CN105154169A - Tungsten disulfide/molybdenum disulfide/montmorillonite compound and preparation method thereof - Google Patents
Tungsten disulfide/molybdenum disulfide/montmorillonite compound and preparation method thereof Download PDFInfo
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- CN105154169A CN105154169A CN201510416871.6A CN201510416871A CN105154169A CN 105154169 A CN105154169 A CN 105154169A CN 201510416871 A CN201510416871 A CN 201510416871A CN 105154169 A CN105154169 A CN 105154169A
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- molybdenumdisulphide
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Abstract
The invention relates to a tungsten disulfide/molybdenum disulfide/montmorillonite compound and a preparation method thereof, and relates to the technical fields of lubricants and photocatalysts. The method comprises the following steps: activating the surface of montmorillonite by a strong acid; hydrolyzing thioacetamide under a highly acidic condition to generate hydrogen sulfide for sulfurating molybdate in order to obtain amorphous molybdenum sulfide; acidifying tungstate by a strong acid to obtain tungsten oxide hydrate, and co-precipitating the amorphous molybdenum sulfide and the tungsten oxide hydrate on activated montmorillonite from a reaction system to generate a compound precursor; and mixing the precursor with elemental sulfur, carrying out heating sulfuration to convert tungsten oxide into tungsten disulfide, and heating the amorphous molybdenum sulfide to carry out calcining desulphurization in order to obtain the tungsten disulfide/molybdenum disulfide/montmorillonite compound. The preparation method has the advantages of simplicity, fast reaction, low production cost, and suitableness for batch production.
Description
Technical field
The present invention relates to lubricant and photocatalyst technology field, specifically relate to a kind of tungsten disulfide/molybdenumdisulphide/montmorillonite composite and preparation method thereof.
Background technology
Polynite is a kind of natural layered silicate mineral, exists apply widely in fields such as polymer modification, catalyzer, lubricants.Tungsten disulfide and molybdenumdisulphide are two kinds of typical stratiform transition metal binary sulfides, are conventional solid lubricant and Hydrobon catalyst, and some researchs in recent years show that these two kinds of sulfide also have good photocatalysis performance.Although the lubricity of tungsten disulfide and molybdenumdisulphide and catalytic performance are well, their performance need further lifting in many situations.Some researchs recently show may there is certain collaborative lubrication and concerted catalysis effect between different inorganic lubricants or catalyzer.The mixture preparing different lubricant or catalyzer has mechanical blending method and chemical synthesis, and chemical synthesis can overcome the shortcoming of mechanical blending method, can realize the chemical grade dispersion between different inorganics, thus promote the performance of mixture to greatest extent.
Utilize sulfide and molybdate to react in acid condition and can prepare non-crystalline state moly-sulfide (main component is non-crystalline state moly-sulfide) (Chinese patent 200710019871.8), then can molybdenumdisulphide be obtained calcine desulfurization under protective atmosphere after; In addition, research shows that strong acid can the surface of active natural mineral, molybdenumdisulphide can be made to be deposited on natural mineral surface equably, thus obtain the mixture (Chinese patent 201210078581.1) of finely dispersed molybdenumdisulphide and natural mineral.But use the same method and be difficult to prepare tungsten disulfide, mainly because tungstate easily generates the oxide compound (Chinese patent 201210078592.X) of wolframic acid or tungsten under salt acidic condition, if to want under salt acidic condition, co-precipitation goes out presoma is difficult by calcining acquisition tungsten disulfide/molybdenumdisulphide/montmorillonite composite again.
Summary of the invention
In order to overcome the above-mentioned defect existed in prior art, an object of the present invention is the tungsten disulfide/molybdenumdisulphide/montmorillonite composite providing a kind of superior performance, for realizing this object, present invention employs following technical scheme:
A kind of tungsten disulfide/molybdenumdisulphide/montmorillonite composite, is made up of tungsten disulfide, molybdenumdisulphide, polynite three kinds of components.
