WRF Webcast Hexavalent Chromium Treatment Testing with New Ion Exchange Resins and Reduction/Coagulation/Microfiltration

Transcription

1 No part of this presentation may be copied, reproduced, or otherwise utilized without permission. WRF Webcast Hexavalent Chromium Treatment Testing with New Ion Exchange Resins and Reduction/Coagulation/Microfiltration May 12, 2015

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3 Webcast Agenda WRF Introduction Hsiao-wen Chen Cr(VI) Research Program in Glendale, California Donald Froelich Glendale, California, Findings Nicole Blute o WRF Project 4423 o WRF Project 4365 California Water Services Company s Implementation of Research Tarrah Henrie Q & A

4 Co-Funding Utilities Project 4365, Microfiltration in the RCF Process for Hexavalent Chromium Removal From Drinking Water Glendale Water & Power Project 4423 Assessment of Single-Pass Ion Exchange and Adsorptive Media for Hexavalent Chromium Removal from Drinking Water California Water Service Company Glendale Water & Power Tailored Collaboration Program:

5 Outline Introduction to the Research Program Glendale California Findings WRF 4423 WRF 4365 California Water Service Company s Implementation of Research

6 Research in Water utility leaders Glendale, California recommended two technologies LADWP MWD General call to providers of treatment systems EBMUD with potential to remove Cr6 from water UCLA Utah State Univ. U. Colorado CDPH USEPA ($400,000) ($750,000) ($9,000,000) Phase to technologies tested at university labs. Led by LADWP Phase to technologies tested at small flow rates. Led by Glendale Phase to treatment facilities serving water to meet City Council chromium 6 goal of 5 ppb. Led by Glendale

7 Project Advisory Committee Dr. Bruce Macler, U.S. Environmental Protection Agency Mr. Eugene Leung, California Department of Public Health Dr. Sun Liang, Metropolitan Water District of Southern California Dr. Pankaj Parekh, Los Angeles Department of Water and Power Dr. Rick Sakaji, East Bay Municipal Utility District Dr. Issam Najm, WQTS (WRF 4365)

8 Research Team City of Glendale Mr. Michael De Ghetto (Assistant General Manager) Mr. Donald Froelich, PE (Research Program Project Manager) Mr. Leighton Fong, PE (Project Engineer) Mr. Peter Kavounas, PE (Former Principal Investigator) Mr. Ramon Abueg, PE (Assistant General Manager) Consulting Team Hazen and Sawyer Dr. Nicole Blute, PE (Principal Investigator) Dr. Ying Wu, PE CDM-Smith Mr. Charles Cron (Plant Operations Manager) Mr. Dan Hutton California Water Service Company Ms. Tarrah Henrie (Co-Principal Investigator) Ms. Shreya Ramesh (Cal Water District WQ Manager) Mr. Frank Vallejo (Cal Water District Superintendent) ARCADIS Ms. Katie Porter, PE Mr. Greg Imamura Dr. Yanguang Song, PE Dr. Michael J. McGuire, PE

9 Funding Partners San Fernando Valley Industry Group

10 Summary of Overall Research Program The research is a success. For more than three years, Glendale has proven treatment of groundwater with WBA and RCF to less than the 5 ppb treatment goal. Communicating with the public and other water utilities is important as regulations are implemented. California Department of Public Health based the draft MCL on Glendale s research showing the feasibility and cost of Chromium-6 removal from drinking water.

11 Summary of Overall Research Program Other researchers have relied on Glendale s research and actual operations, confirming its use in other groundwater basins and refining the processes. Glendale has operated the treatment facilities for over three years, reliably serving water to its customers at a quality more strict than the proposed state limit.

12 Outline Introduction to the Research Program Glendale California Findings WRF 4423 WRF 4365

13 Chromium Regulations Cr(VI) Cr(III) Total Cr New California MCL No Federal MCL yet California MCL 50 ppb Federal MCL 100 ppb

14 Options for Achieving Cr6 Rule Compliance Non-treatment Use of other sources Blending with non-impaired sources Treatment Best Available Technologies (BATs) include: Ion exchange Coagulation Filtration (with upstream reduction) Reverse Osmosis

15 Best Available Technologies Weak- Base Anion Exchange (WBA) Strong- Base Anion Exchange (SBA) Reduction Coagulation Filtration (RCF or RCMF) Reverse Osmosis (RO)

