Effect of Phosphine on Coke Formation during Steam Cracking of Propane
Abstract
:1. Introduction
2. Experimental Section
Procedure and Chemicals
3. Results and Discussion
3.1. Coking Rates
3.2. SEM and EDX Analyses
4. Conclusions
- (1)
- For the 25/35 NiCr: decrease in catalytic coking rate by 14% in the first and second coking cycles, asymptotic coking rates reduced by 25% and 33%, respectively.
- (2)
- For the Al-containing alloy: the catalytic coking rates were lower by 12% and 10% in the first and second coking cycles and asymptotic coking rates were reduced by 16% and 24%, respectively.
Author Contributions
Funding
Conflicts of Interest
Nomenclature
A | Atomic mass of element [g.mol−1]c |
DMDS | dimethyl disulfide |
EDX | Energy Dispersive X-ray analysis |
FID | Flame Ionization Detector |
F | Flow rate [10−6 kg s−1] |
H | Penetration depth [µm] |
CCi | Coking-decoking Cycle number, i |
PFR | Plug flow reactor |
L | Nominal thickness [μm] |
mtj | mass of coke at time j [kg] |
MOT | maximum operating temperature [K] |
Mc | amount of coke deposited on the sample [g] |
Ptot | reactor pressure [MPa] |
rc | coking rate [kg·s−1·m−2] |
rc,initial | initial catalytic coking rate [kg·s−1·m−2] |
rc,asymptotic | asymptotic coking rate [kg·s−1·m−2] |
RGA | Refinery Gas Analyzer |
S | surface area of the coupon [m2] |
SEM | Scanning Electron Microscopy |
TCD | Thermal Conductivity Detector |
T | temperature [K] |
V | Accelerating voltage [kV] |
z | Atomic number |
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Materials | C | Mn | Si | P | S | Ni | Cr | Al | Additions |
---|---|---|---|---|---|---|---|---|---|
25/35 CrNi | 0.35/0.60 | 1.00/1.50 | 1.00/2.00 | - | - | 33/38 | 23/28 | - | Nb, Ti, and others |
Al-cont. | 0.6 | - | 1 | 0.03 | 0.03 | 29/46 | 22/28 | 2/4 | Nb, Ti, and others |
Process Steps | Duration (h) | Gas-Phase Temperature (K) | Gas Feed Flow (10−6 kg s−1) | Steam Flow (10−6 kg s−1) | ||
---|---|---|---|---|---|---|
Propane | Air | Nitrogen | ||||
Pretreatment | 13.00 | 1223 | - | - | - | 8.33 |
Presulfiding | 0.50 | 1100 | - | - | - | |
1st CC | 4.00 | 1223 | 20.83 | - | 6.66 | |
0.75 | 1323 | 20.83 | - | 6.66 | ||
Decoking | 0.50 | 1073 | - | 8.33 | - | |
Presulfiding | 0.50 | 1100 | - | - | - | |
2nd CC | 4.00 | 1223 | 20.83 | - | 6.66 | |
0.75 | 1323 | 20.83 | - | 6.66 |
Process Steps | Duration (h) | Gas-Phase Temperature (K) | Gas Feed Flow (10−6 kg s−1) | Steam Flow (10−6 kg s−1) | ||||
---|---|---|---|---|---|---|---|---|
Propane | Air | N2 + PH3 | Phosphine | |||||
Pretreatment | 13.00 | 1223 | - | - | - | - | 8.33 | |
Presulfiding | 0.50 | 1100 | - | - | - | - | ||
1st CC | 4.00 | 1223 | 20.83 | - | 6.66 | 1.38 × 10−6 | ||
0.75 | 1323 | 20.83 | - | 6.66 | 1.38 × 10−6 | |||
Decoking | 0.50 | 1073 | - | 8.33 | - | - | ||
Presulfiding | 0.50 | 1100 | - | - | - | - | ||
2nd CC | 4.00 | 1223 | 20.83 | - | 6.66 | 1.38 × 10−6 | ||
0.75 | 1323 | 20.83 | - | 6.66 | 1.38 × 10−6 |
Experiment | DMDS with PH3 | Only DMDS | |||
---|---|---|---|---|---|
Al-Content | 25/35 CrNi | Al-Content | 25/35 CrNi | ||
Conditions | Propane flow (10−6 kg s−1) | 20.83 | 20.83 | ||
Steam flow (10−6 kg s−1) | 8.33 | 8.33 | |||
CA DMDS (ppmw S/HC) | 41 | 41 | |||
CA PH3 (ppbw P/HC) | 66 | - | |||
Temperature (K) | 1223 | 1223 | |||
Pressure (barg) | 1.02 | 1.02 | |||
Dilution (kg H2O/kg C3H8) | 0.4 | 0.4 | |||
Catalytic coking rates (10−6 kg m−2s−1) | 1st Coking cycle | 2.38 | 3.01 | 2.71 | 3.51 |
2nd Coking cycle | 2.38 | 3.54 | 2.65 | 4.12 | |
Pyrolytic coking rates (10−6 kg m−2s−1) | 1st Coking cycle | 1.38 | 1.45 | 1.65 | 1.95 |
2nd Coking cycle | 1.17 | 1.57 | 1.54 | 2.35 | |
Component yields (wt %) | - | DMDS with PH3 | Only DMDS | ||
- | |||||
H2 | - | 1.93 | 1.90 | ||
CO2 | - | 0.01 | 0.01 | ||
CO | - | 0.01 | 0.02 | ||
CH4 | - | 25.02 | 24.74 | ||
C2H6 | - | 1.79 | 1.78 | ||
C2H4 | - | 37.71 | 37.48 | ||
C3H8 | - | 11.32 | 11.93 | ||
C3H6 | - | 7.99 | 8.07 | ||
C2H2 | - | 2.88 | 2.84 | ||
1,3-C4H6 | - | 2.41 | 2.38 | ||
Benzene | - | 4.27 | 4.22 |
Elements (±2 wt %) | DMDS with Phosphine | Only DMDS | ||
---|---|---|---|---|
25/35 CrNi | Al-Cont. | 25/35 CrNi | Al-Cont. | |
Ni | 7.3 | 4.5 | 23.8 | 4.6 |
Fe | 10.9 | 7.2 | 26.3 | 7.9 |
Cr | 78.6 | 14.8 | 36.6 | 15.1 |
Si | 2.3 | 4.1 | 8.6 | 4.3 |
Mn | 0.89 | 1.2 | 2.5 | 2.89 |
Nb | 0.01 | - | 2.2 | - |
Al | - | 68.2 | - | 65.21 |
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Patil, M.; Djokic, M.; Verbeken, K.; Reyniers, M.-F.; Van Geem, K.M. Effect of Phosphine on Coke Formation during Steam Cracking of Propane. Materials 2021, 14, 5075. https://doi.org/10.3390/ma14175075
Patil M, Djokic M, Verbeken K, Reyniers M-F, Van Geem KM. Effect of Phosphine on Coke Formation during Steam Cracking of Propane. Materials. 2021; 14(17):5075. https://doi.org/10.3390/ma14175075
Chicago/Turabian StylePatil, Manjunath, Marko Djokic, Kim Verbeken, Marie-Françoise Reyniers, and Kevin M. Van Geem. 2021. "Effect of Phosphine on Coke Formation during Steam Cracking of Propane" Materials 14, no. 17: 5075. https://doi.org/10.3390/ma14175075