CN109554542B - Preparation method of tungsten-molybdenum ore pellets and method for pyrometallurgy of low-grade tungsten-molybdenum ore - Google Patents
Preparation method of tungsten-molybdenum ore pellets and method for pyrometallurgy of low-grade tungsten-molybdenum ore Download PDFInfo
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Abstract
The invention discloses a preparation method of tungsten-molybdenum ore pellets and a method for pyrometallurgy of low-grade tungsten-molybdenum ore, belonging to the field of resource utilization of low-grade tungsten-molybdenum ore. The method comprises the following steps: pretreating mineral powder, namely adding the mineral powder into a ball mill for ball milling; step two: mixing and pelletizing, namely adding a composite reducing agent into the mineral powder for dry mixing, wherein the composite reducing agent comprises modified silicon carbide, modified quartz and an additive; and after the uniform mixing is finished, adding a binder into the mixture, preparing the tungsten-molybdenum ore pellets through a disc pelletizer, adding the mineral powder mixture into the disc pelletizer, and adding water on the disc pelletizer to prepare the tungsten-molybdenum ore pellets. The invention has good reduction effect on low-grade tungsten-molybdenum ore through mutual promotion of the modified silicon carbide, the modified quartz and the additive; the silicon powder coated on the surface of the modified silicon carbide has better reaction performance and is in contact with CaMoO4、CaWO4The reduction efficiency of the low-grade tungsten-molybdenum ore can be improved by the reaction.
Description
The patent application of the invention is a divisional application with an application number of 2017105225005, and the application date of the original application is as follows: 2017-06-30, the name of invention and creation is: a preparation method of a composite reducing agent and a method for smelting the composite reducing agent.
Technical Field
The invention relates to the field of resource utilization of low-grade tungsten-molybdenum ores, in particular to a preparation method of a composite reducing agent and a smelting method of the composite reducing agent.
Background
The reducing agent is a substance that loses electrons or has an electron deviation in a redox reaction. The reducing agent itself has reducing properties and is oxidized, and the product is called an oxidation product. The reduction and the oxidation reaction are carried out simultaneously, that is, the reducing agent itself is oxidized to become an oxide while the reducing agent is oxidized with the reduced material. The metal is produced by reducing the metal oxide in the mineral by adopting the reducing agent, and the metal can be effectively extracted from the metal oxide.
With the increasing consumption of tungsten and molybdenum element resources, the mining amount of tungsten and molybdenum mineral resources is gradually increased; and limited high-quality tungsten-molybdenum mineral resources are gradually reduced, and during the mineral separation process of the tungsten-molybdenum mineral, the mineral pulp discharged after the effective components are selected is naturally dehydrated to form solid waste. The low-grade tungsten-molybdenum ore solid waste is not utilized any more and is left unused in mines, thereby causing huge resource waste and environmental pollution. In the process of the treatment method of the tungsten-molybdenum ore, a wet treatment process is usually adopted, but the wet treatment process has long process flow, acid or alkaline gas is easily generated in the treatment process to pollute the atmosphere, and a large amount of wastewater is generated when the wet treatment is adopted to treat the tungsten-molybdenum ore, so that the environment is not negligibly damaged.
In the smelting process, the prior technical personnel also adopt a pyrogenic process for smelting, such as: the invention relates to a nickel-molybdenum ore nickel and molybdenum separation method (application number: 95110744.5 application date: 1995-05-03) combining dressing and smelting, which can obtain two furnace charges through the enrichment and separation processes of nickel-molybdenum ore combining gravity separation, rough separation, nickel floating inhibition and selective low-temperature pyrogenic reduction of nickel-rich ore, wherein one furnace charge contains 11% of molybdenum, 2% of nickel, 3% of molybdenum and 8% of nickel and is used for smelting molybdenum-nickel-iron alloy or nickel-molybdenum-iron alloy. Adopting a pyrogenic process to smelt tailings and low-grade ores; however, the pyrometallurgical effect of the low-grade tungsten-molybdenum ore is poor due to the difficulty in pyrometallurgical reduction of the low-grade tungsten-molybdenum ore, and a reducing agent specially applied to smelting of the low-grade tungsten-molybdenum ore is urgently needed to be developed.
