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磷钼酸催化废淀粉转化为乙醇酸的实验与动力学研究

Experimental and kinetic study of the conversion of waste starch into glycolic acid over phosphomolybdic acid.

作者信息

Qiao Yongzhen, Wang Xiu, Dai Hongqi

机构信息

Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University Nanjing China 210037

International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University Nanjing China 210037.

出版信息

RSC Adv. 2021 Sep 17;11(49):30961-30970. doi: 10.1039/d1ra05890h. eCollection 2021 Sep 14.

Abstract

The starch used to enhance the paper surface dissolves in water during the production process and forms pollutants that accumulate in water when old corrugated cardboard (OCC) is returned to a paper mill for pulping and reuse. At present, anaerobic fermentation is widely used in the paper industry to treat starch-containing wastewater, producing biogas energy, or oxidative decomposition, which is a huge waste of valuable starch resources. Phosphomolybdic acid (PMo) is a highly selective catalyst for the oxidation of carbohydrates; therefore, PMo can be envisaged as a suitable catalyst to convert waste starch into glycolic acid, an important high added-value chemical. In this paper, the catalytic oxidation technology of PMo was explored to produce glycolic acid from starch contained in OCC papermaking wastewater, and the kinetics and influencing factors of the catalytic oxidation reaction were studied. The results indicated that the PMo-catalyzed oxidation of starch followed a first-order reaction; the reaction rate constant increased with increasing the temperature, the apparent activation energy of starch to monosaccharide was 104.7 kJ mol, the apparent activation energies of starch and monosaccharide to humins were 126.5 and 140.5 kJ mol, and the apparent activation energy of monosaccharide to glycolic acid was 117.2 kJ mol. The yields of monosaccharide and glycolic acid were 80.7 wt% and 12.9 wt%, respectively, and the utilization of starch resources was about 90.0 wt% under the following reaction conditions: temperature, 145 °C; reaction time, 120 min; pH, 2. Therefore, the feasibility of the PMo-catalyzed oxidation of starch to produce high value-added glycolic acid is demonstrated, which has theoretical guiding significance and potential application value for the clean production and resource utilization of waste starch in the OCC papermaking process.

摘要

用于改善纸张表面的淀粉在生产过程中会溶解于水中,并形成污染物。当旧瓦楞纸箱(OCC)返回造纸厂进行制浆和再利用时,这些污染物会在水中积累。目前,厌氧发酵在造纸工业中被广泛用于处理含淀粉废水,产生沼气能源,或者进行氧化分解,这是对宝贵淀粉资源的巨大浪费。磷钼酸(PMo)是碳水化合物氧化的高选择性催化剂;因此,可以设想PMo是一种合适的催化剂,用于将废淀粉转化为乙醇酸,一种重要的高附加值化学品。本文探索了PMo催化氧化技术,以从OCC造纸废水中所含淀粉生产乙醇酸,并研究了催化氧化反应的动力学和影响因素。结果表明,PMo催化淀粉氧化遵循一级反应;反应速率常数随温度升高而增加,淀粉转化为单糖的表观活化能为104.7 kJ/mol,淀粉和单糖转化为腐殖质的表观活化能分别为126.5和140.5 kJ/mol,单糖转化为乙醇酸的表观活化能为117.2 kJ/mol。在以下反应条件下,单糖和乙醇酸的产率分别为80.7 wt%和12.9 wt%,淀粉资源利用率约为90.0 wt%:温度145℃;反应时间120分钟;pH值2。因此,证明了PMo催化氧化淀粉生产高附加值乙醇酸的可行性,这对OCC造纸过程中废淀粉的清洁生产和资源利用具有理论指导意义和潜在应用价值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3ad6/9041357/3a0edc142429/d1ra05890h-f1.jpg

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