CN1548504A - Prepn of tungsten disulfide lubricant - Google Patents
Prepn of tungsten disulfide lubricant Download PDFInfo
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- CN1548504A CN1548504A CNA031223745A CN03122374A CN1548504A CN 1548504 A CN1548504 A CN 1548504A CN A031223745 A CNA031223745 A CN A031223745A CN 03122374 A CN03122374 A CN 03122374A CN 1548504 A CN1548504 A CN 1548504A
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- ammonium tungstate
- tungsten disulfide
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Abstract
The present invention is preparation process of tungsten disulfide lubricant with low running cost, high yield and environment friendship. The preparation process includes the reaction of ammonium tungstate solution with WO3 in 200-350 g/L and ammonium hydroxide in 14-15 N and H2S gas of 0.15-16 kg/sq cm in a sealed container under the temperature below 60 deg.c to produce crystal; purifying and drying crystal; introducing N2 to replace gas inside the furnace under reduction atmosphere; heating at 380-420 deg.c for 3-3.5 hr; heating at 1050-1100 deg.c for 15-16 hr; lower the temperature to room temperature under the N2 protection to obtain scaly tungsten disulfide; and crushing to obtain lubricant level tungsten disulfide.
Description
Technical field
The present invention relates to a kind of preparation method of tungsten compound, particularly relate to preparation method as the tungsten disulfide of lubricant.
Background technology
CN1224718A provides a kind of method of producing superfine scale crystal tungsten disulfide, this method is to be raw material with the tetrathio ammonium tungstate, under the condition of secluding air, thermal degradation tetrathio ammonium tungstate, thermograde with 100-200 ℃/hour during heating rises to 700-1200 ℃ from room temperature, and after being incubated 24-48 hour under this temperature, reduce to room temperature with 30-100 ℃/hour thermograde again, discharging is pulverized.It is said that this method can be produced the ultra-fine squamous tungsten disulfide of hexagonal product, after crushed, granularity is 2-20 μ m, and product purity is 99.50-99.99%.
In aforesaid method, mention that employed raw material tetrathio ammonium tungstate can be commercially available, also can be by method known to a person of ordinary skill in the art, promptly in the solution of ammonium tungstate, feed hydrogen sulfide and obtain.But in whole embodiments of this patent application, what all adopt is commercially available tetrathio ammonium tungstate.Its reason is, to use hydrogen sulfide when producing the tetrathio ammonium tungstate according to ordinary method, and produce hydrogen sulfide and utilize hydrogen sulfide and during ammonium tungstate prepared in reaction tetrathio ammonium tungstate, all can't guarantee that under lower cost hydrogen sulfide does not leak on the engineering.
In addition, the tetrathio ammonium tungstate is thermal degradation under the condition of secluding air, during actual production, can't realize, the product part of gained is oxidized, can only some salable product, and yield is lower.
Summary of the invention
Purpose of the present invention will overcome defective of the prior art exactly, and a kind of low operating cost, yield height and the method that prepare tungsten disulfide lubricant comparatively friendly to environment are provided.
The invention provides a kind of method for preparing tungsten disulfide lubricant, described method comprises the steps:
1) be 200-350g WO to concentration
3Logical liquefied ammonia in the/L ammonium tungstate solution makes the final ammonium hydroxide content of solution reach the resulting ammonium tungstate solution of 14-15N and gaseous tension at 0.35-16kg/cm
2Hydrogen sulfide, in sealed vessel, react, control reaction temperature descends until temperature of reaction below 60 ℃;
2) stop to add hydrogen sulfide in reaction system, behind the discharging tail gas, under the cool to room temperature, make the product crystallization, then, separation, purifying, drying obtain tetrathio ammonium tungstate crystal;
3) thermolysis of resulting tetrathio ammonium tungstate crystal is obtained tungsten disulfide;
4) tungsten disulfide that obtains is pulverized.
In one embodiment of the invention, the crystallization of product step 2) is to feed under the compressed nitrogen to carry out in the product behind discharging tail gas.It specifically is that according to stirring state, control feeds N
2The pressure of gas is generally 4-8kg/cm
2
In another embodiment of the invention, described step 3) is under reducing atmosphere, through logical N
2Behind the gas displacement furnace gas, be warming up to about 400 ℃, be generally and be warming up to 380-420 ℃, constant temperature 3-3.5 hour, be warming up to 1050-1100 ℃ again, constant temperature 15-16 hour, then, at N
2Be cooled to room temperature under the protection, obtain the flakey tungsten disulfide.
