高含硫廢水受控氧化及單質(zhì)硫的形成特性研究
發(fā)布時(shí)間：2018-09-05 07:46
【摘要】：含硫廢水不僅會(huì)對(duì)設(shè)備造成腐蝕,還會(huì)對(duì)水處理工藝系統(tǒng)造成影響,同時(shí)逸出的H2S還會(huì)對(duì)人體造成傷害。而針對(duì)高濃度的含硫廢水,更是需要找到一種有效的處理方法,在減輕污染的同時(shí)實(shí)現(xiàn)污染物質(zhì)的資源化回收利用。論文以模擬的含硫廢水為研究對(duì)象,以S2-的去除率和單質(zhì)硫的收率為指標(biāo),對(duì)Na2S2O5、Na2SO3和H2O2的脫硫效果進(jìn)行評(píng)價(jià),篩選出最佳氧化劑,考察了硫化物氧化動(dòng)力學(xué)的影響因素,并在此基礎(chǔ)上采用響應(yīng)曲面法對(duì)其氧化反應(yīng)條件進(jìn)行優(yōu)化。在最佳氧化劑的優(yōu)化條件下,采用改變氧化劑的投加方式、控制反應(yīng)體系的氧化還原電位(ORP)和反應(yīng)分離耦合等手段強(qiáng)化單質(zhì)硫的轉(zhuǎn)化。利用X射線衍射儀(XRD)、掃描電鏡(SEM)和粒度分析儀對(duì)體系中固相產(chǎn)物的結(jié)構(gòu)、形態(tài)特征進(jìn)行了表征。結(jié)果表明： (1)在Na2S2O5投加量為9g/L,初始pH值為6,反應(yīng)時(shí)間為30min的最佳條件下,S2-的去除率和單質(zhì)硫的收率分別為95.16%和42.32%。在Na2SO3投加量為5g/L,初始pH值為5,反應(yīng)時(shí)間為20min的最佳條件下,S2-的去除率和單質(zhì)硫的收率分別為78.71%和26.68%。在H2O2投加量為10mL/L,初始pH值為6,反應(yīng)時(shí)間為14min的最佳條件下,S2-的去除率和單質(zhì)硫的收率分別為95.68%和60.78%。H2O2是脫硫效果最好的氧化劑。H2O2氧化硫化物遵循表觀二級(jí)反應(yīng)動(dòng)力學(xué),表觀反應(yīng)速率常數(shù)為K=1.0669L.g-1.min-1。其反應(yīng)速率常數(shù)受H2O2的投加量、反應(yīng)溫度和反應(yīng)初始pH的影響。氧化劑投加量增加,反應(yīng)速率常數(shù)增大；溫度升高,反應(yīng)速率常數(shù)增大；初始pH增大,反應(yīng)速率常數(shù)減小。 (2)采用響應(yīng)曲面法對(duì)H2O2氧化含硫廢水的反應(yīng)條件進(jìn)行優(yōu)化,優(yōu)化后的反應(yīng)條件為：初始pH為6.5,投加量為9mL/L,反應(yīng)時(shí)間為15min。此條件下得出的單質(zhì)硫的收率為65.85%,相對(duì)于優(yōu)化前提高了5.07%。 (3)在H202氧化含硫廢水的過程中,相對(duì)于一次性投加,H2O2的分次投加使單質(zhì)硫的收率降低了8.25～26.05%,與預(yù)期的效果相反；采用反應(yīng)分離耦合的方式強(qiáng)化單質(zhì)硫的轉(zhuǎn)化,在分離因數(shù)為1082的條件下,單質(zhì)硫的收率達(dá)到了74.98%,相對(duì)于未強(qiáng)化前提高了9.13%；控制體系中的ORP值強(qiáng)化單質(zhì)硫的轉(zhuǎn)化具有最好的效果,當(dāng)ORP值控制在(30±5)mV時(shí),單質(zhì)硫的收率達(dá)到了76.35%,相對(duì)于未控制前提高了10.50%。 (4)XRD分析表明,H2O2氧化含硫廢水所得的固相產(chǎn)物為室溫下結(jié)構(gòu)穩(wěn)定的S8。SEM及粒度分析儀對(duì)液相中的單質(zhì)硫進(jìn)行分析表明,體系中的單質(zhì)硫顆粒逐漸增大,由納米硫顆粒組成的層狀逐漸變成團(tuán)聚卷積在一起的微米級(jí)顆粒狀；增大的機(jī)理為晶體的生長和納米顆粒的團(tuán)聚,并由此推斷單質(zhì)硫的S8結(jié)構(gòu)的形成機(jī)制是以Sx2-為中間產(chǎn)物。
[Abstract]:The sulfur-containing wastewater will not only corrode the equipment, but also affect the water treatment process system. At the same time, the H _ 2S released from the wastewater will also cause harm to the human body. It is necessary to find an effective treatment method for high concentration sulfur-containing wastewater, which can reduce the pollution and realize the recycling of pollutants. In this paper, the desulfurization effect of Na2S2O5,Na2SO3 and H2O2 was evaluated with the removal rate of S2- and the yield of elemental sulfur as the index, and the optimum oxidant was screened out. The factors influencing the oxidation kinetics of sulfides were investigated. On this basis, the reaction conditions were optimized by response surface method. Under the optimum conditions of oxidant, the conversion of elemental sulfur was enhanced by changing the way of adding oxidant, controlling the redox potential (ORP) of the reaction system and the coupling of reaction separation and so on. The structure and morphology of solid products in the system were