Sheldon J.B. Duff

Coagulation and precipitation of a mechanical pulping effluent—I. Removal of carbon, colour and turbidity

Abstract This study examined the effects of metal coagulant concentration, effluent dilution and pH on the removal of total carbon, colour and turbidity from a combined bleached chemithermomechanical/thermomechanical (BCTMP/TMP) effluent. Both chloride and sulphate salts of iron and aluminum were effective in treating the mechanical pulping effluent in batch jar screening tests. pH had a pronounced affect on precipitation. In terms of minimizing the total carbon (TC), colour and turbidity levels, the optimum adjusted pH ranges were: 4.0–6.5 for ferric chloride, above 7.4 for ferrous sulphate, 5.0–6.0 for aluminum chloride and 5.8 to 6.8 for aluminum sulphate. Removal of TC, colour and turbidity of up to 88, 90 and 98%, respectively, were observed. The precipitation yielded a supernatant which was virtually clear and colourless.

Effect of inhibitory compounds found in biomass hydrolysates on growth and xylose fermentation by a genetically engineered strain of S. cerevisiae

The effect of inhibitors on the recombinant xylose fermenting strain Saccharomyces cerevisiae 259ST was compared to three reference strains, including the parent strain (S. cerevisiae 259A) and an industrial strain adapted to spent sulfite liquor (SSL). Interaction effects between the inhibitors were verified by a fractional factorial design. S. cerevisiae 259ST was found to be as hardy as the reference strains towards acetic acid, ammonium, furfural, and osmotic effects, which are inhibitory compounds in SSL. Ammonium toxicity appeared to be due to osmotic effects. For all of the inhibitors tested, growth rate was more severely inhibited than the ethanol yield during fermentation of glucose. The ability of S. cerevisiae 259ST to ferment xylose was more severely affected than the ability to ferment glucose. At the concentrations expected in softwood SSL (pH 5), acetic acid will decrease the growth rate by 15%, while the ethanol yield on xylose would decrease by 50%, while ammonium will decrease the yeast growth rate by 20% and decrease the ethanol yield from xylose by 45%.

Extraction and hydrolysis of levoglucosan from pyrolysis oil.

Fermentable sugar obtained from lignocellulosic material exhibits great potential as a renewable feedstock for the production of bio-ethanol. One potentially viable source of fermentable sugars is pyrolysis oil, commonly called bio-oil. Depending on the type of lignocellulosic material and the operating conditions used for pyrolysis, bio-oil can contain upwards of 10 wt% of 1,6-anhydro-beta-D-glucopyranose (levoglucosan, LG), an anhydrosugar that can be hydrolyzed to glucose. This research investigated the extraction of levoglucosan from pyrolysis oil via phase separation, the acid-hydrolysis of the levoglucosan into glucose, and the subsequent fermentation of this hydrolysate into ethanol. Optimal selection of water-to-oil ratio, temperature and contact time yielded an aqueous phase containing a levoglucosan concentration of up to 87 g/L, a yield of 7.8 wt% of the bio-oil. Hydrolysis conditions of 125 degrees C, 44 min and 0.5 M H(2)SO(4) resulted in a maximum glucose yield of 216% (when based on original levoglucosan), inferring other precursors of glucose were present in the aqueous phase. The aqueous phase contained solutes which inhibited fermentation, however, up to 20% hydrolysate solutions were efficiently fermented (yield=0.46 g EtOH/g glucose; productivity=0.55 g/L h) using high yeast inoculums (1 g/L in flask) and micro-aerophilic conditions.

Effect of oxygen delignification on the rate and extent of enzymatic hydrolysis of lignocellulosic material

In this study, we examined the effect of oxygen delignification on the rate and extent of enzymatic hydrolysis (using commercial cellulase and beta-glucosidase) of a number of lignocellulosic substrates, including kraft pulp (model substrate), pulp mill primary clarifier sludge (PCS) and steam-exploded Douglas fir chips. Oxygen delignification removed up to 67% of the lignin from softwood pulp and improved the rate of, and yield from, hydrolysis by up to 111% and 174%, respectively. Glucose yield varied linearly with fractional lignin removal. Oxygen delignification of primary clarifier sludge improved hydrolysis yield by up to 90%. However steam-exploded Douglas fir was very resistant to hydrolysis at low enzyme loading, and oxygen delignification decreased hydrolysis rate and yield.

Effect of HRT, SRT and temperature on the performance of activated sludge reactors treating bleached kraft mill effluent

Abstract Laboratory scale research on the effects of hydraulic retention time (HRT), solids residence time (SRT), high operating temperatures and temperature shocks on activated sludge (AS) treatment of kraft pulping effluent was performed using two 51 continuously fed bioreactors. Baseline performance of the reactors was established at 35°C by operating the reactors at steady state (HRT 10–12 h; SRT 12–15 d) for a period of two months. During this period percent removal of BOD, COD, and toxicity averaged 87.9 ± 4.3, 32.4 ± 9.0, 97.7 ± 0.4, respectively. Reactor MLVSS was 1675 ± 191 mg/l, effluent VSS was 45.5 ± 11.2 mg/l and specific oxygen uptake rate was 16.5 ± 3.3 mg O2/g MLVSS·h. Varying HRT between 12 and 4 h and SRT between 5 and 15 d indicated that HRT had more of an effect on treatment performance than SRT. Longer HRTs led to improved BOD, COD, toxicity and AOX removal, while longer SRTs were not shown to significantly affect performance. Shorter HRTs and longer SRTs led to significant increases in specific oxygen uptake rates (SOURs). For reactors operated at temperatures between 41 and 50°C, removal of BOD and acute toxicity was comparable to that observed at mesophilic temperatures. COD removal was improved over that observed at mesophilic temperatures, possibly as a result of improved dissolution of organic compounds at the higher temperatures. The effect of temperature shocks (decreases of 7°, 16.5°, 32° and 40.5°C) on reactor performance was proportional to the size of the disturbance. Reactor performance returned to pre-shocking levels within 12–24 h for the two smaller temperature shocks. Approximately 72 h was needed for the system to recover from the two larger temperature shocks (32° and 40.5°C).

