Highly selective synthesis of LPG from CO2 hydrogenation over In2O3/SSZ-13 binfunctional catalyst
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摘要: 通过In2O3/SSZ-13双功能催化剂实现了二氧化碳(CO2)加氢高选择性合成液化石油气(LPG,
${\rm{C}}_3^0 $ 和${\rm{C}}_4^0 $ )。利用X射线衍射(XRD)、N2吸附-脱附、扫描电镜(SEM)、透射电镜(TEM)、NH3程序升温脱附(NH3-TPD)等表征手段对双功能催化剂的物化性质进行了表征。在固定床反应器上研究了氧化铟的晶粒尺寸、反应条件对In2O3/SSZ-13催化二氧化碳加氢制液化石油气性能的影响。结果表明,SSZ-13分子筛的八元环结构和强酸性位点有利于丙烷的选择性生成,初始晶粒尺寸为5 nm的氧化铟具有最高的CO2转化率(11.7%)和CO选择性(61.0%),而烃类产物分布受In2O3晶粒尺寸影响较小,其中,烃类产物中LPG的选择性基本维持在90%左右,丙烷选择性约为75%。增加反应压力、降低反应空速均有利于LPG收率的提高,在350 ℃,3 MPa,9000 mL/(gcat·h)的反应条件下,In2O3/SSZ-13双功能催化剂反应100 h未观察到显著失活现象。本研究为CO2加氢高选择合成液化石油气提供了新的探索途径。-
关键词:
- CO2加氢 /
- LPG合成 /
- In2O3/SSZ-13双功能催化剂 /
- 尺寸影响 /
- 反应条件
Abstract: Highly selective synthesis of liquefied petroleum gas (LPG,${\rm{C}}_3^0 $ and${\rm{C}}_4^0 $ ) from CO2 hydrogenation have realized over the In2O3/SSZ-13 bifunctional catalyst. The physicochemical properties of the bifunctional catalyst were characterized by X-ray diffraction spectroscopy (XRD), N2 physical adsorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NH3 temperature-programmed desorption (NH3-TPD). The particle size effect of In2O3 and reaction conditions were investigated for CO2 hydrogenation to LPG over the In2O3/SSZ-13 bifunctional catalyst. Results indicate that CO2 conversion and CO selectivity are related to the particle size of In2O3, and fresh 5 nm In2O3 shows the highest CO2 conversion (11.7%) and the highest CO selectivity (61.0%), since it is more prone to reverse water gas reaction (RWGS). However, the hydrocarbon distribution does not exhibit a dependence of In2O3 size changes, and the selectivity of LPG maintains at 90% and the selectivity of propane reaches up to 76.8% due to the 8-MR micropores and strong acid sites of SSZ-13 zeolite. Additionally, the yield of LPG shows a volcano type with increasing reaction temperature, and the optimal reaction temperature is 370 ℃. Low space velocity is more favorable to the CO2 conversion, and LPG selectivity in hydrocarbon products still maintains about 90%. High reaction pressure is beneficial to improving the yield of LPG via promoting the secondary hydrogenation reaction over the SSZ-13 zeolite and inhibiting CO formation. Furthermore, no obvious deactivation is observed after a time on stream (TOS) of 100 h over the In2O3/SSZ-13 bifunctional catalyst at 350 ℃, 3 MPa and 9000 mL/(gcat·h). The research provides a new strategy for highly selective synthesis of LPG from CO2 hydrogenation.-
Key words:
- CO2 hydrogenation /
- LPG synthesis /
- In2O3/SSZ-13 composite catalyst /
- size effect /
- reaction condition
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表 1 In2O3/SSZ-13双功能催化剂的结构性质
Table 1 Texture properties of the In2O3–x/SSZ-13 composite catalysts
Sample SBET/
(m2·g–1)Smicro/
(m2·g–1)vmeso/
(cm3·g–1)vmicro/
(cm3·g–1)SSZ-13 487 460 0.35 0.23 In2O3-300/SSZ-13 447 380 0.30 0.19 In2O3-500/SSZ-13 410 371 0.28 0.18 In2O3-600/SSZ-13 394 363 0.28 0.17 In2O3-650/SSZ-13 373 344 0.26 0.17 In2O3-700/SSZ-13 350 318 0.25 0.16 表 2 双功能催化剂In2O3-x/SSZ-13上的CO2加氢制LPG催化性能
