CN1260118C - Preparation for metal sulfide - Google Patents
Preparation for metal sulfide Download PDFInfo
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- CN1260118C CN1260118C CN 200410060903 CN200410060903A CN1260118C CN 1260118 C CN1260118 C CN 1260118C CN 200410060903 CN200410060903 CN 200410060903 CN 200410060903 A CN200410060903 A CN 200410060903A CN 1260118 C CN1260118 C CN 1260118C
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Abstract
The present invention relates to a method for preparing metal sulfide, elemental sulfur and metal or metal protosulfide are placed in an organic solvent together and react for 6 to 120 hours at the temperature of 100 to 500 DEG C and under the atmospheric pressure of 1 to 800 to obtain metal sulfide. The method of the present invention has the obvious advantages that compared with a method for synthesizing the metal and the elemental sulfur at high temperature, the risk is obviously reduced, a large amount of toxic gas is not used or generated, the raw material has low cost and can be easily obtained, the production technology is simple, the reaction conditions can be controlled easily, the present invention is favorable to the mass production of metal sulfide material, etc. The present invention can be used for preparing the metal sulfide only containing a single metal element or composite metal sulfide containing various metal elements. The prepared sulfide product is usually superfine powder whose fundamental particle dimension is less than 5 mu, and the prepared sulfide product can also be directly used as a catalyst and battery material.
Description
Technical Field
The invention relates to a preparation method of a metal sulfide.
Background
Many metal sulfides exhibit excellent physical properties such as photoelectric properties, thermoelectric properties, electromagnetic properties, semiconductors and the like, and have wide applications in physical electric and magnetic devices. Also, many metal sulfides (e.g., sulfides of Mo, W, etc.) have excellent catalytic properties in chemistry; in addition, some sulfides (such as sulfides of Fe, Co and Ni) can also be used as positive and negative electrode materials of the medium-low temperature battery. But due to the limitations of the synthesis method, the sulfide material is difficult to be produced in batches.
Generally, the metal sulfide can be prepared by mixing and reacting elemental metal and sulfur together. In many cases, the production of sulfides (e.g., many transition metal sulfides) is generally carried out at higher temperatures because the solid-solid reaction at low temperatures is difficult to occur. The reaction process is as follows:
to avoid oxidation by oxygen, the reactor needs to be sealed. Because of the strong corrosiveness of sulfur vapor at high temperatures, only quartz reactors are generally used. In this method, the reactants are sealed into the quartz reactor, typically in a vacuum environment, and fired at high temperatures. Since, on the one hand, the sulfur vapor pressure at high temperatures is too high; on the other hand, the reaction process of metal and sulfur vapor is very violent and often explosive, and quartz is not a good pressure-resistant material, so that the method is very dangerous. The complexity of the operation and the potentially great risk make this process unsuitable for the mass production of metal sulphides.
The substitution of elemental sulfur for lower vapor pressure, readily reducible sulfides is sometimes used to produce more stable sulfides (as described in the patent publication CN: 1086493 a) to reduce the demand of the sulfidation reaction on the reactor materials, but obviously complicates the production process and leads to the introduction of unnecessary metallic impurity elements into the product.
The expected product can be obtained by sulfurizing metal oxide and metal salt in hydrogen sulfide at 200-500 ℃; some metal sulfides can be prepared by deposition of water-soluble salts of metals with water-soluble salts of sulfur in an aqueous phase, but in many cases the product tends to be amorphous and tends to contain OH groups, and treatment of this product as a precursor in high-temperature hydrogen sulfide gas makes it possible to obtain various sulfides and sulfide complexes (Inorganic Chemistry, 42, 1764 (2003)). The products synthesized by these methods tend to have poor crystallinity and involve toxic gas H2S is used in a large amount. A similar method is also to react the metal salt with Na at a temperature above 300 DEG C2S2The reaction to produce metal sulfides, and mixing the product with byproducts to form a solid solution (J.chem.SoC.Dalton trains., 12, 1872 (2001)), and sulfide production methods such as the very similar chloride method (Inorganic Chemistry, 20, 2631(1981)), the sulfate method (Inorganic Chemistry, 23, 872(1984)), and the like are also included.
The thermal decomposition of sulfur-containing organometallic compounds (J.solid State chem., 101, 115 (1992); 109, 70(1994)) is also a common method for producing small amounts of sulfides, and apparently has many disadvantages such as expensive raw materials.
