羟肟酸类捕收剂的合成及其对钛铁矿的浮选性能研究
摘要
高效低成本低毒的浮选捕收剂的研制是钛铁矿浮选的关键,对提高我国矿产资源利用率具有重要的战略意义。论文选题来源于国家973项目“难处理金属矿高效浮选捕收剂的分子组装与合成”(编号：2007CB613602-3)。
通过对羟肟酸捕收剂合成工艺的优化,合成了对叔丁基苯甲羟肟酸、辛基羟肟酸、苯甲羟肟酸和水杨羟肟酸等一系列羟肟酸螯合捕收剂。在醇酸比为4.5,DBSA物质的量为酸的15%的条件下,酯化反应10 h。在不除去酯化产物中甲醇和DBSA的条件下,固定羟肟化反应溶剂中水醇重量比为5,按当量酯：盐酸羟胺：碱=1：1.2：2.2的反应物摩尔配比,50℃水浴搅拌反应4 h,对叔丁基苯甲羟肟酸的合成总转化率为82.83%。改进工艺合成的羟肟酸产品无需酸化提纯可直接应用于浮选。
采用单矿物实验考察羟肟酸捕收剂对钛铁矿、方解石、白云石及石英的浮选性能,结果表明：对叔丁基苯甲羟肟酸对钛铁矿的捕收效果最好,辛基羟肟酸次之。当对叔丁基苯甲羟肟浓度大于300 mg/L时,钛铁矿浮选回收率可以稳定在90%以上,辛基羟肟酸在达到200mg/L的浓度时,回收率在75%以上。用对叔丁基苯甲羟肟酸和辛基羟肟酸均可在矿浆pH=8时实现钛铁矿和石英的有效分离。攀枝花钛铁矿实际矿物浮选实验表明：采用改进工艺合成的羟肟酸捕收剂对实际矿物的捕收效果比羟肟酸纯品和单用传统选钛捕收剂更为显著,对攀枝花钛铁矿一步粗选的浮选回收率在84%左右,钛粗精矿品位为36%,体现出了组合用药的优势。
采用Zeta-电位测定、红外光谱分析、矿物表面电性分析以及矿物和羟肟酸的溶液化学分析,探讨了羟肟酸与钛铁矿的作用机理。Zeta-电位测定和红外光谱分析均表明,羟肟酸阴离子捕收剂与钛铁矿之间的作用为化学吸附作用。
The development of colloctors with high efficiency, low cost and low toxicity is not only the key to flotation of ilmenit, but also the significance for the exploitation of mineral resources. The thesis stems from the National 973 Program "molecular assembly and synthesis of high efficiency collectors for difficult processing ores" (No. 2007CB613602-3).
In this paper, a series of hydroximic acid collertors, including tert-butyl benzoic hydroximic acid, octanoic hydroximic acid, benzoic hydroximic acid and salicylic hydroximic acid, were prepared after searching and optimizing. For tert-butyl benzoic hydroximic acid, the results majorized as follow:alcohol-acid ratio was regulated at 4.5; the DBSA of 15% acid in mole as catalyst was introduced into the system and then esterificated for 10 h; the hydroxylamine hydrochloride was reacted with sodium hydroxide on condition that the ratio of equivalent ester, hydroxylamine hydrochloride and sodium hydroxide was 1:1.2:2.2; the mass ratio of water and alcohol in the hydroximation solvent was regulated at 5; without any purification, direct hydroximation sustained for 4 hours at the temperature of 50℃and the total conversion of 82.83% can be achieved. The hydroximic acids synthetized through improved process can be uesd as collectors derectly.
The monomineral experiments of ilmenite, calcite, dolomite and quartz present that the tert-butyl benzoic hydroximic acid and octanoic hydroximic acid collectors exhibit strong flotation capability on ilmenite while the benzoic hydroximic acid and salicylic hydroximic acid exhibit weak. The recovery of ilmenite is 75% under the condition that the concentration of octanoic hydroximic acid is 200 mg/L, and the recovery can preserve over 90% when the concentration of tert-butyl benzoic hydroximic acid reaches 300 mg/L. Therefore both of collectors are available to separate ilmenite from quartz. Accordingly, the actual mineral experiment of ilmenite form Panzhihua show that the hydroximic acids synthetized through improved process exhibit better results than pure collectors including oleic acid, hydroximic acids, oxidation paraffin soap and so on. Furthermore, using the tert-butyl benzoic hydroximic acid or octanoic hydroximic acid collectors can obtain a recovery of 84% with a content of 36% going by a roughing flotation.
