CN109554542A - A kind of method of the preparation method and the low-grade tungsten mine of pyrometallurgical smelting of tungsten mine pelletizing - Google Patents
A kind of method of the preparation method and the low-grade tungsten mine of pyrometallurgical smelting of tungsten mine pelletizing Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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Abstract
The invention discloses a kind of preparation method of tungsten mine pelletizing and the methods of the low-grade tungsten mine of pyrometallurgical smelting, belong to low-grade tungsten ore resourcesization and utilize field.Step 1 of the present invention: miberal powder is added in ball mill and carries out ball milling by miberal powder pretreatment；Step 2: complex reducing agent is added to miberal powder and carries out dry-mixed by mixed pelletizing, and complex reducing agent includes modified silicon carbide, modified quartz and additive；Binder is added into mixture again after the completion of mixing, and tungsten mine pelletizing is prepared by disc balling machine, mineral powder mixed material is added in disc balling machine, adds water that tungsten mine pelletizing is prepared on disc balling machine.The present invention passes through mutually promoting for modified silicon carbide, modified quartz and additive, has good reduction to low-grade tungsten mine；The modified surface coated silicon powder of silicon carbide has preferable reactivity worth, and and CaMoO4、CaWO4Reaction, can be improved the reduction efficiency of low-grade tungsten mine.
Description
Present patent application is for application No. is 2017105225005 divisional applications, the applyings date of original application are as follows:
2017-06-30, invention and created name are as follows: a kind of preparation method of complex reducing agent and its method for smelting.
Technical field
The present invention relates to low-grade tungsten ore resourcesization to utilize field, more specifically to a kind of complex reducing agent
Preparation method and its method for smelting.
Background technique
Reducing agent is to lose electronics in redox reaction or have the substance of electronics deviation.Reducing agent itself has also
Originality is oxidized, and product is oxidation product.Reduction is carried out simultaneously with oxidation reaction, i other words, reducing agent with gone back
While the original carries out oxidation reaction, itself is also oxidized, and becomes oxide.Using the metal oxygen in reducing agent reduction mineral
Compound produces metal, and metal can be effectively extracted from metal oxide.
With the increasingly consumption of tungsten element resource, the yield of tungsten mineral products money is gradually increased；And cause limited excellent
Matter tungsten mineral resources just gradually decrease, and tungsten mine during ore dressing, is discharged after choosing active principle therein
The solid waste that ore pulp is formed through natural-dehydration.Low-grade tungsten mine solid waste is just no longer utilized, and is idle in mine
The huge wasting of resources and environmental pollution are caused in mountain.During the processing method of tungsten mine, frequently be wet-treating work
Skill, but wet processing process process flow is long, and is easy to produce acid or alkaline gas in treatment process and generates dirt to atmosphere
Dye can also generate a large amount of waste water when being handled using wet process, very important harm is caused to environment.
Also there is existing technical staff to smelt during smelting using pyrogenic process, such as: the title of innovation and creation
Pass through weight for a kind of nickel-molybdenum ore nickel for selecting smelting to combine, molybdenum separation method (application number: 95110744.5 applyings date: 1995-05-03)
Choosing, rough segmentation, suppression nickel float the nickel-molybdenum ore enrichment of molybdenum and selective low temperature fire reduction nickel-rich phase combination, separating technology, can get two
Kind of furnace charge, i.e., a kind of to be up to 11% containing molybdenum, nickeliferous is 2% or so, another kind for containing molybdenum 3% or so, it is nickeliferous up to 8% furnace
Material, for smelting Monimax or dynamax.Using pyrometallurgical smelting tailing and low-grade mine；But due to low-grade
Tungsten mine is difficult to restore by pyrometallurgical smelting, causes the pyrometallurgical smelting effect of low-grade tungsten mine poor, and urgent need develops one
Kind is specifically applied to the reducing agent of low-grade tungsten mining and metallurgy refining.
