难选氧化锑矿分选利用基础理论及工艺研究
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摘要
摘要：氧化锑矿的浮选回收是选矿界的一个难题,浮选工艺和基础理论相关的研究还很少。本文以黄锑矿、石英和方解石晶体结构和主要解理面性质差异研究为基础,通过单矿物浮选试验研究了阴、阳离子捕收剂浮选体系中三种矿物的浮选行为,并结合表面电位、吸附量、X射线光电子能谱、红外光谱及量子化学计算等方法,对浮选药剂与矿物间的作用机理进行了研究。主要研究结果如下：(1)三种矿物晶体结构及表面性质研究
黄锑矿和石英主要解理面(001)面的表面能分别为1.646J/m2和2.675J/m2,方解石主要解理面(104)面的表面能为0.887J/m2。黄锑矿、石英和方解石表面在费米能级附近的态密度主要均由O2p轨道构成,氧是黄锑矿和石英表面的活性位点,因此二者的表面性质有一定的相似性。XPS检测结果表明：石英和黄锑矿表面氧的相对含量较为接近,方解石表面氧的相对含量则相对较低,表面含氧量差异导致了三种矿物表面电位及浮选药剂在矿物表面作用的差异。黄锑矿、石英和方解石的零电点PZC分别测得为2.4、2.6和7.6。
(2)阳离子捕收剂浮选体系
季铵盐31系列捕收剂对黄锑矿具有较强的捕收能力,且随着碳链长度的增加而增强,可浮选的pH区间也相应扩大,但季铵盐31和27系列捕收剂对石英和方解石的捕收能力强于黄锑矿,难以实现黄锑矿与石英和方解石的浮选分离。十二胺为捕收剂,pH>10.5时黄锑矿的浮选受到抑制,而石英和方解石回收率可达85%以上,可实现黄锑矿与石英和方解石的反浮选分离。十二胺在矿物表面吸附量和矿物表面电位的变化与十二胺对三种矿物的浮选行为一致,说明静电作用起重要作用。十二胺分子、水分子和十二胺离子在黄锑矿表面吸附能从大到小顺序为DDA>H2O>DDA+。十二胺阳离子不仅能排挤开黄锑矿表面的水分子而形成疏水吸附层,而且比十二胺分子更容易在黄锑矿表面形成静电吸附和氢键吸附。碱性条件下,十二胺分子仍能在石英和方解石表面产生一定的吸附,却很难吸附于黄锑矿表面,是实现黄锑矿与石英和方解石浮选分离的原因。
(3)金属离子对三种矿物的活化
不添加金属离子时,油酸钠对黄锑矿和石英均没有捕收作用,但对方解石具有较好的捕收效果。Ca2+、Mg2+在高碱度条件下能活化石英,但对黄锑矿基本上没有活化作用。Al3+.Fe3+离子能活化黄锑矿,但石英同时也受到活化。Pb2+离子能选择性活化黄锑矿和石英,但二者分选的pH区间较小,Cu2+能实现黄锑矿和石英的选择性活化,可在较大的pH区间实现二者的浮选分离。无论添加何种金属离子,方解石均能得到较高的浮选回收率。
(4)阴离子捕收剂浮选体系
以铜离子为活化剂,油酸钠和十二烷基硫酸钠分别在pH=6.7和pH=6.1左右,可实现黄锑矿与石英的浮选分离,对应pH条件下,油酸钠及十二烷基硫酸钠在铜离子活化的黄锑矿表面发生了化学吸附,而在石英表面仅发生物理吸附。两种捕收剂对三种矿物的浮选行为与矿物表面电位及捕收剂吸附量变化规律一致。CuOH+和Cu(OH)2为油酸钠在黄锑矿表面吸附的活性质点,而CuOH+是十二烷基硫酸钠在黄锑矿表面吸附的活性质点。CuOH+和Cu(OH)2均起到“架桥”作用,把黄锑矿表面和捕收剂连接起来,实现黄锑矿的活化。
(5)两种阴离子捕收剂结构性能差异
油酸钠和十二烷基硫酸钠对黄锑矿浮选行为差异的原因在于两者结构的差异,[SDS]-、[OH]-、[01]-在氢氧化铜沉淀活化的黄锑矿表面吸附能顺序为[SDS]>[OH]->[01]-,[SDS]-不能排开在氢氧化铜表面重新吸附的[OH]-,而[01]-则能排开氢氧化铜表面重新吸附的[OH]-,实现黄锑矿的浮选。[SDS]-与[Ol]-相比,前者对氢氧化铜的静电排斥作用更强,化学吸附活性相对弱。
(6)锡矿山氧化锑矿浮选工艺研究
对锡矿山北选厂含Sb品位1.11%的氧化锑矿,以“直接浮选”工艺可以得到Sb品位2.57%,回收率78.7%的指标。采用“直接浮选-硫化焙烧-浮选”工艺可以得到Sb品位21.8%,回收率64.81%的指标。
Abstract：The recocery of antimony oxide by flotation is now a difficulty subject in mineral processing, and there are few studies on the technology and basic theory for antimony oxide flotation.In this dissertation, based on the studies of crystal structure and the main cleavage plane property differences for three minerals,the flotation behaviors of three minerals in anion and cation flotation collector system have been investigated by flotation.At the same time,the action mechanisms between flotation reagents and minerals have also been revealed by means of surface potential,adsorption capacity, X-ray photoelectron spectroscopy, infrared spectroscopy and quantum chemical calculations.Main conclusions are obtained as following:(1)Crystal structure and surface properties of three minerals