The adsorption mechanism of the hydroximic acids on ilmenite has been investigated through Zeta-potential, IR spectrum measurements, surface electrical and solution chemical analysis. Zeta-potential and IR spectrum measurements confirm that the interaction between hydroximic acid collertors and ilmenit must be the chemical action.
通过对羟肟酸捕收剂合成工艺的优化,合成了对叔丁基苯甲羟肟酸、辛基羟肟酸、苯甲羟肟酸和水杨羟肟酸等一系列羟肟酸螯合捕收剂。在醇酸比为4.5,DBSA物质的量为酸的15%的条件下,酯化反应10 h。在不除去酯化产物中甲醇和DBSA的条件下,固定羟肟化反应溶剂中水醇重量比为5,按当量酯：盐酸羟胺：碱=1：1.2：2.2的反应物摩尔配比,50℃水浴搅拌反应4 h,对叔丁基苯甲羟肟酸的合成总转化率为82.83%。改进工艺合成的羟肟酸产品无需酸化提纯可直接应用于浮选。
采用单矿物实验考察羟肟酸捕收剂对钛铁矿、方解石、白云石及石英的浮选性能,结果表明：对叔丁基苯甲羟肟酸对钛铁矿的捕收效果最好,辛基羟肟酸次之。当对叔丁基苯甲羟肟浓度大于300 mg/L时,钛铁矿浮选回收率可以稳定在90%以上,辛基羟肟酸在达到200mg/L的浓度时,回收率在75%以上。用对叔丁基苯甲羟肟酸和辛基羟肟酸均可在矿浆pH=8时实现钛铁矿和石英的有效分离。攀枝花钛铁矿实际矿物浮选实验表明：采用改进工艺合成的羟肟酸捕收剂对实际矿物的捕收效果比羟肟酸纯品和单用传统选钛捕收剂更为显著,对攀枝花钛铁矿一步粗选的浮选回收率在84%左右,钛粗精矿品位为36%,体现出了组合用药的优势。
采用Zeta-电位测定、红外光谱分析、矿物表面电性分析以及矿物和羟肟酸的溶液化学分析,探讨了羟肟酸与钛铁矿的作用机理。Zeta-电位测定和红外光谱分析均表明,羟肟酸阴离子捕收剂与钛铁矿之间的作用为化学吸附作用。
The development of colloctors with high efficiency, low cost and low toxicity is not only the key to flotation of ilmenit, but also the significance for the exploitation of mineral resources. The thesis stems from the National 973 Program "molecular assembly and synthesis of high efficiency collectors for difficult processing ores" (No. 2007CB613602-3).
In this paper, a series of hydroximic acid collertors, including tert-butyl benzoic hydroximic acid, octanoic hydroximic acid, benzoic hydroximic acid and salicylic hydroximic acid, were prepared after searching and optimizing. For tert-butyl benzoic hydroximic acid, the results majorized as follow:alcohol-acid ratio was regulated at 4.5; the DBSA of 15% acid in mole as catalyst was introduced into the system and then esterificated for 10 h; the hydroxylamine hydrochloride was reacted with sodium hydroxide on condition that the ratio of equivalent ester, hydroxylamine hydrochloride and sodium hydroxide was 1:1.2:2.2; the mass ratio of water and alcohol in the hydroximation solvent was regulated at 5; without any purification, direct hydroximation sustained for 4 hours at the temperature of 50℃and the total conversion of 82.83% can be achieved. The hydroximic acids synthetized through improved process can be uesd as collectors derectly.
The monomineral experiments of ilmenite, calcite, dolomite and quartz present that the tert-butyl benzoic hydroximic acid and octanoic hydroximic acid collectors exhibit strong flotation capability on ilmenite while the benzoic hydroximic acid and salicylic hydroximic acid exhibit weak. The recovery of ilmenite is 75% under the condition that the concentration of octanoic hydroximic acid is 200 mg/L, and the recovery can preserve over 90% when the concentration of tert-butyl benzoic hydroximic acid reaches 300 mg/L. Therefore both of collectors are available to separate ilmenite from quartz. Accordingly, the actual mineral experiment of ilmenite form Panzhihua show that the hydroximic acids synthetized through improved process exhibit better results than pure collectors including oleic acid, hydroximic acids, oxidation paraffin soap and so on. Furthermore, using the tert-butyl benzoic hydroximic acid or octanoic hydroximic acid collectors can obtain a recovery of 84% with a content of 36% going by a roughing flotation.
