TW201438820A - A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrrhotite by exploiting the synergy of multiple depressants - Google Patents
A method for improving selectivity and recovery in the flotation of nickel sulphide ores that contain pyrrhotite by exploiting the synergy of multiple depressants Download PDFInfo
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本申請案主張2012年4月12日申請的美國專利申請案第61/623,459號，名為「藉由使用複數抑制劑之協同作用以促進含磁黃鐵礦之硫化鎳礦浮選作用之選擇性和回收率的方法」的優先權，且其以全文引用的方式併入本文中。 U.S. Patent Application Serial No. 61/623,459, filed on Apr. 12, 2012, entitled <RTIgt;"""""" The priority of the method of Sexuality and Recovery, and it is incorporated herein by reference in its entirety.
本發明係關於一種使用抑制劑試劑之組合選擇性泡沫浮選硫化物礦物的方法。 This invention relates to a process for the selective foam flotation of sulfide minerals using a combination of inhibitor agents.
硫化物礦物浮選已於20世紀早期付諸實施。由於來自浮選之精礦可較經濟地熔煉且提煉來提供原料金屬，浮選之工業重要性得到公認。泡沫浮選係藉由利用廢物脈石材料表面疏水性之差異從其中選擇性地分離有價值礦物的方法。一般而言，浮選方法包括在高密度砂漿中研磨壓碎礦至解離範圍(liberation size)，繼而在合適稀礦漿中以不同試劑來調節該壓碎礦。試劑包括捕集劑、抑制劑、起泡劑、調節劑等等。捕集劑藉由物理/化學吸附作用使所需礦物之表面呈疏水性，該吸附作用有助於氣泡之附著，該等氣泡致使礦物粒子浮動至砂漿表 面且形成穩定泡沫，其經捕集用於進一步處理。抑制劑具有與捕集劑相反之作用，其藉由吸附親水性組分或藉由移除用於捕集劑之吸附之活性部位，因此允許該等粒子保留於尾礦部分中來使得非所需礦物粒子之表面變得親水。起泡劑有助於在砂漿中穩定合適尺寸之氣泡以捕獲且轉移粒子至泡沫區域。調節劑通常用於pH值控制。所採用之泡沫浮選之不同方案通常相當複雜以使存在之有價值礦物之級別及回收率最大化且使商業價值極少之岩石及硫化物礦物之廢棄最大化。 Sulfide mineral flotation was implemented in the early 20th century. The industrial importance of flotation is recognized because concentrates from flotation can be smelted and refined to provide raw metal. Froth flotation is a method by which valuable minerals are selectively separated by utilizing the difference in hydrophobicity of the surface of the waste gangue material. In general, the flotation process involves grinding the crushed ore in a high density mortar to a liberation size, which is then adjusted with different reagents in a suitable dilute slurry. Reagents include collectors, inhibitors, foaming agents, conditioning agents, and the like. The collector makes the surface of the desired mineral hydrophobic by physical/chemical adsorption, which promotes the adhesion of the bubbles, which cause the mineral particles to float to the mortar table. The surface forms a stable foam that is captured for further processing. The inhibitor has the opposite effect of the collector by adsorbing the hydrophilic component or by removing the active site for adsorption of the collector, thereby allowing the particles to remain in the tailings portion The surface of the mineral particles is required to become hydrophilic. The blowing agent helps to stabilize the bubbles of the appropriate size in the mortar to capture and transfer the particles to the foam area. Conditioners are commonly used for pH control. The different options for froth flotation are often quite complex to maximize the level and recovery of valuable minerals present and to maximize the abandonment of rock and sulfide minerals with minimal commercial value.
在處理硫化礦供回收非鐵有開採價值金屬時，經過處理之常見有價值礦物包括鎳黃鐵礦及針鎳礦、黃銅礦及輝銅礦及斑銅礦、方鉛礦及閃鋅礦，其分別相對於金屬Ni、Cu、Pb及Zn。然而，此等有價值礦物與硫化鐵(亦即磁黃鐵礦、黃鐵礦及白鐵礦，其不具有商業價值且被視為硫化物脈石)天然結合。浮選中之硫化鐵之選擇性廢棄可顯著提高精礦之經濟價值且亦減少在熔煉爐處之SO2排放物(在熔煉爐處硫化鐵係此等氣態排放物之重要貢獻者)。然而，磁黃鐵礦廢棄具有挑戰性。其不僅係關於磁黃鐵礦在礦中之豐度，亦係關於磁黃鐵礦之晶體結構(亦即單斜的、六角形的或隕硫鐵)。此外，磁黃鐵礦與其他礦物緊密地結合，主要與鎳黃鐵礦。對磁黃鐵礦之選擇性抑制不損害Cu及Ni在浮選期間之回收率係在工業礦物加工廠中創建商業價值之關鍵。 Common minerals that have been treated in the treatment of sulphide ore for the recovery of non-ferrous, mining-value metals include pentlandite and needle nickel, chalcopyrite and chalcopyrite and porphyrite, galena and sphalerite It is relative to the metals Ni, Cu, Pb and Zn, respectively. However, such valuable minerals are naturally combined with iron sulphide (i.e., pyrrhotite, pyrite, and pyrite, which are not of commercial value and are considered to be sulfide gangues). The selective disposal of iron ore in the flotation can significantly increase the economic value of the concentrate and also reduce the SO 2 emissions at the smelting furnace (an important contributor to such gaseous emissions in the smelting furnace). However, pyrrhotite disposal is challenging. It is not only about the abundance of pyrrhotite in the ore, but also about the crystal structure of pyrrhotite (ie, monoclinic, hexagonal or sulphur iron). In addition, pyrrhotite is tightly bound to other minerals, mainly with pentlandite. The selective inhibition of pyrrhotite does not impair the recovery of Cu and Ni during flotation, which is the key to creating commercial value in industrial mineral processing plants.
美國專利第5,074,993號描述一種硫化物之浮選之方法，其中藉由以>50g/mt細磨礦物混合物之量使用水溶性多元胺來抑制磁黃鐵礦。該水溶性多元胺較佳為二伸乙三胺(DETA)，且亦可選自包括三伸乙四胺、四伸乙五胺、五伸乙六胺、2-[(胺基乙基)胺基]乙醇、參-(2-胺基乙基)胺、N-甲基乙二胺及1,2二胺基2甲基丙烷之清單。 U.S. Patent No. 5,074,993 describes a process for the flotation of sulfides wherein the pyrrhotite is inhibited by the use of a water-soluble polyamine in an amount of >50 g/mt finely ground mineral mixture. The water-soluble polyamine is preferably diethylenetriamine (DETA), and may also be selected from the group consisting of triethylenetetramine, tetraethyleneamine, pentaethyleneamine, 2-[(aminoethyl) A list of amino]ethanol, cis-(2-aminoethyl)amine, N-methylethylenediamine, and 1,2-diamino-2-methylpropane.
美國專利第5,411,148號描述用於改良地分離來自硫化鐵之單-或多-金屬硫化物礦物之方法。該方法包含在浮選前以至少一種水溶性 含硫無機化合物進行之調節階段作為先決條件步驟，隨後藉由描述於美國專利第5,074,993號中之含氮有機螯合劑進一步調節。該水溶性含硫無機化合物較佳為亞硫酸鈉(Na2SO3)，且亦可以50至600g/mt範圍內之經處理之乾燥固體之量選自由硫化物、二硫磺酸鹽、四硫磺酸鹽及二氧化硫組成之群。該含氮有機螯合劑較佳為諸如二伸乙三胺(DETA)之聚伸乙多胺，其以對於特定浮選饋料充分之劑量使用。磁黃鐵礦由於以特定次序添加之含硫化合物及含氮有機化合物之聯合效果而受到抑制。 U.S. Patent No. 5,411,148 describes a method for the improved separation of mono- or poly-metal sulfide minerals from iron sulfide. The process comprises a conditioning stage with at least one water-soluble sulfur-containing inorganic compound prior to flotation as a prerequisite step, followed by further adjustment by a nitrogen-containing organic chelating agent as described in U.S. Patent No. 5,074,993. The water-soluble sulfur-containing inorganic compound is preferably sodium sulfite (Na 2 SO 3 ), and the amount of the treated dry solid in the range of 50 to 600 g/mt is selected from the group consisting of sulfide, disulfonate, and tetrasulfonate. And a group of sulfur dioxide. The nitrogen-containing organic chelating agent is preferably a polyethylene polyamine such as diethylenetriamine (DETA), which is used in a sufficient dosage for a particular flotation feed. Pyrrhotite is inhibited by the combined effect of sulfur-containing compounds and nitrogen-containing organic compounds added in a specific order.
