Properties of Sr modified Cu-based catalysts for hydrogenation of fructose to mannitol

doi:10.11949/j.issn.0438-1157.20181006

Abstract

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

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

CLC Number:

O 643.38

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.

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.

Figures/Tables 14

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

Fig.1 TEM images of reduced catalysts

Fig.2 XRD patterns of calcined catalysts and reduced catalysts

Fig.3 H2-TPR profiles of calcined catalysts

Fig.4 FT-IR spectra of calcined catalysts

Fig.5 Cu 2p XPS spectra of reduced catalysts

Fig.6 Cu LMM Auger spectra of reduced catalysts

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

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

Fig.7 CO2-TPD patterns of calcined catalysts

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	—	—	—

Fig.8 Effect of reaction temperature on fructose hydrogenation

Fig.9 Effect of hydrogen pressure on fructose hydrogenation

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

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

References 31

1	Castoldi M C M , Câmara L D T , Aranda D A G . Kinetic modeling of sucrose hydrogenation in the production of sorbitol and mannitol with ruthenium and nickel-Raney catalysts[J]. Reaction Kinetics & Catalysis Letters, 2009, 98(1): 83-89.
2	刘维, 张群峰, 李小年 . 钼改性雷尼镍催化剂的葡萄糖加氢性能[J]. 工业催化, 2010, 18(11): 36-40.
	Liu W , Zhang Q F , Li X N . Glucose hydrogenation performance of molybdenum modified Raney nickel catalyst [J]. Industrial Catalysis, 2010, 18(11): 36-40.
3	Heinen A W , Papadogianakis G , Sheldon R A , et al . Factors effecting the hydrogenation of fructose with a water soluble Ru-TPPTS complex. A comparison between homogeneous and heterogeneous catalysis[J]. Journal of Molecular Catalysis A Chemical, 1999, 142(1): 17-26.
4	Heinen A W , Peters J A , Van B H . Hydrogenation of fructose on Ru/C catalysts [J]. Carbohydrate Research, 2000, 328(4): 449-457.
5	胡明进, 朱年磊 . 甘露醇合成及分离研究进展[J]. 山东化工, 2008, 37(2): 16-18.
	Hu M J , Zhu N L . Progress in synthesis and separation of mannitol[J]. Shandong Chemical Industry, 2008, 37(2): 16-18.
6	Zhang X , Wilson K , Lee A F . Heterogeneously catalyzed hydrothermal processing of C₅—C₆ sugars[J]. Chemical Reviews, 2016, 116(19): 12328-12368.
7	Ahmed M J , Kadhum A A H . Hydrogenation of D-fructose over activated charcoal supported platinum catalyst[J]. Journal of the Taiwan Institute of Chemical Engineers, 2011, 42(1): 114-119.
8	Zhang J , Wu S , Liu Y , et al . Hydrogenation of fructose over magnetic catalyst derived from hydrotalcite precursor[J]. Chemical Engineering Science, 2013, 99(32): 171-176.
9	Kuusisto J , Mikkola J P , Casal P P , et al . Kinetics of the catalytic hydrogenation of D -fructose over a CuO-ZnO catalyst[J]. Chemical Engineering Journal, 2005, 115(1/2): 93-102.
10	Zelin J , Meyer C I , Regenhardt S A , et al . Selective liquid-phase hydrogenation of fructose to D-mannitol over copper-supported metallic nanoparticles[J].Chemical Engineering Journal, 2017, 319: 48-56.
11	胡菊, 潘亚林, 黎汉生, 等 . 铈改性甲醇合成铜基催化剂的制备及其性能[J]. 化工学报, 2014, 65(7): 2770-2775.
	Hu J , Pan Y L , Li H S , et al . Preparation and properties of copper-based catalysts for the synthesis of hydrazine-modified methanol[J]. CIESC Journal, 2014, 65(7): 2770-2775.
12	Hegedüs M , Göbölös S , Margitfalvi J L . Stereoselective hydrogenation of D-fructose to D-mannitol on skeletal and supported copper-containing catalysts[J]. Studies in Surface Science & Catalysis, 1993, 78: 187-194.
13	Toukoniitty B , Kuusisto J , Mikkola J P , et al . Effect of ultrasound on catalytic hydrogenation of D-fructose to D-mannitol[J]. Industrial & Engineering Chemistry Research, 2005, 44(25): 9370-9375.
