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

详细信息

中图分类号: TQ645.8
计量
- 文章访问数: 180
- HTML全文浏览量: 181
- PDF下载量: 0
- 被引次数: 0
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

HTML全文

图 1 SO₄^2-/Nd₂O₃/C催化剂的TEM照片

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

下载: 全尺寸图片幻灯片

图 2 SO₄^2-/Nd₂O₃/C催化剂的XRD谱图

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

下载: 全尺寸图片幻灯片

图 3 SO₄^2-/Nd₂O₃/C催化剂的XPS谱图

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

参考文献(16)

[1]	舒庆, 余长林, 熊道陵.生物柴油科学与技术[M].1版.北京:冶金工业出版社, 2012. SHU Qing, YU Chang-lin, XIONG Dao-ling.Science and technology of biodiesel[M].1st ed.Beijing:Metallurgical Industry Press, 2012.
[2]	AMISH P V, JASWANT L V, SUBRAHMANYAM N.A review on FAME production processes[J].Fuel, 2010, 89(1):1-9. doi: 10.1016/j.fuel.2009.08.014
[3]	SOUSA L L, LUCENA I L, FEMANDES F A N.Transesterification of castor oil:Effect ofthe acid value and neutralization of the oil with glycerol[J].Fuel Process Technol, 2010, 91(2):194-196. doi: 10.1016/j.fuproc.2009.09.016
[4]	梁金花, 任晓乾, 王锦堂, 姜岷, 李振江.双核碱性离子液体催化棉籽油酯交换制备生物柴油[J].燃料化学学报, 2010, 38(3):275-280. doi: 10.1016/S1872-5813(10)60033-3 LIANG Jin-hua, REN Xiao-qian, WANG Jin-tang, JIANG min, LI Zhen-jiang.Preparation of biodiesel by transesterification from cottonseed oil using the basic dication ionic liquids as catalyst[J].J Fuel Chem Technol, 2010, 38(3):275-280. doi: 10.1016/S1872-5813(10)60033-3
[5]	GOLE V L, GOGATE P R.Intensification of synthesis of biodiesel from non-edible oil using sequential combination of microwave and ultrasound[J].Fuel Process Technol, 2013, 106(106):62-69.
[6]	舒庆, 刘宝, 巢志聪, 谌田雨, 程文辉.硅钨杂多酸制备、表征及催化酯化反应制备生物柴油活性研究[J].有色金属科学与工程, 2013, 4(2):19-24. http://www.cnki.com.cn/Article/CJFDTOTAL-JXYS201302005.htm SHU Qing, LIU Bao, CHAO Zhi-cong, CHEN Tian-yu, CHENG Wen-hui.Studies on the preparation, characterization and catalytic activity test with oleic acid esterification of silicotungstic heteropoly acid[J].Nonferrous Met Sci Eng, 2013, 4(2):19-24. http://www.cnki.com.cn/Article/CJFDTOTAL-JXYS201302005.htm
[7]	MACARIO A, GIORDANO G.Catalytic conversion of renewable sources for biodiesel production:a comparison between biocatalysts and inorganic catalysts[J].Catal Lett, 2013, 143(2):159-168. doi: 10.1007/s10562-012-0949-3
[8]	陈颖, 孙雪, 李慧, 白云波.稀土改性对SO₄^2-/ZrO₂固体酸催化剂结构与催化性能的影响[J].燃料化学学报, 2012, 40(4):412-417. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17919.shtml CHEN Ying, SUN Xue, BAI Yun-bo.Effect of rare earth modification on structureand catalytic properties of SO₄^2-/ZrO₂ solid acid catalyst[J].J Fuel Chem Technol, 2012, 40(4):412-417. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17919.shtml
[9]	PENG B X, SHU Q, WANG J F, WANG G R, WANG D Z, HAN M H.Biodiesel production from waste oil feedstocks by solid acid catalysis[J].Process Saf Environ Prot, 2008, 86(6):441-447. doi: 10.1016/j.psep.2008.05.003
[10]	SHU Q, NAWAZ Z, GAO J X, WANG D Z, WANG J F.Synthesis of biodiesel from waste oil feedstocks using a carbon-based solid acid catalyst:Reaction and separation[J].Bioresour Technol, 2010, 101(14):5374-5384. doi: 10.1016/j.biortech.2010.02.050
[11]	SHU Q, ZHANG Q, XU G H, NAWAZ Z, WANG D Z, WANG J F.Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst[J].Fuel Process Technol, 2009, 90(7/8):1002-1008.
[12]	SHU Q, YUAN H, LIU B, ZHU L H, ZHANG C X, WANG J F.Synthesis of biodiesel from model acidic oil catalyzed by a novel solid acid catalyst SO₄^2-/C/Ce⁴⁺[J].Fuel, 2015, 143:547-554. doi: 10.1016/j.fuel.2014.11.081
[13]	陈同云.低温陈化法制备稀土复合固体超强酸SO₄^2-/ZrO₂/Nd₂O₃及其稳定性研究[J].中国稀土学报, 2008, 26(3):286-290. CHEN Tong-yun.Ageing at low temperature and stability of complex solid superacid of rare earths[J].J Chin Rare Earth Soc, 2008, 26(3):286-290.
[14]	SUGANUMA S, NAKAJIMA K, KITANO M, YAMAGUCHI D, KATO H, HAYASHI S, HARA M.Hydrolysis of cellulose by amorphous carbon bearing SO₃H, COOH, and OH groups[J].J Am Chem Soc, 2008, 130(38):12787-12793. doi: 10.1021/ja803983h
[15]	SULTANA N, PATHAK A K, GURIA C.Response surface method and genetic algorithm assisted optimal synthesis of biodiesel from high free fatty acid sal oil (Shorea robusta) using ion-exchange resin at high temperature[J].J Environ Chem Eng, 2015, 3(4):2378-2392. doi: 10.1016/j.jece.2015.08.015
[16]	OLKIEWICZ M, PLECHKOVA N V, EARLE M J, FABREGAT A, STUBER F, FORTUNY A, FONT J, BENGOA C.Biodiesel production from sewage sludge lipids catalysed by Brönsted acidic ionic liquids[J].Appl Catal B:Environ, 2016, 181:738-746. doi: 10.1016/j.apcatb.2015.08.039