Surfactant Enhanced In Situ Chemical Oxidation (S ISCO )

Transcription

1 Surfactant Enhanced In Situ Chemical Oxidation (S ISCO ) Presented by Absorbance Free Radical Screening Assay 2 B Wavelength (nm) Day 0 Day 1 Day 3 Day 7 George E. Hoag, Ph.D. Senior Vice President VeruTEK Technologies, Inc. Bloomfield, Connecticut USA 8 Marts 2010

2 Presentation Outline Purpose Balance Scientific Fundamentals with Applications Introduction Overview of Surfactant Behavior Reactions of Surfactants and Oxidants Laboratory Scale Results Full Scale Applications Conclusions

3 Surfactant Enhanced In Situ Chemical Oxidation The focus of S ISCO is to treat Light and Dense Non Aqueous Phase Liquids (NAPLs) & Sorbed Phase Contaminants Chlorinated Solvents, Hydrocarbons, Coal Tars, Fuels Pesticides, Hydraulic Oils, Heat Exchange Fluids, PCBs Coupled Subsurface Coelution of Cosolvent/Surfactants to Solubilize and Free Radical Oxidants to Destroy NAPLs and Sorbed Residuals Also Applicable for Ex Situ, Construction Materials, Oily Wastewater, Oil Drilling Cuttings

4 Purpose of S ISCO Chemical Oxidation Reactions are Basically Aqueous Phase Reactions Immiscible Organic Liquids by Definition Do Not Exist in the Aqueous Phase Aqueous Solubilities of NAPLs Varies Depending on Hydrophobicities and Structure For ISCO to be Effective on NAPLs and Source Areas Need to Increase the Aqueous Solubility of Organic Compounds Surfactants Increase Solubility of NAPLs in Water Benzene Tetrachloroethylene Naphthalene Pyrene Benzo[a]pyrene 2,2',4,4',5,5' Hexachlorobiphenyl 1,780 mg/l 150 mg/l 31 mg/l 0.13 mg/l mg/l mg/l

5 Key Factors to Make S ISCO Work Emulsify/Solubilize NAPL Phase and Desorb Source Zone Contaminants using Surfactants and Cosolvents Make Free Radicals by Activating/Catalyzing Oxidants Oxidize Solubilized Contaminants with Free Radicals Do The Above by Simultaneous Subsurface Injections of Surfactants, Oxidants and Catalysts This is Called Reactive Transport or Co Elution Monitor Surfactants, Oxidants and Catalysts During Application

6 S ISCO TM Technology Ingredients Injected S-ISCOS Chemical Mixture Nonionic Surfactant Water Soluble Head Oil Soluble Tail DNAPL Contaminated Soil DNAPL Saturated Soil Zone Sand Particle DNAPL Treated Soil and Groundwater Remediated Clean Soil Molecular Level Process Level Oxidant Surfactant Mixture Nonionic Surfactant + DNAPL DNAPL Solubilization And DNAPL Destruction Zone = Solubilized DNAPL + Chemical Oxidant = Destroyed Contaminant + Destroyed Surfactant

7 Chlorinated Solvent DNAPL Dyed with Suidan IV and Complete Dissolution in VeruSOL 3 Dissolved DNAPL DNAPL

8 TCE Column Experiment ISCO vs. S ISCO Alkaline Persulfate Treatment 14 Days S ISCO with Alkaline Persulfate Treatment 14 Days ISCO S ISCO TM

9 Australia Chlorinated DNAPL Soil Column Experiment Column 1 ISCO Alkaline Persulfate Column 2 S ISCO with Alkaline Persulfate (DNAPL dyed red with Suidan IV) Time = 0 days Prior to Injections Time = 2 days Time = 5 days

10 Surfactants Surfactants are Surface Active Agents that Lower the Surface Tension of a Liquid and Decrease the Interfacial Tension between Two Liquids Surfactants are Amphiphilic they have Hydrophobic Groups (tails) and Hydrophilic Groups (heads) Surfactants Form Micelles Oil in Water Emulsions Water in Oil Emulsions Used to Solubilize Oils Used to Mobilize Oils Copyright VeruTEK 2010 Copyright VeruTEK 2010

