Synthesis of 5-hydroxymethylfurfural (5-HMF) from biomass derived mono- and poly-saccharides is gaining importance because of its usefulness in the preparation of important chemicals. In our work, we have synthesized several silicoaluminophosphate (SAPO) catalysts, and have shown that in the absence of any other pH modifying reagents, those are active in converting mono- and poly-saccharides into 5-HMF under biphasic reaction condition at 175 °C. Particularly, SAPO-44 catalyst showed the best activity in the conversion of fructose to yield 78% 5-HMF with 88% selectivity. On the contrary, all other catalysts showed lower yields (H-MOR: 63%, SAPO-5: 32%, 2DCT: 60%). Over SAPO-44, good yields for 5-HMF were observed when glucose (67%), maltose (57%), cellobiose (56%) and starch (68%) were used as substrates. Recycle study carried out with SAPO-44 catalyst in the fructose conversion reaction showed marginal decrease in the activity up to 3rd run and then afterwards constant activity was observed up to 5th run (1st: 78%, 2nd: 71%, 3rd: 66%, 4th: 65%, 5th: 65%). Catalyst characterizations revealed that SAPO catalysts have higher hydrophilic nature than H-MOR (Si/Al = 10) and hence it is postulated that this property may help in achieving better results. Further studies on the catalyst characterizations revealed that SAPO-44 undergoes modifications in its structure. However, ICP-OES data suggests that Al and/or P are not leached out in the solution indicating that change in local environment around elements is possible. The influence of acid amount, type of acid site etc. on the catalytic activity is discussed and found out that strong acid sites are required to boost the 5-HMF yields.
由
生物质衍生的
单糖和
多糖合成
5-羟甲基糠醛(5-
HMF)正变得越来越重要,因为它在重要
化学品的制备中具有重要价值。在我们的研究中,我们合成了几种
硅铝
磷酸盐(
SAPO)催化剂,并且在没有任何其他pH调节剂的情况下,证明这些催化剂在175 °C的双相反应条件下能有效地将
单糖和
多糖转化为5-
HMF。特别是,
SAPO-44催化剂在
果糖转化中表现出最佳活性,能够产生78%的5-
HMF,并具有88%的选择性。相反,其他所有催化剂的产率均较低(H-MOR: 63%,
SAPO-5: 32%,2DCT: 60%)。在
SAPO-44催化剂下,当以
葡萄糖(67%)、
麦芽糖(57%)、细胞二糖(56%)和淀粉(68%)作为底物时,观察到5-
HMF的良好产率。在
果糖转化反应中进行的
SAPO-44催化剂回收实验显示,活性在第3次反应时略有下降,之后在第5次反应中保持恒定(第1次:78%,第2次:71%,第3次:66%,第4次:65%,第5次:65%)。催化剂表征结果表明,
SAPO催化剂具有比H-MOR(Si/Al = 10)更高的亲
水特性,因此推测这一特性可能有助于获得更好的结果。对催化剂特征的进一步研究表明,
SAPO-44的结构发生了变化。然而,ICP-OES数据表明铝和/或
磷未从溶液中浸出, indicating 周围元素的局部环境变化是可能的。讨论了酸量、酸位点类型等对催化活性的影响,发现需要强酸位点以提高5-
HMF的产率。