In addition, through search, the method for directly smelting the nickel-molybdenum-iron alloy from the low-grade nickel-molybdenum ore (application number: 201410308642.8, application date 2014.07.02) comprises two steps of adding alkali into the nickel-molybdenum ore for roasting and directly thermally reducing metal in an intermediate frequency furnace, and specifically comprises the following steps of: the nickel-molybdenum ore is added with 15-20% of strong alkaline substance to form a mixture, the mixture is roasted for 20-30min at the temperature of 630-680 ℃, the roasted product is obtained, the direct thermal reduction of the desulfurized roasted product and the carbon-added ferrosilicon in an intermediate frequency furnace is realized, and the roasted product is completely reduced by stages in the reduction process by controlling the reaction temperature and the temperature rise time to obtain the nickel-molybdenum-iron alloy. But the process is difficult to be used for smelting low-grade tungsten-molybdenum ore.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defect of poor utilization effect of low-grade tungsten-molybdenum ore in the prior art, and provides a preparation method of tungsten-molybdenum ore pellets and a method for pyrometallurgy of low-grade tungsten-molybdenum ore.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a preparation method of a tungsten-molybdenum ore pellet, which is characterized by comprising the following steps:
the method comprises the following steps: pretreatment of ore powder
Adding the mineral powder into a ball mill for ball milling; the specific surface area of the mineral powder after ball milling is more than 0.15m2/g；
Step two: mixed pelletizing
Adding a composite reducing agent into the mineral powder for dry mixing, wherein the composite reducing agent comprises modified silicon carbide, modified quartz and an additive, the mass ratio of the modified silicon carbide to the modified quartz is alpha, the value of alpha is 0.7-1.5, and the additive comprises coke powder; and after the uniform mixing is finished, adding a binder into the mixture, preparing the tungsten-molybdenum ore pellets through a disc pelletizer, adding the mineral powder mixture into the disc pelletizer, and adding water on the disc pelletizer to prepare the tungsten-molybdenum ore pellets with the particle size of 5-8 mm.
Preferably, the ratio of the reducing agent to the mineral powder is
Wherein the value of gamma is 5-6, and alpha is the mass ratio of the modified silicon carbide to the modified quartz; then
W1To CaWO in mineral powder4Mass percent of (1);
W2is CaMoO in mineral powder4Mass percent of (1);
W3ca in the ore powder5(PO4)3Mass percent of F.
Preferably, kaolin is added into the silicon carbide powder and the silicon powder, and water is added for mixing to obtain the modified silicon carbide.
Preferably, the modified quartz is a quartz coated on the surface with a coating component including asphalt.
Preferably, the mineral powder mixture is added into a disc pelletizer, water is sprayed into the mixture of the low-grade tungsten-molybdenum ore, the composite reducing agent and the binder on the disc pelletizer, the binder absorbs water to form cement, the cement in the pellets is squeezed and discharged from the inside to the outside under the action of the rolling mechanical force of the disc pelletizer, the mixed powder of the low-grade tungsten-molybdenum ore, the composite reducing agent and the binder is adhered to the surfaces of the pellets, and the pellets are discharged from the disc pelletizer until qualified pellets are formed, so that the tungsten-molybdenum ore pellets are obtained.
Preferably, modified silicon carbide is prepared:
(1) adding kaolin into the silicon carbide powder and the silicon powder, drying in a drying oven, adding the kaolin into the silicon carbide powder, and uniformly stirring in a stirrer;
(2) adding silicon powder into the stirrer while adding the atomized water solution into the stirrer, continuously and uniformly mixing to form granules after adding the silicon powder, and heating and drying to obtain modified silicon carbide; the mass ratio of the silicon carbide powder to the silicon powder is 2-4: 1.
Preferably, a modified quartz is prepared:
(1) firstly, acid washing is carried out on quartz by adopting an acid solution, water glass is added after the acid washing is finished and is uniformly mixed, and then the quartz is washed by water, filtered and dried by taking precipitate;
(2) mixing the dried quartz and the coating component in a reaction kettle, wherein the mass ratio of the quartz of the modified quartz to the coating component is 6-7: 1, heating the reaction kettle to 50-90 ℃, and continuously mixing and stirring to obtain the modified quartz.
The method for pyrometallurgy of low-grade tungsten-molybdenum ore comprises the steps of preparing tungsten-molybdenum ore pellets by the method, drying the tungsten-molybdenum ore pellets in an oven, cooling to room temperature after drying, heating and reducing the pellets in a vacuum furnace, wherein the vacuum degree is controlled to be 100-150 Pa, and the smelting temperature is 1300-1500 ℃.
Preferably, the temperature rising system of the vacuum furnace is as follows: firstly, heating to 800 ℃ at a speed of 10 ℃/min; then heating to 1200 ℃ at the speed of 8 ℃/min; and heating the mixture at a speed of 5 ℃/min until the smelting temperature is 1300-1500 ℃, and the smelting time is 1-3 h.
