Chemical Engineering Journal 172 (2011) 771782

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Chemical Engineering Journal

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Optimization of coagulationocculation process for wastewater derived from sauce manufacturing using factorial design of experiments
M.A. Martn , I. Gonzlez, M. Berrios, J.A. Siles, A. Martn
Departamento de Qumica Inorgnica e Ingeniera Qumica, Facultad de Ciencias, Universidad de Crdoba, Campus Universitario de Rabanales, Ctra. Madrid-Cdiz, km 396, Edicio C-3, planta baja, CP 14071 Crdoba, Spain

a r t i c l e

i n f o

a b s t r a c t
A coagulationocculation process was used to pre-treat wastewater derived from sauce manufacturing prior to a subsequent biological treatment. A 52 full factorial experimental design and response surface methodology were employed to evaluate and optimize the coagulant and occulant dosages and to achieve a compromise between efciency, operational costs and the effects of a possible subsequent biological treatment. The inuence of pH was also evaluated to determine the most suitable pH condition (alkaline, neutral or acidic). Although the results were quite similar under all pH conditions, alkaline pH was selected as it permitted ease of operation and lower operational costs due to the elimination of pH adjustment stages. The best regression coefcients (R2 ) were obtained for chemical oxygen demand (COD), turbidity and total soluble organic carbon (TOCsoluble ) at alkaline pH, reaching values of 0.9136, 0.8397 and 0.8512, respectively. At alkaline pH, the most signicant factor in the analysis of variance (ANOVA) study was coagulant dosage for COD and turbidity removals. However, coagulant and occulant dosages were both signicant factors. Multiple response optimization ts the optimum values of the factors and the responses as 0.4 mL/L of coagulant, 7.0 mL/L of occulant and 82, 72 and 13% of COD, turbidity and TOCsoluble removal at alkaline pH, respectively. 2011 Elsevier B.V. All rights reserved.

Article history: Received 4 April 2011 Received in revised form 20 June 2011 Accepted 21 June 2011 Keywords: Optimization Sauce manufacturing Coagulationocculation Turbidity Organic matter removal

1. Introduction Petroleum rening, metal manufacturing and machining involve large amounts of lipids in the food industry. These lipids, which are mainly grease, fats or oils, are passed on to the processed water and consequently to wastewater [1,2], causing adverse environmental effects. Given the importance of the sauce manufacturing industry and that this market is expected to grow signicantly by the year 2015 [3], the oily wastewaters generated by the industry must be treated before spillage in order to meet current quality standards related to environmental protection. According to Zheng et al. [4], these wastewaters contain a large amount of chemical oxygen demand (COD), suspended solids (residues of broken colloid and indissoluble particles), soluble organic compounds, microorganisms and inorganic salts. Due to their oily composition, these wastewaters can hinder the diffusion of oxygen required for many forms of aquatic life or block water drainage lines [5]. Several physical, chemical and biological treatment methods have been proposed to deal with the oily wastewater problem. These methods include otation, membrane pro-

Corresponding author. Tel.: +34 957 212273; fax: +34 957 218625. E-mail address: iq2masam@uco.es (M.A. Martn). 1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cej.2011.06.060

cesses (microltration and ultraltration), chemical destabilization (conventional coagulation), electrochemical destabilization (electrocoagulation) and activated sludge [6,7]. It is common to combine physicalchemical processes for pre-treatment and biological treatment. The coagulationocculation process is used worldwide in wastewater treatment before spillage of the treated water as it is efcient and simple to operate. Many coagulants are widely used in conventional wastewater treatment processes [8,9]. These coagulants can be inorganic (e.g. aluminum sulfate and polyaluminum chloride), synthetic organic polymers (e.g. polyacrylamide derivatives) or naturally occurring occulants (e.g. microbial occulants). These coagulants and occulants are used for different purposes depending on their chemical characteristics [9,10]. Specically, in the coagulationocculation of an emulsion, dispersed oil droplets are destabilized by the neutralization of charges followed by the removal of the separated oil as ocs. Ferric and aluminum salts are the most widely used coagulantocculant agents for demulsication. However, other reactants have proven to be very efcient in wastewater treatment processes [9,1115]. The addition of the reactants is carried out sequentially for neutralization of charges by coagulation and subsequent agglomeration of particles by occulation. Flotation and settling are the most widely used methods for the removal of the ocs. Many factors can inuence the efciency of the process such as the type and dosage of coagulant and occu-

