Ultrafiltration of partially degraded starch solution Contribution of fouling mechanisms to the flux decline and effect of operating parameters Doctoral Thesis by Berhanu A. Demessie Submitted to Department of Chemical Engineering Norwegian University of Science and Technology (NTNU) In partial fulfillment of the requirement for degree of Doctor Engineering (Dr. Ing.) Trondheim, 2002 URN:NBN:no-3327 Dr. Ing thesis NTNU 2002:87 By: Berhanu A. Demessie Supervisor: Professor Norvald Nesse August, 2002 ISBN 82-471-5487-0 ISSN 0809-108X URN:NBN:no-3327 Summary iii Summary Desizing wastewater is largely responsible for the chemical oxygen demand (COD) load in the textile industry wastewater. A larger portion of COD comes from degraded starch in desizing wastewater. Removing the starch from the wastewater by an ultrafiltration process may reduce the environmental problem caused by the textile factory. If the treatment is made in such a way that all starch components are removed from the wastewater, the treated water can be reused by the factory. If the starch in the concentrate is stable, it can also be reused as a sizing agent. This will give the factory an economic advantage. In this thesis we have studied the fouling mechanisms involved in the ultrafiltration of solution with partially degraded starch in order to find the treatibility of such solutions. The work has mainly been directed to uncover how the different fouling mechanisms depend on the operating parameters, and to find the performance of selected membranes. In addition, different models were evaluated for their validity in predicting the performance of the membranes and the data was fitted to the model that give the best prediction and are physically more meaningful. In addition, the starch solution was concentrated, and the flux, concentration, retention and rejection profiles as a function of concentrating time were investigated. For the study, we used a partially degraded starch solution as a model solution. The solution was prepared in the laboratory by enzymatic degradation of potato starch to different levels. In order to evaluate the reproducibility of the degraded starch, three replicates were prepared. The reproducibility was determined by comparing the molar mass distribution from HPLSEC analysis and the concentration of reducing sugar from a DNS test for the replicates. The analyses show very good reproducibility. Three starch model solutions with three different degradation levels were chosen for our ultrafiltration experiments to investigate the effect of average molar mass of the starch. For the ultrafiltration of the solution ES625 (from PCI) and MPT-U20 (from KOCH) membranes were used. Both membranes were used in the URN:NBN:no-3327 iv Summary investigation of the contribution of different fouling mechanisms to the flux decline during ultrafiltration of the solution. In the evaluation of the performance of ultrafiltration of the starch solution, however, only the ES625 membrane was used. According to the manufacturers, both membranes have nearly equal pure water flux and MWCO. But in our test, we observed a higher and different pure water flux for each type of membrane. The ES625 had a lower flux (higher retention) than the MPT- U20 membrane. In the ultrafiltration of partially degraded starch solution the permeate flux declines very fast and, for a low feed concentration, it reaches a steady state in a very short time. The steady state time was observed to increase with concentration, molar mass and transmembrane pressure drop, and to decrease with cross flow velocity. All the three fouling mechanisms (concentration polarization, adsorption and deposition) were responsible for the flux decline. The major observed contributors are, however, adsorption and deposition. Adsorption is largely responsible at low-pressure operation while the deposition fouling effect is dominant at higher pressures, near or beyond the limiting flux. For the ES625 membrane, the contribution of adsorptive fouling increases with concentration and decreases with molar mass of the starch, temperature and pH at a given transmembrane pressure and cross flow velocity. The effect of the operating parameters on the depositional fouling is in line with literature. It increases with pressure, concentration, molar mass and temperature, and decreases with cross flow velocity. Its dependence on pressure can be expressed by a power function with exponent larger than 1.0. This seems to due to an increase in thickness and compaction of the starch gel/deposit at the membrane surface as the transmembrane pressure drop is increased. The contribution of the concentration polarization is also dependent on concentration, cross flow velocity and pressure. Its relative contribution increases with concentration while it decreases with an increase in cross flow velocity. In the turbulent flow regime the relation between the resistance contributed by concentration polarization increases almost linearly with transmembrane pressure drop. In the laminar flow regime, however, the