16 Research Needs Identified When Projects Began Alternate WBA resins SBA testing in different water qualities Adsorptive media testing RCF optimization to improve Cr(VI) removal, reduce footprint and cost Operational requirements of treatment options

17 New Studies WBA SBA RCF/RCMF Adsorptive media Tests 3 resins 3 resins, no regeneration Water quality Glendale water Glendale and Livermore water MF, lower reduction time, chlorination Glendale water 1 media Glendale water Special tests Formaldehyde leaching from one resin Pilot and demonstration

18 Weak Base Anion (WBA) Process Results Summary and Conclusions

19 WBA Process Simple, once-through treatment High Cr(VI) capacity One proven resin has formaldehyde leaching Two new resins are certified to meet NSF/ANSI 61 standards CO 2 or acid Raw water Treated water Bag filters Resin vessels Aeration or Caustic

20 WBA Process Bed Volume = Gallons of Water Treated Gallons of Resin Example: 425 gpm system containing 180 cf of resin in a vessel results in 455 BV per day (1 year is approximately 166,000 BV at 100% utilization)

21 WBA Resins Manufacturer Product Name Matrix Functional Group Dow PWA7* Phenol-formaldehyde polycondensate Secondary amine Purolite S106 Epoxy polyamine Polyamine ResinTech SIR-700 Epoxy polyamine Proprietary amine *Full scale operations for more than 3 years

22 Hexavalent Chromium (µg/l) PWA7 Tested in Two Water Qualities 60 Influent (Glendale) PWA7 with CO2 (Glendale) Bed Volumes

23 Hexavalent Chromium (µg/l) PWA7 Tested in Two Water Qualities Influent (Livermore) PWA7 with HCl (Livermore) Influent (Glendale) PWA7 with CO2 (Glendale) Increased resin life at Livermore possibly due to lower Cr(VI) and/or other water quality parameters 10 0 Bed Volumes

24 Hexavalent Chromium (µg/l) Cr(VI) Initial Leakage Verification - ResinTech ResinTech SIR700 (2006) Influent (2013) Influent (2012) Cr(VI) initial leakage still occurred with solid ph control Bed Volumes

25 Hexavalent Chromium (µg/l) Cr(VI) Initial Leakage Verification - ResinTech ResinTech SIR700 (2013) ResinTech SIR700 (2012) ResinTech SIR700 (2006) Influent (2013) Influent (2012) Cr(VI) initial leakage still occurred with solid ph control Bed Volumes

26 Hexavalent Chromium (µg/l) Cr(VI) Initial Leakage Verification Purolite resin Cr(VI) initial leakage still occurred with solid ph control Purolite S106 (2013) Purolite S106 (2012) Influent (2013) Influent (2012) Bed Volumes

27 Hexavalent Chromium (µg/l) Cr(VI) Leakage Mitigated by Lead-Lag Configuration 30 Raw water Lead column effluent Lag column effluent ,000 6,000 9,000 12,000 15,000 18,000 21,000 Bed Volumes for Lead Column

28 Constituents Leaching at Startup ResinTech SIR-700 Purolite S106 DOW PWA7 No formaldehyde leaching Nitrosamines, VOCs, SVOCs, aldehydes and ketones non-detect or at very low levels Low formaldehyde level (7.2 ppb) below California Notification Level Nitrosamines, VOCs, SVOCs, aldehydes and ketones non-detect or at very low levels Using a new preconditioning procedure, the manufacturer developed a method that decreased formaldehyde below the Notification Level of 100 µg/l in California

29 Summary and Conclusions (WBA) High capacity of new resins Lead/lag mitigates initial leakage Less leaching from new resins Extended time to breakthrough for lower Cr(VI) water All spent resins are likely non-rcra California hazardous and TENORM

30 Follow up Other WBA Studies WRF 4450 WRF 4449 Testing of WBA in 10 other water qualities Testing of WBA in two wells at CVWD Similarly long time to breakthrough

31 SBA Process Results Summary and Conclusions

32 SBA More complex treatment with regeneration Brine residuals are key cost and operational driver Capacity of resins required testing

33 SBA Process More complex treatment with regeneration Brine tank Brine residuals are key cost and operational driver Capacity of resins required testing Raw water Resin vessels Bag filters Treated water Spent brine and slow rinse to treatment Fast rinse to sewer

34 SBA Resins Manufacturer Product Name Type Matrix Functional Group Dow SAR Type II Styrene-DVB, gel Dimethylethanol amine Purolite A600E/9149 Type I Polystyrene crosslinked with divinylbenzene, gel Quaternary ammonium Envirogen HyperSorb A3-2-1 Type I Chlormethylated copolymer of styrene and divinylbenzene Trimethylamine

