Engineering of sulfate ions migration in Fe2O3-doped NiSO4/Al2O3 catalysts to enhance the selective trimerization of propylene

doi:10.1016/S1872-2067(25)64663-8

Abstract

Abstract:

Propylene, a readily accessible and economically viable light olefin, has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes. The distribution of products is profoundly influenced by the catalyst structure. In this study, Fe₂O₃-doped NiSO₄/Al₂O₃ catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions. Significantly, the 0.25Fe₂O₃-NiSO₄/Al₂O₃ catalyst demonstrates an enhanced reaction rate (48.5 mmol_C3/(g_cat.·h)), alongside a high yield of C9 (~ 32.2%), significantly surpassing the performance of the NiSO₄/Al₂O₃ catalyst (C9: ~24.1%). The incorporation of Fe₂O₃ modifies the migration process of sulfate ions, altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution. This shift is primarily ascribed to the heightened energy barrier for the β-H elimination reaction in the C6 alkyl intermediates on the doped catalyst, further promoting polymerization to yield a greater quantity of Type II C9. Furthermore, the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed. It is noteworthy that the 0.25Fe₂O₃-NiSO₄/Al₂O₃ catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene. These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.

Key words: Propylene trimerization, Fe₂O₃-doped NiSO₄/Al₂O₃ catalyst, Sulfate ions migration, Poisson distribution, Cossee-Arlman mechanism

Xu Liu, Yu Ling, Xiao Chen, Changhai Liang. Engineering of sulfate ions migration in Fe₂O₃-doped NiSO₄/Al₂O₃ catalysts to enhance the selective trimerization of propylene[J]. Chinese Journal of Catalysis, 2025, 72: 376-391.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64663-8

https://www.cjcatal.com/EN/Y2025/V72/I5/376

Figures/Tables 16

Scheme 1. Simplified schematic diagram of fixed-bed continuous flow microreactor for propylene oligomerization.

Fig. 1. (a) Scheme for the synthesis route of catalyst with a total metal loading of 10 wt% prepared using a stepwise impregnation method. (b) XRD patterns of xFe2O3-NiSO4/Al2O3 samples and Fe2O3-SO42-/Al2O3 sample. HAADF-STEM image along with the corresponding EDS elemental mappings (c) and line-scanning profiles (d) of 0.5Fe2O3-NiSO4/Al2O3 sample.

Fig. 2. H2-TPR profiles (a) and Raman spectra (b) of xFe2O3-NiSO4/Al2O3 samples sand the referred Fe2O3-SO42-/Al2O3 sample. (c) Schematic diagram of the hypothetical electron transfer in xFe2O3-NiSO4/Al2O3 samples.

Fig. 3. Ni K-edge XANES (a) and k2-weighted Fourier-transformed EXAFS (b) spectra of xFe2O3-NiSO4/Al2O3 samples, compared with Ni foil and NiO (Ni2+) standard references. (c-f) Wavelet transform plots of xFe2O3-NiSO4/Al2O3 samples.

Fig. 4. XPS of Ni 2p (a) and Fe 2p (b) for xFe2O3-NiSO4/Al2O3 samples and the referred Fe2O3-SO42-/Al2O3 sample.

Fig. 5. NH3-TPD curves (a) and Py-FTIR spectra (b) in the desorption temperature at 150 °C for xFe2O3-NiSO4/Al2O3 samples and the referred Fe2O3-SO42-/Al2O3 sample.

Fig. 6. The propylene oligomerization reaction data for xFe2O3-NiSO4/Al2O3 samples, the referred Fe2O3-SO42-/Al2O3 sample, and Al2O3 sample under conditions of T = 70 °C, P = 2.5 MPa, WHSV = 2.1 gC3/(gcat.?h). (a) Propylene consumption rate and conversion versus time on stream. (b) The yield of the target product in the early stage of the reaction and (c) the selectivity of the oligomerized products.

Table 1 Summary of initial conversion and product distribution for the oligomerization of propylene over xFe2O3-NiSO4/Al2O3 samples along with other reference samples (Fe2O3-SO42-/Al2O3 and sulfonic acid resins). (Reaction conditions: 70 °C, 2.5 MPa, 2.1 gC3/(gcat.?h).

