evaluation of sensors and analysers
DESCRIPTION
Sensors and Analysers for Wastewater treatment.TRANSCRIPT
7th 7th Anque’sAnque’s international Congressinternational Congress
Water in industryWater in industryAquaFit4Use SP2 : Waste water treatmentAquaFit4Use SP2 : Waste water treatment
EVALUATION OF SENSORS EVALUATION OF SENSORS
AND ANALYSERSAND ANALYSERS
Marie MAURELMarie MAUREL
Yannik LADEGAILLERIEYannik LADEGAILLERIE
VEOLIA ENVIRONNEMENTVEOLIA ENVIRONNEMENT
SP2 meeting SP2 meeting –– OviedoOviedo
14.06.201014.06.2010
AND ANALYSERSAND ANALYSERS
AgendaAgenda
�� Task 2.1.1 Evaluation of Sensors and AnalysersTask 2.1.1 Evaluation of Sensors and Analysers
�� Context and ObjectivesContext and Objectives
�� Material and MethodsMaterial and Methods
�� Results about CODResults about COD
OnOn--going and future workgoing and future work�� OnOn--going and future workgoing and future work
Context & ObjectivesContext & Objectives
Task 2.1.1 Task 2.1.1 -- EVALUATION OF SENSORS AND ANALYSERSEVALUATION OF SENSORS AND ANALYSERS
Context & ObjectivesContext & Objectives
Context & General objectivesContext & General objectives
�� ContextContext
�� Process modelling and control needs adequate measurementsProcess modelling and control needs adequate measurements
�� Parameters must be chosen among the list set by WP 1.1Parameters must be chosen among the list set by WP 1.1
�� ObjectivesObjectives
�� Define sensors benchmark and criteria of comparison Define sensors benchmark and criteria of comparison
�� Execute labExecute lab--scale tests for sensor evaluationscale tests for sensor evaluation
�� Execute test for sensor evaluation on real industrial waste water Execute test for sensor evaluation on real industrial waste water samplessamples
Main Parameter chosen: Main Parameter chosen:
the Chemical Oxygen Demand (COD)the Chemical Oxygen Demand (COD)
�� Definition:Definition:�� Indirect measurement of organic compounds in waterIndirect measurement of organic compounds in water�� Mass of oxygen consumed to oxidize one litter of solutionMass of oxygen consumed to oxidize one litter of solution
�� Interest:Interest:�� Good indicator of the efficiency of a process Good indicator of the efficiency of a process �� This parameter is interesting at all stages of all processesThis parameter is interesting at all stages of all processes�� This parameter is interesting at all stages of all processesThis parameter is interesting at all stages of all processes
�� Concentrations:Concentrations:�� Pure water:Pure water: 00�� Potable water:Potable water: < 2 mgO2/L (~TOC)< 2 mgO2/L (~TOC)�� Surface water:Surface water: 20 mgO2/L (~TOC)20 mgO2/L (~TOC)�� Raw Waste water:Raw Waste water: 1000 mgO2/L1000 mgO2/L�� Outlet of industrial waste water plant: Outlet of industrial waste water plant: < 150 mgO2/L< 150 mgO2/L
Secondary Parameters chosen: Secondary Parameters chosen:
Total Nitrogen (N), Calcium (Ca), Lead (Pb)Total Nitrogen (N), Calcium (Ca), Lead (Pb)
�� Definition:Definition:�� Total N = NH4 + organic N + NOTotal N = NH4 + organic N + NO33 + NO+ NO22
�� Interest:Interest:�� Total N: salt, able to inhibit biological activity, necessary control of N to Total N: salt, able to inhibit biological activity, necessary control of N to
avoid eutrophisation in case of dischargeavoid eutrophisation in case of discharge�� Ca: indicator of water hardness, source of depositsCa: indicator of water hardness, source of deposits�� Ca: indicator of water hardness, source of depositsCa: indicator of water hardness, source of deposits�� Pb: example of heavy metal Pb: example of heavy metal
�� Concentrations for Total N:Concentrations for Total N:�� Potable waterPotable water < 50 mgN/L< 50 mgN/L
�� Raw Waste water :Raw Waste water : 100 mgN/L100 mgN/L
�� Outlet of waste water plant: Outlet of waste water plant: < 10< 10--15 mgN/L15 mgN/L
�� Industrial waste water:Industrial waste water: > 1000 mgN/L> 1000 mgN/L
Material & MethodMaterial & Method
Task 2.1.1 Task 2.1.1 -- EVALUATION OF SENSORS AND ANALYSERSEVALUATION OF SENSORS AND ANALYSERS
Material & MethodMaterial & Method
�� Analyse of the absorption for the whole Analyse of the absorption for the whole spectrum:spectrum:�� Spectro::Lyser (S::CAN)Spectro::Lyser (S::CAN)
�� Carbovis (WTW)Carbovis (WTW)
�� Analyse of absorption for only 1 or 2 Analyse of absorption for only 1 or 2
Instruments tested for CODInstruments tested for COD
�� Analyse of absorption for only 1 or 2 Analyse of absorption for only 1 or 2 wavelengths:wavelengths:�� Uvas (HachUvas (Hach--Lange)Lange)
�� Trescon SAC Module (WTW)Trescon SAC Module (WTW)
�� Oxidation with UV activated TiO2 photoOxidation with UV activated TiO2 photo--catalyst:catalyst:�� PeCOD P100 (AquaDiagnostic)PeCOD P100 (AquaDiagnostic)
Absorption Absorption -- Measurement principleMeasurement principle
�� The COD can be correlated with the UVThe COD can be correlated with the UV--VIS measurement (254 nm).VIS measurement (254 nm).
