A method for treating acid-process tungsten slag

Abstract

The present application relates to a kind of acid method tungsten slag processing method, comprising the following steps: S1 dissolution: the tungsten slag is mixed with water, heating treatment is carried out, obtains A material;S2 filtration: the A material is filtered, separates out slag C and the tungsten-containing material liquid, the slag C is washed with water, and the washing water is collected by filtration;S3 ball milling: the washed slag C is mixed with auxiliary material B and then ball milled, to obtain material D;S4 sizing: the material D and the washing water are mixed, sizing is carried out, to obtain material E;S5 leaching: phosphoric acid is added, the phosphoric acid concentration in material liquid is controlled to be greater than or equal to 8g / l, then sulfuric acid is added, the residual acid concentration of material liquid is adjusted to 15-50g / l, then heating leaching is carried out, to obtain material F;S6 filtration: the material F is filtered, to obtain tungsten-containing concentrate liquid and filter residue.The method uses new technology to process acid method tungsten slag, not only reduces the consumption of raw materials, but also the loss of tungsten entrained by slag is lower, and the application prospect is wide.

Description

TECHNICAL FIELD

[0001] The present application relates to tungsten slag recovery processing technology, especially a kind of acid method tungsten slag processing method. BACKGROUND

[0002] White tungsten slag refers to the solid waste generated after white tungsten ore is treated by acid method process. Generally, white tungsten ore is leached by sulfur-phosphorus mixed acid process, and the composition of the sulfur-phosphorus mixed acid is: the phosphoric acid content is 5-10 g / l before leaching, and the sulfuric acid content is 300-400 g / l before leaching.

[0003] Such slag contains acid and tungsten, and the content of acid is relatively high, and the content of tungsten is about 10%. In order to recover such white tungsten slag, the current treatment method of such slag is to first wash and remove soluble heteropoly acid, then dissolve tungsten in the slag into sodium tungstate, and then form white tungsten by auxiliary material precipitation; finally return to leaching. Figure 1 As shown in the figure: the white tungsten slag is first washed by slurry preparation to remove the acid and soluble tungsten in the slag; then the slurry is filtered and separated, the separated filtrate is returned to slurry preparation to enrich tungsten, and the obtained slag is again slurry prepared, and the tungsten in the slag is dissolved by adding auxiliary materials, and after repeated filtration and separation operations, the separated material liquid is added to calcium chloride for tungsten precipitation treatment, and white tungsten is obtained after filtration.

[0004] The treatment method has long process flow, many types of auxiliary materials are added, and the water consumption is large; the solution and slag formed in the process will take away part of the tungsten, resulting in high tungsten loss. SUMMARY

[0005] The purpose of the present application is to overcome the problems existing in the recovery of tungsten from white tungsten slag obtained by acid smelting of white tungsten ore, and to provide a treatment method for acid method tungsten slag, which contains a large amount of heteropoly acid. The present application first adds water and heat to the acid method tungsten slag to separate the soluble part of the acid and part of the tungsten from the solid phase, and obtains a tungsten-containing liquid and a slag C; secondly, auxiliary material B is used to adjust the pH of slag C in a ball mill, and material D is formed after preliminary reaction; finally, tungsten in material D is dissolved by controlling the acid leaching conditions under high phosphorus and low acid conditions. The probability of forming tungstic acid in low acid condition is low, so the tungsten entrainment of the slag can be guaranteed, and the tungsten content is less than 2wt%.

[0006] The specific scheme is as follows:

[0007] A treatment method for acid method tungsten slag, the acid method tungsten slag is a slag obtained after white tungsten ore is treated by sulfur-phosphorus mixed acid, comprising the following steps:

[0008] S1 dissolution: mix the tungsten slag with water and heat to obtain A material;

[0009] S2 filtering: filtering the A material, separating out residue C and a tungsten-containing material liquid, washing the residue C with water, and collecting the washing water by filtration;

[0010] S3 ball milling: mixing the washed residue C with auxiliary material B, and then ball milling to obtain material D;

[0011] S4 slurry mixing: mixing the material D with the washing water, and then slurry mixing to obtain material E;

[0012] S5 leaching: adding phosphoric acid to the material E to control the phosphoric acid concentration in the material liquid to be greater than or equal to 8 g / l, then adding sulfuric acid to adjust the residual acid concentration of the material liquid to be 15-50 g / l, and then performing heating leaching at a temperature of 80-100°C for 0.5-3 h to obtain material F;

[0013] S6 filtering: filtering the material F to obtain a tungsten-enriched liquid and a filter residue.

