Visual analysis of mass transfer enhanced active site utilization efficiency of FCC catalyst

doi:10.11949/0438-1157.20240115

Abstract

Abstract:

The mass transfer performance of fluid catalytic cracking (FCC) catalysts inhibits the utilization efficiency of active sites, which is a key factor affecting its catalytic performance. In this paper, FCC catalyst samples prepared by 6 different matrix materials were selected, and the catalytic pore structure and acid properties were systematically analyzed. The mass transfer and diffusion behavior of heavy oil macromolecules were simulated by laser confocal fluorescence microscopy and adsorption penetration curve method. The utilization efficiency of active sites of the catalysts was investigated by using single molecule fluorescence imaging technique, and the number of oligomers produced by the oligomerization of thiophene catalyzed by B acid site was used as the criterion. It was found that compared with traditional kaolin and pseudo-boehmite as matrix materials, the macro-porous matrix material (APM-9) with abundant B acid sites designed and developed by our team significantly optimized the uploading performance of macromolecules on FCC catalysts, thus significantly improving the utilization efficiency of active sites. In this paper, a novel method to establish the structure-activity relationship between FCC catalyst structure parameters, its mass transfer performance and acid center utilization efficiency is developed, which can provide data support and theoretical guidance for the design and optimization of catalyst matrix materials.

Key words: FCC catalyst, macro-porous matrix, fluorescence microscopic imaging technique, mass transfer, acid catalysis

摘要：

流化催化裂化(FCC)催化剂传质性能抑制活性位利用效率是影响其催化性能的关键因素，选用6种不同基质材料制备的FCC催化剂样品，在系统分析催化孔结构和酸性质的基础上，利用激光共聚焦荧光显微成像技术和吸附穿透曲线法模拟考察了重油大分子的传质扩散行为；并运用单分子荧光成像技术，以B酸中心催化噻吩低聚反应生成低聚物的数量作为判据考察了系列催化剂的活性位利用效率。研究发现，相比于传统的高岭土和拟薄水铝石作为基质材料，本课题组设计开发的大孔富B酸的基质材料(APM-9)明显优化了大分子在FCC催化剂上的传质性能，从而显著提升了活性位的利用效率。发展了一种新颖的FCC催化剂结构参数与其传质性能、酸中心利用效率构效关系建立的方法，可为催化剂基质材料的设计和优化提供数据支撑和理论指导。

关键词: FCC催化剂, 大孔基质, 荧光显微成像技术, 传质, 酸催化

CLC Number:

O 603

Ran WANG, Huan WANG, Xiaoyun XIONG, Huimin GUAN, Yunfeng ZHENG, Cailin CHEN, Yucai QIN, Lijuan SONG. Visual analysis of mass transfer enhanced active site utilization efficiency of FCC catalyst[J]. CIESC Journal, 2024, 75(9): 3198-3209.

王冉, 王焕, 熊晓云, 关慧敏, 郑云锋, 陈彩琳, 秦玉才, 宋丽娟. FCC催化剂传质强化活性位利用效率的可视化分析[J]. 化工学报, 2024, 75(9): 3198-3209.

