On the formation of diphenylmethane structures in lignin under kraft, EMCC®, and soda pulping conditions

1998 ◽  
Vol 76 (5) ◽  
pp. 506-512 ◽  
Author(s):  
Behzad C Ahvazi ◽  
Gerry Pageau ◽  
Dimitris S Argyropoulos
Keyword(s):  
Picea Mariana ◽  
Nmr Spectra ◽  
Kraft Pulp ◽  
Model Compound ◽  
Kraft Pulping ◽  
Hydroxyl Groups ◽  
Milled Wood Lignin ◽  
Kraft Process ◽  
Soda Pulping ◽  
Phenolic Hydroxyl Groups

This paper describes our efforts focused at defining the formation of diphenylmethane moieties in lignin during conventional kraft and soda pulping conditions. This objective was realized by confirming, initially, the assignment of a 31P NMR signal as being due exclusively to the presence of phosphitylated diphenylmethane (DPM) phenolic hydroxyl groups. More specifically, softwood milled wood lignin (Picea mariana) was subjected to kraft pulping conditions in the presence and absence of varying amounts of formaldehyde. After quantitative recovery of the lignin, the 31P NMR spectra were recorded and the spectra revealed selective signal growth in the region confined between 142.8 and 144.3 ppm, in accordance with previous model compound work and detailed calculations based on the Hammett principles. To further substantiate our conclusions we also carried out two series of isothermal (120°C) kraft and soda pulping experiments followed by quantitative determinations of the DPM moieties, and correlated our findings with the differences in chemistry known to occur between the two processes. Finally, diphenylmethane phenolic moieties were determined in isolated residual lignins from two western hemlock kraft pulp samples produced via an EMCC® mill protocol and a laboratory batch digester, respectively. These structures prevailed amongst the condensed phenolic units of the conventional pulp, providing additional evidence to support the fact that modern modified pulping technologies beneficially alter the structure of residual kraft lignin.Key words: phenyl groups, kraft pulping, modified kraft process, nuclear magnetic resonance (NMR), phosphorus spectroscopy.

A new and facile method for isolation of lignin from wood based on complete wood dissolution

Holzforschung ◽  
2008 ◽  
Vol 62 (1) ◽  
pp. 15-23 ◽  
Author(s):  
Mario Fasching ◽  
Philipp Schröder ◽  
R. Petra Wollboldt ◽  
Hedda K. Weber ◽  
Herbert Sixta
Keyword(s):  
Beech Wood ◽  
High Yield ◽  
Resonance Spectroscopy ◽  
Hydroxyl Groups ◽  
Milled Wood Lignin ◽  
Lignin Fraction ◽  
Extraction Step ◽  
Elemental Analyses ◽  
Phenolic Hydroxyl Groups ◽  
Total Dissolution

Abstract A new method for the isolation of lignin in high yield from wood and pretreated wood is presented, avoiding the liquid-solid extraction step of the classical milled wood lignin (MWL) isolation. Dissolved wood lignin (DWL) was obtained by total dissolution of ball milled wood in dimethylsulfoxide and N-methylimidazole (DMSO/NMI) followed by precipitation in dioxane/water in the course of which lignin and carbohydrate fractions were separated. The lignin fraction was purified. High lignin yields and the low number of separation steps belong to the advantages of the described method. DWL lignin was isolated from beech wood (Fagus sylvatica L.) and the sample was compared to MWL obtained by the classical Björkman method. Elemental analyses, methoxyl group content, potassium permanganate oxidation, infrared spectroscopy, and 1D and 2D nuclear magnetic resonance spectroscopy indicated that both lignin preparations are quite similar. However, MWL contained significantly more phenolic hydroxyl groups than DWL. The results indicated that MWL contains higher amounts of smaller fractions with broken β-O-4 linkages than DWL.