[0014] Further, the tungsten content in the tungsten refining residue in S1 is greater than or equal to 5 wt%, the calcium sulfate content is 20-40 wt%, and the molybdenum content is 0.06%-0.1 wt%; preferably, the tungsten content in the tungsten refining residue is 9-15 wt%.

[0015] Further, the heating treatment temperature in S1 is 70-90°C, preferably 75-85°C, and the reaction time is 1-2 hours, so that the residue C obtained by filtering and washing the A material in S2 is neutral.

[0016] Further, in S2, the washing with water uses hot water at a temperature of 40-90°C, preferably hot water at a temperature of 80-90°C.

[0017] Further, the auxiliary material B in S3 is at least one of sodium carbonate, calcium carbonate, lime, and caustic soda, and the mass ratio of the auxiliary material B to the residue C after mixing is 1:8-15, and the pH of the material D obtained after reaction and shaping is greater than 9.

[0018] Further, the auxiliary material B in S3 is sodium carbonate, and the mass ratio of sodium carbonate to the residue C after mixing is 1:9-12, and the particle size of the material D obtained after ball milling is 0.1-100 microns, and the tungsten content in the filter residue obtained after the S4, S5, and S6 steps is less than 1.5 wt%.

[0019] Further, in S5, the phosphoric acid is added to control the phosphoric acid concentration in the material liquid to be 8-15 g / l, preferably 8-10 g / l.

[0020] Optionally, in S5, a mixed acid is added, and the acidity of the mixed acid is greater than 60 g / l.

[0021] Further, sulfuric acid is added in S5 to adjust the residual acid concentration of the feed liquid to 18-42 g / l, and the tungsten content is less than 2 wt%; the residual acid concentration is preferably 20-40 g / l, and more preferably 20-30 g / l.

[0022] Further, heating leaching is performed in S5, the heating temperature is 90-100℃, and the temperature is kept for 0.5-3h, so that the tungsten content in the filter residue produced after S6 filtration of the material F is less than 1 wt%.

[0023] Further, the method further comprises mixing the tungsten-containing feed liquid in S3 and the tungsten-containing enriched liquid in S6 to recover tungsten, and using the mixed liquid as a mother liquor for treating tungsten ore, so as to recover tungsten.

[0024] Beneficial effects:

[0025] In the present application, the treatment method of acid leaching tungsten slag first washes the slag, then mixes the washed slag with auxiliary material B through ball milling, and finally returns the ball milled slag directly to leaching. The whole process is short, the auxiliary material is added little, the formed slag and solution are little, the tungsten loss is relatively reduced, and the method has good environmental protection value and economic benefit. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the present application, the following will briefly introduce the drawings. Obviously, the drawings described below only relate to some embodiments of the present application, and not limit the present application.

[0027] Figure 1 is the process flow chart of the treatment of acid leaching tungsten slag in the prior art provided by the present application;

[0028] Figure 2 is the process flow chart of the treatment of acid leaching tungsten slag provided by an embodiment 2 of the present application. DETAILED DESCRIPTION

[0029] The following gives the definition of some terms used in the present application, and other terms not mentioned have the definition and meaning known in the art:

[0030] Acid leaching tungsten slag: In the present application, the acid leaching tungsten slag is white tungsten ore leached by sulfur-phosphorus mixed acid process, the tungsten content in the tungsten leaching slag is greater than or equal to 5 wt%, and the slag has the characteristics of high calcium sulfate, low tungsten and molybdenum impurities. The residual acid concentration of the acid leaching tungsten slag is 10-40 g / l.

[0031] The main steps of the treatment method of acid leaching tungsten slag in the present application are as follows:

[0032] S1 dissolution: mix the tungsten leaching slag with water, and perform heating treatment to obtain A material;

[0033] S2 filtering: filtering the A material, separating out the residue C and the tungsten-containing material liquid, washing the residue C with water, and collecting the washing water by filtration;

[0034] S3 ball milling: mixing the washed residue C with the auxiliary material B and then ball milling to obtain material D;

[0035] S4 slurry preparation: mixing the material D with the washing water to prepare a slurry, and obtaining material E;

[0036] S5 leaching: adding phosphoric acid to the material E to control the concentration of phosphoric acid in the material liquid to be greater than or equal to 8 g / l, then adding sulfuric acid to adjust the residual acid concentration of the material liquid to be 15-50 g / l, and then performing heating leaching at a temperature of 80-100 ℃ for 0.5-3 h to obtain material F;

[0037] S6 filtering: filtering the material F to obtain a tungsten-rich liquid and a filter residue.

[0038] The purpose of S1 dissolution and S2 filtering is to remove the soluble part of tungsten by washing and to wash the residue to be neutral, so as to avoid corrosion of the mill during acidic ball milling and waste of auxiliary materials.

