新型铁矿阳离子捕收剂的浮选及泡沫性能研究
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摘要
我国铁矿资源以贫、细、杂为主,提铁降硅是浮选工业中最重要的一环,目前我国阴离子捕收剂应用比较普遍,但是阴离子反浮选工艺存在许多不足：药剂制度复杂(需使用调整剂、抑制剂、活化剂、捕收剂),操作复杂,药剂费用高,需加温浮选,另外矿浆pH较高对设备腐蚀也有影响。相比较而言,阳离子反浮选有很大的优势。
本论文在总结和分析大量国内外相关文献的基础上,针对传统阳离子捕收剂泡沫丰富的缺点,开展了新型阳离子捕收剂的合成研究工作,通过试验研究,合成了一系列新型阳离子捕收剂。
本论文成功筛选了一种新型阳离子捕收剂DHPA-3,合成工艺为摩尔比DDA:HOB为1：1.4,反应温度为60℃,反应时间为6小时。
实际矿石试验结果表明：对含41.95%Fe的粗铁精矿,在自然pH条件下,添加DHPA-3捕收剂250g/t,淀粉1000g/t,仅经一次浮选获得了铁精矿62.60%Fe,铁回收率为53.87%的良好指标。
捕收剂DHPA-3、十二胺、十二烷基二甲基叔胺和十二烷基三甲基氯化铵的粗铁精矿反浮选表明,DHPA-3和十二胺均取得了较好的浮选指标,十二烷基二甲基叔胺和十二烷基三甲基氯化铵的浮选指标则不太理想,捕收能力强弱顺序为：十二胺>DHPA-3>十二烷基二甲基叔胺>十二烷基三甲基氯化铵。
三相泡沫试验结果表明：十二胺的三相泡沫最丰富,而且最不容易消泡,其它三种药剂泡沫性能则相差不大,消泡速度快慢顺序为：十二烷基三甲基氯化铵>DHPA-3>十二烷基二甲基叔胺>十二胺。
二相泡沫试验结果表明：捕收剂DHPA-3、十二胺、十二烷基二甲基叔胺和十二烷基三甲基氯化铵比较而言,十二烷基二甲基叔胺的起泡能力弱于其它三种药剂,其它三种药剂的起泡能力则相差不大,从消泡时间来看,十二烷基三甲基氯化铵的消泡时间最短,其次为DHPA-3,后面是十二胺,消泡最慢是十二烷基二甲基叔胺,二相泡沫表现与三相泡沫稍有不同。
淀粉在阳离子反浮选中不仅可以作为铁矿物的抑制剂,而且还能改善阳离子泡沫性能,适量淀粉的加入,使得阳离子捕收剂的泡沫量显著下降。
The main characteristics of Chinese iron ore resources are poor, fine grained and complicated. It is important to add the flotation process to separate silicate from the iron ore. The anionic reverse flotation process is more popular currently, but there are many shortages:the complicated reagent system (with the regulator, depressant, activator, collector), complicated operation, high cost of reagents, higher flotation temperature, equipment corrosion. In comparison, cationic reverse flotation has great advantages.
On the basis of the summary and analysis of many related references, a series of new cationic collectors are synthesized through lots of experimental research to improve the froth performance of traditional cationic collectors.
A new cationic collector DHPA-3 is synthesized, the synthesis conditions:DDA:HOB=1:1.4(molar ratio), reaction temperature:60℃, reaction time:6 h.
The test results of the real ore show that an iron concentrate of 62.60% Fe was obtained with a recovery of 53.87% through one roughing when using 1000g/t starch as depressant and 250g/t DHPA-3 as collector at natural pH. The feed grade is 41.95%.
Flotation results show that using DHPA-3 and dodecyl amine as collectors tests achieved good separation while dodecyl dimethyl amine and dodecyl trimethyl ammonium chloride didn't work well, and their collecting abilities are in the sequence of dodecyl amine> DHPA-3> dodecyl dimethyl amine> dodecyl trimethyl ammonium chloride.
Tests of Three-phase froth indicated that dodecyl amine created biggest volume of froth and defoamed at the slowest rate, and their defoaming rate is in the sequence of dodecyl trimethyl ammonium chloride> DHPA-3> dodecyl dimethyl amine> dodecyl amine.
