CN109368698B - Method for preparing ammonium tetrathiomolybdate through hydrothermal-gas phase vulcanization device - Google Patents
Method for preparing ammonium tetrathiomolybdate through hydrothermal-gas phase vulcanization device Download PDFInfo
- Publication number
- CN109368698B CN109368698B CN201811500462.4A CN201811500462A CN109368698B CN 109368698 B CN109368698 B CN 109368698B CN 201811500462 A CN201811500462 A CN 201811500462A CN 109368698 B CN109368698 B CN 109368698B
- Authority
- CN
- China
- Prior art keywords
- hydrothermal
- reaction
- cup
- shaped container
- ammonium tetrathiomolybdate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing ammonium tetrathiomolybdate by a hydrothermal-gas phase vulcanization device, which is characterized in that an open cup-shaped container is placed in a polytetrafluoroethylene inner container of a high-pressure reaction kettle; during preparation, the (NH) is put into a cup-shaped container4)2MoO4Putting a sulfur source water solution into a polytetrafluoroethylene inner container, sealing the reaction kettle, then carrying out reaction, and after the reaction is finished, carrying out vacuum drying on a sample in a cup-shaped container to obtain (NH)4)2MoS4. The reaction device of the invention is cheap and easy to obtain, the operation method is simple and easy to implement, the whole process is reacted in a closed dark system, and (NH) is avoided4)2MoS4The photo-oxidation effect improves the purity of the product; the device has no loss of hydrogen sulfide gas and tail gas absorption, does not need to be filtered in product collection, and has no waste liquid (NH)4)2MoS4The yield can reach 100 percent, and the requirement of green synthesis is met.
Description
Technical Field
The invention relates to a green preparation method of ammonium tetrathiomolybdate, belonging to the field of inorganic salt preparation.
Background
Ammonium tetrathiomolybdate has wide application, such as preparation of molybdenum disulfide as precursor[1]As medicaments[2,3]And as novel hydrogen sulfide donors[4]Etc., which have attracted considerable interest to researchers. At present, the preparation method of ammonium tetrathiomolybdate is mainly a liquid phase synthesis method[5,6]Taking a mixed solution of ammonium sulfide, ammonia water and water as a sulfur source, adding ammonium molybdate into the mixed solution, reacting for a proper time at 60-80 ℃, cooling, crystallizing, filtering, washing and drying to obtain (NH)4)2MoS4. This method is simple and easy to implement, but also has two distinct disadvantages: aIs low in yield due to (NH)4)2MoS4Readily soluble in water and difficult to crystallize out of solution after sulfidation, and thus (NH)4)2MoS4The yield is lower; secondly, the residual filtrate can not be recycled, because the sulfur source used by the method is ammonium sulfide aqueous solution, and the concentration of the industrial normal pressure analysis pure-grade ammonium sulfide aqueous solution is only 20 percent, the residual filtrate needs to be added into the ammonium sulfide solution again if being recycled, so that the water content in the solution is increased continuously, and (NH) is reduced4)2MoS4The concentration is too low to crystallize out. If the remaining filtrate can not be recycled, a large amount of waste liquid containing sulfur and molybdenum is generated, which not only causes environmental protection pressure, but also seriously wastes resources and increases synthesis cost. For this reason, there is a literature proposing the use of hydrogen sulfide as a sulfur source to improve (NH)4)2MoS4Synthetic process of[7]. However, this improved approach still presents significant problems: because the reaction efficiency of hydrogen sulfide is low due to the low-pressure sulfuration reaction, a lot of hydrogen sulfide gas in tail gas needs to be absorbed by alkali liquor, so that hydrogen sulfide is wasted, and the recovery cost is increased.
Reference documents:
[1]MoS prepared by taking ammonium tetrathiomolybdate as precursor2And Ni-Mo-S catalyst hydrodesulfurization reaction Performance study [ J]Petroleum refining and chemical industry 2014(6) 48-53.
[2] Zhang Xia Qing, ammonium tetrathiomolybdate enhances the function of cisplatin in resisting esophageal squamous carcinoma and the molecular mechanism [ D ]. Zheng Zhou university, 2018
[3] Mechanism of copper transport and action with platinum drugs of copper chaperone protein Atox1 & gt, syagons [ D ]. university of science and technology in china, 2013.
