Use of Chemical Technical Rcp for the Inhibition of Scaling from Hard Water by a Green Inhibitor: Quercitine

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1 4-6 December 2016, Riyadh, Saudi Arabia Use of Chemical Technical Rcp for e Inhibition of Scaling from Hard Water by a Green Inhibitor: Quercitine S. Ghizellaoui, R. Menzri, S. Ghizellaoui and H. Olivier 1 Department of Chemical, University of Frères Mentouri, road Ain El Bey Algeria 2 Ecole Nationale Supérieure de Biotechnologie Ville universitaire Ali Mendjeli, BP E Constantine, Algérie 3 EPF 3bis, Rue Lakanal92330 Sceaux, France Abstract: Groundwater of Negrine, Fourchi and Hamma at supply e cities of Tébessa, Ain M'lila and Constantine wi drinking water are from limestone reservoirs. These water are very hard as ey are loaded wi calcium hydrogenocarbonate and may deposit large quantities of calcium carbonate (82% in weight). The incrusting deposits formed on e walls of pipes and on e industrial installations consist primarily of CaCO 3 as calcite. The techniques and economic impacts of tartar consequences are: Partial or total obstruction of pipes togeer wi weakening of water flow rates, Decreasing of heat transfer, Jamming stopping devices (valves, taps) Clogging of heat exchangers, filters etc.. The anti-scale struggle has several scale inhibitors (phosphates, carboxylates) at are not used for drinking water. It also has several processes at are used to prevent e precipitation of tartar. A number of chemicals, electrochemical and nanofiltration treatments have been used to limit e precipitation of tartar. Oer studies have focused on e influence of metal cations (Cu, Fe, Zn and Mn) on e precipitation of calcium carbonate by using e scaling potentiality, RCP and polyeylene test. The aim of our work is to evaluate and inhibit e furring Hamma hard waters by using e RCP test (rapid controlled precipitation) use for softening hard water wi green inhibitor: Quercitine. Key words: Water Hardness CaCO Inhibition RCP Quercitine 3 INTRODUCTION meod [8-10] and polyeylene test [11], were used to limit e precipitation of tartar. Uncontrolled formation of compact and adherent Studies have focused on e influence of foreign ions deposits of calcium carbonate on e walls of pipes precipitation of calcium carbonate [12-13], but e for industrial or domestic installations (scaling), supplied experimental conditions were often different from ose wi natural waters or distribution of technical and encountered in natural waters. economic consequences are disastrous. This is e The main goal at we have set ourselves is to case of groundwater Hamma supplying e city of determine e possible changes in e furring hard water Constantine in drinking water. During eir movement power (Hamma) by a green inhibitor quercitine using a wiin e distribution system, is water gives rise to chemical process of rapid controlled precipitation. scale. Increasing e ickness of is layer leads to We chose quercitine because it is a green scale reductions in roughput and can lead to jamming of e inhibitory molecule, non-toxic and biodegradable. valves and taps. The test speed controlled precipitation was developed by For is, several chemical processes [1-2], Ledion et al.,[10] allows to follow e kinetics of e electrochemical [3-4], nanofiltration treatments [5-6], e process of germination - grow of calcium carbonate in scaling potentiality [7], fast controlled precipitation specific water. Corresponding Auor: S. Ghizellaoui, Department of Chemical, University of Frères Mentouri, road Ain El Bey Algeria 25

2 Fig. 1: Experimental apparatus used in e process of rapid controlled precipitation MATERIAL AND METHODS mg/l, is performed by comparing treated and untreated water. Thus collects a treated water sample and a sample Device Used: The test apparatus, is shown in Fig.1 of untreated water, which are en brought to e same composed of: temperature 30 C in a ermostated ba. The two samples are en identifies e values??of initial ph and Two magnetic P SELECTA stirrers resistivity, en e two samples stirred at 800 rev/min at Two bar magnets. e same time. The tap frequency measurements are also A digital ph meter JENWAY 3505 ph meter equipped identical to e two waters every 5 minutes. The maximum wi a saturated calomel electrode and a temperature duration of e test is 100 minutes. To avoid pollution of sensor. It has a measurement accuracy of 1/100 of water to e oer, e electrode is