CN111250246A - Method for preparing cementing material by using tungsten-molybdenum tailings valuable mineral step separation component - Google Patents

Method for preparing cementing material by using tungsten-molybdenum tailings valuable mineral step separation component Download PDF

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CN111250246A
CN111250246A CN202010254215.1A CN202010254215A CN111250246A CN 111250246 A CN111250246 A CN 111250246A CN 202010254215 A CN202010254215 A CN 202010254215A CN 111250246 A CN111250246 A CN 111250246A
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tungsten
tailings
cementing material
molybdenum tailings
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CN111250246B (en
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彭伟军
曹亦俊
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Zhengzhou University
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Zhengzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C21/00—Disintegrating plant with or without drying of the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • 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
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • 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
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/002—Inorganic compounds
    • 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
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/007—Modifying reagents for adjusting pH or conductivity
    • 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
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • 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
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/06—Depressants
    • 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
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Abstract

The application discloses a method for preparing a cementing material by using tungsten-molybdenum tailings valuable mineral gradient separation components, which comprises the following specific steps: (1) the tungsten-molybdenum tailings are obtained by screening, reserving products on a screen as fine aggregates, directly mixing the products under the screen to perform magnetic separation, and drying magnetic products (component B) and non-magnetic products (component C); (2) concentrating and size mixing the component C, then carrying out flotation, carrying out primary roughing, secondary scavenging, four-time fine concentration and primary fine scavenging to obtain a fluorite concentrate product, and respectively drying the fine scavenging tailings (component E) and the scavenging tailings (component D); (3) mixing the component B and the component D according to a certain mass ratio to form a component F, and (4) ball-milling a mixture of the component F, fly ash, slag, gypsum, an exciting agent and a water reducing agent for a certain time to obtain the cementing material. The invention firstly carries out step separation on valuable minerals in the tungsten-molybdenum tailings, and adds various valuable components in the tungsten-molybdenum tailings according to a certain proportion to prepare the cementing material with excellent performance.

Description

Method for preparing cementing material by using tungsten-molybdenum tailings valuable mineral step separation component
Technical Field
The invention belongs to the field of tungsten-molybdenum tailing recovery, and particularly relates to a method for preparing a cementing material by using graded separation components of valuable minerals of tungsten-molybdenum tailings.
Background
The reserves of tungsten and molybdenum tailings in China are at the top of the world, the yield of the tungsten and molybdenum tailings is as high as 99%, the discharge amount of the tungsten and molybdenum tailings is also rapidly increased along with the rapid increase of the yield of the tungsten and molybdenum tailings, the accumulation of a large amount of tungsten and molybdenum tailings not only wastes resources, but also pollutes the environment, and the development of the reduction and recycling technology of the tungsten and molybdenum tailings is urgent.
The tailings utilization can be divided into two types of tailings integral utilization and tailings comprehensive utilization. The whole utilization of the tailings is to use the tailings as building material raw materials and mine filling materials, and also can be used for land reclamation, tourist attractions and the like. The comprehensive utilization of the tailings is to extract valuable minerals in the tailings firstly and then prepare the residual valuable resources into a new material with high added value and multiple functions and the like, so that the tailings are recycled and harmless, waste is changed into valuable, and the social and economic benefits are improved.
Chinese patent CN105060717A discloses an architectural decoration glass ceramics using molybdenum ore as main raw material and its preparation method, the utilization rate is about 40%, the utilization rate is low, the sintering temperature is high, and it is not good for saving resources. Patent CN110590198A discloses a tungsten tailing cementing material and a preparation method thereof, wherein the tungsten tailing dosage is 50% -70%, and valuable minerals fluorite and garnet are not recycled, thereby causing resource waste. Patent CN108672094A discloses a beneficiation method for recovering fluorite from black and white tungsten ore flotation tailings, and the final fluorite concentrate CaF2The content is higher than 95%, the recovery rate is higher than 75%, but the secondary tailings after fluorite flotation are not comprehensively utilized and still need to be stockpiled.
In conclusion, the comprehensive utilization of the tungsten-molybdenum tailings still has the problems that useful components in the tailings cannot be eaten, dried and squeezed out and the use of the useful components is made the best. Therefore, the method for preparing the cementing material by using the tungsten-molybdenum tailings valuable mineral step separation component is developed, not only can the fluorite be efficiently recovered, but also the useful components in the tailings can be used to the maximum extent, and has very important significance.