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lant, pH, mixing speed and time, temperature or retention time [16]. The optimization of these factors may signicantly improve process efciency and ensure the efciency of the subsequent biological treatment. A factorial experimental design and response surface methodology can be summarized as a collection of statistical tools and techniques for exploring an approximate functional relationship between a response variable and a set of factors [13,17]. Basically, the main variations in the optimization process involve performing the statistically designed experiments, estimating the coefcient of the mathematical model, predicting the response and checking the adequacy of the model [14]. The classical method to optimize signicant variables in the coagulationocculation process (one factor at a time) is an extremely time-consuming, expensive, and complicated process for a multivariable system. To overcome this difculty, statistical experimental design techniques using the response surface methodology are often applied [18]. Several authors have used response surface methodology and optimization to improve the coagulationocculation processes of wastewater of different origins [9,11,13,14,16,18]. These authors agree that the type and dosage of coagulant and occulant reactants are decisive to the success of the coagulationocculation process. The aim of this study is to evaluate and optimize variables of the coagulationocculation process in wastewater from sauce manufacturing from the standpoint of a compromise between efciency and operational costs. This work is novel as it statistically analyzes experimental data in order to improve a real industrial process, which is usually carried out under optimal conditions. 2. Materials and methods 2.1. Materials The wastewater used in this study was derived from the manufacturing process carried out by the Musa S.A. Company (Cordoba, Spain), which chiey produces mayonnaise in addition to garlic mayonnaise, ketchup, mustard and other special sauces such as roquefort dressing or tartar sauce. The company manufactures around 35,000 metric tons of sauce per year, accounting for approximately 15% of total Spanish sauce production (Annual Company Report), and generates around 15,00030,000 m3 wastewater/year at a ow rate of 34 m3 /h. Due to the variability in wastewater composition, three 100-L samples were taken from the homogenization tank in order to optimize the experimental representativity of the physicalchemical treatment carried out at laboratory scale. The mean value and standard deviation of the most relevant variables are shown in Table 1. As can be seen, organic matter content is considerably high (around 18 g COD total/L) due to the presence of fat, sugars and acetic acid in the manufactured

products. Moreover, given that alkaline solutions are used for washing the production lines, the wastewater pH is nearly alkaline (7.9). Aluminum polychloride 18 wt% was used as a coagulant agent (pH: 3.9 0.2, boiling point: 110 10 C, density (20 C): 1.36 0.02 g/mL. Brenntag Quimica, S.A.) and Actipol A-401 (1 g/L) (anionic polyacrylamide-based occulant, active at pH 49. Brenntag Qumica S.A.) as a occulant reactant. 2.2. Equipment The experimental set-up used for the coagulationocculation experiments at laboratory scale consisted of a Jar-test device (Magna Equipments S.L., F6 Model) in which six stirring blades were connected to a motor that operated under adjustable conditions. The system permitted the experiments to be performed with ease and the different variables affecting the removal of suspended fat and organic matter to be interpreted such as pH, stirring time and speed, retention time or reactant concentrations. 2.3. Experimental procedure As pH is one of the most restrictive parameters in the coagulation step and affects the hydrolysis equilibrium produced by the presence of the coagulant agent [19] (Company, 2000), the experiments were carried out at pH 7.9 as this was the natural pH value determined in the original wastewater, pH 7.0 following the specications of the coagulant manufacturer, and pH 5.3 in order to evaluate the effectiveness of the pre-treatment under acidic conditions. A wider pH range was not evaluated in order to prevent problems in the subsequent biological treatment and to reduce the costs of pre-treatment. The pH conditions were modied by adding diluted sulfuric acid. Coagulant dosages (aluminum polychloride 18 wt%) varied in the range of 0.21.0 mL/L (equivalent to 0.010.05 mg Al3+ /L), while occulant dosages (Actipol A-401 1 g/L) ranged from 2 to 10 mL/L. The technical limitations for the reactants dosage at full-scale have conditioned the selection of its lowest level. Moreover, the highest level coincides with the concentration that was being used by the company, which prevented achieving satisfactory efciency. During the initial design of the reactants dosage, lower dosages were chosen in order to optimize the treatment, while minimizing its cost. As these concentrations improved treatment efciency, it was not necessary to evaluate higher dosages. Twenty-ve experiments were carried out under each pH condition. After the addition of coagulant, the wastewater was stirred at 160180 rpm for 2 min. The occulant was then added and the medium stirred at 4050 rpm for 1 min. Samples were taken from the supernatant and analyzed after leaving the medium to stand for 20 min. Total chemical oxygen demand (COD), turbidity and soluble total organic carbon (TOCsoluble ) were determined in the samples taken across the coagulationocculation treatment. All the analyses were performed in accordance with the Standard Methods of the APHA [20]. 2.4. Statistical analysis

Table 1 Wastewater characterization. Variable pH Conductivity (mS/cm) Turbidity (NTU) CODtotal (mg O2 /L) CODsoluble (mg O2 /L) Fat (mg/L) TCsoluble (mg/L) TOCsoluble (mg/L) ICsoluble (mg/L) TSS (mg/L) VSS (mg/L) MSS (mg/L) Value 7.87 3.07 3260 18,160 3555 6395 1435 1465 30 7860 7755 105 0.90 0.09 270 1095 52 310 110 115 3 100 100 20

A factorial experimental design was used to determine the inuence of the reactants dosages on the efciency of the coagulationocculation process. A full 52 factorial experimental design (two factors each at ve levels) was used in the study. Three sets of experiments were carried out under alkaline, neutral or acidic pH conditions. Twenty-ve experiments were carried out under each pH condition studied. COD, turbidity and TOCsoluble removal responses were selected to evaluate wastewater treatment efciency. The factors chosen were coagulant (aluminum polychloride) and occulant (Actipol A-401) dosages. These fac-

