1 Reduction of Biochemical Oxygen Demand and Chemical Oxygen Demand of Metalworking Fluid Wastewater by Electrochemical Oxidation J. M. Burke STLE Houghton International A. Petlyuk, PhD STLE Houghton International J. F. Warchol, PhD Houghton International R. J. Coin ELTECH Systems Corporation K.L. Hardee, PhD ELTECH Systems Corporation
2 INTRODUCTION Metalworking Fluids are widely used within our industry.
3 INTRODUCTION Metalworking Fluids are widely used within our industry. Many metalworking fluid exhibit high biochemical oxygen demand (BOD 5 ) and chemical oxygen demand after conventional pre-treatment methods.
4 INTRODUCTION Metalworking Fluids are widely used within our industry. Many metalworking fluid exhibit high biochemical oxygen demand (BOD 5 ) and chemical oxygen demand after conventional pre-treatment methods. Regulators continue to enforce BOD 5 and COD limitations.
5 INTRODUCTION Metalworking Fluids are widely used within our industry. Many metalworking fluid exhibit high biochemical oxygen demand (BOD 5 ) and chemical oxygen demand after conventional pre-treatment methods. Regulators continue to enforce BOD 5 and COD limitations. Cost effective and user friendly advanced technology solutions are necessary and in demand to resolve BOD 5 and COD issues.
6 WHAT ARE CONTAMINANTS IN MWF WASTEWATERS? Increasing Solubility Hydrocarbon Products (Floatable, Suspended / emulsifiable, and Settleable Organics) Petroleum Oils, Waxes, Fatty Acid Soaps (Ca, Fe Al), Chlorinated esters and paraffins Floatable, Suspended, and Settleable Solids Graphite, Vibratory Debur, Floor dirt
7 WHAT ARE CONTAMINANTS IN MWF WASTEWATERS? Increasing Solubility Hydrocarbon Products (Floatable, Suspended / emulsifiable, and Settleable Organics) Petroleum Oils, Waxes, Fatty Acid Soaps (Ca, Fe Al), Chlorinated esters and paraffins Floatable, Suspended, and Settleable Solids Graphite, Vibratory Debur, Floor dirt Metals Iron, Aluminum, Copper, Lead, Chrome, Zinc, Nickel, Manganese, Molybdenum Non-metals Arsenic, Selenium
8 WHAT ARE CONTAMINANTS IN MWF WASTEWATERS? Increasing Solubility Hydrocarbon Products (Floatable, Suspended / emulsifiable, and Settleable Organics) Petroleum Oils, Waxes, Fatty Acid Soaps (Ca, Fe, Al), Chlorinated esters and paraffins Floatable, Suspended, and Settleable Solids Graphite, Vibratory Debur, Floor dirt Metals Iron, Aluminum, Copper, Lead, Chrome, Zinc, Nickel, Manganese, Molybdenum Non-metals Arsenic, Selenium Dissolved Solids Salts (Sodium and Potassium Salts) Dissolved Organics Amines, Amides, Esters, Glycols, Surfactants, Detergents, Fatty Acids, Fatty Alcohols, biocides, phosphate esters
9 THE ISSUE Spent Metalworking Fluids Current Technology is limited Pre-treatment System State Waters Municipal Sewer System POTW Fed/State Discharge Controls
10 Current Established Technology Options Chemical Treatment Salt Splitting Polymer Treatment Membrane Separation Ultrafiltration Microfiltraion Evaporation Thermal Evaporation Mechanical Vapor Recompression Biological Aerobic Anaerobic Adsorption Carbon Clay Or Combined technologies from above
11 Current Options Combined Technologies Chemical / Biological Chemical / Carbon or Clay Adsorption
12 Current Options Combined Technologies Chemical / Biological Chemical / Carbon or Clay Adsorption Distillation / Ultrafilter (MVR/ UF)
13 Current Options Combined Technologies Chemical / Biological Chemical / Carbon or Clay Adsorption Distillation / Ultrafilter (MVR/ UF) Ultrafiltration / Biological / Ultrafiltration (MBR) Ultrafilter / Reverse Osmosis (UF /RO) Ultrafiltration / Carbon or Clay Adsorption
14 Current Options Combined Technologies Chemical / Biological Chemical / Carbon or Clay Adsorption Distillation / Ultrafilter (MVR/ UF) Ultrafiltration / Biological / Ultrafiltration (MBR) Ultrafilter / Reverse Osmosis (UF /RO) Ultrafiltration / Carbon or Clay Adsorption Proposed New Option Ultrafilter / Electrochemical Oxidative Process
15 Separation Effectiveness and Costs Fluid Type @ 5% v/v Feed BOD5 - mg/l After Chemical Or Ultrafiltration Combined Technologies Combined Technologies Operating Costs USD per Liter Emulsions 30K 300K 600 6,000 20-300 $ 0.25 0.45 Semi- Synthetic 4,000 25,000 800 6,000 30-600 $ 0.25 0.45 Synthetic 3,000 9,000 500 5,000 30-600 $ 0.25 0.45
16 Separation Effectiveness and Costs Fluid Type @ 5% v/v Feed COD mg/l After Chemical Or Ultrafiltration Combined Technologies Combined Technologies Operating Costs USD per Liter Emulsions 500,000-1,100,000 2,000 9,000 300 900 $ 0.25 0.45 Semi- Synthetic 20,000 55,000 3,000 6,000 300-1,100 $ 0.25 0.55 Synthetic 25,000-35,000 20,000 30,000 250-900 $ 0.25 0.55
17 Spent MWF CURRENT TECHNOLOGY IS LIMITED Combined technologies are gaining in popularity. Primary Method Dissolved Organics And Salts Secondary Method Lower BOD 5 and COD Only Solved ½ the Problem Oil Phase For ultimate Recycle Separated Organic Sludge Phase Low Reuse Potential?
