On demand production of ethers or alcohols from furfural and HMF by selecting the composition of a Zr/Si catalyst

Zaccheria, Federica; Bossola, Filippo; Scotti, Nicola; Evangelisti, Claudio; Santo, Vladimiro Dal; Ravasio, Nicoletta

doi:10.1039/d0cy01427c

Cited by 27 publications

(26 citation statements)

References 109 publications

(184 reference statements)

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“…Hf-TUD-1(x) catalysts are the first Hf-mesoporous silicates reported for Fur conversion using secROH. The catalytic results for Hf-TUD-1(x) were compared with literature data for fully inorganic heterogeneous non-noble metal catalysts tested for Fur conversion to AMFs in alcohol medium ( Table 2 ) [ 34 , 36 , 37 , 39 , 42 , 43 , 61 , 62 , 65 , 67 , 78 , 79 , 80 , 81 , 82 , 83 , 84 , 85 ]. The present work does not concern noble metal catalysts for Fur conversion, which may be found in a vast literature such as the following references, just to cite a few [ 86 , 87 , 88 ].…”

Section: Resultsmentioning

confidence: 99%

“…The highest AMF yield reported in the literature was 96% for the mixed metal oxide ~70wt%ZrO 2 /SiO 2 at 120 °C/4 h, using a Cat/Fur mass ratio of 1.0 and [Fur] 0 of 0.13 M (entry 19 [ 34 ]). AMF yields in the range 70–89% were reported for Zr-SBA-15 (entry 6 [ 37 ]), ZrO 2 /SBA-15 (17 wt% Zr, entry 8 [ 39 ]), and MP-ZrAl-Beta-m (entry 12 [ 65 ]).…”

Section: Resultsmentioning

confidence: 99%

“…The reaction of Hmf was studied over the Hf-TUD-1(x) catalysts at 150 °C, targeting bis(2-alkoxymethyl)furans (BAMFs). Literature studies reported the conversion of Hmf to BAMFs in alcohol medium, which may involve 2,5-bis(hydroxymethyl)furan (BHMF) as intermediate, although sometimes no measurable amounts were reported [ 33 , 34 , 40 , 41 , 44 , 82 ]. For the Hf-TUD-1(50) catalyst, BAMF was the only product formed in measurable amounts (up to 93% yield) under different reaction conditions ( Figure S13 ): 2BuOH or 2PrOH; 150 or 170 °C; catalyst dosage of 20 g cat L −1 or 1 g cat L −1 at 150 °C(which gave 10% BAMF yield at 13% Hmf conversion, 8 h, in the presence of Hf-TUD-1(50), Figure S13d–f ).…”

Section: Resultsmentioning

confidence: 99%

“…Hf-TUD-1(50) led to 65% AMF at 150 • C/8 h, using a Cat/Fur mass ratio of 0.25 and [Fur] 0 of 0.2 M (entry 2); a similar 63% yield was reached by increasing x from 50 to 75 and changing the reaction conditions (entry 1). The highest AMF yield reported in the literature was 96% for the mixed metal oxide ~70wt%ZrO 2 /SiO 2 at 120 • C/4 h, using a Cat/Fur mass ratio of 1.0 and [Fur] 0 of 0.13 M (entry 19 [34]). AMF yields in the range 70-89% were reported for Zr-SBA-15 (entry 6 [37]), ZrO 2 /SBA-15 (17 wt% Zr, entry 8 [39]), and MP-ZrAl-Beta-m (entry 12 [65]).…”

Section: Literature Survey For Fur Conversion Via Cht/alcohol Strategiesmentioning

confidence: 98%

“…BAMFs can be blended with commercial diesel in up to 40 vol%, contributing to reduced emissions of fumes, oxynitrides, and oxysulfides [ 31 ]. BAMFs may have more value than the respective monoethers due to the superior miscibility with diesel and higher stability of the former [ 32 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

et al. 2021

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Heterogeneous catalysis, which has served well the petrochemical industry, may valuably contribute towards a bio-based economy by sustainably enabling selective reactions to renewable chemicals. Carbohydrate-containing matter may be obtained from various widespread sources and selectively converted to furanic platform chemicals: furfural (Fur) and 5-(hydroxymethyl)furfural (Hmf). Valuable bioproducts may be obtained from these aldehydes via catalytic transfer hydrogenation (CTH) using alcohols as H-donors under relatively moderate reaction conditions. Hafnium-containing TUD-1 type catalysts were the first of ordered mesoporous silicates explored for the conversion of Fur and Hmf via CTH/alcohol strategies. The materials promoted CTH and acid reactions leading to the furanic ethers. The bioproducts spectrum was broader for the reaction of Fur than of Hmf. A Fur reaction mechanism based on literature data was discussed and supported by kinetic modelling. The influence of the Hf loading and reaction conditions (catalyst load, type of alcohol H-donor, temperature, initial substrate concentration) on the reaction kinetics was studied. The reaction conditions were optimized to maximize the yields of 2-(alkoxymethyl)furan ethers formed from Fur; up to 63% yield was reached at 88% Fur conversion, 4 h/150 °C, using Hf-TUD-1(75), which was a stable catalyst. The Hf-TUD-1(x) catalysts promoted the selective conversion of Hmf to bis(2-alkoxymethyl)furan; e.g., 96% selectivity at 98% Hmf conversion, 3 h/170 °C for Hf-TUD-1(50).

