摘要
随着经济的发展和对矿产资源需求的增加,矿石中有用成分含量日趋降低,共生关系也显得更复杂,因而对矿物分选过程中的选择性提出了更高的要求。硅酸盐矿物广泛存在于自然界中,结构复杂,种类繁多,其中一些可以提取稀有金属,一些可以作为矿物材料的来源。在大多数情况下,硅酸盐矿物作为脉石矿物存在,影响有用矿物的浮选分离。因而,研究硅酸盐矿物的浮选分离具有重要的理论和实践意义。
常规的浮选过程中先添加调整剂,后添加捕收剂使矿物产生浮游差,从而使矿物分离。但有研究表明,调整剂和捕收剂添加顺序的不同对矿物浮选的影响不同,调整剂在捕收剂之后添加能提高对矿物浮选的选择性,至今国内外在这方面义献较少,尚没有系统的研究成果。目前对于硅酸盐矿物浮选分离的研究,在硅酸盐矿物的晶体结构、表面特性和矿物浮游行为之间的关系及硅酸盐矿物浮选理论、药剂和工艺方面进行了大量的研究,取得了较大的进展和较好的经济效益。但是对于硅酸盐矿物浮选过程中,调整剂与捕收剂添加顺序对矿物浮选的影响,还没有系统的研究报道。
本课题选取硅酸盐矿物中典型代表矿物石榴子石、绿柱石、锂辉石、角闪石、白云母、长石和氧化物石英为试验矿样,采用油酸钠和十二胺作为捕收剂,FeCl3、 Al2(SO4)3、Pb(NO3)2、CuSO4、CaCl2、Na2SiO3、(NaPO3)6、Na2S、NaF、酒石酸、柠檬酸和淀粉作为调整剂,系统地研究了硅酸盐矿物浮选过程中,调整剂与捕收剂不同添加顺序对矿物浮选的影响,并以此为基础进行了绿柱石-锂辉石人工混合矿的浮选分离试验,通过浮选溶液分析、红外光谱测试和药剂吸附量测定解释了浮选药剂的作用机理。
研究结果表明,调整剂和捕收剂添加顺序的不同,对硅酸盐矿物浮选的影响不同。与调整剂在捕收剂之前添加对矿物浮选的影响相比,调整剂在捕收剂之后添加可以增加或者削弱对矿物浮选的影响,有的时候还有相反的作用,从而可能提高部分硅酸盐矿物分离的选择性。
绿柱石和锂辉石人工混合矿分离试验表明,在相同药剂用量的条件下,FeCl3和Na2S在油酸钠之前添加两种矿物均上浮,在油酸钠之后能有效地能选择性抑制锉辉石,使两种矿物得到分离。在油酸钠用量为270mg/L,FeCl3用量为36mg/L,Na2S用量为108mg/L时,人工混合矿的分离指数达到最大为15.34,此时精矿中BeO的品位13.76%,回收率83.87%,尾矿中Li2O的品位为6.09%,回收率为97.84%。
药剂浮选溶液化学计算、晶体化学分析、红外光谱和吸附量测定结果表明:调整剂在油酸钠之前和之后添加对油酸钠的作用方式不同;FeCl3在油酸钠之前添加能明显增加油酸钠在绿柱石和锂辉石表面的吸附,在油酸钠之后添加降低了油酸钠在两种矿物表面的吸附,具有一定的选择性;FeCl3和Na2S在油酸钠之前添加降低了油酸钠在两种矿物表面的吸附,锂辉石表面油酸钠吸附量降低的程度大于绿柱石;FeCl3和Na2S在油酸钠之后添加则能使油酸钠选择性地吸附在绿柱石表面,增加油酸钠在绿柱石表面的吸附,锂辉石表面油酸钠吸附量基本不变,从而使绿柱石和锂辉石分离。
With the development of economy and the demand increase for mineral resources, the useful components of minerals are increasingly lower, the Symbiotic relationships are more complex, so we need higher separation selectivity in mineral processing.Silicate minerals are found widely in nature, which have complex structures and contents. Some of these are extracted for precious metals, some of these are used as a source of mineral materials. In most cases, the silicate minerals exist as gangue minerals, which greatly affect the flotation separation of useful minerals. Thus, there are greatly theoretical and practical significances.