In yet another embodiment of the present invention, described step 4) is to utilize 2-16kg/cm
2Compression N
2Gas is used as power, and by air-flow it is ground into the particle that diameter is 2-4 μ m.
In one embodiment of the invention, described reducing atmosphere is to be produced by the high purity carbon of placing in the stove in the reaction later stage.
In another embodiment of the invention, the pressure of hydrogen sulfide is 0.5-2kg/cm in the step 1)
2
In yet another embodiment of the present invention, in step 1), after in ammonium tungstate solution, feeding liquefied ammonia,, the temperature of solution is elevated to 20-30 ℃ according to the situation of room temperature.
In embodiments of the invention, described method further comprises discharge tail gas in the burning entire method process.
Particularly, method provided by the present invention adopts ammonium tungstate solution and H
2S gas is at airtight vulcanizing apparatus (10) internal reaction, H
2S gas weighs in container and decides a steady pressure, produces and is suspended with the turbid liquid of tetrathio ammonium tungstate crystalline, and turbid liquid generates tetrathio ammonium tungstate crystal through crystallisation by cooling, through vacuum filtration, washing, cryodrying, makes tetrathio ammonium tungstate crystal.The thermolysis under reducing atmosphere in fixed-bed pyrolysis stove (13) of tetrathio ammonium tungstate crystal, earlier 380-420 ℃, preferably at 400 ℃ of constant temperature 3-3.5 hours, be preferably 3 hours, continue to be warmed up under 1050 ℃-1100 ℃, constant temperature 15-16 hour, make the flakey tungsten disulfide lubricant.At N
2Through comminution by gas stream, be the tungsten disulfide lubricant finished product under the gas shiled.
The used ammonium tungstate solution concentration of the present invention is 200-350g WO
3/ L, this solution aqua ammonia content is 0.1-10N, logical liquefied ammonia makes aqua ammonia content reach 14-15N.Ammonium tungstate solution concentration can not be greater than 350g WO
3/ L, otherwise ammonium tungstate can not fully dissolve.
When ammonium tungstate solution and stink damp precursor reactant, gaseous tension is no less than 0.035kg/cm
2, generally be at 0.35kg/cm
2-16kg/cm
2In, production control is at 0.5kg/cm
2-2kg/cm
2Scope in.Still contain some original tungsten in the turbid liquid that generates, all the other are mother liquor and saturated tetrathio ammonium tungstate.Logical H
2The time of S reaction is by container inner pressure, the decision of ammonium tungstate liquid concentration.The temperature of reaction upper limit is controlled at 50-60 ℃.
Entire reaction course is to carry out H under air-tight state
2S gas almost completely is absorbed and consumes, and has avoided H
2The waste of S gas is reconciled the Air Valve Control reaction pressure automatically by gas, keep-ups pressure to be stabilized on the value that needs.This reaction is thermopositive reaction.Liberated heat can elevate the temperature about 20-30 ℃ in reaction process.When temperature descends, show to react completely.
Stop to add H
2Unnecessary gas is discharged in other reactor in the S, vulcanizing apparatus (10).After the emptying, open blow-off valve emptying and burn, logical water quench, preferably feeding pressure is 4-8kg/cm
2Compression N
2Gas mixing is mixed, and makes tetrathio ammonium tungstate crystallisation by cooling, and when temperature is lower than room temperature, tapping is advanced vacuum filter (11) and separated, and obtains solid-state tetrathio ammonium tungstate crystal.
The tetrathio ammonium tungstate washing with ethanol after with " zwitterion exchange deionized water " washing on the strainer of vacuum filter (11) again, is removed impurity and remained in mother liquor on the tetrathio ammonium tungstate plane of crystal.Wash water is added in the mother liquor and reuses.The ethanol washing lotion is reusable, up to saturated, reclaims ethanol with distillation method then.Precipitation tungsten reclaims and uses in the washing lotion.
Contain ammonium hydroxide in the centrifugation mother liquor, ammonium tungstate, tetrathio ammonium tungstate and ammonium sulfide, this mother liquor add the logical liquefied ammonia Returning reacting system vulcanizing apparatus (10) of ammonium tungstate, continue preparation tetrathio ammonium tungstate with the hydrogen sulfide reaction.
With the tetrathio ammonium tungstate crystal that obtains, in loft drier (12), under 60 ℃, carry out drying, promptly obtain butt tetrathio ammonium tungstate crystal.