Table 2 Catalytic performance for CO2 hydrogenation to LPG over bifunctional catalysts containing In2O3 oxides with different crystal sizes and SSZ-13 zeolites
Sample CO2 conv. /% CO sel. /% Hydrocarbon distribution/% STYLPG/
(mmol·gcat–1·h–1)CH4 ${\rm{C}}_2^0 $ LPG (${\rm{C}}_3^0 $) ${\rm{C}}_2^= $– ${\rm{C}}_4^= $ C5+ In2O3-300/SSZ13 11.7 61.0 3.4 2.2 90.6 (76.8) 2.3 1.5 3.99 In2O3-500/SSZ13 11.3 57.8 3.2 2.4 89.2 (75.7) 3.1 2.2 4.10 In2O3-600/SSZ13 9.8 56.7 3.5 2.3 89.9 (76.7) 2.1 2.2 3.68 In2O3-650/SSZ13 9.0 54.2 3.5 2.3 89.8 (76.4) 2.3 2.1 3.57 In2O3-700/SSZ13 7.6 53.8 3.6 2.4 88.6 (75.5) 3.0 2.4 3.00 standard reaction conditions: In2O3 (0.4 g) + SSZ-13 (0.8 g), 350 ℃, 3.0 MPa, H2/CO2 = 3, WHSV = 9000 mL/(gcat·h) results from 12 h time on stream 表 3 In2O3-300/SSZ-13在不同温度下催化CO2加氢制液化石油气的反应性能
Table 3 Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 catalysts under different reaction temperatures
Temperature/℃ CO2 conv. /% CO sel. /% Hydrocarbon distribution/% STYLPG/
(mmol·gcat–1·h–1)CH4 ${\rm{C}}_2^0 $ LPG (${\rm{C}}_3^0 $) ${\rm{C}}_2^= $– ${\rm{C}}_4^= $ C5+ 310 5.8 50.5 4.2 2.2 89.5 (74.3) 1.9 2.2 2.48 330 9.7 58.8 3.5 2.5 90.8 (77.0) 1.9 1.3 3.50 350 11.7 61.0 3.4 2.2 90.6 (76.8) 2.3 1.5 3.99 370 22.9 72.2 3.9 3.0 88.5 (75.8) 2.5 2.1 5.43 390 29.4 78.3 6.1 3.6 84.8 (72.7) 3.5 2.0 5.22 standard reaction conditions: In2O3 (0.4 g)+SSZ-13 (0.8 g), 3 MPa, WHSV = 9000 mL/(gcat·h) results from 12 h time on stream 表 4 In2O3-300/SSZ-13在不同空速下催化CO2加氢制液化石油气的反应性能
Table 4 Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 catalysts under different reaction space velocity
Space velocity/
(mL·gcat–1·h–1)CO2 conv. /% CO sel. /% Hydrocarbon distribution/% STYLPG/
(mmol·gcat–1·h–1)CH4 ${\rm{C}}_2^0 $ LPG (${\rm{C}}_3^0 $) ${\rm{C}}_2^= $– ${\rm{C}}_4^= $ C5+ 3000 14.9 67.1 3.6 2.4 90.7 (77.8) 1.8 1.5 4.29 6000 11.9 62.8 3.6 2.3 91.1 (77.7) 2.3 0.7 3.89 9000 11.7 61.0 3.4 2.2 90.6 (76.8) 2.3 1.5 3.99 12000 10.0 55.4 3.6 2.2 89.1 (75.4) 2.9 2.2 3.83 15000 8.9 55.0 3.7 2.1 89.0 (75.2) 3.4 1.8 3.44 standard reaction conditions: In2O3 (0.4 g)+SSZ-13 (0.8 g), 350 ℃, 3 MPa results from 12 h time on stream 表 5 In2O3-300/SSZ-13在不同压力下催化CO2加氢制液化石油气的反应性能
Table 5 Catalytic performance for CO2 hydrogenation to LPG over In2O3-300/SSZ-13 catalysts under different reaction pressure
Pressure/MPa CO2 conv. /% CO sel. /% Hydrocarbon distribution/% STYLPG/
(mmol·gcat–1·h–1)CH4 ${\rm{C}}_2^0 $ LPG (${\rm{C}}_3^0 $) ${\rm{C}}_2^= $– ${\rm{C}}_4^= $ C5+ 1.0 8.1 70.9 2.6 3.3 81.8 (70.8) 11.1 1.2 1.86 2.0 9.7 65.3 3.1 2.3 88.1 (75.5) 4.5 2.0 2.86 3.0 11.7 61.0 3.4 2.2 90.6 (76.8) 2.3 1.5 3.99 4.0 13.4 57.6 3.7 2.4 89.4 (75.6) 2.0 2.5 4.90 5.0 15.9 57.1 3.8 2.5 90.2 (75.9) 1.4 2.1 5.93 standard reaction conditions: In2O3 (0.4 g)+SSZ-13 (0.8 g), 350 ℃, WHSV = 9000 mL/(gcat·h) results from 12 h time on stream -
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