本文選題：紅土鎳礦 + 酸浸-共沉淀法��； 參考：《北京科技大學(xué)》2016年博士論文

【摘要】：隨著硫化鎳礦資源的匱乏以及日益增長的鎳需求,占世界鎳資源儲量72%的低品位紅土鎳礦將成為提取鎳的主要資源。本文針對紅土鎳礦的組成及結(jié)構(gòu)特點(diǎn),提出了酸浸-共沉淀-煅燒法和堿熔-水浸-固相燒結(jié)法綜合利用紅土鎳礦制備尖晶石鐵氧體的新型工藝路線；闡明了各流程階段紅土鎳礦中元素的分布及走向規(guī)律；揭示了選擇性浸出及分離富集過程對于制備尖晶石鐵氧體材料的組成、結(jié)構(gòu)及磁性能的微觀影響機(jī)制。新型工藝流程不僅能夠高效回收紅土鎳礦中的Ni、Co、Mn、Mg、Fe等有價金屬元素,同時制備得到了高附加值鐵氧體磁性材料,實(shí)現(xiàn)了紅土鎳礦資源的高效綜合利用。采用水熱酸浸-水熱共沉淀-煅燒法,從單一腐泥土型紅土鎳礦制備合成了Co-Mn-Al共摻雜鐵酸鎳(NiFe2O4)。系統(tǒng)研究了水熱酸浸過程中水熱反應(yīng)溫度和初始鹽酸溶液濃度對于金屬選擇性浸出和金屬摩爾比RFe/Ni勺影響;闡明了水熱共沉淀法實(shí)現(xiàn)溶液中Ni、Co、Mn、Fe金屬元素與Mg的分離機(jī)理；探討了選擇性浸出分離過程對于制備共摻雜鐵酸鎳微觀結(jié)構(gòu)及磁性能的影響規(guī)律。結(jié)果表明：當(dāng)浸出溫度控制在200℃,鹽酸濃度為2.0 mol-L-1,液固比為6：1 mL·g-1時,Fe和Ni的浸出率可控制為17.0%和85.0%,此時得到的浸出液中Fe與Ni、Co、Mn的摩爾比約為2.0;調(diào)節(jié)酸浸液pH值為7.0,在水熱溫度為200℃,水熱反應(yīng)2 h,溶液中的Ni、Co、Mn、Fe和Al發(fā)生共沉淀反應(yīng)而實(shí)現(xiàn)與溶液中Mg離子的完全分離：將沉淀在1000℃煅燒2 h可以獲得高純度和結(jié)晶度、性能良好的尖晶石共摻雜NiFe204.采用常壓酸浸-共沉淀-煅燒法,從腐泥土型和褐鐵礦型紅土鎳礦混合礦制備合成了Ni-Co-Mn或者M(jìn)n-Al-Cr共摻雜鐵酸鎂(MgFe2O4)。系統(tǒng)研究了常壓酸浸過程中初始鹽酸溶液濃度、液固比和浸出時間對于金屬浸出的影響規(guī)律；探討了共沉淀過程中沉淀劑、溶液pH值、沉淀過程加料方式以及酸浸液中金屬離子濃度對于共沉淀過程金屬離子的沉淀行為、分離和富集的影響機(jī)理;研究并揭示了不同沉淀劑和初始酸濃度對于制備單一鐵氧體結(jié)構(gòu)和磁性能的影響機(jī)制。結(jié)果表明：采用100℃冷凝回流法,當(dāng)初始HCl溶液濃度為2.75 mol·L-1,液固比為10 mL·-g-1,浸出時間為60 min時,Fe、Ni、Co、 Mn、Mg的浸出率分別為94.6%、96.1%、81.5%、83.2%和71.8%；在沉淀過程中,分別以氨水溶液和氫氧化鈉溶液為沉淀劑,控制反應(yīng)終了溶液的pH值為11.0和12.0,采用反向加料方式,反應(yīng)時間為30 min,攪拌速度為300rpm時,Ni、Co、Al和Cr的回收率分別達(dá)到了93.0%、92.0%、92.0%和90.0%,同時得到的沉淀可以用于制備尖晶石鐵氧體材料；在煅燒過程中,以氨水溶液和氫氧化鈉溶液作為沉淀劑時,制備合成單一尖晶石鐵氧體相的最佳MS/L分別為9：1和7：3 g·g-1,煅燒溫度和時間為1000℃和2 h時,分別制備得到了Mn-Al-Cr共摻雜MgFe2O4和Ni-Co=Mn共摻雜MgFe204.采用共沉淀-煅燒法,從腐泥土型和褐鐵礦型紅土鎳礦混合礦酸浸液中分別制備合成了不同Zn摻雜量和Ni摻雜量的尖晶石鐵氧體。系統(tǒng)研究了Zn摻雜和Ni摻雜對于Ni-CO-Mn-Mg鐵氧體結(jié)構(gòu)和磁性能的影響。結(jié)果表明：隨著Zn摻雜量的增加,鐵氧體的晶胞參數(shù)、平均粒徑和X-ray密度都在增大；隨著Ni摻雜量的增加,晶胞參數(shù)在減小。磁性能測試結(jié)果表明：當(dāng)Zn摻雜量為0.4時,產(chǎn)物飽和磁化強(qiáng)度Ms最大為55.6 emu.g-1,矯頑力Hc約為40 Oe；Ni摻雜量為0.9時,產(chǎn)物飽和磁化強(qiáng)度Ms為41.0 emu·-1,矯頑力約為62 Oe。通過對比發(fā)現(xiàn),適量的Zn摻雜(0.4)更有利于鐵氧體磁性能的改善。采用固相燒結(jié)法,從堿熔-水浸預(yù)處理的腐泥土型和褐鐵礦型紅土鎳礦混合礦中制備合成了Ni-Co-Mn共摻雜MgFe2O4.系統(tǒng)研究了堿熔-水浸過程中堿熔溫度、時間和礦堿比對于雜質(zhì)元素Si、Al和Cr去除的影響；探究了MTSL/TLL、煅燒溫度及雜質(zhì)SiO2對于制備鐵氧體結(jié)構(gòu)和磁性能的影響規(guī)律。結(jié)果表明：在堿熔溫度和時間為550℃和30 min,礦堿質(zhì)量比為1：1、1：1.25和1：1.5時,分別得到了Si02含量約為5%、3%和2%的預(yù)處理混合礦,同時Al2O3和Cr2O3的含量分別從0.65%和0.18%降低到0.43%和0.12%；MTSL/TLL為6：4的預(yù)處理混合礦在1000℃煅燒2 h可以制備得到單一尖晶石鐵氧體相；隨著Si02含量從2%增加到3%,樣品的飽和磁化強(qiáng)度從45.4 emu·g-1略微減小到43.0 emu·g-1當(dāng)SiO2含量繼續(xù)增加到5%時,飽和磁化強(qiáng)度急劇下降到31.5 emu·g-1;隨著尖晶石鐵氧體中Si02含量從2%增加到5%,樣品的矯頑力從120 Oe減小到75 Oe.針對建立的新型工藝中各元素分布走向及相應(yīng)綜合利用率進(jìn)行了定量計算。結(jié)果表明：腐泥土型和褐鐵礦型紅土鎳礦混合礦處理工藝的金屬綜合回收率可以達(dá)到89.2%、85.4%和99.5%.
[Abstract]:With the shortage of nickel sulfide mineral resources and the increasing demand for nickel, the low grade laterite nickel ore, which accounts for 72% of the world's nickel reserves, will be the main resource of nickel extraction. In this paper, the composition and structure characteristics of the laterite nickel ore are made, and the comprehensive utilization of the nickel ore nickel ore by the acid leaching co precipitation calcination and the alkali melting water immersion solid sintering method is put forward in this paper. A new process for the crystallization of the ferrite is introduced, and the distribution and trend of elements in the laterite