In most cases, the modifers are added before collectors in the processing of flotation, making the differences of flotation and realizing the seperation of minerals. Some researches show that the addition orders of modifers and collectors affect the flotation processings, sometimes the modifers added after collectors get a higher separation selectivity for minerals.there is little paper in this area, no matter in China and abroad. At present, there are a great many studies for the relationships of the flotation behavior,the crystal structure and the surface characteristics of silicate minerals,there is no found of such systematic research report in the area of the different addition orders between modifers and collectors for the flotation of silicate minerals.
In this paper, garnet, beryl, spodumene, amphibole, mica, feldspar and quartz were made as research ores, sodium oleate and dode cylamine were used as collectors, FeCl3, A12(SO4)3, Pb(NO3)2, CuSO4, CaCl2, Na2Si03,(NaPO3)6, Na2S, NaF, tartaric acid, citric acid and starch were used as modifers. The effects of add order between modifers and collectors were studied on the flotation process of silicate minerals. Based on the study of pure minerals, the flotation seperations of beryl-spodumene mixture were carried out. The further mechanisms were discussed by IR and the adsorption of reagent.
The research shows that the modifers added before and after collectors have different effects for the flotation of silicate minerals. Compared with modifers added before collectors in the flotation of silicate minerals, modifers added after collectors can inhance.or weaken the effects, sometimes oposite effects also can be gotten. This can enhance the separation selectivity for silicate minerals on the flotation process.
The flotation separation tests of beryl-spodumene mixture showed that:with the same amount of FeCl3, Na2S and NaOl, FeCl3and Na2S added before NaOl can not effectively seperate the beryl-spodumene mixture, FeCl3and Na2S added after NaOl can make the beryl-spodumene mixture effectively seperated. When the dosage of FeCl3was36mg/L, the dosage of Na2S was108mg/L, the dosage of NaOl is270mg/L, the best results were obtained:the grade of BeO was13.76%, the recovery was83.87%in the concentrate; the grade of Li2O was6.09%, the recovery was97.84%in the tailing.
The mechanism was discussed by IR and the adsorptions of reagents. FeCl3added before NaOl can signifcantly increase the adsorption of NaOl on the surfaces of beryl and spodumene; FeCl3added after NaOl can decrease the adsorption of NaOl on the surfaces of beryl and spodumene; FeCl3and Na2S added before NaOl can decrease the adsorption of NaOl on the surfaces of beryl and spodumene; FeCl3and Na2S added after NaOl can remove the inhibition of FeCl3for beryl, and NaOl selective adsorbed on the surface of bryl. So the beryl-spodumene mixture was selectively separated by flotation.
引文
1.周乐光主编.矿石学基础,北京:冶金工业出版社[M],2005,156.
2. Manser.R.M. Handbook of Silicate Flotation[M]. England, DOB. Services Ltd. 1975.
3. Fuerstenau.D. W.,硅酸盐矿物结晶化学、表面性质和浮选行为[J],国外金属矿选矿,1978,(9):28-45.
4.孙传尧,印万忠.《硅酸盐矿物浮选原理》[M],北京:科学出版社,2001.
5.印万忠,孙传尧.硅酸盐矿物浮游性研究及晶体化学分析[J],有色金属(选矿部分),1983,(3):1-6.
6.印万忠.硅酸盐矿物晶体化学特征与表面特性及浮游性关系的研究[D],沈阳:东北大学,1999.
7.孙传尧,印万忠.关于硅酸盐矿物的浮游性与其晶体结构及表面特性关系的研究[J],矿冶,1998,(4):8-11.
8.孙传尧,印万忠.同一矿体中锂辉石、霓石浮游性差异分析[J],中国矿业大学学报,2001,30(6):531-536.