14	林慧, 颜春荣, 徐春祥, 等 . HPLC-ELSD法同时测定食品中的10种糖和糖醇[J]. 食品科学, 2013, 34(12): 286-291.
	Lin H , Yan C R , Xu C X , et al . Simultaneous determination of ten sugars and sugar alcohols in food by HPLC-ELSD[J]. Food Science, 2013, 34(12): 286-291.
15	Xie T , Xu L , Liu C , et al . Magnetic composite ZnFe₂O₄/SrFe₁₂O₁₉: preparation, characterization, and photocatalytic activity under visible light[J]. Applied Surface Science, 2013, 273(2): 684-691.
16	Wang Z , Brouri D , Casale S , et al . Exploration of the preparation of Cu/TiO₂, catalysts by deposition-precipitation with urea for selective hydrogenation of unsaturated hydrocarbons[J]. Journal of Catalysis, 2016, 340: 95-106.
17	Wei X , Wang A Q , Yang X F , et al . Synthesis of Pt-Cu/SiO₂ catalysts with different structures and their application in hydrodechlorination of 1, 2-dichloroethane[J]. Applied Catalysis B Environmental, 2012, 121/122(10): 105-114.
18	Zhu Y , Zhu Y , Ding G , et al . Highly selective synthesis of ethylene glycol and ethanol via hydrogenation of dimethyl oxalate on Cu catalysts: influence of support[J]. Applied Catalysis A General, 2013, 468(12): 296-304.
19	Zhao Y , Zhang Y , Wang Y , et al . Structure evolution of mesoporous silica supported copper catalyst for dimethyl oxalate hydrogenation[J]. Applied Catalysis A General, 2017, 539: 59-69.
20	Zhang Y , Ye C , Guo C , et al . In₂O₃ -modified Cu/SiO₂, as an active and stable catalyst for the hydrogenation of methyl acetate to ethanol[J]. Chinese Journal of Catalysis, 2018, 39(1): 99-108.
21	Ding J , Popa T , Tang J , et al . Highly selective and stable Cu/SiO₂, catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol[J]. Applied Catalysis B Environmental, 2017, 209: 530-542.
22	Zheng X , Lin H , Zheng J , et al . Lanthanum oxide-modified Cu/SiO₂ as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol[J]. American Chemical Society Catalysis, 2013, 3(3): 2738-2749.
23	Ding T , Tian H , Liu J , et al . Highly active Cu/SiO₂ catalysts for hydrogenation of diethyl malonate to 1, 3-propanediol[J]. Chinese Journal of Catalysis, 2016, 37(4): 484-493.
24	Baidya T , Vegten N V , Verel R , et al . SrO-Al₂O₃ mixed oxides: a promising class of catalysts for oxidative coupling of methane[J]. Journal of Catalysis, 2011, 281(2): 241-253.
25	Kobayashi Y , Omata K , Yamada M . Screening of additives to a Co/SrCO₃ catalyst by artificial neural network for preferential oxidation of Co in excess H₂ [J]. Ind. Eng. Chem. Res., 2010, 49(4): 1541-1549.
26	Mierczynski P , Chalupka K A , Maniukiewicz W , et al . SrAl₂O₄, spinel phase as active phase of transesterification of rapeseed oil[J]. Applied Catalysis B Environmental, 2015, 164: 176-183.
27	Gawande M B , Goswami A , Felpin F , et al . Cu and Cu-based nanoparticles: synthesis and applications in catalysis[J]. Chemical Reviews, 2016, 116(6): 3722.
28	Wang B , Cui Y , Chao W , et al . Role of copper content and calcination temperature in the structural evolution and catalytic performance of Cu/P25 catalysts in the selective hydrogenation of dimethyl oxalate[J]. Applied Catalysis A General, 2016, 509: 66-74.
29	Chen L F , Guo P J , Qiao M H , et al . Cu/SiO₂ catalysts prepared by the ammonia-evaporation method: texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol[J]. Journal of Catalysis, 2008, 257(1): 172-180.
30	Raytchev P D , Bendjeriou A , Dutasta J P , et al . A new step towards solid base catalysis: azidoproazaphosphatranes immobilized in nanopores of mesoporous silica[J]. Advanced Synthesis & Catalysis, 2011, 353(11/12): 2067-2077.
31	Hattori H . Heterogeneous basic catalysis [J]. Chemical Reviews, 1995, 95(3): 537-558.