前述方法藉由選擇性磁黃鐵礦抑制在提高Ni及Cu精礦級別及回收率時極其有效。然而，使用DETA可能使關於流出物中所排放之全體(可溶及不溶的)之Cu及Ni之廢水處理之操作複雜化。DETA係與重金屬離子(諸如Cu及Ni)形成穩定錯合物之強化學螯合劑。此等錯合物不可藉由如在廢水處理廠通常進行之提高pH值至11以上來沈澱。取而代之，添加諸如NALMET® 8702(購自Nalco Company,Naperville,IL)之多元胺沈澱劑至廢水中來與DETA-金屬錯合物反應且形成沈澱。然而，該等沈澱係極精細之粒子，其在澄清器中並不沈降，使得難以自廢水有效移除Cu及Ni。為了避免使用DETA時廢水中之Cu及Ni之高含量，努力確定替代性硫化鐵抑制劑以減少或消除DETA之使用。 The foregoing method is extremely effective in improving the Ni and Cu concentrate grades and recovery rates by selective pyrrhotite inhibition. However, the use of DETA may complicate the operation of wastewater treatment of Cu and Ni with respect to the entire (soluble and insoluble) discharged from the effluent. DETA is a strong chemical chelating agent that forms stable complexes with heavy metal ions such as Cu and Ni. Such complexes cannot be precipitated by increasing the pH to above 11 as is customary in wastewater treatment plants. Instead, a polyamine precipitant such as NALMET® 8702 (available from Nalco Company, Naperville, IL) is added to the wastewater to react with the DETA-metal complex and form a precipitate. However, these precipitates are extremely fine particles that do not settle in the clarifier, making it difficult to effectively remove Cu and Ni from the wastewater. In order to avoid the high levels of Cu and Ni in the wastewater when using DETA, efforts have been made to identify alternative iron sulfide inhibitors to reduce or eliminate the use of DETA.
來自LignoTech之一個當前專利(美國專利第8,221,709號)描述使用硬木木質磺酸鹽自金屬硫化礦分離脈石材料之方法。該專利詳細說明自具有不同硫或磺酸鹽含量及分子量之桉樹、楓樹及樺樹獲得之三種硬木木質磺酸鹽，且比較其在包含硫化銅、硫化鋅或硫化鉛之細磨礦砂漿與硫化鐵之細磨礦石砂漿之浮選中以約250-500g/mt之劑量添加NaCN時之性能。可在其他試劑及pH值調節劑之前或之後添加木質磺酸鹽。然而，在工業過程中僅添加木質磺酸鹽，並未改良Cu/Ni硫化物及磁黃鐵礦之間的選擇性。 A current patent from LignoTech (U.S. Patent No. 8,221,709) describes the use of hardwood lignosulfonates to separate gangue materials from metal sulfide ore. The patent details three hardwood lignosulfonates obtained from eucalyptus, maple and birch with different sulfur or sulfonate content and molecular weight, and compares them in fine grinding mortar containing copper sulfide, zinc sulfide or lead sulfide. The performance of the flotation of the finely ground ore mortar with iron sulfide at a dose of about 250-500 g/mt. The lignosulfonate can be added before or after other reagents and pH adjusters. However, only the lignosulfonate was added in the industrial process, and the selectivity between the Cu/Ni sulfide and the pyrrhotite was not improved.
在此意義上，目前先進技術缺乏用於a)改良與硫化鐵結合之Cu/Ni硫化物礦物之浮選中之選擇性及回收率，及b)減少或消除使用有問題的多元胺化學品(諸如DETA)以使對環境之負面影響降至最低之方法。 In this sense, current state-of-the-art technologies lack the selectivity and recovery for a) improving the flotation of Cu/Ni sulfide minerals combined with iron sulfide, and b) reducing or eliminating the use of problematic polyamine chemicals. (such as DETA) to minimize the negative impact on the environment.
考慮到上述問題及未滿足之需求，本發明揭示一種使用複數抑制劑之協同作用以改良硫化鐵之抑制作用而不損害非鐵金屬硫化物之浮選中之有價值硫化物礦物之回收率，同時減少或消除使用環境上有問題的化學品(諸如多元胺)之方法。該方法具有重要經濟及環境效益。浮選具有磁黃鐵礦之Cu/Ni硫化礦石之實例包括在內，該硫化礦石在浮選法期間或呈新鮮細磨砂漿形式，或呈經預處理且為細粉狀之製程中間物形式。 In view of the above problems and unmet needs, the present invention discloses a synergistic effect of a plurality of inhibitors to improve the inhibition of iron sulfide without compromising the recovery of valuable sulfide minerals in the flotation of non-ferrous metal sulfides, At the same time reduce or eliminate the use of environmentally problematic chemicals such as polyamines. This method has important economic and environmental benefits. An example of flotation of a Cu/Ni sulfide ore having pyrrhotite is included in the form of a fresh fine mortar during the flotation process, or in the form of a pretreated and fine powder process intermediate. .
該方法之要素包括使用複數抑制劑、利用各個化學品之個體抑制效果及產生協同效應以改良選擇性及回收率且減少至少50%之多元胺用量，或只要有可能便消除其用量。所使用之三種化學品包括：1)多元胺，諸如DETA；2)水溶性含硫無機化合物，諸如亞硫酸鈉；及3)硬木木質磺酸鹽產品，較佳為具有6kDa分子量、5%磺酸鹽及2%糖之木質磺酸鈣，且特定言之來自LignoTech之D-912產品。單獨使用之該等化學品或a)不產生充足磁黃鐵礦抑制作用，或b)減少Cu/Ni回收率，或c)造成廢水處理廠環境排放問題，此係由於潛在地較高程度之重金屬所致。 Elements of the method include the use of multiple inhibitors, the use of individual inhibitors of individual chemicals, and synergistic effects to improve selectivity and recovery and reduce the amount of polyamine used by at least 50%, or eliminate the amount whenever possible. The three chemicals used include: 1) polyamines such as DETA; 2) water-soluble sulfur-containing inorganic compounds such as sodium sulfite; and 3) hardwood lignosulfonate products, preferably having a molecular weight of 6 kDa, 5% sulfonate And 2% sugar calcium sulfonate, and specifically from LignoTech's D-912 product. The chemicals used alone or a) do not produce sufficient pyrrhotite inhibition, or b) reduce Cu/Ni recovery, or c) cause environmental problems in wastewater treatment plants due to potentially higher levels of Caused by heavy metals.
三種化學品可同時分別添加，或無較佳次序依次添加，或預混合成具有較佳比率之單一溶液。類似地，可使兩種組分預混合成具有較佳比率之單一溶液且以不同量分別添加至第三種組分中。可在其他浮選試劑之前或之後添加抑制劑。 The three chemicals may be added separately at the same time, or sequentially added in no preferred order, or pre-mixed into a single solution having a preferred ratio. Similarly, the two components can be pre-mixed into a single solution having a preferred ratio and added separately to the third component in different amounts. Inhibitors can be added before or after other flotation reagents.
本發明之態樣促進與硫化鐵結合之非鐵有開採價值金屬之選擇 性回收率之改良。 The invention of the invention promotes the selection of non-ferrous mining value metals combined with iron sulfide Improvement in sexual recovery.
本發明之態樣促進抑制劑及捕集劑之間的協同作用，使得多元胺(亦即DETA)劑量相對於通常以DETA/Na2SO3組合使用者減少至少50%，而不損害在浮選期間之選擇性及回收率。 The aspect of the invention promotes synergy between the inhibitor and the collector such that the dose of polyamine (i.e., DETA) is reduced by at least 50% relative to the user typically in combination with DETA/Na 2 SO 3 without damaging the float Selectivity and recovery rate during the selection period.