The preparation method of the composite reducing agent comprises the steps of putting modified silicon carbide, modified quartz and an additive into a stirrer, uniformly mixing at the temperature of 30-40 ℃, wherein the modified silicon carbide is a mixture of silicon carbide powder and silicon powder, the modified quartz is quartz with a coating component coated on the surface, and the coating component comprises asphalt; the additive comprises coke powder.
Preferably, the specific steps are as follows:
s1: preparation of modified silicon carbide
Adding kaolin into the silicon carbide powder, uniformly stirring in a stirrer, adding the silicon powder into the stirrer, and uniformly mixing to obtain modified silicon carbide;
s2: preparation of modified Quartz
Mixing the coating component and quartz, adding into a vacuum stirrer, and mixing and stirring at 50-90 deg.C to obtain modified quartz, wherein the coating component comprises asphalt;
s3: preparation of composite reducing agent
Adding the modified silicon carbide, the modified quartz and the additive into a stirrer, and uniformly mixing to obtain the composite reducing agent.
Preferably, the mass ratio of the modified silicon carbide to the modified quartz is alpha, and the value of alpha is 0.7-1.5; the additive accounts for 1-4% of the total mass of the modified silicon carbide and the modified quartz.
Preferably, S1: the preparation method of the modified silicon carbide comprises the following specific steps:
(1) adding kaolin into the silicon carbide powder and the silicon powder, drying in a drying oven, adding the kaolin into the silicon carbide powder, and uniformly stirring in a stirrer;
(2) adding silicon powder into the stirrer while adding the atomized water solution into the stirrer, continuously and uniformly mixing to form granules after adding the silicon powder, and heating and drying to obtain modified silicon carbide; the mass ratio of the silicon carbide powder to the silicon powder is 2-4: 1.
Preferably, S2: the specific preparation method for preparing the modified quartz comprises the following steps:
(1) firstly, acid washing is carried out on quartz by adopting an acid solution, water glass is added after the acid washing is finished and is uniformly mixed, and then the quartz is washed by water, filtered and dried by taking precipitate;
(2) mixing the dried quartz and the coating component in a reaction kettle, wherein the mass ratio of the quartz of the modified quartz to the coating component is 6-7: 1, heating the reaction kettle to 50-90 ℃, and continuously mixing and stirring to obtain the modified quartz.
Preferably, the pH of the acid solution is 5-6, the acid washing temperature is 50-60 ℃, and the acid washing solution is an HCl solution.
Preferably, the asphalt needs to be pretreated before being added, the asphalt with the particle size less than 100um is obtained by liquid-solid separation after crushing and wet grinding, and then diatomite, NaCl and rubber powder are added into the asphalt; then heating to 150-200 ℃ for fusion to obtain the asphalt used by the additive, and crushing and wet grinding to obtain asphalt powder.
Preferably, the aluminum powder also comprises aluminum powder, and the aluminum powder has a particle size of-300 meshes and is 80%.
The invention relates to a method for pyrometallurgy of low-grade tungsten molybdenum ore, which is characterized in that the composite reducing agent is prepared by adopting the preparation method of the composite reducing agent, and then the composite reducing agent is added into mineral powder to be uniformly mixed, wherein the mineral powder is the low-grade tungsten molybdenum ore; and preparing tungsten-molybdenum ore pellets through a disc pelletizer, and smelting tungsten-molybdenum ore in the pellets in a vacuum furnace, wherein the vacuum degree is controlled to be 100-150 Pa, and the smelting temperature is 1300-1500 ℃.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) when the composite reducing agent prepared by the invention is used for low-grade tungsten-molybdenum ore under a vacuum condition, the composite reducing agent has a good reducing effect on the low-grade tungsten-molybdenum ore through mutual promotion of modified silicon carbide, modified quartz and an additive; at the beginning of the reaction, the silicon powder coated on the surface of the modified silicon carbide has better reaction performance, can quickly intervene in the reaction under the promotion of the modified quartz, and reacts with the CaMoO4、CaWO4The reaction is carried out, and the modified quartz can effectively reduce the reaction resistance; the modified silicon carbide has stronger reducing capability and can reduce the CaMoO in low-grade ores4、CaWO4Reducing to obtain metal tungsten and metal molybdenum; the modified silicon carbide also generates CO gas with reducibility in the reaction process, and the reduction process of the modified silicon carbide comprises thermal reduction reaction, carbothermal reduction reaction and CaSiO3Solid phase generation reaction is carried out, so that the reduction efficiency of the low-grade tungsten-molybdenum ore is improved;
(2) the modified quartz of the composite reducing agent prepared by the invention can reduce Ca5(PO4)3F reaction free energy is increased, and Ca of composite reducing agent is increased5(PO4)3F has reducing power and can react with Ca under the promotion of modified quartz5(PO4)3F, reacting the modified silicon carbide and the coke powder in the additive with Ca under the promotion of the modified quartz5(PO4)3F reacting and reducing the formed P2The steam being separated from the solid material to promote the entire reduction reactionCarrying out the following steps;
(3) the invention relates to a method for pyrometallurgy of low-grade tungsten-molybdenum ore, which adopts a composite reducing agent comprising modified silicon carbide, modified quartz and an additive, reduces under a vacuum condition, has good reduction effect on the low-grade tungsten-molybdenum ore through mutual promotion of the modified silicon carbide, the modified quartz and the additive, and improves the reduction efficiency.