�� This measurement must be compensated with turbidity (visible wave This measurement must be compensated with turbidity (visible wave length)length)
PeCOD PeCOD –– Measurement principleMeasurement principle
�� Analyse of gas from thermal oxidation Analyse of gas from thermal oxidation (total Nitrogen):(total Nitrogen):
�� QuickTONb (ANAEL) QuickTONb (ANAEL)
�� Selective electrodes for Calcium (Ca):Selective electrodes for Calcium (Ca):
�� Orion (Thermo)Orion (Thermo)
Instruments tested for Total N, Ca and PbInstruments tested for Total N, Ca and Pb
�� Orion (Thermo)Orion (Thermo)
�� MetrohmMetrohm
�� Schott (WTW)Schott (WTW)
�� Selective electrodes for Lead (Pb):Selective electrodes for Lead (Pb):
�� Orion (Thermo)Orion (Thermo)
�� MetrohmMetrohm
�� Schott (WTW)Schott (WTW)
�� Full combustion and thermal oxidation of the sample at 1200Full combustion and thermal oxidation of the sample at 1200°°CC
�� Condensation of the gas at 4Condensation of the gas at 4°°CC
�� Use of specific sensorUse of specific sensor
Thermal oxidation Thermal oxidation –– Measurement principleMeasurement principle
Selective electrodes Selective electrodes –– Measurement principleMeasurement principleSelective electrodes Selective electrodes –– Measurement principleMeasurement principle
�� Measurement of electrical potential for a targeted ionMeasurement of electrical potential for a targeted ion
�� Comparison with a reference electrodeComparison with a reference electrode
Reference Measurement for CODReference Measurement for COD
�� Based on ISO 15705Based on ISO 15705
�� Measurement of the mass of potassium dichromate that reacts with the Measurement of the mass of potassium dichromate that reacts with the oxidizable substances in sample under the working conditions of the method.oxidizable substances in sample under the working conditions of the method.
�� Reaction time of 2 hours at 148 Reaction time of 2 hours at 148 °°C. C.