With the tetrathio ammonium tungstate of preparation, the molybdenum of packing into is done in the pot, in thermal decomposition furnace (13), is preferably fixed bed reduction furnace internal medicine and puts, and puts a small amount of high purity carbon in the furnace chamber, as, Graphite Electrodes causes reducing atmosphere.Logical N
2The displacement furnace gas after the displacement, is warmed up to earlier about 400 ℃, and about 3 hours of constant temperature then, is warming up to 1050-1100 ℃, and about 16 hours of constant temperature is at N
2Gas shiled is cooling down, treats that material reduces to the room temperature discharging, makes qualified flakey tungsten disulfide.The gas igniting that produces when intensification and constant temperature is burned.
In micronizer mill (14), utilize pressure to be 2-16kg/cm the tungsten disulfide of preparation
2Compression N
2Gas is used as power, and circulation is pulverized 3-5 time, makes particle diameter reach 2-4 μ m, gets product.
In described preparation method, preferably:
(1) ammonium tungstate adopts wolframite, and ion exchange method or extraction process make.Also available ammonium paratungstate makes through ammonia solvent.
(2) H
2S adopts H
2Gas and simple substance S are synthetic to be made, and special cylinder takes up.
(3) tail gas that whole process of production produced adopts incinerator to burn.
Adopt the inventive method, in the whole process of production of preparation tetrathio ammonium tungstate, hydrogen sulfide adopts incinerator to burn, no hydrogen sulfide emission, and the quantity discharged of sulfurous gas reaches 800mg/m
3, reach national requirements for environmental protection.If in the methods of the invention, further adopt synthesis method to produce hydrogen sulfide, then be easier to control.In the step of preparation tetrathio ammonium tungstate, adopt airtight fixed-bed reactor to prepare liquid tetrathio ammonium tungstate, the danger of no hydrogen sulfide gas leakage, operational condition is superior.
In the step of crystallization tetrathio ammonium tungstate,, make uniform crystal particles, tetrathio ammonium tungstate crystal grain stable content, not segregation owing to adopt nitrogen to do the power agitation condition; Just can produce component of the same race, crystalline tungsten disulfide of the same race with this crystalline tetrathio ammonium tungstate.
WS prepared by this method
2Lubricant is a hexagonal system scale laminate structure, and there is good adsorption property the metallic surface, not with the metallic surface react with, is the quality matetrial of doing lubricant.
Description of drawings
Fig. 1 prepares the schematic flow sheet of tungsten disulfide lubricant for the present invention.
Fig. 2 is the X-ray diffraction spectrogram photo of the tungsten disulfide lubricant utmost point of embodiment 1 preparation.
Embodiment
Embodiment 1
A. prepare the tetrathio ammonium tungstate
In the 5000ml beaker, and the adding ammonium tungstate solution (commercially available, GB10116-38) 3000ml, strength of solution: 200gWO
3/ l adds ammoniacal liquor 200ml, gives solution heat temperature raising to 30 ℃, feeds H in beaker
2S gas 4 hours, 3 times of theoretical amount (normal pressure) with the water bed cooling, are reduced to solution temperature≤20 ℃, occur the crystallization of a large amount of tetrathio ammonium tungstate in the beaker, obtain tetrathio ammonium tungstate crystal 6 50g behind the filtering drying.
B. pyrolysis tetrathio ammonium tungstate prepares tungsten disulfide lubricant
Use 100mlAl
2O
34 of crucibles are filled tetrathio ammonium tungstate crystal 160g/ respectively, amount to 640g, crucible is put into retort furnace and insert 200 gram Graphite Electrodess, be warming up to 400 ℃, constant temperature is after 3 hours, continue to be warming up to 1050 ℃, constant temperature 20 hours is added Graphite Electrodes 100g during cooling.Treat below the retort furnace temperature drop to 100 ℃, the discharging of blow-on door, remove a little assorted material (low-level oxidation thing or suboxide) of crucible upper strata after, obtain tungsten disulfide lubricant finished product 518g.Purity＞98%, yield 91.67%.
Fig. 2 proves that for the lubricated level of tungsten disulfide X-ray diffraction spectrogram photo it is a hexagonal system structure.