Catalysts	NiSO₄/Al₂O₃	0.25Fe₂O₃-NiSO₄/ Al₂O₃	0.5Fe₂O₃-NiSO₄/ Al₂O₃	0.75Fe₂O₃-NiSO₄/ Al₂O₃	Fe₂O₃-SO₄^2-/ Al₂O₃	Sulfonic acid resins
Dimers distributions (%)
1Hex ^Ⅰ	0.7	0.7	0.8	1.2	0.5	n.d.
2Hex ^Ⅰ	32.6	33.8	28.0	25.9	21.5	n.d.
3Hex ^Ⅰ	9.0	9.8	6.8	4.3	5.3	n.d.
4M1P ^Ⅱ	1.6	2.2	3.7	7.2	4.8	2.7
4M2P ^Ⅱ	43.3	46.3	52.8	52.6	43.9	22.8
2M1P ^Ⅱ	1.0	0.4	0.4	0.4	1.0	4.4
2M2P ^Ⅱ	6.8	3.2	3.4	3.2	8.6	30.0
23DM2B ^Ⅱ	4.2	2.2	2.8	3.9	11.1	27.2
3M2P ^Ⅲ	0.8	1.4	1.3	1.3	3.3	12.9
Trimers distributions (%)
4N ^Ⅰ	10.8	0.9	0.4	0.5	0.5	n.d.
2M3O ^Ⅰ	0.9	0.3	0.2	0.1	0.2	n.d.
7M3O ^Ⅰ	4.7	0.6	0.4	0.3	0.3	n.d.
26DM3Hept ^Ⅰ	13.6	6.0	5.3	7.1	7.6	n.d.
23DM2Hept ^Ⅱ	3.4	3.1	2.2	1.5	1.3	2.0
23DM3Hept ^Ⅱ	33.9	48.5	47.8	47.9	47.8	43.6
445TM3Hex ^Ⅱ	2.4	2.6	3.2	3.2	3.3	1.2
4E3Hept ^Ⅱ	16.0	17.6	17.6	18.0	17.8	21.9
344TM2Hex ^Ⅲ	4.4	7.4	7.9	7.5	6.6	10.7
35DM3Hept ^Ⅲ	3.9	8.0	8.7	8.8	9.1	16.4
Others	6.0	5.0	6.3	5.1	5.5	4.2

Fig. 7. (a) Pseudo-first-order kinetic fitting diagram of propylene oligomerization. Propylene conversion (b,c) and C9 distribution selectivity (d,e) as a function of contact time on NiSO4/Al2O3 sample and 0.25 Fe2O3-NiSO4/Al2O3 sample. Reaction conditions: 70 °C, 2.5 MPa.

Fig. 8. 2D HSQC spectra (a,b) and 1H-NMR spectra (c,d) of products that obtained from the oligomerization of propylene over the 0.25 Fe2O3-NiSO4/Al2O3 sample at contact time of 5 gcat./(gC3·min) and 30 gcat./(gC3·min), respectively. (e) GC×GC-MS spectrum of the product that obtained from the oligomerization of propylene over the 0.25 Fe2O3-NiSO4/Al2O3 sample at a contact time of 5 gcat./(gC3·min). (Reaction conditions: 70 °C, 2.5 MPa).

Scheme 2. Propylene oligomerization reaction network according to the Cossee-Arlman mechanism.

Fig. 9. (a) Relationship between the consumption rate of propylene and Lewis acid concentration (CL). (b) Relationship between the induction period of the reaction and the binding energy of Ni species. Influence of Fe species on the distribution of oligomerization products (c) and C3H6-TPSR-MS profiles (m/z = 84) (d) of xFe2O3-NiSO4/Al2O3 samples.

Fig. 10. (a) Reaction paths of dimer formation at metal sites based on Cossee-Arlman mechanism. (b) Two routes for propylene oligomerization leading to trimer products. (c) Type I C9 produced by propylene oligomerization through Route I.

Fig. 11. Results of stability testing for the 0.25Fe2O3-NiSO4/Al2O3 sample at 70 °C, 2.5 MPa, and 2.1 gC3/(gcat.·h).

Fig. 12. TG-MS curves of the fresh (a,b) and spent (c,d) 0.25Fe2O3-NiSO4/Al2O3 sample.

Fig. 13. XPS spectra of Ni 2p (a) and Fe 2p (b) for the fresh and spent 0.25Fe2O3-NiSO4/Al2O3 sample.