35 Hexavalent Chromium (µg/l) Cr(VI) Breakthrough Average Influent Dow SAR Purolite A600E/9149 Envirogen HyperSorb A Glendale Sulfate 111 mg/l Nitrate 8.5 mg/l N 0 Bed Volumes Short resin life for all three resins Purolite A600E/9149 and Dow SAR showed similar larger capacities, followed by Envirogen HyperSorb A3-2-1

36 Hexavalent Chromium (µg/l) Cr(VI) Breakthrough 12 Average Influent Dow SAR Envirogen HyperSorb A3-2-1 Purolite A600E/ Livermore Sulfate 55 mg/l Nitrate 10.5 mg/l N 0 Bed Volumes Longer resin performance than at Glendale because of lower Cr(VI) and sulfate concentrations

37 Constituents Leaching at Startup DOW SAR Purolite A600E/9149 Envirogen HyperSorb A3-2-1 No significant leaching of nitrosamines, VOCs, SVOCs, aldehydes and ketones No significant leaching of nitrosamines, VOCs, SVOCs, aldehydes and ketones 15 constituents detected at levels higher than raw water, including nitrosamines, VOCs, SVOCs, aldehydes and ketones Formaldehyde above CA Notification Level at Glendale, but not at Livermore

38 Summary and Conclusions (SBA) Capacity shorter than WBA for all three SBA resins at both Glendale and Livermore Livermore had higher resin capacity due to lower Cr(VI) and sulfate levels Results highlighted importance of testing new resins, as two resins lasted between 3 5 times longer than the other

39 Follow up Other SBA Studies WRF 4449 WRF 4450 WRF 4488 Testing of SBA in two wells at CVWD Additional work has looked at regeneration Testing in 10 other water qualities Testing of different variables at Soquel Creek Impact of water quality on SBA resin regeneration frequency

40 Bed Volumes Follow up Other SBA Studies SBA Bed Volumes as a Function of Sulfate 35,000 30,000 Breakthrough to greater than 2 ug/l Breakthrough to greater than 8 ug/l 25,000 20,000 15,000 10,000 5,000 0 y = x R² = y = x R² = Sulfate (mg/l)

41 Reduction/Coagulation/Filtration (RCF) Process Results Summary and Conclusions

42 RCF and RCMF Process Backwash waste Ferrous Polymer if granular media Filtration Treated Water Raw Water Reduction Oxidation of ferrous with air or chlorine Backwash

43 Reduction/Coagulation/ Filtration (RCF) Two studies: 1. Microfiltration pilot study to evaluate Cr(VI) removal using microfiltration instead of granular media filtration (WRF 4365) 2. Optimization of RCF to reduce footprint and cost by decrease reduction time and use chlorine instead of aeration (WRF 4423)

44 WRF #4365 Objectives 1) Determine the effectiveness of MF membranes for removing total Cr and Cr(VI) to the sub-µg/l levels 2) Assess whether iron fouling is problematic in direct filtration mode 3) Identify design criteria for full-scale MF in an RCMF treatment process

45 Pilot Unit Characteristics Parameter GE/Zenon Unit Pall Unit Membrane Type Submerged Polymeric Pressure Polymeric Membrane Module ZeeWeed 1000 UNA 620A Nominal Pores Size 0.02 µm (UF) 0.1 µm (MF) Membrane Material Proprietary polymer Polyvinylidenefluoride (PVDF) Membrane Area 450 ft 2 per module (One module in the pilot skid) 538 ft 2 per module (Two modules in the pilot skid) Flow Direction Outside-in Outside-in Maximum Allowable Operating Pressure -13 psi 43.5 psi

46 6/1 6/4 6/6 6/8 6/11 6/13 6/15 6/18 6/20 6/22 6/25 6/27 6/29 7/ < Hexavalent Chromium (ppb) MF Flux (gfd) Cr(VI) Removal by RCMF MF pre-treatment: 2 mg/l iron, 45-min reduction time, aeration and chlorination SP-001 Raw Water SP-603 GE Influent SP-602 PALL Effluent SP-604 GE Effluent PALL Flux GE Flux