9.印万忠,孙传尧.硅酸盐矿物浮选原理研究现状[J],矿产利用与保护,2001,(3):17-22.
10.林慧博,印万忠,孙传尧.硅酸盐矿物表面金属离子吸附规律的XPS分析[J],有色矿冶,2003,19(3):21-24.
11.孙传尧,吕永信.用络合侵蚀浮选法分离霓石和铁矿物[J],有色金属(季刊),1982,(2):22-28.
12.孙传尧.分离钠铁硅酸盐霓石和铁矿物的新方法——络合侵蚀浮选法[D],北京:北京矿冶研究总院,1981.
13.孙传尧.霓石、赤铁矿对月桂胺、油酸和淀粉的吸附特性[J],北京矿冶研究总院报,1984,(3):44-50.
14.贾木欣.硅酸盐矿物表面特性的结构分析及对金属离子的吸附特性[D],沈阳:东北大学,2001.
15.贾小欣,孙传尧.几种硅酸盐矿物晶体化学与浮选表面特性研究[J].矿产保护与利用,2001(5):25-29.
16.贾木欣,孙传尧.几种硅酸盐矿物对金属离子吸附特性的研究[J].矿冶,2001,10(3):25-30.
17.贾木欣,孙传尧.几种硅酸盐矿物零电点、浮游性及键价分析[J].有色金属(选矿部分),2001,(6):1-9.
18.孙传尧,贾木欣.用油酸钠作捕收剂几种硅酸盐矿物浮游性的分析[J].有色金属,2001,53(4):57-61.
19.翁达,周灵初.烷基磺酸盐捕收红柱石作用机理初探[J],武汉冶金科学大学学报,1998,21(10):135-137.
20.K.S.孟,D.W.Fuerstenau从多种铝硅酸盐矿物中选择性浮选锂辉石的表面晶体化学研究[J],国外金属矿选矿,2004,(4):25-31.
21.C.德米尔等.在HF介质中用一价盐从微斜长石中选择性浮选钠长石[J],国外金属矿选矿,2004,(7):21-24.
22.刘亚川,龚焕高,张克仁.油酸钠和十二胺盐酸盐在长石和石英表面的吸附[J],东北工学院学报,1993,13(2):27-3.
23.梅光军,余军,葛英勇等.氟硅酸铵在赤铁矿与含铁硅酸盐浮选分离中[J].矿冶工程,2005,25(4):24-29.
24.陈湘清,胡岳华,王毓华.氟化钠在铝硅酸盐矿物浮选中的作用机理研究[J].金属矿山,2004,340(10):32-35.
25.彭兰,曹学锋,杜平.铝硅酸盐矿物捕收剂的设计研究[J].广西民族学院学报(自然科学版),2005,11(2):90-93.
26.凌石生,刘四清.铝土矿反浮选脱硅药剂评述[J].矿产保护与利用,2008(3):51-54.
27.张泽强.酸性水玻璃在磷矿浮选中的作用[J].中国非金属矿工业导刊,2003(2):39-41.
28.麦笑宇,梅光军,余永富.有机酸抑制剂对含铁硅酸盐矿物的抑制机理研究[J].矿冶工程,2001,21(4):25-28.
29.王毓华,于福顺,陈兴华,黄传兵,胡业民,兰叶.锂辉石与绿柱石浮选分离的试验研究[J],稀有金属,2005,29(3):320-323.
30. Jerzy A.Mielczarski, Ela Mielczarski. Activation and Collector Adsorption in Quartz-albite Flotation System[C], Proceedings of XXIV IMPC,2008:993-999.
31. Y. H. Wang. The Selective Flotation of Lithium and Beryl Minerals from Pegmatic Ore[C], Proceedings of XXIV IMPC,2008:1303-1307.
32. L. C. Zhou, Y. M. Zhang. The Flotation Study of Andalusite[C], Proceedings of XXIV IMPC,2008:1402-1406.
33.D.福马西罗等.Cu(Ⅱ)和Ni(Ⅱ)在石英、蛇纹石和绿泥石浮选中的活化作用[J].国外金属矿选矿,2006(10):16-20.
