OEC Measurement to VDI Guideline 3885/1 and the Electronic Noses · 2014-05-27 · a big car factory (1,800 cars per day) 4. PfProof of effi ifficiency of didosing chilhemicals itinto

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011

OEC MeasurementOEC Measurementaccording to the new VDI Guideline 3885/1

and the need for Electronic NosesThis material may be used &

distributed freely if cited correctly

Franz‐Bernd Frechen & Stefan M. Giebel, University of Kassel/Germany

Chair, IWA Specialist Group “Odour and Volatile Emissions”

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1 Department of Sanitary and Environmental Engineering (DESEE) Head: Prof. Dr.‐Ing. F.‐B. Frechen

Chair, DWA Committee “Emissions of waste water facilities”

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Overview

Wh th d f Where the odour comes from ... ... and why we have to measure it in liquids: The Odour Emission

Capacity OEC – VDI 3885/1

Online Measurement of Sulphide and OEC: the Sulphide and Online Measurement of Sulphide and OEC: the Sulphide and OEC measurement Unit SOU – and that’s why we will need ...

El t i Electronic noses

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Where does the odour come from?

Industry Sewer System, esp. pressure mains Wastewater and Sludge Treatment and Disposal

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g p

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011All starts in the sewer system

Odorants Odorantsemit from

Odorantsemit from Odour Odour

Odorants dischargedi t are pre-

sent in thewastewater

emit fromwastewaterinto the

sewer air

emit fromsewer

into am-bient air

impact inambientair

annoy-ance

into sewer

Odorants produced in sewer air bient air airproduced in the sewer

The consequence of this is that is is essential to measure the amount of odorants (and other compounds) in the liquid phase

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Another reason why measuring the liquid is inevitable

A standard sewer with natural ventilation via the manholesA standard sewer with natural ventilation via the manholes ...Any kind of monitoring device (e.g. H2Sg)

( h h i h i h h l )(at whatever height in the manhole)

odour

l = low pressure areah = high pressure area

d odourhllh

odour

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011A short detour to Sulphide/H2S

S l hid i d i t t d t ith Sulphide is a very common and important odorant with wastewaters

H2S is extremely odorous: 1 ppm H2S equals 1,000 ouE/m3

H2S can severely damage concrete:2 y g

If H S i t d ill b t If H2S is present, odour will occur, but: If no H2S is present, other odorants may still be relevant!

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Odour measurement in the liquid: The OEC

The Odour Emission Capacity OEC of a liquid is the total amount of odorants present in that liquid that can be stripped from this liquid under standardized

conditions. [Frechen and Köster, Wat.Sci.Tech.,1998]

It is given in European odour units per cubic meter of liquid Its unit is ou /m3liquid. Its unit is ouE/m3

liquid

The OEC method is covered by the new VDI guideline 3885/1 ItThe OEC method is covered by the new VDI guideline 3885/1. It will be published 2012/2013

A t i ff th d t i t i tifi ti b d bAs we strip off the odorants into air, quantification can be done by the standard olfactometric method according to CEN 13725:2003

Also, different analytical procedures can be applied to the stripped air, resulting in Emission Capacities of the substances analysed

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011OEC test reactor

Off gas outlet / sampling portOff gas outlet & sampling point

m

Liquid sample

0.10

0.354 m

pH‐measurement

sample30 Liter

5 m

Flowmeasurement

aerator 0.34

5

P t l Franke

odourless air Pressure control

Odourless air © Frechen

, odourless air

0.315 m

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011OEC Evaluation

2.000Lu

ftr

1 500

olfaktometrische Meßwerte

GE E

/m3 L

OEC = (c d‐c100)/V dVLu E/m

3 ai olfactometric measurement results

1.500

berechneton in

G OEC = (cod c100)/Vp dVLwith Vp = 30 L

c odin o

test duration

1.000 extrapoliert

Test-Dauerzent

rati

tration

test duration

extrapolated

500

offk

onz

concent

0100chss

tood

our c

00 200 400 600

Luftmenge in Liter

Ger

uo

air volume in Liter

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Luftmenge in Literair volume in Liter

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011H2S cannot replace odour as a parameter

