插层阴离子对以类水滑石为前体Ni-Al2O3催化剂催化乙酰丙酸加氢性能的影响

doi:10.11949/0438-1157.20200121

摘要/Abstract

摘要：

分别以 $N O 3 -$ 以及 $C O 3 2 -$ 插层类水滑石为前体制备了Ni/Al摩尔比为3∶1的NiAl-N-R以及NiAl-C-R催化剂，并考察了其催化乙酰丙酸加氢性能。采用N₂-物理吸附、ICP-OES、TG/DTG、XRD、H₂-TPR/TPD、TEM、NH₃-TPD、in-situ Py-FTIR等表征手段对前体及催化剂进行了表征。研究结果表明，类水滑石插层阴离子对催化剂中活性金属-载体相互作用、活性金属分散度、表面酸性质以及催化乙酰丙酸加氢性能有重要影响。以 $C O 3 2 -$ 插层类水滑石为前体的催化剂表现出高的金属分散度、丰富的L酸酸性中心、高的CO加氢活性和高的循环使用稳定性。当以甲醇为溶剂、160℃、4 MPa氢气压力条件下反应1 h时，γ-戊内酯收率可达71.8%。

关键词: 乙酰丙酸, Ni-Al₂O₃催化剂, γ-戊内酯, 催化加氢

Abstract:

Ni₃Al-N-R and Ni₃Al-C-R catalysts with Ni/Al mole ratio of 3∶1 were prepared by using $N O 3 -$ and $C O 3 2 -$ intercalated hydrotalcites as precursors respectively, and their catalytic properties for the hydrogenation of levulinic acid were investigated. The precursors and catalysts were characterized by N₂-physical adsorption, ICP-OES, TG/DTG, XRD, H₂-TPR / TPD, TEM, NH₃-TPD, in-situ Py-FTIR and other characterization methods. The results showed that the intercalation anions played an important effect on the active metal-support interaction, active metal dispersion, surface acid properties, and catalytic performance of catalysts for levulinic acid hydrogenation. The catalyst derived from $C O 3 2 -$ intercalated hydrotalcite exhibited high metal dispersion, rich L acid acidic centers, high CO hydrogenation activity, and high recycle stability. When methanol was used as the solvent at 160℃ and 4 MPa hydrogen pressure for 1 h, the yield of γ-valerolactone could reach 71.8%.

Key words: levulinic acid, Ni-Al₂O₃ catalyst, γ-valerolactone, catalytic hydrogenation

中图分类号:

TQ 028.8

张因, 郭健健, 任欢杰, 程娟, 李海涛, 武建兵, 赵永祥. 插层阴离子对以类水滑石为前体Ni-Al₂O₃催化剂催化乙酰丙酸加氢性能的影响[J]. 化工学报, 2020, 71(8): 3614-3624.

Yin ZHANG, Jianjian GUO, Huanjie REN, Juan CHENG, Haitao LI, Jianbing WU, Yongxiang ZHAO. Effect of intercalation anions on catalytic performance of hydrotalcite-like precursor Ni-Al₂O₃ catalyst for levulinic acid hydrogenation[J]. CIESC Journal, 2020, 71(8): 3614-3624.

图/表 16

表1 NiAl-N-LDH与NiAl-C-LDH的组成分析

Table 1 Composition of NiAl-N-LDH and NiAl-C-LDH

Sample

Ni/Al molar ratio^①

Sample formula^②

Theoretical mass loss on thermal decomposition^③ /%

Mass loss on thermal decomposition measured by TG^④/%

C content^⑤/

%(mass)

N content^⑤/

%(mass)

NiAl-N-LDH

3.05

[Ni_0.753Al_0.247(OH)₂]^0.247[NO₃^-]_0.247?mH₂O

[Ni_0.757Al_0.243(OH)₂]^0.243[CO₃^2-]_0.121?mH₂O

图1 NiAl-N-LDH与NiAl-C-LDH的TG-DTG曲线

Fig.1 TG-DTG profiles of NiAl-N-LDH and NiAl-C-LDH

图2 NiAl-N-LDH与NiAl-C-LDH的FTIR谱图

Fig.2 FTIR spectra of NiAl-N-LDH and NiAl-C-LDH

图3 NiAl-N-LDH与NiAl-C-LDH的XRD谱图

Fig.3 XRD patterns of NiAl-N-LDH and NiAl-C-LDH

表2 催化剂的织构参数

Table 2 Textural parameters of the catalysts

Catalyst

BET specific surface area/

(m²/g)

Pore volume/ (cm³/g)

