J \ INTERACTIONS, BETWEEN NATURAL AND SYNTHETIC ORGANIC:S. IN THE COAGULATION PROCESS. EVANGELOS DIAMADOPOULOS, Pip!. Eng., M.Eng.

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1 , d J \ INTERACTIONS, BETWEEN NATURAL AND SYNTHETIC '. ORGANIC:S. IN THE COAGULATION PROCESS " by EVANGELOS DIAMADOPOULOS, Pip!. Eng., M.Eng. A Thesis Submitted to the.school o( Graduate Studies in Partial FuIfillrli'ent of the Rs<Juirements for the p:legree Doctor of Philosophy McMaster University 1984

2 INTERACTIONS BETWEEN NATURAL AND. SYNTHETIC ORGANICS '.

3 .., DOCTOR OF PHILOSOPHY (I 984) (Chemical Engineering) McMaster University Hamilton, Ontario TITLE: Interactions between Natural and Synthetic Organics in the Coagulation '.I AUTHOR: ". Process Evangelos Di,amadopoulos Dip!. Eng (Aristotle University of Thessaloniki, Greece) M. Eng. (McMaster University).-/ j SUPERVISOR: Dr. Donald R. Woods ).~.. '. NUMBER OF PAGES: " xvi, 194., t ii

4 r, ( i)bstract The removal of fulvic acid, the. most soluble fraction of humic matter, with aluminum and polyacrylamide was investigated. Th.e expe(fmental conditions were similar to those usually encountered in -5 practice. The ph ranged from 6 to 8, the aluminum dosage from 10 M to, -3 ~. 0.5 x 10 M, and the polymer concentration from a to I mg/l. The fulvic acid concentration was constant at 10 mg/l. The removal of fulvic acid with aluminum was found to depend on J the particle size of the aluminum-fulvic acid flocs. This was demonstrated by both the increased removals when filters with a pore size of 0.10 I'm were used (as opposed to filters with a pore size of 0.45 I'm) and the beneficial effect of the presence of nonionic polyacrylamide. The nonionic polymer promoted both the removal after settling and the ~ removal after filtration. The'latter was attributed to the flocculation of m~cro-c:olloidalparticles which in the 'absence of the polymer passerl through the pores of the fijer... Based on a three-level factorial experimental:design an empirical statistical model of the removal of fulvic acid was developed. The model was based on the consideration,at, for a narrow operating region, the response surface may be approximated with a quadratic mathematical. expression. By applying this technique th~ effect of the ph, aluminum ~.. : dosage and polymer dosage were quantitatively modelled. A polymer '" dosage of 0.1 mg/l was found to be optimal because it gave the minimum.. cost of chemicals, for the desired high degree of removal. iii

5 Fina~ly, the most s ignificant factors that affected t~e removal of,. fulvie acid with aluminum, in addition to the ph, the aluminum dosare and the polymer dosage, were the calcium present in the water and the interaction of calcium with the ph. The effect of calcium was larger at "ph g than at ph 7. The effect of the polymer properties was not "as large as the effect of the calcium, with.the effect of the polymer mol~r mass " ~ being more important th~he e.ffect of the degree of hydrolysis ~f the polyacrylamide.. - J 0 ) iv..

6 ALKNOWLEDGEMENTS Many people have shared the high and low points with me durink the last several years. The list ofall those who, in on~ way or another, contributed in the comflletion of this I'(ork is far too)ong to acknowledge here. Es"ecially, t~en, I would like to express my appreciation to the following: /. The Department of Chemical Engineering for the financial. assistance. through.out the course of my studies. My supervisor, Dr. Donald R. Woods, for his caring support, discussions. \.." Roberto Narbaitz, for being a good friend and a model listener to.. the problems of my research.'. Audrey Mckay, for the. careful and patient typing.of this thesis. Last, bu't' not 1.k'St, I thank my wife Anne, for helping me to keep. life, love and labour in some perspective.."'4 v

7 .. l,.! TABLE OF CONTENTS. Chapter.. Page. Introduction 2 Literature. Review and Objectives 2.1 Humic Substance;; \ Classification Chemical Characterization 7," P~ysical Characterization Interactions with Metal Ions 12 17,.t Organics Removal By.Coagulation ~ Aluminum Coagulation. of Humic SUbstanc~ Polymer ~OagUlation'~..., 2.3 of Hunic SUbstance,; \ Questions posed by t~e literature revie~ Experimental My,terials e.~ I F lvic.acid 3. ' luminum Coagulants.1.3 Polymers.. Coagulation Studies' ~ Jar Test )2 ph Control Filtration vi '" 56

8 Chapter J 3.3 Analytical Methods Fulvic Acid ph Measurements Turbidity Mea,surements, Electron Microscopy., ~ 3.4 Statistical Treatment Variables Model DeveloJ<menr 4. The Effect of Filter Pore Size on the Evaluation of Aluminum Coagulants to Remove Fulvic Acid from Water 4. I.Results and Discussion 4.2 Conclusions 5 Fulvi~ Acid Removal by Aluminum S~lts in the Absence and Presense of Nonionic Polyacrylamide 5.1 Results and Discllssion. ~. 5.2 Conclusions. " ' 6 ModelJing the Removal of Fulvic Acid with Aluminum,~ 6.1 Results and Discussion 6.2 Conclusions 7 Fulvic Acid Removal with Aluminum and Polymer: Modelling and Optimization, 7.1 Results and' Discussion 7..2 Conclusi,ons vii t

