A method for agglomeration flotation of refractory spodumene ore

Abstract

The invention provides a method for agglomeration flotation of refractory spodumene ore, belonging to the technical field of ore dressing. The method comprises the steps of grinding raw ore, stirring and slurrying, shearing agglomeration, spodumene roughing, spodumene concentration, spodumene scavenging and the like, and finally obtains spodumene concentrate. The method of the invention can effectively improve the recovery effect of fine spodumene, and is a stable, efficient, adaptable and high recovery index new ore dressing method, which is suitable for promotion and application.

Description

Technical Field

[0001] The invention belongs to the technical field of ore dressing, and in particular relates to a method for agglomeration flotation of refractory spodumene ore. Background Art

[0002] Spodumene is one of the important raw materials for lithium extraction in my country, but my country's spodumene has the characteristics of various mineral compositions and complex embedding characteristics. In particular, the particle size of spodumene embedding is different. A large number of fine spodumene particles are easily produced during the ore crushing process. These spodumene particles have small mass and low kinetic energy, and cannot effectively break through the energy barrier of the foam, making them difficult to recover. At the same time, due to the close co-existence relationship between spodumene and feldspar, the two have similar chemical compositions, similar mineral crystals and surface chemical properties, making flotation separation difficult. Under the traditional collector system, fine feldspar particles non-selectively adhere to the surfaces of various minerals, reducing the difference in surface properties between feldspar and spodumene, further affecting the improvement of concentrate quality.

[0003] In order to obtain high-quality spodumene concentrate, the traditional mineral processing method adopts the desludging flotation process to remove fine mineral particles and reduce the influence of fine mineral mud on the flotation of spodumene, thereby causing a large amount of fine spodumene to be lost with the fine mud; in addition, some studies have adopted the full mud direct flotation process, which adds large doses of sodium carbonate and sodium hydroxide to scrub the mineral surface to reduce the adsorption cover of fine mud on the mineral surface, but it still fails to effectively solve the problem of flotation recovery of fine spodumene particles, resulting in the loss of fine spodumene particles with the tailings, resulting in poor development and utilization of spodumene and serious loss of lithium resources.

[0004] Therefore, it is urgent to develop an efficient beneficiation and recovery method for fine-grained spodumene, so as to selectively increase the apparent particle size of fine-grained spodumene, solve the efficient flotation recovery of fine-grained spodumene and its efficient flotation separation from gangue, and ensure the efficient development and utilization of spodumene resources. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems of difficulty in flotation recovery of fine-grained spodumene and poor separation effect of spodumene from gangue minerals such as feldspar in the prior art, and to provide a method for agglomeration flotation of difficult-to-select spodumene ore with good separation effect, high separation index, good stability and strong adaptability, so as to realize the efficient development and utilization of spodumene resources.

[0006] The present invention is achieved by a method for agglomeration flotation of refractory spodumene ore, comprising the following steps:

[0007] (1) grinding the raw spodumene ore;

[0008] (2) adding NaOH and Na2CO3 to the slurry ground in step (1) to adjust the pH value of the slurry;

[0009] (3) adding CaCl2 to the slurry prepared in step (2);

[0010] (4) adding collector ZSL-02 to the slurry treated in step (3) and performing shearing, agglomeration and stirring;

[0011] (5) subjecting the ore pulp after shearing, agglomeration and stirring in step (4) to rough separation of spodumene to obtain a rough spodumene concentrate and flotation tailings I;

[0012] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are returned to the previous operation in sequence; wherein the process conditions for scavenging the flotation tailings I twice are: adding 100-400 g / t of collector ZSL-02 to scavenging I, and adding 50-100 g / t of activator CaCl2 and 50-200 g / t of collector ZSL-02 to scavenging II;

[0013] (7) The spodumene rough concentrate obtained in step (5) is beneficiated three times to obtain a spodumene concentrate and three beneficiated intermediates, and the three beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the spodumene rough concentrate three times are: adding 200-500 g / t of adjusting agent Na2CO3 in beneficiation I, adding 100-300 g / t of adjusting agent Na2CO3 in beneficiation II, and adding 50-200 g / t of adjusting agent Na2CO3 in beneficiation III;

[0014] Preferably, in step (1), the grinding fineness is -0.074 mm and the content accounts for 60 to 80%.

