CN101311122A - Process for preparation of iron sulfide - Google Patents
Process for preparation of iron sulfide Download PDFInfo
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- CN101311122A CN101311122A CNA2007100996347A CN200710099634A CN101311122A CN 101311122 A CN101311122 A CN 101311122A CN A2007100996347 A CNA2007100996347 A CN A2007100996347A CN 200710099634 A CN200710099634 A CN 200710099634A CN 101311122 A CN101311122 A CN 101311122A
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Abstract
The invention discloses a method for synthesizing ferrous sulfide material, which adopts green vitriol and carbon powder as raw materials that are evenly mixed and then synthesized by high-temperature solid-phase reaction under the protection of inert gases to obtain the product of the invention. The obtained ferrous sulfide powder by adopting the method of the invention has high purity, single phase, simple preparation conditions and low cost, which can be synthesized in batch.
Description
Technical field
The present invention relates to the preparation method of a kind of FeS, adopt FeSO
47H
2O and C are blended in the container of sealing through high temperature solid-state is synthetic and obtain the Iron sulfuret product, belong to technical field of new material preparation.
Background technology
Iron sulfuret has the phosphorus sheet structure similar to molybdenumdisulphide or graphite, and hardness is low, and fusing point is up to 1100 ℃.It is the antiferromagnetism semiconductor material, itself be easy to carry out viscous deformation along basal slip, its plastic deformation ability is good, has good lubricating property, thereby be widely used in industrially, often do solid lubricant, electrode and processing and contain waste water of Cr (VI) etc.In addition, Iron sulfuret Chang Zuowei electrode materials is used for secondary fused salt lithium cell.Along with the development of society, FeS also will be subjected to more and more the attention and application.
At present, the preparation method that FeS is commonly used mainly contains: the high temperature solid-state synthetic method and the precipitator method.The high temperature solid-state synthetic method is that to adopt specpure Fe and S be raw material, and Fe is lathed iron filings, adopts hydrogen high temperature reduction device that iron filings are reduced processing.Take by weighing Fe and S by stoichiometry, be packaged in the silica tube that is filled with high-purity argon gas, place in the vertical High Temperature Furnaces Heating Apparatus.Temperature of reaction is 400～1200 ℃.After the cooling,, behind the silica tube of packing into, encapsulate after charging into high-purity argon gas the sample grind into powder.Because Fe powder and reaction of Salmon-Saxl are the reactions of a strong heat release, local superheating " sintering " appears in easy the generation in persulfide or the reaction in the reaction process, thereby stops further carrying out of reaction, and causing products therefrom is the FeS of non-stoichiometric.The another kind method precipitator method are to adopt divalent iron salt such as ferrous sulfate to generate Iron sulfuret with sulfonium ion in the aqueous solution to precipitate, but Iron sulfuret through moisture is very easy to oxidation and generates Z 250 and sulphur in air, therefore this method must secluding air in sedimentation and filtration, drying process, the bad control of process and having relatively high expectations.
Except the several method of the synthetic FeS material introduced above, some other special preparation methods have also been reported in the document, as methods such as microemulsion method, homogeneous precipitation method, electric glow discharge methods, though these methods FeS product purity is higher, but starting material, processing units are relatively more expensive, and production capacity is low, just no longer addresses here.
Summary of the invention
In order to obtain the approach of more excellent preparation FeS material, at the deficiencies in the prior art, it is simple to the purpose of this invention is to provide a kind of method, and process is controlled easily, FeS material preparation method with low cost.Adopt FeSO
47H
2O and C Hybrid Heating, at high temperature SO
4 2-In S be reduced into S by C
2-, generate the FeS material.
The present invention seeks to realize by following method:
(1) be that 5: 0.7～1 mixed is even with ferrous sulfate and C powder by mass ratio;
(2) mixture is placed airtight quartz devices heat, the temperature rise rate with 5～13 ℃/min under protective atmosphere (rare gas element) protection is warmed up to 280～350 ℃, constant temperature 20～60min;
(3) continue down to heat in protective atmosphere (rare gas element) protection behind the constant temperature, be warmed up to 600～800 ℃, under the protection of protective atmosphere (rare gas element), be cooled to room temperature behind constant temperature 3～8h, promptly obtain the Iron sulfuret powder with the temperature rise rate of 5～8 ℃/min.
In above-mentioned method, in step (2), remove crystal water in the ferrous sulfate by vacuum-drying.
In the method for the invention, be to adopt ferrous sulfate as Fe source and S source, C is as reductive agent.Wherein reductive agent C powder is selected from any in graphite, activated carbon, the carbon black, is preferably activated carbon.
In the process of preparation of the present invention FeS, the feeding protective atmosphere is with secluding air in the process of comprise intensifications, insulation, lowering the temperature, and described protective atmosphere is any in nitrogen, argon gas, the helium.