[0039] In S3 ball milling, the auxiliary material B is used to make the residue C transform in the ball mill, and the following reactions mainly occur:

[0040] CaWO4+ Na2CO3 = Na2WO4+ CaCO3

[0041] In S4 slurry preparation, the washing water in the entire process is used, which contains low tungsten and can be used for slurry preparation. At the same time, the temperature can be heated to 80-90 ℃, which prepares for the subsequent leaching.

[0042] In S5 leaching, sulfuric acid and phosphoric acid are used to treat the residue and recover tungsten in the residue. The key to the residue treatment is to reduce the content of residual tungsten in the residue as much as possible. Therefore, the concentration of phosphorus before leaching is controlled to be greater than 8 g / l, and sulfuric acid is used to reduce the corrosion of the equipment.

[0043] The preferred embodiments of the present application will be described in more detail below. Although the preferred embodiments of the present application are described below, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. If a specific technique or condition is not specified in the examples, it is performed according to the technique or condition described in the literature in the art or according to the product manual. If the manufacturer of the reagent or instrument is not specified, it is a conventional product that can be obtained by purchase. In the following examples, unless otherwise specified, "%" refers to the percentage by weight.

[0044] The main element content of the acid-leached tungsten residue used in the following examples is shown in Table 1.

[0045] Table 1 Main components of acid method tungsten smelting slag

[0046] Ingredients Ca W Mo Fe Pb Zn Sr Content / wt% 27.29 11.54 0.06 0.07 0.01 0.02 0.01

[0047] Example 1 Recovery process of conventional acid method tungsten smelting slag

[0048] Referring to Figure 1 , take 300g of acid method tungsten smelting slag, and process according to the following steps:

[0049] Step 1, after slurry is prepared with 100ml hot water, heat to above 80℃, and separate by filtration to obtain slag A;

[0050] Step 2, slag A is again slurry-prepared, 5ml phosphoric acid is added, and pH is adjusted to 10 with flake alkali; after reaction at above 85℃ for 1h, separate by filtration; the obtained tungsten-containing filtrate is used to precipitate tungsten with calcium chloride to obtain calcium tungstate.

[0051] Step 3, calcium tungstate is returned to the leaching process.

[0052] In the above process, tungsten loss: 2wt% in step 2; 0.8wt% in step 3, so the total tungsten recovery rate is low.

[0053] Example 2 New process of the application

[0054] Referring to Figure 2 , take 300g of acid method tungsten smelting slag, and process according to the following steps:

[0055] S1 dissolution: mix the tungsten smelting slag with water, and perform heating treatment to obtain A material. The water used for dissolution can be the filtration and washing water from the previous batch of material processing, to realize water recycling. Heating is performed to fully dissolve the heteropoly acid in the slag, and the heating temperature is 90℃, and heating is performed for 1h.

[0056] S2 filtration: filter the A material to separate slag C and tungsten-containing material liquid, and wash the slag C with water, and collect the washing water by filtration. The obtained slag C is washed to be neutral, which is beneficial to reduce the consumption of auxiliary material B in the next step.

[0057] S3 ball milling: mix the washed slag C with auxiliary material B, and perform ball milling to obtain material D. The auxiliary material B is sodium carbonate, and the addition amount is 1:10 of the mass ratio of auxiliary material B and slag C, and the particle size of the material D after ball milling is 5-6 microns.

[0058] S4 slurry preparation: mix the material D with the washing water to prepare slurry, and obtain material E;

[0059] S5 leaching: phosphoric acid was added to the material E, the concentration of phosphoric acid in the slurry was controlled to be equal to 8 g / l, then sulfuric acid was added, the residual acid concentration of the slurry was adjusted to 38 g / l, and then heating leaching was performed, the heating temperature was 90°C, and the holding time was 1 h, to obtain material F;

[0060] S6 filtration: the material F was filtered to obtain a tungsten-containing rich liquid and a filter residue, wherein the tungsten content in the filter residue was 1.2 wt%, and thus the tungsten recovery rate was 98.8 wt%.

[0061] S7 tungsten recovery: the tungsten-containing rich liquid in S3 and the tungsten-containing rich liquid in S6 were mixed to perform tungsten recovery, and the return flow containing tungsten washing water was used as a mother liquor for treating ore, so as to realize tungsten recovery.

[0062] Compared with example 1, the tungsten loss is the tungsten loss taken away by 2% and 0.8% slag respectively generated after step 2 and step 3, and the new process in this embodiment does not have the 2% tungsten loss in step 2 in example 1.