Tests of Two-phase froth indicated that dodecyl dimethyl amine has weaker foaming ability, and three other reagents have the same foaming ability. Lauryl trimethyl ammonium chloride defoams fastest, while DHPA-3 defoams faster than dodecyl amine, dodecyl dimethyl amine defoams slowest. Two-phase froth has a little different performance from Three-phase froth.
In the cationic reverse flotation of iron ore, starch not only can be used as depressant, but also can be used to improve the froth performance. Adding right amount of starch can significantly decrease the volume of froth.
本论文在总结和分析大量国内外相关文献的基础上,针对传统阳离子捕收剂泡沫丰富的缺点,开展了新型阳离子捕收剂的合成研究工作,通过试验研究,合成了一系列新型阳离子捕收剂。
本论文成功筛选了一种新型阳离子捕收剂DHPA-3,合成工艺为摩尔比DDA:HOB为1：1.4,反应温度为60℃,反应时间为6小时。
实际矿石试验结果表明：对含41.95%Fe的粗铁精矿,在自然pH条件下,添加DHPA-3捕收剂250g/t,淀粉1000g/t,仅经一次浮选获得了铁精矿62.60%Fe,铁回收率为53.87%的良好指标。
捕收剂DHPA-3、十二胺、十二烷基二甲基叔胺和十二烷基三甲基氯化铵的粗铁精矿反浮选表明,DHPA-3和十二胺均取得了较好的浮选指标,十二烷基二甲基叔胺和十二烷基三甲基氯化铵的浮选指标则不太理想,捕收能力强弱顺序为：十二胺>DHPA-3>十二烷基二甲基叔胺>十二烷基三甲基氯化铵。
三相泡沫试验结果表明：十二胺的三相泡沫最丰富,而且最不容易消泡,其它三种药剂泡沫性能则相差不大,消泡速度快慢顺序为：十二烷基三甲基氯化铵>DHPA-3>十二烷基二甲基叔胺>十二胺。
二相泡沫试验结果表明：捕收剂DHPA-3、十二胺、十二烷基二甲基叔胺和十二烷基三甲基氯化铵比较而言,十二烷基二甲基叔胺的起泡能力弱于其它三种药剂,其它三种药剂的起泡能力则相差不大,从消泡时间来看,十二烷基三甲基氯化铵的消泡时间最短,其次为DHPA-3,后面是十二胺,消泡最慢是十二烷基二甲基叔胺,二相泡沫表现与三相泡沫稍有不同。
淀粉在阳离子反浮选中不仅可以作为铁矿物的抑制剂,而且还能改善阳离子泡沫性能,适量淀粉的加入,使得阳离子捕收剂的泡沫量显著下降。
The main characteristics of Chinese iron ore resources are poor, fine grained and complicated. It is important to add the flotation process to separate silicate from the iron ore. The anionic reverse flotation process is more popular currently, but there are many shortages:the complicated reagent system (with the regulator, depressant, activator, collector), complicated operation, high cost of reagents, higher flotation temperature, equipment corrosion. In comparison, cationic reverse flotation has great advantages.
On the basis of the summary and analysis of many related references, a series of new cationic collectors are synthesized through lots of experimental research to improve the froth performance of traditional cationic collectors.
A new cationic collector DHPA-3 is synthesized, the synthesis conditions:DDA:HOB=1:1.4(molar ratio), reaction temperature:60℃, reaction time:6 h.
The test results of the real ore show that an iron concentrate of 62.60% Fe was obtained with a recovery of 53.87% through one roughing when using 1000g/t starch as depressant and 250g/t DHPA-3 as collector at natural pH. The feed grade is 41.95%.
Flotation results show that using DHPA-3 and dodecyl amine as collectors tests achieved good separation while dodecyl dimethyl amine and dodecyl trimethyl ammonium chloride didn't work well, and their collecting abilities are in the sequence of dodecyl amine> DHPA-3> dodecyl dimethyl amine> dodecyl trimethyl ammonium chloride.