In addition, through retrieving, a kind of low ore grade nickel molybdenum ore directly smelt dynamax method (application number:
201410308642.8, applying date 2014.07.02), this method includes that nickel-molybdenum ore sodium carbonate roasting and intermediate frequency furnace metal directly heat are gone back
Former two steps, specifically: nickel-molybdenum ore roasts at 630-680 DEG C with addition of the mixture of the strong alkaline substance composition of 15-20%
20-30min, which completes to roast, is made calcining, and realizes that desulfurization, calcining are directly heat-treated in intermediate frequency furnace with carbon duriron, restores
Journey is restored completely stage by stage by control reaction temperature and heating-up time, control calcining, and dynamax is made.But the technique
But it is difficult to use in the smelting of low-grade tungsten mine.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome the shortcomings of that prior art middle-low grade tungsten mine utilizing status is poor, a kind of tungsten is provided
The method of the low-grade tungsten mine of the preparation method and pyrometallurgical smelting of molybdenum ore pelletizing, by using including modified silicon carbide, modified stone
The complex reducing agent of English and additive, reducing agent each component are mutually promoted, and the reduction efficiency to low-grade tungsten mine can be improved.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of preparation method of tungsten mine pelletizing of the invention, it is characterised in that:
Step 1: miberal powder pretreatment
Miberal powder is added in ball mill and carries out ball milling；The specific surface area of miberal powder is greater than 0.15m after the completion of ball milling2/g；
Step 2: mixed pelletizing
Complex reducing agent is added to miberal powder and carries out dry-mixed, complex reducing agent includes modified silicon carbide, modified quartz and adds
Add agent, wherein the mass ratio of modified silicon carbide and modified quartz is α, α value is 0.7~1.5, and additive includes coke powder；It is mixed
Binder is added into mixture again after the completion of even, and tungsten mine pelletizing is prepared by disc balling machine, miberal powder is mixed
Material is added in disc balling machine, adds water that the tungsten mine pelletizing of 5~8mm is prepared on disc balling machine.
Preferably, the proportion of reducing agent and miberal powder is
Wherein the value of γ is 5~6, and wherein α is the mass ratio of modified silicon carbide and modified quartz；Then
W1For CaWO in miberal powder4Mass percentage, %；
W2For CaMoO in miberal powder4Mass percentage, %；
W3For Ca in miberal powder5(PO4)3The mass percentage of F, %.
Preferably, kaolin is added in carborundum powder and silicon powder, modified silicon carbide is obtained after adding water to mix.
Preferably, modified quartz is the quartz that cladding component is coated on surface, which includes pitch.
Preferably, mineral powder mixed material is added in disc balling machine, to low-grade tungsten mine, compound on disc balling machine
It sprays water in the mixture of reducing agent and binder, becomes clay after binder water suction, in the work of disc balling machine rolling machine power
Under, clay in the agglomerate row of squeezing from inside to outside, to pelletizing surface after bond low-grade tungsten mine, complex reducing agent and binder
Mixed powder obtain tungsten mine pelletizing until forming qualified pelletizing is discharged disc balling machine.
Preferably, modified silicon carbide is prepared:
(1) kaolin will be added in carborundum powder and silicon powder to dry in an oven, kaolin is first added into carborundum powder
And it is stirred evenly in blender；
(2) aqueous solution that another side is atomized to blender, is added silicon powder into blender on one side, continuess to mix after adding
It is formed uniformly graininess, and heating, drying obtains modified silicon carbide；The mass ratio of the carborundum powder and silicon powder is 2~4: 1.
Preferably, the modified quartz of preparation:
(1) pickling is first carried out to quartz using acid solution, waterglass is added after the completion of pickling and is uniformly mixed, washing, mistake
Filter, taking precipitate are dried；
(2) quartz after drying is mixed in a kettle with cladding component, the quartz and cladding group of modified quartz
The mass ratio divided is 6-7: 1, and reaction kettle heats up 50-90 DEG C, continuess to mix and stirs to get modified quartz.
The method of the low-grade tungsten mine of pyrometallurgical smelting of the invention, adopts and prepares tungsten mine pelletizing with the aforedescribed process, by tungsten
Molybdenum ore pelletizing, which is put into baking oven, is dried, and is cooled to room temperature after the completion of drying, then by pelletizing heating reduction in a vacuum furnace,
Vacuum degree control is 100~150Pa, and smelting temperature is 1300~1500 DEG C.
Preferably, the temperature increasing schedule of vacuum drying oven are as follows: be first warming up to 800 DEG C with 10 DEG C/min；Then it is warming up to 8 DEG C/min
1200℃；And with 5 DEG C/min be warming up to smelting temperature be 1300~1500 DEG C, 1~3h of the duration of heat.
A kind of preparation method of complex reducing agent of the invention enters modified silicon carbide, modified quartz and additive to stirring
It mixes in machine and is uniformly mixed, mixing temperature is 30~40 DEG C, and the modification silicon carbide is the mixture of carborundum powder and silicon powder,
The modified quartz is the quartz that cladding component is coated on surface, which includes pitch；The additive includes
Coke powder.
Preferably, specific steps are as follows:
S1: modified silicon carbide is prepared
Kaolin is added into carborundum powder and is stirred evenly in blender, then silicon powder is added to blender, after mixing
Obtain modified silicon carbide；
S2: the modified quartz of preparation
It is added in vacuum mixer after cladding component and quartz mixing, is mixed and is changed at a temperature of 50-90 DEG C
Property quartz, cladding component include pitch；
S3: complex reducing agent is prepared
Modified silicon carbide, modified quartz and additive are added in blender, and is uniformly mixed and obtains complex reducing agent.