The adsorption mechanism of the hydroximic acids on ilmenite has been investigated through Zeta-potential, IR spectrum measurements, surface electrical and solution chemical analysis. Zeta-potential and IR spectrum measurements confirm that the interaction between hydroximic acid collertors and ilmenit must be the chemical action.
引文
[1]Popperle J. Hydroxamate composition and method for froth flotation. German Patent,700735,1940-6-15
[2]Fueratenau M C. Flotation agent. United States Patent,3438494,1969-4-5
[3]Peterson H D. Transaction of American Institute of Mining, Metallurgical. Mining and Petroleum Engineers,1965(232):4～6
[4]Fuerstenau D W R, Herrera-Urbina D W. Studies on the applicability of chelating agents as universal collectors for copper minerals. International Journal of Mineral Processing,2000(58):15～33
[5]Bralurna S K, Charkraburtty A K. Studies of rare-earth with salicylhydroxamic acid. Journal of the Indian Chemical Society,1981(6):615～618
[6]Padma Desaraju, Anthony Winston. Synthesis and iron complexation studies of bis-hydroxamic acid. Journal of Coordination Chemistry,1986(14):241～248
[7]Hu Xicheng, Gregory L. Effect of metal ions on the quantitative determination of hydroxamic acids. Analytical Chemistry,1996,68(10):1812～1815
[8]李鸿波.聚醚桥连二异羟肟酸的合成及其双核钻(Ⅱ)配合物的氧加合性能.化学学报,2002,60(5)：886～891
[9]吕志凤.异羟肟酸过渡金属络合物在乙苯氧化中的催化性能研究.现代化工2000,20(5)：32～36
[10]章威,侯廷军,徐筱杰.MMP-2和Hydroxamate类抑制剂绝对自由能的计算.现代化工,2002,60(2)：221～227
[11]Willem Jacob van der Burg. Preparation of hydroxamic acid. United States Patent,3468936,1969-9-23
[12]James A. Hartlage. Method for preparation fatty hydroxamates. United States Patent,3933872,1976-1-20
[13]Sumual S Wang, Naragaj D R. Novel collectors and processes for making and using same. United States Patent,4871499,1989-10-3
[14]Shchukina N E, Ryaboi V I. Laboratory and industrial methods for the production of alkylhydroxamic acids. Chemical Abstracts,1974(80):95199k
[15]Gorlovskii S I, Khobotova N P. Synthesis of surfactant complex-forming hydroxamic acids and their use in beneficiation of rare metal. Chemical Abstracts,1976(66):4983g
[16]Gorlovskii S I, Golikor V V. Flotation agent. United States Patent,513970, 1976-5-15
[17]Hughes Terence Charles. Preparation of fatty hydroxamate. WIPO Patent, 02/10122A1,2002-2-7
[18]Terence Charles Hughes. Hydroxamate composition and method for froth flotation. United States Patent,70078005B2,2006-5-7
[19]Shchukina N E, Ryaboi V I. Synthesis of alkylhydroxamic acids in an aqueous-alkaline medium. Chemical Abstracts,1973(78):29193m
[20]Alan S Rothenburg, Lino Giovanni. Magliocco Mineral collector compositions and processes for making and using same. United States Patent,6739454B2, 2004-5-25
[21]黄林旋,张新民,徐根灿等.一种稀土矿物捕收剂的合成工艺.中国专利,1068247C，2001-7-11
[22]Chih Youg Ho, Eric David Strobel. Preparation of hydroxamic acids from esters in solution and on the solid phase. United States Patent,0009658Al,2006-1-12
[23]Pradip, Rai, Beena. Process for preparation of hydroxamic acid flotation collector and uses thereof. India Patent,2007MU00539A,2008-11-28
[24]周玉林,袁昊.水杨羟肟酸合成工艺的改进.现代矿业,2009,1(477)：47～49
[25]周玉林,袁昊.一种水杨羟肟酸的改进生产方法.中国专利,101519365A,2009-09-02
[26]Sekar Reddy A, Suresh Kumar M, Ravindra Reddy G. A convenient method for the preparation of hydroxamic acids. Tetrahedron Letters,2000(41):6285～6288
[27]邱显扬,高玉德.苯甲羟肟酸与但铌锰矿作用机理的研究.有色金属(选矿部分),2005(6)：37～40
[28]姬俊梅.烷基羟肟酸盐与铌铁金红石的作用机理研究.有色金属(选矿部分),2004(4)：42～44
[29]Natarajan R, Nirdosh I. Application of topochemical, topostructural, physicochemical and geometrical parameters to model the flotation efficiencies of N-arylhydroxamic acids. International Journal of Mineral Processing, 2003(71):113～129.