deposits at various stages are clarified, and the microcosmic influence mechanism of selective leaching and separation and enrichment on the composition, structure and magnetic properties of spinel ferrite materials is revealed. The new technological process can not only efficiently recover the laterite and nickel ores. The valuable metal elements such as Ni, Co, Mn, Mg, Fe and other valuable metal elements were prepared, and the high added value ferrite magnetic materials were prepared. The high efficiency and comprehensive utilization of the laterite and nickel ore resources were realized. By the hydrothermal acid leaching and hydrothermal coprecipitation calcination method, the Co-Mn-Al Co Doped Nickel ferrites (NiFe2O4) were synthesized from the single clay type laterite nickel ore, and the hydrothermal acid leaching was systematically studied. The effect of hydrothermal reaction temperature and initial hydrochloric acid solution concentration on metal selective leaching and metal molar ratio RFe/Ni spoon, and the separation mechanism of Ni, Co, Mn, Fe metal elements and Mg in solution by hydrothermal coprecipitation method, and the microstructure and magnetic properties of Co Doped Nickel ferrites were discussed. The results show that when the leaching temperature is controlled at 200, the concentration of hydrochloric acid is 2 mol-L-1 and the liquid to solid ratio is 6:1 mL. G-1, the leaching rate of Fe and Ni can be controlled to 17% and 85%, and the molar ratio of Fe to Ni, Co, Mn is about 2 in the leaching solution; the pH value of the acid leaching solution is 7, the hydrothermal temperature is 200, the hydrothermal reaction 2 h, solution Ni, Co, Mn, Fe and Al have coprecipitation reaction to complete the complete separation of Mg ions from the solution: high purity and crystallinity can be obtained by calcining 2 h at 1000 C. The good properties of the spinel Co doped NiFe204. are prepared by the normal pressure acid leaching co precipitation calcination method, and the preparation of Ni-Co-M from the humic and limonite laterite nickel ore is made. N or Mn-Al-Cr Co doped magnesium ferrites (MgFe2O4). The influence of initial hydrochloric acid solution concentration, liquid solid ratio and leaching time on metal leaching in the process of atmospheric acid leaching was systematically studied. The precipitator, pH value of solution, feeding mode of precipitation process and metal ion concentration in the acid leaching process were discussed. The influence mechanism of precipitation, separation and enrichment of ions is studied. The influence mechanism of different precipitants and initial acid concentration on the structure and magnetic properties of single ferrite is studied and revealed. The results show that when the concentration of the initial HCl solution is 2.75 mol. L-1, the liquid to solid ratio is 10 mL. -g-1, the leaching time is 60 min. The leaching rates of Fe, Ni, Co, Mn, Mg are 94.6%, 96.1%, 81.5%, 83.2% and 71.8%, respectively. In the process of precipitation, the pH value of the solution is 11 and 12, respectively, and the reaction time is 30 min and the stirring speed is 300rpm, Ni, Co, Al and Cr. 93%, 92%, 92% and 90% were reached, and the precipitates obtained