本文選題：碳質(zhì)還原劑 + 工業(yè)硅　； 參考：《昆明理工大學(xué)》2017年博士論文

【摘要】：木炭因具有較高比電阻以及較高反應(yīng)活性,是工業(yè)硅冶煉生產(chǎn)常用的碳質(zhì)還原劑。木炭來(lái)源主要以砍伐大量的森林為代價(jià),對(duì)生態(tài)環(huán)境具有嚴(yán)重的破壞性。石油焦較高的固定碳和較低的灰分,理論上是一種理想碳質(zhì)還原劑,但因具有一定石墨化結(jié)構(gòu),尤其高溫條件下極易發(fā)生石墨化,將導(dǎo)致其化學(xué)反應(yīng)活性大幅度降低以及導(dǎo)電性大幅度提高,進(jìn)而不利于工業(yè)硅冶煉生產(chǎn)。另一方面,石油焦較高的硫含量不僅對(duì)工業(yè)硅冶煉過(guò)程有重要的影響,而且高硫石油焦使用過(guò)程中會(huì)產(chǎn)生大量對(duì)環(huán)境有害的SO_2氣體。因此,針對(duì)目前工業(yè)硅冶煉生產(chǎn)用碳質(zhì)還原劑存在高成本、低性能以及工業(yè)硅冶煉過(guò)程高能耗等問(wèn)題進(jìn)行研究具有非常重要的意義。具體研究?jī)?nèi)容主要包括以下幾點(diǎn):(1)結(jié)合TGA和XRD分析石油焦的反應(yīng)性能,研究石油焦添加劑(K_2CO_3)質(zhì)量比為0.5、0.8、1.0和1.5%在CO_2氣氛條件下的熱反應(yīng)行為,以及不同介質(zhì)中(蒸餾水和無(wú)水乙醇兩種具有代表性的介質(zhì))混合處理后對(duì)石油焦物理性能的影響,研究發(fā)現(xiàn)相同添加劑條件下,有機(jī)介質(zhì)對(duì)石油焦的反應(yīng)性能具有明顯的改善效果,反應(yīng)完成時(shí)間最大可以縮短67%。(2)真空強(qiáng)化高硫石油焦脫硫方法,從工藝角度系統(tǒng)研究了石油焦樣品顆粒:350~450μm,300~350μm,180~300μm,150~180μm,125~150μm和~125μm;料層厚度:0~30mm,30~60mm和60~90mm;溫度:600-1500℃(間隔為100℃);保溫時(shí)間:0.5h,1.0h,1.5h,2.0h,2.5h和3.0h;真空度:10~(-2) Pa,1Pa,和100 Pa對(duì)石油焦脫硫效果,對(duì)比發(fā)現(xiàn)同等條件下真空條件下脫硫效果比常壓下提高了約20%。結(jié)合XRD分析方法探討了真空條件下石油焦的脫硫機(jī)理是一個(gè)石油焦中有機(jī)硫即C-S鍵的斷裂和C-C鍵重新組合的一個(gè)過(guò)程。(3)通過(guò)TGA分析幾種典型生物質(zhì)原料反應(yīng)性能,并通過(guò)研究生物質(zhì)原料和石油焦混合物料比分別為:0:100,20:80,40:60,60:40,80:20和100:0的反應(yīng)特性,引用了催化指數(shù)對(duì)不同生物質(zhì)原料對(duì)石油焦協(xié)同反應(yīng)效果進(jìn)行了評(píng)估。研究結(jié)果顯示同種生物質(zhì)原料和石油焦不同質(zhì)量比混合反應(yīng),隨著生物質(zhì)原料的質(zhì)量比增加,混合物料化學(xué)活化能降低最大幅度達(dá)50%。通過(guò)理論計(jì)算值和實(shí)驗(yàn)值對(duì)比發(fā)現(xiàn)生物質(zhì)和石油焦混合反應(yīng)不僅僅是單獨(dú)原料的反應(yīng)加和,而他們之間發(fā)生了協(xié)同作用,其作用的機(jī)制主要是生物質(zhì)原料中堿金屬/堿土金屬對(duì)原料中碳成分產(chǎn)生了催化效果。(4)通過(guò)連續(xù)生產(chǎn)3個(gè)多月的實(shí)驗(yàn)數(shù)據(jù),系統(tǒng)分析了工業(yè)硅冶煉過(guò)程45%能量來(lái)源于電能。并將有效能或收益能和支付能或總能的比值既?效率來(lái)評(píng)估工業(yè)硅生產(chǎn)過(guò)程,表示如下:分析顯示工業(yè)硅冶煉過(guò)程的?效率僅僅為30%,而其余的70%的能量通過(guò)煙氣、冷卻水、爐渣、爐子的輻射或熱交換損失。(5)等高線方法分析了工業(yè)硅冶煉過(guò)程原料帶入的主要雜質(zhì)Fe_2O_3、Al_2O_3,Ca O以及微量雜質(zhì)氧化物對(duì)工業(yè)硅冶煉過(guò)程電耗的影響,結(jié)果顯示了主要氧化物對(duì)電耗的影響強(qiáng)弱順序?yàn)?Ca OFe_2O_3Al_2O_3,微量氧化物雜質(zhì)含量對(duì)工業(yè)硅冶煉過(guò)程電耗的影響強(qiáng)弱順序?yàn)?Ti O_2Cr_2O_3Mg OK_2O,揭示各種雜質(zhì)氧化物的熔點(diǎn)和對(duì)過(guò)程電耗的影響基本一致。(6)采用統(tǒng)計(jì)學(xué)分析方法分析了碳質(zhì)還原劑工業(yè)成分對(duì)工業(yè)硅過(guò)程電耗和?效率的影響,并通過(guò)等高線分析方法分析了不同碳質(zhì)還原劑組合條件下工業(yè)成分兩兩相互作用對(duì)工業(yè)硅冶煉過(guò)程電耗以及?效率的影響。結(jié)果顯示了工業(yè)成分對(duì)電耗和?效率的影響情況:固定碳揮發(fā)分水分。另外通過(guò)人工神經(jīng)網(wǎng)絡(luò)模型預(yù)測(cè)了碳質(zhì)還原劑不同工業(yè)成分對(duì)工業(yè)硅電耗值和實(shí)際電耗值之間均方根R~2=0.9393,?效率預(yù)測(cè)值和實(shí)際值之間均方根R~2=0.8723,可以看出模型可以成功應(yīng)用于碳質(zhì)還原劑工業(yè)成分對(duì)電耗和?效率影響的預(yù)測(cè)。(7)在明確不同碳質(zhì)還原劑以及碳質(zhì)還原劑中化學(xué)成分以及工業(yè)成分對(duì)工業(yè)硅生產(chǎn)的影響情況下。通過(guò)優(yōu)化原料配比以及還原劑成分,實(shí)驗(yàn)制備球團(tuán)碳質(zhì)復(fù)合還原劑,進(jìn)行物理化學(xué)性能測(cè)試分析。將其用于工業(yè)硅冶煉生產(chǎn),綜合分析結(jié)果顯示噸硅生產(chǎn)成本降低50~150元,具有相對(duì)可觀的經(jīng)濟(jì)價(jià)值。
