焙烧温度对CuMgAl催化剂催化糠醇加氢制戊二醇的影响

doi:10.11949/j.issn.0438-1157.20181466

摘要/Abstract

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

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

中图分类号:

O 643.36

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.

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.

图/表 12

图1 糠醇加氢反应路径

Fig.1 Reaction scheme for FFA hydrogenation

图2 CMA-HT催化剂和CMA-t的XRD谱图

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

图3 还原态CMA-t催化剂的XRD谱图

Fig.3 XRD patterns of reduced CMA-t catalysts

图4 CMA-HT和CMA-t催化剂的SEM图

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

图6 CMA-HT的TG曲线及分解释放气体质谱图

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

图7 CMA-HT 以及CMA-t 催化剂的红外谱图

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

表1 催化剂的织构参数

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

图8 CMA-t催化剂的H2 -TPR谱图

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

图9 还原态CMA-t催化剂的CO2-TPD和NH3-TPD谱图

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

图10 CMA-t催化剂催化糠醇加氢路线

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

表2 CMA-t催化剂上糠醇加氢120℃反应选择性和转化率对比

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

图11 CMA-t催化剂140℃反应条件下糠醇加氢催化性能与催化剂表面金属位及碱性位的关系

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

参考文献 34

1	IborraS, HuberG W, CormaA. Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering[J]. Chemical Reviews, 2006, 106(9): 4044-4089.
2	VeltyA, IborraS, CormaA. Chemical routes for the transformation of biomass into chemicals[J]. Chemical Reviews, 2007, 107(6): 2411-2502.
3	TilmanD, SocolowR, FoleyJ A, et al. Beneficial biofuels—the food, energy, and environment trilemma[J]. Science, 2009, 325(5938): 270-271.
4	ZhouB W, SongJ L, ZhangZ R, et al. Highly selective photocatalytic oxidation of biomass-derived chemicals to carboxyl compounds over Au/TiO₂[J]. Green Chemistry, 2017, 19: 1075-1081.
5	CuiJ, TanJ, ZhuY, et al. Aqueous hydrogenation of levulinic acid to 1,4-pentanediol over Mo-modified Ru/activated carbon catalyst[J]. ChemSusChem, 2018, 11(8): 1316-1320.
6	AdkinsH, ConnorR. The catalytic hydrogenation of organic compounds over copper chromite[J]. Journal of the American Chemical Society, 1931, 53(3): 1091-1095.
7	ConnorR, AdkinsH. Hydrogenolysis of oxygenated organic compounds[J]. Journal of the American Chemical Society, 1932, 54(12): 4678-4690.
8	ConnorR, FolkersK, AdldnsH. The preparation of copper-chromium oxide catalysts for hydrogenation[J]. Journal of the American Chemical Society, 1932, 54(3): 1138-1145.
9	LiX, JiaP, WangT. Furfural: a promising platform compound for sustainable production of C₄ and C₅ chemicals[J]. ACS Catalysis, 2016, 6: 7621-7640.
10	SunD, SatoS, UedaW, et al. Production of C₄ and C₅ alcohols from biomass-derived materials[J]. ChemInform, 2016, 47(26): 2579-2597.
11	MizugakiT, YamakawaT, NagatsuY, et al. Direct transformation of furfural to 1,2-pentanediol using a hydrotalcite-supported platinum nanoparticle catalyst[J]. ACS Sustainable Chemistry & Engineering, 2014, 2(10): 2243-2247.
12	LiuH, HuangZ, KangH, et al. Selective hydrogenolysis of biomass-derived furfuryl alcohol into 1, 2- and 1, 5-pentanediol over highly dispersed Cu-Al₂O₃ catalysts[J]. Chinese Journal of Catalysis, 2016, 37(5): 700-710.
13	SchlafM. Selective deoxygenation of sugar polyols to α, ω-diols and other oxygen content reduced materials—a new challenge to homogeneous ionic hydrogenation and hydrogenolysis catalysis[J]. Dalton Transactions, 2006, 29(39): 4645-4653.
14	SatoM, OtabeN, TujiT, et al. Highly-selective and high-speed Claisen rearrangement induced with subcritical water microreaction in the absence of catalyst[J]. Green Chemistry, 2009, 11(6): 763-766.
15	ChatterjeeM, KawanamiH, IshizakaT, et al. An attempt to achieve the direct hydrogenolysis of tetrahydrofurfuryl alcohol in supercritical carbon dioxide [J]. Catalysis Science & Technology, 2011, 1(8): 1466-1471.
