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monanfang01

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Noyori and co-workers [67,94] also reported the hydrogenation
of carbon dioxide in its supercritical phase with
dimethylamine. By using a catalyst [Ru(PMe3)4Cl2], up to
370,000 mol of DMF (N,N-dimethylformamide) per 1 mol
catalyst are found in less than 37 h as shown in Eq. (5). Under
the comparatively drastic reaction conditions (100 8C, 210 atm),
the condensation of dimethylammonium formate to DMF
takes place in liquid phase. Most of the DMF formed then is
dissolved in the supercritical phase, while the water content of
the liquid phase increases. In this way, all of the dimethylamine
used is converted into DMF quantitatively [65,94].
     Recently, DMF is also reported to be produced with
heterogeneous ruthenium catalysts [4]. Silylether ruthenium
complexes were anchored in a silica matrix by condensing
with Si(OEt)4 (tetraethoxysilane) as shown in Scheme 2 [4].
All gels were micro- to meso-porous and the organometallic
complexes were immobilized as monomers. The hybrid gel
catalysts can easily be separated from the reaction mixture.
The silica matrix-stabilized ruthenium complexes affords
the TOF up to 18,000 h1 and 100% selectivity from CO2, H2
and dimethylamine for the formation of DMF [4,95,96].
     The hydrogenation of CO2 to CO, the reverse water gas shift
reaction, is shown in Eq. (6). The hydrogenation of CO2 beyond
formic acid, formaldehyde and CO produces methanol,
methane and occasionally higher alcohols and hydrocarbons
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南京工大

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monanfang01: 金币+30, 翻译EPI+1, ★★★很有帮助 2013-04-29 00:05:14
monanfang01: 金币+30 2013-05-01 00:09:07
Noyori和他的同事也报道了二氧化碳在超临界状态与二甲胺可以发生加氢反应。通过使用(。。。)作为催化剂,如同方程5所示,每1 mol催化剂在37 h内可以催化得到370000 mol的DMF。在较为极端的反应条件(100°C,210 atm)下,二甲基铵甲酸盐的冷凝得到DMF的过程发生在液相中。绝大多数生成的DMF溶解到超临界相中,同时伴随着液相中水的含量的增大。通过这种方式,所有的二甲基胺都定量的转化为DMF。
最近,也有关于使用非均相钌催化剂制备DMF的方法也见于报道。由图2显示,甲硅烷基醚-钌的复合物通过与正硅酸四乙酯发生冷凝作用,被锚定在二氧化硅的基质上。所有的凝胶都具有微孔或中孔的多孔结构,有机金属复合物被固定作为单体。该杂化凝胶催化剂易于从反应混合物中分离。这种二氧化硅基质稳定的钌复合物使其在通过二氧化碳、氢气、二甲基胺制备DMF的过程的有效作用时间达到18000 h,选择性达到100%。
方程6所示的反应为二氧化碳加氢得到一氧化碳的反应,即水煤气转化反应的逆反应。除同甲酸、甲醛、一氧化碳的加氢反应外,二氧化碳的加氢反应还可以得到甲醇、甲烷,以及偶尔生成的高碳数醇和碳氢化合物。
2楼2013-04-28 23:44:42
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wxdlmc

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3楼2013-04-29 20:40:07
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