The surface energy of major cleavage plane (001)of cervantite and quartz are1.646J/m2and2.675J/m2,respectively.The surface energy of calcite's major cleavage plane(104) is0.887J/m2.The density of states near Fermi level of cervantite and quartz are almost from the O2p orbit. It indicates that the reactive sites on surface of cervantite and quartz are O, which results in the similarity of their nature.XPS results show that the relative content of oxygen on quartz and cervantite surface is closer to each other, and the calcite surface relative content of oxygen is the lowest, and these cause the differences both of surface potential and the action of reagent with mineral surface.The measured PZC of cervantite,quartz,and calcite are2.4,2.6,and7.6,respectively.
(2) Cationic collector flotation system
31series quaternary ammonium salt collector have strong collect ability for flotation of cervantite,and the flotation pH range of cervantite expands with the increasing of collectore's carbon chain length.However, the collecting capacity of31and27series collector for quartz and calcite are stronger than that of cervantite,and it makes difficult to achieve flotation separation of cervantite from quartz and calcite.The flotation of cervantite is depressed while the recovery of quartz is more than85%at pH>10.5,so the reverse flotation separation of cervantite from quartz and calcite can be achieved under this condition.Changes of surface potential and adsorption capacity of dodecylamine on mineral's surface are consistent with flotation behaviors of minerals using dodecylamine as collector, indicating that electrostatic interaction play an important role in flotation of three minerals by dodecylamine. The order of adsorption energy of dodecylamine molecules,water molecules and dodecylamine ions on cervantite surface is DDA>H2O>DDA+.Dodecylamine cation can not only supplant water molecules from cervantite surface to form hydrophobic layer, but also easy to adsorb on cervantite surface by electrostatic and hydrogen bond adsorption than dodecylamine molecular. The reason for achieving separation of cervantite from quartz and calcite under alkalinite conditions is that dodecylamine molecule can adsorb on quartz and calcite surface to some extent, while it is difficult for dodecylamine molecule adsorbing on cervantite surface in the pulp.
