CN107986333A - A kind of molybdate solution or tungstate solution containing molybdenum and trithiocyanuric acid（Salt）The method of reaction synthesis Thiomolybdate - Google Patents
A kind of molybdate solution or tungstate solution containing molybdenum and trithiocyanuric acid（Salt）The method of reaction synthesis Thiomolybdate Download PDFInfo
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- CN107986333A CN107986333A CN201711331704.7A CN201711331704A CN107986333A CN 107986333 A CN107986333 A CN 107986333A CN 201711331704 A CN201711331704 A CN 201711331704A CN 107986333 A CN107986333 A CN 107986333A
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- C01G39/00—Compounds of molybdenum
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Abstract
The invention discloses a kind of method of molybdate solution or tungstate solution containing molybdenum and trithiocyanuric acid (salt) reaction synthesis Thiomolybdate.In solution system, molybdate carries out thio reaction with trithiocyanuric acid (salt) and obtains Thiomolybdate, it can will contain molybdenum tungstate solution using the reaction to react with trithiocyanuric acid (salt), molybdenum acid ion is selectively vulcanized, obtain the tungstate solution containing Thiomolybdate, this method is used as vulcanizing agent using trithiocyanuric acid (salt), and reaction process is discharged without pernicious gases such as hydrogen sulfide, and H is completely eliminated2The generation of S, hence it is evident that improve production environment, and molybdenum micro in a large amount of sodium tungstate solutions can be made selectively to vulcanize, be conducive to subsequently use extraction, ion-exchange or precipitation method etc. to carry out tungsten separation.
Description
Technical field
The present invention relates to a kind of preparation method of Thiomolybdate, and in particular to utilizes trithiocyanuric acid (TTCA) or trimerization
The method that molybdate vulcanization is prepared Thiomolybdate as sulfiding reagent by rhodanate, more particularly to directly utilize wolframic acid containing molybdenum
Salting liquid prepares Thiomolybdate with trithiocyanuric acid or cyclo-trithocyanates making choice property vulcanization reaction, is advantageously implemented tungsten
The separated method of molybdenum, belongs to chemical industry metallurgical inorganic matter purification field.
Background technology
Tungsten separation is the problem that tungsten metallurgy is faced always, based on the difference of tungsten parent's sulphur ability, makes tungstates
Molybdenum and thioated reagent generation molybdenum dithiophosphate salt in solution, and tungsten does not generate thiqtung state, then passes through ion exchange, extraction
Take, precipitate etc. except the Thiomolybdate of birth, being separated so as to fulfill tungsten.Therefore, molybdenum is isolated from tungstate solution to lead to
Often it is required for first adding vulcanizing agent, under certain condition, makes the complete thioated of molybdenum, and tungsten then hardly cures.Industry at present
On the vulcanizing agent that uses be mostly (NH4)2S and Na2Although these vulcanizing agents of S can obtain good vulcanization effect, these
The price of vulcanizing agent is all higher, and inorganic sulfur agent inevitably produces H under weak basic condition2S gases, deteriorate production
Environment.Make vulcanizing agent according to S, the system being applicable in is the system containing certain sodium hydroxide, and thioated is carried out in two steps, sulphur
The generationization time is larger, and reaction controlling is more difficult, is not promoted industrially.(" Novel vulcanization reagent prepares Thiomolybdate to document
Research ", rare metal and hard alloy, Xi Xiaoli etc., in December, 1999 total 139th phase, 3-5 pages) disclose using RS (two sulphur
Change carbon) sulfiding reagent is used as, it uses carbon disulfide can be by molybdenum high performance vulcanization as sulfiding reagent, but carbon disulfide is in itself
It is a kind of toxic liquid, and H is still unavoidable from its sulfidation2The generation of S gases.
The content of the invention
For defect present in molybdenum sulfidation in the prior art, the purpose of the invention is to provide a kind of three polysulfides
The method that cyanic acid (salt) carries out vulcanization reaction generation Thiomolybdate with molybdate, this method use trithiocyanuric acid (salt) conduct
Vulcanizing agent reaction process is discharged without hydrogen sulfide gas, and H is completely eliminated2The generation of S, hence it is evident that improve production environment, and molybdic acid can be made
Salt high performance vulcanization.