Drawings
FIG. 1 is a graph showing the effect of comparative example on the reduction ratio between example 1 of the present invention and comparative example;
fig. 2 is a flow chart of a method for preparing the composite reducing agent according to the present invention.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
Example 1
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and although these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
Example 1
The invention relates to a composite reducing agent for smelting low-grade tungsten-molybdenum ore, which comprises modified silicon carbide, modified quartz and an additive; the modified silicon carbide is a mixture of silicon carbide powder and silicon powder, the modified quartz is quartz coated with a coating component on the surface, and the coating component is asphalt; the coating component and the quartz are mixed and stirred at the temperature of 50-90 ℃ to obtain the modified quartz, wherein the mass ratio of the quartz of the modified quartz to the coating component is 6-7: 1, and the mass ratio is 7: 1 in the embodiment.
Firstly adding quartz into a reaction kettle, heating to 40-50 ℃, preserving heat for 20min, then heating to 50-90 ℃, wherein the temperature is 60 ℃ in the embodiment; and adding asphalt powder into the reaction kettle, coating the asphalt powder on the surface of quartz to obtain modified quartz, and keeping the temperature for 10 min.
Adding kaolin into the silicon carbide powder and the silicon powder, and adding water for mixing to obtain modified silicon carbide; the mass ratio of the silicon carbide powder to the silicon powder is 2-4: 1, and the mass ratio of the silicon carbide powder to the silicon powder is 3: 1 in the embodiment; the-325 mesh of the kaolin is 90%, i.e. the particles smaller than 325 mesh are greater than 90%, in this example 91%. The specific preparation steps of the modified silicon carbide are as follows: adding kaolin into silicon carbide powder and silicon powder, drying in an oven, adding kaolin into the silicon carbide powder, uniformly stirring in a stirrer, adding the silicon powder into the stirrer while adding the atomized aqueous solution into the stirrer, continuously uniformly mixing to form particles after adding, and heating and drying to obtain the modified silicon carbide. Wherein the kaolin is medium-low temperature hydrothermally altered residual kaolin, also called Suzhou soil; the alumina content of this example was 36% and the silica 48%.
The mass ratio of the modified silicon carbide to the modified quartz is alpha, the value of alpha is 0.7-1.5, and alpha is removed to be 1 in the embodiment; the additive accounts for 1-4% of the total mass of the modified silicon carbide and the modified quartz.
The additive comprises coke powder, wherein the coke powder is subjected to ball milling in a ball mill, and the particles of the coke powder after ball milling in the ball mill are smaller than 200 meshes.
As shown in fig. 2, the preparation method of the composite reducing agent of the present invention specifically comprises the following steps:
s1: preparation of modified silicon carbide
Adding kaolin into the silicon carbide powder, uniformly stirring in a stirrer, adding the silicon powder into the stirrer, and uniformly mixing to obtain modified silicon carbide; the method comprises the following specific steps:
(1) adding kaolin into silicon carbide powder and silicon powder, drying in an oven, adding kaolin into the silicon carbide powder, and uniformly stirring in a stirrer, wherein the adding amount of the kaolin is 1.5% of the total mass of the silicon carbide powder and the silicon powder;
(2) adding silicon powder into the stirrer while adding the atomized water solution into the stirrer, continuously and uniformly mixing to form granules after adding the silicon powder, and heating and drying to obtain modified silicon carbide; the mass ratio of the silicon carbide powder to the silicon powder is 2-4: 1, and in the embodiment, the mass ratio of the silicon carbide powder to the silicon powder is 3;
s2: preparation of modified Quartz
Mixing the coating component and quartz, adding into a vacuum stirrer, and mixing and stirring at 50-90 deg.C to obtain modified quartz, wherein the coating component comprises asphalt; the detailed description is as follows:
(1) firstly, acid washing is carried out on quartz by adopting an acid solution, water glass is added after the acid washing is finished and is uniformly mixed, and then the quartz is washed by water, filtered and dried by taking precipitate;
(2) mixing the dried quartz and the coating component in a reaction kettle, wherein the mass ratio of the quartz of the modified quartz to the coating component is 6-7: 1, heating the reaction kettle to 50-90 ℃, and continuously mixing and stirring to obtain the modified quartz. The pH value of the acid solution is 5-6, the pickling temperature is 50-60 ℃, and the pickling solution is HCl solution.