Table 2 Experimental matrix (random) and selected responses. Alkaline pH (7.9) Coagulant dosage (A) 2 1 1 2 1 1 2 0 2 1 0 2 2 0 2 2 1 0 1 0 1 2 1 2 1 Flocculant dosage (B) 0 1 0 0 0 1 1 2 2 2 1 2 2 1 2 1 1 2 2 0 2 1 1 1 2 COD removal Turbidity (%) removal (%) 6.3 50.3 78.6 68.4 47.7 37.5 29.1 68.8 62.7 53.1 66.7 25.6 68.2 58.0 25.6 70.0 75.7 50.0 59.7 70.2 69.7 70.3 63.4 11.6 42.9 0.0 6.9 91.3 71.8 29.0 14.3 13.0 64.9 56.4 3.5 61.5 17.9 60.9 93.6 3.4 67.2 91.4 90.6 73.9 91.1 72.6 63.2 75.2 12.7 1.1 TOCsoluble removal (%) 9.0 10.5 12.9 10.8 11.1 8.7 9.8 13.6 9.4 9.8 11.5 0.5 12.2 10.5 11.1 12.5 10.1 7.3 5.2 11.8 11.5 10.5 13.2 4.7 5.9 Neutral pH (7.0) Coagulant dosage (A) 1 2 1 2 2 0 1 2 1 1 2 1 2 0 0 2 0 2 1 2 0 1 2 1 1 Flocculant dosage (B) 2 1 0 2 2 2 1 0 2 1 2 1 0 1 1 1 2 1 1 1 0 2 2 0 2 COD removal Turbidity (%) removal (%) 79.3 78.5 76.8 79.9 70.0 57.7 82.7 78.1 55.4 75.9 77.1 83.7 78.7 71.9 76.3 77.6 80.7 79.7 77.6 82.6 76.1 83.7 81.1 79.7 81.3 94.3 93.3 91.6 93.9 84.0 76.5 95.1 91.4 69.9 92.0 88.6 96.6 92.3 78.4 88.3 93.1 90.9 96.2 91.7 94.6 89.0 90.9 96.3 93.4 93.4 TOCsoluble removal (%) 14.3 9.8 15.3 14.2 17.4 10.1 21.0 9.8 7.3 13.2 8.7 20.1 19.2 11.8 14.6 18.8 15.3 19.9 15.0 10.5 11.8 15.9 12.5 18.4 19.5 Acidic pH (5.3) Coagulant dosage (A) 1 2 1 2 0 2 1 1 1 1 1 0 0 2 0 2 2 1 0 2 2 2 1 1 2 Flocculant dosage (B) 2 2 1 1 0 1 2 0 2 2 1 1 2 0 2 1 0 0 1 1 2 2 1 1 2 COD removal Turbidity (%) removal (%) 72.7 77.8 70.2 85.5 71.7 76.7 77.1 69.7 72.7 66.6 69.7 69.9 71.9 69.6 80.8 73.6 81.2 74.7 73.0 81.7 73.8 82.7 73.9 74.6 85.3 82.7 90.6 83.3 85.9 84.4 85.3 85.7 85.4 78.5 83.9 86.2 90.6 83.1 89.1 91.3 86.3 87.6 91.3 85.4 89.4 81.6 87.3 87.6 90.3 90.3 TOCsoluble removal (%) 15.7 17.8 17.4 16.7 15.0 15.7 15.7 16.4 15.7 15.3 15.7 17.4 22.0 17.1 17.4 17.1 16.0 18.1 15.7 14.6 17.8 15.0 13.6 15.7 16.0 M.A. Martn et al. / Chemical Engineering Journal 172 (2011) 771782 773

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Table 3 ANOVA for COD removal response surface models under three pH conditions. Source Alkaline pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2 Neutral pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2 Acidic pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2
a b

Sum of squaresb 9027.16 7176.23 269.23 1559.98 14.78 7.25 853.20 9880.36 0.9136 486.72 10.66 326.78 60.34 12.81 76.13 667.97 1154.70 0.4215 508.47 260.11 19.88 202.67 3.38 22.43 143.82 652.29 0.7795

Degree of freedomc 5 1 1 1 1 1 19 24

Mean squared 1805.43 7176.23 269.23 1559.98 14.78 7.25 44.91

F-valuee 40.21 159.81 6.00 34.74 0.32 0.16

p-Valuef 0.0000a 0.0000a 0.0242a 0.0000a 0.5768 0.6924

5 1 1 1 1 1 19 24

97.34 10.66 326.78 60.34 12.81 76.13 35.16

2.77 0.30 9.29 1.72 0.36 2.17

0.0483a 0.5883 0.0066a 0.2058 0.5532 0.1575

5 1 1 1 1 1 19 24

101.69 260.11 19.88 202.67 3.38 22.43 7.57

13.43 34.36 2.63 26.77 0.45 2.96

0.0000a 0.0000a 0.1216 0.0001a 0.5119 0.1015

Signicant at the 95% condence level. Sum of squares: the sum of squares is a mathematical approach to determining the dispersion of data points. The sum of squares is used as a mathematical way to nd the function which best ts (varies least) from the data. c Degrees of freedom: an estimate of the number of independent categories in a particular statistical test or experiment. d Mean square: the mean square of a set of values is the arithmetic mean of the squares of their differences from some given value, namely their second moment about that value. e F-value: value calculated by the ratio of two sample variances. The F statistic can test the null hypothesis: (1) that the two sample variances are from normal populations with a common variance; (2) that two population means are equal; (3) that no connection exists between the dependent variable and all or some of the independent variables. f p-Value: p value is associated with a test statistic. It is the probability, if the test statistic really were distributed as it would be under the null hypothesis, of observing a test statistic [as extreme as, or more extreme than] the one actually observed.

