金属盐(SO42-/Cl-)固体酸催化剂在污泥制生物柴油中的应用

朱芬芬; 胡博; 韩媚玲; 张荣岩

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中国环境科学 ›› 2021, Vol. 41 ›› Issue (9) : 4176-4183.

固体废物

金属盐(SO₄^2-/Cl^-)固体酸催化剂在污泥制生物柴油中的应用

朱芬芬¹, 胡博¹, 韩媚玲¹, 张荣岩²

作者信息 +

Application of modified metal salt hydrates containing SO₄²^-/Cl^- in the production of biodiesel from sewage sludge

ZHU Fen-fen¹, HU Bo¹, HAN Mei-ling¹, ZHANG Rong-yan²

Author information +

文章历史 +

摘要

研究NaHSO₄·H₂O（布朗斯特酸位为主）和AlCl₃·6H₂O（路易斯酸位为主）两类金属盐固体酸催化剂在污泥制取生物柴油过程中的催化性能.结果表明，经过130℃脱水的NaHSO₄·H₂O较AlCl₃·6H₂O表现更为优异，两种催化剂的最优催化条件为催化剂投加量1.2g/10g冷冻干燥污泥、反应温度130℃、反应时间4h.虽然对粗脂肪的酯化率NaHSO₄·H₂O低于AlCl₃·6H₂O，分别为（63.4±2.6）％和（68.9±1.4）％（对应的生物柴油产率分别为9.73%~10.69％和10.80%~11.39％（污泥干基）），但经过GC-MS分析发现NaHSO₄·H₂O催化的生物柴油纯度更高，品质更好；两种催化剂的重复使用性<3~5次.两种催化剂均可实现低成本、高性能且环境友好的催化污泥制备生物柴油.

Abstract

The catalytic performance of two kinds metal salt solid acid catalysts (NaHSO₄·H₂O that mainly were Bronsted acid sites and AlCl₃·6H₂O that mainly were Lewis acid sites) for biodiesel production from sludge was compared. The results showed that NaHSO₄·H₂O dehydrated at 130℃ had better performance than AlCl₃·6H₂O. The optimal catalytic conditions of the two catalysts were as follows:catalyst dosage of 1.2g/10g freeze-drying sludge, reaction temperature of 130℃, reaction time of 4h. The esterification rate of crude fat catalysed by NaHSO₄·H₂O (63.4±2.6)% was lower than that of AlCl₃·6H₂O (68.9±1.4)%, the corresponding biodiesel yields were 9.73%~10.69% and 10.80%~11.39% (sludge dry base). However, the GC-MS analysis showed that the biodiesel catalysed by NaHSO₄·H₂O had higher purity and better quality. The reusability of the two catalysts was <3~5times. Therefore, both of the two catalysts were excellent in biodiesel production from sludge with low cost, high performance and environmental friendliness.

导出引用

朱芬芬, 胡博, 韩媚玲, 张荣岩. 金属盐(SO₄^2-/Cl^-)固体酸催化剂在污泥制生物柴油中的应用[J]. 中国环境科学. 2021, 41(9): 4176-4183

ZHU Fen-fen, HU Bo, HAN Mei-ling, ZHANG Rong-yan. Application of modified metal salt hydrates containing SO₄²^-/Cl^- in the production of biodiesel from sewage sludge[J]. China Environmental Science. 2021, 41(9): 4176-4183

