新型有机硅捕收剂对铝硅矿物浮选性能研究
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摘要
本文以甲基氯硅烷和脂肪胺为原料合成了常温下在水中具有良好溶解能力的仲胺类有机硅阳离子捕收剂DTS12，并系统地研究了该捕收剂和脂肪胺对一水硬铝石、高岭石、叶腊石及伊利石四种铝硅酸盐矿物的浮选行为。单矿物浮选实验表明,该药剂在pH=6～10时对一水硬铝石、高岭石、叶腊石和伊利石均有较强的捕收能力。在浓度为280mg/L时,四种铝硅酸盐矿物的浮选回收率均在86%以上,其捕收能力高于同浓度下的脂肪胺。
通过单矿物抑制实验和人工混合矿浮选实验,研究了铝土矿反浮选脱硅的工艺条件。实验表明,可溶性淀粉能有效抑制仲胺类有机硅阳离子捕收剂DTS12对一水硬铝石的捕收。对不同品位的混合矿,在pH=8,捕收剂DTS12浓度为280mg/L,可溶性淀粉浓度为300mg/L,给矿的铝硅比A/S=2.679时,一水硬铝石几乎被完全抑制,两者的可浮性差异可达93%,精矿铝硅比A/S=15.02。因此通过反浮选可以实现—水硬铝石与高岭石、伊利石和叶腊石的有效分离。
论文通过矿物的Zeta-电位测定和红外光谱分析等方法,研究了有机硅阳离子捕收剂DTS12与铝硅矿物的作用机理。Zeta(?)电位测定结果表明,一水硬铝石、高岭石、伊利石和叶腊石的零电点分别为6.2、3.6、3.1和2.4。捕收剂与铝硅酸盐矿物作用后矿物表面的Zeta-电位全部为正。红外光谱测定表明,药剂与铝硅酸盐矿物作用后在3000～2800cm-1处出现了甲基和亚甲基的伸缩振动吸收峰,而其他峰没有发生变化。因此,DTS12有机硅阳离子捕收剂与铝硅酸盐矿物之间的作用力主要是静电吸附物理作用。
A novel organosilicone cationic collector DTS12 with good solubility in water at room temperature was synthesized by methyl chlorosilane and aliphatic amine. The flotation behaviors of diaspore and the main gangue minerals-kaolinite, pyrophyllite and illite with the organosilicon collector and aliphatic amine were studied comparatively. The pure mineral flotation experiments showed that the organic silicone cationic collector DTS12 exhibited strong flotation capability on diaspore, illite, pyrophyllite and kaolinite in the pH range of 6～10. Using DTS12 as collector, with the concentration of 280mg/L, the flotation recoveries of the four aluminosilicate minerals are all over 86%. Research exhibits that the capturing ability of DTS12 is better than that of aliphatic amine under the same concentration.
In order to find suitable conditions of bauxite desilication of reverse flotation system, the flotation of the single mineral with the existence of depressor was investigated. The results show that the soluble starch is an effective depressor agent for diaspore. And the depression of soluble starch is much more prominent. The separation of mixed mineral of diaspore and kaolinite by reverse flotation was studied preliminarily in this dissertation. The results show that the artificial mixed mineral of diaspore and kaolinite can be separated well when A/S of feeding mineral is 2.679 (diaspore:kaolinite=2:1) and the concertrate of A/S=15.02 can be obtained when 280mg/L DTS12 is employed as reverse flotation collector and 300mg/L soluble starch being depressor, while the pH value of the system maintained at 8, In addition, the recovery rates of the two ores are both more than 99%,and diaspore can be almost completely inhibited under the action of soluble starch with the flotation difference more than 93% between two ores. In a word, with suitable amount of DTS12 and soluble starch as collector and depressor respectively, diaspore could be effectively separated from kaolinite, illite and pyrophyllite through reverse flotation.
The adsorption mechanism of the novel collector on the four minersls has been investigated through Zeta-potential and IR spectrum measurements. The PZC (Point of Zero Charge) of diaspore, kaolinite, illite and pyrophyllite are 6.2,3.6,3.1 and 2.4 respectively, and theζ-potential of kaolinite, pyrophyllite and illite shows a pronounced shift towards more positive zeta potentials in the presence of the collector. The IR spectrums of clay minerals treated by DTS12 both exhibit new peaks around at 3000-2800cm-1, which previously attributes to the stretching bands of-CH3 and -CH2, and no other peak shift was observed. So it can be concluded that the adsorption between organosilicon cationic collector DTS12 and the four aluminosilicates is dominated by physical electrostatic adsorption.