tors were selected due to our interest in reducing the operational costs of the wastewater treatment. In the same way, the factor levels were marked by operational limits and preliminary tests. Coagulant dosages ranged from 0.2 to 1.0 mL/L (equivalent to 0.010.05 mg Al3+ /L) at 0.2 mL/L intervals (0.01 mg Al3+ /L) (coded factors: 2, 1, 0, 1, 2), while occulant dosages varied in the range of 210 mL/L at 2 mL/L intervals (coded factors: 2, 1, 0, 1, 2). The experimental matrix for the factorial design and the results of COD, turbidity and TOCsoluble removal are shown in Table 2. The experiments were run at random to minimize errors due to possible systematic trends in the variables. The use of factorial design and analysis allowed the selected factors to be evaluated in terms of their signicance and the optimum values to be determined. This was done to obtain the best COD and turbidity removals from the polynomial models and to study TOCsoluble removal relative to the COD and turbidity removals obtained. The coagulationocculation process is not the most suitable method for removing soluble organic matter. However, TOCsoluble removal was evaluated in order to study the subsequent biological treatment.

3. Results and discussion The mechanism by which the coagulationocculation process takes place may vary depending on the experimental conditions. In general, the typical steps that occur are charge neutralization, agglutination of the neutralized particles and separation by settlement or otation [19]. If ion adsorption is due to chemical interactions, hydrogen, covalent or ionic bonds are formed between the adsorpted molecules and the colloidal surface. The molecules adhere to xed adsorption points and their number might increase until modifying the colloidal charge (from negative to positive) with the consequent stabilization process. Moreover, should the adsorption points be abundant, a higher coagulant concentration will be required, thus favoring the adsorption of the largest polymers. This fact could explain why the coagulation step is not always carried out at zero potential and may not even take place if the coagulant dosage is too high, as chemical adsorption takes place instead of electrostatic interaction [21]. On the other hand, heavy polymeric molecules (containing long ionic chains) may be chemically adsorpted on the colloidal particles. In this case, coagulation is not mainly inuenced by electrostatic interactions, but by the colloid phenomenon at one or more xed adsorption points. This leaves the rest of the chain free, which may oat or adhere to another colloidal particle. In this case, molecular bonds are formed among particles, leading to their agglutination and the generation of ocs. However, coagulation by incorporation does not exclude

2.5. Software STATGRAPHICS Plus 5.1 was used to perform the statistical analysis, optimize the responses, and t the experimental data presented in this work.

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the possibility of simultaneous coagulation by chemical bonding or even coagulation by adsorptionneutralization. Consequently, coagulationocculation may occur through different superimposed and complementary mechanisms [21]. Following the literature [9,11,13,14,16,18] and based on the preliminary results, coagulant and occulant dosages were selected as the variable factors for optimization. Although pH was also analyzed, it was not included in the factorial design. The experiments and selected responses are shown in Table 2. The results were analyzed using STATGRAPHICS Plus 5.1 to determine the estimated effects and interactions between the factors, test the statistical signicance of the effects, nd the regression equation and optimize the responses. 3.1. COD removal

removal response was found to vary since a high level of coagulant dosage led to a high COD removal percentage at alkaline pH and a low COD removal percentage at acidic pH. At neutral pH, the occulant dosage was more signicant than the coagulant dosage. Fig. 1 shows the individual effect of coagulant and occulant dosages for COD removal under all pH conditions tested. The extreme coded levels (2 or 2) cause the most signicant variation in COD removal as can be observed, for example, at acidic pH. The coded level 2 for coagulant dosage prompts the best COD removal (82%). These results show that the coagulationocculation mechanism differs depending on the pH value. The following regression equations (in coded factors) were obtained under each pH condition, where CODr (%) is the COD removal percentage: Alkaline pH:

The analysis of variance test (ANOVA) for the second-order response surface model is provided in Table 3 for the three pH conditions tested. Since the p-value for the model was lower than 0.05, there was a statistical relationship between COD removal and the selected variables at a 95% condence level under all pH conditions. As can be observed in the ANOVA table (Table 3) and the main effects plotted in Fig. 1, coagulant dosage was the most significant factor under alkaline and acidic pH conditions. However, COD

CODr (%) = 63.292 11.980A + 2.321B 4.721A2 + 0.381AB 0.322B2 (1)

r 2 = 0.9136 Neutral pH: CODr (%) = 77.114 + 0.462A + 2.556B + 0.928A2 0.358AB 1.043B2 (2)

Basic pH
80

COD removal (%)

70 60 50 40 30 20

r 2 = 0.4215 Acidic pH: CODr (%) = 70.562 + 2.281A + 0.631B + 1.702A2

-2,0 2,0 -2,0 2,0

+ 0.184AB + 0.566B2

(3)

Coagulant dosage

Flocculant dosage

Neutral pH
82

r 2 = 0.7795

COD removal (%)

79 76 73 70 67

-2,0

2,0

-2,0

2,0

Coagulant dosage

Flocculant dosage

Acidic pH
84

81 78 75 72 69

-2,0

2,0

-2,0

2,0

Coagulant dosage

Flocculant dosage

Fig. 1. Main effects plot for COD removal under all pH conditions.

