CN113461061A - Preparation method of high-purity molybdenum disulfide - Google Patents
Preparation method of high-purity molybdenum disulfide Download PDFInfo
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- CN113461061A CN113461061A CN202110855801.6A CN202110855801A CN113461061A CN 113461061 A CN113461061 A CN 113461061A CN 202110855801 A CN202110855801 A CN 202110855801A CN 113461061 A CN113461061 A CN 113461061A
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- molybdenum disulfide
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 46
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 26
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 17
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 16
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 16
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 7
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 4
- 230000023556 desulfurization Effects 0.000 claims abstract description 4
- -1 1, 3-dimethyl imidazole tetrafluoroborate Chemical compound 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 6
- 238000007323 disproportionation reaction Methods 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 229910052961 molybdenite Inorganic materials 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 1
- 229910019964 (NH4)2MoS4 Inorganic materials 0.000 description 1
- LLAPDLPYIYKTGQ-UHFFFAOYSA-N 1-aminoethyl Chemical group C[CH]N LLAPDLPYIYKTGQ-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910016003 MoS3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical compound [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000007280 thionation reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of molybdenum disulfide preparation, and particularly relates to a preparation method of high-purity molybdenum disulfide. Taking ammonium molybdate and elemental sulfur as raw materials, carrying out a co-heating reaction in an ionic liquid, and filtering after the reaction is finished to obtain an ammonium tetrathiomolybdate intermediate product; acidifying the ammonium tetrathiomolybdate intermediate product to obtain molybdenum trisulfide; and desulfurizing the molybdenum trisulfide to obtain the molybdenum disulfide. This application uses elemental sulfur as the thio-compound, and molybdenum trisulfide produces elemental sulfur when the desulfurization turns into molybdenum disulfide, and elemental sulfur can be circulated to this reaction again and be the raw materials, does not produce the waste of material, has further reduced manufacturing cost.
Description
Technical Field
The invention belongs to the technical field of molybdenum disulfide preparation, and particularly relates to a preparation method of high-purity molybdenum disulfide.
Background
The molybdenum disulfide black is slightly silver gray, has metallic luster, has a greasy feeling when being touched, is insoluble in water, is an important solid lubricant, and is particularly suitable for high-temperature, high-pressure, low-temperature and high-vacuum environments. The molybdenum disulfide product has the advantages of good dispersibility and non-caking property, can be added into various greases to form a colloidal state without caking, and can increase the lubricating property and extreme pressure property of the greases; the device is also suitable for mechanical working states with high temperature, high pressure, high rotating speed and high load, and the service life of the device is prolonged.
Existing preparation of MoS2The methods of materials can be mainly divided into two main categories: physical methods and chemical methods. The physical method mainly comprises the following steps: common molybdenum disulfide mechanical crushing and grading method, Physical Vapor Deposition (PVD) method, micro mechanical force stripping method, liquid phase stripping method and the like. The chemical method mainly comprises the following steps: hydrothermal method, Chemical Vapor Deposition (CVD), sulfidation method, electrochemical deposition method, and the like. However, these methods have the following disadvantages: the preparation process has high energy consumption, low yield, high cost and no environmental protection, and seriously hinders MoS2The large-scale, mass production of materials has resulted in a limited range of applications.
Chinese patent application CN108640154A discloses a molybdenum disulfide nano material and a preparation method thereof, wherein ionic liquid is adopted as electrolyte, and a molybdenum disulfide rod electrolysis method is adopted to prepare nano molybdenum disulfide, but the ionic liquid has high price and harsh electrolysis conditions, and the post-treatment process is complicated, so that the large-scale production is not facilitated. Chinese patent application CN108862387A discloses a preparation method of anisotropic nano molybdenum disulfide, which comprises the steps of firstly using various oxide nano particles as carriers, using ammonium molybdate as a molybdenum precursor to impregnate the oxide carriers, drying, roasting, then preparing a load-type molybdenum disulfide material under a specific vulcanization condition, and finally removing the oxide carriers by hydrofluoric acid chemical etching, thus obtaining the special-shaped nano molybdenum disulfide material with the range of several nanometers to dozens of nanometers, wherein the cost is high, the corrosion of the used hydrofluoric acid is serious, and the harm to human bodies is large.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing high-purity molybdenum disulfide, so as to solve the problems of complicated preparation and environmental pollution of the existing molybdenum disulfide.