34.N.J.沙克莱顿等.在镍黄铁矿-辉石浮选系统中利用胺络合剂控制辉石的意外活化[J].国外金属矿选矿,2004(11):33-38.
35.G布鲁特等.比特利斯蓝晶石矿石的浮选行为[J],国外金属矿选矿,2004(8):28-32.
36.张开永.混合捕收剂在硅线石与白云母浮选分离中的应用研究[J].非金属矿,2003,26(6):38-39.
37.Л.A.格拉茹诺夫.无机药剂对萤石浮选的影响[J],国外金属矿选矿,2001(3):39-40.
38.A.维蒂亚德哈尔等.在长石与石英分离中阳离子捕收剂与阴离子捕收剂混合物在矿物表面上的吸附和浮选的选择性[J],国外金属矿选矿,2003(5):12-18.
39. E.C. Orhan, I. Bayraktar.Amine-oleate interactions in feldspar flotation[J], Minerals Engineering,2006(19):48-55.
40. WANG Yu-hua, YU Fu-shun.Effects of Metallic Ions on the Flotation of Spodumene and Beryl[J], China Univ Mining & Technol,2007,17(1):35-39
41. C.T. O'Connor, V. Malysiak, N.J.Shackleton. The interaction of xanthates and amines with pyroxene activated by copper and nickel[J], Minerals Engineering,2006 (19):799-806.
42. A.Vidyadhar, K.Hanumantha Rao. Adsorption mechanism of mixed cationic/anionic collectorsin feldspar-quartz flotation system[J], Journal of Colloid and Interface Science,2007 (306):195-204
43. V. Malysiak, N.J. Shackleton, C.T. O'Connor. An investigation into the floatability of a pentlandite-pyroxene system[J], Int. J. Miner. Process,2004 (74): 251-262
44.陈晔,陈建华,覃华.胺类捕收剂对异极矿等4种矿物浮选行为的影响[J],矿业研究与开发,2008,28(8):32-34.
45.胡振亚.对硅线石、石英和长石浮选行为的研究[J],有色矿冶,2005(增刊): 39-42
46.P.G.肖特里奇等.多糖抑制剂的化学成成份和分子量对滑石浮选的影响[J],国外金属矿选矿,2002(8):29-32
47.张宇平,黄可龙,刘素琴.反浮选法分离粉石英和斜绿泥石及其机理[J],中南大学学报(自然科学版),2007,38(2):285-289
48.S.普拉布哈卡尔等.硅灰石的溶解、浮选及其与牛脂1,3-氨基丙烷(DuomeenT)之间的表面作用[J],国外金属矿选矿,2006(5):15-20
49.G.E.莫里斯等.滑石-水界面上的聚合物抑制剂:吸附等温线、微量浮选和动电研究[J],国外金属矿选矿,2003(3):12-18
50.张国范,卢毅屏,冯其明.金川二矿区富矿石选矿新药剂应用研究[J],湖南有色金属,2001,17(5):6-7.
51.李晔,雷东升,许时.矿浆中金属离子对硅线石与石英浮选分离的影响[J],硅酸盐学报,2002,30(3):6-7
52.冯其明,刘谷山,喻正军等.铜离子和镍离子对滑石浮选的影响及作用机理[J],硅酸盐学报,2005,33(8):1018-1022.
53.冯其明,刘谷山,喻正军等.铁离子和亚铁离子对滑石浮选的影响及作用机理[J],中南大学学报(自然科学版),2006,37(3):42-44.
54.X.马等.术质素磺酸盐对滑石浮游性的影响[J],国外金属矿选矿,2008(3):28-33.
55.梅光军,薛玉兰,余永富,蔡辉莲.小分子有机酸抑制剂的研究[J].IM&P化工矿物与加工,2000(2):1-4.
56. H.H.Li, G.Franks. Role of Temperature-sensitive Polymers in Hydrophobic Aggregation/Flotation of Silicate Minerals[C], Proceedings of XXIV IMPC,2008: 1261-1269.