[30]费九光.影响羟肟酸合成质量指标主要因素的分析.有色矿冶,1999(3)：26～30
[31]曾庆兴,李芳积.一种氟碳铈矿选择性捕收剂.中国专利,1090226A,1994-08-06
[32]任俊,卢寿慈,池汝安.1-羟基-2-萘羟肟酸浮选氟碳铈矿作用机理.中国有色金属学报,1996,6(4)：24～28
[33]Ren J, Lu S, Song S, et al. A new collector for rare earth mineral flotation. Minerals Engineering,1997,10(12):1395～1404
[34]朱申红,荀志远,冯婕.浮选氟碳铈矿的捕收剂及药剂混用的研究.金属矿山,2000(8)：32～34
[35]高玉德,邱显扬,冯其明.钽铌矿捕收剂的研究.广东有色金属学报,2003,13(2)：79～82
[36]戴子林,张秀玲,高玉德.苯甲羟肟酸浮选细粒黑钨矿的研究.矿冶工程,1995,15(2)：24～27
[37]高玉德,邱显扬,冯其明.苯甲羟肟酸捕收白钨矿浮选溶液化学研究.有色金属(选矿部分),2003(4)：28～30
[38]刘德全,周春山,王淀佐.铜铁灵与苯异羟肟酸浮选锡石的交互作用及其机理.中国有色金属学报,1994,4(4)：46～49
[39]Sreenivas T, Padmanabhan N P H. Surface chemistry and flotation of cassiterite with alkylhydroxamates. Colloids and Surfaces,2005,205:47～59
[40]杨佳,李奎,唐爱涛,等.钛铁矿资源综合利用现状与发展.材料导报,2003(8)：44～46
[41]文孝廉,郭明彬,冉定伟.攀枝花地区钛资源利用现状、存在的问题及对策.金属矿山,2008(8)：5～8
[42]周友斌.攀枝花细粒钛铁矿浮选工艺在生产中应用探讨.金属矿山,2000(1)：32～36
[43]傅文章,张渊,洪秉信,等.攀枝花微细粒级钛铁矿选矿试验研究.金属矿山,2000(2)：37～45
[44]朱阳戈,张国范,冯其明,等.微细粒钛铁矿的自载体浮选.中国有色金属学报,2009(3)：554～560
[45]韦连军,黄庆柒,廖江南.云南文山某细粒钛铁矿选矿试验研究.金属矿山,2010(7)：51～54
[46]张元军,熊大和SLon磁选机分选超细粒级钛铁矿的试验研究.江西理工大学学报,2009(5)：18～20
[47]王彦莉,曲鸿鲁.山东某钛铁矿的磁选试验研究.有色金属(选矿部分),2010(1)：29～32
[48]戴新宇.原生钛铁矿选矿技术的进展.中国矿业,2002,11(2)：52～58
[49]戴惠新,张宗华.细粒钛铁矿选矿新工艺研究.国外金属矿选矿,1998(5)： 22～24
[50]朱玉霜,朱建光.浮选药剂的化学原理.长沙：中南工业大学出版社,1988：125～128
[51]冯其明,席振伟,张国范,等.脂肪酸捕收剂浮选钛铁矿性能研究.金属矿山,2009(5)：46～49
[52]Gutierreza C. Influence of previous aeration in water or heming in air of ilmenite on its flotation with oleic acid. International Journal of Mineral Processing,1976, 3(3):247～256
[53]Parkins E J, Shergold H L. The effect of temperature on the conditioning and flotation ofan ilmenite ore. A.M. Gaudin Memorial,1976(1):561～579
[54]Fan X, Rowson N A. The effect of Pb(NO3)2 on ilmenite flotation. Minerals Engineering,2000,13(2):205～215
[55]Laapas Heikki R. Flotation with oleic acid. United States Patent,3913742, 1975-6-25
[56]周军.攀枝花细粒级钛铁矿混合药剂浮选研究.矿冶工程,1996(9)：35～38
[57]唐德身.用异羟肟酸浮选钛铁矿的实验研究.矿产综合利用,1977(1)：17～21
[58]董宏军,陈正学.水杨羟肟酸浮选细粒钛铁矿的研究.矿冶工程,1991(3)：19～22
[59]贺智明,董雍赓.金红石和钛铁矿的浮选性能研究明.稀有金属,1993,4(7)：250～254
[60]胡永平,张毅瑾.混合捕收剂浮选细粒钛铁矿的研究.有色金属,1994,64(3)：31～35
[61]任志民.苯乙烯膦酸作捕收剂浮选攀枝花钛铁矿研究.矿冶工程,1980(10)：29～34
[62]任志民.应用强磁-浮选法苯乙烯膦酸作捕收剂浮选攀枝花钛铁矿.矿冶工程,1982(1)：22～29
[63]胡永平,梁绪树,崔林.双膦酸捕收剂浮选钛铁矿的研究.有色金属,1992(4)：26～30
[64]王钊军,劳晓峰.一种含羟基烷叉双膦酸钛铁矿捕收剂的合成及浮选性能研究.矿产综合利用,2010(4)：24～26
[65]Song Quanyuan. Flotation of ilmenit using benzyl arsenic adid and acidified sodium silicate. Mineral Process,1989(26):111～121
[66]魏民.新型钛铁矿浮选捕收剂的研究：[硕士学位论文].长沙：长沙矿冶研究院,2006
[67]许宜蔚.煤油对苯乙烯磷酸浮选钛铁矿的作用.矿冶工程,1981(4)：12～17
[68]Belardi G. Improve TiO2 in the scrap through physical method. International Journal of Mineral Processing,1998,53(3):145～146