Tests of Three-phase froth indicated that dodecyl amine created biggest volume of froth and defoamed at the slowest rate, and their defoaming rate is in the sequence of dodecyl trimethyl ammonium chloride> DHPA-3> dodecyl dimethyl amine> dodecyl amine.
Tests of Two-phase froth indicated that dodecyl dimethyl amine has weaker foaming ability, and three other reagents have the same foaming ability. Lauryl trimethyl ammonium chloride defoams fastest, while DHPA-3 defoams faster than dodecyl amine, dodecyl dimethyl amine defoams slowest. Two-phase froth has a little different performance from Three-phase froth.
In the cationic reverse flotation of iron ore, starch not only can be used as depressant, but also can be used to improve the froth performance. Adding right amount of starch can significantly decrease the volume of froth.
引文
[1]谢承祥,李厚民,王瑞江,等.中国查明铁矿资源储量的数量、分布及保障程度分析.地球学报,2009,30(3)：387～393
[2]牛志霖.关于中国钢铁工业发展问题的思考.北京建筑工程学院学报,2010,26(3)：8～12
[3]刘贤信.我国铁矿石可供性分析及评价体系框架.矿业研究与开发,2010,30(5)：107～109
[4]宋仁峰,李维兵,刘华艳.我国铁矿石选矿技术发展特点及展望.金属矿山,2009,(1)：1-8
[5]陈亮亮,刘养洁.世界铁矿资源分布对我国钢铁工业发展的影响.经济研究导刊,2010,(5)：35～37
[6]王淑丽.我国铁矿资源评估与可供性研究：[硕士学位论文].北京：中国地质大学,2010
[7]吴荣庆.国产铁矿尚有潜力.中国金属通报,2009,(32)：12～15
[8]魏志江.铁矿资源开发利用分析与预测.中国矿业,2010,19(3)：10～12
[9]谢承祥,李厚民,王瑞江,等.中国已查明的铁矿资源的结构特征.地质通报,2009,28(1)：80-84
[10]侯宗林.中国铁矿资源现状与潜力.地质找矿论丛,2005,20(4)：242-247
[11]邱俊,吕宪俊,陈平,等.铁矿选矿技术.北京：化学工业出版社,2009.1～217
[12]宋占利.浅析南芬选矿厂可持续发展.矿业工程,2005,(5)：22～24
[13]李振,刘炯天,魏德洲,等.铁矿分选技术进展.金属矿山,2008,(5)：2-3
[14]张国庆,李维兵,白晓鸣.调军台选矿厂工艺流程研究及实践.金属矿山,2006,(3)：39～41
[15]陈江安,曾捷,龚恩民,等.褐铁矿选矿工艺的现状及发展.江西理工大学学报,2010,31(5)：5-8
[16]A.C. Araujo, P.R.M. Viana, A.E.C. Peres. Reagents in iron ores flotation. Minerals Engineering,2005,18(2):219-224
[17]葛英勇,余俊,朱鹏程.铁矿浮选药剂评述.现代矿业,2009,(11)：6-10
[18]王淀佐,邱冠周,胡岳华.资源加工学.北京：科学出版社,2005.237-240
[19]郭祥峰,贾丽华.阳离子表面活性剂及应用.北京：化学工业出版社,2002.2-10
[20]刘静,张建强,刘炯天.铁矿浮选药剂现状综述.中国矿业,2007,(2)：106-108
[21]陈达,葛英勇,余永富.磁选铁精矿再提纯反浮选工艺和药剂的研究.矿产保护与利用,2005,(4)：46～49
[22]R.R.Klimpel. Selection of chemical reagents for flotation. Mineral Processing Plant Design,1980, (2):907-934
[23]R.S.Dean, P.M.Ambrose. Development and use of certain flotation reagents. U.S.Bureau of Mines Bulletin,1944
