Journal of Inorganic Materials ›› 2026, Vol. 41 ›› Issue (5): 645-652.DOI: 10.15541/jim20250373
• RESEARCH ARTICLE • Previous Articles Next Articles
LI Na1(
), WEI Jin1, CAO Ruixiao1,2, LIU Yu1, HUANG Guiwen1, XIAO Hongmei1(
)
Received:2025-09-26
Revised:2025-11-26
Published:2026-01-06
Online:2026-01-06
Contact:
XIAO Hongmei, professor. E-mail: hmxiao@mail.ipc.ac.cnAbout author:LI Na (1987-), female, PhD. E-mail: lina110@mail.ipc.ac.cn
Supported by:CLC Number:
LI Na, WEI Jin, CAO Ruixiao, LIU Yu, HUANG Guiwen, XIAO Hongmei. Self-developed Ortho-para Hydrogen Conversion Catalyst: Catalytic Testing and Optimization of Batch Preparation Process[J]. Journal of Inorganic Materials, 2026, 41(5): 645-652.
| Sample | Aperture of crushing sieve/mm | Particle size/mm | Granulation and post-processing technology | Secondary activation process |
|---|---|---|---|---|
| Commercial catalyst | / | 0.315-0.600 (30-50 mesh ) | / | / |
| 1# | 1.0 | 0.315-0.900 (20-50 mesh) | Primary crushing, washing | With low-temperature activation |
| 2# | 0.8 | 0.315-0.900 (20-50 mesh) | Primary crushing, washing | With low-temperature activation |
| 3# | 1.0 | 0.315-0.900 (20-50 mesh) | Secondary granulation, washing | With low-temperature activation |
| 4# | 0.8 | 0.315-0.900 (20-50 mesh) | Secondary granulation, washing | With low-temperature activation |
| 5# | 0.8 | 0.315-0.900 (20-50 mesh) | Without washing | / |
| 6# | 0.8 | 0.315-0.600 (30-50 mesh) | Primary crushing, washing | Without low-temperature activation |
| 7# | 0.8 | 0.315-0.900 (20-50 mesh) | Primary crushing, washing | Without low-temperature activation |
| 8# | 1.0 | 0.315-0.600 (30-50 mesh) | Secondary granulation, washing | Without low-temperature activation |
| 9# | 1.0 | 0.315-0.900 (20-50 mesh) | Secondary granulation, washing | Without low-temperature activation |
Table 1 Preparation parameters of self-developed catalysts
| Sample | Aperture of crushing sieve/mm | Particle size/mm | Granulation and post-processing technology | Secondary activation process |
|---|---|---|---|---|
| Commercial catalyst | / | 0.315-0.600 (30-50 mesh ) | / | / |
| 1# | 1.0 | 0.315-0.900 (20-50 mesh) | Primary crushing, washing | With low-temperature activation |
| 2# | 0.8 | 0.315-0.900 (20-50 mesh) | Primary crushing, washing | With low-temperature activation |
| 3# | 1.0 | 0.315-0.900 (20-50 mesh) | Secondary granulation, washing | With low-temperature activation |
| 4# | 0.8 | 0.315-0.900 (20-50 mesh) | Secondary granulation, washing | With low-temperature activation |
| 5# | 0.8 | 0.315-0.900 (20-50 mesh) | Without washing | / |
| 6# | 0.8 | 0.315-0.600 (30-50 mesh) | Primary crushing, washing | Without low-temperature activation |
| 7# | 0.8 | 0.315-0.900 (20-50 mesh) | Primary crushing, washing | Without low-temperature activation |
| 8# | 1.0 | 0.315-0.600 (30-50 mesh) | Secondary granulation, washing | Without low-temperature activation |
| 9# | 1.0 | 0.315-0.900 (20-50 mesh) | Secondary granulation, washing | Without low-temperature activation |
| Parameter | Control sample | Test sample |
|---|---|---|
| Inner tube diameter | φ12.1 mm | φ8.9 mm |
| Working pressure | 0.1-0.2 MPa | 0.1-0.2 MPa |
| Hydrogen flow rate | 0.3-0.5 L/min | 0.4-1.6 L/min |
| Test section length | 65 mm | 32 mm |
| Catalyst packing volume | 4-5 mL | 1 mL |
