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Improved Sulfide Mitigation in Sewers Through On-Line Control of Ferrous Salt Dosing

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Improved Sulfide Mitigation in Sewers Through On-Line Control of Ferrous Salt Dosing Accepted Manuscript Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing Ramon Ganigué, Guangming Jiang, Yiqi Liu, Keshab Sharma, Yue-Cong Wang, José Gonzalez, Tung Nguyen, Zhiguo Yuan PII: S0043-1354(18)30121-0 DOI: 10.1016/j.watres.2018.02.022 Reference: WR 13574 To appear in: Water Research Received Date: 9 October 2017 Revised Date: 16 January 2018 Accepted Date: 8 February 2018 Please cite this article as: Ganigué, R., Jiang, G., Liu, Y., Sharma, K., Wang, Y.-C., Gonzalez, José., Nguyen, T., Yuan, Z., Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing, Water Research (2018), doi: 10.1016/j.watres.2018.02.022. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. ACCEPTED MANUSCRIPT MANUSCRIPT ACCEPTED ACCEPTED MANUSCRIPT 1 Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing 2 3 Ramon Ganigué 1,2 , Guangming Jiang 1, Yiqi Liu 1,3 , Keshab Sharma 1, Yue-Cong Wang 4, 4 José Gonzalez 4, Tung Nguyen 4, Zhiguo Yuan 1* 5 1. Advanced Water Management Centre, Building 60, Research Road, The University of 6 Queensland, St. Lucia, Brisbane QLD 4072, Australia. (e-mail: [email protected]; 7 [email protected]; [email protected]) 8 2. Center for Microbial Ecology and Technology, Ghent University, Coupure Links 653, 6 B- 9 9000 Ghent, Belgium (e-mail: [email protected]) 10 3. School of Automation Science & Engineering, South China University of Technology, 11 Guangzhou, 510640, P.R. China. (e-mail: [email protected]) 12 4. Sydney Water Corporation, 1 Smith St, Parramatta, NSW 2150, Australia. (e-mail: yue- 13 [email protected]; [email protected], 14 [email protected]) MANUSCRIPT 15 * Corresponding author 16 17 Abstract 18 Water utilities worldwide spend annually billions of dollars to control sulfide-induced 19 corrosion in sewers. Iron salts chemically oxidise and/or precipitate dissolved sulfide in 20 sewage and are especially used in medium- and large-size sewers. Iron salt dosing rates are 21 defined ad hoc, ACCEPTEDignoring variaton in sewage flows and sulfide levels. This often results in iron 22 overdosing or poor sulfide control. Online dosing control can adjust the chemical dosing rates 23 to current (and future) state of the sewer system, allowing high-precision, stable and cost- 24 effective sulfide control. In this paper, we report a novel and robust online control strategy 25 for the dosing of ferrous salt in sewers. The control considers the fluctuation of sewage flow, 1 ACCEPTED MANUSCRIPT 26 pH, sulfide levels and also the perturbation from rainfall. Sulfide production in the pipe is 27 prediced using auto –regressive models (AR) based on current flow measurements, which in 28 turn can be used to determine the dose of ferrous salt required for cost-effective sulfide 29 control. Following comprehensive model-based assesment, the control was sucessfully 30 validated and its effectiveness demonstrated in a 3-week field trial. The online control 31 algorithm controlled sulfide below the target level (0.5 mg S/L) while reducing chemical 32 dosing up to 30%. 33 Keywords: Chemical dosing; Corrosion; Online control; Sewer systems; Sulfide control. 34 35 1. Introduction 36 Water utilities worldwide spend annually billions of dollars to mitigate pipe corrosion and 37 malodour nuisances caused by biogenic sulfide in sewers (Jiang et al., 2015; Pikaar et al., 38 2014; US EPA, 1992). The dosing of chemicals (e.g. oxygen, nitrate, iron salt, magnesium 39 hydroxide, among others) is commonly applied toMANUSCRIPT prevent sulfide formation, remove it from 40 solution or mitigate its negative effects (WERF, 2007). Among these chemicals, the use of 41 iron salt is widespread due to their cost-effectiveness (Barjenbruch, 2003; Bertrán de Lis et 42 al., 2007; Jameel, 1989; Padival et al., 1995). A recent industry survey conducted in Australia 43 highlighted the preferential use of iron salt dosing in medium to large sewer systems, as its 44 working principle makes it the best suited for sulfide control in such pipes (Ganigué et al., 45 2011). 