The asphalt needs to be pretreated before being added, wherein the asphalt is spherical asphalt, the asphalt is crushed at the temperature of 10-20 ℃, wet-milled and subjected to liquid-solid separation to obtain the asphalt with the granularity of less than 100um, and then the diatomite, the NaCl and the rubber powder are added into the asphalt, and the mass ratio of the diatomite to the NaCl to the rubber powder is as follows: 1: 3; the mass sum of the diatomite, the NaCl and the rubber powder accounts for 10 percent of the mass of the asphalt; then heating to 150-200 ℃ for fusion to obtain the asphalt used by the additive, crushing and wet grinding the asphalt at the temperature of 5-15 ℃ to obtain asphalt powder, and obtaining asphalt particles with the particle size of less than 50 um.
S3: preparation of composite reducing agent
Adding the modified silicon carbide, the modified quartz and the additive into a stirrer, stirring for 15-30min, and uniformly mixing to obtain the composite reducing agent.
A method for smelting low-grade tungsten-molybdenum ore by a pyrogenic process comprises the following specific steps:
the method comprises the following steps: pretreatment of ore powder
Adding the mineral powder into a ball mill for ball milling, wherein the proportion of the mineral powder with the particle size of-75 mu m is more than 95 percent, namely the mass ratio of the particle size of less than-75 mu m is more than 95 percent; the specific surface area of the mineral powder after ball milling is more than 0.15m2/g；
Step two: mixed pelletizing
(1) Detecting the components in the mineral powder to obtain the low-grade tungsten-molybdenum ore CaWO424.1% of CaMoO45.5 percent; ca, Ca5(PO4)3F was 22.1%.
(2) Adding a composite reducing agent into mineral powder for dry mixing, wherein the ratio of the reducing agent to the mineral powder is (10-20) to 100; the specific proportion of the reducing agent and the mineral powder is
Wherein the value of gamma is 5-6, and alpha is the mass ratio of the modified silicon carbide to the modified quartz; then
Wherein alpha is 1 and gamma is 5.
W1To CaWO in mineral powder4Mass percent of (1);
W2is CaMoO in mineral powder4Mass percent of (1);
W3ca in the ore powder5(PO4)3The mass percentage of the F is that,％；
and the mixture ratio is calculated as follows:
Step three: smelting tungsten-molybdenum ore
Putting the tungsten-molybdenum ore pellets into an oven for drying, cooling to room temperature after drying, adding the tungsten-molybdenum ore pellets into a vacuum furnace for reduction smelting, heating and reducing in the vacuum furnace, wherein the vacuum degree is controlled to be 100-150 Pa, and the vacuum degree is 100Pa in the embodiment; the smelting temperature is 1300-1500 ℃, wherein the temperature rising system of the vacuum furnace is as follows: firstly, heating to 800 ℃ at a speed of 10 ℃/min; then heating to 1200 ℃ at the speed of 8 ℃/min; and heating at the speed of 5 ℃/min until the smelting temperature is 1300-1500 ℃, the temperature is 1400 ℃ in the embodiment, the smelting time is 1-3 h, the time is 1.5h in the embodiment, and the reduction process is completed. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). The reduction ratio of tungsten was 71.3%, and the reduction ratio of molybdenum was 65.5%, as shown in fig. 1.
The reduction rate is calculated by the formula:
note: m isFront sideIs the total mass of the mineral powder before reaction, omegaBefore MoCaMoO in ore before reaction of ore powder4The percentage content of Mo, omega, is obtained after conversionAfter Mo-percentage of Mo in the product after the reaction of low grade tungsten and molybdenum ores; omegaW frontCaWO in ore before reaction of low-grade tungsten and molybdenum ore4Converting to obtain the percentage content of W; omegaW back ofThe percentage of W in the product after the reaction of the low-grade tungsten-molybdenum ore.
Comparative example 1
The basic contents of this comparative example are the same as example 1, except that: the reducing agent adopted in the comparative example is silicon carbide, and the reduction process is completed. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). Wherein the reduction rate of tungsten is 45.1%, and the reduction rate of molybdenum is 33.5%.
Comparative example 2
The basic contents of this comparative example are the same as example 1, except that: the reducing agent used in this comparative example was carbon, completing the reduction process. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). Wherein the reduction rate of tungsten is 43.5 percent, and the reduction rate of molybdenum is 36.9 percent.
