CN105154169B - A kind of tungsten disulfide/molybdenum disulfide/montmorillonite composite and preparation method thereof - Google Patents
A kind of tungsten disulfide/molybdenum disulfide/montmorillonite composite and preparation method thereof Download PDFInfo
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Abstract
A kind of tungsten disulfide/molybdenum disulfide/montmorillonite composite and preparation method thereof, is related to lubricant and photocatalyst technology field.Utilize strong acid activation montmorillonite surface；It is hydrolyzed under strongly acidic conditions by thioacetamide again and generates hydrogen sulfide come molybdenum sulfide hydrochlorate, so as to obtain amorphous state molybdenum sulfide；Meanwhile tungstates is acidified by strong acid and obtains aqua oxidation tungsten, amorphous state molybdenum sulfide is co-precipitated from reaction system in the montmorillonite of activation with aqua oxidation tungsten, generates compound precursor；The presoma and elemental sulfur are mixed and heated vulcanization again makes tungsten oxide be changed into tungsten disulfide, and then reheating makes amorphous state molybdenum sulfide calcine desulfurization, obtains tungsten disulfide/molybdenum disulfide/montmorillonite composite.Preparation process is simple, and rapid reaction, production cost is low, suitable for mass production.
Description
Technical field
The present invention relates to lubricants and photocatalyst technology field, are specifically related to a kind of tungsten disulfide/molybdenum disulfide/illiteracy
De- soil compound and preparation method thereof.
Background technology
Montmorillonite is a kind of natural layered silicate mineral, is existed in fields such as polymer modification, catalyst, lubricants wide
General application.Tungsten disulfide and molybdenum disulfide are two kinds of typical stratiform transition metal binary sulfides, are common solid profits
Lubrication prescription and Hydrobon catalyst, more in recent years research shows that both sulfide also have good photocatalysis performance.Although
The greasy property of tungsten disulfide and molybdenum disulfide is good with catalytic performance, but their performance need into one in many situations
Step is promoted.Recently some research shows that, between different inorganic lubricant or catalyst there may be certain collaboration lubrication with
Concerted catalysis acts on.The compound for preparing different lubricants or catalyst has mechanical blending method and chemical synthesis, chemical synthesis
Method can overcome the shortcomings that mechanical blending method, the chemical grade dispersion between different inorganic matters can be realized, so as to carry to the maximum extent
Rise the performance of compound.
Amorphous state molybdenum sulfide can be prepared (main component is non-by being reacted in acid condition with molybdate using sulfide
Crystalline state molybdenum sulfide) (Chinese patent 200710019871.8), then can obtain molybdenum disulfide after calcining desulfurization under protective atmosphere；This
Outside, research shows that strong acid can make molybdenum disulfide be uniformly deposited on natural minerals surface with the surface of active natural mineral, from
And obtain the compound (Chinese patent 201210078581.1) of finely dispersed molybdenum disulfide and natural minerals.However with equally
Method be difficult to prepare tungsten disulfide, be primarily due to the oxide that tungstates easily generates wolframic acid or tungsten under the conditions of salt acidic
(Chinese patent 201210078592.X), if wanting, presoma is co-precipitated out under the conditions of salt acidic obtains curing by calcining again
Tungsten/molybdenum disulfide/montmorillonite composite is difficult.
Invention content
In order to overcome drawbacks described above in the prior art, one of the objects of the present invention is to provide a kind of superior performances
Tungsten disulfide/molybdenum disulfide/montmorillonite composite, to realize the purpose, present invention employs following technical schemes：
A kind of tungsten disulfide/molybdenum disulfide/montmorillonite composite, by three kinds of tungsten disulfide, molybdenum disulfide, montmorillonite components
It forms.
Another object of the present invention is to provide a kind of preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite,
To realize the purpose, present invention employs following technical schemes：
A kind of preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite utilizes strong acid activation montmorillonite surface；
It is hydrolyzed in acid condition by thioacetamide again and generates hydrogen sulfide come molybdenum sulfide hydrochlorate, so as to obtain amorphous state molybdenum sulfide；
Meanwhile tungstates is acidified by hydrochloric acid and obtains wolframic acid (aqua oxidation tungsten), amorphous state molybdenum sulfide and wolframic acid from reaction system
It is co-precipitated in montmorillonite into compound precursor；The compound precursor and elemental sulfur are mixed and heated vulcanization again makes tungsten oxide
It is changed into tungsten disulfide, then reheating makes amorphous state molybdenum sulfide calcine desulfurization, and finally cooling obtains tungsten disulfide/curing
Molybdenum/montmorillonite composite.