本發明之態樣有助於避免廢水處理廠之重金屬及DETA之排放超過法定限度，此種情形可能會由於形成DETA-金屬錯合物而出現。 The aspect of the invention helps to avoid emissions of heavy metals and DETA from wastewater treatment plants exceeding legal limits, which may occur due to the formation of DETA-metal complexes.
本發明之此等態樣之額外優點及新穎特性會在如下描述中部分地闡述，且在檢查下文或藉由實施本發明來學習之後，該等優點及特性對於熟習此項技術者會部分地變得明顯。 Additional advantages and novel features of this aspect of the invention will be set forth in part in the description which follows. Become obvious.
參見以下圖式(但不限於)，將詳述系統及方法之不同例示性態樣，其中：圖1係說明在粗浮選中僅使用D-912之無效磁黃鐵礦抑制作用之曲線圖；圖2係說明在粗浮選中使用D-912及Na2SO3之有效磁黃鐵礦抑制作用之曲線圖；圖3A及3B係說明使用D-912及Na2SO3對於中間流之較低回收率之曲線圖；圖4A及4B係說明使用D-912、Na2SO3、DETA及PAX對於中間流之磁黃鐵礦抑制之協同作用的曲線圖-劑量及添加次序之影響；圖5係說明使用D-912、Na2SO3、DETA及PAX對於中間流之磁黃鐵礦抑制之協同作用的曲線圖-根據因子設計測試之最佳劑量；圖6A及6B係說明使用D-912、Na2SO3及DETA對於中間流之磁黃鐵礦抑制之協同作用的曲線圖-根據最佳化及重複測試之協同作用研究；圖7係說明使用D-912、Na2SO3及DETA之磁黃鐵礦抑制作用的曲 線圖-添加試劑之次序/方法之影響；圖8A及8B係說明在中間流中使用D-912、Na2SO3及DETA之磁黃鐵礦抑制之協同作用的曲線圖；及圖9A及9B係說明使用D-912、Na2SO3及DETA之磁黃鐵礦抑制作用的柱狀圖-分別在精礦及尾礦水中降低殘餘DETA、Cu、及Ni之濃度。 Referring to the following figures (but not limited to), various exemplary aspects of the system and method will be described in detail, wherein: Figure 1 is a graph illustrating the inhibition of ineffective pyrrhotite using only D-912 in coarse flotation. Figure 2 is a graph showing the effective pyrrhotite inhibition effect of D-912 and Na 2 SO 3 in coarse flotation; Figures 3A and 3B illustrate the use of D-912 and Na 2 SO 3 for intermediate flow Graphs of lower recovery; Figures 4A and 4B are graphs showing the synergistic effect of D-912, Na 2 SO 3 , DETA and PAX on the inhibition of pyrrhotite in the intermediate stream - the effect of dosage and order of addition; Figure 5 is a graph illustrating the synergistic effect of D-912, Na 2 SO 3 , DETA and PAX on the inhibition of pyrrhotite in the intermediate flow - the optimum dose according to the factor design test; Figures 6A and 6B illustrate the use of D -912, Na 2 SO 3 and DETA for the synergistic effect of the intermediate flow pyrrhotite inhibition - according to the synergistic study of optimization and repeated testing; Figure 7 illustrates the use of D-912, Na 2 SO 3 And the graph of the inhibition of pyrrhotite of DETA - the effect of the order/method of adding reagents; Figures 8A and 8B are illustrated Stream using D-912, a graph of Na 2 SO 3 and the synergistic inhibition of DETA pyrrhotite; and 9A and 9B illustrate system using D-912, Na 2 SO 3 and pyrrhotite inhibition of DETA The histogram of the action - reducing the concentration of residual DETA, Cu, and Ni in the concentrate and tailings water, respectively.
以下實施方式並不希望以任何方式來限制本發明之範疇、適用性或組態。更特定言之，以下實施方式提供用於建構本發明之例示性特性所需之理解。使用本文所提供之教示時，熟習此項技術者無需推斷本發明之範疇即可識別可使用之合適替代物。 The following embodiments are not intended to limit the scope, applicability or configuration of the invention in any way. More specifically, the following embodiments provide the understanding needed to construct the exemplary features of the invention. Using the teachings provided herein, one skilled in the art can identify suitable alternatives that can be used without inferring the scope of the invention.
本發明描述一種使用複數抑制劑之協同作用以選擇性地浮選硫化物礦物之方法，該等硫化物礦物含有至少一或多種非鐵有開採價值金屬且與主要由磁黃鐵礦組成之硫化鐵結合來達到非鐵有開採價值金屬之極佳級別及回收率。藉由利用由使用複數抑制劑所得到之協同作用，可顯著減少關鍵化學品之一(亦即DETA)的劑量，藉此減輕對環境之潛在負面影響。該方法包含： The present invention describes a method for selectively flotation of sulfide minerals using synergistic effects of a plurality of inhibitors comprising at least one or more non-ferrous, exploitable metals and vulcanized with mainly consisting of pyrrhotite Iron combines to achieve an excellent level and recovery of non-ferrous metals. By utilizing the synergistic effect obtained by the use of complex inhibitors, the dose of one of the key chemicals (i.e., DETA) can be significantly reduced, thereby mitigating potential negative effects on the environment. The method includes:
i)在捕集劑、起泡劑、pH值調節劑及遍佈砂漿之載體氣體及複數抑制劑存在下在含水鹼性砂漿中處理硫化礦(新鮮細磨砂漿或經預處理且呈細粉狀之製程中間物)，其含有至少一或多種具有硫化鐵(磁黃鐵礦)之非鐵有開採價值金屬硫化物礦物(Cu/Ni)。 i) treatment of sulfide ore in fresh alkaline mortar in the presence of a collector, a foaming agent, a pH adjuster and a carrier gas and a plurality of inhibitors throughout the mortar (fresh fine mortar or pretreated and finely powdered) Process intermediate) comprising at least one or more non-ferrous, exploitable metal sulfide minerals (Cu/Ni) having iron sulfide (maghemite).
˙待處理之砂漿含有高達約80%之硫化鐵。非鐵有開採價值金屬硫化物可為鎳黃鐵礦及針鎳礦、黃銅礦及輝銅礦及斑銅礦、方鉛礦及閃鋅礦，其分別為相對於Ni、Cu、Pb及Zn之有價值礦物。硫化鐵可為磁黃鐵礦、黃鐵礦及白鐵礦。 The mortar to be treated contains up to about 80% iron sulfide. Non-ferrous mining value metal sulfides may be nickel pyrite and needle nickel, chalcopyrite and chalcopyrite and porphyrite, galena and sphalerite, which are relative to Ni, Cu, Pb and A valuable mineral of Zn. The iron sulfide may be pyrrhotite, pyrite and pyrite.
˙捕集劑可選自黃原酸酯(xanthate)、二硫代磷酸酯、硫代胺基 甲酸酯、二硫代胺基甲酸酯、二硫代亞膦酸酯、黃原酸甲酸酯、黃原酸酯(xanthic ester)或其混合物中之至少一者。使用戊基黃原酸鉀作為一個實例。為了有開採價值金屬之良好回收率，根據抑制劑之劑量調節捕集劑之劑量。 The ruthenium trapping agent may be selected from the group consisting of xanthate, dithiophosphate, and thioamine. At least one of a formate, a dithiocarbamate, a dithiophosphinate, a xanthate formate, a xanthic ester, or a mixture thereof. Potassium pentyl xanthate was used as an example. In order to have a good recovery of the exploitable metal, the dose of the collector is adjusted according to the dose of the inhibitor.
˙測試之起泡劑係聚乙二醇醚(F160-13，Flottec)，但亦可選自天然油、烷氧基鏈烷烴、脂肪醇、聚乙二醇醚、聚丙二醇中之至少一者。起泡劑非本發明之主要因素。 The foaming agent tested is a polyethylene glycol ether (F160-13, Flottec), but may also be selected from at least one of a natural oil, an alkoxy paraffin, a fatty alcohol, a polyethylene glycol ether, and a polypropylene glycol. . The foaming agent is not a major factor of the invention.
