Introduction
Catalyst contaminants | Maximum recommended contaminant levels |
---|---|
Hydrogen sulfide (H2S) and carbonyl sulfide (COS) | <20 ppb |
Sulfur dioxide (SO2) | <20 ppb |
Oxygen (O2) | <500 ppm |
Ammonia (NH3) | <75 ppb |
Hydrogen chloride (HCl) | <35 ppb |
Nitric acid (HNO3) | <50 ppb |
Total organic and inorganic particulate matter (PM) | <500 µg/m3
|
Objectives
Experimental
Integrated biorefinery
Experimental
Biomass feedstock
Chemical species | Wt.% (dry basis) |
---|---|
Carbon | 50.0 |
Hydrogen | 5.97 |
Oxygen | 42.3 |
Nitrogen | 0.23 |
Sulfur | 0.01 |
Chlorine | 0.001 |
Calcium | 0.20 |
Potassium | 0.11 |
Aluminum | 0.003 |
Magnesium | 0.02 |
Iron | 0.007 |
Sodium | 0.02 |
Carbon analysis | Wt.% (dry basis) |
---|---|
Volatile organic carbon | 86.2 |
Fixed carbon (elemental) | 13.8 |
Energy content | MJ/kg (dry basis) |
---|---|
Lower heating value (LHV) | 17.57 |
Higher heating value (HHV) | 20.48 |
Oxygen input
Real-time syngas analysis
Oxygen input | Syngas composition (vol.%)a
| |||||
---|---|---|---|---|---|---|
N2
| H2
| CO | CH4
| CO2
| H2/CO | |
225 ppm | <0.20 | 49 | 23 | 12 | 17 | 2.1 |
1.0 vol.% | 3.7 | 44 | 22 | 13 | 16 | 2.0 |
1.6 vol.% | 5.9 | 44 | 22 | 13 | 16 | 2.0 |
2.5 vol.% | 9.2 | 43 | 19 | 11 | 20 | 2.3 |
4.1 vol.% | 15.3 | 37 | 17 | 9 | 23 | 2.2 |
Integrated syngas sampling
Characterization of integrated samples
-
Thermal optical analysis of total organic C (organic particulate contaminants) and total elemental C on quartz filters
-
GC/MS analysis of C1–C11 gas-phase volatile organic compounds (VOCs) and chlorinated VOCs (>50) in Summa stainless steel sampling canisters
-
Ion chromatography (IC) of chlorides, nitrates and sulfates on quartz filters
-
IC analysis of HCl, HNO3 and SO2 on K2CO3 impregnated cellulose filters
-
GC/TCD and GC/FID analysis of major syngas constituents (6 species)
-
GC/MS analysis of higher MW VOCs (C8–C20) (>25 species) collected on Tenax cartridges
-
HPLC analysis of DNPH derivatives of C1–C7 carbonyl compounds (14 species)
-
Colorimetric analysis of ammonia from citric acid impregnated cellulose filters
-
X-ray fluorescence (XRF) analysis of AgNO3-impregnated filters for measurement of H2S (as AgS)
-
XRF analysis of teflon filters for measurement of elemental constituents (51 species)
Results
Oxygen input | Syngas contaminants (mg/m3)a
| ||
---|---|---|---|
Particulate organic carbon | Particulate elemental carbon | Total carbon containing particulates | |
225 ppm | 3.3 | 0.6 | 3.9 |
1.0 vol.% | 6.4 | 4.1 | 10.5 |
1.6 vol.% | 57 | 10 | 67 |
2.5 vol.% | 194 | 75 | 269 |
4.1 vol.% | 122 | 98 | 220 |
Oxygen input | Syngas contaminants | |||||
---|---|---|---|---|---|---|
Particulate sulfates (µg/m3) | Gas-phase SO2 (µg/m3) | Ratio sulfates/SO2