Another object of the present invention is to be that providing one kind utilizes trithiocyanuric acid (salt) to be used for sulphur as sulfiding reagent
Change the method that the molybdenum in tungstates containing molybdenum obtains Thiomolybdate, this method is reacted using trithiocyanuric acid (salt) as vulcanizing agent
Process is discharged without hydrogen sulfide gas, and H is completely eliminated2The generation of S, hence it is evident that improve production environment, and a large amount of sodium tungstate solutions can be made
In micro molybdenum selectively vulcanize, the Thiomolybdate of generation is easy to separate with tungstate solution, is conducive to subsequently using extraction
Method, ion-exchange or precipitation method etc. carry out tungsten separation.
In order to realize above-mentioned technical purpose, the present invention provides a kind of molybdate and trithiocyanuric acid (salt) reaction synthesis sulphur
For the method for molybdate, this method is in solution system, and molybdate carries out sulphur with trithiocyanuric acid and/or cyclo-trithocyanates
Generation reaction, obtains Thiomolybdate.
Preferable scheme, trithiocyanuric acid and the cyclo-trithocyanates integral molar quantity are the 4~20 of molybdate mole
Times.Preferably 10~20 times；More preferably it is 10~16 times.Trithiocyanuric acid and cyclo-trithocyanates integral molar quantity rub for molybdate
You amount 4 times when, curing efficiency can reach more than 60%, and trithiocyanuric acid and cyclo-trithocyanates integral molar quantity are molybdate
At 10 times of mole, curing efficiency can reach more than 90%, and trithiocyanuric acid and cyclo-trithocyanates integral molar quantity are molybdenum
At 20 times of hydrochlorate mole, curing efficiency can reach 100%, and consider from cost and curing efficiency, preferably three polysulfides
Cyanic acid and cyclo-trithocyanates integral molar quantity are 10~16 times of molybdate mole.
More preferably scheme, the molybdate include alkali metal molybdate and/or dimolybdate salt.
More preferably scheme, the cyclo-trithocyanates are trithiocyanuric acid ammonium salt and/or trithiocyanuric acid alkali metal salt.
More preferably scheme, the condition of the thio reaction are：Temperature is 40 DEG C~70 DEG C, and the reaction time is small for 4~12
When.
Present invention also offers a kind of method that Thiomolybdate is prepared by tungstate solution containing molybdenum, this method is tungsten containing molybdenum
Acid salt solution carries out thio reaction with trithiocyanuric acid and/or cyclo-trithocyanates, and it is molten to obtain the tungstates containing Thiomolybdate
Liquid.
Preferable scheme, molybdenum exists with molybdenum acid ion in the tungstate solution containing molybdenum, and the concentration of molybdenum is 0.5~4g/
L, tungsten exist with tungstate ion, and the concentration of tungsten is with WO3Metering, is 100~200g/L.
More preferably scheme, trithiocyanuric acid and the cyclo-trithocyanates integral molar quantity are molybdenum in tungstate solution containing molybdenum
4~20 times of mole.Preferably 10~20 times；More preferably it is 10~16 times.
More preferably scheme, the condition of the thio reaction are：Temperature is 40 DEG C~70 DEG C, and the reaction time is small for 4~12
When.Preferable reaction temperature is 50~70 DEG C, more preferably 60~70 DEG C.In 40~70 DEG C of temperature ranges, appropriate rise temperature
Degree is conducive to the progress of thio reaction, and curing efficiency improves, but temperature easily causes the decomposition of vulcanizing agent more than 70 DEG C, on the contrary
Curing efficiency can be reduced, therefore is preferably optimal reaction temperature in 60~70 DEG C of temperature.The preferable reaction time is 6~12h,
More preferably it is 8~12h, more preferably 10~12h.In the range of 4~12h, the proper extension reaction time is conducive to thio reaction
Progress, curing efficiency improves, but the reaction time extends to 12h, and curing efficiency is close to 100%, therefore preferably in 10~12h
For the optimal reaction time.
More preferably scheme, the thio reaction add alkali as neutralization reagent with control reaction end pH 8~9 it
Between.
What technical scheme mainly solved is in the prior art using vulcanized sodium, NaHS and carbon disulfide etc.
To in a small amount of molybdenum making choice property sulfidation in tungstate solution containing molybdenum, there is easily release pernicious gas, and vulcanizing in vulcanizing agent
The problems such as efficiency is low, complex process.Technical scheme uses a kind of organic sulfurizing agent trithiocyanuric acid (salt) first, its
With stable triazine structure, molybdenum match ion can be generated with molybdenum acid ion reaction, does not have hydrogen sulfide in reaction process
Discharged Deng pernicious gas, working environment can be improved, the extractibility of the molybdenum match ion particularly generated is strong, after being conducive to
Continuous tungsten separation.
