A method for preparing a ceramic tile colloidal raw material by using tungsten tailings, the ceramic tile colloidal raw material, and a ceramic tile

Abstract

The application relates to the technical field of ore dressing, and discloses a method for preparing ceramic tile glue raw materials from tungsten tailings, ceramic tile glue raw materials and ceramic tile glue. The method comprises the following steps: (1) preparing the tungsten tailings into ore slurry with a concentration of 10-20 wt%, and sequentially performing magnetic separation and concentration desliming on the ore slurry to obtain magnetic separation concentrate sand with a sand concentration of 25-35 wt%; (2) performing rough flotation of sulfur on the magnetic separation concentrate sand together with an adjusting agent, copper sulfate, a collecting agent I and 2# oil to obtain sulfur flotation tailings with a sulfur content of not more than 0.1 wt%; and (3) performing impurity removal flotation on the sulfur flotation tailings together with a collecting agent II to obtain impurity removal concentrate, and sequentially performing dehydration and drying on the impurity removal concentrate to obtain ceramic tile glue raw materials with a water content of not more than 0.5 wt%. By adopting the method, ceramic tile glue raw materials with a total sulfur content of less than 0.1 wt%, argillaceous mineral content and mica content of less than 1 wt% can be obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore dressing, in particular to a method for preparing ceramic tile glue raw material from tungsten tailings, ceramic tile glue raw material and ceramic tile glue. BACKGROUND

[0002] China is rich in tungsten resources, accounting for about 40% of the world's total reserves, and is an advantage mineral resource. However, tungsten ore is brittle and easy to over-crush, resulting in fine mud. In addition, most of the tungsten ore has fine grain size, and is associated with many useful metal minerals. The gangue minerals are closely related to tungsten minerals, making separation difficult. Many fine tungsten particles cannot be recovered, resulting in tailings.

[0003] According to statistics, about 1 / 5 of the tungsten-containing minerals in the world are lost in the form of fine particles. This loss is fundamentally due to the difficulty in effectively sorting and recovering fine particles, which not only wastes limited tungsten resources, but also adversely affects the environment around the mine.

[0004] The main minerals in tungsten tailings are mainly calcite, dolomite, quartz and feldspar, among which the content of calcite and dolomite is 10-50%, and the content of quartz and feldspar is 10-40%. Impurities include pyrite, pyrrhotite, chalcopyrite and sphalerite metal sulfides, as well as non-metallic impurities such as chlorite, amphibole and mica.

[0005] Therefore, how to efficiently recover the aforementioned mineral materials from tungsten tailings has important theoretical and practical significance for the comprehensive utilization of tungsten resources.

[0006] CN113105158A discloses a method for recovering quartz from tungsten tailings and preparing artificial stone. The method is to crush and screen the hand-picked waste rock and tailings into different particle sizes, and each particle size is selected by a color sorter to obtain different aggregates. The undersize product is ground by a ball mill and a screen to form a closed circuit for grinding the tungsten tailings. Then, the ground product is deslimed by hydraulic classification, and the tungsten tailings are purified by magnetic separation to obtain magnetic separation concentrate. The magnetic separation concentrate is finally obtained by flotation to obtain filler. The obtained aggregate, filler, coupling agent, unsaturated resin and curing agent are mixed, and finally inverted mold, vacuum vibration pressing, curing and drying are performed to obtain artificial stone products.

[0007] CN111686927A discloses a tungsten ore waste rock and tungsten tailings resource utilization method. The method fully recovers and classifies underground tungsten ore waste rock, hand-picked tungsten ore waste rock and tungsten tailings by using pre-screening pretreatment, screening and beneficiation, pre-dehydration pretreatment, screening and gravity separation, and concentration pressure filtration process, to obtain target products classified as quartz concentrate, tungsten concentrate, machine-made sand, aggregate 1, aggregate 2, aggregate 3 and pressure filtration cake.