Average pore diameter/nm

Total acid sites^①/(μmol/g)

图4 催化剂的H2-TPR谱图

Fig.4 H2-TPR profiles of catalysts

图5 焙烧及还原后催化剂的XRD谱图

Fig.5 XRD patterns of calcined and reduced catalysts

图6 还原后催化剂的TEM图

Fig.6 TEM images of reduced catalysts

图7 催化剂的Py-FTIR谱图

Fig.7 Py-FTIR spectra of catalysts

图8 催化剂的NH3-TPD图

Fig.8 NH3-TPD profiles of catalysts

图9 醇类溶剂中乙酰丙酸加氢制γ-戊内酯反应路径

Fig.9 Reaction pathway for the hydrogenation of LA using alcohols as solvents

表3 在不同溶剂中催化剂催化乙酰丙酸加氢性能

Table 3 Catalytic performance of catalysts for the hydrogenation of levulinic acid using different solvents

Catalysts	Solvent	Conversion of LA/%	Selectivity of GVL/%	Yield of GVL/%	TOF_C=O/ min^-1①
NiAl-N-R	methanol methanol	66.6	63.2	42.1	3.45
NiAl-C-R	methanol methanol	86.7	82.9	71.8	4.37
NiAl-N-R	ethanol ethanol	62.9	60.4	37.9	3.11
NiAl-C-R	ethanol ethanol	74.5	86.7	64.6	3.92
NiAl-N-R	propanol propanol	54.5	61.2	33.4	2.74
NiAl-C-R	propanol propanol	67.3	84.8	57.1	3.47
NiAl-N-R	butanol butanol	46.7	62.3	29.1	2.39
NiAl-C-R	butanol butanol	58.9	85.3	50.2	3.05

图10 醇类溶剂中乙酰丙酸加氢制γ-戊内酯示意图

Fig.10 Hydrogenation of levulinic to γ-valerolactone using alcohols as solvents

图11 还原温度对催化剂乙酰丙酸加氢性能的影响

Fig.11 Effect of reduction temperatures on catalytic performance of catalysts (Reaction conditions: LA 1.67 g, catalyst 0.1 g, stirrer 400 r/min, reaction temperature 160℃, hydrogen pressure 4 MPa, methanol 40 ml as solvent, reaction time 1 h)

表4 反应时间对催化剂催化乙酰丙酸加氢性能的影响

Table 4 Effect of reaction time on catalytic performance of catalysts for hydrogenation of levulinic acid

Catalyst	Reaction time / h	Conversion of LA / %	Selectivity of GVL / %	Yield of GVL / %
NiAl-N-R	0.5	47.1	56.2	26.4
	1.0	66.6	63.2	42.1
	1.5	82.7	68.3	56.5
	2.0	86.2	70.4	60.7
NiAl-C-R	0.5	61.2	77.0	47.2
	1.0	86.7	82.7	71.8
	1.5	95.9	84.8	81.3
	2.0	98.3	85.1	83.7

图12 催化剂的循环使用稳定性

Fig.12 Effect of recycle times on catalytic performance of catalysts (Reaction conditions: LA 1.67 g, catalyst 0.1 g, stirrer 400 r/min, reaction temperature 160℃, hydrogen pressure 4 MPa, methanol 40 ml as solvent, reaction time 1 h)

