why the ftir? · 2021. 1. 4. · why the ftir? ifrf goal is to use ftir for in-flame measurement...

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Page 1: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)
Page 2: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Why the FTIR?Why the FTIR?

IFRF goal is to use FTIR for in-flame measurement t ti f it i (NO NO HCN NH N O)concentration of nitrogen species (NO, NO2, HCN, NH3, N2O)

Punctual concentrations of NOX species and precursors are X p pextremely valuable for the study of the NOX formation kinetics

In addition the FTIR approach offers other important informationIn addition the FTIR approach offers other important information such as H2O and SO2 concentrations (and others species)

Page 3: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

What is the FTIR?What is the FTIR?The FTIR is a real time gas analyser

Species Range Minimum

Initial measured species Additional species added for spectra analysis

H2O 0-25% vol. 0-1% vol.CO2 0-70% vol. 0-200 ppmCO 0-20% vol. 0-20 ppmN2O 0-100 ppm 0-50 ppm

Species RangeCH4 0-20000 ppmC2H6 0-100 ppmC3H8 0-100 ppmC4H10 0-100 ppmC H 0 100

30%100%Ppm measurement

N2O 0 100 ppm 0 50 ppmNO 0-1500 ppm 0-100 ppmNO2 300 ppm 0-100 ppmSO2 2000 ppm 0-30 ppmNH3 200 ppm 0-20 ppm

C2H4 0-100 ppmC2H2 0-100 ppmCHOH 0-100 ppmHCl 0-100 ppmHF 0-100 ppmC3H6 0-100 ppm3 00 pp 0 0 pp

HCN 300 ppm 0-50 ppm C4H6 0-100 ppm

Page 4: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Working principles of FTIRWorking principles of FTIR

Step 1Mi h l i t f t

Moving mirror

ensi

ty

Infrared

Michelson interferometerMirror position 1

Source

Beamsplitter

Radiation to the sample gas and detector

Fixed mirror

Ligh

t int

e

Broadband source

wavelength

Cell full of li

Light detector

FTIR analysisSpectrum point

sampling gasrecord the intensity

Page 5: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Working principles of FTIRWorking principles of FTIR

Step 2Mi h l i t f t

Light signal centred at a different wavelength

Moving mirror

ensi

ty

Infrared

Michelson interferometerMirror position 2

Source

Beamsplitter

Radiation to the sample gas and detector

Fixed mirror

Ligh

t int

e

Broadband source

wavelength

Cell full of li

Light detector

FTIR analysisSpectrum point 1

Spectrum point 2

sampling gasrecord the intensity

Page 6: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Working principles of FTIRWorking principles of FTIR

Residual spectrum Typical spectrum of FTIR (and CO2 spectrum)

CO2

Page 7: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

IFRF FTIR systemIFRF FTIR system

Page 8: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

11stst FTIR inFTIR in--measurements testsmeasurements tests

The first tests with the FTIR measurement system were carried out on the 14th May 2010 in Fosper during NG testsout on the 14 May 2010 in Fosper during NG tests

14 July 2010Port 2 CO2 vs radial distance

2

4

6

8

10C

O2

%Port 2 CO2 vs radial distance

CO2 FTIR

CO2 ENELSomething is not

-1000 -800 -600 -400 -200 0

-4

-2

0

2

Radial distance from burner axismm

is not right….

Page 9: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

11stst FTIR inFTIR in--measurements testsmeasurements tests

The first tests with the FTIR measurement system were carried out on the 14th May 2010 in Fosper during NG testsout on the 14 May 2010 in Fosper during NG tests

The FTIRdidn’tresolve theresolve the spectrum!!!

Page 10: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

IssuesIssues

• High concentration of water vapourg p• High concentration of unburnt

hydrocarbons (different kind of FTIR??)hydrocarbons (different kind of FTIR??)

H O and h drocarbons absorbs inH2O and hydrocarbons absorbs in the infrared rangethe infrared range

Th fi l i l t tThe final signal saturates (more precisely the signal at the FTIR detector is too low)

Page 11: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

List of tests with FTIRList of tests with FTIR

• July 2010 – Fosper NG – FTIR testsN /D 2010 F C l O• Nov/Dec 2010 – Fosper Coal - Oxycorr

• Aug/Sept 2011 – Lab tests – FTIR tests• Sept 2011- Fosper NG – ENEA probes testSept 2011 Fosper NG ENEA probes test• Sept 2012 – Casper NG – FTIR tests• March/ April 2013 – IPFR – Nitrogen species tests

N 2013 F C l R l• Nov 2013 – Fosper Coal – Relcom• June 2014 – CIUDEN PC boiler Coal – Relcom

More than 200 measurement points (at least 9 chemical species per point)

More than 3000 spectra

Page 12: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Ideas for developmentIdeas for development

• Dilution of sampled gases p gwith N2

E h t l l i• Enhance spectral analysis

Page 13: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Dilution system schemeDilution system scheme

Page 14: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Results of dilutionResults of dilution

NO measured /calculated vs dilution ratio

No measurement of N2 flow Constant CO2 method

21 September 2011

Measurement of N2 flow

300

350

400

450

NO measured /calculated vs dilution ratiodiffusion flame

50.00

60.00

70.00

pCO2 vs dilution ratio port 14

0

50

100

150

200

250

NO

ppm NO meas diff

NO calc diff

0 00

10.00

20.00

30.00

40.00

CO2

%

CO2 FTIR

CO2 ENEL

0 5 10 15 20 25 30 350

1/ϕ 0 5 10 15 20 25 300.00

1/ϕ15 September 2011

Methods comparison

300.0

400.0

500.0

O m

pNO measured /calculated vs dilution ratio

NO meas

-100.0

0.0

100.0

200.0NO

ppm NO meas

NO calc by CO2

NO calc by N2

0 5 10 15 20 25 30 351/ϕ

Page 15: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Spectral analysisSpectral analysis

The spectral analysis may be improved by:

Addi i t f i i• Adding more interfering species• Adjusting the frequency range of comparison for the

different species p

Page 16: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Spectral analysisSpectral analysisDefault analysis

Improved analysisImproved analysis

Thi h d d lid i d i i i iThis method needs validation and it is time consuming

Page 17: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Latest Latest measurements measurements resultsresultsAir coal combustion CIUDEN

CO2 NO SO2

1314151617181920

CO

2%

6507007508008509009501000

NO

ppm

300400500600700800

SO2

ppm

CO2 NO 2

???-2500 -2000 -1500 -1000 -500 0

10111213

Furnace axis distancemm

CO2 FTIR port 3

-2500 -2000 -1500 -1000 -500 0500550600650

Furnace axis distancemm

NO FTIR port 3

-2500 -2000 -1500 -1000 -500 00100200

Furnace axis distancemmSO2 FTIR port 3

OK!!! OK!!!???

Oxy-coal combustion CIUDEN

CO2 ENEL port 3 NO ENEL port 3 SO2 ENEL port 3

CO2 SO2NO

8808284868890

CO

2% 800

900

1000

1100

1200

NO

ppm 2250

2500

2750

3000

SO2

ppm

2 SO2NO

-2500 -2000 -1500 -1000 -500 07072747678

Furnace axis distancemm

-2500 -2000 -1500 -1000 -500 0400

500

600

700

Furnace axis distancemm

N p-2500 -2000 -1500 -1000 -500 0

1500

1750

2000

Furnace axis distancemm

S p

OK!!!??? ???

CO2 FTIR port 3

CO2 ENEL port 3

NO FTIR port 3

NO ENEL port 3

mmSO2 FTIR port 3

SO2 ENEL port 3

Page 18: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Actual IFRF analyser performance Actual IFRF analyser performance -- 11

• FTIR is a reliable instrument for emission measurements at h hi i i b i di ithe chimney in air combustion condition

• In coal flames the FTIR manage to resolve the spectra at theIn coal flames the FTIR manage to resolve the spectra at the majority of positions. Just few points (2 or 3 out of 30 in the last campaign) are still not measureable. But…

th lt f th FTIR b diff t f ti l• ….the results of the FTIR can be different from conventional analysers (Siemens, ABB)

• In gas flames the FTIR cannot perform measurements in the region very close to the burner exit

Page 19: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Actual IFRF analyser performance Actual IFRF analyser performance -- 22

• In laboratory with bottles of pure gases there are no diff b h f h FTIR ddifferences between the measurements of the FTIR and conventional (Siemens, ABB) analysers

• Hence the differences must be due to the presence of water vapour or of different chemical species at the same time

Page 20: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Valuable outcomes Valuable outcomes –– IPFR testsIPFR testsN-species in-flame measurements

IPFR b t• IPFR precombustor• NG-air combustion• Flame doped with central injection of

NH3/water solution at different

Flame borderflowrates

Burner

Flue gasFlame axis

Page 21: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Valuable outcomes Valuable outcomes –– IPFR testsIPFR testsOther species in-flame measurements

CH4 C2H2

1500

2000

2500

ion

[ppm

]

100

150

200

ion

[ppm

]

fl

0

500

1000

Conc

entr

at flue gas

flame axis

flame border

0

50

100

Conc

entr

at flue gas

flame axis

flame border

0 100 200 300 400 500

NH3 solution flowrate [g/h]0 100 200 300 400 500

NH3 solution flowrate [g/h]

50

H2O

20

30

40

50

trat

ion

[vol

-%]

flue gas

flame axis

0

10

0 100 200 300 400 500

Conc

ent

NH3 solution flowrate [g/h]

flame border

Page 22: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Further developmentsFurther developments

• Calibration with a mixture of gas (possibly g (p ywith water vapour)

• Coupling of two FTIR results (nitrogenCoupling of two FTIR results (nitrogen species and hydrocarbon)

• Enhance spectral analysis and validation• Enhance spectral analysis and validation of the method

• Other ideas???

Page 23: Why the FTIR? · 2021. 1. 4. · Why the FTIR? IFRF goal is to use FTIR for in-flame measurement concen tti fit itration of nitrogen spec ies (NO NO(NO, NO 2, HCN NHHCN, NH 3, N 2O)

Thank you for yourThank you for yourThank you for your Thank you for your attentionattentionattention attention

!!