Influence of calcination temperature on CuMgAl catalytic performance for hydrogenation of furfuralcohol to pentanediol

doi:10.11949/j.issn.0438-1157.20181466

Abstract

Abstract:

The CuMgAl hydrotalcite-type (CMA-HT) precursors was prepared by co-precipitation process, in which the molar ratio of n(Cu²⁺)∶n(Mg²⁺)∶n(Al³⁺) was 10∶65∶25. The CuMgAl hydrotalcite catalysts were obtained by calcining at various temperatures. The catalysts were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), X-ray powder diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), N₂-adsorption, H₂-temperature programmed reduction (H₂-TPR), H₂-temperature programmed desorption (H₂-TPD), CO₂-temperature programmed desorption (CO₂-TPD) and NH₃-temperature programmed desorption (NH₃-TPD). The catalytic performance of CMA catalysts for the hydrogenation of furfuryl alcohol to 1,2-pentanediol and 1,5-pentanediol were investigated in the autoclave. The results indicated that the calcination temperatures had significantly influence on the structure and catalytic activity of the catalyst. The metal sites and basic sites increased firstly and then decreased with rising the calcined temperatures. The sample calcined at 600℃ possesses the suitable metal and basic sites. It exhibited the superior activity for the hydrogenolysis of furfuryl alcohol as the synergistic effect between the surface metal sites and the basic sites. Under the condition of 140℃ and H₂ pressure of 4 MPa, the conversion of sterol and the yield of pentanediol reached 74.13% and 58.36%, respectively, after 8 h of reaction.

Key words: furfuryl alcohol, 1,2-pentanediol, 1,5-pentanediol, hydrogenation, LDHs

摘要：

采用共沉淀法制得物质的量比为n(Cu²⁺)∶n(Mg²⁺)∶n(Al³⁺)=10∶65∶25的CuMgAl类水滑石前体（CMA-HT），经过不同温度焙烧制得CuMgAl水滑石催化剂。通过傅里叶变换红外光谱（FTIR）、热重分析（TG）、X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、N₂-物理吸附、程序升温还原（H₂-TPR）、H₂-程序升温脱附（H₂-TPD）、CO₂-程序升温脱附（CO₂-TPD）和NH₃-程序升温脱附（NH₃-TPD）等对催化剂的结构进行表征，在高压反应釜中考察了CuMgAl水滑石催化剂催化糠醇（FFA）加氢制1,2-戊二醇（1,2-PeD）和1,5-戊二醇（1,5-PeD）的催化性能。研究结果表明，焙烧温度对催化剂的结构及其催化性能具有显著的影响，金属活性中心和碱性位随焙烧温度的升高先增加后减少。经600℃焙烧的CMA催化剂表面存在适宜的金属中心和碱性位，在金属位和碱性中心的协同催化下，表现出了优异的催化性能。在140℃，H₂压力为4 MPa的条件下，反应8 h，糠醇的转化率和戊二醇的收率分别达74.13%和58.36%。

关键词: 糠醇, 1,2-戊二醇, 1,5-戊二醇, 加氢, 类水滑石

CLC Number:

O 643.36

Caiyun WEI, Jingjing TAN, Xiaoli XIA, Yongxiang ZHAO. Influence of calcination temperature on CuMgAl catalytic performance for hydrogenation of furfuralcohol to pentanediol[J]. CIESC Journal, 2019, 70(4): 1409-1419.

卫彩云, 谭静静, 夏晓丽, 赵永祥. 焙烧温度对CuMgAl催化剂催化糠醇加氢制戊二醇的影响[J]. 化工学报, 2019, 70(4): 1409-1419.

Figures/Tables 12

Fig.1 Reaction scheme for FFA hydrogenation

Fig.2 XRD patterns of CMA-HT and CMA-t catalysts

Fig.3 XRD patterns of reduced CMA-t catalysts

Fig.4 SEM images of CMA-HT and CMA-t catalysts

Fig.6 TG curve and MS analysis of released gases of CMA hydrotalcite-type precursor

Fig.7 FTIR spectrum of CMA-HT and CMA-t catalysts

Table 1 Textural properties of catalysts

Catalyst	S_BET/(m²/g)	V_p/(cm³/g)	D_p/nm	n_Cu/(mmol/g)^①
CMA-300	131.03	0.69	14.13	0.32
CMA-400	220.34	1.11	13.41	0.50
CMA-500	192.30	1.05	16.27	0.42
CMA-600	204.19	1.09	16.31	1.07
CMA-700	171.21	1.04	19.94	0.74

Fig.8 H2-TPR profiles of CMA-t catalysts

Fig.9 CO2-TPD and NH3-TPD profiles of reduced CMA-t catalysts

Fig.10 Proposed reaction paths for FFA hydrogenation over CMA-t catalyst

Table 2 Selevitity and conversion of CMA-t catalysts in hydrogenation of FFA on 120℃

Catalyst	Conversion/%	Selevitity/%					Yield/%
Catalyst	Conversion/%	2-MF	n-POH	THFA	1,2-PeD	1,5-PeD	Yield/%
CMA-300	19.89	5.90	9.57	3.80	51.11	29.62	16.06
CMA-400	35.54	3.30	7.45	7.11	52.9	29.24	29.19
CMA-500	45.08	4.91	11.16	3.91	53.95	26.06	36.07
CMA-600	52.44	2.06	9.06	3.40	59.27	26.21	44.83
CMA-700	34.64	5.31	10.62	3.73	30.43	29.91	27.83

Fig.11 Relationship between catalytic activities of CMA-t and metal and basic sites for hydrogenation of FFA at 140℃（reaction conditions: FFA: 0.5 g; catalyst: 0.2 g; H2: 4 MPa; isopropyl alcohol 10 g as solvent; T=140℃; t=8 h)FFA—furfuryl alcohol; PeD—1,2+1,5-pentanediol

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