Ecologically friendly and catalytic process "Research and Development of catalysts for selective synthesis of ethylenediamine"

生态友好的催化工艺“乙二胺选择性合成催化剂的研发”

• 批准号: 09450300
• 负责人: SEGAWA Kohichi
• 金额: $ 9.02万
• 依托单位: Sophia university
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450300/
• 关键词: mordenite; selective synthesis; ethanolamine; ethylenediamine; by-products; dealumination; pyridine adsorption (IR spectra); Bronsted acid; ブレンステッド酸点; 形状選択性; 固体酸触媒; ゼオライト; 骨格外アルミ; 脱アルミ

The synthesis of EDA (ethylenediamine) from EA (ehtanolamine) with NH_3 over acidic types of zeofite catalyst was investigated. Among the zeolites tested in this study, H-EDTA-MOR (H-type mordenite dealuminated with H_4EDTA) was the best catalyst. The reaction proved to be highly selective for EDA over H-EDTA-MOR, with small amounts of ethyleneimine and piperazine derivatives as the side products. The catalytic activity for EDA synthesis rises with increasing partial pressure of NH_3. The initial product of reaction was El, and the formation of EDA followed. The results suggest that the formation of EDA required stronger acidic sites in the mordenite channels with excess amounts of NH_3. The mordenite channels may retard the formation of bulkier piperazine derivatives and other polyamines. The reactions of EA proceed through ammonio-ions by the addition of protons of H-EDTA-MOR ; then intramolecular condensation of ammonioions of EA occurred to produce an El intermediate over the active sites of the catalyst. ethyleneimine is protonated by the stronger acidic sites with excess amounts of NH_3 to produce EDA.Dealuminated mordenites by H_4EDTA and hydrochloric acid of different concentration were investigated with IR (pyridine adsorption), XRD, XRF, MAS NMR.Each catalyst was used to test the catalytic activity and the produsts were analyzed with GO-MS.The amount of adsorbed pyridine (calculated from IR spectra) increased as the dealumination proceeds. It reached its maximum around Si/Al (bulk) =5, and then decreased. The catalytic activity increased as the amount of pyridine increased, and it decreased as the crystallinity and the pyridine amount decreased. That is, the curve of catalytic reaction strongly relates to the acid amount, especially Bronsted acid. It is under investigation the reason the acid amount increased with dealumination.

研究了EA(乙醇胺)与NH_3在酸性沸石催化剂上合成EDA(乙二胺)的过程。在本研究测试的沸石中，H-EDTA-MOR（用H_4EDTA脱铝的H型丝光沸石）是最好的催化剂。事实证明，该反应对 EDA 的选择性高于 H-EDTA-MOR，并产生少量副产物乙撑亚胺和哌嗪衍生物。 EDA合成的催化活性随着NH_3分压的增加而增加。反应的初始产物是E1，随后形成EDA。结果表明，EDA的形成需要丝光沸石通道中具有更强的酸性位点和过量的NH_3。丝光沸石通道可以阻止较大的哌嗪衍生物和其他多胺的形成。 EA通过氨离子通过添加H-EDTA-MOR质子进行反应；然后EA的铵离子发生分子内缩合，在催化剂的活性位点上产生El中间体。乙撑亚胺在过量NH_3的较强酸性位点被质子化，生成EDA。用H_4EDTA和不同浓度的盐酸对丝光沸石进行脱铝，采用IR（吡啶吸附）、XRD、XRF、MAS NMR进行考察。对各催化剂进行催化活性测试，并用GO-MS对产物进行分析。 吸附的吡啶（根据红外光谱计算）随着脱铝的进行而增加。它在 Si/Al（体积）=5 左右达到最大值，然后下降。催化活性随着吡啶用量的增加而增加，随着结晶度和吡啶用量的减少而降低。也就是说，催化反应的曲线与酸的量，特别是布朗斯台德酸的量密切相关。酸量随着脱铝而增加的原因正在调查中。