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

doi:10.11949/0438-1157.20241443

摘要/Abstract

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

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

中图分类号:

TQ 032.4

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.

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.

图/表 12

图1 果糖连续醇解反应装置示意图

Fig.1 Schematic diagram of continuous alcoholysis of fructose to methyl lactate

图2 TS-1催化果糖连续醇解产物分布随连续运行时间的变化

Fig.2 Time on stream data on the continuous catalytic alcoholysis of fructose over TS-1 zeolites

图3 In-TS-1催化果糖连续醇解产物分布随连续运行时间的变化

Fig.3 Time on stream data on the continuous catalytic alcoholysis of fructose over In-TS-1 zeolites

图4 新鲜和使用后催化剂的XRD谱图

Fig.4 XRD patterns of the fresh and spent catalysts

图5 新鲜和使用后催化剂的氮气等温吸脱附试验

Fig.5 N2 adsorption-desorption isotherm tests of the fresh and spent catalysts

表1 新鲜和使用后催化剂的结构性质

Table 1 Textural properties of the fresh and spent catalysts

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

图6 新鲜和使用后催化剂的Py-FTIR光谱图

Fig.6 Py-FTIR spectra of the fresh and spent catalysts

表2 新鲜和使用后催化剂的酸性质

Table 2 Acidic properties of the fresh and spent catalysts

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

图7 新鲜和使用后催化剂的热重和差示扫描量热试验

Fig.7 TG and DSC profiles of the fresh and spent catalysts

表3 新鲜和使用后催化剂的Ti和In含量

Table 3 Ti and In contents of the fresh and spent catalysts

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

表4 TS-1和In-TS-1催化间歇反应和连续反应MLA的收率

Table 4 Yield of MLA in TS-1 and In-TS-1 catalyzed batch and continuous reactions

反应形式	不同催化剂的MLA收率/%
反应形式	TS-1	In-TS-1
间歇	40.5^[31]	71.9^[30]
连续	49~50	59~60

表5 糖类连续醇解稳定性比较

Table 5 Stability comparison of sugar continuous alcoholysis

催化剂	反应条件	MLA最高收率/%	运行时间/h	MLA收率降低程度/%	文献
Sn-Beta	0.65%（质量）葡萄糖甲醇溶液；165℃，4 MPa，滴流床	45	120	8	[27]
Sn-Beta	1%（质量）葡萄糖甲醇水混合溶液，160℃，固定床	75	60	42	[32]
Sn-Beta	1.25%（质量）果糖甲醇水混合溶液，160℃，固定床	54	456	5	[28]
In-TS-1	1%（质量）果糖甲醇溶液，200℃，固定床	60	144	未降低	本工作
TS-1	1%（质量）果糖甲醇溶液，200℃，固定床	50	144	未降低	本工作

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