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The spent pulping liquor (SPL) obtained from straw processed by soda (alkaline) pulping contains dissolved non-sulfonated lignin. The lignin can be separated from SPL using acid or cationic flocculants which are potentially hazardous to the environment. In this study, the performance of the biobased protein flocculant hemoglobin (HEM) with and without added calcium chloride was compared with that of a high charge density synthetic cationic flocculant, poly (diallyldimethylammonium chlorides) (pDADMAC). Turbidity measurements gave overly broad concentration ranges for optimal lignin removal which may be related to the mechanism of flocculation which requires several major steps: Conversion of dissolved lignin to particulate lignin, formation of particulate lignin flocs, and subsequent sedimentation of these flocs. An optimal flocculant concentration or concentration range was estimated using the three methods: average Zeta potential corresponding to the lowest turbidity range; a novel method using the maximum percent pellet mass calculated using the dried masses of the pellet and supernatant after centrifugation; measurement of supernatant lignin using spectroscopy. HEM light absorption interfered with spectroscopic lignin determination, and a method for correcting the measurements was devised. This study shows that HEM is an effective flocculant for nonsulfonated lignin in SPL. The HEM-lignin complex is a potential high protein component of animal feed.

In industrial process, acidification causes non-sulfonated lignin insolubility. The flocculants poly(diallyldimethylammonium chloride) (pDADMAC) and bovine blood (BB) also caused lignin insolubility while cationic polyacrylamide, chitosan, and soy protein PF 974 were ineffective. Turbidity determined optimal flocculant, but turbidity magnitude with BB was greater than expected. pDADMAC caused negative lignin Zeta potential to became positive, but BB-lignin Zeta potential was always negative. Insoluble lignin did not gravity sediment, and flocculant-lignin mixtures were centrifuged. Pellet and supernatant dry mass and corrected spectroscopic results were in good agreement for optimal pDADMAC and BB. Spectroscopy showed 87-92% loss of supernatant lignin. Nitrogen analysis showed BB concentrated in the pellet until the pellet became saturated with BB. Subtracting ash and BB mass from pellet and supernatant mass confirmed optimal BB. Low levels of alum caused increased lignin flocculation at lower levels of pDADMAC and BB, but alum did not affect optimal flocculant.

Lignin represents a vastly under-utilized natural polymer co-generated during papermaking and biomass fractionation. Different types of lignin exist, and these differ with regard to isolation protocol and plant resource (i.e., wood type or agricultural harvesting residue). The incorporation of lignin into polymeric systems has been demonstrated, and this depends on solubility and reactivity characteristics. Several industrial utilization examples are presented for sulfur-free, water-insoluble lignins. These include materials for automotive brakes, wood panel products, biodispersants, polyurethane foams, and epoxy resins for printed circuit boards.

The reactions between aspen milled wood lignin (MWL) and 2-naphthol, resorcinol, and p-hydroxybenzoic acid were studied under simulated autohydrolysis conditions. The material after the reaction was separated into a dioxane-insoluble fraction (DI), a dioxane-soluble but ether-insoluble fraction (DSEI), and an ether-soluble fraction (ES). In the absence of additive, the lignin first depolymerized and remained solvent soluble, then repolymerized to become insoluble. With 2-naphthol as additive, the amount of DI lignin decreased proportionally to the amount of additive present. When more than 0.1 mole of 2-naphthol/C-9 unit was present, no DI lignin was formed, that is, all the lignin was soluble. Gel permeation chromatography studies indicated that the additive was acting effectively as a blocking agent, preventing lignin repolymerization. Small amounts of resorcinol acted as a repolymerizing agent since two or more fragments of lignin could readily condense with a molecule of the very active additive. As a result of this bridging effect, the amount of DI lignin increased. As the amount of resorcinol was increased, it behaved more like a blocking agent and a reduction in the amount of DI lignin was observed. The presence of a large excess of resorcinol resulted in the formation of soluble lignin only. The molecular weight distributions supported the proposed dual role of resorcinol as a bridging or blocking agent. The use of an excess of p-hydroxybenzoic acid prevented the formation of DI material and resulted in low molecular weight soluble lignin.

In a previous article the authors have described changes in molecular weight which occur when aspen milled wood lignin is subjecte to autocatalyzed hydrolysis (autohydrolysis) in the presence of three aromatic additives: 2-naphthol, resorcinol, and p-hydroxybenzoic acid. In the present work, the reactions of these additives have been studied from the viewpoint of their effect on the structure of the lignin. The use of milled wood lignin instead of aspen wood served to distinguish those reactions between the additives and the lignin, without involving the other wood components. The reaction products have been charactrized by elemental analysis and UV and IR spectroscopy. It was concluded that keto groups, generated on the lignin side-chain during autohydrolysis, condense with the additives, which become incorporated into the lignin. This occurs most probably through an aromatic eletrophilic substitution reaction. While 2-naphthol condensed primarily with the β-keto carbonyl groups, resorcinol attacked also the α-keto carbonyl groups. When p-hydroxybenzoic acid was the additive, its incorporation was accompanied by an increase in lignin carboxylic acid groups.