[4] The identification of Mengfui, Chen Li, Xun fit, et al, ammonium tetrathiomolybdate as novel hydrogen sulfide donor and its protective effect on skin cells [ J ]. J. pathophysiology, 2015,31(12):2271-2276.
[5] The preparation method of ammonium tetrathiomolybdate is improved from Chaoyngming, Zhaohui, Liuyuqi, et al, the industry of inorganic salts, 2007,39(5):12-15.
[6] Study on improvement of synthesis methods of ammonium tetrathiomolybdate and ammonium tetrathiotungstate [ J ] proceedings of Jilin academy of Industrial science, 1994,15(3):56-59
[7] Plum, He Jian, Zhang Xiang, et al, a green preparation method of ammonium tetrathiomolybdate powder is Chinese 104556229.3[ P ] 2015-04-29.
Disclosure of Invention
In order to solve the problems of purity, yield, cost and pollution of the existing liquid-phase and gas-phase synthesis of ammonium tetrathiomolybdate, the invention provides a method for preparing the ammonium tetrathiomolybdate by a hydrothermal-gas-phase vulcanization device, and aims to obtain a high-quality ammonium tetrathiomolybdate product by a green synthesis method.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention discloses a method for preparing ammonium tetrathiomolybdate by a hydrothermal-gas phase vulcanization device, which is characterized by comprising the following steps of: as shown in fig. 1, the hydrothermal-gas phase vulcanizing device is characterized in that an open cup-shaped container is placed in a polytetrafluoroethylene inner container of a high-pressure reaction kettle;
during preparation, the (NH) is put into a cup-shaped container4)2MoO4Putting a sulfur source water solution into a polytetrafluoroethylene liner, sealing the reaction kettle, and then reacting for 10-36 hours at the temperature of 50-100 ℃; after the reaction is finished, taking out the sample in the cup-shaped container, and drying in vacuum to obtain (NH)4)2MoS4。
Further, after the reaction is finished, the sulfur source water solution in the polytetrafluoroethylene liner can be recycled.
Further, will (NH)4)2MoO4After being wetted by water, the mixture is added into a cup-shaped container, so that the reaction speed can be accelerated, and the reaction time can be shortened.
Further, (NH)4)2MoO4And mixing with a sulfur source water solution according to the mol ratio of Mo to S of 1: 4-6.
Further, the sulfur source water solution is a thiourea water solution with the mass concentration of 30-60%, a thioacetamide water solution with the mass concentration of 20-30%, or a mixture of sulfur and a liquid reducing substance according to the mass volume ratio of 4 g: 15-20 mL of the mixture. Still further, the aqueous solution of a sulfur source is preferably an aqueous solution of thiourea.
Furthermore, the reducing substance is formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, citral and hydrazine hydrate.
The hydrothermal-gas phase sulfurizing device separates a molybdenum source from a sulfur source, and hydrogen sulfide gas generated by slow reaction of the sulfur source is used as (NH)4)2MoO4After absorption is converted into (NH)4)2MoS4. The product does not need to be filtered, and pure (NH) can be obtained only by vacuum drying4)2MoS4. The specific reaction is as follows:
(NH4)2MoO4+4H2S＝(NH4)2MoS4+4H2O
compared with the prior art, the invention has the beneficial effects that:
1. the reaction device is cheap and easy to obtain, the operation method is simple and easy to implement, no waste liquid is generated, the post-treatment is simple, and the requirement of green chemistry is met.
2. The invention diffuses and is (NH) by hydrogen sulfide gas generated by slow reaction of sulfur source4)2MoO4Conversion to (NH) after surface absorption4)2MoS4The method improves the sulfuration efficiency, the conversion and yield of the molybdenum can reach 100 percent, and the method can be used for large-scale production.
3. The whole reaction is carried out in a high-pressure closed reaction kettle, the loss of hydrogen sulfide gas is avoided, the sulfur source is saved, tail gas absorption is not needed, the reaction cost is reduced, and meanwhile, a closed dark system also avoids (NH)4)2MoS4The photo-oxidation effect of the method improves the purity of the product.
Drawings
FIG. 1 is a schematic illustration of the preparation of ammonium tetrathiomolybdate by a hydrothermal-vapor phase sulfidation apparatus in accordance with the present invention;
FIG. 2 is a photograph of ammonium tetrathiomolybdate obtained in the present invention, from which it can be seen that the ammonium tetrathiomolybdate is a reddish crystal showing a greenish luster.
