CN109852458B - Tungsten disulfide/fly ash compound lubricant and preparation method thereof - Google Patents
Tungsten disulfide/fly ash compound lubricant and preparation method thereof Download PDFInfo
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- 239000010881 fly ash Substances 0.000 title claims abstract description 97
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 239000000314 lubricant Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 24
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000001050 lubricating effect Effects 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010883 coal ash Substances 0.000 claims 3
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- 239000010687 lubricating oil Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 titanium dioxide compound Chemical class 0.000 description 1
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- Processing Of Solid Wastes (AREA)
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Abstract
A tungsten disulfide/fly ash compound lubricant and a preparation method thereof relate to the technical field of recycling of lubricants and solid wastes. Calcining the fly ash, carrying out ball milling acid and alkali liquor immersion in sequence to carry out surface activation, putting the fly ash into tungstate solution to react, and depositing tungsten oxide on the surface of the fly ash; heating the deposited load and elemental sulfur to react and vulcanize under the protective atmosphere, then removing excessive sulfur through heating and evaporation, and obtaining the tungsten disulfide/fly ash compound which can be used as a lubricant after cooling, wherein the flaky tungsten disulfide nano particles with the average particle size of less than 100nm are coated on the surface of the fly ash spherical particles. The tungsten disulfide in the compound is uniformly deposited on the surface of the fly ash, a typical lamellar structure of the compound is reserved, the compound can fully exert the synergistic lubricating effect of tungsten disulfide particles with lamellar structures and the fly ash, and the compound lubricant is a compound lubricant with excellent performance. In addition, the composite has potential application value in the field of catalysts.
Description
Technical Field
The invention relates to the technical field of recycling of lubricants and solid wastes, in particular to a tungsten disulfide/fly ash compound lubricant and a preparation method thereof.
Background
The resource utilization of the fly ash is one of the research hotspots in the field of solid waste disposal, compared with developed countries, the comprehensive utilization technology of the fly ash in China is relatively lagged behind, and the fly ash is mainly used in the fields of building materials with low added values, agricultural fertilizers and the like at present, so that a utilization method with high added values needs to be found.
Tungsten disulfide has a structure similar to that of graphite and a low friction coefficient, is one of common solid lubricants, is favored in the field of lubrication all the time, and although tungsten disulfide has excellent lubricating performance, the price and the preparation cost of tungsten disulfide are relatively high, so that the application range of tungsten disulfide is limited. The lubricating agent is compounded with other cheap raw materials, and the synergistic effect of different particles is one of the methods for improving the lubricating performance of the tungsten disulfide and reducing the production cost.
The compounds which can be prepared by the method of tungstate and sulfide at present comprise a tungsten disulfide/titanium dioxide compound (Chinese patent CN 201510416849.1) and a tungsten disulfide/attapulgite compound (Chinese patent CN 201510416850.4), wherein the compounds are prepared by activating the surface by strong acid and then depositing tungsten oxide on the surface. Unlike titanium dioxide and sericite, fly ash is a high-temperature combustion product, the product particles are mainly spherical, the surface is relatively stable, and the product particles are difficult to activate into a surface on which tungsten disulfide can be deposited by simple acid treatment, so a new treatment method needs to be explored.
Disclosure of Invention
The invention aims to provide a tungsten disulfide/fly ash compound lubricant and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a tungsten disulfide/fly ash compound lubricant is characterized in that flaky tungsten disulfide nanoparticles with the average particle size of less than 100nm are coated on the surface of fly ash spherical particles.
A preparation method of a tungsten disulfide/fly ash compound lubricant comprises the following steps of firstly, activating the surfaces of fly ash particles to load tungsten oxide particles generated by reaction, and then vulcanizing to obtain tungsten disulfide/fly ash compound nanoparticles:
1) activation of fly ash
Firstly, calcining the fly ash, then putting the calcined fly ash into a ball mill for ball milling, and then alternately dipping the fly ash in acid and alkali liquor for surface activation to be suitable for tungsten oxide deposition;
2) deposition load
Putting the activated fly ash particles into a tungstate solution, adjusting the pH value by hydrochloric acid under stirring and heating conditions, and initiating a reaction to deposit tungsten oxide on the surface of the fly ash;
3) and vulcanization treatment
And heating the deposition load and elemental sulfur to react and vulcanize under a protective atmosphere, heating and evaporating to remove excessive sulfur, and cooling to obtain the tungsten disulfide/fly ash compound capable of being used as a lubricant.
