Deep Eutectic Solvents as Catalysts for Upgrading Biomass

06 May.,2024

 

Deep Eutectic Solvents as Catalysts for Upgrading Biomass

Lewis acid-type DESsChCl:2FeCl3Bagasse ligninFractionation of lignin 74% selectivity for methyl

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-hydroxycinnamate, after 8 h, at 160 °C.6 runs[80]ChCl:ZnCl2
ChCl:2ZnCl2
ChCl:3ZnCl2 Soybean oilTransesterification of soybean oil to biodiesel 55% transesterification yield. 16:1, Methanol: oil ratio. (ChCl:2ZnCl2) DES 10% at 70 °C for 72 h. Unable to recycle[67]ChCl:2FeCl3SeaweedProduction of Fe3O4/Fe-doped graphene nanosheets (GNs) from seaweedFormation of Fe3O4/Fe-GN with high surface area and electrical conductivity under 95% N2 and 5% H2, pyrolysis of DES + seaweed at 700–900 °CNot reported[68]10dimethylurea:3ZnCl2Cellulose Synthesis of cellulose methyl carbamate (CMeC)The degree of substitution was 0.17 after 3 h of reaction at 150 °C. Not reported[79] FeCl3·6H2O-based DESs (different ratios)CelluloseConversion of cellulose to gluconic acid2FeCl3·6H2O:ethylene glycol DES provided the highest yield (53%) of gluconic acid at 120 °C for 60 min.5 runs (FeCl3·6H2O:ethylene glycol)[66]4dimethylurea:
Zn(OAc)2Polyethylene terephthalate (PET)Glycolysis of PET to yield bis(hydroxyalkyl) terephthalate (BHET) With 5 g PET, 20 g ethylene glycol, 0.25 g DES at 190 °C for 20 min, the yield of BHET was 82%.6 runs[81]ChCl:4.43oxalic acid·2H2O:
0.1FeCl3·6H2OBleached
eucalyptus Kraft pulp (BEKP)Fabricate cellulose nanocrystals (CNCs) from BEKPThe yield of CNCs was higher than 90% under mild conditions, i.e., 80 °C and 6 h. 3 runs[82]Brønsted acid-type DESsChCl:oxalic acidCorncobChange corncob to furfuryl alcohol46% furfural alcohol yield at 120 °C for 30 min. 3 runs[83]ChCl:

p

-TSA 2Alkali ligninDegradation of alkali lignin (cleavage of

β-O

-4)At 130 °C, the content of phenolic hydroxyl species increased. Alakali lignin underwent decarbonylation during treatment.Not reported[84]ChCl:2urea
ChCl:2ZnCl2
ChCl:2CrCl3·
6H2O
ChCl:malonic acid
ChCl:oxalic acid·2H2O
2ChCl:citric acid·H2O
2ChCl:citric acidFructoseConversion of fructose to hydroxymethylfurfural (HMF)Most DESs were effective to convert fructose (91–100%). The Lewis acid-based DESs were not efficient to produce HMF. More than 90% of fructose conversion was obtained with ChCl:malonic acid/oxalic acid/citric acid·H2O at 80 °C for 1 h8 runs (2ChCl:citric acid·H2O)[69]ChCl:oxalic acid·2H2O
2ChCl:citric acid·H2OInulinConversion of inulin to HMFUsing (ChCl: oxalic acid·2H2O) and (2ChCl: citric acid·H2O), at 80 °C for 2 h, the yields of HMF were 64 and 57%, respectively.6 runs (ChCl:oxalic acid·2H2O)[70]ATPPB 1:3