| Particulate nitrates (µg/m3) | Gas-phase HNO3 (µg/m3) | Ratio nitrates/HNO3
| |
225 ppm | 1.4 | 1.8 | 0.8 | 2.2 | 1.3 | 1.7 |
1.0 vol.% | 5.6 | 3.8 | 1.5 | 1.4 | 2.9 | 0.48 |
1.6 vol.% | 8.1 | 13 | 0.6 | 2.3 | 11.4 | 0.20 |
2.5 vol.% | 201 | 240 | 0.8 | 4.8 | 18.6 | 0.26 |
Oxygen input | Syngas contaminants | ||||||
---|---|---|---|---|---|---|---|
Benzene (ppm) | Toluene (ppm) | Xylenes (ppm) | Naphthalene (mg/m3) | Methyl naphthalene (mg/m3) | Fluorene (mg/m3) | Acenapthene (mg/m3) | |
225 ppm | 5845 | 3.9 | 0.0 | 1.8 | 0.0 | 0.0 | 0.0 |
1.0 vol.% | 960 | 25 | 0.21 | 5.4 | 0.014 | 0.004 | 0.075 |
1.6 vol.% | 1350 | 44 | 0.58 | 38.4 | 0.31 | 0.122 | 1.47 |
2.5 vol.% | 1260 | 27 | 0.27 | 11.3 | 0.25 | 0.034 | 1.54 |
Oxygen input | Syngas particulate-phase contaminants (µg/m3) | |||
---|---|---|---|---|
Hydroxy-naphthalenes | Dihydroxy-naphthalenes | Dihydro-inden-2-ones | Benzo-pyranones | |
225 ppm | 0.0 | 0.0 | 0.0 | 0.0 |
1.0 vol.% | 288 | 97 | 32 | 105 |
1.6 vol.% | 930 | 311 | 90 | 131 |
2.5 vol.% | 732 | 244 | 83 | 195 |
Oxygen input | Syngas gas-phase contaminants (ppb) | ||
---|---|---|---|
Formaldehyde | Acetaldehyde | Benzaldehyde | |
225 ppm | 2.1 | 365 | 9.3 |
1.0 vol.% | 1.0 | 47.5 | 0.6 |
1.6 vol.% | 0.7 | 109 | 3.7 |
2.5 vol.% | 1.4 | 199 | 3.5 |
Oxygen input | Syngas particulate contaminants (µg/m3) | |||
---|---|---|---|---|
Calcium | Silicon | Potassium | Sodium | |
225 ppm | 0.0 | 1.6 | 0.3 | 23 |
1.0 vol.% | 1.4 | 1.3 | 9.0 | – |
1.6 vol.% | 6.4 | 9.8 | 27 | 4 |
2.5 vol.% | 32 | 8.6 | 128 | 15 |
4.1 vol.% | 86 | 91 | 127 | 20 |
Syngas component | Decrease in syngas constituents relative to concentration of ethane | |||
---|---|---|---|---|
1,3-Butadiene | Acetylene | Propene | Ethene | |
Relative concentration decrease with increased oxygen | 9.3 times | 5.2 times | 4.5 times | 3.4 times |
Catalyst contaminants | 3-Day average syngas contaminant concentrations | Maximum recommended contaminant levels |
---|---|---|
Hydrogen sulfide (H2S) and carbonyl sulfide (COS) | 0.1 ppb | <20 ppb |
Sulfur dioxide (SO2) | 0.7 ppb | <20 ppb |
Oxygen (O2) | 225 ppm | <500 ppm |
Ammonia (NH3) | 53 ppb | <75 ppb |
Hydrogen chloride (HCl) | <0.2 ppb | <35 ppb |
Nitric acid (HNO3) | 5 ppb | <50 ppb |
Total particulate matter (PM) | 25 µg/m3
| <500 µg/m3
|
Components | kg of C in TCC products |
---|---|
H2
| 0.0 |
CO | 417.0 |
CH4
| 285.0 |
CO2
| 122.6 |
C2–C5 HCs | 4.2 |
Biochar | 135.5 |
C in scrubber water | 13.0 |
Total kg carbon | 977.3 |
Discussion
Conclusions
Total particulate contaminant concentrations (mg/m3) | |||
---|---|---|---|
This study
2-stage steam reforming TCC system (225 ppm% O2 input) | Typical fluidized bed system (with air input) | Typical downdraft system (with air input) | Typical updraft system (with air input) |
3.9 | 1000 | 10,000 | 100,000 |