47 6/1 6/4 6/6 6/8 6/11 6/13 6/15 6/18 6/20 6/22 6/25 6/27 6/29 7/ <1 < <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 < <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 < < Total Chromium (ppb) MF Flux (gfd) Total Cr Removal by RCMF MF pre-treatment: 2 mg/l iron, 45-min reduction time, aeration and chlorination SP-001 Raw Water SP-603 GE Influent SP-602 PALL Effluent SP-604 GE Effluent PALL Flux GE Flux

48 Summary and Conclusions (RCMF) RCMF removed total Cr to below 1 µg/l A ferrous iron dose of 2 mg/l was effective for both low and high Cr(VI) waters A small dose of chlorine protected membranes from fouling

49 RCF Optimization (Part of WRF #4423) Decrease reduction time Oxidizing ferrous using chlorination instead of aeration

50 <0.02 < < < < <0.02 <0.02 < Cr(VI) Concentration (µg/l) RCF Filter Effluent Cr(VI) Results Test conditions: 3 mg/l iron, 5-minute chlorine contact time, 24 or 72 hrs filter run 100 Test Run 1 Test Run 2 Test Run 3 Test Run Cr(III) reoxidation by chlorine occurred at times minutes reduction w/ chlorination 72 hours filter run minutes reduction w/ aeration 24 hours filter run 30 minutes reduction w/ chlorination 24 hours filter run 15 minutes reduction w/ chlorination 24 hours filter run

51 < <0.2 < Total Cr Concentration (µg/l) RCF Filter Effluent Total Cr Results Test conditions: 3 mg/l iron, 5-minute chlorine contact time, 24 or 72 hrs filter run System optimization was needed Test Run 1 Test Run 2 Test Run 3 Test Run minutes reduction w/ chlorination 72 hours filter run minutes reduction w/ aeration 24 hours filter 30 minutes reduction w/ chlorination 24 hours filter run minutes reduction w/ chlorination 24 hours filter run

52 Summary and Conclusions (RCF) Chlorination achieved effective ferrous oxidation Cr(III) reoxidation was observed some times Effective filter backwash is critical for total Cr removal

53 Follow up Other RCF Studies WRF 4450 Bench testing showing lower reduction time WRF 4516 Testing of 5 min reduction time and MF at CVWD effective Additional Glendale studies Effectiveness of lower reduction time with good chlorine mixing Investigation of MF backwash recycle

54 Additional Testing Adsorptive Media

55 Final Thoughts Market Evolution Innovation in unit processes New resins Smaller footprint Package wellhead treatment systems New technologies

56 Outline Introduction to the Research Program Glendale California Findings WRF 4423 WRF 4365 California Water Service Company s Implementation of Research

57 Way Back in 2012 Testing limited to Glendale Significantly different water quality at Cal Water

58 Cal Water Epiphany ph adjustment for WBA Very hard water Strong base ion exchange performed well Much lower sulfate and chromium 7,600 BV to breakthrough Tested as single pass

59 Subsequent Research

60 Subsequent Research 9 additional sites Purolite A600E/9149 best performer Between 10,000 and 40,000 BV Tested as regenerable

61 Hydraulic Loading Rate

62 Cl Cond, Cr Brine Waste Minimization Sulfate Return Recovered Waste Brine Recovered Rinse Heads and subheads Bulleted lists Text Images and videos 90,000 80,000 70,000 60,000 50,000 Cond (ms/cm) Cr tot (mg/l) Cl (mg/l) , , , , Projected waste volume with sulfate return = < 0.5 BV

63 Construction

64 Subsequent RCF Research Existing Fe and Mn treatment 1 and 2 min. reaction times 1, 2 and 3 mg/l ferrous doses

65 Cr(VI) (mg/l) Results Cr(VI) Inf, 1 min, 2 mg/l-fe Cr(VI) Inf, 5 min, 2 mg/l-fe Cr(VI) Eff, 1 min, 2 mg/l-fe Cr(VI) Eff, 5 min, 2 mg/l Fe Elapsed Filter Run Time (min)

66 Planned Research WRF Project 4456 Cost-Effective Cr(VI) Residuals Management Strategies

67 Cal Water Acknowledgments Cal Water Employees: Robert Thompson Shreya Ramesh Nelson Lui UC Davis: Dr. Jeannie Darby Lifei Huang

68 Useful Links Project 4365: Project 4423: Webcasts on Demand: Cr(VI) resources: =1&k=Hexavalent%20Chromium

69 Thank You Michael De Ghetto, Don Froelich, Nicole Blute, Tarrah Henrie, Hsiao-wen Chen, Project 4365 Alice Fulmer, Project 4423 For more information visit

70 Questions and Answers