[0015] Preferably, in step (2), the amount of NaOH is 600-1400 g / t, the amount of Na2CO3 is 700-1200 g / t, and the pH value of the slurry is 8.5-9.5.

[0016] Preferably, in step (3), the amount of CaCl2 used is 100-250 g / t.

[0017] Preferably, in step (4), the amount of collector ZSL-02 is 800-1600 g / t, and the shear agglomeration stirring intensity is 6-15 KJ / (m 3 ·min), the shearing agglomeration stirring time is 15~30min

[0018] Preferably, the collector ZSL-02 is obtained by mixing sodium ricinoleate, styrenephosphonic acid, N-alkanoylaminocaproic acid, and lauryltrimethylammonium chloride in a ratio of 2:4:1:3 by mass.

[0019] The present invention overcomes the shortcomings of the prior art and provides a method for agglomeration flotation of refractory spodumene ore, which has the following technical features:

[0020] (1) The present invention ingeniously adopts a high-intensity shear stirring method, and in the highly selective collector ZSL-02 system, achieves the selective agglomeration of fine spodumene particles, increases the apparent particle size of spodumene, increases the apparent kinetic energy of fine mineral particles, promotes the effective mineralization of fine spodumene particles on flotation foam, achieves the effective recovery of fine spodumene, improves the flotation recovery rate of spodumene, and solves the problem of recycling and utilizing fine spodumene.

[0021] (2) The present invention adopts ZSL-02 as a collector, utilizes the selective coordination effect of the anionic collector vinylphosphonic acid in the reagent on the surface of spodumene after calcium ion activation, improves the flotation separation effect of spodumene and gangue such as feldspar, utilizes the synergistic effect of unsaturated fatty acids in castor oil and styrenephosphonic acid to improve the hydrophobicity of the spodumene surface, utilizes the molecular association between amphoteric collectors, cationic collectors N-alkanoylaminohexanoic acid, lauryltrimethylammonium chloride and anionic collectors to further form multilayer adsorption on the spodumene surface, thereby improving the hydrophobicity of the surface of fine-grained spodumene, strengthening the agglomeration effect, and solving the problem of flotation separation of spodumene and feldspar. The collector ZSL-02 used in the present invention is obtained through a large number of reagent adsorption tests and flotation tests, and its reagent components and proportions are not disclosed and not easy to be thought of in the field of this technology.

[0022] Compared with the prior art, the advantages of the present invention are:

[0023] ① The present invention is a non-de-sliming direct flotation process, which realizes fine particle agglomeration through high-intensity shear stirring, increases the apparent particle size of fine spodumene particles, enables them to be effectively mineralized and recovered on the foam surface, avoids the problem of fine spodumene loss with fine mud in the de-sliming flotation process, solves the problem of fine spodumene being difficult to recover in the non-de-sliming direct flotation process, and improves the utilization level of spodumene resources.