16	XuW J, WangH F, WangY P, et al. Direct catalytic conversion of furfural to 1, 5-pentanediol by hydrogenolysis of the furan ring under mild conditions over Pt/Co₂AlO₄ catalyst[J]. Chemical Communication, 2011, 47(3): 3924-3926.
17	ZhangB, ZhuY, DingG, et al. Selective conversion of furfuryl alcohol to 1, 2-pentanediol over a Ru/MnO_x catalyst in aqueous phase[J]. Green Chemistry, 2012, 14(12): 3402-3409.
18	CuiJ, TanJ, CuiX, et al. Conversion of xylose to furfuryl alcohol and 2-methylfuran in a continuous fixed-bed reactor[J]. ChemSusChem, 2016, 9(11): 1259-1262.
19	XiaS X , NieR F , LuX Y , et al. Hydrogenolysis of glycerol over Cu_0.4/Zn_5.6-_xMg_xAl₂O_8.6 catalysts: the role of basicity and hydrogen spillover[J]. Journal of Catalysis, 2012, 296(7): 1-11.
20	PinnavaiaT J. Intercalated clay catalysts[J]. Science, 1983, 220(4595): 365-371.
21	WęgrzynA, Rafalska-ŁasochaA, MajdaD, et al. The influence of mixed anionic composition of Mg-Al hydrotalcites on the thermal decomposition mechanism based on in situ study[J]. Journal of Thermal Analysis & Calorimetry, 2010, 99(2): 443-457.
22	ForgionnyA, FierroG, MondragonF, et al. Effect of Mg/Al ratio on catalytic behavior of Fischer-Tropsch cobalt-based catalysts obtained from hydrotalcites precursors[J]. Topic Catalysis, 2016, 59(2/4): 230-240.
23	ZhouM, ZengZ, ZhuH, et al. Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts: model reaction for upgrading of bio-oil[J]. Journal of Energy Chemistry, 2014, 23(1): 91-96.
24	DebeckerD P, GaigneauxE M, G. ExploringBysca, tuning, and exploiting the basicity of hydrotalcites for applications in heterogeneous catalysis[J]. Chemistry, 2009, 15(16): 3920-3935.
25	JiangZ, HaoZ P, YuJ J, et al. Catalytic combustion of methane on novel catalysts derived from Cu-Mg/Al-hydrotalcites[J]. Catalysis Letters, 2005, 9(3/4): 157-163.
26	ZengY, ZhangT, XuY, et al. Cu/Mg/Al hydrotalcite-like hydroxide catalysts for o-phenylphenol synthesis[J]. Applied Clay Science, 2016, 126: 207-214.
27	ParkerL M, MilestoneN B, NewmanR H. The use of hydrotalcite as an anion absorbent[J]. Industrial & Engineering Chemistry Research, 1995, 34(4): 1196-1202.
28	Melián-CabreraI, López GranadosM, FierroJ L G. Thermal decomposition of a hydrotalcite-containing Cu-Zn-Al precursor: thermal methods combined with an in situ DRIFT study[J]. Physical Chemistry Chemical Physics, 2002, 4(13): 3122-3127.
29	KannanS, RivesV, KnozingerH. High-temperature transformations of Cu-rich hydrotalcites[J]. Journal of Solid State Chemistry, 2004, 177(1): 319-331.
30	BonuraG, CordaroM, CannillaC, et al. The changing nature of the active site of Cu-Zn-Zr catalysts for the CO₂ hydrogenation reaction to methanol[J]. Applied Catalysis B: Environmental, 2014, 152/153: 152-161.
31	Pérez-Ramı́RezJ, MulG, MoulijnJ A. In situ Fourier transform infrared and laser Raman spectroscopic study of the thermal decomposition of Co-Al and Ni-Al hydrotalcites[J]. Vibrational Spectroscopy, 2001, 27(1): 75-88.
32	RousselotI, Tavioto-GuehC, BesseJ P, Synthesis and characterization of mixed Ga/Al-containing layered double hydroxides: study of their basic properties through the Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate, and comparison to other LDHs[J]. International Journal of Inorganic Materials, 1999, 1: 165-174.
33	BasąGS, PiwowarskaZ, KowalczykA, et al. Cu-Mg-Al hydrotalcite-like materials as precursors of effective catalysts for selective oxidation of ammonia to dinitrogen—the influence of Mg/Al ratio and calcination temperature[J]. Applied Clay Science, 2016, 129: 122-130.
34	CormaA, FornesV, Martin-ArandaR M, et al. ChemInform abstract: determination of base properties of hydrotalcites: condensation of benzaldehyde with ethyl acetoacetate[J]. Journal of Catalysis, 1992, 134(1): 58-65.