[0008] However, the foregoing method cannot completely remove impurities, and the concentration of the ore slurry is too high in the magnetic separation process, affecting the magnetic separation effect; at the same time, the concentration of the ore slurry after the magnetic separation in the prior art is low, and the ore slurry must be concentrated again before entering the flotation, resulting in a more complex process. SUMMARY

[0009] The present application aims to overcome the aforementioned defects in the prior art and provide a method for preparing ceramic tile glue raw materials from tungsten tailings.

[0010] To achieve the above-mentioned purpose, the first aspect of the present application provides a method for preparing ceramic tile glue raw materials from tungsten tailings, which comprises:

[0011] (1) The tungsten tailings are prepared into an ore slurry with a concentration of 10-20wt%, and the ore slurry is sequentially subjected to magnetic separation and concentration desliming to obtain a magnetic separation concentrate sand with a sand concentration of 25-35wt%;

[0012] (2) The magnetic separation concentrate sand is subjected to rough flotation of sulfur with an adjusting agent, copper sulfate, a collector I and 2# oil to obtain a sulfur flotation tailings with a sulfur content of not more than 0.1wt%; wherein the collector I is selected from at least one of butyl xanthate and amyl xanthate, and the amount of the adjusting agent is controlled so that the pH value of the sulfur flotation tailings is 7-9;

[0013] (3) The sulfur flotation tailings are subjected to impurity removal flotation with a collector II to obtain an impurity removal concentrate, and the impurity removal concentrate is sequentially subjected to dewatering and drying to obtain a ceramic tile glue raw material with a water content of not more than 0.5wt%; wherein the collector II is a combination of an amine cationic collector and a soap anionic collector with a content mass ratio of 1:3-5.

[0014] The second aspect of the present application provides a ceramic tile glue raw material prepared by the method of the first aspect.

[0015] The third aspect of the present application provides a ceramic tile glue containing the ceramic tile glue raw material of the second aspect.

[0016] The present application can effectively remove impurities such as argillaceous minerals, mica and sulfides by two desliming and two flotation, so that the total sulfur content in the finally obtained ceramic tile glue raw material is less than 0.1wt%, and the content of argillaceous minerals and mica is less than 1wt%; and the method provided by the present application also has the characteristics of simple process flow and easy operation. DETAILED DESCRIPTION

[0017] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numeric range recited is intended to include all values between the recited upper and lower values, inclusive of the recited values. In other words, the endpoints of the ranges are not limited to the precise values recited as the exact dimensions are not critical to the invention. The endpoints of the ranges and any values disclosed herein should be understood to be open-ended to the extent that the lower or upper limits are not stated to be the exact value and should be understood to include values approximating the value.

[0018] As described previously, the first aspect of the present application provides a method for preparing ceramic tile glue raw materials from tungsten tailings, the method comprising:

[0019] (1) preparing the tungsten tailings into a slurry with a concentration of 10-20wt%, and sequentially subjecting the slurry to magnetic separation and thickening desliming to obtain a magnetic separation concentrate sand with a sand concentration of 25-35wt%;

[0020] (2) subjecting the magnetic separation concentrate sand to rough flotation of sulfur with an adjusting agent, copper sulfate, a collector I and 2# oil to obtain a sulfur flotation tailings with a sulfur content of not more than 0.1wt%; wherein the collector I is selected from at least one of butyl xanthate and amyl xanthate, and the amount of the adjusting agent is controlled so that the pH value of the sulfur flotation tailings is 7-9;

[0021] (3) subjecting the sulfur flotation tailings to impurity removal flotation with a collector II to obtain an impurity removal concentrate, and sequentially subjecting the impurity removal concentrate to dewatering and drying to obtain a ceramic tile glue raw material with a water content of not more than 0.5wt%; wherein the collector II is a combination of an amine cationic collector and a soap anionic collector with a content mass ratio of 1:3-5.

[0022] The present application does not have special requirements for the specific operation method of the magnetic separation, and the magnetic separation can be performed by a method known in the art. Illustratively, the present application performs the magnetic separation in a magnetic separator, and the magnetic separation comprises one-time strong magnetic roughing and at least one-time scavenging operation.