18 Spent MWF Advanced Oxidation Process Technology Option Primary Method Dissolved Organics And Salts Out Gas N 2, CO 2, O 2 AOP No Sludge Oil Phase For ultimate Recycle Lower BOD 5, And COD
19 What are some of the AOP s Sodium Periodate Sodium Perborate Hydroxyl Radical Ultraviolet Ozone Hydrogen Peroxide UV / Titanium Dioxide Chlorine Electrochemical Oxidation
20 Relative Oxidation Potential of Selected Oxidants Oxidant Oxidation Potential, Volts Fluorine 3.0 Hydroxyl radical 2.8 Ozone 2.1 Hydrogen peroxide 1.8 Potassium permanganate 1.7 Chlorine dioxide 1.5 Chlorine 1.4
21 Electrons are Less Expensive Reagent Cents/Mole Electrons @ 6 cents/kwh, 3.5 V 0.6 Hydrogen Peroxide 3.8 Hydrazine 14 Sodium Hydrosulfite 25 Sodium Dichromate 39 Potassium Permanganate 45 Sodium Borohydride 170
22 MWF Ultrafilter Schematic Feed Return Permeate To Electro- Chemical Oxidation Feed Feed Tank Ultrafilter Membrane Surface Pump
23 Ultrafiltration Size Comparison 0.005 µm
24 Ultrafiltration Permeate, Typical
25 Electrochemical Oxidation Multiple Reactions Direct Oxidation Reaction occurs directly on the anode surface Indirect Oxidation Anode oxidizes a chemical which then oxidizes a substance in solution away from the anode surface
26 Direct Oxidation Electrode Reactions Desired Anode Reaction COOH - = CO 2 + H + + 2 e - Competing Anode Reaction H 2 O = 2 H + + 1/2 O 2 + 2 e - Typical Cathode Reactions 2 H 2 O + 2 e - = 2 OH - + H 2 (Base) 2 H + + 2e - = H 2 (Acid) May Require Anode with High Oxygen Potential
27 More Complex Molecules More Electrons Required Methanol CH 3 OH + 6 OH - = CO 2+ 5 H 2 O + 6 e - Isopropanol CH 3 CH 3 CHOH + 12 OH - = 3 CO 2 + 7 H 2 O + 12 e - Acetone CH 3 COCH 3 + 16 OH - = 3 CO 2 + 11 H 2 O + 16 e -
28 Basic Concept Electrolizer - + Direct Current Anode Titanium with Electrocatalytic Coating High Surface Area Flow-Through Cathode Wastewater
29 Anode Surface Reactions Direct Electron Transfer Plus Mixed Oxidants from Direct Surface Reactions + e - OH O 3 O
30 Laboratory Electrochemical Cell CATHODE MULTI-LAYER MESH ANODE - + BATCH TANK ELECTROLYZER CIRCULATION PUMP
31 Bench Scale Anode High Surface Area, Flow Through Enhances Reaction Rates Titanium Support/Current Conductor Multiple Layers of Fine Ti Mesh (MLM with DSA Coating) DSA, Multi-Layer Mesh and MLM are trademarks of ELTECH Systems Corporation in the United States
32 Bench Scale MLM Anode Test Cell
33 EXPERIMENTAL SET UP Sample MWF Electrolyte As necessary Direct Current Power Supply.. Feed Return Feed Tank Pump U F Chemical Cell Electro- Ultrafilter Permeate Storage Permeate Analysis for BOD5, COD ph
34 Wastewater After UF No Added Electrolyte 44% Reduction COD COD vs Time 10000 COD (mg/l) 8000 6000 4000 2000 0 0 100 200 300 400 500 600 Elapsed Time (min)
35 Wastewater After UF No Added Electrolyte 53% reduction BOD BOD vs Time BOD (mg/l) 8000 7000 6000 5000 4000 3000 2000 1000 0 0 100 200 300 400 500 600 Elapsed Time (min)
36 INITIAL TESTING SIGNIFICANT VARIATIONS IN WASTEWATER Very site dependant Variations from day to day Difficult to Prove Concept with excess feed variation Need to try a standard Three amine blend
