Drillox Technology Technology Covered by Patent Application
Presentation Outline Calcium Peroxide Properties The Drillox Technology Principle Comparison with other oxidants Testing protocol Lab studies Summary Comments/Questions 2010, SOLVAY Chemicals, Inc. 2
IXPER 75C Calcium Peroxide Appearance Composition Calcium peroxide (%) Available oxygen (%) Impurities Bulk density (g/ml) Particle size distribution Yellowish white particles CaO 2, Ca(OH) 2, other Ca prod. 75% min (typical 78 ± 2) 16.65% min (typical 17.3 ± 0.44) Meets Food Chemicals Codex 0.5 ± 0.075 50% <20µ 100% <75µ 2010, SOLVAY Chemicals, Inc. 3
Effect of Water Very low solubility in H 2 O (<0.01% @ 20 C) ph of suspensions depends upon conc. 0.05% 8 0.2% 11 1% 11.7 10% 12.7 25% 12.8 2010, SOLVAY Chemicals, Inc. 4
Effect of Water At ph 11 very slow decomposition generating oxygen and heat 2 CaO 2 + 2 H 2 O 2 Ca(OH) 2 + O 2 Rate of oxygen generation depends upon conditions and can last a year Oxygen enhances bioremediation 2010, SOLVAY Chemicals, Inc. 5
Effect of Acid In buffered systems at lower ph progressively increasing generation of H 2 O 2 Ca(OH) 2 + 2H + Ca 2+ (aq) + 2H 2 O CaO 2 + 2H + Ca 2+ (aq) + 2H 2 O 2 2010, SOLVAY Chemicals, Inc. 6
Effect of Acid The peroxide generated could lead to competing reactions H 2 O 2 + OH - H 2 O + HOO - (oxidation) HOO - + substrate oxidized substrate + OH - H 2 O 2 + Fe 2+ HO (Fenton oxidation) HO + substrate oxidized substrate 2H 2 O 2 2H 2 O + O 2 (g) (decomposition) O 2 enhances microbial growth (bioremediation) 2010, SOLVAY Chemicals, Inc. 7
ph Effect on H 2 O 2 Produced 100 H2O2 (% from Theoretical) 80 60 40 20 0 3 4 5 6 7 8 9 10 11 ph Add H 2 SO 4 to CaO 2 slurry to reach desired ph Draw & filter sample of slurry as ph stabilizes. Add more acid & repeat to obtain lower ph reading. 2010, SOLVAY Chemicals, Inc. 8
Drillox Technology Principle can be applied for generating Modified Fenton Chemistry with IXPER 75C CaO 2 Technology can be applied for in-situ Chemical Oxidation of contaminants in soil and groundwater (ISCO) Solvay patent application (WO 2005/118170) H 2 O 2 for fast reaction + exotherm (contaminant desorption) IXPER 75C Calcium Peroxide for slow H 2 O 2 release + bioremediation Fe citrate to produce Modified Fenton Chemistry 2010, SOLVAY Chemicals, Inc. 9
Oxidation Systems Reagent Oxidation Potential (V) Fenton - H 2 O 2 /Fe 2+ /H + (OH ) 2.8 Semi Fenton - H 2 O 2 /Fe 2+ (OH ) 2.8 Drillox - CaO 2 /H 2 O 2 /Fe 2+ (OH ) 2.8 Ozone/H 2 O 2 (OH ) 2.8 Persulfate (SO 4 - ) (activated) 2.5 Ozone (O 3 ) 2.1 Persulfate (S 2 O 2-8 ) 2.0 Hydrogen peroxide (H 2 O 2 ) 1.8 Permanganate (MnO 4- ) 1.7 Source: ITRC Technical and Regulatory Guidelines for ISCO + Solvay for Drillox 2010, SOLVAY Chemicals, Inc. 10
Advantages / Disadvantages Technology Features Fenton s Reagent Modified Fenton s Drillox (Modified Fenton w/ CaO 2 ) Ozone/H 2 O 2 Activated Persulfate Active Species OH OH OH OH SO 4 - ph Range Acid Neutral Neutral to High Neutral High or Low Stability after Mixing Contaminant Mass Reduction Low Low Medium Low Medium High High High - Moderate High High - Moderate Reaction Time Fast Fast Fast to Medium Fast Medium By-Products or Fouling Potent.enhance aerobic biorem. Iron Iron Iron and Citrate (biodegradable) None Yes Yes Yes Yes No Capital Cost Low Low Low High Low Sulfate Chemical Cost Low Moderate High Moderate High 2010, SOLVAY Chemicals, Inc. 11