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-TSA 2Low-grade crude palm oil (LGCPO)Biodiesel production from LGCPO via esterification processThe esterification in 1 wt% DES, 10:1 methanol to LGCPO, at 60 °C in 30 min. <2% free fatty acid (FFA).4 runs[85]2ChCl:citric acid·H2OXylan and xyloseConversion of xylan and xylose to furfural, co-catalyzed by the DES and metal chloridesIn monophasic approach (DES + metal chloride), furfural yield from xylose and xylan were 59 and 54%, respectively. The yields increased to 73.1 and 67% in biphasic system (DES + metal chloride + methyl isobutyl ketone (MIBK)).5 runs[71]DEACl 3:3

p

-TSA 2Crude palm oilDecreasing the level of FFAs for biodiesel productionThe FFAs were reduced to <1%. The DES: palm oil was 0.75% (wt/wt). Methanol:oil ratio was 8:1 at 60 °C for 30 min. 4 runs[86]ChCl:3

p

-TSA 2Acidic crude palm oil (ACPO)Biodiesel production from ACPO (conversion of FFAs in ACPO to fatty acid methyl esters (FAME))The 1:10 molar ratio of Methanol:oil with 0.75 mass ratio of DES:ACPO reduced FFAs to <1% at 60 °C in 30 min. 3 runs[87]ChCl:oxalic acidXylose and xylanFurfural production from xylose and xylan using monophasic (DES) or biphasic (DES + MIBK) systemsAddition of metal chlorides to the DES led to improved furfural yields (14–44%). In the biphasic procedure, the yields from xylose and xylan were, respectively, 60 and 56% in AlCl3·6H2O presence. 5 runs[88]ChCl:

p

-TSA 2 (1:0.5 to 1:2)FructoseConversion of fructose to 5-HMF91% 5-HMF yield at 80 °C for 1 h in (ChCl: p-TSA) DES.Not reported[89]ChCl:2urea
ChCl:4

p

-TsOH 2
ChCl:3glycerolPyrolysis oil (PO)Esterification of acids in PO to fatty acid methyl esters (FAME)Highest total acid number (TAN) reduction (86.62%) was achieved with (ChCl:4

p

-TsOH) DES with 1:50 molar ratio of oil: methanol in 40 min. Not reported[76]ChCl:4

p

-TSA 2

Pongamia pinnata

seed oilBiodiesel production from seed oil using either silica support DES (So-DES) and no support DES (Un-DES)Using So-DES at 353 K for 240 min with catalyst loading of 5 (wt%/v), the biodiesel conversion was 89%.
Using Un-DES at 343 K for 120 min with catalyst loading of 1 (wt%/v), the biodiesel conversion was 98%.4 runs (Un-DES)
7 runs (So-DES)[64]ChCl:4KOH
ChCl:4

p

-TsOH 2
ChCl:3glycerol
ChCl:3FeCl3De-oiled

Jatropha curcas

cakeHydrothermal liquefaction of de-oiled

Jatropha curcas

cake to produce biocrude oilDESs formed with HBDs preferentially favored the production of aromatic oil through condensation and hydrolysis of lipids. The highest biocrude yield was achieved by (ChCl: 4KOH) DES (44%).Not reported[6]DEACl 3:0.5

p

-TSA 2FructoseDehydration of fructose to 5-HMF85% HMF yield at 80 °C with a 5% feed ratio at 1 h.Not reported[90]ChCl:acetic acid
ChCl:lactic acid
ChCl:levulinic acid
ChCl:glycerolHardwood (poplar) and softwood (D. fir)Extraction of lignin from woody biomassThe purity of the extracted lignin was 95%. The DESs could selectively cleavage the ether linkage in wood. Not reported[72]ChCl:3

p

-TSA 2
ChCl:5

p

-TSA 2
ChCl:7

p

-TSA 2Glycerol and whole Jatropha curcas seedCo-liquefaction of glycerol and whole Jatropha curcas seed to produce biocrude oilThe biocrude oil yield was 9-wt% with 30-wt% glycerol, 6 wt% moisture, 22 wt% oxygen content and 1:3 molar ratio of the DES.Not reported[7]ATPPB1:3

p

-TSA 2Oleic acidEsterification of FFAs with glycerolWith 5 wt% DES and 6:1 molar ratio of glycerol: oleic acid and at 150 °C for 30 min, 95% of FFA is converted to yield 85% mono- and di-glyceride.5 runs[91]ChCl:oxalic acid·2H2O
ChCl:malonic acid
ChCl:citric acid·H2OSoybean oilEpoxidation of soybean oilThe (ChCl:oxalic acid·2H2O) DES yielded high selectivity (94%) and conversion (89%) at 50 °C for 8 h 5 runs (ChCl:oxalic acid·2H2O)[8]ChCl:2formic acid
ChCl:4acetic acid
ChCl:6glycolic acid
ChCl:4levulinic acidHerbal residues of