The goodness of t of the models was tested by checking the determination coefcient (R2 ). The determination coefcient indicates the sample variation explained by the model. As the pH decreased, the determination coefcient decreased from 0.914 to 0.422 and 0.780 for alkaline, neutral and acidic pH, respectively, thus showing that the model at neutral pH does not sufciently explain the variability of the experimental data. The plots of the experimental value versus the predicted value for COD removal are shown in Fig. 2. The experimental values are distributed relatively near to the straight line except at neutral pH where data dispersion was detected. The 3D response surface graph is the most common graphical representation of the regression equation and can be observed in Fig. 3 for COD removal. COD removal behaved differently under each pH condition. At alkaline pH, COD removal increased at low coagulant dosage levels and high occulant dosage levels. At neutral pH, however, the highest COD removal was observed at very high coagulant dosage levels (2 or 2) and at intermediate occulant dosage levels. On the other hand, the best result for COD removal at acidic pH was found at high coagulant dosage levels for all the occulant dosages tested. When the main goal of a study is to obtain the highest COD removal, COD removal must be optimized to maximize the response. Optimization was achieved using STATGRAPHICS Plus

COD removal (%)

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Basic pH
80

Basic pH

COD removal (%)

80 60 40 20 0 -2 -1 0 1 Coagulant dosage 2 2 1 0 -1 -2 Flocculant dosage

experimental values

60

40

20

0 0 20 40 60 80

Neutral pH

COD removal (%)

predicted values

Neutral pH
85

83 79 75 71 67 -2 -1 0 -2 -1 0 1 2

experimental values

80 75 70 65 60

Coagulant dosage

Flocculant dosage

Acidic pH

COD removal (%)

55 55 60 65 70 75 80 85

predicted values

Acidic pH
90

experimental values

86 82 78 74 70 66 66 70 74 78 82 86 90

87 84 81 78 75 72 69 -2

-1

Coagulant dosage

-2

-1

Flocculant dosage

Fig. 3. Response surface plots for COD removal as a function of coagulant and occulant dosages.

predicted values
Fig. 2. Experimental values versus predicted values for the COD removal models.

5.1 software. Optimum COD removal and the optimum values of the coagulant and occulant dosages are shown in Table 4. 3.2. Turbidity removal The results of the second-order response surface model in the form of analysis of variance for turbidity under each pH condition
Table 4 Single response optimizations under all pH conditions. pH COD removal (%) Optimum A (mL/L) Alkaline Neutral Acidic 0.36 1.00 1.00 Optimum B (mL/L) 10.00 7.77 10.00 Optimum response 73.31 82.56 86.19 Turbidity removal (%) Optimum A (mL/L) 0.38 1.00 1.00

are shown in Table 5. The analysis shows that the model is highly signicant as the p-value was lower than 0.05 for all pH conditions tested. Hence, there is a statistical relationship between turbidity removal and the selected variables at a 95% condence level. As can be observed in Table 5, the signicant terms in the model were the main effect (A) and the second-order effect (A2 ) of coagulant dosage for alkaline pH; the main effect of occulant dosage (B) and the second-order effect (A2 ) of coagulant dosage for neutral pH; and the main effect of occulant dosage (B) for acidic pH. Other model terms were not signicant. Fig. 4 shows the main effects of the two factors under each pH condition. The plots at neutral and acidic pH behaved in a similar manner to the factors in the response. This behavior is a consequence of the chemical adsorption mechanism, which is thought to be the predominant procedure taking place at neutral and acidic pH. However, the coagulant dosage was more signicant at alkaline pH than under other pH conditions. This

TOCsoluble removal (%) Optimum response 83.80 96.74 89.69 Optimum A (mL/L) 0.46 1.00 0.20 Optimum B (mL/L) 7.81 6.24 2.00 Optimum response 12.77 19.62 18.02

Optimum B (mL/L) 5.29 7.77 7.83

M.A. Martn et al. / Chemical Engineering Journal 172 (2011) 771782 Table 5 ANOVA for turbidity removal response surface models under all pH conditions. Source Alkaline pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2 Neutral pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2 Acidic pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2
a

777

Sum of squares 31842.00 23750.00 145.96 7213.26 25.31 707.52 6079.24 37921.30 0.8397 563.05 8.31 338.42 121.36 10.99 83.97 460.59 1023.64 0.5501 123.91 14.57 81.03 7.16 2.90 18.24 143.64 267.54 0.4631

Degree of freedom 5 1 1 1 1 1 19 24

Mean square 6368.40 23750.00 145.96 7213.26 25.31 707.52 319.96

F-value 19.90 74.23 0.46 22.54 0.08 2.21

p-Value 0.0000a 0.0000a 0.5075 0.0001a 0.7816 0.1534

5 1 1 1 1 1 19 24

112.61 8.31 338.42 121.36 10.99 83.97 24.24

4.65 0.34 13.96 5.01 0.45 3.46

0.0061a 0.5650 0.0014a 0.0374a 0.5089 0.0783

5 1 1 1 1 1 19 24

24.78 14.57 81.03 7.16 2.90 18.24 7.56

3.28 1.93 10.72 0.95 0.38 2.41

0.0266a 0.1811 0.0040a 0.3426 0.5431 0.1368

Signicant at the 95% condence level.

