CN101722110A - Collector for scheelite concentration and use thereof - Google Patents
Collector for scheelite concentration and use thereof Download PDFInfo
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- CN101722110A CN101722110A CN201010300301A CN201010300301A CN101722110A CN 101722110 A CN101722110 A CN 101722110A CN 201010300301 A CN201010300301 A CN 201010300301A CN 201010300301 A CN201010300301 A CN 201010300301A CN 101722110 A CN101722110 A CN 101722110A
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- 239000012141 concentrate Substances 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 229910021532 Calcite Inorganic materials 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 4
- 239000010436 fluorite Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000010937 tungsten Substances 0.000 abstract description 2
- 238000005188 flotation Methods 0.000 description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 description 12
- 239000011707 mineral Substances 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000011575 calcium Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- -1 etc. as collectors Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005456 ore beneficiation Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FGEMVHCDHVPYQX-UHFFFAOYSA-M triethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](CC)(CC)CC FGEMVHCDHVPYQX-UHFFFAOYSA-M 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Detergent Compositions (AREA)
Abstract
本发明公开了一种白钨矿精选捕收剂及其应用。充分根据白钨矿的特点，以及季铵盐对WO4 2-具有较强的亲和能力，开发了一种季铵盐类，实现了捕收剂对白钨矿、方解石、萤石的选择性捕收。该捕收剂具有良好的选择能力和捕收性能，实现了常温精选，简化了整个工艺流程，且药剂用量大大减少。该捕收剂克服了常规选钨方法要通过加温精选才能得到合格产品的劣势，实现了白钨矿的常温精选。通过使用该捕收剂，处理原矿品位为0.38％的白钨矿，可以得到回收率为60％，品位为51.63％的精矿。The invention discloses a scheelite fine-tuning collector and application thereof. Fully based on the characteristics of scheelite and the strong affinity of quaternary ammonium salts to WO 4 2- , a quaternary ammonium salt was developed to realize the selectivity of collectors to scheelite, calcite, and fluorite catch. The collector has good selection ability and collection performance, realizes normal temperature selection, simplifies the entire process, and greatly reduces the dosage of chemicals. The collector overcomes the disadvantage that the conventional tungsten separation method requires heating and concentration to obtain qualified products, and realizes the normal temperature concentration of scheelite. By using the collector to treat the scheelite with a raw ore grade of 0.38%, a concentrate with a recovery rate of 60% and a grade of 51.63% can be obtained.
Description
技术领域technical field
本发明属于选矿领域，具体涉及一种白钨矿的浮选捕收剂，以及在白钨矿的常温精选领域的应用。The invention belongs to the field of ore dressing, and in particular relates to a flotation collector of scheelite and its application in the field of normal temperature beneficiation of scheelite.
背景技术Background technique
由于含钙矿物白钨矿(CaWO4)、方解石(CaCO3)、萤石(CaF2)具有相似的表面结构和溶解性能，白钨矿的浮选分离一直缺乏有效的高选择性的捕收剂。目前应用最为广泛为脂肪酸类捕收剂如油酸、氧化石蜡皂等。这类捕收剂由于与含钙矿物的作用机理相同，均是通过脂肪酸上的羧基与矿物表面Ca2+作用产生化学吸附或钙盐沉淀而实现矿物的浮选，对于白钨矿的选择性较低，通常要依靠大量调整剂的配合使用以及加温矿浆才能实现。目前，白钨矿的浮选通常采用以油酸、氧化石蜡皂等为捕收剂，碳酸钠、水玻璃为调整剂，首先进行粗选，然后用彼得洛夫法进行精选的工艺。但这一工艺能耗高，污染大。Because the calcium-containing minerals scheelite (CaWO 4 ), calcite (CaCO 3 ), and fluorite (CaF 2 ) have similar surface structures and solubility properties, the flotation separation of scheelite has been lacking in effective and highly selective collection. agent. At present, the most widely used are fatty acid collectors such as oleic acid, oxidized paraffin soap, etc. Due to the same mechanism of action as calcium-containing minerals, this type of collector realizes flotation of minerals through the interaction between carboxyl groups on fatty acids and Ca 2+ on the surface of minerals to produce chemical adsorption or calcium salt precipitation. The selectivity for scheelite Lower, usually rely on the combined use of a large number of regulators and heated pulp to achieve. At present, the flotation of scheelite usually uses oleic acid, oxidized paraffin soap, etc. as collectors, and sodium carbonate and water glass as regulators. Firstly, rough separation is carried out, and then the petrov method is used for concentration. But this process consumes a lot of energy and pollutes a lot.
