Yongshui Qu

Microwave-assisted conversion of microcrystalline cellulose to 5-hydroxymethylfurfural catalyzed by ionic liquids

Ionic liquid (IL) has been widely investigated in 5-HMF production from biomass. However, most of studies employed IL as reaction solvent which requires a large amount of IL. In the present study, IL was utilized as catalyst in the conversion of microcrystalline cellulose (MCC) to 5-HMF under microwave irradiation (MI) in N,N-dimethylacetamide (DMAc) containing LiCl. 1,1,3,3-tetramethylguanidine (TMG)-based ILs, including 1,1,3,3-tetramethylguanidine tetrafluoroborate ([TMG][BF4]) and 1,1,3,3-tetramethylguanidine lactate ([TMG]L) which were commonly used in the absorption of SO2 and CO2 from flue gas, were synthesized and applied in the conversion of MCC to 5-HMF for the first time. Of the catalysts employed, [TMG]BF4 showed high catalytic activity in 5-HMF production from MCC. The condition including the ratio of IL to MCC, temperature and time for MCC conversion was optimized using Central Composite Design (CCD) and Response Surface Methodology (RSM). The highest 5-HMF yield of 28.63% was achieved with the optimal condition.

Microwave irradiation - A green and efficient way to pretreat biomass

As a non-traditional heating way, microwave irradiation (MWI) has long been used for lignocellulose pretreatment with the advent of commercial microwave oven since the 1970s. MWI pretreatment using MWI as heating source is similar to other pretreatment methods. Although MWI pretreatment solves some problems caused by other pretreatment methods, such as low heating rate and thermal efficiency, uneven heating, it brings some new challenges such as reaction vessel selection and pretreatment process design. Over 30 years of development, researchers have achieved good pretreatment performance with MWI which has been applied gradually from laboratory scale to pilot-scale. It should be noted that MWI pretreatment is facing some problems: high cost of pretreatment, short of large-scale equipment, the non-thermal effects in pretreatment is still controversial. If MWI pretreatment reaction mechanism could be further clarified and large-scale industrialized reactor be designed, MWI pretreatment might be widely used in biorefinery.

Comparison on structural modification of industrial lignin by wet ball milling and ionic liquid pretreatment

Graphical abstract

Microwave-Assisted Conversion of Lignin

Lignin is the most abundant natural aromatic compounds in the world consisting of three phenylpropane units: coumaryl alcohol, coniferyl alcohol and syringyl alcohol, which are cross-linked to each other with a variety of different chemical bonds . Although the compositional property of lignin has great potential as a feedstock for high-value chemicals , its complex structure requires development of efficient procedures. The application of microwave to the transformation of lignin by microwave pyrolysis to produce bio-oil with or without catalysts has proven to be feasible and efficient, which will be as the emphasis in this chapter. In addition, lignin (or lignin model compounds ) degradation to produce phenol , acetovanillone or other phenolic compounds with microwave as heating source will also be introduced. The objective of this chapter is to introduce the major works in microwave-assisted conversion of lignin and the methods to summarize the methods for microwave direct chemical (or catalytic) conversion of lignin to high value-added products.

One-pot conversion of disaccharide into 5-hydroxymethylfurfural catalyzed by imidazole ionic liquid

Conversion of carbohydrate into 5-hydroxymethylfurfural (5- HMF), a versatile, key renewable platform compound is regarded as an important transformation in biomass-derived carbohydrate chemistry. A variety of ILs, not only acidic but also alkaline ILs, were synthesized and used as catalyst in the production of 5-HMF from disaccharide. Several factors including reaction temperature, IL dosage, solvent and reaction time,were found to influence the yield of 5-HMF from cellobiose. Of the ILs tested, hydroxy-functionalized ionic liquid (IL), 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate ([AEMIM]BF4) showed the highest catalytic activity and selectivity. 5-HMF yield of 68.71% from sucrose was obtained after 6 hrs at 160 °C. At the same condition with cellobiose as substrate, 5-HMF yield was 24.73%. In addition, 5-HMF also exhibited good stablity in this reaction system. Moreover, a kinetic analysis was carried out in both acidic and alkaline IL-catalyzed system, suggesting main side reaction in the conversion of fructose catalyzed by acidic and alkaline IL was polymerization of fructose and 5-HMF degradation, respectively.

Changes on structural properties of biomass pretreated by combined deacetylation with liquid hot water and its effect on enzymatic hydrolysis

A novel combined pretreatment of deacetylation and liquid hot water (LHW) was invented which has been proved to be effective in increasing enzymatic hydrolysis yield of biomass. In order to further understand the effect of this new pretreatment process on biomass, the variation on structural properties including cellulose crystallinity index (CrI), specific surface area (SSA) and degree of polymerization (DP) before/after pretreatment and how these properties affected the enzymatic hydrolysis of biomass were explored. The improvement of pretreatment severity (PS) could increase CrI, SSA and reduce DP. Whereas the enhancement of degree of deacetylation could decrease SSA and DP. An optimal formula (E12Y=0.347(100-CrI)(-0.375)×(SSA)(0.203)×(1700-DP)(0.281)) was achieved to express the correlation between structural properties and enzymatic hydrolysis after 12h. The enzymatic yield was more sensitive to CrI than to SSA and DP.

Removal of chromophore in enzymatic hydrolysis by acid precipitation to improve the quality of xylo-oligosaccharides from corn stalk

As the most representative functional sugar, the application areas and market demands of xylo-oligosaccharides (XOS) have been expanding year by year. Owing to the complex structure of corn stalk (CS), XOS obtained from CS are accompanied by problems such as low purity and high color value, which degrade the product. To improve the quality of XOS from CS, the enzymatic hydrolysis was precipitated by acid; then, the ethanol elution concentration was systematically investigated after optimizing the adsorption conditions. The results showed that the purity of XOS was increased to 87.28% from 67.31%, and the color value was decreased to 1050 from 4682 when the acid precipitation pH was 2. On the basis of acid precipitation, if the corresponding optimal conditions of XOS adsorption and elution were used, the highest purity of XOS was 97.87% obtained, with the lowest color value, 780, which reached the standard of the commercial XOS.

Investigating desorption during ethanol elution to improve the quality and antioxidant activity of xylo-oligosaccharides from corn stalk

As the most representative of lignocellulosic materials, corn stalk (CS) will be a great candidate to produce xylo-oligosaccharides (XOS). Owing to the high impurity content of the XOS produced by directly enzymatic hydrolysis of xylan extracted from CS, subsequent refining steps are essential. The present study was aimed to investigate desorption during ethanol elution to improve the quality and antioxidant activity of XOS from CS. The desorption was systematically investigated after optimizing the elution conditions. The results showed that it had an elution watershed when the volume ratio was 2:1. More interestingly, XOS had a obvious priorities of desorption during ethanol gradient elution. The highest purity of XOS was 98.12% from 30% ethanol eluate. Antioxidant activity assay showed that the highest radical scavenging activity of XOS was 89.89% obtained from 70% ethanol eluate at a concentration of 3 mg/mL, which could be used in antioxidant food, feed additives.