[0023] The present application does not have special requirements for the specific operation method of the thickening desliming, and the thickening desliming can be performed by a method known in the art. Illustratively, the present application performs the thickening desliming by using a hydrocyclone.

[0024] The present application does not have special requirements for the specific operation method of the rough flotation of sulfur and the impurity removal flotation, and the rough flotation of sulfur and the impurity removal flotation can be performed by a method known in the art. Illustratively, the rough flotation of sulfur and the impurity removal flotation of the present application are both performed in a flotation machine, and each of the rough flotation of sulfur and the impurity removal flotation independently comprises one-time roughing and at least one-time scavenging.

[0025] The present application does not have special requirements for the specific operation method of the dewatering, and only needs to be able to obtain a ceramic tile glue raw material with a water content of not more than 0.5wt%.

[0026] Preferably, in step (1), the method further comprises: mixing the tungsten tailings with water to obtain a slurry with a concentration of 10-20wt%.

[0027] Preferably, in step (1), the conditions of the magnetic separation at least include: a magnetic field strength of 1-1.8T.

[0028] According to a particularly preferred embodiment of the present application, in step (2), the adjusting agent is sodium carbonate.

[0029] It should be noted that the adjusting agent in the present application is a sodium carbonate aqueous solution, and the present application does not have a particular requirement for the concentration of the sodium carbonate aqueous solution, which only needs to meet the requirements of the present application. Exemplarily, the concentration of the sodium carbonate aqueous solution is 4-6wt%.

[0030] The present application does not have a particular requirement for the amount of the adjusting agent, which only needs to meet the requirements of the present application. Specifically, it only needs to make the pH value of the sulfur flotation tailings be 7-9. Exemplarily, the amount of the adjusting agent is 500-700g with respect to 1t of the tungsten tailings.

[0031] Preferably, in step (2), the amount of the copper sulfate is 100-500g, more preferably 200-300g, with respect to 1t of the tungsten tailings. The inventors found in the research process that the specific embodiment of the preferred case can obtain a ceramic tile glue raw material with higher yield.

[0032] Preferably, in step (2), the amount of the collector I is 50-150g, and the amount of the 2# oil is 10-100g, with respect to 1t of the tungsten tailings.

[0033] More preferably, in step (2), the amount of the collector I is 50-100g, with respect to 1t of the tungsten tailings. The inventors found in the research process that the specific embodiment of the preferred case can obtain a ceramic tile glue raw material with higher yield under the premise of reducing impurities.

[0034] Preferably, in step (2), the conditions of the sulfur flotation roughing at least include: a temperature of 15-35℃ and a time of 3-5min.

[0035] Preferably, in step (3), the amount of the collector II is 70-400g, with respect to 1t of the tungsten tailings.

[0036] According to a particularly preferred embodiment of the present application, in step (3), the amine cationic collector is selected from dodecylamine and / or octadecylamine.

[0037] According to a particularly preferred embodiment of the present application, in step (3), the soap anionic collector is naphthenate soap.

[0038] Preferably, in step (3), the conditions of the impurity removal flotation at least include: temperature of 15-35℃, and time of 3-5min.

[0039] Preferably, in step (3), the conditions of the drying at least include: temperature of 300-500℃, and time of 10-30min.

[0040] As mentioned above, the second aspect of the present application provides a ceramic tile glue raw material prepared by the method of the first aspect.

[0041] Preferably, the ceramic tile glue raw material contains calcite, dolomite, quartz and feldspar, and the content of the calcite is 20-50wt%, the content of the dolomite is 0-15wt%, the content of the quartz is 20-50wt% and the content of the feldspar is 5-15wt% based on the total mass of the ceramic tile glue raw material.

[0042] As mentioned above, the third aspect of the present application provides a ceramic tile glue containing the ceramic tile glue raw material of the second aspect.

[0043] The present application will be described in detail below by way of examples. In the following examples, the various raw materials used are commercially available unless otherwise specified.