Table 6 ANOVA for TOCsoluble removal response surface models under all pH conditions. Source Alkaline pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2 Neutral pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2 Acidic pH Model Coagulant dosage (A) Flocculant dosage (B) AA AB BB Residual Corrected total R2
a

Sum of squares 204.43 48.87 98.97 12.20 18.60 25.79 35.74 240.17 0.8512 286.93 226.17 32.45 0.51 11.95 15.85 93.82 380.75 0.7536 10.48 4.92 0.48 0.63 2.46 2.00 51.27 61.75 0.1698

Degree of freedom 5 1 1 1 1 1 19 24

Mean square 40.89 48.87 98.97 12.20 18.60 25.79 1.88

F-value 21.74 25.98 52.61 6.49 9.89 13.71

p-Value 0.0000a 0.0001a 0.0000a 0.0197a 0.0053a 0.0015a

5 1 1 1 1 1 19 24

57.39 226.17 32.45 0.51 11.95 15.85 4.94

11.62 45.80 6.57 0.10 2.42 3.21

0.0000a 0.0000a 0.0190a 0.7507 0.1363 0.0891

5 1 1 1 1 1 19 24

2.10 4.92 0.48 0.63 2.46 2.00 2.70

0.78 1.82 0.18 0.23 0.91 0.74

0.5784 0.1929 0.6792 0.6355 0.3518 0.3995

Signicant at the 95% condence level.

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Basic pH
Turbidity removal (%)
87 120

Basic pH

experimental values
-2,0 2,0 Coagulant dosage -2,0 2,0 Flocculant dosage

67 47 27 7 -13

90 60 30 0 -30 -30 0 30 60 90 120

Neutral pH
Turbidity removal (%)
96 92

predicted values Neutral pH

99

experimental values

88 84 80

94 89 84 79 74 69 69 74 79 84 89 94 99

-2,0 2,0 Coagulant dosage

-2,0 2,0 Flocculant dosage

Acidic pH
Turbidity removal (%)
90 88

predicted values Acidic pH

86 84 82

93 90 87 84 81 78 78 81 84 87 90 93

-2,0 2,0 Coagulant dosage

-2,0 2,0 Flocculant dosage

Fig. 4. Main effects plot for turbidity removal under all pH conditions.

could be due to the hydrolysis and precipitation of the coagulant as hydroxide is favored at alkaline pH [22]. Therefore, higher levels of coagulant dosage at alkaline pH can increase turbidity due to chemical interactions. The following regression equations (coded factors) were obtained under each pH condition where Turbr (%) is the turbidity removal percentage: Alkaline pH: Turbr (%) = 71.704 21.795A 1.709B 10.151A + 0.503AB 3.179B2
2

experimental values

predicted values
Fig. 5. Experimental values versus predicted values for the turbidity removal models.

Acidic pH: Turbr (%) = 86.909 + 0.540A + 1.273B + 0.320A2 (4) r 2 = 0.4631 0.170AB 0.511B2 (6)

r 2 = 0.8397 Neutral pH: Turbr (%) = 89.797 + 0.408A + 2.602B + 1.317A2 0.331AB 1.095B2 (5)

r 2 = 0.5501

The goodness of t of the models was again evaluated by the determination coefcients (R2 ). The determination coefcient decreased when pH varied from 7.9 to 5.3. In the case of alkaline pH, the 84.0% sample variation observed for turbidity removal was attributed to the independent variables selected (coagulant and occulant dosages), while the model did not explain 16.0% of the total variations. Another way to assess the goodness of t of the model is by plotting the experimental values versus the predicted values for turbidity removal. Fig. 5 shows these plots for the three pH conditions. As can be seen, the models approximately represent the

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779

Basic pH
14,5

Basic pH TOC removal (%)

Turbidity removal (%)

90 70 50 30 10 -10 -30

12,5 10,5 8,5 6,5

-2

-1

Coagulant dosage

-2

-1

Flocculant dosage

-2,0

2,0

-2,0

2,0

Neutral pH
Turbidity removal (%)
97 94 91 88 85 82 79 -2 -1 0 1
Coagulant dosage

Coagulant dosage

Flocculant dosage

Neutral pH
21

TOC removal (%)

19 17 15 13 11

-2

-1

Flocculant dosage

Acidic pH
Turbidity removal (%)
91 89 87 85 83 81 -2

-2,0

2,0

-2,0

2,0

Coagulant dosage

Flocculant dosage

Acidic pH
17,4

TOC removal (%)

17 16,6 16,2 15,8 15,4 15

-1

Coagulant dosage

-2

-1

2 1 0 Flocculant dosage

Fig. 6. Response surface plots for turbidity removal as a function of coagulant and occulant dosages.