˙測試之pH值調節劑係pH值為9.5之石灰，但亦可為蘇打灰或氫氧化鈉。pH值可在8至12範圍內變化。 The pH adjuster tested is a lime having a pH of 9.5, but may also be soda ash or sodium hydroxide. The pH can vary from 8 to 12.
˙所使用之載體氣體係空氣。其亦可為氮、富氮空氣或富氧空氣或二氧化碳(富集空氣)。 载体 The carrier gas system air used. It can also be nitrogen, nitrogen-enriched air or oxygen-enriched air or carbon dioxide (enriched air).
˙調節步驟必需在添加捕集劑或抑制劑之後。 The ̇ adjustment step must be after the addition of the collector or inhibitor.
˙浮選機可為標準丹佛(Denver)浮選機，其具有2.2L之池及1200rpm之馬達速度，或1.1L之池及900rpm之馬達速度。 The helium flotation machine can be a standard Denver flotation machine with a 2.2 L pool and a motor speed of 1200 rpm, or a 1.1 L pool and a 900 rpm motor speed.
ii)複數抑制劑含有至少一種有機聚合物(來自硬木之木質磺酸鈣)、至少一種含硫化合物及至少一種含氮有機化合物(多元胺)，後者在混合物所存在之量低於其單獨或與一種含硫化合物組合使用所需之量。 Ii) a complex inhibitor comprising at least one organic polymer (calcium lignosulfonate from hardwood), at least one sulfur-containing compound and at least one nitrogen-containing organic compound (polyamine), the latter being present in the mixture in a lower amount than it is alone or The amount required for use in combination with a sulfur-containing compound.
˙該「有機聚合物」係至少一種選自由木質磺酸鹽、糊精、瓜爾豆膠、木薯、澱粉或纖維素中之一或多者組成之群之水溶性有機帶負電聚合物。較佳者為來自硬木之木質磺酸鈣，其具有6kDa分子量、5%磺酸鹽及2%糖。此類產品為來自LignoTech之「D-912」，如LignoTech專利所鑑別。 The "organic polymer" is at least one water-soluble organic negatively charged polymer selected from the group consisting of lignosulfonate, dextrin, guar gum, tapioca, starch or cellulose. Preferred are calcium lignosulfonates from hardwood having a molecular weight of 6 kDa, 5% sulfonate and 2% sugar. Such products are "D-912" from LignoTech, as identified by the LignoTech patent.
˙該「含硫化合物」係至少一種選自由硫化物、亞硫酸鹽、亞硫酸氫鹽、間-重硫酸鹽、二硫磺酸鹽、四硫磺酸鹽及二氧化硫中之一或多者組成之群之水溶性無機含硫化合物。較佳者為亞硫酸鈉 (Na2SO3)。 The "sulfur-containing compound" is at least one selected from the group consisting of sulfide, sulfite, bisulfite, meta-heavy sulfate, disulfide, tetrasulfonate, and sulfur dioxide. A water-soluble inorganic sulfur-containing compound. Preferred is sodium sulfite (Na 2 SO 3 ).
˙該「含氮有機化合物」係至少一種具有選自由一或多個具有OCNCCCNCNC及NCCN結構之聚乙烯-多元胺組成之群之組態之含氮有機化合物，該或該等聚乙烯-多元胺包括二伸乙三胺、三伸乙四胺、四伸乙五胺、五伸乙六胺、羥基乙基-DETA、二乙醇胺及胺基乙基乙醇胺。較佳者為二伸乙三胺(DETA)。 The "nitrogen-containing organic compound" is at least one nitrogen-containing organic compound having a configuration selected from the group consisting of one or more polyethylene-polyamines having an OCNCCCNCNC and an NCCN structure, the polyethylene-polyamine Including diethylenetriamine, triethylenetetramine, tetraethyleneamine, pentaethyleneamine, hydroxyethyl-DETA, diethanolamine and aminoethylethanolamine. Preferred is diethylenetriamine (DETA).
iii)複數抑制劑之添加伴以一定調節時間具有以下選擇，其允許： Iii) the addition of a plurality of inhibitors with a certain adjustment time has the following options, which allow:
˙該等抑制劑同時分別添加；或 ̇ these inhibitors are added separately at the same time; or
˙該等抑制劑無任何較佳次序依次添加，彼此之間具有或不具有調節；或 The inhibitors are added sequentially without any preferred order, with or without adjustment between each other; or
˙該等抑制劑可預混合成具有確定較佳比率之單一溶液；或 The inhibitors may be premixed into a single solution having a determined preferred ratio; or
˙該等組分中之兩者可預混合成具有確定較佳比率之單一溶液，第三組分按需要以不同量分別添加至第三組分中。 ̇ Two of the components may be pre-mixed into a single solution having a determined preferred ratio, with the third component being separately added to the third component in varying amounts as needed.
˙可伴以一定調節，在捕集劑之前或之後添加抑制劑。 The hydrazine can be adjusted with some adjustment, and the inhibitor is added before or after the collector.
iv)用於協同作用及減少多元胺用量之抑制劑之劑量取決於礦石類型、級別及其礦物組成且應因此以實驗方式確定。對於經測試之礦石樣品，D-912劑量在50至150g/t範圍內，Na2SO3 100g/t，及DETA為0至50g/t。引述之劑量回頭參照細磨礦石，即使對於中間流亦如此。DETA劑量保持儘可能低而不損害整體選擇性及回收率，以避免廢水中之重金屬之較高含量。 Iv) The dose of the inhibitor used to synergize and reduce the amount of polyamine used depends on the type, grade and mineral composition of the ore and should therefore be determined experimentally. For tested ore samples, the D-912 dose is in the range of 50 to 150 g/t, Na 2 SO 3 100 g/t, and DETA is 0 to 50 g/t. The quoted doses are referred back to the finely ground ore, even for intermediate flows. The DETA dose is kept as low as possible without compromising overall selectivity and recovery to avoid higher levels of heavy metals in the wastewater.
v)由於捕集劑與抑制劑之間存在競爭，為了最佳冶金會相應地調整捕集劑劑量。 v) Due to the competition between the collector and the inhibitor, the collector dose is adjusted accordingly for optimal metallurgy.
在較佳實施例中，本發明涉及一種使用複數抑制劑之協同作用以選擇性浮選至少一或多種硫化物礦物之方法，該或該等硫化物礦物含有至少一或多種非鐵有開採價值金屬且與硫化礦中之硫化鐵結合， 該方法包含： In a preferred embodiment, the present invention is directed to a method of selectively flotation of at least one or more sulfide minerals using a synergistic effect of a plurality of inhibitors, the sulfide minerals having at least one or more non-ferrous mineralized values Metal and combined with iron sulfide in sulfide ore, The method includes:
i)在含水鹼性砂漿中在捕集劑、起泡劑、pH值調節劑、遍佈該砂漿之載體氣體及包括至少一種有機聚合物、至少一種含硫化合物及/或至少一種含氮有機化合物之選定複數抑制劑存在下處理硫化礦(新鮮細磨砂漿或預處理且呈細粉狀之製程中間物)，其含有與至少一種硫化鐵礦物結合之至少一種該等有價值硫化物礦物；及 i) in an aqueous alkaline mortar, in a collector, a foaming agent, a pH adjuster, a carrier gas throughout the mortar, and comprising at least one organic polymer, at least one sulfur-containing compound and/or at least one nitrogen-containing organic compound Treating sulfide ore (fresh fine mortar or pretreated and finely divided process intermediate) in the presence of a plurality of selected inhibitors, comprising at least one such valuable sulfide mineral in combination with at least one iron sulfide mineral; and
ii)執行泡沫浮選來抑制硫化鐵，同時允許有價值非鐵硫化物之浮選。 Ii) Perform froth flotation to inhibit iron sulfide while allowing the flotation of valuable non-ferrous sulfides.
