The rapid accumulation of municipal solid waste is a significant environmental concern in our rapidly growing world. Due to its low cost, high energy recovery and limited environmental impact anaerobic digestion (AD) is a promising solution for stabilizing the organic fraction of municipal solid waste (OFMSW). Hydrolysis is often the rate-limiting step during AD of wastes with high solid content; this step can be accelerated by pretreatment of waste prior to AD. This thesis presents the results of alkaline pretreatment of OFMSW using NaOH and KOH. Four different pH levels 10, 11, 12 and 13 at two temperatures 23±1°C and 80±1°C were examined to study the effects of the pretreatment on (i) enhancing the solubility of the organic fraction of the waste, and (ii) enhancing the AD process and the biogas production. The effects on solubility were investigated by measuring changes in the soluble COD (SCOD) concentrations of pretreated wastes and the enhanced AD was investigated by measuring volatile solids (VS) destruction, total COD (TCOD) and SCOD removal in addition to biogas and methane production using biochemical methane potential (BMP) assay and semi-continuous laboratory reactor experiments. Pretreatment at pH 13 at 80±1°C demonstrated the maximum solubility for both NaOH and KOH pretreated samples; however the BMP analysis demonstrated that pretreatment at pH 12 at 23±1°C showed the greatest biogas yield relative to the removed VS for both chemicals. Thus pretreatment at pH 12 at 23±1°C using NaOH and KOH were examined using semi-continuous reactors at three different HRTs: 10, 15 and 20 days. Pretreatment demonstrated a significant improvement in the AD performance at SRTs of 10 and 15 days.

Thesis (M.S.)--Virginia Polytechnic Institute, 1961. / Vita. Abstract. Includes bibliographical references (leaves 83-89). Also available via the Internet.

Thesis (PH. D.)--University of Michigan, 1926. / "By A.L. Ferguson and A.W. Schluchter." Also issued in print.

Thesis (PH. D.)--University of Michigan, 1926. / "By A.L. Ferguson and A.W. Schluchter." eContent provider-neutral record in process. Description based on print version record.

The rapid accumulation of municipal solid waste is a significant environmental concern in our rapidly growing world. Due to its low cost, high energy recovery and limited environmental impact anaerobic digestion (AD) is a promising solution for stabilizing the organic fraction of municipal solid waste (OFMSW). Hydrolysis is often the rate-limiting step during AD of wastes with high solid content; this step can be accelerated by pretreatment of waste prior to AD. This thesis presents the results of alkaline pretreatment of OFMSW using NaOH and KOH. Four different pH levels 10, 11, 12 and 13 at two temperatures 23±1°C and 80±1°C were examined to study the effects of the pretreatment on (i) enhancing the solubility of the organic fraction of the waste, and (ii) enhancing the AD process and the biogas production. The effects on solubility were investigated by measuring changes in the soluble COD (SCOD) concentrations of pretreated wastes and the enhanced AD was investigated by measuring volatile solids (VS) destruction, total COD (TCOD) and SCOD removal in addition to biogas and methane production using biochemical methane potential (BMP) assay and semi-continuous laboratory reactor experiments. Pretreatment at pH 13 at 80±1°C demonstrated the maximum solubility for both NaOH and KOH pretreated samples; however the BMP analysis demonstrated that pretreatment at pH 12 at 23±1°C showed the greatest biogas yield relative to the removed VS for both chemicals. Thus pretreatment at pH 12 at 23±1°C using NaOH and KOH were examined using semi-continuous reactors at three different HRTs: 10, 15 and 20 days. Pretreatment demonstrated a significant improvement in the AD performance at SRTs of 10 and 15 days.