Preferably, the mass ratio of modified silicon carbide and modified quartz is α, and α value is 0.7~1.5；The additive
Account for the 1~4% of modified silicon carbide and modified quartzy gross mass.
Preferably, the specific steps of modified silicon carbide S1: are prepared are as follows:
(1) kaolin will be added in SiClx powder and silicon powder to dry in an oven, kaolin first is added simultaneously into carborundum powder
It is stirred evenly in blender；
(2) aqueous solution that another side is atomized to blender, is added silicon powder into blender on one side, continuess to mix after adding
It is formed uniformly graininess, and heating, drying obtains modified silicon carbide；The mass ratio of the carborundum powder and silicon powder is 2~4: 1.
Preferably, S2: the modified quartz of preparation specific the preparation method comprises the following steps:
(1) pickling is first carried out to quartz using acid solution, waterglass is added after the completion of pickling and is uniformly mixed, washing, mistake
Filter, taking precipitate are dried；
(2) quartz after drying is mixed in a kettle with cladding component, the quartz and cladding group of modified quartz
The mass ratio divided is 6-7: 1, and reaction kettle heats up 50-90 DEG C, continuess to mix and stirs to get modified quartz.
Preferably, the PH of the acid solution is 5~6, and pickling temperature is 50~60 DEG C, and pickling solution is HCl solution.
Preferably, the pitch is pre-processed before addition, is crushed, is carried out solid-liquor separation acquisition grain after wet-milling
The pitch of < 100um is spent, then diatomite, NaCl and rubber powder are added into pitch；150-200 DEG C is then warming up to be fused
Pitch used in additive is obtained, broken, wet-milling obtains asphalt powder.
It preferably, further include aluminium powder, -300 mesh of aluminium powder is 80%.
The method of the low-grade tungsten mine of a kind of pyrometallurgical smelting of the invention, using the preparation side of above-mentioned complex reducing agent
Complex reducing agent is prepared in method, then complex reducing agent is added in miberal powder and is mixed, and the miberal powder is low-grade tungsten mine；
And tungsten mine pelletizing is prepared by disc balling machine, pelletizing is then smelted to tungsten mine, vacuum degree control in a vacuum furnace
For 100~150Pa, smelting temperature is 1300~1500 DEG C.
3. beneficial effect
Using technical solution provided by the invention, compared with existing well-known technique, there is following remarkable result:
(1) complex reducing agent that is prepared of the present invention under vacuum conditions low-grade tungsten mine when, pass through carbon modified
SiClx, modified quartz and additive are mutually promoted, and have good reduction to low-grade tungsten mine；In reaction beginning
Just, the modified surface coated silicon powder of silicon carbide has preferable reactivity worth, and can rapidly be situated between under the promotion of modified quartz
Enter reaction, and and CaMoO4、CaWO4Reaction, and modified quartz can effectively reduce reaction resistance；Then modified silicon carbide tool
There is stronger reducing power, and can be by the CaMoO in low-grade ore4、CaWO4Reduction obtains tungsten and metal molybdenum；Modified carbonization
Silicon also generates the CO gas with reproducibility during reaction, and modified silicon carbide reduction process includes thermal reduction reaction, carbon
Thermal reduction reaction and CaSiO3Solid phase generates reaction, to improve the reduction efficiency of low-grade tungsten mine；
(2) the modification quartz for the complex reducing agent that the present invention is prepared can reduce Ca5(PO4)3F free energy of reaction, mentions
High complex reducing agent is to Ca5(PO4)3The reducing power of F, and under the promotion of modified quartz, energy and Ca5(PO4)3F reaction, it is modified
Coke powder in silicon carbide and additive also in the case where modified quartz promotes with Ca5(PO4)3F reaction, and restore the P of generation2Steam from
It is separated in solid material, to promote the progress of entire reduction reaction；
(3) a kind of method of the low-grade tungsten mine of pyrometallurgical smelting of the present invention, using include modified silicon carbide, modified quartz and
The complex reducing agent of additive, and restored under vacuum conditions, pass through the phase of modified silicon carbide, modified quartz and additive
Mutually promote, there is good reduction to low-grade tungsten mine, improve reduction efficiency.
Detailed description of the invention
The comparative example effect picture of reduction rate of the Fig. 1 between the embodiment of the present invention 1 and comparative example；
Fig. 2 is a kind of flow chart of the preparation method of complex reducing agent of the invention.
Specific embodiment
Hereafter to the detailed description of exemplary embodiment of the present invention with reference to attached drawing, which forms one of description
Point, although these exemplary embodiments are described in sufficient detail so that those skilled in the art can implement the present invention,
It should be understood that can realize other embodiments and can make without departing from the spirit and scope of the present invention to the present invention various
Change.Required the scope of the present invention is hereafter not limited to the more detailed description of the embodiment of the present invention, and only
Only for being illustrated and not limiting the description to the features of the present invention and feature, to propose to execute best side of the invention
Formula, and it is sufficient to make those skilled in the art that can implement the present invention.Therefore, the scope of the present invention only by appended claims Lai
It limits.
