Fe～ⅡEDTA湿法络合脱硝液的再生及资源化初探
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摘要
Fe~ⅡEDTA湿法络合脱硝是二十世纪八十年代发展起来的一种高效烟气脱硝技术方法，但是由于烟气中氧气对吸收剂的消耗，导致处理成本高。本文针对这一缺陷，进行了脱硝剂再生及吸收液资源化初探，研究了Fe~ⅡEDTA络合吸收NO及其机理，Na_2SO_3还原再生的机理及反应动力学，在成本核算的基础上，形成了一套基于再生及资源化技术的、成本较低的Fe~ⅡEDTA湿法络合脱硝整体工艺。
研究表明，还原剂还原吸收液和电解再生吸收液具有不同的机理。Fe~ⅡEDTA和Na_2SO_3共同吸收NO时，Na_2SO_3调节吸收液的pH值到弱碱性，使吸收更易进行；同时，SO_3~(2-)可将Fe~ⅢEDTA还原为Fe~ⅡEDTA。循环伏安法研究表明，采用Na_2SO_3还原再生吸收液Fe~ⅡEDTA时，SO_3~(2-)主要转化为S_2O_6~(2-)和SO_4~(2-)。电解法还原再生Fe~ⅡEDTA研究发现，Fe~ⅢEDTA的电化学还原过程是一个快速化学反应过程，伴随着一个电子转移。采用准稳态极化曲线和恒电位阶跃测试得到298K时Fe~ⅢEDTA在铂电极表面还原的标准速率常数为k~0为0.0263 cm s~(-1)；扩散活化能为24.93 KJ mol~(-1)，表观活化能为25.74 kJ mol~(-1)，电子转移活化能为16.56kJmol~(-1)；整个还原过程由扩散过程控制。理论计算说明加快传质过程能极大地提高电化学还原的整体速率，对Fe~ⅢEDTA电化学再生有重要的工程指导意义。
研究络合脱硝后的废水资源化利用包括两个步骤。第一步，采用NaOH和H_2SO_4回收Fe~ⅡEDTA脱硝后废水中的EDTA，实验表明EDTA回收率达到67％；第二步，回收EDTA后的废液中加入氨水，可以生成铁氨肥、硝酸氨和硫酸氨等复合肥，实现脱硝废水的资源化利用。
本研究可为湿法络合脱硝吸收液的再生和资源化提供有益的探索，推进了湿法络合脱硝技术的工程化应用。
The absorption of NO by Fe~ⅡEDTA was developed in1980s. Compared with other methods, wet process of NO by means of Fe~ⅡEDTA is highly efficient. The main issue this method confronts is high cost which prevents it from wide use in industry. In present paper the absorption and this drawback were discussed. The regeneration was realized by reduction methods with it kinetic studies also studied. Finally the resource utilization and cost accounting was investigated for the purpose of establishing a whole schematic diagram.
Experiments showed that the regeneration mechanism of Fe~ⅡEDTA by Na_2SO_3 and by electrochemical reduction were not the same. When Na_2SO_3 was added into EDTA to absorb NO, Na_2SO_3 adjusted pH value of absorption solution toward weak alkaline and reduced the oxidized Fe~ⅡEDTA. In result the absorption easily ran. When there was SO_2 residual after FGD, SO_2 hydrolyzed and formed SO_3~(2-) which compensated the consumed Na_2SO_3. It was confirmed by cyclic voltammetry that the final reduction products formed from SO_3~(2-) were S_2O_6~(2-) and SO_4~(2-) when Na_2SO_3 was applied to reduce Fe~ⅡEDTA. Electrochemical reduction proved that Fe~ⅢEDTA reduction was a fast reversible process with one electron transferred on Pt electrode surface. Standard rate constant k~0 of Fe~ⅢEDTA reduction at 298 K was found to be 0.0263 cm s~(-1). According to the calculated diffusion activation energy of 24.93 kJ mol~(-1), apparent activation energy of 25.74 kJ mol~(-1) and the electron transfer activation energy of 16.56 kJ mol~(-1), the rate determining step for Fe~ⅢEDTA reduction was diffusion step.
