溴氨酸的零价铁法降解实验研究
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摘要
蒽醌染料废水是染料行业较难降解的废水之一，目前相对其它染料废水研究得较少。溴氨酸广泛应用于蒽醌染料的合成，并存在于排放的废水中，本文采用零价铁法固定床和流化床对溴氨酸溶液进行脱色实验，研究了溴氨酸的零价铁法处理脱色效率和操作运行条件，并对溴氨酸的脱色机理和降解反应动力学进行了研究。
实验表明，零价铁法固定床和流化床处理溴氨酸溶液最终出水的脱色效率均达到97％以上，其中流化床脱色反应速率高于固定床。在实验条件下，固定床最佳运行条件分别为pH值取3～5之间，铁炭比例10左右，最佳进水流量1500 ml／min；流化床进水pH值取3～5较好，在气提气流量小于临界悬浮气流量时，色度去除速率随气提流量的增大而增大，随着铁粉投加量的增加，所需的临界悬浮气流量增大。
填料板结实验研究表明，固定床填料板结是由于零价铁表面氧化和FeO(OH)、Fe_2O_3·H_2O等不同形态的铁锈生成物在填料表面的共沉积作用造成的。固定床间歇运行较连续运行容易板结，填料脱水状态下易发生板结。采用反冲洗和定期活化可对填料表面活性较大程度恢复，填料经长期运行，活化后处理效率低于70％时，建议更换填料。流化床不存在填料板结问题，但存在填料流失现象，应严格控制空气流量。
溴氨酸的脱色为一级反应，其反应动力学可用一级指数衰减模型C_t=ae~(-kt)+b很好的拟合。实验结果表明，溴氨酸的脱色机理主要是在零价铁电化学腐蚀反应基础上，通过新生成的[H]、Fe~(2+)等物质的还原作用，溴氨酸分子发色基团被破坏，可见光范围的最大吸收波长向短波方向偏移，色度明显降低。溴氨酸反应产物在电化学反应产物Fe(OH)_2和Fe(OH)_3的吸附絮凝作用下，从溶液中沉淀脱除。
In this paper, decoloration experiment of 1-amino-4-bromo-anthraquinone-2-sulfonic acid (BAK) was studied in immobile bed and fluidized bed by zero-valent iron. The efficiency and operation condition of zero-valent iron method was studied. Degradation kinetics and decolorization mechanisms of BAK were also studied.
The result of experiment indicated that the decolorization efficency of BAK in immobile bed and fluidized bed both reached above 97%, and the react velocity of fluidized bed is higher compared with immobile bed. On experinment conditions, the best run conditon for immobile bed was that pH is about 3-5 and scale of iron and coke is about 10, the best inflow flux of BAK solution is 1500 ml/min, the best pH is about 3 in fluidized bed. When gas inflow flux was less than critical suspend gas inflow flux, the efficiency of decolorization was higher with increasing gas inflow flux, the Qc increased when more iron powder was put into fluidized bed.
Agglomeration expeiment for filling-up indicated that immobile bed filling harden was worked by the sediment of differ configuration iron rust resultants : FeO(OH), Fe2O3 H2O and oxidion on the iron surpace. Immobile bed was easier hardened when intermissionrun compared to continuous run. When the filling was dehydrated, the immobile bed was much easier hardened. The activition of filling surpace can be resumed by bounce-back wash and scheduled time activation. When the disposal effiency was under 70% after activation, the filling should be insteaded. The filling harden didn't happen in iron powder fluidized bed, but the phenomenon of filling loss probably occur, so the gas flux should be strictly controlled.
The decolorization of BAK accord with first order reaction .Its reaction kinetics was well accorded by first order exponential decay model Ct= ae-kt+b. The experiment result indicated that decolorization kinetics of BAK was mostly that based on zero valent iron electrochemistry corruption principle , and the BAK molecule group for chromogenic radicle was destroyed under the function of new produced [H], Fe2+, OH and etc.The most absorb wavelengh excursed to shortwave in visible light extent and the chroma of BAK was distinctly descended. The reaction production was settled and pulled off by adsorption and flocculation of Fe(OH)a and Fe(OH)3, which were produced by electrode reaction.