Embodiment 1
Hereafter to the detailed description of exemplary embodiment of the present invention with reference to attached drawing, which forms one of description
Point, although these exemplary embodiments are described in sufficient detail so that those skilled in the art can implement the present invention,
It should be understood that can realize other embodiments and can make without departing from the spirit and scope of the present invention to the present invention various
Change.Required the scope of the present invention is hereafter not limited to the more detailed description of the embodiment of the present invention, and only
Only for being illustrated and not limiting the description to the features of the present invention and feature, to propose to execute best side of the invention
Formula, and it is sufficient to make those skilled in the art that can implement the present invention.Therefore, the scope of the present invention only by appended claims Lai
It limits.
Embodiment 1
Of the invention is a kind of for smelting the complex reducing agent of low-grade tungsten mine, including modified silicon carbide, modified quartz
And additive；The modification silicon carbide is the mixture of carborundum powder and silicon powder, and the modified quartz is in surface cladding
There is the quartz of cladding component, which is divided into pitch；Cladding component and quartz are mixed at a temperature of being mixed in 50-90 DEG C and obtain
Modified quartz, wherein the quartz of modified quartz and the mass ratio of cladding component are 6-7: 1, the present embodiment 7: 1.
First quartz is added in reaction kettle and is warming up to 40-50 DEG C, and keeps the temperature 20min, then be warming up to 50-90 DEG C, this reality
Applying example is 60 DEG C；Asphalt powder is added in reaction kettle again, and asphalt powder is coated on quartz surfaces and obtains modified quartz, and
Keep the temperature 10min.
Kaolin is added in carborundum powder and silicon powder in modified silicon carbide, and modified silicon carbide is obtained after adding water to mix；It is described
The mass ratio of carborundum powder and silicon powder is 2~4: 1, the present embodiment 3: 1；Kaolinic -325 mesh is 90%, i.e., less than 325
Purpose particle is greater than 90%, the present embodiment 91%.The specific preparation step of modified silicon carbide are as follows: will be in carborundum powder and silicon powder
Kaolin is added to dry in an oven, kaolin is first added into carborundum powder and is stirred evenly in blender, then on one side
The aqueous solution being atomized to blender, is added silicon powder into blender on one side, continuess to mix after adding and is formed uniformly graininess, and
Heating, drying obtains modified silicon carbide.Wherein kaolin is medium-low temperature fluid alteration remnants type kaolin, also referred to as Suzhou soil；
The alumina content of the present embodiment is 36%, silica 48%.
The mass ratio of modified silicon carbide and modified quartz is α, and α value is 0.7~1.5, and the present embodiment goes to α=1；It is described
Additive account for the 1~4% of modified silicon carbide and modified quartzy gross mass.
Additive of the invention includes coke powder, and the coke powder carries out ball milling in the ball mill, burnt after ball milling in the ball mill
The particle of powder is less than 200 mesh.
As shown in Fig. 2, a kind of preparation method of complex reducing agent of the invention, specific steps are as follows:
S1: modified silicon carbide is prepared
Kaolin is added into carborundum powder and is stirred evenly in blender, then silicon powder is added to blender, after mixing
Obtain modified silicon carbide；Specific steps are as follows:
(1) kaolin will be added in carborundum powder and silicon powder to dry in an oven, kaolin is first added into carborundum powder
And stirred evenly in blender, kaolinic additional amount is the 1.5% of carborundum powder and silicon powder gross mass；
(2) aqueous solution that another side is atomized to blender, is added silicon powder into blender on one side, continuess to mix after adding
It is formed uniformly graininess, and heating, drying obtains modified silicon carbide；The mass ratio of the carborundum powder and silicon powder is 2~4: 1,
The present embodiment is that the mass ratio of carborundum powder and silicon powder is 3；
S2: the modified quartz of preparation
It is added in vacuum mixer after cladding component and quartz mixing, is mixed and is changed at a temperature of 50-90 DEG C
Property quartz, cladding component include pitch；Detailed description are as follows:
(1) pickling is first carried out to quartz using acid solution, waterglass is added after the completion of pickling and is uniformly mixed, washing, mistake
Filter, taking precipitate are dried；
(2) quartz after drying is mixed in a kettle with cladding component, the quartz and cladding group of modified quartz
The mass ratio divided is 6-7: 1, and reaction kettle heats up 50-90 DEG C, continuess to mix and stirs to get modified quartz.The PH of the acid solution
It is 5~6, pickling temperature is 50~60 DEG C, and pickling solution is HCl solution.