[Abstract]:Charcoal is a common carbonaceous reducing agent in industrial silicon smelting because of its high specific resistance and high reactive activity. The source of charcoal is mainly deforestation at the cost of a large number of forests, and has serious destructiveness to the ecological environment. The high fixed carbon and low ash content of petroleum coke are ideal carbon reducing agent in theory, but it is one of the ideal carbonaceous reducing agents. Graphitization, especially at high temperature, will lead to a large reduction in chemical reaction activity and a large increase in electrical conductivity, which is not conducive to industrial silicon smelting. On the other hand, the high sulfur content of petroleum coke not only has an important influence on the process of industrial silicon smelting, but also the process of using high sulfur petroleum coke. A large number of SO_2 gases which are harmful to the environment will be produced. Therefore, it is of great significance to study the high cost, low performance and high energy consumption of the industrial silicon smelting process for the current industrial silicon smelting production. The main contents of this study include the following points: (1) the analysis of the inverse of petroleum coke with the combination of TGA and XRD. The thermal reaction behavior of petroleum coke additive (K_2CO_3) with the mass ratio of 0.5,0.8,1.0 and 1.5% in CO_2 atmosphere and the effect of mixed treatment on the physical properties of petroleum coke in different media (distilled and anhydrous ethanol two kinds of representative medium) were investigated. The reaction performance of the coke has obvious improvement effect. The maximum reaction time can shorten the 67%. (2) vacuum enhanced high sulfur petroleum coke desulfurization method. From the process point of view, the sample particles of petroleum coke are systematically studied: 350~450 mu m, 300~350 mu m, 180~300 mu m, 150~180 u m, 125~150, m and ~125 muon; temperature: 600-1500 0.5h, 1.0h, 1.5h, 2.0h, 2.5h and 3.0h, vacuum degree: 10~ (-2) Pa, 1Pa, and 100 Pa on the desulfurization of petroleum coke. The comparison of the desulfurization effect under the same conditions under the same condition was found under the same condition. The desulfurization mechanism of petroleum coke under vacuum conditions was discussed in a petroleum coke under vacuum conditions. Organic sulfur is a process of breaking the C-S bond and recombining the C-C bond. (3) the reaction properties of several typical biomass materials were analyzed by TGA, and the catalytic index was used for the petroleum coke of different biomass raw materials by studying the reaction characteristics of biomass raw materials and petroleum coke mixture ratio: 0:100,20:80,40:60,60:40,80:20 and 100:0 respectively. The results of the synergistic reaction were evaluated. The results showed that the mass ratio of the same biomass and petroleum coke was higher than that of the mixture. With the increase of the mass ratio of biomass, the maximum reduction of chemical activation energy of the mixture was 50%. and the comparison between the theoretical calculation value and the experimental value showed that the mixture of biomass and petroleum coke was not only single. The reaction of the single raw