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收稿日期:
2024-05-20
修回日期:
2024-06-27
出版日期:
2024-07-18
通讯作者:
肖永厚
作者简介:
郭强(1998—),男,硕士研究生,guoqiang202103@163.com
基金资助:
Qiang GUO2(), Qidong ZHAO3, Yonghou XIAO1,2,3()
Received:
2024-05-20
Revised:
2024-06-27
Online:
2024-07-18
Contact:
Yonghou XIAO
摘要:
双回流(DR)变压吸附(PSA)工艺具有不受压力比影响的优势,有望突破传统变压吸附(PSA)的热力学限制同时获得两种高纯气体。本工作基于两塔四步DR PSA工艺,分别考察了活性炭(AC)、13X和5A分子筛复合吸附剂以及Cu(I)/AC单吸附剂的分离效果,实现了同时制备高纯H2和CO产品。利用Aspen Adsorption模拟平台开发了一个由质量、动量和能量平衡方程组成的非等温吸附模型,并通过固定床吸附实验验证了模型的可靠性。结果表明,AC、13X和5A分子筛复合吸附剂的DR PSA工艺分离效率欠佳,但表现出更强的CO解吸能力;而单独以Cu(I)/AC为吸附剂,可以显著提升分离效率,即以CO/H2=0.5/0.5(体积比)合成气为原料,获得纯度>99.999%的H2产品,其中CO含量<0.20 mL/m3,收率达96.69%;同时CO产品纯度>97.00%,收率达99.16%。增大轻、重组分回流比可以进一步提高H2和CO产品气的纯度。
中图分类号:
郭强, 肇启东, 肖永厚. 双回流变压吸附高效分离CO/H2制备高纯H2和CO[J]. 化工学报, DOI: 10.11949/0438-1157.20240535.
Qiang GUO, Qidong ZHAO, Yonghou XIAO. Preparation of high-purity H2 and CO by efficient separation of CO/H2 using dual-reflux pressure swing adsorption process[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240535.
Parameters | AC/13X/5A | Cu(I)/AC | Units |
---|---|---|---|
Height of adsorbent layer | 0.50/0.50/0.80 | 2.0 | m |
Diameter of adsorbent layer | 0.13 | 0.20 | m |
Thickness of bed wall | 0.0050 | 0.0020 | / |
Inter-particle voidage | 0.43/0.35/0.35 | 0.35 | / |
Intra-particle voidage | 0.61/0.65/0.65 | 0.33 | / |
Bulk solid density of adsorbent | 708.00/851.29/715.70 | 625.00 | kg/m3 |
Adsorbent particle radius | 2.0 | 1.4 | mm |
Feed gas pressure | 5.0 | 5.0 | bar |
Feed flow rate | 33.33 | 33.33 | SLPM |
表1 吸附床的性质和操作条件
Table 1 Properties of the adsorption bed and operating conditions
Parameters | AC/13X/5A | Cu(I)/AC | Units |
---|---|---|---|
Height of adsorbent layer | 0.50/0.50/0.80 | 2.0 | m |
Diameter of adsorbent layer | 0.13 | 0.20 | m |
Thickness of bed wall | 0.0050 | 0.0020 | / |
Inter-particle voidage | 0.43/0.35/0.35 | 0.35 | / |
Intra-particle voidage | 0.61/0.65/0.65 | 0.33 | / |
Bulk solid density of adsorbent | 708.00/851.29/715.70 | 625.00 | kg/m3 |
Adsorbent particle radius | 2.0 | 1.4 | mm |
Feed gas pressure | 5.0 | 5.0 | bar |
Feed flow rate | 33.33 | 33.33 | SLPM |
Model equation | Expression | Equation |
---|---|---|
Mass balance | (1) | |
Energy balance | Gas phase | (2) |
Solid phase | (3) | |
Bed wall | (4) | |
(5) | ||
(6) | ||
(7) | ||
Momentum balance | (8) | |
LDF | (9) | |
(10) | ||
Ideal gas law | (11) |
表2 DR PSA模型中使用的方程
Table 2 The equations employed in DR PSA model
Model equation | Expression | Equation |
---|---|---|
Mass balance | (1) | |
Energy balance | Gas phase | (2) |
Solid phase | (3) | |
Bed wall | (4) | |
(5) | ||
(6) | ||
(7) | ||
Momentum balance | (8) | |
LDF | (9) | |
(10) | ||
Ideal gas law | (11) |
Adsorbent | Parameters | H2 | Ar | CO |