[1]	杨欣, 王文, 徐凯, 马凡华. 高压氢气加注过程中温度特征仿真分析[J]. 化工学报, 2023, 74(S1): 280-286.
[2]	曹跃, 余冲, 李智, 杨明磊. 工业数据驱动的加氢裂化装置多工况切换过渡状态检测[J]. 化工学报, 2023, 74(9): 3841-3854.
[3]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[4]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[5]	白天昊, 王晓雯, 杨梦滋, 段新伟, 米杰, 武蒙蒙. 类水滑石衍生锌基氧化物高温煤气脱硫过程中COS释放行为及其抑制研究[J]. 化工学报, 2023, 74(4): 1772-1780.
[6]	张江淮, 赵众. 碳三加氢装置鲁棒最小协方差约束控制及应用[J]. 化工学报, 2023, 74(3): 1216-1227.
[7]	梁梦欣, 郭艳, 王世栋, 张宏伟, 袁珮, 鲍晓军. 氮化碳负载钯催化剂的制备及对SBS选择性催化加氢性能的研究[J]. 化工学报, 2023, 74(2): 766-775.
[8]	黄宽, 马永德, 蔡镇平, 曹彦宁, 江莉龙. 油脂催化加氢转化制备第二代生物柴油研究进展[J]. 化工学报, 2023, 74(1): 380-396.
[9]	沈辰阳, 孙楷航, 张月萍, 刘昌俊. 二氧化碳加氢合成甲醇氧化铟及其负载金属催化剂研究进展[J]. 化工学报, 2023, 74(1): 145-156.
[10]	张军, 胡升, 顾菁, 袁浩然, 陈勇. 甲醇体系电镀污泥衍生磁性多金属材料催化糠醛加氢转化[J]. 化工学报, 2022, 73(7): 2996-3006.
[11]	金科, 王晨光, 马隆龙, 张琦. 核壳纳米材料制备及其在CO/CO₂热催化加氢中的应用[J]. 化工学报, 2022, 73(3): 990-1007.
[12]	王吴玉, 史玉竹, 严龙, 张兴华, 马隆龙, 张琦. 负载型Co基双功能催化剂上戊酸酯生物燃料的制备[J]. 化工学报, 2022, 73(2): 689-698.
[13]	尤红运, 林景骏, 黄凯越, 舒日洋, 田志鹏, 王超, 陈颖. 溶剂效应对木质素酚类化合物加氢反应的影响机理[J]. 化工学报, 2022, 73(10): 4498-4506.
[14]	王峥, 许锋, 罗雄麟. 乙炔加氢串联反应器全周期乙炔转化率最优分配研究[J]. 化工学报, 2022, 73(10): 4551-4564.
[15]	董桂霖, 罗祖伟, 曹约强, 周静红, 李伟, 周兴贵. 液相还原温度对草酸酯加氢制乙醇酸甲酯银硅催化剂性能的影响[J]. 化工学报, 2022, 73(1): 232-240.