37 Synthetic Feed Mixture and Additive Ratios The Three Amines Chemical Mixture CAS # % - Volume Monoethanolamine 141-43-5 30 Triethanolamine 102-71-6 30 Monoisopropanolamine 78-96-6 40 Then dilute above mixture 99:1 with H 2 0 To create COD 4,000
38 SYNTHETIC FEED / With Electrolyte #1 83% reduction COD 4500 4000 3500 3000 COD, ppm 2500 2000 1500 1000 500 0 0 50 100 150 200 250 300 350 400 450 Time, minutes
39 SYNTHETIC FEED / With Electrolyte #1 60 Minutes 460 Minutes
40 UF Permeate Premium New MWF at 2% with Electrolyte #1 91.0% COD reduction 9000 8000 7000 6000 COD, ppm 5000 4000 3000 2000 1000 0 0 50 100 150 200 250 300 350 400 450 Time, minutes
UF Permeate COD and BOD5 Reduction versus Time. Virgin MWF,5%; Electrolyte #1 18000 16000 16000 14000 12000 mg/l 10000 8000 6000 6080 7200 COD 5600 4000 2000 0 BOD 0 100 200 300 400 500 600 4000 1620 75% 73.4% 41 Time, min
42 18000 16000 UF Permeate COD Reduction Versus Time Effect of Electrolytes Virgin MWF, 5% COD, mg/l 14000 12000 10000 8000 6000 El #3 El #4 El #2 El #1 4000 2000 0 0 100 200 300 400 500 600 700 800 900 1000 Time, min
43 18000 16000 14000 12000 10000 8000 6000 4000 2000 0 UF Permeate Relative and Absolute Reduction of COD Concentration Effect. Virgin MWF, 7 hours, Electrolyte #1 5% 2.5% 74.4% 34800 mg 87.8% 20298 mg 0 1 2 3 Hours 4 5 6 7 8 9 10
44 Relative and Absolute Reduction of COD Concentration and Treated Volume Effect Used MWF, 7 hours, Electrolyte #3 COD, mg/l 20000 18000 16000 14000 12000 10000 8000 6000 4000 V=3L V=2L 40000 30000 20000 10000 0 Absolute Reduction 3L 2L 3L, 1:3 60.3% 32514 mg 69.1% 24880 mg 2000 0 V=3L, dilution 1:3 0 100 200 300 400 500 600 Time, min 43.2% 7830 mg
45 Process Control Data Electrolyte #3 25 20 15 10 Amps Rec,V Cell Voltage (V) ph Conductivity 5 0 0 200 400 600 800 1000 Time, min
46 Premium MWF #3 @ 5% 100 ppm hard water, UF Permeate, Electrolyte #3 99.9% Reduction of Phenol (4AAP) Phenol versus time 400 350 350 Phenol mg/l 300 250 200 150 100 50 0 1.3 0.2 <0.1 0 50 100 150 Elapsed Time (min)
47 Electrolyzer
48 Full Scale Electrolyzer
49 Skid Mounted System
50 Some Engineering System Considerations Chemical resistance to oxidation Current density Anode / cathode lifetime Current efficiency electrolyte addition Solution concentration Mass transfer Fluid velocity Concentration Volume Footprint of physical equipment Oxidation reduction by-products to air Available operating area Fits with partner processes and industry comfort factor UF / Chem treat vs. biological Ease of operation and maintenance Capital and operating cost
51 Summary Additional experimental work still in progress. Electrolyte addition increases the efficiency of the overall process - electrolyte cost is insignificant. BOD 5 and COD reductions in the range of 60% to 80% in 7-8 hours are achievable. Operating cost (energy and anode life) to drive electrolytic cell estimated to be $ 0.012- $0.017 per liter at rate of $ 0.06 / KWH, per 8 hours of run time. Compact design. No sludge to dispose of. Can selectively oxidize certain organic compounds ( phenol ) in the presence of more difficult to oxidize organic compounds. Ultrafiltration with Electrochemical Oxidation is a promising method.