characterized by (XRD), scanning electron microscope (SEM) and particle size analyzer. The results showed that: (1) under the optimum conditions of Na2S2O5 dosage of 9 g / L, initial pH value of 6 and reaction time of 30min, the removal rate of S2- and the yield of elemental sulfur were 95.16% and 42.32%, respectively. Under the optimum conditions of Na2SO3 dosage of 5 g / L, initial pH value of 5 and reaction time of 20min, the removal rate of S2- and the yield of elemental sulfur were 78.71% and 26.68%, respectively. When the dosage of H2O2 is 10 mL / L, the initial pH value is 6, and the reaction time is 14min, the removal rate of S2- and the yield of elemental sulfur are 95.68% and 95.68%, respectively. The oxidant, H2O2, which is the best oxidant for desulfurization, follows the apparent second-order reaction kinetics. The apparent reaction rate constant is KN 1.0669L 路g-1.min-1. The reaction rate constant is affected by the dosage of H2O2, the reaction temperature and the initial pH. With the increase of oxidant dosage, the reaction rate constant increases; the temperature increases, the reaction rate constant increases; the initial pH increases and the reaction rate constant decreases. (2) the reaction conditions for H2O2 oxidation of sulfur-containing wastewater are optimized by response surface method. The optimized reaction conditions are as follows: the initial pH is 6.5, the dosage is 9 mL / L, and the reaction time is 15 min. Under these conditions, the yield of sulfur is 65.85, which is 5.07% higher than that before optimization. (3) in the process of oxidation of sulfur-containing wastewater by H202, Compared with the one-off addition of H _ 2O _ 2, the yield of elemental sulfur decreased by 8.25% 26.05, which was contrary to the expected effect, and the reaction separation coupling method was used to strengthen the conversion of elemental sulfur under the condition of separation factor of 1082. The yield of elemental sulfur reached 74.98%, which was 9.13% higher than that before strengthening, the ORP value of control system enhanced the conversion of elemental sulfur had the best effect, when the ORP value was controlled at (30 鹵5) mV, The yield of elemental sulfur reached 76.35, which was 10.50% higher than that before control. (4) XRD analysis showed that the solid phase product of H _ 2O _ 2 oxidation of sulfur-containing wastewater was S8.SEM with stable structure at room temperature and the analysis of elemental sulfur in liquid phase by particle size analyzer. The elemental sulfur particles in the system gradually increased, and the layers composed of nano-sulfur particles gradually became micron-sized particles of agglomeration and convolution, and the mechanism of the increase was the growth of crystals and the agglomeration of nanocrystalline particles. It is inferred that the formation mechanism of S _ 8 structure of elemental sulfur is Sx2- as the intermediate product.
