ION EXCHANGE IN WATER SOFTENING

Objective: Determine the exchange capacity of a cationic resin in water softening. Introduction: Water softening is a process to reduce hardness in water and prevent the build-up of lime scale and calcium deposits in pipes and equipment. Hardness is normally measured by the amount of calcium and magnesium that is present in water and is reported as the concentration of CaCO3. To get an idea of scale, the Saskatoon Water Treatment and Meters Branch reports the potable water has an average hardness of 126 mg/L as CaCO3. The river water has an average hardness of 176 mg/L. 120 mg/L as CaCO3 or greater is considered hard. Ion exchange is an important technique to reduce hardness in water. It is the reversible interchange of ions between a solid (ion exchange material) and a liquid. The ions in solution become attached to the solid and the displaced ions will be forced into solution. The process of exchange continues until both ions reach equilibrium on the surface and in solution. This process is dynamic and can be reversible depending on the relative concentrations of the ions in solution. Ion exchange has been used on an industrial basis since 1910 with the introduction of water softening. Cation exchange is widely used to soften water. The most usual ion exchange material employed in water softening is a sulphonated styrene-based resin, supplied by the makers in the sodium form. In the process, calcium and magnesium ions in water are exchanged for sodium ions on the resins. Ferrous iron and other metals such as manganese and aluminum, sometimes present in small quantities, are also exchanged

Figure 1. Ion Exchange Columns (Picture courtesy to www.stockinterview.com/News/) after calcium and magnesium are removed, but are unimportant in the softening process. Removal of the hardness, or scale-forming calcium and magnesium ions, produces soft

2 water. Softening can be carried out as a batch process by stirring a suspension of the ion exchange resin in the water for a period until equilibrium, or an acceptable level of hardness, is reached. However, it is more convenient to operate a continuous flow process by passing the water downwards through a column of resin beads. Theory: The exchange reaction for water softening with a sulphonated styrene-based resin in the form of sodium can be described below. 2Na+R- + Ca2+(aq) Ca2+R-2+ 2Na+(aq) where R represents the resin chain and the exchange point on the beads. The reaction takes place rapidly enough for the upper layers of the bed to approach exhaustion before the lower layers being able to exchange ions. There is thus, a zone of active exchange which moves down the column until the resin at all depths becomes exhausted. The position at an intermediate stage can be illustrated as shown in Figure 2a. Plotting the hardness readings as CaCO3 (mg/L) in the effluent against the volume of water treated (L) generates the breakthrough curve as shown in Fig.2b. The breakthrough point can be determined at which the concentration of CaCO3 in the effluent reaches an acceptable level of hardness or the hardness of the feed. It is usually the limit of the exhaustion cycle. (1)

Figure 2a. Ion Exchange Zone

Figure 2b. Idealized Breakthrough Point

When the resin is exhausted, it can be regenerated with a copious amount of sodium salt such as sodium chloride. The excess salt will shift the equilibrium (Eq.1) to the left and sodium ions will replace calcium and be present on the solid.

3 If the hardness is measured by CaCO3, the ion exchange capacity of the resin can be determined as follows:

Exchange Capacity =
where

Removed Mass of CaCO 3 (mg) X0.02 (meq/mg) Vol of Wet Bed (mL)

(2)

D 2 Volume of Wet Bed (mL) = XFinal Depth of Resin Bed (cm) 4

where D is the diameter of the column (cm), equal to 1.5 cm in this investigation.

(3)

The mass of CaCO3 removed from the tap water up to the breakthrough point can be calculated. Graphically, this is given by the area in the graph of breakthrough curve between the curve plotted and the horizontal line, representing the original hardness of the water. The mass of CaCO3 (mg) can be converted to milliequivalent (meq) by multiplying a factor of 0.02. (DOWEX, Ion Exchange Resins, Water Conditioning Manual, p.74.) Knowing the wet volume of the resin bed, the exchange capacity of the resin can be calculated as meq/mL. If other minerals such as magnesium carbonate, calcium oxide and so on are removed, they can be converted to the equivalent concentration as CaCO3 by certain conversion factors. The conversion factors of common substances are given in literature (DOWEX, Ion Exchange Resins, Water Conditioning Manual, p.75). Once the exchange capacity of the resin bed is determined, it can be used to design a column packed with the resins for water softening at large scale. The required resin volume can be determined in the following equation:

Resin Volume (L) =

Feed Hardness (meq/L)X Throughput (L) 3 X10 (L/mL) Exchange Capacity (meq/mL)
(4)

where the throughput refers to the volume treated per exhausted cycle of resin.