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Literature Survey For Fur Conversion Via Cht/alcohol Strategiesmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

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Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

et al. 2021

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5‐Hydroxymethylfurfural and its Downstream Chemicals: A Review of Catalytic Routes

Chen,

Lv,

et al. 2024

Advanced Materials

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Biomass assumes an increasingly vital role in the realm of renewable energy and sustainable development due to its abundant availability, renewability, and minimal environmental impact. Within this context, 5‐hydroxymethylfurfural (HMF), derived from sugar dehydration, stands out as a critical bio‐derived product. It serves as a pivotal multifunctional platform compound, integral in synthesizing various vital chemicals, including furan‐based polymers, fine chemicals, and biofuels. The high reactivity of HMF, attributed to its highly active aldehyde, hydroxyl, and furan ring, underscores the challenge of selectively regulating its conversion to obtain the desired products. This review highlights the research progress on efficient catalytic systems for HMF synthesis, oxidation, reduction, and etherification. Additionally, it outlines the techno‐economic analysis (TEA) and prospective research directions for the production of furan‐based chemicals. Despite significant progress in catalysis research, and certain process routes demonstrating substantial economics, with key indicators surpassing petroleum‐based products, a gap persists between fundamental research and large‐scale industrialization. This is due to the lack of comprehensive engineering research on bio‐based chemicals, making the commercialization process a distant goal. These findings provide valuable insights for further development of this field.This article is protected by copyright. All rights reserved

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Liquid Organic Hydrogen Carriers (LOHCs) as H‐Source for Bio‐Derived Fuels and Additives Production

Valentini

Marrocchi

Vaccaro

2022

Advanced Energy Materials

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consumption combined with a resource efficient circular economy approach, with the final goal of minimizing the impact of health, safety, security and environment.In the design of a greener future, the replacement of depleting sources with renewable ones is at the center of a sustainable development. [2] Biomass is a natural, abundant, renewable, carbon-neutral source; its use represents a promising strategy to address the need for substituting fossil feedstock in the preparation of chemicals, fuels, and materials, besides energy production. [3][4][5][6][7][8][9][10][11][12][13][14] The major issues that limit the large-scale utilization of biomass in fuel production are the differences in cost and process efficiencies compared to those for fossil fuels. [15] After the Covid-19 crisis, this aspect has become even more evident, as reported by the International Agency of Energy, ultimately causing the first contraction in biofuel production over the past two decades. [16] The reduced transport fuel demand and the decreased petroleum-based fuel prices have transitorily lowered the economic interest for biofuel production. In this pandemic and emergency scenario, therefore, has emerged even more clearly the importance of developing efficient strategies for biomass conversion into fuels, making economically attractive the use of environmentally friendly renewable energy systems (Figure 1). [17] Among the plethora of biomass transformations, hydrogenation and hydrodeoxygenation reactions are widely used for decreasing the oxygen content of biomass-derived platforms to increase their potential as fuels. [18][19][20] In this context, as well as in the challenging goal of creating a decarbonized energy system, hydrogen plays a prominent role in the chemical industry. [21][22][23][24] It is important to notice that the vast majority of the worldwide hydrogen production (45-65 Mt/year) features a significant CO 2 footprint as a consequence of different hydrocarbon reforming processes (i.e., steam-reforming of fossil fuels, thermal cracking of natural gas, solar-thermal reforming of methane) or of coal gasification. [25] Several efforts have been directed during the past years toward the definition of possible effective approaches to a green H 2 production by water splitting. [26][27][28][29][30][31] To date, however, both water electrolysis and photo-driven water splitting are economically and energetically unfavorable, with a long way ahead to hold the promise of a zero-carbon energy system. Indeed, the associated energy demand as well as the low market prices of oxygen, inevitably co-produced from water electrolysis, hinder the shaping of a large-scale employment of this technology.Liquid organic hydrogen carriers (LOHCs) are attractive materials for their ability to generate in situ hydrogen that may be directly used to produce target biofuel precursors, fuels or fuel additives. Indeed, the replacement of fossil feedstock is an urgent necessity for shifting toward a carbon neutral energy economy. Several desired chemica...

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On demand production of ethers or alcohols from furfural and HMF by selecting the composition of a Zr/Si catalyst

Abstract: Zr/Si mixed oxides with a different amounts of silica (0 - 50 wt%) were prepared by a simple sol-gel method. These catalysts were tested in a cascade reaction of furfural...

Cited by 27 publications

References 109 publications

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

5‐Hydroxymethylfurfural and its Downstream Chemicals: A Review of Catalytic Routes

Liquid Organic Hydrogen Carriers (LOHCs) as H‐Source for Bio‐Derived Fuels and Additives Production

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