(3) Activation of metal ions on three minerals
Without adding metal ions,sodium oleate has no collectting capacity for cervantite and quartz, but has a good collectting capacity for calcite. Quartz can be activated by Ca+and Mg+under high alkalinity conditions,but cervantite can not be activated.Cervantite can be activated by Al3+and Fe3+, while quartz can be activated meanwhile. Flotation separation of cervantite from quartz and calcite can not be achieved. Cervantite and quartz can be selectively activated by Pb2+ions in a small range of pH. Cervantite and quartz can be selectively activated by Cu2+ions to achieve flotation separation in a lager pH range.Calcite gets a high flotation recovery with adding six metal ions.
(4) Anionic collector flotation system
Sodium oleate and sodium dodecyl sulfate are the effective collectors for the flotation of cervantite from quartz using copper ions as the activator at pH of6.7and6.1,respectively.Sodium oleate and sodium dodecyl sulfate occured chemical adsorption on activated cervantite surface by copper ions,and only physical adsorption on quartz surface under conditions of pH=6.7and6.1,respectively. Changes of surface potential and adsorption capacity of three minerals in the presence of two reagents are consistent with flotation behavior of three minerals. CuOH+and Cu(OH)2become active sites for oleate ion adsorbing on cervantite surface.CuOH+becomes active site for sodium dodecyl sulfate adsorbing on cervantite surface. CuOH+and Cu(OH)2both act as a "bridge" to connect cervantite surface and anionic collectors, play an important role in activating cervantite.
(5)Differences of structure and property of two anionic collectors
The different flotation behavior on cervantite are caused by the different structure of sodium oleate and sodium dodecyl sulfate.The adsorption energy order ofthree adsorbates on activated cervantite surface by Cu(OH)2is [SDS]->[OH]->[Ol]-.Dodecyl sulfate ions can not repel hydroxyl ions on activated cervantite surface by Cu(OH)2while oleic acid ions can repel hydroxyl ions on activated cervantite surface by Cu(OH)2to achieve flotation.Different from oleic acid ion, dodecyl sulfate ion has stronger electrostatic repulsion to copper hydroxide and weaker chemical adsorption activity.
(6) Research on flotation process of Xikuangshan antimony oxide ore
A antimony oxide ore with Sb grade about1.11%from Xikuangshan is used as raw material for flotation tests.By "direct flotation" technological process, a concentrate obtained with Sb grade and recovery of2.57%and78.7%, respectively. By"direct flotation-sulfidation roasting-flotation" process, the Sb grade and recovery of obtained concentrate are21.8%and64.81%, respectively.
黄锑矿和石英主要解理面(001)面的表面能分别为1.646J/m2和2.675J/m2,方解石主要解理面(104)面的表面能为0.887J/m2。黄锑矿、石英和方解石表面在费米能级附近的态密度主要均由O2p轨道构成,氧是黄锑矿和石英表面的活性位点,因此二者的表面性质有一定的相似性。XPS检测结果表明：石英和黄锑矿表面氧的相对含量较为接近,方解石表面氧的相对含量则相对较低,表面含氧量差异导致了三种矿物表面电位及浮选药剂在矿物表面作用的差异。黄锑矿、石英和方解石的零电点PZC分别测得为2.4、2.6和7.6。
