Selective 5-hydroxymethylfurfural production from cellulose formate in DMSO-H2O media

Jin, Caidi; Xiang, Ning; Zhu, Xiao; Shuang, E; Sheng, Kuichuan; Zhang, Ximing

doi:10.1016/j.apcatb.2020.119799

Cited by 39 publications

(30 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In order to suppress the formation of levulinic acid and humin type polymer during the synthesis of HMF, most of the studies employ organic solvents as reaction medium for HMF production, which could be roughly divided into three species of Scontained organic solvents (such as DMSO) (Jin et al, 2021;Rasrendra et al, 2012), N-contained organic solvents (including amide derivates and the imidazolium ionic liquids) (Binder & Raines, 2009;Zhang et al, 2017), and O-contained organic solvents (tetrahydrofuran (THF), methyl isobutyl ketone (MIBK), butanol, γ-valerolactone (GVL), etc.). Compared with other organic solvents, the O-contained organic solvents have several advantages of renewable, easy recyclable and low environmental pollution, so these O-contained organic solvents show potential application in HMF production process.…”

Section: Introductionmentioning

confidence: 99%

Conversion of Cellulose Into 5-Hydroxymethylfurfural (HMF) In a H2O/Tetrahydrofuran/Cyclohexane Biphasic System With Al2(SO4)3 As Catalyst

Shi

Zhu

Qin

et al. 2021

Preprint

View full text Add to dashboard Cite

A simple and efficient biphasic system consisting of H2O, tetrahydrofuran (THF), cyclohexane (CHX) and Al2(SO4)3 was employed to convert cellulose into 5-hydroxymethylfurfural (HMF) with high yield of 71.2%. The real volumes of organic phase (Vorg) and aqueous phase (Vaque) of the biphasic system at reaction temperature were measured to found out that over 80% of the added H2O was dissolved into the organic phase at reaction temperature, leading to high Vorg/Vaque (over 44/1) and high concentration of Al2(SO4)3 (over 0.34 g/mL) in aqueous phase. The high concentration of Al2(SO4)3 in aqueous phase could efficiently catalyze the conversion of cellulose into HMF, while the high Vorg/Vaque could protect the formed HMF from rehydration, all of which are responsible for the high efficiency of the system on conversion of cellulose into HMF. The addition of CHX into reaction mixture could decrease the solubility of Al2(SO4)3 and H2O in the organic phase, which could improve the stability of HMF in the reaction system, resulting higher yield of HMF from cellulose. Because of the high Vorg/Vaque of the reaction system, one microemulsion-like system and liquid film catalytic model are proposed for the cellulose-to-HMF process.

show abstract

Section: Introductionmentioning

confidence: 99%

Conversion of Cellulose Into 5-Hydroxymethylfurfural (HMF) In a H2O/Tetrahydrofuran/Cyclohexane Biphasic System With Al2(SO4)3 As Catalyst

Shi

Zhu

Qin

et al. 2021

Preprint

View full text Add to dashboard Cite

show abstract

“…The most common solvent for these studies, both in the production of furfural and HMF, is dimethylsulfoxide (DMSO), and it is used from highly aqueous to water-free systems (Table 2.1). [81][82][83][84][85][86][87][88][89][90][91][92][93][94][95] Highly aqueous conditions (7:3 v-v water-DMSO monophasic systems), paired with microwave heating and a metal catalyst (i.e., CrCl3 or Al(NO3)3), resulted in a relatively high fructose-to-HMF selectivity (approx. 65 mol%) when compared with fully aqueous monophasic conditions.…”

Section: Dimethylsulfoxidementioning

confidence: 99%

“…22,[33][34][35][36][37][38][39][40]81 The use of DMSO enables the effective solubilization of rather recalcitrant starting materials (e.g., coffee grounds, bread waste or cellulose formate). [81][82][83] Moving from a fully aqueous monophasic system to a 1:1 water-DMSO mixture, with HCl and AlCl3 as cocatalysts, has resulted into a 35 mol% selectivity improvement in the conversion of cellulose formate to HMF, with a concomitant reduction of the production of levulinic acid. 83 This selectivity improvement is explained by specific interactions between the reactant (i.e., formylated sugars) and the aprotic solvent (see above).…”