[69]Ibrahim S S. Refining of silicates by flotation to meet glassmaking applications. Tenside Surfactants Detergents,2003,40(3):135～138
[70]朱建光,朱玉霜,王升鹤,等.利用协同效应最佳点配制钛铁矿捕收剂.有色金属(选矿部分),2000(4)：39～41
[71]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 12717-2007.工业用乙酸酯类试验方法.北京：中国标准出版社,2007-10-17
[72]Nery R. The colorimetric determination of hydroxamic acids. Analyst,1966, 91(1083):388～394
[73]Roncucci R, Simon M J, Briesen V, et al. Automatic colorimetric determination of hydroxamic acids at the microgram level. Analytical Letters,1971,4(4): 197～203
[74]Sang L K. Determination of salicylhydroxamic acid, salicylic acid. Analytical Chemistry,1970(42):554～556
[75]Kyoichi Kobashi, Kazuo Sakaguchi, Sachiko Takebe, et al. A colorimetric method for the determination of hydroxamic acid by iodine oxidation. Analytical Biochemistry,1985,146(1):7～12
[76]Bednar H J, Willis R B. Determination of salicylhydroxamic acid by spectrophotometry. Journal of Chemical Ecology,1987(13):337～380
[77]Rosemary L K. Separation and determination of collectors by TLC. Journal of Analytical Toxicology,1991(15):270～276
[78]Zhou Chunshan, Xiong Xingan, Wu Mingjian. HPLC determination of collectors used for the flotation of heavy metal minerals. Journal of Analytical Chemistry, 1997(357):894～896
[79]Proskurine M A, Orlova N V, Pikhtar A V, et al. Determination of hydroxamic acids by thermal-lens spectrometry. Journal of Analytical Chemistry,2004, 59(5):433～437
[80]Katan P, Sylvie M, Duncan I. Simultaneous determination of decitabine and vorinostat (Suberoylanalide hydroxamic acid, SAHA) by liquid chromatography tandem mass spectrometry for clinical studies. Journal of Chromatography,2008, 863(1):19～25
[81]Zhang Baoyuan, Zhong Hong. Determination of hydroxamic acids by direct spectrophotometry of coloured complex in acidic solution. Research on Chemical Intermediates,2010,36(5):495～501
[82]关鲁雄.化学基本操作与物质制备实验.长沙：中南大学出版社,2002：284～285
[83]刘承先.对甲苯磺酸催化合成苯甲酸丙酯.化学工程师,2005,118(7)：13～14
[84]孟庆民,张爱黎.用十二烷基苯磺酸催化合成没食子酸正戊酯.当代化工,2002,31(3)：136～138
[85]李忠荣,蒲劲松.原生钛铁矿选矿技术的进展.国外金属矿选矿,2001(3)：20～22
[86]朱建光.金红石与钛铁矿的浮选.有色矿冶,1997(3)：28～35
[87]朱俊士.中国钒钛磁铁矿选矿.北京：冶金工业出版社,1996：55～60
[88]彭文世,刘高魁.矿物红外光谱图集.北京：科学技术出版社,1982：107
[2]Fueratenau M C. Flotation agent. United States Patent,3438494,1969-4-5
[3]Peterson H D. Transaction of American Institute of Mining, Metallurgical. Mining and Petroleum Engineers,1965(232):4～6
[4]Fuerstenau D W R, Herrera-Urbina D W. Studies on the applicability of chelating agents as universal collectors for copper minerals. International Journal of Mineral Processing,2000(58):15～33
[5]Bralurna S K, Charkraburtty A K. Studies of rare-earth with salicylhydroxamic acid. Journal of the Indian Chemical Society,1981(6):615～618
