ZEOLITE ANAMMOX DE-AMMONIFICATION PROCESS Robert Collison PhD PE UPDATED 07/20/15 ZEOLITE ANAMMOX DE-AMMONIFICATION PROCESS Robert Collison PhD PE rob.collison@ymail.com 707 452 1088 Zeolite-anammox.com

INTRODUCTION What is special about zeolite-anammox? Combines advantages of zeolite and anammox. Zeolite immobilizes ammonia; system works at any concentration of ammonia. Anammox cuts nitrogen cycle in half, no nitrate. Lowest cost treatment system. Simple to run. Reduces energy requirements. Slashes construction costs.

OLD DIGESTER TANK

HOW DOES ZE-AN WORK? IMMOBILIZATION - The zeolite-anammox process uses zeolite to immobilize ammonium by CEC. COLONIZATION - Bacteria find ammonium- coated zeolite very attractive, and colonize it. REGENERATION - The bacteria eat the NH4 and regenerate the zeolite in-situ (it never becomes saturated). SINGLE STAGE - It is a single stage process converting NH4 to N2.

FISHING ANALOGY Net = zeolite; Fish = ammonium; Fishermen = anammox

ANAMMOX Anammox derive their energy from eating NH4. They combine NH4 with nitrite (NO2) to form nitrogen gas: NH4 + NO2 = N2 + 2H2O. The NH4 is provided in the influent. The NO2 is from the first stage of nitrification (NH4→NO2 → NO3). Note: anammox are capable of dissimilatory reduction of nitrate to nitrite (DNRA).

ZEOLITE - 40’ thick seam

TRADITIONAL N-REMOVAL Traditional nitrogen removal is nitrification- denitrification. Nitrification oxidizes ammonia to nitrate (via nitrite). De-nitrification reduces nitrate to nitrogen gas (requires 4 units of BOD for each unit of nitrate). Nitri/Deni are tried and tested systems – but expensive: two sets of infrastructure; high energy usage; intensive monitoring.

ADVANTAGES OF ZE-AN OVER NITRI-DENI HALF – needs half the infrastructure. HALF – uses half the air. HALF – releases half the greenhouse gas. FOOD - does not require BOD / methanol. EASY – simple to operate. SELF – self-regulating. LOW – low O&M costs.

REVISED NITROGEN CYCLE Anammox removes LHS of N-cycle

ADVANTAGES OVER OTHER ANAMMOX SYSTEMS LESS COMPLICATED. Less complicated because it is a fixed film reactor designed to be self-sustaining. LESS EXPENSIVE CONSTRUCTION. Can use tanks; existing infrastructure; earth berms; ponds – or any container filled with zeolite and water.. LESS EXPENSIVE TO RUN. Reduced O & M costs; self-regulating; minimal monitoring and maintenance.

PARAMETERS CONCENTRATION All anammox, including ze-an, treat sidestreams (500 to 3000mg/L NH4-N). Ze-an is the only anammox system that can treat mainstream (30 to 50 mg/L NH4-N). Ze-an is the only anammox system that can treat water re- cycling & re-use (1 to 10mg/L NH4-N). TEMPERATURE It can function at ambient temperatures (in CA). AERATION Options - systems can be aerated, or non-aerated.

ZEOLITE-ANAMMOX PERFORMANCE TABLE Side-stream; mainstream; re-use. INFLUENT CONC. TEMP REMOVAL EFFLUENT SOURCE (mg/L NH4) °(F) (gNH4/m^3) (lbs/1000cf) Side-stream 1600 90 500 31 100 89 350 22 Mainstream 40 59-68 6 3 Re-use 5 to 10 40-60 10 to 25 0.6 to 1.5 0.1

SIDESTREAM Centrate or filtrate from anaerobic digesters. “Low hanging fruit”. Significant % of WWTP ammonia. High temperatures (90F). High NH4 concentrations (500 to 3000 mg/L).

SIDESTREAM AERATED FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME MGD Mg/L Hrs 0.1 - 3 500 - 3000 100 0.1 6-12

MAINSTREAM WWTP final and secondary effluent. Typically removes <98% ammonia. Effluent nitrate typically <5mg/L. 50% of cost of nitri-deni. Self-regulating.

