Application of bis 1, 6-hexylidene triamine penta (methylene phosphonic acid) sodium in flotation separation of scheelite and calcium-containing gangue

Abstract

The invention discloses application of bis 1, 6-hexylidene triamine penta (methylene phosphonic acid) sodium in flotation separation of scheelite and calcium-containing gangue, and belongs to the technical field of mineral separation. According to the invention, the bis 1, 6-hexylidene triamine penta (methylene phosphonic acid) sodium is applied to a scheelite flotation system for the first time. The inhibitor is selectively adsorbed on the surface of the calcium-containing gangue through chelation, a hydrophilic film is formed on a mineral interface, the floatability difference between a target mineral and the gangue is remarkably enlarged, the inhibitor has the advantages of being high in selectivity, good in inhibition effect, small in dosage, free of toxicity, free of pollution and the like, and the separation efficiency of scheelite and the calcium-containing gangue can be remarkably improved.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing, and in particular relates to an application of sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonate)) in the flotation separation of scheelite and calcium-containing gangue. Background Art

[0002] Tungsten, due to its unique physical and chemical properties, holds irreplaceable application value in aerospace, high-end manufacturing, and other fields. China, the world's largest tungsten resource country, accounts for over 70% of its tungsten reserves in scheelite (CaWO4). With the increasing depletion of high-grade, easily beneficiated wolframite, the efficient development and utilization of scheelite has become crucial for the sustainable development of the tungsten industry.

[0003] At present, froth flotation is still the main technical means for the recovery of scheelite. However, due to the interaction between scheelite and calcium-containing gangue (such as apatite Ca 10 (PO4)6(OH,F,Cl)2, calcite CaCO3, fluorite CaF2) all contain Ca in their crystal structures. 2+ Active sites result in highly similar surface chemical properties, making effective separation difficult using traditional fatty acid collectors. In industrial practice, water glass is often used to suppress calcium gangue or heated flotation processes (80-90°C) are used to improve separation results. However, these processes are subject to technical bottlenecks such as high reagent usage (often reaching 2-5 kg / t of water glass), high energy costs (heating energy consumption accounts for over 30%), and lengthy processes (requiring multiple selections). These processes also pose significant environmental pressures (increased costs for treating high-alkali wastewater). Summary of the Invention

[0004] To address the technical challenge of flotation separation of scheelite and calcium-containing gangue due to the similar surface physicochemical properties, this paper proposes the application of sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonic acid)) (BHMTPMPA) in the flotation separation of scheelite and calcium-containing gangue. This inhibitor enables flotation separation of scheelite and calcium-containing gangue, which is of great significance for the efficient and comprehensive utilization of scheelite.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] Application of sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonate)) in the flotation separation of scheelite and calcium-containing gangue.

[0007] Furthermore, the sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonic acid) acid is used as an inhibitor for the flotation separation of scheelite and calcium-containing gangue.

[0008] The present invention is the first to apply sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonate)) to the scheelite flotation system. The inhibitor binds to the surface of calcium-containing gangue through the polyphosphonic acid groups in its molecular structure. 2+A chelation reaction occurs to form a stable hydrophilic complex, thereby selectively inhibiting the floating behavior of calcium-containing gangue such as apatite, calcite, and fluorite, solving the industry's common problem of low inhibition efficiency of calcium-containing gangue during the flotation process of scheelite.

[0009] Furthermore, the flotation separation method comprises the following steps:

[0010] (1) Crushing and grinding the scheelite ore to be processed, and then adding it to the flotation tank for slurry preparation;

[0011] (2) adding a pH adjuster to the slurry obtained in step (1) to adjust the pH of the slurry to 8.0-10.0 and stirring thoroughly;

[0012] (3) adding an inhibitor and a collector to the slurry obtained in step (2) in sequence, and enriching the scheelite by a flotation process;

[0013] The inhibitor is sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonate)) (BHMTPMPA); and the collector is sodium oleate (NaOL).

[0014] Furthermore, after the scheelite ore is crushed and ground in step (1), the particle size is 38-74 μm, accounting for 80%-90%.

[0015] Furthermore, the time for preparing the slurry in step (1) is 3-5 minutes, and the mass concentration of the obtained slurry is 20-30%.

[0016] Furthermore, in step (2), the pH adjuster is selected from sodium carbonate or sodium bicarbonate; and the stirring time is 3-5 minutes.

[0017] Furthermore, the flotation process in step (3) adopts a "one roughing, one sweeping and three refining" process, and the specific parameters are:

[0018] Roughing operation: the dosage of inhibitor is 30-50g / t, and the dosage of collector is 200-300g / t;

[0019] Sweeping operation: the collector dosage is 100-200g / t;

[0020] Select operation: The total amount of inhibitor is 20-40g / t.