Disclosure of Invention
The invention aims to provide a method for preparing a cementing material by using tungsten-molybdenum tailings valuable mineral step separation components, which can realize the best use of useful components in the tailings and large-scale comprehensive utilization.
Based on the purpose, the invention adopts the following technical scheme:
a method for preparing a cementing material by using tungsten molybdenum tailings valuable mineral step separation components comprises the following steps:
(1) sieving tungsten-molybdenum tailings, reserving an oversize product (marked as component A) as fine aggregate, and carrying out magnetic separation on an undersize product to obtain a magnetic product marked as component B and a nonmagnetic product marked as component C;
(2) performing flotation on the component C, adopting a flotation process flow of primary roughing, secondary scavenging and four times of fine concentration and primary fine scavenging, wherein the flotation concentrate is fluorite, the scavenged II tailings are marked as a component D, and the fine scavenged tailing is marked as a component E;
(3) and respectively mixing the component B and the component D according to a certain mass ratio to form a component F, carrying out ball milling, mixing the ball-milled component F, fly ash, slag, gypsum, an excitant and a water reducing agent according to a certain mass ratio, carrying out ball milling, and carrying out ball milling on the ball-milled product to obtain the cementing material.
Further, the specific process of step (1) is as follows: sieving tungsten-molybdenum tailings by using a 150-micron (100-mesh) sieve, wherein the component A is a product with the particle size larger than 150 microns, and performing magnetic separation on the product under the sieve by using a magnetic separator to obtain a non-magnetic product (component C) and a magnetic product (component B), wherein the component B mainly comprises iron-containing magnetic minerals (magnetite and garnet);
furthermore, the magnetic field intensity of the magnetic separator is 0.5-1.5T during magnetic separation, and the ore pulp concentration is 10% -30%;
further, in the step (1), the component B can be further separated by adopting a magnetic separation or gravity-magnetic combined process to obtain independent products of magnetite and garnet;
further, in the step (2), acidic water glass is used as an inhibitor, or a mixture of aluminum sulfate and acidic water glass (the mass ratio is 0.3-1.0: 1) is used as a mixed inhibitor, sodium carbonate is used as a pulp pH regulator, and sodium oleate is used as a collecting agent.
Further, in the step (2), based on the mass of the tungsten-molybdenum tailings, the acid sodium silicate added for rough concentration is 600g/t, the sodium oleate serving as a collecting agent is 800 g/t, and the pH value is 9-10.
Further, in the step (2), based on the mass of the tungsten molybdenum tailings, the acid water glass added as the inhibitor in the scavenging process I is 80-300g/t, the sodium oleate serving as the collecting agent is 100-300 g/t, and the pH value is 9-10.
Further, in the step (2), based on the mass of the tungsten molybdenum tailings, the acid water glass added as an inhibitor in the scavenging II is 50-200g/t, the sodium oleate serving as a collecting agent is 50-150 g/t, and the pH value is 9-10.
Further, in the step (2), based on the mass of the tungsten-molybdenum tailings, the mixed inhibitor added in the concentration I is 400g/t, the collecting agent sodium oleate is 50-200g/t, and the pH value is 9-10.
Further, in the step (2), based on the mass of the tungsten-molybdenum tailings, the mixed inhibitor added in the fine sweeping is 40-180g/t, the collecting agent sodium oleate is 80-300g/t, and the pH value is 9-10.
Further, in the step (2), the mixed inhibitor added in the concentration II is 60-250g/t according to the mass of the tungsten-molybdenum tailings, and no collecting agent is added.
Further, in the step (2), the mixed inhibitor added in the concentration III is 50-190g/t according to the mass of the tungsten-molybdenum tailings, and no collecting agent is added.
Further, in the step (2), the mixed inhibitor added in the concentration IV is 50-160g/t according to the mass of the tungsten-molybdenum tailings, and no collecting agent is added.
The main component of the scavenging II tailings 1 (component D) is silicate mineral, and the main component of the fine scavenging tailings 2 (component E) is calcite.
Furthermore, in the step (3), the mass ratio of the component B to the component D in the component F is (1-2) to (6-10), the ball milling time of the component F is 5-8h, and a zirconia ball is used as a milling ball.