57.王毓华,于福啧.新型捕收剂浮选锂辉石和绿柱石[J].中南大学学报(自然科学版),2006.36(5):807-811.
58.王毓华.新型捕收剂浮选锂辉石试验研究[J].矿产综合利用,2002(5):11-13.
59.A.古尔等.细品石和锆石的浮选行为[J],国外金属矿选矿,2004(8):33-34.
60.赵世民,胡岳华,王淀佐,徐克.N-(2-氨乙基)-月桂酰胺浮选铝硅盐矿物的研究[J].物理化学学报,2003,19(6):573-576.
61.赵世民,胡岳华,王淀佐,张岳贵.N-(3-氦丙基)-月桂酰胺浮选铝硅酸盐矿物的研究[J].中国有色金属学报,2003,10(5):1273-1276.
62.胡岳华,曹学锋,蒋玉仁,李海普,杜平.N-烷基-1,3-丙二胺类捕收剂的结构与浮选铝硅酸盐矿物性能的研究[J].矿产保护与利用,2002,(6):33-37.
63.杜平,曹学锋,胡岳华,将玉仁,李海普.胺类捕收剂的结构与性能研究[J].轻金属,2003(1):27-31.
64.赵声贵,钟宏,刘广义.季铵盐捕收剂对铝硅矿物的浮选行为[J].金属矿山,2007(2):45-47.
65.潘迪来,刘宁江.浮选尾矿回收锂辉石的试验与生产实践[J],新疆有色金属,2008(6):58-59.
66.赵红芬.某金红石选矿试验研究[J],矿产保护与利用,2001(2):23-25.
67.吴艳妮,丁晓姜,杨丽珍.内蒙×××蓝晶石矿可选性试验研究[J],化工矿产地质,2008,30(2):103-107.
68.岳铁兵,曹进成,牛兰成,王燕.蓝晶石英岩型矿石选矿提纯工艺探索[J],中国非金属矿导刊,2003,34(4):61-62.
69.杨大兵,张一敏,赵自光.隐山蓝晶石矿选矿石工艺流程及综合利用研究[J],矿产保护与利用,2003(3):17-19.
70.苏永江,余郑生,赵东力,姬道新.含铁质蓝晶石选矿工艺研究[J],非金属矿,2003,23(6):35-37.
71.A.B.索萨等.葡萄牙锂辉石矿石的选矿研究[J].国外金属矿选矿,2001(10):29-31.
72.李玉红,李永聪.利用静态浮选柱回收白云母的研究[J].矿业快报,2006,443(5):13-16.
73.岳紫龙,李宏建,周亚飞.江西某钽铌矿浮选药剂调整研究[J].中国矿山工程,2006,35(5):7-9.
74.O.Y.古尔索伊等.由土耳其低品级伟晶岩矿石生产钾长石[J].国外金属矿选矿,2006(6):20-23.
75.邵广全.焦家金矿选矿厂尾矿综合利用选矿工艺研究[J].国外金属矿选矿2006(7):41-43.
76.王毓华,黄传兵,陈兴华,邓海波,伍喜庆.从某钽铌尾矿中回收长石和石英的试验研究[J].中国矿业,2005,14(9):38-40.
77.陈雯,曹佳宏,罗立群.氟少酸浮选分离石英与长石的试验研究[J].矿冶工程,2003,23(3):35-37.
78.M.S.塞利克等.从长石矿石中浮选有颜色的杂质矿物[J],国外金属矿选矿,2001(12):17-20.
79. V.Bozkurt, Y.Ucbas, S.Koca, H.Ipek. Recovery of feldspar from trachyte by flotation[J]. Minerals Engineering,2006(19):1216-1217.
80. C.Karaguzel, I.Gulgonul, C.Demir, M.Cinar, M.S. Celik. Concentration of K-feldspar from a pegmatitic feldspar ore by flotation[J]. Int. J. Miner. Process, 2006(81):122-132.
81.O.巴耶特等.在浮选土耳其长石矿石时不同捕收剂混合使用的效果[J],国外金属矿选矿,2006(10):14-15.
