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溴胺酸的生物降解及降解途径的研究

Study on Biodegradation and Pathway of 1-Amino-4-bromoanthraquinone-2-sulfonic Sodium

【作者】 黄丽萍

【导师】 杨凤林; 周集体;

【作者基本信息】 大连理工大学 , 环境工程, 2001, 博士

【摘要】 溴胺酸是一种生产活性染料和酸性艳蓝的蒽醌型结构中间体,在其合成和制备过程中产生大量的废水。这类废水具有颜色深、浓度大、化学好氧量高、不易降解等特点,严重污染了环境。本文第一章通过有关文献的综述,阐述了蒽醌类中间体及染料对环境的污染,重点介绍了生物法处理蒽醌类中间体及染料废水的研究进展,从而明确了本文关于高效降解菌处理蒽醌染料中间体的研究在理论和实际中的意义。 本文利用从活性污泥中筛选的高效降解菌HP3,考察了其降解溴胺酸的动力学特性;通过对降解中间产物和最终产物的分析与测定,得出了菌体作用下溴胺酸可能的降解途径;同时,对菌体胞外酶特性进行了研究。本论文主要得出以下结论: 1、菌株HP3是一高效降解溴胺酸的菌株,经鉴定为动胶菌属;在最佳降解条件下,溴胺酸浓度在200~1200mg/L时,其降解遵从负指数方程,溴胺酸浓度大于1200mg/L时,降解受到显著的抑制;温度是影响菌体生长及降解溴胺酸的最显著因素,建立了菌体比生长速率-温度和溴胺酸降解率-温度曲线方程。 2、外加不同金属化合物、不同浓度NaCl、不同碳源或氮源对菌体降解溴胺酸有不同程度的促进或抑制作用;葡萄糖和硫酸铵的同时加入对溴胺酸的降解有协同作用,对葡萄糖和硫酸铵的加入量进行了优化。 3、动胶菌HP3作用下溴胺酸可能的降解途径为蒽醌环开裂生成中间产物邻苯二甲酸,邻苯二甲酸被进一步降解;溴胺酸降解后的最终产物为2-氨基-3-羟基-5-溴苯磺酸钠和2,3-二羟基-5-溴苯磺酸钠。 4、动胶菌HP3分泌的胞外组成酶可使溴胺酸脱色,溴胺酸降解中间产物邻苯二甲酸的降解场所在胞内;与邻苯二甲酸的降解相比,溴胺酸的脱色是反应的控制步骤。 of 5、动胶菌HP3不能降解活性艳蓝KN.R、弱酸性绿GS及毛用活性蓝HW.R等葱醒型染料,且染料的存在对菌体降解淇胺酸有不同程度的抑制作用:动胶菌*P3可以降解卜氨基葱酮毛-磺酸钠、1,4-二羟基恳醒上-磺酸钠。l人5,8-四羟基葛酮、葱酮及苯酚、邻苯二酚、苯胺、邻苯二甲酸等苯系化合物,而不降解苯磺酸钠、对氨基苯磺酸钠;在溪胺酸、苯酚、邻苯二酚、苯胺、邻苯二甲酸中,苯胺是动胶菌HP3的天然底物。 总之,通过本论文的工作,筛选并找到了一株高效降解澳胺酸的菌株,对其降解滨胺酸的特性及降解途径进行了深入的研究,不仅在理论上有助于诠释动胶菌与溪胺酸反应的实质,而且为该菌株处理溪胺酸等葱酿类染料中间体的实际运用中操作参数的设计和选择提供依据。

【Abstract】 Bromamine acid (l-Amino-4-bromoanthraquinone-2-sulfonic sodium) called ABAS for short is an important intermediate in production of reactive dyes and acid dyes. ABAS manufacturing wastewater exhibits very high COD and color. In Chapter One, different treatments of ABAS wastewater, especially biological treatment have been reviewed. Therefore, the significance and background of this study in the paper has been showed.HP3 screened from active sludge could efficiently degrade ABAS. The dynamic characters of ABAS degraded by HP3 were studied. By analysis of intermediates and products of ABAS degraded by HP3, the possible pathway of ABAS degradation was discussed. The characters of extracellular enzymes produced by HP3 were also examined in this paper. The main conclusions are drawn as follows:1. HP3 identified as Zoogloea sp. is an effectively strain. Under the optimal degradation condition and ABAS concentration of 200~1200mg/L, the ABAS degradation followed negative exponential model. With the ABAS concentration increasing, the ABAS degradation was greatly regressed. Temperature was the most important factor influencing ABAS degradation. The functions of specific growth rate and temperature, degradation rate of ABAS and temperature were constructed respectively.2. Addition of metal compounds, NaCl, different carbon and nitrogen sources could enhance or inhibit the degradation rate of ABAS. Glucose could cooperate with (NH4)2SO4 to enhance the degradation rate of ABAS. The optimal addition of glucose and (NH4)2SO4 were discussed in this paper.3. The possible pathway of ABAS degraded by Zoogloea HP3 was that ABAS was first cleaved to produce o-phthalic acid and products. The former wasfurther degraded and the composites of the latter were 2-amino-3-hydroxyl-5-bromobenzenic sulfonic sodium and 2,3-dihydroxyl-5-bromobenzenic sulfonic sodium.4. ABAS could be decolored by extracellular composite enzymes secreted by Zoogloea HP3. The degradation place of o-pathalic acid was in-cell. Compared with the degradation of o-pathalic acid, the decoloring of ABAS controlled the degradation of ABAS.5. C. I. Reactive blue KN-R, Alizarin brilliant green G and Hostlam blue R could not be degraded by Zoogloea HP3. Furthermore, ABAS degradation was regressed under the exisitence of the above dyes. l-Aminoanthraquinone-2-sulfonic sodium, 1,4-dihydroxylanthraquinone-2 -sulfonic sodium, 1,4,5,8-tetrahydroxylanthraquinone, anthraquinone, aniline, phenol, catechol and o-phthalic acid could be degraded by Zoogloea HP3. Aniline was the most degradable substrate among ABAS, aniline, phenol, catechol and o-phthalic acid. However, benzenesulfonic sodium and p-amino benzenesulfonic sodium were not?degraded by it.Overall, this paper is proved to be meaningful in both theoretical explanation and practical application of biodegradation of anthraquinone resembles .

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