Further, the ball milling time of the mixture of the component F, the fly ash, the slag, the gypsum and the excitant in the step (3) is 0.5-2.5h, and a ceramic ball is used as a milling ball;
further, the activator in the step (3) is cement or a mixture of cement and the component E, and when the activator is the mixture, the mass ratio of the cement to the component E is (1-4): (0.5-2.5);
further, the mass ratio of the component F, the fly ash, the slag, the gypsum and the excitant after ball milling in the step (3) to prepare the cementing material is (35-60): (10-20): (10-25): (5-15): (1-5), wherein the addition amount of the water reducing agent accounts for 0.2-1.5% of the total mass of the cementing material;
further, the slag in the step (3) is S95 grade slag;
further, the water reducing agent in the step (3) is a polycarboxylic acid water reducing agent or a naphthalene water reducing agent.
Compared with the prior art, the invention has at least the following advantages:
a) in the invention, the tungsten-molybdenum tailings are classified in advance, and the tailings particles larger than 150 μm are screened out to be used as fine aggregates, so that the workload of subsequent separation can be reduced, and the fine aggregates can also be added into a cementing material according to a certain proportion as required;
b) according to the invention, a certain amount of magnetic products are separated by magnetic separation, and the nonmagnetic products are subjected to flotation to recover fluorite, so that the flotation operation load is reduced, the production cost is reduced, and the part of magnetic products with higher hardness can be mixed with the component D according to a certain proportion to prepare a cementing material according to the requirement, thereby improving the mechanical property of the concrete test block;
c) the invention adopts flotation to recover fluorite, inhibits siliceous minerals in rough concentration operation, and realizes the step separation of silicate minerals, calcite and fluorite by mixing flotation fluorite and calcite.
d) According to the invention, the magnetic mineral (component B), the silicate mineral (component D) and the calcite (component B) which are subjected to step separation from the tungsten-molybdenum tailings can be added according to certain proportion according to the performance requirement of the gel material, so that the performance of the gel material can be conveniently regulated and controlled.
e) The invention realizes grading, quality-separating, sorting and comprehensive utilization of tungsten-molybdenum tailings, not only efficiently extracts fluorite in the tailings, but also makes the most of valuable components in the tailings, and achieves reduction and recycling to the maximum extent.
In the invention, the technical schemes may be changed according to different compositions and contents of tungsten-molybdenum tailings, and the technical schemes can be combined and adjusted with each other to achieve the optimal synergistic effect.
Drawings
FIG. 1 is a process flow diagram of the step separation of tungsten-molybdenum tailings.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be noted that these examples are only for better understanding of the present invention, and do not limit the scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
The adopted tungsten-molybdenum tailings are tungsten-molybdenum tailings of certain places in Henan, the tailings mainly contain quartz, garnet, fluorite, calcite, magnetite, feldspar, mica and other minerals, and the main chemical component is SiO2（56.78wt%）、Al2O3（7.46wt%）、CaO（5.35wt%）、CaF2（11.14wt%）、MgO（7.14wt%）、Fe2O3（10.47wt%）、Na2O（1.17wt%）、K2O（0.49wt%）、Mo （0.0037%），WO3(0.013%), etc., and the tungsten-molybdenum tailings have fine granularity, light color and large hardness, and the slag in the following examples is S95 grade slag.