The vulcanizing agent of the present invention is trithiocyanuric acid (salt), and (trithiocyanuric acid is also known as 2,4,6- tri-thiol-S- triazines, sulphur
For cyanuric acid, tri-thiol s-triazine, vulcanizing agent TMT, three thio cyanuric acids, thiocyanuric acid, symmetrical three mercaptan；Trithiocyanuric acid
Salt can be trithiocyanuric acid alkali metal salt or trithiocyanuric acid ammonium salt；Cyclo-trithocyanates include a salt, disalt or three salt).
The molecular structure of TTCA and its trisodium salt and three ammonium salts exemplified below：
The shape of trithiocyanuric acid (salt) can be flaxen powder or bulk, if block, can suitably it crush
After use, can also wiring solution-forming use.A relatively stable triazine heterocycle and 3 is included in trithiocyanuric acid (salt) molecular structure
A sulfydryl (or sulphur anion).Vulcanization reaction is illustrated by taking trithiocyanuric acid as an example, its sulfydryl is carried out with molybdenum acid ion
The molybdenum sulphur complex of reaction generation ion centered on molybdenum atom.Specific reaction is as follows：
The sodium salt or ammonium salt of TTCA carries out reaction generation molybdenum sulphur of ion centered on molybdenum atom with molybdenum acid ion and matches somebody with somebody
Compound, specific reaction are as follows：
Wherein RS3-Structure it is as follows：
Since trithiocyanuric acid (or a salt or disalt) can ionize out hydrogen ion, mixing is molten for the thioated reaction of the present invention
The acidity of liquid can be raised somewhat, and pH value can decline, and the adjusting such as sodium hydroxide, carbonate and ammonium hydroxide can be added in system
The pH value of thio reaction product.
Compared with the prior art, the advantageous effects that technical scheme is brought：
Technical solution of the present invention successfully synthesizes sulphur using trithiocyanuric acid (salt) as sulfiding reagent with molybdic acid reactant salt first
For molybdate.
Technical scheme using trithiocyanuric acid (salt) as sulfiding reagent compared with the prior art in vulcanizing agent tool
There is obvious advantage, be mainly manifested in safe and non-toxic, no pernicious gas release, and curing efficiency is high, the Thiomolybdate of generation
Can be strong with extractibility, be conducive to tungsten separation.
Vulcanizing agent of the present invention is nontoxic solid, can greatly reduce the expense in terms of storage, transport, should not during use
The equipment of increase ventilation discharge hydrogen sulfide gas, can achieve the purpose that clean and safe production, and the thioated time can contract significantly
It is short, it is about the 1/4~1/3 of the traditional handicraft time.
Brief description of the drawings
【Fig. 1】Tungsten extract and separate effect song is carried out using various concentrations extractant after over cure for tungstates containing molybdenum
Line.
【Fig. 2】For the infrared figure of the Thiomolybdate of the present invention.
Embodiment
Son is further described below the present invention in conjunction with specific embodiments：All specific implementations of the invention below
In example, for vulcanizing agent all using novel organic sulfur agent described above, feed liquid is ammonium tungstate or sodium tungstate solution containing molybdenum.System
Preparation Method is carried out by above method, is described again here.
Embodiment 1
Vulcanizing agent is powdery TTCA, and feed liquid is the ammonium tungstate solution containing molybdenum that laboratory is prepared：Contain Mo1g/L, WO in feed liquid3
100g/L.The original pH=9.5 of feed liquid.200mL feed liquids are taken, adding TTCA1.47g, (molar ratio of molybdenum and vulcanizing agent is 1：4), mix
Close, stirring, is heated to 70 DEG C.Insulation reaction 12h, the terminal pH that solution is adjusted with ammonium hydroxide is 8.5 or so.
Thioated degree is examined with extraction, organic phase composition used is：10%N263+30%+60% sulfonated kerosenes, extraction
Take and be in a ratio of 1：Stratification after ten minutes is shaken at 1,25 DEG C under Kang Shi oscillators, separates molybdenum in water phase post analysis raffinate
Content.Since thiomolybdate is extracted by N263 very capable, therefore think that the content of molybdenum in raffinate does not cure as
Molybdenum, then the vulcanization rate of molybdenum is calculated by minusing.
Testing result：The thio rate of molybdenum is 60.24% in the present embodiment.