Figures/Tables 17

References 39

1	Vogt E T C, Weckhuysen B M. Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis[J]. Chemical Society Reviews, 2015, 44(20): 7342-7370.
2	王铃. 2030年炼油催化剂市场规模将达到150亿美元[J]. 石油炼制与化工, 2023, 54(11): 33.
	Wang L. In 2030, the market size of refining catalyst will reach 15 billion US dollars[J]. Petroleum Processing and Petrochemicals, 2023, 54(11): 33.
3	张玉明, 纪德馨, 朱翰文, 等. 微型流化床中萘裂解生成小分子气体的反应动力学研究[J]. 化工学报, 2021, 72(5): 2604-2615.
	Zhang Y M, Ji D X, Zhu H W, et al. Reaction kinetics of naphthalene cracking into small molecule gas in a micro fluidized bed[J]. CIESC Journal, 2021, 72(5): 2604-2615.
4	Fleury M, Pirngruber G, Jolimaitre E. Probing diffusional exchange in mesoporous zeolite by NMR diffusion and relaxation methods[J]. Microporous and Mesoporous Materials, 2023, 355: 112575.
5	Liu X L, Wang C M, Zhou J, et al. Molecular transport in zeolite catalysts: depicting an integrated picture from macroscopic to microscopic scales[J]. Chemical Society Reviews, 2022, 51(19): 8174-8200.
6	周鹏. 基质Lewis酸性调控及其催化轻烃裂化反应性能研究[D]. 徐州: 中国矿业大学, 2023.
	Zhou P. Lewis acidity regulation of matrix and its effects on the catalytic cracking of light hydrocarbons[D]. Xuzhou: China University of Mining and Technology, 2023.
7	洪梅, 高金强, 李彤, 等. 原位刻蚀调控多级孔分子筛策略及其应用进展[J]. 化学学报, 2023, 81(8): 937-948.
	Hong M, Gao J Q, Li T, et al. In-situ etching strategy for manipulation of hierarchical zeolite and its application[J]. Acta Chimica Sinica, 2023, 81(8): 937-948.
8	万艳春, 王玉军, 骆广生. 并流滴加法制备大孔容纤维状γ-氧化铝[J]. 化工学报, 2018, 69(11): 4840-4847.
	Wan Y C, Wang Y J, Luo G S. Preparation of fibrous γ-alumina with large pore volume via co-current dropwise addition method[J]. CIESC Journal, 2018, 69(11): 4840-4847.
9	熊晓云, 曹庚振, 杜学敏, 等. 炭黑模板法制备大孔原位晶化型催化裂化催化剂[J]. 无机盐工业, 2023, 55(9): 134-139.
	Xiong X Y, Cao G Z, Du X M, et al. Preparation of macroporous in situ crystallized FCC catalyst by carbon black template method[J]. Inorganic Chemicals Industry, 2023, 55(9): 134-139.
10	魏娟, 王玉军, 骆广生. 铝源孔容和焙烧升温过程对碳热还原法制备氮化铝粉体的影响[J]. 化工学报, 2021, 72(2): 1156-1168.
	Wei J, Wang Y J, Luo G S. Influence of pore volume and heating process on preparation of aluminum nitride powder by carbothermal reduction method[J]. CIESC Journal, 2021, 72(2): 1156-1168.
11	熊晓云, 潘志爽, 胡清勋, 等. 高岭土酸碱复合改性制备多孔材料及其应用[J]. 石油炼制与化工, 2023, 54(7): 46-51.
	Xiong X Y, Pan Z S, Hu Q X, et al. Preparation and application of porous materials by combining base and acid modification of kaolin[J]. Petroleum Processing and Petrochemicals, 2023, 54(7): 46-51.
12	Bondarenko A V, Bondarenko V V, Petukhova, G A, et al. Adsorption properties of kaolinite and montmorillonite activated by thermochemical treatment[J]. Protection of Metals and Physical Chemistry of Surfaces, 2023, 59(5): 828-836.
13	张莉, 刘超伟, 胡清勋, 等. 高岭土族矿物原位晶化合成Y型分子筛催化剂的研究进展[J]. 工业催化, 2020, 28(11): 1-8.
	Zhang L, Liu C W, Hu Q X, et al. Research progress on in situ crystallization of zeolite catalyst from kaolin group minerals for RFCC[J]. Industrial Catalysis, 2020, 28(11): 1-8.
14	黄校亮, 姚文君, 郑云锋, 等. 改性高岭土在催化裂化催化剂中的应用研究[J]. 炼油与化工, 2011, 22(6): 25-27, 63.
	Huang X L, Yao W J, Zheng Y F, et al. Modification of kaolin and its application in FCC catalyst[J]. Refining and Chemical Industry, 2011, 22(6): 25-27, 63.
15	Baker B R, Pearson R M. Water content of pseudoboehmite: a new model for its structure[J]. Journal of Catalysis, 1974, 33(2): 265-278.
16	闫涛, 袁程远, 柴军军, 等. 硅改性拟薄水铝石的合成及其在FCC催化剂中的应用[J]. 石油化工, 2021, 50(11): 1115-1120.
	Yan T, Yuan C Y, Chai J J, et al. Synthesis of silica-modified pseudo boehmite and its application in FCC catalyst[J]. Petrochemical Technology, 2021, 50(11): 1115-1120.
17	郑金玉, 欧阳颖, 罗一斌, 等. 无序介孔硅铝材料的合成、表征及性能研究[J]. 石油炼制与化工, 2015, 46(9): 47-51.
	Zheng J Y, Ouyang Y, Luo Y B, et al. Synthesis, characterization and catalytic cracking performance of disordered mesoporous silica-alumina material[J]. Petroleum Processing and Petrochemicals, 2015, 46(9): 47-51.
18	熊晓云, 高雄厚, 胡清勋, 等. 富B酸多级孔材料在催化裂化催化剂中的应用[J]. 精细石油化工, 2019, 36(3): 24-27.
	Xiong X Y, Gao X H, Hu Q X, et al. Application of hierarchical porous material rich in bronsted acid in FCC catalyst[J]. Speciality Petrochemicals, 2019, 36(3): 24-27.
19	Kärger J, Freude D, Haase J. Diffusion in nanoporous materials: novel insights by combining MAS and PFG NMR[J]. Processes, 2018, 6(9): 147.
