介孔氧化硅固载Yb(OTf)3的制备及催化葡萄糖生产乳酸

doi:10.3969/j.issn.1673-5854.2019.03.003

摘要/Abstract

摘要：

采用溶剂法和焙烧法制备了SBA-15和MCM-41两类介孔氧化硅，并以此为载体制备固载型三氟甲基磺酸镱(Yb(OTf)₃)催化剂。通过小角X射线衍射(SAXD)、氮气吸附/脱附、²⁹Si固体核磁共振光谱(NMR)、透射电子显微镜(TEM)及热重分析(TG)等方法对载体及催化剂进行表征，研究其在葡萄糖制备乳酸反应中的催化性能。结果表明：溶剂法制备的氧化硅表面羟基含量比焙烧法高，负载的磺酸基团和三氟甲基磺酸镱都更多，催化活性更高；SBA-15的平均孔径比MCM-41的大3 nm左右，这使得SBA-15具有更好的传质性能以及Yb(OTf)₂-SBA-15具有更好的催化性能。以Yb(OTf)₂-SBA-15-S为催化剂，在2 MPa N₂压力、190 ℃下反应60 min，乳酸的收率达到42.35%。

关键词: 介孔氧化硅, 三氟甲基磺酸镱, 葡萄糖, 乳酸

Abstract:

Two kinds of SBA-15 and MCM-41 mesoporous silica were prepared by solvent and calcination method, and they were used as the carrier of the supported ytterbium triflate(Yb(OTf)₃) catalysts. The carriers and catalysts were characterized by small angle X-ray diffraction(SAXD), nitrogen adsorption/desorption, ²⁹Si solid state nuclear magnetic resonance spectroscopy(NMR), transmission electron microscope(TEM) and thermogravimetric analysis(TG), and the catalytic performances of these catalysts in the preparation of lactic acid from glucose were evaluated. The experimental results showed that the amount of hydroxyl group of mesoporous silica by solvent method was higher than that of mesoporous silica by calcination method, so its catalytic activity was higher. The average pore size of SBA-15 was about 3 nm larger than that of MCM-41, which led to better mass transfer performance of SBA-15 and better catalytic performance of Yb(OTf)₂-SBA-15. The yield of lactic acid could reach 42.35% when it reacted at 2 MPa N₂ pressure and 190 ℃ for 60 min with Yb(OTf)₂-SBA-15-S as catalyst.

Key words: mesoporous silica, ytterbium triflate, glucose, lactic acid

中图分类号:

TQ35

王石维,王启宝. 介孔氧化硅固载Yb(OTf)₃的制备及催化葡萄糖生产乳酸[J]. 生物质化学工程, 2019, 53(3): 15-23.

Shiwei WANG,Qibao WANG. Preparation of Yb(OTf)₃ Immobilized on Mesoporous Silica and Its Catalytic Activity for Lactic Acid Productionfrom Glucose[J]. Biomass Chemical Engineering, 2019, 53(3): 15-23.

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样品 sample	晶面间距interplanar spacing/nm			晶胞参数/nm crystal cell parameters	S_BET/ (m²·g^-1)	孔体积/(cm³·g^-1) pore volume	孔径/nm pore size
样品 sample	d₁₀₀	d₁₁₀	d₂₀₀	晶胞参数/nm crystal cell parameters	S_BET/ (m²·g^-1)	孔体积/(cm³·g^-1) pore volume	孔径/nm pore size
SBA-15-C	105.10	61.31	53.18	12.14	650.81	0.92	7.4
SBA-15-S	110.35	62.17	53.18	12.74	623.48	0.77	5.9
MCM-41-C	40.50	23.61	20.92	4.68	883.00	0.97	3.8
MCM-41-S	41.64	24.53	21.43	4.81	794.28	0.89	3.4

样品 samples	峰面积peak area			质量分数mass fraction/%
样品 samples	A₁	A₂	A₃	w_Q₁	w_Q₂
MCM-41-C	241.9	1512.1	1199.7	4.2	13.2
MCM-41-S	341.9	1672.6	824.2	6.1	14.8
SBA-15-C	192.1	1395.8	1166.5	3.6	13.1
SBA-15-S	332.1	1628.7	801.7	6.1	14.9

催化剂catalysts	n(S)/n(Si)	S/ (mmol·g^-1)	Yb/ (mmol·g^-1)
Yb(OTf)₂-SBA-15-C	21%	1.21	0.234
Yb(OTf)₂-SBA-15-S	21%	1.51	0.286
Yb(OTf)₂-MCM-41-C	21%	0.63	0.119
Yb(OTf)₂-MCM-41-S	21%	0.91	0.169

催化剂 catalysts	葡萄糖转化率/% conversation rate of glucose	收率yield/%
催化剂 catalysts	葡萄糖转化率/% conversation rate of glucose	HMF	乳酸lactic acid
Yb(OTf)₂-SBA-15-C	63.14	3.67	38.22
Yb(OTf)₂-SBA-15-S	65.29	3.24	42.35
Yb(OTf)₂-MCM-41-C	30.64	3.15	14.86
Yb(OTf)₂-MCM-41-S	34.03	3.53	16.41

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介孔氧化硅固载Yb(OTf)₃的制备及催化葡萄糖生产乳酸

Preparation of Yb(OTf)₃ Immobilized on Mesoporous Silica and Its Catalytic Activity for Lactic Acid Productionfrom Glucose

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