本文選題：濕法脫硫 + CaSO_3　； 參考：《華北電力大學(xué)(北京)》2017年碩士論文

【摘要】：為滿足日益嚴(yán)苛的排放標(biāo)準(zhǔn),需要進(jìn)一步研究燃煤電廠SO_2脫除技術(shù)。濕法脫硫技術(shù)應(yīng)用廣泛,但仍存在一些問題。其中石灰石石膏法的中間產(chǎn)物亞硫酸鈣(CaSO_3)氧化不足,則不能形成足夠的石膏晶種使石膏晶體迅速增長,將造成石膏脫水困難,是導(dǎo)致設(shè)備結(jié)垢的原因之一,因此需要選取合適的添加劑促進(jìn)氧化。本論文采用鼓泡床反應(yīng)裝置,鼓泡反應(yīng)器容積為2.4L。主要研究了成品CaSO_3的氧化過程、SO_2脫除過程中間產(chǎn)物CaSO_3的氧化特性。其中CaSO_3的氧化實驗分別在無添加劑、加入不同種類添加劑條件下進(jìn)行;SO_2脫除過程中CaSO_3氧化率的實驗則模擬石灰石-石膏法脫硫過程,研究SO_2吸收過程中間產(chǎn)物CaSO_3的氧化率等問題。在CaSO_3的氧化實驗中,探究了CaSO_3的宏觀反應(yīng)特性,得知亞硫酸根(SO_3~(2-))氧化速率對O_2濃度的反應(yīng)級數(shù)為0.76;初始pH值越低則反應(yīng)速率越快。加入適當(dāng)添加劑能明顯加快反應(yīng)進(jìn)程,二價錳鹽、三價鐵鹽、二價鎂鹽、二價銅鹽和不同類型鍋爐飛灰都能加快CaSO_3的氧化速率,其中二價錳鹽促進(jìn)氧化效果最好,適當(dāng)?shù)臐舛认驴梢詫⒀趸俾侍岣咧炼蹲笥?三價鐵鹽促進(jìn)效果明顯,而二價鐵鹽在一定濃度時會對氧化過程起抑制作用。加入某些物質(zhì)會對氧化過程起阻礙作用,阻礙氧化的效果硬脂酸鈉腐植酸鈉硫代硫酸鈉,其中腐植酸鈉阻止CaSO_3氧化的效果約為硬脂酸鈉的6倍;Na_2S2O_3對CaSO_3有很強的阻止氧化效果,當(dāng)加入質(zhì)量為0.3g時,氧化速率降為原來的3%左右。不同電廠飛灰對氧化過程都有促進(jìn)作用,但效果相差不大,用XRF(X射線熒光光譜分析)測得其中物質(zhì)成分,但催化機理需進(jìn)一步研究。在模擬石灰石-石膏法脫硫?qū)嶒炛?探究了O_2濃度、MnCl2和Na2S2O_3對脫硫中間產(chǎn)物CaSO_3氧化率的影響。在該實驗裝置中,O_2濃度大于5%時,脫硫生成的CaSO_3能被全部氧化,O_2濃度為3%時,反應(yīng)前100min的氧化率約為84.9%;加入MnCl_2可提高CaSO_4在脫硫產(chǎn)物中的比率,加入量大于0.06g/L時,前100min脫硫產(chǎn)生的CaSO_3可被全部氧化;加入量大于0.04g/L時,前100min CaSO_3氧化率約為95.2%。Na_2S2O_3加入濃度為0.05g/L時,反應(yīng)前100min生成的CaSO_3被氧化的比率約為44.2%,濃度增大為0.15g/L時,反應(yīng)前100min生成的CaSO_3氧化率降至11.2%,即石灰石漿液吸收的SO_2中接近90%都以CaSO_3的形式存在,極大的阻礙了CaSO_3的氧化過程。
[Abstract]:In order to meet the increasingly stringent emission standards, further research is needed on SOS _ 2 removal technology in coal-fired power plants. Wet desulfurization technology is widely used, but there are still some problems. If calcium sulfite, the intermediate product of limestone gypsum method, is not oxidized enough, the gypsum crystal can not be formed enough to make the gypsum crystal grow rapidly, which will lead to the difficulty of dehydration of gypsum, which is one of the reasons leading to the scaling of the equipment. Therefore, it is necessary to select suitable additives to promote oxidation. In this paper, a bubbling bed reactor was used and the volume of the bubbling reactor was 2.4 L. The oxidation characteristics of caso _ 3, an intermediate product in the process of so _ 2 removal, were studied in this paper. The oxidation experiments of CaSO3 were carried out under the condition of adding different kinds of additives, and the oxidation rate of CaSO3 was simulated by limestone gypsum desulphurization process. The oxidation rate of CaSOS _ 3, an intermediate product of so _ 2 absorption process, was studied. In the oxidation experiment of CaSO3, the macroscopic reaction characteristics of CaSO3 were investigated. It was found that the reaction order of the oxidation rate on the concentration of O _ 2 was 0.76; the lower the initial pH value, the faster the reaction rate. The addition of appropriate additives can obviously speed up the reaction process. The oxidation rate of CaSO3 can be accelerated by the addition of manganese divalent salt, ferric salt, magnesium salt, copper salt and fly ash of different types of boilers, among which the oxidation rate of CaSO3 is the best. The oxidation rate can be increased to about two times at proper concentration, and the effect of trivalent iron salt is obvious, while the divalent iron salt can inhibit the oxidation process at a certain concentration. The effect of sodium stearate sodium humate sodium thiosulfate on the oxidation of CaSO3 is about six times that of sodium stearate, and the effect of sodium humate on preventing the oxidation of CaSO3 is about six times that of sodium stearate, and the effect of sodium stearate sodium humic acid sodium humate sodium thiosulfate on the oxidation of CaSO3 is about six times that of sodium stearate. When the mass was 0.3 g, the oxidation rate decreased to about 3%. The fly ash from different power plants can promote the oxidation process, but the effect is not different. The composition of the fly ash is determined by XRF X ray fluorescence spectrometry, but the catalytic mechanism needs further study. In the simulated Limestone-gypsum desulfurization experiment, the effects of the concentration of O _ 2, MnCl _ 2 and Na _ 2S _ 2O _ 3 on the oxidation rate of CaSO3, an intermediate product of desulfurization, were investigated. In this experimental device, when the concentration of O _ 2O _ 2 is greater than 5 and the number of CaSO3 produced by desulphurization is 3, the oxidation rate of 100min before reaction is about 84.9.The addition of MnCl _ 2 can increase the ratio of CaSO4 in desulphurized products, when the amount of CaSO3 added is more than 0.06g / L, CaSO3 produced by pre-100min desulphurization can be completely oxidized; when the amount of CaSO3 added is greater than 0.04g / L, the oxidation rate of 100min CaSO3 is about 95.2g / L. When the concentration is 0.05g / L, the ratio of CaSO3 produced by 100min before reaction is about 44.2 g / L, and when the concentration increases to 0.15g / L, The oxidation rate of CaSO3 produced by 100min before the reaction decreases to 11.2%, that is, nearly 90% of the SO2 absorbed by limestone slurry exists in the form of CaSO3, which greatly hinders the oxidation process of CaSO3.
【學(xué)位授予單位】：華北電力大學(xué)(北京)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ132.32

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