(2)阳离子捕收剂浮选体系
季铵盐31系列捕收剂对黄锑矿具有较强的捕收能力,且随着碳链长度的增加而增强,可浮选的pH区间也相应扩大,但季铵盐31和27系列捕收剂对石英和方解石的捕收能力强于黄锑矿,难以实现黄锑矿与石英和方解石的浮选分离。十二胺为捕收剂,pH>10.5时黄锑矿的浮选受到抑制,而石英和方解石回收率可达85%以上,可实现黄锑矿与石英和方解石的反浮选分离。十二胺在矿物表面吸附量和矿物表面电位的变化与十二胺对三种矿物的浮选行为一致,说明静电作用起重要作用。十二胺分子、水分子和十二胺离子在黄锑矿表面吸附能从大到小顺序为DDA>H2O>DDA+。十二胺阳离子不仅能排挤开黄锑矿表面的水分子而形成疏水吸附层,而且比十二胺分子更容易在黄锑矿表面形成静电吸附和氢键吸附。碱性条件下,十二胺分子仍能在石英和方解石表面产生一定的吸附,却很难吸附于黄锑矿表面,是实现黄锑矿与石英和方解石浮选分离的原因。
(3)金属离子对三种矿物的活化
不添加金属离子时,油酸钠对黄锑矿和石英均没有捕收作用,但对方解石具有较好的捕收效果。Ca2+、Mg2+在高碱度条件下能活化石英,但对黄锑矿基本上没有活化作用。Al3+.Fe3+离子能活化黄锑矿,但石英同时也受到活化。Pb2+离子能选择性活化黄锑矿和石英,但二者分选的pH区间较小,Cu2+能实现黄锑矿和石英的选择性活化,可在较大的pH区间实现二者的浮选分离。无论添加何种金属离子,方解石均能得到较高的浮选回收率。
(4)阴离子捕收剂浮选体系
以铜离子为活化剂,油酸钠和十二烷基硫酸钠分别在pH=6.7和pH=6.1左右,可实现黄锑矿与石英的浮选分离,对应pH条件下,油酸钠及十二烷基硫酸钠在铜离子活化的黄锑矿表面发生了化学吸附,而在石英表面仅发生物理吸附。两种捕收剂对三种矿物的浮选行为与矿物表面电位及捕收剂吸附量变化规律一致。CuOH+和Cu(OH)2为油酸钠在黄锑矿表面吸附的活性质点,而CuOH+是十二烷基硫酸钠在黄锑矿表面吸附的活性质点。CuOH+和Cu(OH)2均起到“架桥”作用,把黄锑矿表面和捕收剂连接起来,实现黄锑矿的活化。
(5)两种阴离子捕收剂结构性能差异
油酸钠和十二烷基硫酸钠对黄锑矿浮选行为差异的原因在于两者结构的差异,[SDS]-、[OH]-、[01]-在氢氧化铜沉淀活化的黄锑矿表面吸附能顺序为[SDS]>[OH]->[01]-,[SDS]-不能排开在氢氧化铜表面重新吸附的[OH]-,而[01]-则能排开氢氧化铜表面重新吸附的[OH]-,实现黄锑矿的浮选。[SDS]-与[Ol]-相比,前者对氢氧化铜的静电排斥作用更强,化学吸附活性相对弱。
(6)锡矿山氧化锑矿浮选工艺研究
对锡矿山北选厂含Sb品位1.11%的氧化锑矿,以“直接浮选”工艺可以得到Sb品位2.57%,回收率78.7%的指标。采用“直接浮选-硫化焙烧-浮选”工艺可以得到Sb品位21.8%,回收率64.81%的指标。
Abstract：The recocery of antimony oxide by flotation is now a difficulty subject in mineral processing, and there are few studies on the technology and basic theory for antimony oxide flotation.In this dissertation, based on the studies of crystal structure and the main cleavage plane property differences for three minerals,the flotation behaviors of three minerals in anion and cation flotation collector system have been investigated by flotation.At the same time,the action mechanisms between flotation reagents and minerals have also been revealed by means of surface potential,adsorption capacity, X-ray photoelectron spectroscopy, infrared spectroscopy and quantum chemical calculations.Main conclusions are obtained as following:(1)Crystal structure and surface properties of three minerals
The surface energy of major cleavage plane (001)of cervantite and quartz are1.646J/m2and2.675J/m2,respectively.The surface energy of calcite's major cleavage plane(104) is0.887J/m2.The density of states near Fermi level of cervantite and quartz are almost from the O2p orbit. It indicates that the reactive sites on surface of cervantite and quartz are O, which results in the similarity of their nature.XPS results show that the relative content of oxygen on quartz and cervantite surface is closer to each other, and the calcite surface relative content of oxygen is the lowest, and these cause the differences both of surface potential and the action of reagent with mineral surface.The measured PZC of cervantite,quartz,and calcite are2.4,2.6,and7.6,respectively.
