CN106861918A - A kind of flotation carbon inhibitor and its application - Google Patents
A kind of flotation carbon inhibitor and its application Download PDFInfo
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- CN106861918A CN106861918A CN201710148002.9A CN201710148002A CN106861918A CN 106861918 A CN106861918 A CN 106861918A CN 201710148002 A CN201710148002 A CN 201710148002A CN 106861918 A CN106861918 A CN 106861918A
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- flotation
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- copper
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003112 inhibitor Substances 0.000 title claims abstract description 42
- 238000005188 flotation Methods 0.000 title claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000004088 foaming agent Substances 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002940 vitrain Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 7
- 239000011707 mineral Substances 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 230000001629 suppression Effects 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- 239000003814 drug Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910001779 copper mineral Inorganic materials 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052948 bornite Inorganic materials 0.000 description 1
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 description 1
- 229910052947 chalcocite Inorganic materials 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000004079 vitrinite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
技术领域technical field
本发明属于有色金属浮选药剂的应用技术领域，涉及一种浮选抑制剂及其应用，特别是一种适用于硫化铜矿浮选过程中的碳高效抑制剂及其应用。The invention belongs to the technical field of application of nonferrous metal flotation agents, and relates to a flotation inhibitor and its application, in particular to a carbon high-efficiency inhibitor suitable for the flotation process of copper sulfide ore and its application.
背景技术Background technique
在浮选技术中，有效的抑制脉石矿物，使目的矿物与脉石矿物得以有效分离是实现浮选捕收的关键所在。有色金属铜是重要的工业原料。工业用铜大部分源于硫化铜的浮选获得，随着铜矿需求量的不断加大，铜矿资源却不断地减少，贫、细、杂成为铜矿的主要特点，一些含碳质脉石型铜矿也逐渐被开发利用。由于碳质密度低、疏水性强极易上浮，从而影响精矿品位；其次碳质吸附并消耗浮选捕收剂，造成药剂消耗量大，生产成本增加。制约含碳硫化铜浮选技术的一大因素就是碳的抑制问题。研究探索硫化铜矿浮选中高效的浮选碳抑制剂，对提升硫化铜矿资源浮选利用水平具有重要意义。In flotation technology, effectively suppressing gangue minerals and effectively separating target minerals from gangue minerals is the key to flotation collection. Non-ferrous metal copper is an important industrial raw material. Most of the copper for industrial use is obtained from the flotation of copper sulfide. With the increasing demand for copper ore, copper ore resources continue to decrease. Poor, fine, and miscellaneous have become the main characteristics of copper ore. Some carbonaceous veins Stone-type copper deposits have also been gradually developed and utilized. Due to the low density of carbonaceous and strong hydrophobicity, it is easy to float up, which affects the grade of concentrate; secondly, carbonaceous adsorption and consumption of flotation collectors lead to large consumption of reagents and increased production costs. A major factor restricting carbon-containing copper sulfide flotation technology is the problem of carbon suppression. Researching and exploring efficient flotation carbon inhibitors in the flotation of copper sulfide ore is of great significance for improving the level of flotation utilization of copper sulfide ore resources.
发明内容Contents of the invention
本发明针对浮选硫化铜矿时，脉石矿物较难抑制的问题，提供一种具有强选择性的高效的浮选碳抑制剂及其应用，用以实现硫化铜和碳质的分离。Aiming at the problem that gangue minerals are difficult to suppress during flotation of copper sulfide ore, the invention provides a highly selective and efficient flotation carbon inhibitor and its application to realize the separation of copper sulfide and carbon.
本发明的目的是通过下述方式实现的：The purpose of the present invention is achieved in the following manner:
硫化铜矿中碳抑制剂：结构式如下：Carbon inhibitor in copper sulfide ore: the structural formula is as follows:
R1、R2均为含有羟基或羧基的基团，n的取值5-10。Both R 1 and R 2 are groups containing hydroxyl or carboxyl, and the value of n is 5-10.
所述的碳抑制剂，所述含有羟基或羧基的基团的碳原子取值1-4。In the carbon inhibitor, the carbon atom of the hydroxyl or carboxyl group has a value of 1-4.
所述的碳抑制剂优选R1为-CH2COOH、R2为羟基。The carbon inhibitor is preferably R 1 is -CH 2 COOH, and R 2 is hydroxyl.
所述的碳抑制剂的应用，将所述的碳抑制剂用于硫化铜矿的浮选中。尤其将所述的碳抑制剂用于含有碳质或镜煤的硫化铜矿浮选中，从而可以有效抑制该类杂质的上浮，达到高效回收硫化铜矿的目的。The application of the carbon inhibitor is to use the carbon inhibitor in the flotation of copper sulfide ore. In particular, the carbon inhibitor is used in the flotation of copper sulfide ore containing carbonaceous or viritrite, so that the floating of such impurities can be effectively suppressed, and the purpose of efficiently recovering copper sulfide ore can be achieved.