20	Hernandez-Tamargo C, Silverwood I P, O'Malley A J, et al. Quasielastic neutron scattering and molecular dynamics simulation study on the molecular behaviour of catechol in zeolite beta[J]. Topics in Catalysis, 2021, 64(9): 707-721.
21	Talmon Y, Shtirberg L, Harneit W, et al. Molecular diffusion in porous media by PGSE ESR[J]. Physical Chemistry Chemical Physics, 2010, 12(23): 5998-6007.
22	Wessig M, Spitzbarth M, Drescher M, et al. Multiple scale investigation of molecular diffusion inside functionalized porous hosts using a combination of magnetic resonance methods[J]. Physical Chemistry Chemical Physics, 2015, 17(24): 15976-15988.
23	Ajith V J, Patil S. Translational diffusion of a fluorescent tracer molecule in nanoconfined water[J]. Langmuir, 2022, 38(3): 1034-1044.
24	Beschieru V, Rathke B, Will S. Particle diffusion in porous media investigated by dynamic light scattering[J]. Microporous and Mesoporous Materials, 2009, 125(1/2): 63-69.
25	秦玉才, 高雄厚, 石利飞, 等. 原位晶化FCC催化剂传质性能的频率响应法辨析[J]. 物理化学学报, 2016, 32(2): 527-535.
	Qin Y C, Gao X H, Shi L F, et al. Discrimination of the mass transfer performance of in situ crystallization FCC catalysts by the frequency response method[J]. Acta Physico-Chimica Sinica, 2016, 32(2): 527-535.
26	Yasuda Y. Determination of vapor diffusion coefficients in zeolite by the frequency response method[J]. The Journal of Physical Chemistry, 1982, 86(10): 1913-1917.
27	Mehlhorn D, Inayat A, Schwieger W, et al. Probing mass transfer in mesoporous faujasite-type zeolite nanosheet assemblies[J]. Chemphyschem: a European Journal of Chemical Physics and Physical Chemistry, 2014, 15(8): 1681-1686.
28	Vattipalli V, Qi X D, Dauenhauer P J, et al. Long walks in hierarchical porous materials due to combined surface and configurational diffusion[J]. Chemistry of Materials, 2016, 28(21): 7852-7863.
29	Xiao Y, Xu W L. Single-molecule fluorescence imaging for probing nanocatalytic process[J]. Chem, 2023, 9(1): 16-28.
30	González R M, Maris J J E, Wagner M, et al. Fluorescent-probe characterization for pore-space mapping with single-particle tracking[J]. Angewandte Chemie International Edition, 2024, 63(4): e202314528.
31	Lezcano-González I, Oord R, Rovezzi M, et al. Molybdenum speciation and its impact on catalytic activity during methane dehydroaromatization in zeolite ZSM-5 as revealed by operando X-ray methods[J]. Angewandte Chemie International Edition, 2016, 55(17): 5215-5219.
32	Werny M J, Siebers K B, Friederichs N H, et al. Advancing the compositional analysis of olefin polymerization catalysts with high-throughput fluorescence microscopy[J]. Journal of the American Chemical Society, 2022, 144(46): 21287-21294.
33	Omori N, Candeo A, Mosca S, et al. Multimodal imaging of autofluorescent sites reveals varied chemical speciation in SSZ-13 crystals[J]. Angewandte Chemie International Edition, 2021, 60(10): 5125-5131.
34	Lee H, Kim K, Kang C M, et al. In situ confocal fluorescence lifetime imaging of nanopore electrode arrays with redox active fluorogenic amplex red[J]. Analytical Chemistry, 2023, 95(2): 1038-1046.
35	Buurmans I L C, Ruiz-Martínez J, Knowles W V, et al. Catalytic activity in individual cracking catalyst particles imaged throughout different life stages by selective staining[J]. Nature Chemistry, 2011, 3(11): 862-867.
36	Kox M H, Mijovilovich A, Sättler J J, et al. The catalytic conversion of thiophenes over large H-ZSM-5 crystals: an X-ray, UV/vis, and fluorescence microspectroscopic study[J]. ChemCatChem, 2010, 2(5): 564-571.
37	Hendriks F C, Meirer F, Kubarev A V, et al. Single-molecule fluorescence microscopy reveals local diffusion coefficients in the pore network of an individual catalyst particle[J]. Journal of the American Chemical Society, 2017, 139(39): 13632-13635.
38	刘现玉, 袁程远, 高雄厚, 等. 拟薄水铝石@高岭土复合材料的合成及其在FCC催化剂中的应用[J]. 石油化工, 2020, 49(3): 219-223.
	Liu X Y, Yuan C Y, Gao X H, et al. Synthesis of pseudo-boehmite@kaolinite composite and its application in FCC catalyst[J]. Petrochemical Technology, 2020, 49(3): 219-223.
39	Thommes M, Kaneko K, Neimark A V, et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report)[J]. Pure and Applied Chemistry, 2015, 87(9/10): 1051-1069.

样品	比表面积/ （m²·g^-1）	微孔面积/ （m²·g^-1）	介孔面积/（m²·g^-1）	总孔体积/（cm³·g^-1）	微孔体积/（cm³·g^-1）	介孔体积/（cm³·g^-1）
CAT-1	156	88	68	0.167	0.046	0.121
CAT-2	186	95	91	0.198	0.050	0.148
CAT-3	188	95	93	0.202	0.050	0.152
CAT-4	185	98	87	0.218	0.056	0.162
CAT-5	190	101	89	0.229	0.059	0.170
CAT-6	193	104	88	0.248	0.061	0.187

样品	比表面积/ （m²·g^-1）	微孔面积/ （m²·g^-1）	介孔面积/（m²·g^-1）	总孔体积/（cm³·g^-1）	微孔体积/（cm³·g^-1）	介孔体积/（cm³·g^-1）
CAT-1	156	88	68	0.167	0.046	0.121
CAT-2	186	95	91	0.198	0.050	0.148
CAT-3	188	95	93	0.202	0.050	0.152
CAT-4	185	98	87	0.218	0.056	0.162
CAT-5	190	101	89	0.229	0.059	0.170
CAT-6	193	104	88	0.248	0.061	0.187

样品	弱酸量/ (mmol·g^-1)	中强酸量/ (mmol·g^-1)	强酸量/ (mmol·g^-1)
CAT1	4.07	11.55	15.70
CAT2	4.11	12.45	15.79
CAT3	5.10	14.09	16.70
CAT-4	5.98	16.75	18.87
CAT-5	6.58	21.37	18.99
CAT-6	6.50	21.77	19.41

样品	弱酸量/ (mmol·g^-1)	中强酸量/ (mmol·g^-1)	强酸量/ (mmol·g^-1)
CAT1	4.07	11.55	15.70
CAT2	4.11	12.45	15.79
CAT3	5.10	14.09	16.70
CAT-4	5.98	16.75	18.87
CAT-5	6.58	21.37	18.99
CAT-6	6.50	21.77	19.41

样品	酸量/(mmol·g^-1)
	150℃		400℃
	B酸	L酸	B酸	L酸
CAT-1	0.065	0.064	0.043	0.010
CAT-2	0.069	0.070	0.047	0.014
CAT-3	0.087	0.071	0.067	0.010
CAT-4	0.072	0.082	0.056	0.009
CAT-5	0.086	0.135	0.057	0.005
CAT-6	0.089	0.137	0.061	0.010