9 Chapter.' Page 8 An Investigation of the Factors Affecting. the Removal of Fulvic Acid by' Aluminum and Polymer~ ~ 8.1 Results and Discussion 8.2 Conclusions 9 Conclusions and Recommendations /' 9.1 Conclusions 9.2 Recommendations, References., Appendices Al Hydrolysis of Polyacrylamide A2 Experimental Data A2.1 A2.2 Filtration Study. \ Fulvic Add Remaining in Solution, after Tre.atment with Aluminum A2.3 'Fulyic Acid Remaining in Solution,, after Treatment with Aluminum., and Polymer A2.4 Results' of ttte Fractional Factorial Experimental Design , A3 Calib~a.!ron of the spectrophotometer at 254 nm ~4~. p~ measurements AS Error Analysis 192 "I ' viii

10 ix \

11 FIGURE PAGE 4.2 Filtrate absorbance of a fulvic acid solution Absorbance of the solution = Filtrate absorbance ot" the aluminum-treated fulvic II' acid solution Filtrate absorbance of the aluminum-treated Iulvic ~ ~\.' acid solution Filtrate absorbance of the aluminum-treated fulvic "''d "''''00'. ~" 4.6 Filt.rate ab~orbance of the aluminum-treat:d fulvic' ~? ) acid solution Filtrate absorbance of the aluminum-treated. fulvic acid solution Efficiency of aluminum coa~ulants to remove fulvic / acid from water Electoron micrograph of aluminum-fulvic acid particles Fulvic acid remaining in soiution after the addition of aluminum chloride ~ 5.2 Fulvic acid remaining in" solution after the addition of 86 aluminum sulfate (alum) Electron micrographs of aluminum-fulvic acid particles Turbidity of the allfminum-treated fulvic acid solution.~ before settling Fulvic acid remaining in solution after filtration through, 0.10 umfilters as a function of the turbidity of the -" unsettled suspension 95 x

12 FIGURE 5.6 '-0<' ~ ~......, ;~ IC acid remaining inso1>jtion after 20min of PAGE se tling 98 ~ Ivic acid remaining in solution after 20min of settlingk Fulvic ac remaii;ling in solution.. \ afte.r 20.rnin of settling "- Aluminum concent,r'iltion = 0.71 x10 ~ Fulvic acid remaining in solution after filtration \ Aluminum concentration = 0.5x 10 M Fulvicacid remaining in solution after filtrition Aluminum concentration = x 10 M Fulvic acid remaining in solution after filtration ~ Aluminum concentration = 0.71 x 10 M. filter pore size = 0.45 urn Fulvic acid remaining in solution after filtration Filter pore size = 0.10 um Aluminum concentration = 0.71 x 10 M Fulvic acid remaining in solution after filtration Aluminum,concentration.= 0.71 x 10 M Fulvic.acid remaining in solution after filtration Aluminum concentration'=, 10 M R',;moval after filtration' for,he AIel.,study without.".'. -, transformation'ofthe 'observations 115, 6.2 Removal after 'filtration (or the Alum study wi!hout transformationof' tpe observations, <. ' 116.,: -: Maximi~ed Likelihoo'dFunction an.d Residual Sum' of' Squares as functions of the trahsformation parameter ' xi

13 FIGURE PAGE 6.4 Model predictions for the removal after filtration for the AI C I study Model prediction for the removal after filtration for the Alum study Removal after filtration for the AICI study of the 6.7 reo/jced region Re~val after filtration for the Alum study of the reduced re~ion Removal after 20 min of settling for the AICI study 129 I 6~ Removal after 20 min of settling for the Alum study Removal predictions. for Region I - Remov..lpr~dictions for RegIon 11 ph = Combined cost of ~emicals for different degrees" of removal for Region I ph = Combined cost of chemicals,from different degrees of. removal for Region I ph = 8.0 '\ Plot of'the residuals.on probability paper "- _. Removal pr,edictions for Regio~ 11 ph = 7.0 " - Removal prediction.s for \egion 11 ph =, Combined cost of chemlc;js'for different degrees of removal for Region II. ph = ', xii

14 FIGURE PAGE 7.9 Combined cost of chemicals for different degrees of removal for Region II' 8.1 A.I ph = 8.0 Normal plot of effects Apparatus for the hydrolysis of the p~lymer o ".,",. xiii I

15 , LIST OF TABLES.- TABLE Elemental analysis of soil humus Elemental analysis of aquatic humus 9 PAGE Oxygen-containing functional groups in humic substances (meq/g) Summary of the experimental conditions of published articles regarding the removal of humic substances during coagulation Optimum ph range as reported in the literature Summary of the experimental conditions of published research regarding the removal of the humic substances with polymers alone or in combination with aluminum Independent variables of the fractional factorial -> experim~tal design Parameter estimates for the exponential decay model Parameter estimation for the modelling of the removal after'filtration without transformation of" the ~ observations ANOYA Table for the!\1c I ca'ie ANOY A Table for the Alum case Parameter estimation in the modelling of the reduced expertimental region without transformation of the observations 127 <, ) xiv

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