Comparative example 3
The basic contents of this comparative example are the same as example 1, except that: the reducing agents used in this comparative example were silicon carbide, quartz and additives, wherein the silicon carbide and quartz were not modified to complete the reduction process. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). Wherein the reduction rate of tungsten is 55.9%, and the reduction rate of molybdenum is 44.7%.
According to the comparison of comparative examples 1, 2 and 3 with example 1, the adoption of the composite reducing agent of example 1 can be found to greatly improve the reduction efficiency of the low-grade tungsten-molybdenum ore. The specific reasons are not completely clear, and through many seminars, the applicant believes that the possible reaction mechanisms are concentrated: when the prepared composite reducing agent is used for low-grade tungsten-molybdenum ore under the vacuum condition, the low-grade tungsten-molybdenum ore is subjected to mutual promotion of modified silicon carbide, modified quartz and additivesThe metawolframite has good reduction effect and reduces reaction conditions; at the beginning of the reaction, because the silicon carbide has better temperature property at high temperature, the reduction performance of the silicon carbide is relatively poorer at lower temperature; the silicon powder coated on the surface of the modified silicon carbide has better reaction performance, can quickly intervene in reaction under the promotion of the modified quartz, and reacts with CaMoO4、CaWO4The reaction is carried out, and the modified quartz can effectively reduce the reaction resistance and promote the reaction to be carried out, thereby promoting the silicon powder to reduce CaMoO4、CaWO4(ii) a Along with the rise of the reaction temperature and under the promotion of the reaction product on the surface of the silicon powder, the modified silicon carbide has stronger reducing capability and can reduce the CaMoO in low-grade ore4、CaWO4Reducing to obtain metal tungsten and metal molybdenum; meanwhile, CO gas with reducibility is also generated in the reaction process of the modified silicon carbide, so the reduction process of the modified silicon carbide comprises thermal reduction reaction (solid phase reduction), carbothermal reduction reaction (indirect reduction is mainly) and CaSiO3Solid phase forming reaction, thereby improving the reduction efficiency.
In addition, the modified quartz can reduce Ca5(PO4)3F reaction free energy is increased, and Ca of composite reducing agent is increased5(PO4)3The reducing power of F, especially the asphalt coating layer on the surface of the modified quartz can be heated to generate fine carbon particles in the reaction process, has strong reactivity, and can be promoted by the modified quartz to react with Ca5(PO4)3F reacts, and meanwhile, the modified silicon carbide and the coke powder in the additive are promoted to react with Ca under the action of the modified quartz5(PO4)3F is reacted and Ca is reacted5(PO4)3Reduction of F to P2And SiF4The generated steam is separated from the solid material, so that the whole reduction reaction is promoted to be carried out, a plurality of reduction reactions compounded by a plurality of reactions are often carried out in the whole process, and redundant reducing agents cannot form carbides with tungsten and molybdenum, so that the reduction efficiency of the low-grade tungsten-molybdenum ore is improved. Moreover, the whole reaction is not a single reaction process, which is the existing common catalystThe effect which cannot be achieved by the agent. The composite reducing agent mainly undergoes the following reactions in the reduction process:
CaMoO4(s)+1.5Si(s)＝CaSiO3(s)+0.5SiO2(s)+Mo(s)
CaWO4(s)+1.5Si(s)＝CaSiO3(s)+0.5SiO2(s)+W(s)
Ca5(PO4)3F(s)+3.5Si(s)＝3.5CaSiO3(s)+1.5CaO(s)+1.5P2(g)+F(g)
CaMoO4(s)+SiC(s)＝CaSiO3(s)+CO(g)+Mo(s)
CaWO4(s)+SiC(s)＝CaSiO3(s)+CO(g)+W(s)
Ca5(PO4)3F(s)+2.5SiC(s)＝2.25CaSiO3(s)+2.75CaO(s)+2.5CO(g)+1.5P2(g)+0.25SiF4(g)
when the composite reducing agent is used for low-grade tungsten-molybdenum ore under a vacuum condition, the composite reducing agent has a good reducing effect on the low-grade tungsten-molybdenum ore through mutual promotion of the modified silicon carbide, the modified quartz and the additive; at the beginning of the reaction, the silicon powder coated on the surface of the modified silicon carbide has better reaction performance, can quickly intervene in the reaction under the promotion of the modified quartz, and reacts with the CaMoO4、CaWO4The reaction is carried out, and the modified quartz can effectively reduce the reaction resistance; the modified silicon carbide has stronger reducing capability and can reduce the CaMoO in low-grade ores4、CaWO4Reducing to obtain metal tungsten and metal molybdenum; the modified silicon carbide also generates reductive CO gas in the reaction process, thereby improving the reduction efficiency of the low-grade tungsten-molybdenum ore.
