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Management Alternatives for Reverse Treatment Concentrate David Pannucci(1) and Arie Kremen(2) (1) Progressive Waste (2) Cornerstone Environmental

FNYSWA Spring Conference The Sagamore, Bolton Landing, New York

May 17, 2016 Leachate Disposal Cost (Cap & Op Ex)

$0.45

$0.40 Old and closed Operating Landfills Landfills $0.35

$0.30

$0.25

$0.20

$0.15

$0.10

$0.05

$0.00

© 2016 Cornerstone. All rights reserved. MSW Leachate Characteristic Composition

Specific Leachate Production: 180 – 200 gallon/acre/day

Young Medium Old Age (yr) <1 1-5 >5 pH <6.5 6.5-7.5 >7.5 COD (mg/l) >15,000 3,000-15,000 <3,000

BOD5/COD 0.5-1.0 0.1-0.5 <0.1 TOC/COD <0.3 0.3-0.5 >0.5

NH3-N (mg/l) <400 400 >400 Metals (mg/l) >2.0 <2.0 <2.0 Organic Compounds 80% VFA 5-30% VFA, HA, HA, FA FA (VFA – Volatile Fatty Acid, HA – Humic Acid, FA – Fulvic Acid)

© 2014 Cornerstone. All rights reserved. Evolution of Organic Constituents

Landfill Age young medium old

Landfill Gas

Leachate

McBean and Rovers (1998) Statistical Procedures for Analysis of Environmental Monitoring Data and Risk Assessment, Prentice-Hall Publishing Co.

© 2016 Cornerstone. All rights reserved. Contaminant Classification

• BOD Biodegradable • COD Biochemical Organics Recalcitrant • BOD/COD

Nutrients Nitrogen, Phosphorus • Ammonia

Trace Organic Pollutants, • Benzene, Vinyl chloride, … Pollutants • Arsenic, Lead, ….

(TDS) Chloride, , Potassium, • Electrical Conductance

© 2014 Cornerstone. All rights reserved. Solid Separation: Size Comparison

Dissolved Colloid Particulate

© 2016 Cornerstone. All rights reserved.

Osmosis: movement of through a semi-permeable to equalize solute concentration Reverse Osmosis: application of external pressure, forces water to the low concentration side Reverse Osmosis vs. : filtration relies of size exclusion, whereas RO is also relying diffusion and pressures

7 © 2015 Cornerstone. All rights reserved. Dissolved Organics in Leachate

Filtration Reverse Osmosis

Effluent 1.5μm .45μm .22μm 100kDa 30kDa 10kDa 5kDa 3kDa 1kDa 500Da

Source: John T Novak, PhD Virginia Polytechnic Institute

© 2014 Cornerstone. All rights reserved. RO Design Rules of Thumb

• Recovery is a design parameter Concentration Recovery Factor • Higher recoveries: 50% 2 Lower concentrate volume 75% 4 80% 5 Lower quality permeate 83% 6 Accelerated membrane and scaling • Fouling, buildup of particles and colloids on membrane

© 2015 Cornerstone. All rights reserved. Membrane Performance

Species Rejection* Feed/Concentrate Permeate Concentration Recovery Concentration Ammonium 80-90% (pH<7.8) Chloride 92-98% 100 ppm 0% 20ppm

Sodium 92-98%

Potassium 92-96% Calcium 93-99%

Iron 96-98% 80% Sulfate 96-99% 200 ppm 50% Rejection 40ppm Borate 30-50% Membrane

Cyanide 90-99%

Magnesium 93-98% Phosphate 96-98% * Polyamide composite membrane at 25°C 400 ppm 75% 80ppm

© 2015 Cornerstone. All rights reserved. Real World Example

Concentration Parameter (mg/l) Leachate Concentrate : Factor

NH3-N 1,831 4,951 2.70

NO3, NO2-N 0.251 0.797 3.18 BOD 3,509 7,405 2.11 COD 7,934 20,032 2.52 TDS 15,150 38,606 2.55 >35,000 Sulfate 120 12,812 107 Conductivity (μS/cm) 40,971 60,956 1.47 >50,000

Concentration Factor (avg.) 2.6 Recovery (calculated) 62% =

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© 2015 Cornerstone. All rights reserved. Concentrate Management Options

• Offsite disposal • Onsite treatment • Multistage RO • Evaporation • Solidification/Resource Recovery • Eutectic Freeze

© 2015 Cornerstone. All rights reserved. Offsite Disposal

• Compared to sanitary , RO concentrate is … concentrated:

RO typ. Sanitary Enrichment Parameter (mg/) Concentrate Wastewater Factor

NH3-N 4,951 20 x250 BOD 7,405 250 x30 TDS 38,606 500 x75 Conductivity (μS/cm) 60,965 500 x120 • Requires large design-flow POTW to rely on dilution • Subject to monitoring and discharge limitations, e.g.: • Metals, Volatiles, recalcitrant COD, Dissolved Organic Nitrogen • Cost

© 2015 Cornerstone. All rights reserved. Cascading RO Stages

Objective: Reduce concentrate volume Constraint: Maintain membrane cross-flow velocities Diminishing returns, increasing costs

3 300

2.5 250

2 200 ( ppm)

1.5 150

1 100 Permeate (ppm) Concentrate 0.5 50

0 0 0 1 2 3 4 5 6 7 RO Stage

© 2015 Cornerstone. All rights reserved. Real World Example (cont’d)

Recovery Rate of 62% is result of dual stage RO with optional permeate polishing:

Greater concentrate reduction not economically feasible.