Thioferamite sulfide (FeS) as a catalyst and a battery material2、CoS2Etc.) a process known as the hydrothermal method was employed. For example, Japanese patent laid-open No. 59-183831 discloses a method of using sulfuric acid heptahydrateFeS is synthesized by taking ferrous, sodium sulfide and sulfur as raw materials through a hydrothermal method2. Similarly, FeS was synthesized hydrothermally in deionized water at 200 ℃ from the literature (proceedings of Beijing university of science and technology, 18(1), 69(1996)) using ferrous sulfate heptahydrate, sodium thiosulfate and sulfur2It is found that the reaction is greatly influenced by the pH value and is not suitable for control,and the product recovery rate is lower. One disadvantage of using an aqueous solution process for the preparation of metal sulfides is that metal sulfides are susceptible to hydrolysis.
Correspondingly, the solvothermal method is also used for producing metal sulfides. The document (j.solid State chem., 146, 484(1999)) reports a process for the solvothermal reaction of a plurality of transition metal sulfides of a single metal element starting from a metal nitrate, chloride salt or sulfate with an excess of S in an organic solvent at 120 ℃. This reaction achieves the sulfurization of the metal element by means of a disproportionation reaction of sulfur, but at the same time also leads to SCl2And the like, and the generation of toxic gases in large quantities. The literature (mater. chem. phys., 66(1), 97(2000)) reports anhydrous metal chlorides and Na2S3FeS is prepared by a solvothermal method in an organic solvent at 180 DEG C2、CoS2The raw materials are not easily available in this method.
Under the condition of room temperature, for example, copper powder and solid sulfur powder are mixed and hardly react; however, if sulfur is dissolved in acetone, it reacts with copper metal to form Cu2And S. Obviously, the reaction activity of S can be improved by dissolving the S in an organic solvent, but on one hand, the solid-liquid phase reaction is difficult to be completely carried out at normal temperature and normal pressure, and a high-purity product is difficult to obtain; on the other hand, many pyrite-type sulfides (FeS)2、CoS2、NiS2Etc.) cannot be produced at all by this method at normal temperature and pressure, and thus, it is impossible to produce a metal sulfide in large quantities by this method under conventional conditions.
The invention content is as follows:
the invention aims to provide a preparation method of a metal sulfide, which is simple, low in production cost, relatively environment-friendly and beneficial to batch production.
The inventionThe technical scheme is as follows: process for the preparation of metal sulphides by reacting elemental sulphur with a metal (Me) or metal oligosulphide (MeS)x) Putting the components together in an organic solvent, and reacting the components at 100-500 ℃ under 20-800 atmospheric pressure for 6-120 hours by a solvothermal method to prepare the metal sulfide MeSy(wherein y>0, 0<x<y). The metal oligosulfides are metal sulfides that have a lower stoichiometric sulfur content than the target metal sulfide. The "metal (Me)" of the present invention may contain only a single metal element or may be a combination of two or more metal elements. For example, the metal may include a simple substance, an alloy, a metal mixture, and the like, and the metal sulfide may be a sulfide of only one metal element, or may be a composite metal sulfide including two or more metal elements. The metal sulfide is a metal sulfide composed of a metal and sulfur in a bonding action.
The metal includes at least one and more transition metal elements.
The primary particle size of the above metal or metal oligosulfide is less than 50 microns.
The organic solvent can be at least one of chloroalkanes (such as chloroform, carbon tetrachloride, etc.), chloroolefins (such as dichloroethylene), benzene-containing rings (such as benzene, toluene, etc.), sulfur-containing organic solvents (such as carbon disulfide, etc.), and various ethers, ketones, alcohols, glycerols, pyridines, and ionic liquids.
The addition amount of sulfur in the raw materials is just to generate MeSyOr excessive, preferably the adding amount of the elemental sulfur is 1.01-1.03 times of the chemical reaction amount.
Wherein the reaction time by the solvothermal method is not more than 5 days.
Sulfide MeS producedyComprising a sulfide catalyst containing a transition metal element and a transition metal disulfide of the pyrite type.
Compared with the prior art, the invention mainly utilizes the high reaction activity of the dissolved sulfur under certain temperature and pressure to directly generate addition reaction with metal or metal hyposulfide, thereby preparing some functional metal sulfide materials in a milder environment. The method of the invention comprises the following steps: the danger of the implementation process is obviously reduced compared with the direct high-temperature synthesis method of metal and sulfur simple substance; does not involve the use of large quantities of toxic gases or the generation of toxic gases; the raw material cost is low and the raw material is easy to obtain; the production process is simple, and the reaction conditions are easy to control; the method is beneficial to the mass production of metal sulfide materials and the like. The invention can be used for preparing metal sulfides containing only a single metal element or composite metal sulfides containing a plurality of metal elements.
