CN113105158A - Method for recovering quartz from tungsten tailings and preparing artificial stone - Google Patents
Method for recovering quartz from tungsten tailings and preparing artificial stone Download PDFInfo
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- CN113105158A CN113105158A CN202110250188.5A CN202110250188A CN113105158A CN 113105158 A CN113105158 A CN 113105158A CN 202110250188 A CN202110250188 A CN 202110250188A CN 113105158 A CN113105158 A CN 113105158A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a method for recovering quartz from tungsten tailings and preparing artificial stones, which comprises the following steps: firstly, manually selected waste rocks and tailings are crushed and sieved into different size fractions, and each size fraction is subjected to mineral separation through a color sorter to obtain different aggregates. Grinding the tungsten tailings by a closed circuit formed by the undersize product through a ball mill and a sieve, then desliming the ground product through hydraulic classification, purifying the tungsten tailings through magnetic separation to obtain magnetic separation concentrate, and finally obtaining the filler through flotation of the magnetic separation concentrate; mixing the obtained aggregate, the filler, the coupling agent, the unsaturated resin and the curing agent, and finally obtaining the artificial stone product through die reversing, vacuum vibration and pressure molding, curing and drying. The invention can realize the resource recovery and high value-added utilization of quartz in the tungsten tailings, has simple process flow and low energy consumption, and has good economic, social and environmental benefits.
Description
Technical Field
The invention relates to the field of comprehensive utilization of tailings, in particular to a method for recovering quartz from hand-selected waste stone of tungsten mine and tungsten tailings and preparing artificial stone.
Background
The tungsten concentrate yield in China is the first in the world and the quantity of tungsten tailings generated in each year exceeds 2000 ten thousand tons. Tungsten tailings, as a solid waste, are currently mainly stored in tailings ponds or backfilled into mines, which causes resource waste, occupies land, pollutes the environment and harms human health. Therefore, based on the actual situation of tungsten tailing resources, the comprehensive utilization research of the tungsten tailings is developed, the high-value utilization of the tungsten tailings is realized, and the method has very important significance for improving the resource utilization rate and the ecological environment.
At present, tungsten tailings cannot be properly utilized, the comprehensive utilization rate is less than 20%, a large amount of land is occupied, a large amount of potential safety hazards exist, the ecological environment of an area is damaged, and waste of scarce mineral resources is caused. SiO in tungsten tailings2The content is about 60 percent generally, and quartz is a main raw material in the industries of glass, ceramics, refractory materials and the like, but the added value is lower.
Disclosure of Invention
The invention aims to solve the technical problem of providing the method for recovering quartz from tungsten tailings and preparing the artificial stone, which has simple process flow, environmental protection and excellent economic benefit.
The invention adopts the following technical scheme:
a method for recovering quartz from tungsten tailings and preparing artificial stones comprises the following steps:
(1) crushing and screening: the method comprises the following steps of (1) roughly crushing the tungsten mine hand-selected waste rocks, then carrying out medium crushing and fine crushing on the tungsten mine hand-selected waste rocks and tungsten mine tailings, screening the finely crushed materials into products with five particle sizes of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm and-0.124 mm;
(2) color selection: respectively carrying out ore dressing on four products of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm after screening through a color sorter, and respectively naming qualified products as aggregate 1, aggregate 2, aggregate 3 and aggregate 4; returning the products with unqualified color sorting to the step (1) for re-crushing and screening;
(3) grinding: adding water into the product with the size fraction of-0.124 mm obtained in the step (1), putting the product into a ball mill for grinding, wherein the grinding concentration is 30-50%, and the grinding time is adjusted to control the particle size of the product to be less than 0.074 mm;
(4) screening: sieving the ground product by a 0.074mm cylinder sieve, returning the product on the sieve to the step (3) for re-grinding, wherein the product under the sieve is mineral particles smaller than 0.074 mm;
(5) settling and desliming: removing fine mud from mineral particles with the undersize of less than 0.074mm by a hydraulic classifier to obtain a deslimed settlement product;
(6) magnetic separation: removing mechanical iron entrainment of the settled product through weak magnetism, and then removing impurities and purifying through medium-magnetic and high-gradient magnetic separation to obtain a magnetic separation product;
(7) flotation: removing impurity minerals from the magnetic separation product through flotation, and then filtering and drying to obtain a quartz product which is named as a filling material;
(8) mixing and uniformly stirring the aggregates 1, 2, 3 and 4 according to a certain proportion, then adding the unsaturated resin uniformly mixed with the coupling agent and the curing agent, uniformly stirring and mixing, and finally adding the filler with a certain mass, and uniformly mixing;
(9) pouring the uniformly mixed product into a mold, then placing the mold and the product into vacuum vibration-compression molding equipment for molding, and placing the molded product and the mold into an oven for curing for 1-3h at 70-90 ℃;
(11) and demolding and polishing the cured product to obtain the artificial stone product.
