Product-oriented decomposition of lignocellulose catalyzed by novel polyoxometalates-ionic liquid mixture

Si, Nan; Liu, Dong; Huang, Qiang; Guo, Zhongshan; Jiang, Ruixue; Wang, Rui; Chen, Qingtai; Li, Min; Shen, Guobo; Wen, Fusheng

doi:10.1016/j.biortech.2019.03.048

Cited by 14 publications

(13 citation statements)

References 40 publications

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“…Recently, ionic liquids (ILs) have received interest as solvents that enable lignocellulose deconstruction. [11,12] This relatively new group of desiger solvents comprises liquids entirely composed of ions. A key feature is that ionic liquids are not volatile.…”

Section: Introductionmentioning

confidence: 99%

“…[33] Moreover, their acid-base and redox properties can be tailored specifically by substituting one or more constituents and by changing the counter-cation. The so-called Keggin-type polyoxometalates with the general structure [XM 12 O 40 ] nÀ (X = heteroatom, M = metal) are well known as excellent homogeneous and heterogeneous acid and oxidation catalysts, [34][35][36][37][38][39] including liquid phase reactions. Examples are the hydration of olefins, the esterification of glycerol and acetic acid or the esterification of methanol and oleic acid for biodiesel production.…”

Section: Introductionmentioning

confidence: 99%

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Combining Cost‐Efficient Cellulose and Short‐Chain Carboxylic Acid Production: The Polyoxometalate (POM)‐Ionosolv Concept

et al. 2020

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Full cost‐effective exploitation of all wood components is key to growing a commercially successful biorefining industry. An innovative process is reported that combines fractionation of lignocellulosic biomass using a low‐cost ionic liquid (Ionosolv) and production of bio‐derived formic acid using polyoxometalates and molecular oxygen (OxFA process). We show that the hemicellulose and part of the lignin were selectively dissolved into the ionic liquid triethylammonium hydrogen sulfate and oxidised in situ to short‐chain, distillable carboxylic acids by a Keggin‐type polyoxometalate with high yields and selectivities. Characterization by several techniques, including ICP‐OES, FTIR, GC, HPLC and NMR spectroscopy confirmed stability of the catalyst over three consecutive POM‐Ionosolv recycles and stable formic acid yields.High formic acid yields of 26 % (pine chips), 23 % (beech chips), and 18 % (Miscanthus) were obtained with respect to the initial carbon content of the biomass, with unprecedented oxidation selectivities for formic acid of 54–62 % depending on vanadium substitution in the polyoxometalate, the processing temperature and the water content in the reaction mixture.. We also demonstrate that the cellulose rich pulp is a suitable source of glucose via enzymatic saccharification. We report cellulose yields of 37% for Miscanthus (from originally 48% glucan content), 33% for pine (from originally 49%) and 31% for beech (from originally 41%) were achieved, and a saccharification yield of up to 25% without optimisation. With further optimisation, this concept has the potential to generate two chemical products directly from lignocellulose in high yields and selectivities and hence a novel avenue for full utilisation of cellulose, hemicellulose and lignin.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Combining Cost‐Efficient Cellulose and Short‐Chain Carboxylic Acid Production: The Polyoxometalate (POM)‐Ionosolv Concept

et al. 2020

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“…They have grown due to their unique tunable characteristics, such as high Brønsted acidity, reversible redox properties, high thermal and chemical stability, nontoxicity, ease of handling, and environmental compatibility . The anion part of POMs can react with various IL cations via electrostatic interaction to form similar new organic–inorganic hybrid molecular materials . Recently, POM-based ILs have attracted great attention, particularly as catalysts for several reactions …”

Section: Introductionmentioning

confidence: 99%

Design of [BmIm]₃PW₁₂O₄₀ Ionic Liquid Encapsulated-ZIF-8 Nanocomposite for Cationic Dye Adsorptive Removal: Modeling by Response Surface Methodology

Ranjbari

Ayati

Shahrak

et al. 2023

Ind. Eng. Chem. Res.

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In this study, the modification of metal−organic frameworks with polyoxometalate-based ionic liquids was assessed and their efficient role in the improvement of their adsorption performance was studied. Metal−organic framework ZIF-8 was encapsulated with [BmIm] 3 PW 12 O 40 , a polyoxometalate-based ionic liquid, through reaction with the ZIF-8 imidazolate groups. The novel ZIF-8-[BmIm] 3 PW 12 O 40 nanocomposite was characterized using XRD, FTIR, SEM, EDX, and BET analyses, which confirmed the successful insertion of [BmIm] 3 PW 12 O 40 on the surface of the ZIF-8 structure. It was used to study the adsorptive removal of a methylene blue (MB) cationic dye model and showed high adsorption performance between pH 2 and 11 with an optimum sorbent dosage of 4 g/L. The adsorption kinetics corresponded well to the pseudo-second-order kinetic model. Moreover, response surface methodology was used to optimize experimental conditions and determine the highest MB removal percentage. The correlation between variables (time, pH, and sorbent dosage) and responses (removal percentage) were well fitted to the second-order polynomial model (R 2 = 0.949, Adj. R 2 = 0.9032, and pred. R 2 = 0.6129). The optimal conditions were found to be adsorbent amount = 0.04 g/L, pH = 11, and contact time = 45 min. Under these conditions, the highest removal percentage and amount of desirability were found to be 95.75% and 0.9, respectively.