at the same time could be used to prepare spinel ferrite materials. In the process of calcination, the best MS/L for preparing single spinel ferrite phase was 9:1 and 7:3 G. G-1 respectively, when the calcined temperature and time were 1000 and 2 h, when the ammonia solution and sodium hydroxide solution were used as precipitant. Mn-Al-Cr Co doped MgFe2O4 and Ni-Co=Mn Co doped MgFe204. were prepared by co precipitation calcining method. The spinel ferrite with different Zn doping content and Ni doping content was prepared from the acid leaching solution of soil type and limonite laterite nickel ore respectively. The Zn doping and Ni doping for Ni-CO-Mn-Mg ferrite junction were studied systematically. The effect of structure and magnetic properties shows that with the increase of Zn doping, the cell parameters, average particle size and X-ray density of ferrite are all increasing. With the increase of Ni doping, the cell parameters are reduced. The magnetic energy test results show that when the doping amount of Zn is 0.4, the maximum saturation and magnetization of the product is 55.6 emu.g-1, and the coercive force Hc is about Hc. When the amount of Ni doping is 40 Oe, the saturation magnetization of the product is 41 EMU. -1 and the coercive force is about 62 Oe. by contrast, and a proper amount of Zn doping (0.4) is more beneficial to the improvement of the ferrite magnetic properties. The solid phase sintering method has been used to synthesize Ni-Co-M from the soaking soil type and the limonite nickel ore and nickel ore mixture. N Co doped MgFe2O4. system has studied the effect of alkali melting temperature, time and ore base ratio on the removal of impurity elements Si, Al and Cr during the alkali melt water leaching process. The influence of MTSL/TLL, calcining temperature and impurity SiO2 on the structure and magnetic properties of ferrite was investigated. The results showed that the alkali melting temperature and time were 550 and 30 min, and the mineral alkali content was at the alkali melting temperature and time. When the quantity ratio is 1:1,1:1.25 and 1:1.5, the pretreated mixed ore with Si02 content of 5%, 3% and 2%, respectively, the content of Al2O3 and Cr2O3 decreased from 0.65% and 0.18% to 0.43% and 0.12%, respectively, and the pre treated mixed ore with MTSL/TLL for 6:4 can be prepared by calcining 2 h at 1000 C, and with the Si02 content from 2. % increase to 3%, the saturation magnetization of the sample decreases slightly from 45.4 EMU. G-1 to 43 EMU. G-1 when SiO2 content continues to increase to 5%, the saturation magnetization drops sharply to 31.5 EMU. G-1; with the increase of Si02 content in the spinel ferrite from 2% to 5%, the coercive force of the sample decreases from 120 Oe to 75 Oe. for each element in the new technology established. The results show that the comprehensive recovery of the metal in the mixed ore of the humic and limonite laterite nickel ores can reach 89.2%, 85.4% and 99.5%..

【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TM277;TD98

【參考文獻(xiàn)】

相關(guān)期刊論文 前2條

1 張月圓;;沉淀法對重金屬離子溶液的處理[J];廣西輕工業(yè);2010年07期

2 蔣繼波;王吉坤;;紅土鎳礦濕法冶金工藝研究進(jìn)展[J];濕法冶金;2009年01期

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本文編號：1799261