中图分类号： X705

参考文献

[1] Kwon E, Kim S, Jeon Y, et al. Biodiesel production from sewage sludge:new paradigm for mining energy from municipal hazardous material[J]. Environmental Science & Technology, 2012,46(18):10222-10228.
[2] 迟夏,李安婕,李美茜.曝气量对颗粒污泥制备生物柴油的影响[J]. 中国环境科学, 2018,38(2):651-657.Chi X, Li A J, Li M Q. Effect of aeration rate on granular sludge for biodiesel production[J]. China Environmental Science, 2018,38(2):651-657.
[3] 刘晓红,李甜甜,曾现来.核桃果皮基磁性固体酸催化剂的制备及其催化性能研究[J]. 中国环境科学, 2018,38(11):207-212.Liu X H, Li T T, Zeng X L. Preparation of magnetic solid acid catalyst from walnut peel and its catalytic activity in synthesis of biodiesel[J]. China Environmental Science, 2018,38(11):207-212.
[4] Siddiquee M N, Rohani S. Lipid extraction and biodiesel production from municipal sewage sludges:a review[J]. Renewable and Sustainable Energy Reviews, 2011,15(2):1067-1072.
[5] 葛文锋,胡晓萍,吴嘉.硫酸氢钠催化合成乙酸乙酯动力学[J]. 化学反应工程与工艺, 2010,26(3):264-268.Ge W F, Hu X P, Wu J. Kinetics for esterification of acetic acid with eethanol catalyzed by sodium acid sulfate[J]. Chemical Reaction Engineering and Technology, 2010,26(3):264-268.
[6] Mardhiah H H, Ong H C, Masjuki H H, et al. A review on latest developments and future prospects of heterogeneous catalyst in biodiesel production from non-edible oils[J]. Renewable & Sustainable Energy Reviews, 2017,67:1225-1236.
[7] 张秋云,罗丹,吴忠富,等.固载化氯化铝催化材料的制备及性能研究[J]. 无机盐工业, 2017,49(10):71-74.Zhang Q Y, Luo D, Wu F Z, et al. Preparation of immobilized AlCl₃ catalytic materials and catalytic properties thereof[J]. Inorganic Chemicals Industry, 2017,49(10):71-74.
[8] Sani Y M, Daud W M A W, Abdul A A R. Activity of solid acid catalysts for biodiesel production:A critical review[J]. Applied Catalysis A General, 2014,470:140-161.
[9] GB/T 5009.5-1985食品中蛋白质的测定方法[S].GB/T 5009.5-1985 Method for determination of protein in food[S].
[10] 董颖博,张圆,林海,等.焙烧温度对天然沸石物化性能的影响[J]. 中国有色金属学报, 2017,(7):1520-1526.Dong Y B, Zhang Y, Lin H, et al. Effects of calcination temperature on physicochemical properties of natural zeolite[J]. The Chinese Journal of Nonferrous Metals, 2017,(7):1520-1526.
[11] 杜艳霞,郭昭华,王宏宾.结晶氯化铝煅烧技术对氧化铝性能的影响研究[J]. 轻金属, 2019,(2):18-22.Du Y X, Guo Z H, Wang H B. Study on the effect of calcination technology of crystalline aluminum chloride on the properties of alumina[J]. Light Metals, 2019,(2):18-22.
[12] 李波,邵玲玲.氧化铝、氢氧化铝的XRD鉴定[J]. 无机盐工业, 2008,40(2):54-57.Li B, Shao L L. Appraisal of alumina and aluminium hydroxide by XRD[J]. Inorganic Chemicals Industry, 2008,40(2):54-57.
[13] Hou Z, Yashima T. Meso-porous Ni/Mg/Al catalysts for methane reforming with CO₂[J]. Applied Catalysis A:General, 2004,261(2):205-209.
[14] Gerpen J V. Biodiesel processing and production[J]. Fuel Processing Technology, 2005,86(10):1097-1107.
[15] 赵芳,田志茗.CaO/MgO混合催化剂的制备及催化合成生物柴油[J]. 工业催化, 2017,25(3):58-62.Zhao F, Tian Z M. Preparation and catalytic properties of CaO/MgO mixed catalyst for biodiesel synthesis[J]. Industrial Catalysis, 2017, 25(3):58-62.
[16] 李兴鹏,舒庆.Lewis酸型固体酸催化剂Ce-Ag-PW的制备,表征及催化酯化反应合成生物柴油性能研究[J]. 有色金属科学与工程, 2020,11(2):42-50.Li X P, Shu Q. Preparation, characterization of Lewis acidic solid acid catalyst Ce-Ag-PW and its catalytic application in biodiesel production via esterification[J]. Nonferrous Metals Science and Engineering, 2020,11(2):42-50.
[17] 张秋云,杨松,李虎.制备生物柴油的固体酸催化剂研究进展[J]. 化工进展, 2013,(3):575-583.Zhang Q Y, Yang S, Li H. Research progress in the preparation of biodiesel with solid acid as the catalyst[J]. Chemical Industry and Engineering Progress, 2013,(3):575-583.
[18] Revellame E, Hernandez R, French W, et al. Production of biodiesel from wet activated sludge[J]. Journal of Chemical Technology & Biotechnology, 2011,86(1):61-68.
[19] 万祯.生物柴油的合成及影响因素研究[D]. 重庆:重庆大学, 2007.Wan Z. Study on the Synthesis Factors of Biodiesel[D]. Chongqing:Chongqing University, 2007.