不同形态硫组分的提取和测试技术及其在生物厌氧反应器中的应用

发布时间：2018-10-04 19:55

【摘要】：大气中以及水体中的硫的测试方法很多,但是对于厌氧环境中硫的转化仍然有许多不确定的因素(如硫化物、硫代硫酸盐、亚硫酸盐、硫酸盐及单质硫),导致其测定准确性、可靠性收到一定的限制。本文围绕各类硫组分(包括硫化物、硫代硫酸盐、亚硫酸盐、硫酸盐及单质硫等)的存在形态进行分析及定量测试。我们在借用前人检测方法的同时,独立设计了多种检测方法(S~0,SO_3~(2-)和S_2O_3~(2-)),从而总结出多种不同形态硫的提取及测试方法利用萃取单质硫的方法,通过高效液相色谱法来检测溶解态单质硫。利用DTNB作为衍生剂,对沉积物中硫代硫酸盐和亚硫酸盐进行分析测试。从而在酸盐还原菌(SRB)生物厌氧反应器中结合其他硫组分测试,分析了硫酸盐产物的整体变化趋势。得到以下结论:(1)在比较实验基础上选取丙酮作为萃取剂,经过10分钟超声萃取后,可稳定高效的萃取出单质硫。(2)新设计了一种硫单质检测方法,并计算出:单质硫的检出限为1.25×10~(-3)mg/L(2.5×10~(-3)μg/kg),检测下限为4.18×10~(-3)mg/L(8.36×10~(-3)μg/kg);利用高效液相色谱法对单质硫进行测试的加标回收率在100%-120%之间。厌氧发酵产物中硫化物浓度均在该检测范围内,因此可利用这种方法对发酵产物中单质硫进行检测。(3)硫代硫酸盐和亚硫酸盐测定方法研究中,选取DTNP作为衍生试剂,采用多步梯度淋洗的方式,选择合适的液相色谱操作条件可得到较好的测试效果。其中硫代硫酸盐的检出限为1.25×10~(-3)mg/L,亚硫酸盐的检出限为1.25×10~(-3)mg/L,测试的加标回收率均在100%左右。(4)在对SRB降解硫酸盐反应器中间产物的硫代硫酸根和亚硫酸根测试中,发现它们的浓度相对于硫酸根的还原量很小,平均只有0.16mg,几乎可以忽略不计。其各含硫组分含量顺序为S~(2-)S~0H_2SSO_3~(2-)/(S_2O_3~(2-))。大约70%的产物是以硫化物形式存在的,10%是以单质硫形式存在的,其余的硫是以SO_3~(2-),S_2O_3~(2-),S_2O_5~(2-),S_2O_4~(2-)等形式存在。掺入针铁矿的反应器中发现有17.2%的硫损失,主要以FeS,FeS_2及有机硫等形式损失。
[Abstract]:There are many methods for the measurement of sulfur in the atmosphere and in water, but there are still many uncertain factors (such as sulfides, thiosulfate, sulfite, sulfate and elemental sulfur) for sulfur conversion in anaerobic environment, which lead to the accuracy of the determination. Reliability is subject to certain limitations. In this paper, the species of various sulfur components (including sulfides, thiosulfate, sulfite, sulfate and elemental sulfur) are analyzed and quantitatively tested. At the same time, we have independently designed a variety of detection methods (S0 / so _ 3 ~ (2-) and S _ 2O _ 3 ~ (2-),) to sum up the extraction and test methods of different forms of sulfur by using the methods of extraction of elemental sulfur. The dissolved elemental sulfur was determined by high performance liquid chromatography (HPLC). The thiosulfate and sulfite in sediment were analyzed and tested by using DTNB as derivative. So the overall change trend of sulfate products was analyzed in (SRB) biofilm reactor combined with other sulfur components test. The following conclusions are obtained: (1) acetone is selected as extractant on the basis of comparative experiments, and after 10 minutes of ultrasonic extraction, simple sulfur can be extracted stably and efficiently. (2) A new method for the determination of sulfur is designed. The detection limit of elemental sulfur is 1.25 脳 10 ~ (-3) mg/L (2.5 脳 10 ~ (-3) 渭 g/kg) and the detection limit is 4.18 脳 10 ~ (-3) mg/L (8.36 脳 10 ~ (-3) 渭 g/kg). The concentration of sulfides in anaerobic fermentation products is all within the range of detection, so we can use this method to detect the elemental sulfur in fermentation products. (3) in the study of the determination method of thiosulfate and sulfite, DTNP is chosen as the derivative reagent. The method of multi-step gradient elution and the suitable operating conditions of liquid chromatography can obtain better test results. The detection limit of thiosulfate is 1.25 脳 10 ~ (-3) mg/L, sulfite, and the detection limit is 1.25 脳 10 ~ (-3) mg/L,. It is found that their concentration is very small relative to sulfate, with an average of only 0.16 mg, which is almost negligible. The order of the content of sulfur components is S ~ (2-) S ~ (2) H _ (2SO) _ 3 ~ (2-) / (S _ 2O _ 3 ~ (2-).) About 70% of the products are in the form of sulfide, 10% of the products are in the form of simple sulfur, and the rest of the sulfur is in the form of SO_3~ (2-) S2O3- (2-) S _ 2O _ 5- / S _ 2O-S _ 2O _ (4-), etc. In the reactor mixed with goethite, 17.2% of sulfur loss was found, mainly in the form of FeS,FeS_2 and organic sulfur.
【学位授予单位】：合肥工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X703;X830

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