rinsed wi distilled ph. water after each test. A conductivity meter HANNA EC214 equipped wi a conductivity cell wi integrated temperature RESULTS AND DISCUSSIONS sensor, A stopwatch. Evaluation of e Quality of Raw Water Hamma: A ermostatic ba. Experimental Procedure: The two balloons are cleaned before used in a diluted hydrochloric acid ba at 50% and en rinsed wi water Hamma. Before e sampling, each of e two containers is rinsed wi water during e test at contain (raw or treated). Bo magnetic stirrers are set to exactly e same rotational speed (800 rev/min). The ph HCO 3 - mg/l The oxygen consumed by organic matter TH mg/l CaCO meter is calibrated wi two buffer solutions of ph = 4 and 2+ Ca mg/l ph = 7, e meter is being calibrated beforehand. The 2+ Mg mg/l electrodes of e ph meter and conductivity are rinsed - Cl mg/l wi distilled water prior to each measurement. To test a tartar treatment Quercitine (0,05, 0,2, 1, 10, 20, 30 and 40) Table 1: Analysis of water Hamma Parameter Hamma Water Standards WHO T C ph EC ms/cm Dissolved oxygen mg/l SO 4 2- mg/l NO 3 - mg/l

3 Temperature: It is important to know e water Bicarbonates: The bicarbonate or calcium bicarbonate, temperature wi a good precision (it should be measured in situ). Indeed, it plays a role in e solubility of gases in e dissociation of dissolved salts and ph determination, to know e origin of e water and any mixtures, etc... In present in hard water is one of e causes of e water hardness. It is unstable in solution in water and tends to turn into calcium carbonate (calcite) to form scale encrusting. The baking stability is related addition, is measurement is very useful for limnological to e water temperature and e presence of studies. In general, e water temperature is influenced by e source from which it comes from (superficial or deep) [14]. In our study area e water temperature Hamma is 32?, which shows at its origin is a ermal spring. dissolved carbon dioxide. Concentration must be held between 100 and 300 mg/l and ideally 200 mg/l to approximately maintain a stable ph and to avoid having scaling waters. For e waters of Hamma it is to 417 mg/l. ph: The ph of water is presenting its acidity or alkalinity. The ph of natural waters is related to e nature of e terrain traversed. In most natural waters, e ph dependent equilibrium calcocarbonic. The ph is an important parameter to define how aggressive or embedding is e water. It is involved in ese phenomena wi oer parameters such as hardness, alkalinity and temperature. The ph is an indicator of e water quality. WHO advocates for drinking water ph between 6.5 and 8.5. This is verified for Hamma water wi a ph of Conductivity: The water conductivity is a measure of its ability to conduct electrical current. The conductivity measurement allows to determining quickly but very roughly mineralization of e water and follow e change. Table (2) establishes a relationship between e degree of mineralization and conductivity according to French regulations. The conductivity of Hamma water is ms/cm, resulting in significant mineralization. Dissolved Oxygen: The content of oxygen in water depends on e origin of e water. Surface waters may contain relatively large amounts near e saturation (8-10) mg/l at 20 C. His role in is case is predominant in e assimilative pollutant loads. Compared wi groundwater, it does contain usually a few mg/l. We know at for a high temperature, e oxygen content decreases, due to its lower solubility and is is not always confirmed by e pumping station Hamma where agitation is important. For Hamma (6.68 mg/l). Table 2: Relationship between conductivity and mineralization Conductivity (ìs/cm) Mineralization Very low mineralization low mineralization Accentuated average mineralization mineralization accentuated significant mineralization >1000 high mineralization The Oxygen Consumed by Organic Matter: Determining e amount of oxygen transferred by KMnO 4 to oxidize e organic matter contained in water expressed as O 2 mg/l of water, represents e total organic matter content. High organic matter content should always be suspected microbial contamination. Observations on e waters of Hamma, we indicate a value of 2 mg/l of O 2. Which is a common value. WHO recommends admitted to drinking water limit value of 2 mg/l. Total Hardness: Hardness expressed e ability of water to react wi soap. Or e hardness (TH) of water essentially corresponds to e total content of calcium and