In step (2) and step (3), the pressure of protective atmosphere is 1 * 10
4～5 * 10
4Pa.
In step (1) and step (2), also (2 ') in steps, be about to mixture and be under 100～130 ℃ the vacuum dry 3～5 hours in temperature.Because it is synthetic that step of the present invention (2) and step (3) all are high temperature solid state reactions, and chronic, so this step (2 ') also can be omitted.Wherein, in step (2 '), vacuum drying vacuum tightness is 133～10
4Pa.
The present invention need not to add the sulphur source, relies on reductive agent C with FeSO
47H
2Sexavalence S among the O is reduced into S
2-, realize that Fe and S mol ratio are 1: 1 accurate proportioning, thereby avoided the shortcoming of the easy oxidation of moist FeS in the shortcoming of conventional solid-state method " local sintering " and the liquid-phase precipitation method.Products production equipment realizes easily, and raw material is easy to get, with low cost.
The present invention compares in prior art has following advantage:
1. operation is simple, need not control;
2. product is difficult for oxidation, and exsiccant FeS is difficult for oxidation in atmosphere;
3. the product thing is mutually single, does not have other impurity and exists mutually;
4. equipment is simple, and raw material is easy to get, and is with low cost;
5. realize scale production easily.
For further understanding the present invention, be detailed description with embodiment below, and provide the characteristic present that accompanying drawing is described the FeS that the present invention obtains.
Description of drawings
Fig. 1 obtains the X-diffraction spectrogram of product for embodiment 1;
Fig. 2 obtains the X-diffraction spectrogram of product for embodiment 2.
Embodiment:
Embodiment 1
With analytically pure FeSO
47H
2O5.117g and activated carbon 0.883g mix, and in the quartz glass tube of packing into, after vacuumizing, are 10 at pressure
4Under the nitrogen protection of Pa silica tube is put into tube type resistance furnace, rise to 300 ℃ with the temperature rise rate of 10 ℃/min, insulation 30min after vacuumizing once more, is 1.5 * 10 at pressure
4Temperature rise rate with 7 ℃/min under the nitrogen protection of Pa rises to 800 ℃, constant temperature after 6 hours naturally cooling obtain product, product purity＞98.5%, for the spacer of single phase is the FeS of P63/mmc, the XRD diffracting spectrum is seen Fig. 1.
Embodiment 2
According to embodiment same material and step, with analytically pure FeSO
47H
2O5.001g and graphite 0.862g mix, and are that 120 ℃, vacuum tightness are vacuum-drying 3 hours under the condition of 133Pa in temperature, in the quartz glass tube of after the drying material being packed into, after vacuumizing, are 3 * 10 at pressure
4Under the nitrogen protection of Pa silica tube is put into tube type resistance furnace, rise to 300 ℃ with the temperature rise rate of 13 ℃/min, insulation 30min is after vacuumizing once more, 2 * 10
4Temperature rise rate with 8 ℃/min under the nitrogen protection of Pa rises to 800 ℃, constant temperature 6 hours, and back naturally cooling obtains product, and purity is with embodiment 1, and for the spacer of single phase is the FeS of P63/mmc, the XRD diffracting spectrum is seen Fig. 2.
Embodiment 3
With analytically pure FeSO
47H
2O5.000g and activated carbon 0.723g mix, and in the quartz glass tube of packing into, after vacuumizing, are 2 * 10 at pressure
4Under the Pa protection of nitrogen gas silica tube is put into tube type resistance furnace, rise to 300 ℃ with the temperature rise rate of 10 ℃/min, insulation 40min after vacuumizing once more, is 5 * 10 at pressure
4Temperature rise rate with 7 ℃/min under the nitrogen protection of Pa rises to 800 ℃, constant temperature 6 hours, and back naturally cooling obtains product, and purity is with embodiment 1, for the spacer of single phase is the FeS of P63/mmc.
Embodiment 4
With analytically pure FeSO
47H
2O5.000g and activated carbon 0.996g mix, and in the quartz glass tube of packing into, after vacuumizing, are 2.5 * 10 at pressure
4Under the nitrogen protection of Pa silica tube is put into tube type resistance furnace, rise to 310 ℃ with the temperature rise rate of 12 ℃/min, insulation 30min after vacuumizing once more, is 2 * 10 at pressure
4Temperature rise rate with 6 ℃/min under the nitrogen protection of Pa rises to 800 ℃, constant temperature 6 hours, and back naturally cooling obtains product, and purity is with embodiment 1, for the spacer of single phase is the FeS of P63/mmc.
