Siloxanes in Biogas: Approaches of Sampling Procedure and GC-MS Method Determination
Abstract
:1. Introduction
- C8Si3O2H24 + 16 O2 → 3 SiO2 + 8 CO2 + 12 H2O (linear VMS—L3)
- C10Si5O5H30 + 20 O2 → 5 SiO2 + 10 CO2 + 15 H2O (cyclic VMS—D5)
2. Results
2.1. Procedure Validation
2.2. Gas Chromatographic Siloxanes Determination
2.2.1. Agriculture Biogas
2.2.2. WWTP Biogas
2.2.3. Landfill Biogas
2.3. Sampling Approaches
2.4. Further Routes of Development
3. Materials and Methods
3.1. Standards, Reagents, and Calibration Curves Preparation
3.2. Biogas Samples and Sample Preparation
3.3. GC-MS System
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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Bond Type | Si–Si | Si–C | Si–H | C–C | C–O | C–H | Si–O |
---|---|---|---|---|---|---|---|
Free energies of ionization (kcal/mol) | 45< | 69 | 72 | 81 | 84 | 100 | 103 |
Name | Hexamethyl- Disiloxane | Octamethyl- Trisiloxane | Decamethyl- Tertasiloxane | Hexamethylcyclo- Trisiloxan | Octamethylcyclo- Tetrasiloxan | Decamethylcyclo- Pentasiloxane | Dodecamethylcyclo- Hexasiloxane | References |
---|---|---|---|---|---|---|---|---|
Abbreviation | L2 | L3 | L4 | D3 | D4 | D5 | D6 | |
Structure | ||||||||
Molecular formula | C6H18OSi2 | C8H24O2Si3 | C10H30O3Si4 | C6H18O3Si3 | C8H24O4Si4 | C10H30O5Si5 | C12H36O6Si6 | |
Physical properties | Liquid, colorless, odorless | Liquid, colorless, odorless | solid | Solid, white, with a hydrocarbon odor | Liquid, colorless, oily, odorless | Liquid, oily | Liquid, colorless, faint odor | [10] |
Molecular weight (Da) | 162.38 | 236.54 | 310.7 | 222.47 | 296.61 | 370.80 | 444.93 | [10,12] |
Boiling point, °C | 101 | 153 | 193.95 | 135 | 175.5 | 210 | 245 | [10,12] |
Melting point, °C | −59 | −82 | no data | 64 | 17.5 | 7.5 | −3 | [10,13] |
Water solubility mg/L w 23 °C | 0.93 | 0.034 | 0.006 (at 25 °C) | 1.56 | 0.056 | 0.017 | 0.005 | [10,12,14] |
Vapor density (air = 1) | 5.5 | 8.16 | no data | 8.00 | >1 | no data | no data | [10,15] |
Viscosity, cP at 25 °C | 0.86 | 1.2 | 1.7 (at 20 °C) | no data | 2.6 | no data | no data | [10,12,13] |
Vapor pressure, mm Hg at 25 °C | 42.2 | 13.90 | 0.43 (0.55) | 3.53 | 1.05 | 0.20 | 0.049 | [10,12,13,16] |
Henry’s constant | 2.4 ± 0.2, at 27 °C | 121 ± 12, at 27 °C | no data | no data | 24 ± 3, at 28 °C | 12 ± 2, at 26 °C | 5.9 ± 2.9, at 26 °C | [6,17] |
Octanol/water partition coefficient (Log Pow) | 4.2 | 4.8 | no data | 4.47 | 5.1 | 5.2 | 5.86 | [13,14,18,19] |
Structure | ||||||||
Molecular formula | C6H18OSi2 | C8H24O2Si3 | C10H30O3Si4 | C6H18O3Si3 | C8H24O4Si4 | C10H30O5Si5 | C12H36O6Si6 | [12,19,20,21,22,23,24] |
Molar volume (g/cm3) at 20 °C | 210.0 | 287.3 | 364.6 | 231.9 | 309.2 | 386.5 | 463.8 | [12,19,20,21,22,23,24] |
Density (g/cm3) at 20 °C | 0.765 | 0.820 | 0.854 | 0.856 | 0.953 | 0.955 | 0.959 | [12,19,20,21,22,23,24] |
