【摘要】：稀土元素是在新能源、新材料和尖端科技等領域應用日益廣泛,具有“工業(yè)味精”的美譽,是不可再生的重要戰(zhàn)略資源。受技術水平和生產條件的限制,稀土礦回收技術指標較低。尾礦中還有許多稀土礦物沒有得到回收。這些尾礦的流失,既造成資源的浪費,又構成了污染礦山外部環(huán)境的隱患。隨著德昌稀土大規(guī)模生產不斷進行,對尾礦進行二次開發(fā)利用其中的多種有價元素,可產生極為可觀的經濟效益和社會效益。本文以研究德昌大陸槽稀土尾礦中的稀土回收方案和新型羥肟酸類捕收劑的合成為主要研究內容。詳細的研究了尾礦的性質,考察了磨礦工藝條件,并進行了稀土尾礦浮選試驗。主要結果如下:經尾礦篩分分析可知:稀土尾礦試樣中47.6%的礦物粒度大于100目,78.02%的礦物粒度大于200目。通過XRD衍射組分分析:尾礦中的主要稀土礦物為氟碳鈰礦,脈石礦物主要為石英、長石、方解石、螢石、石膏、天青石和伊利石,少量的重晶石、方鉛礦等其它礦物。4,4-二羥基聯(lián)苯與干冰、三氯苯制備4,4-二羥基-3,3-聯(lián)苯二甲酸,產率55.07%;向鹽酸羥胺的氫氧化鈉溶液中滴加4,4-二羥基-3,3-聯(lián)苯二甲酸二甲酯溶液,得目標產物4,4-二羥基-3,3-聯(lián)苯二甲羥肟酸,產率49.66%。采用核磁共振、紅外光譜、質譜、元素分析對目標產物的結構進行了表征,確定合成了目標產物。3-羥基-2-萘甲酸甲酯和鹽酸羥胺的氫氧化鈉溶液可制備H205,產率74%,并采用核磁共振氫譜對目標產物的結構進行了表征,確定合成了目標產物。在磨礦條件試驗中主要考察的因素為:磨礦時間、礦漿濃度、助磨劑種類及用量。通過試驗得出:最佳磨礦時間為10 min,適宜礦漿濃度為70%;助磨劑添加量依次為:1.25 kg/t、1.05 kg/t、0.75 kg/t、0.75 kg/t;-200目粒級含量分別增加了12.25%、6.5%、5%、4.75%。其中,六偏磷酸鈉的助磨效果最好。在助磨劑對稀土尾礦浮選影響的試驗中,硅酸鈉添加量為0.75 kg/t時,精礦中的Ce O2品位較清水選礦時提高了0.82%,其它助磨劑皆有不良影響。通過抑制劑、活化劑種類和用量試驗;測定稀土精礦的Ce O2含量和稀土回收率,并通過XRD衍射半定量分析了浮選精礦的礦物組分。試驗結果顯示:硅酸鈉、碳酸鈉、氯化銨、氟化鈉的最佳添加量分別為1000 g/t、500 g/t、500 g/t、300 g/t,Ce O2品位分別為8.52%、5.25%、5.09%、5.62%、,回收率分別為54.90%、80.11%、91.97%、85.54%。在捕收劑種類及用量對浮選效果影響的試驗中,三種捕收劑的捕收能力為:3-羥基-2-萘甲羥肟酸4,4-二羥基-3,3-聯(lián)苯二甲羥肟酸水楊羥肟酸;選擇性為:羥肟酸4,4-二羥基-3,3-聯(lián)苯二甲羥肟酸3-羥基-2-萘甲羥肟酸。精選試驗中,以水楊羥肟酸為捕收劑,硅酸鈉、碳酸鈉、氯化銨、氟化鈉為調整劑,礦漿p H=9,通過一次粗選、兩次精選可得到Ce O2品位為31.47%的合格稀土精礦。
[Abstract]:Rare earth elements are widely used in the fields of new energy, new materials and cutting-edge science and technology, and have the reputation of "industrial monosodium glutamate", which is an important non-renewable strategic resource. The technical index of rare earth ore recovery is low due to the limitation of technical level and production conditions. There are also many rare earth minerals in the tailings that have not been recovered. The loss of these tailings not only causes the waste of resources, but also constitutes the hidden trouble of polluting the external environment of mines. With the continuous large-scale production of rare earths in Dechang, the secondary development and utilization of various valuable elements in tailings can bring about considerable economic and social benefits. In this paper, the scheme of rare earth recovery and the synthesis of new hydroxamic acid collector in rare earth tailings of Dechang continental trough are studied. The properties of tailings were studied in detail, the grinding process conditions were investigated, and the flotation tests of rare earth tailings were carried out. The main results are as follows: according to the analysis of tailings, the mineral particle size of 47.6% of rare earth tailings is more than 100 mesh and 78.02% is more than 200 mesh. The main rare earth minerals in the tailings are fluorocarbon cerium, the gangue minerals are quartz, feldspar, calcite, fluorite, gypsum, celadite and Illite, and a small amount of barite. Galena and other minerals, such as