The work described in this dissertation focused on chemistry related to the use of aqueous sodium hydroxide as a treatment in the processing of wheat straw. A major emphasis was the comprehensive evaluation of straw component partitioning due to sodium hydroxide (NaOH) processing. This was evaluated over a range of NaOH concentrations (0­‐10%, w/v), all at 50°C, 5 h treatment period, and 3% solid loading. Solid and liquid phases resulting from NaOH treatments were evaluated. Total solids recovered in the NaOH­‐treated solid phase ranged from 47.4­‐88.0%. Overall carbohydrate recovery in the combined solid and liquid phases was negatively correlated with the alkali concentration of the treatment liquor. The glucan content of the NaOH‐treated solid phase ranged from 37.2­‐67.4%. Glucan recovery in the solid phase was relatively high in all cases, the minimum value being ~98%. Increasing amounts of xylan partitioned into the liquid phase as sodium hydroxide concentrations increased – it ranged from 31­‐83% of the xylan being recovered in the soluble phase. Carbohydrate analyses of the pretreated liquor revealed that the majority of carbohydrate loss from the solid fraction could be recovered in the liquid phase in form of oligomers and monomers due to alkaline degradation. The interconversion of glucose, fructose, and mannose under the alkaline condition played an important role in the presence of those sugars. Increase in NaOH concentration contributed to increase in amount of cellulose­‐derived and hemicellulose‐derived oligomers in the pretreated liquor. All oligomers except fructooligomers in NaOH pretreated liquor were higher than those found in water extraction at 50°C, 5 h. Total carbohydrate recovery from the solid and liquid fractions was as high as 99% for glucose and glucan in 5% NaOH treatment and 80‐95% for xylose and xylan in 1-­10% NaOH treatment. The presence of NaOH as extraction reagent dramatically induced lignin and ash removal from the pretreated solid with up to 63% acid insoluble lignin (AIL) and 87% ash extraction. Solid fractions resulting from NaOH pretreatments (up to 5% NaOH) were tested for their susceptibility to enzymatic saccharification using cellulase and cellulase/xylanase enzyme preparations. The cellulase/xylanase enzyme preparation was found to be more effective at cellulose saccharification than the cellulase enzyme preparation alone. Maximum glucose yield, which corresponded to the 5% NaOH treatment, was 82% over the standard 48 h saccharification period. Extended saccharifications times to 120 h showed that the conversion yield approached 90%. Sequential treatments of the straw (i.e. initial alkali treatment – first enzyme saccharification – second alkali treatment ‐ second enzyme treatment) revealed the NaOH treatment has the potential to render essentially all (~99%) of the straw glucan susceptible to enzyme saccharification. This suggests that the layered molecular arrangement of cellulose, hemicellulose, and lignin in the cell wall impacts biomass recalcitrance and glucan conversion yield. The other major focus of this dissertation research was the characterization of alkali neutralization, which occurs during the aqueous alkali processing of wheat straw. The approach taken was to evaluate the time course of alkali uptake and to determine the underlying nature of alkali uptake. The knowledge generated from this study is useful for understanding the nature of the alkali‐induced chemistry that is at the heart of alkali processing of agricultural byproducts, foods, and forest products. Alkali uptake/acid generation measurements were monitored for wheat straw suspensions at pH 11 and 30°C. The first phase of alkali uptake corresponded to the 30‐second time period over which the pH of the wheat straw suspension was adjusted from its original pH (~6.6) to pH 11. Alkali neutralization during this period was attributed to the instantaneous ionization of solvent accessible Bronstad acids. Following pH adjustment to 11.0, the time course of subsequent alkali uptake was recorded. The time course appeared biphasic. The early phase, which corresponded to the relatively rapid uptake of alkali, was evident during the first 24 hours. The later phase, which was characterized by the relatively slow uptake of alkali, was maintained for the length of the study (up to 96 hours). Alkali uptake during the early phase of the time course appears to be determined by the rate of hydrolysis of readily accessible esters – primarily acetic acid esters (acetyl groups). Alkali uptake during the later phase of the time course appears to be impacted by the rate of alkali penetration into the straw and the rate of production of alkali‐induced acid degradation products. The uptake of alkali in the pH adjustment phase was ~ 120 μEq per gram wheat straw, the uptake of alkali in the early phase of time course was ~ 1,064 μEq per gram wheat straw, and the rate of uptake in the later phase of the time course 6.10 μEq per gram wheat straw per hour. Amount of acetyl groups, ferulic acid, and p-­coumaric acid generated during 96-­h pretreatment revealed that they are major esters being hydrolyzed under the studied condition. Combined, these ester-­derived acids contributed up to ~ 28% of overall alkali uptake. In addition, alkaline degradation products quantified in this study showed additional ~ 28% contribution to the overall alkali uptake. / Graduation date: 2012

Processed turkey rolls were prepared with 1 or 3% whey protein concentrates WPC-50 (pH=5. 8 0) , WPC-60 (pH=4. 53) and WPC-75 (pH=6.85) containing 50, 60 and 75% protein along with controls (phosphate and no phosphate) . Control rolls made with 0.5% phosphate had the highest bind strength, and sensory evaluation scores. Only WPC-75 (1%) was acceptable as a binding agent and flavor enhancer. WPC-60 reduced pink discoloration of rolls, but flavor, bind and cohesiveness scores were unacceptably low. WPC-50 was not an effective binding agent. In general, rolls made with 3% WPC had lower scores for intensity of turkey flavor. Bind strength and sensory characteristics were compared for restructured beef rolls formulated with 1% salt, 0.375% sodium tripolyphosphate (STPP) or 0.07% sodium hydroxide (NaOH), and 5, 10 or 20% added water. Controls also had 1% x salt, but no STPP or NaOH. Relative bind strength of rolls was STPP > NaOH > controls. Addition of 20% water reduced bind strength. Cooked yield, moisture content, beef flavor and texture of NaOH rolls were similar to STPP rolls. Bind strength and cohesiveness of NaOH rolls were lower than STPP rolls, but still acceptable. For measuring bind strength of turkey and beef rolls, a sensitive and inexpensive penetrometer was developed. It was equipped with a top-loading balance, accessories, IBM-compatible personal computer and Quick-Basic program that allowed continuously collected penetration force data. at specific time intervals. Penetrometer bind strength and taste panel cohesiveness of turkey and beef rolls were highly correlated (r=0.89 and r=0.93, respectively).