Critical temperature (°C) | 245.15 | 297.95 | 333.35 | 281.05 | 313.35 | 346.05 | 382.25 | [12,19,20,21,22,23,24] |
Critical pressure (atm) | 19.4 | 17.3 | 14.9 | 17.7 | 13.2 | 11.5 | 12.9 | [12,19,20,21,22,23,24] |
Critical volume (m3/kmol) | 629.0 | 906.0 | 1173.7 | 707.1 | 979.0 | 1216.0 | 1493.1 | [12,19,20,21,22,23,24] |
References | [25] | [26] | [12,27] | [28,29] | [30,31] | [32] | [33] |
Siloxanes Concentrations (mg\m3 ± RSD) | |||||||||
---|---|---|---|---|---|---|---|---|---|
Method: GC-MS | |||||||||
Biogas Type: VMS/Extraction Solvent | Landfill | Sewage Treatment | Agriculture | ||||||
Acetone | Methanol | d-decane | Acetone | Methanol | d-decane | Acetone | Methanol | d-decane | |
Sampling: Micro-Impinger | |||||||||
L2 | 3.4 ± 0.3 | 3.2 ± 0.3 | 0.2 ± 0.1 | 1.4 ± 0.1 | 1.0 ± 0.1 | n.d | n.d | n.d | n.d |
L3 | 0.2 ± 0.1 | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d |
L4 | 0.1 ± 0.1 | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d |
D3 | 9.5 ± 0.1 | 9.0 ± 0.1 | 7.0 ± 0.2 | 1.8 ± 0.1 | 1.3 ± 0.2 | n.d | n.d | n.d | n.d |
D4 | 63.5 ± 0.2 | 60.4 ± 0.3 | 59.8 ± 0.3 | 5.9 ± 0.1 | 4.5 ± 0.2 | 1.6 ± 0.1 | 0.6 ± 0.2 | n.d | n.d |
D5 | 29.7± 0.2 | 25.8 ± 0.3 | 0.2 ± 0.1 | 19.9 ± 0.1 | 17.2 ± 0.1 | 3.9 ± 0.1 | 0.9 ± 0.1 | 0.3 ± 0.1 | n.d |
D6 | 1.7 ± 0.1 | 1.3 ± 0.2 | n.d | 0.2 ± 0.1 | 0.2 ± 0.1 | n.d | n.d | n.d | n.d |
Sampling: Regular Impinger | |||||||||
L2 | 3.5 ± 0.3 | 3.5 ± 0.3 | 0.3 ± 0.1 | 1.4 ± 0.1 | 1.2 ± 0.1 | n.d | n.d | n.d | n.d |
L3 | 0.2 ± 0.1 | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d |
L4 | 0.1 ± 0.1 | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d |
D3 | 10.6 ± 0.1 | 9.4 ± 0.2 | 7.1 ± 0.2 | 2.0 ± 0.1 | 1.6 ± 0.2 | n.d | n.d | n.d | n.d |
D4 | 65.8 ± 0.2 | 62.4 ± 0.2 | 60.0 ± 0.3 | 6.1 ± 0.1 | 4.8 ± 0.2 | 1.9 ± 0.1 | 0.8 ± 0.2 | n.d | n.d |
D5 | 30.0 ± 0.2 | 26.4 ± 0.2 | 0.3 ± 0.1 | 20.5 ± 0.1 | 17.8 ± 0.1 | 4.0 ± 0.1 | 1.1 ± 0.1 | 0.4 ± 0.1 | n.d |
D6 | 1.8 ± 0.1 | 1.4 ± 0.2 | n.d | 0.2 ± 0.1 | 0.3 ± 0.1 | n.d | n.d | n.d | n.d |
Sampling: AC Tube | |||||||||
L2 | 3.2 ± 0.3 | 2.9 ± 0.3 | n.d | 1.3 ± 0.1 | 1.1 ± 0.1 | n.d | n.d | n.d | n.d |
L3 | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d |
L4 | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d | n.d |
D3 | 10.6 ± 0.1 | 8.1 ± 0.2 | 5.9 ± 0.2 | 1.9 ± 0.1 | 1.5 ± 0.1 | 0.6 ± 0.1 | n.d | n.d | n.d |
D4 | 65.2 ± 0.2 | 58.2 ± 0.2 | 50.3 ± 0.2 | 5.8 ± 0.1 | 5.0 ± 0.1 | 2.3 ± 0.2 | 0.7 ± 0.1 | 0.3 ± 0.1 | n.d |
D5 | 29.6 ± 0.2 | 22.4 ± 0.2 | n.d | 20.0 ± 0.1 | 18.8 ± 0.2 | 12.0 ± 0.2 | 0.3 ± 0.1 | 0.4 ± 0.1 | n.d |
D6 | 1.7 ± 0.1 | 1.0 ± 0.2 | n.d | 0.2 ± 0.1 | 0.2 ± 0.1 | n.d | n.d | n.d | n.d |
Sampling: TedlarBag (direct injection) | |||||||||
Landfill Biogas | Sewage Biogas | Agriculture Biogas | |||||||