在另一較佳實施例中，本發明涉及一種使用複數抑制劑之協同作用以選擇性地浮選至少Ni/Cu/Co硫化物礦物之方法，該等硫化物礦物含有至少Ni、Cu、Co、Pt、Pd、Au及Ag有開採價值金屬且其與硫化礦中包括至少磁黃鐵礦之硫化鐵礦物結合，該方法包含： In another preferred embodiment, the present invention is directed to a method of selectively flotation of at least Ni/Cu/Co sulfide minerals using a synergistic effect of a plurality of inhibitors, the sulfide minerals comprising at least Ni, Cu, Co , Pt, Pd, Au, and Ag have a mining value metal and are combined with a sulfide mineral comprising at least pyrrhotite in the sulfide ore, the method comprising:
i)在含水鹼性砂漿中在捕集劑、起泡劑、pH值調節劑、遍佈該砂漿之載體氣體及包括木質磺酸鈣產品(較佳為諸如D-912之產品)、亞硫酸鈉(Na2SO3)及/或DETA之複數抑制劑存在下處理Ni/Cu/Co硫化礦(新鮮細磨砂漿或預處理且呈細粉狀之製程中間物)，其含有與至少磁黃鐵礦結合之至少鎳黃鐵礦及輝銅礦礦物；及 i) in an aqueous alkaline mortar, in a collector, a foaming agent, a pH adjuster, a carrier gas throughout the mortar, and a product comprising calcium lignosulfonate (preferably a product such as D-912), sodium sulfite (Na) Treatment of Ni/Cu/Co sulfide ore (fresh fine mortar or pretreated and fine powdered process intermediate) in the presence of 2 SO 3 ) and/or DETA complex inhibitors, containing at least pyrierite At least pentlandite and chalcopyrite minerals; and
ii)執行泡沫浮選來抑制磁黃鐵礦，同時允許有價值鎳黃鐵礦及輝銅礦之浮選。 Ii) Perform froth flotation to suppress pyrrhotite while allowing the flotation of valuable pentlandite and chalcopyrite.
或者，添加三種抑制劑之方法可包含1)分別地，但皆同時；及2)伴以個別調節依次地。 Alternatively, the method of adding the three inhibitors may comprise 1) separately, but all at the same time; and 2) with individual adjustments in sequence.
另外，可在捕集劑之前或之後添加抑制劑溶液。 Additionally, an inhibitor solution can be added before or after the collector.
發現用於協同作用及減少多元胺用量之抑制劑之劑量取決於礦石類型、級別及其礦物組成且應因此以實驗方式確定。對於經測試之礦石樣品，D-912劑量在50至150g/t範圍內，Na2SO3 100g/t，及DETA為0至50g/t。引述之劑量回頭參照細磨礦石，即使對於中間流 亦如此。 The doses of inhibitors found to act synergistically and reduce the amount of polyamines depend on the type, grade and mineral composition of the ore and should therefore be determined experimentally. For tested ore samples, the D-912 dose is in the range of 50 to 150 g/t, Na 2 SO 3 100 g/t, and DETA is 0 to 50 g/t. The quoted doses are referred back to the finely ground ore, even for intermediate flows.
使用複數抑制劑(亦即藉由合併DETA、Na2SO3及D-912)時所得到之協同磁黃鐵礦抑制作用係藉由使磁黃鐵礦抑制作用最大化(藉由各抑制劑處於最小劑量得到)得到。更特定言之，DETA、Na2SO3及D-912在硫化鐵抑制作用中具有其自身獨特功能。磁黃鐵礦浮選具有三個建議機制，1)銅活化來促進捕集劑(黃原酸酯)吸附；2)形成聚-硫來在氣泡附著之磁黃鐵礦表面上產生一些疏水性部位；及3)形成針對疏水性部位之二黃原酸。DETA可能移除或遮蔽硫化鐵上之Cu2+活化部位來抑制表面上之捕集劑吸附。Na2SO3可能藉由移除形成於硫化鐵表面上之吸附捕集劑或聚-硫來防止硫化鐵浮選。D-912係一種帶負電親水性聚合物，其可能經由活性部位(諸如Fe(OH)2+、Ca2+或Cu2+)吸附於硫化鐵表面上，以使其表面呈親水性，從而抑制硫化鐵。 Synergic pyrrhotite inhibition obtained using a complex inhibitor (ie, by combining DETA, Na 2 SO 3 and D-912) is achieved by maximizing pyrrhotite inhibition (by each inhibitor) Obtained at the minimum dose). More specifically, DETA, Na 2 SO 3 and D-912 have their own unique functions in the inhibition of iron sulfide. The pyrrhotite flotation has three suggested mechanisms, 1) copper activation to promote the adsorption of the collector (xanthate); 2) formation of poly-sulfur to produce some hydrophobicity on the surface of the pyrrhotite to which the bubbles are attached a portion; and 3) forming diaphoric acid for the hydrophobic portion. DETA may remove or mask the Cu 2+ activation site on the iron sulfide to inhibit trapping agent adsorption on the surface. Na 2 SO 3 may prevent iron sulfide flotation by removing the adsorptive collector or poly-sulfur formed on the surface of the iron sulfide. D-912 is a negatively charged hydrophilic polymer which may be adsorbed on the surface of iron sulfide via an active site such as Fe(OH) 2+ , Ca 2+ or Cu 2+ to render its surface hydrophilic. Suppress iron sulfide.
單獨使用任一種抑制劑，無法在不損害有開採價值金屬回收率或不使得廢水中之重金屬之含量較高的情況下得到有效的磁黃鐵礦抑制作用。藉由同時使用三種不同抑制劑，產生協同作用。自三種試劑中之每一者可獲得一種益處，導致硫化鐵抑制作用最大化，同時有價值礦物之回收率之減小最小化。 The use of either of the inhibitors alone does not provide effective pyrrhotite inhibition without compromising the recovery of the exploitable metal or the high content of heavy metals in the wastewater. Synergism is produced by using three different inhibitors simultaneously. One benefit is obtained from each of the three reagents, resulting in maximum inhibition of iron sulfide while minimizing the reduction in recovery of valuable minerals.
以下實例意欲說明，而非以任何方式來限制所主張之本發明之範疇、適用性或組態。 The following examples are intended to illustrate, but not to limit, the scope, applicability, or configuration of the claimed invention.
在圖式中，應注意短格式已用於對於礦物之軸標題。此等符號包括在內：Pn(鎳黃鐵礦)、Cp(黃銅礦)，及Po(磁黃鐵礦)。 In the drawing, it should be noted that the short format has been used for the axis title for minerals. These symbols are included: Pn (nickel pyrite), Cp (chalcopyrite), and Po (magnetic pyrite).
圖1呈現在含有約1.5% Ni(3.7%鎳黃鐵礦)、1.5% Cu(4.3%黃銅礦)及21% Fe(19.7%磁黃鐵礦)及72.3%岩石(其他矽酸鹽)之鎳-銅礦石之粗 浮選(其係根據美國專利第8,221,709號(LignoTech)僅使用硬木木質磺酸鹽產品D-912作為磁黃鐵礦抑制劑之程序處理)中，鎳黃鐵礦及磁黃鐵礦之累積回收率之結果。在此測試中，1kg礦石在棒磨機中研磨至達到P80~106μm，伴以添加5g/t之捕集劑(PAX-戊基黃原酸鉀)及400g/t之石灰。增量粗選測試以pH值9.5伴以石灰作為調節劑來進行。在分別添加抑制劑及捕集劑之後存在2分鐘之調節且在製程水中存在15ppm起泡劑(F160-13)。以1200rpm轉軸使用2.2L丹佛浮選池且在浮選中施用3L/min空氣。在0.5、1、2、5、8及12分鐘後捕集精礦。添加至粗選槽之化學品添加物概述於表1中。 Figure 1 is presented in containing about 1.5% Ni (3.7% nickel pyrite), 1.5% Cu (4.3% chalcopyrite) and 21% Fe (19.7% pyrrhotite) and 72.3% rock (other tannins) Nickel-copper ore Flotation (according to U.S. Patent No. 8,221,709 (LignoTech) using only hardwood lignosulfonate product D-912 as a procedure for pyrrhotite inhibitors), cumulative recovery of pentlandite and pyrrhotite The result of the rate. In this test, 1 kg of ore was ground in a rod mill to reach P80-106 μm with the addition of 5 g/t of collector (PAX-pentyl xanthate potassium) and 400 g/t of lime. The incremental rough selection test was carried out with a pH of 9.5 with lime as a conditioning agent. There was a 2 minute adjustment after the addition of the inhibitor and the collector, respectively, and 15 ppm of a blowing agent (F160-13) was present in the process water. A 2.2 L Denver flotation cell was used at 1200 rpm and 3 L/min air was applied in the flotation. Concentrates were collected after 0.5, 1, 2, 5, 8 and 12 minutes. The chemical additions added to the coarse selection tank are summarized in Table 1.