发明内容Contents of the invention
本发明充分根据白钨矿的特点，以及季铵盐对WO4 2-具有较强的亲和能力，开发了一种季铵盐类，实现了捕收剂对白钨矿、方解石、萤石的选择性捕收。该捕收剂具有良好的选择能力和捕收性能，实现了常温精选，简化了整个工艺流程，且药剂用量大大减少。Fully based on the characteristics of scheelite and the strong affinity of quaternary ammonium salts to WO 4 2- , the present invention develops a kind of quaternary ammonium salts, which realizes the collector’s ability to bind scheelite, calcite, and fluorite Selective harvesting. The collector has good selection ability and collection performance, realizes normal temperature selection, simplifies the entire process, and greatly reduces the dosage of chemicals.
本发明的目的是通过以下方式实现的。The purpose of the present invention is achieved in the following ways.
一种白钨矿精选捕收剂：其为如结构式1所示的季铵盐，A kind of scheelite concentrated collector: it is a quaternary ammonium salt as shown in structural formula 1,
式1Formula 1
其中，R1为C12-C16的烷烃，R2为C1-C3的烷烃。Wherein, R 1 is a C 12 -C 16 alkane, and R 2 is a C 1 -C 3 alkane.
上述的捕收剂的应用于白钨矿粗精矿精选时用量为80-120g/t。并且精选前将白钨粗精矿的pH值调节至不低于8。The amount of the above-mentioned collector used in the beneficiation of scheelite rough concentrate is 80-120g/t. And adjust the pH value of scheelite coarse concentrate to not less than 8 before beneficiation.
本发明完整具体工艺为：The complete specific process of the present invention is:
a)将白钨矿碎磨至-0.074mm占85-95％，在磨矿过程中加入600g/t的碳酸钠；a) Grinding the scheelite to -0.074mm, accounting for 85-95%, adding 600g/t of sodium carbonate during the grinding process;
b)加碳酸钠3500g/t；加入石灰2000g/t；加入水玻璃3500g/t；b) Add sodium carbonate 3500g/t; add lime 2000g/t; add water glass 3500g/t;
c)加入600g/t油酸；c) adding 600g/t oleic acid;
d)经过一次粗选两次精选得到白钨粗精矿，并将pH值调节至不低于8；d) After one roughing and two beneficiation, scheelite coarse concentrate is obtained, and the pH value is adjusted to not less than 8;
e)对粗精矿加入80-120g/t该新型捕收剂，进行一次精选，得到最终白钨精矿。e) Add 80-120g/t of the new collector to the rough concentrate and perform a beneficiation to obtain the final scheelite concentrate.
传统白钨矿浮选捕收剂为脂肪酸类捕收剂，其作用机理为脂肪酸上的羧基与矿物表面Ca2+作用产生化学吸附或钙盐沉淀而实现白钨矿的浮选。但是白钨矿(CaWO4)往往与其它含钙脉石矿物(方解石CaCO3，萤石CaF2)共生，这些矿物表面同样具有能与脂肪酸作用的活性钙质点。因此这类捕收剂对白钨矿的选择性极低，通常需要依靠其它有效抑制剂的选择性抑制作用以及加温矿浆才能实现白钨矿的分选。Traditional scheelite flotation collectors are fatty acid collectors. The mechanism of action is that the carboxyl groups on the fatty acid interact with Ca 2+ on the mineral surface to produce chemical adsorption or calcium salt precipitation to achieve scheelite flotation. However, scheelite (CaWO 4 ) often coexists with other calcium-containing gangue minerals (calcite CaCO 3 , fluorite CaF 2 ), and the surfaces of these minerals also have active calcium points that can interact with fatty acids. Therefore, the selectivity of this type of collector to scheelite is extremely low, and it is usually necessary to rely on the selective inhibition of other effective inhibitors and heating the pulp to achieve the separation of scheelite.
