1. Chapter 5 Ion Exchange

2. Lecture Outline  Uses  Fundamental Concepts  Process Operation  Practice  Operation and Maintenance

3. Uses  Both in water and wastewater treatment  Softening  Demineralization  Ammonia removal  Removal of metals  Concentration of radionuclides

5. Fundamental Concepts  A reversible chemical reaction wherein an ion from solution is exchanged for a similarly charged ion attached to an immobile solid particle. Courtesy of Astom Corp: http://www.astom-corp.jp/images/en-fig-02.jpg

6. Ion exchange materials http://ethesis.helsinki.fi/julkaisut/mat/kemia/vk/leinonen/fig2.gif http://en.wikivisual.com/images/e/e8/ZeolitesUSGOV.jpg Particles can be a natural material, soils, zeolites or synthetic polymers produced specifically for this purpose.

7. Ion exchange materials

8. Ion Exchange Operation http://www.ianrpubs.unl.edu/live/g1491/build/g1491.pdf

9. Ion Exchange Operation Breakpoint = Breakthrough arbitrarily set based on design criteria C exhaustion = 0.95 C o

12. Operation

15. Types of resins  Strong acid: Ca(HCO 3 ) 2 + 2 SO 3 -Na +  (SO 3 ) 2 Ca 2+ + 2NaHCO 3  Weak acid: Ca(HCO 3 ) 2 + 2 COO-H +  (COO) 2 Ca 2+ + 2H 2 CO 3  Strong base: NR 3 + -OH - + Cl -  NR 3 + -Cl + OH -  Weak base: NH 2 + HCl  NH 2 ·HCl

21. Fundamental Concepts  General equilibrium reaction: n[R-A + ] + B n+  nR-B n+ +nA +  Apparent equilibrium constant or selectivity coefficient Courtesy of Astom Corp: http://www.astom-corp.jp/images/en-fig-02.jpg

31. Selectivity coefficient  General equilibrium reaction: n[R - A + ] + B n+  nR-B n+ +nA +  Problem is that while activities of solution concentrations can be approximated with molar concentrations, the resin concentrations are very high. Valid for narrow conc. Ranges. Courtesy of Astom Corp: http://www.astom-corp.jp/images/en-fig-02.jpg

32. Selectivity  Preference of the ion exchange material for one ion over another  Selectivity coefficient where S and R denote the solution and resin concentrations, respectively.  Q s = 1 no preference for A + over B n+  Qs > 1 B n+ is preferred over A +  Qs < 1 A + is preferred over B n+

33. Selectivity  Ions of higher valence preferred over ones with lower valence  Fe 3+ >Mg 2+ >Na + ; PO 4 3- >SO 4 2- >NO 3 -  Increases with decreasing hydrated radius and increasing atomic number Ca 2+ >Mg 2+ >Be 2+ ; K + >Na + >Li +  Decreases with increasing crosslinking (for large molecules)

34. Selectivity  Advantages of choosing a resin with high affinity for the targeted ion: Sharp breakthrough curve Shorter ion exchange column Greater flow rate applied to column  Disadvantages Higher regenerant concentration required

35. Ion exchange capacity  Total capacity (theoretical or ultimate capacity): measure of the total capacity of ions which theoretically can be exchanged per unit mass or per unit volume of resin (meq/L, eq/L, meq/g)  Operating capacity: measure of the useful capacity of the resin for exchanging ions from a solution flowing through a fixed bed of resin particles under specified conditions.

36. Operating capacity  Depends on Flowrate through column Bed depth Selectivity coefficient Exchange ion size Amount of regenerant used (extent of regeneration) Composition and concentration of feed solutions Temperature Desired quality of product water

37. Limiting Operating Capacity  Monovalent-divalent exchange

38. Limiting Operating Capacity  Monovalent-monovalent exchange

39. Example 1  Nitrate is to be removed by ion exchange from a water containing a chloride concentration of 3.0 meq/L and nitrate concentration of 1.5 meq/L. A strong base anion resin is to be used. The total resin capacity is 1.3 eq/L and. What is the limiting operating capacity of the resin?

40. Example 2  Nitrate is to be removed by ion exchange from a water containing a sulfate concentration of 3.0 meq/L and nitrate concentration of 1.5 meq/L. A strong base anion resin is to be used. The total resin capacity is 1.3 eq/L and. What is the limiting operating capacity of the resin?

41. Water softening  Preferable to lime-soda ash softening when Raw water contains low color and turbidity (no pretreatment required) Hardness is largely not associated with alkalinity (substantial NCH) Variable hardness levels (process control difficult)

42. Water softening: design criteria  Surface loading rate: 400 -800 m 3 /d · m 2 of bed cross-sectional area  Backwash rate: Want 50 to 75% expansion of the resin bed. Rate is dependent on density of the resin and temperature of the backwash water.  Regeneration: For strong acid and strong base resins: 2 to 10% solutions, weak acid and base resins: 1 to 5% solutions.

43. Water softening: design criteria  Regeneration: Minimum contact time of 30 min Flow rate of 60 -120 m 3 /d · m 2 of cross sectional area Quantity of resin depends on manufacturer specifications  Rinsing to remove excess regenerant: 2 to 5 times the bed volume (BV) of resin  Bed depth: minimum of 0.9 m  Freeboard: Length of 50 to 75% of the bed depth

44. Example 3 Design a fixed-bed ion exchange column to soften 20 MGD of water at a temperature of 10 C. The raw water has a total hardness of 400 mg/L as CaCO 3. It must be softened to 100 mg/L as CaCO 3. The maximum column diameter is to be 10 ft. Use a Duolite C-20 resin. Sodium chloride is to be used to regenerate the exhausted resin and the resin is available in the sodium form.

45. Example 3  Softening capacity With 10 lb/ft 3 salt as regenerant: resin capacity is 1.35 to 1.55 eq/L  Leakage: Maximum of 1% of untreated water hardness  Bed depth: 30 to 36 in  Back wash bed expansion 50% or more. The required backwash flowrate varies with temperature (see Figure)

46. Example 3 Operating conditions (from manufacturer) OperationRateSolutionTime (min) Service2-5 gpm/ft 3 Water--- BackwashSee FigureWater5 to 15 Regeneration0.2-1 gpm/ft 3 10-20% NaCl30 to 60 Rinse1-5 gpm/ft 3 Water10 to 40

47. Example 3

48. Outcomes Based on this lecture and Chapter 5, you should be able to  Describe the physical and chemical, phenomena that underlie the design and operation of ion exchange systems  Design individual unit processes and operations used in environmental engineering