Oxidants Comparison Formula Active Concentration in Commercial Product (%) Available Oxygen Content (% w/w) Oxygen in 20bs Oxidant per lb Contaminant (lb) Hydrogen Peroxide [Large decomposition] H 2 O 2 100 47 9.4 Calcium Peroxide (IXPER 75C) [Slow release] CaO 2 75 17 3.4 Sodium Percarbonate [Fast decomposition] Na 2 CO 3. 1.5H 2 O 2 85 13 2.6 Sodium Persulfate [Moderate stability] Na 2 S 2 O 8 100 6.6 1.3 Persulfate:CaO2 50:50 [Combined properties] Na 2 S 2 O 8 + CaO 2 50 + 38 3.3 + 8.5 2.4 2010, SOLVAY Chemicals, Inc. 12
Calculating Oxygen Demand Determine the total contaminant concentration in soil/water including background NOD from soil Assuming the contaminant is benzene, then each mole needs 7.5 moles oxygen for complete oxidation C 6 H 6 + 7.5 O 2 = 6CO 2 + 3 H 2 O Molecular weight calculation: [C = 12, H = 1 and O = 16] C 6 H 6 [12*6 + 1*6] = 78 7.5 O 2 [7.5 x (16*2)] = 240 It would take 240 pounds of oxygen to fully degrade 78 pounds of benzene, or 3.08 (240/78) pounds of oxygen per pound of benzene. A rule of thumb is to assume 3lbs oxygen needed per lb of contaminant + average soil/water NOD 2010, SOLVAY Chemicals, Inc. 13
Factors Affecting Oxidant Dose Each Oxidant has a different active oxygen content Each product releases its active oxygen in the field at a different rate Only the active oxygen released is available for oxidation and contributes to remediation H 2 O 2 decomposes very quickly Sodium percarbonate has a fast decomposition rate Persulfate is moderately stable IXPER 75C CaO 2 is the most stable but has very low solubility and will not release all its H 2 O 2 at neutral ph Residue enhances bioremediation For these reasons, a safety factor must be accounted for at least 20% is recommended for all oxidants (to add to the 3lbs O/lb contaminant 2010, SOLVAY Chemicals, Inc. 14
Oxidant Dose Calculation Assumption: 3lbs Oxygen per lb Contaminant needed All active Oxygen is released in the soil and is available for oxidation Formula Active Concentration in Product (%) Oxygen Content (% w/w) Oxidant Containing 3lbs Oxygen (lbs) Oxidant/lb Contaminant with 20% Safety Factor Hydrogen Peroxide 100% (Commercial grade 35%) H 2 O 2 100 47 6 7 Calcium Peroxide (IXPER 75C CaO2) CaO 2 75 17 18 21 Sodium Percarbonate Na 2 CO 3. 1.5H 2 O 2 85 13 23 28 Sodium Persulfate Na 2 S 2 O 8 100 6.6 46* 55 * FMC web site reports 45.8g persulfate required per g of benzene 2010, SOLVAY Chemicals, Inc. 15
Comparison of Calculation Methods Assumption: All active Oxygen is released in the soil and is available for oxidation Hydrogen Peroxide (100%) Calcium Peroxide (75%) (IXPER 75C CaO2) Sodium Percarbonate (85%) Sodium Persulfate (100%) Using rule of 20lbs Oxidant/lb contaminant 20lbs Oxidant (9.4lbs Oxygen per lb contaminant) 20lbs Oxidant (3.3lbs Oxygen per lb contaminant) 20lbs Oxidant (2.6lbs Oxygen per lb contaminant) 20lbs Oxidant (1.3lbs Oxygen per lb contaminant) Oxidant (lbs) to obtain 3lbs Oxygen/lb contaminant + 20% Safety Factor 7 (6lbs + safety factor) 21 (18lbs + safety factor) 28 (23lbs + safety factor) 55 (45lbs + safety factor) 2010, SOLVAY Chemicals, Inc. 16
