【摘要】：氟硅酸鈉作為磷化工產(chǎn)業(yè)鏈的主要副產(chǎn)物之一,有著很強的腐蝕性和較強的毒性,任其排放會對環(huán)境造成嚴重影響。據(jù)統(tǒng)計,每生產(chǎn)100萬噸磷肥(折P2O5),就有將近超過6萬噸的氟硅酸鈉副產(chǎn)物,而2016年國內(nèi)磷肥產(chǎn)量預計可達2060萬噸(折P2O5)左右,屆時副產(chǎn)物氟硅酸鈉將會超過100萬噸,加上其他行業(yè)產(chǎn)生的量,氟硅酸鈉年產(chǎn)生量將達近兩百萬噸。如此數(shù)量的氟硅酸鈉如不加以利用而直接廢棄,不僅會造成資源的嚴重浪費,還會給環(huán)境帶來巨大的破壞。本課題采用兩種不同化學工藝,以氟硅酸鈉為基本原料,將氟硅酸鈉中的氟源轉(zhuǎn)化成氟化鈉,硅源轉(zhuǎn)化成白炭黑,同時獲得兩種附加值更高的化工產(chǎn)品。在獲得經(jīng)濟效益的同時,減少污染,保護環(huán)境,意義重大。本實驗制氟化鈉和白炭黑采用了外加晶種分步法和表面活性劑純堿法兩種方法,討論了兩種方法的多個單因素對實驗的影響,并通過正交實驗分析分別對兩種制備工藝進行優(yōu)化,獲得制備白炭黑和氟化鈉的最佳工藝條件。外加晶種分步法制白炭黑和氟化鈉的工藝路線是以磷肥副產(chǎn)氟硅酸鈉和氨水為原料,先制備晶種,后經(jīng)在玻璃反應(yīng)器中添加晶種、原料沉淀反應(yīng)、攪拌陳化、過濾分離得濾液和濾渣,濾液經(jīng)加氫氧化鈉溶液、真空反應(yīng)濃縮、結(jié)晶、過濾、干燥得氟化鈉產(chǎn)品,濾渣經(jīng)硫酸調(diào)pH、過濾洗滌、干燥得白炭黑產(chǎn)物。外加晶種分步法制備白炭黑的最佳工藝條件:稀氨水占制晶種反應(yīng)體積的4.7%,表面活性劑濃度為0.5%,外加晶種添加量占反應(yīng)總體積的5%,快速反應(yīng)滴加的氨水與總氨水體積比為0.2,反應(yīng)溫度為70℃,氟硅酸鈉與總氨水的摩爾比為1:8,反應(yīng)pH終點為8.5,陳化6小時。外加晶種分步法制備氟化鈉的最佳工藝條件:反應(yīng)濃縮溫度60℃,蒸發(fā)量為80%,氫氧化鈉的濃度為20mol/L,陳化溫度為20℃,陳化時間為30min。表征結(jié)果顯示制備得到的白炭黑一次粒子粒度分布為正態(tài)分布,中位徑在20nm,DBP值為3.52ml/g,比表面積為178.19m2/g;制備得到的氟化鈉晶體的平均粒徑在110μm,在XRD圖中有著明顯氟化鈉的晶形衍射峰。表面活性劑純堿法制備白炭黑和氟化鈉的工藝路線是以磷行業(yè)副產(chǎn)氟硅酸鈉和純堿為原料,先加表面活性劑,后分步加純堿,再經(jīng)液固流態(tài)化分離裝置分離得氟化鈉和白炭黑后,再經(jīng)后續(xù)處理工藝得到更加純凈的白炭黑和氟化鈉。表面活性劑純堿法制白炭黑和氟化鈉的較佳工藝條件:快速加入的碳酸鈉溶液與總碳酸鈉體積比為0.3,氟硅酸鈉和碳酸鈉的摩爾比為1:3,表面活性劑濃度為0.3%,反應(yīng)溫度為85℃,反應(yīng)時間為3h,分離裝置母液流速為24L/h。通過自行設(shè)計的液固流態(tài)化分離裝置,氟化鈉和白炭黑能有效的分離,二氧化硅和氟化鈉的純度分別92.18%和98.92%。表征結(jié)果顯示制備得到的白炭黑粒度分布呈正態(tài)分布,中位徑在208nm,DBP值為3.16ml/g,比表面積為112.24m2/g;制備得到的氟化鈉晶體的平均粒徑在170μm,在XRD圖中有著明顯氟化鈉的晶形衍射峰。試驗證明,本課題建立的外加晶種分步法和表面活性劑純堿法的兩種工藝路線,都能使氟硅酸鈉中的氟、硅元素得到有效利用,轉(zhuǎn)化成經(jīng)濟價值更高的氟化鈉和白炭黑,工藝路線可行。
[Abstract]:Sodium fluosilicate, as one of the main by-products of phosphorus chemical industry chain, is highly corrosive and toxic, and its discharge will seriously affect the environment. According to statistics, for every 1 million tons of phosphate fertilizer (P2O5), there are nearly 60,000 tons of sodium fluosilicate by-products, and in 2016 the domestic phosphate fertilizer output is expected to reach 20.6 million tons (P2O5). About 1 million tons of sodium fluosilicate, the by-product, will be produced by other industries, and the annual output of sodium fluosilicate will reach nearly 2 million tons. In order to obtain economic benefits, reduce pollution and protect the environment, it is of great significance to convert the fluorine source of sodium fluosilicate into sodium fluoride and silicon source into silica. The influence of several single factors of the two methods on the experiment was discussed, and the optimum technological conditions for the preparation of silica and sodium fluoride were obtained by orthogonal experimental analysis. The technological route for the preparation of silica and sodium fluoride by-product of phosphate fertilizer was the step-by-step method with the addition of crystal seeds. Sodium silicate and ammonia water were used as raw materials to prepare seeds, then added seeds in glass reactor, precipitation