The preferable technical proposal of the preparation method of the tungsten disulfide/fly ash compound lubricant of the invention is as follows:
the step 1) of calcining the fly ash is to calcine the fly ash in a muffle furnace for 5 to 8 hours at a temperature of 500 to 600 ℃. The rotation speed of the fly ash during ball milling is 400-600 r/min, and the ball-to-material ratio is 3-6: 1, the ball milling time is 3-5 h. The acid and alkali liquid alternate treatment is that firstly hydrochloric acid is used and then potassium hydroxide solution is used for dipping treatment; the concentration of hydrochloric acid and potassium hydroxide solution for impregnation is 2-5 mol/L, and the mass ratio of the fly ash to the impregnating hydrochloric acid and potassium hydroxide is 1: 0.5-100, soaking for 8-24 h, repeatedly washing the soaked fly ash with deionized water to be neutral, and drying to obtain the activated modified fly ash, wherein tungsten oxide particles are easy to deposit on the surface of the activated modified fly ash.
In the step 2), the tungstate is sodium tungstate or ammonium tungstate, and the mass ratio of the fly ash to the tungstate is 1: 0.5-5, wherein the mass ratio of the fly ash to water for preparing tungstate is 1: 50 to 250. And (3) adjusting the pH value to be below 4 by using hydrochloric acid to perform liquid phase reaction, wherein the reaction temperature is 50-90 ℃, and the reaction time is 5-10 h.
The mass ratio of the deposition load to the elemental sulfur in the step 3) is 1: 0.2-20 ℃, the heating and vulcanizing temperature is 250-445 ℃, and the heating and vulcanizing time is 0.2-4 h. The heating evaporation desulphurization is carried out at 446-800 ℃ in a nitrogen or rare gas environment, and the heating desulphurization time is 0.2-4 h.
Compared with the prior art, the invention has the beneficial effects that:
1) the tungsten disulfide/fly ash compound organically combines the advantages of two components of tungsten disulfide and fly ash, has excellent lubricating property on one hand, and reduces the cost to a great extent at the same time, so that the development of the tungsten disulfide/fly ash compound has good application prospect. In addition, the fly ash has wide source and low price, and particularly, the fly ash is used as industrial waste and pollutes the environment, and the development of the comprehensive utilization technology of the fly ash can be promoted after the fly ash and the industrial waste are compounded.
2) The preparation method provided by the invention is characterized in that the tungsten oxide is loaded on the fly ash, and the tungsten disulfide/fly ash compound is prepared after vulcanization. The tungsten disulfide in the compound is uniformly deposited on the surface of the fly ash, a typical lamellar structure of the compound is reserved, the compound can fully exert the synergistic lubricating effect of tungsten disulfide particles with lamellar structures and the fly ash, and the compound lubricant is a compound lubricant with excellent performance. In addition, the composite has potential application value in the field of catalysts.
Drawings
The tungsten disulfide/fly ash composite lubricant and the preparation method thereof according to the present invention are further described in detail below with reference to the examples and the accompanying drawings.
FIGS. 1 and 2 are the X-ray diffraction pattern and the scanning electron micrograph of the tungsten disulfide/fly ash composite prepared in example 1, respectively.
Detailed Description
Example 1
Calcining 5g of fly ash in a muffle furnace at 600 ℃ for 6h, cooling, and putting the fly ash into a ball mill, wherein the ball-to-material ratio is 3: 1, ball milling for 4 hours at 600 r/min. Soaking the ball-milled fly ash in 2.5g of 5mol/L hydrochloric acid for 15h, then soaking the ball-milled fly ash in 2.5g of 5mol/L potassium hydroxide solution for 12h, filtering, repeatedly washing the ball-milled fly ash with deionized water to be neutral, and drying to obtain the activated modified fly ash easy to deposit tungsten oxide particles.
Uniformly mixing activated modified fly ash with 2.5g of sodium tungstate and 1250g of water, heating to 70 ℃, adjusting the pH value to 2 by using hydrochloric acid and initiating a reaction for 5 hours to generate a tungsten oxide/fly ash precursor, mixing the filtered and dried precursor with elemental sulfur (the weight ratio of the two is 1: 20), heating and vulcanizing at 350 ℃ for 0.2 hour in a nitrogen atmosphere, then heating to 800 ℃ and preserving heat for 2 hours to evaporate excessive sulfur, and cooling the product to obtain the tungsten disulfide/fly ash compound.
FIGS. 1 and 2 are the X-ray diffraction pattern and the scanning electron micrograph of the tungsten disulfide/fly ash composite prepared in example 1, respectively. The X-ray diffraction pattern in figure 1 shows that the product is tungsten disulfide/fly ash composite, and the flaky particles with the average particle size of less than 100nm in the scanning electron microscope image in figure 2 are tungsten disulfide flaky nano particles, and the tungsten disulfide particles are distributed on the surface of fly ash particles.
Example 2
Calcining 5g of fly ash in a muffle furnace at 550 ℃ for 5h, cooling, and putting the fly ash into a ball mill, wherein the ball-to-material ratio is 6: 1, ball milling for 3 hours at 500 r/min. Soaking the ball-milled fly ash in 500g of 3.5mol/L hydrochloric acid for 8h, then soaking in 500g of 2mol/L potassium hydroxide solution for 8h, filtering, repeatedly washing with deionized water to neutrality, and drying to obtain the activated modified fly ash easy to deposit tungsten oxide particles.