[0024] ② The present invention solves the problem of flotation separation of spodumene and feldspar and other gangue under the traditional fatty acid anionic collector system through the synergistic effect of anionic collectors, amphoteric collectors and cationic collectors, improves the spodumene sorting efficiency, and improves the quality of spodumene concentrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The optical microscope images of the spodumene agglomeration effect under different shear stirring intensities of the present invention are shown in Figure (a), wherein Figure (b) is an optical microscope image of spodumene under the condition of no shear stirring; Figure (b) is an optical microscope image of spodumene under the condition of the present invention with a shear stirring intensity of 3.68KJ / (m 3 ·min) under the condition of optical microscope of spodumene; Figure (c) is the method of the present invention, the shear stirring intensity is 6.90KJ / (m 3·min) under the condition of optical microscope of spodumene; Figure (d) is the method of the present invention, the shear stirring intensity is 10.12KJ / (m 3 ·min) under the condition of optical microscope of spodumene; Figure (e) is the method of the present invention, the shear stirring intensity is 12.88KJ / (m 3 The results show that the shear stirring method used in the present invention can effectively achieve the agglomeration of fine-grained spodumene, thereby increasing the apparent particle size of fine-grained spodumene, and the agglomeration effect is better with the increase of shear stirring intensity.

[0026] Figure 2 It is a flow chart of the steps of the agglomeration flotation method for difficult-to-select spodumene ore of the present invention. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0028] Example 1

[0029] 200 g of sodium ricinoleate, 400 g of styrenephosphonic acid, 100 g of N-alkanoylaminocaproic acid and 300 g of lauryltrimethylammonium chloride were mixed and prepared. The mixing process was carried out in a constant temperature water bath at 60° C. and normal pressure. A beaker was used as a container and a linkage stirrer was used for stirring (stirring time was 30 min). No other auxiliary facilities and additives were required. After mixing evenly, the collector ZSL-02 was obtained.

[0030] Example 2

[0031] The selected ore is granite pegmatite-type spodumene ore, the original ore contains 1.51% Li2O. The main components of the ore are spodumene, albite, plagioclase, potassium feldspar, quartz, and a small amount of muscovite, sericite, apatite, beryl, chlorite. The mineral embedding size varies, mainly fine-grained.

[0032] The spodumene shearing agglomeration flotation recovery ore dressing method of the present invention is used to sort the spodumene, and the sorting steps are as follows:

[0033] (1) grinding the spodumene ore to a grinding fineness of -0.074 mm and a content of 70%;

[0034] (2) adding 800 g / t NaOH and 1000 g / t Na2CO3 to the slurry ground in step (1), at which time the pH value of the slurry is 8.5;

[0035] (3) Adding 150 g / t CaCl2 to the slurry prepared in step (2);

[0036] (4) Add collector ZSL-02 1200g / t to the slurry treated in step (3) and perform shear agglomeration stirring at a shear stirring intensity of 10.5KJ / (m 3 ·min), the shear stirring time is 25min;

[0037] (5) subjecting the ore pulp after shearing, agglomeration and stirring in step (4) to rough separation of spodumene to obtain a rough spodumene concentrate and flotation tailings I;

[0038] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are returned to the previous operation in sequence; wherein the process conditions for scavenging the flotation tailings I twice are: adding 150 g / t of collector ZSL-02 to scavenging I, and adding 50 g / t of activator CaCl2 and 100 g / t of collector ZSL-02 to scavenging II;

[0039] (7) The spodumene rough concentrate obtained in step (5) is beneficiated three times to obtain a spodumene concentrate and three beneficiated intermediates, and the three beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the spodumene rough concentrate three times are: adding 300 g / t of adjusting agent Na2CO3 in beneficiation I, adding 200 g / t of adjusting agent Na2CO3 in beneficiation II, and adding 150 g / t of adjusting agent Na2CO3 in beneficiation II;

[0040] The spodumene concentrate obtained in this embodiment contains 6.27% Li2O and has a recovery rate of 86.32%.

[0041] Example 3

[0042] The selected ore is a granite pegmatite-type spodumene ore, the original ore contains 1.24% Li2O, and the main mineral components of the ore are spodumene, spodumene, quartz, albite, plagioclase, quartz, muscovite, kaolinite, apatite, calcite, chlorite, topaz, etc. The spodumene in the ore is fine-grained, the ore is severely weathered and altered, and the degree of mudification is high.