Municipal sewer Meat industry

OdourOEC: 5,210,000 ouE/m3

liquid

OdourOEC: 594,000 ouE/m3

liquid

H2S

H2S

Dimethylsulphide

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Application

1 Characterizing different liquids concerning their odour1. Characterizing different liquids concerning their odour relevance (results so far):

Sewage: 80,000 (5,000 – 400,000) ouE/m3liquid

Excess sludge fresh: 30,000 (9,000 – 150,000) ouE/m3liquid

Filtrate stabilized sludge: 110,000 (5,000 – 400,000) ouE/m3liquidq

Filtrate raw sludge: 2,000,000 (up to 10,000,000) ouE/m3liquid

Sewage exceeding 50,000 ouE/m3liquid is generally accepted as critical

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Example pressure mains

400.000

450.000

y = 90117x + 2419,9R² = 0,9805

300 000

350.000sigkeit

quid

250.000

300.000

E/m

3 Flüss

u E/m

3 liq

150.000

200.000

P in GE E

C in

ou

50 000

100.000GEP

OEC

0

50.000

0 1 2 3 4 50 1 2 3 4 5Aufenthaltszeit Druckrohrleitung in hhydraulic residence time in the pressure main in h

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1 Characterizing different liquids concerning their odour1. Characterizing different liquids concerning their odour relevance

2 Characterizing industrial discharges set standard and control2. Characterizing industrial discharges, set standard and control whether standards are met:

Brewery: up to 3,000,000 ouE/m3liquid

Chemical industry: up to 12,000,000 ouE/m3liquid

Paper industry: up to 6,000,000 ouE/m3liquid

Tannery: up to 15,000,000 ouE/m3liquid

Meat industry: up to 10,000,000 ouE/m3liquid

Yeast industry: up to 40,000,000 ouE/m3liquid

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1 Characterizing different liquids concerning their odour1. Characterizing different liquids concerning their odourrelevance

2 Characterizing industrial discharges set standard and control2. Characterizing industrial discharges, set standard and control whether standards are met

3 Identification of problems e ample paint shop rec cle ater at3. Identification of problems: example paint shop recycle water at a big car factory (1,800 cars per day)

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4 P f f ffi i f d i h i l i t th t4. Proof of efficiency of dosing chemicals into the sewer system for odour suppression/reduction

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5 E ti ti f d l t d5. Estimation of odour release at drops

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5 E ti ti f d l t d5. Estimation of odour release at drops6. Forecast the impact of system changes on the odour emissions

fof a system

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011

E l H b di h f

Forecast of system changes

Example Hamburg: discharge ofa yeast industry wastewater via5 k i i t d fa 5 km pressure main instead of

discharge into a gravity sewer( t l it ti ) h f(actual situation): change ofquality concerning odour?

Test in DESEE’s research pressuremain: OEC measurement of the

© DESEE

“fresh” wastewaterand of the waste‐water after varyinghydraulic residencetimes in thepressure main © DESEE © DESEE

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5 E ti ti f d l t d5. Estimation of odour release at drops6. Forecast the impact of system changes on the odour emissions

fof a system7. Online Sulphide and OEC measurement Unit (SOU)for process

l f h l d hcontrol purposes of chemical dosing into the new sewer emscher:kanal utilizing H2Sg sensors and electronic noses

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Overview emscher:kanal

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Overview emscher:kanal

Gravity flow sewer „emscher:kanal“ (cost > 2 billion €, ready 2016) 51 km long, depth up to 40 m 113 manholes (every 300 – 600 m), Diameter 12 m 1 or 2 pipes, max. 2,800 mm wide Technical ventilation: design DMTg

Deutsche Montan TechnologieGmbH – Bergbau Service‐Wettertechnikg

38 waste air treatment facilities: design 38 waste air treatment facilities: designUniversity of Kassel, Department ofSanitary and EnvironmentalSanitary and EnvironmentalEngineering (DESEE)

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011basic considerations for chemical dosing

A di t t i l i ti t’ ti d t t According to a material scientist’s expertise, due to concrete corrosion prevention, a maximum of 1 ppm H2Sg in the air inside th t t b d dthe sewer must not be exceeded