Another object of the present invention is to the preparation method that a kind of tungsten disulfide/molybdenumdisulphide/montmorillonite composite is provided, for realizing this object, present invention employs following technical scheme:
A preparation method for tungsten disulfide/molybdenumdisulphide/montmorillonite composite, utilizes strong acid to activate polynite surface; Be hydrolyzed generation hydrogen sulfide in acid condition by thioacetamide again and carry out moly-sulfide hydrochlorate, thus obtain non-crystalline state moly-sulfide; Meanwhile, by hcl acidifying tungstate obtain wolframic acid (aqua oxidation tungsten), non-crystalline state moly-sulfide and wolframic acid from reaction system in polynite co-precipitation become compound precursor; This compound precursor being mixed also baking with elemental sulfur makes Tungsten oxide 99.999 change tungsten disulfide into again, then reheats and makes non-crystalline state moly-sulfide calcine desulfurization, and finally cooling obtains tungsten disulfide/molybdenumdisulphide/montmorillonite composite.
Concrete, the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite, step is as follows:
1., raw material is prepared by following proportioning
The mass ratio of molybdate and thioacetamide is 1: 1 ~ 50;
The mass ratio of tungstate and elemental sulfur is 1: 0.2 ~ 20;
The mass ratio of molybdate and tungstate total mass and water is 1: 10 ~ 2000;
The mass ratio 1: 0.1 ~ 10 of molybdate and tungstate total mass and polynite;
2., thioacetamide, molybdate, tungstate are dissolved in enough water, polynite is added in above-mentioned solution, be heated to 60 ~ 100 DEG C, then add hydrochloric acid and be less than 1 to pH value, moly-sulfide and wolframic acid compound precursor is obtained by coprecipitation reaction, the filtration of co-precipitation presoma, washing are mixed with enough elemental sulfurs with after drying, then puts into N
2or baking in rare gas protective atmosphere, then heating and calcining desulfurization, and by excessive elemental sulfur evaporative removal, obtain tungsten disulfide/molybdenumdisulphide/montmorillonite composite finally by cooling.
As the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite of the present invention, described molybdate is at least one in Sodium orthomolybdate, ammonium molybdate and potassium molybdate.Described tungstate is at least one in sodium wolframate, ammonium tungstate and potassium wolframate.Baking temperature is 250 ~ 445 DEG C, and the baking time is 5 ~ 200 minutes.Calcining desulfurization temperature is 446 ~ 1000 DEG C, and calcining desulfurization time is 5 ~ 200 minutes.
The preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite, reacts according to following process:
Step one (hydrolysis of polynite surface active, thioacetamide, precipitin reaction):
Polynite+H
+→ polynite (surface active)
CH
3CSNH
2+H
++H
2O→H
2S↑+CH
3COOH+NH
4 +
H
2s+MoO
4 2-+ WO
4 2-+ H
+→ H
2wO
4(WO
3h
2o)/MoS
3/ polynite ↓+H
2o
(baking Tungsten oxide 99.999 tungsten disulfide in protective atmosphere, with N for step 2
2for example, 250-445 DEG C):
(if Heating temperature > 390 DEG C).
Step 3 (heats in protective atmosphere, with N
2for example, 446-1000 DEG C):
(being greater than the boiling point of sulphur, evaporation sulphur removal)
Compared with prior art, beneficial effect of the present invention shows:
1), tungsten disulfide/molybdenumdisulphide/montmorillonite composite is made up of tungsten disulfide, molybdenumdisulphide and polynite three kinds of components, it utilizes the triangular collaborative lubrication of tungsten disulfide, molybdenumdisulphide and polynite and synergic catalytic effect, lubricity and the catalytic performance of three kinds of components can be given full play to, and then make it have in known or tera incognita to apply more widely.
2), preparation method of the present invention avoids the step of directly synthesis non-crystalline state tungsten sulfide, moly-sulfide and polynite ternary complex, and first in the polynite of strong acid activation, obtain non-crystalline state moly-sulfide and wolframic acid mixture, tungsten disulfide/molybdenumdisulphide/montmorillonite composite is synthesized again after baking and calcining desulfurization, there is precipitin reaction in acid condition in the hydrogen sulfide that the coprecipitation reaction method that it adopts one is molybdate, thioacetamide hydrolysis produces; Another is that tungstate generates wolframic acid precipitation in acid condition.
3), the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite can either reduce synthesis cost, shorten generated time, tungsten disulfide, dispersiveness between molybdenumdisulphide and polynite component can also be improved, to improve lubricity and the catalytic performance of this mixture further.Preparation technology is simple, and fast, production cost is low in reaction, is applicable to batch production.
Accompanying drawing explanation
Fig. 1 is the x-ray diffractogram of powder spectrum of the tungsten disulfide/molybdenumdisulphide/montmorillonite composite synthesized by method provided by the invention.