僅使用捕集劑(PAX)之測試並不顯示磁黃鐵礦抑制作用。使用DETA/Na2SO3之測試呈現可接受之磁黃鐵礦抑制作用及有開採價值金屬回收率。 The test using only the collector (PAX) did not show pyrrhotite inhibition. The test using DETA/Na 2 SO 3 exhibited acceptable pyrrhotite inhibition and a recoverable metal recovery.
相比於使用DETA及Na2SO3之組合(亦即「基線」化學品)，以25至50g/t之劑量使用硬木木質磺酸鹽產品D-912作為磁黃鐵礦抑制劑不會改良磁黃鐵礦抑制作用。相比於DETA及Na2SO3之組合，250g/t之較高D-912劑量的鎳黃鐵礦顯著抑制而非改良鎳黃鐵礦/磁黃鐵礦之選擇性。 Compared to the combination of DETA and Na 2 SO 3 (also known as "baseline" chemicals), the use of hardwood lignosulfonate product D-912 as a pyrrhotite inhibitor at 25 to 50 g/t does not improve. Magnesite inhibition. Compared to DETA and Na 2 SO 3 combination of high dose D-912 nickel 250g / t of pyrite not significantly improved selectivity for inhibition pentlandite / pyrite magnetic.
圖2呈現在與實例1所用相同鎳-銅礦石之粗浮選(其中Na2SO3伴以D-912添加至粗選槽)中，鎳黃鐵礦及磁黃鐵礦之累積回收率之結果。礦石係以與實例1相同之方式研磨，包括5g/t之捕集劑(PAX)添加物及400g/t之石灰添加物。當Na2SO3劑量200g/t時，觀測到磁黃鐵礦抑制作用。添加至粗浮選之化學品概述於表2中。 Figure 2 presents the cumulative recovery of nickel pyrite and pyrrhotite in the crude flotation of the same nickel-copper ore used in Example 1 (where Na 2 SO 3 is accompanied by D-912 addition to the coarse tank). The result. The ore was ground in the same manner as in Example 1, including a 5 g/t collector (PAX) additive and a 400 g/t lime additive. When Na 2 SO 3 dose At 50 g/t, pyrrhotite inhibition was observed. The chemicals added to the crude flotation are summarized in Table 2.
僅使用捕集劑(PAX)之測試並不顯示磁黃鐵礦抑制作用。使用DETA/Na2SO3之測試呈現可接受之磁黃鐵礦抑制作用及有開採價值金 屬回收率。 The test using only the collector (PAX) did not show pyrrhotite inhibition. The test using DETA/Na 2 SO 3 exhibited acceptable pyrrhotite inhibition and a recoverable metal recovery.
已證明單獨使用200g/t Na2SO3之劑量對磁黃鐵礦抑制作用具有一些影響，但其結果不如使用基線化學品DETA及Na2SO3得到之結果良好。在使用D-912及Na2SO3之測試中，當Na2SO3之劑量>100g/t時，觀測到磁黃鐵礦抑制作用之一些指示。當Na2SO3劑量200g/t且D-912劑量50g/t時，使用D-912/Na2SO3得到之鎳黃鐵礦/磁黃鐵礦選擇性曲線與基線DETA/Na2SO3類似。將D-912之劑量自25g/t提高至100g/t且將Na2SO3之劑量自200g/t提高至400g/t不會顯著改變鎳黃鐵礦/磁黃鐵礦選擇性曲線之形狀(亦即鎳黃鐵礦回收率隨磁黃鐵礦回收率之減少而下降)。 The dose of 200 g/t Na 2 SO 3 alone has been shown to have some effect on pyrrhotite inhibition, but the results are not as good as those obtained using the baseline chemicals DETA and Na 2 SO 3 . In the tests using D-912 and Na 2 SO 3 , some indications of pyrrhotite inhibition were observed when the dose of Na 2 SO 3 was >100 g/t. When Na 2 SO 3 dose 200g/t and D-912 dose At 50 g/t, the pentlandite/magpyrite selectivity curve obtained using D-912/Na 2 SO 3 was similar to the baseline DETA/Na 2 SO 3 . Increasing the dose of D-912 from 25g/t to 100g/t and increasing the dose of Na 2 SO 3 from 200g/t to 400g/t does not significantly alter the shape of the pentlandite/pyrrolite selectivity curve. (ie, the recovery of pentlandite decreases as the recovery of pyrrhotite decreases).
關於此饋料，不需要添加DETA，此舉對於環境問題較佳。 Regarding this feed, there is no need to add DETA, which is better for environmental problems.
圖3A及3B分別呈現在含有約7.6% Cu(21.9%黃銅礦)、6.4% Ni(17.3%鎳黃鐵礦)及37% Fe(39.8%磁黃鐵礦)及21%岩石(其中Na2SO3伴以D-912添加進精選槽)之中間流精浮選中，累積鎳黃鐵礦/磁黃鐵礦及黃銅礦/磁黃鐵礦選擇性之結果。此研究涉及粗浮選及精浮選測試且抑制劑於精選階段添加。添加總共10g/t之捕集劑(PAX)至粗浮選且捕集粗選精礦持續6min。在精選階段以pH值9.5伴以石灰作為調節劑來處理粗選精礦。在分別添加抑制劑及捕集劑之後存在2分鐘之調節且在製程水中存在15ppm起泡劑(F160-13)。以900rpm轉軸使用1.1L丹佛浮選池且在精浮選中施用1L/min空氣。在1.5、3、5、及16分鐘後捕集精選精礦。添加至精浮選之化學品概述於表3中。 Figures 3A and 3B are respectively shown to contain about 7.6% Cu (21.9% chalcopyrite), 6.4% Ni (17.3% nickel pyrite) and 37% Fe (39.8% pyrrhotite) and 21% rock (where Na 2 SO 3 with D-912 added to the middle of the selected tank) fine flotation, accumulating nickel pyrite / pyrrhotite and chalcopyrite / pyrrhotite selectivity results. This study involved coarse flotation and fine flotation tests with inhibitors added during the selection phase. A total of 10 g/t of collector (PAX) was added to the coarse flotation and the coarse concentrate was captured for 6 min. The rough concentrate is treated in the selection stage with a pH of 9.5 with lime as a regulator. There was a 2 minute adjustment after the addition of the inhibitor and the collector, respectively, and 15 ppm of a blowing agent (F160-13) was present in the process water. A 1.1 L Denver flotation cell was used with a 900 rpm spindle and 1 L/min of air was applied at the fine flotation. The selected concentrates were captured after 1.5, 3, 5, and 16 minutes. The chemicals added to the fine flotation are summarized in Table 3.
觀測到當D-912劑量50g/t且伴以200g/t之Na2SO3時，選擇性得到改良且甚至比DETA/Na2SO3基線更佳。然而，黃銅礦之回收率減少約15%。若D-912之劑量進一步減少(25g/t)或PAX之劑量增加，會損 害選擇性。此對於工業生產不可接受。 Observed when D-912 dose 50g / t, and SO 3 when accompanied by 200g / t of Na 2, and even more preferably improved selectivity ratio of DETA / Na 2 SO 3 baseline. However, the recovery rate of chalcopyrite is reduced by approximately 15%. If the dose of D-912 is further reduced ( An increase in the dose of 25 g/t) or PAX will impair selectivity. This is not acceptable for industrial production.
