduces a good prospect for the development of hierarchical catalysts with excellent catalytic performance in the methanol to aromatic hydrocarbons conversion (MTA) process. Hierarchical H-ZSM5 zeolites, with a tailored pore size and different Si/Al ratios, were synthesized directly using natural kaolin clay as a low-cost silica and aluminium resource. Further explored for the direct synthesis of hierarchical HZSM-5 structures was the steam assisted conversion (SAC) with a cost-effective and green affordable saccharide source of high fructose corn syrup (HFCS), as a secondary mesopore agent. The fabricated zeolites exhibiting good crystallinity, 2D and 3D nanostructures, high specific surface area, tailored pore size, and tunable acidity. Finally, the catalyst performance in the conversion of methanol to aromatic hydrocarbons was tested in a fixed bed reactor. The synthesized H-ZSM5 catalysts exhibited superior methanol conversion (over 100?h up to 90%) and selectivity (over 85%) in the methanol conversion to aromatic hydrocarbon products.

| S-EPMC6879614 | biostudies-literature

Improving formaldehyde consumption drives methanol assimilation in engineered E. coli.

Project description:Due to volatile sugar prices, the food vs fuel debate, and recent increases in the supply of natural gas, methanol has emerged as a promising feedstock for the bio-based economy. However, attempts to engineer Escherichia coli to metabolize methanol have achieved limited success. Here, we provide a rigorous systematic analysis of several potential pathway bottlenecks. We show that regeneration of ribulose 5-phosphate in E. coli is insufficient to sustain methanol assimilation, and overcome this by activating the sedoheptulose bisphosphatase variant of the ribulose monophosphate pathway. By leveraging the kinetic isotope effect associated with deuterated methanol as a chemical probe, we further demonstrate that under these conditions overall pathway flux is kinetically limited by methanol dehydrogenase. Finally, we identify NADH as a potent kinetic inhibitor of this enzyme. These results provide direction for future engineering strategies to improve methanol utilization, and underscore the value of chemical biology methodologies in metabolic engineering.

| S-EPMC6008399 | biostudies-literature

Development of Bacillus methanolicus methanol dehydrogenase with improved formaldehyde reduction activity.

Project description:Methanol dehydrogenase (MDH), an NAD+-dependent oxidoreductase, reversibly converts formaldehyde to methanol. This activity is a key step for both toxic formaldehyde elimination and methanol production in bacterial methylotrophy. We mutated decameric Bacillus methanolicus MDH by directed evolution and screened mutants for increased formaldehyde reduction activity in Escherichia coli. The mutant with the highest formaldehyde reduction activity had three amino acid substitutions: F213V, F289L, and F356S. To identify the individual contributions of these residues to the increased reduction activity, the activities of mutant variants were evaluated. F213V/F289L and F213V/F289L/F356S showed 25.3- and 52.8-fold higher catalytic efficiency (kcat/Km) than wild type MDH, respectively. In addition, they converted 5.9- and 6.4-fold more formaldehyde to methanol in vitro than the wild type enzyme. Computational modelling revealed that the three substituted residues were located at MDH oligomerization interfaces, and may influence oligomerization stability: F213V aids in dimer formation, and F289L and F356S in decamer formation. The substitutions may stabilise oligomerization, thereby increasing the formaldehyde reduction activity of MDH.

| S-EPMC6102214 | biostudies-literature

Evaluation of synthetic formaldehyde and methanol assimilation pathways in Yarrowia lipolytica.

Project description:Background:Crude glycerol coming from biodiesel production is an attractive carbon source for biological production of chemicals. The major impurity in preparations of crude glycerol is methanol, which is toxic for most microbes. Development of microbes, which would not only tolerate the methanol, but also use it as co-substrate, would increase the feasibility of bioprocesses using crude glycerol as substrate. Results:To prevent methanol conversion to CO2 via formaldehyde and formate, the formaldehyde dehydrogenase (FLD) gene was identified in and deleted from Yarrowia lipolytica. The deletion strain was able to convert methanol to formaldehyde without expression of heterologous methanol dehydrogenases. Further, it was shown that expression of heterologous formaldehyde assimilating enzymes could complement the deletion of FLD. The expression of either 3-hexulose-6-phosphate synthase (HPS) enzyme of ribulose monosphosphate pathway or dihydroxyacetone synthase (DHAS) enzyme of xylulose monosphosphate pathway restored the formaldehyde tolerance of the formaldehyde sensitive ?fld1 strain. Conclusions:In silico, the expression of heterologous formaldehyde assimilation pathways enable Y. lipolytica to use methanol as substrate for growth and metabolite production. In vivo, methanol was shown to be converted to formaldehyde and the enzymes of formaldehyde assimilation were actively expressed in this yeast. However, further development is required to enable Y. lipolytica to efficiently use methanol as co-substrate with glycerol.

| S-EPMC6918578 | biostudies-literature

Lanthanide-Dependent Methanol and Formaldehyde Oxidation in Methylobacterium aquaticum Strain 22A.