[0044] Tungsten tailings: specifically from Xiangdong Tungsten Industry in Zhuzhou;

[0045] Adjusting agent: sodium carbonate solution with a concentration of 5wt%;

[0046] Collector I-1: butyl xanthate, purchased from Zhuzhou Ore Dressing Reagent Factory;

[0047] Collector I-2: amyl xanthate, purchased from Zhuzhou Ore Dressing Reagent Factory;

[0048] 2# oil: purchased from Zhuzhou Ore Dressing Reagent Factory;

[0049] Collector II: amine cationic collector-1, dodecylamine, purchased from Zhuzhou Ore Dressing Reagent Factory;

[0050] Collector II: amine cationic collector-2, octadecylamine, purchased from Zhuzhou Ore Dressing Reagent Factory;

[0051] Collector II: soap anionic collector, sodium naphthenate, purchased from Zhuzhou Ore Dressing Reagent Factory;

[0052] In the following examples, the model of the magnetic separator is SLon-1250, which is purchased from Ganzhou Jinhuang Magnetic Separation Equipment Co., Ltd.; the model of the hydrocyclone is FX-150, which is purchased from Weihai Haiwang Hydrocyclone Co., Ltd.

[0053] Example 1

[0054] The present embodiment provides a method for preparing ceramic tile glue raw material from tungsten tailings, which comprises the following steps:

[0055] (1) 1 t of tungsten tailings is added into 5.7 t of water to obtain a slurry with a concentration of 15 wt%, and then the slurry is introduced into a magnetic separator with a magnetic field strength of 1.5 T for magnetic separation to obtain a magnetic separation concentrate, and the magnetic separation concentrate is introduced into a hydrocyclone for concentration and desliming to obtain a magnetic separation concentrate sand with a sand concentration of 35 wt%;

[0056] (2) the magnetic separation concentrate sand obtained in the foregoing step is subjected to rough flotation of sulfur with 600 g of an adjusting agent, 300 g of copper sulfate, 90 g of a collector I-1 and 45 g of 2# oil to obtain a sulfur flotation tailing with a sulfur content of 0.06 wt%;

[0057] wherein the conditions for the rough flotation of sulfur are that the temperature is 25°C and the time is 4 min;

[0058] The amount of the adjusting agent is controlled so that the pH value of the sulfur flotation tailing is 8.5;

[0059] (3) the sulfur flotation tailing obtained in the foregoing step is subjected to impurity removal flotation with 180 g of a collector II (a combination of an amine cationic collector-1 and a soap anionic collector with a content mass ratio of 1:3.5) to obtain an impurity removal concentrate, and the impurity removal concentrate is sequentially subjected to dewatering and drying to obtain a ceramic tile glue raw material with a water content of 0.1 wt%;

[0060] wherein the conditions for the impurity removal flotation are that the temperature is 25°C and the time is 4 min;

[0061] The conditions for the drying are that the temperature is 450°C and the time is 20 min.

[0062] Example 2

[0063] The present embodiment provides a method for preparing ceramic tile glue raw material from tungsten tailings, which comprises the following steps:

[0064] (1) 1 t of tungsten tailings is added into 4 t of water to obtain a slurry with a concentration of 20 wt%, and then the slurry is introduced into a magnetic separator with a magnetic field strength of 1.8 T for magnetic separation to obtain a magnetic separation concentrate, and the magnetic separation concentrate is introduced into a hydrocyclone for concentration and desliming to obtain a magnetic separation concentrate sand with a sand concentration of 33 wt%;

[0065] (2) the magnetic separation concentrate sand obtained above is subjected to rough flotation of sulfur with 500 g of the adjusting agent, 260 g of copper sulfate, 60 g of the collector I-1 and 45 g of 2# oil to obtain a sulfur flotation tailing with a sulfur content of 0.08 wt%;

[0066] The rough flotation of sulfur is carried out at a temperature of 25°C for 3 min.

[0067] The amount of the adjusting agent is controlled so that the pH value of the sulfur flotation tailing is 8.

