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废FCC催化剂源二氧化硅泡沫基固态胺吸附剂的烟气CO2吸附性能研究
Spent FCC catalyst-derived mesocellular silica foam-based solid amine adsorbents for flue gas CO2 capture
- 低碳化学与化工 2025: 1-10.
- 作者机构：
1.中国海洋石油集团有限公司液化天然气及低碳技术重点实验室，北京 100028
2.中国石油大学（北京） 化学工程与环境学院，北京 102200
3.中国石油大学（北京） 碳中和未来技术学院，北京 102200
4.山东石油化工学院，山东 东营 257061
- 作者简介：
明红芳（1988—），硕士，高级工程师，研究方向为碳捕集技术，E-mail：minghf@cnooc.com.cn。
樊燕芳（1985—），博士，副教授，研究方向为吸附材料，E-mail：yanfang.fan@cup.edu.cn；
刘梦溪（1974—），博士，教授，研究方向为多相流分离与强化，E-mail：liumx@cup.edu.cn。
- 基金信息：中国海洋石油集团有限公司液化天然气及低碳技术重点实验室主任基金(KJQZ-2024-1105)
DOI：10.12434/j.issn.2097-2547.20240499
中图分类号： TQ424;TE65收稿日期：2024-12-23，
修回日期：2025-01-19，
网络出版日期：2025-05-14，
- 稿件说明：
移动端阅览
明红芳,贾晓浩,陈峰等.废FCC催化剂源二氧化硅泡沫基固态胺吸附剂的烟气CO2吸附性能研究[J].低碳化学与化工,
MING Hongfang,JIA Xiaohao,CHEN Feng,et al.Spent FCC catalyst-derived mesocellular silica foam-based solid amine adsorbents for flue gas CO2 capture[J].Low-Carbon Chemistry and Chemical Engineering,
明红芳,贾晓浩,陈峰等.废FCC催化剂源二氧化硅泡沫基固态胺吸附剂的烟气CO2吸附性能研究[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20240499.
MING Hongfang,JIA Xiaohao,CHEN Feng,et al.Spent FCC catalyst-derived mesocellular silica foam-based solid amine adsorbents for flue gas CO2 capture[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20240499.
摘要
将流化催化裂化（FCC）废催化剂作为廉价硅源，制备固态胺CO
2
吸附剂，能够实现废催化剂的高值化利用，并同时达到碳减排的双重目标，从而实现“以废制废”。首先采用碱溶法从FCC废催化剂中提取硅，制备了一系列介孔二氧化硅泡沫材料（MCF-N
x
）作为载体；随后，通过聚乙烯亚胺（PEI）负载改性，制备了具有高CO
2
吸附量和优异循环稳定性的固态胺吸附剂MCF-N
x
-PEI
y
。研究中调节了矿化剂NH
4
F与模板剂三嵌段共聚物（P123）的质量比（
x
= 0.0113、0.0226或0.0339），以优化MCF-N
x
的孔结构。通过XRD、N
2
等温吸/脱附、SEM、TEM和红外等表征手段，分析了泡沫载体和吸附剂的结构与形貌；并考察了PEI负载量、吸附温度以及水汽对MCF-N
x
-PEI
y
在模拟烟气（10%CO
2
/90%N
2
，体积分数）中CO
2
吸附性能的影响。结果表明，当NH
4
F与P123的质量比为0.0226时，获得了最优结构的载体MCF-N0.0226，其孔径为10.7 nm，有利于PEI的负载。在该载体上负载50%质量分数的PEI所制备的MCF-N0.0226-PEI50表现出最佳的CO
2
吸附量。在吸附热力学与动力学的共同作用下，MCF-N0.0226-PEI50的CO
2
吸附量随着吸附温度的升高先增大后减小，在75 ℃时，达到烟气条件下的最大值3.13 mmol/g；此外，在烟气中加入水汽可显著促进CO
2
的吸附，使得CO
2
吸附量增大至6.08 mmol/g。在30次烟气吸附-解吸循环中，吸附剂的CO
2
吸附量保持稳定，展现出优异的循环稳定性。废FCC催化剂源的介孔二氧化硅泡沫载体具有三维孔道结构和高孔容，这有利于PEI的分散，同时促进了CO
2
的扩散，从而在增强CO
2
吸附量的同时显著提高了胺效率，显示出在烟气CO
2
捕集中的应用潜力。
Abstract
Utilizing spent fluid catalytic cracking (FCC) catalysts as a low-cost silicon source to prepare solid amine CO
2
adsorbents enables the high-value utilization of waste catalysts while simultaneously achieving carbon emission reduction
thereby realizing “waste against waste treatment”. First
a series of mesocellular silica foam materials (MCF-N
x
) were synthesized as supports by extracting silicon from spent FCC catalysts via an alkaline dissolution method. Subsequently
solid amine adsorbents MCF-N
x
-PEI
y
with high CO
2
adsorption capacity and excellent cyclic stability were prepared by polyethyleneimine (PEI) impregnation. The pore structure of MCF-N
x
was optimized by adjusting the mass ratio (
x
= 0.0113
0.0226 or 0.0339) of mineralizer NH
4
F to template agent triblock copolymer (P123). The structure and morphology of the foam supports and adsorbents were characterized by XRD
N
2
isothermal adsorption/desorption
SEM
TEM
and FTIR. Furthermore
the effects of PEI loading
adsorption temperature and water vapor on the CO
2
adsorption performance of MCF-N
x
-PEI
y
in simulated flue gas (10%CO
2
/90%N
2
volume fraction) were investigated. The results show that when the NH
4
F/P123 mass ratio is 0.0226
the optimal structural support MCF-N0.0226 is obtained
with a pore diameter of 10.7 nm
which facilitates PEI loading. The MCF-N0.0226-PEI50
prepared by impregnating the optimal support with 50% (mass fraction) PEI
exhibits the highest CO
2
adsorption capacity. Under the combined effects of adsorption thermodynamics and kinetics
the CO
2
adsorption capacity of MCF-N0.0226-PEI50 first increases and then decreases with increasing adsorption temperature
reaching a maximum of 3.13 mmol/g at 75 °C under simulated flue gas conditions. Moreover
the presence of water vapor in the flue gas significantly enhances CO
2
adsorption
increasing the CO
2
adsorption capacity to 6.08 mmol/g. During 30 flue gas adsorption-desorption cycles
the CO
2
adsorption capacity of MCF-N0.0226-PEI50 remains stable
demonstrating excellent cyclic stability. The mesocellular silica foam support derived from spent FCC catalysts features a three-dimensional pore structure and high pore volume
which promote PEI dispersion and facilitate CO
2
diffusion
thereby enhancing CO
2
adsorption capacity while significantly improving amine efficiency. These findings highlight the promising application potential of this material for CO
2
capture in flue gas.
关键词
Keywords
references
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