参考文献 39

1	Mehdi H, Fábos V, Tuba R, et al. Integration of homogeneous and heterogeneous catalytic processes for a multi-step conversion of biomass: from sucrose to levulinic acid, γ-valerolactone, 1,4-pentanediol, 2-methyl-tetrahydrofuran, and alkanes[J]. Top. Catal., 2008, 48: 49-54.
2	盛栋. 镍基催化剂催化乙酰丙酸制备γ-戊内酯[D]. 杭州: 浙江大学, 2015.
	Sheng D. Nickel-based catalyst catalyzes the preparation of levulinic acid to γ-valerolactone [D]. Hangzhou: Zhejiang University, 2015.
3	朱龙云. 负载型Ni催化剂催化乙酰丙酸加氢合成γ-戊内酯的研究[D]. 杭州: 浙江工业大学, 2015.
4	Tan J J. Basic research on the application of Ru-based catalysts in aqueous hydrogenation of levulinic acid [D]. Taiyuan: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, 2016.
5	Bond J Q, Alonso D M, Wang D, et al. Integrated catalytic conversion of γ-valerolactone to liquid alkenes for transportation fuels[J]. Science, 2010, 327: 1110-1114.
6	Serrano-Ruiz J C, Wang D, Dumesic J A. Catalytic upgrading of levulinic acid to 5-nonanone[J]. Green Chem., 2010, 12(4): 574-577.
7	Contino F, Dagaut P, Dayma G, et al. Combustion and emissions characteristics of valeric biofuels in a compression ignition engine[J]. Journal of Energy Engineering, 2014, 140: 171-175.
8	Kumar V V, Naresh G, Sudhakar M, et al. An investigation on the influence of support type for Ni catalysed vapour phase hydrogenation of aqueous levulinic acid to γ-valerolactone[J]. RSC Adv., 2016, 6: 9872-9879.
9	孙卓文. 肉桂醛与乙酰丙酸选择性加氢的研究[D]. 大连: 大连理工大学, 2014.
	Sun Z W. Study on selective hydrogenation of cinnamaldehyde and levulinic acid [D]. Dalian: Dalian University of Technology, 2014.
10	Hengst K, Schubert M, Carvalho H W P, et al. Synthesis of γ-valerolactone by hydrogenation of levulinic acid over supported nickel catalysts[J]. Applied Catalysis A: General, 2015, 502: 18-26.
11	Hengst K, Ligthart D A J M, Doronkin D E, et al. Continuous synthesis of γ-valerolactone in a trickle-bed reactor over supported nickel catalysts[J]. Industrial & Engineering Chemistry Research, 2017, 56: 2680-2689.
12	Yan K, Chen A. Efficient hydrogenation of biomass-derived furfural and levulinic acid on the facilely synthesized noble-metal-free Cu-Cr catalyst[J]. Energy, 2013, 58: 357-363.
3	Zhu L Y. Study on supported Ni catalyst for hydrogenation of levulinic acid to γ-valerolactone [D]. Hangzhou: Zhejiang University of Technology, 2015.
4	谭静静. Ru基催化剂在乙酰丙酸水相加氢中的应用基础研究[D]. 太原: 中国科学院山西煤炭化学研究所, 2016.
13	Yan K, Chen A. Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu-Fe catalyst[J]. Fuel, 2014, 115: 101-108.
14	Long X, Sun P, Li Z, et al. Magnetic Co/Al₂O₃ catalyst derived from hydrotalcite for hydrogenation of levulinic acid to γ-valerolactone[J]. Chinese Journal of Catalysis, 2015, 36: 1512-1518.
15	Gupta S S R, Kantam M L. Selective hydrogenation of levulinic acid into γ-valerolactone over Cu/Ni hydrotalcite-derived catalyst[J]. Catalysis Today, 2017, 8(7): 231-236.
16	蒋龙飞. 铜基类水滑石的制备及其催化合成γ-戊内酯的研究[D]. 广州: 华南理工大学, 2012.
	Jiang L F. Preparation of copper-based hydrotalcite and study on its catalytic synthesis of γ-valerolactone [D]. Guangzhou: South China University of Technology, 2012.
17	谢鲜梅. 类水滑石化合物的制备、性能及应用研究[D]. 太原: 太原理工大学, 2007.
	Xie X M. Study on preparation, properties and application of hydrotalcite-like compounds [D]. Taiyuan: Taiyuan University of Technology, 2007.
18	Claudio R, Soria M A, Madeira L M. Effect of interlayer anion on the CO₂ capture capacity of hydrotalcite-based sorbents[J]. Separation and Purification Technology, 2019, 219: 290-302.
19	Wu X, Du Y L, Liu X Z, et al. Facile synthesis of NiAl-LDHs with tunable establishment of acid-base activity sites[J]. Materials Chemistry and Physics, 2018, 211: 72-78.
20	Oliver M, Frank R, Rainer A, et al. Impact of organic interlayer anions in hydrotalcite precursor on the catalytic activity of hydrotalcite-derived mixed oxides[J]. ChemCatChem, 2010, 2(3): 314-321.
21	Gupta S A R, Kantam M L. Selective hydrogenation of levulinic acid into γ-valerolactone over Cu/Ni hydrotalcite-derived catalyst[J]. Catalysis Today, 2018, 309: 189-194.