Example 1
A method for preparing a cementing material by using tungsten molybdenum tailings valuable mineral step separation components is shown in figure 1, and comprises the following steps:
(1) sieving tungsten-molybdenum tailings by a 100-mesh sieve, reserving products on the sieve (marked as component A) to be used as fine aggregate, mixing the products under the sieve, and carrying out magnetic separation (the magnetic field intensity of a magnetic separator is 0.5T, and the pulp concentration is 10%) to obtain magnetic products and nonmagnetic products (component C), wherein the magnetic products are marked as component B after being dried;
(2) directly concentrating and pulping a nonmagnetic product (the concentration of ore pulp is 20 percent), then carrying out flotation, and carrying out flotation process flow of once roughing, twice scavenging, four times of fine concentration and once fine scavenging, wherein the specific process is as follows: the roughing tailings enter scavenging I, the concentrate obtained by scavenging I returns to roughing, the scavenging I tailings enter scavenging II, the concentrate obtained by scavenging II returns to scavenging I, and scavenging
Figure 444836DEST_PATH_IMAGE001
The tailings 1 are marked as a component D, the rough concentration concentrate enters a fine concentration I, and the concentrate obtained by the fine concentration I enters the fine concentration
Figure 361976DEST_PATH_IMAGE001
The tailings obtained from the fine concentration I enter the fine cleaning, the concentrate obtained from the fine cleaning returns to the fine concentration I, the tailings 2 obtained from the fine cleaning is marked as a component E, and the fine concentration
Figure 204030DEST_PATH_IMAGE001
The obtained concentrate is subjected to concentration III and concentration
Figure 599240DEST_PATH_IMAGE001
Returning the obtained tailings to the concentration I, and feeding the concentrate obtained by the concentration III to the concentration
Figure DEST_PATH_IMAGE002
The tailings obtained from the concentration III are returned to the concentration II for concentration
Figure 226661DEST_PATH_IMAGE002
The obtained concentrate is fluorite concentrate, and the concentrate is refined
Figure 49124DEST_PATH_IMAGE002
The obtained tailings are returned to the concentration III, the adding condition of the flotation reagent in the ore flotation operation is shown in the table 1, and the fluorite concentrate CaF is finally floated2The content is 88 percent, the recovery rate is 63 percent, the tailings 2 (component E) is cleaned and the scavenging is carried out
Figure 378474DEST_PATH_IMAGE001
Respectively drying the tailings 1 (component D);
(3) mixing the component B and the component D according to the mass ratio of 1:10 to form a component F, and ball-milling the component F for 5 hours by adopting zirconium balls (according to the mass ratio of phi 10mm, phi 8mm, phi 6mm, phi 5mm and phi 3mm of 1:2:3:2: 2);
(4) ball-milling a mixture of the component F, fly ash, slag, gypsum, an activator and a water reducing agent (the component F is 35 parts, the fly ash is 20 parts, the slag is 25 parts, the gypsum is 15 parts, the activator is 5 parts, and the addition amount of a polycarboxylic acid water reducing agent accounts for 0.2% of the mass of the gel material) for 0.5h by using porcelain balls (the mass ratio of the component F to the fly ash to the slag to the gypsum to the activator is 1:2: 2), so as to obtain the tungsten-molybdenum tailing gelled material, wherein the activator is formed by mixing cement and the component E according to the mass ratio of 1: 2.5.
Table 1 flotation reagent addition in example 1
Figure DEST_PATH_IMAGE004
Note: in table 1 the collector was sodium oleate and the pH adjuster was sodium carbonate.
Example 2
A method for preparing a cementing material by using tungsten molybdenum tailings valuable mineral step separation components comprises the following steps:
(1) sieving tungsten-molybdenum tailings by a 100-mesh sieve, reserving products on the sieve (marked as component A) to be used as fine aggregate, mixing the products under the sieve, carrying out magnetic separation (the magnetic field intensity is 1.0T, the ore pulp concentration is 20%) to obtain magnetic products and nonmagnetic products (component C), and marking the dried magnetic products as component B;
(2) directly concentrating and pulping the nonmagnetic product (the concentration of the ore pulp is 30 percent), then carrying out flotation, carrying out primary roughing, secondary scavenging, four-time concentration and primary fine scavenging, wherein the adding condition of the flotation agent in ore flotation operation is shown in table 2, and finally carrying out flotation on fluorite concentrate CaF2The content is 91 percent, the recovery rate is 58 percent, and the fine scavenging tailings 2 (component E) and the scavenging II tailings 1 (component D) are respectively dried;
(3) mixing the component B and the component D according to the mass ratio of 1:5 to form a component F, and ball-milling the component F for 7 hours by adopting zirconium balls (according to the mass ratio of phi 10mm, phi 8mm, phi 6mm, phi 5mm and phi 3mm of 1:2:3:2: 2);
(4) and ball-milling the component F, fly ash, slag, gypsum, an activator and a water reducing agent mixture (by mass parts, 45 parts of the component F, 20 parts of the fly ash, 20 parts of the slag, 12 parts of the gypsum, 3.0 parts of the activator and 0.2% of the polycarboxylic acid water reducing agent accounting for the mass of the gel material) for 1.0h by adopting porcelain balls (according to the mass ratio of phi 10mm, phi 8mm, phi 6mm, phi 5mm and phi 3mm of 1:2:3:2: 2) to obtain the tungsten-molybdenum tailing gelled material, wherein the activator is cement and the component E is in a mass ratio of 1: 1.
Table 2 flotation reagent addition in example 2
Figure 888958DEST_PATH_IMAGE006
Note: in table 1 the collector was sodium oleate and the pH adjuster was sodium carbonate.