82.赵平,刘新海,张艳娇,常学勇.高铁硅线石矿选矿试验研究[J],非金属矿2007,31(3):22-24
83.张银年,张克仁,李洪潮等.硅灰石矿提纯新工艺研究[J],矿产保护与利用,2001(4):31-35
84.刘宁江.可可托海稀有矿V26、V38矿体锂辉石浮选试验研究[J],新疆有色金属,2001,17(5):6-7.
85.郭秀平,全文欣,张志强.某共生镜铁矿的反浮选试验研究[J],金属矿山,2004(2):32-34.
86.姜广大,王常任,李艳军.石油磺酸钠浮选铁矿工业试验中的几个问题分析[J],金属矿山,2004,10(增):364-367.
87.2A·布尔顿等.用聚丙烯酰胺聚合物选择性抑制黄铁矿[J],国外金属矿选矿,2001,3:36-38.
88.A·波尔顿,等.锌粗选中硫化铁矿物浮选的抑制[J].国外金属矿选矿,2002,(1):26-30(38).
89.陈经华,孙传尧.月桂胺浮选体系中菱锌矿和异极矿的浮游性研究[J],有色金属(选矿部分),2006,(2):45-47.
90.胡为柏.浮选[M],北京:冶金工业出版社,1989,132-154.
91.北京矿冶研究总院有机浮选药剂分析组编著.有机浮选药剂分析浮选,北京:冶金工业出版社,1987,269-272.
92.孙传尧,印万忠.硅酸盐矿物浮选原理[M],北京:科学出版社,2001,74-92.
93.胡熙庚等.浮选理论与工艺[M].长沙:中南大学工业出版社,1991.
94.孙传尧,印万忠.硅酸盐矿物浮选原理[M],北京:科学出版社,2001,366-381.
95.王文潜.有色金属(选矿部分).1977(1):20-23.
96.王淀佐,胡岳华.浮选溶液化学,长沙:湖南科学出版社,1988,35-37.
97.王淀佐,胡岳华.浮选溶液化学,长沙:湖南科学出版社,1988,32-35.
98.王淀佐,胡岳华.浮选溶液化学,长沙:湖南科学出版社,1988,132-138.
99. Poling G W.Flotation. Gaudin A M Memorial, VOl1, Fuerstenau M C, editor, 1976, chap.11:334-363.
100. Wadsworth M E and Doby P. Advances in Mineral Processing. Proceeding of a symp. Honoring Arbiter N on his 75th birthday. New Orleans. Somasundaran P, Editor, 1986, chap.26.
101.印万忠.硅酸盐矿物晶体化学特征与表面特性及浮游性关系的研究[D],沈阳:东北大学,1999,82-86.
102.贾木欣.硅酸盐矿物表面特性的结构分析及对金属离子的吸附特性[D],沈阳:东北大学,2001.
103.印万忠.硅酸盐矿物晶体化学特征与表面特性及浮游性关系的研究[D],沈阳:东北大学,1999,86-88.
104.王淀佐,胡岳华.浮选溶液化学,长沙:湖南科学出版社,1988,23-24.
105.孙传尧,印万忠.《硅酸盐矿物浮选原理》[M],北京:科学出版社,2001,287-294.
106.王淀佐,胡岳华.浮选溶液化学,长沙:湖南科学出版社,1988,21-23.
107.李毓康.含绿柱石、锂辉石矿石浮选分离工艺及“三碱”调整剂作用机理的研究[J],国外金属矿选矿,1991,(7-8),89-96.
108.张忠汉等.关于碳酸钠、氟化钠、硫化钠对Ca2+、Fe3+活化的绿柱石、锂辉石作用规律及作用机理的研究,1982,1(2),3-9.
109.印万忠.硅酸盐矿物晶体化学特征与表而特性及浮游性关系的研究[D],沈阳:东北大学,1999,105-106.
110.彭文世,刘高魁.矿物红外光谱图集.北京:北京石油出版社,1982,154-230.