新型碳基固体酸SO42-/Nd2O3/C制备及催化油酸与甲醇酯化反应合成生物柴油研究

舒庆; 侯小鹏; 朱丽华; 申邦坡; 马飞; 王金福

新型碳基固体酸SO₄^2-/Nd₂O₃/C制备及催化油酸与甲醇酯化反应合成生物柴油研究

舒庆^{1, 2, ,},
侯小鹏¹,
朱丽华¹,
申邦坡¹,
马飞¹,
王金福²

基金项目:

国家自然科学基金 21206062, 21466013

江西省自然科学 (青年) 基金计划重大项目 20143ACB21018

化学工程联合国家重点实验室 (清华大学) 开放课题基金 SKL-chE-14A04

国家民委化学工程与技术重点实验室 (北方民族大学) 开放课题基金和国家级大学生创新训练项目 201410407004

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中图分类号: TQ645.8
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出版历程
- 收稿日期: 2015-09-17
- 修回日期: 2015-11-26

Preparation of a novel solid acid catalyst SO₄^2-/Nd₂O₃/C and study of its performance for the synthesis of biodiesel from esterification reaction of oleic acid and methanol

More Information

Corresponding author: Tel: 15216127106, E-mail: shuqing@tsinghua.org.cn

摘要

摘要: 在流化床管式炉中, 通过对废山茶油壳进行高温炭化处理制备了一种碳基材料。以该碳基材料为载体, 并对其进行稀土金属离子钕和硫酸磺化改性, 合成了一种新型碳基固体酸催化剂SO₄^2-/Nd₂O₃/C。对制备而成的催化剂进行了多种物理化学表征分析, 并以其为经甲醇和油酸酯化反应来合成生物柴油的催化剂, 对其催化活性和稳定性进行了研究。结果表明, 当甲醇和油酸物质的量比为2:1, 催化剂与反应物质量比为2%, 反应时间为120 min, 反应温度为90℃, 油酸的转化率为96.70%。催化剂经循环使用三次后, 油酸的转化率仍高达86.74%。高催化活性可归因如下:由于Nd、O、S元素的电负性分别为1.14、3.44和2.58, 因而Nd易向O和S元素的2p空轨道提供孤对电子, 使Nd³⁺与SO₄^2-之间形成稳定的配位键。并且, 由于S=O键具有强吸电子作用, 而导致了与SO₄^2-配位的Nd³⁺所产生的静电场增大, 当有水 (强配体) 存在时, 可使SO₄^2-/Nd₂O₃/C催化剂呈现出强Br nsted酸性。
- 生物柴油 /
- 钕与硫酸改性 /
- 碳基固体酸 /
- 酯化反应 /
- 配位键
Abstract: A carbon material was prepared from the high temperature carbonization of waste camellia seed shell in a fluidized bed tubular reactor.The carbon material was applied as the catalyst support to prepare a new catalyst SO₄^2-/Nd₂O₃/C after it was simultaneously modified by Nd³⁺ and sulfonated by concentrated sulfuric acid through impregnation method.The catalyst was characterized by several physical and chemical characterization methods.The catalytic activity and reusability of SO₄^2-/Nd₂O₃/C were evaluated using it to catalyze the esterification of methanol and oleic acid for the synthesis of biodiesel.Results showed that the conversion of oleic acid was 96.70% when the methanol/oleic acid molar ratio was 2:1, reaction temperature was 90℃, and catalyst/reactants was 2% under reflux condensation for 120 min.After recycling of three times, the conversion of oleic acid was still 86.74%.High activity can be explained as follows:the electro-negativity of Nd is 1.14, which is smaller than O (3.44) and S (2.58), so it will provide lone electron pair to the empty 2p orbit of O and S, resulting in the formation of a stable coordination bond between Nd³⁺ and SO₄^2-.In addition, S=O double bond can induce a strong electron withdrawing effect, which can increase the electrostatic field of Nd³⁺ when it was coordinated with SO₄^2-.And finally, it should be noticed that H₂O is a strong ligand.Hence, SO₄^2-/Nd₂O₃/C exhibited a strong Br nsted acidity when H₂O existed in the reaction medium.
- biodiesel /
- Nd³⁺ and sulfuric acid modification /
- carbon-based solid acid /
- esterification /
- coordination bond

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图 1 SO₄^2-/Nd₂O₃/C催化剂的TEM照片

Figure 1. TEM image of SO₄^2-/Nd₂O₃/C catalyst

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图 2 SO₄^2-/Nd₂O₃/C催化剂的XRD谱图

Figure 2. XRD patterns of SO₄^2-/Nd₂O₃/C catalyst

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图 3 SO₄^2-/Nd₂O₃/C催化剂的XPS谱图

Figure 3. XPS patterns of SO₄^2-/Nd₂O₃/C catalyst

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图 4 SO₄^2-/Nd₂O₃/C催化剂的热重分析曲线

Figure 4. TG-DTG curves of SO₄^2-/Nd₂O₃/C catalyst

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图 5 SO₄^2-/Nd₂O₃/C催化剂的Raman谱图

Figure 5. Raman patterns of SO₄^2-/Nd₂O₃/C catalyst

a: carbon; b: SO₄^2-/Nd₂O₃/C

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图 6 SO₄^2-/Nd₂O₃/C催化剂的NH₃-TPD谱图

Figure 6. NH₃-TPD profile of the SO₄^2-/Nd₂O₃/C catalyst

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图 7 反应温度对油酸转化率的影响

Figure 7. Influence of reaction temperature on the conversion of oleic acid

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图 8 反应时间对油酸转化率的影响

Figure 8. Influence of reaction time on the conversion of oleic acid

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图 9 甲醇与油酸的物质的量比对油酸转化率的影响

Figure 9. Influence of molar ratio of methanol/oleic acid on the conversion of oleic acid

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图 10 催化剂用量对油酸转化率的影响

Figure 10. Influence of catalyst loading on the conversion of oleic acid

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图 11 催化剂循环使用次数对油酸转化率的影响

Figure 11. Influence of catalyst cycling times on the conversion of oleic acid

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