Pitch is pre-processed before adding, and the pitch is pelletted pitch, first by pitch at a temperature of 10-20 DEG C
Broken, progress solid-liquor separation acquisition granularity < 100um after wet-milling pitch, then diatomite, NaCl and rubber are added into pitch
Powder, the mass ratio of diatomite, NaCl and rubber powder are as follows: 1: 1: 3；Diatomite, NaCl and rubber powder quality sum account for asphalitine
The 10% of amount；It is then warming up to 150-200 DEG C to be fused to obtain pitch used in additive, and to pitch in 5-15 DEG C of temperature
Lower broken, wet-milling obtains asphalt powder, obtains the pitch particle of granularity < 50um.
S3: complex reducing agent is prepared
Modified silicon carbide, modified quartz and additive are added in blender, stir 15-30min, and be uniformly mixed and obtain
Complex reducing agent.
A kind of method of the low-grade tungsten mine of pyrometallurgical smelting, the specific steps are as follows:
Step 1: miberal powder pretreatment
Miberal powder is added in ball mill and carries out ball milling, so that the ratio that miberal powder partial size is -75 μm is greater than 95%, i.e. particle
Mass ratio of the granularity less than -75 μm is greater than 95%；The specific surface area of miberal powder is greater than 0.15m after the completion of ball milling2/g；
Step 2: mixed pelletizing
(1) ingredient in miberal powder is detected, detection obtains low-grade tungsten mine CaWO4For 24.1%, CaMoO4It is 5.5%；,
Ca5(PO4)3F is 22.1%.
(2) by complex reducing agent be added to miberal powder carry out it is dry-mixed, wherein the proportion of reducing agent and miberal powder be (10~20):
100；Specifically the proportion of reducing agent and miberal powder isWherein the value of γ is 5~6, and wherein α is modified carbonization
The mass ratio of silicon and modified quartz；ThenIt is 5 that wherein α, which takes 1, γ value,.
W1For CaWO in miberal powder4Mass percentage, %；
W2For CaMoO in miberal powder4Mass percentage, %；
W3For Ca in miberal powder5(PO4)3The mass percentage of F, %；
And proportion is calculated are as follows:
That is the proportion of complex reducing agent and miberal powder isMix after the completion of again to
Binder is added in mixture, the binder is organic binder, and it is starch, the proportion of binder that the present embodiment, which uses,
It is the 1% of complex reducing agent and low-grade tungsten mine gross mass；Miberal powder is low-grade tungsten mine；And it is prepared by disc balling machine
Tungsten mine pelletizing is obtained, mineral powder mixed material is added in disc balling machine, to low-grade tungsten mine, compound on disc balling machine
It sprays water in the mixture of reducing agent and binder, becomes clay after binder water suction, in the work of disc balling machine rolling machine power
Under, clay in the agglomerate row of squeezing from inside to outside, to pelletizing surface after bond low-grade tungsten mine, complex reducing agent and binder
Mixed powder, repeatedly ball is made to grow up repeatedly, until forming qualified pelletizing is discharged disc balling machine, obtains tungsten mine ball
Group；Add water that the tungsten mine pelletizing of 5~8mm is prepared on disc balling machine.
Step 3: tungsten mine is smelted
Tungsten mine pelletizing is put into baking oven and is dried, drying after the completion of be cooled to room temperature, add in vacuum drying oven into
Row reducing and smelting, heating reduction in vacuum drying oven, vacuum degree control are 100~150Pa, the present embodiment 100Pa；Smelting temperature is
1300~1500 DEG C, the wherein temperature increasing schedule of vacuum drying oven are as follows: be first warming up to 800 DEG C with 10 DEG C/min；Then with 8 DEG C/min heating
To 1200 DEG C；And smelting temperature is warming up to as 1300~1500 DEG C with 5 DEG C/min, the present embodiment is 1400 DEG C, the duration of heat 1~
3h, the present embodiment 1.5h complete reduction process.Detection and analysis (W, Mo, P content) after being cooled to room temperature, being broken.Wherein tungsten
Reduction rate is 71.3%, and the reduction rate of molybdenum is 65.5%, as shown in Figure 1.
The calculation formula of reduction rate are as follows:
Note: mBeforeTo react preceding miberal powder gross mass, ωBefore MoTo CaMoO in mine before miberal powder reaction4The percentage of Mo is obtained after conversion
Content, ωAfter MoAfter the reaction of low-grade tungsten mine in product Mo percentage composition；ωBefore WTo in mine before low-grade tungsten mine reaction
CaWO4The percentage composition of W is obtained after conversion；ωAfter WAfter the reaction of low-grade tungsten mine in product W percentage composition.
Comparative example 1
The basic content of this comparative example with embodiment 1, the difference is that: the reducing agent that this comparative example uses for carbonization
Silicon completes reduction process.Detection and analysis (W, Mo, P content) after being cooled to room temperature, being broken.Wherein the reduction rate of tungsten is 45.1%,
The reduction rate of molybdenum is 33.5%.