The main diffraction peak (according to PDF card 130135) of polynite all can find from figure, shows there is polynite in product; But molybdenumdisulphide and tungsten disulfide structural similitude, and their x-ray diffractogram of powder on PDF card (molybdenumdisulphide and tungsten disulfide are respectively 872416 and No. 841398 PDF cards) are composed basically identical, therefore x-ray diffractogram of powder spectrum can only show to exist one or both in tungsten disulfide and molybdenumdisulphide, carry out chemical analysis again on this basis, containing molybdenum, W elements in final certification product, two kinds of constituent contents change than along with reactant ratio change, more than show successfully to have synthesized tungsten disulfide/molybdenumdisulphide/montmorillonite composite.
Embodiment
Embodiment 1
1 part of Sodium orthomolybdate, 1.5 parts of sodium wolframates and 3 parts of thioacetamides are dissolved in 120 parts of water, add 2 parts of polynites, heat while stirring to 82 DEG C, add concentrated hydrochloric acid adjust ph to 0.5, at this moment coprecipitation reaction starts, after reaction terminates through filtering, washing, drying obtain the presoma of mixture, presoma is mixed with 10 parts of elemental sulfurs, then mixture is put into passes into N
2tube furnace in be heated to 300 DEG C and be incubated 60 minutes, subsequently temperature be elevated to 600 DEG C and be incubated 30 minutes, being finally cooled to room temperature and sample is taken out obtaining tungsten disulfide/molybdenumdisulphide/montmorillonite composite.(as shown in Fig. 1 collection of illustrative plates).
Embodiment 2
By 1 part of ammonium molybdate, 1.5 parts of ammonium tungstates and 3 parts of thioacetamides are dissolved in 120 parts of water, add 0.5 part of polynite, heat while stirring to 82 DEG C, add concentrated hydrochloric acid adjust ph to 0.5, at this moment coprecipitation reaction starts, through filtering after reaction terminates, washing, drying obtains the presoma of mixture, presoma is mixed with 10 parts of elemental sulfurs, again mixture is put into the tube furnace passing into Ar gas be heated to 300 DEG C and be incubated 60 minutes, subsequently temperature be elevated to 600 DEG C and be incubated 30 minutes, finally be cooled to room temperature and sample taking-up is obtained tungsten disulfide/molybdenumdisulphide/montmorillonite composite (being similar to shown in Fig. 1 collection of illustrative plates).
Embodiment 3
1 part of potassium molybdate, 1.5 parts of potassium wolframates and 3 parts of thioacetamides are dissolved in 120 parts of water, add 10 parts of polynites, heat while stirring to 82 DEG C, add concentrated hydrochloric acid adjust ph to 0.5, at this moment coprecipitation reaction starts, after reaction terminates through filtering, washing, drying obtain the presoma of mixture, presoma is mixed with 10 parts of elemental sulfurs, then mixture is put into passes into N
2tube furnace in be heated to 300 DEG C and be incubated 60 minutes, subsequently temperature be elevated to 600 DEG C and be incubated 30 minutes, being finally cooled to room temperature and sample is taken out obtaining tungsten disulfide/molybdenumdisulphide/montmorillonite composite (being similar to shown in Fig. 1 collection of illustrative plates).
Embodiment 4
1 part of Sodium orthomolybdate, 2 parts of ammonium tungstates and 20 parts of thioacetamides are dissolved in 500 parts of water, add 3 parts of polynites, heat while stirring to 70 DEG C, add concentrated hydrochloric acid adjust ph to 0.1, at this moment coprecipitation reaction starts, after reaction terminates through filtering, washing, drying obtain the presoma of mixture, presoma is mixed with 20 parts of elemental sulfurs, then mixture is put into passes into N
2tube furnace in be heated to 420 DEG C and be incubated 30 minutes, subsequently temperature be elevated to 500 DEG C and be incubated 60 minutes, being finally cooled to room temperature and sample is taken out obtaining tungsten disulfide/molybdenumdisulphide/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 wolframate and 30 parts of thioacetamides are dissolved in 1000 parts of water, add 10 parts of polynites, heat while stirring to 95 DEG C, add concentrated hydrochloric acid adjust ph to 0.2, at this moment coprecipitation reaction starts, after reaction terminates through filtering, washing, drying obtain the presoma of mixture, presoma is mixed with 2 parts of elemental sulfurs, then mixture is put into passes into N
2tube furnace in be heated to 380 DEG C and be incubated 50 minutes, subsequently temperature be elevated to 900 DEG C and be incubated 10 minutes, being finally cooled to room temperature and sample is taken out obtaining tungsten disulfide/molybdenumdisulphide/montmorillonite composite (being similar to shown in Fig. 1 collection of illustrative plates).
