m（SA-CS）BPM的制备及其在电合成乙醛酸中的应用
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摘要
分别用戊二醛和二价锡离子改性壳聚糖(CS)和海藻酸钠(SA),制备m(SA-CS)BPM。用扫描电镜作膜形貌观察,IR分析表明该聚合物膜两边分别含有-NRH_2~+、-COO~-官能团。该膜溶胀率较小,并能稳定存在于酸碱溶液中。
以制备出的m(SA-CS)BPM作为双阳极室圆筒电解槽的隔膜,应用于电合成乙醛酸体系。在电场的作用下,双极膜中的水离解产生H~+和OH~-,生成的H~+及时传输入阴极室中补充电生成乙醛酸时H~+的消耗。电流密度38.4 mA/cm~2,电解14 h,产率92.5%,平均电流效率82.6%,电解槽工作电压仅2.3 V。
将m(SA-CS)BPM作为双阴阳极电解槽的隔膜,应用于双成对电合成乙醛酸体系。在电场的作用下双极膜中水电离后生成的H~+透过mSA阳离子膜进入阴极室,以补充草酸电还原生成乙醛酸过程中H~+的消耗;OH~-透过mCS阴离子膜进入阳极室,与乙二醛电氧化生成乙醛酸过程中产生的H~+结合生成H_2O,促进反应向正方向进行,从而增大了在电流密度为30 mA/cm~2,20℃下电解,双阴极室的电流效率分别可达86.94%和82.81%,双阳极室的电流效率可达81.99%和78.62%,电解电压稳定在3.0V左右。
Modified m(SA-CS)bipolar membrane was prepared after chitosan(CS)and alginate(SA)were modified by glutaraldehyde and ferric chloride as linking reagents, respectively.The sectional structure of m(SA-CS)bipolar membrane were studied by SEM.IR spectrum indicated that the bipolar membrane contains -NRH_2~+ and-COO~-functional groups in CS membrane and SA membrane respectively,m(SA-CS)bipolar membrane was quite stable in acid and alkali solution.
The cylinder electrolytic cell was constituted by double anode,using m(SA-CS) bipolar membrane as septum in electrolysis cell for electro-generating glyoxylic acid. Under the function of electric field,water was dissociated to produce H~+ and OH~- in the bipolar membrane.H~+ transmit into the cathode chamber to supply the consuming of H~+ in the process of electro-generating glyoxylic acid.When the current density was 38.4 mA/cm~2,the yield was 92.5%,and the current efficiency reached to 97.3%,The electrolysis voltage was as low as 2.3 V.
Using m(SA-CS)BPM as septum in electrolysis cell for electro-generating glyoxylic acid.The experiment results show that H~+ generated by BPM moves into cathode chamber in time through mSA to supplement H~+ consumed by electro-reduction of oxalic acid to generate glyoxylic acid;OH~- moves into anode chamber in time through mCS to combine with H~+ produced by electro-oxygenation of glyoxal to generate glyoxylic acid and improves the reaction go along.The current efficiency was up to 87.53%,84.4%and 80.97%,76.15%,respectively at 20℃during the current density was 30 mA/cm~2.
以制备出的m(SA-CS)BPM作为双阳极室圆筒电解槽的隔膜,应用于电合成乙醛酸体系。在电场的作用下,双极膜中的水离解产生H~+和OH~-,生成的H~+及时传输入阴极室中补充电生成乙醛酸时H~+的消耗。电流密度38.4 mA/cm~2,电解14 h,产率92.5%,平均电流效率82.6%,电解槽工作电压仅2.3 V。
将m(SA-CS)BPM作为双阴阳极电解槽的隔膜,应用于双成对电合成乙醛酸体系。在电场的作用下双极膜中水电离后生成的H~+透过mSA阳离子膜进入阴极室,以补充草酸电还原生成乙醛酸过程中H~+的消耗;OH~-透过mCS阴离子膜进入阳极室,与乙二醛电氧化生成乙醛酸过程中产生的H~+结合生成H_2O,促进反应向正方向进行,从而增大了在电流密度为30 mA/cm~2,20℃下电解,双阴极室的电流效率分别可达86.94%和82.81%,双阳极室的电流效率可达81.99%和78.62%,电解电压稳定在3.0V左右。
Modified m(SA-CS)bipolar membrane was prepared after chitosan(CS)and alginate(SA)were modified by glutaraldehyde and ferric chloride as linking reagents, respectively.The sectional structure of m(SA-CS)bipolar membrane were studied by SEM.IR spectrum indicated that the bipolar membrane contains -NRH_2~+ and-COO~-functional groups in CS membrane and SA membrane respectively,m(SA-CS)bipolar membrane was quite stable in acid and alkali solution.
The cylinder electrolytic cell was constituted by double anode,using m(SA-CS) bipolar membrane as septum in electrolysis cell for electro-generating glyoxylic acid. Under the function of electric field,water was dissociated to produce H~+ and OH~- in the bipolar membrane.H~+ transmit into the cathode chamber to supply the consuming of H~+ in the process of electro-generating glyoxylic acid.When the current density was 38.4 mA/cm~2,the yield was 92.5%,and the current efficiency reached to 97.3%,The electrolysis voltage was as low as 2.3 V.
Using m(SA-CS)BPM as septum in electrolysis cell for electro-generating glyoxylic acid.The experiment results show that H~+ generated by BPM moves into cathode chamber in time through mSA to supplement H~+ consumed by electro-reduction of oxalic acid to generate glyoxylic acid;OH~- moves into anode chamber in time through mCS to combine with H~+ produced by electro-oxygenation of glyoxal to generate glyoxylic acid and improves the reaction go along.The current efficiency was up to 87.53%,84.4%and 80.97%,76.15%,respectively at 20℃during the current density was 30 mA/cm~2.
引文
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