Example 3
A method for preparing a cementing material by using tungsten molybdenum tailings valuable mineral step separation components comprises the following steps:
(1) sieving tungsten and molybdenum by a 100-mesh sieve, reserving an oversize product (marked as component A) as a fine aggregate, mixing the undersize product, performing magnetic separation (the magnetic field intensity is 1.5T and the pulp concentration is 30%) to obtain a magnetic product and a non-magnetic product (component C), and marking the dried magnetic product as component B;
(2) directly concentrating and pulping the nonmagnetic product (the concentration of the ore pulp is 35 percent), then carrying out flotation, carrying out primary rough concentration and secondary scavenging for four times of fine concentration and primary fine scavenging, wherein the adding condition of the flotation agent in ore flotation operation is shown in table 3, and finally carrying out flotation on fluorite concentrate CaF2The content is 93 percent, the recovery rate is 49 percent, and the fine scavenging tailings 2 (component E) and the scavenging II tailings 1 (component D) are respectively dried;
(3) mixing the component B and the component D according to the mass ratio of 1:3 to form a component F, and ball-milling the component F for 8 hours by adopting zirconium balls (according to the mass ratio of phi 10mm, phi 8mm, phi 6mm, phi 5mm and phi 3mm of 1:2:3:2: 2);
(4) ball-milling the component F, fly ash, slag, gypsum, an excitant and a water reducer mixture (by mass parts, 60 parts of the component F, 14 parts of the fly ash, 20 parts of the slag, 5 parts of the gypsum, 1 part of the excitant and 0.2 percent of the polycarboxylic acid water reducer in the mass ratio of the component F to the fly ash, 14 parts of the fly ash, 1 part of the polycarboxylic acid water reducer) for 0.5h by adopting porcelain balls (according to the mass ratio of phi 10mm, phi 8mm, phi 6mm, phi 5mm and phi 3mm of 1:2: 2) to obtain the tungsten-molybdenum tailing gelled material, wherein the excitant is cement and the component E in the mass ratio of 3: 1.
Table 3 flotation reagent addition in example 3
Figure 620154DEST_PATH_IMAGE008
Note: in table 1 the collector was sodium oleate and the pH adjuster was sodium carbonate.
Comparative example 1
The only difference compared to example 1 is that this comparative example does not add a trigger.
Comparative example 2
The difference compared to example 1 is only that the activators of this comparative example are all cements.
Comparative example 3
The only difference compared to example 1 is that the boosters of this comparative example are all component E.
The gelled materials prepared in the above examples and comparative examples are made into concrete test blocks (the water consumption of each cubic concrete and the mass ratio of the gelled materials are 0.35:1, the concrete test blocks are placed into a mold for molding and then cured at room temperature), the compressive strength and the setting time of curing for 3 days and 28 days are shown in table 4, wherein the initial setting time/final setting time is measured according to JC/T727-2005 'determinator for standard consistency and setting time of cement paste' and GB/T1346-2011 'detection method for water consumption, setting time and stability of standard consistency of cement'; the compressive strength of the concrete test block is determined according to GB/T50081-2002 Standard of mechanical Properties test method of ordinary concrete.
TABLE 4 compressive strength and setting time of concretes made of W-Mo tailing cementing material
Figure DEST_PATH_IMAGE009
As can be seen from the data of examples 1 to 3 in Table 4, the tungsten-molybdenum tailing concrete test block prepared from the tungsten-molybdenum tailing cementing material has high compressive strength and short setting time. Although the compressive strength of the concrete test block is reduced along with the increase of the doping amount of the tungsten-molybdenum tailings, the compressive strength of the tungsten-molybdenum tailings concrete test block prepared by the tungsten-molybdenum tailings cementing material is more than 40 MPa. Therefore, the invention greatly consumes tungsten-molybdenum tailings on the basis of maintaining the excellent performance of the cementing material.
As can be seen from the comparative example 1, the addition of the activator in the invention not only can shorten the setting time, but also can obviously improve the compressive strength of the concrete test block prepared from the tungsten-molybdenum tailing cementing material.
As can be seen from comparative examples 2 and 3, the exciting effect of cement on the raw material is superior to that of component E (calcite as a main component), and the exciting effect of the exciting agent formed by mixing component E and cement on the raw material is superior to that of cement alone as the exciting agent and component E as the exciting agent. The component E added into the excitant can not only further absorb the useful mineral-calcite in the tungsten-molybdenum tailings, but also improve the compressive strength of the concrete test block prepared from the tungsten-molybdenum tailings cementing material.