Apparatus: Water softening in this investigation is carried by the Armfield Ion Exchange Apparatus W9. The sketch is shown below in Figure 3. The system consists of a column packed with a sulphonated styrene-based resin, a pump to supply liquids to the column, four tanks to store solutions of HCl, NaCl, test and deionized water and a sump tank. A rotameter is used to measure the flowrate of the feed. A conductivity meter is used to monitor the concentration of sodium in the effluent. An anion exchange column was set up for the experiment of demineralization but not used in this investigation.

4 A Mettler Toledo DL28 automatic titrator with an attached DP5 Phototrode is used for determination of CaCO3 concentration in the effluent. For this purpose, 100 ml plastic sample cups are provided.

Figure 3. Diagram of Ion Exchange Apparatus

5 Materials and Methods: The hardness of the test water passing through the ion exchange column is determined by titrating the effluent of the W9 Ion Exchange apparatus with a complexometric reaction. (Appendix A). The concentration of sodium ions [Na+] in solution is measured by the conductivity of the collected effluent. The required chemicals are: Ammonia buffer ~pH10 Calcium chloride dihydrate Sodium chloride pH 4, 7, & 10 buffer solutions Disodium ethylenediamine-tetraacetic acid dihydrate (EDTA) solution 0.01 M Calmagite 1% solution indicator

Procedure: A. Adding Cation Resin to the Column 1. Drain the column by first placing a waste vessel at valve 10, then opening valves 6 and 10 Remove the cation column by undoing the plastic holders on each end of the column. The column pulls out towards you and has no catches. Fill the cation column to ~300 mm of cationic resin (golden-brown colored granules). Replace the column and close valves 6 and 10

2.

3.

4. B.

Regenerate the Cationic Resin This may already be done for you, check with your TA Regeneration is required at the beginning of the experiment to ensure that the cation column has the requisite amount of Na+ ions. You are assuming that the column is depleted. For apparatus configuration see Data Sheet I, Figure 1c. 1. Select Tank B, open valves 2 and 12 turn on the main switch.

2. 3.

Add 30 g of salt to a beaker. Add RO water. Set the flow meter to 20 -50 mL/min and add the salt to the column. Continue until the conductivity reaches 1.1 x 10-2 Siemens for three minutes or all the salt has been placed in the column. This means that the column has reached the saturation point and has an excess of Na+ ions. Select Tank D and flush the column for 5 minutes at 70 ml/min. Close all valves afterwards.

3. 4. C.

Fluidizing the Resin Bed The Resin is pre-regenerated with excess sodium. Backwashing ensures that the remaining regeneration solution and debris from the last experimental run are washed out of the column. Plus it expands the resin beads so that no air pockets remain in the resin bed. For apparatus configuration see Data Sheet I (Page 9 of this manual), Figure 1b. 1. 2. 3. Make sure all valves are closed. Open valves 3 and 6. Select Tank D and turn on the pump, then backwash the cation column at a flow rate of 50-70 ml/min for 5 minutes.
Large air bubbles can be gotten rid of by closing valve 6 and opening 12 until the water has reached the top of the column. Then close 12 and re-open 6. Repeat if necessary.

4.

When the air bubbles have been eliminated and the resin has settled, turn off valves 3 and 6. Measure the final depth of the resin.

5. D.

Softening of Water Sample For apparatus configuration see Data Sheet I, Figure 1d. 1. 2. 3. Select Tank C containing the test water. Open valves 2 and 10. The TA will provide the appropriate flow rate

7 4. Collect the initial 2 samples at 300-400 ml intervals, the remainder at 100400 ml intervals. Determine the hardness of each sample as per Appendix A and continue testing each sample until hardness rises above 100 mg/L as CaCO3.

5.

E.

Shutdown 1. 2. 3. Select Tank D and flush the column at max flow for 5 minutes Turn off the pump, open valve 10 and completely drain the resin column. Rinse the beakers and equipment with RO water.

