The polarity of phenolic-oil can decrease with improved miscibility in gasoline or diesel, if the phenolic mixture can be converted to aryl ethers. As the following work of early-stage studies, in this work, based on the prior well-estimated catalyst of KH2PO4/Al2O3, a novel process with addition of blending component was put forward and the effects of blending components on the vapor-phase etherification of phenols with methanol were investigated systematically, using phenolic-oil as research object. Five blending components (acetic acid, formic acid, acetone, furan and ethyl acetate) were screened and the effect of acetone was found to be the best in promoting the conversion of alkylphenols to aryl ethers. The effect of acetone dosage was examined at a constant temperature of 500℃. It was found that the liquid recovery deceased with increasing dosage of acetone before 70wt%, and then turned to a stable trend at even higher dosages. Guaiacol or any other alkoxyphenol was not detected in all cases. Alkylphenols decreased remarkably at higher acetone dosages compared with that without blending component. Aryl ethers were most generated at the acetone dosage of 50wt%. With even higher dosage of acetone, aromatics and other compounds were more generated, leading to a remarkable decrease of aryl ethers. Furthermore, with the optimized acetone percentage of 50wt%, the influence of temperature on the alkylation reaction was investigated. It was found that the liquid recovery deceased with increasing of the temperature, and decreased even faster in the range from 500 to 550℃. The content of aryl ethers reached to a maximum value (29.06area%) at 500℃ and aromatics were most generated (26.01area%) at 450℃ Considering the both factors of liquid recovery and polarity of liquid product, the optimized conditions were determined as 450℃ with 50wt% of acetone dosage, with summary content of aromatics and aryl ethers (52.90area%). It was speculated that the carbonyl group of acetone interacted with the hydroxyl group of phenols, leading to the release of CO2, and meanwhile aromatics and arylethers were generated from alkylphenols and alkoxyphenols respectively.
Bo YUAN Ze WANG Wenli SONG Songgeng LI
. Effect of blending component on etherification of phenolic-oil over KH2PO4/Al2O3[J]. The Chinese Journal of Process Engineering, 2019
, 19(6)
: 1101
-1110
.
DOI: 10.12034/j.issn.1009-606X.219155
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