(2) Cationic collector flotation system
31series quaternary ammonium salt collector have strong collect ability for flotation of cervantite,and the flotation pH range of cervantite expands with the increasing of collectore's carbon chain length.However, the collecting capacity of31and27series collector for quartz and calcite are stronger than that of cervantite,and it makes difficult to achieve flotation separation of cervantite from quartz and calcite.The flotation of cervantite is depressed while the recovery of quartz is more than85%at pH>10.5,so the reverse flotation separation of cervantite from quartz and calcite can be achieved under this condition.Changes of surface potential and adsorption capacity of dodecylamine on mineral's surface are consistent with flotation behaviors of minerals using dodecylamine as collector, indicating that electrostatic interaction play an important role in flotation of three minerals by dodecylamine. The order of adsorption energy of dodecylamine molecules,water molecules and dodecylamine ions on cervantite surface is DDA>H2O>DDA+.Dodecylamine cation can not only supplant water molecules from cervantite surface to form hydrophobic layer, but also easy to adsorb on cervantite surface by electrostatic and hydrogen bond adsorption than dodecylamine molecular. The reason for achieving separation of cervantite from quartz and calcite under alkalinite conditions is that dodecylamine molecule can adsorb on quartz and calcite surface to some extent, while it is difficult for dodecylamine molecule adsorbing on cervantite surface in the pulp.
(3) Activation of metal ions on three minerals
Without adding metal ions,sodium oleate has no collectting capacity for cervantite and quartz, but has a good collectting capacity for calcite. Quartz can be activated by Ca+and Mg+under high alkalinity conditions,but cervantite can not be activated.Cervantite can be activated by Al3+and Fe3+, while quartz can be activated meanwhile. Flotation separation of cervantite from quartz and calcite can not be achieved. Cervantite and quartz can be selectively activated by Pb2+ions in a small range of pH. Cervantite and quartz can be selectively activated by Cu2+ions to achieve flotation separation in a lager pH range.Calcite gets a high flotation recovery with adding six metal ions.
(4) Anionic collector flotation system
Sodium oleate and sodium dodecyl sulfate are the effective collectors for the flotation of cervantite from quartz using copper ions as the activator at pH of6.7and6.1,respectively.Sodium oleate and sodium dodecyl sulfate occured chemical adsorption on activated cervantite surface by copper ions,and only physical adsorption on quartz surface under conditions of pH=6.7and6.1,respectively. Changes of surface potential and adsorption capacity of three minerals in the presence of two reagents are consistent with flotation behavior of three minerals. CuOH+and Cu(OH)2become active sites for oleate ion adsorbing on cervantite surface.CuOH+becomes active site for sodium dodecyl sulfate adsorbing on cervantite surface. CuOH+and Cu(OH)2both act as a "bridge" to connect cervantite surface and anionic collectors, play an important role in activating cervantite.
(5)Differences of structure and property of two anionic collectors
The different flotation behavior on cervantite are caused by the different structure of sodium oleate and sodium dodecyl sulfate.The adsorption energy order ofthree adsorbates on activated cervantite surface by Cu(OH)2is [SDS]->[OH]->[Ol]-.Dodecyl sulfate ions can not repel hydroxyl ions on activated cervantite surface by Cu(OH)2while oleic acid ions can repel hydroxyl ions on activated cervantite surface by Cu(OH)2to achieve flotation.Different from oleic acid ion, dodecyl sulfate ion has stronger electrostatic repulsion to copper hydroxide and weaker chemical adsorption activity.
(6) Research on flotation process of Xikuangshan antimony oxide ore
A antimony oxide ore with Sb grade about1.11%from Xikuangshan is used as raw material for flotation tests.By "direct flotation" technological process, a concentrate obtained with Sb grade and recovery of2.57%and78.7%, respectively. By"direct flotation-sulfidation roasting-flotation" process, the Sb grade and recovery of obtained concentrate are21.8%and64.81%, respectively.
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