The technical scheme adopted by the invention is as follows:
a preparation method of high-purity molybdenum disulfide comprises the following steps:
1) taking ammonium molybdate and elemental sulfur as raw materials, carrying out a co-heating reaction in an ionic liquid, and filtering after the reaction is finished to obtain an ammonium tetrathiomolybdate intermediate product;
2) acidifying the ammonium tetrathiomolybdate intermediate product to obtain molybdenum trisulfide;
3) and (3) desulfurizing the molybdenum trisulfide to obtain molybdenum disulfide, and returning the desulfurized byproduct elemental sulfur to the step 1) to be used as the raw material for reutilization.
The molar ratio of the ammonium molybdate to the elemental sulfur is 1: 4-10; the mass ratio of the ammonium molybdate to the ionic liquid is 1: 5-20.
The ionic liquid is 1, 3-dimethyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, 1-propyl-3-methyl imidazole tetrafluoroborate, 1-butyl-3-methyl imidazole tetrafluoroborate, 1, 3-dimethyl imidazole hexafluorophosphate, 1-ethyl-3-methyl imidazole hexafluorophosphate, 1-propyl-3-methyl imidazole hexafluorophosphate or 1-butyl; the temperature of the co-heating reaction is 200-360 ℃ and the time is 1-12 hours.
During acidification in the step 3), dispersing ammonium tetrathiomolybdate into water, adding dilute sulfuric acid (20 wt%) to acidify to a pH value of 2-3, and producing molybdenum trisulfide; the mass ratio of ammonium tetrathiomolybdate to water is 1: 5-10.
The step 4) of desulfurization comprises the following steps: putting the molybdenum trisulfide into an oxygen-free atmosphere furnace, controlling the temperature at 200 ℃ and 450 ℃ to carry out disproportionation reaction, and converting the molybdenum trisulfide into molybdenum disulfide.
The principle of the reaction steps of the method of the invention is as follows:
1、(NH4)2MoO4+4S+4[BMIM]PF6---(NH4)2MoS4+4[BMIM]PF6-O
2、(NH4)2MoS4----MoS3+(NH4)2S
3、MoS3---MoS2+S。
compared with the prior art, the invention has the beneficial technical effects that:
1. the raw material adopted in the application is ammonium molybdate, metal impurities are not contained in the ammonium molybdate, the metal impurities are avoided in the preparation process, and molybdenum disulfide without the metal impurities can be prepared.
2. Elemental sulphur is less reactive than sulphides, and sulphides are generally chosen for the replacement of oxygen with conventional sulphur, and are not preferred because sulphides are more easily replaced, for example with ammonium sulphide. However, in the preparation of ammonium tetrathiomolybdate, the conventional ammonium sulfide which is easier to replace is not adopted as a vulcanizing agent, and the elemental sulfur is selected. Because elemental sulfur is not easy to participate in the reaction, in order to overcome the technical problem, a special ionic liquid environment is selected during the reaction, the special ionic liquid has the characteristics of high boiling point, extremely low vapor pressure, strong dissolving capacity, greenness and nontoxicity, the high temperature resistance is good, and the gasification and volatilization of other organic matters at high temperature can not be generated in the co-heating process. Meanwhile, cations contained in the ionic liquid belong to organic cations, so that the ionic liquid can play a role in catalyzing the reaction of hydrogen substituted by sulfur, and the substituted cations are absorbed by the ionic liquid.
3. When the ammonium sulfide is used as the sulfide to participate in the reaction, harmful gases such as hydrogen sulfide and the like can be generated, the environmental protection is influenced, and the ammonium sulfide is discharged after being treated and cannot be reused. The method uses elemental sulfur as a raw material, does not generate harmful gas, and is very green and environment-friendly.
4. This application uses elemental sulfur as the thio-compound, and molybdenum trisulfide produces elemental sulfur when the desulfurization turns into molybdenum disulfide, and elemental sulfur can be circulated to this reaction again and be the raw materials, does not produce the waste of material, has further reduced manufacturing cost.
Detailed Description
The following examples are given to illustrate specific embodiments of the present invention, but are not intended to limit the scope of the present invention in any way.