References

[1]	M. Marchionna, M. D. Girolamo, R. Patrini, Catal. Today, 2001, 65, 397-403.
[2]	Z. N. Lashchinskaya, A. A. Gabrienko, A. G. Stepanov, ACS Catal., 2024, 14, 4984-4998.
[3]	T. K. Phung, T. L. M. Pham, K. B. Vu, G. Busca, J. Environ. Chem. Eng., 2021, 9, 105673.
[4]	J. H. Carter, T. Bere, J. R. Pitchers, D. G. Hewes, B. D. Vandegehuchte, C. J. Kiely, S. H. Taylor, G. J. Hutchings, Green Chem., 2021, 23, 9747-9799.
[5]	A. Alzamly, M. Bakiro, S. Hussein Ahmed, L. A. Siddig, H. L. Nguyen, Coord. Chem. Rev., 2022, 462, 214522.
[6]	J. A. Martens, W. H. Verrelst, G. M. Mathys, S. H. Brown, P. A. Jacobs, Angew. Chem. Int. Ed., 2005, 44, 687-5690.
[7]	G. Wang, H. Song, R. Li, Z. Li, J. Chen, Chin. J. Catal., 2018, 39, 1110-1120.
[8]	C. P. Nicholas, Appl. Catal. A, 2017, 543, 82-97.
[9]	H. Olivier-Bourbigou, P. A. R. Breuil, L. Magna, T. Michel, M. F. Espada Pastor, D. Delcroix, Chem. Rev., 2020, 120, 7919-7983.
[10]	R. Rajapaksha, P. Samanta, E. A. Quadrelli, J. Canivet, Chem. Soc. Rev., 2023, 52, 8059-8076.
[11]	A. Finiels, F. Fajula, V. Hulea, Catal. Sci. Technol., 2014, 4, 2412-2426.
[12]	D. K. Steelman, D. C. Aluthge, M. C. Lehman, J. A. Labinger, J. E. Bercaw, ACS Catal., 2017, 7, 4922-4926.
[13]	A. Jonathan, E. G. Tomashek, M. P. Lanci, J. A. Dumesic, G. W. Huber, J. Catal., 2021, 404, 954-963.
[14]	N. J. LiBretto, Y. Xu, A. Quigley, E. Edwards, R. Nargund, J. C. Vega-Vila, R. Caulkins, A. Saxena, R. Gounder, J. Greeley, G. Zhang, J. T. Miller, Nat. Commun., 2021, 12, 2322.
[15]	L. V. Parfenova, A. K. Bikmeeva, P. V. Kovyazin, L. M. Khalilov, Molecules, 2024, 29, 502.
[16]	D. Liu, L. Cao, G. Zhang, L. Zhao, J. Gao, C. Xu, Fuel Process. Technol., 2021, 216, 106770.
[17]	M. Guisnet, N. Gnep, D. Aittaleb, Y. J. Doyemet, Appl. Catal. A, 1992, 87, 255-270.
[18]	S. Vernuccio, E. E. Bickel, R. Gounder, L. J. Broadbelt, ACS Catal., 2019, 9, 8996-9008.
[19]	E. E. Bickel, S. Lee, R. Gounder, ACS Catal., 2023, 13, 1257-1269.
[20]	Y. Ling, X. Chen, H. Tong, W. Guan, P. Chen, Z. Huang, C. Liang, Ind. Eng. Chem. Res., 2021, 60, 6959-6970.
[21]	Y. Ling, X. Chen, J. Meng, C. Liang, Appl. Catal. A, 2022, 640, 118661.
[22]	Y. Ling, X. Chen, J. Meng, C. Wang, C. Li, A. H. Clark, B. Du, C. Liang, Appl. Catal. A, 2023, 663, 119289.
[23]	T. Cai, Catal. Today, 1999, 51, 153-160.
[24]	Y. Peng, M. Dong, X. Meng, B. Zong, J. Zhang, AlChE J., 2009, 55, 717-725.
[25]	B. Maleki, S. S. Ashraf Talesh, Renewable Energy, 2022, 182, 43-59.
[26]	J. Yoo, S. Park, J. H. Song, S. Yoo, I. K. Song, Int. J. Hydrogen Energy, 2017, 42, 28377-28385.
[27]	A. Muñoz-Murillo, L. M. Martínez T, M. I. Domínguez, J. A. Odriozola, M. A. Centeno, Appl. Catal. B, 2018, 236, 420-427.
[28]	N. D. Charisiou, C. Italiano, L. Pino, V. Sebastian, A. Vita, M. A. Goula, Renewable Energy, 2020, 162, 908-925.
[29]	C. Italiano, N. T. J. Luchters, L. Pino, J. V. Fletcher, S. Specchia, J. C. Q. Fletcher, A. Vita, Int. J. Hydrogen Energy, 2018, 43, 11755-11765.
[30]	Z. Yu, X. Hu, P. Jia, Z. Zhang, D. Dong, G. Hu, S. Hu, Y. Wang, J. Xiang, Appl. Catal. B, 2018, 237, 538-553.
[31]	N. Lohitharn, J. Goodwinjr, J. Catal., 2008, 257, 142-151.
[32]	Y. Feng, N. Wang, X. Guo, S. Zhang, Fuel, 2020, 276, 117942.
