铁催化硬脂酸选择性氢化制硬脂醇

doi:10.6023/cjoc201902031

摘要/Abstract

长链脂肪酸是一种重要的生物质原料，其氢化制备的脂肪醇由于用途广泛以及市场价值不断增长，近年来引起了人们的广泛关注.报道了一例使用非均相铁催化硬脂酸选择性加氢制备硬脂醇的实例.与其他非贵金属元素（如钴和镍）相比，铁在地壳中的丰度高出3000~30000倍，价格仅为20~150分之一，因此该方法更经济，更有吸引力.催化剂是通过将铁和氮掺杂碳前驱体同时热解到氧化铝载体上制备的.制备催化剂时最佳热解温度为900℃，最佳铁的质量分数为20%.反应最佳反应温度为320℃，最佳氢气压力为4 MPa.产物随时间分布曲线表明硬脂酸在0.5 h内迅速转化为硬脂醇，收率为88.6%.4 h后逐渐转化为十八烷，收率为90%.

关键词: 生物质转化, 氢化, 铁, 脂肪酸, 脂肪醇

The utilization of sustainable resources such as biomass to produce fuels and chemicals has recently attracted significant attention due to the depletion of fossil reserves, increasing energy demand, and growing environmental concerns. Long-chain fatty acids, which are major constituents of plant oil, are important feedstock for biorefinery. Besides producing well-known biodiesels, the hydrogenation of fatty acids to fatty alcohols has recently drawn significant attention due to the versatility and growing market value of fatty alcohols. An example of heterogenous iron-catalyzed selective hydrogenation of stearic acid to stearyl alcohol is reported. Comparing with other reported non-noble metal centers, such as Co and Ni, Fe is 3000~30000 times more abundant and 20~150 times cheaper, thus making our method more economic and attractive. The iron catalyst was prepared by simultaneous pyrolysis of iron precursor[Fe(acac)₃] and nitrogen-doped carbon precursor (melamine) onto alumina, bearing Fe₃C active phase and nitrogen-doped carbon-alumina hybrid support. The optimization of preparation parameter showed that the optimal pyrolysis temperature is 900℃, while the best mass fraction of iron is 20%. The replacement of Fe(acac)₃ with Fe(NO₃)₃ led to inferior catalytic performance, which was due to undesired redox reaction between NO₃^- and melamine during pyrolysis that hampered the reaction between Fe and melamine to form Fe₃C active phase. Instead, hercynite phase became the predominant phase. The exploration of reaction parameter showed that the optimal reaction temperature is 320℃, and the best H₂ pressure is 4 MPa. The time course for stearic acid conversion shows that stearic acid was rapidly converted into stearyl alcohol with yield of 88.6% within 0.5 h, and then gradually converted into octadecane with yield of 90% at 4 h. The unsatisfactory stability of the iron catalyst is probably due to the decomposition of Fe₃C active phase to metallic Fe phase during recycling tests.

Key words: biomass conversion, hydrogenation, iron, fatty acid, fatty alcohol

引用此文

李江, 万童, 张俊杰, 傅尧. 铁催化硬脂酸选择性氢化制硬脂醇[J]. 有机化学, 2019, 39(11): 3258-3263.

Li Jiang, Wan Tong, Zhang Junjie, Fu Yao. Iron-Catalyzed Selective Hydrogenation of Stearic Acid to Stearyl Alcohol[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3258-3263.

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图/表 8


Entry	Catalyst	Conv./%	Yield ^b/%				Carbon balance
Entry	Catalyst	Conv./%	C18-OH	C17	C18	C17-CHO	Carbon balance
1	—	33.3	0.5	0.5	0.1	0.2	3.9
2	20% Fe-N-C@Al₂O₃-900	＞99	88.6	1.1	2.4	0.4	92.5
3	20% Fe-Al₂O₃-900	21.6	0.9	0.9	0.1	2.2	19.0
4	N-C@Al₂O₃-900	42.3	0.5	0.5	0.4	0.4	4.3
5	Al₂O₃	43.3	7.9	1.0	0.9	4.1	32.1
6	20% Fe-N-C@Al₂O₃-550	98.3	80.4	1.5	14.3	0	97.9
7	20% Fe-N-C@Al₂O₃-700	95.7	34.1	0.7	3.8	3.0	43.5
8	20% Fe-N-C@Al₂O₃-1100	97.1	47.9	1.6	11.8	2.6	65.8
9	20% Fe-N-C@SiO₂-900	88.5	1.0	1.3	0.1	1.1	4.0
10	20% Fe-N-C-900	92.1	4.3	1.6	0.7	1.8	9.1
11	20% Fe-N-C@TiO₂-900	66.9	3.6	0.9	0.4	3.0	11.8
12	20% Fe(NO₃)₃-N-C@Al₂O₃-900	80.6	10.8	1.2	0.6	2.2	18.4
13	20% Fe-phen-C@Al₂O₃-900	96.2	58.8	0.9	4.4	3.5	70.3
14	3% Fe-N-C@Al₂O₃-900	89.4	52.6	1.0	1.1	2.9	64.4
15	5% Fe-N-C@Al₂O₃-900	94.7	21.6	0.6	0.8	3.9	28.4
16	10% Fe-N-C@Al₂O₃-900	98.0	62.0	0.6	0.6	1.8	66.3
17	30% Fe-N-C@Al₂O₃-900	99.3	46.0	0.8	1.5	2.2	50.9

表 1. 催化剂筛选a

Table 1. Catalyst screening

图 1. 不同条件下制备的Fe-N-C@Al2O3和Fe-Al2O3-900催化剂的XRD谱图(A)和Fe-N-C@Al2O3-900催化剂的SEM谱图(B)

Figure 1. XRD patterns of Fe-N-C@Al2O3 catalyst prepared under different conditions and Fe-Al2O3-900 catalyst (A), and SEM image of Fe-N-C@Al2O3-900 catalyst (B)

图 2. 不同铁含量的Fe-N-C@Al2O3催化剂和对照样Fe2O3的Fe L边XANES谱图

Figure 2. Fe L-edge XANES spectra of Fe-N-C@Al2O3-900 catalysts with different mass fraction of Fe and control sample Fe2O3

图 3. 反应温度对于铁催化硬脂酸氢化制硬脂醇的影响

Figure 3. Effect of reaction temperature on iron-catalyzed hydrogenation of stearic acid to stearyl alcohol

图 4. 反应氢压对于铁催化硬脂酸氢化制硬脂醇的影响

Figure 4. Effect of H2 pressure on iron-catalyzed hydrogenation of stearic acid to stearyl alcohol

图 5. 铁催化硬脂酸转化过程时间曲线

Figure 5. Time course for iron-catalyzed conversion of stearic acid

图 6. 铁催化硬脂酸转化过程可能的反应路径

Figure 6. Proposed reaction pathway for iron-catalyzed conversion of stearic acid

图 7. (a) 铁催化剂稳定性实验以及(b)新鲜和重复使用的Fe-N-C@Al2O3-900催化剂的XRD谱图

Figure 7. (a) Stability test of iron catalysts, and (b) XRD patterns of fresh and reused Fe-N-C@Al2O3-900 catalysts

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