CN108101005A - A kind of preparation method of alkaline earth sulfide - Google Patents
A kind of preparation method of alkaline earth sulfide Download PDFInfo
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- CN108101005A CN108101005A CN201810055257.5A CN201810055257A CN108101005A CN 108101005 A CN108101005 A CN 108101005A CN 201810055257 A CN201810055257 A CN 201810055257A CN 108101005 A CN108101005 A CN 108101005A
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- alkaline earth
- sulfide
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- chloride
- metal chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/42—Sulfides or polysulfides of magnesium, calcium, strontium, or barium
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A kind of preparation method of alkaline earth sulfide, it is placed in the mixture of alkali metal chloride, alkaline earth metal chloride or both in reactor, it is heated up to after melting as reaction medium, at 300 ~ 750 DEG C, in an inert atmosphere, by soluble metal sulfide or by the above-mentioned soluble metal sulfide of stoichiometric and the mixture of alkaline earth metal chloride, add in or using container be contained up in above-mentioned reaction medium 1 ~ 4 it is small when, solid product is taken out after reaction, and alkaline earth sulfide is obtained after being cleaned by ultrasonic using dimethyl sulfoxide.The present invention provide a kind of low energy consumption, process safety alkaline earth sulfide preparation method.
Description
Technical field
A kind of preparation method of the preparation method, more particularly to magnesium sulfide, calcium sulfide of alkaline-earth metal metal sulfide.
Background technology
Alkaline earth sulfide purposes is quite extensive, can prepare the chemical products such as thiocarbamide/akali sulphide/sulphur/sulfuric acid, can be with
As phosphor, fluorescent material, it can also be used to medicine, environmental protection, heavy metal processing etc..Calcium sulfide may be used as in wastewater treatment
Vulcanizing agent, luminescent material, tanning depilatory agent, agriculture chemicals fungicide, lubricant additive etc..Magnesium sulfide takes off available for steel
Sulphur produces fluorescent powder, the semiconductor as wide band gap.
The sulfide of alkaline-earth metal is met water and is easily hydrolyzed.Therefore, these metal sulfides can not possibly use wet method from solution
Middle preparation, and dry method can only be used.The preparation method of calcium sulfide is mainly produced by oxidation-reduction method, and reducing agent mainly has
Coal, carbon monoxide, hydrogen etc., oxidant mainly include calcium sulfate, gypsum etc..Also part is produced by acid-base neutralization method, it is main
If prepared by the reactions such as hydrogen sulfide and calcium oxide, lime stone.The preparation method of magnesium sulfide then includes magnesium metal or ammonium magnesium chloride
It is heated in hydrogen sulfide air-flow or magnesium sulfate is prepared in carbon disulfide air-flow high temperature（800 ~ 1000 DEG C of reaction temperature）.With
Upper method high energy consumption, and in safety in production, there are great risks.Therefore the extensive use of Yi Shang sulfide receives greatly
Limitation is supplied in the market even without magnesium sulfide.
The content of the invention
The purpose of the present invention is for deficiency existing for above-mentioned prior art, provide a kind of low energy consumption, the alkali of process safety
The preparation method of earth metal sulfide.
The purpose of the present invention is what is be achieved through the following technical solutions：With alkali metal chloride, alkaline earth metal chloride or
The mixture of both persons is placed in reactor, is heated up to after melting as reaction medium, at 300 ~ 750 DEG C, in inert atmosphere
In, by soluble metal sulfide or by the above-mentioned soluble metal sulfide of stoichiometric and mixing for alkaline earth metal chloride
Close object, add in or using container be contained up in above-mentioned reaction medium 1 ~ 4 it is small when, solid product is taken out after reaction, using two
First sulfoxide obtains alkaline earth sulfide after being cleaned by ultrasonic.
The alkali metal chloride is the mixture of one or several kinds of compositions in Li, Na or K chloride.
The alkaline earth metal chloride is MgCl2Or CaCl2。
The metal sulfide is Li2S、Na2S、K2S or Al2S3In one or more.
It is one kind in nitrogen, argon gas or helium under the inert atmosphere.
The container material quality is higher than 750 DEG C of titanium, stainless steel, molybdenum or tungsten for aluminium oxide, graphite or fusing point.