[24]K.B.Quast. A review of hematite flotation using 12-carbon chain collector. Minerals Engineering,2000, (13):1361-1376
[25]S.Takeda, I.Matsuoka. The effect of n-hexylamine on the flotation of quartz from artificial mixture with hematite. Colloids and Surfaces,1990, (47):105-115
[26]J.S.Laskowski. Weak-electrolyte type collectors. Mineral Processing and Process Control,1987,(2):137-154
[27]A.E.C. Peres, M.I. Correa.Depression of iron oxides with iron starches.Minerals Engineering,1996,9 (12):1227-1234
[28]S.Usui, S.Takeda. Effect of particle size on reverse flotation of quartz from hematite using dodecyl amine in alkaline media. Nippon Kogyo kaishim.1983, 99 (1149):995-998
[29]R.M.Papini, P.R.G.Brandao, A.E.C. Peres. Cationic flotation of iron ores:amine characterization and performance. Minerals and Metallurgical Processing, 2001,18(1):5-9
[30]S.R.N.Pereira. The use of monpolar oils in the cationic reverse flotation of an iron ore. M.Sc. thesis project. CPGEM-UFMG,2003
[31]余新阳,钟宏,刘广义.阳离子反浮选脱硅捕收剂研究现状.轻金属,2008,(6)：6～9
[32]伍喜庆,刘长淼,黄志华.一种铁矿物与石英分离的有效浮选药剂.矿冶工程,2005,25(2)：41-43
[33]葛英勇,余永富,陈达,等.脱硅耐低温捕收剂GE-609的浮选性能研究.武汉理工大学学报,2005,(8)：17-19
[34]刘文刚,魏德洲,王本英,等.N-十二烷基-1,3-丙二胺的捕收性能研究.金属矿山,2009,(2)：79-81
[35]任建伟,王毓华.铁矿反浮选脱硅的试验研究.矿产保护与利用,2004,(1)： 31-34
[36]刘长淼,曹学锋,胡岳华,等.十二叔胺系列捕收剂对石英的浮选研究.矿冶工程,2009,(3)：37-39
[37]胡龙,郑怀,昌肖刚.铁矿浮选工艺的发展.现代矿业,2010,(1)：23-26
[38]Keith Quest.Flotation of hematite using C6-C18 saturated fatty acids.minerals Engineering,2006, (19):582-597
[39]林祥辉,路平.高效新品种捕收剂RA-315的制取及应用研究.矿冶工程,1993,13(3)：31～34
[40]林祥辉,林苑,黄俊.铁矿选矿与药剂新技术-RA系列药剂的研制、生产及选矿应用.第三届全国选矿专业学术年会,2006
[41]葛英勇,袁武谱,等.阴离子捕收剂MG常温反浮选铁矿的应用研究.有色金属(选矿部分),2008,(5)：41-43
[42]梁振绪.提铁降硅阴离子反浮选工艺在磁铁矿选矿中的应用.矿业工程,2003,(2)：29-30
[43]齐银山,张业清,张清河,等.磁选粗精矿MD-30阴离子捕收剂的研制及应用.金属矿山,2007,(1)：40-44
[44]葛英勇,肖国光,林祥辉.螯合捕收剂RN-665浮选东鞍山难选赤铁矿的研究.矿冶工程,2001,(2)：41-42
[45]张平民.工科大学化学.长沙：湖南教育出版社,2002.380-383
[46]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
[47]谢国先,廉明,张树洪.胺类捕收剂在铁精矿脱硅反浮选中的作用机制.金属矿山,2009,(8)：42-44
[48]刘长淼.铝硅矿物的叔胺类捕收剂的合成、性能及作用机理研究：[博士学位论文].长沙：中南大学,2009
[49]王淀佐,林强,蒋玉仁.选矿与冶金药剂分子设计.长沙：中南工业大学出版社,1996.31-131