Additional measures concerning the wastewater, i.e. dosing of h l blchemicals, are inevitable

Depending upon circumstances, possible strategies are an oxygen carrier (such as calciumnitrate) can be used to prevent

anaerobic conditions and subsequent sulphide formation or t l lt b d f i it ti f h d l hidmetal salt can be used for precipitation of hydrogen sulphideNon‐sulphur odorants can be oxidized e.g. with H2O2

In order to minimize consumption of chemicals a closed loop In order to minimize consumption of chemicals, a closed‐loop process control is under research at DESEE incorporating SOUtechnology that is able to prevent overdosing and unnecessarytechnology that is able to prevent overdosing and unnecessary costs

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Dosing of chemicals for odour emission suppression

Load (sulphide, OEC) Dosing amount

100 % safe“ but much too expensive

OE

C)

„100 % safe , but much too expensive

cheaper“ but still

hide

, O

„cheaper , but still overdosing, some-

times overload

(sul

ph

Closed loop processcontrol assuring optimal

Load

control assuring optimal dosing regarding cost and

efficiency

time

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Dosing of chemicals for odour emission suppression

mg/

L]at

ion

[mfo

rma

lphi

de

sul

time [h]

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Online Sulphide + OEC measurement Unit (SOU)

1st t t SOU ( t K l t )Reactor for OECmeasurement

1st test SOU (at Kassel wwtp)

Reactor for H2S‐ /sulphidemeasurement

Colour display/data storage &

PCS

measurement data storage &processing

Measurement of sulphideby lowering pH down to 4and air stripping /H2Spp g /measurement

OEC by stripping andAir supply

OEC by stripping andusing eNose

measurement interval10 mins

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Dosing process control (schematic example)

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4th IWA OVE Conference Vitoria/Brazil, 18.10.20112nd + 3rd SOU in operation at the Bottrop Sewer

© Frechen

Purpose: avoid overdosing avoid underdosing avoid underdosing

© Frechen

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© Frechen

4th IWA OVE Conference Vitoria/Brazil, 18.10.20112nd + 3rd SOU in operation at the Bottrop Sewer

© Frechen© DESEE

Purpose:

© DESEE

avoid overdosing avoid underdosing avoid underdosing

© DESEE

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© DESEE

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Simple dosing schme

H2S FeCl2YH2Sexistent

FeCl2dosing

Y

N

OEC H2O2Y> 50.0002 2

dosingY

N

okay

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Sensors needed for an online measuring SOU

f th l hid t f th SOU f H S i for the sulphide part of the SOU, a sensor for H2Sg is necessary (readily available on the market)

for the OEC part of the SOU, a sensor is needed that might be able to indicate the odour (thus replacing the test person panel): an “electronic nose”

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011eNoses under research (excerpts)

© Frechen

© Frechen

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© Frechen

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Principles of eNoses

S i d t t h d t d t l ti Semiconductor: current changes due to odorants accumulating in the detector sensitive layer

Oscillating Quartz: frequency changes due to mass of odorants accumulating in the detector sensitive layer

Usually 4 to 10 different sensor signals: different sensors (sensor materials) or different measurement conditions (heating profiles, ) ( g p ,dilution)

100%S1 (aromatic)

S10 (methane

AK Bottrop

20%

40%

60%

80% S2 (broadr.)

S3 (aromatic)S9 (sulphur, chlor)

S10 (methane-aliph)

Schwarzbach

Dr ckrohrleit ng0%

0%

S4 (hydrogen)S8 (broad, alcohol)

Druckrohrleitung

Biogasanlage: Mais-Silo (feucht)

S5 (arom-aliph)

S6 (broad, methane)

S7 (sulphur, organic) Bauernhof: Gülletank

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Legende: S1…S10 sind die Sensoren des Multisensormessgerätes

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Can eNoses measure the olfactometric odour conc.?