MAINSTREAM AERATED NON-AERATED FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME MGD Mg/L Hrs 0.1 - 50 20 - 40 3 0.1 3-10 5 FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME MGD Mg/L Hrs 0.1 - 5 20 - 40 3 0.1 3-10 12

WATER RECYCLING Very pertinent with CA drought. Simplistic & easy to operate. Can use existing infrastructure – e.g. old tanks (settling; elutriation; digesters; aeration basins; bypass channels; etc.). Easy to adjust targets. Flexible (e.g. can limit to nitrification).

WATER RECYCLING AERATED NON-AERATED FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME MGD Mg/L Hrs 0.1 - 20 10 - 20 0.1 – 3 0.1 0.1 - 3 5 FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME MGD Mg/L Hrs 0.1 - 5 10 - 20 0.1 – 3 0.1 0.1 - 3 20

ONSITE & SEPTIC Septic tanks serve 25% of US households. Significant source of nitrate. Zeolite-anammox treated effluent <3mg/l NH4 & <3mg/L NO3. Ambient temperatures (CA central valley).

ONSITE & SEPTIC AERATED NON-AERATED FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME gpd Mg/L Hrs 50 - 500 100 3 0.1 10 5 FLOW INF NH4 EFF NH4 INF NO3 EFF NO3 DET TIME gpd Mg/L Hrs 50 - 500 100 3 0.1 10 20

EXAMPLE PROJECTS Union Sanitary District treating 35mg/L NH4- N secondary effluent. Gravity flow, no pumping, no aeration. Oro Loma Sanitary District treating 500mg/L NH4-N sidestream. Aerated system. San Francisco PUC (SouthEast) treating 1600mg/L NH4-N sidestream. Aerated system. Central Contra Costa Sanitary District treating 30mg/L NH4-N final effluent. Aerated and non-aerated systems.

EXAMPLE 1 - USD Union Sanitary District – 5,000gpd Pilot Plant treating part of 3MGD flow to Hayward Marsh. Influent is 35mg/L NH4-N. Effluent is <3mg/LNH4-N, and <3mg/L NO3- N. Very low energy use: gravity flow to marsh, no pumping, no aeration.

USD PILOT PLANT 2012-13

USD PILOT PLANT 2012-2013 Notes for previous graph: Ammonium concentration versus time. Generally influent increases from 25 to 40mg/L over life of project. Total flow distance = 144LF. NH4-N removed by half distance. NH4 spikes orange, purple, green – no breakthrough. Effluent nitrate (not shown) <3mg/L NO3-N.

EXAMPLE 2 - OLSD Oro Loma Sanitary District – two phases: (i) Pilot plant – six 50 gallon reactors. (ii) Intermediate Phase – 20,000 gall. Baker tank. Treats 14,000gpd (10% of total flow) Side-stream effluent at 500mg/L NH4-N. Cost $80K for 20,000 gallon reactor. Cost to treat full flow (0.15MGD) estimated at $1.1M.

OLSD PILOT PLANT 2013-14

OLSD SIDESTREAM PHASE 1 & 2 Notes for previous graphs: Influent NH4; effluent NH4; effluent NO3 concentrations versus time. Average influent around 500mg/L NH4-N. Target is effluent NH4 <100mg/L, and effluent NO3 <100mg/L. Targets achieved for both phases.

OLSD PHASE 2

EXAMPLE 3 – SFPUC San Francisco SouthEast WWTP. Pilot started April 2014. 80 liter (20 galls) reactor. Side-stream at 1600mg/L NH4-N NH4-N removal rate 0.4 to 0.5 kg/m^3/day. Effluent nitrate <100mg/L NH4-N.

EXAMPLE 4 - CCCSD Contra Costa Central Sanitation District. 5,000 gpd pilot plant 2014 to 2016. Aerated system and non-aerated systems. Mainstream final effluent. Plant flow 35MGD Water re-use component.

CONCLUSIONS Ze-an is the easiest sidestream treatment process. Ze-an is the only anammox system for mainstream treatment. Ze-an is the only anammox system for water re- use. KEY POINTS Flexibility – treats all concentrations; wide temperature range. Simplicity – largely self regulating; easy to run and maintain. Cost – construction, monitoring/maintenance costs, energy use, all significantly lower.

APPENDIX (A) Full Equation Nitrite Simplified: NH4 + NO2 = N2 + 2H2O Nitrate Detailed: NH4 + 1.31NO2 + 0.066HCO3 + 0.13H → 1.02N2 + 0.26NO3 + 0.066CH2O0.5N0.15 + 2.03 H2O. ------------------------------------------------- Also Nitrate equation: 3NO3 + 5NH4 →4N2 + 9H2O + 2H