L2 | n.d | n.d | n.d | ||||||
L3 | n.d | n.d | n.d | ||||||
L4 | n.d | n.d | n.d | ||||||
D3 | 5.9 ± 0.3 | 0.7 ± 0.2 | n.d | ||||||
D4 | 49.1 ± 0.2 | 2.6 ± 0.2 | n.d | ||||||
D5 | 16.6 ± 0.1 | 11.6 ± 0.3 | n.d | ||||||
D6 | n.d | n.d | n.d |
System: Varian 3800, CTC, Saturn IT2200/GC-MS | ||||||
---|---|---|---|---|---|---|
VMS | Calibration Curves Parameters Impinger Method (Solvent: Acetone) | Range of Linearity (mg/m3) | ||||
y = ax + b | ||||||
a ± RSD | B ± RSD | LoD | LoQ | R2 | ||
(mg/m3) | ||||||
Landfill Biogas—Direct from TedlarBag | ||||||
L2 | 219.16 ± 19.08 | −425.05 ± 12.52 | 0.08 | 0.10 | 0.989 | 0.14–5.00 |
L3 | 409.12 ± 10.06 | −504.13 ± 20.86 | 0.06 | 0.11 | 0.986 | 0.12–2.83 |
L4 | 502.36 ± 14.69 | −917.23 ± 14.09 | 0.09 | 0.11 | 0.985 | 0.14–2.00 |
D3 | 409.52 ± 10.67 | −103.81 ± 20.06 | 0.03 | 0.06 | 0.992 | 0.10–30.62 |
D4 | 301.08 ± 17.04 | −612.00 ±103.04 | 0.02 | 0.06 | 0.997 | 0.10–70.06 |
D5 | 326.06 ± 10.27 | −5490.23 ± 103.16 | 0.02 | 0.04 | 0.991 | 0.10–30.60 |
D6 | 336.69 ± 11.15 | 452.20 ± 50.01 | 0.04 | 0.09 | 0.992 | 0.11–2.06 |
Sewage Biogas—AC Tube (with extraction, solvent: acetone/methanol) | ||||||
L2 | 286.56 ± 12.03 | −619.06 ± 13.15 | 0.04 | 0.08 | 0.994 | 0.12–5.06 |
L3 | 319.25 ± 8.12 | −114.96 ± 2.06 | 0.04 | 0.08 | 0.993 | 0.12–3.08 |
L4 | 293.22 ± 9.06 | −63.11 ± 19.85 | 0.04 | 0.06 | 0.991 | 0.14–1.06 |
D3 | 366.06 ± 13.57 | −106.25 ± 8.22 | 0.03 | 0.05 | 0.992 | 0.10–40.09 |
D4 | 488.14 ± 19.03 | 99.11 ± 2.98 | 0.01 | 0.04 | 0.991 | 0.11–80.84 |
D5 | 477.02 ± 19.06 | −63.00 ± 9.14 | 0.01 | 0.05 | 0.995 | 0.11–40.09 |
D6 | 611.42 ± 10.04 | 62.22 ± 14.93 | 0.01 | 0.04 | 0.992 | 0.11–3.95 |
Agriculture Gas (Impinger Method) | ||||||
L2 | 504.55 ± 19.06 | −247.00 ± 15.03 | 0.03 | 0.05 | 0.997 | 0.11–10.52 |
L3 | 18.06 ± 2.06 | −85.09 ± 6.16 | 0.02 | 0.06 | 0.994 | 0.12–10.06 |
L4 | 1274.51 ± 15.23 | −52.85 ± 14.00 | 0.02 | 0.05 | 0.998 | 0.10–25.16 |
D3 | 506.76 ± 3.85 | −85.04 ± 13.02 | 0.02 | 0.05 | 0.997 | 0.10–50.62 |
D4 | 607.55 ± 14.06 | 106.07 ± 26.33 | 0.01 | 0.04 | 0.997 | 0.10–100.74 |
D5 | 1019.00 ± 52.03 | −69.04 ± 8.04 | 0.01 | 0.05 | 0.996 | 0.11–50.20 |
D6 | 704.03 ± 23.06 | 106.08 ± 25.88 | 0.01 | 0.04 | 0.996 | 0.14–10.60 |
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Piechota, G. Siloxanes in Biogas: Approaches of Sampling Procedure and GC-MS Method Determination. Molecules 2021, 26, 1953. https://doi.org/10.3390/molecules26071953
Piechota G. Siloxanes in Biogas: Approaches of Sampling Procedure and GC-MS Method Determination. Molecules. 2021; 26(7):1953. https://doi.org/10.3390/molecules26071953
Chicago/Turabian StylePiechota, Grzegorz. 2021. "Siloxanes in Biogas: Approaches of Sampling Procedure and GC-MS Method Determination" Molecules 26, no. 7: 1953. https://doi.org/10.3390/molecules26071953