[33]	R. R. Choudhury, R. Chitra, I. P. Makarova, V. L. Manomenova, E. B. Rudneva, A. E. Voloshin, M. V. Koldaeva, J. Appl. Crystallogr., 2019, 52, 1371-1377.
[34]	S. Ghosh, S. Ullah, J. P. A. de Mendonça, L. G. Moura, M. G. Menezes, L. S. Flôres, T. S. Pacheco, L. F. C. de Oliveira, F. Sato, S. O. Ferreira, Spectrochim. Acta, Part A, 2019, 218, 281-292.
[35]	A. Sivakumar, S. S. J. Dhas, L. Dai, P. Sivaprakash, T. Vasanthi, V. N. Vijayakumar, R. S. Kumar, V. Pushpanathan, S. Arumugam, I. Kim, S. A. M. B. Dhas, JOM, 2023, 75, 4611-4618.
[36]	Y. El Mendili, J. F. Bardeau, N. Randrianantoandro, A. Gourbil, J. M. Greneche, A. M. Mercier, F. Grasset, Raman Spectrosc., 2010, 42, 239-242.
[37]	M. Sendova, B. D. Hosterman, A. Grebe, J. Raman Spectrosc., 2017, 48, 618-622.
[38]	O. Saur, M. Bensitel, A. B. M. Saad, J. C. Lavalley, C. P. Tripp, B. A. Morrow, J. Catal., 1986, 99, 104-110.
[39]	A. D. Fortes, K. S. Knight, A. S. Gibbs, I. G. Wood, Phys. Chem. Miner., 2018, 45, 695-712.
[40]	L. Li, S. Chavan, Y. Ganjkhanlou, E. Groppo, E. Sagstuen, S. Bordiga, U. Olsbye, K.-J. Jens, Appl. Catal. A, 2022, 637, 118598.
[41]	H. B. Yang, S.-F. Hung, S. Liu, K. Yuan, S. Miao, L. Zhang, X. Huang, H.-Y. Wang, W. Cai, R. Chen, J. Gao, X. Yang, W. Chen, Y. Huang, H. M. Chen, C. M. Li, T. Zhang, B. Liu, Nat. Energy, 2018, 3, 140-147.
[42]	R. Ma, J. Gao, J. Kou, D. P. Dean, C. J. Breckner, K. Liang, B. Zhou, J. T. Miller, G. Zou, ACS Catal., 2022, 12, 12607-12616.
[43]	G. Zhang, C. Yang, J. T. Miller, ChemCatChem, 2018, 10, 961-964.
[44]	Y. Sun, L. Li, F. Ju, H. Ling, Sep. Purif. Technol., 2022, 283, 120204.
[45]	R. An, G. Xu, C. Chang, J. Bai, S. Fang, J. Energy Chem., 2017, 26, 556-563.
[46]	J. Yao, T. Jin, Y. Li, S. Xiao, B. Huang, J. Jiang, J. Alloys Compd., 2021, 886, 161238.
[47]	D. S. Belov, G. Tejeda, K. V. Bukhryakov, ChemPlusChem, 2021, 86, 924-937.
[48]	Y. Wang, J. Lai, Q. Gou, R. Gao, G. Zheng, R. Zhang, Z. Song, Q. Yue, Z. Guo, Coord. Chem. Rev., 2025, 522, 216195.
[49]	D. Fiorito, S. Scaringi, C. Mazet, Chem. Soc. Rev., 2021, 50, 1391-1406.
[50]	Y. Chauvin, D. Commereuc, F. Hugues, J. J. A. C. Thivolle-Cazat, Appl. Catal., 1988, 42, 205-216.
[51]	G. V. S. Seufitelli, J. J. W. Park, P. N. Tran, A. Dichiara, F. L. P. Resende, R. Gustafson, J. Catal., 2021, 401, 40-53.
[52]	A. N. Mlinar, G. B. Baur, G. G. Bong, A. B. Getsoian, A. T. Bell, J. Catal., 2012, 296, 156-164.
[53]	G. J. P. Britovsek, R. Malinowski, D. S. McGuinness, J. D. Nobbs, A. K. Tomov, A. W. Wadsley, C. T. Young, ACS Catal., 2015, 5, 6922-6925.
[54]	G. J. P. Britovsek, S. A. Cohen, V. C. Gibson, P. J. Maddox, M. van Meurs, Angew. Chem. Int. Ed., 2002, 41, 489-491.
[55]	B. Zhang, M. E. Ford, E. Ream, I. E. Wachs, Catal. Sci. Technol., 2023, 13, 217-225.
[56]	B. Zhang, I. E. Wachs, Catal. Sci. Technol., 2024, 14, 4716-4724.
[57]	S. Moussa, P. Concepción, M. A. Arribas, A. Martínez, ACS Catal., 2018, 8, 3903-3912.
[58]	J. Rabeah, J. Radnik, V. Briois, D. Maschmeyer, G. Stochniol, S. Peitz, H. Reeker, C. La Fontaine, A. Brückner, ACS Catal., 2016, 6, 8224-8228.

Engineering of sulfate ions migration in Fe₂O₃-doped NiSO₄/Al₂O₃ catalysts to enhance the selective trimerization of propylene

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 16

References

Related Articles 0

Recommended Articles

Metrics