本发明捕收剂为阳离子型捕收剂，通过静电作用只选择性地与白钨矿的钨酸基团作用，而其它含钙脉石矿物表面没有该捕收剂的活性位点，因此对白钨矿具有良好的选择能力和捕收性能，在粗精矿精选阶段，可以不依靠抑制剂的作用，常温浮选就可以实现白钨矿的有效分选，从而简化了整个工艺流程，且药剂用量大大减少。The collector of the present invention is a cationic collector, which only selectively interacts with the tungstic acid groups of scheelite through electrostatic interaction, while other calcium-containing gangue minerals have no active sites of the collector on the surface. Tungsten ore has good selectivity and collection performance. In the rough concentrate ore beneficiation stage, normal temperature flotation can realize effective separation of scheelite ore without relying on the effect of inhibitors, thus simplifying the entire process flow, and The dosage of medicine is greatly reduced.
本发明首次将季铵盐类捕收剂应用到白钨矿的常温精选领域，处理原矿品位为0.38％的白钨矿，可以得到回收率为60％，品位为51.63％的精矿。这一指标与常规加温精选的基本相当。For the first time, the present invention applies quaternary ammonium salt collectors to the normal-temperature beneficiation field of scheelite, and can process scheelite with a raw ore grade of 0.38% to obtain a concentrate with a recovery rate of 60% and a grade of 51.63%. This indicator is basically equivalent to that of conventional heating and selection.
附图说明Description of drawings
图1为本发明采用的工艺流程图。其中，K为精矿产品，X为尾矿产品。Fig. 1 is the process flow chart that the present invention adopts. Among them, K is the concentrate product, and X is the tailings product.
具体实施方式Detailed ways
以下实施例旨在进一步说明本发明，而非限制本发明。The following examples are intended to further illustrate the present invention, but not limit the present invention.
实施例1Example 1
采用本发明捕收剂对白钨矿(CaWO4)和方解石(CaCO3)的纯矿物进行试验。The pure minerals of scheelite (CaWO 4 ) and calcite (CaCO 3 ) were tested using the collector of the present invention.
单矿物浮选实验在XFG挂槽浮选机上进行。称取2.0g矿物放入40ml浮选槽中，加入30ml蒸馏水，调浆1min后，用HCl或NaOH调节pH值至8，加入2×10-4mol/l十二烷基三乙基氯化铵搅拌3min，浮选4min，浮选过程采取手工刮泡，浮选完成后将刮出的泡沫(精矿)烘干、称量，计算回收率。The single mineral flotation experiment was carried out on the XFG hanging cell flotation machine. Weigh 2.0g of minerals into a 40ml flotation tank, add 30ml of distilled water, adjust the slurry for 1min, adjust the pH value to 8 with HCl or NaOH, add 2×10 -4 mol/l dodecyl triethyl chloride Ammonium stirring for 3 minutes, flotation for 4 minutes, the flotation process adopts manual foam scraping, after the flotation is completed, the scraped foam (concentrate) is dried, weighed, and the recovery rate is calculated.
采用该捕收剂以后，得到白钨矿的回收率为98％，方解石的回收率为20％，分选效果极佳。After using the collector, the recovery rate of scheelite is 98%, and the recovery rate of calcite is 20%, and the separation effect is excellent.
实施例2Example 2
人工混合矿实验的其他实验条件以及捕收剂与实施例1的单矿物实验相同，只是称取的2.0g原矿样品为白钨矿与方解石质量按1∶1配比的混合样。浮选的产品过滤、烘干称重，然后使用盐酸浸泡精矿和尾矿产品，溶解去除其中的方解石，过滤，烘干称重，计算精矿白钨矿的品位和回收率。Other experimental conditions and collectors of the artificial mixed ore experiment are the same as the single mineral experiment in Example 1, except that the 2.0g raw ore sample weighed is a mixed sample of scheelite and calcite in a ratio of 1:1. The flotation products are filtered, dried and weighed, and then the concentrate and tailings products are soaked in hydrochloric acid to dissolve and remove the calcite, filtered, dried and weighed to calculate the grade and recovery rate of the concentrate scheelite.
采用该捕收剂后，得到WO3品位为61.52％，回收率为90％的精矿产品。After using the collector, a concentrate product with a grade of WO 3 of 61.52% and a recovery rate of 90% was obtained.
实施例3Example 3
采用本发明捕收剂对柿竹园某白钨矿进行浮选试验。原矿WO3品位为0.38％。A scheelite ore in Shizhuyuan was subjected to a flotation test using the collector of the present invention. The grade of ore WO 3 is 0.38%.