圖4A及4B分別呈現根據與實例3所用相同的中間流之精浮選，累積鎳黃鐵礦/磁黃鐵礦及黃銅礦/磁黃鐵礦選擇性之結果。在此實例中，DETA伴以Na2SO3及D-912添加至精選槽，但與DETA及Na2SO3作為「基線」調節之一部分一起使用相比，劑量減少。此研究涉及如實例3中所描述之粗浮選及精浮選測試。添加至精浮選之化學品概述於表4中。 4A and 4B show the results of accumulating pentlandite/pyroxite and chalcopyrite/pyroxite selectivity, respectively, according to the same intermediate flow precision flotation as used in Example 3. In this example, DETA accompanied by Na 2 SO 3 and D-912 was added to the selection slot, but DETA and Na 2 SO 3 as part of the "base" as compared with the use of adjustment, dose reduction. This study involved coarse flotation and fine flotation tests as described in Example 3. The chemicals added to the fine flotation are summarized in Table 4.
在各種化學品之劑量固定(T18309、T18310、T18311)之測試中，添加化學品之次序有變化。在結果中未看到顯著差異。 In the test of the dose fixing of various chemicals (T18309, T18310, T18311), the order of adding chemicals changed. No significant differences were seen in the results.
在抑制劑及捕集劑之劑量有變化之測試中，或者鎳黃鐵礦及黃銅礦之選擇性極佳但回收率遠低於目標(T18309、T18310、T18311)，或者鎳黃鐵礦及黃銅礦之回收率可接受但選擇性顯著降低(T18358、T18360)。 In the test of changes in the dosage of inhibitors and collectors, or the selectivity of pentlandite and chalcopyrite is excellent but the recovery rate is much lower than the target (T18309, T18310, T18311), or pentlandite and Chalcopyrite recovery is acceptable but selectivity is significantly reduced (T18358, T18360).
僅僅當捕集劑與抑制劑之間達到平衡(T18359)時，選擇性及回收率接近「基線」結果。當D-912、DETA及Na2SO3及捕集劑(PAX)處於恰當劑量時，得到良好選擇性及回收率。 When the balance between the collector and the inhibitor is reached (T18359), the selectivity and recovery are close to the "baseline" results. When D-912, DETA and Na 2 SO 3 and the collector (PAX) are in the proper dosage, good selectivity and recovery are obtained.
圖5呈現D-912、DETA及捕集劑(PAX)之間的相互作用同時保持Na2SO3之劑量固定之23因子設計研究之結果。根據實例4之結果表明三種化學品之組合作為抑制劑產生協同作用，其允許DETA劑量減少同時保持良好選擇性及有開採價值金屬回收率。同時，發現捕集劑之 劑量起到極其重要之作用。為了進一步確認協同作用且測定各種化學品劑量之最佳範圍，進行關於PAX、DETA及D-912之劑量之3因子-2階(23)因子設計研究，其中化學品添加至精選階段。饋料係與描述於實例3中之彼等相同。粗-精浮選程序係與實例3所描述相同。在所有此等測試中，Na2SO3以200g/t之固定劑量添加。DETA、D-912及PAX之劑量及測試條件詳細說明於表5。 5 presents D-912, and the interaction between the DETA trapping agent (the PAX) while maintaining the results of the study of Na 2 SO 3 factorial design of fixed doses of 23. The results according to Example 4 indicate that the combination of the three chemicals acts as an inhibitor to produce a synergistic effect that allows for a reduction in DETA dosage while maintaining good selectivity and a recoverable metal recovery. At the same time, it has been found that the dose of the collector plays an extremely important role. To further confirm synergy and determine the optimal range of various chemical doses, a 3-factor-2 order ( 23 ) factor design study was performed on doses of PAX, DETA, and D-912, with chemicals added to the selection stage. The feed lines are the same as those described in Example 3. The coarse-fine flotation procedure is the same as described in Example 3. In all of these tests, Na 2 SO 3 was added at a fixed dose of 200 g/t. The dosages and test conditions of DETA, D-912 and PAX are detailed in Table 5.
在測試設計中，選擇劑量之準則包括：a)DETA劑量應低於在DETA/Na2SO3組合中使用之含量(亦即通常50g/t)；b)由於前述結果顯示D-912劑量<50g/t不起作用，且上限未知，故擴展劑量至較高含量；及c)因為實例5之結果顯示鎳黃鐵礦及黃銅礦之回收率在10至15g/t之PAX劑量時足夠，故不需要達到比通常(亦即5g/t)高得多之劑量。 In the test design, the criteria for selecting the dose include: a) the DETA dose should be lower than the amount used in the DETA/Na 2 SO 3 combination (ie typically 50 g/t); b) because the aforementioned results show the D-912 dose < 50g/t does not work, and the upper limit is unknown, so the dosage is extended to a higher content; and c) because the result of Example 5 shows that the recovery of pentlandite and chalcopyrite is sufficient at a PAX dose of 10 to 15 g/t Therefore, it is not necessary to reach a dose much higher than usual (i.e., 5 g/t).
在D-912之較高劑量之一群(FD2、FD3、FD5及FD7)中，得到較高精礦級別與極低鎳黃鐵礦回收率(20~50%)，表明150g/t之D-912含量過高。在PAX之劑量較高且D-912之劑量較低之另一群(FD8及FD9)中，鎳黃鐵礦/磁黃鐵礦選擇性降低，導致精礦級別低於目標。使用處於範圍之中間點(FD1)之劑量產生位於此等限度之間的結果。可見10g/t PAX、50g/t D-912及15g/t DETA(FD6)得到良好鎳黃鐵礦/磁黃鐵礦選擇性，其結果接近DETA/Na2SO3基線。此等劑量之黃銅礦回收率亦極佳(約90%)。 In the higher dose group of D-912 (FD2, FD3, FD5 and FD7), higher concentrate grade and very low nickel pyrite recovery (20~50%) were obtained, indicating D-150g/t The 912 content is too high. In another group (FD8 and FD9) where the dose of PAX is higher and the dose of D-912 is lower (FD8 and FD9), the selectivity of pentlandite/pyrrolite is reduced, resulting in a concentrate level lower than the target. The use of a dose at the midpoint of the range (FD1) produces a result between these limits. It can be seen that 10g/t PAX, 50g/t D-912 and 15g/t DETA (FD6) give good pentlandite/magopite selectivity, and the result is close to the DETA/Na 2 SO 3 baseline. The recovery rate of these doses of chalcopyrite is also excellent (about 90%).
圖6呈現最佳化測試及基線測試之結果，進行此等測試來證實當D-912、DETA及Na2SO3一起使用時在實例5中所展示的可重複的協同作用且使化學品之劑量最佳化。粗-精浮選程序係與實例3所描述相 同。中間流與描述於實例3中之彼等相同。添加至精選槽之化學品之劑量詳細說明於表6。自得到良好結果之狀況(FD6：具有15g/t DETA、50g/t D-912及10g/t PAX)開始，當排除D-912(T18558)或DETA(T18560)或Na2SO3(T18612)時，鎳黃鐵礦/磁黃鐵礦選擇性不如當所有化學品一起使用時良好。 Figure 6 presents the results of the optimization test and the baseline test, which were performed to demonstrate the reproducible synergy shown in Example 5 when D-912, DETA, and Na 2 SO 3 were used together and to make the chemical The dose is optimized. The coarse-fine flotation procedure is the same as described in Example 3. The intermediate flows are the same as those described in Example 3. The dosages of the chemicals added to the selected tank are detailed in Table 6. Starting with a good result (FD6: with 15g/t DETA, 50g/t D-912 and 10g/t PAX), when D-912 (T18558) or DETA (T18560) or Na 2 SO 3 (T18612) is excluded At the time, the pentlandite/pyrromeite selectivity is not as good as when all chemicals are used together.
另一重複及最佳化結果全部位於相同鎳黃鐵礦/磁黃鐵礦選擇性範圍內，表明穩定之性能。可見a)將D-912劑量提高至75g/t使鎳黃鐵礦及黃銅礦回收率減少幾個百分點；b)將DETA劑量從15g/t變成25g/t及接著變成35g/t並不會影響回收率及選擇性，以致較低的DETA劑量(15g/t)為較佳；及c)稍微降低PAX劑量(亦即自10至7.5g/t)對結果並無重大影響。 The other repeat and optimization results are all within the same range of pentindrite/magpyrite selectivity, indicating stable performance. It can be seen that a) increasing the D-912 dose to 75 g/t reduces the recovery of pentlandite and chalcopyrite by a few percentage points; b) changing the DETA dose from 15 g/t to 25 g/t and then to 35 g/t. It will affect recovery and selectivity, so that a lower DETA dose (15 g/t) is preferred; and c) a slight decrease in PAX dose (ie, from 10 to 7.5 g/t) has no significant effect on the results.