Specifically, the preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite, step are as follows：
1., by following proportioning prepare raw material
The mass ratio of molybdate and thioacetamide is 1: 1~50；
The mass ratio of tungstates and elemental sulfur is 1: 0.2~20；
Molybdate and the mass ratio of tungstates gross mass and water are 1: 10~2000；
Molybdate and tungstates gross mass and the mass ratio of montmorillonite 1: 0.1~10；
2., thioacetamide, molybdate, tungstates be dissolved in enough water, add in montmorillonite in above-mentioned solution, add
Then heat adds in hydrochloric acid to pH value and is less than 1, before obtaining molybdenum sulfide and wolframic acid compound by coprecipitation reaction to 60~100 DEG C
Body is driven, co-precipitation presoma is filtered, washed and is mixed with after drying with enough elemental sulfurs, is then placed in N2Or rare gas is protected
It protects and vulcanization is heated in atmosphere, then heating and calcining desulfurization, and by excessive elemental sulfur evaporative removal, most two sulphur are obtained through cooling afterwards
Change tungsten/molybdenum disulfide/montmorillonite composite.
The preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite as the present invention, the molybdate are molybdic acid
At least one of sodium, ammonium molybdate and potassium molybdate.The tungstates is at least one of sodium tungstate, ammonium tungstate and potassium tungstate.Heating
Curing temperature is 250~445 DEG C, and heating vulcanization time is 5~200 minutes.It is 446~1000 DEG C to calcine desulfurization temperature, calcining
Desulfurization time is 5~200 minutes.
The preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite, is reacted as follows：
Step 1 (montmorillonite surface active, thioacetamide hydrolysis, precipitation reaction)：
Montmorillonite+H+→ montmorillonite (surface active)
CH3CSNH2+H++H2O→H2S↑+CH3COOH+NH4 +
H2S+MoO4 2-+WO4 2-+H+→H2WO4(WO3·H2O)/MoS3/ montmorillonite ↓+H2O
Step 2 (heats sulfidation-oxidation tungsten tungsten disulfide, with N in protective atmosphere2For, 250-445 DEG C)：
(if 390 DEG C of heating temperature ＞).
Step 3 (heats, with N in protective atmosphere2For, 446-1000 DEG C)：
(being more than the boiling point of sulphur, evaporate sulphur removal)
Compared with prior art, beneficial effects of the present invention are shown：
1), tungsten disulfide/molybdenum disulfide/montmorillonite composite is by three kinds of tungsten disulfide, molybdenum disulfide and montmorillonite components
It forms, it is using tungsten disulfide, molybdenum disulfide and the triangular collaboration of montmorillonite lubricates and synergic catalytic effect, can be abundant
The greasy property and catalytic performance of three kinds of components are played, and then it is made to have in known or tera incognita and is more broadly applied.
2), preparation method of the invention avoids directly synthesis amorphous state tungsten sulfide, molybdenum sulfide and montmorillonite tri compound
The step of object, and amorphous state molybdenum sulfide and wolframic acid compound are first obtained in the montmorillonite of strong acid activation, vulcanize using heating
Synthesize tungsten disulfide/molybdenum disulfide/montmorillonite composite with after calcining desulfurization, the coprecipitation reaction method used, first, molybdenum
Precipitation reaction occurs in acid condition for the hydrogen sulfide that hydrochlorate, thioacetamide hydrolysis generate；Another is tungstates in acid item
Wolframic acid precipitation is generated under part.
3), the preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite can either reduce synthesis cost, shorten and close
Into the time, the dispersibility between tungsten disulfide, molybdenum disulfide and montmorillonite component can also be improved, it is compound to further improve this
The greasy property and catalytic performance of object.Preparation process is simple, and rapid reaction, production cost is low, suitable for mass production.
Description of the drawings
Fig. 1 is the powder X-ray of tungsten disulfide/molybdenum disulfide/montmorillonite composite synthesized by method provided by the invention
X ray diffraction collection of illustrative plates.
