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Nitrification of Complex Effluent
Levapor is an innovative organization specializing in bioprocess improvement for treating high-strength industrial and municipal wastewater, particularly through nitrification and denitrification techniques. They develop tailored bio carriers to enhance microbial efficiency, facilitating the removal of complex pollutants effectively. The technology demonstrated significant advantages in process stability, performance, and lower energy consumption compared to traditional systems.
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Nitrification of Complex Effluent
- 1. LEVAPOR – porous,adsorbing carrier for bioprocess improvement Dr. Imre Pascik LEVAPOR /Biofilm Tech GmbH www. levapor.com Leverkusen, Germany
- 2. About us • InnovativeOrganization • Fixed Film Based Process Solutions • Complex Effluent, Municipal Wastewater, Polluted Gas • CEO Dr. Imre Pascik • 40 years of experience with Bayer AG, Environmental Bio Technology Centre, Leverkusen
- 3. About us • Developmentof innovative processes • Two Step nitrification of high Ammonia containing effluents • Landfill Leachate Treatment • Bayer Tower Biology (Otto Award) • Degradation of toxic effluents using Anaerobic-Aerobic Processes
- 4. What We do •Problem analysis for the treatment of high strength industrial and municipal wastewater treatment • Define treatment goals and conceptual process design • Development of optimal process and design parameters with pilot tests • Manufacturing of high performance tailor made bio carriers for the application • Process Start up
- 5. Industries We serve •Chemicals and Pharmaceuticals • Petrochemicals and Refineries • Pulp and Paper • Coal Conversion : coke plant, coal gasification, pyrolysis • Textile finishing and Leather manufacturers • Municipal Wastewater Treatment • Special effluents like land fill leachate and sludge processing unit
- 6. Biological Removal ofnitrogen NITRIFICATION is a biological oxidation followed by biological reduction, DENITRIFICATIONNH4 + +1.5 O2 Nitrosomonas → NO2 - + 2 H+ + H2O ammonium pH-value decreases ! NO2 - + 0.5 O2 Nitrobacter → NO3 - NITRIFICATION = NH4 + bio-oxidation NO3 - NH4 + +1.5 O2 Nitrosomonas → NO2 - + 2 H+ + H2O ammonium pH-value decreases ! NO2 - + 0.5 O2 Nitrobacter → NO3 - NITRIFICATION = NH4 + bio-oxidation NO3 -
- 7. Nitrosomonas and Nitrobacter Attributesof nitrifying bacteria • slow growth: generation time: 12 to 24 hrs • low cell yield: 3 % from N-oxidized • weak flocculation • high sensitivity to certain chemicals
- 8. FACTORS AFFECTING NITRIFICATION 1.SUBSTRATE– WASTE WATER MATRIX • 2. INHIBITORS • 3. NITRIFYING BIOMASS • 4. PROCESS CONDITIONS • 5. PROCESS CONCEPT
- 9. FACTORS AFFECTING NITRIFICATION WASTEWATER MATRIX • Organic pollutants - structure,concentr.,effect (tensides) • COD: NH4N - ratio • Inorganic pollutants-salinity, Ca2+ ,heavy metals(Cd,Cu) • INHIBITORS - effect (reversible, irrevers.), concentration • QUALITY FLUCTUATIONS BIOMASS • Bioactivity - (gNoxidized /kgBiomass*day) • Stability - resistance to inhibiting influences PROCESS PARAMETERS • Food : Mass-Ratio (gN/kgBiomass*day) • C/N - ratio • Temperature, pH, dissolved O2
- 10. Types of upsets Biomasswash-out Disturbed process Inhibited process Phenomena biomass doesn´t settle, can´t be separated and leaves the reactor Lower degree of nitrification,slower process Total inhibition Bioactivity in the reactor Unchanged, but lower efficiency due to lower MLVSS in the reactor Lower, but able to recovery after elimination of the causes No bioactivity Possible reasons - biomass morphology: bulking or small flocs - high salinity - deficit in nutrients -overloaded separation • Waste water matrix: structure and concentration of organic and inorganic pollutants • Fluctuations: quality and quantity of pollutants • Remarkable changes of process para- meters: pH, temperature * plant operators