[0063] Example 3

[0064] 300 g of acid taking tungsten slag was treated according to the following steps:

[0065] S1 dissolution: the tungsten slag was mixed with water and heated to obtain A material. The water used for dissolution can be the filter washing water in the previous batch of material treatment, to realize water recycling. Heating is performed to fully dissolve the heteropoly acid in the slag, and the heating temperature is 90°C and the heating time is 1 h.

[0066] S2 filtration: the A material was filtered to separate slag C and a tungsten-containing material liquid, and the slag C was washed with water and the washing water was collected by filtration. The obtained slag C was washed to be neutral, which is beneficial to reduce the consumption of auxiliary material B in the next step.

[0067] S3 ball milling: the washed slag C was mixed with auxiliary material B to perform ball milling to obtain material D. The auxiliary material B is lime, and the addition amount is that the mass ratio of auxiliary material B to slag C after mixing is 1:10, and the particle size of the material D after ball milling is 5-6 microns.

[0068] S4 slurry preparation: the material D and the washing water were mixed to prepare a slurry to obtain material E;

[0069] S5 leaching: phosphoric acid was added to the material E, the concentration of phosphoric acid in the slurry was controlled to be equal to 8 g / l, then sulfuric acid was added, the residual acid concentration of the slurry was adjusted to 46 g / l, and then heating leaching was performed, the heating temperature was 90°C, and the holding time was 1 h, to obtain material F;

[0070] S6 filtering: filtering the material F to obtain a tungsten-containing enrichment liquid and a filter residue, wherein the tungsten content in the filter residue is 5.1wt%, and thus the tungsten recovery rate is 94.9wt%.

[0071] S7 tungsten recovery: mixing the tungsten-containing liquid in S3 and the tungsten-containing enrichment liquid in S6 to perform tungsten recovery, returning the tungsten-containing washing water to the process to be used as a mother liquor for treating ores, thereby achieving tungsten recovery.

[0072] Example 4

[0073] Take 300g of tungsten refining slag by acid method, and process it according to the following steps:

[0074] S1 dissolution: mix the tungsten refining slag with water and perform heating treatment to obtain material A. The water used for dissolution can be the filter washing water from the previous batch of material processing, achieving water recycling. Heating is performed to fully dissolve the heteropoly acid in the slag, and the heating temperature is 90°C, and the heating time is 1h.

[0075] S2 filtering: filter the material A to separate out slag C and a tungsten-containing liquid, wash the slag C with water, and collect the washing water by filtration. Washing the obtained slag C makes it neutral, which is conducive to reducing the consumption of auxiliary material B in the next step.

[0076] S3 ball milling: mix the washed slag C with auxiliary material B to perform ball milling to obtain material D. The auxiliary material B is calcium carbonate, and the addition amount is such that the mass ratio of auxiliary material B to slag C after mixing is 1:10. The particle size of the material D after ball milling is 5-6 microns.

[0077] S4 slurry preparation: mix the material D with the washing water to prepare a slurry to obtain material E;

[0078] S5 leaching: add phosphoric acid to the material E to control the phosphoric acid concentration in the liquid to be equal to 8g / l, then add sulfuric acid to adjust the residual acid concentration of the liquid to be 41g / l, and then perform heating leaching at a temperature of 90°C for 1h to obtain material F;

[0079] S6 filtering: filtering the material F to obtain a tungsten-containing enrichment liquid and a filter residue, wherein the tungsten content in the filter residue is 4.9wt%, and thus the tungsten recovery rate is 95.1wt%.

[0080] S7 tungsten recovery: mixing the tungsten-containing liquid in S3 and the tungsten-containing enrichment liquid in S6 to perform tungsten recovery, returning the tungsten-containing washing water to the process to be used as a mother liquor for treating ores, thereby achieving tungsten recovery.

[0081] Example 5

[0082] The embodiment is based on the embodiment 2, and studies the S5 leaching condition. The material D is taken, and is added with salt-free water to obtain material E. Different acids in table 2 are added respectively to carry out leaching treatment, the temperature of heating after adding the acid is 90 DEG C, and the temperature is kept for 1h. The material F is obtained to carry out filtration, and the tungsten rich liquid and the filter residue are obtained. The tungsten content of the filter residue is detected, and the result is shown in table 2.