Drillox Treatability Studies Performed at Western Michigan University
Lab Set-up One port equipped with activated carbon traps to capture VOCs Mechanical stirring at 400rpm Duration: until oxidant is consumed (12-21 days) 2010, SOLVAY Chemicals, Inc. 18
Treatability Study 1 2kg soil + 2L liquid Control water Drillox Technology CaO 2 slurry in ~1% H 2 O 2 (120g or 60g Drillox) Fe citrate solution ph ~4.5 Separate additions Persulfate activated with NaOH to ph 11 120g persulfate mixed with NaOH H 2 O 2 Modified Fenton 240g H 2 O 2 (13% solution) Dissolvine E-FE-13 (ratio H 2 O 2 :Fe 20:1) Separate additions 2010, SOLVAY Chemicals, Inc. 19
Manufactured Gas Plant Site Analyte Result Sand-sized particles (% w/w) 79 Silt-sized particles (% w/w) 20 Clay-sized particles (% w/w) 1 Native organic material (NOM) (% w/w) 0.1 Total carbonates (% w/w) 3 ph 7.8 ± 0.1 (5) a Total PAH concentration (mg/kg) 20,347 ± 1463 (4) Total TPH concentration (mg/kg) 35,160 ± 2158 (4) Cr (VI) concentration (mg/l) BDL b (4) a mean ± standard deviation (number of measurements). b BDL=below detection limit of 0.2 mg/l. 2010, SOLVAY Chemicals, Inc. 20
ph Profile 12.0 ph 11.0 10.0 9.0 8.0 7.0 NaOH SPS Drillox Hi H2O2 MF Control 6.0 0 5 10 Time (days) 2010, SOLVAY Chemicals, Inc. 21
Dissolved Oxygen Profile DO (mg/l) 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 0 5 10 Time (days) NaOH SPS Drillox Lo Drillox Hi H2O2 MF Control 2010, SOLVAY Chemicals, Inc. 22
Persulfate Concentration Persulfate Conc. (g/l) 50 45 40 35 30 25 20 15 10 5 0 0 2 4 6 8 10 12 Time (days) 2010, SOLVAY Chemicals, Inc. 23
PAH Removal PAH Conc. (mg/kg) 25000 20000 15000 10000 5000 NaOH SPS Drillox Lo Drillox Hi H2O2 MF Control 0 Temperature after 3 days Drillox ~37 C NaOH-SPS ~68 C Control ~22 C 0 5 10 Time (days) Volatilization of PAH Drillox ~0.5% NaOH-SPS ~2% H2O2 MF ~1.5% 2010, SOLVAY Chemicals, Inc. 24
Chromium (VI) Formation 35.0 Cr (VI) Conc. (mg/l) 30.0 25.0 20.0 15.0 10.0 5.0 NaOH SPS Drillox Lo Drillox Hi H2O2 MF Control 0.0 0 5 10 Time (days) 2010, SOLVAY Chemicals, Inc. 25
Treatability Study 2 & 3 2kg soil + 2L liquid Control water Drillox Technology CaO 2 slurry in 7% H 2 O 2 (100g or 50g Drillox) Fe citrate solution Separate additions 100g of commercial product (50 g persulfate + 50g CaO 2 ) in water 2010, SOLVAY Chemicals, Inc. 26
Wood Treating Site ph 6.8 Sand (62.5 μm-2 mm) (%) 64 Fines (<62.5 μm) (%) 36 Native Organic Matter Not measured Total PAH (mg/kg) 15,486 ± 1,231 a PCP (mg/kg) 2,405 ± 317 a BTEX (mg/kg) 1,321 ± 103 a Benzene (mg/kg) 371 ± 29 a a = arithmetic mean ± standard deviation for 6 replicates 2010, SOLVAY Chemicals, Inc. 27
ph Profile ph 13 12 11 10 9 8 7 6 5 4 0 5 10 15 20 25 Time (days) Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 2010, SOLVAY Chemicals, Inc. 28
Dissolved Oxygen Profile 120 DO (% saturation) 100 80 60 40 20 Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 0 0 5 10 15 20 25 Time (days) 2010, SOLVAY Chemicals, Inc. 29