The main diffraction peak (according to PDF cards 130135) of montmorillonite can be found from figure, show there is montmorillonite in product；
However molybdenum disulfide is similar to tungsten disulfide structure, and they in PDF cards, (molybdenum disulfide and tungsten disulfide are respectively 872416
With No. 841398 PDF cards) on x-ray diffractogram of powder spectrum it is basically identical, therefore x-ray diffractogram of powder spectrum can only show to deposit
In one or both of tungsten disulfide and molybdenum disulfide, chemical analysis has been carried out again on this basis, in final certification product
Containing molybdenum, wolfram element, two kinds of constituent content ratios change as reactant ratio changes, indicated above successfully to have synthesized two sulphur
Change tungsten/molybdenum disulfide/montmorillonite composite.
Specific embodiment
Embodiment 1
1 part of sodium molybdate, 1.5 parts of sodium tungstates and 3 parts of thioacetamides are dissolved in 120 parts of water, add in 2 parts of montmorillonites,
It heats while stirring to 82 DEG C, adds in concentrated hydrochloric acid and adjust pH value to 0.5, at this moment coprecipitation reaction starts, and passes through after reaction
The presoma of compound is filtered, washed, being dried to obtain, presoma is uniformly mixed with 10 parts of elemental sulfurs, then mixture is put into logical
Enter N2Tube furnace in be heated to 300 DEG C and keep the temperature 60 minutes, then by temperature be increased to 600 DEG C and keep the temperature 30 minutes, finally
It is cooled to room temperature and takes out sample to obtain tungsten disulfide/molybdenum disulfide/montmorillonite composite.(as shown in Fig. 1 collection of illustrative plates).
Embodiment 2
1 part of ammonium molybdate, 1.5 parts of ammonium tungstates and 3 parts of thioacetamides are dissolved in 120 parts of water, it is de- to add in 0.5 part of illiteracy
Soil heats while stirring to 82 DEG C, addition concentrated hydrochloric acid adjusting pH value to 0.5, and at this moment coprecipitation reaction starts, and passes through after reaction
The presoma of compound is filtered, washed, be dried to obtain, presoma is uniformly mixed, then mixture is put into 10 parts of elemental sulfurs
It is passed through in the tube furnace of Ar gas and is heated to 300 DEG C and keeps the temperature 60 minutes, temperature is then increased to 600 DEG C and keeps the temperature 30 minutes,
It is finally cooled to room temperature and takes out to obtain tungsten disulfide/molybdenum disulfide/montmorillonite composite by sample (be similar to Fig. 1 collection of illustrative plates institute
Show).
Embodiment 3
1 part of potassium molybdate, 1.5 parts of potassium tungstates and 3 parts of thioacetamides are dissolved in 120 parts of water, add in 10 parts of montmorillonites,
It heats while stirring to 82 DEG C, adds in concentrated hydrochloric acid and adjust pH value to 0.5, at this moment coprecipitation reaction starts, and passes through after reaction
The presoma of compound is filtered, washed, being dried to obtain, presoma is uniformly mixed with 10 parts of elemental sulfurs, then mixture is put into logical
Enter N2Tube furnace in be heated to 300 DEG C and keep the temperature 60 minutes, then by temperature be increased to 600 DEG C and keep the temperature 30 minutes, finally
It is cooled to room temperature and takes out sample to obtain tungsten disulfide/molybdenum disulfide/montmorillonite composite (being similar to shown in Fig. 1 collection of illustrative plates).
Embodiment 4
1 part of sodium molybdate, 2 parts of ammonium tungstates and 20 parts of thioacetamides are dissolved in 500 parts of water, add in 3 parts of montmorillonites, side
Heating side is stirred to 70 DEG C, addition concentrated hydrochloric acid adjusting pH value to 0.1, and at this moment coprecipitation reaction starts, filtered after reaction,
The presoma of compound is washed, be dried to obtain, presoma is uniformly mixed, then mixture is put into and is passed through N with 20 parts of elemental sulfurs2
Tube furnace in be heated to 420 DEG C and keep the temperature 30 minutes, then by temperature be increased to 500 DEG C and keep the temperature 60 minutes, finally cool down
Sample taken out to room temperature to obtain tungsten disulfide/molybdenum disulfide/montmorillonite composite (being similar to shown in Fig. 1 collection of illustrative plates).
