Enzymatic Mild Acidolysis Lignin Research Articles

Chemical Structure and Thermochemical Properties of Enzymatically Acidolyzed Lignins from Soft and Hard Wood

Enzymatic/Mild Acidolysis Lignin (EMAL) was isolated from Cunninghamia lanceolata and eucalyptus woods. The chemical structure and thermochemical properties were characterized by means of elemental analysis, Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TG), and pyrolysis-gas chromatography combined with mass spectrometry (Py-GC/MS). The EMAL isolated from Cunninghamia lanceolata (C-EMAL) had larger HHV (higher heat value) in comparison to the EMAL isolated from eucalyptus (E-EMAL) due to the greater carbon content of the C-EMAL. The E-EMAL had more syringyl units, whereas the C-EMAL contained more guaiacyl units. It was observed that thermal decomposition occurred over a wide temperature range, and that at a given starting temperature, within the same sample, a higher heating rate produced a higher temperature at which maximum weight loss peaked. The pyrolysis products were mainly composed of carboxylic acids, alcohols, ketones, aldehydes, olefins, alkanes, esters, ethers, and phenols. At all pyrolysis temperatures, the largest components of the pyrolysis products obtained from C-EMAL were the phenols.

Impact of Pseudolignin versus Dilute Acid-Pretreated Lignin on Enzymatic Hydrolysis of Cellulose

To evaluate the inhibition effects of pseudolignin to enzymatic hydrolysis of cellulose in comparison to lignin, enzymatic mild acidolysis lignin (EMAL) was isolated from poplar after an 8 min pretreatment at 170 °C using 0.5% H2SO4. Fourier transform infrared (FT-IR) and 13C NMR characterization revealed that the poplar lignin was partially degraded during the pretreatment and did not contain detectable amounts of pseudolignin. Holocellulose was treated with varying amounts of pseudolignin and/or EMAL dissolved in p-dioxane and then dried. The treated and control holocellulose was then treated to a standard cellulase treatment, and the results from enzymatic hydrolysis of these samples showed that the dilute acid-pretreated lignin inhibited hydrolysis in the initial stage but had a negligible impact on the overall cellulose-to-glucose conversion yield. In contrast, pseudolignin significantly reduced the overall enzymatic conversion yield of cellulose to glucose. This study suggests that pseudolignin form...

Molecular Weight Distributions and Linkages in Lignocellulosic Materials Derivatized from Ionic Liquid Media

A novel and reproducible method is described for accurately determining the molecular weight distribution by size exclusion chromatography (SEC) of whole lignocellulosic materials. This approach offers the opportunity to compare the molecular weight distributions of intact milled woods and its component fractions, lignins and holocelluloses, all from the same source, thus highlighting the potential of the technique and the contributions of the individual components to the chromatogram. The method is based on the dissolution of the ball-milled samples in the ionic liquid 1-allyl-3-methylimidazolium chloride ([amim]Cl). Under these homogeneous ionic liquid media, a derivatization reaction was performed with benzoyl chloride in the presence of pyridine. The thoroughly benzoylated wood with its associated carbohydrate and lignin components was found to be completely soluble in the THF SEC eluent with marked UV detector sensitivity. This methodology, when applied to the individually isolated holocellulose and lignin (enzymatic mild acidolysis lignin; EMAL) materials from Norway spruce ( Eucalyptus grandis ) wood and corn stover, offered a better understanding as to the possible ways the lignin and the carbohydrates may interact within these three different species. Finally, the applicability of the methodology is shown for a series of pure cellulosic samples under intense mechanical defibration conditions, offering a visualization of the molecular weight distribution changes induced during the production of nanofibrillated cellulose.

Products properties from fast pyrolysis of enzymatic/mild acidolysis lignin

The conversion of enzymatic/mild acidolysis lignin (EMAL) isolated from moso bamboo to aromatic chemicals by fast pyrolysis were investigated under nitrogen atmosphere and atmospheric pressure. The experiment of EMAL pyrolyzing was set on a tubular reactor furnace at the temperature levels of 400, 500, 600, 700, 800 and 900 °C, and the products derived from EMAL pyrolyzing were classified into three-phase of gas, condensed liquid (tar), and solid (char). The chemical structure and surface morphology of solid product were characterized by fourier transforms infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the ingredients of gas product and liquid (tar) were analyzed with gas chromatography (GC) and gas chromatography/mass spectrometer (GC/MS). The analysis results indicated that the yield of char decreased rapidly from 43% to 28% with an increase of temperature, and the yield of gas product increased gradually from 6% to 26%, and the yield of tar attained a maximum at 700 °C. SEM showed that char took on lots of vesicles that resulted from the gas release from EMAL pyrolyzing. The ingredients of gas product were comprised of H 2, CO, CO 2 and light hydrocarbons (CH 4, C 2H 4 and C 2H 6), and the amount of H 2, CO were high. Besides a huge amount of phenols, the tar contained aromatic hydrocarbons, chain hydrocarbons, monoaromatic aromatic hydrocarbons and some ketones, and the carbon number of chemical compounds were C 6–C 10.