[0083] Table 2 tungsten loss under different leaching conditions

[0084] Serial number First acid Second acid Residual tungsten content in slag / wt% 1 Sulfuric acid None 14 2 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l None 12 3 Phosphoric acid, concentration of phosphoric acid in the solution is 5g / l Sulfuric acid, residual acid concentration of the solution is 40.1g / l 8.8 4 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 100g / l 7.9 5 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 83.4g / l 8.4 6 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 62.7g / l 6.7 7 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 50.8g / l 2.4 8 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 40.2g / l 1.3 9 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 31g / l 1.7 10 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 20.9g / l 0.95 11 Phosphoric acid, concentration of phosphoric acid in the solution is 8g / l Sulfuric acid, residual acid concentration of the solution is 1.6g / l 7.5 12 Phosphoric acid, concentration of phosphoric acid in the solution is 9g / l Sulfuric acid, residual acid concentration of the solution is 40.1g / l 6.8

[0085] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above-described embodiments. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0086] In addition, it should be noted that each specific technical feature described in the above-described specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the present application.

[0087] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, and it should be considered as disclosed content of the present application.

Claims

1. A method for treating acid-process tungsten slag, wherein the acid-process tungsten slag is obtained by treating scheelite with a sulfur-phosphorus mixed acid, characterized in that: The following steps are involved: S1 dissolution: mixing the tungsten slag with water and heating the mixture to obtain material A; the tungsten slag contains 5wt% or more of tungsten, 20-40wt% of calcium sulfate, and 0.06%-0.1wt% of molybdenum; S2 filtration: filtering the material A to separate the slag C and the tungsten-containing liquid, washing the slag C with water, and filtering and collecting the washing water; S3 ball milling: mixing the washed slag C with auxiliary material B and then ball milling to obtain material D; S4 slurry preparation: mixing the material D and the washing water, performing slurry preparation, and obtaining material E; S5 leaching: adding phosphoric acid to the material E to control the phosphoric acid concentration in the liquid to 8-15 g / l, then adding sulfuric acid to adjust the residual acid concentration of the liquid to 15-50 g / l, and then heating and leaching at a temperature of 80-100° C. for 0.5-3 hours to obtain material F; S6 filtration: filtering the material F to obtain a tungsten-containing enriched liquid and a filter residue; the auxiliary material B is sodium carbonate, and the mass ratio of sodium carbonate to the slag C is 1:9-12. The particle size of the material D obtained after ball milling is 0.1-100 microns, and the pH of the material D is greater than 9. The tungsten content in the filter residue obtained after steps S4, S5, and S6 is less than 1.5wt%.

2. The method for treating acid tungsten slag according to claim 1, characterized in that: The tungsten content in the tungsten slag in S1 is 9-15wt%.

3. The method for treating acid tungsten slag according to claim 1, characterized in that: The temperature of the heating treatment in S1 is 70-90° C., and the reaction time is 1-2 hours, so that the residue C obtained by filtering and washing the material A in S2 is neutral.

4. The method for treating acid tungsten slag according to claim 3, characterized in that: The temperature of the heating treatment in S1 is 75-85°C.

5. The method for treating acid tungsten slag according to claim 1, characterized in that: Water is added to S2 for washing, and hot water with a temperature of 40-90°C is used.

6. The method for treating acid tungsten slag according to claim 5, characterized in that: Water is added to S2 for washing, and hot water with a temperature of 80-90°C is used.

7. The method for treating acid tungsten slag according to claim 1, characterized in that: Phosphoric acid is added to S5 to control the phosphoric acid concentration in the feed solution to 8-10 g / l.

8. The method for treating acid tungsten slag according to claim 7, characterized in that: In S5, a miscellaneous acid is added, wherein the acidity of the miscellaneous acid is greater than 60 g / l.

9. The method for treating acid tungsten slag according to claim 7, characterized in that: Sulfuric acid is added to S5 to adjust the residual acid concentration of the feed solution to 18-42 g / l and the tungsten content to less than 2 wt%.

10. The method for treating acid tungsten slag according to claim 9, characterized in that: Sulfuric acid is added to S5 to adjust the residual acid concentration of the feed solution to 20-40 g / l.

11. The method for treating acid tungsten slag according to claim 10, characterized in that: Sulfuric acid is added to S5 to adjust the residual acid concentration of the feed solution to 20-30 g / l.

12. The method for treating acid tungsten slag according to claim 9, characterized in that: In S5, heating leaching is performed at a temperature of 90-100°C and the temperature is kept for 0.5-3 hours, so that the tungsten content in the filter residue generated after the material F is filtered through S6 is less than 1 wt%.

13. The method for treating acid tungsten slag according to any one of claims 1 to 12, characterized in that: It also includes recovering tungsten after mixing the tungsten-containing feed liquid in S2 and the tungsten-containing enriched liquid in S6, and using the mixed liquid as a mother liquid for processing tungsten ore, thereby achieving tungsten recovery.

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