The invention adopts a step sorting method to firstly separate the iron-containing magnetic minerals (magnetite and garnet), calcite, fluorite and silicate minerals in the tungsten-molybdenum tailings, thereby realizing the high-efficiency recovery of fluorite, and realizing the CaF of fluorite2The content is more than 85 percent, and the standard of fluorite for metallurgy is met. Then the iron-containing magnetic mineral, the silicate mineral and the calcite are proportioned according to a certain mass ratio according to the performance requirement of the cementing material, so that the mass large-scale comprehensive utilization of the valuable components of the tungsten-molybdenum tailings is realized.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention.

Claims (9)

1. The method for preparing the cementing material by using the tungsten molybdenum tailings valuable mineral step separation component is characterized by comprising the following steps of:
(1) sieving tungsten-molybdenum tailings, wherein an oversize product is marked as a component A, and an undersize product is magnetically separated to obtain a magnetic product which is marked as a component B, and a nonmagnetic product which is marked as a component C;
(2) performing flotation on the component C, adopting a flotation process flow of primary roughing, secondary scavenging and four times of fine concentration and primary fine scavenging, wherein the flotation concentrate is fluorite, the scavenged II tailings are marked as a component D, and the fine scavenged tailing is marked as a component E;
(3) and mixing the component B and the component D according to a certain mass ratio to form a component F, carrying out ball milling, mixing the ball-milled component F, fly ash, slag, gypsum, an exciting agent and a water reducing agent according to a certain mass ratio, and carrying out ball milling to obtain a product, namely the cementing material.
2. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 1, is characterized in that in the step (1): the sieve of 150 μm is used for sieving, the magnetic field intensity of the magnetic separator is 0.5T-1.5T during magnetic separation, and the ore pulp concentration is 10wt% -30 wt%.
3. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 1, wherein in the step (2): during flotation, acidic water glass is used as an inhibitor or a mixture of aluminum sulfate and the acidic water glass in a mass ratio of 0.3-1.0:1 is used as a mixed inhibitor, sodium carbonate is used as a pulp pH regulator, and sodium oleate is used as a collecting agent.
4. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 3, is characterized in that in the step (2): according to the mass of the tungsten-molybdenum tailings, the acid water glass added for rough concentration is 600g/t, the sodium oleate serving as a collecting agent is 800 g/t and the pH value is 9-10; the acid water glass of the inhibitor added in the scavenging I is 80-300g/t, the collecting agent sodium oleate is 100-300 g/t, and the pH value is 9-10; adding 50-200g/t of inhibitor acid water glass, 50-150 g/t of collecting agent sodium oleate and 9-10 of pH value in the scavenging II; the mixed inhibitor added in the fine selection I is 400g/t, the collecting agent sodium oleate is 50-200g/t, and the pH value is 9-10; adding 40-180g/t of mixed inhibitor in fine sweep, 80-300g/t of sodium oleate serving as a collecting agent, and controlling the pH to be 9-10; selecting the mixed inhibitor added in II to be 60-250 g/t; selecting the mixed inhibitor added in the III to be 50-190 g/t; the mixed inhibitor added in the selection IV is 50-160 g/t.
5. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 1, is characterized in that in the step (3): the mass ratio of the component B to the component D in the component F is (1-2): (6-10), wherein the ball milling time of the component F is 5-8h, and zirconia balls are used as milling balls.
6. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 1, is characterized in that in the step (3): the mass ratio of the component F, the fly ash, the slag, the gypsum and the excitant mixture is (35-60): (10-20): (10-25): (5-15): (1-5), the water reducing agent accounts for 0.2-1.5 wt% of the total mass of the cementing material; the ball milling time of the mixture is 0.5-2.5h, and ceramic balls are adopted as milling balls.
7. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 1, is characterized in that in the step (3): the activator is cement or a mixture of cement and a component E, and when the activator is the mixture, the mass ratio of the cement to the component E is (1-4): (0.5-2.5).
8. The method for preparing the cementing material by using tungsten molybdenum tailings valuable mineral step separation components according to the claim 1, is characterized in that in the step (3): the slag is S95 grade slag, and the water reducing agent is a polycarboxylic acid water reducing agent or a naphthalene water reducing agent.
9. A cementitious material produced by the method of any one of claims 1 to 8.
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