[6]Padma Desaraju, Anthony Winston. Synthesis and iron complexation studies of bis-hydroxamic acid. Journal of Coordination Chemistry,1986(14):241～248
[7]Hu Xicheng, Gregory L. Effect of metal ions on the quantitative determination of hydroxamic acids. Analytical Chemistry,1996,68(10):1812～1815
[8]李鸿波.聚醚桥连二异羟肟酸的合成及其双核钻(Ⅱ)配合物的氧加合性能.化学学报,2002,60(5)：886～891
[9]吕志凤.异羟肟酸过渡金属络合物在乙苯氧化中的催化性能研究.现代化工2000,20(5)：32～36
[10]章威,侯廷军,徐筱杰.MMP-2和Hydroxamate类抑制剂绝对自由能的计算.现代化工,2002,60(2)：221～227
[11]Willem Jacob van der Burg. Preparation of hydroxamic acid. United States Patent,3468936,1969-9-23
[12]James A. Hartlage. Method for preparation fatty hydroxamates. United States Patent,3933872,1976-1-20
[13]Sumual S Wang, Naragaj D R. Novel collectors and processes for making and using same. United States Patent,4871499,1989-10-3
[14]Shchukina N E, Ryaboi V I. Laboratory and industrial methods for the production of alkylhydroxamic acids. Chemical Abstracts,1974(80):95199k
[15]Gorlovskii S I, Khobotova N P. Synthesis of surfactant complex-forming hydroxamic acids and their use in beneficiation of rare metal. Chemical Abstracts,1976(66):4983g
[16]Gorlovskii S I, Golikor V V. Flotation agent. United States Patent,513970, 1976-5-15
[17]Hughes Terence Charles. Preparation of fatty hydroxamate. WIPO Patent, 02/10122A1,2002-2-7
[18]Terence Charles Hughes. Hydroxamate composition and method for froth flotation. United States Patent,70078005B2,2006-5-7
[19]Shchukina N E, Ryaboi V I. Synthesis of alkylhydroxamic acids in an aqueous-alkaline medium. Chemical Abstracts,1973(78):29193m
[20]Alan S Rothenburg, Lino Giovanni. Magliocco Mineral collector compositions and processes for making and using same. United States Patent,6739454B2, 2004-5-25
[21]黄林旋,张新民,徐根灿等.一种稀土矿物捕收剂的合成工艺.中国专利,1068247C，2001-7-11
[22]Chih Youg Ho, Eric David Strobel. Preparation of hydroxamic acids from esters in solution and on the solid phase. United States Patent,0009658Al,2006-1-12
[23]Pradip, Rai, Beena. Process for preparation of hydroxamic acid flotation collector and uses thereof. India Patent,2007MU00539A,2008-11-28
[24]周玉林,袁昊.水杨羟肟酸合成工艺的改进.现代矿业,2009,1(477)：47～49
[25]周玉林,袁昊.一种水杨羟肟酸的改进生产方法.中国专利,101519365A,2009-09-02
[26]Sekar Reddy A, Suresh Kumar M, Ravindra Reddy G. A convenient method for the preparation of hydroxamic acids. Tetrahedron Letters,2000(41):6285～6288
[27]邱显扬,高玉德.苯甲羟肟酸与但铌锰矿作用机理的研究.有色金属(选矿部分),2005(6)：37～40
[28]姬俊梅.烷基羟肟酸盐与铌铁金红石的作用机理研究.有色金属(选矿部分),2004(4)：42～44
[29]Natarajan R, Nirdosh I. Application of topochemical, topostructural, physicochemical and geometrical parameters to model the flotation efficiencies of N-arylhydroxamic acids. International Journal of Mineral Processing, 2003(71):113～129.
