Preparation of acid-rich 13X molecular sieve and its ultra-deep adsorption removal of mercaptan in biodiesel

doi:10.11949/0438-1157.20241238

Abstract

Abstract:

In view of the difficulty in removing trace sulfides from biodiesel, the acid-rich Ce-13X molecular sieve was constructed by ion exchange method and used in the adsorption desulfurization system of biodiesel. The phase composition, structure and morphology, acid strength, element valence and acidity were analyzed by a series of characterizations. The results showed that the introduction of Ce increased the concentration of strong B acid sites and weak L acid sites in 13X zeolite. Under the optimal experimental conditions (temperature of 40℃, agent-oil ratio of 1∶80), after 30 min, the sulfur content in biodiesel dropped from 8 μg·g^-1 to below the target concentration of 2 μg·g^-1. The adsorption kinetics showed that the adsorption process conformed to the quasi-second-order kinetic model and the whole adsorption process was mainly controlled by liquid film diffusion and intraparticle diffusion. The adsorption thermodynamics showed that the adsorption of mercaptan by Ce-13X was a spontaneous exothermic process. This study not only proposed a construction method of acid-rich 13X molecular sieve, but also constructed an efficient adsorption desulfurization system to achieve ultra-deep removal of trace sulfides in biodiesel.

Key words: adsorption, desulfurization, ion exchange, mercaptan, biodiesel

摘要：

针对生物柴油中微量硫化物难脱除的问题，采用离子交换法构筑了富酸位Ce-13X分子筛，将其用于生物柴油吸附脱硫体系。通过一系列表征对其物相组成、结构形貌、酸强度、元素价态和酸性等性质进行分析。结果表明，Ce的引入增加了13X分子筛的强B酸位点以及弱L酸位点浓度。在最优实验条件温度40℃，剂油比为1∶80下，经过30 min，生物柴油中的硫含量从8 μg·g^-1降至目标浓度2 μg·g^-1以下。吸附动力学表明该吸附过程符合准二级动力学模型且整个吸附过程主要由液膜扩散和颗粒内扩散控制，吸附热力学表明Ce-13X对硫醇的吸附为自发放热过程。该研究不仅提出了一种富酸位13X分子筛的构筑方法，而且能够构筑高效吸附脱硫体系，实现生物柴油中微量硫化物超深度脱除。

关键词: 吸附, 脱硫, 离子交换, 硫醇, 生物柴油

CLC Number:

TE 624

Zhichao XU, Zhendong YU, Haofeng WU, Peiwen WU, Hongxiang WU, Yanhong CHAO, Wenshuai ZHU, Zhichang LIU, Chunming XU. Preparation of acid-rich 13X molecular sieve and its ultra-deep adsorption removal of mercaptan in biodiesel[J]. CIESC Journal, 2025, 76(5): 2198-2208.

徐智超, 俞镇东, 吴昊峰, 吴沛文, 武洪翔, 巢艳红, 朱文帅, 刘植昌, 徐春明. 富酸位13X分子筛的制备及其超深度吸附脱除生物柴油中硫醇[J]. 化工学报, 2025, 76(5): 2198-2208.

Figures/Tables 21

Fig.1 Sulfide composition analysis of biodiesel

Fig.2 XRD spectra of 13X and Ce-13X

Fig.3 SEM images of 13X (a) and Ce-13X (b)

Fig.4 FTIR spectra of 13X and Ce-13X

Fig.5 N2 adsorption-desorption isotherms (a) and pore size distribution (b) of 13X and Ce-13X

Table 1 Pore structure parameters and elemental analysis of adsorbents

n(SiO₂)/

n(Al₂O₃)

Fig.6 XPS full spectra (a) and Ce 3d spectra (b) of Ce-13X

Fig.7 NH3-TPD spectra of 13X and Ce-13X

Fig.8 Py-IR spectra of 13X(a) and Ce-13X(b)

Table 2 Distribution of Brønsted and Lewis acidity in the adsorbents

吸附剂	脱附温度/℃	酸量/(μmol·g^-1)
吸附剂	脱附温度/℃	B酸	L酸
13X	200	—	196.4
13X	350	—	153.1
Ce-13X	200	318.5	151.2
Ce-13X	350	324.1	54.5

Fig.9 Effects of ion exchange solution concentration (a) and solid-liquid ratio (b) on adsorption desulfurization performance

Fig.10 Effect of temperature on equilibrium concentration (a) and adsorption rate (b)

Fig.11 Effect of adsorbent to oil ratio on adsorption performance

Fig.12 Pseudo-first-order kinetics (a) and pseudo-second-order kinetics (b) of Ce-13X adsorption desulfurization

Table 3 Fitting parameters of Ce-13X adsorption kinetics

温度/℃	q_e,exp/(mg·g^-1)	准一级动力学			准二级动力学
温度/℃	q_e,exp/(mg·g^-1)	k₁/min^-1	q_e1,cal/(mg·g^-1)	R²	k₂/(g·mg^-1·min^-1)	q_e2,cal/(mg·g^-1)	R²
30	0.69	0.0213	0.49	0.9483	0.0657	0.76	0.9980
40	0.70	0.0324	0.19	0.9780	0.3961	0.71	0.9999