圖7呈現對添加化學品之次序及方法之評價的結果。中間流與描述於實例3中之彼等相同。粗-精浮選程序係與實例3所描述相同，伴以以下狀況：1)在調節的同時添加三種化學品(D-912、DETA及Na2SO3)；2)依次添加Na2SO3、DETA及D-912，各添加物伴以調節時間；3)預混合DETA及D-912成一種溶液且將此溶液作為單一試劑、伴以調節與Na2SO3一起添加至礦漿；及4)預混合DETA、D-912及Na2SO3成一種溶液且伴以調節將此溶液作為單一試劑添加至礦漿。 Figure 7 presents the results of an evaluation of the order and method of adding chemicals. The intermediate flows are the same as those described in Example 3. The coarse-fine flotation procedure is the same as described in Example 3, with the following conditions: 1) Adding three chemicals (D-912, DETA, and Na 2 SO 3 ) while conditioning; 2) Adding Na 2 SO 3 in sequence , DETA and D-912, each additive is accompanied by adjustment time; 3) premixing DETA and D-912 into a solution and adding this solution as a single reagent with adjustment to Na 2 SO 3 to the slurry; and 4 Premixing DETA, D-912, and Na 2 SO 3 into a solution with adjustment to add this solution to the slurry as a single reagent.
所添加之化學品及添加至精選槽之添加方法之條件概述於表7中。 The conditions for the added chemicals and the addition method to the selected tank are summarized in Table 7.
由於添加化學品之方法不同而導致所得結果有差異不重要，因為所有結果均顯示良好選擇性。分別添加三種化學品具有能夠單獨地調整各劑量之益處。使用預混合溶液對於化學儲存罐及輸送線之配置提供更簡單的解決方案，當條件已充分建立時，其係良好的。 It is not important that the results obtained differ due to the different methods of adding chemicals, as all results show good selectivity. The addition of three separate chemicals has the benefit of being able to individually adjust each dose. The use of premixed solutions provides a simpler solution for the configuration of chemical storage tanks and conveyor lines, which are good when conditions are fully established.
圖8A及8B呈現顯示添加D-912、Na2SO3及DETA對於磁黃鐵礦在中間流中之抑制作用之影響的結果。使用含有1.0% Cu(2.7%黃銅礦)、2.0% Ni(4.3%鎳黃鐵礦)、44.6% Fe(65.7%磁黃鐵礦)及27.3%岩石之中間饋料進行兩階段粗-精浮選測試。添加化學品至粗選槽及精選階段概述於表8中。 Figures 8A and 8B present the results showing the effect of the addition of D-912, Na 2 SO 3 and DETA on the inhibition of pyrrhotite in the intermediate stream. Two-stage coarse-fine grinding using an intermediate feed containing 1.0% Cu (2.7% chalcopyrite), 2.0% Ni (4.3% nickel pyrite), 44.6% Fe (65.7% pyrrhotite), and 27.3% rock Flotation test. The addition of chemicals to the coarse selection tank and the selection stage are summarized in Table 8.
圖8A呈現藉由僅添加抑制劑至粗選階段得到之結果。相比於僅具有PAX(T20013)之情況，添加D-912導致磁黃鐵礦回收率顯著減少。合併D-912及Na2SO3(T20027)對於磁黃鐵礦抑制作用之影響不如當D-912、Na2SO3及DETA一起使用(T20030)時好。來自具有三種化學品之測試之結果更靠近DETA/Na2SO3基線(T20016)，但DETA添加低得多(約DETA之40%)。 Figure 8A presents the results obtained by adding only the inhibitor to the roughing stage. Compared to the case with only PAX (T20013), the addition of D-912 resulted in a significant reduction in the recovery of pyrrhotite. The combined effect of D-912 and Na 2 SO 3 (T20027) on pyrrhotite inhibition is not as good as when D-912, Na 2 SO 3 and DETA are used together (T20030). The results from tests with three chemicals were closer to the DETA/Na 2 SO 3 baseline (T20016), but the DETA addition was much lower (about 40% of DETA).
圖8B呈現藉由添加抑制劑至粗選和精選階段二者中得到之結果。當使用三種化學品(D-912、DETA及Na2SO3)之組合時，添加充分量之D-912至粗選階段中最關鍵。若此劑量在粗選階段不夠高(亦即D-912為<75g/t)，將產生極少磁黃鐵礦抑制作用。D-912之劑量在粗選階段較高，添加更多D-912至精選階段可進一步改良鎳黃鐵礦/磁黃鐵礦選擇性。總之，D-912、DETA、Na2SO3及PAX之充分劑量對於在較高磁黃鐵礦中間流浮選中達成良好鎳黃鐵礦/磁黃鐵礦選擇性係必需。 Figure 8B presents the results obtained by adding an inhibitor to both the roughing and selection stages. When using a combination of three chemicals (D-912, DETA, and Na 2 SO 3 ), it is most critical to add a sufficient amount of D-912 to the roughing stage. If this dose is not high enough during the roughing stage (i.e., D-912 is <75 g/t), very little pyrrhotite inhibition will result. The dose of D-912 is higher during the roughing stage, and the addition of more D-912 to the selection stage can further improve the pentlandite/pyrroxene selectivity. In summary, adequate dosing of D-912, DETA, Na 2 SO 3 and PAX is necessary to achieve good ferrite/magopite selectivity in the intermediate pyrolysis of higher pyrrhotite.
圖9A及9B分別說明使用實例5及6中鑑別之新抑制劑混合物對於 精礦及尾礦水之品質之影響。使用描述於實例3中之程序，在與實例1所使用相同之鎳-銅礦上進行粗-精浮選測試。使用「基線」條件，伴以50g/t DETA、200g/t Na2SO3來進行第一測試。使用新條件，伴以50g/t D-912、15g/t DETA及200g/t Na2SO3來進行第二測試。條件之設定均事先顯示以產生類似浮選冶金。在浮選之後，捕集來自各測試之精礦及尾礦水且分析殘餘DETA、Cu及Ni。分析之結果概述於表9中。伴以使用D-912、DETA及Na2SO3之新混合物所得之DETA、Cu及Ni之殘餘含量減少可清楚地看到。 Figures 9A and 9B illustrate the effect of using the new inhibitor mixture identified in Examples 5 and 6, respectively, on the quality of concentrate and tailings water. The coarse-fine flotation test was carried out on the same nickel-copper ore as used in Example 1 using the procedure described in Example 3. Use "baseline" condition, accompanied by 50g / t DETA, 200g / t Na 2 SO 3 to the first test. Using the new criteria, accompanied by 50g / t D-912,15g / t DETA and 200g / t Na 2 SO 3 to the second test. The conditions are set in advance to produce a similar flotation metallurgy. After flotation, concentrates and tailings water from each test were captured and analyzed for residual DETA, Cu and Ni. The results of the analysis are summarized in Table 9. A reduction in the residual content of DETA, Cu and Ni obtained with a new mixture of D-912, DETA and Na 2 SO 3 can be clearly seen.
已知不同尾礦固體各自具有穩定吸附DETA之特定能力。表9中給出之結果證實藉由使用D-912、DETA及Na2SO3之組合，伴以減少之DETA劑量，製程水中之DETA殘餘量可顯著減少。DETA之量可吸附於尾礦固體上而對廢水處理廠無任何負面影響。 It is known that different tailings solids each have a specific ability to stably adsorb DETA. The results are given in Table 9 was confirmed by the use of D-912, DETA and Na 2 SO 3 combination of, accompanied by reducing the dose of DETA, DETA residual amount of process water can be significantly reduced. The amount of DETA can be adsorbed on the tailings solid without any negative impact on the wastewater treatment plant.
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