Drawings
The FIGURE is an X-ray analysis plot of several metal sulfides prepared by the method of the present invention. Wherein (a) SnS and (b) NiS2、(c)CoS2、(d)FeS2、(e)Fe0.7Co0.3S2。
Detailed Description
The raw material for preparing the metal sulfide in the invention comprises a metal component and elemental sulfur, wherein the metal component is defined in the invention to be metal elemental, alloy, metal mixture and the like, and can be other forms of metal sulfides and composite metal sulfides which have lower sulfur content than the target product and are easy to prepare. The metal component powder, elemental sulfur and an organic solvent capable of dissolving sulfur are placed in a high-pressure reaction kettle together, heating is carried out within the temperature range of 100-500 ℃, during the heating, 1-800 atmospheres of pressure are applied to the substances in the reaction kettle, and through the thermal reaction of the solvent, the metal sulfide or the composite metal sulfide can be generated relatively easily.
When the reaction kettle is used for feeding, the metal component powder and the elemental sulfur are not required to be uniformly mixed. As the organic solvent can dissolve the sulfur, the organic solvent transports the sulfur to a required place after the reaction starts, thereby ensuring the required supply of elemental sulfur. This sulfur is supplied in a manner similar to the supply of oxygen in blood, with high efficiency and uniformity.
The reaction process is equivalent to a solid-liquid phase reaction under heating and pressurizing, on one hand, the dissolved sulfur under heating and pressurizing has high reaction activity and can directly react with the metal component to generate a target product, and on the other hand, the environment under heating and pressurizing is favorable for solid-phase diffusion of sulfur so as to realize complete vulcanization of the metal component powder. The use of smaller sized (less than 50 microns) metal component powders and extended reaction times are advantageous for obtaining high purity target metal sulfides. The whole reaction time varies according to the properties of target products and raw materials, and generally does not exceed 5 days.
The metal sulfideis generally insoluble and non-hydrolyzable in the organic solvent, and thus exists in the form of a solid in the reactor, and product separation is easily achieved. The product prepared by the invention is metal sulfide powder, the basic particle size of the metal sulfide powder is generally less than 5 microns, and the metal sulfide powder can be directly used as a catalyst or a battery material. The elemental sulfur is sometimes in proper excess when the metal sulfide is prepared, and the excess sulfur is generally dissolved in an organic solvent and can be removed by filtration. However, since the specific surface area of the product is too large and a small amount of organic solvent and elemental sulfur are easily adsorbed, the product is generally washed with a solvent such as carbon disulfide to remove the residual organic solvent and elemental sulfur.
In the preparation of the complex metal sulfide, if a metal is used as a raw material, it is necessary to highly disperse various metal elements in the raw material, for example, alloy powder or a mixture of metal powders dispersed very uniformly is used as a raw material of a metal component.
Another way is to use highly dispersed low sulfur complex sulfides as the metal component raw material for producing complex metal sulfides. In particular, for example, FexCo(1-x)S2When x is more than 0 and less than 1, the highly dispersed composite metal sulfide Fe can be obtained by an aqueous solution codeposition methodxCo(1-x)S (x is more than 0 and less than 1) is used as a metal component raw material. Nevertheless, there are results showing that Fe was produced by this aqueous solution co-deposition methodxCo(1-x)A small amount of hydroxyl groups may be contained in S (0<x<1), but the experimental results show that the preparation of the target product is not influenced.
The invention can adopt a mode of compact solid particle accumulation when the raw materials are added into the autoclave, thereby improving the single-kettle reaction yield. The method of the invention can be used for mass production of metal sulfides.
The following describes embodiments of the present invention in detail.
Example 1: placing 16 g of single copper powder and single sulfur in an atomic ratio of 2: 1 in a 30ml high-pressure reaction kettle, adding acetone to 90% of the reactor, keeping the temperature of the reaction kettle at 110 ℃ for 3 days under 20 atmospheres, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain Cu2S15.3 g, X-ray analysis showed the product to be Cu2S。
Example 2: 12.8 g of simple substance Sn powder and simple substance sulfur in the atomic ratio of 1: 1.03 are put into a 30ml high-pressure reaction kettle, and toluene is added to 90 percent of the reactor. And (3) keeping the temperature of the reaction kettle at 220 ℃ for 3 days under the atmospheric pressure of about 300, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain 12.2 g of SnS, wherein the result of X-ray analysis shows that the product is SnS.