22	龙向东, 孙鹏, 李泽龙, 等. 水滑石基磁性Co/Al₂O₃催化剂在乙酰丙酸加氢制备γ-戊内酯反应中的应用[J]. 催化学报, 2015, 36(9): 1512-1518.
	Long X D, Sun P, Li Z L, et al. Application of hydrotalcite-based magnetic Co/Al₂O₃ catalyst in the hydrogenation of levulinic acid to γ-valerolactone [J]. Chinese Journal of Catalysis, 2015, 36(9): 1512-1518.
23	王杰, 徐亚琳, 张因, 等. 制备方法对Ni-Al₂O₃催化剂乙酰丙酸加氢性能的影响[J]. 工业催化, 2018, 26: 15-20.
	Wang J, Xu Y L, Zhang Y, et al. Effect of preparation methods on Ni-Al₂O₃ catalyst for levulinic acid hydrogenation [J]. Industrial Catalysis, 2018, 26: 15-20.
24	刘洁翔, 张晓光. 阴离子插层镁铝水滑石结构及相互作用的理论研究[J]. 燃料化学学报, 2013, 41(6): 761-768.
	Liu J X, Zhang X G. Theoretical study on the structure and interaction of anion intercalated magnesium aluminum hydrotalcite [J]. Journal of Fuel Chemistry and Technology, 2013, 41(6): 123-130.
25	罗青松, 李蕾, 王作新, 等. 镁铝水滑石层板与层间阴离子相互作用的理论研究[J]. 无机化学学报, 2001, 17(6): 835-842.
	Luo Q S, Li L, Wang Z X, et al. Theoretical study on anion interaction between magnesium aluminum hydrotalcite laminates and interlayers [J]. Journal of Inorganic Chemistry, 2001, 17(6): 835-842.
26	Wu X, Ci C, Du Y, et al. Facile synthesis of NiAl-LDHs with tunable establishment of acid-base activity sites[J]. Materials Chemistry and Physics, 2018, 211: 72-78.
27	Linda M P, Neil B M, Roger H N. The use of hydrotalcite as an anion absorbent[J]. Ind. Eng. Chem. Res., 1995, 34: 1196-1202.
28	李蕾. 类水滑石材料新制备方法及结构与性能的理论研究[D]. 北京: 北京化工大学, 2002.
	Li L. A new preparation method of hydrotalcite-like material and theoretical study on structure and performance [D]. Beijing: Beijing University of Chemical Technology, 2002.
29	李海涛, 陈昊然, 张因, 等. 炭包覆氧化铝负载镍催化剂的制备和表征及其催化加氢性能[J]. 催化学报, 2011, 32(1): 127-133.
	Li H T, Chen H R, Zhang Y, et al. Preparation and characterization of nickel catalyst coated with alumina and its catalytic hydrogenation performance[J]. Journal of Catalysis, 2011, 32(1): 127-133.
30	李广燕, 刘长久, 吴华斌, 等. 稀土Nd³⁺与Cu²⁺掺杂非晶态纳米Ni(OH)₂材料的电化学性能[J]. 化学工程, 2009, 37(12): 55-58.
	Li G Y, Liu C J, Wu H B, et al. Electrochemical properties of rare earth Nd³⁺ and Cu²⁺ doped amorphous nano Ni(OH)₂ materials [J]. Chemical Engineering(China), 2009, 37(12): 55-58.
31	王佳. 层状前驱体制备高分散负载型纳米镍基催化剂及其性能的研究[D]. 北京: 北京化工大学, 2012.
	Wang J. Study on preparation and performance of highly dispersed supported nano nickel-based catalysts by layered precursors[D]. Beijing: Beijing University of Chemical Technology, 2012.
32	Sònia A, Danny V, Blaise B, et al. Activated takovite catalysts for partial hydrogenation of ethyne, propyne, and propadiene[J]. Journal of Catalysis, 2008, 259(1): 85-95.
33	Clause O, Goncalves C M, Gazzano M, et al. Synthesis and thermal reactivity of nickel-containing anionic clays[J]. Applied Clay Science, 1993, 8(2): 169-186.
34	Rebours B, Jean-Baptiste D D L C, Clause O. Decoration of nickel and magnesium oxide crystallites with spinel-type phases[J]. J. Am. Chem. Soc., 1995, 116(5): 1707-1717.
35	Zhu Y F, Kong X, Zhu S H, et al. Construction of Cu/ZrO₂/Al₂O₃ composites for ethanol synthesis: synergies of ternary sites for cascade reaction[J]. Applied Catalysis B: Environmental, 2015, 12(15): 551-559.
36	Federica P, Giovanna G, Robert D, et al. Investigation of acid-base properties of catalysts obtained from layered double hydroxides[J]. J. Phys. Chem. B, 2000, 104(47): 11117-11126.
37	张因, 郭健健, 王杰, 等. 以NiAl-NO₃-LDH为前驱体制备Ni-Al₂O₃催化剂及其催化乙酰丙酸加氢性能[J]. 高等学校化学学报, 2019, 40(8): 1686-1696.
	Zhang Y, Guo J J, Wang J, et al. Preparation of Ni-Al₂O₃ catalyst using NiAl-NO₃-LDH as precursor and its catalytic performance for hydrogenation of levulinic acid [J]. Chemical Journal of Chinese Universities, 2019, 40(8): 1686-1696.
38	Al-shaal M G, Wright W R H, Palkovits R. Exploring the ruthenium catalysed synthesis of γ-valerolactone in alcohols and utilisation of mild solvent-free reaction conditions[J]. Green Chemistry, 2012, 14(5): 1260-1263.
39	Hengne A M, Rode C V. Cu-ZrO₂ nanocomposite catalyst for selective hydrogenation of levulinic acid and its ester to γ-valerolactone[J]. Green Chem., 2012, 14: 1064-1072.