11 Winsor Type Lexicon Winsor Type I Micelles have a Hydrophilic Exterior and a Hydrophobic Interior Water is the Continuous Phase and the Oil (NAPL) is Inside the Micelle Example Milk This is What VeruTEK Uses Oil Loving Hydrophobic Tail Hydrophilic Head Water Loving Winsor Type II Micelles have Hydrophobic Exterior and a Hydrophilic Interior Oil is the Continuous Phase and Water is Inside the Micelle Example Butter Winsor Type III Middle Phase Emulsion Coinciding with Ultralow IFT Causing a Third Mobile Phase

12 Surfactants That Make Oil in Water Emulsions Have Specific Balance of Hydrophilic and Hydrophobic Groups Termed Hydrophile Lipophile Balance (HLB) Are Non Ionic (not charged) Do Not Sorb on Soils Can be Made from Edible Oils Can be Food Grade Micelles can be in the Nanoemulsion Size Range Cleaning Movie

13 Our Premier Formulation VeruSOL 3 Mixture of Ethoxylated Castor Oil, Coconut Oils and Citrus Terpenes and Other Minor Compounds Surfactant and Cosolvent Mixture Enables Excellent Solubilization of All Petroleum Distillates, Industrial Solvents, MGP and Creosote DNAPLs, and Tar Sands U.S. FDA Generally Recognized as Safe (GRAS) Components Found in Fruit Juice, Various Foods and Consumer Care Products such as Cosmetics, Fragrances, Air Deodorizers These Plant Based Surfactants are Nonionic

14 Free Radical Production Hydrogen Peroxide and Sodium Persulfate Generate Free Radicals but Requires Activation or Catalysis Activation/Catalysis of Peroxide and Persulfate Essential No Activation = No Free Radicals = No Destruction Fe EDTA, Fe EDDS and other Fe Chelates Green Synthesized Nanoscale Zero Valent Iron (2 joint EPA/VeruTEK Patents Pending) Iron TAML Organometallic Catalyst not a chelate (Exclusive Supply Agreement with GreenOX Catalysts) Microemulsion Catalysis, ph, Heat and Peroxide Persulfate

15 Free Radical Production

16 Free Radical ISSUES Hydrogen Peroxide Unless Stabilized Well it Decomposes Quickly (Hours to a Day) in Soil and Groundwater Hydrogen Peroxide Infrequently Monitored in Groundwater During Remediation Is Hydrogen Peroxide Really There? Must Be Catalyzed/Activated to Make Free Radicals Is the Catalyst Really There? Sodium Persulfate Decomposes Slowly In Soils Weeks to Months Persulfate Infrequently Monitored in Groundwater During Remediation Is it Really There? Must Be Catalyzed/Activated to Make Free Radicals Is the Catalyst Really There? Does the Catalyst Last as Long as Persulfate Problem Solved! Don t Be Fooled Again! Now You Can Easily Measure the Presence of Free Radicals At Sites Where Advanced Oxidation Process are the Operative Destruction Method

17 New Method to Measure Presence of Free Radicals in Groundwater Probe Compound Only Degrades by Free Radical Pathway ph<6 ph=7 ph>7.6 Bromothymol Blue Acidic ph Range

18 Sodium Persulfate Generated Free Radicals Measured with Bromothymol Blue

19 Bromothymol Blue Used as a Probe Compound to Measure Mixture Stability of Persulfate with Na EDTA, Fe EDTA and Alkaline Conditions With and Without VeruSOL 3 Na-EDTA Fe-EDTA Alkaline

20 Bromothymol Blue Used as a Probe Compound to Measure Stabilization of Alkaline Persulfate with VeruSOL 3 VS-3 = 0 VS-3 = 5 VS-3 = 10 VS-3 = 10 (g/l) Control VS-3 = 20 g/l SP = 0

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22 MGP DNAPL VeruSOL 3 TM Solubilization Dissolved DNAPL DNAPL MGP DNAPL Dyed with Suidan IV and Near Complete Dissolution in VeruSOL TM

23 Microemulsion of Solubilized MGP DNAPL Typical Concentration Range of Operations Does Not Mobilize MGP DNAPL Even at Concentrations Greater Than Applied in Field

24 VeruSOL 3 TM Effect on Interfacial Tension As the VeruSOL 3 Dose is Increased, the Interfacial Tension Between the Two Liquids Decreases

25 VeruSOL 3 TM MGP Solubility As the VeruSOL 3 Dose is Increased, the MGP DNAPL Solubility Increases Because of Creating Oil in Water Emulsions

26 MGP Emulsion Particle Size As the VeruSOL 3 Dose is Increased, the MGP Emulsion Particle Size Decreases Inflection at Critical Micelle Concentration