FIG. 3 is an XRD pattern of an ammonium tetrathiomolybdate sample obtained by the method, and the diffraction peak of the product is found to correspond to the position of a standard diffraction peak of the ammonium tetrathiomolybdate by comparing with a standard XRD card (JPCDS: 48-1662), and no impurity peak exists, so that the ammonium tetrathiomolybdate prepared by the method has good crystallinity and high purity.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof will be described in detail with reference to the following examples. The following is merely exemplary and illustrative of the inventive concept and various modifications, additions and substitutions of similar embodiments may be made to the described embodiments by those skilled in the art without departing from the inventive concept or exceeding the scope of the claims defined thereby.
Example 1
This example prepares ammonium tetrathiomolybdate as follows:
weighing 10g (NH)4)2MoO4Putting the mixture into a cup-shaped container, adding 50mL of 32 wt% thiourea aqueous solution into a polytetrafluoroethylene inner container of a reaction kettle, putting the cup-shaped container containing ammonium molybdate into the polytetrafluoroethylene inner container to form a nested relation, and reacting for 24 hours at 70 ℃. And after the reaction is finished, cooling to room temperature, and drying the obtained product in vacuum at 60 ℃ to obtain an ammonium tetrathiomolybdate product.
Example 2
This example prepares ammonium tetrathiomolybdate as follows:
weighing 10g (NH)4)2MoO4Wetting with 5mL of water, and then putting into a cup-shaped container; adding 50mL of 32 wt% thiourea aqueous solution into a polytetrafluoroethylene inner container of a reaction kettle; and then putting the cup-shaped container containing the ammonium molybdate into a polytetrafluoroethylene inner container to form a nested relation, and reacting for 10 hours at 70 ℃. And after the reaction is finished, cooling to room temperature, and drying the obtained product in vacuum at 60 ℃ to obtain an ammonium tetrathiomolybdate product.
By comparison with example 1, it was found that the sulfidation time was reduced after wetting the ammonium molybdate with water, since the hydrogen sulfide gas dissolved in water reacts more readily with the ammonium molybdate.
Example 3
This example prepares ammonium tetrathiomolybdate as follows:
weighing 10g (NH)4)2MoO4Wetting with 5mL of water, and then putting into a cup-shaped container; adding 4g of sulfur and 15mL of acetaldehyde into a polytetrafluoroethylene inner container of a reaction kettle; and putting the cup-shaped container containing ammonium molybdate into a polytetrafluoroethylene liner to form a nested relation, reacting for 18 hours at 70 ℃, cooling to room temperature after the reaction is finished, and drying the obtained product in vacuum at 60 ℃ to obtain an ammonium tetrathiomolybdate product.
By comparison with example 2, it was found that the reaction rate was slower with sulfur and acetaldehyde as the sulfur source.
Claims (4)
1. A method for preparing ammonium tetrathiomolybdate by a hydrothermal-gas phase vulcanization device is characterized by comprising the following steps: the hydrothermal-gas phase vulcanization device is characterized in that an open cup-shaped container is placed in a polytetrafluoroethylene inner container of a high-pressure reaction kettle;
during preparation, the (NH) is put into a cup-shaped container4)2MoO4Putting a sulfur source water solution into a polytetrafluoroethylene liner, sealing the reaction kettle, and then reacting for 10-36 hours at the temperature of 50-100 ℃; after the reaction is finished, taking out the sample in the cup-shaped container, and drying in vacuum to obtain (NH)4)2MoS4；
The sulfur source water solution is a thiourea water solution with the mass concentration of 30-60%, a thioacetamide water solution with the mass concentration of 20-30%, or the mass volume ratio of sulfur to liquid reducing substances is 4 g: 15-20 mL of a mixture;
the reducing substances are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, citral and hydrazine hydrate.
2. The method for preparing ammonium tetrathiomolybdate through a hydrothermal-vapor phase sulfidation apparatus according to claim 1, wherein: after the reaction is finished, the sulfur source water solution in the polytetrafluoroethylene liner can be recycled.
3. The method for preparing ammonium tetrathiomolybdate through a hydrothermal-vapor phase sulfidation apparatus according to claim 1, wherein: will be (NH)4)2MoO4Moistened with water and added to the cup-shaped container.