Example 1:
a preparation method of high-purity molybdenum disulfide comprises the following steps:
1) taking 39.2g of ammonium molybdate and 25.6g of elemental sulfur as raw materials, and carrying out a co-heating reaction in 196g of ionic liquid (1, 3-dimethyl imidazole tetrafluoroborate); the temperature of the co-heating reaction is 200 ℃, the time is 12 hours, and after the reaction is finished, the hot reaction product is filtered to obtain a filter cake, namely 51.5g of an ammonium tetrathiomolybdate intermediate product, wherein the yield is 98.82%;
2) dispersing ammonium tetrathiomolybdate into 300g of water, adding 20% dilute sulfuric acid until the pH value of the solution is 2-3, and acidifying the ammonium tetrathiomolybdate to obtain 38g of molybdenum trisulfide, wherein the yield is 98.96%;
3) putting molybdenum trisulfide in a dynamic tube type oxygen-free atmosphere furnace, controlling the temperature at 200 ℃ to carry out disproportionation reaction, desulfurizing to obtain 31.6g of molybdenum disulfide, wherein the yield is 98.75%, and 6.35g of desulfurized byproduct elemental sulfur is returned to the step 1) to be used as raw materials for reutilization. The quality result of the obtained molybdenum disulfide product is as follows through detection: MoS2: 99.31%, Fe: not detected, SiO2: not detected, Pb: not detected, Cu: not detected, Ca, not detected.
Example 2:
a preparation method of high-purity molybdenum disulfide comprises the following steps:
1) taking 19.6g of ammonium molybdate and 22.4g of elemental sulfur as raw materials, carrying out a co-heating reaction in 254.8g of ionic liquid (1-ethyl-3-methylimidazole tetrafluoroborate), wherein the co-heating reaction temperature is 360 ℃, the time is 1 hour, and filtering while hot after the reaction is finished to obtain a filter cake, namely 26.01g of an ammonium tetrathiomolybdate intermediate product, wherein the yield is 99.9%. Cooling, crystallizing and filtering the filtrate to obtain 9g of excessive elemental sulfur for returning;
2) dispersing ammonium tetrathiomolybdate into 200g of water, adding 20% dilute sulfuric acid to acidify to the pH value of 2-3, and acidifying the ammonium tetrathiomolybdate to obtain 19.02g of molybdenum trisulfide with the yield of 99.06%;
3) putting the molybdenum trisulfide in a dynamic tubular oxygen-free atmosphere furnace, controlling the temperature to be 300 ℃ to carry out disproportionation reaction, desulfurizing to obtain 15.8g of molybdenum disulfide, wherein the yield is 98.90%, and 3.2g of desulfurized byproduct elemental sulfur is returned to the step 1) to be used as raw materials for reutilization. The quality result of the obtained molybdenum disulfide product is as follows through detection: MoS2: 99.46%, Fe: not detected, SiO2: not detected, Pb: not detected, Cu: not detected, Ca, not detected.
Example 3:
a preparation method of high-purity molybdenum disulfide comprises the following steps:
1) taking 29.4g of ammonium molybdate and 48g of elemental sulfur as raw materials, carrying out a co-heating reaction in 294g of ionic liquid (1-ethyl-3-methylimidazole hexafluorophosphate), wherein the temperature of the co-heating reaction is 280 ℃, the time is 5 hours, filtering while hot after the reaction is finished to obtain a filter cake, namely 38.69g of an ammonium tetrathiomolybdate intermediate product, and the yield is 99.1%. Cooling and filtering the filtrate to obtain 28.6g of solid elemental sulfur for recycling;
2) dispersing ammonium tetrathiomolybdate into 300g of water, adding 20% dilute sulfuric acid for acidification, and acidifying the ammonium tetrathiomolybdate to obtain 28.4g of molybdenum trisulfide with the yield of 98.6%;
3) putting molybdenum trisulfide in a dynamic tubular oxygen-free atmosphere furnace, controlling the temperature at 450 ℃ to carry out disproportionation reaction, desulfurizing to obtain 23.91g of molybdenum disulfide, wherein the yield is 99.6% g, and returning 4.5g of desulfurized byproduct elemental sulfur to the step 1) to be used as raw materials for reutilization. The quality result of the obtained molybdenum disulfide product is as follows through detection: MoS2: 99.28%, Fe: not detected, SiO2: not detected, Pb: not detected, Cu: not detected, Ca, not detected.