27 Chlorinated Solvent DNAPL Dyed with Suidan IV and Complete Dissolution in VeruSOL 3 Dissolved DNAPL DNAPL

28 Chlorinated Hydrocarbon Dissolution Example Effect of VeruSOL TM on DNAPL Solubilization (Concentration VeruSOL TM vs. Solubilized VOCs) Carbon Tetrachloride (CTC) Tetrachloroethene (PCE) Hexachlorobutadiene (HCBD) Total VOCs 40 Solubilized Contaminants (g/l) VeruSOL TM (g/l)

29 VOC Chlorinated Hydrocarbon Dissolution Example Solubility Enhancement log 0.8 g/l VeruSOL Solubility Enhancement 4.2 g/l g/l 83.3 g/l VeruSOL CTC PCE HCBD hr 8 hr 24 hr ß i = C w,i, (VS) /C w,i

30 Creosote DNAPL Solubilization 450, x Enhancement 400, , x Enhancement VOCs and SVOCs COC concentration (ug/l) 300, , , , x Enhancement 7.83x Enhancement 156, , ,640 SVOCs VOCs 100,000 50, ,500 14,484 13,600 14,800 63,120 56,000 68,320 T2-I1 (Control) T2-I2 (1.0 g/l VeruSOL-3) T2-I3 (2.5 g/l VeruSOL-3) T2-I4 (5.0 g/l VeruSOL-3) T2-I5 (10 g/l VeruSOL-3) TPH 8,000 7,000 6,380 7,598 TPH (ppm) 6,000 5,000 4,000 3,000 2,000 1, g TPH Dissolved/1.0 g VeruSOL , x Enhancement 3, x Enhancement 54.5x Enhancement 64.9x Enhancement T2-I1 (Control) T2-I2 (1.0 g/l VeruSOL-3) T2-I3 (2.5 g/l VeruSOL-3) T2-I4 (5.0 g/l VeruSOL-3) T2-I5 (10 g/l VeruSOL-3)

31 Solubilization and Oxidation of Chlorinated DNAPL Alkaline Persulfate

32 Oxidation of Emulsified/Solubilized NAPLs

33 Activated Persulfate Oxidation of Solubilized MGP DNAPL Contaminant Concentration (mg/l) TPH Solubilization and Oxidation of MGP DNAPL with VeruSOL TM -1 TPH SOLUBILIZATION T2-2 T2-4 T2-6 T2-2 VS-1 VS-1 VS-1 (oxidation) 2 g/l 10 g/l 50 g/l TPH Percent Removal OXIDATION T2-4 (oxidation) T2-6 (oxidation) Notes: (1) Solubilized TPH concentration were estimated based on estimates relationship between T-64 concentration and TPH solubilized from Test 1. (2) Oxidized with 200 g/l sodium persulfate activated with ph>12 using NaOH. 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Percent Removal (%).

34 Large Landfill CVOC Site Soil Column Test Results Soil Column Experiments COC Destruction of Treated Soils 350, , , , ,200 COC Concentration (ug/l) 200, , ,713 VOCs SVOCs Arsenic 100,000 89,120 50,000 0 Initial Soil 27,590 17,648 5,900 10,125 1,159 4,550 4,250 3,550 Column 1 30 Day Treated Soil Column Soil Column 2 14 Day Treated Soil Column 3 14 Day Treated Soil Column 1 Sodium Persulfate 50 g/l, ph> 11, VeruSOL 3 5 g/l, 10oC, 30 days Column 2 Sodium Persulfate 100 g/l, ph> 11, VeruSOL 3 5 g/l, 10oC, 14 days Column 3 Sodium Persulfate 100 g/l, ph> 8, Fe TAML 0.1 µmm VeruSOL 3 5 g/l, 14 days All Columns run at 10 o C

35 Large Landfill CVOC Site Soil Column Test Results 120,000 Soil Column Experiments Destruction of Target Compounds 100, ,000 COC Concentration (ug/l) 80,000 60,000 40,000 79,000 44,000 41,000 20, ,000 Initial Soil 6,700 14,050 10,350 5,950 5,500 3,350 5,000 2, ,500 2, ,900 Column 1 30 Day Treated Soil Column 2 14 Day Treated Soil Column 3 14 Day Treated Soil Column Soil Toluene Total Xylenes TCE PCE Hexachlorobenzene Naphthalene