The Kismet of Residual During LMS Delignification of High-Kappa Kraft Pulps

Holzforschung ◽  
2000 ◽  
Vol 54 (6) ◽  
pp. 647-653 ◽  
Author(s):  
F.S. Chakar ◽  
A.J. Ragauskas
Keyword(s):  
Spectral Analysis ◽  
Carboxylic Acid ◽  
Kraft Pulp ◽  
Structural Changes ◽  
Phenolic Hydroxyl ◽  
Hydroxyl Groups ◽  
Alkaline Extraction ◽  
Kraft Pulps ◽  
Before And After ◽  
Phenolic Hydroxyl Groups

SummaryA series of laccase-mediator treatments (LMS) with 1-hydroxybenzotriazole (HBT) andN-acetyl-Nphenylhydroxylamine(NHAA) (Fig. 1) as the mediators were performed on a laboratory prepared southern softwood conventional kraft pulp (kappa # 75.4). Subsequent to the LMS treatments, the treated pulps were subjected to various oxidatively reinforced alkaline extraction stages (E*). The kappa results suggested that both LMSHBTand LMSNHAAtreatments delignified this high-kappa pulp. The E* stages were beneficial in countering the darkening effect observed after the LMS treatments. Structural changes in residual lignins isolated before and after laccase-mediator (LMSNHAA(E*) and LMSHBT(E*)) treatments were explored. The spectral analysis of phosphitylated residual lignins revealed an increase in carboxylic acid content and a depletion of phenolic hydroxyl groups in non-condensed at C-5 lignin moieties. Aliphatic hydroxyl groups were substantially decreased when NHAA was used. Overall, it appears that LMSHBTand LMsNHAAtreatments on high-kappa kraft pulps primarily attack phenolic hydroxyl groups in non-condensed at C-5 lignin structures.

The role of non-phenolic lignin in chlorate-forming reactions during chlorine dioxide bleaching of softwood kraft pulp

Holzforschung ◽  
2005 ◽  
Vol 59 (2) ◽  
pp. 110-115 ◽  
Author(s):  
Doug R. Svenson ◽  
Hou-min Chang ◽  
Hasan Jameel ◽  
John F. Kadla
Keyword(s):  
Chlorine Dioxide ◽  
Kraft Pulp ◽  
Hypochlorous Acid ◽  
Phenolic Hydroxyl ◽  
Hydroxyl Groups ◽  
Kraft Pulps ◽  
Kinetic Rates ◽  
Softwood Kraft Pulp ◽  
Phenolic Hydroxyl Groups ◽  
Inorganic Reactions

Abstract The affect of phenolic hydroxyl groups on the reaction efficiency during chlorine dioxide pre-bleaching of a softwood kraft pulp was investigated. The removal of phenolic hydroxyl groups via pulp methylation did not adversely affect the chlorine dioxide bleaching efficiency or the amount of chlorate formed during exposure to chlorine dioxide. Ion analysis of the reaction systems revealed that the formation of chloride and chlorite ions during the bleaching process were very similar between the kraft and methylated kraft pulps. These results indicate that the kinetic rates of lignin oxidation by chlorine dioxide and its reduction products, chlorite and hypochlorous acid, are much faster than the rate of inorganic reactions leading to chlorate formation.

Brownstock washing: A review of the literature

TAPPI Journal ◽  
2014 ◽  
Vol 13 (1) ◽  
pp. 9-19 ◽  
Author(s):  
RICARDO B. SANTOS ◽  
PETER W. HART
Keyword(s):  
High Efficiency ◽  
Black Liquor ◽  
Material Balance ◽  
Kraft Pulping ◽  
Wash Water ◽  
Pulp Fibers ◽  
Kraft Process ◽  
Cooking Process ◽  
Materials Used ◽  
Entrapped Air

Brownstock washing is a complex, dynamic process in which dirty wash water or weak black liquor (dissolved organic and inorganic material obtained from the pulp cooking process) is separated from pulp fibers. The use of material balance techniques is of great importance to identify potential problems and determine how well the system is operating. The kraft pulping industry was the first known to combine pulp washing with the recovery of materials used and produced in the wood cooking process. The motivation behind materials recovery is economic, and more recently, environmentally driven. The chemicals used in the kraft process are expensive as compared to those used in the sulfite process. For the kraft process to be economically viable, it is imperative that a very high percentage of the cooking chemicals be recovered. To reach such high efficiency, a variety of washing systems and monitoring parameters have been developed. Antifoam additives and processing aids have also played an important role in increasing washing effectiveness. Antifoam materials help attain washing effectiveness by preventing entrapped air from forming in the system, which allows for an easier, unimpeded flow of filtrate through the screens and washers.