During production of different Hyaluronic acid (HA) products Galderma use a high concentration of NaOH in the crosslinking process of HA. HA’s degradation kinetics are widely unknown at higher pH’s and is interesting for the future of product development of HA. Static Light Scattering (SLS) was used to determine the weight average molecular weight (MW ) of samples with four different NaOH concentrations, four temperatures, three reaction times and one t0  sample. The results were evaluated in forms of Arrhenius-graphs for different NaOH concentrations, the activation energy (EA ) with respect to pH and the reaction rate for each temperature with respect to NaOH concentration. It was found that the degradation of HA was more strongly affected by temperature than by NaOH concentration and that the EA  did not show any significant signs of change between higher concentrations of NaOH.

Arbetet handlade om att ta reda på om det går att byta ut natriumhydroxid mot natriumkarbonat som alkalikälla på CTMP-linjen, och gjordes på uppdrag av Stora Enso Skoghalls bruk. De områdena som studerades var impregnering och blekning av CTMP (kemitermomekanisk pappersmassa) samt hantering av natriumkarbonatlösning. Natriumkarbonatens löslighet vid olika temperaturer verifierades, blekning av CTMP med natriumkarbonat och natriumhydroxid utfördes, titrering av natriumhydroxid och natriumkarbonat mot natriumbisulfitlösning och en enklare laborationsimpregnering gjordes. Även aspekten av utrustning, kostnader och eventuell utfällning av kalciumkarbonat studerades. Resultaten visade att det krävs mer natriumkarbonat för att ersätta natriumhydroxid än vad man trott och att det totalt sett blir dyrare. Det finns dock en möjlighet att andra delar av bruket kan utföra bytet av alkali och gå med större vinst än vad CTMP-linjen går med förlust. Försöken visade även på temperaturökning vid tillredning av natriumkarbonatlösningen, utfällning av kristallsoda och behov av att den befintliga utrustningen kompletteras utifrån rekommendationer från kemikalieleverantören. Tidigare studier visade på eventuella försämringar av papperskvaliteten när natriumkarbonat används vid blekning av CTMP. Trots att natriumkarbonat är ett billigare alternativ till natriumhydroxid, och att det teoretiskt sett skulle fungera bra som en utbrytare, är det mycket som man behöver ta hänsyn till vad gäller natriumkarbonat och det krävs eftertanke för att saker ska görs på rätt sätt. Utifrån resultaten kan man dra slutsatsen att det inte ser ut som en bra ide att utföra bytet. / The objective of this project was to see if it is possible to replace sodium hydroxide with sodium carbonate as an alkali source on the CTMP line, and it was done on behalf of the Stora Enso Skoghall Mill. The areas that were studied were the impregnation and bleaching of CTMP and also the handling of sodium carbonate solution. The solubility of sodium carbonate at various temperatures was confirmed, bleaching of CTMP with sodium hydroxide and sodium carbonate, titration of the sodium hydroxide and sodium carbonate against sodium bisulfite solution and a simpler laboratory impregnation was performed. Aspects of equipment, costs and the possibility of precipitation of calcium carbonate were also studied. The results indicate that more sodium carbonate is needed than one thought for the substitution to be possible, and that it also becomes more expensive. There is a possibility that other parts of the mill can perform the replacement of alkali and go with greater profit than the CTMP line goes with loss. Experiments also showed an increase in temperature when preparing the sodium carbonate solution, precipitation of natron and the need for the existing equipment to be supplemented on the basis of recommendations from the chemical supplier. Previous studies showed possible deterioration of the paper quality when bleaching CTMP with sodium carbonate. Although sodium carbonate is a cheaper alternative to sodium hydroxide, and that it would theoretically work well as a substitute, it is much that one has to take into consideration in terms of using sodium carbonate and it is necessary to think things through before usage, so that things can be done properly. Based on the results, it is shown that the swap of alkali will be suboptimal.

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