[50]伍越寰,李伟昶,沈晓明.有机化学.合肥：中国科技大学出版社,2002.427-447
[51]徐寿昌.有机化学.北京：高等教育出版社,1993.367-381
[52]吴大诚.表面、界面和胶体一原理及应用.北京：化学工业出版社,2005.228-230
[53]赵晓东.泡沫稳定性综述.钻井液与完井液,1992,9(1)：7-14
[54]万里平,孟英峰,赵晓东.泡沫流体稳定性机理研究.新疆石油学院学 报,2003,15(1)：70-73
[55]王蒙蒙,郭东红.泡沫剂的发泡性能及其影响因素.精细石油化工进展,2007,8(12)：40～42
[56]王淀佐.浮选剂作用原理及应用.北京：冶金工业出版社,1982.183-200
[57]罗陶涛.高分子表面活性剂增强泡沫性能研究：[硕士学位论文].成都：西南石油大学,2010
[58]王克亮,杜姗.稳泡剂对泡沫性能影响室内实验研究.内蒙古石油化,2008,(22)：4-5
[59]杨燕,蒲万芬,周明.驱油泡沫稳定剂的性能研究.西南石油学院报,2002,24(4)：60～62
[2]牛志霖.关于中国钢铁工业发展问题的思考.北京建筑工程学院学报,2010,26(3)：8～12
[3]刘贤信.我国铁矿石可供性分析及评价体系框架.矿业研究与开发,2010,30(5)：107～109
[4]宋仁峰,李维兵,刘华艳.我国铁矿石选矿技术发展特点及展望.金属矿山,2009,(1)：1-8
[5]陈亮亮,刘养洁.世界铁矿资源分布对我国钢铁工业发展的影响.经济研究导刊,2010,(5)：35～37
[6]王淑丽.我国铁矿资源评估与可供性研究：[硕士学位论文].北京：中国地质大学,2010
[7]吴荣庆.国产铁矿尚有潜力.中国金属通报,2009,(32)：12～15
[8]魏志江.铁矿资源开发利用分析与预测.中国矿业,2010,19(3)：10～12
[9]谢承祥,李厚民,王瑞江,等.中国已查明的铁矿资源的结构特征.地质通报,2009,28(1)：80-84
[10]侯宗林.中国铁矿资源现状与潜力.地质找矿论丛,2005,20(4)：242-247
[11]邱俊,吕宪俊,陈平,等.铁矿选矿技术.北京：化学工业出版社,2009.1～217
[12]宋占利.浅析南芬选矿厂可持续发展.矿业工程,2005,(5)：22～24
[13]李振,刘炯天,魏德洲,等.铁矿分选技术进展.金属矿山,2008,(5)：2-3
[14]张国庆,李维兵,白晓鸣.调军台选矿厂工艺流程研究及实践.金属矿山,2006,(3)：39～41
[15]陈江安,曾捷,龚恩民,等.褐铁矿选矿工艺的现状及发展.江西理工大学学报,2010,31(5)：5-8
[16]A.C. Araujo, P.R.M. Viana, A.E.C. Peres. Reagents in iron ores flotation. Minerals Engineering,2005,18(2):219-224
[17]葛英勇,余俊,朱鹏程.铁矿浮选药剂评述.现代矿业,2009,(11)：6-10
[18]王淀佐,邱冠周,胡岳华.资源加工学.北京：科学出版社,2005.237-240
[19]郭祥峰,贾丽华.阳离子表面活性剂及应用.北京：化学工业出版社,2002.2-10
[20]刘静,张建强,刘炯天.铁矿浮选药剂现状综述.中国矿业,2007,(2)：106-108
[21]陈达,葛英勇,余永富.磁选铁精矿再提纯反浮选工艺和药剂的研究.矿产保护与利用,2005,(4)：46～49
[22]R.R.Klimpel. Selection of chemical reagents for flotation. Mineral Processing Plant Design,1980, (2):907-934
[23]R.S.Dean, P.M.Ambrose. Development and use of certain flotation reagents. U.S.Bureau of Mines Bulletin,1944
[24]K.B.Quast. A review of hematite flotation using 12-carbon chain collector. Minerals Engineering,2000, (13):1361-1376
[25]S.Takeda, I.Matsuoka. The effect of n-hexylamine on the flotation of quartz from artificial mixture with hematite. Colloids and Surfaces,1990, (47):105-115
[26]J.S.Laskowski. Weak-electrolyte type collectors. Mineral Processing and Process Control,1987,(2):137-154