relative contribution of the resistance due to concentration polarization increases for the lower range of pressure and decreases for the higher range of pressure. Its relative contribution also increases with temperature and decreases with increasing molar mass. But the overall fouling resistance in the ultrafiltration of the starch solution increases with feed concentration, molar mass of the starch and transmembrane pressure drop and decreases with cross flow velocity and temperature. URN:NBN:no-3327 Summary v The trend of the flux loss due to all fouling mechanisms for MPT-U20 membrane is similar to ES625 membrane except for adsorption and concentration polarization with changes in concentration and molar mass. The difference could be a result of the difference in morphological properties between the two membranes and the experimental procedures used in determining flux data that used for calculating the contributions. From the pure water flux and the retention data, the ES625 membrane seemed to have a smaller pore size than the MPT-U20 membrane. Among the ultrafiltration models, the resistances-in-series model was chosen for its provision to include all the fouling mechanisms into the model. When our permeate flux data was fitted to the model, it gives a good fit. However, the model fails to give realistic estimates of the contribution of the individual fouling mechanisms. In order to improve this problem, the model was modified by introducing osmotic pressure across the membrane in such a way that the effect of concentration polarization is accounted for. This modified model is more physically meaningful and gives a realistic estimate of the contribution the reversible and irreversible fraction of the overall resistance. In concentrating mode operation, the permeate was continuously withdrawn and hence, the concentration of starch in the feed tank was increased. At an early stage of ultrafiltration, the permeate flux appeared to increase slightly, which seems, a result a shear thinning of the starch solution when the solution was pumped through the system. For the rest of the operation, the flux was decreasing, the retention was increasing and the rejection of the membrane was shifted to a lower molar mass as the solution in the feed tank got more concentrated as expected. The shift of rejection to the lower molar mass region is due to the fouling layer that reduces the accessibility of the pores of the membrane. Generally, the flux we obtained in ultrafiltration of a partially degraded starch solution with the ES625 tubular membrane is equal or better than the reported values from an existing ultrafiltration plant that has been used in the textile industry to recover a synthetic sizing agent (PVA) from the desizing wastewater. The retention is, however, rather low. Two or more stages of treatment are needed to get all starch components removed from the wastewater and make the treated water reusable (recycled). URN:NBN:no-3327 URN:NBN:no-3327 vii Preface I started my study for the Doctor Engineering (Dr. Ing.) degree at the Department of Chemical Engineering, the Norwegian University of Science and Technology (NTNU) in February 1997 under the supervision of Professor Norvald Nesse. The study was planned to for three and half years. The research has been aimed to be purely experimental, which involves membrane pilot plant. At first, I thought experimental research would be simple. Now, I do have a true picture of it. It is expensive and time consuming, tedious and boring, and has a lot of disappointment… to get it run. In the end, however, I could see that the experience is invaluable. I would say, for beginner like me, the experience itself is much more regarding than the results. If I have a chance again, I would be glad to be in the laboratory but not as a student. Rush is the enemy for experimental work. Since I secured properly working pilot plant it is one and half years ago. Now, it is June 2002. Our initial plan was to work on wastewater from Ethiopian textile factories Due to lack financial support for the project we changed our mind. We therefore decided to explore the behavior of the most pollutant ingredient, starch, in desizing wastewater (from one of the unit processes in textile industry) during ultrafiltration of the solutions. The study was conducted on a model solution containing stable partially degraded starch. The concentration of the starch solution used in the experiment was relatively low due to the limitation of the equipment used for the preparation of model starch solution. We believe that the results obtained from the experimental study introduce new information on the contribution of the fouling mechanisms involved and performance of ultrafiltration of partially degraded starch. It may also be used as springboard for further study on partially degraded starch solution and for the treatment of wastewater rich in partially degraded starch, in particular from textile industries. In this thesis, the results are presented as a monograph. The results have not been published yet.