[30]费九光.影响羟肟酸合成质量指标主要因素的分析.有色矿冶,1999(3)：26～30
[31]曾庆兴,李芳积.一种氟碳铈矿选择性捕收剂.中国专利,1090226A,1994-08-06
[32]任俊,卢寿慈,池汝安.1-羟基-2-萘羟肟酸浮选氟碳铈矿作用机理.中国有色金属学报,1996,6(4)：24～28
[33]Ren J, Lu S, Song S, et al. A new collector for rare earth mineral flotation. Minerals Engineering,1997,10(12):1395～1404
[34]朱申红,荀志远,冯婕.浮选氟碳铈矿的捕收剂及药剂混用的研究.金属矿山,2000(8)：32～34
[35]高玉德,邱显扬,冯其明.钽铌矿捕收剂的研究.广东有色金属学报,2003,13(2)：79～82
[36]戴子林,张秀玲,高玉德.苯甲羟肟酸浮选细粒黑钨矿的研究.矿冶工程,1995,15(2)：24～27
[37]高玉德,邱显扬,冯其明.苯甲羟肟酸捕收白钨矿浮选溶液化学研究.有色金属(选矿部分),2003(4)：28～30
[38]刘德全,周春山,王淀佐.铜铁灵与苯异羟肟酸浮选锡石的交互作用及其机理.中国有色金属学报,1994,4(4)：46～49
[39]Sreenivas T, Padmanabhan N P H. Surface chemistry and flotation of cassiterite with alkylhydroxamates. Colloids and Surfaces,2005,205:47～59
[40]杨佳,李奎,唐爱涛,等.钛铁矿资源综合利用现状与发展.材料导报,2003(8)：44～46
[41]文孝廉,郭明彬,冉定伟.攀枝花地区钛资源利用现状、存在的问题及对策.金属矿山,2008(8)：5～8
[42]周友斌.攀枝花细粒钛铁矿浮选工艺在生产中应用探讨.金属矿山,2000(1)：32～36
[43]傅文章,张渊,洪秉信,等.攀枝花微细粒级钛铁矿选矿试验研究.金属矿山,2000(2)：37～45
[44]朱阳戈,张国范,冯其明,等.微细粒钛铁矿的自载体浮选.中国有色金属学报,2009(3)：554～560
[45]韦连军,黄庆柒,廖江南.云南文山某细粒钛铁矿选矿试验研究.金属矿山,2010(7)：51～54
[46]张元军,熊大和SLon磁选机分选超细粒级钛铁矿的试验研究.江西理工大学学报,2009(5)：18～20
[47]王彦莉,曲鸿鲁.山东某钛铁矿的磁选试验研究.有色金属(选矿部分),2010(1)：29～32
[48]戴新宇.原生钛铁矿选矿技术的进展.中国矿业,2002,11(2)：52～58
[49]戴惠新,张宗华.细粒钛铁矿选矿新工艺研究.国外金属矿选矿,1998(5)： 22～24
[50]朱玉霜,朱建光.浮选药剂的化学原理.长沙：中南工业大学出版社,1988：125～128
[51]冯其明,席振伟,张国范,等.脂肪酸捕收剂浮选钛铁矿性能研究.金属矿山,2009(5)：46～49
[52]Gutierreza C. Influence of previous aeration in water or heming in air of ilmenite on its flotation with oleic acid. International Journal of Mineral Processing,1976, 3(3):247～256
[53]Parkins E J, Shergold H L. The effect of temperature on the conditioning and flotation ofan ilmenite ore. A.M. Gaudin Memorial,1976(1):561～579
[54]Fan X, Rowson N A. The effect of Pb(NO3)2 on ilmenite flotation. Minerals Engineering,2000,13(2):205～215
[55]Laapas Heikki R. Flotation with oleic acid. United States Patent,3913742, 1975-6-25
[56]周军.攀枝花细粒级钛铁矿混合药剂浮选研究.矿冶工程,1996(9)：35～38
[57]唐德身.用异羟肟酸浮选钛铁矿的实验研究.矿产综合利用,1977(1)：17～21
[58]董宏军,陈正学.水杨羟肟酸浮选细粒钛铁矿的研究.矿冶工程,1991(3)：19～22
[59]贺智明,董雍赓.金红石和钛铁矿的浮选性能研究明.稀有金属,1993,4(7)：250～254
[60]胡永平,张毅瑾.混合捕收剂浮选细粒钛铁矿的研究.有色金属,1994,64(3)：31～35
[61]任志民.苯乙烯膦酸作捕收剂浮选攀枝花钛铁矿研究.矿冶工程,1980(10)：29～34
[62]任志民.应用强磁-浮选法苯乙烯膦酸作捕收剂浮选攀枝花钛铁矿.矿冶工程,1982(1)：22～29
[63]胡永平,梁绪树,崔林.双膦酸捕收剂浮选钛铁矿的研究.有色金属,1992(4)：26～30
[64]王钊军,劳晓峰.一种含羟基烷叉双膦酸钛铁矿捕收剂的合成及浮选性能研究.矿产综合利用,2010(4)：24～26
[65]Song Quanyuan. Flotation of ilmenit using benzyl arsenic adid and acidified sodium silicate. Mineral Process,1989(26):111～121