将白钨矿碎磨至-0.074mm占90％，在磨矿过程中加入600克/吨的碳酸钠；然后先后加碳酸钠调3500g/t，石灰2000g/t，水玻璃3500g/t，捕收剂油酸800g/t，经粗选和两次精选得到白钨粗精矿；调节粗精矿矿浆pH值至8，加入100g/t十四烷基三乙基氯化铵，对白钨粗精矿进行一次精选，得到最终白钨精矿。Grind the scheelite to -0.074mm, accounting for 90%, add 600g/ton of sodium carbonate during the grinding process; then add sodium carbonate to adjust 3500g/t, lime 2000g/t, water glass 3500g/t, 800g/t of oleic acid as a collecting agent, after roughing and twice beneficiation, scheelite coarse concentrate is obtained; adjust the pH value of the coarse concentrate pulp to 8, add 100g/t tetradecyltriethylammonium chloride, to scheelite The rough concentrate is subjected to a beneficiation to obtain the final scheelite concentrate.
采用本发明捕收剂后，可以得到回收率为60％，品位βwo3＝51.63％的白钨矿精矿。After adopting the collector of the present invention, a scheelite concentrate with a recovery rate of 60% and a grade of βwo 3 =51.63% can be obtained.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225371A (en) * | 2011-05-27 | 2011-10-26 | 北京矿冶研究总院 | Method for flotation of scheelite |
| CN102489393A (en) * | 2011-12-04 | 2012-06-13 | 华南师范大学 | Ore dressing method for separation and recovery of scheelite and fluorite from sulfur flotation tailings of polymetallic ore |
| CN104236279A (en) * | 2014-08-13 | 2014-12-24 | 湖南有色新田岭钨业有限公司 | Dehydrating and drying method for scheelite concentrate and device thereof |
| CN107583769A (en) * | 2016-07-06 | 2018-01-16 | 长春黄金研究院 | A kind of method that flotation tailing normal temperature selects tungsten |
| CN111185307A (en) * | 2020-01-13 | 2020-05-22 | 南昌航空大学 | Application of gemini quaternary ammonium salt collecting agent |
| CN111715408A (en) * | 2020-06-30 | 2020-09-29 | 中南大学 | A flotation agent for flotation of fluorite in scheelite and its flotation method |
| CN111822152A (en) * | 2020-07-15 | 2020-10-27 | 江西理工大学 | A method for separation of scheelite and calcite by ultrasonic flash-asynchronous flotation |
| WO2021128922A1 (en) * | 2019-12-23 | 2021-07-01 | 中南大学 | Application of 2-(3-substituted ureido)-n-hydroxy-2-oxoacetimide cyanide compound in flotation |
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| US4995998A (en) * | 1988-05-31 | 1991-02-26 | Henkel Kommanditgesellschaft Auf Aktien | Surfactant mixtures as collectors for the flotation of non-sulfidic ores |
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| US4995998A (en) * | 1988-05-31 | 1991-02-26 | Henkel Kommanditgesellschaft Auf Aktien | Surfactant mixtures as collectors for the flotation of non-sulfidic ores |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225371A (en) * | 2011-05-27 | 2011-10-26 | 北京矿冶研究总院 | Method for flotation of scheelite |
| CN102489393A (en) * | 2011-12-04 | 2012-06-13 | 华南师范大学 | Ore dressing method for separation and recovery of scheelite and fluorite from sulfur flotation tailings of polymetallic ore |
| CN102489393B (en) * | 2011-12-04 | 2013-05-15 | 华南师范大学 | A mineral processing method for separating and recovering scheelite and fluorite from polymetallic ore floating sulfur tailings |
| CN104236279A (en) * | 2014-08-13 | 2014-12-24 | 湖南有色新田岭钨业有限公司 | Dehydrating and drying method for scheelite concentrate and device thereof |
| CN107583769A (en) * | 2016-07-06 | 2018-01-16 | 长春黄金研究院 | A kind of method that flotation tailing normal temperature selects tungsten |
| WO2021128922A1 (en) * | 2019-12-23 | 2021-07-01 | 中南大学 | Application of 2-(3-substituted ureido)-n-hydroxy-2-oxoacetimide cyanide compound in flotation |
| CN111185307A (en) * | 2020-01-13 | 2020-05-22 | 南昌航空大学 | Application of gemini quaternary ammonium salt collecting agent |
| CN111715408A (en) * | 2020-06-30 | 2020-09-29 | 中南大学 | A flotation agent for flotation of fluorite in scheelite and its flotation method |
| CN111822152A (en) * | 2020-07-15 | 2020-10-27 | 江西理工大学 | A method for separation of scheelite and calcite by ultrasonic flash-asynchronous flotation |
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