Table 2 Experimental operating parameters
| Parameter | Control sample | Test sample |
|---|---|---|
| Inner tube diameter | φ12.1 mm | φ8.9 mm |
| Working pressure | 0.1-0.2 MPa | 0.1-0.2 MPa |
| Hydrogen flow rate | 0.3-0.5 L/min | 0.4-1.6 L/min |
| Test section length | 65 mm | 32 mm |
| Catalyst packing volume | 4-5 mL | 1 mL |
| Hydrogen flow rate/ (L·min-1) | Calculation parameter | Commercial catalyst | 1# | 2# | 3# | 4# |
|---|---|---|---|---|---|---|
| 0.4 | k value/(mol·(L·s)-1) | 0.6697 | 0.5881 | 0.7330 | 0.8825 | 0.4920 |
| Catalytic conversion rate/% | 98.86 | 98.03 | 99.25 | 99.72 | 96.26 | |
| 0.8 | k value/(mol·(L·s)-1) | 0.7313 | 0.7396 | 0.8375 | 0.8767 | 0.6531 |
| Catalytic conversion rate/% | 91.31 | 91.54 | 93.90 | 94.65 | 88.71 | |
| 1.2 | k value/(mol·(L·s)-1) | 0.8033 | 0.8716 | 1.0104 | 1.0037 | 0.7041 |
| Catalytic conversion rate/% | 83.28 | 85.64 | 89.46 | 89.30 | 79.15 | |
| 1.6 | k value/(mol·(L·s)-1) | 0.8706 | 0.9468 | 1.1240 | 1.0911 | 0.7587 |
| Catalytic conversion rate/% | 76.63 | 79.43 | 84.70 | 83.83 | 71.83 |
Table 3 Reaction rate constant (k) and catalytic conversion rates of various samples by the three-point method
| Hydrogen flow rate/ (L·min-1) | Calculation parameter | Commercial catalyst | 1# | 2# | 3# | 4# |
|---|---|---|---|---|---|---|
| 0.4 | k value/(mol·(L·s)-1) | 0.6697 | 0.5881 | 0.7330 | 0.8825 | 0.4920 |
| Catalytic conversion rate/% | 98.86 | 98.03 | 99.25 | 99.72 | 96.26 | |
| 0.8 | k value/(mol·(L·s)-1) | 0.7313 | 0.7396 | 0.8375 | 0.8767 | 0.6531 |
| Catalytic conversion rate/% | 91.31 | 91.54 | 93.90 | 94.65 | 88.71 | |
| 1.2 | k value/(mol·(L·s)-1) | 0.8033 | 0.8716 | 1.0104 | 1.0037 | 0.7041 |
| Catalytic conversion rate/% | 83.28 | 85.64 | 89.46 | 89.30 | 79.15 | |
| 1.6 | k value/(mol·(L·s)-1) | 0.8706 | 0.9468 | 1.1240 | 1.0911 | 0.7587 |
| Catalytic conversion rate/% | 76.63 | 79.43 | 84.70 | 83.83 | 71.83 |
Fig. 8 SEM morphology comparison of the prepared samples (a, c) before and (b, d) after washing following (a, b) primary crushing and (c, d) secondary granulation
| Peak area | Hydrogen flow rate | Average value | RSD/% | Equilibrium para-hydrogen content/% | ||
|---|---|---|---|---|---|---|
| 0.3 L/min | 0.4 L/min | 0.5 L/min | ||||
| Peak area at 298 K/(μV·s) | 378.5 | 356.6 | 252.1 | 328.1 | 16.97 | 24.88 |
| 371.1 | 342.9 | 244.9 | ||||
| 375.1 | 329.7 | 284.3 | ||||
| Average peak area/(μV·s) | 374.9 | 343.0 | 266.6 | |||
| Corrected | 374.9 | 0.99 | ||||
| Peak area at 77 K/(μV·s) | 9131.7 | 9021.9 | 8919.2 | 9056.3 | 0.89 | 50.30 |
| 9161.6 | 9030.5 | 9020.0 | ||||
| 9131.6 | 9092.6 | 8995.6 | ||||
| Average peak area/(μV·s) | 9141.6 | 9048.3 | 8979.2 | |||
| Peak area at 21 K/(μV·s) | 26481.2 | 26501.7 | 26622.3 | 26531.7 | 0.37 | 99.55 |
| 26477.7 | 26486.8 | 26602.1 | ||||
| 26461.9 | 26444.0 | 26708.0 | ||||
| Average peak area/(μV·s) | 26473.6 | 26477.5 | 26644.1 | |||
Table S1 Calibration data at different temperatures
| Peak area | Hydrogen flow rate | Average value | RSD/% | Equilibrium para-hydrogen content/% | ||
|---|---|---|---|---|---|---|
| 0.3 L/min | 0.4 L/min | 0.5 L/min | ||||
| Peak area at 298 K/(μV·s) | 378.5 | 356.6 | 252.1 | 328.1 | 16.97 | 24.88 |
| 371.1 | 342.9 | 244.9 | ||||
| 375.1 | 329.7 | 284.3 | ||||