[66]魏民.新型钛铁矿浮选捕收剂的研究：[硕士学位论文].长沙：长沙矿冶研究院,2006
[67]许宜蔚.煤油对苯乙烯磷酸浮选钛铁矿的作用.矿冶工程,1981(4)：12～17
[68]Belardi G. Improve TiO2 in the scrap through physical method. International Journal of Mineral Processing,1998,53(3):145～146
[69]Ibrahim S S. Refining of silicates by flotation to meet glassmaking applications. Tenside Surfactants Detergents,2003,40(3):135～138
[70]朱建光,朱玉霜,王升鹤,等.利用协同效应最佳点配制钛铁矿捕收剂.有色金属(选矿部分),2000(4)：39～41
[71]中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB/T 12717-2007.工业用乙酸酯类试验方法.北京：中国标准出版社,2007-10-17
[72]Nery R. The colorimetric determination of hydroxamic acids. Analyst,1966, 91(1083):388～394
[73]Roncucci R, Simon M J, Briesen V, et al. Automatic colorimetric determination of hydroxamic acids at the microgram level. Analytical Letters,1971,4(4): 197～203
[74]Sang L K. Determination of salicylhydroxamic acid, salicylic acid. Analytical Chemistry,1970(42):554～556
[75]Kyoichi Kobashi, Kazuo Sakaguchi, Sachiko Takebe, et al. A colorimetric method for the determination of hydroxamic acid by iodine oxidation. Analytical Biochemistry,1985,146(1):7～12
[76]Bednar H J, Willis R B. Determination of salicylhydroxamic acid by spectrophotometry. Journal of Chemical Ecology,1987(13):337～380
[77]Rosemary L K. Separation and determination of collectors by TLC. Journal of Analytical Toxicology,1991(15):270～276
[78]Zhou Chunshan, Xiong Xingan, Wu Mingjian. HPLC determination of collectors used for the flotation of heavy metal minerals. Journal of Analytical Chemistry, 1997(357):894～896
[79]Proskurine M A, Orlova N V, Pikhtar A V, et al. Determination of hydroxamic acids by thermal-lens spectrometry. Journal of Analytical Chemistry,2004, 59(5):433～437
[80]Katan P, Sylvie M, Duncan I. Simultaneous determination of decitabine and vorinostat (Suberoylanalide hydroxamic acid, SAHA) by liquid chromatography tandem mass spectrometry for clinical studies. Journal of Chromatography,2008, 863(1):19～25
[81]Zhang Baoyuan, Zhong Hong. Determination of hydroxamic acids by direct spectrophotometry of coloured complex in acidic solution. Research on Chemical Intermediates,2010,36(5):495～501
[82]关鲁雄.化学基本操作与物质制备实验.长沙：中南大学出版社,2002：284～285
[83]刘承先.对甲苯磺酸催化合成苯甲酸丙酯.化学工程师,2005,118(7)：13～14
[84]孟庆民,张爱黎.用十二烷基苯磺酸催化合成没食子酸正戊酯.当代化工,2002,31(3)：136～138
[85]李忠荣,蒲劲松.原生钛铁矿选矿技术的进展.国外金属矿选矿,2001(3)：20～22
[86]朱建光.金红石与钛铁矿的浮选.有色矿冶,1997(3)：28～35
[87]朱俊士.中国钒钛磁铁矿选矿.北京：冶金工业出版社,1996：55～60
[88]彭文世,刘高魁.矿物红外光谱图集.北京：科学技术出版社,1982：107