Embodiment 2
A. the preparation of tetrathio ammonium tungstate
At 2.0m
3But add ammonium tungstate liquid 1.7m in the closed reactor
3, the concentration of liquid is for containing WO
3240g/l.Logical liquefied ammonia 20kg in reactor, and with solution heat temperature raising to 30 ℃.Logical H in reactor
2S gas keeps a jar internal pressure 0.5kg/cm
2, temperature is at 50-60 ℃ in the controlling tank.Ventilated 10 hours, to the logical water coolant of tank body chuck, crystallisation by cooling, during temperature in jar≤20 ℃, discharging tail gas to other reactor, logical N
2Gas mixing is mixed, pressure-controlling 4-8kg/cm
2, filter wet tetrathio ammonium tungstate crystal 6 85kg, after the oven dry tetrathio ammonium tungstate crystal 5 80kg, consume H
2S gas 280kg contains WO in the mother liquor
314g/l, volume 1.4m
3
B. tetrathio ammonium tungstate pyrolysis system tungsten disulfide lubricant
With the 580kg tetrathio ammonium tungstate crystal that obtains, with several 5000ml molybdenum crucible splendid attires, place in the bed furnace, in stove, put into a small amount of Graphite Electrodes simultaneously, heat temperature raising treats that temperature rises to 400 ℃, and constant temperature is after 3 hours, continue to be warming up to 1050 ℃, constant temperature 16 hours is at N
2Be cooled under the gas shiled below 100 ℃, the discharging of blow-on door after selecting materials puts together the qualified product unification, and carries out coarse reduction, then at N
2The gas shiled downstream is pulverized 3-5 time, and granularity is controlled at 2-4 μ m by processing requirement, gets tungsten disulfide lubricant level qualified product: 410kg.Purity＞98%, yield 92%.
Claims (8)
1. method for preparing tungsten disulfide lubricant, described method comprises the steps:
1) be 200-350g WO to concentration
3Logical liquefied ammonia in the/L ammonium tungstate solution makes the final ammonium hydroxide content of solution reach the resulting ammonium tungstate solution of 14-15N and gaseous tension at 0.35-16kg/cm
2Hydrogen sulfide, in sealed vessel, react, control reaction temperature descends until temperature of reaction below 60 ℃;
2) stop to add hydrogen sulfide in reaction system, behind the discharging tail gas, under the cool to room temperature, make the product crystallization, then, separation, purifying, drying obtain tetrathio ammonium tungstate crystal;
3) thermolysis of resulting tetrathio ammonium tungstate crystal is obtained tungsten disulfide;
4) tungsten disulfide that obtains is pulverized.
2. method as claimed in claim 1 is characterized in that step 2) described in the crystallization of product be that to feed pressure in the product behind discharging tail gas be 4-8kg/cm
2Carry out under the compressed nitrogen.
3. method as claimed in claim 1 is characterized in that, described step 3) is under reducing atmosphere, through logical N
2Behind the gas displacement furnace gas, be warming up to 380-420 ℃, constant temperature 3-3.5 hour, be warming up to 1050-1100 ℃ again, constant temperature 15-16 hour, then, at N
2Be cooled to room temperature under the protection, obtain the flakey tungsten disulfide.
4. method as claimed in claim 1 is characterized in that, described step 4) is to utilize 2-16kg/cm
2Compression N
2Gas is used as power, and by air-flow it is ground into the particle that diameter is 2-4 μ m.
5. method as claimed in claim 3 is characterized in that, described reducing atmosphere is to be produced by the high purity carbon of placing in the stove in the reaction later stage.
6. method as claimed in claim 1 is characterized in that, the pressure of hydrogen sulfide is 0.5-2kg/cm in the step 1)
2
7. method as claimed in claim 1 is characterized in that, in step 1), feed liquefied ammonia in ammonium tungstate solution after, the temperature of solution is elevated to 20-30 ℃.
8. method as claimed in claim 1 is characterized in that, described method further comprises burns discharge tail gas in the entire method process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031223745A CN1548504A (en) | 2003-05-19 | 2003-05-19 | Prepn of tungsten disulfide lubricant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031223745A CN1548504A (en) | 2003-05-19 | 2003-05-19 | Prepn of tungsten disulfide lubricant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1548504A true CN1548504A (en) | 2004-11-24 |
Family
ID=34321007
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031223745A Pending CN1548504A (en) | 2003-05-19 | 2003-05-19 | Prepn of tungsten disulfide lubricant |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420423A (en) * | 2013-08-09 | 2013-12-04 | 深圳市威勒达科技开发有限公司 | Preparation method for tungsten disulfide |
-
2003
- 2003-05-19 CN CNA031223745A patent/CN1548504A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420423A (en) * | 2013-08-09 | 2013-12-04 | 深圳市威勒达科技开发有限公司 | Preparation method for tungsten disulfide |
| CN103420423B (en) * | 2013-08-09 | 2015-05-13 | 深圳市威勒达科技开发有限公司 | Preparation method for tungsten disulfide |
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