Persulfate Concentration 30000 Persulfate Conc. (mg/l) 25000 20000 15000 10000 5000 0 0 5 10 15 20 25 Time (days) 2010, SOLVAY Chemicals, Inc. 30
PAH Removal Total PAH Conc. (mg/kg) 18000 16000 14000 12000 10000 8000 6000 4000 2000 0 0 5 10 15 20 25 Time (days) Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 2010, SOLVAY Chemicals, Inc. 31
PCP Removal 3000 PCP Conc. (mg/kg) 2500 2000 1500 1000 500 Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 0 0 5 10 15 20 25 Time (days) 2010, SOLVAY Chemicals, Inc. 32
BTEX Removal BTEX Conc. (mg/kg) 1600 1400 1200 1000 800 600 400 200 0 0 5 10 15 20 25 Time (days) Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 2010, SOLVAY Chemicals, Inc. 33
Benzene Removal Benzene Conc. (mg/kg) 450 400 350 300 250 200 150 100 50 0 0 5 10 15 20 25 Time (days) Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 2010, SOLVAY Chemicals, Inc. 34
Dry Cleaner Site ph 7.1 Sand (62.5 μm-2 mm) (%) 92 Fines (<62.5 μm) (%) 8 Native Organic Matter PCE (mg/kg) Negligible (no products of reductive chlorination) 10,672 ± 799 a a = arithmetic mean ± standard deviation for 6 replicates 2010, SOLVAY Chemicals, Inc. 35
ph Profile ph 13.0 12.0 11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 0 5 10 15 20 25 Time (days) Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 2010, SOLVAY Chemicals, Inc. 36
Dissolved Oxygen Profile DO (% Saturation) 105 100 95 90 85 80 75 70 65 60 0 5 10 15 20 25 Time (days) Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 2010, SOLVAY Chemicals, Inc. 37
Persulfate Concentration 30000 Persulfate Conc. (mg/l) 25000 20000 15000 10000 5000 0 0 5 10 15 20 25 Time (days) 2010, SOLVAY Chemicals, Inc. 38
PCE Removal 14000 PCE Conc. (mg/kg) 12000 10000 8000 6000 4000 2000 Control 100 g Persulfate/CaO2 50 g Drillox 100 g Drillox 0 0 5 10 15 20 25 Time (days) 2010, SOLVAY Chemicals, Inc. 39
Drillox Technology Summary Suitable for treating high concentrations of PAHs, TPH, BTEX, PCP, and PCE (possibly others) Minimal mobilization of Cr (VI) vs. alkaline persulfate Adaptable to in-situ or ex-situ applications All chemicals are green Chelating agent is biodegradable Fe is a component of soil CaO 2 decomposes to oxygen, water and lime Patent pending 2010, SOLVAY Chemicals, Inc. 40
Advantages of Drillox Technology H 2 O 2 addition Higher concentration in CaO2 slurry (up to 7%) Enhances performance Some bubbling expected on injection (less than H 2 O 2 MF) Use of very low levels (~1%) also successful Reduced soil temperature Reduced PAH volatilization Protection of underground structures Increased operational safety 2010, SOLVAY Chemicals, Inc. 41
Advantages of Drillox Technology Cost effective Simple application using Direct Push Technology No water or NAPL extraction Products non corrosive No detrimental effect on concrete structures More sustainable than technologies requiring heavy machinery or ozone generation Does not require continual energy input 2010, SOLVAY Chemicals, Inc. 42
Thank you for your Attention Comments/Questions? For Additional Information, Visit our Web Site www.solvaychemicals.us or Call: Noel Boulos (713-525-6590)