In the method, a multi-layer sieve is adopted for sieving in the step 1), and the sizes of the sieve holes are 1.19mm, 0.42mm, 0.22mm and 0.124mm respectively.
In the method, the color selector adopted in the step 2) is a photoelectric color selector.
In the method, the ore grinding in the step 3) adopts an overflow ball mill or a grate ball mill.
In the method, in the step 6), the intensity of the weak magnetic separation magnetic field is less than 0.2T, the intensity of the medium magnetic separation magnetic field is 0.4-0.6T, and the intensity of the strong magnetic separation magnetic field is 0.8-1.2T.
In the method, the collecting agent adopted in the flotation in the step 7) is an amine cation collecting agent, the inhibitor is starch, and the regulator is sulfuric acid or sodium hydroxide.
In the method, the unsaturated resin used in the step 8) includes, but is not limited to, ortho-benzene type unsaturated polyester resin, meta-benzene type unsaturated polyester resin, bisphenol A type unsaturated polyester resin and vinyl resin.
The method, the coupling agent used in the step 8) includes but is not limited to KH-550, KH560 and KH 570.
The method, the curing agent used in the step 8) includes but is not limited to methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide; the addition amounts of the unsaturated resin, the coupling agent and the curing agent used in the step 8) are respectively 10-15%, 6-10% and 10-15% of the weight of the quartz powder.
In the method, the proportion of the aggregate 1, the aggregate 2, the aggregate 3, the aggregate 4 and the filler in the step 8) is 10-15%, 15-20%, 25-30% and 35-40%.
The invention has the following advantages:
1. the method for recovering the quartz from the tungsten tailings makes the recovery of the quartz in the tungsten tailings with low grade and high impurity become possible, and meanwhile, the quartz further manufactures artificial stones, thereby improving the additional value of the tailings products.
2. The invention belongs to the comprehensive utilization of tailing resources, not only protects the environment, but also has certain economic value, and has wider applicable market.
3. The quartz/resin artificial stone plate prepared by the invention can reduce the production of finished products in the early market, and has the advantages of large market capacity, wide application prospect and remarkable economic benefit.
Drawings
FIG. 1 is a process flow diagram of the present invention;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
the method for manually selecting waste stone and tungsten tailings from tungsten mines in some places in Jiangxi, recycling quartz by using the waste stone and the tungsten tailings and preparing the artificial stone comprises the following steps;
(1) crushing and screening: the method comprises the steps of roughly crushing the tungsten mine hand-selected waste rocks, then carrying out medium crushing and fine crushing on the tungsten mine hand-selected waste rocks and tungsten mine tailings, screening the fine crushed materials into products with five particle sizes of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm and-0.124 mm.
(2) Color selection: and (4) respectively carrying out ore dressing on the screened four products of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm by a color sorter, and respectively naming the qualified products as aggregate 1, aggregate 2, aggregate 3 and aggregate 4. Returning the products with unqualified color sorting to the step (1) for re-crushing and screening.
(3) Grinding: adding water into the tungsten tailings, then putting the tungsten tailings into a ball mill for milling, wherein the milling concentration is 30%, and the particle size in the product is controlled to be less than 0.074mm by adjusting the milling time.
