Sr改性Cu催化剂的果糖加氢制备甘露醇性能

doi:10.11949/j.issn.0438-1157.20181006

摘要/Abstract

摘要：

使用共沉淀法制备负载Cu催化剂。通过添加碱土金属Sr，对Cu催化剂进行了改性，以提高Cu催化剂在果糖加氢制备甘露醇过程中的活性和选择性。采用ICP-MS、TEM、XRD、H₂-TPR、XPS和CO₂-TPD等对所制备的催化剂进行了系统表征。结果表明：Sr的添加能增大催化剂的比表面积，促进活性组分Cu的分散，从而提高了催化剂的活性，并且增加了催化剂的碱性，使果糖优先形成β-呋喃糖中间体，从而提高了甘露醇的选择性。在果糖浓度为1.1 mol·L^-1、催化剂用量为反应物质量的6%、反应温度为373 K、反应氢压为4.0 MPa、Cu/Sr原子比为7∶1的反应条件下，果糖转化率为99%，甘露醇的选择性为79%。催化剂循环使用了20次，其催化稳定性基本保持不变。

关键词: Sr, 催化剂, 果糖, 加氢, 甘露醇, 活性, 选择性

Abstract:

A supported Cu catalyst was prepared by using a co-precipitation method. The Cu catalyst was modified by adding alkaline earth metal strontium to improve the activity and selectivity for the hydrogenation of fructose to prepare mannitol. Systematic characterizations, with ICP-MS, XRD, TEM, H₂-TPR, XPS and CO₂-TPD, showed that the increase catalytic activity of the catalyst is due to the fact that the formation of SrCO₃ formed on the surface of the support can increase the specific surface area of the catalyst and improve the dispersion of the copper species. In addition, the medium-strong basic sites formed on the surface of SrCO₃ can activate the carbonyl group into β-furanose which can be easily hydrogenated into mannitol. Fructose conversion of around 100% and mannitol selectivity of 79% were achieved in the conditions of 1.1 mol·L^-1 fructose concentration, catalyst dosage of 6% of reactant quality, reaction temperature of 373 K, hydrogen pressure of 4.0 MPa and Cu/Sr atomic ratio of 7∶1. The excellent stability of the Cu-Sr/SiO₂ catalyst remained basically unchanged after recycling for 20 times.

Key words: Sr, catalyst, fructose, hydrogenation, mannitol, activity, selectivity

中图分类号:

O 643.38

胡凤腾, 姚建龙, 李小青, 李思汉, 严新焕. Sr改性Cu催化剂的果糖加氢制备甘露醇性能[J]. 化工学报, 2019, 70(4): 1420-1428.

Fengteng HU, Jianlong YAO, Xiaoqing LI, Sihan LI, Xinhuan YAN. Properties of Sr modified Cu-based catalysts for hydrogenation of fructose to mannitol[J]. CIESC Journal, 2019, 70(4): 1420-1428.

图/表 14

表1 催化剂形貌及结构表征

Table 1 Physicochemical characterizations of catalysts

催化剂	Cu/ %（mass）	Sr/ %（mass）	S _BET ^①/ (m²·g^－1)	D _pro ^②/ nm	V _pro ^③/(cm³·g^－1)
Cu/SiO₂	9.8	0	131.2	16.97	0.51
0.5Sr+Cu/SiO₂	9.6	0.46	161.0	16.15	0.71
1.0Sr+Cu/SiO₂	9.8	0.98	168.4	16.65	0.71
1.5Sr+Cu/SiO₂	9.5	1.37	186.1	15.97	0.74
2.0Sr+Cu/SiO₂	9.8	1.86	197.8	15.89	0.70
3.0Sr+Cu/SiO₂	9.7	2.75	180.9	16.10	0.75

图1 还原后催化剂TEM图

Fig.1 TEM images of reduced catalysts

图2 催化剂煅烧后和催化剂还原后XRD谱图

Fig.2 XRD patterns of calcined catalysts and reduced catalysts

图3 煅烧后催化剂H2-TPR谱图

Fig.3 H2-TPR profiles of calcined catalysts

图4 煅烧后催化剂FT-IR谱图

Fig.4 FT-IR spectra of calcined catalysts

图5 还原后催化剂Cu 2p XPS图

Fig.5 Cu 2p XPS spectra of reduced catalysts

图6 还原后催化剂Cu LMM图

Fig.6 Cu LMM Auger spectra of reduced catalysts

表2 还原后催化剂表面的铜种类

Table 2 Cu species on reduced catalysts

催化剂	KE^①/eV		AP^②/eV		2p_3/2 BE^③/eV	$X C u 0$ ^④/%
催化剂	Cu⁺	Cu⁰	Cu⁺	Cu⁰	2p_3/2 BE^③/eV	$X C u 0$ ^④/%
Cu/SiO₂	914.2	918.0	1846.9	1850.7	932.7	44
0.5Sr+Cu/SiO₂	914.1	918.0	1846.8	1850.7	932.7	51
1.0Sr+Cu/SiO₂	914.1	918.0	1846.8	1850.7	932.7	55
1.5Sr+Cu/SiO₂	914.1	917.7	1846.9	1850.5	932.8	57
2.0Sr+Cu/SiO₂	914.2	917.8	1846.9	1850.5	932.7	61
3.0Sr+Cu/SiO₂	914.1	917.8	1846.9	1850.6	932.8	48

表2 还原后催化剂表面的铜种类

Table 2 Cu species on reduced catalysts

催化剂	KE^①/eV		AP^②/eV		2p_3/2 BE^③/eV	$X C u 0$ ^④/%
催化剂	Cu⁺	Cu⁰	Cu⁺	Cu⁰	2p_3/2 BE^③/eV	$X C u 0$ ^④/%
Cu/SiO₂	914.2	918.0	1846.9	1850.7	932.7	44
0.5Sr+Cu/SiO₂	914.1	918.0	1846.8	1850.7	932.7	51
1.0Sr+Cu/SiO₂	914.1	918.0	1846.8	1850.7	932.7	55
1.5Sr+Cu/SiO₂	914.1	917.7	1846.9	1850.5	932.8	57
2.0Sr+Cu/SiO₂	914.2	917.8	1846.9	1850.5	932.7	61
3.0Sr+Cu/SiO₂	914.1	917.8	1846.9	1850.6	932.8	48

图7 煅烧后催化剂CO2-TPD谱图

Fig.7 CO2-TPD patterns of calcined catalysts

表3 催化剂性能测试结果

Table 3 Catalytic performance test results

催化剂	Cu/Sr比例	果糖转化率/%	甘露醇选择性/%
Cu/SiO₂	—	60	64
0.5Sr+Cu/SiO₂	29:1	85	69
1.0Sr+Cu/SiO₂	14:1	96	71
1.5Sr+Cu/SiO₂	10:1	97	75
2.0Sr+Cu/SiO₂	7:1	99	79
3.0Sr+Cu/SiO₂	5:1	89	73
SrCO₃/SiO₂	—	—	—

图8 反应温度的影响

Fig.8 Effect of reaction temperature on fructose hydrogenation

图9 反应氢分压的影响

Fig.9 Effect of hydrogen pressure on fructose hydrogenation

图10 Cu+2%Sr/SiO2催化剂稳定性

Fig.10 Stability of Cu+2%Sr/SiO2 catalyst

图11 Cu+2%Sr/SiO2 催化剂反应前后TEM图

Fig.11 TEM images of fresh and used Cu+2%Sr/SiO2 catalyst

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