Pyrolytic lignin removal for the valorization of biomass pyrolysis crude bio‐oil by catalytic transformation

BACKGROUND: The catalytic processes for valorizing the bio‐oil obtained from lignocellulosic biomass pyrolysis face the problem that a great amount of carbonaceous material is deposited on the catalyst due to the polymerization of phenol‐derived compounds in the crude bio‐oil. This carbonaceous material blocks the catalytic bed and contributes to rapid catalyst deactivation. This paper studies an on‐line two‐step process, in which the first one separates the polymerizable material and produces a reproducible material whose valorization is of commercial interest. RESULTS: The establishment of a step for pyrolytic lignin deposition at 400 °C avoids the blockage of the on‐line catalytic bed and attenuates the deactivation of a HZSM‐5 zeolite based catalyst used for hydrocarbon production. The origin of catalyst deactivation is coke deposition, which has two fractions (thermal and catalytic), whose content is attenuated by prior pyrolytic lignin separation and by co‐feeding methanol. The morphology and properties of the material deposited in the first step (pyrolytic lignin) are similar to lignins obtained as a by‐product in wood pulp manufacturing. CONCLUSIONS: The proposed reaction strategy, with two steps (thermal and catalytic) in series, valorizes the crude bio‐oil by solving the problems caused by the polymerization of phenolic compounds, which are obtained in the pyrolysis of the lignin contained in lignocellulosic biomass. Given that a by‐product (pyrolytic lignin) is obtained with similar properties to the lignin from wood pulping manufacturing, the perspectives for the viability of lignocellulosic biomass valorization are promising, which is essential for furthering its implementation in biorefinery processes. Copyright © 2009 Society of Chemical Industry     

The Use of Lewis Acids During Rapid Steam Hydrolysis

Mixed hardwood chips were treated with various concentrations of aluminum chloride hexahydrate, aluminum sulfate hydrate, and ferric chloride and were subjected to rapid steam hydrolysis pretreatment (RASH). The three levels included 0.01, 0.03, and 0.05 moles of catalyst per 1000 grams of wood. Rapid steam hydrolysis (RASH) was done from 180° to 260°C at 20°C intervals for one minute. The Lewis acid catalyst affected the overall recovery yield of solids, the recovery values of the individual components, the enzymatic rates, and the methanol and water solubility. Overall recovery of pretreated solids generally decreased with the increase in levels of the catalyst. The one exception was AlCl₃ ·6H₂O where the minimum recovery levels were reached at 0.03 moles per 1000 grams of wood and increased at the higher level of catalyst. Cellulose degradation occurred in the temperature range of 250° to 260°C for the control and at the two lower concentrations of the catalyst. At the higher levels of catalyst, appreciable amounts of cellulose degradation occurred at lower temperatures. Hemicellulose solubilization and degradation were extremely sensitive to the RASH temperature and to the levels of catalyst. Almost all hemicellulose was lost at high temperatures or at high levels of catalyst. Losses of lignin appeared to be affected mainly by the RASH temperature and not by the changes in the levels of catalyst.

In contrast, both the temperature and the level of catalyst strongly affected the rates of enzymatic hydrolysis. Generally, the intermediate level of catalyst seemed to give the highest rates of enzymatic hydrolysis at the lowest temperature. Methanol and water solubles increased in the presence of the catalyst and reached a maximum at levels of 0.03 moles between 230° to 250°C.     

Preliminary Results on an Approach for the Quantification of Lignin-Carbohydrate Complexes (LCC) in Hardwood Pulps

Abstract

The literature on biomass research contains many references to lignin-carbohydrate complexes (LCC) decreasing the rate of delignification in chemical pulp production, decreasing the yield of cellulosic ethanol via fermentation, and decreasing forage digestibility. However, it is difficult to find correlations between rates of the processes above and initial LCC concentration. One of the main reasons for the lack of such correlations is the absence of methods for accurate quantification of LCC. In this investigation, repeatable and reproducible determinations of bound sugars at monomeric concentrations as low as 0.3 wt% on enzymatic lignin (EL) have been achieved. The bound sugars are hydrolyzed by H₂SO₄, most likely as low molecular weight oligomers. In the same H₂SO₄ treatment, the oligomers are hydrolyzed to monomers which are subsequently quantified by ¹H NMR analyses. A significant enrichment of bound arabinan was previously reported when a crude milled wood lignin (MWL) was compared to the starting wood meal. A similar arabinan enrichment was observed for ELs from kraft and soda-AQ (SAQ) pulps in the present study. Also, well-resolved cross-peaks have been obtained in 2D HSQC NMR analyses of ELs. It has so far been confirmed that the EL from a 30.6 kappa number SAQ pulp from sugar maple contained ～30% more benzyl ethers linked to primary-OH groups in sugar units than the corresponding EL from a 33.7 kappa number kraft pulp.     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 2: Structural Characterization

Extraction of ground spruce sapwood with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min resulted in isolation of galactoglucomannans and aromatic substances, including lignin. The isolated lignin preparations were characterized by spectrometric (UV, FT-IR, ¹H NMR, liquid and solid-state ¹³C NMR), chromatographic (RP-HPLC, HP-SEC, GC-FID, and GC-MS), conventional pyrolysis, thermally assisted hydrolysis, and methylation techniques in tandem with GC-MS, and classical wet chemistry (methoxyl groups, total and phenolic hydroxyl groups, derivatization followed by reductive cleavage—DFRC). The content of β-O-4 bonds in isolated lignins was similar to that in MWL and their proportion decreased with extraction time. The oxidation of isolated lignins and content of total hydroxyl groups were significantly increased with extraction time. The lignin structure underwent condensation and demethylation reactions during hot-water extraction. The induction of new phenylcoumaran substructures was proposed in isolated lignins.     