Recycle of EDTA and resource reuse include two steps. First, NaOH and H_2SO_4 were employed to recycle EDTA. The results showed that the recycle efficiency was 67%. And then ammonia was added into the recycled solution to make fertilizers.As a consequence, (NH_4)_2EDTA, NH_4NO_3 and (NH_4)_2SO_4 were produced. This method provided a new pathway to realizing wastes water resource reuse and harmless utilization of absorbents, meanwhile, promoting the industrialization of wet absorption of NO by Fe~ⅡEDTA.
研究表明，还原剂还原吸收液和电解再生吸收液具有不同的机理。Fe~ⅡEDTA和Na_2SO_3共同吸收NO时，Na_2SO_3调节吸收液的pH值到弱碱性，使吸收更易进行；同时，SO_3~(2-)可将Fe~ⅢEDTA还原为Fe~ⅡEDTA。循环伏安法研究表明，采用Na_2SO_3还原再生吸收液Fe~ⅡEDTA时，SO_3~(2-)主要转化为S_2O_6~(2-)和SO_4~(2-)。电解法还原再生Fe~ⅡEDTA研究发现，Fe~ⅢEDTA的电化学还原过程是一个快速化学反应过程，伴随着一个电子转移。采用准稳态极化曲线和恒电位阶跃测试得到298K时Fe~ⅢEDTA在铂电极表面还原的标准速率常数为k~0为0.0263 cm s~(-1)；扩散活化能为24.93 KJ mol~(-1)，表观活化能为25.74 kJ mol~(-1)，电子转移活化能为16.56kJmol~(-1)；整个还原过程由扩散过程控制。理论计算说明加快传质过程能极大地提高电化学还原的整体速率，对Fe~ⅢEDTA电化学再生有重要的工程指导意义。
研究络合脱硝后的废水资源化利用包括两个步骤。第一步，采用NaOH和H_2SO_4回收Fe~ⅡEDTA脱硝后废水中的EDTA，实验表明EDTA回收率达到67％；第二步，回收EDTA后的废液中加入氨水，可以生成铁氨肥、硝酸氨和硫酸氨等复合肥，实现脱硝废水的资源化利用。
本研究可为湿法络合脱硝吸收液的再生和资源化提供有益的探索，推进了湿法络合脱硝技术的工程化应用。
The absorption of NO by Fe~ⅡEDTA was developed in1980s. Compared with other methods, wet process of NO by means of Fe~ⅡEDTA is highly efficient. The main issue this method confronts is high cost which prevents it from wide use in industry. In present paper the absorption and this drawback were discussed. The regeneration was realized by reduction methods with it kinetic studies also studied. Finally the resource utilization and cost accounting was investigated for the purpose of establishing a whole schematic diagram.
Experiments showed that the regeneration mechanism of Fe~ⅡEDTA by Na_2SO_3 and by electrochemical reduction were not the same. When Na_2SO_3 was added into EDTA to absorb NO, Na_2SO_3 adjusted pH value of absorption solution toward weak alkaline and reduced the oxidized Fe~ⅡEDTA. In result the absorption easily ran. When there was SO_2 residual after FGD, SO_2 hydrolyzed and formed SO_3~(2-) which compensated the consumed Na_2SO_3. It was confirmed by cyclic voltammetry that the final reduction products formed from SO_3~(2-) were S_2O_6~(2-) and SO_4~(2-) when Na_2SO_3 was applied to reduce Fe~ⅡEDTA. Electrochemical reduction proved that Fe~ⅢEDTA reduction was a fast reversible process with one electron transferred on Pt electrode surface. Standard rate constant k~0 of Fe~ⅢEDTA reduction at 298 K was found to be 0.0263 cm s~(-1). According to the calculated diffusion activation energy of 24.93 kJ mol~(-1), apparent activation energy of 25.74 kJ mol~(-1) and the electron transfer activation energy of 16.56 kJ mol~(-1), the rate determining step for Fe~ⅢEDTA reduction was diffusion step.
Recycle of EDTA and resource reuse include two steps. First, NaOH and H_2SO_4 were employed to recycle EDTA. The results showed that the recycle efficiency was 67%. And then ammonia was added into the recycled solution to make fertilizers.As a consequence, (NH_4)_2EDTA, NH_4NO_3 and (NH_4)_2SO_4 were produced. This method provided a new pathway to realizing wastes water resource reuse and harmless utilization of absorbents, meanwhile, promoting the industrialization of wet absorption of NO by Fe~ⅡEDTA.
引文
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