36 Column MGP S ISCO Treatment Before After TPH (mg/kg) 70,000 60,000 50,000 40,000 30,000 20,000 10, ,250 Column 100 SP 20 g/l + VSOL 5 g/l + Fe-EDTA 250 mg/l 58, % 99.9% 99.9% Destruction Destruction Destruction 5, Column 101 SP 50 g/l + VSOL 10 g/l + Fe-EDTA 250 mg/l Column 102 SP 10 g/l + VSOL 2 g/l + Fe-EDTA 250 mg/l Notes: 1)DNAPL spiked soil was prepared using hexane to dissolve the DNAPL and uniformly contaminate the soil, followed by evaporation of the hexane prior to treatment. 2)1kg of AFS sand (200 µ to 300 µ particle size) was used in each of Columns 100 and )1kg of AFS sand was used in Column )5 g MGP DNAPL was dissolved in 100 ml hexane for Columns 100 and 101 and 1 g MGP DNAPL was dissolved in 100 ml hexane for Column 102 5)For each column the DNAPL-hexane mixture was poured into the sand and periodically mixed in a pan and allowed to evaporate over a 24 hour period 6)Each column was then packed in the columns in small lifts by place the sand in standing water then vibrating to consolidate sand. This procedure was repeated until 1kg was placed in the column 7)Columns effluents were sampled daily (complete composite) for persulfate, ph, ORP, conductivity, turbidity, flow rate, interfacial tension and TPH 8)After completion of tests each column was sacrificed, composited into three aliquots (top, middle and bottom) and analyze for TPH 9)Experiments were run for 28 days 10)Flow rates for each column were 0.5 ml/min

37 Full Scale MGP Gasworks Site

38 Full Scale MGP Gasworks Site Gasworks Contamination at Large Site This Portion of Site Received Process Wastewater and Coal Tar Contamination from 1.2 m to ~ 9.0 m Below Ground Surface over 0.33 ha Extensive Coal Tar Saturated Soils Present in Lenses (Shallower, Deeper and Upgradient Contamination Discovered After Project Started) Fine to Medium Sand 1.0 m to Water Table 21 m to Aquitard Required Targeting Upper 10 m

39 Full Scale MGP Gasworks Site Injected Chemicals May 2009 to November ,000 kg Sodium Persulfate 45,000 kg Fe EDTA 13,000 kg VeruSOL 3 42 Monitoring Wells in 18 Clusters 12 Injection Wells Typically 15 g/l to 25 g/l Persulfate, <5 g/l VeruSOL 3 and 250 mg/l of Fe EDTA as Fe Interim Soil Samples Taken After 75% of Chemical Injected (10/09) (Represents 50% of S ISCO Chemicals Reacted) 56,000 Metric Tons Soils (29,250 m 3 ) Treated 49,000 kg TPH Destroyed 79% Reduction 50% Chemical Reacted ~2.9 g Persulfate/kg Soil Applied to Treatment Zone

40 Full Scale MGP Gasworks Site Continuous Chemical Feed System 29 Chemical Feed Pumps Injecting into 9 Injection Wells, Batch Water From Hydrant Fed to Large Water Equilization Tank 1 Metric Ton Batching of Persulfate More than 3,000 hours of Operation without a Reportable Safety Incident

41 Full Scale MGP Gasworks Site 75% Injection Completed

42 Full Scale MGP Gasworks Site 75% Injection Completed Highest Coal Tar DNAPL Contamination at Site

43 Full Scale MGP Gasworks Site Typical Monitoring Results Electrolytic Conductivity and Persulfate Concentrations Electrolytic Conductivity (ms/cm) WCMW 16S Electrolytic Conductivity (ms/cm) and Persulfate Concentration (g/l) 3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/ m Screened Interval m Screened Interval Date Electrolytic Conductivity (ms/cm) Cond. (ms/cm) Persulfate Conc. (g/l) Persulfate Concentration (g/l) Electrolytic Conductivity (ms/cm) WCMW 16I2 Electrolytic Conductivity (ms/cm) and Persulfate Concentration (g/l) 3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13 Date WCMW 16I Electrolytic Conductivity (ms/cm) and Persulfate Concentration (g/l) 3/28 5/17 7/6 8/25 10/14 12/3 1/22 3/13 Cond. (ms/cm) Persulfate Conc. (g/l) Persulfate Concentration (g/l) Date Cond. (ms/cm) Persulfate Conc. (g/l) Persulfate Concentration (g/l) m Screened Interval

