4.7 Article

Effect of La-Fe/Si-MCM-41 catalysts and CaO additive on catalytic cracking of soybean oil for biofuel with low aromatics

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ELSEVIER
DOI: 10.1016/j.jaap.2019.104693

Keywords

Catalytic cracking; Biofuel; La-Fe/Si-MCM-41; CaO; Bronsted/Lewis acidity; Aromatics

Funding

  1. National Natural Science Foundation of China [21808207]
  2. Zhejiang Provincial Natural Science Foundation of China [LQ18B060006]
  3. Biodiesel Laboratory of China Petroleum and Chemical Industry Federation
  4. Zhejiang Province Key Laboratory of Biofuel

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La-Fe modified Si-MCM-41 (La-Fe/Si-MCM-41) catalysts were prepared by the wet impregnation method and used in catalytic cracking of soybean oil (CCS) for biofuel production. The catalysts were characterized by BET, XRD, XPS, Py-FTIR and CO2-TPD. The results showed that the aromatics content increased with the increase in B/L value, while the content of oxygenated compounds decreased, indicating that Bronsted acid sites were the major active sites for deoxygenation and aromatization reactions. Compared with Si-MCM-41, the Bronsted acidity of LFM-6 sharply decreased from 22.49 to 5.86 mu mol g(-1). Accordingly, the aromatics content was re- duced from 37.51 wt.% to 14.52 wt.% which was lower than the limitation (15 wt.%) according to the global environmental legislation. However, for the LFM-6 catalyst, the excessive loss of Bronsted acid sites and sharp decrease in BET surface area and pore volume led to the decrease in deoxygenation. As a result, the fatty acids content increased from 2.71 wt.% to 16.67 wt.% and the acid value reached 35.20 mgKOH g(-1). When the La-Fe loading increased to 15 wt.%, part of fatty acids were converted into ketones by the active sites on Fe2O3/La2O3 and strong Lewis acid sites on catalysts. Besides, the new weak Lewis acid and basic sites on Fe2O3/La2O3 exhibited the synergistic effect on promoting the generation of alkenes. The CaO/LFM-6 composite catalysts prepared by the mechanical mixing of LFM-6 and Ca0 were used in CCS to reduce the acid value of biofuel. LFM6-C-3 was proved to be an effective catalyst for CCS to produce biofuel with low aromatics (12.31 wt.%) and fatty acids (2.76 wt.%) content.

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