【學(xué)位授予單位】：西南石油大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X741
本文編號(hào)：2223638
[Abstract]:The sulfur-containing wastewater will not only corrode the equipment, but also affect the water treatment process system. At the same time, the H _ 2S released from the wastewater will also cause harm to the human body. It is necessary to find an effective treatment method for high concentration sulfur-containing wastewater, which can reduce the pollution and realize the recycling of pollutants. In this paper, the desulfurization effect of Na2S2O5,Na2SO3 and H2O2 was evaluated with the removal rate of S2- and the yield of elemental sulfur as the index, and the optimum oxidant was screened out. The factors influencing the oxidation kinetics of sulfides were investigated. On this basis, the reaction conditions were optimized by response surface method. Under the optimum conditions of oxidant, the conversion of elemental sulfur was enhanced by changing the way of adding oxidant, controlling the redox potential (ORP) of the reaction system and the coupling of reaction separation and so on. The structure and morphology of solid products in the system were characterized by (XRD), scanning electron microscope (SEM) and particle size analyzer. The results showed that: (1) under the optimum conditions of Na2S2O5 dosage of 9 g / L, initial pH value of 6 and reaction time of 30min, the removal rate of S2- and the yield of elemental sulfur were 95.16% and 42.32%, respectively. Under the optimum conditions of Na2SO3 dosage of 5 g / L, initial pH value of 5 and reaction time of 20min, the removal rate of S2- and the yield of elemental sulfur were 78.71% and 26.68%, respectively. When the dosage of H2O2 is 10 mL / L, the initial pH value is 6, and the reaction time is 14min, the removal rate of S2- and the yield of elemental sulfur are 95.68% and 95.68%, respectively. The oxidant, H2O2, which is the best oxidant for desulfurization, follows the apparent second-order reaction kinetics. The apparent reaction rate constant is KN 1.0669L 路g-1.min-1. The reaction rate constant is affected by the dosage of H2O2, the reaction temperature and the initial pH. With the increase of oxidant dosage, the reaction rate constant increases; the temperature increases, the reaction rate constant increases; the initial pH increases and the reaction rate constant decreases. (2) the reaction conditions for H2O2 oxidation of sulfur-containing wastewater are optimized by response surface method. The optimized reaction conditions are as follows: the initial pH is 6.5, the dosage is 9 mL / L, and the reaction time is 15 min. Under these conditions, the yield of sulfur is 65.85, which is 5.07% higher than that before optimization. (3) in the process of oxidation of sulfur-containing wastewater by H202, Compared with the one-off addition of H _ 2O _ 2, the yield of elemental sulfur decreased by 8.25% 26.05, which was contrary to the expected effect, and the reaction separation coupling method was used to strengthen the conversion of elemental sulfur under the condition of separation factor of 1082. The yield of elemental sulfur reached 74.98%, which was 9.13% higher than that before strengthening, the ORP value of control system enhanced the conversion of elemental sulfur had the best effect, when the ORP value was controlled at (30 鹵5) mV, The yield of elemental sulfur reached 76.35, which was 10.50% higher than that before control. (4) XRD analysis showed that the solid phase product of H _ 2O _ 2 oxidation of sulfur-containing wastewater was S8.SEM with stable structure at room temperature and the analysis of elemental sulfur in liquid phase by particle size analyzer. The elemental sulfur particles in the system gradually increased, and the layers composed of nano-sulfur particles gradually became micron-sized particles of agglomeration and convolution, and the mechanism of the increase was the growth of crystals and the agglomeration of nanocrystalline particles. It is inferred that the formation mechanism of S _ 8 structure of elemental sulfur is Sx2- as the intermediate product.
【學(xué)位授予單位】：西南石油大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X741
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