本文關鍵詞：氯化鋁低溫氯化法五氧化二釩提純工藝研究　出處：《中國科學院大學(中國科學院過程工程研究所)》2017年碩士論文　論文類型：學位論文

  更多相關文章： 無水氯化鋁 低溫氯化 氨解 提純 高純五氧化二釩

【摘要】：隨著科技的不斷進步,全釩液流電池、釩鋁合金、鋰電池以及催化劑等眾多領域對高純度五氧化二釩產(chǎn)品的需求量越來越大。高純五氧化二釩的傳統(tǒng)制備工藝大都停留在實驗室研究階段,面臨著成本高、流程長、污染重、產(chǎn)品純度低等問題,高純五氧化二釩產(chǎn)品的低成本短流程清潔制備技術已成為釩化工行業(yè)的研究熱點。本論文提出了一種通過無水氯化鋁低溫氯化分離工業(yè)級五氧化二釩產(chǎn)品中鐵、鋁、硅等雜質進而提純并制備高純五氧化二釩的新方法。首先,通過理論分析和探索實驗確定了原則工藝流程;然后,系統(tǒng)研究了氯化反應的工藝條件和反應機理,以及氯化反應所得三氯氧釩中間體氨解過程中各因素對沉釩率和產(chǎn)品純度的影響規(guī)律,并制備得到了五氧化二釩高純產(chǎn)品;最后,進一步拓展了原料范圍,選用三種不同的含釩原料對整體流程進行了驗證。本論文在以下幾方面取得了創(chuàng)新結果:(1)在熱力學計算、物性分析及探索實驗的基礎上,確定了無水氯化鋁低溫氯化法制備高純五氧化二釩新工藝的整體流程。研究結果表明,無水氯化鋁與五氧化二釩之間的氯化反應在低溫下可行,且結合各雜質氯化物的物化性質分析,確定此氯化反應對實現(xiàn)原料中釩與其他雜質的分離具備有利作用。反應溫度為160℃C時,氯化反應發(fā)生并生成三氯氧釩中間體,中間體經(jīng)過氨解煅燒過程制備出高純V205。(2)系統(tǒng)研究了反應溫度、原料配比、添加劑用量等因素對氯化反應的影響規(guī)律,確定了較適宜的氯化反應工藝條件,并借助TG-DSC、SEM、EDS等手段分析了氯化反應的機理。在反應溫度為170℃、無水氯化鋁與原料中五氧化二釩的化學計量比為3:1、氯化鈉添加量x=nAlCl3/(nAlCl3+mNaCl)=0.6,且添加氯化鈉后,反應時間可縮短到1h,三氯氧釩產(chǎn)品收率最高可達83.35%,反應產(chǎn)物純度≥99.95%。氯化反應過程中有中間體AlOCl生成,最終A1C13全部轉化成A1203。(3)研究了氨解過程各工藝參數(shù)對五氧化二釩產(chǎn)品純度和沉釩率的影響規(guī)律,確定了較適宜的氨解工藝參數(shù)。在釩濃度介于13.4～68.8g/L之間、氨解溫度為35℃C、加氨系數(shù)為0.8～1.0、攪拌強度為15 r/s時,氨解反應過程釩收率最高。'借助ICP、XRD、XRF、XPS等手段,對五氧化二釩產(chǎn)品的純度及表面元素化學計量比進行了詳細的分析,確定制備的五氧化二釩產(chǎn)品純度≥99.97%。(4)分別以釩渣鈉化提釩工藝生產(chǎn)的工業(yè)級五氧化二釩(96.487%)、石煤提釩工藝生產(chǎn)的工業(yè)五氧化二釩(96.675%)以及釩渣(25.46%V205)為原料,采用低溫氯化法工藝,制得了純度分別為≥99.84%、≥99.97%、≥99.70%的五氧化二釩產(chǎn)品,為含釩原料氯化提釩的研究提供了新思路。
[Abstract]:With the continuous progress of science and technology, VRB, vanadium Aluminum Alloy, many areas of the lithium battery and the catalyst great demands for high purity five of two vanadium products. The traditional preparation of high purity five of two vanadium production process mostly stay in the laboratory stage, facing a high cost, long process, heavy pollution problems, low product purity, low cost clean short process for preparing high purity five of two vanadium vanadium products has become a research hotspot in the chemical industry. This paper presents a kind of low temperature chloride anhydrous aluminum chloride by separation of industrial grade five of two vanadium products of iron, aluminum, silicon and other impurities and purification method preparation of high purity and five of two vanadium. Firstly, through theoretical analysis and exploration of experiment to determine the principle process; then, process conditions of chlorination reaction system and reaction mechanism, and the reaction to three vanadium oxychloride Between the ammonolysis of factors in influence of precipitation rate and product purity, and prepared five of two vanadium high purity products; finally, to further expand the range of raw materials, selected three kinds of whole process was proved vanadium containing raw materials. This paper has made the innovation results in the following aspects: (1) in the thermodynamic calculation, physical analysis and exploration based on the experiment, the whole process of new technology of low temperature aluminum chloride anhydrous chloride prepared by high purity five of two vanadium. The results show that the reaction between chloride and anhydrous aluminium chloride and five of two vanadium at low temperature and is feasible. Combined with the analysis of physicochemical properties of the impurities of chloride, the reaction of chloride determination of separation of vanadium in raw material and other impurities have beneficial effects. The reaction temperature is 160 DEG C, chloride reaction and generate three vanadium oxychloride intermediates, intermediates by aminolysis of calcined Burning process of preparing high pure V205. (2) system of reaction temperature, raw material ratio, effect of additive dosage on the chlorination reaction, the chlorination of determining suitable process conditions, and with the help of TG-DSC, SEM, EDS and other means of analysis of the mechanism of chlorination reaction. The reaction temperature is 170 DEG C, the stoichiometry of anhydrous aluminum chloride and raw materials in five of two vanadium ratio was 3:1, the adding amount of sodium chloride x=nAlCl3/ (nAlCl3+mNaCl) =0.6, and after the addition of sodium chloride, the reaction time can be shortened to 1H, three vanadium oxychloride products yield up to 83.35%, with intermediate product purity AlOCl generation reaction over 99.95%. chlorination reaction process finally, A1C13 into A1203. (3) studied the aminolysis process parameters on the five of two vanadium product purity and precipitation rate were investigated, to determine the optimum solution of ammonia process parameters. In vanadium concentration from 13.4 to 68.8g/L, Ammonia solution temperature of 35 DEG C, ammonia coefficient is 0.8 ~ 1, the stirring intensity is 15 r/s, ammonolysis process of vanadium yield. With the help of ICP, XRD, XRF, XPS and other means of purity and surface elements of stoichiometric five of two vanadium products than the detailed analysis, to determine the five oxidation the preparation of two vanadium product purity not less than 99.97%. (4) respectively in vanadium slag sodium extraction industrial grade five vanadium oxide production of two vanadium (96.487%), stone coal extraction industry five vanadium oxide production process of vanadium and vanadium slag is two (96.675%) (25.46%V205) as raw materials by low temperature chlorination process, prepared the purity was more than 99.84%, more than 99.97%, five more than 99.70% of two vanadium oxidation products, provides a new idea for raw materials containing vanadium vanadium chloride is studied.

【學位授予單位】：中國科學院大學(中國科學院過程工程研究所)
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ135.11

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