Embodiment 5
1 part of potassium molybdate, 0.5 part of sodium tungstate and 30 parts of thioacetamides are dissolved in 1000 parts of water, it is de- to add in 10 parts of illiteracies
Soil heats while stirring to 95 DEG C, addition concentrated hydrochloric acid adjusting pH value to 0.2, and at this moment coprecipitation reaction starts, and passes through after reaction
The presoma of compound is filtered, washed, be dried to obtain, presoma is uniformly mixed with 2 parts of elemental sulfurs, then mixture is put into logical
Enter N2Tube furnace in be heated to 380 DEG C and keep the temperature 50 minutes, then by temperature be increased to 900 DEG C and keep the temperature 10 minutes, finally
It is cooled to room temperature and takes out sample to obtain tungsten disulfide/molybdenum disulfide/montmorillonite composite (being similar to shown in Fig. 1 collection of illustrative plates).
Claims (4)
1. a kind of preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite, it is characterised in that：It is activated and covered using strong acid
De- soil surface；It is hydrolyzed under strongly acidic conditions by thioacetamide again and generates hydrogen sulfide come molybdenum sulfide hydrochlorate, it is non-so as to obtain
Crystalline state molybdenum sulfide；Meanwhile tungstates is acidified by strong acid and obtains aqua oxidation tungsten, amorphous state molybdenum sulfide and aqua oxidation tungsten are from anti-
Co-precipitation in system is answered in the montmorillonite of activation, to generate compound precursor；The presoma is mixed and added with elemental sulfur again
Heat cure makes tungsten oxide be changed into tungsten disulfide, and then reheating makes amorphous state molybdenum sulfide calcine desulfurization, obtains tungsten disulfide/bis-
Molybdenum sulfide/montmorillonite composite；
It is as follows：
1., by following proportioning prepare raw material
The mass ratio of molybdate and thioacetamide is 1: 1~50；
The mass ratio of tungstates and elemental sulfur is 1: 0.2~20；
Molybdate and the mass ratio of tungstates gross mass and water are 1: 10~2000；
Molybdate and tungstates gross mass and the mass ratio of montmorillonite 1: 0.1~10；
2., thioacetamide, molybdate, tungstates be dissolved in enough water, add in montmorillonite in above-mentioned solution, be heated to
60~100 DEG C, then add in hydrochloric acid to pH value be less than 1, by the coprecipitation reaction in the montmorillonite of activation obtain molybdenum sulfide/
Presoma is filtered, washed and is mixed with after drying with enough elemental sulfurs, so by aqua oxidation tungsten/montmorillonite composite presoma
After be put into N2Or vulcanization is heated in rare gas protective atmosphere, it is then heated to 446~1000 DEG C and calcines desulfurization 5~200 minutes,
And by excessive elemental sulfur evaporative removal, most tungsten disulfide/molybdenum disulfide/montmorillonite composite is obtained through cooling afterwards.
2. the preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite as described in claim 1, it is characterised in that：Institute
Molybdate is stated as at least one of sodium molybdate, ammonium molybdate and potassium molybdate.
3. the preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite as described in claim 1, it is characterised in that：Institute
Tungstates is stated as at least one of sodium tungstate, ammonium tungstate and potassium tungstate.
4. the preparation method of tungsten disulfide/molybdenum disulfide/montmorillonite composite as described in claim 1, it is characterised in that：Add
Heat cure temperature is 250~445 DEG C, and heating vulcanization time is 5~200 minutes.
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| CN109852458B (en) * | 2019-03-22 | 2022-06-21 | 合肥学院 | Tungsten disulfide/fly ash compound lubricant and preparation method thereof |
| CN110295078B (en) * | 2019-07-18 | 2021-10-08 | 南京理工大学 | Functional graphene/montmorillonite/modified molybdenum sulfide lubricating oil additive |
| CN111569908A (en) * | 2020-06-04 | 2020-08-25 | 深圳市汇德丰控股集团有限公司 | Hydrodenitrogenation catalyst and preparation method and application thereof |
| CN111701599B (en) * | 2020-08-24 | 2021-01-01 | 山东海科创新研究院有限公司 | montmorillonite/TiO2@MoS2Preparation method of composite catalyst, product obtained by preparation method and application of composite catalyst |
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