Example 2
The basic contents of this embodiment are different from those of embodiment 1 in that: the additive also comprises plastic powder and biomass, the mass ratio of the coke powder to the plastic powder to the biomass is 5: 2, the plastic powder and the biomass are soaked in an alkaline solution of NaOH and NaCl at the temperature of 60-80 ℃, and the plastic powder and the biomass are dried after soaking; after drying, stirring the coke powder, the plastic powder and the biomass at the temperature of 150-And mixing to enable the plastic powder and the biomass to adhere to the coke powder, wherein the particles of the plastic powder and the biomass are smaller than 250 meshes. The plastic powder is any one or a mixture of polyethylene, polyformaldehyde, polyamide, polypropylene, polystyrene, polycarbonate, polymethyl methacrylate and polyester. The plastic powder in this embodiment is polypropylene, polystyrene, polycarbonate; the mass ratio of the polypropylene to the polystyrene to the polycarbonate is as follows: 3: 1: 2. CO and H generated by decomposition of biomass and plastic powder in additive2Other reducing gases have stronger reducing property and promote the indirect reduction reaction, thereby improving the reduction effect; in addition, the carbonaceous substance generated by the decomposition of the biomass and the plastic powder has stronger reactivity and reducibility and is resistant to CaMoO4、CaWO4Has better reduction effect. Heating to the smelting temperature of 1300-1500 ℃, in the embodiment 1500 ℃, and the smelting time is 1-3 hours, in the embodiment 2 hours, completing the reduction process, cooling to the room temperature, and detecting and analyzing (content of W, Mo and P) after crushing. Wherein the reduction rate of tungsten is 72.1%, and the reduction rate of molybdenum is 68.3%.
Example 3
The basic contents of this embodiment are different from those of embodiment 1 in that: the reducing agent also comprises aluminum powder, wherein the aluminum powder has a mesh size of-300 of 80 percent, namely, the aluminum powder contains 80 percent of particles smaller than 300; the aluminum powder is prepared in an external mode, the aluminum powder accounts for 1.2% of the total mass of the modified silicon carbide and the modified quartz, the temperature is increased to 1300-1500 ℃ in the embodiment, the temperature is 1380 ℃, the smelting time is 1-3 h in the embodiment, and the reduction process is completed in the embodiment for 3 h. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). Wherein the reduction rate of tungsten is 73.1 percent, and the reduction rate of molybdenum is 66.9 percent.
During the reduction process, the aluminum powder in the composite reducing agent emits a large amount of heat during the process of reducing oxides, the heat promotes the composite reducing agent and the mineral powder to be melted into a liquid state, and meanwhile, the modified silicon carbide can be formed in the melted liquid phase [ Si]、[C]Then the reaction is carried out again, the solid-solid reaction is changed into liquid-solid reaction and liquid-liquid reaction, the reaction performance is greatly improved, and the reduction and the liquid-liquid reaction of the modified silicon carbide are promotedCaMoO4、CaWO4Thereby improving the reaction rate and improving the reduction effect of the composite reducing agent on the low-grade tungsten-molybdenum ore.
Example 4
The basic contents of this embodiment are different from those of embodiment 1 in that: the reducing agent also comprises aluminum powder, ferrosilicon and iron scale, wherein the aluminum powder has a particle size of 80 percent in a range of-300 meshes; aluminum powder, ferrosilicon and iron scale are prepared externally, the sum of the mass of the aluminum powder, the ferrosilicon and the iron scale accounts for 1% of the total mass of the modified silicon carbide and the modified quartz, the temperature is increased to 1300-1500 ℃ in the embodiment, the smelting time is 1-3 h, the smelting time is 2.5h in the embodiment, and the reduction process is completed. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). Wherein the reduction rate of tungsten is 71.1%, and the reduction rate of molybdenum is 67.1%.