(4) Screening: and (3) screening the ground product by a 0.074mm cylindrical screen, returning the product on the screen to the step (1) for re-grinding, and obtaining the product under the screen which is mineral particles with the particle size of less than 0.074 mm.
(5) Settling and desliming: removing fine mud from mineral particles with the size smaller than 0.074mm below the screen by a hydraulic classifier to obtain a deslimed settling product.
(6) Magnetic separation: removing mechanical iron entrainment of the settled product through a magnetic roller with the magnetic field intensity of 0.2T, and then removing impurities and purifying through a plate type medium magnetic separator with the magnetic field intensity of 0.5T and vertical ring pulsating high gradient magnetic separation with the magnetic field intensity of 1.2T to obtain a magnetic separation product.
(7) Flotation: and (3) performing flotation on the magnetic separation product, removing impurity minerals by using a collecting agent which is dodecylamine and an inhibitor which is starch, and filtering and drying to obtain a quartz product. Finally obtained quartz SiO2The purity was 98.9%.
(8) Mixing and uniformly stirring the aggregate 1, the aggregate 2, the aggregate 3 and the aggregate 4 according to a certain proportion, then adding the o-benzene type unsaturated polyester resin uniformly mixed with the coupling agent KH560 and the curing agent methyl ethyl ketone peroxide, uniformly stirring and mixing, finally adding a certain mass of filler, and uniformly mixing. The addition amounts of the unsaturated resin, the coupling agent and the curing agent are respectively 10 percent, 6 per mill and 10 per mill of the weight of the quartz powder. The proportion of the aggregate 1, the aggregate 2, the aggregate 3, the aggregate 4 and the filling material is 15%, 15%, 20%, 20% and 30%.
(9) And pouring the uniformly mixed product into a mold, and then putting the mold and the product into vacuum compacting molding equipment for molding.
(10) And putting the formed quartz and the mould into an oven, and curing for 2 hours at the temperature of 80 ℃.
(11) And demolding, polishing and cutting the cured product to obtain the artificial stone product. The artificial stone plate has the Mohs hardness of 65, the tensile strength of 19.36MPa, the bending strength of 46MPa and the bending elastic modulus of 8300MPa, and meets the performance index requirements of the composite artificial stone plate.
Example 2:
the method for preparing the artificial stone by recovering quartz from the mine tailings and hand-selected waste rocks of tungsten mines selected from places in Hunan comprises the following steps;
(1) crushing and screening: the method comprises the steps of roughly crushing the tungsten mine hand-selected waste rocks, then carrying out medium crushing and fine crushing on the tungsten mine hand-selected waste rocks and tungsten mine tailings, screening the fine crushed materials into products with five particle sizes of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm and-0.124 mm.
(2) Color selection: and (4) respectively carrying out ore dressing on the screened four products of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm by a color sorter, and respectively naming the qualified products as aggregate 1, aggregate 2, aggregate 3 and aggregate 4. Returning the products with unqualified color sorting to the step (1) for re-crushing and screening.
(3) Grinding: adding water into the tungsten tailings, then putting the tungsten tailings into a ball mill for grinding, wherein the grinding concentration is 25%, and the particle size in the product is controlled to be less than 0.074mm by adjusting the grinding time.
(2) Screening: and (3) screening the ground product by a 0.074mm cylindrical screen, returning the product on the screen to the step (1) for re-grinding, and obtaining the product under the screen which is mineral particles with the particle size of less than 0.074 mm.
(3) Settling and desliming: removing fine mud from mineral particles with the size smaller than 0.074mm below the screen by a hydraulic classifier to obtain a deslimed settling product.
(4) Magnetic separation: removing mechanical iron entrainment of the settled product through a magnetic roller with the magnetic field intensity of 0.2T, and then removing impurities and purifying through a plate type medium magnetic separator with the magnetic field intensity of 0.6T and vertical ring pulsating high gradient magnetic separation with the magnetic field intensity of 1.0T to obtain a magnetic separation product.
