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Production of Valuable Chemicals from Renewable Resources through a New Liquid Phase Oxidation Method.

通过新的液相氧化方法从可再生资源生产有价值的化学品。

基本信息

批准号：
11650806
负责人：
MAE Kazuhiro
金额：
$ 2.3万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650806/
关键词：
Liquid phase oxidation Biomass wastes Small-molecule carboxylic acid Fenton reagent Gasification

项目摘要

A new oxidative degradation method was developed for separating hemicellulose, cellulose and lignin from an oil palm shell waste, and for converting them into valuable chemicals. The method is basically a two-step process, in which the shell pretreated in a hot water at 180 ℃ was oxidized with 30%-H_2O_2 at 60 ℃ (first stage oxidation) under ambient pressure with or without a Fe catalyst. To increase the product yield and selectivity, a second stage oxidation of the water-soluble components obtained from the first stage oxidation was also performed in the presence of the Fenton reagent at 25 ℃. Through the hot water treatment hemicellulose in the palm oil shell was successfully recovered as saccharides, leaving lignin and cellulose. Through the first stage oxidation without the Fe catalyst lignin was converted to water-soluble compounds containing small molecular weight fatty acids such as HCOOH and CH_3COOH, and almost pure cellulose was recovered in 22 % of yield on carbon basis. Aft … More er the second stage oxidation, the yield of small molecular weight fatty acids reached 30 wt.% on the oil palm shell basis.In the above method, it is meaningful and useful to find another methods to utilize the water-soluble compounds (WSL) that are obtained in 48 % yield as intermediates from the oil palm shell. Since the water-soluble organic compounds consist of partly oxidized lignin, their gasification rate is expected to be larger than the gasification rate of the original shell. We examined the possibility to utilize the water-soluble compounds as a feedstock for the gasification by comparing the gasification rates among WSL, the original oil palm shell (OPS) and the shell pretreated by hot water (HTS) using the so-called temperature-programmed reaction (TPR) method in a helium and oxygen gas mixture.The gasification of OPS and HTS proceeded in two steps. It is supposed that the first stage and the second stage gasifications correspond to the gasifications of cellulose and lignin, respectively. On the other hand, WSL was rapidly gasified below 340 ℃. From the in-situ FTIR measurements it was found that the lignin decomposed into cross-linked structure before being gasified for HTS.On the other hand, WSL was gasified without the cross-linking reaction developing aromatic ring structure. The gasification rate of WSL increased with the progress of conversion and was 500 times larger than that of the oil palm shell at the conversion of 0.9.Thus, the proposed method was expected to be a new route for converting low grade resources into valuable chemicals. Less

研究了一种新的氧化降解方法，用于分离油棕壳废弃物中的半纤维素、纤维素和木质素，并将其转化为有价值的化学物质。该方法基本上是一个两步过程，在180℃的热水中预处理的壳在60℃的环境压力下用30%-H_2O_2氧化（第一阶段氧化），有或没有铁催化剂。为了提高产物收率和选择性，在Fenton试剂存在下，在25℃条件下，对第一阶段氧化所得的水溶性组分进行了第二阶段氧化。通过热水处理，棕榈油壳中的半纤维素被成功地回收为糖类，剩下木质素和纤维素。在没有铁催化剂的情况下，通过第一阶段氧化，木质素转化为含有小分子量脂肪酸的水溶性化合物，如HCOOH和CH_3COOH，以碳基收率的22%回收了几乎纯纤维素。经第二阶段氧化后，以油棕壳为原料的小分子量脂肪酸收率达到30 wt.%。在上述方法中，寻找另一种方法利用产率为48%的油棕壳水溶性化合物（WSL）作为中间体是有意义和有益的。由于水溶性有机化合物由部分氧化的木质素组成，因此它们的气化速率预计将大于原始壳的气化速率。我们考察了利用水溶性化合物作为气化原料的可能性，通过比较WSL、原始油棕壳（OPS）和热水预处理的壳（HTS）在氦气和氧气混合物中使用所谓的温度程序化反应（TPR）方法的气化率。OPS和HTS的气化分两个步骤进行。推测第一阶段和第二阶段气化分别对应于纤维素和木质素的气化。另一方面，在340℃以下，WSL快速气化。通过原位FTIR测量发现，木质素在气化用于高温加热前已分解成交联结构。另一方面，WSL在气化过程中没有发生交联反应，形成芳香环结构。WSL的气化率随着转化的进行而增加，在转化率为0.9时比油棕壳的气化率大500倍。因此，该方法有望成为将低品位资源转化为有价值化学品的新途径。少