material is added, and the synergistic effect occurs between them. The main mechanism is that the alkali metal / alkaline earth metal has a catalytic effect on the carbon composition in the raw material. (4) through the continuous production of the experimental data for more than 3 months, the 45% energy of the industrial silicon smelting process is derived from the energy. The ratio of income energy and payout or total energy not only the efficiency to evaluate the industrial silicon production process, which is as follows: the analysis shows that the efficiency of the industrial silicon smelting process is only 30%, while the rest of the 70% energy passes through the flue gas, cooling water, slag, radiation or heat exchange loss of the furnace. (5) the method of contour analysis of the industrial silicon smelting process raw material into the process. The effect of the main impurities, Fe_2O_3, Al_2O_3, Ca O and trace impurity oxides on the electrical consumption of industrial silicon smelting process, shows that the order of the influence of the main oxides on the power consumption is Ca OFe_2O_3Al_2O_3, the order of the influence of the content of trace oxide impurities on the electrical consumption of industrial silicon smelting process is Ti O_2Cr_2O_3Mg OK_2O. The melting point of the kind of impurity oxide is basically the same as the influence on the process power consumption. (6) the effects of the industrial composition of the carbonaceous reducing agent on the electrical consumption and the efficiency of the industrial silicon process are analyzed by statistical analysis. The industrial composition 22 interaction under different carbonaceous reductant combination strips is analyzed by the method of contour analysis. The effects of the power consumption and efficiency of the process. The results show the effects of the industrial composition on the power consumption and efficiency: the fixed carbon volatilization water. In addition, the artificial neural network model is used to predict the R~2=0.9393, the efficiency and the actual value of the industrial silicon electricity consumption value and the actual electricity consumption value. The mean square root R~2=0.8723 can be seen that the model can be successfully applied to the prediction of the effects of the industrial components of a carbonaceous reducing agent on the power consumption and efficiency. (7) under the influence of the chemical composition and the industrial composition of different carbonaceous reductants and carbonaceous reductants on industrial silicon production, the composition of the raw materials and the reductant components are optimized. The pellet carbonaceous compound reductant is tested and analyzed in physical and chemical properties. It is used in industrial silicon smelting. The comprehensive analysis results show that the production cost of tons silicon is reduced by 50~150 yuan, which has relatively considerable economic value.

【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TQ127.2

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