galena, 4-dihydroxy biphenyl and dry ice, trichlorobenzene is used to prepare 4- 4- dihydroxy-3-, 3-biphenyl dicarboxylic acid in the yield of 55.070.The sodium hydroxide solution of hydroxylamine hydrochloride is added to the solution of dimethyl biphenyl dimethyl 4-dihydroxy-3-tetrachloroic acid by dripping into the sodium hydroxide solution of hydroxylamine hydrochloride. The target product 4o 4-dihydroxy-3 o-3-biphenyl dimethyl hydroxamic acid was obtained in 49.66% yield. The structure of the target product was characterized by NMR, IR, MS and elemental analysis. H205 was prepared in the solution of sodium hydroxide of methyl 3-hydroxy-2-naphthyl formate and hydroxylamine hydrochloride. The structure of the target product was characterized by nuclear magnetic resonance spectroscopy (NMR), and the target product was synthesized. The main factors investigated in grinding condition test are grinding time, pulp concentration, type and amount of grinding aids. The results show that the optimum grinding time is 10 min, the optimum pulp concentration is 70 and the content of grinding aids is increased by 12.25% 1.25 kg/t,1.05 kg/t,0.75 kg/t;-200 and 4.75% respectively. Among them, sodium hexametaphosphate is the best grinding aid. In the experiment of the effect of grinding aids on the flotation of rare earth tailings, when the amount of sodium silicate was 0.75 kg/t, the grade of Ce O 2 in the concentrate increased by 0.82%, and the other grinding aids had a bad effect. The content of Ce O 2 and the recovery rate of rare earth in rare earth concentrate were determined by depressant, activator type and dosage test, and the mineral components of flotation concentrate were semi-quantitatively analyzed by XRD diffraction. The results show that the optimum addition amount of sodium silicate, sodium carbonate, ammonium chloride and sodium fluoride is 1000 g / t ~ (500) g / t ~ (3) ~ (3) g / t ~ (3) C ~ (2) and 5.09 ~ 5.25 ~ (5.25) ~ (5.25) ~ (5.62) O _ 2, respectively, and the recovery rate is 54.9080.11 ~ 91.97% ~ 85.54, respectively. In the experiment of the effect of collector type and dosage on the flotation effect, the collecting ability of the three kinds of collectors was as follows: 1. 3 hydroxyl-2-naphthyl hydroxamic acid 4-4-dihydroxy-3-biphenyl-dihydroxamic acid-salicylhydroxamic acid; The selectivity of hydroxamic acid was 4- dihydroxy-3-biphenyl-dimethoxime acid, 3-hydroxy-2-naphthyl hydroxamic acid. In the cleaning test, using salicylhydroxamic acid as collector, sodium silicate, sodium carbonate, ammonium chloride and sodium fluoride as adjuvant, pulp pH _ (9) can be obtained by one rough separation and two times cleaning. The qualified rare earth concentrate with Ce O _ 2 grade of 31.47% can be obtained.
【學位授予單位】：成都理工大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TD923

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