Test protocolTest protocol
�� Protocol developed:Protocol developed:
�� Laboratory tests (on synthetic samples)Laboratory tests (on synthetic samples)
�� Evaluation of sensor performances (static, dynamic)Evaluation of sensor performances (static, dynamic)
�� Pilot tests (on real water)Pilot tests (on real water)
�� Evaluation of maintenance costsEvaluation of maintenance costs�� Evaluation of maintenance costsEvaluation of maintenance costs
�� Evaluation of interferencesEvaluation of interferences
LOD
SDC20
SDC80B20
B80
0
10
20
30
40
50
60
70
80
90
100
110
120
130
X - Time
Y -
Re
sp
on
se
in
%
Delay Time Response Time
Fall TimeRiseTime
Choice of a synthetic sample for CODChoice of a synthetic sample for COD
�� Choice between 3 existing synthetic samples:Choice between 3 existing synthetic samples:�� Brenntaplus (Brenntag GmbH):Brenntaplus (Brenntag GmbH):
�� Acetic acid (25 % Acetic acid (25 % -- 50 %),50 %),�� Dark brown liquid Dark brown liquid �� COD ~ 1000 gOCOD ~ 1000 gO22/L/L
�� Canadian formula:Canadian formula:�� Potassium Biphtalate, phosphatePotassium Biphtalate, phosphate�� Potassium Biphtalate, phosphatePotassium Biphtalate, phosphate�� COD ~ 1 gOCOD ~ 1 gO22/L /L
�� OCDE:OCDE:�� Main compound : Viandox (Main compound : Viandox (salty sauce with a little meat extract and salty sauce with a little meat extract and
flavored)flavored)�� Dark brown liquidDark brown liquid�� COD ~ 79 gOCOD ~ 79 gO22/L/L
�� OCDE was chosen due to similarity with urban waste waterOCDE was chosen due to similarity with urban waste water
Choice of a synthetic sample for CODChoice of a synthetic sample for COD
Absorption spectra of synthetic samples of COD = 1000 mg/L
2
2,5
Ab
so
rpti
on
(1/m
)
OCDE
Canadian receip
BrenntaPlus
Urban Waste Water
0
0,5
1
1,5
150 200 250 300 350 400 450 500
Wavelength (nm)
Ab
so
rpti
on
(1/m
)
Results about CODResults about COD
Task 2.1.1 Task 2.1.1 -- EVALUATION OF SENSORS AND ANALYSERSEVALUATION OF SENSORS AND ANALYSERS
Results about CODResults about COD
Results about CODResults about COD
�� Tests performed for 5 devices:Tests performed for 5 devices:�� Use of OCDEUse of OCDE�� Scale: Scale: 0 mgO2/L < COD < 1000 mgO2/L0 mgO2/L < COD < 1000 mgO2/L
�� Interpretation of results needs to be completed in Interpretation of results needs to be completed in collaboration with the supplierscollaboration with the supplierscollaboration with the supplierscollaboration with the suppliers
Results about COD:Results about COD:
Carbovis (WTW) Carbovis (WTW) –– AccuracyAccuracy
550
600
650
700
750
800
850
900
Carbovis WTW Reference
-50
0
50
100
150
200
250
300
350
400
450
500
11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 16:30 17:00 17:30
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Carbovis (WTW) Carbovis (WTW) –– DynamicsDynamics
550
600
650
700
750
800
850
900
Carbovis WTW Reference
-50
0
50
100
150
200
250
300
350
400
450
500
550
11:31 12:01 12:31 13:01 13:31 14:01 14:31 15:01 15:31 16:01 16:31 17:01 17:31 18:01
Time (hour:minute)
CO
D (
mg
/L)
Results for COD: Results for COD:
Trescon (WTW) Trescon (WTW) –– AccuracyAccuracy
550
600
650
700
750
800
850
900
TresCon WTW Reference
-50
0
50
100
150
200
250
300
350
400
450
500
11:53 12:23 12:53 13:23 13:53 14:23 14:53 15:23 15:53 16:23 16:53 17:23 17:53
Time (hour:minute)
CO
D (
mg
/L)
Results for COD: Results for COD:
Trescon (WTW) Trescon (WTW) –– DynamicsDynamics
550
600
650
700
750
800
850
900
-50
0
50
100
150
200
250
300
350
400
450
500
550
11:45 12:15 12:45 13:15 13:45 14:15 14:45 15:15 15:45 16:15 16:45 17:15 17:45 18:15
Time (hour:minute)
CO
D (
mg
/L)
Reference TresCon WTW
Results for COD:Results for COD:
Spectro::Lyser (S::CAN) Spectro::Lyser (S::CAN) –– AccuracyAccuracy
550
600
650
700
750
800
850
900
Spectrolyser SCAN Reference
-50
0
50
100
150
200
250
300
350
400
450
500
550
10:52 11:22 11:52 12:22 12:52 13:22 13:52 14:22 14:52 15:22 15:52 16:22 16:52 17:22
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Spectro::Lyser (S::CAN) Spectro::Lyser (S::CAN) –– DynamicsDynamics
550
600
650
700
750
800
850
900
SpectroLyser SCAN Reference
-50