Pyrolytic products from rice straw and enzymatic/mild acidolysis lignin (EMAL)

A pyrolysis tube furnace system was designed to assess the impact of different components on pyrolysis characteristics under nitrogen atmosphere, and pyrolysis temperature (400 to 900oC) as important factors acting on the samples during pyrolysis. The obtained pyrolysate was classified into three groups, i.e. the condensed liquid product (bio-oil), solid product (bio-char), and light gas. Gas chromatography (GC) was used to analyze ingredients of the light gas released during pyrolysis, and a gas chromatography/mass spectrometer (GC/MS) was used to analyze bio-oil. The results revealed that the volatiles from rice straw pyrolysis exceeded that from lignin at temperatures below 700oC as a result of the higher char generation from lignin pyrolysis. With an increase of pyrolysis temperature, the yield of char decreased and light gas persistently increased, and the yield of bio-tar was maximized at 500oC. In the gas product, H2, CO, CO2 and some light hydrocarbons (CH4, C2H4 and C2H6) could be found, and H2 and CO were abundant. Compounds of bio-oil derived from lignin were simple and consisted of aromatic hydrocarbons, chain hydrocarbon, monoaromatics, and a minor amount of ketones. Phenolic compounds, which comprised 50 to 60%, can be converted easily to obtain high-value chemicals and high quality biofuels.

Fast pyrolysis of enzymatic/mild acidolysis lignin from moso bamboo

The characteristics of enzymatic/mild acidolysis lignin (EMAL) isolated from moso bamboo were investigated using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Pyrolysis temperature as a factor on products was studied, and the pyrolysis mechanism was inferred with respect to the dominating products. Research results showed that pyrolysis products derived from EMAL pyrolysis were mainly heterocyclic (2,3-dihydrobenzofuran), phenols, esters, and a minor amount of acetic acid. Pyrolysis temperature had a distinct impact on yields of pyrolysis products. As pyrolysis temperature increased, the yield of 2,3-dihydrobenzofuran rapidly decreased; however, yields of phenols increased smoothly. It can be obtained that, at the low temperatures (250-400oC), pyrolysis products were mainly 2,3-dihydrobenzofuran, and the highest yield was 66.26% at 320oC; at the high temperatures (400-800oC), pyrolysis products were mainly phenols, and yields hit their highest level of 56.43% at 600 oC. A minor amount of acetic acid only emerged at 800°C. Knowledge of pyrolysis products releasing from EMAL and the pyrolysis mechanism could be basic and essential to the understanding of thermochemical conversion of EMAL to chemicals or high-grade energy.

Microwave-Assisted Lignin Isolation Using the Enzymatic Mild Acidolysis (EMAL) Protocol

The use of microwaves is explored in an effort to further improve the recently developed lignin isolation protocol termed EMAL (enzymatic mild acidolysis lignin). Because the presence of the lignin-carbohydrate linkages seems to be rather pronounced within wood, a microwave reactor was used to replace traditional refluxing during the mild acidolysis step. This was done in an attempt to augment the selectivity of this step toward cleaving lignin-carbohydrate bonds as well as reducing the overall intensity of this step toward inducing changes in the lignin structure, thus affording lignin in greater yields and purities. Consequently, in this study the yields, purities, and structures of lignins isolated from spruce (softwood) by the EMAL protocol under various microwave conditions were examined. The variables studied included microwave power, microwave heating time, hydrochloric acid concentration and water content of the reaction medium. Microwave heating afforded EMAL samples of high purity (90%, comparable to the conventional protocol) but in significantly greater gravimetric yields. Quantitative (31)P NMR and SEC data confirmed that the structure of lignin was similar to that obtained by traditional EMALs, with comparable contents of beta-aryl ether bonds, phenolic hydroxyls (condensed and uncondensed), and carboxylic acids.

On the propensity of lignin to associate: A size exclusion chromatography study with lignin derivatives isolated from different plant species

Despite evidence that lignin associates under both aqueous and organic media, the magnitude and nature of the underlying driving forces are still a matter of discussion. The present paper addresses this issue by examining both solution properties and size exclusion behaviour of lignins isolated from five different species of softwoods, as well as from the angiosperms Eucalyptus globulus and wheat straw. This investigation has used the recently described protocol for isolating enzymatic mild acidolysis lignin (EMAL), which offers lignin samples highly representative of the overall lignin present in the wood cell wall. The molecular weight distributions of these EMALs were found to be dependent upon the wood species from which they were isolated and upon the incubation conditions used prior to size exclusion chromatography. While the chromatograms of EMALs isolated from softwoods displayed a bimodal behaviour, the elution profiles of EMAL from E. globulus and straw were nearly unimodal. A marked tendency to dissociate prevailed under incubation at room temperature for all examined species with the exception of the straw lignin preparation; furthermore, lignin solutions incubated at 4 °C showed an associative behaviour manifested by an increase in the weight and number average molecular weights for some species. The extent of such association/dissociation, as well as the time needed for the process to reach completion, was also found to depend upon the wood species, i.e. lignins from softwoods were found to associate/dissociate to a greater extent than lignins from E. globulus and straw. The origin of such effects within the lignin structure is also discussed.

Comparative Evaluation of Three Lignin Isolation Protocols for Various Wood Species

Milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL) were isolated from different wood species and characterized by various techniques. The EMAL protocol offered gravimetric lignin yields 2-5 times greater than those of the corresponding MWL and CEL. The purities of the EMALs were 3.75-10.6% higher than those of their corresponding CELs, depending upon the wood species from which they were isolated. Molecular weight analyses showed that the EMAL protocol isolates lignin fractions that are not accessed by the other procedures evaluated, while 31P NMR spectroscopy revealed that MWL is more condensed and bears more phenolic hydroxyl groups than EMAL and CEL. The yields and purities of EMAL, MWL, and CEL from hardwood were greater than those obtained for the examined softwoods. Structural details obtained by DFRC (derivatization followed by reductive cleavage)/31P NMR revealed different contents of condensed and uncondensed beta-O-aryl ether structures, dibenzodioxocins, and condensed and uncondensed phenolic hydroxyl and carboxylic acid groups within lignins isolated from different wood species.