浮选时，碳抑制剂先于捕收剂和起泡剂加入，效果更佳。用量可视矿中的碳杂质浮选难易情况而定，所述的碳抑制剂的用量为100～200g/t原矿。In flotation, the carbon inhibitor is added before the collector and foaming agent, and the effect is better. The dosage depends on the difficulty of flotation of carbon impurities in the ore, and the dosage of the carbon inhibitor is 100-200g/t raw ore.
本发明用于硫化铜矿浮选活化时具有以下优点：When the present invention is used for the flotation activation of copper sulfide ore, it has the following advantages:
1.由于碳质表面主要有芳香环构成，所设计的该抑制剂亲碳基团具有联苯的分子大平面结构可与碳质表面的芳香基通过π-π堆积作用相互吸引而“锚固”于其表面。1. Since the carbonaceous surface is mainly composed of aromatic rings, the designed carbonophilic group of the inhibitor has a large molecular planar structure of biphenyl, which can attract and "anchor" the aromatic groups on the carbonaceous surface through π-π stacking interaction on its surface.
2.联苯结构上的连接的羧基、羟基可与碳质表面的羟基形成氢键作用，进一步增加其对碳表面的吸附强度。2. The connected carboxyl and hydroxyl groups on the biphenyl structure can form hydrogen bonds with the hydroxyl groups on the carbonaceous surface, further increasing its adsorption strength on the carbon surface.
3.当抑制剂吸附于碳质表面后，抑制剂中羧基的电离使得碳质颗粒带上负电荷，在颗粒周围形成扩散双电层。当两个带有相同电荷的碳质颗粒相互靠近时，扩散双电层重叠产生的静电斥力迫使带电的碳质颗粒享福分开，阻止了其合并，促进了碳质在矿浆中的分散。此外碳质表面荷负电也可以有效通过静电斥力阻碍阴离子捕收剂在碳表面的吸附，从而增强对碳质颗粒的抑制作用。3. When the inhibitor is adsorbed on the carbonaceous surface, the ionization of the carboxyl group in the inhibitor causes the carbonaceous particles to be negatively charged, forming a diffuse electric double layer around the particles. When two carbonaceous particles with the same charge are close to each other, the electrostatic repulsion generated by the overlapping of the diffuse electric double layer forces the charged carbonaceous particles to separate, prevents them from merging, and promotes the dispersion of carbonaceous in the slurry. In addition, the negative charge on the carbonaceous surface can also effectively hinder the adsorption of anion collectors on the carbon surface through electrostatic repulsion, thereby enhancing the inhibition of carbonaceous particles.
4.该抑制剂结构中拥有的亲水性的聚氧乙烯醚，当碳质颗粒表面吸附该类抑制剂后，聚氧乙烯醚这端会伸展进入水溶液中，从而在所吸附的碳质颗粒表面形成有一定厚度的亲水性立体吸附层。当碳颗粒相互靠近时，吸附层开始重叠，即在碳质颗粒间产生空间位阻作用，重叠越多，空间位阻斥力越大，对碳质颗粒间凝聚作用的阻碍也越大，从而使得矿浆溶液中碳质得到很好的分散。同时由于这一层稳定的溶剂化水膜，不但具有极大的位阻斥力而且还具有极强的亲水性，这使得捕收剂更难以接近碳质表面。这即保证了碳质杂质的充分抑制，又大大降低了因碳质吸附所引起的捕收剂消耗。4. The hydrophilic polyoxyethylene ether possessed in the structure of the inhibitor, when the surface of the carbonaceous particle adsorbs this type of inhibitor, the end of the polyoxyethylene ether will extend into the aqueous solution, so that the adsorbed carbonaceous particles A hydrophilic three-dimensional adsorption layer with a certain thickness is formed on the surface. When the carbon particles are close to each other, the adsorption layer begins to overlap, that is, steric hindrance is generated between the carbonaceous particles. The more the overlap, the greater the steric repulsion, and the greater the hindrance to the cohesion between the carbonaceous particles, so that The carbonaceous in the pulp solution is well dispersed. At the same time, because of this layer of stable solvated water film, it not only has great steric repulsion but also has strong hydrophilicity, which makes it more difficult for collectors to approach the carbonaceous surface. This not only ensures the full suppression of carbonaceous impurities, but also greatly reduces the consumption of collectors caused by carbonaceous adsorption.
