Crystallinity Index Of Biomass Research Articles

Quantitative (13)C MultiCP solid-state NMR as a tool for evaluation of cellulose crystallinity index measured directly inside sugarcane biomass.

BackgroundThe crystallinity index (CI) is often associated with changes in cellulose structure after biological and physicochemical pretreatments. While some results obtained with lignocellulosic biomass demonstrate a progressive increase in the CI as a function of pretreatments, it is also shown that the CI can significantly vary depending on the choice of the measurement method. Besides, the influence of the CI on the recalcitrance of biomass has been controversial for a long time, but the most recent results tend to point out that the efficiency of pretreatments in reducing the recalcitrance is not clearly correlated with the decrease of the CI. Much of this controversy is somewhat associated with the inability to distinguish between the CI of the cellulose inside the biomass and the CI of the full biomass, which contains other amorphous components such as lignin and hemicellulose.ResultsCross polarization by multiple contact periods (Multi-CP) method was used to obtain quantitative 13C solid-state nuclear magnetic resonance (ssNMR) spectra of sugarcane bagasse biomass submitted to two-step pretreatments and/or enzymatic hydrolysis. By comparing the dipolar filtered Multi-CP 13C NMR spectra of untreated bagasse samples with those of samples submitted to acid pretreatment, we show that a 1% H2SO4-assisted pretreatment was very effective in removing practically all the hemicellulose signals. This led us to propose a spectral editing procedure based on the subtraction of MultiCP spectra of acid-treated biomass from that of the extracted lignin, to obtain a virtually pure cellulose spectrum. Based on this idea, we were able to evaluate the CI of the native cellulose inside the sugarcane bagasse biomass.ConclusionsThe results show the validity of the proposed method as a tool for evaluating the variations in the CI of the cellulose inside biomasses of similar kinds. Despite a clear increase in the CI of biomass as measured by X-ray diffraction, no significant variations were observed in the CI of the cellulose inside the biomass after a particular 1% H2SO4/0.25–4% NaOH chemical-assisted pretreatments. The CI of cellulose inside the biomass solid fraction that remained after the enzymatic hydrolysis was also evaluated. The results show a slight increase in crystallinity.

Kinetic features of xylan de-polymerization in production of xylose monomer and furfural during acid pretreatment for kenaf, forage sorghums and sunn hemp feedstocks

Abstract: A kinetic study of acid pretreatment was conducted for sorghum non-brown mid rib (SNBMR) (Sorghum bicolor L Moench), sorghum-brown mid rib (SBMR), sunn hemp (Crotalaria juncea L) and kenaf (Gossypiumhirsutum L), focusing on rates of xylose monomer and furfural formation. The kinetics was investigated using two independent variables, reaction temperature (150 and 160°C) and acid concentration (1 and 2 wt%), with a constant dry biomass loading of 10 wt% and a treatment time up to 20 min while sampling the mixture every 2 min. The experimental data were fitted using a two-step kinetic model based on irreversible pseudo first order kinetics at each step. Varied kinetic orders on the acid concentration, ranging from 0.2 to >3, were observed for both xylose and furfural formation, the values depending on the feedstock. The crystallinity index of raw biomass was shown to be a major factor influencing the rate of both xylose and furfural formation. A positive correlation was observed between the activation energy and biomass crystallinity index for xylose formation. Keywords: acid pretreatment, sunn hemp, sorghum brown-mid rib (BMR), sorghum non brown- mid rib (SNBMR), kenaf, reaction kinetics, activation energy, reaction order DOI: 10.3965/j.ijabe.20140704.010 Citation: Kamireddy S R, Kozliak E I, Tucker M, Ji Y. Kinetic features of xylan de-polymerization in production of xylose monomer and furfural during acid pretreatment for kenaf, forage sorghums and sunn hemp feedstocks. Int J Agric & Biol Eng, 2014; 7(4): 86－98.

Understanding changes in cellulose crystalline structure of lignocellulosic biomass during ionic liquid pretreatment by XRD

X-ray diffraction (XRD) was used to understand the interactions of cellulose in lignocellulosic biomass with ionic liquids (ILs). The experiment was designed in such a way that the process of swelling and solubilization of crystalline cellulose in plant cell walls was followed by XRD. Three different feedstocks, switchgrass, corn stover and rice husk, were pretreated using 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]) at temperatures of 50-130°C for 6h. At a 5 wt.% biomass loading, increasing pretreatment temperature led to a drop in biomass crystallinity index (CrI), which was due to swelling of crystalline cellulose. After most of the crystalline cellulose was swollen with IL molecules, a low-order structure was found in the pretreated samples. Upon further increasing temperature, cellulose II structure started to form in the pretreated biomass samples as a result of solubilization of cellulose in [C4mim][OAc] and subsequent regeneration.

Analysis of Crystallinity Index and Hydrolysis Rates in the Bioenergy Crop Sorghum bicolor

Maximum yield from any cellulosic bioenergy crop is largely dependent upon total dry weight at harvest and process-specific bioconversion rates. Using enzymatic hydrolysis rate as a bioconversion metric, we have investigated the relationship between the biomass crystallinity index (CI) and hydrolysis yield potential (HYP) among ∼20 Sorghum bicolor varieties grown in two environments. The comparison of HYP to CI revealed a significant negative correlation in both environments indicating that high cellulose crystallinity in sorghum can have an impact on conversion yield. Interestingly, no correlation was seen between CI and HYP after pretreatment. Compositional analysis revealed a significant positive correlation between lignin content and CI, as well as a significant negative correlation between lignin content and HYP. Additionally, CI and HYP were found to be significantly correlated only after 24 h of hydrolysis. These results suggest that when a sorghum cultivar is being considered for industrial scale production, the inclusion of cellulose crystallinity should be factored into the decision along with total biomass yield and lignin composition.