Example 5
The basic contents of this embodiment are different from those of embodiment 2 in that: the additive comprises coke powder, plastic powder, biomass and blast furnace ash, wherein alkaline substances in the blast furnace ash promote the cracking of the plastic powder and the biomass under high temperature, so that the reduction reaction is promoted. Heating to the smelting temperature of 1300-1500 ℃, in this embodiment 1460 ℃, for 1-3 h, in this embodiment 1h, and completing the reduction process. Cooling to room temperature, crushing, detecting and analyzing (content of W, Mo and P). Wherein the reduction rate of tungsten is 73.7 percent, and the reduction rate of molybdenum is 68.1 percent.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (8)
1. A preparation method of tungsten-molybdenum ore pellets is characterized by comprising the following steps:
the method comprises the following steps: pretreatment of ore powder
Adding the mineral powder into a ball mill for ball milling; the specific surface area of the mineral powder after ball milling is more than 0.15m2/g；
Step two: mixed pelletizing
Adding a composite reducing agent into the mineral powder for dry mixing, wherein the composite reducing agent comprises modified silicon carbide, modified quartz and an additive,
the modified silicon carbide is a mixture of silicon carbide powder and silicon powder, the modified quartz is quartz coated with a coating component on the surface, and the coating component is asphalt;
wherein the mass ratio of the modified silicon carbide to the modified quartz is alpha, the value of alpha is 0.7-1.5, and the additive comprises coke powder; and after the uniform mixing is finished, adding a binder into the mixture, preparing the tungsten-molybdenum ore pellets through a disc pelletizer, adding the mineral powder mixture into the disc pelletizer, and adding water on the disc pelletizer to prepare the tungsten-molybdenum ore pellets with the particle size of 5-8 mm.
2. The method for preparing tungsten-molybdenum ore pellets according to claim 1, wherein the method comprises the following steps:
the proportion of the reducing agent and the mineral powder is
Wherein the value of gamma is 5-6, and alpha is the mass ratio of the modified silicon carbide to the modified quartz; then
W1To CaWO in mineral powder4Mass percent of (1);
W2is CaMoO in mineral powder4Mass percent of (1);
W3ca in the ore powder5(PO4)3Mass percent of F.
3. The method for preparing tungsten-molybdenum ore pellets according to claim 1, wherein the method comprises the following steps: adding kaolin into the silicon carbide powder and the silicon powder, and adding water for mixing to obtain the modified silicon carbide.
4. The method for preparing tungsten-molybdenum ore pellets according to claim 1, wherein the method comprises the following steps: adding the mineral powder mixture into a disc pelletizer, spraying water into the mixture of the low-grade tungsten-molybdenum ore, the composite reducing agent and the binder on the disc pelletizer, forming the binder into daub after the binder absorbs water, extruding and discharging the daub in the pellet from inside to outside under the action of the rolling mechanical force of the disc pelletizer, adhering the mixed powder of the low-grade tungsten-molybdenum ore, the composite reducing agent and the binder to the surface of the pellet, discharging the mixed powder out of the disc pelletizer until qualified pellets are formed, and obtaining the tungsten-molybdenum ore pellets.
5. The method for preparing tungsten-molybdenum ore pellets according to claim 3, wherein the method comprises the following steps: preparing modified silicon carbide:
(1) adding kaolin into the silicon carbide powder and the silicon powder, drying in a drying oven, adding the kaolin into the silicon carbide powder, and uniformly stirring in a stirrer;
(2) adding silicon powder into the stirrer while adding the atomized water solution into the stirrer, continuously and uniformly mixing to form granules after adding the silicon powder, and heating and drying to obtain modified silicon carbide; the mass ratio of the silicon carbide powder to the silicon powder is 2-4: 1.
6. The method for preparing the tungsten-molybdenum ore pellets according to any one of claims 1 to 5, wherein the method comprises the following steps: preparing modified quartz:
(1) firstly, acid washing is carried out on quartz by adopting an acid solution, water glass is added after the acid washing is finished and is uniformly mixed, and then the quartz is washed by water, filtered and dried by taking precipitate;
(2) mixing the dried quartz and the coating component in a reaction kettle, wherein the mass ratio of the quartz of the modified quartz to the coating component is 6-7: 1, heating the reaction kettle to 50-90 ℃, and continuously mixing and stirring to obtain the modified quartz.
7. The method for smelting the low-grade tungsten-molybdenum ore by the pyrogenic process is characterized by comprising the following steps: the method of any one of claims 1 to 6 is adopted to prepare the tungsten-molybdenum ore pellets, the tungsten-molybdenum ore pellets are placed into an oven to be dried, the dried tungsten-molybdenum ore pellets are cooled to room temperature after being dried, then the pellets are heated and reduced in a vacuum furnace, the vacuum degree is controlled to be 100-150 Pa, and the smelting temperature is 1300-1500 ℃.
8. The pyrometallurgical method of smelting low-grade tungsten-molybdenum ore according to claim 7, characterized in that: the temperature rising system of the vacuum furnace is as follows: firstly, heating to 800 ℃ at a speed of 10 ℃/min; then heating to 1200 ℃ at the speed of 8 ℃/min; and heating the mixture at a speed of 5 ℃/min until the smelting temperature is 1300-1500 ℃, and the smelting time is 1-3 h.
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