[1]	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.
[2]	王立晖, 刘焕, 李赫宇, 郑晓冰, 姜艳军, 高静. 核壳结构磁性树枝状纤维形有机硅固定化脂肪酶制备及其应用[J]. 化工学报, 2021, 72(9): 4861-4871.
[3]	张茜, 王艳华. 温控相分离纳米Ir催化α，β-不饱和醛、酮选择加氢[J]. 化工学报, 2019, 70(9): 3396-3403.
[4]	屠佳成, 桑乐, 艾宁, 徐建鸿, 张吉松. 连续微反应加氢技术在有机合成中的研究进展[J]. 化工学报, 2019, 70(10): 3859-3868.
[5]	王杰, 张因, 郭健健, 赵丽丽, 赵永祥. Ni/ZrO₂-SiO₂催化剂催化乙酰丙酸加氢合成γ-戊内酯[J]. 化工学报, 2018, 69(8): 3452-3459.
[6]	吕喜蕾, 阮厚航, 陈皓, 吕秀阳. 近临界乙醇中Zr-SBA-15催化糠醛一步法制备乙酰丙酸乙酯[J]. 化工学报, 2018, 69(6): 2488-2495.
[7]	李晨阳, 冯淼, 崔海峰, 曹贵平, 吕慧, 陈荣起. 蜂窝陶瓷骨架微结构修饰调控制备Pd/CNTs@CHC催化剂用于PS加氢[J]. 化工学报, 2017, 68(7): 2746-2754.
[8]	常春, 白净, 安冉, 邓琳, 戚小各, 徐艳丽. 硫酸铁催化生物基糠醇制取乙酰丙酸丁酯[J]. 化工学报, 2017, 68(6): 2368-2375.
[9]	安冉, 孔鹏飞, 徐桂转, 常春, 白净, 方书起. 脱铝超稳Y沸石负载Cu催化纤维素醇解合成乙酰丙酸乙酯[J]. 化工学报, 2016, 67(11): 4643-4651.
[10]	张阳阳, 罗璇, 庄绪丽, 仝新利. 混合酸催化葡萄糖选择性转化合成乙酰丙酸甲酯[J]. 化工学报, 2015, 66(9): 3490-3495.
[11]	常翠荣, 王华, 韩金玉. 固体酸表面B酸和L酸与果糖转化制乳酸甲酯产物分布[J]. 化工学报, 2015, 66(9): 3428-3436.
[12]	陈伦刚, 刘勇, 定明月, 张兴华, 李宇萍, 张琦, 王铁军, 马隆龙. Ru催化加氢选择性脱除F-T合成水相中的含氧化合物[J]. 化工学报, 2014, 65(11): 4347-4355.
[13]	姜楠1，谢楠1，齐崴1，2，3，苏荣欣1，2，3，何志敏1，2，3. 硫酸催化葡萄糖制备乙酰丙酸的过程强化[J]. 化工进展, 2014, 33(11): 2888-2893.
[14]	孙梅娟1，黄晓典1，关清卿1，张春云2，柴欣生2，田森林1，宁平1，谷俊杰1. 超临界乙醇体系中苯酚催化加氢的降解规律[J]. 化工进展, 2014, 33(07): 1902-1907.
[15]	高学艺，武彦伟，王克冰. 沙柳酸催化水解制备乙酰丙酸及分离提纯[J]. 化工进展, 2014, 33(01): 242-246.

插层阴离子对以类水滑石为前体Ni-Al₂O₃催化剂催化乙酰丙酸加氢性能的影响

Effect of intercalation anions on catalytic performance of hydrotalcite-like precursor Ni-Al₂O₃ catalyst for levulinic acid hydrogenation

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 16

参考文献 39

相关文章 15

编辑推荐

Metrics

本文评价