| Average peak area/(μV·s) | 374.9 | 343.0 | 266.6 | |||
| Corrected | 374.9 | 0.99 | ||||
| Peak area at 77 K/(μV·s) | 9131.7 | 9021.9 | 8919.2 | 9056.3 | 0.89 | 50.30 |
| 9161.6 | 9030.5 | 9020.0 | ||||
| 9131.6 | 9092.6 | 8995.6 | ||||
| Average peak area/(μV·s) | 9141.6 | 9048.3 | 8979.2 | |||
| Peak area at 21 K/(μV·s) | 26481.2 | 26501.7 | 26622.3 | 26531.7 | 0.37 | 99.55 |
| 26477.7 | 26486.8 | 26602.1 | ||||
| 26461.9 | 26444.0 | 26708.0 | ||||
| Average peak area/(μV·s) | 26473.6 | 26477.5 | 26644.1 | |||
| Sample No. | Test data | Hydrogen flow rate | |||
|---|---|---|---|---|---|
| 0.4 L/min | 0.8 L/min | 1.2 L/min | 1.6 L/min | ||
| Commercial catalyst | Average peak area/(μV·s) | 9096.6 | 8425.2 | 7709.0 | 7116.4 |
| RSD/% | 0.21 | 0.63 | 0.31 | 0.31 | |
| 1# | Average peak area/(μV·s) | 9025.0 | 8444.0 | 7920.3 | 7365.0 |
| RSD/% | 0.38 | 0.27 | 0.18 | 0.24 | |
| 2# | Average peak area/(μV·s) | 9134.1 | 8656.6 | 8261.8 | 7833.5 |
| RSD/% | 0.25 | 0.17 | 0.38 | 0.33 | |
| 3# | Average peak area/(μV·s) | 9174.6 | 8721.3 | 8244.6 | 7756.4 |
| RSD/% | 0.27 | 0.10 | 0.33 | 0.12 | |
| 4# | Average peak area/(μV·s) | 8868.2 | 8192.3 | 7339.9 | 6687.0 |
| RSD/% | 0.12 | 0.13 | 0.42 | 0.19 | |
Table S2 Catalytic test data for various samples at 77 K
| Sample No. | Test data | Hydrogen flow rate | |||
|---|---|---|---|---|---|
| 0.4 L/min | 0.8 L/min | 1.2 L/min | 1.6 L/min | ||
| Commercial catalyst | Average peak area/(μV·s) | 9096.6 | 8425.2 | 7709.0 | 7116.4 |
| RSD/% | 0.21 | 0.63 | 0.31 | 0.31 | |
| 1# | Average peak area/(μV·s) | 9025.0 | 8444.0 | 7920.3 | 7365.0 |
| RSD/% | 0.38 | 0.27 | 0.18 | 0.24 | |
| 2# | Average peak area/(μV·s) | 9134.1 | 8656.6 | 8261.8 | 7833.5 |
| RSD/% | 0.25 | 0.17 | 0.38 | 0.33 | |
| 3# | Average peak area/(μV·s) | 9174.6 | 8721.3 | 8244.6 | 7756.4 |
| RSD/% | 0.27 | 0.10 | 0.33 | 0.12 | |
| 4# | Average peak area/(μV·s) | 8868.2 | 8192.3 | 7339.9 | 6687.0 |
| RSD/% | 0.12 | 0.13 | 0.42 | 0.19 | |
| Hydrogen flow rate/(L·min-1) | Para-hydrogen content/% | Calibration method | ||||
|---|---|---|---|---|---|---|
| Commercial catalyst | 1# | 2# | 3# | 4# | ||
| 0.4 | 50.01 | 49.80 | 50.11 | 50.23 | 49.35 | Three-point method |
| 0.8 | 48.09 | 48.15 | 48.75 | 48.94 | 47.43 | |
| 1.2 | 46.05 | 46.65 | 47.62 | 47.58 | 45.00 | |
| 1.6 | 44.36 | 45.07 | 46.41 | 46.19 | 43.14 | |
| 0.4 | 49.78 | 49.57 | 49.88 | 50.00 | 49.13 | Two-point method |
| 0.8 | 47.86 | 47.91 | 48.52 | 48.71 | 47.20 | |
| 1.2 | 45.82 | 46.42 | 47.39 | 47.35 | 44.76 | |
| 1.6 | 44.12 | 44.83 | 46.17 | 45.95 | 42.90 | |
Table S3 Para-hydrogen content of various samples at 77 K calculated by three-point and two-point methods
| Hydrogen flow rate/(L·min-1) | Para-hydrogen content/% | Calibration method | ||||
|---|---|---|---|---|---|---|
| Commercial catalyst | 1# | 2# | 3# | 4# | ||
| 0.4 | 50.01 | 49.80 | 50.11 | 50.23 | 49.35 | Three-point method |
| 0.8 | 48.09 | 48.15 | 48.75 | 48.94 | 47.43 | |
| 1.2 | 46.05 | 46.65 | 47.62 | 47.58 | 45.00 | |
| 1.6 | 44.36 | 45.07 | 46.41 | 46.19 | 43.14 | |
| 0.4 | 49.78 | 49.57 | 49.88 | 50.00 | 49.13 | Two-point method |
| 0.8 | 47.86 | 47.91 | 48.52 | 48.71 | 47.20 | |
| 1.2 | 45.82 | 46.42 | 47.39 | 47.35 | 44.76 | |
| 1.6 | 44.12 | 44.83 | 46.17 | 45.95 | 42.90 | |
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