[0021] Furthermore, the selection operation is divided into three stages, specifically:

[0022] Selected stage: the inhibitor dosage is 10-20g / t;

[0023] Second stage of selection: the inhibitor dosage is 5-10g / t;

[0024] Selected third stage: the inhibitor dosage is 5-10g / t.

[0025] Furthermore, the inhibitor is added in the form of an aqueous solution, and the mass concentration of the inhibitor in the aqueous solution is 1-2 g / L.

[0026] Furthermore, the collector is added in the form of an aqueous solution, and the mass concentration of the collector in the aqueous solution is 3-5 g / L.

[0027] Compared with the prior art, the present invention has the following advantages and technical effects:

[0028] (1) The present invention uses sodium bis(1,6-hexamethylenetriamine penta(methylenephosphonate)) as a selective inhibitor. The inhibitor selectively adsorbs on the surface of calcium-containing gangue through chelation, forming a hydrophilic film at the mineral interface, significantly increasing the floatability difference between the target mineral and the gangue, thereby achieving efficient separation using conventional fatty acid collectors (such as sodium oleate).

[0029] (2) The inhibitor sodium di-1,6-hexamethylenetriamine penta(methylenephosphonate) provided by the present invention has the advantages of strong selectivity, good inhibitory effect, small dosage, non-toxicity and no pollution, and can significantly improve the separation efficiency of scheelite and calcium-containing gangue. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0031] Figure 1 This is a flotation flow chart of an embodiment of the present invention. DETAILED DESCRIPTION

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0033] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0034] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0035] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0036] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0037] An embodiment of the present invention provides an application of sodium bis(1,6-hexamethylenetriamine penta(methylenephosphonate)) in the flotation separation of scheelite and calcium-containing gangue. The sodium bis(1,6-hexamethylenetriamine penta(methylenephosphonate))) is used as an inhibitor for the flotation separation of scheelite and calcium-containing gangue.

[0038] The embodiment of the present invention provides a method for flotation separation of scheelite and calcium-containing gangue, comprising the following steps:

[0039] (1) Crushing and grinding the scheelite ore to be processed, and then adding it to the flotation tank for slurry preparation;

[0040] (2) adding a pH adjuster to the slurry obtained in step (1) to adjust the pH of the slurry to 8.0-10.0 (as an example, in the following embodiments of the present invention, the pH of the slurry can be adjusted to 9.0) and stirring thoroughly;

[0041] (3) adding an inhibitor, sodium bis(1,6-hexamethylenetriamine penta(methylenephosphonate), and a collector, sodium oleate, to the slurry obtained in step (2) in sequence, and enriching the scheelite by a flotation process;

[0042] In the following preferred embodiments of the present invention, the particle size of the scheelite ore after crushing and grinding in step (1) is 38-74 μm, accounting for 80%-90%. As an example, in the following embodiments of the present invention, the particle size of the scheelite ore after crushing and grinding is 38-74 μm, accounting for 85%.

[0043] In the following preferred embodiments of the present invention, the time for preparing the slurry in step (1) is 3-5 min. As an example, in the following embodiments of the present invention, the slurry preparation can be selected to be 3 min. The mass concentration of the obtained slurry is 20-30%. As an example, in the following embodiments of the present invention, the mass concentration of the obtained slurry can be selected to be 25%.

[0044] In the following preferred embodiments of the present invention, the pH adjuster in step (2) is selected from sodium carbonate or sodium bicarbonate. As an example, in the following embodiments of the present invention, the pH adjuster can be sodium carbonate; and the stirring time is 3-5 minutes. As an example, in the following embodiments of the present invention, the stirring time can be 3 minutes.

[0045] In the following preferred embodiment of the present invention, the flotation process in step (3) adopts a "one roughing, one sweeping and three refining" process, and the specific parameters are:

[0046] Roughing operation: the inhibitor dosage is 30-50 g / t (as an example, in the following embodiments of the present invention, the inhibitor dosage can be selected as 30 g / t or 40 g / t), the collector dosage is 200-300 g / t (as an example, in the following embodiments of the present invention, the collector dosage can be selected as 200 g / t or 300 g / t);

[0047] Sweeping operation: the amount of collector is 100-200 g / t (as an example, in the following embodiments of the present invention, the amount of collector can be selected as 100 g / t or 120 g / t);

[0048] Concentrating process: The total inhibitor dosage is 20-40g / t (including: concentrating stage 1: inhibitor dosage is 10-20g / t; concentrating stage 2: inhibitor dosage is 5-10g / t; concentrating stage 3: inhibitor dosage is 5-10g / t). As an example, in the following embodiments of the present invention, the inhibitor dosage for concentrating stage 1 can be selected as 10g / t; the inhibitor dosage for concentrating stage 2 can be selected as 5g / t; and the inhibitor dosage for concentrating stage 3 can be selected as 5g / t.