[27]A.E.C. Peres, M.I. Correa.Depression of iron oxides with iron starches.Minerals Engineering,1996,9 (12):1227-1234
[28]S.Usui, S.Takeda. Effect of particle size on reverse flotation of quartz from hematite using dodecyl amine in alkaline media. Nippon Kogyo kaishim.1983, 99 (1149):995-998
[29]R.M.Papini, P.R.G.Brandao, A.E.C. Peres. Cationic flotation of iron ores:amine characterization and performance. Minerals and Metallurgical Processing, 2001,18(1):5-9
[30]S.R.N.Pereira. The use of monpolar oils in the cationic reverse flotation of an iron ore. M.Sc. thesis project. CPGEM-UFMG,2003
[31]余新阳,钟宏,刘广义.阳离子反浮选脱硅捕收剂研究现状.轻金属,2008,(6)：6～9
[32]伍喜庆,刘长淼,黄志华.一种铁矿物与石英分离的有效浮选药剂.矿冶工程,2005,25(2)：41-43
[33]葛英勇,余永富,陈达,等.脱硅耐低温捕收剂GE-609的浮选性能研究.武汉理工大学学报,2005,(8)：17-19
[34]刘文刚,魏德洲,王本英,等.N-十二烷基-1,3-丙二胺的捕收性能研究.金属矿山,2009,(2)：79-81
[35]任建伟,王毓华.铁矿反浮选脱硅的试验研究.矿产保护与利用,2004,(1)： 31-34
[36]刘长淼,曹学锋,胡岳华,等.十二叔胺系列捕收剂对石英的浮选研究.矿冶工程,2009,(3)：37-39
[37]胡龙,郑怀,昌肖刚.铁矿浮选工艺的发展.现代矿业,2010,(1)：23-26
[38]Keith Quest.Flotation of hematite using C6-C18 saturated fatty acids.minerals Engineering,2006, (19):582-597
[39]林祥辉,路平.高效新品种捕收剂RA-315的制取及应用研究.矿冶工程,1993,13(3)：31～34
[40]林祥辉,林苑,黄俊.铁矿选矿与药剂新技术-RA系列药剂的研制、生产及选矿应用.第三届全国选矿专业学术年会,2006
[41]葛英勇,袁武谱,等.阴离子捕收剂MG常温反浮选铁矿的应用研究.有色金属(选矿部分),2008,(5)：41-43
[42]梁振绪.提铁降硅阴离子反浮选工艺在磁铁矿选矿中的应用.矿业工程,2003,(2)：29-30
[43]齐银山,张业清,张清河,等.磁选粗精矿MD-30阴离子捕收剂的研制及应用.金属矿山,2007,(1)：40-44
[44]葛英勇,肖国光,林祥辉.螯合捕收剂RN-665浮选东鞍山难选赤铁矿的研究.矿冶工程,2001,(2)：41-42
[45]张平民.工科大学化学.长沙：湖南教育出版社,2002.380-383
[46]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
[47]谢国先,廉明,张树洪.胺类捕收剂在铁精矿脱硅反浮选中的作用机制.金属矿山,2009,(8)：42-44
[48]刘长淼.铝硅矿物的叔胺类捕收剂的合成、性能及作用机理研究：[博士学位论文].长沙：中南大学,2009
[49]王淀佐,林强,蒋玉仁.选矿与冶金药剂分子设计.长沙：中南工业大学出版社,1996.31-131
[50]伍越寰,李伟昶,沈晓明.有机化学.合肥：中国科技大学出版社,2002.427-447
[51]徐寿昌.有机化学.北京：高等教育出版社,1993.367-381
[52]吴大诚.表面、界面和胶体一原理及应用.北京：化学工业出版社,2005.228-230
[53]赵晓东.泡沫稳定性综述.钻井液与完井液,1992,9(1)：7-14
[54]万里平,孟英峰,赵晓东.泡沫流体稳定性机理研究.新疆石油学院学 报,2003,15(1)：70-73
[55]王蒙蒙,郭东红.泡沫剂的发泡性能及其影响因素.精细石油化工进展,2007,8(12)：40～42
[56]王淀佐.浮选剂作用原理及应用.北京：冶金工业出版社,1982.183-200
[57]罗陶涛.高分子表面活性剂增强泡沫性能研究：[硕士学位论文].成都：西南石油大学,2010
[58]王克亮,杜姗.稳泡剂对泡沫性能影响室内实验研究.内蒙古石油化,2008,(22)：4-5
[59]杨燕,蒲万芬,周明.驱油泡沫稳定剂的性能研究.西南石油学院报,2002,24(4)：60～62