The present invention is based on following principles：The solubility of alkali metal sulphide and alkaline earth sulfide in molten chloride
It differing greatly, document report aluminium sulfide solubility in magnesium chloride-sodium chloride-potassium chloride fused salt is 3.3mol%, and magnesium sulfide,
Solubility of the calcium sulfide in above-mentioned system almost can be ignored.Li2S、Na2S、K2S in corresponding molten chloride all
With higher solubility.Therefore, in molten chloride, the cation of magnesium chloride or calcium chloride separate out is and above-mentioned
The sulphion of sulfide separate out in fused salt combines generation and precipitates.By taking aluminium sulfide and magnesium sulfide as an example, the following institute of reaction equation
Show：
Al2S3+ 3MgCl2=2AlCl3+3MgS↓
By above-mentioned reaction, aluminium sulfide constantly dissolves, magnesium sulfide then continuous Precipitation, so as to complete by aluminium sulfide to magnesium sulfide
Conversion.Therefore, the Li that the technology of the present invention will can in the market be easy to get2S、Na2S、K2S、Al2S3At relatively low temperatures, exist
Magnesium sulfide, the prepare with scale of calcium sulfide are realized under safe and feasible and production technology simple for process.
Specific implementation method
The following examples are the further descriptions to the present invention, these descriptions are intended merely to that the present invention is better described,
Rather than limitation of the present invention.
Embodiment 1
After the commercially available vulcanized sodium powder for measuring ratio and anhydrous magnesium chloride are inserted graphite crucible, crucible is immersed into molar ratio 1:1
In the fused salt mixt of NaCl and KCl, in argon gas atmosphere, temperature be 660 DEG C, impregnate 1 it is small when after by crucible propose fused salt liquid level
And product is taken out after being cooled to room temperature in the reactor, obtain magnesium sulfide after being cleaned by ultrasonic using dimethyl sulfoxide.
Embodiment 2
After the commercially available vulcanization lithium powder for measuring ratio and anhydrous magnesium chloride are inserted alumina crucible, crucible is immersed into LiCl fused salts
In, in nitrogen atmosphere, temperature is 700 DEG C, impregnate 2 it is small when after crucible proposed into fused salt liquid level and be cooled in the reactor normal
Product is taken out after temperature, magnesium sulfide is obtained after being cleaned by ultrasonic using dimethyl sulfoxide.
Embodiment 3
After the commercially available potassium sulfide powder for measuring ratio and anhydrous magnesium chloride are inserted titanium crucible, crucible is immersed into molar ratio 5:3:2
MgCl2, in KCl, NaCl fused salt, in helium atmosphere, temperature is 400 DEG C, impregnate 4 it is small when after crucible proposed into fused salt liquid level simultaneously
Product is taken out after being cooled to room temperature in the reactor, magnesium sulfide is obtained after being cleaned by ultrasonic using dimethyl sulfoxide.
Embodiment 4
After the commercially available vulcanization aluminium powder for measuring ratio and anhydrous magnesium chloride are inserted molybdenum crucible, crucible is immersed into molar ratio 5:2:2:1
MgCl2, in KCl, NaCl, LiCl fused salt, in nitrogen atmosphere, temperature is 350 DEG C, impregnate 3 it is small when after crucible is proposed it is molten
Salt liquid level simultaneously takes out product after being cooled to room temperature in the reactor, and magnesium sulfide is obtained after being cleaned by ultrasonic using dimethyl sulfoxide.
Embodiment 5
After the commercially available vulcanized sodium powder for measuring ratio and anhydrous calcium chloride are inserted stainless steel crucible, crucible is immersed into molar ratio 1:3
CaCl2, in NaCl fused salts, in argon gas atmosphere, temperature is 600 DEG C, impregnate 2.5 it is small when after crucible proposed into fused salt liquid level simultaneously
Product is taken out after being cooled to room temperature in the reactor, calcium sulfide is obtained after being cleaned by ultrasonic using dimethyl sulfoxide.
Embodiment 6
Commercially available vulcanized sodium powder is put into anhydrous magnesium chloride fused salt, in argon gas atmosphere, temperature is 750 DEG C, when immersion 1.5 is small
Afterwards, product is taken out after being cooled to room temperature in the reactor, magnesium sulfide is obtained after being cleaned by ultrasonic using dimethyl sulfoxide.