通过单矿物抑制实验和人工混合矿浮选实验,研究了铝土矿反浮选脱硅的工艺条件。实验表明,可溶性淀粉能有效抑制仲胺类有机硅阳离子捕收剂DTS12对一水硬铝石的捕收。对不同品位的混合矿,在pH=8,捕收剂DTS12浓度为280mg/L,可溶性淀粉浓度为300mg/L,给矿的铝硅比A/S=2.679时,一水硬铝石几乎被完全抑制,两者的可浮性差异可达93%,精矿铝硅比A/S=15.02。因此通过反浮选可以实现—水硬铝石与高岭石、伊利石和叶腊石的有效分离。
论文通过矿物的Zeta-电位测定和红外光谱分析等方法,研究了有机硅阳离子捕收剂DTS12与铝硅矿物的作用机理。Zeta(?)电位测定结果表明,一水硬铝石、高岭石、伊利石和叶腊石的零电点分别为6.2、3.6、3.1和2.4。捕收剂与铝硅酸盐矿物作用后矿物表面的Zeta-电位全部为正。红外光谱测定表明,药剂与铝硅酸盐矿物作用后在3000～2800cm-1处出现了甲基和亚甲基的伸缩振动吸收峰,而其他峰没有发生变化。因此,DTS12有机硅阳离子捕收剂与铝硅酸盐矿物之间的作用力主要是静电吸附物理作用。
A novel organosilicone cationic collector DTS12 with good solubility in water at room temperature was synthesized by methyl chlorosilane and aliphatic amine. The flotation behaviors of diaspore and the main gangue minerals-kaolinite, pyrophyllite and illite with the organosilicon collector and aliphatic amine were studied comparatively. The pure mineral flotation experiments showed that the organic silicone cationic collector DTS12 exhibited strong flotation capability on diaspore, illite, pyrophyllite and kaolinite in the pH range of 6～10. Using DTS12 as collector, with the concentration of 280mg/L, the flotation recoveries of the four aluminosilicate minerals are all over 86%. Research exhibits that the capturing ability of DTS12 is better than that of aliphatic amine under the same concentration.
In order to find suitable conditions of bauxite desilication of reverse flotation system, the flotation of the single mineral with the existence of depressor was investigated. The results show that the soluble starch is an effective depressor agent for diaspore. And the depression of soluble starch is much more prominent. The separation of mixed mineral of diaspore and kaolinite by reverse flotation was studied preliminarily in this dissertation. The results show that the artificial mixed mineral of diaspore and kaolinite can be separated well when A/S of feeding mineral is 2.679 (diaspore:kaolinite=2:1) and the concertrate of A/S=15.02 can be obtained when 280mg/L DTS12 is employed as reverse flotation collector and 300mg/L soluble starch being depressor, while the pH value of the system maintained at 8, In addition, the recovery rates of the two ores are both more than 99%,and diaspore can be almost completely inhibited under the action of soluble starch with the flotation difference more than 93% between two ores. In a word, with suitable amount of DTS12 and soluble starch as collector and depressor respectively, diaspore could be effectively separated from kaolinite, illite and pyrophyllite through reverse flotation.
The adsorption mechanism of the novel collector on the four minersls has been investigated through Zeta-potential and IR spectrum measurements. The PZC (Point of Zero Charge) of diaspore, kaolinite, illite and pyrophyllite are 6.2,3.6,3.1 and 2.4 respectively, and theζ-potential of kaolinite, pyrophyllite and illite shows a pronounced shift towards more positive zeta potentials in the presence of the collector. The IR spectrums of clay minerals treated by DTS12 both exhibit new peaks around at 3000-2800cm-1, which previously attributes to the stretching bands of-CH3 and -CH2, and no other peak shift was observed. So it can be concluded that the adsorption between organosilicon cationic collector DTS12 and the four aluminosilicates is dominated by physical electrostatic adsorption.
引文
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[7]Vasan S S, Modak J M, Natarajan K A. Some recent advances in the bioprocessing of bauxite [J]. International Journal of Mineral Processing,2001,62:173～186.
[8]钮因健,邱冠周,周吉奎,等.硅酸盐细菌的选育及铝土矿细菌脱硅效果[J].中国有色金属学报,2004,14(2)：280～285.
[9]孙德四,张强.硅酸盐细菌的选育及其脱硅效果研究[J].西安科技大学学报,2006,26(2)：235～239.
[10]惠明,王慧,田青,等.一株脱硅胶质芽孢杆菌的分离与初步鉴定[J].河南科技学院学报(自然科学版),2007,35(3)：15～18.
[11]Eygeles M A. Selective flotation of kaolinite-hydrargillite [J]. Colloid Interface Sci,2000 (1):84～86.
[12]Ishchenko V V. Solubilization enhancing effect of A-B-type silicone surfactants in microemulsions [J]. Dispersion Sci Technol,2001,22:245～253.
[13]张国范,冯其明,卢毅屏,等.油酸钠对一水硬铝石和高岭石的捕收机理[J].中国有色金属学报,2001,11(2)：298～301.
[14]陈志友,李旺兴,陈湘清,等.三水铝石型铝土矿的浮选脱硅试验研究[J].轻金属,2008(7)：7～10.
[15]杨小生,李艳军,韩跃新,等.浮选方法提高三水铝石铝硅比的研究[J].金属矿山,2006,359(5)：14～17.
[16]胡岳华,王毓华,王淀佐,等.铝硅矿物浮选化学与铝土矿脱硅[J].北京：科学出版社,2004：10～255.
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