Claims (7)
1. tungsten disulfide/molybdenumdisulphide/montmorillonite composite, is characterized in that: this tungsten disulfide/molybdenumdisulphide/montmorillonite composite is made up of tungsten disulfide, molybdenumdisulphide and polynite three kinds of components.
2. a preparation method for tungsten disulfide/molybdenumdisulphide/montmorillonite composite as claimed in claim 1, is characterized in that: utilize strong acid to activate polynite surface; Be hydrolyzed generation hydrogen sulfide under strongly acidic conditions by thioacetamide again and carry out moly-sulfide hydrochlorate, thus obtain non-crystalline state moly-sulfide; Meanwhile, obtain aqua oxidation tungsten by strong acid acidifying tungstate, the co-precipitation from reaction system of non-crystalline state moly-sulfide and aqua oxidation tungsten, in the polynite activated, generates compound precursor; This presoma being mixed also baking with elemental sulfur makes Tungsten oxide 99.999 change tungsten disulfide into again, then reheats and makes non-crystalline state moly-sulfide calcine desulfurization, obtain tungsten disulfide/molybdenumdisulphide/montmorillonite composite.
3. the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite as claimed in claim 2, is characterized in that: step is as follows:
1., raw material is prepared by following proportioning
The mass ratio of molybdate and thioacetamide is 1: 1 ~ 50;
The mass ratio of tungstate and elemental sulfur is 1: 0.2 ~ 20;
The mass ratio of molybdate and tungstate total mass and water is 1: 10 ~ 2000;
The mass ratio 1: 0.1 ~ 10 of molybdate and tungstate total mass and polynite;
2., thioacetamide, molybdate, tungstate are dissolved in enough water, polynite is added in above-mentioned solution, be heated to 60 ~ 100 DEG C, then add hydrochloric acid and be less than 1 to pH value, moly-sulfide/aqua oxidation tungsten/montmorillonite composite presoma is obtained by the coprecipitation reaction in the polynite of activation, presoma filtration, washing are mixed with enough elemental sulfurs with after drying, then puts into N
2or baking in rare gas protective atmosphere, then heating and calcining desulfurization, and by excessive elemental sulfur evaporative removal, obtain tungsten disulfide/molybdenumdisulphide/montmorillonite composite finally by cooling.
4. the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite as claimed in claim 2 or claim 3, is characterized in that: described molybdate is at least one in Sodium orthomolybdate, ammonium molybdate and potassium molybdate.
5. the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite as claimed in claim 2 or claim 3, is characterized in that: described tungstate is at least one in sodium wolframate, ammonium tungstate and potassium wolframate.
6. the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite as claimed in claim 2 or claim 3, it is characterized in that: baking temperature is 250 ~ 445 DEG C, the baking time is 5 ~ 200 minutes.
7. the preparation method of tungsten disulfide/molybdenumdisulphide/montmorillonite composite as claimed in claim 2 or claim 3, is characterized in that: calcining desulfurization temperature is 446 ~ 1000 DEG C, and calcining desulfurization time is 5 ~ 200 minutes.
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Cited By (4)
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| CN109852458A (en) * | 2019-03-22 | 2019-06-07 | 合肥学院 | A kind of tungsten disulfide/flyash compound lubricant and preparation method thereof |
| CN110295078A (en) * | 2019-07-18 | 2019-10-01 | 南京理工大学 | A kind of functional graphene/montmorillonite/modified molybdenum sulphide lube 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 |
| CN111701599A (en) * | 2020-08-24 | 2020-09-25 | 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109852458A (en) * | 2019-03-22 | 2019-06-07 | 合肥学院 | A kind of tungsten disulfide/flyash compound lubricant and preparation method thereof |
| CN110295078A (en) * | 2019-07-18 | 2019-10-01 | 南京理工大学 | A kind of functional graphene/montmorillonite/modified molybdenum sulphide lube oil additive |
| 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 |
| CN111701599A (en) * | 2020-08-24 | 2020-09-25 | 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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