-2,0

2,0

-2,0

2,0

Coagulant dosage

Flocculant dosage

experimental data over the range studied. The plot at alkaline pH shows the best t as it may also be observed by the regression coefcient in ANOVA (Table 5). Fig. 6 shows 3D response surface plots for turbidity removal. The best results for turbidity removal were obtained at very high coagulant dosage levels and intermediate occulant dosage levels as can be observed by the saddle shape at neutral and acidic pH. On the other hand, the mound shape at alkaline pH indicates that the highest percentages can be obtained at intermediate values of the factors. To maximize turbidity removal, a single response optimization was carried out as explained in the section on COD removal. The results are summarized in Table 4. 3.3. TOCsoluble removal The models were tested statistically using ANOVA. The results of the ANOVA for TOCsoluble removal under each pH condition are shown in Table 6. The quadratic regression shows that the model was signicant for alkaline and acidic pH since the p-value of the models was lower than 0.05 at the 95% condence level. Fig. 7 shows the main effects plots for TOCsoluble removal. The TOCsoluble removal responses varied under the three pH conditions. TOCsoluble refers mainly to dissolved organic matter that is removed from the aqueous solution by sweeping the coagulationocculation process. Hence, no clear trend was observed regarding the inuence of coagulant and occulant dosages. For example, under neutral pH conditions, TOCsoluble increases linearly with enhanced coagulant

Fig. 7. Main effects plot for TOCsoluble removal under all pH conditions.

dosages. At alkaline and acidic pH, however, the opposite behavior is observed. At pH values in which the medium is charged, the adsorption of dissolved organic matter is hindered as the charge may ionize or reduce polarity and thus prevent adsorption on the ocs. The following equations refer to the regression models (coded factors) with the experimental results under each pH condition tested, where TOCr (%) is the TOCsoluble removal percentage: Alkaline pH: TOCr (%) = 11.778 0.989A + 1.407B 0.412A2 +0.431AB 0.607B2 (7)

r 2 = 0.8512 Neutral pH: TOCr (%) = 15.704 + 2.127A + 0.806B 0.086A2 0.346AB 0.476B2 (8)

r 2 = 0.7536

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Acidic pH: TOCr (%) = 16.269 0.314A 0.098B 0.095A2 +0.157AB + 0.169B2 (9)
14

Basic pH
experimental values

11 8 5 2 -1 -1 2 5 8 11 14

r 2 = 0.1698

3.4. Model validation and multiple response optimization To further validate the models under even higher reactant dosages, an additional experiment (0.2 mL/L of coagulant, equivalent to 0.01 mg Al3+ /L, and 12.0 mL/L of occulant) was performed in each set of experiments. The conditions selected for coagulant and occulant dosages were constant under all pH conditions. The conditions are listed in Table 7 along with the predicted and measured results. As can be seen in the table, the three responses were close to the responses that were estimated using response surface methodology. The variation coefcients were lower than 5% for COD and turbidity removals and lower than 20% for TOCsoluble removal. Although the regression coefcients were low in some experiments at neutral or acidic pH, the experimental results were quite similar to the predicted results when the models were applied to higher factor levels as can be observed in Table 7. Therefore, it can be concluded that the models accurately represent COD, turbidity and TOCsoluble removals over the experimental range studied and at even higher factor levels. The multiple response optimization method is an algorithm provided by STATGRAPHICS Plus 5.1 software and combines the three selected responses to obtain the best operational conditions.
Table 7 Validation of the models at 0.2 mL/L of coagulant and 12.0 mL/L of occulant. pH COD removal (%) Experimental Alkaline Neutral Acidic 68.22 81.72 77.89 Predicted 70.15 80.33 78.69

experimental values

Table 6 also shows the determination coefcients (R2 ) for all pH conditions. The models at alkaline and neutral pH explain 85.1% and 75.4% of the total variation, respectively, while the acidic pH model shows a worse t (R2 = 0.170). The prediction of the experimental data was quite satisfactory at alkaline and neutral pH as the lines have a slope close to 1 as shown in Fig. 8. Hence, the plots of the experimental values versus the predicted values for TOCsoluble removal provide a visual representation of the models performance. The plot therefore highlights the deciency of the response surface model at acidic pH (R2 = 0.1698). Contour plots of the response surface methodology are drawn as a function of two factors at a time, while maintaining all other factors at xed levels (normally at intermediate levels) [18]. Fig. 9 shows the contour plots for TOCsoluble removal. The contour curve for alkaline pH has a considerable curvature, thus indicating that the interaction between the factors was signicant [16]. The mound contour at alkaline pH indicated that the best TOCsoluble removal percentages were obtained at intermediate levels of the factors. For neutral pH, the best results were observed at high coagulant dosage levels and intermediate occulant dosage levels. Finally, the saddle contour obtained at acidic pH demonstrated that the TOCsoluble removal percentages were quite low at zero levels of both factors. The single maximization results for TOCsoluble removal in the coagulationocculation process can be observed in Table 4.

predicted values

Neutral pH
21

experimental values

18 15 12 9 6 6 9 12 15 18 21

predicted values

Acidic pH
23 21 19 17 15 13 13 15 17 19 21 23

predicted values
Fig. 8. Experimental values versus predicted values for the TOCsoluble removal models.

