LEVAPOR – porous, adsorbing carrier for bioprocess improvement

Dr. Imre Pascik LEVAPOR /Biofilm Tech GmbHwww. levapor.com Leverkusen, Germany

About us

• Innovative Organization • 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

About us

• Development of 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

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

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

Biological Removal of nitrogen

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

-

Nitrosomonas and Nitrobacter

Attributes of nitrifying bacteria • slow growth: generation time: 12 to 24 hrs• low cell yield: 3 % from N-oxidized• weak flocculation• high sensitivity to certain chemicals

FACTORS AFFECTING NITRIFICATION

1.SUBSTRATE – WASTE WATER MATRIX

• 2. INHIBITORS

• 3. NITRIFYING BIOMASS

• 4. PROCESS CONDITIONS

• 5. PROCESS CONCEPT

FACTORS AFFECTING NITRIFICATIONWASTE WATER 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

Types of upsets

Biomass wash-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

Type of the upset 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

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

Our REQUESTS on OPTIMAL 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

Our Technology

• LEVAPOR Bio 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

Our Technology

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

Advantages • Fixing of weakly 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

Applications• Nitrification-Denitrification of Petro Chemicals effluent • COD removal, Nitrification of Highly toxic Agro Chemicals

effluent • Nitrification of municipal effluent under cold climate• Nitrification of Hyper Saline Effluent

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

A typical Effluent Characteristics

• 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

The Problem • Adversely affect 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

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

Pilot Testing

• Proposed Micro Aerobic-Anaerobic-Aerobic Scheme with denitrification

• Tested for two years at site•

Pollutant Removal

Pollutantinfluent

concentrationsremoval %

overall in 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

Biodegradation of HerbicidesComponent 26.10.05

Influent degree of removal, overall

% removal insingle steps

mg/L absol. S D % MAE ANA AER

Atrazine 20,4 19,6 96,1 57,1 18,4 24,5Simazine 1,9 1,9 100,0 57,9 10,5 31,6Terb.Azine 14,1 13,3 94,3 51,9 34,6 13,5Ametryn 1,7 1,7 100,0 52,9 11,8 35,3Prometryn 1,9 1,9 100,0 47,4 31,6 21,0Tris 12,6 11,9 90,0 52,1 31,9 16,0Unknown 60,3 53,1 88,1 62,3 23,4 14,3Terbutryn 1,4 1,4 100,0 42,9 28,6 28,5Linuron 11,3 11,3 100,0 92,9 7,1Bromacil 1,0 0,8 80,0 50,0 50,0 0,0Dicuran 7,4 6,8 91,9 20,6 29,4 50,0Diuron 3,2 3,2 100,0 43,8 6,3 49,9SHerbicides 161,9 148,1 91,5 60,6 9,2 30,2

Full Scale Plant

• 1.8 MLD • 8-12,000 mg/lit COD• 300-600 mg/lit TKN • 12-25,000 mg/lit

Salinity

Full Scale Plant

COD reduction

COD-removal

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

total

microaerobic

Nitrogen Reduction

0,0

50,0

100,0

150,0

200,0

250,0

300,0

350,0

400,0

450,0

NO3Neffl NH4Neffl

N (mg/L) TKNinfl

Plant for the biological removal of 8100 kg/d NH4+ in the

petrochemical industry in Germany (startup: 1981)

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-richeffluents !Several contractors refused the projectExisting pretreatment: API-separator + flotation

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

DUE TO NUMEROUS INFLUENCING 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

On-line pilot tests serve for

• confirming of process under practical conditions • fine optimisation

• demonstration of technique

• staff education and training

How Can We Associate

• 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

Thank You !!!!