0
50
100
150
200
250
300
350
400
450
500
09:00 09:30 10:00 10:30 11:00 11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 16:30
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Spectro::Lyser (S::CAN) Spectro::Lyser (S::CAN) –– LinearityLinearity
500
550
600
650
700
750
800
850
Spectrolyser SCAN Reference
-50
0
50
100
150
200
250
300
350
400
450
500
11:18 11:48 12:18 12:48 13:18 13:48 14:18 14:48 15:18
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Uvas (HachUvas (Hach--Lange) Lange) –– LinearityLinearity
550
600
650
700
750
800
850
900
Uvas LANGE Reference
-50
0
50
100
150
200
250
300
350
400
450
500
550
11:43 12:13 12:43 13:13 13:43 14:13 14:43 15:13 15:43
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
All devices: table of main evaluation criteriaAll devices: table of main evaluation criteria
Trescon (WTW)Trescon (WTW)Carbovis Carbovis
(WTW)(WTW)
Uvas (HachUvas (Hach--
Lange)Lange)
Spectro::Lyser Spectro::Lyser
(S::CAN)(S::CAN)
Response time (minutes)Response time (minutes) 77 33 22 11
OffsetOffset 1010 9292 2525 99
Limit of detection (LOD)Limit of detection (LOD) 1313 00 1212 1111Limit of detection (LOD)Limit of detection (LOD) 1313 00 1212 1111
Bias at 20%Bias at 20%
(B20)(B20)1212 8181 --112112 --77
Bias at 20%Bias at 20%
(B80)(B80)2020 8787 --102102 2323
Smallest detectable change at 20%Smallest detectable change at 20%
(SDC20)(SDC20)22 104104 3434 7575
Smallest detectable change at 80%Smallest detectable change at 80%
(SDC80)(SDC80)1111 123123 3131 102102
mg
(Om
g(O
22)/
L)/
L
Results for COD:Results for COD:
All devices: comparison radar diagramAll devices: comparison radar diagram
-4
-2
0
2
4
6
8
Response time
OffsetSDC80
Trescon (WTW)
-10
-8
-6
-4
LOD
B20B80
SDC20
Carbovis (WTW)
Uvas (Hach-Lange)
Spectro::Lyser (S::CAN)
Results for COD:Results for COD:
All devices: preconisationsAll devices: preconisations
Trescon Trescon
(WTW)(WTW)
Carbovis Carbovis
(WTW)(WTW)
Uvas (HachUvas (Hach--
Lange)Lange)
Spectro::Lyser Spectro::Lyser
(S::CAN)(S::CAN)
Price (per unit)Price (per unit) 7 000 7 000 €€ 13 000 13 000 €€ 6 000 6 000 €€ 23 000 23 000 €€
�� Which sensor should you choose ?Which sensor should you choose ?�� Which sensor should you choose ?Which sensor should you choose ?
�� Choice depends on the requirements for the applicationChoice depends on the requirements for the application
�� What specifications are needed ?What specifications are needed ?
�� Tests have to be achieved on real industrial waste water Tests have to be achieved on real industrial waste water samples to complete the evaluationsamples to complete the evaluation
OnOn--going & future workgoing & future work
Task 2.1.1 Task 2.1.1 -- EVALUATION OF SENSORS AND ANALYSERSEVALUATION OF SENSORS AND ANALYSERS
OnOn--going & future workgoing & future work
OnOn--going an future workgoing an future work
�� OnOn--going work:going work:
�� Final interpretation of the results about CODFinal interpretation of the results about COD
�� Evaluation of Total N analyser and Ca and Pb sensorsEvaluation of Total N analyser and Ca and Pb sensors
�� Future work:Future work:�� Future work:Future work:
�� Evaluation of COD sensors on real industrial waste Evaluation of COD sensors on real industrial waste water sampleswater samples
Thank you Thank you
for your attentionfor your attention
☺☺
Merci pour votre attentionMerci pour votre attention
Gracias por su atención Gracias por su atención
Danke für Ihre AufmerksamkeitDanke für Ihre Aufmerksamkeit
Grazie per la vostra attenzione Grazie per la vostra attenzione
Dank u voor uw aandachtDank u voor uw aandacht
Early results for CODEarly results for COD
�� Issue: comparison of different physical quantities for CODIssue: comparison of different physical quantities for COD
�� Absorption: mAbsorption: m--11 �� Trescon SAC Module (WTW), UVAS (Lange)Trescon SAC Module (WTW), UVAS (Lange)
SensorSensor ComputerComputer
Absorption Absorption [m[m--11]]
COD COD [mgO[mgO22/L]/L]SampleSample
�� COD: mgOCOD: mgO22/L/L
Measurement of Measurement of absorptionabsorption
External offline conversion: External offline conversion: specific to each sensorspecific to each sensor
SensorSensor
Measurement and Measurement and internal online calculationinternal online calculation
COD COD [mgO[mgO22/L]/L]SampleSample
Tasks / Deliverables and StatusTasks / Deliverables and Status�� Selection of sensors and definition of the test protocolSelection of sensors and definition of the test protocol
�� Internal report (2.1.1.1) finalizedInternal report (2.1.1.1) finalized
�� Evaluation of sensorsEvaluation of sensors�� Completed: COD analysers tests on synthetic samplesCompleted: COD analysers tests on synthetic samples
�� In progress: In progress: �� In progress: In progress: �� Completion of COD analysers tests on real industrial water samples Completion of COD analysers tests on real industrial water samples
(June 2010)(June 2010)
�� Total N analyser, Ca and Pb sensors evaluation (July 2010)Total N analyser, Ca and Pb sensors evaluation (July 2010)
�� Internal report (2.1.1.2) due month 28 (September 2010)Internal report (2.1.1.2) due month 28 (September 2010)
�� Interactions with other WPsInteractions with other WPs�� Samples received form ATM (food industry waste water)Samples received form ATM (food industry waste water)
Results for COD:Results for COD:
Carbovis (WTW) Carbovis (WTW) –– LinearityLinearity
600
700
800
900
CO
D (
mg
/L)
Carbovis WTW Reference
0
100
200
300
400
500
11:13 11:43 12:13 12:43 13:13 13:43 14:13 14:43 15:13 15:43 16:13
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Uvas (HachUvas (Hach--Lange) Lange) –– AccuracyAccuracy
50
55
60
65
70
75
80
CO
D (
mg
/L)
Uvas LANGE Reference
0
5
10
15
20
25
30
35
40
45
11:00 11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 16:30 17:00 17:30
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Uvas (HachUvas (Hach--Lange) Lange) –– DynamicsDynamics
600
700
800
900
1000
CO
D (
mg
/L)
Uvas LANGE Reference
0
100
200
300
400
500
600
12:02 12:32 13:02 13:32 14:02 14:32 15:02 15:32 16:02 16:32 17:02 17:32 18:02 18:32
Time (hour:minute)
CO
D (
mg
/L)
Results for COD: Results for COD:
Trescon (WTW) Trescon (WTW) –– LinearityLinearity
600
700
800
900
TresCon WTW Reference
0
100
200
300
400
500
11:14 11:44 12:14 12:44 13:14 13:44 14:14 14:44 15:14
Time (hour:minute)
CO
D (
mg
/L)
Results about COD:Results about COD:
Carbovis (WTW) Carbovis (WTW) –– AccuracyAccuracy
35
45
55
65
CO
D (
mg
/L)
Carbovis WTW Reference
-5
5
15
25
35
11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 16:30 17:00 17:30
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Carbovis (WTW) Carbovis (WTW) –– DynamicsDynamics
550
650
750
850
950
Carbovis WTW Reference
-50
50
150
250
350
450
550
11:31 12:01 12:31 13:01 13:31 14:01 14:31 15:01 15:31 16:01 16:31 17:01 17:31 18:01
Time (hour:minute)
CO
D (
mg
/L)
Results for COD: Results for COD:
Trescon (WTW) Trescon (WTW) –– AccuracyAccuracy
35
40
45
50
55
60TresCon WTW Reference
-10
-5
0
5
10
15
20
25
30
11:53 12:23 12:53 13:23 13:53 14:23 14:53 15:23 15:53 16:23 16:53 17:23 17:53
Time (hour:minute)
CO
D (
mg
/L)
Results for COD: Results for COD:
Trescon (WTW) Trescon (WTW) –– DynamicsDynamics
600
700
800
900
Reference TresCon WTW
0
100
200
300
400
500
11:45 12:15 12:45 13:15 13:45 14:15 14:45 15:15 15:45 16:15 16:45 17:15 17:45 18:15
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Spectro::Lyser (S::CAN) Spectro::Lyser (S::CAN) –– AccuracyAccuracy
200
250
300
350
Spectrolyser SCAN Reference
-50
0
50
100
150
200
10:52 11:22 11:52 12:22 12:52 13:22 13:52 14:22 14:52 15:22 15:52 16:22 16:52 17:22
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Spectro::Lyser (S::CAN) Spectro::Lyser (S::CAN) –– DynamicsDynamics
600
700
800
900
SpectroLyser SCAN Reference
0
100
200
300
400
500
09:00 09:30 10:00 10:30 11:00 11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 16:00 16:30
Time (hour:minute)
CO
D (
mg
/L)
Results for COD:Results for COD:
Spectro::Lyser (S::CAN) Spectro::Lyser (S::CAN) –– LinearityLinearity
600
700
800
900
Spectrolyser SCAN Reference
0
100
200
300
400
500
11:18 11:48 12:18 12:48 13:18 13:48 14:18 14:48 15:18
Time (hour:minute)
CO
D (
mg
/L)