reaction of raw materials, agitation aging, filtration and separation of filtrate and filter residue, filtrate through sodium hydroxide solution, vacuum reaction concentration, crystallization, filtration, drying of sodium fluoride products, filtrate residue through sulfuric acid pH adjustment, filtration washing, drying of silica products. The optimum technological conditions for the preparation of silica were as follows: dilute ammonia water accounted for 4.7% of the reaction volume, the concentration of surfactant was 0.5%, the addition of seed accounted for 5% of the total reaction volume, the volume ratio of ammonia water to total ammonia water was 0.2, the reaction temperature was 70%, the molar ratio of sodium fluosilicate to total ammonia water was 1:8, and the reaction pH was 0.5%. The optimum technological conditions for the preparation of sodium fluoride were as follows: reaction concentration temperature 60 C, evaporation rate 80%, concentration of sodium hydroxide 20 mol / L, aging temperature 20 C, aging time 30 min. The characterization results showed that the primary particle size distribution of the prepared silica was normal, and the median diameter was 20 nm, D BP value is 3.52 ml/g, specific surface area is 178.19 m2/g; the average diameter of the prepared sodium fluoride crystal is 110 micron, and there is obvious crystal diffraction peak of sodium fluoride in XRD diagram. The technological route of preparing white carbon black and sodium fluoride by-product sodium fluosilicate and soda ash in phosphorus industry is to add surfactant first, then step by step. Sodium fluoride and silica were separated by Liquid-Solid Fluidization separator with soda ash, and then purified silica and sodium fluoride were obtained by subsequent treatment. The optimum technological conditions for the preparation of silica and sodium fluoride by surfactant soda were as follows: the volume ratio of sodium carbonate solution added quickly to total sodium carbonate was 0.3, sodium fluosilicate and sodium carbonate was 0.3. The molar ratio of sodium fluoride to silica was 1:3, the concentration of surfactant was 0.3%, the reaction temperature was 85 C, the reaction time was 3 h, and the mother liquor flow rate was 24 L/h. The purity of silica and sodium fluoride were 92.18% and 98.92% respectively. The particle size distribution of silica was normal distribution with a median diameter of 208 nm, DBP value of 3.16 ml/g and a specific surface area of 112.24 m2/g. The average particle size of the prepared sodium fluoride crystal was 170 micron, and there were obvious diffraction peaks of sodium fluoride in the XRD diagram. The technological route can effectively utilize fluorine and silicon in sodium fluosilicate and convert it into sodium fluoride and silica with higher economic value. The technological route is feasible.
【學位授予單位】：南昌大學
【學位級別】：碩士
【學位授予年份】：2016
【分類號】：TQ127.2;TQ131.12

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