浏览全部资源
扫码关注微信
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, 50(9): 17-26.
- 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 102249
3.中国石油大学（北京） 碳中和未来技术学院，北京 102249
4.山东石油化工学院 化学工程学院，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，
纸质出版日期：2025-09-25
- 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,2025,50(9):17-26.
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,2025,50(9):17-26.
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,2025,50(9):17-26. 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,2025,50(9):17-26. 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“以废治废”。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
。通过调节矿化剂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），优化了MCF-N
x
的孔结构。通过XRD、N
2
吸/脱附、SEM、TEM和FT-IR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，其平均孔径为10.7 nm，有利于PEI的负载。在该载体上负载质量分数50%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，从而在增大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 of mineralizer NH
4
F to template agent triblock copolymer (P123) (
x
= 0.0113
0.0226 or 0.0339). The structure and morphology of the foam supports and adsorbents were characterized by XRD
N
2
adsorption/desorption
SEM
TEM
and FT-IR. Furthermore
the effects of PEI loading amounts
adsorption temperatures 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 mass ratio of NH
4
F and P123 is 0.0226
the optimal structural support MCF-N0.0226 is obtained
with a average 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 ℃ 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 increasing 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
李琢宇 , 余美琪 , 陈孝彦 , 等 . 炼油废催化剂吸附去除水中硝基苯的特性与机制 [J ] . 化工进展 , 2025 , 44 ( 2 ): 1076 - 1087 .
LI Z Y , YU M Q , CHEN X Y , et al . Effects and mechanism on the removal of nitrobenzene from water by adsorption of refining waste catalysts [J ] . Chemical Industry and Engineering Progress , 2025 , 44 ( 2 ): 1076 - 1087 .
王铃 . 石油炼制催化剂未来需求展望 [J ] . 石油炼制与化工 , 2024 , 55 ( 2 ): 35 .
WANG L . research progress on sulfur and phosphorus poisoning in diesel vehicle exhaust oxidation catalysts [J ] . Petroleum Processing and Petrochemicals , 2024 , 55 ( 2 ): 35 .
赵晓敏 . FCC废催化剂的综合回收利用 [J ] . 炼油技术与工程 , 2017 , 47 ( 4 ): 51 - 55 .
ZHAO X M . Recovery and utilization of waste FCC catalysts [J ] . Petroleum Refinery Engineering , 2017 , 47 ( 4 ): 51 - 55 .
周新荣 , 李铁 , 赵晓 , 等 . 废催化剂综合处理技术现状及前景分析 [J ] . 中国资源综合利用 , 2024 , 42 ( 3 ): 83 - 85 .
ZHOU X R , LI T , ZHAO X . et al . Analysis on status and prospect of comprehensive treatment technology for waste catalysts [J ] . China Resources Comprehensive Utilization , 2024 , 42 ( 3 ): 83 - 85 .
王彬宇 , 李莉 , 李菁 , 等 . 用工业固体废料合成沸石分子筛的研究进展 [J ] . 高等学校化学学报 , 2021 , 42 ( 1 ): 40 - 59 .
WANG B Y , LI L , LI J . et al . Recent progresses on the synthesis of zeolites from the industrial solid wastes [J ] . Chemical Journal of Chinese Universities , 2021 , 42 ( 1 ): 40 - 59 .
XU X C , SONG C S , ANDRESEN J M , et al . Novel polyethylenimine-modified mesoporous molecular sieve of MCM-41 type as high-capacity adsorbent for CO 2 capture [J ] . Energy & Fuels , 2002 , 16 ( 6 ): 1463 - 1469 .
FAN Y F , JIA X H . Progress in amine-functionalized silica for CO 2 capture: Important roles of support and amine structure [J ] . Energy & Fuels , 2022 , 36 ( 3 ): 1252 - 1270 .
FAN Y F , LABRECHE Y , LIVELY R P , et al . Dynamic CO 2 adsorption performance of internally cooled silica-supported poly(ethylenimine) hollow fiber sorbents [J ] . AIChE Journal , 2014 , 60 ( 11 ): 3878 - 3887 .
HARLICK P J E , SAYARI A . Applications of pore-expanded mesoporous silica. 5. triamine grafted material with exceptional CO 2 dynamic and equilibrium adsorption performance [J ] . Industrial & Engineering Chemistry Research , 2007 , 46 ( 2 ): 446 - 458 .
HEYDARI-GORJI A , YANG Y , SAYARI A . Effect of the pore length on CO 2 adsorption over amine-modified mesoporous silicas [J ] . Energy & Fuels , 2011 , 25 ( 9 ): 4206 - 4210 .
SUN Y , LIU X , SUN C G , et al . Synthesis and functionalisation of spherical meso-, hybrid meso/macro- and macro-porous cellular silica foam materials with regulated pore sizes for CO 2 capture [J ] . Journal of Materials Chemistry A , 2018 , 6 ( 46 ): 23587 - 23601 .
BAI F T , LIU X , SANI S , et al . Amine functionalized mesocellular silica foam as highly efficient sorbents for CO 2 capture [J ] . Separation and Purification Technology , 2022 , 299 : 121539 .