46 ACCEPTED 47 Various metal salts (e.g. ferrous chloride, ferric chloride and, in some cases, ferrous sulfate) 48 can react chemically with dissolved sulfide to form relatively insoluble metal sulfides, thus 49 decreasing the concentration of dissolved sulfide in sewage and subsequently H2S in sewer 50 gas (WERF, 2007). Ferric ions (Fe 3+ ) oxidize sulfide to elemental sulfur while being reduced 2 ACCEPTED MANUSCRIPT 51 into ferrous ions (Fe 2+ ). Fe 3+ also directly participate with OH - and phosphate, but will 52 eventually be available for sulfide removal (Zhang et al., 2009). Subsequently, Fe 2+ can 53 combine with sulfide to form highly insoluble metallic precipitates (Dohnalek and 54 Fitzpatrick, 1983). FeS is the most common iron sulfur precipitate in aqueous solutions, 55 although other Fe-S precipitates such as Fe 2S2 and Fe 3S4 can also form (Rickard et al., 2007). 56 Equations 1-4 illustrate the hydrogen sulfide equilibria, and the stoichiometries of sulfide 57 oxidation by ferric ions and FeS formation by ferrous ions. 58 59 + pKa = 7.05 (1) 60 + pKa = 12.89 (2) 61 2 + → 2 + () (3) -18 62 + → () Ksp = 1·10 (4) 63 MANUSCRIPT 64 The dosage of iron for sulfide control can be estimated based on the theoretical 65 stoichiometries (Equations 3 and 4). However, real life Fe:S dosing ratios differ from those 66 due to the fact that only the ionic sulfide species react directly with Fe 2+ /Fe 3+ . The formation 67 of FeS precipitates requires the presence in solution of both Fe 2+ and S 2− at concentrations 68 sufficiently high so that the solubility product, defined as [Fe 2+ ]·[S 2-]- is higher than the 69 solubility constant (Ksp). Thus, higher ratios need to be applied to reach low total dissolved 70 sulfide (TDS) levels (WERF, 2007). This results also in an increase of the concentration of ACCEPTED 71 residual iron in solution. As an example, in the Los Angeles sanitation district, FeCl 2 was 72 added to large diameter gravity sewers to control sulfide. An Fe:S molar ratio of 1.76:1 was 73 necessary to reach target TDS levels above 0.4 mg S/L, while ratios of 3.77:1 and 25.4:1 74 were required to achieve sulfide levels of 0.1-0.4 mg S/L and below 0.1 mg S/L, respectively 75 (Padival et al., 1995). Besides, the availability of S 2- is governed by pH. The lower the pH, 3 ACCEPTED MANUSCRIPT 76 the less S 2- in equilibrium in the liquid phase, requiring higher Fe 3+ /Fe 2+ concentrations to 77 reach the FeS supersaturation point (ion product higher than the Ksp). According to Firer and 78 co-workers, sewage pH below neutrality may require Fe:S ratios much higher than the 79 theoretical stoichiometry (Firer et al., 2008). However, this should have limited influence on 80 iron dosing for sulfide control in domestic sewers as sewage pH is mostly in the pH range 81 7.5-8.5 (Nielsen et al., 1998, Houhou et al., 2009, Sharma et al., 2013). 82 83 Sewers are very dynamic systems and sewage flow and characteristics show large variations 84 throughout the day, week and year (Sharma et al., 2013). However, in current practice, iron 85 salt dosing rates are defined ad hoc , based on the typical sewage flow pattern of the system 86 and sulfide levels at discharge (de Haas et al., 2008, Ganigué et al., 2011). As a result, 87 generous chemical dosing safety factors need to be applied, especially when targeting tight 88 sulfide discharge limits. Overdosing can be more severe during wet weather conditions, when 89 sulfide production declines due to the shorter hydrMANUSCRIPTaulic retention time (HRT) of diluted 90 sewage in the pipe (as a consequence of the higher flow rates with the rainwater inflow or 91 infiltration) (Chen et al., 2014; Ganigué et al., 2016). Online dosing control can adjust the 92 chemical dosing rates to current (and future) state of the sewer system, allowing high- 93 precision, stable and effective sulfide control with minimal chemical dosing (Sharma and 94 Yuan, 2009). Recently, Ganigué and co-workers reported the successful development of the 95 first on-line chemical dosing controller for sulfide mitigation in sewers (Ganigué et al., 2016). 96 The algorithm controlledACCEPTED in real-time the Mg(OH) 2 dosing rate based on pH measurements 97 and allowed improved sulfide control with reduced chemical consumption. 98 99 The sulfide control mechanism of iron salt relies on the chemical oxidation of sulfide by Fe 3+ 100 and/or the precipitation of dissolved sulfide with Fe 2+ into FeS (Dohnalek and Fitzpatrick, 4 ACCEPTED MANUSCRIPT 101 1983), and is fundamentally different from that of Mg(OH) 2 (elevation of the wastewater pH 102 to minimise the fraction of sulfide as H 2S, to prevent its transfer from the liquid to the gas 103 phase) (Gutierrez et al., 2009). Therefore, it requires a completely different control approach. 104 To date there are no studies focusing on the online control of iron salt dosing in sewers.
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