Data Analysis: a) Plot the hardness as CaCO3 concentration (mg/L) against effluent volume (L). Identify the breakthrough point. Determine the total amount of CaCO3 (mg) removed by the column up to the breakthrough point. b) Calculate the exchange capacity (meq/mL). c) Design a column (area and height) to reduce the hardness of 10,000 L of water to 100 mg/L of CaCO3. The initial hardness of water is the same as your experimental. Keep the height-to-diameter ratio of the wet resin bed the same as that of the resin column used in this experiment. Provide brief discussion on your design results including the feasibility of using one column and one exhausted cycle to complete the task. Hint: you need to first determine the required resin volume for this project. A safety factor should be applied to the exchange capacity figure to compensate for non-ideal operating conditions and resin aging on a working plant. Typical safety margin is 5% for cation resins. Column sizing should be adjusted to allow for resin expansion if backwashing is performed (80100% of the settled resin bed height) and resin swelling during service, approximately 5-8% for strong acid cation resin. Suggestion: Determine the hardness of the untreated test water at the beginning of the experiment. (5 ml sample)

8 Data Sheet I Configuration of Ion Exchange Apparatus

Appendix A
Complexometric Titration for the Determination of Water Hardness Titration Procedure Water Hardness Titration Disodium Ethylenediamine-tetraacetic acid dihydrate (EDTA or Na2H2Y2H2O) forms a chelated soluble complex when added to a solution of certain metal cations. If a small amount of dye (Calmagite) is added to a solution containing calcium and magnesium ions at a pH of 10 1, the solution becomes wine red due to the MgIn- formation. If EDTA is added as a titrant, the calcium and magnesium will become complexed. The calcium will be complexed out first as it has a larger formation constant with EDTA than magnesium. When all of the calcium ions have been complexed with EDTA, the trace amount of magnesium ions in the buffer will react. Once the trace amount of magnesium is complexed, the solution will change to a blue. The addition of the trace amount of magnesium is required for the complexometric titration and eliminates the need for a blank correction titration. pH is very important in this experiment as having a higher value than 10.5 will precipitate out CaCO3 or Mg(OH)2 immediately. However, even at a pH of 10 Ca2+ will precipitate out eventually. Thus, a maximum of 5 minutes from the addition of the buffer solution should be observed, to prevent interference from Calcium (III) hydroxide precipitation. Mettler Toledo DL28 with Phototrode DP5 A Mettler Toledo DL28 auto-titrator is used for the titrations. The main switch is in the back. The Phototrode DP5 allows for an automatic titration based on a colorimetric endpoint. Procedure: 1. 2. 3. 4. Take 10-25 mL of collected sample then add calgomite and buffer.. Press F3 to reset the display, if needed. Press 100, OK The end point is dark blue (24 mV) or 50 mL max EDTA Dispose of all solutions in the waste container provided.

Calculation of Hardness: Ideally, 1 mL EDTA used is equivalent to 1 mg CaCO3 titrated.

10

Volume of EDTA Added (mL) x Correction Factor x 1000 mL/L = mg/L CaCO 3 as hardness Volume of Water Sample (mL)
The correction factor will be provided by the Lab Demonstrator. Example 1 If 9.5 mL of EDTA is added to 25 mL of sample and there is a correction factor of 0.909: 9.5 mL x 0.909 x 1000 = 345.4 mg/L CaCO3 as hardness 25 mL

11 References: Armfield Instruction Manual. 2000. Ion Exchange Apparatus W9. Issue 14. WO014461. Dowex, 2007. Water Condition Manual A Practical Handbook for Engineers and Chemists. Dow Liquid Separations. http://www.reskem.com/pages/resinpdfs.php. Bailey, S. J., et al. 2003. Standard Test Method for Hardness in Water, D1126-02. Annual Book of ASTM Standards, Vol 11.01. ASTM International, West Conshohocken, PA. Pg 98-101. Frason, M. 2005. 2340C EDTA Titrimetric Method. Standard Methods for the Examination of Water and Wastewater. 21st Ed. American Public Health Association, Washington D.C. Pg 2-37 2-39. Harris, D. 2003. EDTA Determination of Total Water Hardness. Quantitative Chemical Analysis. 6th Ed. W.H. Freeman, New York. Pg. 259-267, 272-277.