Eucalyptus globulus Kraft Pulp Residual Lignin. Part 2. Modification of Residual Lignin Structure in Oxygen Bleaching

Holzforschung ◽  
2001 ◽  
Vol 55 (6) ◽  
pp. 645-651 ◽  
Author(s):  
A.P. Duarte ◽  
D. Robert ◽  
D. Lachenal

Summary Residual lignins were isolated from unbleached and oxygen-bleached Eucalyptus kraft pulps by acid hydrolysis. The structural changes and degradation of residual lignin occurring during kraft pulping and oxygen bleaching were followed and identified by elemental analysis, residual carbohydrate analysis, molecular mass distribution, as well as qualitative and quantitative solution 13C NMR. The dissolved lignins in the kraft cooked and oxygen bleached liquors were also studied and compared with the corresponding residual lignins. Milled wood lignin treated under acid hydrolysis conditions served as a reference for the structural comparison. The results show that etherified syringyl structures were quite resistant towards degradation in the oxygen bleaching, causing little depolymerisation in residual lignin and a small increase in carboxylic acid content, but producing appreciable amounts of saturated aliphatic methylene groups.

Holzforschung ◽  
1999 ◽  
Vol 53 (4) ◽  
pp. 416-422 ◽  
Author(s):  
Størker T. Moe ◽  
Arthur J. Ragauskas

Summary The chemistry of oxygen delignification of high-yield kraft pulp was studied by analysis of residual lignin extracted from kraft and kraft-oxygen pulps using the acid hydrolysis/dioxane extraction method. For reference pulps cooked to kappa numbers between 20 and 25, the content of free phenolic groups decreased to about 50% the original value upon oxygen delignification, while the content of carboxylic acid groups increased by 50–100%. For lignins isolated from high-yield kraft pulp and oxygen delignified high-yield kraft pulp, it was shown that high-yield kraft pulping with polysulfide (PS) and anthraquinone (AQ) gives a residual lignin which is chemically different from that of kraft pulps cooked to lower kappa numbers. Lignin extracted from oxygen delignified high-yield PS/AQ kraft pulp was more similar to lignins extracted from kraft pulps cooked to lower kappa numbers.


Holzforschung ◽  
2006 ◽  
Vol 60 (2) ◽  
pp. 137-142 ◽  
Author(s):  
Zhi-Hua Jiang ◽  
Jean Bouchard ◽  
Richard Berry

Abstract The finding that hexenuronic acid (HexA) groups can be selectively removed from kraft pulps by acid hydrolysis has provided an opportunity to reduce bleaching chemicals. However, there is evidence that the acid hydrolysis is not uniform. In this report, we evaluate the kinetics of acid hydrolysis of HexA in a xylan sample enriched with HexA, a conventional kraft pulp, and three modified kraft pulps: anthraquinone pulp (Kraft-AQ), polysulfide pulp (PS), and polysulfide-anthraquinone pulp (PS-AQ). We found that HexA present in the xylan and conventional kraft pulp behaved similarly toward the acid hydrolysis throughout. On the other hand, HexA present in the Kraft-AQ, PS-AQ and PS pulps was heterogeneous toward acid hydrolysis and the reaction can be separated into two pseudo-first-order kinetic phases, each of which has a different rate constant. The kinetic data provide evidence for the formation of lignin-HexA-xylan complexes during modified kraft pulping processes.


Holzforschung ◽  
2002 ◽  
Vol 56 (2) ◽  
pp. 179-184 ◽  
Author(s):  
Eva-Lena Hult ◽  
Per Tomas Larsson ◽  
Tommy Iversen

Summary The supermolecular structure of polysaccharides in unbleached sulphite pulps and kraft pulps was investigated by CP/MAS 13C-NMR (Cross Polarisation Magic Angle Carbon-13 Nuclear Magnetic Resonance) in combination with spectral fitting. The cellulose crystallinity was found to be higher in the kraft pulps than in the sulphite pulps. Acellulose Iα to cellulose Iβ conversion was observed during kraft pulping but not during sulphite pulping. The sulphite pulps exhibited smaller lateral fibril aggregate dimensions than the kraft pulps. The spectral behaviour of the hemicelluloses in the sulphite pulps was different from that in the kraft pulps. The general observation is that the supermolecular structure of the polysaccharides in the investigated sulphite pulps is very similar to the structure observed in wood.


Holzforschung ◽  
2000 ◽  
Vol 54 (4) ◽  
pp. 365-372 ◽  
Author(s):  
Ana Paula Duarte ◽  
Danielle Robert ◽  
Dominique Lachenal

Summary Residual lignins of Eucalyptus globulus kraft pulp were shown to be structurally different depending upon the type of extraction chosen. Enzymatic hydrolysis releases a residual lignin with a well preserved etherified structure but substantially contaminated by protein and carbohydrate moieties coming from the enzyme. Moreover, the extraction yield is poor and obviously it does not work as well as in the case of softwood kraft pulp. The residual lignin extracted by acid hydrolysis has less etherified units and more free phenolic functions than that of the enzymatic hydrolysis. It contains some unsaturated structures but no carbohydrate contaminants. Comparison with Milled Wood Lignin (MWL) treated under the acid hydrolysis conditions shows that ether splitting occurs during this extraction. The different residual lignin fractions were characterised by HPSEC, FT-IR, 13C NMR and sugar analysis.