[0049] In the following preferred embodiments of the present invention, the inhibitor is added in the form of an aqueous solution, and the mass concentration of the inhibitor solution is 1-2 g / L. As an example, in the following embodiments of the present invention, the mass concentration of the inhibitor solution can be selected as 1 g / L.

[0050] In the following preferred embodiments of the present invention, the collector is added in the form of an aqueous solution, and the mass concentration of the collector solution is 3-5 g / L. As an example, in the following embodiments of the present invention, the mass concentration of the collector solution can be selected to be 4 g / L.

[0051] The raw materials used in the present invention are all purchased from the market.

[0052] Figure 1 This is a flotation flow chart of an embodiment of the present invention.

[0053] The technical solution of the present invention is further illustrated by the following examples.

[0054] Example 1

[0055] The ore to be processed is made of four pure minerals: scheelite, calcite, fluorite and dolomite, which are artificially mixed to form a WO3 grade of 0.85%. The purity of each mineral reaches more than 90%.

[0056] (1) Grind the artificial mixed ore raw materials to a particle size of 38-74 μm, accounting for 85%. Take 100 g of the ground mineral raw materials and add them to the flotation cell of a 0.5 L hanging trough flotation machine. Add 300 mL of water to prepare a slurry with a mass concentration of 25%. Set the speed of the flotation machine to 1900 r / min, and then mix the slurry for 3 minutes.

[0057] (2) adding a pH adjuster, NaCO3, to the slurry obtained in step (1) to adjust the slurry pH to 9.0 and stirring for 3 minutes;

[0058] (3) adding BHMTPMPA to water to obtain a BHMTPMPA solution with a mass concentration of 1 g / L; adding sodium oleate to water to obtain a sodium oleate solution with a mass concentration of 4 g / L;

[0059] (4) Adding BHMTPMPA solution and sodium oleate solution to the slurry obtained in step (2) in sequence, and using the "one coarse, one sweep, three fine" process to enrich the scheelite, the specific parameters are:

[0060] Roughing operation: the dosage of BHMTPMPA solution is 30g / t, and the dosage of sodium oleate solution is 200g / t;

[0061] Sweeping operation: the dosage of sodium oleate solution is 120g / t;

[0062] Concentrating operation: The total consumption of BHMTPMPA solution is 20g / t (including: concentrating stage 1: BHMTPMPA solution consumption is 10g / t; concentrating stage 2: BHMTPMPA solution consumption is 5g / t; concentrating stage 3: BHMTPMPA solution consumption is 5g / t).

[0063] The WO3 content in the final product obtained reaches 58% and the recovery rate is 85%.

[0064] Example 2

[0065] The ore sample in this embodiment comes from a mineral processing plant in Hunan Province, and contains 0.93% WO3. The associated minerals mainly include calcite, fluorite, garnet, quartz and other minerals.

[0066] (1) Grind the mineral raw materials to a particle size of 38-74 μm, accounting for 85%. Add water to the ground mineral raw materials to prepare a slurry with a mass concentration of 25%. Set the speed of the flotation machine to 1900 r / min, and then mix the slurry for 3 minutes.

[0067] (2) adding a pH adjuster, NaCO3, to the slurry obtained in step (1) to adjust the slurry pH to 9.0 and stirring for 3 minutes;

[0068] (3) adding BHMTPMPA to water to obtain a BHMTPMPA solution with a mass concentration of 1 g / L; adding sodium oleate to water to obtain a sodium oleate solution with a mass concentration of 4 g / L;

[0069] (4) Adding BHMTPMPA solution and sodium oleate solution to the slurry obtained in step (2) in sequence, and using the "one coarse, one sweep, three fine" process to enrich the scheelite, the specific parameters are:

[0070] Roughing operation: the dosage of BHMTPMPA solution is 40g / t, and the dosage of sodium oleate solution is 300g / t;

[0071] Sweeping operation: the dosage of sodium oleate solution is 100g / t;

[0072] Concentrating operation: The total consumption of BHMTPMPA solution is 20g / t (including: concentrating stage 1: BHMTPMPA solution consumption is 10g / t; concentrating stage 2: BHMTPMPA solution consumption is 5g / t; concentrating stage 3: BHMTPMPA solution consumption is 5g / t).

[0073] During the flotation process, the reagent addition interval was 3 minutes, the flotation machine speed was 1900 rpm, and the scraping time was 5 minutes. The final product had a WO3 content of 53% and a recovery rate of 85%.

[0074] Example 3

[0075] The ore sample in this embodiment comes from a mineral processing plant in Hunan Province, and contains 0.82% WO3. The associated minerals mainly include calcite, fluorite, garnet, quartz and other minerals.