实验表明，零价铁法固定床和流化床处理溴氨酸溶液最终出水的脱色效率均达到97％以上，其中流化床脱色反应速率高于固定床。在实验条件下，固定床最佳运行条件分别为pH值取3～5之间，铁炭比例10左右，最佳进水流量1500 ml／min；流化床进水pH值取3～5较好，在气提气流量小于临界悬浮气流量时，色度去除速率随气提流量的增大而增大，随着铁粉投加量的增加，所需的临界悬浮气流量增大。
填料板结实验研究表明，固定床填料板结是由于零价铁表面氧化和FeO(OH)、Fe_2O_3·H_2O等不同形态的铁锈生成物在填料表面的共沉积作用造成的。固定床间歇运行较连续运行容易板结，填料脱水状态下易发生板结。采用反冲洗和定期活化可对填料表面活性较大程度恢复，填料经长期运行，活化后处理效率低于70％时，建议更换填料。流化床不存在填料板结问题，但存在填料流失现象，应严格控制空气流量。
溴氨酸的脱色为一级反应，其反应动力学可用一级指数衰减模型C_t=ae~(-kt)+b很好的拟合。实验结果表明，溴氨酸的脱色机理主要是在零价铁电化学腐蚀反应基础上，通过新生成的[H]、Fe~(2+)等物质的还原作用，溴氨酸分子发色基团被破坏，可见光范围的最大吸收波长向短波方向偏移，色度明显降低。溴氨酸反应产物在电化学反应产物Fe(OH)_2和Fe(OH)_3的吸附絮凝作用下，从溶液中沉淀脱除。
In this paper, decoloration experiment of 1-amino-4-bromo-anthraquinone-2-sulfonic acid (BAK) was studied in immobile bed and fluidized bed by zero-valent iron. The efficiency and operation condition of zero-valent iron method was studied. Degradation kinetics and decolorization mechanisms of BAK were also studied.
The result of experiment indicated that the decolorization efficency of BAK in immobile bed and fluidized bed both reached above 97%, and the react velocity of fluidized bed is higher compared with immobile bed. On experinment conditions, the best run conditon for immobile bed was that pH is about 3-5 and scale of iron and coke is about 10, the best inflow flux of BAK solution is 1500 ml/min, the best pH is about 3 in fluidized bed. When gas inflow flux was less than critical suspend gas inflow flux, the efficiency of decolorization was higher with increasing gas inflow flux, the Qc increased when more iron powder was put into fluidized bed.
Agglomeration expeiment for filling-up indicated that immobile bed filling harden was worked by the sediment of differ configuration iron rust resultants : FeO(OH), Fe2O3 H2O and oxidion on the iron surpace. Immobile bed was easier hardened when intermissionrun compared to continuous run. When the filling was dehydrated, the immobile bed was much easier hardened. The activition of filling surpace can be resumed by bounce-back wash and scheduled time activation. When the disposal effiency was under 70% after activation, the filling should be insteaded. The filling harden didn't happen in iron powder fluidized bed, but the phenomenon of filling loss probably occur, so the gas flux should be strictly controlled.
The decolorization of BAK accord with first order reaction .Its reaction kinetics was well accorded by first order exponential decay model Ct= ae-kt+b. The experiment result indicated that decolorization kinetics of BAK was mostly that based on zero valent iron electrochemistry corruption principle , and the BAK molecule group for chromogenic radicle was destroyed under the function of new produced [H], Fe2+, OH and etc.The most absorb wavelengh excursed to shortwave in visible light extent and the chroma of BAK was distinctly descended. The reaction production was settled and pulled off by adsorption and flocculation of Fe(OH)a and Fe(OH)3, which were produced by electrode reaction.
引文
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