Comparative example 2
The basic content of this comparative example with embodiment 1, the difference is that: the reducing agent that this comparative example uses is complete for carbon
At reduction process.Detection and analysis (W, Mo, P content) after being cooled to room temperature, being broken.Wherein the reduction rate of tungsten is 43.5%, molybdenum
Reduction rate is 36.9%.
Comparative example 3
The basic content of this comparative example with embodiment 1, the difference is that: the reducing agent that this comparative example uses for carbonization
Silicon, quartz and additive, wherein silicon carbide, quartz are not modified, complete reduction process.Be cooled to room temperature, it is broken after detect
It analyzes (W, Mo, P content).Wherein the reduction rate of tungsten is 55.9%, and the reduction rate of molybdenum is 44.7%.
According to the comparison of comparative example 1,2,3 and embodiment 1, it can be found that using the complex reducing agent of the embodiment 1 used
Substantially increase the reduction efficiency of low-grade tungsten mine.Concrete reason, researcher is not completely clear, by repeatedly discussing
Meeting, applicant think to concentrate possible reaction mechanism are as follows: by the complex reducing agent being prepared low-grade tungsten under vacuum conditions
When molybdenum ore, by mutually promoting for modified silicon carbide, modified quartz and additive, there is good reduction to low-grade tungsten mine
Effect, and reduce reaction condition；At the beginning of reaction starts, due to silicon carbide have at high temperature it is preferable stability, compared with
Under conditions of low temperature, the reducing property of silicon carbide is relatively poor；The modified surface coated silicon powder of silicon carbide has preferable anti-
Performance is answered, and can rapidly intervene reaction, and and CaMoO under the promotion of modified quartz4、CaWO4Reaction, and modified quartz
Reaction resistance can effectively be reduced, and pushed the progress of reaction, and then promote silicon powder reduction CaMoO4、CaWO4；With anti-
The raising of temperature is answered, and under the promotion of silicon powder surface reaction product, modified silicon carbide has stronger reducing power, and can
By the CaMoO in low-grade ore4、CaWO4Reduction obtains tungsten and metal molybdenum；At the same time, mistake of the modified silicon carbide in reaction
Also generate the CO gas with reproducibility in journey, thus modified silicon carbide reduction process include thermal reduction reaction (solid phase reduction),
Carbothermic reduction reaction (based on indirect reduction) and CaSiO3Solid phase generates reaction, to improve reduction efficiency.
In addition to this, modified quartz can reduce Ca5(PO4)3F free energy of reaction improves complex reducing agent to Ca5(PO4)3F
Reducing power, the pitch-coating layer of especially modified quartz surfaces during reaction can by being thermally generated subtle carbon granules,
With stronger reactivity, and under the promotion of modified quartz, energy and Ca5(PO4)3F reaction, is modified silicon carbide at the same time
With the coke powder in additive also in the case where modified quartz promotes with Ca5(PO4)3F reaction, and by Ca5(PO4)3F restores to obtain P2With
SiF4, the steam of generation is separated from solid material, to promote the progress of entire reduction reaction, and in whole process
The often compound a variety of reduction reactions of multiple reactions, and extra reducing agent can't form carbide with tungsten, molybdenum, thus
Improve the reduction efficiency of low-grade tungsten mine.And entirely reaction is not single reaction process, this is existing general
The inaccessiable effect of catalyst institute.Following reaction mainly occurs during reduction for complex reducing agent:
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)
Complex reducing agent of the invention under vacuum conditions low-grade tungsten mine when, pass through modified silicon carbide, modified quartz
With mutually promoting for additive, there is good reduction to low-grade tungsten mine；At the beginning of reaction starts, modified silicon carbide
Surface coated silicon powder has preferable reactivity worth, and reaction can be rapidly intervened under the promotion of modified quartz, and with
CaMoO4、CaWO4Reaction, and modified quartz can effectively reduce reaction resistance；Then modified silicon carbide has stronger reduction
Ability, and can be by the CaMoO in low-grade ore4、CaWO4Reduction obtains tungsten and metal molybdenum；Mistake of the modified silicon carbide in reaction
The CO gas with reproducibility is also generated in journey, to improve the reduction efficiency of low-grade tungsten mine.