- 11. Type of theupset Possible measure Weakly flocculating, slowly settling biomass, wash-out -Addition of biodegradable organic carbon source - Immobilisation on carrier material * Periodical inhibition by reversible inhibitors - Temporary addition of powdered activated carbon - Addition of nitrifying biomass from external plants * Continuous inhibition by reversible acting inhibitors - Identification and source treatment of the inhibitory effluent stream - Adaptation of nitrifying biomass - Semi-continuous addition of separately generated nitrifying biomass * Irreversible inhibition by strong inhibitors -New startup with external biomass - Identification and source treatment of inhibitory effluent streams
- 12. Bio Film Technology •Biodegradation of pollutants occurs via teamwork of microorganisms united in sludge flocs • Important result of research : • Some important, non-flocculating organisms will be washed out from bioreactor, resulting reduced plant efficiency • Solution: Biofilm technology • via immobilisation, cell growth on • solid surfaces, “carriers“ made of • plastics, sand, glass, etc. • Target: Synthesis of biocarrier
- 13. Our REQUESTS onOPTIMAL CARRIER • PROPERTY EFFECT • 1. Adsorbing capacity - binding toxic pollutants - fast colonization + bio film - fast start up at high level • 2. Porosity, high inner surface - protection of the biofilm • (high biomass content) - high space-time-yields • 3. Fast wetting - homogenous fluidisation • 4. Water binding - mass transport, bioactivity • 5. Proper fluidisation - lower energy consumption
- 14. Our Technology • LEVAPORBio Carrier • First synthesized Bio Carrier • Porous, Flexible, Durable PU foam impregnated with surface active pigments like activated carbon • Due to variability of foam and pigment type and their ratios, tailor made carriers can be produced with varying properties
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- 16. Properties High Adsorbing Surface •10 to 12 kg of activated carbon per m3 of foam matrix • PU foam surface area 2500 m2/m3 • 1000-2000 m2/g surface area of activated carbon • Extremely high adsorbing surface Benefits: • Reversible Adsorption • Rapid microbial colonization and biofilm formation • Temporary adsorption of toxic and inhibitory substances • Subsequent biodegradation and thus regeneration of surface
- 17. Advantages • Fixing ofweakly flocculating nitrifying biomass on the carrier material • Temporary adsorption of reversible inhibitors and their subsequent biodegradation on activated carbon present in the carrier material . Also reducing its toxicity in the bulk liquid and thus stabilizing process in suspended phase • Short process start up and higher performance compared to suspended mass based systems (100 to 300%) • Higher process stability against toxic shock loads and fluctuations in reactor conditions • Lower Degree of Filling (12 to 15%) • Smaller foot print • Lower energy consumption for fluidization • Lower sludge production • Simpler process control
- 18. Applications • Nitrification-Denitrification ofPetro Chemicals effluent • COD removal, Nitrification of Highly toxic Agro Chemicals effluent • Nitrification of municipal effluent under cold climate • Nitrification of Hyper Saline Effluent
- 19. Agro Chemicals Manufacturing Unit •Pesticides Manufacturing Agrochemicals industries • A Wide variety of agro chemicals manufactured at site due to hectic crop cycle • Effluents Containing : • Biologically active biocides and often inhibiting raw chemicals , active ingredients and their by products • Solvents like methanol, aromates, dicholoromethane, methyl-isobutyl-ketone(MIBK) from the formulations • Higher Salinity
- 20. A typical EffluentCharacteristics • Up to 12,000 mg/lit COD comprising solvents in it • Up to 600 mg/lit inhibitory , active ingredients and their by products • 500 to 800 mg/lit Total Kjehldahl Nitrogen (TKN) containing mostly Organic-N associated with slowly hydrolysable s- triazine. • Up to 1500 mg/lit Sulfates (SO4-) • 10,000 to 25,000 mg/lit Salt Concentration as NaCl