Section: Dimethylsulfoxidementioning

confidence: 99%

“…[81][82][83] Moving from a fully aqueous monophasic system to a 1:1 water-DMSO mixture, with HCl and AlCl3 as cocatalysts, has resulted into a 35 mol% selectivity improvement in the conversion of cellulose formate to HMF, with a concomitant reduction of the production of levulinic acid. 83 This selectivity improvement is explained by specific interactions between the reactant (i.e., formylated sugars) and the aprotic solvent (see above). 83 However, it has to be noted that some of the mentioned side reactions (e.g., HMF to levulinic acid) are the result of rehydration, so operating in a water-lean environment will also have a non-negligible effect.…”

Section: Dimethylsulfoxidementioning

confidence: 99%

“…83 This selectivity improvement is explained by specific interactions between the reactant (i.e., formylated sugars) and the aprotic solvent (see above). 83 However, it has to be noted that some of the mentioned side reactions (e.g., HMF to levulinic acid) are the result of rehydration, so operating in a water-lean environment will also have a non-negligible effect. 1,2 Experimental evidence supports that the effect of DMSO on the sugar-to-furan selectivity is mainly the result of solvation of the sugar, and not of catalysis by acidic species generated by the degradation of DMSO.…”

Section: Dimethylsulfoxidementioning

confidence: 99%

See 2 more Smart Citations

Furfural manufacture from xylose : routes towards high selectivity and novel processes

Ricciardi

View full text Add to dashboard Cite

Planet Earth is facing a human-induced climate crisis. 1 Scientists from numerous nations have raised concern about this issue at various instances in the past, with one of the latest public warning having arrived in January 2020. 1 The alarming trends observed in the parameters that we use to describe climate and environment (e.g., desertification, availability of fresh water, air pollution) show that drastic, politically driven changes are urgently necessary. 1 With greenhouse gas (GHG) emissions still rapidly rising, and most public discussions focused on global surface temperature only, it is of fundamental importance to understand that this environmental crisis is related to social and economic factors embedded in our society. 1,2 In parallel, and strongly related, to the climate crisis, our society is facing an energy crisis, which is directly connected to the steep rise in energy demand. 3,4 These two crises are intertwined, since the combustion of crude oil, natural gas and coal still is the primary energy sources worldwide, both for transportation of people and goods, fueling industry and infrastructures, and for ensuring the stability of the energy grid. 4 The product of combustion of these fossil fuels is CO2, which is an important contributor to the greenhouse effect. The increased energy demand is due to worldwide industrial development, coupled with an average increase of wealth. [3][4][5] This scenario, in combination with the increasing costs of extraction and manufacture of fossil fuels, is becoming a troubling bottleneck for economic development. [3][4][5] Currently, the addition of green and/or renewable sources of energy (e.g., hydroelectric, solar, wind and nuclear energy) is rapidly growing. 5 Yet, we must realize that just compensating the growing energy demand with these 'clean' energy sources is not sufficient. Reducing the (absolute) contributions of fossil fuels to the energy palette is absolutely necessary to act on the climate crisis and reduce, for example the CO2 levels in the atmosphere. 5 Making humanity fully independent from fossil fuels is an incredibly complex task. 1,2 To do so, the chain of production and consumption of energy, at all levels, needs to be redesigned with drastic, both politically and economically driven international choices. 1,2 Next to these necessary societal changes, research is needed to explore possible alternatives for fossil fuels, which would ease this transition with the aim to avoid, or minimize, an economic crisis. [1][2][3][4][5] Particularly, some sectors of industry and transportation, e.g., heavy industry and aviation, are extremely challenging to decarbonize and cannot solely rely on solar and wind energy, requiring the development of renewable fuels and chemicals. 6 Reducing, and finally eliminating, fossil resources such as oil is exceptionally complex, as these resources are also the basis for the current petrochemical industry. 6,7 The petrochemical industry, one of the largest during the last century, continues to grow t...

show abstract

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

Chen,

Lv,

et al. 2024

Advanced Materials

View full text Add to dashboard Cite

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

show abstract

Selective 5-hydroxymethylfurfural production from cellulose formate in DMSO-H2O media

Cited by 39 publications

References 58 publications

Conversion of Cellulose Into 5-Hydroxymethylfurfural (HMF) In a H2O/Tetrahydrofuran/Cyclohexane Biphasic System With Al2(SO4)3 As Catalyst

Conversion of Cellulose Into 5-Hydroxymethylfurfural (HMF) In a H2O/Tetrahydrofuran/Cyclohexane Biphasic System With Al2(SO4)3 As Catalyst

Furfural manufacture from xylose : routes towards high selectivity and novel processes

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

Contact Info

Product

Resources

About