---|---|---|---|---|
AC | qm (mmol∙g-1) | 10.68 | 7.00 | 6.82 |
b0 (bar-1) | 2.16E-5 | 1.76E-4 | 9.05E-6 | |
ΔH/kJ∙mol-1 | -12.84 | -13.53 | -22.58 | |
13X | qm (mmol∙g-1) | 6.50 | 4.41 | 3.18 |
b0 (bar-1) | 1.33E-4 | 2.92E-4 | 8.49E-5 | |
ΔH/kJ∙mol-1 | -8.00 | -11.00 | -21.00 | |
5A | qm (mmol∙g-1) | 1.15 | 4.24 | 2.24 |
b0 (bar-1) | 2.82E-4 | 1.67E-4 | 6.14E-6 | |
ΔH/kJ∙mol-1 | -9.23 | -13.30 | -29.77 |
表3 AC、13X和5A的扩展型Langmuir吸附模型拟合参数
Table 3 Fitting parameters of extended Langmuir adsorption models for AC, 13X and 5A
Adsorbent | Parameters | H2 | Ar | CO |
---|---|---|---|---|
AC | qm (mmol∙g-1) | 10.68 | 7.00 | 6.82 |
b0 (bar-1) | 2.16E-5 | 1.76E-4 | 9.05E-6 | |
ΔH/kJ∙mol-1 | -12.84 | -13.53 | -22.58 | |
13X | qm (mmol∙g-1) | 6.50 | 4.41 | 3.18 |
b0 (bar-1) | 1.33E-4 | 2.92E-4 | 8.49E-5 | |
ΔH/kJ∙mol-1 | -8.00 | -11.00 | -21.00 | |
5A | qm (mmol∙g-1) | 1.15 | 4.24 | 2.24 |
b0 (bar-1) | 2.82E-4 | 1.67E-4 | 6.14E-6 | |
ΔH/kJ∙mol-1 | -9.23 | -13.30 | -29.77 |
Adsorbate | H2 | Ar | CO | CH4 | N2 | CO2 | |
---|---|---|---|---|---|---|---|
qm (mmol∙g-1) | 38.87 | 6.56 | 2.00 | 3.23 | 7.18 | 5.38 | |
b0 (bar-1) | 1.0E-5 | 1.8E-4 | 1.0E-5 | 5.0E-5 | 1.9E-5 | 7.5E-6 | |
ΔH/kJ∙mol-1 | -8.50 | -13.74 | -31.45 | -20.60 | -15.87 | -26.83 |
表4 Cu(I)/AC的扩展型Langmuir吸附模型拟合参数
Table 4 Fitting parameters of extended Langmuir adsorption model for Cu(I)/AC
Adsorbate | H2 | Ar | CO | CH4 | N2 | CO2 | |
---|---|---|---|---|---|---|---|
qm (mmol∙g-1) | 38.87 | 6.56 | 2.00 | 3.23 | 7.18 | 5.38 | |
b0 (bar-1) | 1.0E-5 | 1.8E-4 | 1.0E-5 | 5.0E-5 | 1.9E-5 | 7.5E-6 | |
ΔH/kJ∙mol-1 | -8.50 | -13.74 | -31.45 | -20.60 | -15.87 | -26.83 |
Duration/s | 100 | 20 | 100 | 20 |
---|---|---|---|---|
Bed1 | AD | VU | PU | PR |
Bed2 | PU | PR | AD | VU |
表5 DR PSA工艺循环时间表
Table 5 Cycle schedule of DR PSA process
Duration/s | 100 | 20 | 100 | 20 |
---|---|---|---|---|
Bed1 | AD | VU | PU | PR |
Bed2 | PU | PR | AD | VU |
图7 一个循环周期内各步骤结束后AC、13X和5A复合吸附剂和Cu(I)/AC吸附床内CO轴向浓度分布
Fig. 7 Axial concentration distribution of CO in AC, 13X and 5A composite adsorbent and Cu(I)/AC adsorption beds after each step within a cycle
图8 不同轻重回流比对产品气纯度的影响(AC、13X和5A分子筛复合吸附剂和Cu(I)/AC单吸附剂床)
Fig. 8 The influence of different light to heavy reflux ratios on the purity of product gas on AC, 13X and 5A composite and Cu(I)/AC adsorbents
图11 多组分竞争吸附条件下H2/CO/CO2/CH4/N2合成气各循环步骤结束时的固相浓度分布
Fig. 11 Solid phase concentration distribution at the end of each cycle of H2/CO/CO2/CH4/N2 synthesis gas under multi-component competitive adsorption conditions
图12 不同进料位置对AD步骤结束后各组分固相浓度分布的影响
Fig. 12 Effects of different feed positions on the solid phase concentration distribution of each component after AD step
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