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“…[20][21][22][23] Among them, ionic liquid (IL)-type H 5 PMo 10 V 2 O 40 presented higher activity in the oxidation of pine samples with complete dissolution and over 90 %d elignification of Southern yellow pine at 110 8Cf or 6hin oxygen atmosphere. [25] Diphenyl ether was converted in 98 %t oc yclohexanonew ith Pd/[OMIM]H 2 PW 12 O 40 @SiO 2 with yields of up to 83 %i nw ater and H 2 (3 MPa)a t1 90 8Cf or 3h. [1] In addition, 83.5 %d elignification of pine was obtained at 110 8Cf or 16 hi na tmospheric air by application of [C 2 mim] 4 H[PV 2 Mo 10 O 40 ].…”

Section: Introductionmentioning

confidence: 99%

“…[24] Phenolicc ompounds have been dominantly obtaineda t1 00 8Cf or 5h with as electivity of 45.1 %a nd ay ield of 4.3 %w ith P 2 W 17 / [Emim]HSO 4 . [25] Diphenyl ether was converted in 98 %t oc yclohexanonew ith Pd/[OMIM]H 2 PW 12 O 40 @SiO 2 with yields of up to 83 %i nw ater and H 2 (3 MPa)a t1 90 8Cf or 3h. [26]…”

Section: Introductionmentioning

confidence: 99%

Full Utilization of Lignocellulose with Ionic Liquid Polyoxometalates in a One‐Pot Three‐Step Conversion

Zhang

et al. 2019

ChemSusChem

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The lignin‐first concept is a new innovation for full utilization of lignocellulose into value‐added chemicals. Ionic liquid (IL) polyoxometalates [MIMPS]2H4P2Mo18O62 [MIMPS=1‐(3‐sulfonic group) propyl‐3‐methyl imidazolium] are reported to be active in the cleavage of β‐O‐4, α‐O‐4, and 4‐O‐5 bonds in three kinds of lignin models and also efficient for converting native lignocellulose. The three components in soft or hard lignocellulose were depolymerized in a one‐pot three‐step treatment. For soft lignocellulose (pine), lignin was first decomposed into guaiacol and phenol with yields of 15.3 and 12.9 % at 98.6 % delignification efficiency at 130 °C for 14 h. Meanwhile, hemicellulose and cellulose were intact during the delignifying process and were subsequently hydrolyzed to 3.5 % xylose at 100 % hemicellulose conversion efficiency at 150 °C for 14 h and 36.4 % glucose at 100 % cellulose conversion efficiency at 170 °C for 12 h, respectively. For hard lignocellulose (poplar), the yields of guaiacol and phenol were 10.1 and 8.7 % at 91.9 % delignification efficiency at 130 °C for 14 h, whereas 12.9 % xylose at 90.4 % hemicellulose conversion efficiency at 150 °C for 12 h and 32.9 % glucose at 100 % cellulose conversion efficiency at 170 °C for 12 h were obtained. [MIMPS]2H4P2Mo18O62 achieved the full utilization of lignocellulose with total conversion in the lignin‐first strategy and also showed the easy separation as a result of temperature‐reversibility with ten recycling runs.

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Product-oriented decomposition of lignocellulose catalyzed by novel polyoxometalates-ionic liquid mixture

Cited by 14 publications

References 40 publications

Combining Cost‐Efficient Cellulose and Short‐Chain Carboxylic Acid Production: The Polyoxometalate (POM)‐Ionosolv Concept

Combining Cost‐Efficient Cellulose and Short‐Chain Carboxylic Acid Production: The Polyoxometalate (POM)‐Ionosolv Concept

Design of [BmIm]₃PW₁₂O₄₀ Ionic Liquid Encapsulated-ZIF-8 Nanocomposite for Cationic Dye Adsorptive Removal: Modeling by Response Surface Methodology

Full Utilization of Lignocellulose with Ionic Liquid Polyoxometalates in a One‐Pot Three‐Step Conversion

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Product-oriented decomposition of lignocellulose catalyzed by novel polyoxometalates-ionic liquid mixture

Cited by 14 publications

References 40 publications

Combining Cost‐Efficient Cellulose and Short‐Chain Carboxylic Acid Production: The Polyoxometalate (POM)‐Ionosolv Concept

Combining Cost‐Efficient Cellulose and Short‐Chain Carboxylic Acid Production: The Polyoxometalate (POM)‐Ionosolv Concept

Design of [BmIm]3PW12O40 Ionic Liquid Encapsulated-ZIF-8 Nanocomposite for Cationic Dye Adsorptive Removal: Modeling by Response Surface Methodology

Full Utilization of Lignocellulose with Ionic Liquid Polyoxometalates in a One‐Pot Three‐Step Conversion

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Product

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Design of [BmIm]₃PW₁₂O₄₀ Ionic Liquid Encapsulated-ZIF-8 Nanocomposite for Cationic Dye Adsorptive Removal: Modeling by Response Surface Methodology