Claims (6)
1. a kind of preparation method of alkaline earth sulfide, it is characterized in that with alkali metal chloride, alkaline earth metal chloride or
The mixture of the two is placed in reactor, and reaction medium is used as after being heated up to melting, at 300 ~ 750 DEG C, in an inert atmosphere,
By soluble metal sulfide or by the above-mentioned soluble metal sulfide of stoichiometric and the mixing of alkaline earth metal chloride
Object, add in or using container be contained up in above-mentioned reaction medium 1 ~ 4 it is small when, solid product is taken out after reaction, using diformazan
Sulfoxide obtains alkaline earth sulfide after being cleaned by ultrasonic.
2. the preparation method of alkaline earth sulfide according to claim 1, it is characterized in that the alkali metal chloride is
The mixture of one or several kinds of compositions in Li, Na or K chloride.
3. the preparation method of alkaline earth sulfide according to claim 1, it is characterized in that the alkaline earth metal chloride
For MgCl2Or CaCl2。
4. the preparation method of alkaline earth sulfide according to claim 1, it is characterized in that the metal sulfide is
Li2S、Na2S、K2S or Al2S3In one or more.
5. the preparation method of alkaline earth sulfide according to claim 1, it is characterized in that being nitrogen under the inert atmosphere
One kind in gas, argon gas or helium.
6. the preparation method of alkaline earth sulfide according to claim 1, it is characterized in that the container material quality is oxidation
Aluminium, graphite or fusing point are higher than 750 DEG C of titanium, stainless steel, molybdenum or tungsten.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810055257.5A CN108101005B (en) | 2018-01-19 | 2018-01-19 | Preparation method of alkaline earth metal sulfide |
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| CN201810055257.5A CN108101005B (en) | 2018-01-19 | 2018-01-19 | Preparation method of alkaline earth metal sulfide |
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| CN108101005A true CN108101005A (en) | 2018-06-01 |
| CN108101005B CN108101005B (en) | 2021-06-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589776A (en) * | 2019-10-28 | 2019-12-20 | 南昌航空大学 | Method for synthesizing magnesium sulfide by mechanical ball milling |
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| JP2008239363A (en) * | 2007-03-26 | 2008-10-09 | National Institute Of Advanced Industrial & Technology | Method for producing composite metal sulfide and method for producing composite metal sulfide sintered compact |
| CN102534218A (en) * | 2012-01-17 | 2012-07-04 | 武汉大学 | Method for producing metal and alloy by reducing metal sulfide with active metal |
| CN102995066A (en) * | 2011-09-09 | 2013-03-27 | 河北联合大学 | Molten salt electrochemical reduction method for removing sulfide inclusions on solid steel surface |
| CN104477965A (en) * | 2014-12-15 | 2015-04-01 | 武汉大学 | Method for synthesizing metal sulfide by gas/molten salt interface reaction |
| CN107321165A (en) * | 2017-09-05 | 2017-11-07 | 华中科技大学 | A kind of method based on fused salt recycling recovery hydrogen sulfide, cos |
-
2018
- 2018-01-19 CN CN201810055257.5A patent/CN108101005B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008239363A (en) * | 2007-03-26 | 2008-10-09 | National Institute Of Advanced Industrial & Technology | Method for producing composite metal sulfide and method for producing composite metal sulfide sintered compact |
| CN102995066A (en) * | 2011-09-09 | 2013-03-27 | 河北联合大学 | Molten salt electrochemical reduction method for removing sulfide inclusions on solid steel surface |
| CN102534218A (en) * | 2012-01-17 | 2012-07-04 | 武汉大学 | Method for producing metal and alloy by reducing metal sulfide with active metal |
| CN104477965A (en) * | 2014-12-15 | 2015-04-01 | 武汉大学 | Method for synthesizing metal sulfide by gas/molten salt interface reaction |
| CN107321165A (en) * | 2017-09-05 | 2017-11-07 | 华中科技大学 | A kind of method based on fused salt recycling recovery hydrogen sulfide, cos |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110589776A (en) * | 2019-10-28 | 2019-12-20 | 南昌航空大学 | Method for synthesizing magnesium sulfide by mechanical ball milling |
| CN110589776B (en) * | 2019-10-28 | 2022-11-08 | 南昌航空大学 | Method for synthesizing magnesium sulfide by mechanical ball milling |
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Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of rare metals, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: GUANGDONG INSTITUTE OF RARE METALS |
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Effective date of registration: 20230907 Address after: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee after: Institute of resource utilization and rare earth development, Guangdong Academy of Sciences Address before: 510651 No. 363, Changxin Road, Guangzhou, Guangdong, Tianhe District Patentee before: Institute of rare metals, Guangdong Academy of Sciences |