Claims (4)
1, the preparation method of a kind of FeS is characterized in that, may further comprise the steps:
(1) be that 5: 0.7～1 mixed is even with ferrous sulfate and C powder by mass ratio;
(2) mixture is placed airtight quartz devices heat, the temperature rise rate with 5～13 ℃/min under the protective atmosphere protection is warmed up to 280～350 ℃, constant temperature 20～60min;
(3) under protective atmosphere, continue heating behind the constant temperature, be warmed up to 600～800 ℃, under protective atmosphere, be cooled to room temperature behind constant temperature 3～8h, promptly get the Iron sulfuret powder with the temperature rise rate of 5～8 ℃/min.
According to the preparation method of the described FeS of claim 1, it is characterized in that 2, described C powder is activated carbon, graphite or carbon black.
According to the preparation method of claim 1 or 2 described FeS, it is characterized in that 3, described protective atmosphere is any in nitrogen, argon gas, the helium.
4, according to the preparation method of the described FeS of claim 3, it is characterized in that, in step (1) and step (2), also (2 ') in steps, be about to mixture and be under 100～130 ℃ the vacuum dry 3～5 hours in temperature.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100996347A CN101311122B (en) | 2007-05-25 | 2007-05-25 | Process for preparation of iron sulfide |
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|---|---|---|---|
| CN2007100996347A CN101311122B (en) | 2007-05-25 | 2007-05-25 | Process for preparation of iron sulfide |
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| CN101311122A true CN101311122A (en) | 2008-11-26 |
| CN101311122B CN101311122B (en) | 2010-09-22 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413945A (en) * | 2013-08-27 | 2013-11-27 | 昆明理工大学 | Manufacturing method of positive material for lithium ion battery |
| CN103663832A (en) * | 2013-12-03 | 2014-03-26 | 安徽国星生物化学有限公司 | Ammoniacal cyanide process paraquat production wastewater pretreatment method and reagent thereof |
| CN104030365A (en) * | 2014-06-17 | 2014-09-10 | 北京石油化工学院 | Preparation method of ferrous sulfide |
| CN106986392A (en) * | 2017-04-13 | 2017-07-28 | 环境保护部南京环境科学研究所 | The synthetic method and synthesizer of a kind of troilite |
| CN109167035A (en) * | 2018-08-22 | 2019-01-08 | 郑州大学 | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation |
| CN110092426A (en) * | 2019-04-29 | 2019-08-06 | 济源市中亿科技有限公司 | The synthetic method of a kind of nanometer of ferrous sulfide and its smelting the application in waste acid arsenic removal |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1439083A1 (en) * | 1986-01-28 | 1988-11-23 | Институт коллоидной химии и химии воды им.А.В.Думанского | Method of producing iron sulfide |
| SU1393794A1 (en) * | 1986-07-09 | 1988-05-07 | Химико-металлургический институт АН КазССР | Method of producing troilite |
| CN1012493B (en) * | 1987-01-26 | 1991-05-01 | 中国科学院海洋研究所技术开发公司 | Source aquatics of ferrous iron ions used for eliminating hydrogen sulfide in marine breeding of aquatics |
| KR20030052323A (en) * | 2001-12-21 | 2003-06-27 | 재단법인 포항산업과학연구원 | PREPARING METHOD OF FeS USING BLAST FURNACE SLAG |
-
2007
- 2007-05-25 CN CN2007100996347A patent/CN101311122B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413945A (en) * | 2013-08-27 | 2013-11-27 | 昆明理工大学 | Manufacturing method of positive material for lithium ion battery |
| CN103663832A (en) * | 2013-12-03 | 2014-03-26 | 安徽国星生物化学有限公司 | Ammoniacal cyanide process paraquat production wastewater pretreatment method and reagent thereof |
| CN103663832B (en) * | 2013-12-03 | 2015-04-22 | 安徽国星生物化学有限公司 | Ammoniacal cyanide process paraquat production wastewater pretreatment method and reagent thereof |
| CN104030365A (en) * | 2014-06-17 | 2014-09-10 | 北京石油化工学院 | Preparation method of ferrous sulfide |
| CN104030365B (en) * | 2014-06-17 | 2015-11-25 | 北京石油化工学院 | The preparation method of Iron sulfuret |
| CN106986392A (en) * | 2017-04-13 | 2017-07-28 | 环境保护部南京环境科学研究所 | The synthetic method and synthesizer of a kind of troilite |
| CN109167035A (en) * | 2018-08-22 | 2019-01-08 | 郑州大学 | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation |
| CN109167035B (en) * | 2018-08-22 | 2021-12-24 | 郑州大学 | Carbon-coated ferrous sulfide negative electrode material, preparation method and sodium ion battery prepared from carbon-coated ferrous sulfide negative electrode material |
| CN110092426A (en) * | 2019-04-29 | 2019-08-06 | 济源市中亿科技有限公司 | The synthetic method of a kind of nanometer of ferrous sulfide and its smelting the application in waste acid arsenic removal |
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|---|---|
| CN101311122B (en) | 2010-09-22 |
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Effective date of registration: 20190625 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals Effective date of registration: 20190625 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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