Selective oxidation of complex, water-insoluble biomass to formic acid using additives as reaction accelerators

Albert, Jakob; Wölfel, R; Bösmann, Andreas; Wasserscheid, Peter

doi:10.1039/c2ee21428h

Cited by 180 publications

(182 citation statements)

References 28 publications

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“…19 Using an additional acid in the biphasic reaction system containing an alcohol as an in-situ extraction solvent provokes again the question whether ester formation between the solubilizer and the extraction agent occurs. This was first investigated by stirring aqueous p-toluene sulfonic acid with both 1-hexanol and 1-heptanol.…”

Section: In-situ Extraction Of Reaction Mixtures From Sucrose and Beementioning

confidence: 99%

“…[17][18][19][20] 17 With a slight modification of the initial protocol, namely, the addition of toluene sulfonic acid as a hydrolysing and phase transfer agent, cellulose, lignin, wood and other complex wet biomasses can also be oxidised via the same method, although the reaction is considerably slower (full conversion requires typically 24 to 120 h). 19 FA yields under these conditions are 35% for beech wood. Research into alternative POM catalyst systems for this application resulted in some improvements regarding the required oxygen pressure.…”

Section: Introductionmentioning

confidence: 99%

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Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Reichert

Brunner

Jess

et al. 2015

Energy Environ. Sci.

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146

139

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a Herein, we report a remarkable finding that biomass oxidation to formic acid (FA) in water-organic biphasic reaction systems is far more selective than the same reaction in a monophasic aqueous media.While literature claims that the yield of FA from carbohydrates and biomass is limited to less than 68%, even for simple substrates such as glucose or glycerol, we demonstrate in this study that FA yields of up to 85% can be obtained from glucose. Using our biphasic reaction protocol, even raw lignocellulosic biomass, such as beech wood, leads to FA yields of 61%. This is realized by applying polyoxometalate H 8 PV 5 Mo 7 O 40 as a homogeneous catalyst, oxygen as the oxidant and water as the solvent in the presence of a long-chain primary alcohol as an in-situ extracting agent. The new, liquid-liquid biphasic operation opens a highly effective way to produce pure FA, a liquid syngas equivalent, from wood in a robust, integrated, and low-temperature process.

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Section: In-situ Extraction Of Reaction Mixtures From Sucrose and Beementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Reichert

Brunner

Jess

et al. 2015

Energy Environ. Sci.

Self Cite

146

139

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“…[25][26][27] The concept essentially overcomes all major problems of classical biomass gasification or reforming processes. 28,29 The interesting difference of the OxFA route compared to reductive biomass valorization approaches is that all the thermally induced formation of solid or gluey by-products is completely avoided.…”

Section: Introductionmentioning

confidence: 99%

Expanding the scope of biogenic substrates for the selective production of formic acid from water-insoluble and wet waste biomass

Albert

Wasserscheid

2015

Green Chem.

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“…Virtually any plant biomass can be oxidized to formic acid, CO 2 , and water with high selectivity to formic acid by using polyoxometallates as oxygen-delivering catalysts [65].…”

Section: Formic Acid From Biomassmentioning

confidence: 99%

Formic Acid

Hietala¹,

Vuori²,

Johnsson³

et al. 2016

Ullmann's Encyclopedia of Industrial Chemistry

143

141

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The article contains sections titled: 1. Introduction 2. Physical Properties 3. Chemical Properties 3.1. Stability 3.2. Carboxylic Acid Reactions 3.3. Other Reactions 4. Production 4.1. Methyl Formate Hydrolysis 4.1.1. Kemira ‐ Leonard Process 4.1.2. BASF Process 4.1.3. USSR Process 4.2. Production from Formates 4.2.1. Formates as Polyol Byproducts 4.2.2. Formates from Carbon Monoxide 4.3. Formic Acid from Carbon Dioxide 4.4. Formic Acid from Biomass 4.5. Other Processes 4.6. Recovery of Formic Acid 5. Environmental Protection 6. Quality Specifications 7. Chemical Analysis 8. Storage and Transportation 9. Legal Aspects 10. Uses 10.1. Biomass Preservation 10.1.1. Silage 10.1.2. Animal Biomass 10.2 Leather 10.3. Textile 10.4. Feed Additives 10.5. Pharmaceuticals and Food Additives 10.6. Other Uses 10.6.1. Rubber Coagulation 10.6.2. Gas desulfurization 10.6.3. Well acidifizers 10.6.4. Formic Acid as Source of Hydrogen and Carbon Dioxide 10.6.5. Cleaning Agents 10.6.6. Solvent Use 11. Economic Aspects 12. Derivatives 12.1. Salts 12.1.1. Sodium Formate 12.1.2. Potassium Formate 12.1.3. Other Formate Salts 12.2. Esters 12.1.1. Methyl Formate 12.1.2. Ethyl Formate 12.2.3. Other Esters 12.3. Performic Acid 13. Toxicology and Occupational Health

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Selective oxidation of complex, water-insoluble biomass to formic acid using additives as reaction accelerators

Cited by 180 publications

References 28 publications

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts – boosting FA selectivity by in-situ extraction

Expanding the scope of biogenic substrates for the selective production of formic acid from water-insoluble and wet waste biomass

Formic Acid

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