Study on continuous alcoholysis of fructose to methyl lactate over TS-1 and In-TS-1

doi:10.11949/0438-1157.20241443

Abstract

Abstract:

Methyl lactate (MLA) is an important biomass-based platform compound, among which the preparation of MLA by continuous alcoholysis of biomass sugar in a fixed bed is the direction of future industrialization. In our previous studies, two long-life catalysts, TS-1 and In-TS-1, were developed in a batch reactor. This study investigated the continuous alcoholysis of fructose to produce MLA using TS-1 and In-TS-1 catalysts in a fixed bed reactor. The results showed that at 200℃ and 4.8 MPa, TS-1 and In-TS-1 catalysts could operate stably for 144 h without deactivation, achieving MLA yields of 50.4% and 60%, respectively. Characterization findings from XRD, N₂ adsorption-desorption, TG-DSC, Py-FTIR, and ICP-OES indicated that the catalysts maintained their crystal structure, pore structure, and surface acidity after the reaction, with minimal loss of Ti and In metals. This confirmed the stability of TS-1 and In-TS-1 catalysts in the fixed bed continuous reaction process. This study provides fundamental data for the development and industrialization of In-TS-1 catalyzed continuous alcoholysis of fructose to produce MLA.

Key words: fixed-bed, fructose alcoholysis, methyl lactate, catalyst, stability

摘要：

乳酸甲酯（MLA）是重要的生物质基平台化合物，其中生物质糖固定床催化连续醇解制备MLA是未来工业化的方向。前期采用间歇釜开发了TS-1和In-TS-1两种长效催化剂，本文开展了在固定床中TS-1和In-TS-1催化果糖连续醇解制备MLA的试验。结果表明，在200℃，系统压力4.8 MPa下，TS-1和In-TS-1可稳定运行144 h且未发生失活，MLA收率分别达到50.4%和60%。XRD、N₂吸脱附试验、TG-DSC、Py-FTIR、ICP-OES等一系列表征结果表明反应后催化剂的晶型、孔道结构、表面酸性质保持稳定，Ti、In金属流失极少，证实了TS-1和In-TS-1催化剂在固定床连续反应过程中的稳定性。本研究为推进In-TS-1催化果糖连续醇解制备MLA技术的开发及工业化提供基础数据。

关键词: 固定床, 果糖醇解, 乳酸甲酯, 催化剂, 稳定性

CLC Number:

TQ 032.4

Bolong LI, Yuxi JIANG, Aotian REN, Wenqi QIN, Jie FU, Xiuyang LYU. Study on continuous alcoholysis of fructose to methyl lactate over TS-1 and In-TS-1[J]. CIESC Journal, 2025, 76(6): 2678-2686.

李愽龙, 蒋雨希, 任傲天, 秦雯琪, 傅杰, 吕秀阳. TS-1/In-TS-1催化果糖一步法醇解制备乳酸甲酯连续化试验[J]. 化工学报, 2025, 76(6): 2678-2686.

Figures/Tables 12

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催化剂	S_BET/ (m²·g^-1)	S_Micro/ (m²·g^-1)	V_Total/ (cm³·g^-1)	V_Micro/ (cm³·g^-1)
新鲜 TS-1	454.5	400.2	0.34	0.17
使用后 TS-1	407.7	353.5	0.29	0.15
新鲜 In-TS-1	405.5	326.0	0.21	0.13
使用后 In-TS-1	391.5	316.7	0.21	0.13

催化剂	S_BET/ (m²·g^-1)	S_Micro/ (m²·g^-1)	V_Total/ (cm³·g^-1)	V_Micro/ (cm³·g^-1)
新鲜 TS-1	454.5	400.2	0.34	0.17
使用后 TS-1	407.7	353.5	0.29	0.15
新鲜 In-TS-1	405.5	326.0	0.21	0.13
使用后 In-TS-1	391.5	316.7	0.21	0.13

催化剂	酸量/(μmol·g^-1)
催化剂	Brønsted酸	Lewis酸	总酸
新鲜 TS-1^[30]	20.8	400.9	421.7
使用后 TS-1	17.6	398.4	416.0
新鲜 In-TS-1	33.5	449.7	483.2
使用后 In-TS-1	32.6	438.7	471.3

催化剂	酸量/(μmol·g^-1)
催化剂	Brønsted酸	Lewis酸	总酸
新鲜 TS-1^[30]	20.8	400.9	421.7
使用后 TS-1	17.6	398.4	416.0
新鲜 In-TS-1	33.5	449.7	483.2
使用后 In-TS-1	32.6	438.7	471.3

催化剂	Ti 含量/%（质量）	In 含量/%（质量）
新鲜 TS-1	2.29	—
使用后 TS-1	2.29	—
新鲜 In-TS-1	1.12	1.31
使用后 In-TS-1	1.11	1.29