Fig.13 Intraparticle diffusion model of Ce-13X

Table 4 Fitting parameters of the intraparticle diffusion model

阶段	k/(mg·g^-1·min^-0.5)	C/(mg·g^-1)	R²
第一阶段	0.0721	0.0399	0.9592
第二阶段	0.0139	0.4794	0.9633
第三阶段	—	0.6936	—

Fig.14 Langmuir adsorption isotherms (a) and Freundlich adsorption isotherms (b) of Ce-13X

Table 5 Langmuir and Freundlich adsorption isotherm parameters of Ce-13X

吸附剂	q_m/(mg·g^-1)	Langmuir吸附等温线		Freundlich吸附等温线
吸附剂	q_m/(mg·g^-1)	K_L/(L·mg^-1)	R²	K_F/(mg·g^-1)(L·mg^-1)^1/ⁿ	1/n	R²
Ce-13X	7.73	0.0026	0.9669	0.1057	0.5995	0.9904

Fig.15 Linear fitting of lnK-1/T

Table 6 Adsorption thermodynamic parameters of Ce-13X at different temperatures

ΔG/(kJ·mol^-1)				ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	R²
303.15 K	313.15 K	323.15 K	333.15 K	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	R²
-9.9114	-9.0445	-7.8336	-7.3374	-36.9286	-89.2170	0.9859