Embodiment 2
The basic content of the present embodiment with embodiment 1, the difference is that: the additive further include molding powder and
Biomass, the mass ratio of coke powder, molding powder and biomass are 5: 2: 2, and molding powder and biomass are first in the alkali of NaOH and NaCl
Property solution in, impregnated at 60-80 DEG C, impregnate after the completion of dried；By coke powder, modeling at 150-250 DEG C after drying
Feed powder and biomass are stirred mixing, so that molding powder and biomass are adhered to each other with coke powder, wherein the molding powder
Particle with biomass is less than 250 mesh.The molding powder is polyethylene, polyformaldehyde, polyamide, polypropylene, polystyrene, gathers
Any one of carbonic ester, polymethyl methacrylate, polyester or a variety of mixtures.Molding powder in the present embodiment is poly-
Propylene, polystyrene, polycarbonate；The mass ratio of polypropylene, polystyrene, polycarbonate are as follows: 3: 1: 2.In additive
Biomass and molding powder decompose the CO and H generated2There is stronger reproducibility Deng other reducibility gas, and promote indirectly also
The progress of original reaction, to improve the effect of reduction；In addition, biomass and molding powder decompose the carbonaceous material generated, have
Stronger reactivity and reproducibility, to CaMoO4、CaWO4With preferable reduction effect.Be warming up to smelting temperature be 1300~
1500 DEG C, the present embodiment is 1500 DEG C, 1~3h of the duration of heat, the present embodiment 2h, completes reduction process, is cooled to room temperature, breaks
(W, Mo, P content) is tested and analyzed after broken.Wherein the reduction rate of tungsten is 72.1%, and the reduction rate of molybdenum is 68.3%.
Embodiment 3
The basic content of the present embodiment with embodiment 1, the difference is that: further include aluminium powder in reducing agent, it is described
- 300 mesh of aluminium powder is 80%, and the as particle in aluminium powder less than 300 accounts for 80%；By the way of matching outside, aluminium powder accounts for be changed aluminium powder
Property silicon carbide and modified quartzy gross mass 1.2%, being warming up to smelting temperature is 1300~1500 DEG C, the present embodiment 1380
DEG C, 1~3h of the duration of heat, the present embodiment 3h complete reduction process.(W, Mo, P contain for detection and analysis after being cooled to room temperature, being broken
Amount).Wherein the reduction rate of tungsten is 73.1%, and the reduction rate of molybdenum is 66.9%.
During reduction, the aluminium powder in complex reducing agent releases a large amount of heat during reduced oxide, should
Heat promotes complex reducing agent and miberal powder melts to form liquid, and being modified silicon carbide at the same time can form in the liquid phase of melting
[Si], [C] then react again, and change solid-solid reaction substantially increases reactivity worth, promote and change into liquid-solid reaction, reactive liquid solution
Property silicon carbide deacidizing and CaMoO4、CaWO4, to improve reaction rate, improve complex reducing agent and low-grade tungsten mine gone back
Former effect.
Embodiment 4
The basic content of the present embodiment with embodiment 1, the difference is that: further include in reducing agent aluminium powder, ferrosilicon and
Iron scale, -300 mesh of aluminium powder are 80%；Aluminium powder, ferrosilicon and iron scale by the way of matching outside, aluminium powder, ferrosilicon and
The quality sum of iron scale accounts for the 1% of modified silicon carbide and modified quartzy gross mass, be warming up to smelting temperature be 1300~
1500 DEG C, the present embodiment is 1300 DEG C, 1~3h of the duration of heat, the present embodiment 2.5h, completes reduction process.Be cooled to room temperature,
(W, Mo, P content) is tested and analyzed after broken.Wherein the reduction rate of tungsten is 71.1%, and the reduction rate of molybdenum is 67.1%.
Embodiment 5
The basic content of the present embodiment with embodiment 2, the difference is that: additive includes coke powder, molding powder, biology
Matter and blast furnace ash, wherein the alkaline matter in blast furnace ash promotes the cracking of molding powder, biomass under the high temperature conditions, to promote
Into the progress of reduction reaction.Being warming up to smelting temperature is 1300~1500 DEG C, and the present embodiment is 1460 DEG C, the duration of heat 1~
3h, the present embodiment 1h complete reduction process.Detection and analysis (W, Mo, P content) after being cooled to room temperature, being broken.Wherein tungsten also
Former rate is 73.7%, and the reduction rate of molybdenum is 68.1%.
The present invention is described in detail above in conjunction with specific exemplary embodiment.It is understood, however, that can not take off
It is carry out various modifications in the case where from the scope of the present invention being defined by the following claims and modification.Detailed description and drawings
Should be to be considered only as it is illustrative and not restrictive, if there is any such modifications and variations, then they all will
It falls into the scope of the present invention described herein.In addition, Development Status and meaning that background technique is intended in order to illustrate this technology,
It is not intended to limit the present invention or the application and application field of the invention.
More specifically, although exemplary embodiment of the present invention has been described herein, the invention is not limited to
These embodiments, but modified, the omission, example that can be appreciated that including those skilled in the art according to the detailed description of front
Any and whole embodiments of combination, adaptive change and/or replacement between such as each embodiment.Restriction in claim
The language according to used in claim and widely explained, and be not limited in foregoing detailed description or implement should
The example described during application, these examples should be considered as nonexcludability.It is in office where to arrange in method or process claims
Any step lifted can execute in any order and be not limited to the sequence proposed in claim.Therefore, model of the invention
Enclosing only to be determined by appended claims and its legal equivalents, rather than by descriptions and examples given above Lai really
It is fixed.