magnesium. It is directly linked to e geological nature of e terrain traversed. Thus, a limestone soil give a "hard" water (strongly mineralized wi calcium and magnesium), while water passing rough a crystal soil (granite) as e sand will be "soft". Groundwater is generally harder an e water surface. This is e case of water having a hardness of Hamma 554 CaCO 3 mg/l (55.4 F). Refer to Table (3) for e classification of hardness. In fact, groundwater is rich in carbonic acid, ey have a high solubilizing power towards soil and rocks. Hard water cover about a ird of calcium and magnesium needs of a man. There is a correlation between e consumption of fresh water and e frequency of appearance of cardiovascular diseases. Thus, hard water, provide protection against ese diseases. Table 3: Ranking of e hardness Hardness Hardness concentration in mg/l of CaCO 3 Fresh 0 60 Moderately sweet Lasts Very hard 180 and more 27

4 Calcium: Calcium is an important element of e hardness of e water. Acceptable values??are e order of 2 to 3 is usually e dominant element of drinking water. It is mg/l. They should not exceed 20 mg/l for fish life. Their especially in e form of bicarbonates and in less origin is mainly anropogenic (fertilizer use in important amounts in e form of sulfates, chlorides. agriculture...). For drinking water at Hamma, it is 2.3 mg/l Calcium salts are obtained mainly during e attack by and it meets e standards. limestone dissolved carbon dioxide (CO 2). It is e dominant element cationic water. The presence of calcium CONCLUSION in e water of Hamma is 148 mg/l, is directly related to e geological nature of e terrain traversed. It should be noted at water at Hamma is well mineralized naturally rich in calcium and magnesium and Magnesium: Magnesium is an important element of e it is wi high hardness. hardness of water and widely distributed in nature. In many minerals and limestone (2.1 % of e Ear's crust). RCP Assays: Geological abundance, its high solubility, its industrial ph: The values obtained during e test allow us to trace use are eir levels in water may be important (a few mg/l e curves ph = f (time). An example of a curve is given in to several hundred mg/l) for Hamma (45 mg/l). Figure (2). For given water, ree distinct phases is observed. Chlorides: Chlorides are present in almost all waters. Initially, ere was an increase in e ph: degassing The concentrations vary widely, passable to ten mg/l to of CO at predominates on e precipitation of CaCO, more an a ousand mg/l. The origin of chlorides is since it has not reached a sufficiently high degree of natural, it is due to contact wi certain geological + supersaturation ( < 40) generates an ion consumption H. formations. The chlorides which are easily soluble in In a second step, e ph tends to decrease due to e water and do not participate to say, e biological precipitation of calcium carbonate, which takes over e process. They play no role in e phenomena of degassing according to e reaction: decomposition. They are conservative. However, eir presence does not necessarily indicate a pollution of Ca CO 3 CaCO 3 (s) human or animal origin, when an increase in eir concentration is observed. The maximum concentration of In a ird step, degassing of CO 2 and e precipitation chloride is given 250 mg/l, because at higher of CaCO 3 tend to balance, so ph stabilization is observed. concentrations, water can have a salty taste. Chlorides are Note at e ph of e raw water before generally also corrosive agents at high concentrations. decreases e treated water (to delay e precipitation) Groundwater Hamma concentration is around 145 mg/l to and decreases more rapidly (differential precipitation e standard for drinking water. kinetics) during use of Quercitine as inhibitor of scaling. Figures (3 and 4). It may be noted at is meod is Sulfates: Sulfates come from gypsum rocks and sulphide especially sensitive to ph delays e precipitation (small oxidation found in rocks such as pyrite. The most difference in kinetics). The shape of e curve changes for frequently encountered sulfates are sodium sulfate, 100% efficiency (Figure 5). ammonium sulfate and magnesium sulfate. It is known at e concentration of sulfate ions in water is variable depending on e nature of e ground crossed. According to our test results, Hamma contains 190 mg/l. Overall, our waters meet standards (WHO) where e sulphate concentration is limited to 400 mg/l. Beyond is value of diarrheal disorders may occur especially in children. 2 3 Nitrates: Nitrates are e most oxidized form of nitrogen. And increasing e nitrate content in water causes a development of algal flora and erefore eutrophication of aquatic phenomenon. In natural waters, e rate of nitrate is very variable depending on e season and e origin Fig. 2: ph curve using e RCP test 28

