Herbert A. Schroeder

The role of ester groups in resistance of plant cell wall polysaccharides to enzymatic hydrolysis

Xylan backbones in native plant cell walls are extensively acety-lated. Previously, no direct investigations as to their role in cellulolytic enzyme resistance have been done, though indirect results point to their importance. An in vitro deesterification of aspen wood and wheat straw has been completed using hydroxylamine solutions. Yields of 90% acetyl ester removal for both materials have been accomplished, with little disruption of other fractions (i.e., lignin). Apparently, as the xylan becomes increasingly deacetylated, it becomes 5–7 times more digestible. This renders the cellulose fraction more accessible, and 2–3 times more digestible. This effect levels off near an acetyl removal of 75%, where other resistances become limiting.

Simultaneous Saccharification and Cofermentation of Peracetic Acid-Pretreated Biomass

Previous work in our laboratories has demonstrated the effectiveness of peracetic acid for improving enzymatic digestibility of lignocellulosic materials. The use of dilute alkali solutions as a pre-pretreatment prior to peracetic acid lignin oxidation increased carbohydrate hydrolysis yields in a synergistic as opposed to additive manner. Deacetylation of xylan is easily achieved using dilute alkali solutions under mild conditions. In this article, we evaluate the effectiveness of peracetic acid combined with an alkaline pre-pretreatment through simulataneous saccharification and cofermentation (SSCF) of pretreated hybrid poplar wood and sugar can ebagasse. Respective ethanol yields of 92.8 and 91.9% of theoretical are achieved using 6% NaOH/15% peracetic acid-pretreated substrates and recombinant Zymomonas mobilis CP4/p ZB5. Reduction of acetyl groups of the lignocellulosic materials is demonstrated following alkaline pre-pretreatments. Such processing may be helpful in reducing peracetic acid requirements. The influence of deacetylation is more significant in combined pretreatments using lower peracetic acid loadings.

Alkaline and Peracetic Acid Pretreatments of Biomass for Ethanol Production

Prehydrolysis with dilute acid and steam explosion constitute the most promising methods for improving enzymatic digestibility of biomass for ethanol production. Despite world wide acceptance, these methods of pretreatment are quite expensive considering costs for the reactor, energy, and fractionation. Using peracetic acid is a lignin-oxidation pretreatment with low-energy input by which biomass can be treated in a silo-type system without need for expensive capitalization. Experimentally, ground hybrid poplar and sugar cane bagasse are placed in plastic bags and a peracetic acid solution is added to the biomass in different concentrations based on ovendried biomass. The ratio of solution to biomass is 6∶1 and a 7-d storage period at ambient temperature (20°C) has been used. As an auxiliary method, a series of pre-pretreatments using stoichiometri camounts of sodium hydroxide and ammonium hydroxide based on 4-methyl-glucuronic acid and acetyl content in the biomass are performed before addition of peracetic acid. The basic solutions are added to the biomass in a ratio of 14∶1 solution to biomass, and mixed for 24 h at the same ambient temperature. Biomass is filtered and washed to a neutral pH before peracetic acid addition. The aforementioned procedures give high xylan content substrates as a function of the selectivity of peracetic acid for lignin oxidation and the mild conditions of the process. Consequently, xylanase/β-glucosidase combinations were more effective than cellulase preparations in hydrolyzing these materials. The pretreatment efficiency was evaluated through enzymatic hydrolysis and simultaneous saccharification and cofermentation (SSCF) tests. Peracetic ac treatment improves enzymatic digestibility of hybrid poplar and sugar cane bagasse with no need of high temperatures. Alkaline treatments are helpful in reducing peracetic acid requirements in the pretreatment.

Optimizing peracetic acid pretreatment conditions for improved simultaneous saccharification and co-fermentation (SSCF) of sugar cane bagasse to ethanol fuel

The use of several lignocellulosic materials for ethanol fuel production has been studied exhaustively in the U.S.A.. Strong environmental legislation has been driving efforts by enterprises, state agencies, and universities to make ethanol from biomass economically viable. Production costs for ethanol from biomass have been decreasing year by year as a consequence of this massive effort. Pretreatment, enzyme recovery, and development of efficient microorganisms are some promising areas of study for reducing process costs.

Iron-catalyzed oxidation of wood carbohydrates

SummaryDouglas-fir and red oak wood meal, cellulose, and an 0-acetyl-4-0-methylglucuronoxylan were exposed to finely divided iron powder under conditions favorable for rusting. Analyses of the wood meal and polysaccharides following exposure indicated that rusting iron causes a decomposition of all wood constituents. Cellulose was oxidized in the presence of rusting iron to form an oxycellulose which was predominantly reducing in character. Direct depolymerization of cellulose and xylan also occurred. The deterioration was favored by an acidic environment, contrary to earlier reports that the primary degradation mechanism is alkalidependent. An iron-catalyzed oxidation of wood constituents is theorized to occur as a result of free-radical production associated with ferrous ion oxidation in the presence of organic compounds. The free radicals produced lead to the formation of hydrogen peroxide which allows Fenton-type reactions to occur.

The characterization of wetwood in Western Hemlock

SummaryOne of the problem areas in the kiln drying of western hemlock lumber is the wide variation in final moisture content of the wood. This variation in moisture content is due to the presence of sinker or wetwood in the heartwood. The features of wetwood which differentiate it from the normal heartwood include higher specific gravity, higher extractives content, and lower permeability. The apparent higher specific gravity can be fully accounted for by the higher extractives content. The principial extractive is α-conidendrin. The wetwood in western hemlock often occurs together with ring shake and under these circumstances the white deposit on the shake surfaces is also α-conidendrin and not matairesinol, the substance usually associated with ring shake in western hemlock.A viewpoint is presented on the origin of wetwood as the endproduct of a reaction by the tree to injury, i.e., ring shake, in which additional extractives are deposited. The extractives result in a greatly lowered permeability, which prevents loss of moisture during heartwood formation and thereby resulting in wetwood. Bacteria usually found in wetwood and responsible for many of the symptoms associated with wetwood are a result of the high moisture content which favors bacterial growth in wood. Presumably, the two primary sources of loss in kiln drying of western hemlock, shake and wetwood, are often intimately associated.