[0076] (1) Grind the raw materials to a particle size of 38-74 μm, accounting for 85%. Add water to the ground mineral raw materials to prepare a slurry with a mass concentration of 25%. Set the speed of the flotation machine to 1900 r / min, and then mix the slurry for 3 minutes.

[0077] (2) adding a pH adjuster, NaCO3, to the slurry obtained in step (1) to adjust the slurry pH to 9.0 and stirring for 3 minutes;

[0078] (3) adding BHMTPMPA to water to obtain a BHMTPMPA solution with a mass concentration of 1 g / L; adding sodium oleate to water to obtain a sodium oleate solution with a mass concentration of 4 g / L;

[0079] (4) Adding BHMTPMPA solution and sodium oleate solution to the slurry obtained in step (2) in sequence, and using the "one coarse, one sweep, three fine" process to enrich the scheelite, the specific parameters are:

[0080] Roughing operation: the dosage of BHMTPMPA solution is 40g / t, and the dosage of sodium oleate solution is 300g / t;

[0081] Sweeping operation: the dosage of sodium oleate solution is 100g / t;

[0082] Concentrating operation: The total consumption of BHMTPMPA solution is 20g / t (including: concentrating stage 1: BHMTPMPA solution consumption is 10g / t; concentrating stage 2: BHMTPMPA solution consumption is 5g / t; concentrating stage 3: BHMTPMPA solution consumption is 5g / t).

[0083] During the flotation process, the reagent addition interval was 3 minutes, the flotation machine speed was 1900 rpm, and the scraping time was 5 minutes. The final product had a WO3 content of 50% and a recovery rate of 86%.

[0084] Comparative Example 1

[0085] Same as Example 1, except that the BHMTPMPA solution is replaced with water glass, and the specific parameters of step (4) are:

[0086] Roughing operation: the dosage of water glass is 800g / t, and the dosage of sodium oleate solution is 300g / t;

[0087] Sweeping operation: the dosage of sodium oleate solution is 100g / t;

[0088] Selection operation: the total amount of water glass used is 500g / t (including: selection stage 1: water glass used is 200g / t; selection stage 2: water glass used is 150g / t; selection stage 3: water glass used is 150g / t).

[0089] The WO3 content in the final product obtained reached 46% and the recovery rate was 77%.

[0090] Comparative Example 2

[0091] Same as Example 1, except that the mass of BHMTPMPA solution was replaced by hydroxyethylidene diphosphonic acid.

[0092] The WO3 content in the final product obtained reached 44% and the recovery rate was 67%.

[0093] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. Application of sodium bis(1,6-hexamethylenetriamine penta(methylenephosphonate)) in the flotation separation of scheelite and calcium-containing gangue.

2. The use according to claim 1, characterized in that The sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonic acid) acid is used as an inhibitor for the flotation separation of scheelite and calcium-containing gangue.

3. The use according to any one of claims 1-2, characterized in that The flotation separation method comprises the following steps: (1) Crushing and grinding the scheelite ore to be processed, and then adding it to the flotation tank for slurry preparation; (2) adding a pH adjuster to the slurry obtained in step (1) to adjust the pH of the slurry to 8.0-10.0 and stirring thoroughly; (3) adding an inhibitor and a collector to the slurry obtained in step (2) in sequence, and enriching the scheelite by a flotation process; Wherein, the inhibitor is sodium bis(1,6-hexamethylenetriaminepenta(methylenephosphonate); and the collector is sodium oleate.

4. The use according to claim 3, characterized in that After the scheelite ore is crushed and ground in step (1), the particle size is 38-74 μm, accounting for 80-90%.

5. The use according to claim 3, characterized in that The time for preparing the slurry in step (1) is 3-5 minutes, and the mass concentration of the obtained slurry is 20-30%.

6. The use according to claim 3, characterized in that The pH adjuster in step (2) is selected from sodium carbonate or sodium bicarbonate; and the stirring time is 3-5 minutes.

7. The use according to claim 3, characterized in that The flotation process in step (3) adopts a "one roughing, one sweeping and three refining" process, and the specific parameters are: Roughing operation: the dosage of inhibitor is 30-50g / t, and the dosage of collector is 200-300g / t; Sweeping operation: the collector dosage is 100-200g / t; Select operation: the total amount of inhibitor is 20-40g / t; The selection work is divided into three sections, specifically: Selected stage: the inhibitor dosage is 10-20g / t; Second stage of selection: the inhibitor dosage is 5-10g / t; Selected third stage: the inhibitor dosage is 5-10g / t.

8. The use according to claim 7, characterized in that The inhibitor is added in the form of an aqueous solution, and the mass concentration of the inhibitor in the aqueous solution is 1-2 g / L.

9. The use according to claim 7, characterized in that The collector is added in the form of an aqueous solution, and the mass concentration of the collector in the aqueous solution is 3-5 g / L.

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