5 Fig. 3: Variation of e ph and resistivity wi time for Hamma water wiout and wi 0.2 mg/l of quercitine Fig. 6: Resistivity curve using e RCP test Fig. 4: Variation of e ph and resistivity wi time for Hamma water wiout and wi 20 mg/l of quercitine Fig. 5: Variation of e ph and resistivity wi time for Hamma water wiout and wi 40 mg/l of quercitine Fig. 7: Evolution of e efficiency as a function of e concentration of quercitine Resistivity: The course of e curve Res =f(t) reveals at, during e precipitation, e Ca and CO3 ions cause a decrease in conductivity, us increasing e resistivity of raw water against e (Figure 6) treated water. As for ph, an antiscalant treatment causes a delay in precipitation. It is also seen rough which e resistivity starts to increase after e raw water. It also slows down e kinetics of precipitation (least significant formation of calcium carbonate). This enables e complete resistivity of ph because it best describes e kinetics of precipitation of e slopes of e lines change (Figures 3-5). Tests at 30 presence of quercitine and provide a curve of increasing effectiveness in function of e amount added, see Figure 7. It is seen at wi addition of 0.05 mg/l, e efficiency is about % and from 40 mg/l of e blocking-grow process of germination of e calcium carbonate is higher and reaches 100 %. 29

6 CONCLUSION 6. Bannoud, A., Elimination de la dureté et des Our work consisted of studying meods to prevent sulfates contenus dans des eaux par nanofiltration. Desalination, 137: encrustation of calcium carbonate on e walls of pipes 7. Ferreux, M., F. Remy and A. Vidonne, Le test de carrying hard water Hamma. For is, a rapid precipitation potentialité à l'entartrage: présentation et application. meod (RCP) has monitored e implementation of e Tribune de l eau. 567/7: process of nucleation-grow of calcium carbonate. The 8. Gauier, G., Y. Chao, O. Horner, O. Alos-Ramos and addition of quercitine at low concentrations (0.05 mg/l) F. Hui, Application of e Fast Controlled has demonstrated significant role for e antiscale- effect. Precipitation meod to assess e scale-forming The total scale inhibition is reached for an addition of ability of raw river waters. Desalination. 299: mg/l of quercitine. It can be concluded at e test 9. Liu, D., W. Dong, F. Li, F. Hui and J. Lédion, (RCP) is easy to implement and quercitine has inhibitory Comparative performance of polyepoxysuccinic effect of scaling. acid and polyaspartic acid on scaling inhibition by static and rapid controlled precipitation meods. REFERENCES Desalination, 304: Ledion J., B. François and J. Vienne, Vermeulen, T., Badawi W. Tleimat and G. Klein, Caractérisation du pouvoir entartrant par Ion-exchange pretreatment for scale prevention in précipitation contrôlée rapide. Journal Européen desalting systems. January. d hydrologie, 28: Ghizellaoui, S., M. Euvrard, J. Lédion and A. Chibani, 11. Abouali, E., O. Jean and J. Ledion, Influence du Inhibition of scaling in e presence of cuivre et du zinc sur le pouvoir entartrant de l eau. copper and zinc by various chemical processes. Journal Européen d'hydrologie. Tome, 27: Desalination, 206: Meyer, H., The influence of impurities on e 3. Belarbi, Z., J. Gamby, L. Makhloufi, B. Sotta grow rate of calcite. Journal of Crystal Grow, and B. Tribollet, Inhibition of calcium 66: carbonat eprecipitation by aqueous extract of 13. Pernot, B., Modification du pouvoir entartrant Paronychiaargentea. J. Cryst. Grow. 386: d'eaux calcifiantes par des cations métalliques: fer, 4. Menzri, R. and S. Ghizellaoui, aluminium, manganèse, zinc. Thèse de doctorat de Chronoamperometry study of e inhibition of l'université de Franche-comté en Chimie-Physique, groundwater scaling deposits in Fourchi. Energ. pp: 153. Proced., 18: Rodier, J. L'analyse de l'eau, Eaux naturelles, Eaux 5. Ghizellaoui, S., Comparaison et optimisation des résiduaires, Eaux de mer. Dunod technique, procédés d adoucissement chimique. Application aux décembre, pp: eaux du Hamma. Thèse de doctorat de l université de Constantine en chimie analytique et traitement des eaux, pp: