Recent development in catalytic technologies for methanol synthesis from renewable sources: A critical review

Ali, Khozema Ahmed; Abdullah, Ahmad Zuhairi; Mohamed, Abdul Rahman

doi:10.1016/j.rser.2015.01.010

Cited by 185 publications

(81 citation statements)

References 100 publications

(112 reference statements)

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“…Copper‐based catalysts are widely used for technical applications in methanol chemistry, well‐known examples include methanol synthesis from syngas with an optimized CO/CO 2 ratio, hydrogenation/photoreduction of CO 2 to produce “renewable” methanol, and methanol steam reforming (MSR) as the reversal of the synthesis reaction from CO 2. The ability to control product selectivity is a key criterion for technical usage. Therefore, to realize the efficient on‐board production of clean hydrogen in, for example, automotive applications, the key targets for MSR are high CO 2 selectivity, low CO content, and maximum H 2 yield in the reformate .…”

Section: Figurementioning

confidence: 89%

Boosting Hydrogen Production from Methanol and Water by in situ Activation of Bimetallic Cu−Zr Species

et al. 2016

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Ab imetallic Cu/Cu 51 Zr 14 precatalyst,a ctivated in situ, for hydrogen generation from methanol and water providesv ery high CO 2 selectivity (> 99.9 %) and high H 2 yields. Referenced to the geometrics urface area of our model surface, highera ctivity of at least one order of magnitude was observed in comparison to supportedC u/ZrO 2 and Cu/ZnO/ZrO 2 catalysts. Evolution of structurala ctivation monitored by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and electron microscopy indicatest ransformation of the bimetallic Cu/Cu 51 Zr 14 precatalyst into an active, selective, and self-stabilizing state with coexistence of dispersed Cu and partially hydroxylated tetragonal ZrO 2 .The outstanding performance is assigned to the presence of ah igh interface-site concentration following in situ decompositiono ft he intermetallic compound. These actives ites result from the cooperation of Cu, responsible for methanol activation,a nd tetragonal ZrO 2 ,w hich activates the water by surface hydroxylation.Copper-based catalysts are widely used for technical applications in methanolc hemistry,w ell-known examples include methanol synthesis from syngasw ith an optimized CO/CO 2 ratio, hydrogenation/photoreduction of CO 2 to produce "renewable" methanol, and methanol steam reforming (MSR) as the reversal of the synthesis reactionf rom CO 2.[1] The ability to control product selectivity is ak ey criterion for technical usage. Therefore, to realize the efficient on-boardp roduction of clean hydrogen in, for example, automotive applications, the key targets for MSR are high CO 2 selectivity,l ow CO content,a nd maximum H 2 yield in the reformate.[2] With respect to the catalytic functiono fZ rO 2 in MSR, the simple addition of ZrO 2 to the conventionally used Cu/ZnO catalysts overcomes the inherent drawback of purely ZnO-based catalysts,t hat is, the poor sinterings tability.[2] Beneficial synergistic effectsf or methanol synthesis have also been described for Cu/Zn and the ternary Cu/Zn/Al system prepared by ac o-precipitation technique.[3]Synergistic Cu-ZrO 2 interactions have also been reported for Cu/ZrO 2 catalysts without ZnO, involving CuÀOÀZr bonds at the phase boundary. The Cu-ZrO 2 interactions are believed to play ac rucial role in steering the methanol reforming reaction to maximum CO 2 selectivity.[4] Specifically,ananocrystalline Cu/ tetragonal ZrO 2 catalyst synthesized by ap olymer templating technique [5] was reported to be more active, selective, and stable in MSR than the technical Cu/ZnO/Al 2 O 3 methanol synthesis catalyst.[6] Although the beneficial effects of the redox chemistry of Cu and the Cu 0 /Cu oxidized ratio at the interface has been suggesteda sa ni mportants electivity descriptor,a longside disorder and strain phenomena within the metallicC u phase, [2] ac ontradictingi nfluence hasa lso been reported. Both beneficial [4a, b] and adverse [4d] effectso ft he reducibility of Cu can be found in the literature. Nevertheless, any influence appears strongly connected to the quantity...