(5) Flotation: and (3) performing flotation on the magnetic separation product, removing impurity minerals by using a collecting agent which is dodecylamine and an inhibitor which is starch, and filtering and drying to obtain a quartz product. Finally obtained quartz SiO2The purity was 99.2%.
(6) Mixing the aggregate 1, the aggregate 2, the aggregate 3 and the aggregate 4 according to a certain proportion, uniformly stirring, then adding the o-benzene type unsaturated polyester resin uniformly mixed with the coupling agent KH570 and the curing agent methylisobutylketone peroxide, uniformly stirring and mixing, finally adding a certain mass of filler, and uniformly mixing. The addition amounts of the unsaturated resin, the coupling agent and the curing agent are respectively 15%, 10% and 8% of the weight of the aggregate and the filling material. The proportion of the aggregate 1, the aggregate 2, the aggregate 3, the aggregate 4 and the filling material is 10%, 10%, 20%, 25% and 35%.
(7) And pouring the uniformly mixed product into a mold, and then putting the mold and the product into vacuum compacting molding equipment for molding.
(8) And putting the formed quartz and the mould into an oven, and curing for 3 hours at 90 ℃.
(9) And demolding, polishing and cutting the cured product to obtain the artificial stone product. The artificial stone plate has Mohs hardness of 62, tensile strength of 18.96MPa, bending strength of 45MPa and bending elastic modulus of 8100MPa, and meets the performance index requirements of the composite artificial stone plate.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (10)
1. The method for recovering quartz from tungsten tailings and preparing artificial stones is characterized by comprising the following steps of:
(1) crushing and screening: the method comprises the following steps of (1) roughly crushing the tungsten mine hand-selected waste rocks, then carrying out medium crushing and fine crushing on the tungsten mine hand-selected waste rocks and tungsten mine tailings, screening the finely crushed materials into products with five particle sizes of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm and-0.124 mm;
(2) color selection: respectively carrying out ore dressing on four products of +1.19mm, -1.19+0.42mm, -0.42+0.22mm, -0.22+0.124mm after screening through a color sorter, and respectively naming qualified products as aggregate 1, aggregate 2, aggregate 3 and aggregate 4; returning the products with unqualified color sorting to the step (1) for re-crushing and screening;
(3) grinding: adding water into the product with the size fraction of-0.124 mm obtained in the step (1), putting the product into a ball mill for grinding, wherein the grinding concentration is 30-50%, and the grinding time is adjusted to control the particle size of the product to be less than 0.074 mm;
(4) screening: sieving the ground product by a 0.074mm cylinder sieve, returning the product on the sieve to the step (3) for re-grinding, wherein the product under the sieve is mineral particles smaller than 0.074 mm;
(5) settling and desliming: removing fine mud from mineral particles with the size smaller than 0.074mm under the screen by using a hydraulic classifier to obtain a deslimed settling product;
(6) magnetic separation: removing mechanical iron entrainment of the settled product through weak magnetism, and then removing impurities and purifying through medium-magnetic and high-gradient magnetic separation to obtain a magnetic separation product;
(7) flotation: removing impurity minerals from the magnetic separation product through flotation, and then filtering and drying to obtain a quartz product which is named as a filling material;
(8) mixing and uniformly stirring the aggregates 1, 2, 3 and 4 according to a certain proportion, then adding the unsaturated resin uniformly mixed with the coupling agent and the curing agent, uniformly stirring and mixing, and finally adding the filler with a certain mass, and uniformly mixing;
(9) pouring the uniformly mixed product into a mold, then placing the mold and the product into vacuum vibration-compression molding equipment for molding, and placing the molded product and the mold into an oven for curing for 1-3h at 70-90 ℃;
(11) and demolding and polishing the cured product to obtain the artificial stone product.
2. The method of claim 1, further comprising: in the step 1), a multi-layer sieve is adopted for sieving, and the sizes of sieve pores are respectively 1.19mm, 0.42mm, 0.22mm and 0.124 mm.