[0068] (3) the sulfur flotation tailing obtained above is subjected to impurity removal flotation with 180 g of the collector II (a combination of amine cationic collector-2 and soap anionic collector at a content mass ratio of 1:4) to obtain an impurity removal concentrate, and the impurity removal concentrate is sequentially subjected to dehydration and drying to obtain a ceramic tile collagen raw material with a water content of 0.1 wt%;

[0069] The impurity removal flotation is carried out at a temperature of 25°C for 3 min.

[0070] The drying is carried out at a temperature of 450°C for 20 min.

[0071] Example 3

[0072] The embodiment provides a method for preparing a ceramic tile collagen raw material from tungsten tailings, which comprises the following steps:

[0073] (1) 1 t of tungsten tailings is added into 9 t of water to obtain a slurry with a concentration of 10 wt%, and then the slurry is introduced into a magnetic separator with a magnetic field strength of 1.5 T for magnetic separation to obtain a magnetic separation concentrate, and the magnetic separation concentrate is introduced into a hydrocyclone for concentration desliming to obtain a magnetic separation concentrate sand with a concentration of 32 wt%;

[0074] (2) the magnetic separation concentrate sand obtained above is subjected to rough flotation of sulfur with 700 g of the adjusting agent, 200 g of copper sulfate, 50 g of the collector I-2 and 45 g of 2# oil to obtain a sulfur flotation tailing with a sulfur content of 0.09 wt%;

[0075] The rough flotation of sulfur is carried out at a temperature of 25°C for 3 min.

[0076] The amount of the adjusting agent is controlled so that the pH value of the sulfur flotation tailing is 9.

[0077] (3) the sulfur flotation tailing obtained above is subjected to impurity removal flotation with 180 g of the collector II (a combination of amine cationic collector-1 and soap anionic collector at a content mass ratio of 1:4.5) to obtain an impurity removal concentrate, and the impurity removal concentrate is sequentially subjected to dehydration and drying to obtain a ceramic tile collagen raw material with a water content of 0.09 wt%.

[0078] The conditions of the impurity removal flotation are that the temperature is 25°C and the time is 5 min.

[0079] The conditions of the drying are that the temperature is 450°C and the time is 20 min.

[0080] Example 4

[0081] The ceramic tile adhesive raw material is prepared according to the method of Example 1, except that in step (2), the copper sulfate used is 400 g.

[0082] Example 5

[0083] The ceramic tile adhesive raw material is prepared according to the method of Example 1, except that in step (2), the collector I-1 used is 150 g.

[0084] Comparative Example 1

[0085] The ceramic tile adhesive raw material is prepared according to the method of Example 1, except that in step (1), the pulp concentration is 30 wt%.

[0086] The specific operation method comprises:

[0087] (1) 1 t of tungsten tailings is added to 2.3 t of water to obtain a pulp with a concentration of 30 wt%, and then the pulp is introduced into a magnetic separator with a magnetic field strength of 1.5 T for magnetic separation to obtain a magnetic separation concentrate, and the magnetic separation concentrate is introduced into a hydrocyclone for concentration desliming to obtain a magnetic separation concentrate sand with a sand concentration of 15 wt%;

[0088] (2) The same as step (2) in Example 1;

[0089] (3) The same as step (3) in Example 1.

[0090] Comparative Example 2

[0091] The ceramic tile adhesive raw material is prepared according to the method of Example 1, except that in step (3), the collector II is a combination of amine cationic collector-1 and soap anionic collector with a content mass ratio of 1:8.

[0092] Comparative Example 3

[0093] The ceramic tile adhesive raw material is prepared according to the method of Example 1, except that in step (3), the collector II is a combination of amine cationic collector-1 and soap anionic collector with a content mass ratio of 1:1.

[0094] Comparative Example 4

[0095] The tile glue raw material was prepared according to the method of Example 1, except that in step (3), the same mass of amine cationic collector-1 was used to replace the collector II.

[0096] Comparative Example 5

[0097] The tile glue raw material was prepared according to the method of Example 1, except that in step (3), the collector II was a combination of dodecylamine and petroleum sulfonate sodium with a mass ratio of 1:3.5.

[0098] Test Example 1

[0099] The components and contents in the tile glue raw materials prepared in the examples and comparative examples were detected, and the yield was calculated, and the specific detection results are shown in Table 1.