Akebia

Ethanol production from herbal residues of

Akebia

The maximum levels of lignin, xylan and glucan removal with (ChCl: 6glycolic acid) DES at 120 °C.Not reported[73]ChCl:oxalic acidFructoseSynthesis of biofuel ethoxymethyl furfural (EMF) from fructoseUnder microwave irradiation, 92% of fructose was converted to yield 74% EMF in 3 h at 343 K.4 runs[92]ChCl:oxalic acidCellulose and native biomassSelective conversion of cellulose and native biomass into the low molecular weight saccharides The conversion yield and total selectivity of carbohydrate are as high as 85% and 98%, respectively.Not reported[93]3DEACl 3:2oxalic acidSunflower stalkConversion of cellulose to levulinic acid, 5-HMF, furfural and formic acidThe maximum carbon conversion was achieved as 38% at 170 °C in 5 min in microwave reactor. Not reported[94]3ChCl:oxalic acidFurfuralOxidation of furfural to maleic acid and fumaric acid Used H2O2 as the oxidizer at 50 °C. 100% conversion of furfural and the yield of maleic acid and fumaric acid reached 96%. Not reported[12]Taurine:3TfOH 4Isobutane and isobuteneAlkylation of isobutane and isobutene to high-octane alkylate gasolineThe DES in polyethylene glycol-200 (PEG-200) had a high catalytic activity and good recyclability with 83% conversion and 86% C8 selectivity.8 runs[95]ChCl:lactic acid (1:10 to 1:250)

Eucalyptus globulus

chipsDelignification of

Eucalyptus globulus

chips (increase in cleavage rate of

β-O

-4)The pupping experiments were performed at 120 °C for 8 h. The DES: biomass molar ratio was 20:1. Not reported[96]ChCl:2malic acid
ChCl:3malic acid
ChCl:3glycolic acidXylan from BeachwoodFurfural production from xylanHigher furfural yield with (ChCl: 3malic acid) + 0.5 wt% water under microwave heating (25 min) at 150 °C. 3 runs (ChCl:3malic acid)[97]TPAB 5:4ethylene glycol
ChCl:2ethylene glycolHeavy residual
Fuel oil (Mazut280)Upgrading Mazut280 to light fuels(TPAB:4ethylene glycol) DES was more efficient than (ChCl: 2ethylene glycol) DES with higher asphaltene reduction and desulfurization, resulting in high and stable light oil. Not reported[98]betaine: oxalic acid·2H2O
(1:1 to 1:28)α-pineneHydration of α-pinene to α-terpineolThe 1:2.7 molar ratio of the DES achieved the best catalytic and recyclability performance.5 runs[99]TBAB 6:2

p

-TSA 2
TBAC 7:2

p

-TSA 2
ChCl:2

p

-TSA 2
BTAB 8:2

p

-TSA 2
BTAC 9:2

p

-TSA 2Yellow horn seedBiodiesel production from the yellow horn seed via extraction of oil and conversion of fatty acid methyl esters11 wt% of (TBAB: 2p-TSA) DES exhibited the best catalytic activity with the maximum oil extraction (90%) and fatty acid conversion (97%) at 72 °C for 40 min. 5 runs (TBAB:2

p

-TSA)[74]ChCl:urea (1:1 to 1:4)
ChCl:oxalic acid
ChCl:benzoic acid
ChCl:

p

-TSA 2
ChCl:2MnCl2
ChCl:2CuCl2
ChCl:2acetamidePolycarbonateMethanolysis of polycarbonate to obtain bisphenol AThe most effective catalyst was (ChCl:2urea) DES with ~100% polycarbonate conversion at 130 °C for 2.5 h.5 runs (ChCl:2urea)[77]urea:2propionic acid
ChCl:10lactic acid
ChCl:

p

-TSA 22-phenoxy-1- phenyl ethanol (PPE) (a lignin model compound)Cleavage of the

β-O

-4 ether bond in the model biomass(ChCl:

p-

TSA) demonstrated the highest performance in the PPE cleavage.Not reported[100]imidazole:1.5BSA 10FructoseDehydration of fructose to 5-HMFThe 5-HMF yield was 90.1% at 100 °C in 3 min.1 run[101]ATPPB1:3

p

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-TSA 2Vegetable oil deodorizer distillateEsterification of FFA in vegetable oil into glyceridesGlycerolysis reaction reached equilibrium at FFA conversion of 90%. The optimum condition was determined at 160 °C, 5 wt% of DES in 10 min.Not reported[102]ChCl:2oxalic acidCotton fiberProduction of CNCs from cotton fiberThe used DES showed a high recyclability (>85%). 5 runs[103]ChCl:2acetic acid
ChCl:malonic acid
ChCl:oxalic acid
ChCl:citric acid
ChCl:2formic acid
3ChCl:7

p

-TSA 2Levulinic acid Esterification of levulinic acid to produce ethyl levulinate The most active catalyst: (3ChCl:7

p

-TSA) DES. ~100% yield with 5-wt% of the DES at 353 K for 1 h.Not reported[65]ChCl:8formic acidFurfural, xylose and corncobSynthesis of cyclic biofuel intermediatesThe direct conversion of furfural, xylose, and corncob to cyclic biofuel intermediates were as high as 92, 88, and 57%, respectively. Not reported[104]ChCl:2ethylene glycol (CrCl3 had synergistic catalytic effect with ChCl)GlucoseDehydration of glucose to 5-HMFAt 150 °C for 3.64 min, the yield of 5-HMF reached 42%.4 runs[75]ChCl:2lactic acidIsolated lignin from

Eucalyptus

tree and a series of

β-O-

4 lignin model compoundsThe

β-O-

4 bonds in either realistic lignin
or model compounds were cleaved by the DESIncrease of the reaction temperature and time resulted in a decrease of insoluble lignin fraction and average molecular weights, as well as a sustained increase of hydroxyl groups. 1 run[105]ChCl:10lactic acid

Eucalyptus

Depolymerization of the double enzymatic lignin (DEL) via a novel biorefinery processDES pretreatment in 60–140 °C for 6 h: cleavage of C-O and C-C bonds in the lignin, dehydration, and acylation of hydroxyl groups of lignin, and recondensation of lignin.Not reported[106]ChCl:oxalic acid
ChCl:2glycerol

Moso bamboo

Extraction of phenolic lignin from bamboo by subcritical ethanol catalyzed by DESAt 160 °C, the (ChCl: oxalic acid) DES obtained lignin with high UV-blocking and high phenolic hydroxyl content. Not reported[107]ChCl:oxalic acid
2ChCl:oxalic acid:

p

-TSA 2Softwood thermomechanical pulp (TMP)Lignin-containing cellulose nanocrystals
(LCNCs) from TMPLCNCs were isolated from DESs, showing a higher yield (66%) when using the ternary DES (3 h).Not reported[108]ChCl:oxalic acidNative biomass (poly)carbohydratesThe catalytic reactions of the native biomass to transform into value-added chemicalsConversion yield as high as 68 wt% for glucose, 60 wt% for fructose, 73 wt% for xylose, 14 wt% for 5-HMF & 72 wt% for furfural. 0% for cellulose.Not reported[109]ChCl:2formic acid
ChCl:2acetic acid
ChCl:2lactic acidPoplar wood shavingsExtraction of lignin from Poplar biomass and enhance cellulose reactivity6.3–7.9% lignin selectivity & delignification (73–77%) along with increase in the available area and porosity of cellulose were achieved. Not reported[110]TOAB 11:2

p

-TsOH 2Cooked and waste vegetable oilsTransesterification of the cooked and waste vegetable oils into biodieselThe catalytic DES enhanced the direct contact between MeOH and oil. The yield of FAME was 99% at 70.5 °C, DES dosage of 24.6 wt%and a molar ratio of 12.5. 5 runs[111]

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