Comparative example 1:
a preparation method of molybdenum disulfide comprises the following steps:
1) 39.2g of ammonium molybdate and 25.6g of elemental sulfur are used as raw materials, the raw materials are subjected to a co-heating reaction in 196g of ionic liquid (1-aminoethyl, 3-dimethylimidazole tetrafluoroborate), the temperature of the co-heating reaction is 200 ℃, the time is 12 hours, after the reaction is finished, a filter cake is obtained by filtering while the reaction is hot, namely 23.43g of an intermediate product of ammonium tetrathiomolybdate, the yield is 44.75%, the yield is too low, and the analytic reason is that the thioreaction is influenced by the aminoethyl group of the ionic liquid;
2) dispersing ammonium tetrathiomolybdate into water with the mass 10 times that of the ammonium tetrathiomolybdate, adding 20% dilute sulfuric acid to acidify the solution to obtain the pH value of 2-3, and acidizing the ammonium tetrathiomolybdate to obtain 17.2g of molybdenum trisulfide;
3) putting molybdenum trisulfide in a dynamic tube type oxygen-free atmosphere furnace, controlling the temperature at 200 ℃ to carry out disproportionation reaction, desulfurizing to obtain 14g of molybdenum disulfide, and returning 3.1g of desulfurized byproduct elemental sulfur to the step 1) to be used as raw materials for reutilization.
Comparative example 2:
a preparation method of molybdenum disulfide comprises the following steps:
1) 39.2g of ammonium molybdate and 25.6g of elemental sulfur are used as raw materials, the raw materials are subjected to a co-heating reaction in 196g of ionic liquid (1, 3-dimethyl imidazole tetrafluoroborate), the temperature of the co-heating reaction is 170 ℃, the time is 12 hours, after the reaction is finished, the hot reaction product is filtered to obtain 13g of a filter cake, namely an ammonium tetrathiomolybdate intermediate product, the yield is 25.0%, and the analytic reason is that the co-heating temperature is low and is not enough to provide the activation energy of the thionation reaction.
Comparative example 3:
a preparation method of molybdenum disulfide comprises the following steps:
1) 39.2g of ammonium molybdate and 25.6g of elemental sulfur are used as raw materials, the raw materials are subjected to a co-heating reaction in 196g of ionic liquid (1, 3-dimethyl imidazole tetrafluoroborate), the temperature of the co-heating reaction is 400 ℃, the time is 12 hours, after the reaction is finished, a filter cake is obtained by filtering when the reaction is hot, namely 16g of an intermediate product of ammonium tetrathiomolybdate, the yield is 30.73%, and the added sulfur rapidly gasifies and escapes in the system because the co-heating temperature is too high for analysis reasons.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (6)
1. The preparation method of the high-purity molybdenum disulfide is characterized by comprising the following steps:
1) taking ammonium molybdate and elemental sulfur as raw materials, carrying out a co-heating reaction in an ionic liquid, and filtering after the reaction is finished to obtain an ammonium tetrathiomolybdate intermediate product;
2) acidifying the ammonium tetrathiomolybdate intermediate product to obtain molybdenum trisulfide;
3) and (3) desulfurizing the molybdenum trisulfide to obtain molybdenum disulfide, and returning the desulfurized byproduct elemental sulfur to the step 1) to be used as the raw material for reutilization.
2. The method of claim 1, wherein: the molar ratio of the ammonium molybdate to the elemental sulfur is 1: 4-10; the mass ratio of the ammonium molybdate to the ionic liquid is 1: 5-20.
3. The method of claim 1, wherein: the ionic liquid is one of 1, 3-dimethyl imidazole tetrafluoroborate, 1-ethyl-3-methyl imidazole tetrafluoroborate, 1-propyl-3-methyl imidazole tetrafluoroborate, 1-butyl-3-methyl imidazole tetrafluoroborate, 1, 3-dimethyl imidazole hexafluorophosphate, 1-ethyl-3-methyl imidazole hexafluorophosphate, 1-propyl-3-methyl imidazole hexafluorophosphate or 1-butyl-3-methyl imidazole hexafluorophosphate.
4. The method of claim 1, wherein: the temperature of the co-heating reaction is 200-360 ℃, and the time is 1-12 h.
5. The method of claim 1, wherein: during acidification in the step 3), dispersing ammonium tetrathiomolybdate into water, and adding dilute sulfuric acid for acidification to produce molybdenum trisulfide; the mass ratio of ammonium tetrathiomolybdate to water is 1: 5-10.