44 Full Scale MGP Gasworks Site Typical Monitoring Results Oxidation Reduction Potential and ph

45 Full Scale MGP Gasworks Site MW 1 PAH Groundwater

46 Conclusions MGP Gasworks Site Significant Mass Reduction After Only 50% Chemical Reacted 49,000 kg TPH Removed Groundwater Reductions Last to Be Observed Based on the Process, but Reductions are Taking Place No Groundwater PAH Increases Downgradient in the Next Gasworks Contaminated Property Rigorous Monitoring Shows Reactants and Reaction Front Passing Through the Treatment Zones Able to Target Upper 10 m of Saturated Zone More Contamination Initially Present than Estimated by Consultants Upgradient and Shallow Costs for Design, Implementation, Project Management and Monitoring ~ 215DKK/Metric Ton 28.8 /Metric Ton

47 Residential No.2 Heating Oil Remedation Treatment VeruSOLVE 5, Hydrogen Peroxide (5.1%), VeruSOL 3 (30 g/l) Total Injected Liquid 4076 Liters and 121 kg VeruSOL 3 in 2 Days with Direct Geoprobe Injection Initial Mass of No.2 Heating Oil Present 1,600 kg as TPH/DRO Cost 337 DKK/Metric Ton (45.4 /Metric Ton) Clean Up Criteria Met, NJDEP Site Closure Letter Given

48 Pharmaceutical Chlorinated Solvent Site 2,807 Metric Tons Soil Treated, 584 m 3 soil in November 2008 Contaminants 1 1 dichloroethene, 1,2 dichloroethane, benzene and chlorobenzene Total Contaminant Mass 227 kg Soils were Silty Sand with Clay with Significant Contamination of the Backfill Around Many Utility Trenches in Clay with Sand/Clay Backfill 80,533 L liquid Injected with 13.2 kg Fe EDTA, 609 kg VeruSOL 3 Injection Over a 18 days of Injection During 4 Week Period CTDEP Criteria Met for All Contaminants 1,1 dichloroethene (6 ug/l), benzene (530 ug/l), chlorobenzene (6150 ug/l), and 1,2 dichloroethane (90 ug/l) Site Closed in August 2009

49 Area III, Skuldelev Site Denmark Full Scale Application Presented by Lotte Rasmussen, NIRAS Summary Laboratory Treatability Test Presented Here Significant Pure Phase Tetrachloroethylene (PCE) DNAPL Present Lower Concentrations of TCE, cis 1,2 DCE and Vinyl Chloride Treatment using S ISCO with Alkaline Persulfate Laboratory Treatability Test Completed in January 2008 PCE DNAPL Solubilization Tests Emulsion Oxidation Tests Soil Oxidant Demand Tests

50 PCE Solubility Enhancement Tests Skuldelev Area III Solubility Enhancement Factor = 13.7 Interfacial Tension = 39.4 mn/m 5 g PCE, 2.5 g VeruSOL 3 in 500 ml Reactor Solubility Yield = 1.04 g PCE Solubilized/g VeruSOL 3

51 Alkaline Persulfate Oxidation of Solubilized PCE Initial IFT = 40.1 mn/m Final IFT = 60.8 mn/m Initial Persulfate = 50.0 g/l Final Persulfate= 30.6 g/l Initial ph = Final ph = Initial PCE = 2,200 mg/l Final PCE = 85 mg/l

52 Persulfate Soil Oxidant Demand Tests Persulfate SOD Test Conditions and Results

53 Persulfate Soil Oxidant Demand Tests Control with Groundwater Only Had Significant Degradation of Persulfate System was Not Buffered at Alkaline Conditions The SOD Exerted with Soil was 11% Greater than in Groundwater Alone

54 Full Scale Design Area III Skuldelev Site Treatment Area ~75 m2 Treat Larger Area to Ensure Contact Treatment Soil Volume 375 m 3 Estimated Contaminant Mass 1,102 kg DNAPL Design Soil Oxidant Demand (with DNAPL included) 15 g/kg VeruSOL 3 Dose 800 kg NaOH Dose 800 kg (based on Soil Titration Curve) Design Injection Flow 5 gpm (Sandy Site) Design Injection Concentration of Persulfate 100 g/l (Used 25 to 50 g/l to Avoid Density Driven Transport)