[0043] The ore dressing method of the present invention for recovering spodumene by shearing agglomeration flotation is used to sort the complex and difficult-to-select spodumene, and the sorting steps are as follows:

[0044] (1) grinding the spodumene ore to a grinding fineness of -0.074 mm and a content of 75%;

[0045] (2) adding 800 g / t NaOH and 1200 g / t Na2CO3 to the slurry ground in step (1), at which time the pH value of the slurry is 9.2;

[0046] (3) Adding 200 g / t CaCl2 to the slurry prepared in step (2);

[0047] (4) Add collector ZSL-02 1100 g / t to the slurry treated in step (3) and perform shear agglomeration stirring at a shear stirring intensity of 12.0 KJ / (m 3 ·min), the shear stirring time is 30min;

[0048] (5) subjecting the ore pulp after shearing, agglomeration and stirring in step (4) to rough separation of spodumene to obtain a rough spodumene concentrate and flotation tailings I;

[0049] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are returned to the previous operation in sequence; wherein the process conditions for scavenging the flotation tailings I twice are: adding 100 g / t of collector ZSL-02 to scavenging I, and adding 100 g / t of activator CaCl2 and 100 g / t of collector ZSL-02 to scavenging II;

[0050] (7) The spodumene rough concentrate obtained in step (5) is beneficiated three times to obtain a spodumene concentrate and three beneficiated intermediates, and the three beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the spodumene rough concentrate three times are: adding 400 g / t of adjusting agent Na2CO3 in beneficiation I, adding 300 g / t of adjusting agent Na2CO3 in beneficiation II, and adding 200 g / t of adjusting agent Na2CO3 in beneficiation II;

[0051] The spodumene concentrate obtained in this embodiment contains 5.76% Li2O and has a recovery rate of 80.41%.

[0052] Example 4

[0053] The selected ore is a granite pegmatite-type spodumene ore, the original ore contains 1.15% Li2O, the main mineral components of the ore are spodumene, spodumene, potassium feldspar, plagioclase, quartz, sericite, kaolinite, chlorite, topaz, corundum, fluorite, etc. The ore is mainly produced in blocky structure. The spodumene and feldspar, quartz, muscovite, etc. in the ore are distributed in aggregates, or are replaced by muscovite, albite, sericite, etc. There are a lot of yellow clay minerals in the ore, which are mainly weathering products of primary ore bodies.

[0054] The ore dressing method of the present invention for recovering spodumene by shearing agglomeration flotation is used to sort the complex and difficult-to-select spodumene, and the sorting steps are as follows:

[0055] (1) Grinding the spodumene ore to a grinding fineness of -0.074 mm and a content of 70%;

[0056] (2) adding 700 g / t NaOH and 1000 g / t Na2CO3 to the slurry ground in step (1), at which time the pH value of the slurry is 9.0;

[0057] (3) Adding 150 g / t CaCl2 to the slurry prepared in step (2);

[0058] (4) Add collector ZSL-02 1400g / t to the slurry treated in step (3) and perform shear agglomeration stirring at a shear stirring intensity of 8.6KJ / (m 3 ·min), the shear stirring time is 25min;

[0059] (5) subjecting the ore pulp after shearing, agglomeration and stirring in step (4) to rough separation of spodumene to obtain a rough spodumene concentrate and flotation tailings I;

[0060] (6) The flotation tailings I obtained in step (5) are scavenged twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are returned to the previous operation in sequence; wherein the process conditions for scavenging the flotation tailings I twice are: adding 150 g / t of collector ZSL-02 to scavenging I, and adding 50 g / t of activator CaCl2 and 100 g / t of collector ZSL-02 to scavenging II;

[0061] (7) The spodumene rough concentrate obtained in step (5) is beneficiated three times to obtain a spodumene concentrate and three beneficiated intermediates, and the three beneficiated intermediates are returned to the previous operation in sequence; wherein the process conditions for beneficiating the spodumene rough concentrate three times are: adding 500 g / t of adjusting agent Na2CO3 in beneficiation I, adding 300 g / t of adjusting agent Na2CO3 in beneficiation II, and adding 200 g / t of adjusting agent Na2CO3 in beneficiation II;

[0062] The spodumene concentrate obtained in this embodiment contains 6.04% Li2O and has a recovery rate of 82.59%.