Example 3: 10 g of metallic nickel powder and 11.3 g of elemental sulfur are placed in a 50ml high-pressure reaction kettle, and toluene is added to 90 percent of the reactor. Keeping the temperature of the reaction kettle at 220 ℃ under 300 atmospheres for 5 days, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain NiS220.2 g, X-ray and EDX analysis showed the product to be NiS2。
Example 4: mixing NiCl2.6H2O and Na2S.9H2DissolvingO in the water solution to obtain NiS black precipitate, filtering and drying to obtain the self-made NiS. 36.9 g of self-made NiS powder and 13.3 g of elemental sulfur are placed in a 100ml high-pressure reaction kettle, and toluene is added to 90 percent of the reactor. Keeping the temperature of the reaction kettle at 180 ℃ under 200 atmospheres for 5 days, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain NiS247.8 g, X-ray and EDX analysis showed the product to be NiS2。
Example 5: CoS was prepared as in example 3. 14.7 grams of CoS and 5.3 grams of elemental sulfur were placed in a 100ml autoclave and toluene was added to 90% of the reactor.Keeping the reaction kettle at 250 ℃ under 400 atm for 5 days, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain CoS218.4 g, X-ray and EDX analysis showed the product to be CoS2。
Example 6: CoS was prepared as in example 3. 14.7 grams of CoS and 5.3 grams of elemental sulfur were placed in a 100ml autoclave and toluene was added to 90% of the reactor. Keeping the temperature of the reaction kettle at about 800 atmospheric pressure and 180 ℃ for 5 days, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain CoS218.4 g, X-ray and EDX analysis showed the product to be CoS2。
Example 7: FeS was prepared as in example 3 (proper inert gas shielding was used for the preparation of FeS due to its susceptibility to oxidation). 21.4 grams of FeS and 8.0 grams of elemental sulfur were placed in a 50ml autoclave and toluene was added to 90% of the reactor. Keeping the reaction kettle at the constant temperature of about 300 atmospheric pressure for 5 days, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, anddrying to obtain FeS227.7 g, X-ray and EDX analysis showed the product to be FeS2。。
Example 8: preparation of Fe by aqueous solution codeposition0.7Co0.3S, 10 g of Fe0.7Co0.3S and 3.7 g of elemental sulfur are placed in a 30ml high-pressure reaction kettle, and toluene is added to 90 percent of the reactor. Keeping the temperature of the reaction kettle at 250 ℃ under 400 atm for 5 days, naturally cooling, filtering to obtain product powder, washing with carbon disulfide, and drying to obtain Fe0.7Co0.3S2The X-ray analysis of the complex sulfide of 12.5 g shows that the product is a pyrite structure, and the EDX analysis shows that the iron-cobalt metering ratio is 2.33 +/-0.05.
Claims (8)
1. The preparation method of the metal sulfide is characterized by comprising the following steps: and putting the elemental sulfur and the metal or the metal low-sulfide together into an organic solvent, and reacting for 6-120 hours at 100-500 ℃ under 20-800 atmospheric pressure to obtain the metal sulfide.
2. The method of claim 1, wherein: the metal is a single metal element or a composition of two or more metal elements; the metal sulfide is a sulfide of one metal element or a composite metal sulfide of two or more metal elements.
3. The method of claim 2, wherein: the composition of two or more metal elements is an alloy or a metal mixture.
4. The process according to claim 1, 2 or 3, wherein: the metal includes at least one and more transition metal elements.
5. The process according to claim 1, 2 or 3, wherein: the primary particle size of the metal or metal oligosulfide is less than 50 microns.
6. The process according to claim 1, 2 or 3, wherein: the organic solvent is one or more of chloroalkane, chloroolefin, benzene ring-containing, sulfur-containing organic solvent, and ether, ketone, alcohol, glycerol, pyridine or ionic liquid organic solvent.
7. The process according to claim 1, 2 or 3, wherein: the amount of elemental sulfur added is either a chemically reactive amount or an excess amount.
8. The method of claim 7, wherein: the addition amount of the elemental sulfur is 1.01-1.03 times of the chemical reaction amount.
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| CN101786650B (en) * | 2010-02-08 | 2011-11-02 | 许昌学院 | Chemical method for in situ synthesis of platy silver sulphide nano crystal photoelectric film at low temperature |
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| CN102642874B (en) * | 2012-04-27 | 2013-08-14 | 中南大学 | Ferrous disulfide semiconductor film preparation method |
| CN103066254B (en) * | 2012-12-26 | 2015-05-27 | 浙江工业大学 | Sulfur/carbon composite material and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101786650B (en) * | 2010-02-08 | 2011-11-02 | 许昌学院 | Chemical method for in situ synthesis of platy silver sulphide nano crystal photoelectric film at low temperature |
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