Embodiment 2
Feed liquid composition is identical with example 1, but the amount for adding TTCA changes, and distinguishes by the molar ratio of molybdenum and TTCA
For 1:4,1:8,1：10,1:16,1:20 add TTCA.Mixing, stirring, is heated to 70 DEG C.Insulation reaction 12h, is adjusted with ammonium hydroxide
Terminal PH=8.5 or so.By the detection method in embodiment 1, vulcanization rate such as following table of each condition in molybdenum is measured.
Influence of the addition of 1 vulcanizing agent of table to molybdenum vulcanization effect
| n(Mo):n(vulcanizing agent) | 1:4 | 1:8 | 1:10 | 1:16 | 1:20 |
| The vulcanization rate (%) of molybdenum | 60.80 | 78.9 | 92.39 | 98.26 | 100 |
As can be seen from Table 1, when the timing of temperature one, in identical vulcanization time, with the increase of vulcanizing agent dosage, molybdenum
State of cure (vulcanization) dramatically increase.
Embodiment 3
Feed liquid is formed with completely the same in embodiment 1, and the amount for adding TTCA is that (molar ratio of molybdenum and TTCA are 1 to 5.91g:
16), but the temperature of reaction changes, and controlling reaction temperature is respectively 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, insulation reaction 12h,
Control terminal pH=8.5 or so.By the detection method in embodiment 1, vulcanization rate such as following table of each condition in molybdenum is measured.
The influence of 2 reaction temperature molybdenum vulcanization effect of table
| Reaction temperature (DEG C) | 40 | 50 | 60 | 70 |
| The vulcanization rate (%) of molybdenum | 36.74 | 58.34 | 86.57 | 100 |
As can be seen from Table 2 when the timing of dosage one of TTCA, with the raising of reaction temperature, the vulcanization effect of molybdenum significantly carries
Height, therefore appropriate rise temperature is conducive to the thioated of molybdenum.But excessive temperature may result in the decomposition of organic sulfurizing agent.
Embodiment 4
Feed liquid is formed with completely the same in embodiment 1, and the amount for adding TTCA is that (molar ratio of molybdenum and TTCA are 1 to 5.91g:
16) reaction time, is only changed, the reaction time is respectively 4h, 6h, 8h, 10h, 12h.By the detection method in embodiment 1, measure
Vulcanization rate such as following table of each condition in molybdenum.
The influence of 3 reaction time of table molybdenum vulcanization effect
| Reaction time (h) | 4 | 6 | 8 | 10 | 12 |
| The vulcanization rate (%) of molybdenum | 94.75 | 97.82 | 99.48 | 99.77 | 100 |
From table 4, it can be seen that suitably under conditions of certain temperature and control TTCA dosages, extending vulcanization time can be with
The vulcanization rate of molybdenum is improved, the influence of vulcanization time is not so good as vulcanizing agent dosage and reaction temperature is so notable.
Embodiment 5
Feed liquid prepares ammonium tungstate solution containing molybdenum, solution 0.5g/L containing Mo, 1g/L, 2.5g/L, 5.5g/ respectively for laboratory
L, WO3100g/L.200mL solution is taken respectively, is 1 by the molar ratio of molybdenum and TTCA:16 are separately added into vulcanizing agent 2.95g,
5.91g, 14.77g, 32.49g.Reaction temperature is 70 DEG C, reaction time 12h, and it is 8.5 or so to adjust terminal pH with ammonium hydroxide.Press
Detection method in embodiment 1, measures vulcanization rate such as following table of each condition in molybdenum.
Influence of the content of 4 molybdenum of table to molybdenum vulcanization effect
As can be seen from Table 4, no matter the content of molybdenum is how many in ammonium tungstate solution, as long as controlling suitable vulcanizing agent dosage
And temperature, good vulcanization effect can be reached.
Embodiment 6
Feed liquid prepares ammonium tungstate solution containing molybdenum, solution 1g/L containing Mo, WO for laboratory3Content be respectively 100g/L,
120g/L, 160g/L, 200g/L.200mL feed liquids are taken, the amount for adding TTCA is that (molar ratio of molybdenum and TTCA are 1 to 5.91g:16),
Mixing, stirring, is heated to 70 DEG C.Insulation reaction 12h, terminal PH=8.5 or so is adjusted with ammonium hydroxide.By the detection in embodiment 1
Method, measures vulcanization rate such as following table of each condition in molybdenum.