4. The method for preparing ammonium tetrathiomolybdate through a hydrothermal-vapor phase sulfidation apparatus according to claim 1, wherein: (NH)4)2MoO4And mixing with a sulfur source water solution according to the mol ratio of Mo to S of 1: 4-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811500462.4A CN109368698B (en) | 2018-12-10 | 2018-12-10 | Method for preparing ammonium tetrathiomolybdate through hydrothermal-gas phase vulcanization device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811500462.4A CN109368698B (en) | 2018-12-10 | 2018-12-10 | Method for preparing ammonium tetrathiomolybdate through hydrothermal-gas phase vulcanization device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109368698A CN109368698A (en) | 2019-02-22 |
| CN109368698B true CN109368698B (en) | 2021-02-05 |
Family
ID=65372756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811500462.4A Active CN109368698B (en) | 2018-12-10 | 2018-12-10 | Method for preparing ammonium tetrathiomolybdate through hydrothermal-gas phase vulcanization device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109368698B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461061B (en) * | 2021-07-28 | 2022-08-23 | 洛阳申雨钼业有限责任公司 | Preparation method of high-purity molybdenum disulfide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645471B (en) * | 2016-04-08 | 2017-10-03 | 合肥工业大学 | A kind of method that nanometer fibrous poly- molybdic acid class material cures prepare molybdenum disulfide nano tube |
| CN106186070B (en) * | 2016-07-20 | 2017-09-29 | 合肥工业大学 | A kind of preparation method of porous rich defect molybdenum disulfide |
| CN108726573B (en) * | 2017-04-20 | 2021-05-14 | 中国石油化工股份有限公司 | Tetrathiomolybdate solution, preparation method and application thereof |
-
2018
- 2018-12-10 CN CN201811500462.4A patent/CN109368698B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109368698A (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109368698B (en) | Method for preparing ammonium tetrathiomolybdate through hydrothermal-gas phase vulcanization device | |
| CN109626437A (en) | A kind of preparation method of manganese sulfide | |
| CN101624207B (en) | Method for preparing dithio-metal acid ammonium | |
| CN108855207B (en) | Heteroatom Beta zeolite catalyst containing alkali metal and preparation method and application thereof | |
| CN104493194A (en) | Preparation method of Ag-Ag8SnS6 heterodimer nanomaterial | |
| CN107986333B (en) | Method for synthesizing molybdenum-sulfur complex by reacting molybdate solution or molybdenum-containing tungstate solution with trithiocyanic acid (salt) | |
| CN105668635A (en) | Preparation method of ammonium tungsten oxide sulfide | |
| CN103539705B (en) | The process for cleanly preparing of a kind of urea groups anilinechloride | |
| CN103303974B (en) | Method for recycling waste silicon slag discharged in production of zirconyl chloride | |
| CN111018681B (en) | Method for preparing benzoin in micro-reaction device | |
| CN115231608B (en) | Chemical method for preparing multi-sulfide nanocrystalline at normal temperature | |
| CN105668628B (en) | Preparation method of ATTM (Ammonium Tetrathiomolybdate) | |
| CN105037225A (en) | Preparation method of organic vulcanizing agent for hydrogenation catalyst pre-vulcanizing | |
| CN106800303B (en) | Method for preparing potassium iodide by using microchannel reactor | |
| Quin | The Synthesis of Tetrakis-(dichloromethylphosphine)-nickel from Methyldichlorophosphine and Nickel1a | |
| CN113562744A (en) | Environment-friendly synthesis method of potassium thiocyanate | |
| CN109400511B (en) | A method of preparing thiourea derivative co-production mercaptopropionic acid | |
| CN109485544B (en) | Method for continuously preparing trimethylolpropane | |
| CN106430323B (en) | A kind of method for preparing ferrite | |
| CN101948548B (en) | Device and method for preparing dialdehyde starch from corn starch by photo-catalytic oxidation | |
| RU2031167C1 (en) | Method of treating tungsten-molybdenum concentrates | |
| CN105585048A (en) | Preparation method of ammonium thiomolybdate | |
| CN110040765B (en) | Compound NH4InS2And preparation method and application thereof | |
| CN112279795B (en) | Method for continuously producing thiourea by using microchannel reactor | |
| RU2073032C1 (en) | Process for preparing polysulfide polymers, and complex compounds of alkaline metal or ammonium hydrosulfides with sulfur as reagents for realizing this process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |