空氣中臭味還原性硫化物線上濃縮與分析 on-line enrichment and analysis of reduced...
DESCRIPTION
空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere. 報告者 : 林岱縈 指導老師 : 王家麟 教授. Reduced sulfur compounds. H 2 S / COS / CH 3 SH / C 2 H 5 SH / CS 2 / CH 3 SCH 3 / CH 3 SSCH 3 (DMS) (DMDS). S. - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/1.jpg)
空氣中臭味還原性硫化物線上濃縮與分析On-line enrichment and analysis of
reduced sulfur compounds in the atmosphere
報告者 : 林岱縈指導老師 : 王家麟 教授
1
![Page 2: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/2.jpg)
Reduced sulfur compoundsH2S/ COS/ CH3SH/ C2H5SH/ CS2/ CH3SCH3/ CH3SSCH3
(DMS) (DMDS)
CCN
aerosol
RSCs SO42-
Oxidation RegionalTemperature
2
S
![Page 3: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/3.jpg)
SourceNatural emission
Anthropogenic emission
3
Ocean Volcano
Factory Wastewater treatment
DMS H2S, SO2
H2S, CH3SH, DMS, CS2…. H2S, SO2, C2H5SH, DMS, DEDS….
R SC
![Page 4: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/4.jpg)
Preconcentration methods
Sorption on metal surface Solid sorbents
Cryogenic trapping
Au
S SMolecular sieve 5A/ Tenax TA
Ambient concentration levels (ppbv)
H2S SO2 DMS CS2 COS
~0.2 ~0.1 ~0.001 ~0.02 ~0.5
Anal. Chem. 1978, 50, 992-996/ Analytica Chimica Acta,1995, 306, 259-266 / USEPA, Method 15/ Atmospheric Science for Environmental Scientists4
易沾黏、反應性高 Loss 背景濃度低
Detection limit
H2S other RSCs
LN2
![Page 5: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/5.jpg)
The research goal
Molecular sieve 5A/ Tenax (USEPA, Method 15)
電子降溫至 -20°CFind a better sorbent
5
Solid sorbent Cryogenic trap
![Page 6: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/6.jpg)
Experimental setup
GC/ PFPD
N2Sample
GC He
MFC pump
N2Sample
GC He
MFC pump
-20°C HeatCool
Sampling Injection
![Page 7: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/7.jpg)
Principle of PFPD
77
S2* hʋ
1Filling
2Ignition
3Propagation
4Combustion
5Extinction
Wall gasH2/ zero air
Combustor gasH2/ zero air
2200°C
點火室
燃燒室
Time-delay燃燒室時劑圖
![Page 8: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/8.jpg)
Calibration system
MFC I
MFC III
vent
混合室
MFC II
烘箱 30°C
水冷機1°C
C2H5SHDMS DMDS
CS2
Zero air
( 可調控以改變稀釋倍率 )4 L/min
50 mL/min( 固定 )
1 mL/min( 固定 )
H2S
滲透管實圖
8
滲透管
滲透管
![Page 9: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/9.jpg)
Stability test of permeation tube
9
50 70 90 110 130 150 170 190 210 230 250 0E+00
1E+03
2E+03
3E+03
f(x) = 18.0628888888889 x − 604.966666666666R² = 0.996107483809952
C2H5SH
Volumn ( mL )
Res
pons
e
50 70 90 110 130 150 170 190 210 230 250 0E+00
5E+03
1E+04
2E+04
f(x) = 55.7483333333333 x − 182.753333333329R² = 0.998838652748502
DMS
Volumn ( mL )
Res
pons
e
50 70 90 110 130 150 170 190 210 230 250 0
100200300400500600700800900
f(x) = 4.27711111111111 x − 27.6733333333335R² = 0.998770193775762
DMDS
Volumn ( mL )
Res
pons
e
20 40 60 80 100 120 140 160 180 2000E+00
5E+03
1E+04
f(x) = 86.4466666666667 x − 665.400000000001R² = 0.998550999298153
CS2
Volumn ( mL )
Res
pons
e
N=3
N=3
N=3
N=3
Tenax TA
![Page 10: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/10.jpg)
Stability test of permeation tube
10
0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02 0.022 0.0240E+00
1E+03
2E+03
3E+03
f(x) = 116302.142775251 x − 348.348902735718R² = 0.997470683628443
C2H5SH
Dilution rate
Res
pons
e
0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02 0.022 0.0240E+001E+032E+033E+034E+035E+036E+037E+038E+039E+03
f(x) = 340982.672080516 x + 105.048732697243R² = 0.999314823320347
DMS
Dilution rate
Res
pons
e
0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02 0.022 0.0240
100
200
300
400
500
600
700
f(x) = 24078.5071768864 x + 31.7536354170812R² = 0.99657429967726
DMDS
Dilution rate
Res
pons
e
-3E+03
2E+03
7E+03
1E+04
R² = 0
CS2
Dilution rate
Res
pons
e
N=3
N=3
N=3
N=3
Tenax TA
滲透管已可作為標準氣體使用,改變稀釋比例並不影響滲透管穩定輸出的能力
![Page 11: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/11.jpg)
Results and discussion
Desorption temperature
1. Light RSC (H2S)
Micro (<2 nm)Meso (2-50 nm)Macro ( >50 nm)Non
Look for the best material tocompare with Molecular sieve 5A
Look for the best material tocompare with Tenax TA
2. Heavy RSCs (C2H5SH/ DMS/ CS2/ DMDS)
Desorption temperature Meso (2-50 nm)Macro ( >50 nm)
Trapping T.StabilityCalibration
Trapping T.StabilityCalibration
11
ChallengeVolatile
ReactivityH2O
![Page 12: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/12.jpg)
12
Micro-pore < 20Å
MS-5A MS-13X silica gel Carboxen1000
Carboxen 1003
Carbosieve SIII
5 Å 10 Å 20 Å 10-12 Å 5-8 Å 4-11 Å
Ca2+ 沸石 Na+ 沸石 SiO2 CMS CMS CMS
Meso-pore 20-500ÅUnibeads
1SUnibeads
2S MCM-41 MCM-48 Carboxen1016
Carbopack X
PorapakQ
Haysep D
22 Å 60 Å 29 Å 37 Å N/A 100 Å 75 Å 330 ÅSiO2 SiO2 MCM MCM CMS GCB VB/DVB DVB
Macro-pore >500 Å
Tenax TA2000 Å
polymer
Non-poreAu-glass beads glass beads
-- --
Au/SiO2 SiO2
Micro-meso Micro-macroNCL-A9K4 Glass sand
5-300 Å 30-2500 Å
Charcoal SiO2
![Page 13: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/13.jpg)
5A
13X
Silica gel
NCL-A9K4
MCM48
MCM-41
Carbopack X
Porapak Q
Glass beads
Gold
Unibeads 2S
Unibeads 1S
Temperature
Res
pons
e
H
H
LL
1. Light RSC (H2S)Unibeads 1S
13
![Page 14: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/14.jpg)
SiO2 VS carbon in H2S
14
Carboxen 1003
Carboxen 1000
Carbosieve X
0 50 100 150 200 250 300 3500
200400600800
10001200140016001800
Silica gel
Temperature ( °C )
Res
pons
e
Micro
Meso
40 60 80 100 120 140 160 180 2000E+00
1E+04
2E+04
3E+04Unibeads 1S/ 2S
Unibeads 1SUnibeads 2S
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 3000E+00
1E+03
2E+03
3E+03
4E+03
5E+03Carbopack X
Temperature ( °C )
Res
pons
e
推測碳材比 SiO2 對 H2S 有較強作用力,因此脫附效率不佳 !
Carboxen 1016
![Page 15: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/15.jpg)
0 50 100 150 200 250 300 3500E+00
1E+04
2E+04
3E+04 Unibeads 1S/ Glass sand vs MS-5A
5A
Unibeads 1S
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 300 3500E+00
1E+03
2E+03
3E+03
4E+03H2S in Non-porous
Glass beads
Gold
Temperature ( °C )
Res
pons
e
Desorption temperature
0 50 100 150 200 250 300 3500E+00
1E+03
2E+03
3E+03H2S in Micro-pore
5A
13X
Silica gel
NCL-A9K4
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 300 3500E+00
1E+04
2E+04
3E+04H2S in Meso-pore
Unibeads 1S
Unibeads 2S
MCM48
MCM-41
Porapak Q
Carbopack X
Temperature ( °C )
Res
pons
e
![Page 16: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/16.jpg)
0 2 4 6 8 10 12 14 0E+00
1E+03
2E+03
3E+03
4E+03
5E+03
6E+03
7E+03
8E+03
9E+03
1E+04
f(x) = 3483.55852786515 x + 303.763945578226R² = 0.998681072900552
f(x) = 92.980095556474 x + 96.9702878663387R² = 0.998191310122337
Calibration
5ALinear (5A)Unibeads 1S
ng
Res
pons
e
-30 -20 -10 0 10 20 30 400E+00
1E+03
2E+03
3E+03
4E+03
5E+03
6E+03
7E+03
8E+03
9E+03Trapping Temperature
Unibeads
MS-5A
。 C
Res
pons
eTrapping temperature/ Calibration
(Unibeads 1S vs. MS-5A)
N=3
1616
5.12ppb
Stability %RSD (N=10)
Unibeads 1S MS-5A
1.78 % 2.78 %
H2O
約 70 次實驗後, Glass sand 氣通量不足
12.4ppb
![Page 17: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/17.jpg)
0.5-25 ppbv H2S Chromatogram
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10E+001E-012E-013E-014E-015E-016E-017E-018E-019E-011E+00
f(x) = NaN x + NaNR² = 0 Unibeads 1S
ppbvR
espo
nse
N=3
0.5 ppbv
25 ppbv
LOQ (10σ) for H2S: 0.17 ppbvLOD (3 σ) for H2S: 0.13 ppbv
17
![Page 18: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/18.jpg)
18
Meso-pore 20-500ÅUnibeads
1SUnibeads
2S MCM-41 MCM-48 Carbopack X
PorapakQ
Haysep D
22 Å 60 Å 29 Å 37 Å 100 Å 75 Å 330 ÅSiO2 SiO2 MCM MCM GCB VB/DVB DVB
Macro-pore >500 Å
Tenax TA
2000 Å
polymer
Non-poreAu-glass beads glass beads
Non Non
Au/SiO2 SiO2
2. Heavy RSCs (C2H5SH/ CS2/ DMS/ DMDS)
0 50 100 150 200 250 300 3500E+00
1E+04
2E+04
3E+04Meso-pore in H2S
Unibeads 1S
Unibeads 2S
Porapak Q
Carbopack X
Temperature ( °C )
Res
pons
e
![Page 19: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/19.jpg)
19
The chosen material for heavy RSCs
Meso-pore 20-500ÅUnibeads
1SUnibeads
2SPorapak
QHaysep
D22 Å 60 Å 75 Å 330 ÅSiO2 SiO2 VB/DVB DVB
Macro-pore >500 Å
Tenax TA
2000 Å
polymer
Desorption temperature of C2H5SH / CS2 / DMS / DMDS
Compared with Tenax TA
![Page 20: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/20.jpg)
Desorption Temperature
0 50 100 150 200 250 300 3500E+00
1E+03
2E+03
3E+03
4E+03
5E+03
6E+03
7E+03
8E+03
9E+03 DMS
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 300 3500.0E+00
1.0E+03
2.0E+03
3.0E+03
4.0E+03
5.0E+03
6.0E+03
7.0E+03
8.0E+03
9.0E+03CS2
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 300 3500
100
200
300
400
500
600
700 DMDS
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 300 3500.0E+00
2.0E+02
4.0E+02
6.0E+02
8.0E+02
1.0E+03
1.2E+03
1.4E+03C2H5SH
Temperature ( °C )
Res
pons
e
N=3
N=3
N=3
N=3
20
150°C 150°C
150°C150°C
![Page 21: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/21.jpg)
Byproduct: C2H5SSC2H5 (DEDS)
2C2H5SH→ C2H5SSC2H5 + H2
DEDSDEDS
Tenax TAUnibeads 1S
at 150°C
0 50 100 150 200 250 300 3500
200
400
600
800
1000
1200
1400
1600DEDS
Temperature ( °C )
Res
pons
e
0 50 100 150 200 250 300 3500
200
400
600
800
1000
1200
1400C2H5SH
Unibeads1STenax TAUnibeads2SPorapakQHaysep D
Temperature ( °C )
Res
pons
e
![Page 22: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/22.jpg)
Tested Material (peak area at 150°C)
Tenax TA (peak area at 150°C)Normalization =
Ranking
Desorption at 150°C
Unibeads 1S compared with Tenax TA in C2H5SH/ DMS/ CS2/ DMDS22
0
0.5
1
1.5
2
2.5
3C2H5SH
DMS
DMDS
CS2
Nor
mal
izat
ion
Unibeads 1S Unibeads 2S Porapak Q Haysep DTenax TA
DMS
CS2
![Page 23: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/23.jpg)
-30 -20 -10 0 10 20 30 400E+00
1E+04
Tenax TA
C2H5SH
DMS
DMDS
CS2
Temperature( °C )
Res
pons
e
N=3
-30 -20 -10 0 10 20 30 400E+00
5E+03
1E+04
2E+04 Unibeads 1S
Temperature ( °C )
Res
pons
e
N=3
%RSD (N=10) C2H5SH DMS CS2 DMDS
Unibeads 1S 0.8% 0.82% 2.07% 1.76%
Teanx TA 2.56% 1.65% 1.11% 3.24%
( -20 °C )
Trapping temperature
Stability
23
Trapping Temperature (Unibeads 1S vs. Tenax TA)
![Page 24: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/24.jpg)
Calibration
40 60 80 100 120 140 160 180 2000
100
200
300
400
500
600
700
800
f(x) = 3.538126 x + 58.9190399999998R² = 0.996544000799983f(x) = 3.99141666666667 x + 2.53499999999974R² = 0.994939944908261
DMDS
Tenax TA
Volume ( mL )
Res
pons
e
0 2 4 6 8 10 120E+00
5E+00
1E+01
2E+01
f(x) = NaN x + NaNR² = 0f(x) = NaN x + NaNR² = 0 DMS
Tenax TA
Volume ( mL )
Res
pons
e
40 60 80 100 120 140 160 180 2000E+00
1E+03
2E+03
3E+03
4E+03
5E+03
6E+03
f(x) = 32.8794 x − 487.4R² = 0.999223653337739
f(x) = 17.2322333333333 x − 515.877999999999R² = 0.999509232569337
C2H5SH
Volume ( mL )
Res
pons
e
20 40 60 80 100 120 140 1600E+00
1E+04
2E+04
f(x) = 84.15 x + 22.4999999999991R² = 0.99983697407057f(x) = 86.4466666666667 x − 665.400000000001R² = 0.998550999298153
CS2
Volume ( mL )
Res
pons
e
N=3 N=3
N=3 N=3
24
![Page 25: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/25.jpg)
Summary• An on-line TD-GC/PFPD was developed for analyzing ambient RSCs.
• Of all the RSCs, H2S is the most difficult RSC to be enriched due to its high volatility and reactivity.
• Unibeads 1S shows significantly better sorption characteristics than MS 5A and Tenax TA to enrich H2S with LOQ = 0.17 ppbv.
• For other higher boiling RSCs, Unibeads 1S shows comparable sorption characteristics to the conventional MS 5A or Tenax TA.
• Sorbents with smaller pore sizes may reduce the formation of DEDS from C2H5SH.
• Unibeads 1S has never been used as a sorption material for RSCs, and previously it is being used as a packing material for GC columns.
25
![Page 26: 空氣中臭味還原性硫化物線上濃縮與分析 On-line enrichment and analysis of reduced sulfur compounds in the atmosphere](https://reader036.vdocuments.net/reader036/viewer/2022081420/5681638c550346895dd47edd/html5/thumbnails/26.jpg)
Thanks for your attention !
26