6. The method of claim 1, wherein: the step 4) of desulfurization comprises the following steps: putting the molybdenum trisulfide into an oxygen-free atmosphere furnace, controlling the temperature at 200 ℃ and 450 ℃ to carry out disproportionation reaction, and converting the molybdenum trisulfide into molybdenum disulfide.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009000497A1 (en) * | 2007-06-28 | 2008-12-31 | Stc S.R.L. Science Technology & Consulting | Purification process for gas from hydrogen sulfide through regenerated ferric ion solutions |
| CN102616854A (en) * | 2011-01-31 | 2012-08-01 | 中国科学院过程工程研究所 | Preparation method of monodisperse spherical MoS2 ultrafine powder |
| CN105133002A (en) * | 2015-08-29 | 2015-12-09 | 西北有色金属研究院 | (NH4)2Mo3S13 crystal and preparation method thereof |
| CN105462587A (en) * | 2015-12-14 | 2016-04-06 | 上海交通大学 | Method for preparing blue molybdenum disulfide quantum dot solutions |
| CN105645471A (en) * | 2016-04-08 | 2016-06-08 | 合肥工业大学 | Method for preparing molybdenum disulfide nanotubes by vulcanizing nano fibrous polymolybdic acid material |
| CN106268872A (en) * | 2016-07-15 | 2017-01-04 | 朱晨迪 | A kind of support type MoS2/ LDHS Hydrobon catalyst and application |
| CN109133173A (en) * | 2018-11-07 | 2019-01-04 | 洛阳申雨钼业有限责任公司 | A kind of useless molybdenum slag prepares the method for comprehensive utilization of molybdenum disulfide |
| CN109368698A (en) * | 2018-12-10 | 2019-02-22 | 合肥工业大学 | A method of four thio ammonium molybdate is prepared by hydro-thermal-gas-phase presulfiding device |
| CN109759093A (en) * | 2019-03-07 | 2019-05-17 | 陕西理工大学 | A kind of molybdenum disulfide load monatomic catalyst of Ir and the preparation method and application thereof |
| CN111101180A (en) * | 2020-01-14 | 2020-05-05 | 山西大同大学 | Preparation of MoS through electrodeposition in eutectic ionic liquid2Method for producing thin film material |
| CN212882369U (en) * | 2020-06-22 | 2021-04-06 | 洛阳申雨钼业有限责任公司 | Hypergravity reaction unit of molybdenum disulfide |
-
2021
- 2021-07-28 CN CN202110855801.6A patent/CN113461061B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009000497A1 (en) * | 2007-06-28 | 2008-12-31 | Stc S.R.L. Science Technology & Consulting | Purification process for gas from hydrogen sulfide through regenerated ferric ion solutions |
| CN102616854A (en) * | 2011-01-31 | 2012-08-01 | 中国科学院过程工程研究所 | Preparation method of monodisperse spherical MoS2 ultrafine powder |
| CN105133002A (en) * | 2015-08-29 | 2015-12-09 | 西北有色金属研究院 | (NH4)2Mo3S13 crystal and preparation method thereof |
| CN105462587A (en) * | 2015-12-14 | 2016-04-06 | 上海交通大学 | Method for preparing blue molybdenum disulfide quantum dot solutions |
| CN105645471A (en) * | 2016-04-08 | 2016-06-08 | 合肥工业大学 | Method for preparing molybdenum disulfide nanotubes by vulcanizing nano fibrous polymolybdic acid material |
| CN106268872A (en) * | 2016-07-15 | 2017-01-04 | 朱晨迪 | A kind of support type MoS2/ LDHS Hydrobon catalyst and application |
| CN109133173A (en) * | 2018-11-07 | 2019-01-04 | 洛阳申雨钼业有限责任公司 | A kind of useless molybdenum slag prepares the method for comprehensive utilization of molybdenum disulfide |
| CN109368698A (en) * | 2018-12-10 | 2019-02-22 | 合肥工业大学 | A method of four thio ammonium molybdate is prepared by hydro-thermal-gas-phase presulfiding device |
| CN109759093A (en) * | 2019-03-07 | 2019-05-17 | 陕西理工大学 | A kind of molybdenum disulfide load monatomic catalyst of Ir and the preparation method and application thereof |
| CN111101180A (en) * | 2020-01-14 | 2020-05-05 | 山西大同大学 | Preparation of MoS through electrodeposition in eutectic ionic liquid2Method for producing thin film material |
| CN212882369U (en) * | 2020-06-22 | 2021-04-06 | 洛阳申雨钼业有限责任公司 | Hypergravity reaction unit of molybdenum disulfide |
Non-Patent Citations (2)
| Title |
|---|
| 周存: "二硫化钼及其复合材料的制备工艺", 《中国金属通报》 * |
| 胡坤宏等: "纳米二硫化钼的制备及AFM表征", 《合肥学院学报(自然科学版)》 * |
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