© 2015 Cornerstone. All rights reserved. Electrodialisys Reversal (EDR)

Electric current migrates through an stack of altering cationic and anionic exchange . • Feedstock recovery rate: 90+% (water supply); • Self-cleaning through periodic voltage reversal; • Applications: water supply, concentrator

• Nitrate • Total Dissolved Solids • Arsenic • Sulfate • Iron • Radionuclides

Contaminants • Sulfate

© 2015 Cornerstone. All rights reserved. EDR-RO

• Generates highly concentrated brine; • Relative to RO: higher CapEx, lower OpEx • Less susceptible to fouling and scaling; • Dual purpose Hybrid EDR-RO: • Feedstock pre-treatment (softening) • Concentrate post-treatment (brine concentration) Concentrate • No commercial installation (Leachate Concentrate); EDR RO

© 2015 Cornerstone. All rights reserved. Vapor Compression (VCD)

• VCD recovery exceeds 90%, in combination with crystallizer can achieve ZLD; • Processes feedstock with TDS up to 650 g/l; • Operating concept: 1. Compression increases vapor pressure 2. Increases condensation 3. Vapor temperature is used to preheat feedstock; 4. Feedstock is vapor source; • Opportunity cost: $0.02/gal (LFG) • Op Ex: $0.02-$0.04/gal (VCD only)

© 2015 Cornerstone. All rights reserved. Crystallizers

• Commodity salt crystallizers operate on neat ; • Leachate RO concentrate contains large number of dissolved minerals; • Relatively few Mixed Salt Crystallizers (15 units) operate in North America (2011, GE); • Crystallizers are added to VCD units to achieve ZLD; • Crystallizers are constructed from high grade metals or plastics; • Crystallization is very energy intensive;

© 2015 Cornerstone. All rights reserved.

Misting enhanced Evaporation

Residue from Leachate (‘Misting’)

© 2015 Cornerstone. All rights reserved. Thermally Enhanced Evaporation

• Leachate volume by up to 95%: • Evaporation vessels; • Direct injection-devices; • Metals precipitate, fall out as salts; • Organics are volatilized and stripped by vapor; • Energy intensive, requires LFG or waste heat; • Residuals: slurry (vessel) or grit (direct injection); • Esthetic impact: steam plume;

© 2015 Cornerstone. All rights reserved. Evaporation Vessel

• Approx. 24 scf LFG/gal • Residual volume: 3-10% of feedstock • Residual solid content: 10-12% (slurry) • Disposal at working face • Air Quality permitting • Op Ex: $0.055-$0.065/gal • LFG Opportunity cost

© 2015 Cornerstone. All rights reserved. Ammonia Recovery & Uses

• Stripping: ammonium sulfate formation • Requires pH adjustment, absorption by sulfuric acid • Uses: fertilizer, agricultural spray adjuvant • Solidification: struvite precipitation (‘kidney stones’) • Requires: , phosphate, pH adjustment • Uses: fertilizer • landfilling

Struvite

© 2015 Cornerstone. All rights reserved. Thermodynamic Considerations

2,025 Btu/gal 8,920 Btu/gal 4 scfm LFG/gal 50°C/106°F 18 scfm LFG/gal

Parameter Value Specific Heat of Water 4.2 kJ/kg/K Enthalpy of Evaporation 2,257 kJ/kg x7 Enthalpy of Fusion 334 J/kg

© 2015 Cornerstone. All rights reserved.

Thermodynamic equilibrium point where a salt and its transition from solid to liquid state

Temperature A B Solution

Eutectic

T Ice & Solution Salt & Solution

Ice & Salt Eutectic Point

CEutectic Salt Concentration (%wt)

© 2015 Cornerstone. All rights reserved. Summary

• RO can achieve direct discharge limitations • Challenges: concentrate volume, TDS, and ammonia • Multiple ionic species increase complexity • With exception of , industry has limited experience treating Leachate RO Concentrate • Consider Total Cost of Ownership, incl. opportunity cost • Rights and ready access to waste heat can affect project economics

© 2015 Cornerstone. All rights reserved.

Questions? Comments?

David Pannucci, PE [email protected] 315.539.5624 Arie Kremen, PhD [email protected] 845.695.0213

© 2015 Cornerstone. All rights reserved.