Influence of the content of 5 tungsten of table to molybdenum vulcanization effect
| The content (g/L) of tungsten | 100 | 120 | 160 | 200 |
| The vulcanization rate (%) of molybdenum | 100 | 100 | 100 | 100 |
As can be seen from Table 5, no matter the content of tungsten is how many in ammonium tungstate solution, as long as controlling suitable vulcanizing agent dosage
And temperature, good vulcanization effect can be reached
Embodiment 7
Feed liquid prepares ammonium tungstate solution containing molybdenum, solution 1g/L containing Mo, WO for laboratory3Content be respectively 100g/L, take
200mL feed liquids, the amount for adding TTCA are that (molar ratio of molybdenum and vulcanizing agent is 1 to 5.91g:16), mix, stirring, is heated to 70 DEG C.
Insulation reaction 6h, terminal pH=8.5 or so is adjusted with ammonium hydroxide.Used again after solution after reaction is taken out still aging 36h
The vulcanization rate of method detection molybdenum in embodiment 1.The result shows that the vulcanization rate of molybdenum is 97.52%.Compared with non-aged solution
The vulcanization rate of molybdenum does not raise.Illustrate that digestion time has no effect on the vulcanization rate of molybdenum.
Embodiment 8
The sodium tungstate solution containing molybdenum that feed liquid is prepared for laboratory, solution 4g/L containing Mo, containing WO3100g/L, original solution
PH value be 7.5 or so.200mL feed liquids are taken, adding TTCA3g, (molar ratio of molybdenum and TTCA are 1:2), mix, stir, heating
To 70 DEG C of insulation reaction 12h.The vulcanization rate of molybdenum is 99.58% under the conditions of measuring this with the detection method in embodiment 1.
Embodiment 9
It is consistent in feed liquid used and embodiment 8, the pH to 10 of solution is adjusted with NaOH, add TTCA3g (molybdenum and TTCA's
Molar ratio is 1:2), mix, stirring, is heated to 70 DEG C of insulation reaction 12h.With the detection method in embodiment 1, measure at this
The vulcanization rate of molybdenum is 60.15% under part.
Embodiment 10
Feed liquid composition is identical with example 1, is 1 by the molar ratio of molybdenum and TTCA:20 add vulcanizing agent.Mixing, stirring,
It is heated to 70 DEG C.Insulation reaction 12h, terminal pH=9.5 or so is adjusted with ammonium hydroxide.The vulcanization rate of molybdenum is 100% at this time.With
N1923 is extractant, and extractant+sulfonated kerosene that volume fraction is 15%~50% various concentrations (volume fraction) is respectively adopted
Organic phase to after vulcanization feed liquid carry out extraction experiments.As a result it is illustrated in fig. 1 shown below.
Embodiment 11
Vulcanizing agent is powdery TTCA, and feed liquid is the pure ammonium molybdate solution that laboratory is prepared：Contain Mo1g/L in feed liquid.Feed liquid
Original pH=9.5.200mL feed liquids are respectively taken, the molar ratio by molybdenum and TTCA is respectively 1:4,1:8,1：10,1:16,1:20 add
Vulcanizing agent.Mixing, stirring, is heated to 70 DEG C.Insulation reaction 8h, terminal pH=8.5 or so is adjusted with ammonium hydroxide.By in embodiment 1
Detection method, measure vulcanization rate such as following table of each condition in molybdenum.
Influence of the addition of 6 vulcanizing agent of table to molybdenum vulcanization effect
| n(Mo):n(vulcanizing agent) | 1:4 | 1:8 | 1:10 | 1:16 | 1:20 |
| The vulcanization rate (%) of molybdenum | 64.80 | 82.9 | 93.39 | 99.26 | 100 |
Embodiment 12
Vulcanizing agent is the trisodium salt of TTCA, and feed liquid is the pure sodium molybdate solution that laboratory is prepared, 1g/ containing Mo in feed liquid
L.The original pH=7.5 of feed liquid.200mL feed liquids are taken, by molybdenum and RS3-Molar ratio be 1:16 add the sodium salt of TTCA.Mixing, is stirred
Mix, be heated to 70 DEG C.Insulation reaction 8h, terminal pH=7.2 or so is adjusted with sulfuric acid.By the detection method in embodiment 1, measure
Each condition is 90.6% in the vulcanization rate of molybdenum.