Th f t N ld b bl t th REAL d The perfect eNose would be able to measure the REAL odourconcentration. This means that a mathematical model exists that

t 4 t 10 di i t b (th REALconverts 4 to 10 sensors readings into one number (the REAL odour concentration)

To establish such a model, it is necessary to do parallel measurements with eNose olfactometer

The more parallel readings (the bigger the mathematical sample size), the better the mathematical model can be

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011DESEE’s data pool (09/2010)

DESEE’ d t l DESEE’ datapool: 5 eNose brands 3 olfactometry labs 3 olfactometry labs Different origins of odours

project eNose period olfactomery origin of odour numberproject eNose period olfactomery origin of odour numberVienna A 2005 Lab 1 wastewater 382Vienna B 2005 Lab 1 wastewater 156Hilter A 4/2008 ‐ 5/2008 Lab 2 wastewater 40emscher sewer A 1/2007 ‐ 1/2008 Lab 2 wastewater 150Biofilter C 2009 Lab 2 wastewater 12Biofilter C 2009 Lab 2 wastewater 12OEC with wastewater A,A 2010 Lab 2 wastewater 88safety research part 1 A,A 2007 drugs/explosives (8)f h d / l ( )safety research part 2 A,A 2010 drugs/explosives (40)

lab test C 2009 hydrogen sulphide (20)Verden A,A 2010/2011 Lab 3 wastewater 44Aachen A,A 2011 Lab 3 wastewater 156Berlin A,B,D,E 2011 Lab 3 wastewater 366

total with olfactometry: 1 394

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total with olfactometry: 1.394

4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Possible sources of problems and errors

S li Sampling Uncertainty of olfactometric measurement The eNose itself The odour’s nature The odour s nature

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S li Sampling type of eNose (batch‐like measurement or continuous reading) sampling location different constituents of odours sampling location – different constituents of odours Unsynchronized clocks of sampling devices involved (this might be

overcome by doing the eNose measurement from the same sample bag asovercome by doing the eNose measurement from the same sample bag as the olfactometric measurement)

Sample bags storage time

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U t i t f lf t t i t Uncertainty of olfactometric measurement It has to be differentiated between THE REAL ODOUR and THE ODOUR

MEASURED BY OLFACTOMETRYMEASURED BY OLFACTOMETRY Olfactometry measurement has an error itself. According to Boeker (2005)

this can be estimated to be 50%. This means: if an eNose perfectly explains the odour as measured by

olfactometry, (claimed by some vendors of eNoses: R2 = 1 !!), the model has an error of 50%!

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Th N it lf The eNose itself t90‐time

no information provided by the manufacturers no information provided by the manufacturers t90‐time differs from sensor to sensor t90‐time differs from odour to odour90

Some sensor signals do not converge to a final value at all – then there is not90‐time at all …

70.000

80.000

90.000

11 500

12.000

12.500

40.000

50.000

60.000

nsor re

ading

10.500

11.000

11.500

nsor re

ading

10.000

20.000

30.000sen

9.500

10.000

sen

0

1 2 3 4 5 6 7 8 9 10111213141516171819202122232425262728293031323334353637383940414243

time [s]

9.000

1 2 3 4 5 6 7 8 9 10111213141516171819202122232425262728293031323334353637383940414243

time [s]

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Th N it lf The eNose itself t90‐time oscillating readings mean used oscillating readings – mean used

10.420

10.380

10.400

10.340

10.360

reading

10 300

10.320

sensor

10.280

10.300

10.260

1 4 7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52 55 58 61 64 67 70 73 76 79 82 85 88 91 94 97 100

103

106

109

time [s]

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Th N it lf The eNose itself t90‐time oscillating readings mean used oscillating readings – mean used do 2 eNoses of the same type and age deliver the same readings?

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Th N it lf The eNose itself t90‐time oscillating readings mean used oscillating readings – mean used do 2 eNoses of the same type and age deliver the same readings? aging of sensors aging of sensors

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4th IWA OVE Conference Vitoria/Brazil, 18.10.2011Finale ....

Th k f ki d i !Thanks for your kind attention!

this (and more) presentation(s) can be downloaded fromwww uni kassel de\fb14\siwawiwww.uni‐kassel.de\fb14\siwawi

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Documents

OEC Measurement to VDI Guideline 3885/1 and the Electronic Noses · 2014-05-27 · a big car factory (1,800 cars per day) 4. PfProof of effi ifficiency of didosing chilhemicals itinto