Although COD, turbidity and TOCsoluble removals were optimized as individual responses, a compromise between the conditions for the responses is desirable. STATGRAPHICS Plus 5.1 software uses a desirability function approach to achieve the highest removal percentages. Table 8 shows the optimum values for the responses and the factors at each pH. The values were calculated by means of the desirability function and the models obtained using response surface methodology. A comparison of Tables 4 and 8 shows that

Turbidity removal (%) Experimental 57.82 95.09 91.40 Predicted 57.93 94.19 87.35

TOCsoluble removal (%) Experimental 10.59 13.94 17.77 Predicted 8.28 11.32 16.80

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Basic pH Flocculant dosage

2 1 0 -1 -2
-2 -1 0 1 2
COT removal (%) 0,0 1,5 3,0 4,5 6,0 7,5 9,0 10,5 12,0 13,5

Coagulant dosage Neutral pH Flocculant dosage

2 1 0 -1 -2
-2 -1 0 1 2
TOC removal (%) 6,0 7,5 9,0 10,5 12,0 13,5 15,0 16,5 18,0 19,5 21,0

coagulationocculation process [9,1113,16,18]. Ahmad et al. [18] and Bathia et al. [9] treated palm oil mill efuent, obtaining the best results at acidic pH (6.0 and 5.0, respectively). Although similar results were found in our study, the differences in removal percentages across the tested pH conditions were not signicant. Although these removal percentages are higher than 80%, the treated wastewater cannot be spilled and a subsequent biological treatment is needed. Alkaline pH was therefore selected as the most suitable pH condition since it reduces the operational costs of the initial pH adjustment stage and allows the biological treatment to be applied directly without correcting the pH. 4. Conclusions A 52 full factorial experimental design and response surface methodology were used to optimize the coagulationocculation process of wastewater from sauce manufacturing with a view to reducing the number and cost of experiments and improving the process at industrial scale. The goodness of t of the model at each pH was effectively veried by validating the experimental data. The best regression coefcients (R2 ) were obtained for COD, turbidity and TOCsoluble at alkaline pH: 0.9136, 0.8397 and 0.8512, respectively. Coagulant dosage seems to be the most signicant factor in the removal of COD and turbidity under all the pH conditions tested. For TOCsoluble , however, the trend is not clear given that this parameter is an indicator of the dissolved organic matter that is removed from the aqueous solution by sweeping during the coagulationocculation process. Multiple response optimization allowed the coagulant and occulant dosages to be minimized, while maximizing the COD, turbidity and TOCsoluble removal percentages. pH was also evaluated to determine the most suitable pH condition for the coagulationocculation process of wastewater from sauce manufacturing from the standpoint of operational, economic and post-treatment factors. Although the results were quite similar under all pH conditions, alkaline pH was selected due to ease of operation and lower costs resulting from the omission of pH adjustment stages. Nevertheless, although organic matter removal was high, its concentration was still not adequate for spillage, making a subsequent biological treatment mandatory. With regard to TOCsoluble removal, the coagulant and occulant dosages did not show a clear inuence due to the fact that dissolved organic matter is removed for sweeping the coagulationocculation process. Once pH was xed at the alkaline value, the optimum values of the factors and the responses were 0.4 mL/L of coagulant (equivalent to 0.02 mg Al3+ /L), 7.0 mL/L of occulant and 82, 72 and 13% of COD, turbidity and TOCsoluble removal, respectively. Acknowledgements The authors are very grateful to the MUSA S.A. rm, specically the Baldomero Moreno Factory (Cordoba, Spain) for funding this research. We also wish to express our gratitude to laboratory technician Inmaculada Bellido Padillo for her help. References

Coagulant dosage Acidic pH Flocculant dosage

2 1 0 -1 -2
-2 -1 0 1 2
TOC removal (%) 15,0 15,4 15,8 16,2 16,6 17,0 17,4 17,8 18,2

Coagulant dosage
Fig. 9. Contour plots for TOCsoluble removal as a function of coagulant and occulant dosages.

multiple response optimization achieves better overall results than single response optimizations. Thus, the coagulationocculation process can reduce operational costs as lower dosages of reactants are required. The coagulationocculation mechanism occurs once enough coagulant has been dispersed to sufciently destabilize the colloidal particles and the occulant allows particles to agglomerate into larger ocs [18,23,24]. For destabilization to occur, the aluminum polychloride requires sufcient alkalinity for proper hydrolysis. This leads to the formation of insoluble hydroxide whose precipitation reduces COD, turbidity and TOCsoluble [18]. Consequently, an initial alkaline pH could be suitable in order to favor the formation of Al(OH)3 . On the other hand, the high molecular weight occulant used destabilizes the particles by developing bridges with the functional groups, thus forming larger structural units that are readily separated from the aqueous dispersing medium [25]. Other authors have used response surface methodology to select the best operational conditions for the
Table 8 Multiple responses optimization under each pH condition. Optimum values Coagulant dosage (mL/L) Flocculant dosage (mL/L) COD removal (%) Turbidity removal (%) TOCsoluble removal (%) Alkaline pH 0.38 6.93 81.64 71.59 12.66 Neutral pH 1.00 6.13 81.87 96.00 19.62 Acidic pH 0.97 10.00 88.91 85.00 16.42

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