TAPPI Journal ◽  
2013 ◽  
Vol 12 (11) ◽  
pp. 49-53 ◽  
Author(s):  
CHRISTINE CHIRAT ◽  
LUCIE BOIRON ◽  
DOMINIQUE LACHENAL

Autohydrolysis and acid hydrolysis treatments were applied on mixed softwood chips. The cooking ability was studied by varying the alkali and duration of the cook. Pulps with kappa numbers varying from 30 to 70 were obtained. The bleaching ability of these pulps was studied and compared to control kraft pulps. The prehydrolyzed pulps were shown to be more efficiently delignified by oxygen than the control kraft pulps starting from the same kappa number. Furthermore, the final bleaching was also easier for these pulps. It was also shown that extensive oxygen delignification applied on high-kappa pre-hydrolyzed pulps could be a way to improve the overall yield, which is a prerequisite for the development of such biorefinery concepts. Lignin was isolated from the control kraft and the two pre-hydrolyzed kraft pulps and analyzed by 13C NMR. Lignins from pre-hydrolyzed kraft pulps had similar free phenolic groups content to the control kraft lignin, but their aliphatic hydroxyl groups and β-O-4 content were lower than for the control lignin. The quaternary carbon content was the same for all the samples.


Holzforschung ◽  
2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Ricardo Jorge Oliveira ◽  
Bruna Santos ◽  
Maria J. Mota ◽  
Susana R. Pereira ◽  
Pedro C. Branco ◽  
...  

Abstract Lignocellulosic biomass represents a suitable feedstock for production of biofuels and bioproducts. Its chemical composition depends on many aspects (e.g. plant source, pre-processing) and it has impact on productivity of industrial bioprocesses. Numerous methodologies can be applied for biomass characterisation, with acid hydrolysis being a particularly relevant step. This study intended to assess the most suitable procedures for acid hydrolysis, taking Eucalyptus globulus bark as a case study. For that purpose, variation of temperature (90–120 °C) was evaluated over time (0–5 h), through monosaccharides and oligosaccharides contents and degradation. For glucose, the optimal conditions were 100 °C for 2.5 h, reaching a content of 48.6 wt.%. For xylose, the highest content (15.2 wt.%) was achieved at 90 °C for 2 h, or 120 °C for 0.5 h. Maximum concentrations of mannose and galactose (1.0 and 1.7 wt.%, respectively) were achieved at 90 and 100 °C (2–3.5 h) or at 120 °C (0.5–1 h). These results revealed that different hydrolysis conditions should be applied for different sugars. Using this approach, total sugar quantification in eucalyptus bark was increased by 4.3%, which would represent a 5% increase in the ethanol volume produced, considering a hypothetical bioethanol production yield. This reflects the importance of feedstock characterization on determination of economic viability of industrial processes.


Author(s):  
Vipa Thongtus ◽  
Sasikarn Nuchdang ◽  
Papin Chirathivat ◽  
Elvin J. Moore ◽  
Chantaraporn Phalakornkule

2012 ◽  
Vol 36 (6) ◽  
pp. 1163-1172 ◽  
Author(s):  
María Graciela Aguayo ◽  
Regis Teixeira Mendonça ◽  
Paulina Martínez ◽  
Jaime Rodríguez ◽  
Miguel Pereira

Tension (TW) and opposite wood (OW) of Eucalyptus globulus trees were analyzed for its chemical characteristics and Kraft pulp production. Lignin content was 16% lower and contained 32% more syringyl units in TW than in OW. The increase in syringyl units favoured the formation of β-O-4 bonds that was also higher in TW than in OW (84% vs. 64%, respectively). The effect of these wood features was evaluated in the production of Kraft pulps from both types of wood. At kappa number 16, Kraft pulps obtained from TW demanded less active alkali in delignification and presented slightly higher or similar pulp yield than pulps made with OW. Fiber length, coarseness and intrinsic viscosity were also higher in tension than in opposite pulps. When pulps where refined to 30°SR, TW pulps needed 18% more revolutions in the PFI mill to achieve the same beating degree than OW pulps. Strength properties (tensile, tear and burst indexes) were slightly higher or similar in tension as compared with opposite wood pulps. After an OD0(EO)D1 bleaching sequence, both pulps achieved up to 89% ISO brightness. Bleached pulps from TW presented higher viscosity and low amount of hexenuronic acids than pulps from OW. Results showed that TW presented high xylans and low lignin content that caused a decrease in alkali consumption, increase pulp strength properties and similar bleaching performance as compared with pulps from OW.


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