QI G G , FU L L , GIANNELIS E P . Sponges with covalently tethered amines for high-efficiency carbon capture [J ] . Nature communications , 2014 , 5 : 5796 .
WIJESIRI R P , KNOWLES G P , YEASMIN H , et al . CO 2 capture from air using pelletized polyethylenimine impregnated MCF silica [J ] . Industrial & Engineering Chemistry Research , 2019 , 58 ( 8 ): 3293 - 3303 .
ZHANG W C , HONAKER R . Process development for the recovery of rare earth elements and critical metals from an acid mine leachate [J ] . Minerals Engineering , 2020 , 153 : 106382 .
ZHENG S Q , HE L J , YAO H , et al . Synthesis and application of a zeolite-containing composite material made from spent FCC catalyst [J ] . China Petroleum Processing & Petrochemical Technology , 2015 , 17 ( 4 ): 46 - 54 .
YANG Z C , CAI W Q , CHOU J K , et al . Hydrothermal synthesis of plugged micro/mesoporous Al-SBA-15 from spent fluid catalytic cracking catalyst [J ] . Materials Chemistry and Physics , 2019 , 222 : 227 - 229 .
JIA X H , YANG P H , FAN Y F , et al . Spent fluid catalytic cracking catalyst derived MCM-41 supported polyethylenimine for post-combustion CO 2 capture [J ] . Separation and Purification Technology , 2024 , 328 : 124992 .
SCHMIDT-WINKEL P , LUKENS W W , YANG P D , et al . Microemulsion templating of siliceous mesostructured cellular foams with well-defined ultralarge mesopores [J ] . Chemistry of Materials , 2000 , 12 ( 3 ): 686 - 696 .
SUBAGYONO D J N , MARSHALL M , KNOWLES G P , et al . CO 2 adsorption by amine modified siliceous mesostructured cellular foam (MCF) in humidified gas [J ] . Microporous and Mesoporous Materials , 2014 , 186 : 84 - 93 .
YAN H Y , LIU J , LI G Q , et al . Design of blend-amine solid adsorbents for CO 2 capture: Enhances adsorption-equilibrium cycle strategies and mechanism [J ] . Chemical Engineering Journal , 2024 , 498 : 155142 .
XU R H , KIM S , AHN H , et al . Harnessing reaction-controlled regime of amine-impregnated adsorbents via tracking optimal adsorption timing for enhancing CO 2 capture efficiency [J ] . Separation and Purification Technology , 2025 , 356 : 129922 .
ZHAO P Y , YIN Y C , XU X M , et al . Facile fabrication of mesoporosity silica as support for solid amine CO 2 adsorbents with enhanced adsorption capacity and kinetics [J ] . Energy , 2022 , 253 : 124162 .
KWON H T , SAKWA-NOVAK M A , PANG S H , et al . Aminopolymer-impregnated hierarchical silica structures: Unexpected equivalent CO 2 uptake under simulated air capture and flue gas capture conditions [J ] . Chemistry of Materials , 2019 , 31 ( 14 ): 5229 - 5237 .
DONG X L , ZHU S J , CHEN L , et al . Direct air capture of CO 2 using bi-amines-functionlized hierarchical mesoporous silica: Effects of organic amine loading, moisture and temperature [J ] . Separation and Purification Technology , 2025 , 355 : 129647 .
BAI F T , LIU X , LIU Y M , et al . CO 2 capture from dilute sources using triamine functionalized MCF silica at ambient temperature [J ] . Microporous and Mesoporous Materials , 2023 , 349 : 112370 .
BAI F T , LIU X , SANI S , et al . Amine functionalized mesocellular silica foam as highly efficient sorbents for CO 2 capture [J ] . Separation and Purification Technology , 2022 , 299 : 121539 .
ZHAO P Y , ZHANG G J , XU Y , et al . Development of amine-functionalized silica foams with hierarchical pore structure for CO 2 capture [J ] . Energy & Fuels , 2019 , 33 ( 4 ): 3357 - 3369 .
LIU X , ZHOU K X , FARNDON M , et al . Mesocellular silica foam supported polyamine adsorbents for dry CO 2 scrubbing: Performance of single versus blended polyamines for impregnation [J ] . Applied Energy , 2019 , 255 : 113643 .
0
浏览量
0
下载量
0
CNKI被引量
- 网络PDF下载
- XML下载
- Meta-XML下载
- BibTeX下载
- Endnote下载
- RefMan 下载
- NoteExpress下载
- NoteFirst下载
关联资源
相关文章
相关作者
相关机构
- 地址：四川省成都市双流区西航港机场路近都段393号 邮编：610225
- 联系电话：028-85964717 Email：dthxyhg@swchem.com
- 技术支持由北京北大方正电子有限公司提供 蜀ICP备12008600号-10
蜀公网安备51012202001533 - 本系统建议在Chrome、 IE9+ 以上版本浏览器阅读本站内容，360浏览器请切换至极速模式
- Cookies帮助我们提供服务并提供个性化体验。使用本网站，即表示您同意我们使用Cookies
- 总访问量：286963 今日访问量：195