Enzymic Hydrolysis Of Lignin—Carbohydrate Complexes Isolated From Kraft Pulp

Four carbohydrate samples extracted from kraft pulps are used as model substrates for studying the mechanism by which xylanase enhances subsequent bleaching of kraft pulp. Fourier transform infrared spectroscopy confirms that small amounts of aromatic molecules, probably lignin, remain associated with these carbohydrate samples. When the extracts are hydrolyzed with xylanase or acid, size exclusion chromatography shows a decrease in the molecular mass of their UV-absorbing constituents, as well as their carbohydrate constituents as determined by pulsed amperometric detection. The results are consistent with the hypothesis that xylanase prebleaching hydrolyzes the xylan portion of lignin-carbohydrate complexes to leave smaller lignin-containing macromolecules in pulp fiber, thus facilitating the removal of lignin components by bleaching chemicals.     

Spectroscopic studies and evaluation of thermorheological properties of softwood and hardwood lignin

Fourier transform infrared spectroscopy ( FTIR) was used to determine characteristic absorption peaks of softwood kraft lignin and soda hardwood lignin. Remarkable spectral differences were noticed between the different lignins due to their various chemical structures. Proton nuclear magnetic resonance spectrometry (¹H NMR) was employed to analyze the structure of lignin. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry ( MALDI‐TOF) provided important data regarding the molecular weight distribution of lignin. Thermal stability of softwood lignin was found to be remarkably higher than that of hardwood lignin. Softening temperature and glass transition temperature of lignin were measured by differential scanning calorimetry (DSC) which was useful in selecting an optimal temperature profile during extrusion process. Rheological studies provided valuable information about the viscosity of lignins. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Arabinosylated phenolics obtained from SO2‐steam‐pretreated sugarcane bagasse

A pentose‐rich hydrolysate fraction obtained by extraction of steam‐pretreated sugarcane bagasse was analysed with regard to dissolved phenolics. The liquid obtained after steam pretreatment (2% SO₂ (w/w) at 190 °C for 5 min) was divided into two parts: one containing dissolved compounds originating from hemicellulose (with xylose as the dominating compound), and the other containing predominantly dissolved compounds originating from lignin. Using nuclear magnetic resonance, the main dissolved compounds originating from lignin were identified as the glycosylated aromatics, 5‐O‐(trans‐feruloyl)‐L‐Arabinofuranose and 5‐O‐(trans‐coumaroyl)‐L‐Arabinofuranose, together with p‐coumaric acid and small amounts of more common free phenolics such as p‐hydroxybenzaldehyde, p‐hydroxybenzoic acid and vanillin. The phenolic compounds were analysed and quantified using reversed‐phase high‐performance liquid chromatography. The findings show that SO₂ steam explosion opened up new degradation pathways during lignin degradation. Copyright © 2012 Society of Chemical Industry     

Thermogravimetry‐FTIR Analysis of Pyrolysis of Pyrolytic Lignin Extracted from Bio‐Oil

Pyrolytic lignin is attributed to the instability of bio‐oil but is a potential chemical material. To improve the stability and increase the economic viability of bio‐oil, high‐ and low‐molecular‐mass pyrolytic lignin (HMM and LMM) were obtained using solvent extraction. The microstructure of pyrolytic lignin was examined by Fourier transform infrared spectrometry (FTIR). The dissimilar absorption intensities indicated the different content of corresponding functional groups in HMM and LMM. The pyrolysis behavior of HMM and LMM was studied by thermogravimetry coupled with FTIR. Obviously pyrolytic lignin undergoes three weight loss stages.     

木质素纤维黄土渗透性能影响因素研究

为了研究木质素纤维作为改良材料时木质素纤维黄土的渗透特征,通过恒水头三轴渗透试验和扫描电镜试验对不同木质素掺量(掺量为1%、3%、5%和7%)和养护龄期(龄期为0 d、3 d、7 d和28 d)的木质素纤维黄土进行试验,探讨不同条件时木质素纤维黄土的渗透性及微观差异。试验结果表明:木质素纤维黄土的渗透系数随养护龄期增加先增大后减小(趋于稳定),部分后期又增大;施加的围压越大,试样的渗透系数越小;木质素纤维掺量为3%时,渗透系数最小,木质素纤维掺量在1% ~ 7%范围内,渗透系数先减小后增大;木质素纤维掺量越多,木质素纤维间聚集现象更明显,掺量较小时黄土与木质素纤维的复合效果越好。对木质素纤维黄土渗透性影响因素的显著性顺序为木质素纤维掺量 > 围压 > 养护龄期。