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Section: Figurementioning

confidence: 89%

Boosting Hydrogen Production from Methanol and Water by in situ Activation of Bimetallic Cu−Zr Species

et al. 2016

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“…In a first conversion step, highly endothermic steam reforming of natural gas is performed to produce synthesis gas (stoichiometric mixture of one mole CO and three moles H 2 ), where methane reacts with excessive steam at high temperature (>1100 K) and high pressure (>20 bar) over a Ni‐containing catalyst . Secondly, synthesis gas is converted to methanol using Cu‐based heterogeneous catalysts at typically 220–260 °C and 70–80 bar . The next step is the carboxylation of methanol with additional CO to generate the intermediate formic acid methyl ester, which is typically at 80 °C and 45 bar using a Na methoxide catalyst .…”

Section: Introductionmentioning

confidence: 99%

Biogenic Formic Acid as a Green Hydrogen Carrier

Preuster

Albert

2018

Energy Tech

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Formic acid (FA) is an important platform chemical that has numerous applications in the chemical and agricultural industries, as well as in the leather industry. To date, FA is exclusively produced from fossil raw materials using either carbonylation of methanol or acidolysis of formates. Here, sustainable and environmentally friendly approaches to produce biogenic FA from biomass (e.g., OxFA‐process) are presented and combined with different approaches for the catalytic decomposition of bio‐based FA solutions. Several homogeneous and heterogeneous approaches for the catalytic decomposition of aqueous FA to hydrogen and CO2 are compared for their applicability. Moreover, their technical applications in fuel cells, as energy storage vectors, and as hydrogen storage molecules are discussed.

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“…The Mo 3d XPS spectra of the 20Mo 2 C/M41 and xCu20Mo 2 C/M41-I samples are shown in Figure 4. As shown in Figure 4, the doublet peaks, which were assigned to Mo 3d 5 (MoO 3 ), respectively, in which the δ was an intermediate oxidation state between 4 and 6 (4 < δ < 6) [26,41]. By curve fitting the Mo 3d profiles, the ratio of the surface Mo IV and Mo δ species to the total molybdenum species (i.e., (Mo IV + Mo δ )/Mo total (Mo total = Mo II + Mo IV + Mo δ + Mo VI )) was obtained and summarized in Table 4.…”

Section: N 2 Adsorption-desorptionmentioning

confidence: 97%

“…The chemical utilization of CO 2 , which is the cheapest and most abundant C1 resource, has become an important global challenge [3][4][5]. Catalytic hydrogenation of CO 2 can produce various types of valuable chemicals and has been recently identified as one of the most promising processes for the utilization of CO 2 [6].…”

Section: Introductionmentioning

confidence: 99%

Cu-Mo2C/MCM-41: An Efficient Catalyst for the Selective Synthesis of Methanol from CO2

et al. 2016

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Supported molybdenum carbide (yMo 2 C/M41) and Cu-promoted molybdenum carbide, using a mechanical mixing and co-impregnation method (xCuyMo 2 C/M41-M and xCuyMo 2 C/M41-I) on a mesoporous molecular sieve MCM-41, were prepared by temperature-programmed carburization method in a CO/H 2 atmosphere at 1073 K, and their catalytic performances were tested for CO 2 hydrogenation to form methanol. Both catalysts, which were promoted by Cu, exhibited higher catalytic activity. In comparison to 20Cu20Mo 2 C/M41-M, the 20Cu20Mo 2 C/M41-I catalyst exhibited a stronger synergistic effect between Cu and Mo 2 C on the catalyst surface, which resulted in a higher selectivity for methanol in the CO 2 hydrogenation reaction. Under the optimal reaction conditions, the highest selectivity (63%) for methanol was obtained at a CO 2 conversion of 8.8% over the 20Cu20Mo 2 C/M41-I catalyst.

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Recent development in catalytic technologies for methanol synthesis from renewable sources: A critical review

Cited by 185 publications

References 100 publications

Boosting Hydrogen Production from Methanol and Water by in situ Activation of Bimetallic Cu−Zr Species

Boosting Hydrogen Production from Methanol and Water by in situ Activation of Bimetallic Cu−Zr Species

Biogenic Formic Acid as a Green Hydrogen Carrier

Cu-Mo2C/MCM-41: An Efficient Catalyst for the Selective Synthesis of Methanol from CO2

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