近年來國內尼龍（nylon）產業需求的增長，己二腈（Adiponitrile, ADN）作為尼龍產業的上游原料，其需求也在不斷增長，但其生產技術被少數已開發國家掌握。目前國內己二腈處於嚴重依賴國外進口的情況，因此，對己二腈合成方法的研究顯得非常重要。丙烯腈（Acrylonitrile, AN）電解是合成己二腈的主要方法之一，其所用原料丙烯腈毒性小，且只需一步反應即可得到己二腈，在技術上相對容易改善及研究。
本研究參考使用現有電解液組成下，先以電化學阻抗分析法探討各主要成份在還原反應時對於電極表面行為的影響，再針對關鍵添加物—四級銨鹽（TMAH、TEAH、TPAH、MBAP、TBAP），探討碳鏈長度與添加濃度的吸附特性，最後於無隔膜攪拌式批式反應槽中電解合成己二腈，探討碳鏈長度與添加濃度對於己二腈選擇率與電流效率的影響，並以此結果估算連續式反應條件下的己二腈選擇率與電流效率。
結果顯示反應物丙烯腈、四級銨鹽與己二腈會被吸附在電極表面；乙二胺四乙酸（EDTA）則無明顯吸附現象。而不同碳鏈長度的四級銨鹽具有相異的吸附特性，MBAP和TBAP吸附層在較廣的電位範圍下維持結構。經由計算，碳鏈越長的四級銨鹽於電極表面的吸附層層數越多，並且四級銨鹽的濃度從20 mM提高到40 mM皆會增加其在電極表面的吸附量。
於低有機相比例的電解液中，碳鏈較長的四級銨鹽抑制電極產生氫氣的還原電流程度較大，可能是因其吸附層數較多且疏水性較強，同時可能也因親油性較強以及離子直徑較大而吸附層較不緊密，使丙烯腈較易擴散到達電極表面還原，其中以添加TBAP時，效果最為顯著。將四級銨鹽從20 mM提高到40 mM，抑制產氫還原電流程度提高，同時也可能因此使電極表面反應物丙烯腈度更高，有效促進丙烯腈的還原反應，其中以提高TPAH添加濃度有最明顯的濃度效應。
批式定電流電解結果顯示四級銨鹽的碳鏈越長，目標產物己二腈的選擇率與電流效率越高。增加四級銨鹽的濃度，會增加己二腈或三聚物的選擇率，明顯降低丙腈選擇率。當添加的四級銨鹽為20 mM TBAP時，有最高的己二腈選擇率與己二腈電流效率。
將批式定電流電解結果模擬連續式反應條件，結果顯示添加20 mM MBAP時，其己二腈選擇率為78.3 %、己二腈電流效率為75.5 %；添加20 mM TBAP時，己二腈選擇率為85.4 %、己二腈電流效率為83.7 %。

Recently, with the increment of the needs of nylon, the demands of the key raw material, adiponitrile (ADN), also increase, whose production technology has been controlled by developed countries. In Taiwan, ADN strongly relies on the import from foreigner countries now, so the researches of synthesis of ADN are much important obviously. Electrosynthesis of ADN from acrylonitrile (AN) is a one-step reaction, and the toxicity of acrylonitrile is low. Therefore, the production technology is developed and researched comparatively easier.
In this study, the influences of each component in the existing electrolyte on the electrode surface behavior during the reduction reaction were investigated with Electrochemical Impedance Spectroscopy. And the adsorption characteristics of quaternary ammonium salts (QASs) with different carbon chain lengths and added concentrations were investigated. Finally, the ADN was electrosynthesized in an stirring batch cell without diaphragm to investigate the effect of carbon chain lengths and concentrations of QASs on the selectivity and current efficiency of ADN. The results of batch reaction were used to estimate the selectivity and current efficiency of ADN under continuous reaction conditions.
The results showed that AN, QASs and ADN did be adsorbed on the surface of the electrode; ethylenediaminetetraacetic acid (EDTA) did not. The QASs with different carbon chain length have different adsorption characteristics, and the adsorption layers of MBAP and TBAP can maintain the adsorption layer structure over a wider range of potentials. It is calculated that the longer the carbon chain in QAS, the more the number of average adsorption layers on the electrode surface, and that increasing the concentration of the QASs increased the adsorption amount on the electrode surface.
With low organic concentration in an electrolyte, the QAS with longer carbon chain decreased hydrogen evolution reduction current more significantly probably because of larger number of adsorption layers and higher hydrophobicity. Furthermore, probably because the QAS with longer carbon chain had stronger lipophilicity and larger ion diameter to form larger interspacing in the adsorption layer, AN was easier to diffuse to electrode surface for reduction reaction. The effect was most significant with TBAP. Increasing the concentration of the QASs from 20 mM to 40 mM enhanced the decrease in hydrogen evolution reaction current, and probably then increased the concentration of AN on the electrode surface, thereby effectively promoted the reduction reaction of AN. Higher concentration of TPAH was most effectively.
The results of electrosynthesis in batch reactor showed that the QAS with longer carbon chain gave higher selectivity and current efficiency of ADN. Increasing the concentration of the QASs increased the selectivity of ADN or trimer, and decreased the selectivity of propionitrile significantly. When adding 20 mM TBAP, there is the highest ADN selectivity and ADN current efficiency.
The estimation for a continuous reaction condition from the batch reactor reaction showed that the ADN selectivity and current efficiency were 78.3 % and 75.5 % respectively with 20 mM MBAP; the ADN selectivity and current efficiency were 85.4 % and 83.7 % respectively with 20 mM TBAP.

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