Project description:Lanthanides (Ln) are an essential cofactor for XoxF-type methanol dehydrogenases (MDHs) in Gram-negative methylotrophs. The Ln3+ dependency of XoxF has expanded knowledge and raised new questions in methylotrophy, including the differences in characteristics of XoxF-type MDHs, their regulation, and the methylotrophic metabolism including formaldehyde oxidation. In this study, we genetically identified one set of Ln3+- and Ca2+-dependent MDHs (XoxF1 and MxaFI), that are involved in methylotrophy, and an ExaF-type Ln3+-dependent ethanol dehydrogenase, among six MDH-like genes in Methylobacterium aquaticum strain 22A. We also identified the causative mutations in MxbD, a sensor kinase necessary for mxaF expression and xoxF1 repression, for suppressive phenotypes in xoxF1 mutants defective in methanol growth even in the absence of Ln3+. Furthermore, we examined the phenotypes of a series of formaldehyde oxidation-pathway mutants (fae1, fae2, mch in the tetrahydromethanopterin (H4MPT) pathway and hgd in the glutathione-dependent formaldehyde dehydrogenase (GSH) pathway). We found that MxaF produces formaldehyde to a toxic level in the absence of the formaldehyde oxidation pathways and that either XoxF1 or ExaF can oxidize formaldehyde to alleviate formaldehyde toxicity in vivo. Furthermore, the GSH pathway has a supportive role for the net formaldehyde oxidation in addition to the H4MPT pathway that has primary importance. Studies on methylotrophy in Methylobacterium species have a long history, and this study provides further insights into genetic and physiological diversity and the differences in methylotrophy within the plant-colonizing methylotrophs.

| S-EPMC7356819 | biostudies-literature

Anaerobic microbial methanol conversion in marine sediments.

Project description:Methanol is an ubiquitous compound that plays a role in microbial processes as a carbon and energy source, intermediate in metabolic processes or as end product in fermentation. In anoxic environments, methanol can act as the sole carbon and energy source for several guilds of microorganisms: sulfate-reducing microorganisms, nitrate-reducing microorganisms, acetogens and methanogens. In marine sediments, these guilds compete for methanol as their common substrate, employing different biochemical pathways. In this review, we will give an overview of current knowledge of the various ways in which methanol reaches marine sediments, the ecology of microorganisms capable of utilizing methanol and their metabolism. Furthermore, through a metagenomic analysis, we shed light on the unknown diversity of methanol utilizers in marine sediments which is yet to be explored.

| S-EPMC8048578 | biostudies-literature

One-step electric-field driven methane and formaldehyde synthesis from liquid methanol.

Project description:The reaction pathways connecting methanol to methane and formaldehyde are among the most emblematic in chemistry because of their outstanding interest in the fields of energy, synthesis, and bio- and geo-chemistry. Despite of its fundamental nature, the one-pot synthesis of formaldehyde and methane stemming from methanol has never been reported before. Here we present a study, based on ab initio molecular dynamics and free-energy methods, in which the simultaneous oxidation and reduction (i.e., the disproportionation) of liquid methanol into methane and formaldehyde has been achieved at ambient temperature through the application of a static electric field. Because strong electric fields can be generated in the proximity of field emitter tips, this finding shows that the challenge of experimentally disproportionating methanol into formaldehyde and methane could be attempted. We show that the methanol "solvent" molecules play a major role in this process and that the chemical pathway connecting methanol to the detected products in the bulk liquid phase is very different from its reproduced gas-phase counterpart. Finally, we demonstrate that switching on an external electric field drastically modifies the reaction network of methanol, lowering some activation barriers, stabilizing the methane and formaldehyde products, and opening otherwise difficult-to-achieve chemical routes.

| S-EPMC5363374 | biostudies-literature

Two-component system that regulates methanol and formaldehyde oxidation in Paracoccus denitrificans.

Project description:A chromosomal region encoding a two-component regulatory system, FlhRS, has been isolated from Paracoccus denitrificans. FlhRS-deficient mutants were unable to grow on methanol, methylamine, or choline as the carbon and energy source. Expression of the gene encoding glutathione-dependent formaldehyde dehydrogenase (fhlA) was undetectable in the mutant, and expression of the S-formylglutathione hydrolase gene (fghA) was reduced in the mutant background. In addition, methanol dehydrogenase was immunologically undetectable in cell extracts of FhlRS mutants. These results indicate that the FlhRS sensor-regulator pair is involved in the regulation of formaldehyde, methanol, and methylamine oxidation. The effect that the FlhRS proteins exert on the regulation of C(1) metabolism might be essential to maintain the internal concentration of formaldehyde below toxic levels.

| S-EPMC94923 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data