3. The method of claim 1, further comprising: and 2) adopting a color selector as a photoelectric color selector.
4. The method of claim 1, further comprising: and 3) grinding in the step 3) adopts an overflow ball mill or a grate ball mill.
5. The method of claim 1, further comprising: in the step 6), the intensity of the weak magnetic separation magnetic field is below 0.2T, the intensity of the medium magnetic separation magnetic field is 0.4-0.6T, and the intensity of the strong magnetic separation magnetic field is 0.8-1.2T.
6. The method of claim 1, further comprising: in the step 7), the flotation adopts an amine cation collector as a collecting agent, starch as an inhibitor and sulfuric acid or sodium hydroxide as an adjusting agent.
7. The method of claim 1, further comprising: the unsaturated resin used in the step 8) includes, but is not limited to, ortho-benzene type unsaturated polyester resin and meta-benzene type unsaturated polyester resin, bisphenol A type unsaturated polyester resin, and vinyl resin.
8. The method of claim 1, further comprising: the coupling agent used in the step 8) includes, but is not limited to, KH-550, KH560, KH 570.
9. The method of claim 1, further comprising: the curing agent used in the step 8) includes, but is not limited to, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl isobutyl ketone peroxide, benzoyl peroxide, cumene hydroperoxide; the addition amounts of the unsaturated resin, the coupling agent and the curing agent used in the step 8) are respectively 10-15%, 6-10% and 10-15% of the weight of the quartz powder.
10. The method of claim 1, further comprising: in the step 8), the proportion of the aggregate 1, the aggregate 2, the aggregate 3, the aggregate 4 and the filler is 10-15%, 15-20%, 25-30% and 35-40%.
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| CN113582610A (en) * | 2021-07-19 | 2021-11-02 | 广东海龙建筑科技有限公司 | Environment-friendly inorganic artificial stone made of tungsten tailings and preparation method of environment-friendly inorganic artificial stone |
| CN113751187A (en) * | 2021-08-27 | 2021-12-07 | 中铝郑州有色金属研究院有限公司 | Quartz fine sand and preparation method and application thereof |
| CN114656195A (en) * | 2022-04-22 | 2022-06-24 | 陕西省能源化工研究院 | Process method for preparing artificial stone from solid waste |
| CN115448658A (en) * | 2022-09-01 | 2022-12-09 | 华润水泥技术研发有限公司 | Green inorganic artificial stone taking tungsten tailings as main raw material and preparation method thereof |
| CN116477891A (en) * | 2022-11-17 | 2023-07-25 | 华润水泥技术研发有限公司 | Method for preparing low-cost inorganic artificial stone from tungsten tailings |
| CN116943856A (en) * | 2023-09-20 | 2023-10-27 | 矿冶科技集团有限公司 | Method for effectively recovering chromite |
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| CN113751187A (en) * | 2021-08-27 | 2021-12-07 | 中铝郑州有色金属研究院有限公司 | Quartz fine sand and preparation method and application thereof |
| CN113751187B (en) * | 2021-08-27 | 2024-01-30 | 中铝郑州有色金属研究院有限公司 | Quartz refined sand and preparation method and application thereof |
| CN114656195A (en) * | 2022-04-22 | 2022-06-24 | 陕西省能源化工研究院 | Process method for preparing artificial stone from solid waste |
| CN115448658A (en) * | 2022-09-01 | 2022-12-09 | 华润水泥技术研发有限公司 | Green inorganic artificial stone taking tungsten tailings as main raw material and preparation method thereof |
| CN116477891A (en) * | 2022-11-17 | 2023-07-25 | 华润水泥技术研发有限公司 | Method for preparing low-cost inorganic artificial stone from tungsten tailings |
| CN116943856A (en) * | 2023-09-20 | 2023-10-27 | 矿冶科技集团有限公司 | Method for effectively recovering chromite |
| CN116943856B (en) * | 2023-09-20 | 2023-11-28 | 矿冶科技集团有限公司 | Method for effectively recovering chromite |
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