- 21. The Problem • Adverselyaffect the environment • Presence of high amount of biodegradable solvents make wet oxidation processes costly and thus biological degradation would be cost effective alternative • Higher concentrations of inhibitory substances lower the COD removal efficiency of suspended growth only reactors • COD removal also affected due to high fluctuations of load • Severe nitrification inhibition due to fluctuating COD removal efficiency • Aerobic only treatment increases aeration costs and also handling of high amount of toxic sludge
- 22. The solution • MicroAerobic-Anaerobic-Aerobic •Provides most diverse microbial consortia responsible for the biodegradation of complex molecular structures. • During Anaerobic Step the complex molecules are hydrolysed • Much of the COD removed , thus reduce aeration demand • Lower sludge production and thus solids handling costs. • Presence of inhibitory substances, pH changes, salinity fluctuations cause deflocculation and wash out of microbes • Thus, immobilization of microbes on carriers
- 23. Pilot Testing • ProposedMicro Aerobic-Anaerobic-Aerobic Scheme with denitrification • Tested for two years at site •
- 24. Pollutant Removal Pollutant influent concentrations removal % overallin different steps mg/L % microaerob- + anaerobic aerobic Aromatic solvents 1,5-3,0 100,0 90,0 10,0 Methanol 930 - 1980 100,0 95,0-100,0 0-5,0 Dichloromethane 4,0 - 42,0 100,0 100,0 0,0 MIBK 9,0 -330,0 100,0 76,0 24,0 Amines 56,2 - 64,8 100,0 90,0-100,0 0,0-10,0 Triazine derivatives 96,5 - 114,3 100,0 64,2 35,8 Carbamates 17,8 - 24,3 80,0 72,0 28,0 Herbicides total 154,0 - 337,0 91,5 75 25
- 25. Biodegradation of Herbicides Component 26.10.05 Influentdegree of removal, overall % removal in single steps mg/L absol. S D % MAE ANA AER Atrazine 20,4 19,6 96,1 57,1 18,4 24,5 Simazine 1,9 1,9 100,0 57,9 10,5 31,6 Terb.Azine 14,1 13,3 94,3 51,9 34,6 13,5 Ametryn 1,7 1,7 100,0 52,9 11,8 35,3 Prometryn 1,9 1,9 100,0 47,4 31,6 21,0 Tris 12,6 11,9 90,0 52,1 31,9 16,0 Unknown 60,3 53,1 88,1 62,3 23,4 14,3 Terbutryn 1,4 1,4 100,0 42,9 28,6 28,5 Linuron 11,3 11,3 100,0 92,9 7,1 Bromacil 1,0 0,8 80,0 50,0 50,0 0,0 Dicuran 7,4 6,8 91,9 20,6 29,4 50,0 Diuron 3,2 3,2 100,0 43,8 6,3 49,9 SHerbicides 161,9 148,1 91,5 60,6 9,2 30,2
- 26. Full Scale Plant •1.8 MLD • 8-12,000 mg/lit COD • 300-600 mg/lit TKN • 12-25,000 mg/lit Salinity
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- 30. Plant for thebiological removal of 8100 kg/d NH4 + in the petrochemical industry in Germany (startup: 1981)
- 31. SHELL, Wesseling 1977: 8 mio t/yr crude oil, ethylene, methanol,carbamide,coal gasification Waste water situation: • flow = 8000 m³/day • COD = 10.800 kg/d • NH4N = 8000 kg/d Requirement: removal of COD + NH4N( < 15 mg/L) No experience with nitrification/denitrification of N-rich effluents ! Several contractors refused the project Existing pretreatment: API-separator + flotation
- 32. SHELL-PLANT – Wesseling,Germany It was the first plant of this type and capacity in the world Footprint: 11.000 m² surface instead of 50.000 m² for basin construction Daily oxygene uptake: 45.000 kg/d Injector aeration : 10.800 m³/h air instead of 70.000 m³/h (surface aerators) Startup in July 1981
- 35. DUE TO NUMEROUSINFLUENCING FACTORS FOR THE DESIGN OF TREATMENT PLANTS WITH NITRIFICATION, BIOKINETIC PARAMETERS OF THE PROCES MUST BE DETERMINED EXPERI-MENTALLY. In lab scale plants • degree of N-oxidation • velocity of nitrification • optimal F:M-ratio • effect of peak loadings • effect of inhibitors can be determined, while
- 36. On-line pilot testsserve for • confirming of process under practical conditions • fine optimisation • demonstration of technique • staff education and training
- 37. How Can WeAssociate • Problem analysis for the treatment of high ammonia containing effluents • Define treatment goals and conceptual process design • Development of optimal process and parameters • Manufacturing of high performance tailor made bio carriers for the application • Process Start up
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