References 35

1	Jiang H B, Shao Z Y, Chen W B, et al. Study on diesel hydrotreating kinetics and the synergistic effect of CoMo and NiMo catalysts[J]. Energy & Fuels, 2024, 38(7): 6314-6324.
2	Oh P P, Lau H L N, Chen J, et al. A review on conventional technologies and emerging process intensification (PI) methods for biodiesel production[J]. Renewable and Sustainable Energy Reviews, 2012, 16(7): 5131-5145.
3	黄宽, 马永德, 蔡镇平, 等. 油脂催化加氢转化制备第二代生物柴油研究进展[J]. 化工学报, 2023, 74(1): 380-396.
	Huang K, Ma Y D, Cai Z P, et al. Research progress in catalytic hydroconversion of lipid to second-generation biodiesel[J]. CIESC Journal, 2023, 74(1): 380-396.
4	Li Y M, Xu H, Li Z F, et al. Catalytic methanotreating of vegetable oil: a pathway to second-generation biodiesel[J]. Fuel, 2022, 311: 122504.
5	Haruna A, Merican Aljunid Merican Z, Gani Musa S, et al. Sulfur removal technologies from fuel oil for safe and sustainable environment[J]. Fuel, 2022, 329: 125370.
6	Xiong J, Luo J, Di J, et al. Macroscopic 3D boron nitride monolith for efficient adsorptive desulfurization[J]. Fuel, 2020, 261: 116448.
7	Wang Q, Zhang T, Zhang S L, et al. Extractive desulfurization of fuels using trialkylamine-based protic ionic liquids[J]. Separation and Purification Technology, 2020, 231: 115923.
8	Lin Y H, Feng L, Li X H, et al. Study on ultrasound-assisted oxidative desulfurization for crude oil[J]. Ultrasonics Sonochemistry, 2020, 63: 104946.
9	Umar Hussain M, Kainat K, Nawaz H, et al. SERS characterization of biochemical changes associated with biodesulfurization of dibenzothiophene using Gordonia sp. HS126-4N[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2024, 320: 124534.
10	Lee K X, Valla J A. Adsorptive desulfurization of liquid hydrocarbons using zeolite-based sorbents: a comprehensive review[J]. Reaction Chemistry & Engineering, 2019, 4(8): 1357-1386.
11	Danmaliki G I, Saleh T A, Shamsuddeen A A. Response surface methodology optimization of adsorptive desulfurization on nickel/activated carbon[J]. Chemical Engineering Journal, 2017, 313: 993-1003.
12	Yoosuk B, Silajan A, Prasassarakich P. Deep adsorptive desulfurization over ion-exchanged zeolites: individual and simultaneous effect of aromatic and nitrogen compounds[J]. Journal of Cleaner Production, 2020, 248: 119291.
13	Hamad K I, Humadi J I, Abdulkareem H A, et al. Efficient immobilization of acids into activated carbon for high durability and continuous desulfurization of diesel fuel[J]. Energy Science & Engineering, 2023, 11(10): 3662-3679.
14	Zhang C Y, Zhang X W, Tao Z P, et al. Defect engineering and post-synthetic reduction of Cu based metal-organic frameworks towards efficient adsorption desulfurization[J]. Chemical Engineering Journal, 2023, 455: 140487.
15	Neubauer R, Husmann M, Weinlaender C, et al. Acid base interaction and its influence on the adsorption kinetics and selectivity order of aromatic sulfur heterocycles adsorbing on Ag-Al₂O₃ [J]. Chemical Engineering Journal, 2017, 309: 840-849.
16	Liu X J, Yi D Z, Cui Y Y, et al. Adsorption desulfurization and weak competitive behavior from 1-hexene over cesium-exchanged Y zeolites (CsY)[J]. Journal of Energy Chemistry, 2018, 27(1): 271-277.
17	Yang R T, Hernández-Maldonado A J, Yang F H. Desulfurization of transportation fuels with zeolites under ambient conditions[J]. Science, 2003, 301(5629): 79-81.
18	Cha Y H, Lee K B. Examining the impact of different anions in Cu precursors on sulfur adsorption through zeolites with Cu ion-exchange[J]. Chemical Engineering Journal, 2023, 468: 143461.
19	Zu Y, Guan L J, Guo Z S, et al. Deep removal of thiophene and benzothiophene in low-sulfur fuels over the efficient CeAlSBA-15 adsorbent synthesized by sequential alumination and cerium incorporation[J]. Chemical Engineering Journal, 2021, 416: 127984.
20	Lee K X, Tsilomelekis G, Valla J A. Removal of benzothiophene and dibenzothiophene from hydrocarbon fuels using CuCe mesoporous Y zeolites in the presence of aromatics[J]. Applied Catalysis B: Environmental, 2018, 234: 130-142.
21	Lv J M, Ma Y L, Chang X, et al. Removal and removing mechanism of tetracycline residue from aqueous solution by using Cu-13X[J]. Chemical Engineering Journal, 2015, 273: 247-253.
22	Ren X Y, Cao J P, Zhao X Y, et al. Enhancement of aromatic products from catalytic fast pyrolysis of lignite over hierarchical HZSM-5 by piperidine-assisted desilication[J]. ACS Sustainable Chemistry & Engineering, 2018, 6(2): 1792-1802.
23	Zeng Y B, Walker H, Zhu Q Z. Reduction of nitrate by NaY zeolite supported Fe, Cu/Fe and Mn/Fe nanoparticles[J]. Journal of Hazardous Materials, 2017, 324: 605-616.
24	Vinodh R, Deviprasath C, Muralee Gopi C V V, et al. Novel 13X zeolite/PANI electrocatalyst for hydrogen and oxygen evolution reaction[J]. International Journal of Hydrogen Energy, 2020, 45(53): 28337-28349.
25	Xiang X J, Guo T, Yin Y M, et al. High adsorption capacity Fe@13X zeolite for direct air CO₂ capture[J]. Industrial & Engineering Chemistry Research, 2023, 62(12): 5420-5429.
26	Dashtpeyma G, Shabanian S R, Ahmadpour J, et al. The investigation of adsorption desulphurization performance using bimetallic CuCe and NiCe mesoporous Y zeolites: modification of Y zeolite by H4EDTA-NaOH sequential treatment[J]. Fuel Processing Technology, 2022, 235: 107379.
27	Zhu J C, Hu L F, He J, et al. Removal of ethyl mercaptan over Fe and Ce doped hexaniobate nanotubes[J]. Ceramics International, 2022, 48(17): 25267-25276.
28	Ma Y G, Zhang D Y, Sun H M, et al. Fe-Ce mixed oxides supported on carbon nanotubes for simultaneous removal of NO and Hg⁰ in flue gas[J]. Industrial & Engineering Chemistry Research, 2018, 57(9): 3187-3194.
29	Kumar K M, Mahendhiran M, Diaz M C, et al. Green synthesis of Ce³⁺ rich CeO₂ nanoparticles and its antimicrobial studies[J]. Materials Letters, 2018, 214: 15-19.
30	Wei F J, Guo X Q, Liao J J, et al. Ultra-deep removal of thiophene in coke oven gas over Y zeolite: effect of acid modification on adsorption desulfurization[J]. Fuel Processing Technology, 2021, 213: 106632.
31	Luo J, Chao Y H, Tang Z Y, et al. Design of Lewis acid centers in bundlelike boron nitride for boosting adsorptive desulfurization performance[J]. Industrial & Engineering Chemistry Research, 2019, 58(29): 13303-13312.
32	Wang J J, Li L H, Wen Z H, et al. Insight into the relationship between effective active sites and ultra-deep adsorption desulfurization performance of CuCeY with different Cu precursors[J]. Fuel Processing Technology, 2023, 250: 107930.
33	张畅, 秦玉才, 高雄厚, 等. Ce改性对Y型分子筛酸性及其催化转化性能的调变机制[J]. 物理化学学报, 2015, 31(2): 344-352.
	Zhang C, Qin Y C, Gao X H, et al. Modulation of the acidity and catalytic conversion properties of Y zeolites modified by cerium cations[J]. Acta Physico-Chimica Sinica, 2015, 31(2): 344-352.
34	Wang J J, Zhao J C, Wen Z H, et al. Regulating cerium location in Y zeolite and its influence on adsorptive desulfurization for thiophene in benzene[J]. Separation and Purification Technology, 2025, 353: 128517.
35	Luo J, Yan M, Ji H Y, et al. Three-dimensional Ce-MOFs-derived Ce@C-BN nanobundles for adsorptive desulfurization[J]. Applied Surface Science, 2022, 590: 152926.

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