Claims (9)
1. a kind of preparation method of tungsten mine pelletizing, it is characterised in that:
Step 1: miberal powder pretreatment
Miberal powder is added in ball mill and carries out ball milling；The specific surface area of miberal powder is greater than 0.15m after the completion of ball milling2/g；
Step 2: mixed pelletizing
Complex reducing agent is added to miberal powder and carries out dry-mixed, complex reducing agent includes modified silicon carbide, modified quartz and additive,
The mass ratio for being wherein modified silicon carbide and modified quartz is α, and α value is 0.7~1.5, and additive includes coke powder；It mixes and completes
Binder is added into mixture again afterwards, and tungsten mine pelletizing is prepared by disc balling machine, mineral powder mixed material is added
In disc balling machine, add water that the tungsten mine pelletizing of 5~8mm is prepared on disc balling machine.
2. a kind of preparation method of tungsten mine pelletizing according to claim 1, it is characterised in that:
The proportion of reducing agent and miberal powder is
Wherein the value of γ is 5~6, and wherein α is the mass ratio of modified silicon carbide and modified quartz；Then
W1For CaWO in miberal powder4Mass percentage, %；
W2For CaMoO in miberal powder4Mass percentage, %；
W3For Ca in miberal powder5(PO4)3The mass percentage of F, %.
3. a kind of preparation method of tungsten mine pelletizing according to claim 1, it is characterised in that: in carborundum powder and silicon powder
Middle addition kaolin obtains modified silicon carbide after adding water to mix.
4. a kind of preparation method of tungsten mine pelletizing according to claim 1, it is characterised in that: modified quartz is on surface
It is coated with the quartz of cladding component, which includes pitch.
5. a kind of preparation method of tungsten mine pelletizing according to claim 1, it is characterised in that: mineral powder mixed material to be added
It in disc balling machine, sprays water, glues into the mixture of low-grade tungsten mine, complex reducing agent and binder on disc balling machine
Become clay after tying agent water suction, under the action of disc balling machine rolling machine power, clay in the agglomerate row of squeezing from inside to outside is arrived
The mixed powder of low-grade tungsten mine, complex reducing agent and binder is bonded behind pelletizing surface, until forming qualified pelletizing discharge
Disc balling machine obtains tungsten mine pelletizing.
6. a kind of preparation method of tungsten mine pelletizing according to claim 3, it is characterised in that: prepare modified silicon carbide:
(1) will in carborundum powder and silicon powder be added kaolin dry in an oven, first into carborundum powder be added kaolin and
It is stirred evenly in blender；
(2) aqueous solution that another side is atomized to blender, is added silicon powder into blender on one side, continuess to mix after adding uniformly
Graininess is formed, and heating, drying obtains modified silicon carbide；The mass ratio of the carborundum powder and silicon powder is 2~4: 1.
7. a kind of preparation method of tungsten mine pelletizing according to claim 4, it is characterised in that: the modified quartz of preparation:
(1) pickling is first carried out to quartz using acid solution, waterglass is added after the completion of pickling and is uniformly mixed, washing, filtering take
Sediment is dried；
(2) quartz after drying is mixed in a kettle with cladding component, quartz and the cladding component of modified quartz
Mass ratio is 6-7: 1, and reaction kettle heats up 50-90 DEG C, continuess to mix and stirs to get modified quartz.
8. the method for the low-grade tungsten mine of pyrometallurgical smelting, it is characterised in that: using method described in claim 1-7 any one
Tungsten mine pelletizing is prepared, tungsten mine pelletizing is put into baking oven and is dried, is cooled to room temperature after the completion of drying, then by pelletizing
Heating reduction in a vacuum furnace, vacuum degree control are 100~150Pa, and smelting temperature is 1300~1500 DEG C.
9. the method for the low-grade tungsten mine of pyrometallurgical smelting according to claim 9, it is characterised in that: the heating system of vacuum drying oven
Degree are as follows: be first warming up to 800 DEG C with 10 DEG C/min；Then 1200 DEG C are warming up to 8 DEG C/min；And smelting is warming up to 5 DEG C/min
Temperature is 1300~1500 DEG C, 1~3h of the duration of heat.
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| CN201710522500.5A CN107245576B (en) | 2017-06-30 | 2017-06-30 | A kind of preparation method of complex reducing agent and its method for smelting |
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| CN115926549A (en) * | 2022-12-12 | 2023-04-07 | 瑞航(江苏)新材料科技发展有限公司 | Lost foam coating for cast iron and preparation method thereof |
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