5.该抑制剂具有高选择性抑制作用，能够在硫化铜浮选中高效选择抑制含碳杂质，便于实现硫化铜的高效富集回收。5. The inhibitor has a highly selective inhibitory effect, and can efficiently selectively inhibit carbon-containing impurities in copper sulfide flotation, which is convenient for the efficient enrichment and recovery of copper sulfide.
附图说明Description of drawings
图1为本发明含碳硫化铜矿浮选流程图。Fig. 1 is the flow chart of flotation of carbon-containing copper sulfide ore of the present invention.
具体实施方式detailed description
实施例1Example 1
采用本发明所述的抑制剂，对四川某硫化铜进行浮选研究，其主要铜矿物为辉铜矿，其次为斑铜矿、黄铜矿等，矿石含铜0.86％；其他金属矿物有黄铁矿；脉石矿物以石英、粘土矿物(水云母、高岭石等)、碳质为主，次为长石、方解石等，另有少量镜煤碎屑和有机碳等，总碳量10.42％。矿石性质复杂，矿石中铜矿物与碳质关系密切，矿石中含有大量碳质页岩和少量镜煤。这些碳质可浮性好，如果浮选直接浮铜，碳质势必进入铜精矿而影响产品质量，所以解决该矿石浮选的关键，在于有效分离铜矿物与碳质。针对矿石性质，在磨矿中加入碳酸钠2000-2500g/t，磨至-0.074mm占78-82％的细度，然后分别加入碳抑制剂1、碳抑制剂2、抑制剂3(结构如下)100-200g/t进行3min左右的搅拌调浆，加入丁黄药捕收剂120g/t与松醇油起泡剂40g/t进行浮选捕收。然后浮选粗精矿经两次精选，尾矿经两次扫选，中矿顺序返回(如图1)就可以获得较佳指标的铜精矿，结果要优于CMC和木质素磺酸钠等常规碳抑制剂，可见采用该高效抑制剂能够很好的抑制碳的上浮，有利于硫化铜矿的浮选捕收。Adopt inhibitor described in the present invention, carry out flotation research to certain copper sulfide in Sichuan, its main copper mineral is chalcocite, secondly bornite, chalcopyrite etc., ore copper-containing 0.86%; Other metal minerals have Pyrite; gangue minerals are mainly quartz, clay minerals (hydromica, kaolinite, etc.), carbonaceous, followed by feldspar, calcite, etc., and a small amount of viritrinite debris and organic carbon, etc., the total carbon content 10.42%. The nature of the ore is complex, and the copper minerals in the ore are closely related to carbonaceous, and the ore contains a large amount of carbonaceous shale and a small amount of vitrinite. These carbons have good floatability. If flotation directly floats copper, the carbon will inevitably enter the copper concentrate and affect the product quality. Therefore, the key to solving the flotation of this ore is to effectively separate copper minerals and carbon. According to the properties of the ore, add sodium carbonate 2000-2500g/t to the ore grinding, grind to -0.074mm and account for 78-82% fineness, then add carbon inhibitor 1, carbon inhibitor 2, inhibitor 3 respectively (the structure is as follows ) 100-200g/t for about 3min stirring slurry mixing, adding 120g/t of butyl xanthate collector and 40g/t of terpineol oil foaming agent for flotation collection. Then the flotation coarse concentrate is selected twice, the tailings are swept twice, and the middle ore is returned in sequence (as shown in Figure 1) to obtain copper concentrate with better indicators, and the result is better than that of CMC and lignosulfonic acid. Conventional carbon inhibitors such as sodium, it can be seen that the use of this high-efficiency inhibitor can well inhibit the floating of carbon, which is beneficial to the flotation collection of copper sulfide ore.
Claims (7)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686940A (en) * | 2020-07-20 | 2020-09-22 | 中南大学 | Carbon inhibitor in lead-zinc sulfide ore flotation process and application thereof |
| CN111804439A (en) * | 2020-07-20 | 2020-10-23 | 中南大学 | A kind of beneficiation method of carbon-containing lead-zinc sulfide ore |
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| CN102974468A (en) * | 2011-09-06 | 2013-03-20 | 陕西长大石油化工产品有限公司 | Non-ferrous metal mineral flotation agent |
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| CN102974468A (en) * | 2011-09-06 | 2013-03-20 | 陕西长大石油化工产品有限公司 | Non-ferrous metal mineral flotation agent |
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| CN111686940A (en) * | 2020-07-20 | 2020-09-22 | 中南大学 | Carbon inhibitor in lead-zinc sulfide ore flotation process and application thereof |
| CN111804439A (en) * | 2020-07-20 | 2020-10-23 | 中南大学 | A kind of beneficiation method of carbon-containing lead-zinc sulfide ore |
| CN111686940B (en) * | 2020-07-20 | 2021-06-15 | 中南大学 | A carbon inhibitor in the flotation process of lead-zinc sulfide ore and its application |
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