Uniformly mixing activated modified fly ash, 25g of ammonium tungstate and 600g of water, heating to 50 ℃, adjusting the pH value to 3 by using hydrochloric acid, initiating a reaction for 10 hours to generate a tungsten oxide/fly ash precursor, mixing the filtered and dried precursor with elemental sulfur (the weight ratio of the two is 1: 10), heating and vulcanizing at 250 ℃ in a nitrogen atmosphere for 4 hours, then heating to 600 ℃, keeping the temperature for 0.2 hour to evaporate and remove excessive sulfur, and cooling the product to obtain the tungsten disulfide/fly ash composite.
Example 3
Calcining 5g of fly ash in a muffle furnace at 500 ℃ for 8h, cooling, and putting the fly ash into a ball mill, wherein the ball-to-material ratio is 5: 1, ball milling for 5 hours at 400 r/min. And soaking the ball-milled fly ash in 300g of 2mol/L hydrochloric acid for 24h, then soaking the ball-milled fly ash in 300g of 3.5mol/L potassium hydroxide solution for 24h, filtering, repeatedly washing the ball-milled fly ash with deionized water to be neutral, and drying to obtain the activated modified fly ash easy to deposit tungsten oxide particles.
Uniformly mixing activated modified fly ash, 15g of ammonium tungstate and 250g of water, heating to 90 ℃, adjusting the pH value to 4 by using hydrochloric acid and initiating a reaction for 7h to generate a tungsten oxide/fly ash precursor, mixing the filtered and dried precursor with elemental sulfur (the weight ratio of the two is 1: 0.2), heating and vulcanizing at 445 ℃ in a nitrogen atmosphere for 2h, then heating to 446 ℃ and preserving heat for 4h to evaporate excessive sulfur, and cooling the product to obtain the tungsten disulfide/fly ash compound.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (1)
1. A preparation method of a tungsten disulfide/fly ash compound lubricant is characterized by comprising the following steps of firstly, activating the surfaces of fly ash particles to load tungsten oxide particles generated by reaction, and then vulcanizing to obtain tungsten disulfide/fly ash compound nanoparticles:
1) activation of fly ash
Firstly, calcining the fly ash, then putting the calcined fly ash into a ball mill for ball milling, and then alternately dipping the fly ash in acid and alkali liquor for surface activation to be suitable for tungsten oxide deposition;
calcining the fly ash in a muffle furnace at 500-600 ℃ for 5-8 h; the rotation speed of the fly ash during ball milling is 400-600 r/min, and the ball-to-material ratio is 3-6: 1, ball milling for 3-5 h; the acid and alkali liquid alternate treatment is that firstly hydrochloric acid is used and then potassium hydroxide solution is used for dipping treatment; the concentration of hydrochloric acid and potassium hydroxide solution for impregnation is 2-5 mol/L, and the mass ratio of the fly ash to the impregnation hydrochloric acid and potassium hydroxide is 1: 0.5-100, wherein the soaking time is 8-24 h, the soaked coal ash is repeatedly washed by deionized water to be neutral, and the activated modified coal ash is obtained after drying, wherein tungsten oxide particles are easy to deposit on the surface of the activated modified coal ash;
2) deposition load
Putting the activated fly ash particles into a tungstate solution, adjusting the pH value by hydrochloric acid under stirring and heating conditions, and initiating a reaction to deposit tungsten oxide on the surface of the fly ash;
the tungstate is sodium tungstate or ammonium tungstate, and the mass ratio of the fly ash to the tungstate is 1: 0.5-5, wherein the mass ratio of the fly ash to water for preparing tungstate is 1: 50 to 250 parts by weight; adjusting the pH value to be below 4 by using hydrochloric acid to perform liquid phase reaction, wherein the reaction temperature is 50-90 ℃, and the reaction time is 5-10 h;
3) and vulcanization treatment
Heating the deposition load and elemental sulfur to react and vulcanize under the protective atmosphere, then removing excessive sulfur through heating and evaporation, and obtaining a tungsten disulfide/fly ash compound which can be used as a lubricant after cooling;
the mass ratio of the deposition load to the elemental sulfur is 1: 0.2-20 ℃, the heating and vulcanizing temperature is 250-445 ℃, and the heating and vulcanizing time is 0.2-4 h; heating, evaporating and desulfurizing at 446-800 ℃ in a nitrogen or rare gas environment for 0.2-4 h;
in the prepared tungsten disulfide/fly ash compound, the average particle size of tungsten disulfide nano particles is less than 100nm, and the tungsten disulfide nano particles are flaky and uniformly deposited on the surface of the fly ash; because the typical lamellar structure of the composite lubricating oil is kept, the synergistic lubricating effect of the tungsten disulfide particles and the fly ash in the lamellar structure can be fully exerted.
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