119Sn, 13C and 1H NMR Spectra of Tris(1-butyl)stannyl D-Glucuronate

1997 ◽  
Vol 62 (8) ◽  
pp. 1169-1176 ◽  
Author(s):  
Antonín Lyčka ◽  
Jaroslav Holeček ◽  
David Micák
Keyword(s):  
Chemical Shift ◽  
Carbonyl Group ◽  
1H Nmr ◽  
Equatorial Plane ◽  
Title Compound ◽  
Nmr Spectra ◽  
Hydroxyl Groups ◽  
Carboxylic Group ◽  
H Nmr ◽  
Oxygen Atoms

The 119Sn, 13C and 1H NMR spectra of tris(1-butyl)stannyl D-glucuronate have been measured in hexadeuteriodimethyl sulfoxide, tetradeuteriomethanol and deuteriochloroform. The chemical shift values have been assigned unambiguously with the help of H,H-COSY, TOCSY, H,C-COSY and 1H-13C HMQC-RELAY. From the analysis of parameters of 119Sn, 13C and 1H NMR spectra of the title compound and their comparison with the corresponding spectra of tris(1-butyl)stannyl acetate and other carboxylates it follows that in solutions of non-coordinating solvents (deuteriochloroform) the title compound is present in the form of more or less isolated individual molecules with pseudotetrahedral environment around the central tin atom and with monodentately bound carboxylic group. The interaction of tin atom with oxygen atoms of carbonyl group and hydroxyl groups of the saccharide residue - if they are present at all - are very weak. In solutions in coordinating solvents (hexadeuteriodimethyl sulfoxide or tetradeuteriomethanol), the title compound forms complexes with one molecule of the solvent. Particles of these complexes have a shape of trigonal bipyramid with the 1-butyl substituents in equatorial plane and the oxygen atoms of monodentate carboxylic group and coordinating solvent in axial positions.

scholarly journals Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2131
Author(s):  
Leonardo Dalseno Antonino ◽  
Júlia Rocha Gouveia ◽  
Rogério Ramos de Sousa Júnior ◽  
Guilherme Elias Saltarelli Garcia ◽  
Luara Carneiro Gobbo ◽  
...  
Keyword(s):  
Experimental Work ◽  
Chemical Structure ◽  
31P Nmr ◽  
Kraft Lignin ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Diphenylmethane Diisocyanate ◽  
Complex Chemical ◽  
Heterogeneous Reactivity ◽  
Phenolic Hydroxyl Groups

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

Fate of phosphorus in the recovery cycle of the kraft pulping process

TAPPI Journal ◽  
2020 ◽  
Vol 19 (3) ◽  
pp. 139-148
Author(s):  
MARYAM SADEGH MOUSAVI ◽  
NIKOLAI DEMARTINI
Keyword(s):  
Kraft Pulp ◽  
Pulp Mill ◽  
Field Studies ◽  
Kraft Pulping ◽  
Pulp Mills ◽  
Recovery Cycle ◽  
Green Liquor ◽  
Green Liquor Dregs ◽  
Kraft Pulp Mills ◽  
Negative Effect

The accumulation of nonprocess elements in the recovery cycle is a common problem for kraft pulp mills trying to reduce their water closure or to utilize biofuels in their lime kiln. Nonprocess elements such as magne-sium (Mg), manganese (Mn), silicon (Si), aluminum (Al), and phosphorus (P) enter the recovery cycle via wood, make-up chemicals, lime rock, biofuels, and process water. The main purge point for these elements is green liquor dregs and lime mud. If not purged, these elements can cause operational problems for the mill. Phosphorus reacts with calcium oxide (CaO) in the lime during slaking; as a result, part of the lime is unavailable for slaking reactions. The first part of this project, through laboratory work, identified rhenanite (NaCa(PO4)) as the form of P in the lime cycle and showed the negative effect of P on the availability of the lime. The second part of this project involved field studies and performing a mass balance for P at a Canadian kraft pulp mill.

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