[0063] Comparative Example

[0064] The selected ore contains 1.53% Li2O. The main mineral components in the ore are spodumene, common pyroxene, albite, potassium feldspar, quartz, muscovite, biotite, chlorite, amphibole, etc., accompanied by a small amount of rare metal minerals such as tantalum-niobium-iron (manganese) ore and fine-crystal stone. The useful mineral spodumene in the ore has a coarse particle size and exists in the form of aggregates. The existing non-demuding direct flotation process (reference: "Experimental Research on Mineral Processing of a Certain Associated Tantalum-Niobia Spodumene Ore", Luo Hongzhen, Metal Mines, Issue 8, Pages 101-107, August 2022) is used to obtain a spodumene concentrate containing 5.60% Li2O and a Li2O recovery rate of 76.13%.

[0065] In the above embodiments, the contents not described in detail in this specification are known prior art to professionals in the field. The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for agglomeration flotation of refractory spodumene ore, characterized in that: The following steps are involved: (1) Grinding the spodumene ore; (2) adding NaOH and Na2CO3 to the slurry ground in step (1) to adjust the pH value of the slurry; (3) adding CaCl2 to the slurry prepared in step (2); (4) adding collector ZSL-02 to the slurry treated in step (3) to perform shearing, agglomeration and stirring; the collector ZSL-02 is obtained by mixing sodium ricinoleate, styrenephosphonic acid, N-alkanoylaminocaproic acid and lauryltrimethylammonium chloride in a ratio of 2:4:1:3 by weight; (5) subjecting the slurry after shearing, agglomeration and stirring in step (4) to rough separation of spodumene to obtain a rough spodumene concentrate and flotation tailings I; (6) scavenging the flotation tailings I obtained in step (5) twice to obtain flotation tailings and two scavenged tailings, and the two scavenged tailings are returned to the previous operation in sequence; The process conditions for the two scavenging of flotation tailings I are as follows: adding collector ZSL-02 100-400g / t in scavenging I, adding activator CaCl2 50-100 g / t and collector ZSL-02 50-200g / t in scavenging II; (7) The spodumene coarse concentrate obtained in step (5) is beneficiated three times to obtain a spodumene concentrate and three beneficiated intermediates, and the three beneficiated intermediates are returned to the previous operation in sequence; The process conditions for the three-time selection of spodumene rough concentrate are as follows: adding 200-500g / t of adjusting agent Na2CO3 in selection I, adding 100-300g / t of adjusting agent Na2CO3 in selection II, and adding 50-200g / t of adjusting agent Na2CO3 in selection III.

2. A method for agglomeration flotation of a refractory spodumene ore as claimed in claim 1, characterized in that: In step (1), the grinding fineness is -0.074 mm and the content is 60-80%.

3. A method for agglomeration flotation of a refractory spodumene ore as claimed in claim 1, characterized in that: In step (2), the amount of NaOH is 600-1400 g / t, the amount of Na2CO3 is 700-1200 g / t, and the pH value of the slurry is 8.5-9.

5.

4. A method for agglomeration flotation of a refractory spodumene ore as claimed in claim 1, characterized in that: In step (3), the amount of CaCl2 used is 100 to 250 g / t.

5. A method for agglomeration flotation of a refractory spodumene ore as claimed in claim 1, characterized in that: In step (4), the amount of collector ZSL-02 is 800-1600 g / t, and the shear agglomeration stirring intensity is 6-15 KJ / (m 3 •min), the shear agglomeration stirring time is 15 to 30min.

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