Treatment of dilute phenol/PCP wastewaters using the upflow anaerobic sludge blanket (USAB) reactor

Abstract UASB reactors started up well using phenol as the sole carbon source, and by day 46, COD removal efficiency was 100%. Pentachlorophenol (PCP) was then introduced at a concentration of 1 mg/l. Sequential appearance of tri-, di- and ultimately mono-chlorophenols was observed in the reactor effluent. After 70 days of operation, only 3-chlorophenol was detected in the reactor effluent. Increasing PCP concentrations led to transient appearance of PCP and other polysubstituted constituents in the reactor effluent; however, no toxic effects were observed over the range of PCP concentrations examined. Using phenol as an additional carbon source, the upflow anaerobic sludge blanket reactor proved capable of reducing highly chlorinated phenolic compounds into lightly chlorinated phenolics more amenable to subsequent aerobic degradation.

Composting of pulp and paper mill fly ash with wastewater treatment sludge

Abstract Wastewater treatment sludge and power boiler fly ash were combined and composted in mixed and static windrows 50 m long, 4 m high and 6 m wide. Moisture content was maintained above 50%. The final compost had a pH of 8.5, contained high concentrations of specific nutrients, and an average C:N ratio of 43:1. All metal, PCB, chlorophenol and PAH concentrations were below levels stipulated by local regulations. Over the first 8 weeks of the composting period dioxin concentration decreased by 45% to 41 pg/g TEQ. Leachate tests indicated minimal ( 4 −2 ) leaching of contaminants from the composted material. Application of compost (8 cubic yards/acre) at a sod farm improved soil characteristics as measured by a number of parameters. The dioxin concentration in the final soil/compost mixture was 3 pg/g TEQ, allowing the soil/compost mixture to be classified as agricultural soil. It was concluded that composting produced an acceptable soil conditioner attractive for large volume users of inexpensive soil material (sod farms, golf courses, land reclamation sites).

Combined biological and ozone treatment of log yard run-off

Batch biological treatment of log yard run-off reduced biochemical oxygen demand (BOD), chemical oxygen demand (COD) and tannin and lignin (TL) concentration by 99%, 80%, and 90%, respectively. Acute (Microtox) toxicity was decreased over treatment, from an initial EC50 of 1.83% to a value of 50.4% after 48 h of treatment. Kinetics of biodegradation were determined using respirometry and fitted using the Monod and Tessier model. For the Monod model the maximum substrate uptake rate, and Ks values determined were 0.0038 mg BOD/mgVSS min, and 1.4 mg/L, respectively. The efficacy of ozone as a pre- and post- biological treatment stage was also assessed. During ozone pretreatment, TL concentration and acute toxicity were rapidly reduced by 70% and 71%, respectively. Pre-ozonation reduced BOD and COD concentration by < 10%, however a larger fraction of residual COD was non biodegradable after ozonation. Biologically treated effluent was subjected to ozonation to determine whether further improvements in effluent quality could be achieved. A reduction in COD and TL concentration was observed during ozonation, however no further improvement in toxicity was observed. Ozonation increased BOD by 38%, due to conversion of COD to BOD.

Methods for mitigation of bio-oil extract toxicity

Levoglucosan (1,6-anhydro-beta-d-glucopyranose) and other anhydrosugars can be produced in significant quantities during fast pyrolysis of lignocellulosic material. Levoglucosan can be extracted and hydrolyzed to produce fermentable glucose, however co-extraction of fermentation inhibitors can reduce ethanol yields. This work was aimed at evaluating various methods for mitigating the toxicity of bio-oil aqueous extract. Among the detoxification techniques tested, it was found that overliming and solvent extraction were able to improve the fermentability of bio-oil hydrolyzates. Overliming was able to increase the yield of ethanol from bio-oil hydrolyzate by 0.19+/-0.01 (g ethanol/g glucose) at 50% volume hydrolyzate and 0.45+/-0.05 (g ethanol/g glucose) at 40% volume hydrolyzate. A number of extractants were examined and the best solvent was tri-n-octylamine with co-solvent 1-octanol. It was able to selectively (100% glucose retention) remove at least 90+/-6.8% of acetic acid, which was the targeted inhibitor in bio-oil hydrolyzate. This increased the ethanol yield by 0.24 (g ethanol/g glucose) at 40% volume of hydrolyzate. In addition, a technique called adaptive evolution of yeasts was applied, which was capable of increasing the ethanol yield by up to 39% when compared with the unadapted parental strains.

Simultaneous saccharification and extractive fermentation of cellulosic substrates.

Alcohol fermentation has traditionally been carried out in aqueous environments because of the ready solubility of reactant (sugar) and product (ethanol). However, extraction of the product ethanol into a nonmiscible phase can result in kinetic benefits due to reduced inhibition of the fermentation reactions. In this study, we report the development of a novel simultaneous saccharification and extractive fermentation (SSEF) process. Ethanol productivity was increased by up to 65% over conventional (nonextractive) fed‐batch simultaneous saccharification systems when calculated on the basis of aqueous phase volume. The amount of water required for SSEF reactions was dramatically reduced from that required for conventional SSF. In batch SSEF reactors with 2.5% aqueous phase, 50% conversion of 25% (aqueous phase concentration) Solka Floc could be achieved in 48 h using 2 FPU/g cellulase.