[0100] Among them, the yield calculation formula is: (the mass of the final tile glue raw material / the mass of the tungsten tailings raw material) x 100%;

[0101] The total sulfur content was obtained by barium sulfate gravimetric titration, and the calcite, dolomite, quartz, feldspar, mica content and mud content were obtained by MLA automatic mineral parameter analysis system.

[0102] Table 1

[0103]

[0104] From the results in Table 1, it can be seen that the method provided by the present application can not only effectively remove impurities such as argillaceous minerals, mica and sulfides, but also obtain a tile glue raw material with high yield.

[0105] Test Example 2

[0106] The tile glue raw materials prepared in Example 1, Example 4 and Comparative Example 5 were used to prepare tile glue, wherein the tile glue was prepared according to the method specified in JC / T547-2017 Ceramic Glue Adhesive, and the performance of the prepared tile glue was detected according to the requirements of GB / T25181-2019 Ready-mixed Mortar Standard, and the indoor type I tile glue formula table is shown in Table 2. The raw materials purified by tungsten tailings were used to replace 70-140 mesh sand and 200 mesh heavy calcium powder in the formula, and the specific detection results are shown in Table 3.

[0107] Table 2

[0108]

[0109] Table 3

[0110]

[0111] As can be seen from the above table, the ceramic tile adhesive product prepared by using the ceramic tile adhesive raw material provided by the application meets the GB / T25181-2019 premixed mortar standard requirements; and the bonding strength performance of the ceramic tile adhesive product prepared by using the ceramic tile adhesive raw material provided by the application is equivalent to that of the ceramic tile adhesive product obtained by using the basic formula.

[0112] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and fall within the protection scope of the application.

Claims

1. A method for preparing ceramic tile adhesive raw materials using tungsten tailings, characterized in that, The method includes: (1) Prepare a slurry with a concentration of 10-20wt% from tungsten tailings, and subject the slurry to magnetic separation and concentration desliming in sequence to obtain magnetic concentrate with a sand concentration of 25-35wt%. (2) The magnetic concentrate sediment is subjected to flotation roughing with modifier, copper sulfate, collector I and No. 2 oil to obtain flotation tailings with a sulfur content of no more than 0.1 wt%; wherein, collector I is selected from at least one of butyl xanthate and pentoxanthate, and the amount of modifier is controlled so that the pH value of the flotation tailings is 7-9. The modifier is sodium carbonate; the amount of copper sulfate used is 200-300g relative to 1t of tungsten tailings. (3) The sulfur tailings are subjected to impurity removal flotation with collector II to obtain impurity-removed concentrate, and the impurity-removed concentrate is dehydrated and dried in sequence to obtain tile adhesive raw material with a moisture content of not more than 0.5 wt%; wherein, collector II is a combination of amine cationic collector and soap anionic collector with a content mass ratio of 1:3-5. The amount of collector II relative to 1 t of tungsten tailings is 70-400 g; the soap-based anionic collector is naphthenic acid soap; the amine-based cationic collector is selected from dodecylamine and / or octadecylamine; The conditions for impurity removal flotation include at least the following: temperature of 15-35℃ and time of 3-5 min.

2. The method according to claim 1, wherein, In step (1), the conditions for magnetic separation include at least the magnetic field strength of 1-1.8T.

3. The method according to claim 1 or 2, wherein, In step (2), relative to 1 t of the tungsten tailings, the amount of collector I is 50-150 g and the amount of No. 2 oil is 10-100 g.

4. The method according to claim 1 or 2, wherein, In step (2), the conditions for the rough selection of sulfur flotation include at least the following: temperature of 15-35℃ and time of 3-5min.

5. The method according to claim 1 or 2, wherein, In step (3), the drying conditions include at least the following: temperature of 300-500℃ and time of 10-30min.

6. The tile adhesive raw material prepared by the method according to any one of claims 1-5.

7. A type of tile adhesive, characterized in that, The tile adhesive contains the tile adhesive raw material as described in claim 6.

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