[1]	Jie CHEN, Yongsheng LIN, Kai XIAO, Chen YANG, Ting QIU. Study on catalytic synthesis of sec-butanol by tunable choline-based basic ionic liquids [J]. CIESC Journal, 2023, 74(9): 3716-3730.
[2]	Yitong LI, Hang GUO, Hao CHEN, Fang YE. Study on operating conditions of proton exchange membrane fuel cells with non-uniform catalyst distributions [J]. CIESC Journal, 2023, 74(9): 3831-3840.
[3]	Minghao SONG, Fei ZHAO, Shuqing LIU, Guoxuan LI, Sheng YANG, Zhigang LEI. Multi-scale simulation and study of volatile phenols removal from simulated oil by ionic liquids [J]. CIESC Journal, 2023, 74(9): 3654-3664.
[4]	Xuejin YANG, Jintao YANG, Ping NING, Fang WANG, Xiaoshuang SONG, Lijuan JIA, Jiayu FENG. Research progress in dry purification technology of highly toxic gas PH₃ [J]. CIESC Journal, 2023, 74(9): 3742-3755.
[5]	Lingding MENG, Ruqing CHONG, Feixue SUN, Zihui MENG, Wenfang LIU. Immobilization of carbonic anhydrase on modified polyethylene membrane and silica [J]. CIESC Journal, 2023, 74(8): 3472-3484.
[6]	Xin YANG, Xiao PENG, Kairu XUE, Mengwei SU, Yan WU. Preparation of molecularly imprinted-TiO₂ and its properties of photoelectrocatalytic degradation of solubilized PHE [J]. CIESC Journal, 2023, 74(8): 3564-3571.
[7]	Erqi WANG, Shuzhou PENG, Zhen YANG, Yuanyuan DUAN. Evaluation of vapor-liquid equilibrium models for mixtures containing HFOs [J]. CIESC Journal, 2023, 74(8): 3216-3225.
[8]	Feifei YANG, Shixi ZHAO, Wei ZHOU, Zhonghai NI. Sn doped In₂O₃ catalyst for selective hydrogenation of CO₂ to methanol [J]. CIESC Journal, 2023, 74(8): 3366-3374.
[9]	Kaixuan LI, Wei TAN, Manyu ZHANG, Zhihao XU, Xuyu WANG, Hongbing JI. Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde [J]. CIESC Journal, 2023, 74(8): 3342-3352.
[10]	Pan LI, Junyang MA, Zhihao CHEN, Li WANG, Yun GUO. Effect of the morphology of Ru/α-MnO₂ on NH₃-SCO performance [J]. CIESC Journal, 2023, 74(7): 2908-2918.
[11]	Yajie YU, Jingru LI, Shufeng ZHOU, Qingbiao LI, Guowu ZHAN. Construction of nanomaterial and integrated catalyst based on biological template: a review [J]. CIESC Journal, 2023, 74(7): 2735-2752.
[12]	Yuming TU, Gaoyan SHAO, Jianjie CHEN, Feng LIU, Shichao TIAN, Zhiyong ZHOU, Zhongqi REN. Advances in the design, synthesis and application of calcium-based catalysts [J]. CIESC Journal, 2023, 74(7): 2717-2734.
[13]	Qiyu ZHANG, Lijun GAO, Yuhang SU, Xiaobo MA, Yicheng WANG, Yating ZHANG, Chao HU. Recent advances in carbon-based catalysts for electrochemical reduction of carbon dioxide [J]. CIESC Journal, 2023, 74(7): 2753-2772.
[14]	Jipeng ZHOU, Wenjun HE, Tao LI. Reaction engineering calculation of deactivation kinetics for ethylene catalytic oxidation over irregular-shaped catalysts [J]. CIESC Journal, 2023, 74(6): 2416-2426.
[15]	Lixiang ZHU, Moye LUO, Xiaodong ZHANG, Tao LONG, Ran YU. Application of quinone profile method to indicate structure and activity of functional microbial community in trichloroethylene-contaminated soil [J]. CIESC Journal, 2023, 74(6): 2647-2654.