Embodiment 13
Vulcanizing agent is three ammonium salts of TTCA, and feed liquid is the pure molybdic acid ammonia solution that laboratory is prepared, 1g/ containing Mo in feed liquid
L.The original pH=7.5 of feed liquid.200mL feed liquids are taken, by molybdenum and RS3-Molar ratio be 1:16 add the ammonia salt of TTCA.Mixing, is stirred
Mix, be heated to 70 DEG C.Insulation reaction 8h, terminal pH=8.5 or so is adjusted with ammonium hydroxide.By the detection method in embodiment 1, measure
Each condition is 99.6% in the vulcanization rate of molybdenum.
Shown in infared spectrum Fig. 2 of sulfur product, in the FT-IR collection of illustrative plates of the product, 493.36cm-1Locate as Mo-S keys
Stretching vibration peak, illustrates to generate Mo-S keys.
Claims (9)
1. a kind of method of molybdate and trithiocyanuric acid (salt) reaction synthesis Thiomolybdate, it is characterised in that：In solution body
In system, molybdate carries out thio reaction with trithiocyanuric acid and/or cyclo-trithocyanates, obtains Thiomolybdate.
2. the method for a kind of molybdate according to claim 1 and trithiocyanuric acid (salt) reaction synthesis Thiomolybdate,
It is characterized in that：Trithiocyanuric acid and the cyclo-trithocyanates integral molar quantity is 4~20 times of molybdate mole.
3. the method for molybdate according to claim 1 and trithiocyanuric acid (salt) reaction synthesis Thiomolybdate, it is special
Sign is：
The molybdate includes alkali metal molybdate and/or dimolybdate salt；
The cyclo-trithocyanates are trithiocyanuric acid ammonium salt and/or trithiocyanuric acid alkali metal salt.
4. thio molybdic acid is synthesized according to a kind of molybdate of claims 1 to 3 any one of them and trithiocyanuric acid (salt) reaction
The method of salt, it is characterised in that：The condition of the thio reaction is：Temperature is 40 DEG C~70 DEG C, and the reaction time is small for 4~12
When.
A kind of 5. method that Thiomolybdate is prepared by tungstate solution containing molybdenum, it is characterised in that：Tungstate solution containing molybdenum and three
Polysulfide cyanic acid and/or cyclo-trithocyanates carry out thio reaction, obtain the tungstate solution containing Thiomolybdate.
A kind of 6. method that Thiomolybdate is prepared by tungstate solution containing molybdenum according to claim 5, it is characterised in that：
Molybdenum exists with molybdenum acid ion in the tungstate solution containing molybdenum, and the concentration of molybdenum is 0.5~4g/L, and tungsten is deposited with tungstate ion
The concentration of tungsten is with WO3Metering, is 100~200g/L.
A kind of 7. method that Thiomolybdate is prepared by tungstate solution containing molybdenum according to claim 5, it is characterised in that：
Trithiocyanuric acid and the cyclo-trithocyanates integral molar quantity is 4~20 times of molybdenum mole in tungstate solution containing molybdenum.
8. according to a kind of method that Thiomolybdate is prepared by tungstate solution containing molybdenum of claim 5~7 any one of them, its
It is characterized in that：The condition of the thio reaction is：Temperature is 40 DEG C~70 DEG C, when the reaction time is 4~12 small.
A kind of 9. method that Thiomolybdate is prepared by tungstate solution containing molybdenum according to claim 8, it is characterised in that：
The thio reaction adds alkali as neutralization reagent to control reaction end pH between 8~9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534403A (en) * | 2019-01-21 | 2019-03-29 | 中南大学 | A kind of method of molybdenum in Strong acid ion-exchanger tungstate solution |
| CN112077330A (en) * | 2020-08-26 | 2020-12-15 | 贵研铂业股份有限公司 | Superfine spherical tungsten powder and preparation method thereof |
| CN114939482A (en) * | 2022-05-31 | 2022-08-26 | 西安建筑科技大学 | Method for improving molybdenite flotation index through reduction fine grinding |
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| CN109534403A (en) * | 2019-01-21 | 2019-03-29 | 中南大学 | A kind of method of molybdenum in Strong acid ion-exchanger tungstate solution |
| CN112077330A (en) * | 2020-08-26 | 2020-12-15 | 贵研铂业股份有限公司 | Superfine spherical tungsten powder and preparation method thereof |
| CN114939482A (en) * | 2022-05-31 | 2022-08-26 | 西安建筑科技大学 | Method for improving molybdenite flotation index through reduction fine grinding |
| CN114939482B (en) * | 2022-05-31 | 2024-02-20 | 西安建筑科技大学 | Method for improving molybdenite flotation index through reduction fine grinding |
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